(2'-Amino-4,4'-bi-1,3-thia-zol-2-aminium-κN,N')aqua-[citrato(4-)-κO,O',O'')chromium(III) dihydrate.

In the title compound, [Cr(C(6)H(7)N(4)S(2))(C(6)H(4)O(7))(H(2)O)]·2H(2)O, the Cr(III) atom is in a distorted octa-hedral environment, coordinated by one water mol-ecule, two N atoms from a protonated diamino-bithia-zole ligand and three O atoms from a citrate(4-) anion. The complex is zwitterionic, with the H atom from the uncoordinated carboxyl-ate group of the citrate anion transferred to one amino group of the diamino-bithia-zole ligand. O-H⋯O and N-H⋯O hydrogen bonds link the complexes into layers including the two uncoordinated water mol-ecules.

Related literature

For general background concerning transition-metal complexes of diamino­bithia­zole, see: Waring (1981 ▶); Fisher et al. (1985 ▶). For related structures, see: Liu & Xu (2004 ▶); Luo et al. (2004 ▶); Liu et al. (2004 ▶, 2006 ▶).

Experimental

Crystal data

[Cr(C6H7N4S2)(C6H4O7)(H2O)]·2H2O

M = 493.42

Triclinic,

a = 7.7438 (15) Å

b = 11.193 (2) Å

c = 12.057 (2) Å

α = 72.350 (3)°

β = 77.090 (2)°

γ = 82.273 (3)°

V = 968.2 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.87 mm−1

T = 295 K

0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.810, T max = 0.870

5085 measured reflections

3373 independent reflections

2273 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.169

S = 1.06

3373 reflections

263 parameters

H-atom parameters constrained

Δρmax = 0.89 e Å−3

Δρmin = −0.64 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005868/bi2321sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005868/bi2321Isup2.hkl

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

[Cr(C6H7N4S2)(C6H4O7)(H2O)]·2H2O	Z = 2
Mr = 493.42	F(000) = 506
Triclinic, P1	Dx = 1.693 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7438 (15) Å	Cell parameters from 3270 reflections
b = 11.193 (2) Å	θ = 2.0–25.0°
c = 12.057 (2) Å	µ = 0.87 mm−1
α = 72.350 (3)°	T = 295 K
β = 77.090 (2)°	Prism, red
γ = 82.273 (3)°	0.25 × 0.20 × 0.15 mm
V = 968.2 (3) Å3

Bruker APEXII CCD diffractometer	3373 independent reflections
Radiation source: fine-focus sealed tube	2273 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.810, Tmax = 0.870	k = −10→13
5085 measured reflections	l = −10→14

