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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o1990–o1991.
Published online 2010 July 10. doi:  10.1107/S1600536810026164
PMCID: PMC3007582

A monoclinic polymorph of N-eth­oxy­carbonyl-N′-(3-phenyl-1H-1,2,4-triazol-5-yl)thio­urea

Abstract

The title compound, C12H13N5O2S {systematic name: ethyl N-[N-(3-phenyl-1H-1,2,4-triazol-5-yl)carbamothio­yl]carbamate}, is a monoclinic polymorph (space group P21/c) which crystallizes with three similar independent mol­ecules in the asymmetric unit. The triazole ring makes dihedral angles of 6.6 (2), 8.4 (2) and 10.6 (2)° with the phenyl ring in the three independent molecules. The structure was previously reported [Dolzhenko et al. (2010a [triangle]). Acta Cryst., E46, o425] as a triclinic polymorph crystallizing in space group P An external file that holds a picture, illustration, etc.
Object name is e-66-o1990-efi1.jpg. Mol­ecules in both polymorphs possess two S(6) rings generated by intra­molecular N—H(...)S and N—H(...)O hydrogen bonds, resulting in similar mol­ecular geometries. However, the two polymorphs differ in the crystal packing. In contrast to the dimers of the triclinic polymorph, mol­ecules of the monoclinic polymorph are connected by inter­molecular N—H(...)S and N—H(...)N hydrogen bonds, forming pseudosymmetric trimers arranged in sheets parallel to (302).

Related literature

For the synthesis, tautomerism and crystal structure studies of related 1,2,4-triazoles, see: Dolzhenko et al. (2007 [triangle], 2009a [triangle],b [triangle],c [triangle]). For the crystal structure of the triclinic polymorph, see: Dolzhenko et al. (2010a [triangle]). For the crystal structure of N-carbeth­oxy-N′-(3-aryl-1H-1,2,4-triazol-5-yl)thio­urea, see: Dol­zhenko et al. (2010b [triangle]). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1990-scheme1.jpg

Experimental

Crystal data

  • C12H13N5O2S
  • M r = 291.33
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1990-efi2.jpg
  • a = 13.4743 (6) Å
  • b = 20.4817 (9) Å
  • c = 15.0266 (7) Å
  • β = 104.040 (1)°
  • V = 4023.1 (3) Å3
  • Z = 12
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 223 K
  • 0.56 × 0.24 × 0.12 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2001 [triangle]) T min = 0.872, T max = 0.971
  • 28189 measured reflections
  • 9216 independent reflections
  • 5772 reflections with I > 2σ(I)
  • R int = 0.055

Refinement

  • R[F 2 > 2σ(F 2)] = 0.063
  • wR(F 2) = 0.164
  • S = 1.03
  • 9216 reflections
  • 598 parameters
  • 86 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.85 e Å−3
  • Δρmin = −0.52 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810026164/ci5124sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026164/ci5124Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the National Medical Research Council, Singapore (grant No. NMRC/NIG/0019/2008).

supplementary crystallographic information

Comment

In our studies on the triazole tautomerism in solution and crystals (Dolzhenko et al., 2009a,b,c), we reported recently the crystal structure of N-carbethoxy-N'-(3-phenyl-1H-1,2,4-triazol-5-yl)thiourea, which crystallized in the triclinic P1space group (Dolzhenko et al., 2010a). Herein, we present a new monoclinic polymorph of N-carbethoxy-N'-(3-phenyl-1H-1,2,4-triazol-5-yl)thiourea, which crystallized in the P21/c space group with three similar crystallographically independent molecules in the asymmetric unit (Fig. 1). The molecules in both polymorphs exist in the same tautomeric form and possess similar molecular geometry.

In both polymorph, the N—H···S hydrogen bonds between the endocyclic NH group of the triazole ring and the thioureido sulfur atom (Fig. 2 and Table 1) are arranged in a S6 graph-set motif (Bernstein et al., 1995) stabilizing the tautomer structure. The general configurations of the carbethoxythiourea group in the title molecule replicate that of previously reported for triclinic polymorph (Dolzhenko et al., 2010a) and a similar structure (Dolzhenko et al., 2010b). The strong intramolecular hydrogen bonding between carbonyl oxygen atom and thiourea NH group arranged in S(6) graph-set motif which is common for carbethoxythioureas (Dolzhenko et al., 2010a,b). In the three independent molecules, the triazole ring make dihedral angles of 6.6 (2)°, 8.4 (2)° and 10.6 (2)° with the corresponding phenyl rings [cf. 6.59 (10)° for the triclinic polymorph (Dolzhenko et al., 2010a)].

