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Logo of actae2this articlesearchopen accesssubmitActa Crystallographica Section E: Crystallographic CommunicationsActa Crystallographica Section E: Crystallographic Communications
 
Acta Crystallogr E Crystallogr Commun. 2017 September 1; 73(Pt 9): 1316–1319.
Published online 2017 August 8. doi:  10.1107/S2056989017009951
PMCID: PMC5588570

Crystal structures of the 2:2 complex of 1,1′-(1,2-phenyl­ene)bis­(3-m-tolyl­urea) and tetra­butyl­ammonium chloride or bromide

Abstract

The title compounds, tetra­butyl­ammonium chloride–1,1′-(1,2-phenyl­ene)bis­(3-m-tolyl­urea) (1/1), C16H36N+·Cl·C22H22N4O2 or [(n-Bu4N+·Cl)(C22H22N4O2)] (I) and tetra­butyl­ammonium bromide–1,1′-(1,2-phenyl­ene)bis­(3-m-tolyl­urea) (1/1), C16H36N+·Br·C22H22N4O2 or [(n-Bu4N+·Br)(C22H22N4O2)] (II), both comprise a tetra­butyl­ammonium cation, a halide anion and an ortho-phenyl­ene bis-urea mol­ecule. Each halide ion shows four N—H(...)X (X = Cl or Br) inter­actions with two urea receptor sites of different bis-urea moieties. A crystallographic inversion centre leads to the formation of a 2:2 arrangement of two halide anions and two bis-urea mol­ecules. In the crystals, the dihedral angle between the two urea groups of the bis-urea mol­ecule in (I) [defined by the four N atoms, 165.4 (2)°] is slightly smaller than that in (II) [167.4 (2)°], which is probably due to the smaller ionic radius of chloride compared to bromide.

Keywords: crystal structure, phenyl­ene bis-urea, tetra­butyl­ammonium chloride, tetra­butyl­ammonium bromide, anion binding

Chemical context  

Hydrogen bonding, π–π inter­actions, anion–π inter­actions, halogen bonds, and anion–macrodipole inter­actions are some of the crucial principal forces that determine structure, self-assembly and recognition in chemical and biological systems (Lehn, 1990  ; Jentzsch et al., 2013  ). Various urea-based anion receptors of varying complexity and sophistication have been designed and prepared (Amendola et al., 2010  ; Wei et al., 2011  ; Bregovic et al., 2015  ). It has been shown that the efficiency of urea to act as a receptor subunit depends on the presence of two parallel polarized N—H fragments, capable of (i) chelating a spherical anion or (ii) donating two parallel hydrogen bonds to the oxygen atoms of a carboxyl­ate or of an inorganic oxoanion (Custelcean, 2013  ). In our ongoing research on N-rich organic ligand design and synthesis (Wang et al., 2015  ), we report herein the synthesis of the title ortho-phenyl­enedi­amine based methyl substituted neutral organic bis-urea receptor L and crystal structures of the 2:2 adducts of L with tetra­butyl­ammonium chloride (TBACl) or bromide (TBABr) (I) and (II).

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Structural commentary  

The mol­ecular structures of the title compounds are illustrated in Figs. 1  and 2  . The receptor L displays a trans orientation of two urea groups showing non-cooperativity to each other. In the presence of 1.5 equivalents of tetra­butyl­ammonium chloride or bromide in acetone and Et2O the 2:2 host–guest complexes (I) and (II) crystallize in the monoclinic space groups P21/n and P21/c, respectively. The 2:2 adducts are formed via N—H(...)X hydrogen bonds between the halide anions and the urea subunits of two bis-urea receptors. Both NH functions of each urea group are trans to the C=O double bond across the respective C—N bond, thereby the aromatic substituents are cis, with small CAr—N—C=O torsion angles [C1—N1—C13—O2 = 2.7 (4) and C15—N2—C12—O1 = 11.4 (3)° in complex (I), C12—N1—C1—O1 = −0.7 (5) and C14—N3—C13—O2 = 8.5 (4)° in complex (II)]. Moreover, it is also evident that the distance between the two terminal aromatic functions varies considerably due to the torsion angles between the two urea groups and between the two phenyl­ene groups. The angles between the planes through the two urea planes are 55.67 (4)° and 54.51 (5)° in (I) and (II), respectively, with the receptors arranging themselves in a way that in the anion complex the urea groups on the two receptors are oriented in opposite directions therefore establishing inter­actions with two symmetry related anions. This results in the formation of a 2:2 non-capsular assembly via non-cooperative equally shared hydrogen-bonding inter­actions between the urea groups and respective anions. This is possibly additionally ascribed for the both syn geometrical orientation of the meta-substituent (–CH3) with respect to the adjacent N—H part of the urea moiety of a particular receptor.

Figure 1
The mol­ecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
Figure 2
The mol­ecular structure of (II), with atom labels and 50% probability displacement ellipsoids for non-H atoms.

Supra­molecular features  

Structural elucidation reveals that in complex (I), two symmetry-related chloride anions accept four strong N—H(...)Cl bonds, and similarly two symmetry-related bromide anions accept four strong N—H(...)Br bonds (Tables 1  and 2  ). In addition, the non-capsular assembly of two symmetry-related halide ions and two receptors L are additionally stabilized by another two C—H(...)O inter­actions and four weak C—H(...)π supportive inter­actions between the two peripheral TBA units and respective receptor mol­ecules. Additional inter­actions between TBA cations, halide anions and receptor mol­ecules L in terms of several short C—H(...)X contacts and C—H(...)O contacts connect the 2:2 adducts into infinite layers (Tables 1  and 2  , Figs. 3  and 4  ). The layers assemble in the 3-D crystal structures (Figs. 3  and 4  ) via weak inter­molecular forces. In complex (I), the first inter-layer inter­actions are C22—H22A(...)Cl1 and C20—H20B(...)Cl1 with C(...)Cl distances of 3.938 (3) and 3.984 (3) Å, respectively; while in complex (II), the C(...)Br distance is 4.003 (3) Å.

Figure 3
Packing of (I), viewed down the c axis, showing one layer of mol­ecules connected by N—H(...)Cl, C—H(...)Cl and C—H(...)O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted. ...
Figure 4
Packing of (II), viewed along the a axis, showing one layer of mol­ecules connected by N—H(...)Br, C—H(...)Br and C—H(...)O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding have been omitted. ...
Table 1
Hydrogen-bond geometry (Å, °) for (I)
Table 2
Hydrogen-bond geometry (Å, °) for (II)

Database survey  

The crystal structure of L with a meta-substitution of methyl group present in complex (I) and (II) appears not to have been reported previously. However, a search for ortho-phenyl­enedi­amine bis-urea with no methyl or any other substitutions on the phenyl ring resulted in some hits. For example, a 1:1 adduct between the bis-urea ligand and benzoate bound in the bis-urea cleft via four hydrogen bonds has been reported (Brooks et al., 2005a  ). Similarly, a single terephthalate anion is encapsulated by two bis-urea receptors in another case (Brooks et al., 2005b  ). Furthermore, an ortho-phenyl­enedi­amine bis-urea with para-nitro substitution receptor has also been reported, three of which enclose one PO4 3– anion by 12 hydrogen bonds (Li et al., 2013  ), whilst the bis-urea isomer with meta-nitro substitution displayed good selectivity for carboxyl­ate anions forming a 2:1 complex between receptor and anion (Moore et al., 2013  ). Very recently, an ortho-phenyl­enedi­amine based 3-chloro-4-methyl disubstituted bis-urea receptor and its isomeric 4-bromo-3-methyl disubstituted bis-urea receptor have been reported and their affinity with the common anions such as Cl, AcO, CO3 2–, SO4 2– and SiF6 2– has also been studied (Manna et al., 2016  ). Especially, the 4-bromo-3-methyl disubstituted bis-urea forms non-capsular 2:2 host–guest assemblies with chloride ions via non-cooperative hydrogen-bonding inter­actions of the urea moieties. This phenomenon is consistent with that of L in the present study. Similarly to our work, structural elucidation reveals that two symmetry-identical chloride anions accept four strong N—H(...)Cl bonds [N1(...)Cl 3.226 (6); N2(...)Cl 3.312 (5); N3(...)Cl 3.305 (6); N4(...)Cl 3.270 (6) Å; average 3.278 (8) Å].

