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

Jiang, Y.-H.; Qiu, Q.-M.; Liu, M.; Jin, Q.-H.; Zhang, C.-L.

doi:10.1107/S1600536812047058

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3450

doi:10.1107/S1600536812047058

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

Yu-Han Jiang,^a Qi-Ming Qiu,^a Min Liu,^b Qiong-Hua Jin ^a ^* and Cun-Lin Zhang ^c

^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 ) 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

Crystal data

C₁₀H₁₀N₂²⁺·2C₇H₄NS₂⁻
M_r = 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 ) T_min = 0.878, T_max = 0.900
5663 measured reflections
2116 independent reflections
990 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.203
S = 1.04
2116 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812047058/jj2151sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047058/jj2151Isup2.hkl

checkCIF report

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.

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

	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.
	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⁺·2C₇H₄NS₂⁻	F(000) = 508
M_r = 490.66	D_x = 1.359 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1198 reflections
a = 14.3909 (13) Å	θ = 2.7–20.7°
b = 5.6670 (4) Å	µ = 0.42 mm⁻¹
c = 15.5471 (14) Å	T = 298 K
β = 109.023 (2)°	Block, colorless
V = 1198.67 (17) Å³	0.32 × 0.30 × 0.26 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2116 independent reflections
Radiation source: fine-focus sealed tube	990 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
phi and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −17→11
T_min = 0.878, T_max = 0.900	k = −6→6
5663 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.203	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0797P)² + 0.6601P] where P = (F_o² + 2F_c²)/3
2116 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₀H₁₀N₂²⁺·2C₇H₄NS₂⁻	V = 1198.67 (17) Å³
M_r = 490.66	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.3909 (13) Å	µ = 0.42 mm⁻¹
b = 5.6670 (4) Å	T = 298 K
c = 15.5471 (14) Å	0.32 × 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)
T_min = 0.878, T_max = 0.900	R_int = 0.055
5663 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.203	H-atom parameters constrained
S = 1.04	Δρ_max = 0.29 e Å⁻³
2116 reflections	Δρ_min = −0.26 e Å⁻³
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

	x	y	z	U_iso*/U_eq
N1	0.2335 (3)	0.3414 (7)	0.7956 (2)	0.0629 (11)
N2	0.6509 (3)	0.4638 (7)	0.6145 (3)	0.0700 (11)
H2	0.6875	0.5792	0.6419	0.084*
S1	0.16856 (12)	0.6851 (3)	0.68804 (10)	0.1018 (7)
S2	0.30080 (16)	0.3128 (4)	0.65559 (11)	0.1352 (9)
C1	0.2387 (4)	0.4264 (10)	0.7171 (3)	0.0812 (16)
C2	0.1755 (3)	0.4737 (9)	0.8346 (3)	0.0586 (12)
C3	0.1353 (4)	0.6727 (10)	0.7852 (3)	0.0720 (14)
C4	0.0782 (4)	0.8244 (11)	0.8160 (5)	0.102 (2)
H4	0.0515	0.9598	0.7835	0.122*
C5	0.0617 (5)	0.7703 (13)	0.8960 (6)	0.112 (2)
H5	0.0217	0.8680	0.9170	0.135*
C6	0.1030 (5)	0.5758 (13)	0.9448 (4)	0.0991 (19)
H6	0.0921	0.5448	0.9995	0.119*
C7	0.1601 (3)	0.4255 (9)	0.9152 (3)	0.0700 (14)
H7	0.1879	0.2929	0.9491	0.084*
C8	0.5934 (4)	0.3548 (11)	0.6502 (4)	0.0888 (18)
H8	0.5926	0.4038	0.7070	0.107*
C9	0.5343 (4)	0.1726 (11)	0.6091 (4)	0.0888 (17)
H9	0.4955	0.0979	0.6385	0.107*
C10	0.5317 (3)	0.0987 (8)	0.5244 (3)	0.0549 (12)
C11	0.5936 (4)	0.2124 (10)	0.4888 (3)	0.0843 (17)
H11	0.5967	0.1676	0.4322	0.101*
C12	0.6507 (4)	0.3907 (11)	0.5350 (4)	0.0914 (19)
H12	0.6923	0.4653	0.5086	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.068 (2)	0.077 (3)	0.046 (2)	−0.008 (2)	0.0210 (19)	0.002 (2)
N2	0.060 (2)	0.070 (3)	0.072 (3)	−0.015 (2)	0.010 (2)	−0.002 (2)
S1	0.1082 (12)	0.1031 (13)	0.0740 (9)	−0.0164 (10)	0.0019 (8)	0.0351 (9)
S2	0.1740 (19)	0.177 (2)	0.0824 (11)	−0.0039 (16)	0.0806 (12)	0.0087 (12)
C1	0.086 (4)	0.105 (5)	0.051 (3)	−0.020 (3)	0.020 (3)	0.013 (3)
C2	0.057 (3)	0.059 (3)	0.054 (3)	−0.004 (2)	0.010 (2)	0.001 (2)
C3	0.063 (3)	0.058 (3)	0.077 (3)	−0.009 (3)	−0.002 (3)	0.005 (3)
C4	0.074 (4)	0.061 (4)	0.141 (6)	0.008 (3)	−0.004 (4)	0.000 (4)
C5	0.091 (5)	0.094 (6)	0.146 (7)	0.011 (4)	0.031 (5)	−0.035 (5)
C6	0.103 (5)	0.105 (5)	0.095 (4)	0.012 (4)	0.040 (4)	−0.018 (4)
C7	0.076 (3)	0.069 (3)	0.068 (3)	0.005 (3)	0.027 (3)	−0.004 (3)
C8	0.089 (4)	0.108 (5)	0.077 (4)	−0.031 (4)	0.038 (3)	−0.019 (3)
C9	0.085 (4)	0.116 (5)	0.081 (4)	−0.027 (4)	0.049 (3)	−0.015 (4)
C10	0.044 (3)	0.061 (3)	0.057 (3)	0.004 (2)	0.013 (2)	0.011 (2)
C11	0.099 (4)	0.103 (4)	0.054 (3)	−0.035 (4)	0.029 (3)	−0.007 (3)
C12	0.109 (4)	0.112 (5)	0.058 (3)	−0.040 (4)	0.033 (3)	0.001 (3)

