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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3300.
Published online 2010 November 27. doi:  10.1107/S1600536810047999
PMCID: PMC3011373

2,2′-[p-Phenyl­enebis(methyl­idene­aza­ne­di­yl)]dipyridinium bis­(hydrogensulfate) dihydrate

Abstract

The cation of the title salt, C18H20N4 2+·2HSO4 ·2H2O, lies on a center of inversion with the mid-point directly in the middle of the p-phenyl­ene ring. Within the hydrogensulfate ion, the S—O(H) bond is the longest of the S—O bonds. The dihedral angle between the central and terminal ring of the cation is 78.6 (2)°. In the crystal, the cation, anion and water mol­ecule inter­act by O—H(...)O and N—H(...)O hydrogen bonds, generating a three-dimensional network.

Related literature

For the synthesis and structure of 1,4-bis­(pyridine-2-amino­meth­yl)benzene, see: Zou et al. (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3300-scheme1.jpg

Experimental

Crystal data

  • C18H20N4 2+·2HSO4 ·2H2O
  • M r = 522.55
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3300-efi1.jpg
  • a = 7.1718 (5) Å
  • b = 9.3010 (7) Å
  • c = 9.5113 (5) Å
  • α = 97.648 (2)°
  • β = 92.340 (2)°
  • γ = 114.005 (2)°
  • V = 571.25 (7) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.30 mm−1
  • T = 293 K
  • 0.25 × 0.21 × 0.18 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.930, T max = 0.949
  • 5648 measured reflections
  • 2583 independent reflections
  • 1624 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.143
  • S = 1.14
  • 2583 reflections
  • 169 parameters
  • 5 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.42 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002) [triangle]; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810047999/si2312sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047999/si2312Isup2.hkl

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

Acknowledgments

We thank the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Innovation Team of the Education Bureau of Heilongjiang Province (No. 2010 t d03), Heilongjiang Education Department (No. 11531274), Heilongjiang University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The synthesis complements other reports of the coordinating ability of 1,4-bis(2-pyridylaminomethyl)benzene, a relatively flexible N-donor ligand having aromatic as well as aliphatic donor sites. The structure of the neutral ligand has been reported (Zou et al., 2003). Protonation by a strong acid, sulfuric acid, occurs at both pyridyl nitrogen atoms to yield the hydrogensulfate salt, C18H20N42+ 2(HSO4)-.2H2O (Scheme I, Fig. 1). The cation lies on a center-of-inversion with the mid-point directly in the middle of the p-phenylene ring. The hydrogensulfate anion bears a hydrogen atom, so that the S–OH bond is the longest of the S–O bonds. The cation, anion and water molecule interact by O–H···O and N–H···O hydrogen bonds to generate a three-dimensional network (Table 1).

Experimental

1,4-Bis(2-pyridylaminomethyl)benzene (10 mmol, 2.90 g) was dissolved in methanol (50 ml). Strong sulfuric acid was added until the pH was 3. The solution was filtered; colorless crystals were isolated after several days.

Refinement

Carbon-bound hydrogen atoms were placed in calculated positions (C–H 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C). The amino/ammonium and water H atoms were located in a difference Fourier map, and were refined with distance restraints of N–H 0.88±0.01 and O–H 0.84 + 0.01 Å; their temperature factors were refined.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C18H20N42+ 2(HSO4)-.2H2O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The cation lies on a center-of-inversion.

Crystal data

C18H20N42+·2HSO4·2H2OZ = 1
Mr = 522.55F(000) = 274
Triclinic, P1Dx = 1.519 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1718 (5) ÅCell parameters from 3948 reflections
b = 9.3010 (7) Åθ = 3.1–27.4°
c = 9.5113 (5) ŵ = 0.30 mm1
α = 97.648 (2)°T = 293 K
β = 92.340 (2)°Prism, colorless
γ = 114.005 (2)°0.25 × 0.21 × 0.18 mm
V = 571.25 (7) Å3

Data collection

Rigaku R-AXIS RAPID diffractometer2583 independent reflections
Radiation source: fine-focus sealed tube1624 reflections with I > 2σ(I)
graphiteRint = 0.024
Detector resolution: 10.000 pixels mm-1θmax = 27.4°, θmin = 3.1°
ω scansh = −9→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)k = −12→12
Tmin = 0.930, Tmax = 0.949l = −12→12
5648 measured reflections