Synthesis and crystallization  

L: A solution of 1-iso­cyanato-3-methyl­benzene (0.74 mL, 5.5 mmol) in di­chloro­methane (DCM, 20 mL) was slowly added to a solution of benzene-1,2-di­amine (0.30 g, 2.82 mmol) in DCM (100 mL). The mixture was stirred and refluxed for 24 h. Then the reaction mixture was filtered (glass-filter G4) to give a white precipitate. This precipitate was washed with DCM (40 mL × 3), a mixture solvent of DCM and THF (3:1, 40 mL × 3), and diethyl ether (40 mL × 3), respectively. After that, the solid was collected by filtration. Finally, this solid was dried under vacuum overnight to give L as white solid (yield 85%, 0.90 g). m.p: 539–540 K. MS (+): m/z 375.20 [L+H]. 1H NMR (400 MHz, DMSO- d 6): δ 9.01 (s, 2H), 8.06 (s, 2H), 7.59 (m, 2H), 7.32 (s, 2H), 7.24 (d, J = 8.3 Hz, 2H), 7.15 (t, J = 7.8 Hz, 2H), 7.07 (m, 2H), 6.78 (d, J = 7.4 Hz, 2H), 2.27 (s, 6H). 13C NMR (400 MHz, DMSO- d 6): δ 153.24, 139.81, 137.97, 131.32, 128.67, 124.02, 123.97, 122.57, 118.72, 115.39, 21.29. FT–IR (KBr pellet, cm−1): 3293, 1636, 1573, 1488, 1297, 1231, 773, 691. Single crystals of complex (I) or (II) suitable for X-ray diffraction were obtained by slow diffusion of an acetone (2 mL) solution of L (0.02 mmol) in the presence of TBACl or TBABr (0.03 mmol) in a closed flask with plenty of diethyl ether in three weeks.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 3  . H atoms bonded to N were located from a difference map and refined with distance restraints of N—H = 0.86 (0) Å, and with U iso(H) = 1.2U eq(N). Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.96–0.97 Å and with U iso(H) = 1.2 (1.5 for methyl groups) times U eq(C).

Table 3
Experimental details

Supplementary Material

Crystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989017009951/im2480sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017009951/im2480Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989017009951/im2480IIsup3.hkl

CCDC references: 1552391, 1556706

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

We would like to acknowledge the ’Comprehensive Training Platform of Specialized Laboratory, College of Chemistry, Sichuan University’ for IR, NMR and XRD analyses.

supplementary crystallographic information

Tetrabutylammonium chloride–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (I)   Crystal data

C16H36N+·Cl·C22H22N4O2F(000) = 1421.2282
Mr = 652.34Dx = 1.125 Mg m3
Monoclinic, P21/nCu Kα radiation, λ = 1.54184 Å
a = 13.5654 (4) ÅCell parameters from 6812 reflections
b = 20.0993 (6) Åθ = 4.7–72.2°
c = 14.3329 (4) ŵ = 1.16 mm1
β = 99.658 (3)°T = 294 K
V = 3852.53 (19) Å3Plate, clear light colourless
Z = 40.7 × 0.4 × 0.15 mm

Tetrabutylammonium chloride–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (I)   Data collection

Agilent New Gemini, Dual, Cu at zero, EosS2 diffractometer5929 reflections with I≥ 2u(I)
Detector resolution: 15.9595 pixels mm-1Rint = 0.033
ω scansθmax = 72.6°, θmin = 4.4°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)h = −16→16
Tmin = 0.608, Tmax = 1.000k = −24→24
21128 measured reflectionsl = −17→11
7530 independent reflections

Tetrabutylammonium chloride–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (I)   Refinement

Refinement on F20 restraints
Least-squares matrix: full92 constraints
R[F2 > 2σ(F2)] = 0.082H-atom parameters constrained
wR(F2) = 0.252w = 1/[σ2(Fo2) + (0.1696P)2 + 0.5478P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
7530 reflectionsΔρmax = 0.85 e Å3
421 parametersΔρmin = −0.30 e Å3