The monoclinic and triclinic polymorphs are significantly different in crystal packing. In contrast to the dimers of triclinic polymorph (Dolzhenko et al., 2010a), molecules of monoclinic polymorph are connected with intermolecular hydrogen bonding of the C═S···H—N—N···H—N pattern forming pseudosymmetric trimer structures arranged in sheets parallel to the (302) plane.

Experimental

The title compound was synthesized by nucleophilic addition of 3(5)-amino-5(3)-phenyl-1H-1,2,4-triazole (Dolzhenko et al., 2007), to ethoxycarbonyl isothiocyanate in DMF solution at room temperature (Fig.3). Single crystals suitable for crystallographic analysis were grown by recrystallization from toluene.

Refinement

All the H atoms attached to the carbon atoms were constrained in a riding motion approximation [0.94 Å for Caryl–H, 0.98 Å for methylene H atoms and 0.97 Å for methyl groups; Uiso(H) = 1.2Ueq(Caryl and Cmethylene) and 1.5Ueq(Cmethyl)] while the N-bound H atoms were located in a difference map and refined with restraints in bond length and thermal parameters. One of the ethoxy -OCH2CH3 group is disordered over two orientations with occupancies of 0.634 (7) and 0.366 (7). The corresponding bond distances in the disorder components were restrained to be the same. The Uij parameters of disordered atoms were restrained to an approximate isotropic behaviour.

Figures

Fig. 1.
Crystal packing of the title compound, viewed along the c axis.
Fig. 2.
Synthesis of N-carbethoxy-N'-(3-phenyl-1H-1,2,4-triazol-5-yl)thiourea

Crystal data

C12H13N5O2SF(000) = 1824
Mr = 291.33Dx = 1.443 Mg m3
Monoclinic, P21/cMelting point: 454 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 13.4743 (6) ÅCell parameters from 3587 reflections
b = 20.4817 (9) Åθ = 2.4–21.7°
c = 15.0266 (7) ŵ = 0.25 mm1
β = 104.040 (1)°T = 223 K
V = 4023.1 (3) Å3Rod, colourless
Z = 120.56 × 0.24 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer9216 independent reflections
Radiation source: fine-focus sealed tube5772 reflections with I > 2σ(I)
graphiteRint = 0.055
[var phi] and ω scansθmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)h = −17→17
Tmin = 0.872, Tmax = 0.971k = −25→26
28189 measured reflectionsl = −11→19