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) = 0.169	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.076P)2 + 0.5014P] where P = (Fo2 + 2Fc2)/3
3373 reflections	(Δ/σ)max < 0.001
263 parameters	Δρmax = 0.89 e Å−3
0 restraints	Δρmin = −0.64 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
Cr	0.32133 (11)	0.27404 (7)	0.65363 (7)	0.0290 (3)
O1	0.5836 (5)	0.2674 (3)	0.5998 (3)	0.0418 (10)
H1A	0.6573	0.2155	0.6353	0.063*
H1B	0.6172	0.3088	0.5271	0.063*
O11	0.3172 (5)	0.4582 (3)	0.6053 (3)	0.0352 (9)
O12	0.2939 (6)	0.6489 (3)	0.6263 (3)	0.0494 (11)
O13	0.0634 (5)	0.2891 (3)	0.7116 (3)	0.0360 (9)
O14	−0.1244 (5)	0.3834 (4)	0.8348 (3)	0.0443 (10)
O15	0.3302 (4)	0.2688 (3)	0.8123 (3)	0.0306 (8)
O16	0.1701 (7)	0.1124 (5)	1.1262 (5)	0.0875 (19)
O17	0.0189 (6)	0.1239 (4)	0.9877 (4)	0.0590 (12)
N21	0.3201 (6)	0.0846 (4)	0.6822 (4)	0.0326 (10)
N22	0.3901 (7)	−0.0065 (4)	0.8689 (4)	0.0515 (14)
H22A	0.3982	0.0724	0.8481	0.062*
H22B	0.3924	−0.0452	0.9399	0.062*
N23	0.2795 (6)	0.2683 (4)	0.4916 (4)	0.0327 (10)
N24	0.2762 (7)	0.4763 (4)	0.3704 (4)	0.0496 (13)
H24A	0.2657	0.4952	0.4383	0.060*
H24B	0.1941	0.5221	0.3310	0.060*
H24C	0.3837	0.4931	0.3267	0.060*
C11	0.1840 (7)	0.3480 (5)	0.8508 (5)	0.0319 (12)
C12	0.2369 (8)	0.4857 (5)	0.8038 (5)	0.0369 (13)
H12A	0.1390	0.5393	0.8324	0.044*
H12B	0.3377	0.4920	0.8366	0.044*
C13	0.2847 (7)	0.5345 (5)	0.6699 (5)	0.0334 (13)
C14	0.0249 (7)	0.3398 (5)	0.7979 (5)	0.0328 (13)
C15	0.1365 (8)	0.3097 (5)	0.9857 (5)	0.0418 (14)
H15A	0.2314	0.3291	1.0166	0.050*
H15B	0.0293	0.3583	1.0106	0.050*
C16	0.1074 (8)	0.1713 (5)	1.0371 (5)	0.0407 (14)
C21	0.2760 (7)	0.0473 (5)	0.5913 (5)	0.0342 (13)
C22	0.2699 (9)	−0.0764 (5)	0.6137 (5)	0.0492 (16)
H22	0.2430	−0.1147	0.5617	0.059*
C23	0.3463 (8)	−0.0147 (5)	0.7724 (5)	0.0377 (13)
C24	0.2508 (8)	0.1495 (5)	0.4864 (5)	0.0382 (14)
C25	0.2033 (9)	0.1473 (5)	0.3873 (5)	0.0497 (16)
H25	0.1784	0.0753	0.3725	0.060*
C26	0.2541 (8)	0.3550 (5)	0.3931 (5)	0.0380 (13)
S21	0.3177 (2)	−0.15618 (13)	0.75051 (14)	0.0481 (4)
S22	0.1944 (2)	0.29610 (15)	0.29087 (14)	0.0514 (5)
O1W	−0.4052 (7)	0.2295 (5)	0.9370 (5)	0.092 (2)
H1WB	−0.4859	0.2609	0.8983	0.139*
H1WA	−0.3124	0.2878	0.9110	0.139*
O2W	0.8198 (6)	0.1215 (4)	0.7251 (6)	0.092 (2)
H2WA	0.9168	0.1753	0.7039	0.138*
H2WB	0.8400	0.0585	0.7851	0.138*