Tetrabutylammonium chloride–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (I)   Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.81049 (4)0.43129 (4)0.44872 (4)0.0698 (2)
O10.85937 (14)0.63139 (10)0.37918 (12)0.0693 (5)
O20.71380 (15)0.53977 (10)0.12843 (14)0.0753 (5)
N10.83702 (15)0.51476 (11)0.25233 (13)0.0604 (5)
H10.84799 (15)0.49495 (11)0.30626 (13)0.0725 (6)*
N20.99507 (14)0.56294 (10)0.38683 (13)0.0551 (4)
H21.03513 (14)0.53715 (10)0.42311 (13)0.0661 (5)*
N30.94863 (15)0.60015 (10)0.52227 (13)0.0565 (5)
H31.00121 (15)0.57846 (10)0.54698 (13)0.0678 (5)*
N40.67823 (16)0.48559 (12)0.25880 (16)0.0679 (6)
H40.70649 (16)0.46779 (12)0.31106 (16)0.0815 (7)*
N50.65966 (16)0.73314 (11)0.19192 (16)0.0653 (5)
C10.91976 (18)0.54235 (12)0.22120 (16)0.0570 (5)
C120.92846 (16)0.60121 (11)0.42575 (15)0.0518 (5)
C130.74037 (18)0.51570 (11)0.20661 (16)0.0575 (5)
C140.89440 (16)0.62999 (11)0.58629 (16)0.0528 (5)
C150.99990 (18)0.56459 (11)0.28853 (16)0.0553 (5)
C160.91973 (19)0.61169 (12)0.68051 (16)0.0598 (5)
H160.96985 (19)0.58028 (12)0.69760 (16)0.0718 (7)*
C170.57262 (19)0.47988 (13)0.2378 (2)0.0696 (7)
C180.930 (4) (2)0.54390 (15)0.12578 (18)0.0710 (7)
H180.8769 (2)0.53110 (15)0.07955 (18)0.0852 (8)*
C190.82081 (19)0.67721 (14)0.5609 (2)0.0679 (6)
H190.80310 (19)0.69039 (14)0.4982 (2)0.0815 (8)*
C200.5976 (2)0.74753 (15)0.0958 (2)0.0739 (7)
H20a0.5332 (2)0.76464 (15)0.1054 (2)0.0887 (9)*
H20b0.6305 (2)0.78241 (15)0.0658 (2)0.0887 (9)*
C210.8723 (2)0.63902 (15)0.74986 (19)0.0713 (7)
C220.6638 (2)0.79804 (13)0.2472 (2)0.0711 (7)
H22a0.6943 (2)0.83168 (13)0.2128 (2)0.0853 (8)*
H22b0.5958 (2)0.81222 (13)0.2491 (2)0.0853 (8)*
C231.0887 (2)0.58348 (15)0.2611 (2)0.0719 (7)
H231.1424 (2)0.59659 (15)0.3066 (2)0.0863 (8)*
C240.6127 (2)0.67819 (14)0.2424 (2)0.0738 (7)
H24a0.6110 (2)0.63794 (14)0.2048 (2)0.0886 (8)*
H24b0.6556 (2)0.66962 (14)0.3025 (2)0.0886 (8)*
C250.5249 (2)0.46665 (15)0.3142 (3)0.0791 (8)
H250.5632 (2)0.46068 (15)0.3738 (3)0.0950 (10)*
C260.7635 (2)0.70980 (14)0.1819 (2)0.0711 (7)
H26a0.7990 (2)0.69790 (14)0.2442 (2)0.0853 (8)*
H26b0.7571 (2)0.66975 (14)0.1436 (2)0.0853 (8)*
C270.7982 (2)0.68588 (18)0.7230 (2)0.0834 (8)
H270.7649 (2)0.70469 (18)0.7682 (2)0.1001 (10)*
C280.7738 (2)0.70463 (17)0.6306 (3)0.0843 (8)
H280.7244 (2)0.73659 (17)0.6139 (3)0.1011 (10)*
C291.0185 (3)0.56429 (18)0.1000 (2)0.0852 (9)
H291.0241 (3)0.56538 (18)0.0363 (2)0.1023 (11)*
C301.0984 (2)0.58304 (19)0.1665 (2)0.0844 (9)
H301.1584 (2)0.59533 (19)0.1482 (2)0.1013 (10)*
C310.4218 (2)0.46212 (17)0.3040 (3)0.0952 (11)
C320.5179 (2)0.48578 (18)0.1479 (3)0.0880 (9)
H320.5489 (2)0.49406 (18)0.0959 (3)0.1056 (11)*
C330.7197 (3)0.79566 (16)0.3467 (2)0.0840 (8)
H33a0.6880 (3)0.76364 (16)0.3828 (2)0.1008 (10)*
H33b0.7876 (3)0.78073 (16)0.3460 (2)0.1008 (10)*
C340.9012 (3)0.6187 (2)0.8510 (2)0.1019 (12)
H34a0.919 (3)0.5725 (5)0.8541 (2)0.1528 (18)*
H34b0.9571 (17)0.6450 (12)0.8802 (7)0.1528 (18)*
H34c0.8458 (9)0.6256 (16)0.8836 (6)0.1528 (18)*
C350.8258 (3)0.7589 (2)0.1387 (3)0.0981 (11)
H35a0.7871 (3)0.7762 (2)0.0808 (3)0.1177 (13)*
H35b0.8426 (3)0.7958 (2)0.1820 (3)0.1177 (13)*
C360.5078 (3)0.69210 (19)0.2612 (3)0.0952 (10)
H36a0.5067 (3)0.73500 (19)0.2920 (3)0.1142 (12)*
H36b0.4621 (3)0.69420 (19)0.2014 (3)0.1142 (12)*
C370.3671 (3)0.4680 (2)0.2134 (4)0.1108 (14)
H370.2978 (3)0.4646 (2)0.2044 (4)0.1329 (17)*
C20.5797 (3)0.6888 (2)0.0283 (3)0.0994 (11)
H2a0.6427 (3)0.6669 (2)0.0248 (3)0.1193 (13)*
H2b0.5360 (3)0.6569 (2)0.0514 (3)0.1193 (13)*
C30.4133 (3)0.4788 (2)0.1376 (4)0.1123 (14)
H3a0.3749 (3)0.4817 (2)0.0775 (4)0.1348 (17)*
C40.4732 (4)0.6402 (2)0.3216 (4)0.1255 (17)
H4a0.4811 (4)0.5969 (2)0.2937 (4)0.151 (2)*
H4b0.5155 (4)0.6411 (2)0.3833 (4)0.151 (2)*
C50.5325 (3)0.7129 (3)−0.0692 (3)0.1108 (13)
H5a0.5064 (3)0.6747 (3)−0.1069 (3)0.1330 (16)*
H5b0.4764 (3)0.7414 (3)−0.0628 (3)0.1330 (16)*
C60.7226 (4)0.86171 (19)0.3941 (3)0.1203 (16)
H6a0.7506 (4)0.89336 (19)0.3546 (3)0.1443 (19)*
H6b0.6541 (4)0.87517 (19)0.3948 (3)0.1443 (19)*
C70.9182 (3)0.7290 (3)0.1176 (4)0.1218 (15)
H7a0.9528 (3)0.7077 (3)0.1746 (4)0.1462 (18)*
H7b0.9004 (3)0.6944 (3)0.0705 (4)0.1462 (18)*
C80.3717 (3)0.4521 (3)0.3896 (4)0.1278 (17)
H8a0.4103 (17)0.4215 (16)0.4325 (14)0.192 (3)*
H8b0.367 (3)0.4939 (4)0.4209 (18)0.192 (3)*
H8c0.3058 (12)0.434 (2)0.3699 (5)0.192 (3)*
C90.7765 (4)0.8685 (3)0.4886 (3)0.1283 (17)
H9a0.8434 (12)0.852 (2)0.4912 (8)0.193 (2)*
H9b0.779 (3)0.9145 (4)0.5067 (13)0.193 (2)*
H9c0.744 (2)0.8432 (19)0.5312 (6)0.193 (2)*
C100.3654 (4)0.6483 (3)0.3345 (5)0.145 (2)
H10a0.3229 (5)0.648 (3)0.2738 (6)0.218 (3)*
H10b0.3471 (13)0.6123 (14)0.372 (3)0.218 (3)*
H10c0.3577 (9)0.6897 (13)0.366 (3)0.218 (3)*
C110.5996 (6)0.7489 (4)−0.1193 (4)0.175 (3)
H11a0.568 (2)0.755 (3)−0.1838 (13)0.262 (4)*
H11b0.615 (4)0.7912 (13)−0.090 (3)0.262 (4)*
H11c0.660 (2)0.7238 (15)−0.118 (4)0.262 (4)*
C380.9877 (4)0.7749 (4)0.0829 (5)0.175 (3)
H38a0.9520 (10)0.802 (2)0.033 (3)0.263 (4)*
H38b1.018 (4)0.803 (2)0.1337 (13)0.263 (4)*
H38c1.039 (3)0.7500 (4)0.060 (4)0.263 (4)*

Tetrabutylammonium chloride–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (I)   Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0563 (4)0.0869 (5)0.0615 (4)−0.0022 (3)−0.0042 (3)0.0081 (3)
O10.0704 (10)0.0777 (11)0.0550 (9)0.0177 (9)−0.0033 (8)0.0082 (8)
O20.0770 (12)0.0736 (11)0.0672 (11)0.0037 (9)−0.0112 (9)0.0113 (9)
N10.0634 (11)0.0659 (11)0.0478 (10)−0.0068 (9)−0.0022 (8)0.0049 (8)
N20.0512 (9)0.0626 (11)0.0482 (9)0.0017 (8)−0.0007 (7)0.0031 (8)
N30.0558 (10)0.0632 (11)0.0476 (9)0.0098 (8)0.0000 (7)0.0029 (8)
N40.0552 (11)0.0790 (14)0.0651 (12)0.0030 (10)−0.0025 (9)0.0085 (10)
N50.0651 (12)0.0580 (11)0.0705 (13)0.0169 (9)0.0047 (10)0.0125 (9)
C10.0635 (13)0.0538 (11)0.0508 (12)0.0023 (10)0.0017 (10)−0.0001 (9)
C120.0519 (11)0.0517 (11)0.0489 (11)−0.0033 (9)−0.0003 (8)0.0043 (9)
C130.0628 (13)0.0502 (11)0.0536 (12)0.0052 (9)−0.0074 (10)−0.0039 (9)
C140.0515 (11)0.0507 (11)0.0549 (11)−0.0066 (9)0.0055 (9)0.0009 (9)
C150.0581 (12)0.0563 (12)0.0503 (11)0.0018 (9)0.0054 (9)0.0007 (9)
C160.0666 (13)0.0579 (12)0.0522 (12)−0.0044 (10)0.0016 (10)−0.0016 (10)
C170.0568 (13)0.0585 (13)0.0871 (18)0.0039 (10)−0.0066 (12)−0.0026 (12)
C180.0850 (18)0.0746 (16)0.0507 (13)0.0014 (14)0.0035 (12)−0.0038 (11)
C190.0623 (14)0.0705 (15)0.0724 (15)0.0086 (11)0.0152 (11)0.0143 (12)
C200.0713 (16)0.0718 (16)0.0750 (16)0.0209 (13)0.0017 (13)0.0122 (13)
C210.0807 (17)0.0726 (16)0.0624 (15)−0.0123 (13)0.0176 (13)−0.0069 (12)
C220.0760 (16)0.0559 (13)0.0793 (17)0.0106 (12)0.0073 (13)0.0100 (12)
C230.0634 (14)0.0817 (17)0.0717 (16)−0.0078 (13)0.0147 (12)−0.0012 (13)
C240.0809 (17)0.0563 (14)0.0828 (18)0.0094 (12)0.0100 (14)0.0092 (12)
C250.0634 (15)0.0672 (16)0.105 (2)−0.0072 (12)0.0078 (15)0.0023 (15)
C260.0642 (14)0.0692 (15)0.0769 (16)0.0211 (12)0.0033 (12)0.0134 (13)
C270.0841 (19)0.087 (2)0.086 (2)0.0009 (16)0.0334 (16)−0.0125 (16)
C280.0747 (17)0.0857 (19)0.098 (2)0.0188 (15)0.0294 (16)0.0091 (17)
C290.107 (2)0.096 (2)0.0573 (15)0.0050 (17)0.0273 (16)0.0016 (14)
C300.0769 (18)0.106 (2)0.0759 (18)−0.0048 (16)0.0277 (15)0.0040 (16)
C310.0665 (17)0.0706 (18)0.148 (3)−0.0114 (14)0.016 (2)0.0047 (19)
C320.0650 (16)0.093 (2)0.095 (2)0.0048 (15)−0.0167 (15)−0.0013 (17)
C330.100 (2)0.0681 (16)0.0803 (19)0.0143 (15)0.0057 (16)−0.0003 (14)
C340.124 (3)0.125 (3)0.0568 (16)−0.004 (2)0.0180 (17)−0.0088 (17)
C350.0752 (19)0.096 (2)0.125 (3)0.0177 (17)0.0214 (19)0.029 (2)
C360.083 (2)0.082 (2)0.122 (3)0.0082 (16)0.0244 (19)0.017 (2)
C370.0586 (17)0.094 (2)0.173 (4)−0.0089 (16)−0.001 (2)0.011 (3)
C20.107 (3)0.090 (2)0.090 (2)0.021 (2)−0.0157 (19)−0.0022 (18)
C30.071 (2)0.104 (3)0.144 (4)−0.0018 (19)−0.035 (2)0.010 (3)
C40.133 (4)0.077 (2)0.181 (5)0.006 (2)0.069 (4)0.020 (3)
C50.107 (3)0.133 (3)0.085 (2)0.030 (3)−0.007 (2)−0.005 (2)
C60.169 (5)0.0654 (19)0.118 (3)−0.001 (2)−0.002 (3)−0.0022 (19)
C70.080 (2)0.139 (4)0.149 (4)0.009 (2)0.029 (2)0.008 (3)
C80.091 (3)0.117 (3)0.184 (5)−0.023 (2)0.050 (3)0.004 (3)
C90.170 (5)0.110 (3)0.108 (3)−0.014 (3)0.032 (3)−0.035 (3)
C100.118 (3)0.125 (4)0.206 (6)−0.018 (3)0.067 (4)0.024 (4)
C110.201 (7)0.228 (8)0.104 (4)−0.002 (6)0.050 (4)0.012 (4)
C380.102 (3)0.209 (7)0.226 (7)−0.006 (4)0.061 (4)0.044 (6)

