Di­chloro­bis(2,2′-di­amino-4,4′-bi-1,3-thia­zole-κ²N,N′)­nickel(II) dihydrate

The Ni^II atom in the crystal structure of the title compound, [NiCl₂(C₆H₆N₄S₂)₂]·2H₂O, has a distorted cis-octahedral coordination, formed by two Cl atoms [Ni—Cl 2.4767 (17) and 2.4922 (17) Å] and four N atoms of two chelate bi­thia­zole ligands [Ni—N 2.069 (5)–2.138 (5) Å]. The overlapped arrangement and short separation between parallel thia­zole rings belonging to neighbouring complexes [3.47 (3) Å] suggest the existence of π–π stacking interactions. Short intermolecular S...S contacts [3.183 (3) Å] are also observed. The water mol­ecules are involved in hydrogen bonds with the Cl ligands.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.045
• wR factor = 0.101
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



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

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9
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
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 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).

Bis(2,2'-diamino-4,4'-bi-1,3-thiazole-κ²N,N')dichloronickel(II) dihydrate

Crystal data

[NiCl2(C6H6N4S2)2]·2H2O	F(000) = 1144
Mr = 562.18	Dx = 1.767 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9868 reflections
a = 10.814 (2) Å	θ = 3.0–23.0°
b = 13.534 (3) Å	µ = 1.59 mm^−1
c = 15.061 (3) Å	T = 298 K
β = 106.561 (14)°	Prism, blue
V = 2112.8 (8) Å^3	0.22 × 0.16 × 0.12 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3705 independent reflections
Radiation source: fine-focus sealed tube	1887 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.086
ω and φ scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) (SADABS; Bruker, 1999)	h = −12→9
Tmin = 0.710, Tmax = 0.832	k = −16→14
10682 measured reflections	l = −17→17