	U11	U22	U33	U12	U13	U23
Cr	0.0396 (5)	0.0212 (4)	0.0259 (5)	−0.0049 (4)	−0.0082 (4)	−0.0039 (3)
O1	0.041 (2)	0.042 (2)	0.036 (2)	−0.0051 (18)	−0.0061 (18)	−0.0015 (18)
O11	0.054 (2)	0.0220 (18)	0.029 (2)	−0.0064 (16)	−0.0078 (17)	−0.0050 (15)
O12	0.080 (3)	0.021 (2)	0.038 (2)	−0.0078 (19)	0.002 (2)	−0.0038 (17)
O13	0.039 (2)	0.037 (2)	0.034 (2)	−0.0071 (17)	−0.0090 (17)	−0.0099 (17)
O14	0.039 (2)	0.047 (2)	0.042 (2)	−0.0004 (19)	−0.0046 (19)	−0.0078 (19)
O15	0.036 (2)	0.0276 (18)	0.026 (2)	−0.0044 (16)	−0.0078 (16)	−0.0032 (15)
O16	0.103 (4)	0.067 (3)	0.077 (4)	−0.022 (3)	−0.049 (3)	0.031 (3)
O17	0.081 (3)	0.045 (3)	0.052 (3)	−0.027 (2)	−0.011 (2)	−0.006 (2)
N21	0.046 (3)	0.022 (2)	0.029 (3)	−0.0060 (19)	−0.008 (2)	−0.0043 (18)
N22	0.080 (4)	0.034 (3)	0.037 (3)	−0.008 (3)	−0.024 (3)	0.004 (2)
N23	0.047 (3)	0.024 (2)	0.026 (2)	−0.002 (2)	−0.008 (2)	−0.0060 (18)
N24	0.076 (4)	0.033 (3)	0.041 (3)	−0.003 (2)	−0.025 (3)	−0.002 (2)
C11	0.041 (3)	0.025 (3)	0.030 (3)	−0.004 (2)	−0.008 (2)	−0.007 (2)
C12	0.052 (4)	0.027 (3)	0.031 (3)	−0.007 (3)	−0.007 (3)	−0.007 (2)
C13	0.043 (3)	0.021 (3)	0.035 (3)	−0.005 (2)	−0.005 (3)	−0.007 (2)
C14	0.040 (3)	0.024 (3)	0.030 (3)	−0.007 (2)	−0.005 (2)	−0.001 (2)
C15	0.058 (4)	0.036 (3)	0.030 (3)	−0.010 (3)	−0.005 (3)	−0.006 (2)
C16	0.045 (3)	0.043 (3)	0.029 (3)	−0.008 (3)	−0.002 (3)	−0.005 (3)
C21	0.047 (3)	0.024 (3)	0.033 (3)	−0.002 (2)	−0.005 (2)	−0.012 (2)
C22	0.072 (4)	0.033 (3)	0.047 (4)	−0.007 (3)	−0.011 (3)	−0.016 (3)
C23	0.049 (4)	0.022 (3)	0.040 (4)	−0.001 (2)	−0.008 (3)	−0.008 (2)
C24	0.051 (4)	0.030 (3)	0.037 (3)	−0.005 (3)	−0.009 (3)	−0.012 (2)
C25	0.080 (5)	0.034 (3)	0.043 (4)	−0.014 (3)	−0.020 (3)	−0.012 (3)
C26	0.051 (4)	0.034 (3)	0.030 (3)	−0.006 (3)	−0.012 (3)	−0.006 (2)
S21	0.0678 (11)	0.0221 (7)	0.0491 (10)	−0.0039 (7)	−0.0075 (8)	−0.0049 (6)
S22	0.0758 (12)	0.0484 (10)	0.0363 (9)	−0.0050 (8)	−0.0240 (8)	−0.0117 (7)
O1W	0.072 (3)	0.090 (4)	0.092 (4)	−0.034 (3)	−0.045 (3)	0.043 (3)
O2W	0.060 (3)	0.045 (3)	0.164 (6)	−0.012 (2)	−0.038 (3)	−0.005 (3)