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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.14w = 1/[σ2(Fo2) + (0.0586P)2 + 0.3231P] where P = (Fo2 + 2Fc2)/3
2583 reflections(Δ/σ)max = 0.001
169 parametersΔρmax = 0.48 e Å3
5 restraintsΔρmin = −0.42 e Å3

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

xyzUiso*/Ueq
S10.19334 (11)0.92763 (8)0.76081 (7)0.0379 (2)
O10.1234 (3)0.7575 (2)0.7264 (2)0.0508 (5)
O20.2506 (5)0.9842 (3)0.9097 (2)0.0767 (8)
O30.3889 (4)1.0040 (3)0.6846 (3)0.0627 (7)
H30.481 (5)0.981 (5)0.719 (4)0.094*
O40.0542 (3)0.9850 (3)0.7002 (3)0.0566 (6)
O1W0.3282 (4)1.0635 (4)1.2016 (3)0.0730 (8)
H110.286 (7)1.023 (6)1.1157 (19)0.110*
H120.218 (4)1.055 (6)1.235 (5)0.110*
N10.1175 (4)0.3172 (3)0.7485 (2)0.0418 (6)
H10.112 (5)0.220 (2)0.740 (4)0.063*
N20.2258 (4)0.5652 (3)0.8961 (2)0.0388 (5)
H20.202 (5)0.606 (4)0.821 (2)0.058*
C10.5953 (5)0.6591 (3)0.4870 (3)0.0409 (7)
H1A0.65880.76650.47870.049*
C20.4067 (5)0.6003 (3)0.5401 (3)0.0417 (7)
H2A0.34440.66870.56680.050*
C30.3092 (4)0.4410 (3)0.5541 (3)0.0363 (6)
C40.1038 (5)0.3747 (4)0.6143 (3)0.0432 (7)
H4A0.05370.45730.63010.052*
H4B0.00570.28750.54520.052*
C50.1854 (4)0.4078 (3)0.8764 (3)0.0342 (6)
C60.2159 (4)0.3435 (4)0.9964 (3)0.0407 (6)
H60.19070.23620.98740.049*
C70.2830 (5)0.4399 (4)1.1269 (3)0.0492 (8)
H70.30200.39701.20640.059*
C80.3230 (5)0.6011 (4)1.1422 (3)0.0502 (8)
H80.36890.66641.23080.060*
C90.2939 (4)0.6600 (4)1.0261 (3)0.0453 (7)
H90.32060.76761.03450.054*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0398 (4)0.0353 (4)0.0421 (4)0.0194 (3)0.0045 (3)0.0058 (3)
O10.0561 (13)0.0329 (11)0.0647 (14)0.0198 (10)0.0081 (10)0.0079 (9)
O20.106 (2)0.0816 (19)0.0359 (13)0.0403 (17)−0.0082 (12)−0.0100 (11)
O30.0481 (14)0.0637 (16)0.0861 (18)0.0248 (12)0.0202 (12)0.0361 (13)
O40.0494 (13)0.0527 (14)0.0795 (16)0.0314 (11)0.0020 (11)0.0175 (11)
O1W0.0499 (15)0.116 (2)0.0588 (16)0.0458 (16)−0.0023 (12)−0.0032 (15)
N10.0508 (15)0.0357 (13)0.0414 (13)0.0204 (12)0.0084 (10)0.0059 (10)
N20.0420 (13)0.0386 (14)0.0403 (13)0.0204 (11)0.0020 (10)0.0096 (10)
C10.0555 (18)0.0352 (15)0.0354 (15)0.0226 (13)0.0055 (12)0.0047 (11)
C20.0557 (18)0.0433 (17)0.0371 (15)0.0322 (15)0.0059 (12)0.0042 (12)
C30.0449 (16)0.0423 (16)0.0243 (13)0.0220 (13)0.0009 (10)0.0025 (10)
C40.0469 (17)0.0506 (18)0.0346 (15)0.0241 (14)0.0008 (11)0.0033 (12)
C50.0284 (13)0.0360 (15)0.0400 (15)0.0138 (11)0.0075 (10)0.0096 (11)
C60.0418 (16)0.0412 (16)0.0472 (17)0.0216 (13)0.0103 (12)0.0187 (12)
C70.0398 (16)0.073 (2)0.0443 (17)0.0278 (15)0.0096 (12)0.0258 (15)
C80.0475 (18)0.060 (2)0.0428 (17)0.0244 (16)0.0010 (13)0.0023 (14)
C90.0443 (17)0.0401 (17)0.0500 (17)0.0184 (13)0.0012 (13)0.0009 (13)

