Bis(2-amino-5-methyl-1,3,4-thia-diazole-κN(3))dichloridocobalt(II).

In the monomeric title complex, [CoCl(2)(C(3)H(5)N(3)S)(2)], the Co(II) atom is tetra-coordinated by two chloride anions and two N atoms from two monodentate 2-amino-5-methyl-1,3,4-thia-diazole ligands, giving a slightly distorted tetra-hedral stereochemistry [bond angle range about Co = 105.16 (12)-112.50 (10)°]. In the complex, the dihedral angle between the 1,3,4-thia-diazole planes in the two ligands is 72.8 (1)°. There are two intra-molecular N-H⋯Cl inter-actions in the complex unit, while in the crystal, inter-molecular N-H⋯N and N-H⋯Cl hydrogen bonds link these units into a two-dimensional layered structure parallel to (011).

Related literature

For potential applications of complexes containing 2,5-disubstituted 1,3,4-thia­diazo­les, see: Katritzky et al. (2010 ▶); Seed et al. (2007 ▶). For the preparation of the 2-amino-5-methyl-1,3,4-thia­diazole ligand, see: Chubb & Nissenbaum (1959 ▶). For complexes with this ligand, see: Lynch & Ewington (2001 ▶); Neverov et al. (1986 ▶); Antolini et al. (1988 ▶).

Experimental

Crystal data

[CoCl2(C3H5N3S)2]

M = 360.15

Monoclinic,

a = 9.124 (2) Å

b = 20.180 (5) Å

c = 7.2767 (19) Å

β = 99.479 (5)°

V = 1321.5 (6) Å3

Z = 4

Mo Kα radiation

μ = 2.01 mm−1

T = 296 K

0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.670, T max = 0.676

8978 measured reflections

3194 independent reflections

2125 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.110

S = 1.04

3194 reflections

156 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.60 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812020995/zs2204sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020995/zs2204Isup2.hkl

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

[CoCl2(C3H5N3S)2]	F(000) = 724
Mr = 360.15	Dx = 1.810 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5643 reflections
a = 9.124 (2) Å	θ = 0.7–0.7°
b = 20.180 (5) Å	µ = 2.01 mm−1
c = 7.2767 (19) Å	T = 296 K
β = 99.479 (5)°	Block, blue
V = 1321.5 (6) Å3	0.20 × 0.20 × 0.20 mm
Z = 4

Bruker SMART APEX diffractometer	3194 independent reflections
Radiation source: fine-focus sealed tube	2125 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 8.192 pixels mm-1	θmax = 28.2°, θmin = 2.0°
ω–2τ scans	h = −9→12
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −26→26
Tmin = 0.670, Tmax = 0.676	l = −8→9
8978 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.047P)2 + 0.1324P] where P = (Fo2 + 2Fc2)/3
3194 reflections	(Δ/σ)max < 0.001
156 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.60 e Å−3

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.

	x	y	z	Uiso*/Ueq
Co1	0.15275 (5)	0.62934 (2)	0.21631 (7)	0.02936 (16)
S2	0.52153 (11)	0.77737 (5)	0.39642 (15)	0.0386 (3)
S1	0.26820 (12)	0.44424 (5)	−0.08418 (15)	0.0391 (3)
Cl1	0.06975 (11)	0.58762 (5)	0.46557 (14)	0.0410 (3)
Cl2	−0.02720 (11)	0.68410 (5)	0.02491 (16)	0.0457 (3)
C1	0.3446 (4)	0.75138 (19)	0.3006 (5)	0.0320 (8)
N3	0.3324 (3)	0.68679 (14)	0.2864 (4)	0.0302 (7)
N5	0.2217 (3)	0.55309 (15)	0.0748 (4)	0.0303 (7)
N6	0.3037 (3)	0.56944 (15)	−0.0648 (5)	0.0337 (7)
N4	0.4654 (3)	0.65406 (15)	0.3519 (5)	0.0352 (8)
C6	0.1944 (4)	0.48894 (18)	0.0809 (5)	0.0293 (8)
C7	0.3353 (4)	0.5187 (2)	−0.1557 (5)	0.0336 (9)
C8	0.5721 (4)	0.69334 (19)	0.4114 (5)	0.0355 (9)
N1	0.1191 (4)	0.46049 (16)	0.2013 (5)	0.0434 (9)
H1A	0.0845	0.4842	0.2825	0.052*
H1B	0.1050	0.4183	0.1981	0.052*
N2	0.2347 (4)	0.79357 (16)	0.2434 (5)	0.0460 (9)
H2A	0.1488	0.7789	0.1933	0.055*
H2B	0.2494	0.8355	0.2565	0.055*
C20	0.4198 (5)	0.5212 (2)	−0.3141 (6)	0.0453 (11)
H20A	0.4970	0.4884	−0.2961	0.068*
H20B	0.4632	0.5643	−0.3198	0.068*
H20C	0.3538	0.5125	−0.4285	0.068*
C21	0.7265 (5)	0.6726 (2)	0.4872 (7)	0.0552 (13)
H21A	0.7922	0.6872	0.4051	0.083*
H21B	0.7307	0.6252	0.4976	0.083*
H21C	0.7563	0.6920	0.6081	0.083*

