Bis(2,2′-di­amino-4,4′-bi-1,3-thia­zole-N,N′)(di­chloro)­cobalt(II) dihydrate

The crystal structure of the title compound, [Co(C₆H₆N₄S₂)₂Cl₂]·2H₂O, comprises an octahedral Co^II complex and water of crystallization. Two Cl atoms and two di­amino­bi­thia­zole (DABT) ligands coordinate to the Co^II atom in a cis configuration. The overlapped arrangement and the short separation of 3.46 (2) Å between parallel DABT rings suggest the existence of π–π stacking interactions. A short S...S contact of 3.1822 (17) Å is observed between DABT ligands.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.047
• wR factor = 0.108
• Data-to-parameter ratio = 18.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O2     -   H2B    ...          ?

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.99
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(I)

Crystal data

[Co(C6H6N4S2)2Cl2]·2H2O	F(000) = 1140
Mr = 562.44	Dx = 1.748 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10880 reflections
a = 10.8616 (12) Å	θ = 2.5–24.0°
b = 13.6096 (15) Å	µ = 1.47 mm^−1
c = 15.0657 (17) Å	T = 295 K
β = 106.282 (12)°	Prism, pink
V = 2137.7 (4) Å^3	0.28 × 0.22 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	4872 independent reflections
Radiation source: fine-focus sealed tube	2794 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
ω and φ scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −13→14
Tmin = 0.660, Tmax = 0.765	k = −17→10
13046 measured reflections	l = −18→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 0.86	w = 1/[σ^2(Fo^2) + (0.0453P)^2] where P = (Fo^2 + 2Fc^2)/3
4872 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.88 e Å^−3
0 restraints	Δρmin = −0.78 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
Co	0.78650 (5)	0.34418 (4)	0.23843 (4)	0.02050 (15)
Cl1	0.60477 (9)	0.24860 (7)	0.13650 (6)	0.0213 (2)
Cl2	0.92233 (9)	0.30808 (7)	0.13309 (6)	0.0218 (2)
S1	0.58537 (11)	0.62228 (8)	0.07480 (8)	0.0354 (3)
S2	0.53993 (11)	0.41287 (8)	0.44330 (8)	0.0320 (3)
S3	1.12840 (11)	0.52188 (9)	0.44303 (8)	0.0366 (3)
S4	0.98523 (11)	0.06458 (8)	0.39751 (8)	0.0353 (3)
N1	0.6925 (3)	0.4734 (2)	0.1718 (2)	0.0226 (7)
N2	0.6678 (3)	0.3833 (2)	0.3261 (2)	0.0216 (7)
N3	0.9467 (3)	0.4185 (2)	0.3363 (2)	0.0225 (7)
N4	0.8832 (3)	0.2255 (2)	0.3210 (2)	0.0230 (8)
N5	0.7340 (3)	0.4855 (2)	0.0274 (2)	0.0273 (8)
N6	0.6886 (3)	0.2570 (2)	0.4379 (2)	0.0281 (8)
N7	0.9263 (3)	0.5898 (3)	0.3105 (2)	0.0340 (9)
N8	0.7654 (4)	0.0832 (3)	0.2629 (3)	0.0381 (9)
C1	0.6803 (4)	0.5177 (3)	0.0919 (3)	0.0239 (9)
C2	0.5544 (4)	0.6022 (3)	0.1795 (3)	0.0345 (11)
H2	0.5027	0.6419	0.2043	0.041*
C3	0.6156 (4)	0.5209 (3)	0.2202 (3)	0.0241 (9)
C4	0.6049 (4)	0.4720 (3)	0.3036 (3)	0.0244 (9)
C5	0.5343 (4)	0.5001 (3)	0.3597 (3)	0.0322 (11)
H5	0.4887	0.5586	0.3540	0.039*
C6	0.6445 (4)	0.3434 (3)	0.3995 (3)	0.0221 (9)
C7	0.9868 (4)	0.5100 (3)	0.3543 (3)	0.0277 (10)