Tetrabutylammonium chloride–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (I)   Geometric parameters (Å, º)

O1—C121.217 (3)C8—H8B0.960 (16)
O2—C131.218 (3)C8—H8C0.96 (2)
N1—C11.391 (3)C16—H160.930 (4)
N1—C131.364 (3)C18—H180.93 (4)
N2—C121.374 (3)C19—H190.929 (4)
N2—C151.422 (3)C23—H230.931 (4)
N3—C121.365 (3)C25—H250.930 (6)
N3—C141.403 (3)C27—H270.930 (4)
N4—C131.359 (3)C28—H280.930 (5)
N4—C171.418 (3)C29—H290.929 (4)
N5—C201.517 (3)C30—H300.930 (4)
N5—C221.522 (4)C32—H320.930 (5)
N5—C241.517 (4)C34—H34A0.959 (15)
N5—C261.514 (3)C34—H34B0.96 (2)
C1—C151.400 (3)C34—H34C0.959 (13)
C1—C181.398 (4)C37—H370.930 (6)
C14—C161.386 (3)C2—H2A0.970 (6)
C14—C191.381 (3)C2—H2B0.969 (6)
C15—C231.381 (4)C4—H4A0.971 (6)
C16—C211.386 (4)C4—H4B0.970 (8)
C17—C251.388 (5)C5—H5A0.971 (8)
C17—C321.381 (4)C5—H5B0.969 (7)
C18—C291.376 (5)C6—H6A0.970 (6)
C19—C281.386 (4)C6—H6B0.970 (8)
C20—C21.520 (5)C7—H7A0.971 (8)
C21—C271.384 (5)C7—H7B0.971 (8)
C21—C341.493 (4)C9—H9A0.96 (2)
C22—C331.500 (4)C9—H9B0.959 (11)
C23—C301.385 (4)C9—H9C0.96 (3)
C24—C361.519 (4)C10—H10A0.960 (11)
C25—C311.385 (4)C10—H10B0.96 (3)
C26—C351.499 (5)C10—H10C0.96 (3)
C27—C281.363 (5)C11—H11A0.96 (2)
C29—C301.370 (5)C11—H11B0.96 (3)
C31—C371.388 (6)C11—H11C0.96 (3)
C31—C81.513 (6)C20—H20A0.970 (4)
C32—C31.408 (5)C20—H20B0.970 (4)
C33—C61.489 (5)C22—H22A0.970 (4)
C35—C71.467 (5)C22—H22B0.970 (4)
C36—C41.482 (5)C24—H24A0.970 (4)
C37—C31.360 (7)C24—H24B0.971 (4)
C2—C51.515 (5)C26—H26A0.971 (4)
C4—C101.514 (6)C26—H26B0.970 (4)
C5—C111.445 (8)C33—H33A0.970 (5)
C6—C91.433 (6)C33—H33B0.970 (6)
C7—C381.465 (7)C35—H35A0.969 (6)
N1—H10.860 (3)C35—H35B0.969 (6)
N2—H20.860 (3)C36—H36A0.970 (6)
N3—H30.860 (3)C36—H36B0.971 (6)
N4—H40.860 (3)C38—H38A0.96 (4)
C3—H3A0.931 (8)C38—H38B0.96 (3)
C8—H8A0.96 (3)C38—H38C0.96 (4)
C13—N1—C1127.1 (2)C29—C30—H30120.3 (3)
C15—N2—C12122.13 (18)C3—C32—H32121.1 (5)
C14—N3—C12128.19 (19)C17—C32—H32121.3 (4)
C17—N4—C13128.1 (2)C21—C34—H34A109.4 (3)
C22—N5—C20105.98 (19)C21—C34—H34B109.4 (9)
C24—N5—C20111.0 (2)C21—C34—H34C109.5 (9)
C24—N5—C22110.9 (2)H34A—C34—H34B110 (3)
C26—N5—C20110.9 (2)H34A—C34—H34C109 (3)
C26—N5—C22111.2 (2)H34B—C34—H34C109.5 (17)
C26—N5—C24106.91 (19)C5—C2—H2A109.7 (5)
C15—C1—N1118.8 (2)C5—C2—H2B109.8 (5)
C18—C1—N1122.7 (2)C20—C2—H2A109.7 (4)
C18—C1—C15118.3 (2)C20—C2—H2B109.8 (4)
N2—C12—O1123.7 (2)H2A—C2—H2B108.2 (5)
N3—C12—O1124.7 (2)C10—C4—H4A108.8 (6)
N3—C12—N2111.66 (18)C10—C4—H4B108.8 (6)
N1—C13—O2124.0 (2)C36—C4—H4A108.8 (6)
N4—C13—O2124.6 (2)C36—C4—H4B108.8 (5)
N4—C13—N1111.4 (2)H4A—C4—H4B107.6 (6)
C16—C14—N3116.9 (2)C2—C5—H5A108.6 (6)
C19—C14—N3123.8 (2)C2—C5—H5B108.6 (5)
C19—C14—C16119.3 (2)C11—C5—H5A108.7 (5)
C1—C15—N2121.1 (2)C11—C5—H5B108.7 (6)
C23—C15—N2118.4 (2)H5A—C5—H5B107.5 (6)
C23—C15—C1120.3 (2)C9—C6—H6A107.5 (5)
H16—C16—C14119.18 (15)C9—C6—H6B107.5 (5)
C21—C16—C14121.6 (3)C33—C6—H6A107.5 (4)
C25—C17—N4115.9 (3)C33—C6—H6B107.6 (5)
C32—C17—N4123.9 (3)H6A—C6—H6B107.0 (6)
C32—C17—C25120.3 (3)C35—C7—H7A108.5 (5)
C29—C18—C1120.2 (3)C35—C7—H7B108.4 (5)
C28—C19—C14118.9 (3)C38—C7—H7A108.4 (5)
C2—C20—N5115.8 (2)C38—C7—H7B108.3 (6)
C27—C21—C16118.2 (3)H7A—C7—H7B107.3 (7)
C34—C21—C16120.6 (3)C6—C9—H9A109.4 (9)
C34—C21—C27121.1 (3)C6—C9—H9B109.7 (14)
C33—C22—N5115.8 (2)C6—C9—H9C109.6 (13)
H23—C23—C15119.77 (16)H9A—C9—H9B109 (3)
C30—C23—C15120.5 (3)H9A—C9—H9C109 (3)
C36—C24—N5115.5 (2)H9B—C9—H9C110 (3)
C31—C25—C17121.7 (3)C4—C10—H10A109.5 (8)
C35—C26—N5115.7 (2)C4—C10—H10B109.5 (14)
H27—C27—C21119.82 (17)C4—C10—H10C109.5 (10)
C28—C27—C21120.4 (3)H10A—C10—H10B109 (4)
C27—C28—C19121.6 (3)H10A—C10—H10C110 (4)
C30—C29—C18121.3 (3)H10B—C10—H10C109 (3)
C29—C30—C23119.3 (3)C5—C11—H11A109 (2)
C37—C31—C25117.7 (4)C5—C11—H11B110 (3)
C8—C31—C25120.4 (4)C5—C11—H11C110 (2)
C8—C31—C37121.9 (4)H11A—C11—H11B110 (4)
C3—C32—C17117.6 (4)H11A—C11—H11C109 (4)
C6—C33—C22112.1 (3)H11B—C11—H11C110 (4)
C7—C35—C26112.1 (3)N5—C20—H20A108.3 (3)
C4—C36—C24111.8 (3)N5—C20—H20B108.3 (3)
C3—C37—C31121.1 (3)C2—C20—H20A108.3 (3)
C5—C2—C20109.7 (3)C2—C20—H20B108.4 (3)
C37—C3—C32121.5 (4)H20A—C20—H20B107.4 (4)
C10—C4—C36113.7 (4)N5—C22—H22A108.3 (3)
C11—C5—C2114.5 (5)N5—C22—H22B108.3 (3)
C9—C6—C33119.0 (4)C33—C22—H22A108.4 (3)
C38—C7—C35115.6 (5)C33—C22—H22B108.3 (3)
C1—N1—H1116.5 (3)H22A—C22—H22B107.4 (3)
C13—N1—H1116.5 (3)N5—C24—H24A108.4 (3)
C12—N2—H2118.9 (2)N5—C24—H24B108.4 (3)
C15—N2—H2118.9 (2)C36—C24—H24A108.5 (3)
C12—N3—H3115.9 (2)C36—C24—H24B108.4 (3)
C14—N3—H3115.9 (2)H24A—C24—H24B107.5 (4)
C13—N4—H4115.9 (3)N5—C26—H26A108.4 (3)
C17—N4—H4116.0 (3)N5—C26—H26B108.3 (3)
C32—C3—H3A119.2 (5)C35—C26—H26A108.4 (3)
C37—C3—H3A119.2 (5)C35—C26—H26B108.4 (3)
C31—C8—H8A109.5 (14)H26A—C26—H26B107.4 (4)
C31—C8—H8B109.7 (18)C6—C33—H33A109.2 (4)
C31—C8—H8C109.5 (7)C6—C33—H33B109.2 (4)
H8A—C8—H8B110 (2)C22—C33—H33A109.3 (4)
H8A—C8—H8C109 (3)C22—C33—H33B109.2 (3)
H8B—C8—H8C110 (3)H33A—C33—H33B107.9 (4)
C14—C16—H16119.2 (3)C7—C35—H35A109.2 (5)
C21—C16—H16119.2 (3)C7—C35—H35B109.2 (5)
C1—C18—H18120 (4)C26—C35—H35A109.2 (4)
C29—C18—H18119.8 (17)C26—C35—H35B109.1 (4)
C14—C19—H19120.6 (3)H35A—C35—H35B108.0 (5)
C28—C19—H19120.5 (3)C4—C36—H36A109.2 (5)
C15—C23—H23119.7 (3)C4—C36—H36B109.2 (5)
C30—C23—H23119.8 (3)C24—C36—H36A109.3 (4)
C17—C25—H25119.1 (3)C24—C36—H36B109.3 (4)
C31—C25—H25119.2 (4)H36A—C36—H36B107.9 (5)
C21—C27—H27119.9 (3)C7—C38—H38A109.7 (15)
C28—C27—H27119.8 (4)C7—C38—H38B109 (2)
C19—C28—H28119.2 (5)C7—C38—H38C109.5 (16)
C27—C28—H28119.2 (4)H38A—C38—H38B109 (3)
C18—C29—H29119.3 (7)H38A—C38—H38C110 (4)
C30—C29—H29119.4 (5)H38B—C38—H38C109 (4)
C23—C30—H30120.4 (3)