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 0.81	w = 1/[σ^2(Fo^2) + (0.0307P)^2] where P = (Fo^2 + 2Fc^2)/3
3705 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.52 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
Ni	0.78564 (8)	0.34479 (6)	0.24113 (5)	0.0190 (2)
Cl1	0.60388 (15)	0.25261 (10)	0.13659 (10)	0.0199 (4)
Cl2	0.92195 (15)	0.30797 (10)	0.13679 (10)	0.0184 (4)
S1	0.58855 (18)	0.62178 (12)	0.07678 (12)	0.0333 (5)
S2	0.54182 (18)	0.41183 (12)	0.44482 (11)	0.0297 (5)
S3	1.12816 (18)	0.52140 (13)	0.44259 (12)	0.0345 (5)
S4	0.97673 (19)	0.06306 (12)	0.39629 (12)	0.0338 (5)
N1	0.6953 (5)	0.4725 (3)	0.1751 (3)	0.0188 (12)
N2	0.6710 (5)	0.3807 (3)	0.3269 (3)	0.0173 (12)
N3	0.9443 (5)	0.4188 (3)	0.3354 (3)	0.0190 (12)
N4	0.8770 (5)	0.2261 (3)	0.3194 (3)	0.0218 (13)
N5	0.7372 (5)	0.4840 (3)	0.0303 (3)	0.0251 (13)
N6	0.6865 (5)	0.2535 (3)	0.4383 (3)	0.0254 (13)
N7	0.9260 (5)	0.5907 (3)	0.3081 (4)	0.0298 (14)
N8	0.7578 (5)	0.0835 (4)	0.2579 (4)	0.0350 (15)
C1	0.6846 (6)	0.5157 (4)	0.0952 (4)	0.0223 (16)
C2	0.5595 (6)	0.6020 (5)	0.1817 (4)	0.0319 (18)
H2	0.5086	0.6428	0.2065	0.038*
C3	0.6191 (6)	0.5208 (4)	0.2233 (4)	0.0205 (15)
C4	0.6069 (6)	0.4714 (4)	0.3054 (4)	0.0210 (15)
C5	0.5388 (7)	0.5006 (5)	0.3629 (4)	0.0303 (18)
H5	0.4960	0.5608	0.3588	0.036*
C6	0.6437 (6)	0.3417 (4)	0.4001 (4)	0.0191 (15)
C7	0.9869 (6)	0.5099 (5)	0.3537 (4)	0.0268 (17)
C8	1.1292 (6)	0.3957 (5)	0.4567 (4)	0.0326 (18)
H8	1.1930	0.3612	0.5002	0.039*
C9	1.0270 (6)	0.3533 (5)	0.3974 (4)	0.0222 (15)
C10	0.9911 (6)	0.2492 (4)	0.3869 (4)	0.0224 (15)
C11	1.0580 (7)	0.1723 (5)	0.4354 (4)	0.0336 (18)
H11	1.1354	0.1773	0.4822	0.040*
C12	0.8587 (6)	0.1290 (4)	0.3158 (4)	0.0224 (16)
O1	0.3296 (4)	0.3618 (3)	0.1089 (3)	0.0425 (13)
O2	1.2047 (4)	0.3660 (3)	0.2489 (3)	0.0375 (12)
H1A	0.4109	0.3294	0.1203	0.050*
H1B	0.3203	0.3606	0.1702	0.050*
H2A	1.1219	0.3601	0.2292	0.050*
H2B	1.2258	0.3436	0.3050	0.050*
H5A	0.7840	0.4228	0.0431	0.050*
H5B	0.7302	0.5026	−0.0296	0.050*
H6A	0.7458	0.2227	0.4186	0.050*
H6B	0.6993	0.2461	0.4959	0.050*
H7A	0.8480	0.5794	0.2600	0.050*