C8	1.1314 (4)	0.3968 (3)	0.4568 (3)	0.0335 (11)
H8	1.1951	0.3629	0.5002	0.040*
C9	1.0305 (4)	0.3540 (3)	0.3972 (3)	0.0250 (9)
C10	0.9974 (4)	0.2501 (3)	0.3872 (3)	0.0250 (9)
C11	1.0635 (4)	0.1744 (3)	0.4345 (3)	0.0357 (11)
H11	1.1407	0.1800	0.4806	0.043*
C12	0.8655 (4)	0.1284 (3)	0.3190 (3)	0.0263 (10)
O1	0.3346 (3)	0.3599 (2)	0.1107 (2)	0.0458 (9)
O2	1.2026 (3)	0.3670 (2)	0.2475 (2)	0.0400 (8)
H1A	0.4179	0.3294	0.1243	0.050*
H1B	0.3203	0.3606	0.1702	0.050*
H2A	1.1488	0.3274	0.2119	0.050*
H2B	1.2363	0.3296	0.3022	0.050*
H5A	0.7172	0.5133	−0.0270	0.050*
H5B	0.7959	0.4338	0.0449	0.050*
H6A	0.6981	0.2469	0.5010	0.050*
H6B	0.7591	0.2404	0.4211	0.050*
H7A	0.9529	0.6565	0.3285	0.050*
H7B	0.8553	0.5863	0.2555	0.050*
H8A	0.7707	0.0175	0.2663	0.050*
H8B	0.7072	0.1159	0.2179	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0213 (3)	0.0155 (3)	0.0264 (3)	0.0010 (2)	0.0093 (2)	0.0006 (2)
Cl1	0.0218 (5)	0.0167 (5)	0.0260 (5)	−0.0009 (4)	0.0074 (4)	−0.0016 (4)
Cl2	0.0232 (5)	0.0169 (5)	0.0279 (5)	0.0012 (4)	0.0116 (4)	0.0000 (4)
S1	0.0389 (7)	0.0308 (7)	0.0408 (7)	0.0133 (5)	0.0182 (5)	0.0153 (5)
S2	0.0373 (7)	0.0312 (7)	0.0329 (6)	0.0110 (5)	0.0188 (5)	0.0037 (5)
S3	0.0306 (6)	0.0384 (7)	0.0392 (7)	−0.0104 (5)	0.0070 (5)	−0.0105 (5)
S4	0.0425 (7)	0.0258 (7)	0.0372 (7)	0.0118 (5)	0.0102 (5)	0.0076 (5)
N1	0.0244 (19)	0.0170 (18)	0.029 (2)	−0.0001 (14)	0.0117 (15)	−0.0002 (14)
N2	0.0242 (18)	0.0162 (18)	0.0265 (19)	0.0036 (15)	0.0106 (15)	0.0016 (14)
N3	0.0230 (18)	0.022 (2)	0.0233 (18)	0.0005 (15)	0.0078 (14)	−0.0018 (14)
N4	0.0183 (18)	0.023 (2)	0.030 (2)	0.0050 (15)	0.0104 (15)	0.0025 (15)
N5	0.030 (2)	0.026 (2)	0.028 (2)	0.0033 (16)	0.0107 (16)	0.0061 (15)
N6	0.034 (2)	0.022 (2)	0.033 (2)	0.0063 (16)	0.0168 (16)	0.0027 (15)
N7	0.041 (2)	0.018 (2)	0.040 (2)	−0.0052 (17)	0.0064 (18)	−0.0030 (16)
N8	0.037 (2)	0.022 (2)	0.051 (3)	0.0023 (17)	0.0040 (19)	0.0021 (17)
C1	0.026 (2)	0.019 (2)	0.028 (2)	−0.0025 (18)	0.0074 (18)	0.0013 (17)
C2	0.041 (3)	0.028 (3)	0.040 (3)	0.013 (2)	0.020 (2)	0.006 (2)
C3	0.024 (2)	0.021 (2)	0.030 (2)	0.0018 (18)	0.0107 (18)	0.0010 (18)
C4	0.024 (2)	0.022 (2)	0.027 (2)	0.0016 (18)	0.0070 (18)	0.0002 (17)
C5	0.040 (3)	0.026 (3)	0.035 (3)	0.017 (2)	0.017 (2)	0.0068 (19)
C6	0.023 (2)	0.020 (2)	0.027 (2)	0.0010 (18)	0.0119 (17)	−0.0020 (17)
C7	0.029 (2)	0.030 (3)	0.030 (2)	−0.007 (2)	0.0169 (19)	−0.0053 (19)
C8	0.024 (2)	0.039 (3)	0.036 (3)	−0.002 (2)	0.006 (2)	−0.002 (2)
C9	0.023 (2)	0.030 (3)	0.024 (2)	0.0019 (19)	0.0093 (18)	−0.0032 (18)
C10	0.025 (2)	0.026 (2)	0.028 (2)	0.0059 (19)	0.0131 (18)	0.0020 (18)
C11	0.036 (3)	0.035 (3)	0.034 (3)	0.010 (2)	0.007 (2)	0.001 (2)
C12	0.027 (2)	0.023 (2)	0.033 (2)	0.0046 (19)	0.0159 (19)	0.0038 (18)
O1	0.0392 (19)	0.062 (2)	0.040 (2)	0.0137 (17)	0.0172 (15)	0.0166 (16)
O2	0.0408 (19)	0.035 (2)	0.048 (2)	−0.0045 (15)	0.0192 (16)	−0.0021 (15)

Geometric parameters (Å, º)