Geometric parameters (Å, º) top

N1—C1	1.337 (5)	C5—H5	0.9300
N1—C2	1.399 (5)	C6—C7	1.363 (7)
N2—C8	1.294 (6)	C6—H6	0.9300
N2—C12	1.303 (6)	C7—H7	0.9300
N2—H2	0.8600	C8—C9	1.358 (7)
S1—C3	1.728 (6)	C8—H8	0.9300
S1—C1	1.754 (6)	C9—C10	1.371 (6)
S2—C1	1.638 (6)	C9—H9	0.9300
C2—C7	1.370 (6)	C10—C11	1.355 (6)
C2—C3	1.381 (6)	C10—C10ⁱ	1.487 (8)
C3—C4	1.378 (8)	C11—C12	1.352 (7)
C4—C5	1.375 (9)	C11—H11	0.9300
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.361 (9)

C1—N1—C2	115.0 (4)	C5—C6—H6	119.3
C8—N2—C12	116.8 (5)	C7—C6—H6	119.3
C8—N2—H2	121.6	C6—C7—C2	118.6 (5)
C12—N2—H2	121.6	C6—C7—H7	120.7
C3—S1—C1	92.4 (3)	C2—C7—H7	120.7
N1—C1—S2	126.5 (5)	N2—C8—C9	123.5 (5)
N1—C1—S1	109.7 (4)	N2—C8—H8	118.3
S2—C1—S1	123.8 (3)	C9—C8—H8	118.3
C7—C2—C3	120.6 (5)	C8—C9—C10	120.1 (5)
C7—C2—N1	126.0 (4)	C8—C9—H9	120.0
C3—C2—N1	113.4 (4)	C10—C9—H9	120.0
C4—C3—C2	120.3 (5)	C11—C10—C9	115.6 (4)
C4—C3—S1	130.1 (5)	C11—C10—C10ⁱ	121.7 (5)
C2—C3—S1	109.6 (4)	C9—C10—C10ⁱ	122.7 (5)
C5—C4—C3	118.3 (6)	C12—C11—C10	120.3 (5)
C5—C4—H4	120.9	C12—C11—H11	119.8
C3—C4—H4	120.9	C10—C11—H11	119.8
C6—C5—C4	120.8 (6)	N2—C12—C11	123.7 (5)
C6—C5—H5	119.6	N2—C12—H12	118.1
C4—C5—H5	119.6	C11—C12—H12	118.1
C5—C6—C7	121.3 (6)

C2—N1—C1—S2	179.6 (4)	C3—C4—C5—C6	1.9 (10)
C2—N1—C1—S1	0.0 (5)	C4—C5—C6—C7	−1.6 (10)
C3—S1—C1—N1	0.9 (4)	C5—C6—C7—C2	0.1 (8)
C3—S1—C1—S2	−178.8 (4)	C3—C2—C7—C6	1.0 (7)
C1—N1—C2—C7	−178.8 (4)	N1—C2—C7—C6	178.6 (5)
C1—N1—C2—C3	−1.1 (6)	C12—N2—C8—C9	−0.2 (8)
C7—C2—C3—C4	−0.6 (7)	N2—C8—C9—C10	−1.5 (9)
N1—C2—C3—C4	−178.5 (4)	C8—C9—C10—C11	2.4 (8)
C7—C2—C3—S1	179.5 (4)	C8—C9—C10—C10ⁱ	−179.7 (5)
N1—C2—C3—S1	1.7 (5)	C9—C10—C11—C12	−1.8 (8)
C1—S1—C3—C4	178.7 (5)	C10ⁱ—C10—C11—C12	−179.7 (5)
C1—S1—C3—C2	−1.5 (4)	C8—N2—C12—C11	0.9 (8)
C2—C3—C4—C5	−0.8 (8)	C10—C11—C12—N2	0.1 (9)
S1—C3—C4—C5	179.0 (5)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱⁱ	0.86	1.93	2.790 (6)	178

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₂²⁺·2C₇H₄NS₂⁻
M_r	490.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	14.3909 (13), 5.6670 (4), 15.5471 (14)
β (°)	109.023 (2)
V (Å³)	1198.67 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.32 × 0.30 × 0.26

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.878, 0.900
No. of measured, independent and observed [I > 2σ(I)] reflections	5663, 2116, 990
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.203, 1.04
No. of reflections	2116
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.86	1.93	2.790 (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).

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