Cr—O15	1.912 (3)	N24—H24B	0.890
Cr—O11	1.963 (3)	N24—H24C	0.890
Cr—O13	1.966 (4)	C11—C15	1.522 (7)
Cr—O1	1.988 (4)	C11—C14	1.533 (7)
Cr—N21	2.044 (4)	C11—C12	1.549 (7)
Cr—N23	2.071 (4)	C12—C13	1.514 (7)
O1—H1A	0.846	C12—H12A	0.970
O1—H1B	0.858	C12—H12B	0.970
O11—C13	1.287 (6)	C15—C16	1.512 (7)
O12—C13	1.233 (6)	C15—H15A	0.970
O13—C14	1.292 (6)	C15—H15B	0.970
O14—C14	1.234 (6)	C21—C22	1.334 (7)
O15—C11	1.424 (6)	C21—C24	1.456 (7)
O16—C16	1.241 (7)	C22—S21	1.716 (6)
O17—C16	1.256 (7)	C22—H22	0.9300
N21—C23	1.328 (6)	C23—S21	1.733 (6)
N21—C21	1.405 (7)	C24—C25	1.334 (8)
N22—C23	1.314 (7)	C25—S22	1.721 (6)
N22—H22A	0.849	C25—H25	0.9300
N22—H22B	0.837	C26—S22	1.731 (6)
N23—C26	1.321 (6)	O1W—H1WB	0.839
N23—C24	1.399 (7)	O1W—H1WA	0.971
N24—C26	1.328 (7)	O2W—H2WA	0.966
N24—H24A	0.890	O2W—H2WB	0.870
O15—Cr—O11	90.51 (14)	C13—C12—H12A	108.6
O15—Cr—O13	83.15 (15)	C11—C12—H12A	108.6
O11—Cr—O13	88.35 (15)	C13—C12—H12B	108.6
O15—Cr—O1	94.33 (15)	C11—C12—H12B	108.6
O11—Cr—O1	88.97 (15)	H12A—C12—H12B	107.6
O13—Cr—O1	176.30 (16)	O12—C13—O11	121.9 (5)
O15—Cr—N21	96.93 (16)	O12—C13—C12	117.5 (5)
O11—Cr—N21	172.51 (16)	O11—C13—C12	120.6 (4)
O13—Cr—N21	91.64 (16)	O14—C14—O13	124.7 (5)
O1—Cr—N21	91.36 (16)	O14—C14—C11	120.7 (5)
O15—Cr—N23	172.24 (16)	O13—C14—C11	114.5 (5)
O11—Cr—N23	93.22 (15)	C16—C15—C11	112.2 (5)
O13—Cr—N23	90.15 (17)	C16—C15—H15A	109.2
O1—Cr—N23	92.53 (17)	C11—C15—H15A	109.2
N21—Cr—N23	79.28 (16)	C16—C15—H15B	109.2
Cr—O1—H1A	125.5	C11—C15—H15B	109.2
Cr—O1—H1B	113.5	H15A—C15—H15B	107.9
H1A—O1—H1B	119.2	O16—C16—O17	124.3 (6)
C13—O11—Cr	129.5 (3)	O16—C16—C15	118.1 (6)
C14—O13—Cr	111.3 (3)	O17—C16—C15	117.6 (5)
C11—O15—Cr	107.2 (3)	C22—C21—N21	114.6 (5)
C23—N21—C21	110.7 (4)	C22—C21—C24	130.5 (5)
C23—N21—Cr	133.6 (4)	N21—C21—C24	114.8 (4)
C21—N21—Cr	115.7 (3)	C21—C22—S21	111.5 (5)
C23—N22—H22A	97.9	C21—C22—H22	124.2
C23—N22—H22B	143.4	S21—C22—H22	124.2
H22A—N22—H22B	117.1	N22—C23—N21	123.3 (5)
C26—N23—C24	110.4 (5)	N22—C23—S21	123.2 (4)
C26—N23—Cr	134.0 (4)	N21—C23—S21	113.5 (4)
C24—N23—Cr	115.1 (3)	C25—C24—N23	115.5 (5)
C26—N24—H24A	109.5	C25—C24—C21	130.1 (5)
C26—N24—H24B	109.5	N23—C24—C21	114.4 (5)
H24A—N24—H24B	109.5	C24—C25—S22	110.7 (4)
C26—N24—H24C	109.5	C24—C25—H25	124.7
H24A—N24—H24C	109.5	S22—C25—H25	124.7
H24B—N24—H24C	109.5	N23—C26—N24	124.5 (5)
O15—C11—C15	110.0 (4)	N23—C26—S22	113.8 (4)
O15—C11—C14	109.6 (4)	N24—C26—S22	121.7 (4)
C15—C11—C14	110.7 (4)	C22—S21—C23	89.6 (3)
O15—C11—C12	108.6 (4)	C25—S22—C26	89.6 (3)
C15—C11—C12	110.0 (4)	H1WB—O1W—H1WA	108.0
C14—C11—C12	107.9 (4)	H2WA—O2W—H2WB	107.4
C13—C12—C11	114.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2W	0.85	1.85	2.689 (7)	171
O1—H1B···O12i	0.86	1.76	2.597 (5)	164
O1W—H1WB···O15ii	0.84	1.92	2.718 (7)	159
O1W—H1WA···O14	0.97	1.83	2.782 (7)	168
O2W—H2WA···O13iii	0.97	1.85	2.781 (6)	160
O2W—H2WB···O16iv	0.87	1.89	2.690 (8)	152
N22—H22A···O15	0.85	2.12	2.942 (6)	162
N22—H22B···O1Wv	0.84	2.15	2.867 (7)	144
N24—H24A···O11	0.89	2.05	2.864 (6)	152
N24—H24B···O14vi	0.89	2.11	2.901 (6)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2W	0.85	1.85	2.689 (7)	171
O1—H1B⋯O12i	0.86	1.76	2.597 (5)	164
O1W—H1WB⋯O15ii	0.84	1.92	2.718 (7)	159
O1W—H1WA⋯O14	0.97	1.83	2.782 (7)	168
O2W—H2WA⋯O13iii	0.97	1.85	2.781 (6)	160
O2W—H2WB⋯O16iv	0.87	1.89	2.690 (8)	152
N22—H22A⋯O15	0.85	2.12	2.942 (6)	162
N22—H22B⋯O1Wv	0.84	2.15	2.867 (7)	144
N24—H24A⋯O11	0.89	2.05	2.864 (6)	152
N24—H24B⋯O14vi	0.89	2.11	2.901 (6)	148

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .