Aqua-(2,2'-diamino-4,4'-bi-1,3-thia-zole-κN,N)(pyridine-2,6-dicarboxyl-ato-κO,N,O)zinc tetra-hydrate.

The title compound, [Zn(C(7)H(3)NO(4))(C(6)H(6)N(4)S(2))(H(2)O)]·4H(2)O, assumes a distorted octa-hedral coordination geometry around the Zn(2+) cation, formed by a diamino-bithia-zole (DABT) mol-ecule, a pyridine-2,6-dicarboxyl-ate anion and a water mol-ecule. The pyridine-2,6-dicarboxyl-ate anion chelates to the Zn(II) atom with a facial configuration. Within the chelating DABT ligand, the two thia-zole rings are twisted by a dihedral angle of 14.52 (8)° with respect to each other. O-H⋯O and N-H⋯O hydrogen bonds occur in the crystal structure.

Related literature

For potential applications of transition metal complexes of 2,2′-diamino-4,4′-bi-1,3-thia­zole (DABT), see: Sun et al. (1997 ▶). For general background to metal complexes with DABT, see: Liu et al. (2003 ▶). For related structures, see: Liu & Xu (2004 ▶, 2005 ▶); Liu et al. (2005 ▶).

Experimental

Crystal data

[Zn(C7H3NO4)(C6H6N4S2)(H2O)]·4H2O

M = 518.82

Monoclinic,

a = 10.0529 (19) Å

b = 7.0833 (13) Å

c = 27.720 (6) Å

β = 93.960 (3)°

V = 1969.2 (7) Å3

Z = 4

Mo Kα radiation

μ = 1.52 mm−1

T = 295 K

0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.701, T max = 0.796

9851 measured reflections

3471 independent reflections

2238 reflections with I > 2σ(I)

R int = 0.074

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.119

S = 1.03

3471 reflections

281 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.60 e Å−3

Data collection: SMART (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/S1600536811015145/ff2006sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015145/ff2006Isup2.hkl

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

[Zn(C7H3NO4)(C6H6N4S2)(H2O)]·4H2O	F(000) = 1064
Mr = 518.82	Dx = 1.750 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3380 reflections
a = 10.0529 (19) Å	θ = 2.0–25.0°
b = 7.0833 (13) Å	µ = 1.52 mm−1
c = 27.720 (6) Å	T = 295 K
β = 93.960 (3)°	Prism, yellow
V = 1969.2 (7) Å3	0.25 × 0.20 × 0.15 mm
Z = 4

Bruker SMART APEX diffractometer	3471 independent reflections
Radiation source: fine-focus sealed tube	2238 reflections with I > 2σ(I)
graphite	Rint = 0.074
Detector resolution: 10.0 pixels mm-1	θmax = 25.0°, θmin = 2.4°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −8→8
Tmin = 0.701, Tmax = 0.796	l = −22→32
9851 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0374P)2 + 1.648P] where P = (Fo2 + 2Fc2)/3
3471 reflections	(Δ/σ)max < 0.001
281 parameters	Δρmax = 0.40 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
Zn	0.79367 (6)	0.53096 (9)	0.32687 (2)	0.0278 (2)
O1	0.6001 (3)	0.3881 (5)	0.33361 (13)	0.0323 (9)
H1A	0.6206	0.2602	0.3443	0.031 (15)*
H1B	0.5456	0.4465	0.3567	0.06 (2)*
O21	0.6938 (3)	0.8166 (5)	0.32814 (13)	0.0322 (9)
O22	0.6230 (4)	1.0365 (5)	0.37777 (13)	0.0352 (9)
O23	0.8776 (4)	0.2804 (5)	0.36725 (13)	0.0330 (9)
O24	0.9366 (4)	0.1804 (6)	0.44238 (14)	0.0460 (11)
N11	0.7611 (4)	0.5270 (6)	0.25153 (14)	0.0249 (10)
N12	0.5302 (4)	0.4822 (7)	0.23428 (16)	0.0401 (13)
H12A	0.5190	0.4432	0.2673	0.048*
H12B	0.4789	0.4457	0.2116	0.048*
N13	0.9917 (4)	0.5795 (6)	0.30709 (15)	0.0270 (11)
N14	1.1350 (4)	0.5784 (7)	0.37784 (17)	0.0434 (13)
H14A	1.0773	0.6054	0.3991	0.052*
H14B	1.2189	0.5943	0.3857	0.052*
N21	0.7907 (4)	0.6039 (6)	0.39887 (15)	0.0238 (10)
S11	0.68935 (14)	0.5508 (2)	0.16108 (5)	0.0368 (4)
S12	1.23955 (13)	0.5564 (2)	0.29119 (5)	0.0348 (4)
C11	0.8759 (5)	0.5611 (7)	0.22697 (18)	0.0250 (12)
C12	0.8558 (5)	0.5786 (8)	0.1793 (2)	0.0333 (14)
H12	0.9225	0.6026	0.1585	0.040*
C13	0.6547 (5)	0.5153 (7)	0.22092 (18)	0.0265 (12)
C14	1.0006 (5)	0.5681 (7)	0.25667 (19)	0.0255 (12)
C15	1.1253 (5)	0.5557 (8)	0.2422 (2)	0.0323 (13)
H15	1.1467	0.5478	0.2102	0.039*
C16	1.1095 (5)	0.5723 (8)	0.3291 (2)	0.0306 (13)
C21	0.7370 (5)	0.7687 (7)	0.41205 (18)	0.0243 (12)
C22	0.7300 (6)	0.8163 (8)	0.45964 (19)	0.0348 (14)
H22	0.6938	0.9313	0.4682	0.042*
C23	0.7783 (6)	0.6894 (8)	0.4950 (2)	0.0364 (14)
H23	0.7755	0.7193	0.5276	0.044*
C24	0.8303 (5)	0.5195 (7)	0.4814 (2)	0.0324 (14)
H24	0.8614	0.4324	0.5046	0.039*
C25	0.8355 (5)	0.4801 (7)	0.43272 (19)	0.0270 (12)
C26	0.6810 (5)	0.8848 (8)	0.3697 (2)	0.0287 (13)
C27	0.8889 (5)	0.2973 (7)	0.4127 (2)	0.0298 (13)
O1W	0.4314 (4)	0.5366 (7)	0.40173 (16)	0.0453 (11)
H1WA	0.4454	0.6614	0.4085	0.06 (2)*
H1WB	0.4538	0.4785	0.4256	0.08 (3)*
O2W	0.5018 (4)	1.2043 (6)	0.45001 (16)	0.0533 (12)
H2WA	0.5563	1.1778	0.4303	0.06 (2)*
H2WB	0.5413	1.1846	0.4782	0.05 (2)*
O3W	0.9102 (4)	0.1298 (5)	0.54438 (17)	0.0485 (12)
H3WA	0.9229	0.1380	0.5111	0.11 (3)*
H3WB	0.9730	0.0390	0.5580	0.051 (18)*
O4W	0.6334 (4)	0.1492 (6)	0.54252 (14)	0.0465 (11)
H4WA	0.6074	0.0351	0.5539	0.14 (4)*
H4WB	0.7192	0.1338	0.5388	0.05 (2)*

	U11	U22	U33	U12	U13	U23
Zn	0.0276 (4)	0.0333 (4)	0.0226 (4)	0.0023 (3)	0.0028 (3)	0.0000 (3)
O1	0.034 (2)	0.032 (2)	0.031 (2)	0.0021 (18)	0.0031 (18)	0.0038 (18)
O21	0.034 (2)	0.040 (2)	0.022 (2)	0.0082 (18)	−0.0013 (17)	0.0010 (18)
O22	0.045 (2)	0.024 (2)	0.037 (2)	0.0128 (19)	0.0054 (19)	0.0033 (18)
O23	0.037 (2)	0.028 (2)	0.035 (2)	0.0057 (17)	0.0031 (19)	−0.0012 (18)
O24	0.065 (3)	0.033 (2)	0.040 (3)	0.022 (2)	0.004 (2)	0.005 (2)
N11	0.025 (2)	0.027 (3)	0.022 (2)	0.001 (2)	0.0027 (19)	0.003 (2)
N12	0.030 (3)	0.065 (4)	0.024 (3)	0.000 (3)	−0.003 (2)	0.001 (2)
N13	0.022 (2)	0.031 (3)	0.028 (3)	−0.0009 (19)	0.003 (2)	0.000 (2)
N14	0.023 (3)	0.073 (4)	0.035 (3)	−0.003 (2)	0.004 (2)	−0.002 (3)
N21	0.021 (2)	0.026 (3)	0.024 (3)	0.0024 (19)	0.0020 (19)	0.000 (2)
S11	0.0403 (9)	0.0476 (10)	0.0221 (8)	0.0015 (7)	−0.0013 (6)	0.0025 (7)
S12	0.0238 (7)	0.0401 (9)	0.0412 (9)	0.0012 (6)	0.0064 (7)	0.0010 (7)
C11	0.026 (3)	0.025 (3)	0.024 (3)	0.000 (2)	0.002 (2)	−0.005 (2)
C12	0.036 (3)	0.038 (4)	0.027 (3)	−0.002 (3)	0.008 (3)	0.002 (3)
C13	0.028 (3)	0.029 (3)	0.023 (3)	0.006 (2)	0.002 (2)	−0.007 (2)
C14	0.031 (3)	0.021 (3)	0.025 (3)	0.003 (2)	0.004 (2)	−0.002 (2)
C15	0.036 (3)	0.035 (3)	0.027 (3)	0.000 (3)	0.011 (3)	0.003 (3)
C16	0.030 (3)	0.033 (3)	0.030 (3)	−0.001 (3)	0.004 (3)	0.001 (3)
C21	0.027 (3)	0.024 (3)	0.022 (3)	0.000 (2)	0.002 (2)	−0.001 (2)
C22	0.044 (4)	0.031 (3)	0.029 (3)	0.013 (3)	0.004 (3)	−0.003 (3)
C23	0.046 (4)	0.043 (4)	0.020 (3)	0.006 (3)	0.007 (3)	−0.001 (3)
C24	0.044 (3)	0.026 (3)	0.027 (3)	0.011 (3)	0.003 (3)	0.006 (3)
C25	0.027 (3)	0.025 (3)	0.029 (3)	0.000 (2)	0.004 (2)	0.006 (3)
C26	0.027 (3)	0.027 (3)	0.032 (4)	−0.006 (3)	0.003 (3)	−0.003 (3)
C27	0.034 (3)	0.019 (3)	0.038 (4)	0.001 (2)	0.006 (3)	0.002 (3)
O1W	0.045 (3)	0.046 (3)	0.044 (3)	0.007 (2)	0.001 (2)	−0.001 (2)
O2W	0.059 (3)	0.067 (3)	0.035 (3)	0.023 (2)	0.010 (3)	0.010 (2)
O3W	0.054 (3)	0.040 (3)	0.052 (3)	0.021 (2)	0.008 (2)	0.006 (2)
O4W	0.050 (3)	0.050 (3)	0.040 (3)	0.004 (2)	0.006 (2)	−0.002 (2)