	U11	U22	U33	U12	U13	U23
Co1	0.0291 (3)	0.0241 (3)	0.0352 (3)	−0.0010 (2)	0.0060 (2)	−0.0012 (2)
S2	0.0437 (6)	0.0292 (5)	0.0425 (6)	−0.0096 (4)	0.0060 (5)	−0.0050 (5)
S1	0.0487 (6)	0.0273 (5)	0.0421 (6)	0.0026 (4)	0.0100 (5)	−0.0051 (5)
Cl1	0.0442 (5)	0.0428 (6)	0.0381 (6)	−0.0072 (4)	0.0129 (4)	−0.0008 (5)
Cl2	0.0433 (6)	0.0360 (6)	0.0541 (7)	0.0069 (5)	−0.0029 (5)	0.0033 (5)
C1	0.039 (2)	0.0279 (19)	0.031 (2)	−0.0037 (17)	0.0099 (17)	−0.0030 (17)
N3	0.0303 (16)	0.0216 (15)	0.0387 (19)	0.0003 (13)	0.0054 (13)	0.0001 (14)
N5	0.0328 (16)	0.0271 (17)	0.0315 (18)	0.0015 (13)	0.0066 (13)	0.0005 (14)
N6	0.0374 (17)	0.0279 (17)	0.0368 (19)	−0.0001 (14)	0.0092 (14)	0.0041 (15)
N4	0.0330 (17)	0.0275 (16)	0.045 (2)	−0.0003 (14)	0.0046 (15)	0.0001 (16)
C6	0.0294 (18)	0.0277 (19)	0.029 (2)	0.0011 (15)	−0.0004 (15)	0.0013 (16)
C7	0.035 (2)	0.035 (2)	0.031 (2)	0.0025 (17)	0.0041 (16)	0.0003 (18)
C8	0.038 (2)	0.033 (2)	0.036 (2)	−0.0038 (17)	0.0065 (17)	0.0000 (18)
N1	0.057 (2)	0.0255 (17)	0.050 (2)	−0.0062 (16)	0.0168 (18)	0.0004 (16)
N2	0.047 (2)	0.0247 (17)	0.065 (3)	0.0031 (16)	0.0032 (18)	−0.0034 (18)
C20	0.044 (2)	0.058 (3)	0.037 (2)	0.008 (2)	0.0165 (19)	0.000 (2)
C21	0.041 (2)	0.054 (3)	0.067 (3)	0.003 (2)	−0.003 (2)	−0.005 (3)