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0784P)2 + 0.4202P] where P = (Fo2 + 2Fc2)/3
9216 reflections(Δ/σ)max = 0.001
598 parametersΔρmax = 0.85 e Å3
86 restraintsΔρmin = −0.52 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
S10.20531 (6)0.64994 (3)−0.06103 (6)0.0441 (2)
S20.17227 (7)0.48747 (3)0.97238 (6)0.0513 (2)
S30.31718 (9)0.53635 (4)0.83353 (7)0.0713 (3)
O10.23376 (15)0.88193 (8)−0.06109 (14)0.0410 (5)
O20.17439 (15)0.85011 (9)0.06024 (14)0.0404 (5)
O30.04408 (16)0.38003 (9)1.20243 (14)0.0455 (5)
O40.06816 (16)0.30621 (9)1.09867 (14)0.0445 (5)
O60.4656 (2)0.50555 (10)0.59819 (18)0.0682 (7)
N10.07377 (17)0.68052 (10)0.18244 (15)0.0328 (5)
N20.07758 (18)0.57196 (10)0.15331 (16)0.0369 (5)
N30.11842 (18)0.60701 (10)0.09369 (16)0.0347 (5)
H3N0.1465 (19)0.5860 (12)0.0535 (15)0.042*
N40.15156 (17)0.72134 (10)0.06799 (16)0.0327 (5)
H4N0.144 (2)0.7611 (7)0.0893 (18)0.039*
N50.21787 (18)0.77628 (10)−0.03862 (16)0.0354 (5)
H5N0.244 (2)0.7715 (14)−0.0874 (13)0.043*
N60.21916 (17)0.28401 (10)0.88026 (16)0.0339 (5)
N70.28571 (17)0.35600 (10)0.79634 (16)0.0372 (5)
N80.24310 (17)0.38767 (10)0.85782 (16)0.0353 (5)
H8N0.243 (2)0.4314 (5)0.860 (2)0.042*
N90.15402 (17)0.35768 (10)0.97396 (16)0.0340 (5)
H9N0.1309 (19)0.3232 (9)0.9998 (18)0.041*
N100.09302 (18)0.41605 (10)1.08206 (16)0.0361 (5)
H10N0.087 (2)0.4548 (8)1.1074 (18)0.043*
N110.40967 (17)0.69867 (10)0.67246 (16)0.0361 (5)
N120.34161 (18)0.74325 (10)0.78232 (18)0.0418 (6)
N130.34239 (19)0.67680 (10)0.78753 (17)0.0391 (6)
H13N0.318 (2)0.6556 (13)0.8300 (15)0.047*
N140.39497 (18)0.58664 (10)0.70279 (16)0.0349 (5)
H14N0.421 (2)0.5794 (14)0.6543 (13)0.042*
N150.37852 (18)0.47458 (10)0.70418 (17)0.0373 (6)
H15N0.353 (2)0.4418 (10)0.7300 (18)0.045*
C1−0.0235 (2)0.65393 (13)0.3321 (2)0.0389 (7)
H1−0.00210.69670.32390.047*
C2−0.0761 (2)0.64147 (14)0.3989 (2)0.0455 (7)
H2−0.09060.67560.43550.055*
C3−0.1069 (2)0.57897 (14)0.4112 (2)0.0483 (8)
H3−0.14200.57050.45690.058*
C4−0.0870 (2)0.52842 (14)0.3573 (2)0.0462 (8)
H4−0.10900.48580.36590.055*
C5−0.0343 (2)0.54099 (13)0.2905 (2)0.0409 (7)
H5−0.02030.50670.25380.049*
C6−0.0022 (2)0.60396 (12)0.27731 (19)0.0328 (6)
C70.0510 (2)0.61851 (12)0.20477 (19)0.0316 (6)
C80.11565 (19)0.67033 (12)0.11294 (18)0.0303 (6)
C90.1901 (2)0.71755 (12)−0.00656 (19)0.0317 (6)
C100.2060 (2)0.83789 (12)−0.0065 (2)0.0336 (6)
C110.2122 (2)0.94956 (12)−0.0410 (2)0.0422 (7)
H11A0.25140.96180.02050.051*
H11B0.13920.9551−0.04410.051*
C120.2431 (2)0.99114 (13)−0.1123 (2)0.0506 (8)
H12A0.31570.9858−0.10760.061*
H12B0.22861.0366−0.10240.061*
H12C0.20490.9778−0.17290.061*
C130.2936 (2)0.17599 (13)0.7891 (2)0.0432 (7)
H130.26750.16730.84040.052*
C140.3236 (3)0.12477 (14)0.7417 (2)0.0517 (8)
H140.31810.08170.76140.062*
C150.3612 (2)0.13640 (14)0.6660 (2)0.0491 (8)
H150.38090.10150.63340.059*
C160.3697 (3)0.20008 (15)0.6385 (2)0.0531 (8)
H160.39600.20860.58720.064*
C170.3401 (2)0.25111 (14)0.6854 (2)0.0460 (7)
H170.34590.29420.66560.055*
C180.3016 (2)0.23983 (12)0.7617 (2)0.0348 (6)
