organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

4,4′-Bi­pyridine-1,1′-diium bis­­(1,3-benzo­thia­zole-2-thiol­ate)

aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China, bThe College of Materials Science and Engineering, Beijing University of Technology, Beijing 100022, People's Republic of China, and cKey Laboratory of Terahertz Optoelectronics, Ministry of Education, Department of Physics, Capital Normal University, Beijing 100048, People's Republic of China
*Correspondence e-mail: jinqh204@163.com

(Received 2 September 2012; accepted 15 November 2012; online 24 November 2012)

In the title salt, C10H10N22+·2C7H4NS2, the complete 4,4′-bipyridine-1,1′-diium dication is generated by a center of symmetry. In the crystal, N—H⋯N hydrogen bonds are observed between the cations and anions.

Related literature

For ligands based on 2-mercaptobenzothia­zole in coordination chemistry, see: Chen et al. (2010[Chen, S. C., Yu, R. M., Zhao, Z. G., Chen, S. M., Zhang, Q. S., Wu, X. Y., Wang, F. & Lu, C. Z. (2010). Cryst. Growth Des. 10, 1155-1160.]) and for ligands based on 4,4′- bipyridine, see: Biradha et al. (1999[Biradha, K., Domasevitch, K. V., Moulton, B., Seward, C. & Zaworotko, M. J. (1999). Chem. Commun. pp. 1327-1328.]); Ren et al. (2004[Ren, C.-X., Cheng, L., Chen, X.-M. & Ng, S. W. (2004). Acta Cryst. E60, m364-m366.]); Tao et al. (2000[Tao, J., Tong, M. L., Shi, J. X., Chen, X. M. & Ng, S. W. (2000). Chem. Commun. pp. 2043-2044.]); Tong et al. (2000[Tong, M. L., Zheng, S. L. & Chen, X. M. (2000). Polyhedron, 19, 1809-1814.]); Xu et al. (2012[Xu, S., Dai, Y.-C., Qiu, Q.-M., Jin, Q.-H. & Zhang, C.-L. (2012). Acta Cryst. E68, m1222-m1223.]). For a related structure, see: Deng et al. (2005[Deng, Q.-J., Yao, M.-X. & Zeng, M.-H. (2005). Acta Cryst. E61, o2239-o2240.]).

[Scheme 1]

Experimental

Crystal data
  • C10H10N22+·2C7H4NS2

  • Mr = 490.66

  • Monoclinic, P 21 /c

  • a = 14.3909 (13) Å

  • b = 5.6670 (4) Å

  • c = 15.5471 (14) Å

  • β = 109.023 (2)°

  • V = 1198.67 (17) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.42 mm−1

  • T = 298 K

  • 0.32 × 0.30 × 0.26 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2007[Bruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.878, Tmax = 0.900

  • 5663 measured reflections

  • 2116 independent reflections

  • 990 reflections with I > 2σ(I)

  • Rint = 0.055

Refinement
  • R[F2 > 2σ(F2)] = 0.060

  • wR(F2) = 0.203

  • S = 1.04

  • 2116 reflections

  • 145 parameters

  • H-atom parameters constrained

  • Δρmax = 0.29 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2⋯N1i 0.86 1.93 2.790 (6) 178
Symmetry code: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: SMART (Bruker, 2007[Bruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2007[Bruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The 4,4'-bipyridine lignad is ideal for forming supramolecular structures. Many examples in coordination with multifarious metals are observed (Biradha et al., 1999; Tong et al., 2000; Tao et al., 2000; Ren et al., 2004; Xu et al., 2012). However, to our best knowledge, only a few Ag(I)-Hmbt (Hmbt = 2-mercaptobenzothiazole) framework structures have been reported (Chen et al., 2010). In our work synthesizing an Ag(I)-Hmbt complex containing the 4,4'-bipyridine, the title compound, (I), (C10H10N2).(C7H4NS2)2 was unexpectedly obtained.