Geometric parameters (Å, °)

S1—O21.425 (2)C1—H1A0.9300
S1—O11.437 (2)C2—C31.385 (4)
S1—O41.443 (2)C2—H2A0.9300
S1—O31.551 (2)C3—C1i1.390 (4)
O3—H30.84 (1)C3—C41.517 (4)
O1W—H110.84 (1)C4—H4A0.9700
O1W—H120.84 (1)C4—H4B0.9700
N1—C51.331 (4)C5—C61.406 (4)
N1—C41.462 (4)C6—C71.371 (4)
N1—H10.88 (1)C6—H60.9300
N2—C51.356 (3)C7—C81.394 (5)
N2—C91.362 (4)C7—H70.9300
N2—H20.89 (1)C8—C91.341 (4)
C1—C21.382 (4)C8—H80.9300
C1—C3i1.390 (4)C9—H90.9300
O2—S1—O1112.24 (15)C1i—C3—C4119.7 (3)
O2—S1—O4113.33 (16)N1—C4—C3112.3 (2)
O1—S1—O4113.05 (14)N1—C4—H4A109.1
O2—S1—O3107.05 (17)C3—C4—H4A109.1
O1—S1—O3107.22 (14)N1—C4—H4B109.1
O4—S1—O3103.15 (13)C3—C4—H4B109.1
S1—O3—H3109 (3)H4A—C4—H4B107.9
H11—O1W—H12101 (5)N1—C5—N2121.3 (2)
C5—N1—C4125.7 (2)N1—C5—C6121.2 (3)
C5—N1—H1117 (2)N2—C5—C6117.5 (2)
C4—N1—H1115 (2)C7—C6—C5119.6 (3)
C5—N2—C9122.4 (2)C7—C6—H6120.2
C5—N2—H2118 (2)C5—C6—H6120.2
C9—N2—H2120 (2)C6—C7—C8121.0 (3)
C2—C1—C3i120.5 (3)C6—C7—H7119.5
C2—C1—H1A119.7C8—C7—H7119.5
C3i—C1—H1A119.7C9—C8—C7118.4 (3)
C1—C2—C3120.9 (3)C9—C8—H8120.8
C1—C2—H2A119.6C7—C8—H8120.8
C3—C2—H2A119.6C8—C9—N2121.2 (3)
C2—C3—C1i118.6 (3)C8—C9—H9119.4
C2—C3—C4121.7 (3)N2—C9—H9119.4
C3i—C1—C2—C30.3 (5)C9—N2—C5—N1179.5 (3)
C1—C2—C3—C1i−0.3 (4)C9—N2—C5—C60.2 (4)
C1—C2—C3—C4179.0 (2)N1—C5—C6—C7−179.0 (3)
C5—N1—C4—C380.0 (3)N2—C5—C6—C70.3 (4)
C2—C3—C4—N1−115.8 (3)C5—C6—C7—C8−0.5 (4)
C1i—C3—C4—N163.5 (3)C6—C7—C8—C90.2 (5)
C4—N1—C5—N28.5 (4)C7—C8—C9—N20.3 (5)
C4—N1—C5—C6−172.2 (3)C5—N2—C9—C8−0.5 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···O1wii0.84 (1)1.75 (1)2.592 (4)178 (5)
O1w—H11···O20.84 (1)1.93 (2)2.749 (3)164 (5)
O1w—H12···O4iii0.84 (1)1.98 (1)2.813 (3)174 (5)
N2—H2···O10.89 (1)2.02 (2)2.844 (3)154 (3)
N1—H1···O4iv0.88 (1)2.03 (1)2.903 (3)170 (3)

Symmetry codes: (ii) −x+1, −y+2, −z+2; (iii) −x, −y+2, −z+2; (iv) x, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2312).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.
  • Zou, R.-Y., Xu, F.-B., Li, Q.-S., Song, H.-B., Lv, H. & Zhang, Z.-Z. (2003). Acta Cryst. E59, o1312–o1313.

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