C190.2690 (2)0.29402 (12)0.81255 (19)0.0333 (6)
C200.2040 (2)0.34429 (12)0.90587 (19)0.0317 (6)
C210.1390 (2)0.41679 (12)1.00938 (19)0.0329 (6)
C220.0671 (2)0.36185 (13)1.1259 (2)0.0366 (6)
C230.0197 (3)0.32624 (14)1.2587 (2)0.0491 (8)
H23A0.06810.29021.26110.059*
H23B−0.04950.30991.23230.059*
C240.0270 (3)0.35195 (17)1.3519 (3)0.0707 (11)
H24A0.09390.37141.37540.085*
H24B0.01740.31661.39190.085*
H24C−0.02550.38471.34960.085*
C250.4554 (2)0.82809 (14)0.6144 (2)0.0499 (8)
H250.48520.79150.59330.060*
C260.4684 (3)0.88965 (16)0.5801 (3)0.0598 (9)
H260.50720.89480.53640.072*
C270.4241 (3)0.94289 (15)0.6103 (3)0.0633 (10)
H270.43210.98460.58690.076*
C280.3683 (3)0.93515 (15)0.6747 (3)0.0591 (10)
H280.33810.97180.69510.071*
C290.3559 (2)0.87429 (13)0.7100 (2)0.0485 (8)
H290.31810.86970.75460.058*
C300.3992 (2)0.82008 (13)0.6793 (2)0.0403 (7)
C310.3835 (2)0.75410 (12)0.7126 (2)0.0357 (6)
C320.3826 (2)0.65233 (12)0.72182 (19)0.0327 (6)
C330.3652 (2)0.53406 (12)0.7427 (2)0.0353 (6)
C340.4265 (3)0.46419 (14)0.6349 (2)0.0472 (8)
O50.4364 (4)0.4001 (3)0.6227 (3)0.0402 (13)0.634 (7)
C350.4867 (5)0.3865 (3)0.5460 (5)0.0637 (17)0.634 (7)
H35A0.45710.41460.49350.076*0.634 (7)
H35B0.56000.39590.56600.076*0.634 (7)
C360.4716 (6)0.3202 (3)0.5201 (5)0.0745 (18)0.634 (7)
H36A0.50420.31110.47050.089*0.634 (7)
H36B0.39890.31120.49980.089*0.634 (7)
H36C0.50150.29260.57220.089*0.634 (7)
O5A0.3960 (7)0.4021 (5)0.5995 (6)0.041 (2)0.366 (7)
C35A0.4221 (8)0.3748 (5)0.5141 (6)0.076 (3)0.366 (7)
H35C0.37520.33920.48840.091*0.366 (7)
H35D0.41660.40890.46750.091*0.366 (7)
C36A0.5241 (7)0.3513 (7)0.5415 (9)0.088 (3)0.366 (7)
H36D0.54450.33400.48860.106*0.366 (7)
H36E0.52810.31710.58690.106*0.366 (7)
H36F0.56940.38680.56790.106*0.366 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0679 (5)0.0275 (3)0.0481 (5)0.0027 (3)0.0359 (4)−0.0004 (3)
S20.0890 (6)0.0220 (3)0.0586 (5)−0.0087 (3)0.0485 (5)−0.0055 (3)
S30.1328 (9)0.0264 (4)0.0852 (7)−0.0089 (4)0.0859 (7)−0.0078 (4)
O10.0559 (12)0.0216 (9)0.0544 (13)−0.0001 (8)0.0309 (10)0.0031 (9)
O20.0540 (12)0.0286 (9)0.0454 (12)−0.0025 (8)0.0254 (10)−0.0023 (9)
O30.0715 (14)0.0304 (10)0.0441 (12)−0.0072 (9)0.0322 (11)0.0013 (9)
O40.0625 (13)0.0262 (10)0.0512 (13)−0.0044 (9)0.0263 (11)0.0021 (9)
O60.121 (2)0.0318 (11)0.0786 (17)0.0009 (12)0.0760 (16)0.0008 (12)
N10.0418 (13)0.0264 (11)0.0341 (13)0.0006 (9)0.0166 (10)−0.0002 (10)
N20.0496 (14)0.0283 (11)0.0377 (13)−0.0019 (10)0.0198 (11)0.0033 (10)
N30.0477 (14)0.0252 (11)0.0378 (13)0.0000 (10)0.0229 (11)−0.0001 (10)
N40.0452 (13)0.0216 (10)0.0368 (13)0.0009 (9)0.0207 (11)0.0000 (10)
N50.0494 (14)0.0254 (11)0.0393 (14)0.0012 (10)0.0261 (11)0.0027 (10)
N60.0449 (13)0.0208 (10)0.0377 (13)0.0008 (9)0.0135 (11)−0.0021 (10)
N70.0485 (14)0.0272 (11)0.0408 (14)−0.0003 (10)0.0204 (11)−0.0054 (11)
N80.0501 (14)0.0213 (10)0.0411 (14)−0.0016 (10)0.0235 (11)−0.0023 (10)
N90.0490 (14)0.0192 (10)0.0383 (13)−0.0029 (9)0.0198 (11)0.0004 (10)
N100.0510 (14)0.0240 (11)0.0402 (14)0.0000 (10)0.0242 (11)−0.0002 (10)
N110.0446 (14)0.0246 (11)0.0413 (14)−0.0028 (9)0.0146 (11)0.0024 (10)