Co—N4	2.128 (3)	N5—H5B	0.958
Co—N1	2.137 (3)	N6—C6	1.338 (5)
Co—N2	2.155 (3)	N6—H6A	0.938
Co—N3	2.188 (3)	N6—H6B	0.900
Co—Cl1	2.4994 (11)	N7—C7	1.343 (5)
Co—Cl2	2.4998 (11)	N7—H7A	0.968
S1—C2	1.724 (4)	N7—H7B	0.962
S1—C1	1.733 (4)	N8—C12	1.327 (5)
S2—C5	1.719 (4)	N8—H8A	0.897
S2—C6	1.743 (4)	N8—H8B	0.904
S3—C8	1.714 (5)	C2—C3	1.347 (5)
S3—C7	1.739 (4)	C2—H2	0.9300
S4—C12	1.727 (4)	C3—C4	1.455 (5)
S4—C11	1.732 (5)	C4—C5	1.346 (5)
N1—C1	1.320 (5)	C5—H5	0.9300
N1—C3	1.411 (5)	C8—C9	1.340 (5)
N2—C6	1.319 (5)	C8—H8	0.9300
N2—C4	1.382 (5)	C9—C10	1.457 (5)
N3—C7	1.323 (5)	C10—C11	1.341 (6)
N3—C9	1.404 (5)	C11—H11	0.9300
N4—C12	1.335 (5)	O1—H1A	0.964
N4—C10	1.397 (5)	O1—H1B	0.951
N5—C1	1.340 (5)	O2—H2A	0.862
N5—H5A	0.874	O2—H2B	0.951
N4—Co—N1	172.64 (12)	C12—N8—H8B	121.7
N4—Co—N2	96.38 (12)	H8A—N8—H8B	123.6
N1—Co—N2	78.20 (12)	N1—C1—N5	124.0 (4)
N4—Co—N3	77.74 (12)	N1—C1—S1	114.5 (3)
N1—Co—N3	96.98 (12)	N5—C1—S1	121.6 (3)
N2—Co—N3	88.40 (12)	C3—C2—S1	110.4 (3)
N4—Co—Cl1	98.03 (9)	C3—C2—H2	124.8
N1—Co—Cl1	87.04 (9)	S1—C2—H2	124.8
N2—Co—Cl1	90.00 (9)	C2—C3—N1	115.4 (4)
N3—Co—Cl1	175.27 (9)	C2—C3—C4	128.4 (4)
N4—Co—Cl2	86.54 (9)	N1—C3—C4	116.1 (3)
N1—Co—Cl2	98.78 (9)	C5—C4—N2	115.1 (4)
N2—Co—Cl2	176.86 (9)	C5—C4—C3	127.6 (4)
N3—Co—Cl2	91.12 (8)	N2—C4—C3	117.2 (3)
Cl1—Co—Cl2	90.72 (4)	C4—C5—S2	110.8 (3)
C2—S1—C1	89.7 (2)	C4—C5—H5	124.6
C5—S2—C6	89.43 (19)	S2—C5—H5	124.6
C8—S3—C7	89.1 (2)	N2—C6—N6	126.4 (3)
C12—S4—C11	89.6 (2)	N2—C6—S2	113.1 (3)
C1—N1—C3	109.8 (3)	N6—C6—S2	120.4 (3)
C1—N1—Co	135.9 (3)	N3—C7—N7	124.9 (4)
C3—N1—Co	114.1 (2)	N3—C7—S3	114.5 (3)
C6—N2—C4	111.5 (3)	N7—C7—S3	120.6 (3)
C6—N2—Co	134.5 (3)	C9—C8—S3	111.4 (3)
C4—N2—Co	113.9 (2)	C9—C8—H8	124.3
C7—N3—C9	109.8 (3)	S3—C8—H8	124.3
C7—N3—Co	136.7 (3)	C8—C9—N3	115.2 (4)
C9—N3—Co	113.5 (2)	C8—C9—C10	128.5 (4)
C12—N4—C10	110.3 (3)	N3—C9—C10	116.3 (3)
C12—N4—Co	133.9 (3)	C11—C10—N4	115.5 (4)
C10—N4—Co	115.5 (3)	C11—C10—C9	127.7 (4)
C1—N5—H5A	121.2	N4—C10—C9	116.7 (3)
C1—N5—H5B	117.1	C10—C11—S4	110.5 (3)
H5A—N5—H5B	121.5	C10—C11—H11	124.7
C6—N6—H6A	119.4	S4—C11—H11	124.7
C6—N6—H6B	109.2	N8—C12—N4	124.1 (4)
H6A—N6—H6B	112.8	N8—C12—S4	121.9 (3)
C7—N7—H7A	123.6	N4—C12—S4	114.0 (3)
C7—N7—H7B	123.2	H1A—O1—H1B	101.3
H7A—N7—H7B	113.1	H2A—O2—H2B	103.4
C12—N8—H8A	113.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1	0.96	2.27	3.228 (3)	172
O1—H1B···O2^i	0.95	1.96	2.823 (4)	150
O2—H2A···Cl2	0.86	2.43	3.153 (3)	142
N5—H5A···O1^ii	0.87	2.12	2.905 (4)	149
N5—H5B···Cl2	0.96	2.36	3.275 (3)	160
N6—H6A···Cl1^iii	0.94	2.52	3.364 (3)	150
N6—H6A···Cl2^iii	0.94	2.78	3.419 (3)	126
N6—H6B···N4	0.90	2.30	3.137 (5)	155
N7—H7A···Cl2^iv	0.97	2.45	3.386 (4)	164
N7—H7B···N1	0.96	2.41	3.217 (5)	141
N8—H8A···O2^v	0.90	2.09	2.972 (5)	169
N8—H8B···Cl1	0.90	2.29	3.142 (4)	157

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