Zn—N21	2.064 (4)	S11—C13	1.737 (5)
Zn—N11	2.092 (4)	S12—C15	1.717 (6)
Zn—N13	2.129 (4)	S12—C16	1.736 (5)
Zn—O1	2.213 (3)	C11—C12	1.328 (7)
Zn—O23	2.232 (4)	C11—C14	1.452 (7)
Zn—O21	2.260 (4)	C12—H12	0.9300
O1—H1A	0.9713	C14—C15	1.346 (7)
O1—H1B	0.9633	C15—H15	0.9300
O21—C26	1.264 (6)	C21—C22	1.368 (7)
O22—C26	1.250 (6)	C21—C26	1.510 (7)
O23—C27	1.264 (6)	C22—C23	1.393 (7)
O24—C27	1.239 (6)	C22—H22	0.9300
N11—C13	1.321 (6)	C23—C24	1.375 (7)
N11—C11	1.401 (6)	C23—H23	0.9300
N12—C13	1.351 (6)	C24—C25	1.382 (7)
N12—H12A	0.9708	C24—H24	0.9300
N12—H12B	0.8256	C25—C27	1.521 (7)
N13—C16	1.294 (7)	O1W—H1WA	0.9122
N13—C14	1.409 (6)	O1W—H1WB	0.7978
N14—C16	1.359 (7)	O2W—H2WA	0.8216
N14—H14A	0.8749	O2W—H2WB	0.8624
N14—H14B	0.8645	O3W—H3WA	0.9418
N21—C25	1.339 (6)	O3W—H3WB	0.9604
N21—C21	1.347 (6)	O4W—H4WA	0.9116
S11—C12	1.725 (6)	O4W—H4WB	0.8825
N21—Zn—N11	163.19 (16)	C11—C12—S11	111.1 (4)
N21—Zn—N13	106.55 (16)	C11—C12—H12	124.5
N11—Zn—N13	80.18 (16)	S11—C12—H12	124.5
N21—Zn—O1	87.78 (14)	N11—C13—N12	124.0 (5)
N11—Zn—O1	90.03 (15)	N11—C13—S11	113.4 (4)
N13—Zn—O1	159.90 (15)	N12—C13—S11	122.5 (4)
N21—Zn—O23	75.18 (15)	C15—C14—N13	115.0 (5)
N11—Zn—O23	121.17 (15)	C15—C14—C11	127.9 (5)
N13—Zn—O23	85.97 (15)	N13—C14—C11	117.0 (4)
O1—Zn—O23	84.17 (13)	C14—C15—S12	110.5 (4)
N21—Zn—O21	74.03 (14)	C14—C15—H15	124.7
N11—Zn—O21	89.34 (14)	S12—C15—H15	124.7
N13—Zn—O21	106.47 (15)	N13—C16—N14	124.8 (5)
O1—Zn—O21	90.79 (14)	N13—C16—S12	114.8 (4)
O23—Zn—O21	148.96 (13)	N14—C16—S12	120.4 (4)
Zn—O1—H1A	106.4	N21—C21—C22	121.6 (5)
Zn—O1—H1B	113.8	N21—C21—C26	113.3 (4)
H1A—O1—H1B	108.5	C22—C21—C26	125.0 (5)
C26—O21—Zn	115.4 (3)	C21—C22—C23	118.7 (5)
C27—O23—Zn	115.5 (3)	C21—C22—H22	120.6
C13—N11—C11	110.9 (4)	C23—C22—H22	120.6
C13—N11—Zn	134.9 (3)	C24—C23—C22	119.5 (5)
C11—N11—Zn	113.9 (3)	C24—C23—H23	120.3
C13—N12—H12A	118.5	C22—C23—H23	120.3
C13—N12—H12B	112.8	C23—C24—C25	119.1 (5)
H12A—N12—H12B	121.5	C23—C24—H24	120.5
C16—N13—C14	110.3 (4)	C25—C24—H24	120.5
C16—N13—Zn	135.5 (4)	N21—C25—C24	121.2 (5)
C14—N13—Zn	111.7 (3)	N21—C25—C27	114.3 (5)
C16—N14—H14A	126.0	C24—C25—C27	124.5 (5)
C16—N14—H14B	111.6	O22—C26—O21	124.7 (5)
H14A—N14—H14B	118.9	O22—C26—C21	118.9 (5)
C25—N21—C21	119.9 (4)	O21—C26—C21	116.4 (5)
C25—N21—Zn	119.2 (3)	O24—C27—O23	127.1 (5)
C21—N21—Zn	120.8 (3)	O24—C27—C25	117.2 (5)
C12—S11—C13	89.5 (3)	O23—C27—C25	115.7 (5)
C15—S12—C16	89.3 (3)	H1WA—O1W—H1WB	107.4
C12—C11—N11	115.2 (5)	H2WA—O2W—H2WB	106.1
C12—C11—C14	128.9 (5)	H3WA—O3W—H3WB	107.3
N11—C11—C14	116.0 (4)	H4WA—O4W—H4WB	103.6