N120.0541 (15)0.0229 (11)0.0496 (16)−0.0003 (10)0.0148 (13)−0.0021 (11)
N130.0577 (16)0.0243 (11)0.0412 (15)−0.0009 (10)0.0235 (12)−0.0014 (11)
N140.0503 (14)0.0232 (10)0.0381 (14)−0.0002 (10)0.0244 (11)−0.0007 (10)
N150.0537 (15)0.0208 (11)0.0461 (15)−0.0024 (10)0.0287 (12)−0.0028 (10)
C10.0518 (18)0.0317 (14)0.0360 (16)−0.0018 (12)0.0163 (13)0.0029 (13)
C20.066 (2)0.0379 (16)0.0387 (17)0.0036 (14)0.0235 (15)0.0006 (14)
C30.071 (2)0.0423 (17)0.0416 (17)0.0021 (15)0.0328 (16)0.0105 (15)
C40.063 (2)0.0311 (14)0.0522 (19)−0.0042 (13)0.0298 (16)0.0100 (14)
C50.0547 (18)0.0312 (14)0.0425 (17)−0.0002 (12)0.0232 (14)0.0013 (13)
C60.0382 (15)0.0285 (13)0.0336 (15)−0.0001 (11)0.0127 (12)0.0050 (12)
C70.0368 (15)0.0268 (13)0.0335 (15)0.0009 (11)0.0129 (12)0.0015 (12)
C80.0344 (14)0.0258 (12)0.0327 (15)0.0015 (10)0.0118 (12)0.0001 (12)
C90.0354 (14)0.0254 (12)0.0378 (15)−0.0005 (10)0.0155 (12)0.0045 (12)
C100.0333 (15)0.0265 (13)0.0437 (17)−0.0017 (10)0.0146 (13)0.0004 (12)
C110.0544 (18)0.0239 (13)0.0523 (19)0.0022 (12)0.0210 (15)0.0014 (13)
C120.062 (2)0.0268 (14)0.071 (2)0.0003 (13)0.0310 (18)0.0062 (15)
C130.0514 (18)0.0285 (14)0.0544 (19)0.0027 (12)0.0219 (15)−0.0029 (14)
C140.068 (2)0.0262 (14)0.066 (2)0.0040 (14)0.0261 (18)−0.0050 (15)
C150.056 (2)0.0363 (16)0.056 (2)0.0050 (14)0.0173 (16)−0.0157 (15)
C160.069 (2)0.0500 (19)0.048 (2)−0.0010 (16)0.0298 (17)−0.0092 (16)
C170.065 (2)0.0281 (14)0.0504 (19)−0.0030 (13)0.0243 (16)−0.0037 (14)
C180.0348 (15)0.0277 (13)0.0422 (17)−0.0012 (11)0.0099 (12)−0.0042 (12)
C190.0367 (15)0.0278 (13)0.0353 (16)−0.0022 (11)0.0085 (12)−0.0011 (12)
C200.0347 (15)0.0257 (12)0.0340 (15)−0.0011 (10)0.0068 (12)−0.0009 (12)
C210.0406 (15)0.0252 (12)0.0350 (15)0.0001 (11)0.0133 (12)−0.0004 (12)
C220.0437 (16)0.0321 (15)0.0377 (16)−0.0013 (12)0.0169 (13)0.0031 (13)
C230.066 (2)0.0380 (16)0.0505 (19)−0.0121 (14)0.0289 (17)0.0066 (15)
C240.116 (3)0.052 (2)0.062 (2)−0.011 (2)0.059 (2)0.0019 (19)
C250.0508 (19)0.0303 (15)0.069 (2)−0.0012 (13)0.0158 (17)0.0057 (15)
C260.062 (2)0.0415 (18)0.076 (3)−0.0066 (15)0.0177 (19)0.0157 (18)
C270.070 (2)0.0277 (16)0.084 (3)−0.0066 (15)0.004 (2)0.0120 (18)
C280.073 (2)0.0249 (15)0.073 (3)0.0055 (15)0.005 (2)−0.0047 (16)
C290.057 (2)0.0295 (15)0.056 (2)0.0001 (13)0.0076 (16)−0.0052 (14)
C300.0403 (16)0.0268 (13)0.0480 (18)−0.0036 (12)−0.0004 (14)0.0009 (13)
C310.0388 (16)0.0237 (13)0.0425 (17)−0.0014 (11)0.0055 (13)−0.0012 (12)
C320.0366 (15)0.0248 (12)0.0374 (15)−0.0012 (11)0.0101 (12)−0.0020 (12)
C330.0439 (16)0.0266 (13)0.0418 (16)−0.0023 (11)0.0227 (13)−0.0036 (12)
C340.069 (2)0.0275 (14)0.054 (2)0.0017 (14)0.0334 (17)−0.0047 (14)
O50.047 (3)0.0255 (19)0.053 (3)0.002 (2)0.021 (2)−0.010 (2)
C350.067 (4)0.050 (3)0.092 (4)−0.011 (3)0.056 (3)−0.030 (3)
C360.089 (4)0.064 (3)0.086 (4)−0.012 (3)0.051 (3)−0.016 (3)
O5A0.060 (6)0.032 (3)0.026 (3)0.022 (4)0.001 (4)−0.001 (3)
C35A0.077 (5)0.058 (4)0.096 (5)−0.006 (4)0.028 (4)0.024 (4)
C36A0.083 (5)0.080 (6)0.107 (5)−0.016 (5)0.034 (5)0.001 (5)