H7B	0.9449	0.6593	0.3267	0.050*
H8A	0.6941	0.1210	0.2109	0.050*
H8B	0.7338	0.0177	0.2460	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0145 (5)	0.0185 (4)	0.0226 (5)	0.0011 (4)	0.0027 (4)	0.0007 (4)
Cl1	0.0155 (9)	0.0194 (8)	0.0225 (9)	−0.0012 (7)	0.0018 (7)	−0.0019 (7)
Cl2	0.0162 (9)	0.0173 (8)	0.0222 (9)	0.0020 (7)	0.0064 (7)	0.0014 (7)
S1	0.0331 (12)	0.0319 (11)	0.0373 (11)	0.0133 (9)	0.0137 (9)	0.0127 (9)
S2	0.0286 (11)	0.0338 (10)	0.0289 (10)	0.0098 (8)	0.0119 (9)	0.0032 (8)
S3	0.0231 (11)	0.0398 (11)	0.0361 (11)	−0.0099 (9)	0.0009 (9)	−0.0102 (9)
S4	0.0355 (12)	0.0261 (10)	0.0358 (11)	0.0104 (9)	0.0039 (9)	0.0073 (8)
N1	0.012 (3)	0.018 (3)	0.024 (3)	−0.004 (2)	0.001 (2)	0.001 (2)
N2	0.013 (3)	0.017 (3)	0.018 (3)	−0.001 (2)	−0.002 (2)	0.001 (2)
N3	0.013 (3)	0.022 (3)	0.021 (3)	0.002 (2)	0.002 (2)	−0.003 (2)
N4	0.011 (3)	0.024 (3)	0.030 (3)	0.003 (2)	0.006 (3)	0.005 (3)
N5	0.029 (4)	0.026 (3)	0.023 (3)	−0.002 (3)	0.012 (3)	0.000 (2)
N6	0.031 (4)	0.023 (3)	0.024 (3)	0.008 (3)	0.012 (3)	0.002 (3)
N7	0.026 (4)	0.013 (3)	0.045 (4)	−0.006 (3)	−0.001 (3)	−0.004 (3)
N8	0.024 (4)	0.027 (3)	0.046 (4)	−0.004 (3)	−0.004 (3)	−0.003 (3)
C1	0.019 (4)	0.022 (4)	0.024 (4)	−0.003 (3)	0.002 (3)	0.003 (3)
C2	0.028 (4)	0.033 (4)	0.038 (4)	0.015 (3)	0.014 (4)	0.014 (3)
C3	0.019 (4)	0.028 (4)	0.014 (3)	0.002 (3)	0.003 (3)	−0.001 (3)
C4	0.020 (4)	0.020 (4)	0.022 (4)	0.003 (3)	0.005 (3)	0.004 (3)
C5	0.042 (5)	0.027 (4)	0.028 (4)	0.018 (3)	0.019 (4)	0.006 (3)
C6	0.015 (4)	0.022 (3)	0.021 (4)	0.003 (3)	0.005 (3)	−0.003 (3)
C7	0.023 (4)	0.029 (4)	0.029 (4)	−0.008 (3)	0.009 (3)	−0.010 (3)
C8	0.021 (4)	0.039 (4)	0.029 (4)	0.003 (3)	−0.006 (3)	−0.002 (3)
C9	0.016 (4)	0.031 (4)	0.020 (4)	−0.001 (3)	0.006 (3)	−0.003 (3)
C10	0.021 (4)	0.023 (4)	0.023 (4)	0.004 (3)	0.006 (3)	−0.004 (3)
C11	0.026 (5)	0.038 (5)	0.029 (4)	0.010 (3)	−0.005 (3)	−0.004 (3)
C12	0.017 (4)	0.023 (4)	0.026 (4)	0.004 (3)	0.005 (3)	0.002 (3)
O1	0.026 (3)	0.064 (4)	0.036 (3)	0.019 (3)	0.006 (2)	0.017 (3)
O2	0.036 (3)	0.042 (3)	0.037 (3)	0.000 (3)	0.014 (2)	0.008 (2)