The crystal structure of the title compound, (I), consists of one mbt (mercaptobenzothiazole) anion and one 4-pyridyl unit containg a center of symmetry which upon expansion produces a 4,4'-bipyridine-1,1'-diium cation and two mbt cations in the asymmetric unit (Fig. 1). Crystal packing reveals that N—H···N intermolecular hydrogen bonds are observed between the centrosymmetric 4,4'-bipyridine-1,1'-diium cation and two mbt anions (Fig. 2; Table 1). These observed hydrogen bonds are similar to those reported in a similar and related compound, (C10H8N2)(C2H3N3S2)2, (Deng et al., 2005).

Related literature top

For ligands based on 2-mercaptobenzothiazole in coordination chemistry, see: Chen et al. (2010) and for ligands based on 4,4'- bipyridine, see: Biradha et al. (1999); Ren et al. (2004); Tao et al. (2000); Tong et al. (2000); Xu et al. (2012). For a related structure, see: Deng et al. (2005).

Experimental top

A mixture of AgBr (0.2 mmol) and 2-mercaptobenzothiazole (0.2 mmol) in MeOH and CH2Cl2 (10 mL, v/v = 1:1) was stirred for 2 h and triphenylphosphine (PPh3)(0.2 mmol) was added to the mixture which was stirred for another 5 h. The insoluble residues were removed by filtration. The filtrate was then evaporated slowly at room temperature for a week to yield colorless crystalline products. Anal. Calc. for C24H18N4S4: C, 58.70; H, 3.67; N, 11.41. Found: C, 58.49; H, 3.79; N, 11.22%. Melting point: 427–431°K.

Refinement top

All H atoms were located in the calculated sites and included in the final refinement in the riding model approximation with displacement parameters derived from the parent atoms to which they were bonded (Uiso(H) = 1.2Ueq). C—H hydrogen atoms (aromatic) were included with distance set to 0.93 Å and amide N—H hydrogen atoms were included with distance set to 0.86 Å.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular entities of the title compound, showing the atom-numbering scheme of the 4-pyridyl and mercaptobenzothiazole units and the symmetry expanded 4,4'-bipyridine-1,1'-diium cation and two mbt cation units with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of the packing in (I) along the b axis. Dashed lines indicate N—H···N hydrogen bonds. H atoms not involved in hydrogen bonding have been removed for clarity.
4,4'-Bipyridine-1,1'-diium; bis(1,3-benzothiazole-2-thiolate) top
Crystal data top
C10H10N22+·2C7H4NS2F(000) = 508
Mr = 490.66Dx = 1.359 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1198 reflections
a = 14.3909 (13) Åθ = 2.7–20.7°
b = 5.6670 (4) ŵ = 0.42 mm1
c = 15.5471 (14) ÅT = 298 K
β = 109.023 (2)°Block, colorless
V = 1198.67 (17) Å30.32 × 0.30 × 0.26 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
2116 independent reflections
Radiation source: fine-focus sealed tube990 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
phi and ω scansθmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 1711
Tmin = 0.878, Tmax = 0.900k = 66
5663 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.203H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0797P)2 + 0.6601P]
where P = (Fo2 + 2Fc2)/3
2116 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C10H10N22+·2C7H4NS2V = 1198.67 (17) Å3
Mr = 490.66Z = 2
Monoclinic, P21/cMo Kα radiation
a = 14.3909 (13) ŵ = 0.42 mm1
b = 5.6670 (4) ÅT = 298 K
c = 15.5471 (14) Å0.32 × 0.30 × 0.26 mm
β = 109.023 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2116 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
990 reflections with I > 2σ(I)
Tmin = 0.878, Tmax = 0.900Rint = 0.055
5663 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.203H-atom parameters constrained
S = 1.04Δρmax = 0.29 e Å3
2116 reflectionsΔρmin = 0.26 e Å3
145 parameters
Special details top