Co1—N3	2.004 (3)	N4—C8	1.275 (5)
Co1—N5	2.009 (3)	C6—N1	1.330 (5)
Co1—Cl1	2.2416 (12)	C7—C20	1.490 (5)
Co1—Cl2	2.2590 (12)	C8—C21	1.486 (5)
S2—C1	1.731 (4)	N1—H1A	0.8600
S2—C8	1.756 (4)	N1—H1B	0.8600
S1—C6	1.725 (4)	N2—H2A	0.8600
S1—C7	1.735 (4)	N2—H2B	0.8600
C1—N3	1.311 (5)	C20—H20A	0.9600
C1—N2	1.329 (5)	C20—H20B	0.9600
N3—N4	1.395 (4)	C20—H20C	0.9600
N5—C6	1.320 (4)	C21—H21A	0.9600
N5—N6	1.397 (4)	C21—H21B	0.9600
N6—C7	1.277 (5)	C21—H21C	0.9600
N3—Co1—N5	105.16 (12)	N6—C7—S1	114.7 (3)
N3—Co1—Cl1	112.50 (10)	C20—C7—S1	120.9 (3)
N5—Co1—Cl1	107.63 (9)	N4—C8—C21	125.1 (4)
N3—Co1—Cl2	110.78 (9)	N4—C8—S2	113.7 (3)
N5—Co1—Cl2	108.41 (9)	C21—C8—S2	121.2 (3)
Cl1—Co1—Cl2	111.99 (5)	C6—N1—H1A	120.0
C1—S2—C8	87.17 (18)	C6—N1—H1B	120.0
C6—S1—C7	87.32 (18)	H1A—N1—H1B	120.0
N3—C1—N2	124.2 (3)	C1—N2—H2A	120.0
N3—C1—S2	113.2 (3)	C1—N2—H2B	120.0
N2—C1—S2	122.5 (3)	H2A—N2—H2B	120.0
C1—N3—N4	112.7 (3)	C7—C20—H20A	109.5
C1—N3—Co1	130.6 (3)	C7—C20—H20B	109.5
N4—N3—Co1	116.2 (2)	H20A—C20—H20B	109.5
C6—N5—N6	112.5 (3)	C7—C20—H20C	109.5
C6—N5—Co1	131.1 (3)	H20A—C20—H20C	109.5
N6—N5—Co1	116.2 (2)	H20B—C20—H20C	109.5
C7—N6—N5	112.4 (3)	C8—C21—H21A	109.5
C8—N4—N3	113.2 (3)	C8—C21—H21B	109.5
N5—C6—N1	124.5 (4)	H21A—C21—H21B	109.5
N5—C6—S1	113.1 (3)	C8—C21—H21C	109.5
N1—C6—S1	122.4 (3)	H21A—C21—H21C	109.5
N6—C7—C20	124.3 (4)	H21B—C21—H21C	109.5
C8—S2—C1—N3	0.3 (3)	C6—N5—N6—C7	−0.4 (4)
C8—S2—C1—N2	−178.0 (4)	Co1—N5—N6—C7	−175.9 (3)
N2—C1—N3—N4	178.2 (3)	C1—N3—N4—C8	−0.3 (5)
S2—C1—N3—N4	−0.1 (4)	Co1—N3—N4—C8	−173.4 (3)
N2—C1—N3—Co1	−10.0 (6)	N6—N5—C6—N1	179.7 (3)
S2—C1—N3—Co1	171.75 (19)	Co1—N5—C6—N1	−5.7 (6)
N5—Co1—N3—C1	145.3 (3)	N6—N5—C6—S1	0.2 (4)
Cl1—Co1—N3—C1	−97.9 (3)	Co1—N5—C6—S1	174.85 (18)
Cl2—Co1—N3—C1	28.3 (4)	C7—S1—C6—N5	0.0 (3)
N5—Co1—N3—N4	−43.2 (3)	C7—S1—C6—N1	−179.5 (3)
Cl1—Co1—N3—N4	73.7 (3)	N5—N6—C7—C20	179.1 (3)
Cl2—Co1—N3—N4	−160.1 (2)	N5—N6—C7—S1	0.3 (4)
N3—Co1—N5—C6	137.7 (3)	C6—S1—C7—N6	−0.2 (3)
Cl1—Co1—N5—C6	17.5 (4)	C6—S1—C7—C20	−179.0 (3)
Cl2—Co1—N5—C6	−103.8 (3)	N3—N4—C8—C21	−179.3 (4)
N3—Co1—N5—N6	−47.8 (3)	N3—N4—C8—S2	0.6 (4)
Cl1—Co1—N5—N6	−168.0 (2)	C1—S2—C8—N4	−0.5 (3)
Cl2—Co1—N5—N6	70.7 (2)	C1—S2—C8—C21	179.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.86	2.49	3.281 (4)	153
N2—H2A···Cl2	0.86	2.66	3.445 (4)	152
N2—H2B···Cl1i	0.86	2.90	3.331 (4)	113
N2—H2B···N6ii	0.86	2.32	3.114 (5)	153
N1—H1B···Cl2iii	0.86	2.65	3.387 (4)	144
N1—H1A···Cl1iv	0.86	2.88	3.341 (3)	115

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.86	2.49	3.281 (4)	153
N2—H2A⋯Cl2	0.86	2.66	3.445 (4)	152
N2—H2B⋯N6i	0.86	2.32	3.114 (5)	153
N1—H1B⋯Cl2ii	0.86	2.65	3.387 (4)	144

Symmetry codes: (i) ; (ii) .