Tetrabutylammonium chloride–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (I)   Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.86 (1)2.53 (1)3.348 (2)159 (1)
N2i—H2i···Cl10.86 (1)2.62 (1)3.231 (2)129 (1)
N3i—H3i···Cl10.86 (1)2.55 (1)3.285 (2)144 (1)
N4—H4···Cl10.86 (1)2.34 (1)3.191 (2)169 (1)
C26—H26a···O10.97 (1)2.38 (1)3.307 (3)159 (1)
C22ii—H22aii···Cl10.97 (1)3.05 (1)3.938 (3)152 (1)
C20ii—H20bii···Cl10.97 (1)3.11 (1)3.984 (3)150 (1)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+3/2, y−1/2, −z+1/2.

Tetrabutylammonium bromide–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (II)   Crystal data

C16H36N+·Br·C22H22N4O2F(000) = 1489.0393
Mr = 696.80Dx = 1.190 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
a = 10.5879 (2) ÅCell parameters from 7946 reflections
b = 20.3165 (5) Åθ = 4.7–72.6°
c = 18.0828 (3) ŵ = 1.72 mm1
β = 91.0672 (17)°T = 294 K
V = 3889.11 (14) Å3Plate, clear light colourless
Z = 40.5 × 0.3 × 0.2 mm

Tetrabutylammonium bromide–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (II)   Data collection

Agilent New Gemini, Dual, Cu at zero, EosS2 diffractometer6081 reflections with I≥ 2u(I)
Detector resolution: 15.9595 pixels mm-1Rint = 0.039
ω scansθmax = 72.5°, θmin = 4.4°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)h = −8→13
Tmin = 0.444, Tmax = 1.000k = −25→22
21853 measured reflectionsl = −22→19
7582 independent reflections

Tetrabutylammonium bromide–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (II)   Refinement

Refinement on F20 restraints
Least-squares matrix: full92 constraints
R[F2 > 2σ(F2)] = 0.063H-atom parameters constrained
wR(F2) = 0.185w = 1/[σ2(Fo2) + (0.1213P)2 + 0.5505P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.003
7582 reflectionsΔρmax = 1.02 e Å3
421 parametersΔρmin = −0.54 e Å3