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) top
xyzUiso*/Ueq
N10.2335 (3)0.3414 (7)0.7956 (2)0.0629 (11)
N20.6509 (3)0.4638 (7)0.6145 (3)0.0700 (11)
H20.68750.57920.64190.084*
S10.16856 (12)0.6851 (3)0.68804 (10)0.1018 (7)
S20.30080 (16)0.3128 (4)0.65559 (11)0.1352 (9)
C10.2387 (4)0.4264 (10)0.7171 (3)0.0812 (16)
C20.1755 (3)0.4737 (9)0.8346 (3)0.0586 (12)
C30.1353 (4)0.6727 (10)0.7852 (3)0.0720 (14)
C40.0782 (4)0.8244 (11)0.8160 (5)0.102 (2)
H40.05150.95980.78350.122*
C50.0617 (5)0.7703 (13)0.8960 (6)0.112 (2)
H50.02170.86800.91700.135*
C60.1030 (5)0.5758 (13)0.9448 (4)0.0991 (19)
H60.09210.54480.99950.119*
C70.1601 (3)0.4255 (9)0.9152 (3)0.0700 (14)
H70.18790.29290.94910.084*
C80.5934 (4)0.3548 (11)0.6502 (4)0.0888 (18)
H80.59260.40380.70700.107*
C90.5343 (4)0.1726 (11)0.6091 (4)0.0888 (17)
H90.49550.09790.63850.107*
C100.5317 (3)0.0987 (8)0.5244 (3)0.0549 (12)
C110.5936 (4)0.2124 (10)0.4888 (3)0.0843 (17)
H110.59670.16760.43220.101*
C120.6507 (4)0.3907 (11)0.5350 (4)0.0914 (19)
H120.69230.46530.50860.110*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.068 (2)0.077 (3)0.046 (2)0.008 (2)0.0210 (19)0.002 (2)
N20.060 (2)0.070 (3)0.072 (3)0.015 (2)0.010 (2)0.002 (2)
S10.1082 (12)0.1031 (13)0.0740 (9)0.0164 (10)0.0019 (8)0.0351 (9)
S20.1740 (19)0.177 (2)0.0824 (11)0.0039 (16)0.0806 (12)0.0087 (12)
C10.086 (4)0.105 (5)0.051 (3)0.020 (3)0.020 (3)0.013 (3)
C20.057 (3)0.059 (3)0.054 (3)0.004 (2)0.010 (2)0.001 (2)
C30.063 (3)0.058 (3)0.077 (3)0.009 (3)0.002 (3)0.005 (3)
C40.074 (4)0.061 (4)0.141 (6)0.008 (3)0.004 (4)0.000 (4)
C50.091 (5)0.094 (6)0.146 (7)0.011 (4)0.031 (5)0.035 (5)
C60.103 (5)0.105 (5)0.095 (4)0.012 (4)0.040 (4)0.018 (4)
C70.076 (3)0.069 (3)0.068 (3)0.005 (3)0.027 (3)0.004 (3)
C80.089 (4)0.108 (5)0.077 (4)0.031 (4)0.038 (3)0.019 (3)
C90.085 (4)0.116 (5)0.081 (4)0.027 (4)0.049 (3)0.015 (4)
C100.044 (3)0.061 (3)0.057 (3)0.004 (2)0.013 (2)0.011 (2)
C110.099 (4)0.103 (4)0.054 (3)0.035 (4)0.029 (3)0.007 (3)
C120.109 (4)0.112 (5)0.058 (3)0.040 (4)0.033 (3)0.001 (3)
Geometric parameters (Å, º) top
N1—C11.337 (5)C5—H50.9300
N1—C21.399 (5)C6—C71.363 (7)
N2—C81.294 (6)C6—H60.9300
N2—C121.303 (6)C7—H70.9300
N2—H20.8600C8—C91.358 (7)
S1—C31.728 (6)C8—H80.9300
S1—C11.754 (6)C9—C101.371 (6)
S2—C11.638 (6)C9—H90.9300
C2—C71.370 (6)C10—C111.355 (6)
C2—C31.381 (6)C10—C10i1.487 (8)
C3—C41.378 (8)C11—C121.352 (7)
C4—C51.375 (9)C11—H110.9300
C4—H40.9300C12—H120.9300
C5—C61.361 (9)
C1—N1—C2115.0 (4)C5—C6—H6119.3
C8—N2—C12116.8 (5)C7—C6—H6119.3
C8—N2—H2121.6C6—C7—C2118.6 (5)
C12—N2—H2121.6C6—C7—H7120.7
C3—S1—C192.4 (3)C2—C7—H7120.7
N1—C1—S2126.5 (5)N2—C8—C9123.5 (5)
N1—C1—S1109.7 (4)N2—C8—H8118.3
S2—C1—S1123.8 (3)C9—C8—H8118.3
C7—C2—C3120.6 (5)C8—C9—C10120.1 (5)
C7—C2—N1126.0 (4)C8—C9—H9120.0
C3—C2—N1113.4 (4)C10—C9—H9120.0