Geometric parameters (Å, °)

S1—C91.647 (3)C5—C61.390 (4)
S2—C211.651 (3)C5—H50.94
S3—C331.647 (3)C6—C71.473 (4)
O1—C101.332 (3)C11—C121.503 (4)
O1—C111.462 (3)C11—H11A0.98
O2—C101.208 (3)C11—H11B0.98
O3—C221.316 (3)C12—H12A0.97
O3—C231.474 (3)C12—H12B0.97
O4—C221.212 (3)C12—H12C0.97
O6—C341.200 (3)C13—C141.382 (4)
N1—C81.318 (3)C13—C181.383 (4)
N1—C71.367 (3)C13—H130.94
N2—C71.330 (3)C14—C151.374 (4)
N2—N31.364 (3)C14—H140.94
N3—C81.331 (3)C15—C161.381 (4)
N3—H3N0.897 (10)C15—H150.94
N4—C91.346 (3)C16—C171.373 (4)
N4—C81.393 (3)C16—H160.94
N4—H4N0.889 (10)C17—C181.387 (4)
N5—C101.374 (3)C17—H170.94
N5—C91.381 (3)C18—C191.473 (4)
N5—H5N0.890 (10)C23—C241.476 (5)
N6—C201.324 (3)C23—H23A0.98
N6—C191.364 (3)C23—H23B0.98
N7—C191.322 (3)C24—H24A0.97
N7—N81.364 (3)C24—H24B0.97
N8—C201.331 (3)C24—H24C0.97
N8—H8N0.897 (10)C25—C301.382 (4)
N9—C211.357 (3)C25—C261.389 (4)
N9—C201.382 (3)C25—H250.94
N9—H9N0.896 (10)C26—C271.372 (5)
N10—C221.378 (3)C26—H260.94
N10—C211.380 (3)C27—C281.371 (5)
N10—H10N0.892 (10)C27—H270.94
N11—C321.310 (3)C28—C291.381 (4)
N11—C311.371 (3)C28—H280.94
N12—C311.324 (4)C29—C301.384 (4)
N12—N131.363 (3)C29—H290.94
N13—C321.334 (3)C30—C311.474 (4)
N13—H13N0.896 (10)C34—O51.337 (6)
N14—C331.341 (3)C34—O5A1.401 (12)
N14—C321.394 (3)O5—C351.499 (6)
N14—H14N0.891 (10)C35—C361.414 (6)
N15—C341.369 (4)C35—H35A0.98
N15—C331.379 (3)C35—H35B0.98
N15—H15N0.883 (10)C36—H36A0.97
C1—C21.384 (4)C36—H36B0.97
C1—C61.387 (4)C36—H36C0.97
C1—H10.94O5A—C35A1.517 (7)
C2—C31.372 (4)C35A—C36A1.420 (7)
C2—H20.94C35A—H35C0.98
C3—C41.380 (4)C35A—H35D0.98
C3—H30.94C36A—H36D0.97
C4—C51.388 (4)C36A—H36E0.97
C4—H40.94C36A—H36F0.97
C10—O1—C11114.5 (2)C16—C17—C18120.7 (3)
C22—O3—C23115.0 (2)C16—C17—H17119.6
C8—N1—C7102.2 (2)C18—C17—H17119.6
C7—N2—N3102.3 (2)C13—C18—C17118.4 (3)
C8—N3—N2109.5 (2)C13—C18—C19120.2 (3)
C8—N3—H3N130.7 (18)C17—C18—C19121.4 (2)
N2—N3—H3N119.6 (18)N7—C19—N6114.7 (2)
C9—N4—C8127.6 (2)N7—C19—C18122.9 (2)
C9—N4—H4N116.9 (19)N6—C19—C18122.4 (2)
C8—N4—H4N115.4 (19)N6—C20—N8110.8 (2)
C10—N5—C9127.8 (2)N6—C20—N9122.5 (2)
C10—N5—H5N119.5 (19)N8—C20—N9126.7 (2)
C9—N5—H5N112.6 (19)N9—C21—N10116.0 (2)
C20—N6—C19102.4 (2)N9—C21—S2124.9 (2)
C19—N7—N8102.3 (2)N10—C21—S2119.12 (19)
C20—N8—N7109.7 (2)O4—C22—O3125.9 (3)
C20—N8—H8N130 (2)O4—C22—N10124.8 (3)
N7—N8—H8N121 (2)O3—C22—N10109.3 (2)
C21—N9—C20127.8 (2)O3—C23—C24107.8 (2)
C21—N9—H9N115.6 (18)O3—C23—H23A110.2
C20—N9—H9N116.5 (18)C24—C23—H23A110.2
C22—N10—C21127.0 (2)O3—C23—H23B110.2
C22—N10—H10N116.9 (19)C24—C23—H23B110.2
C21—N10—H10N115.7 (19)H23A—C23—H23B108.5
C32—N11—C31102.4 (2)C23—C24—H24A109.5
C31—N12—N13102.4 (2)C23—C24—H24B109.5