Tetrabutylammonium bromide–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (II)   Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br10.34211 (3)0.436876 (19)0.380770 (15)0.06780 (16)
O10.5943 (2)0.53896 (12)0.16204 (11)0.0652 (5)
O20.5000 (2)0.63426 (12)0.36423 (12)0.0708 (6)
N10.5894 (2)0.51747 (12)0.28578 (12)0.0553 (5)
H10.5429 (2)0.50181 (12)0.32004 (12)0.0664 (6)*
N20.4204 (2)0.49196 (13)0.21256 (12)0.0594 (6)
H20.3891 (2)0.48089 (13)0.25431 (12)0.0713 (7)*
N30.6278 (2)0.56443 (11)0.43059 (12)0.0551 (5)
H30.6325 (2)0.53992 (11)0.46931 (12)0.0662 (6)*
N40.4466 (2)0.60268 (12)0.48120 (12)0.0580 (5)
H40.4770 (2)0.58314 (12)0.51979 (12)0.0696 (6)*
N50.4877 (2)0.73056 (13)0.16681 (14)0.0641 (6)
C10.5396 (3)0.51776 (13)0.21594 (14)0.0509 (5)
C120.7096 (3)0.54029 (14)0.30718 (14)0.0534 (6)
C130.5225 (3)0.60358 (13)0.42087 (14)0.0531 (6)
C140.7283 (3)0.56240 (13)0.38032 (16)0.0550 (6)
C150.3253 (3)0.62969 (13)0.48807 (15)0.0556 (6)
C160.3425 (3)0.48110 (14)0.15060 (14)0.0530 (6)
C170.2207 (3)0.45888 (15)0.16407 (16)0.0578 (6)
H170.1967 (3)0.45104 (15)0.21250 (16)0.0693 (7)*
C180.8125 (3)0.53723 (17)0.26118 (17)0.0656 (7)
H180.8009 (3)0.52385 (17)0.21234 (17)0.0787 (9)*
C190.2560 (3)0.60972 (15)0.54806 (18)0.0654 (7)
H190.2911 (3)0.57941 (15)0.58105 (18)0.0785 (9)*
C200.3884 (3)0.67697 (15)0.16932 (18)0.0665 (7)
H20a0.4245 (3)0.63682 (15)0.14980 (18)0.0798 (9)*
H20b0.3684 (3)0.66885 (15)0.22065 (18)0.0798 (9)*
C210.8496 (3)0.57762 (17)0.40527 (19)0.0686 (8)
H210.8624 (3)0.59108 (17)0.45399 (19)0.0824 (9)*
C220.1347 (3)0.44823 (17)0.10692 (19)0.0664 (7)
C230.5244 (3)0.74585 (17)0.08761 (18)0.0704 (8)
H23a0.4507 (3)0.76289 (17)0.06133 (18)0.0845 (10)*
H23b0.5877 (3)0.78041 (17)0.08871 (18)0.0845 (10)*
C240.6001 (3)0.70568 (16)0.21146 (18)0.0661 (7)
H24a0.5718 (3)0.69477 (16)0.26068 (18)0.0793 (9)*
H24b0.6294 (3)0.66527 (16)0.18893 (18)0.0793 (9)*
C250.3791 (3)0.49119 (18)0.07795 (16)0.0670 (8)
H250.4603 (3)0.50570 (18)0.06778 (16)0.0804 (9)*
C260.1355 (3)0.63368 (17)0.5604 (2)0.0768 (9)
C270.4370 (3)0.79435 (16)0.1983 (2)0.0734 (8)
H27a0.5024 (3)0.82761 (16)0.1951 (2)0.0881 (10)*
H27b0.3664 (3)0.80872 (16)0.1673 (2)0.0881 (10)*
C280.1728 (3)0.4587 (2)0.03532 (19)0.0754 (9)
H280.1160 (3)0.4518 (2)−0.00377 (19)0.0905 (10)*
C290.9512 (3)0.57316 (19)0.3592 (2)0.0786 (10)
H291.0321 (3)0.58316 (19)0.3767 (2)0.0943 (11)*
C300.9318 (3)0.5536 (2)0.2865 (2)0.0777 (9)
H300.9997 (3)0.5516 (2)0.2546 (2)0.0932 (11)*
C310.2928 (3)0.4793 (2)0.02111 (17)0.0781 (9)
H310.3170 (3)0.4853 (2)−0.02761 (17)0.0937 (11)*
C320.2736 (3)0.67575 (19)0.4405 (2)0.0770 (9)
H320.3188 (3)0.69045 (19)0.4000 (2)0.0924 (11)*
C330.2667 (3)0.69113 (19)0.1273 (2)0.0822 (10)
H33a0.2353 (3)0.73411 (19)0.1413 (2)0.0987 (12)*
H33b0.2828 (3)0.69188 (19)0.0746 (2)0.0987 (12)*
C340.5761 (4)0.6878 (2)0.0441 (2)0.0837 (10)
H34a0.6413 (4)0.6658 (2)0.0732 (2)0.1004 (12)*
H34b0.5089 (4)0.6565 (2)0.0340 (2)0.1004 (12)*
C350.0860 (3)0.6795 (2)0.5119 (2)0.0832 (10)
H350.0057 (3)0.6966 (2)0.5193 (2)0.0999 (12)*
C360.3937 (4)0.79121 (19)0.2773 (2)0.0885 (11)
H36a0.3246 (4)0.76006 (19)0.2804 (2)0.1062 (13)*
H36b0.4625 (4)0.77515 (19)0.3084 (2)0.1062 (13)*
C370.7107 (4)0.7520 (2)0.2190 (3)0.0901 (12)
H37a0.7391 (4)0.7644 (2)0.1702 (3)0.1081 (14)*
H37b0.6844 (4)0.7917 (2)0.2442 (3)0.1081 (14)*
C20.6311 (4)0.7119 (3)−0.0290 (2)0.0922 (12)
H2a0.6438 (4)0.6744 (3)−0.0611 (2)0.1106 (14)*
H2b0.5706 (4)0.7410 (3)−0.0532 (2)0.1106 (14)*
C30.0019 (4)0.4253 (2)0.1226 (3)0.0939 (13)
H3a−0.0115 (13)0.3826 (9)0.1012 (19)0.1409 (19)*
H3b−0.0092 (12)0.4229 (19)0.1751 (3)0.1409 (19)*
H3c−0.0577 (4)0.4559 (10)0.1015 (19)0.1409 (19)*
C40.1542 (4)0.6998 (2)0.4534 (3)0.0915 (11)
H4a0.1195 (4)0.7308 (2)0.4212 (3)0.1099 (14)*
C50.8161 (4)0.7213 (3)0.2608 (3)0.1035 (14)
H5a0.7852 (4)0.7068 (3)0.3083 (3)0.1241 (17)*
H5b0.8433 (4)0.6825 (3)0.2342 (3)0.1241 (17)*
C60.1691 (4)0.6399 (2)0.1432 (3)0.0967 (12)
H6a0.2039 (4)0.5969 (2)0.1322 (3)0.1161 (15)*
H6b0.1511 (4)0.6410 (2)0.1956 (3)0.1161 (15)*
C70.3513 (6)0.8563 (2)0.3056 (3)0.1212 (19)
H7a0.4176 (6)0.8880 (2)0.2963 (3)0.145 (2)*
H7b0.2779 (6)0.8698 (2)0.2764 (3)0.145 (2)*
C80.0478 (5)0.6480 (3)0.1005 (3)0.1172 (17)
H8a0.0640 (8)0.646 (2)0.0485 (3)0.176 (3)*
H8b−0.0095 (17)0.6135 (14)0.114 (2)0.176 (3)*
H8c0.011 (2)0.6899 (10)0.112 (2)0.176 (3)*
C90.3190 (5)0.8613 (3)0.3830 (3)0.1225 (19)
H9a0.243 (3)0.8368 (19)0.3916 (6)0.184 (3)*
H9b0.387 (2)0.844 (2)0.4130 (3)0.184 (3)*
H9c0.306 (4)0.9067 (4)0.3955 (7)0.184 (3)*
C100.0624 (5)0.6099 (3)0.6255 (4)0.127 (2)
H10a0.057 (4)0.5628 (4)0.6241 (16)0.191 (3)*
H10b0.105 (3)0.623 (2)0.6704 (4)0.191 (3)*
H10c−0.0211 (17)0.628 (2)0.6235 (16)0.191 (3)*
C110.9261 (6)0.7642 (4)0.2737 (4)0.145 (3)
H11a0.961 (3)0.777 (2)0.2271 (4)0.217 (4)*
H11b0.9004 (12)0.8030 (14)0.300 (3)0.217 (4)*
H11c0.989 (2)0.7411 (11)0.303 (3)0.217 (4)*
C380.7528 (5)0.7474 (3)−0.0189 (3)0.133 (2)
H38a0.775 (3)0.768 (2)−0.0646 (10)0.199 (3)*
H38b0.7445 (17)0.780 (2)0.019 (2)0.199 (3)*
H38c0.8177 (13)0.7167 (6)−0.004 (3)0.199 (3)*