Geometric parameters (Å, º)

Ni—N1	2.092 (5)	N5—H5B	0.918
Ni—N2	2.088 (5)	N6—C6	1.348 (7)
Ni—N3	2.138 (5)	N6—H6A	0.884
Ni—N4	2.069 (5)	N6—H6B	0.845
Ni—Cl1	2.4767 (17)	N7—C7	1.358 (7)
Ni—Cl2	2.4922 (17)	N7—H7A	0.954
S1—C2	1.718 (6)	N7—H7B	0.974
S1—C1	1.747 (6)	N8—C12	1.337 (7)
S2—C5	1.716 (6)	N8—H8A	0.977
S2—C6	1.729 (6)	N8—H8B	0.931
S3—C8	1.714 (6)	C2—C3	1.336 (7)
S3—C7	1.728 (7)	C2—H2	0.930
S4—C11	1.735 (7)	C3—C4	1.444 (8)
S4—C12	1.736 (6)	C4—C5	1.346 (8)
N1—C1	1.312 (7)	C5—H5	0.930
N1—C3	1.406 (7)	C8—C9	1.336 (8)
N2—C6	1.329 (7)	C8—H8	0.930
N2—C4	1.401 (7)	C9—C10	1.458 (8)
N3—C7	1.318 (7)	C10—C11	1.356 (8)
N3—C9	1.408 (7)	C11—H11	0.9300
N4—C12	1.328 (7)	O1—H1A	0.953
N4—C10	1.392 (8)	O1—H1B	0.957
N5—C1	1.336 (7)	O2—H2A	0.862
N5—H5A	0.961	O2—H2B	0.865
N4—Ni—N2	95.70 (19)	C12—N8—H8B	134.2
N4—Ni—N1	173.99 (19)	H8A—N8—H8B	104.9
N2—Ni—N1	79.79 (19)	N1—C1—N5	125.7 (6)
N4—Ni—N3	79.79 (19)	N1—C1—S1	113.9 (5)
N2—Ni—N3	89.16 (18)	N5—C1—S1	120.4 (5)
N1—Ni—N3	96.08 (18)	C3—C2—S1	111.6 (5)
N4—Ni—Cl1	97.75 (15)	C3—C2—H2	124.2
N2—Ni—Cl1	90.41 (13)	S1—C2—H2	124.2
N1—Ni—Cl1	86.32 (13)	C2—C3—N1	114.6 (5)
N3—Ni—Cl1	177.45 (14)	C2—C3—C4	129.2 (6)
N4—Ni—Cl2	86.10 (14)	N1—C3—C4	115.9 (5)
N2—Ni—Cl2	178.00 (13)	C5—C4—N2	115.7 (5)
N1—Ni—Cl2	98.35 (14)	C5—C4—C3	127.9 (6)
N3—Ni—Cl2	90.32 (13)	N2—C4—C3	116.4 (5)
Cl1—Ni—Cl2	90.19 (6)	C4—C5—S2	110.8 (5)
C2—S1—C1	89.0 (3)	C4—C5—H5	124.6
C5—S2—C6	89.3 (3)	S2—C5—H5	124.6
C8—S3—C7	88.8 (3)	N2—C6—N6	125.1 (5)
C11—S4—C12	90.0 (3)	N2—C6—S2	114.9 (4)
C1—N1—C3	110.7 (5)	N6—C6—S2	120.0 (4)
C1—N1—Ni	135.3 (4)	N3—C7—N7	123.9 (6)
C3—N1—Ni	113.7 (4)	N3—C7—S3	115.2 (5)
C6—N2—C4	109.1 (5)	N7—C7—S3	120.9 (5)
C6—N2—Ni	137.1 (4)	C9—C8—S3	111.7 (5)
C4—N2—Ni	113.7 (4)	C9—C8—H8	124.2
C7—N3—C9	109.4 (5)	S3—C8—H8	124.2
C7—N3—Ni	138.0 (4)	C8—C9—N3	114.9 (6)
C9—N3—Ni	112.5 (4)	C8—C9—C10	129.2 (6)
C12—N4—C10	110.0 (5)	N3—C9—C10	115.9 (5)
C12—N4—Ni	134.7 (4)	C11—C10—N4	116.6 (6)
C10—N4—Ni	115.0 (4)	C11—C10—C9	126.7 (6)
C1—N5—H5A	116.1	N4—C10—C9	116.7 (5)
C1—N5—H5B	134.3	C10—C11—S4	109.3 (5)
H5A—N5—H5B	109.0	C10—C11—H11	125.4
C6—N6—H6A	118.0	S4—C11—H11	125.4
C6—N6—H6B	118.6	N4—C12—N8	124.5 (6)
H6A—N6—H6B	111.5	N4—C12—S4	114.1 (5)
C7—N7—H7A	116.8	N8—C12—S4	121.3 (5)
C7—N7—H7B	126.2	H1A—O1—H1B	99.4
H7A—N7—H7B	116.0	H2A—O2—H2B	105.3
C12—N8—H8A	120.6

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1	0.95	2.28	3.233 (5)	176
O1—H1B···O2^i	0.96	1.95	2.810 (6)	148
O2—H2A···Cl2	0.86	2.32	3.142 (5)	159
N5—H5A···Cl2	0.96	2.33	3.227 (5)	155
N5—H5B···O1^ii	0.92	2.18	2.900 (6)	134
N6—H6A···N4	0.88	2.34	3.113 (7)	147
N6—H6B···Cl1^iii	0.84	2.61	3.353 (5)	148
N6—H6B···Cl2^iii	0.84	2.81	3.431 (5)	131
N7—H7A···N1	0.95	2.29	3.154 (7)	150
N7—H7B···Cl2^iv	0.97	2.44	3.356 (5)	156
N8—H8A···Cl1	0.98	2.18	3.101 (6)	156
N8—H8B···O2^v	0.93	2.15	2.977 (7)	147

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.