C32—N13—N12109.4 (2)H24A—C24—H24B109.5
C32—N13—H13N128.9 (19)C23—C24—H24C109.5
N12—N13—H13N121.8 (19)H24A—C24—H24C109.5
C33—N14—C32128.3 (2)H24B—C24—H24C109.5
C33—N14—H14N116.7 (19)C30—C25—C26120.7 (3)
C32—N14—H14N114.7 (19)C30—C25—H25119.7
C34—N15—C33126.2 (2)C26—C25—H25119.7
C34—N15—H15N121.2 (19)C27—C26—C25119.6 (4)
C33—N15—H15N112.7 (19)C27—C26—H26120.2
C2—C1—C6120.7 (3)C25—C26—H26120.2
C2—C1—H1119.7C28—C27—C26119.9 (3)
C6—C1—H1119.7C28—C27—H27120.0
C3—C2—C1119.7 (3)C26—C27—H27120.0
C3—C2—H2120.2C27—C28—C29120.9 (3)
C1—C2—H2120.2C27—C28—H28119.5
C2—C3—C4120.8 (3)C29—C28—H28119.5
C2—C3—H3119.6C28—C29—C30119.7 (3)
C4—C3—H3119.6C28—C29—H29120.1
C3—C4—C5119.5 (3)C30—C29—H29120.1
C3—C4—H4120.3C25—C30—C29119.1 (3)
C5—C4—H4120.3C25—C30—C31119.8 (3)
C4—C5—C6120.5 (3)C29—C30—C31121.0 (3)
C4—C5—H5119.8N12—C31—N11114.4 (2)
C6—C5—H5119.8N12—C31—C30123.1 (3)
C1—C6—C5118.9 (3)N11—C31—C30122.5 (3)
C1—C6—C7119.9 (2)N11—C32—N13111.5 (2)
C5—C6—C7121.2 (2)N11—C32—N14121.3 (2)
N2—C7—N1114.5 (2)N13—C32—N14127.2 (2)
N2—C7—C6122.2 (2)N14—C33—N15116.0 (2)
N1—C7—C6123.2 (2)N14—C33—S3124.6 (2)
N1—C8—N3111.5 (2)N15—C33—S3119.4 (2)
N1—C8—N4122.1 (2)O6—C34—O5124.1 (3)
N3—C8—N4126.4 (2)O6—C34—N15125.5 (3)
N4—C9—N5115.6 (2)O5—C34—N15109.7 (3)
N4—C9—S1125.57 (19)O6—C34—O5A125.9 (5)
N5—C9—S1118.8 (2)N15—C34—O5A106.3 (4)
O2—C10—O1125.4 (2)C34—O5—C35111.5 (5)
O2—C10—N5125.2 (2)C36—C35—O5109.2 (5)
O1—C10—N5109.4 (2)C36—C35—H35A109.8
O1—C11—C12106.7 (2)O5—C35—H35A109.8
O1—C11—H11A110.4C36—C35—H35B109.8
C12—C11—H11A110.4O5—C35—H35B109.8
O1—C11—H11B110.4H35A—C35—H35B108.3
C12—C11—H11B110.4C35—C36—H36A109.5
H11A—C11—H11B108.6C35—C36—H36B109.5
C11—C12—H12A109.5H36A—C36—H36B109.5
C11—C12—H12B109.5C35—C36—H36C109.5
H12A—C12—H12B109.5H36A—C36—H36C109.5
C11—C12—H12C109.5H36B—C36—H36C109.5
H12A—C12—H12C109.5C34—O5A—C35A123.3 (9)
H12B—C12—H12C109.5C36A—C35A—O5A106.6 (6)
C14—C13—C18120.7 (3)C36A—C35A—H35C110.4
C14—C13—H13119.6O5A—C35A—H35C110.4
C18—C13—H13119.6C36A—C35A—H35D110.4
C15—C14—C13120.5 (3)O5A—C35A—H35D110.4
C15—C14—H14119.7H35C—C35A—H35D108.6
C13—C14—H14119.7C35A—C36A—H36D109.5
C14—C15—C16119.0 (3)C35A—C36A—H36E109.5
C14—C15—H15120.5H36D—C36A—H36E109.5
C16—C15—H15120.5C35A—C36A—H36F109.5
C17—C16—C15120.7 (3)H36D—C36A—H36F109.5
C17—C16—H16119.7H36E—C36A—H36F109.5
C15—C16—H16119.7
C7—N2—N3—C80.9 (3)C19—N6—C20—N9179.4 (2)
C19—N7—N8—C20−0.2 (3)N7—N8—C20—N60.6 (3)
C31—N12—N13—C32−0.6 (3)N7—N8—C20—N9−179.5 (2)
C6—C1—C2—C30.3 (5)C21—N9—C20—N6176.1 (3)
C1—C2—C3—C4−0.6 (5)C21—N9—C20—N8−3.8 (5)
C2—C3—C4—C50.6 (5)C20—N9—C21—N10−175.3 (3)
C3—C4—C5—C6−0.3 (5)C20—N9—C21—S24.2 (4)
C2—C1—C6—C50.0 (4)C22—N10—C21—N94.6 (4)