C4—C3—C2120.3 (5)C11—C10—C9115.6 (4)
C4—C3—S1130.1 (5)C11—C10—C10i121.7 (5)
C2—C3—S1109.6 (4)C9—C10—C10i122.7 (5)
C5—C4—C3118.3 (6)C12—C11—C10120.3 (5)
C5—C4—H4120.9C12—C11—H11119.8
C3—C4—H4120.9C10—C11—H11119.8
C6—C5—C4120.8 (6)N2—C12—C11123.7 (5)
C6—C5—H5119.6N2—C12—H12118.1
C4—C5—H5119.6C11—C12—H12118.1
C5—C6—C7121.3 (6)
C2—N1—C1—S2179.6 (4)C3—C4—C5—C61.9 (10)
C2—N1—C1—S10.0 (5)C4—C5—C6—C71.6 (10)
C3—S1—C1—N10.9 (4)C5—C6—C7—C20.1 (8)
C3—S1—C1—S2178.8 (4)C3—C2—C7—C61.0 (7)
C1—N1—C2—C7178.8 (4)N1—C2—C7—C6178.6 (5)
C1—N1—C2—C31.1 (6)C12—N2—C8—C90.2 (8)
C7—C2—C3—C40.6 (7)N2—C8—C9—C101.5 (9)
N1—C2—C3—C4178.5 (4)C8—C9—C10—C112.4 (8)
C7—C2—C3—S1179.5 (4)C8—C9—C10—C10i179.7 (5)
N1—C2—C3—S11.7 (5)C9—C10—C11—C121.8 (8)
C1—S1—C3—C4178.7 (5)C10i—C10—C11—C12179.7 (5)
C1—S1—C3—C21.5 (4)C8—N2—C12—C110.9 (8)
C2—C3—C4—C50.8 (8)C10—C11—C12—N20.1 (9)
S1—C3—C4—C5179.0 (5)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N1ii0.861.932.790 (6)178
Symmetry code: (ii) x+1, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC10H10N22+·2C7H4NS2
Mr490.66
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)14.3909 (13), 5.6670 (4), 15.5471 (14)
β (°) 109.023 (2)
V3)1198.67 (17)
Z2
Radiation typeMo Kα
µ (mm1)0.42
Crystal size (mm)0.32 × 0.30 × 0.26
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.878, 0.900
No. of measured, independent and
observed [I > 2σ(I)] reflections
5663, 2116, 990
Rint0.055
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.060, 0.203, 1.04
No. of reflections2116
No. of parameters145
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.26

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N1i0.861.932.790 (6)178.4
Symmetry code: (i) x+1, y+1/2, z+3/2.
 

Acknowledgements

This work was supported by National Natural Science Foundation of China (No.21171119), the National High Technology Research and Development Program 863 of China (No. 2012 A A063201), Beijing Personnel Bureau, the National Keystone Basic Research Program (973 Program) under grant Nos. 2007CB310408 and 2006CB302901 and the Committee of Education of the Beijing Foundation of China (grant No. KM201210028020).

References

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First citationBruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
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First citationTao, J., Tong, M. L., Shi, J. X., Chen, X. M. & Ng, S. W. (2000). Chem. Commun. pp. 2043–2044.  Web of Science CSD CrossRef
First citationTong, M. L., Zheng, S. L. & Chen, X. M. (2000). Polyhedron, 19, 1809–1814.  Web of Science CSD CrossRef CAS
First citationXu, S., Dai, Y.-C., Qiu, Q.-M., Jin, Q.-H. & Zhang, C.-L. (2012). Acta Cryst. E68, m1222–m1223.  CSD CrossRef IUCr Journals

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