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

Abstract

In the title salt, C₁₀H₁₀N₂ ²⁺·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  

• C₁₀H₁₀N₂ ²⁺·2C₇H₄NS₂ ⁻

• M _r = 490.66

• Monoclinic,

• a = 14.3909 (13) Å

• b = 5.6670 (4) Å

• c = 15.5471 (14) Å

• β = 109.023 (2)°

• V = 1198.67 (17) ų

• 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[F ² > 2σ(F ²)] = 0.060

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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).

Experimental

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

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 (U_iso(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.

Figures

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.

Crystal data

C10H10N22+·2C7H4NS2−	F(000) = 508
Mr = 490.66	Dx = 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

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

Refinement

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(Fo2) + (0.0797P)2 + 0.6601P] where P = (Fo2 + 2Fc2)/3
2116 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.