Tetrabutylammonium bromide–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (II)   Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0685 (2)0.0906 (3)0.0443 (2)−0.00528 (15)0.00192 (13)0.00556 (13)
O10.0731 (12)0.0763 (13)0.0464 (10)−0.0165 (10)0.0042 (9)0.0070 (9)
O20.0846 (14)0.0732 (13)0.0547 (11)0.0110 (11)0.0046 (10)0.0153 (10)
N10.0561 (12)0.0684 (14)0.0417 (10)−0.0119 (10)0.0055 (9)−0.0039 (9)
N20.0575 (12)0.0815 (16)0.0392 (11)−0.0067 (11)−0.0001 (9)0.0050 (10)
N30.0647 (13)0.0601 (13)0.0406 (11)0.0002 (10)−0.0003 (9)0.0002 (9)
N40.0658 (13)0.0605 (13)0.0476 (11)0.0095 (10)0.0011 (9)0.0053 (9)
N50.0708 (14)0.0549 (13)0.0666 (14)0.0003 (11)−0.0030 (11)0.0210 (11)
C10.0607 (14)0.0500 (13)0.0422 (12)−0.0001 (11)0.0041 (10)−0.0009 (10)
C120.0585 (14)0.0542 (14)0.0475 (13)−0.0084 (11)0.0040 (11)−0.0006 (10)
C130.0642 (14)0.0502 (13)0.0448 (12)−0.0027 (11)−0.0005 (10)−0.0006 (10)
C140.0609 (15)0.0538 (14)0.0501 (14)−0.0057 (11)−0.0006 (11)−0.0023 (10)
C150.0596 (14)0.0497 (13)0.0572 (14)−0.0014 (11)−0.0061 (11)−0.0071 (11)
C160.0568 (13)0.0568 (14)0.0452 (12)0.0038 (11)−0.0006 (10)0.0030 (10)
C170.0600 (15)0.0628 (16)0.0505 (14)−0.0009 (12)−0.0021 (11)0.0068 (12)
C180.0637 (16)0.0745 (19)0.0588 (16)−0.0063 (14)0.0106 (13)−0.0065 (14)
C190.0755 (18)0.0513 (15)0.0697 (18)0.0041 (13)0.0088 (14)−0.0042 (13)
C200.0740 (18)0.0558 (16)0.0699 (18)−0.0020 (13)0.0038 (14)0.0163 (13)
C210.0664 (18)0.0737 (19)0.0655 (17)−0.0101 (14)−0.0082 (14)−0.0109 (15)
C220.0630 (16)0.0685 (18)0.0675 (18)−0.0026 (13)−0.0073 (14)0.0038 (14)
C230.0761 (19)0.0717 (19)0.0633 (17)−0.0025 (15)−0.0038 (14)0.0268 (14)
C240.0748 (17)0.0603 (16)0.0630 (16)0.0036 (14)−0.0033 (14)0.0187 (13)
C250.0639 (16)0.089 (2)0.0482 (14)−0.0047 (15)−0.0003 (12)0.0054 (14)
C260.0728 (19)0.0630 (18)0.095 (2)−0.0017 (15)0.0122 (17)−0.0199 (17)
C270.082 (2)0.0520 (16)0.086 (2)−0.0013 (14)−0.0037 (16)0.0170 (15)
C280.0743 (19)0.092 (2)0.0589 (17)−0.0072 (17)−0.0177 (15)0.0042 (16)
C290.0558 (17)0.087 (2)0.093 (2)−0.0149 (15)−0.0044 (16)−0.0094 (18)
C300.0611 (18)0.090 (2)0.083 (2)−0.0126 (16)0.0162 (16)−0.0030 (18)
C310.083 (2)0.108 (3)0.0429 (14)−0.0101 (19)−0.0024 (13)0.0070 (15)
C320.0753 (19)0.080 (2)0.075 (2)0.0067 (16)−0.0106 (16)0.0119 (17)
C330.077 (2)0.074 (2)0.095 (3)−0.0052 (17)−0.0055 (18)0.0197 (19)
C340.101 (3)0.085 (2)0.0650 (19)−0.007 (2)−0.0007 (17)0.0179 (17)
C350.0585 (17)0.081 (2)0.110 (3)0.0073 (16)−0.0114 (18)−0.022 (2)
C360.115 (3)0.0616 (19)0.089 (2)0.0140 (19)0.008 (2)0.0103 (17)
C370.095 (3)0.074 (2)0.100 (3)−0.0102 (19)−0.025 (2)0.022 (2)
C20.091 (2)0.118 (3)0.067 (2)−0.005 (2)0.0016 (18)0.019 (2)
C30.066 (2)0.125 (4)0.090 (3)−0.017 (2)−0.0103 (18)0.008 (2)
C40.079 (2)0.090 (3)0.104 (3)0.017 (2)−0.030 (2)0.003 (2)
C50.101 (3)0.108 (3)0.101 (3)−0.011 (3)−0.030 (2)0.023 (3)
C60.085 (2)0.076 (2)0.130 (4)−0.0086 (19)−0.002 (2)0.016 (2)
C70.160 (5)0.062 (2)0.143 (5)0.013 (3)0.027 (4)−0.000 (3)
C80.091 (3)0.135 (4)0.125 (4)−0.032 (3)−0.013 (3)0.000 (3)
C90.114 (4)0.109 (4)0.144 (5)0.030 (3)−0.002 (3)−0.045 (3)
C100.114 (4)0.121 (4)0.149 (5)0.022 (3)0.062 (4)0.003 (4)
C110.120 (4)0.163 (6)0.149 (5)−0.044 (4)−0.054 (4)0.030 (5)
C380.108 (4)0.179 (7)0.112 (4)−0.040 (4)0.013 (3)0.019 (4)

Tetrabutylammonium bromide–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (II)   Geometric parameters (Å, º)