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O22i	0.97	1.84	2.778 (5)	163
O1—H1B···O1W	0.96	1.87	2.827 (6)	174
O1W—H1WA···O4Wii	0.91	2.10	2.812 (6)	134
O1W—H1WB···O2Wi	0.80	2.10	2.775 (6)	142
O2W—H2WA···O22	0.82	1.93	2.692 (6)	155
O2W—H2WB···O4Wiii	0.86	1.97	2.830 (6)	178
O3W—H3WA···O24	0.94	1.94	2.880 (6)	174
O3W—H3WB···O24iv	0.96	1.80	2.694 (6)	153
O4W—H4WA···O2Wii	0.91	2.02	2.863 (6)	153
O4W—H4WB···O3W	0.88	1.92	2.783 (6)	167
N12—H12A···O1	0.97	2.00	2.873 (6)	149
N12—H12B···O21v	0.83	2.19	2.984 (5)	161
N14—H14A···O3Wvi	0.88	2.44	3.043 (6)	126
N14—H14B···O1Wvii	0.86	2.19	3.022 (6)	162

Table 1

Selected bond lengths (Å)

Zn—N21	2.064 (4)
Zn—N11	2.092 (4)
Zn—N13	2.129 (4)
Zn—O1	2.213 (3)
Zn—O23	2.232 (4)
Zn—O21	2.260 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O22i	0.97	1.84	2.778 (5)	163
O1—H1B⋯O1W	0.96	1.87	2.827 (6)	174
O1W—H1WA⋯O4Wii	0.91	2.10	2.812 (6)	134
O1W—H1WB⋯O2Wi	0.80	2.10	2.775 (6)	142
O2W—H2WA⋯O22	0.82	1.93	2.692 (6)	155
O2W—H2WB⋯O4Wiii	0.86	1.97	2.830 (6)	178
O3W—H3WA⋯O24	0.94	1.94	2.880 (6)	174
O3W—H3WB⋯O24iv	0.96	1.80	2.694 (6)	153
O4W—H4WA⋯O2Wii	0.91	2.02	2.863 (6)	153
O4W—H4WB⋯O3W	0.88	1.92	2.783 (6)	167
N12—H12A⋯O1	0.97	2.00	2.873 (6)	149
N12—H12B⋯O21v	0.83	2.19	2.984 (5)	161
N14—H14A⋯O3Wvi	0.88	2.44	3.043 (6)	126
N14—H14B⋯O1Wvii	0.86	2.19	3.022 (6)	162

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