C2—C1—C6—C7178.1 (3)C22—N10—C21—S2−175.0 (2)
C4—C5—C6—C10.0 (4)C23—O3—C22—O41.2 (4)
C4—C5—C6—C7−178.1 (3)C23—O3—C22—N10−177.1 (2)
N3—N2—C7—N1−0.9 (3)C21—N10—C22—O4−10.9 (5)
N3—N2—C7—C6176.8 (2)C21—N10—C22—O3167.5 (3)
C8—N1—C7—N20.6 (3)C22—O3—C23—C24163.0 (3)
C8—N1—C7—C6−177.2 (2)C30—C25—C26—C27−0.6 (5)
C1—C6—C7—N2176.7 (3)C25—C26—C27—C280.6 (5)
C5—C6—C7—N2−5.2 (4)C26—C27—C28—C290.1 (5)
C1—C6—C7—N1−5.7 (4)C27—C28—C29—C30−0.8 (5)
C5—C6—C7—N1172.4 (3)C26—C25—C30—C290.0 (5)
C7—N1—C8—N30.1 (3)C26—C25—C30—C31177.9 (3)
C7—N1—C8—N4−179.7 (2)C28—C29—C30—C250.7 (5)
N2—N3—C8—N1−0.7 (3)C28—C29—C30—C31−177.2 (3)
N2—N3—C8—N4179.1 (2)N13—N12—C31—N110.7 (3)
C9—N4—C8—N1−175.8 (3)N13—N12—C31—C30179.7 (2)
C9—N4—C8—N34.4 (4)C32—N11—C31—N12−0.6 (3)
C8—N4—C9—N5178.4 (2)C32—N11—C31—C30−179.6 (2)
C8—N4—C9—S1−1.1 (4)C25—C30—C31—N12171.4 (3)
C10—N5—C9—N4−3.7 (4)C29—C30—C31—N12−10.6 (4)
C10—N5—C9—S1175.9 (2)C25—C30—C31—N11−9.6 (4)
C11—O1—C10—O2−6.9 (4)C29—C30—C31—N11168.3 (3)
C11—O1—C10—N5172.5 (2)C31—N11—C32—N130.1 (3)
C9—N5—C10—O25.1 (5)C31—N11—C32—N14179.1 (2)
C9—N5—C10—O1−174.3 (2)N12—N13—C32—N110.3 (3)
C10—O1—C11—C12−176.9 (2)N12—N13—C32—N14−178.6 (3)
C18—C13—C14—C15−0.5 (5)C33—N14—C32—N11−175.2 (3)
C13—C14—C15—C160.7 (5)C33—N14—C32—N133.6 (5)
C14—C15—C16—C17−0.6 (5)C32—N14—C33—N15173.9 (3)
C15—C16—C17—C180.4 (5)C32—N14—C33—S3−7.3 (4)
C14—C13—C18—C170.3 (4)C34—N15—C33—N145.8 (4)
C14—C13—C18—C19179.8 (3)C34—N15—C33—S3−173.0 (3)
C16—C17—C18—C13−0.2 (5)C33—N15—C34—O61.1 (6)
C16—C17—C18—C19−179.7 (3)C33—N15—C34—O5172.4 (3)
N8—N7—C19—N6−0.2 (3)C33—N15—C34—O5A−162.6 (4)
N8—N7—C19—C18179.8 (2)O6—C34—O5—C35−9.8 (7)
C20—N6—C19—N70.6 (3)N15—C34—O5—C35178.8 (4)
C20—N6—C19—C18−179.4 (2)O5A—C34—O5—C3593.0 (14)
C13—C18—C19—N7172.0 (3)C34—O5—C35—C36−164.9 (7)
C17—C18—C19—N7−8.6 (4)O6—C34—O5A—C35A8.9 (10)
C13—C18—C19—N6−8.0 (4)O5—C34—O5A—C35A−85.4 (14)
C17—C18—C19—N6171.4 (3)N15—C34—O5A—C35A172.6 (6)
C19—N6—C20—N8−0.7 (3)C34—O5A—C35A—C36A80.4 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3N···S10.90 (1)2.44 (3)2.978 (2)119 (2)
N8—H8N···S20.90 (1)2.42 (3)2.975 (2)121 (2)
N13—H13N···S30.90 (1)2.44 (3)2.997 (2)120 (2)
N8—H8N···S30.90 (1)2.44 (2)3.253 (2)150 (2)
N3—H3N···S2i0.90 (2)2.43 (2)3.238 (2)151 (2)
N13—H13N···S1ii0.90 (2)2.49 (3)3.306 (3)151 (2)
N4—H4N···O20.89 (1)1.94 (2)2.661 (3)137 (2)
N9—H9N···O40.90 (1)1.91 (2)2.648 (3)138 (2)
N14—H14N···O60.89 (1)1.90 (2)2.619 (3)136 (2)
N10—H10N···N2ii0.89 (2)2.51 (2)3.390 (3)170 (2)
N15—H15N···N70.89 (2)2.31 (2)3.197 (3)180 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI5124).

References

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