O1—C11.222 (3)C3—H3B0.960 (8)
O2—C131.219 (3)C3—H3C0.960 (19)
N1—C11.360 (3)C4—H4A0.929 (7)
N1—C121.402 (3)C10—H10A0.959 (10)
N2—C11.367 (3)C10—H10B0.96 (2)
N2—C161.397 (3)C10—H10C0.96 (2)
N3—C131.378 (4)C17—H170.930 (4)
N3—C141.413 (4)C18—H180.930 (4)
N4—C131.367 (4)C19—H190.930 (4)
N4—C151.405 (4)C21—H210.930 (5)
N5—C201.515 (4)C25—H250.931 (5)
N5—C231.523 (4)C28—H280.930 (5)
N5—C241.513 (4)C29—H290.930 (5)
N5—C271.518 (4)C30—H300.931 (5)
C12—C141.408 (4)C31—H310.930 (4)
C12—C181.385 (4)C2—H2A0.969 (7)
C14—C211.387 (4)C2—H2B0.970 (7)
C15—C191.382 (4)C5—H5A0.971 (8)
C15—C321.378 (4)C5—H5B0.970 (8)
C16—C171.392 (4)C6—H6A0.970 (6)
C16—C251.392 (4)C6—H6B0.970 (8)
C17—C221.382 (4)C7—H7A0.970 (8)
C18—C301.376 (5)C7—H7B0.971 (8)
C19—C261.387 (5)C8—H8A0.960 (8)
C20—C331.511 (5)C8—H8B0.96 (3)
C21—C291.376 (5)C8—H8C0.96 (2)
C22—C281.380 (5)C9—H9A0.96 (3)
C22—C31.512 (5)C9—H9B0.96 (2)
C23—C341.524 (5)C9—H9C0.960 (12)
C24—C371.507 (5)C11—H11A0.96 (2)
C25—C311.384 (4)C11—H11B0.96 (4)
C26—C351.376 (6)C11—H11C0.97 (4)
C26—C101.500 (6)C20—H20A0.970 (4)
C27—C361.509 (5)C20—H20B0.970 (5)
C28—C311.367 (5)C23—H23A0.970 (5)
C29—C301.385 (6)C23—H23B0.971 (5)
C32—C41.380 (5)C24—H24A0.970 (5)
C33—C61.498 (5)C24—H24B0.970 (5)
C34—C21.534 (5)C27—H27A0.970 (5)
C35—C41.356 (6)C27—H27B0.971 (5)
C36—C71.491 (6)C33—H33A0.970 (5)
C37—C51.474 (5)C33—H33B0.971 (5)
C2—C381.485 (6)C34—H34A0.969 (6)
C5—C111.470 (7)C34—H34B0.969 (6)
C6—C81.495 (6)C36—H36A0.970 (6)
C7—C91.450 (7)C36—H36B0.969 (6)
N1—H10.860 (3)C37—H37A0.971 (7)
N2—H20.860 (3)C37—H37B0.970 (6)
N3—H30.860 (3)C38—H38A0.96 (3)
N4—H40.860 (3)C38—H38B0.96 (4)
C3—H3A0.96 (2)C38—H38C0.96 (2)
C12—N1—C1126.1 (2)C30—C29—H29120.3 (4)
C16—N2—C1128.9 (2)C18—C30—H30119.9 (4)
C14—N3—C13123.5 (2)C29—C30—H30119.9 (4)
C15—N4—C13128.1 (2)C25—C31—H31119.4 (4)
C23—N5—C20111.4 (3)C28—C31—H31119.5 (4)
C24—N5—C20106.5 (2)C4—C32—H32120.4 (4)
C24—N5—C23111.0 (2)C15—C32—H32120.3 (4)
C27—N5—C20110.6 (2)C4—C35—H35120.0 (5)
C27—N5—C23106.1 (2)C26—C35—H35120.0 (4)
C27—N5—C24111.4 (3)C34—C2—H2A108.9 (6)
N1—C1—O1124.1 (2)C34—C2—H2B109.0 (4)
N2—C1—O1123.4 (2)C38—C2—H2A109.0 (5)
N2—C1—N1112.5 (2)C38—C2—H2B108.9 (6)
C14—C12—N1118.5 (2)H2A—C2—H2B107.9 (5)
C18—C12—N1122.7 (3)C11—C5—H5A108.6 (6)
C18—C12—C14118.7 (3)C11—C5—H5B108.6 (5)
N3—C13—O2123.2 (3)C37—C5—H5A108.5 (5)
N4—C13—O2124.7 (3)C37—C5—H5B108.6 (5)
N4—C13—N3112.1 (2)H5A—C5—H5B107.5 (7)
C12—C14—N3121.2 (3)C8—C6—H6A108.6 (5)
C21—C14—N3119.2 (3)C8—C6—H6B108.6 (5)
C21—C14—C12119.4 (3)C33—C6—H6A108.7 (5)
C19—C15—N4117.0 (3)C33—C6—H6B108.7 (5)
C32—C15—N4124.3 (3)H6A—C6—H6B107.7 (6)
C32—C15—C19118.7 (3)C9—C7—H7A107.8 (6)
C17—C16—N2116.5 (2)C9—C7—H7B107.7 (6)
C25—C16—N2124.3 (3)C36—C7—H7A107.8 (6)
C25—C16—C17119.2 (3)C36—C7—H7B107.9 (5)
C22—C17—C16121.3 (3)H7A—C7—H7B107.0 (6)
C30—C18—C12121.2 (3)C6—C8—H8A109.5 (7)
C26—C19—C15121.8 (3)C6—C8—H8B109.2 (17)
C33—C20—N5115.7 (3)C6—C8—H8C109.5 (17)
C29—C21—C14121.2 (3)H8A—C8—H8B110 (3)
C28—C22—C17118.5 (3)H8A—C8—H8C109 (3)
C3—C22—C17120.6 (3)H8B—C8—H8C109 (2)
C3—C22—C28120.8 (3)C7—C9—H9A109.5 (10)
C34—C23—N5115.3 (3)C7—C9—H9B109.4 (10)
C37—C24—N5116.2 (3)C7—C9—H9C109.4 (10)
C31—C25—C16118.9 (3)H9A—C9—H9B110 (3)
C35—C26—C19118.4 (4)H9A—C9—H9C110 (3)
C10—C26—C19120.2 (4)H9B—C9—H9C109 (3)
C10—C26—C35121.4 (4)C5—C11—H11A109.7 (19)
C36—C27—N5115.8 (3)C5—C11—H11B109.5 (11)
C31—C28—C22120.8 (3)C5—C11—H11C109.6 (15)
C30—C29—C21119.3 (3)H11A—C11—H11B109 (4)
C29—C30—C18120.2 (3)H11A—C11—H11C110 (3)
C28—C31—C25121.1 (3)H11B—C11—H11C109 (4)
C4—C32—C15119.2 (4)N5—C20—H20A108.4 (3)
C6—C33—C20110.9 (3)N5—C20—H20B108.4 (3)
C2—C34—C23110.1 (3)C33—C20—H20A108.4 (3)
C4—C35—C26120.0 (3)C33—C20—H20B108.3 (3)
C7—C36—C27112.8 (4)H20A—C20—H20B107.4 (4)
C5—C37—C24111.1 (3)N5—C23—H23A108.5 (3)
C38—C2—C34113.1 (4)N5—C23—H23B108.5 (3)
C35—C4—C32121.9 (4)C34—C23—H23A108.5 (4)
C11—C5—C37114.8 (5)C34—C23—H23B108.4 (4)
C8—C6—C33114.5 (4)H23A—C23—H23B107.5 (4)
C9—C7—C36118.2 (4)N5—C24—H24A108.2 (3)
C1—N1—H1117.0 (3)N5—C24—H24B108.3 (3)
C12—N1—H1116.9 (3)C37—C24—H24A108.2 (4)
C1—N2—H2115.6 (3)C37—C24—H24B108.2 (4)
C16—N2—H2115.6 (3)H24A—C24—H24B107.4 (4)
C13—N3—H3118.2 (3)N5—C27—H27A108.3 (3)
C14—N3—H3118.3 (3)N5—C27—H27B108.3 (4)
C13—N4—H4115.9 (3)C36—C27—H27A108.4 (4)
C15—N4—H4116.0 (3)C36—C27—H27B108.4 (4)
C22—C3—H3A109.5 (11)H27A—C27—H27B107.4 (4)
C22—C3—H3B109.4 (11)C6—C33—H33A109.5 (4)
C22—C3—H3C109.4 (11)C6—C33—H33B109.5 (4)
H3A—C3—H3B110 (3)C20—C33—H33A109.5 (4)
H3A—C3—H3C110 (2)C20—C33—H33B109.4 (3)
H3B—C3—H3C110 (3)H33A—C33—H33B108.0 (5)
C32—C4—H4A119.2 (5)C2—C34—H34A109.7 (4)
C35—C4—H4A119.0 (5)C2—C34—H34B109.6 (4)
C26—C10—H10A109 (2)C23—C34—H34A109.6 (4)
C26—C10—H10B109.5 (18)C23—C34—H34B109.6 (4)
C26—C10—H10C110 (2)H34A—C34—H34B108.2 (5)
H10A—C10—H10B109 (3)C7—C36—H36A109.1 (5)
H10A—C10—H10C109 (3)C7—C36—H36B109.1 (4)
H10B—C10—H10C110 (3)C27—C36—H36A109.0 (4)
C16—C17—H17119.4 (3)C27—C36—H36B109.0 (4)
C22—C17—H17119.3 (4)H36A—C36—H36B107.9 (5)
C12—C18—H18119.5 (4)C5—C37—H37A109.4 (5)
C30—C18—H18119.4 (4)C5—C37—H37B109.4 (6)
C15—C19—H19119.1 (4)C24—C37—H37A109.5 (5)
C26—C19—H19119.1 (4)C24—C37—H37B109.4 (4)
C14—C21—H21119.4 (4)H37A—C37—H37B107.9 (6)
C29—C21—H21119.4 (4)C2—C38—H38A109.4 (19)
C16—C25—H25120.5 (3)C2—C38—H38B109.4 (13)
C31—C25—H25120.6 (3)C2—C38—H38C109.5 (9)
C22—C28—H28119.6 (4)H38A—C38—H38B110 (3)
C31—C28—H28119.6 (4)H38A—C38—H38C110 (3)
C21—C29—H29120.3 (4)H38B—C38—H38C109 (3)

Tetrabutylammonium bromide–1,1'-(1,2-phenylene)bis(3-m-tolylurea) (1/1) (II)   Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.86 (1)2.75 (1)3.557 (2)157 (1)
N2—H2···Br10.86 (1)2.51 (1)3.359 (2)168 (1)
N3—H3···Br1i0.86 (1)2.76 (1)3.420 (2)135 (1)
N4—H4···Br1i0.86 (1)2.63 (1)3.417 (2)152 (1)
C24—H24a···O20.97 (1)2.38 (1)3.312 (4)162 (1)
C24i—H24ai···O2i0.97 (1)2.38 (1)3.312 (4)162 (1)
C27ii—H27aii···Br1i0.97 (1)3.10 (1)4.003 (3)156 (1)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z+1/2.

Funding Statement

This work was funded by National Natural Science Foundation of China grant 21501123.

This paper was supported by the following grant(s):

National Natural Science Foundation of China 21501123.

References

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