Bis(μ-3-nitro­phthalato-κ2O1:O2)bis­[(thio­urea-κS)zinc] dihydrate

Gao, H.-P.; Guo, M.-L.

doi:10.1107/S1600536812004679

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page m264

doi:10.1107/S1600536812004679

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Bis(μ-3-nitrophthalato-κ²O¹:O²)bis[(thiourea-κS)zinc] dihydrate

Hui-Peng Gao ^a and Ming-Lin Guo ^a ^*

^aSchool of Environment and Chemical Engineering, and Key Laboratory of Hollow Fiber Membrane Materials and Membrane Process, Tianjin Polytechnic University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: guomlin@yahoo.com

(Received 15 January 2012; accepted 3 February 2012; online 10 February 2012)

In the title complex, [Zn₂(C₈H₃NO₆)₂(CH₄N₂S)₄]·2H₂O, the carboxylate groups of the 3-nitrophthalate ligands coordinate in a bis-monodentate mode to the Zn^II cations. This results in the formation of a centrosymmetric dimer containing two Zn^II cations with distorted tetrahedral geometries provided by the O atoms of two different 3-nitrophthalate dianions and the S atoms of two non-equivalent coordinated thiourea molecules. The crystal structure exhibits N—H⋯O and O—H⋯O hydrogen bonds which link the dimers into a three-dimensional network.

Related literature

For the structures of similar bis[(μ₂-homophthalato)bis(thiourea)zinc] complexes, see: Burrows et al. (2000 ). For other metal complexes of dicarboxylate dianions and thiourea, see: Burrows et al. (2004 ); Ke et al. (2002 ); Zhang et al. (2000 ).

Experimental

Crystal data

[Zn₂(C₈H₃NO₆)₂(CH₄N₂S)₄]·2H₂O
M_r = 889.49
Monoclinic, P 2₁ /c
a = 7.661 (3) Å
b = 18.999 (7) Å
c = 11.732 (4) Å
β = 104.960 (6)°
V = 1649.7 (11) Å³
Z = 2
Mo Kα radiation
μ = 1.79 mm⁻¹
T = 294 K
0.20 × 0.10 × 0.08 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.803, T_max = 0.885
13709 measured reflections
3905 independent reflections
3018 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.064
S = 1.00
3905 reflections
245 parameters
19 restraints
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7B⋯O4ⁱ	0.85	2.03	2.870 (2)	169
O7—H7A⋯O1	0.85	1.92	2.769 (2)	175
N4′—H4′B⋯O2ⁱⁱ	0.90	1.91	2.768 (9)	160
N4′—H4′A⋯O1ⁱⁱⁱ	0.90	2.54	3.182 (15)	129
N3′—H3′B⋯O7^iv	0.90	2.48	3.110 (8)	128
N3′—H3′A⋯O3^iv	0.90	2.09	2.971 (12)	166
N4—H4B⋯O2ⁱⁱ	0.90	1.93	2.807 (8)	165
N4—H4A⋯O1ⁱⁱⁱ	0.90	2.05	2.830 (8)	144
N3—H3B⋯O7^iv	0.90	2.59	3.147 (8)	121
N3—H3A⋯O3^iv	0.90	2.44	3.159 (10)	137
N2—H2B⋯O5^v	0.90	2.23	3.119 (2)	168
N2—H2A⋯O4^iv	0.90	2.04	2.874 (2)	153
N1—H1B⋯O7^vi	0.90	2.15	2.968 (2)	151
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+1; (iii) x-1, y, z; (iv) -x+1, -y+1, -z+1; (v) -x, -y+1, -z; (vi) -x+1, -y+1, -z.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812004679/mw2049sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004679/mw2049Isup2.hkl

checkCIF report

Comment top

Thiourea as a ligand has an important role in the formation of metal co-ordination complexes with dicarboxylates because it contain hydrogen bond donors that may serve to link the chains through N–H···O hydrogen bonds (Burrows et al. (2000, 2004); Zhang et al. (2000); Ke et al. (2002)). We have used the 3-nitrophthalate dianion and thiourea as ligands and have obtained the title dimeric, four-coordinate 3-nitrophthalate-zinc complex, (I).

The asymmetric unit in the structure of (I) comprises one Zn atom, one complete 3-nitrophthate dianion and two non-equivalent thiourea molecules. The centrosymmetric dimer and is shown in Fig. 1 which displays the full coordination of the Zn atom.

A rotational disorder about the C10—S2 bond in the C10, N3, N4 unit is observed. Each of the two N atoms bonded to C10 was successfully refined using a split-site model (N3/N3' and N4/N4'), with occupancies of 0.53 (3) for N3 and N4, and 0.47 (3) for N3' and N4'.

The Zn atom shows a distorted tetrahedral coordination comprised of two O atoms from the carboxylate groups of two different 3-nitrophthalates and two S atoms of two non-equivalent coordinated thiourea molecules. The packing is stabilized by weak intra- and intermolecular N—H···O and O—H···O hydrogen bond.(see Table 1). A packing diagram is shown in Fig. 2.

Related literature top

For a similar structure of bis[(µ₂-homophthalato)bis(thiourea)zinc] complexes, see: Burrows et al. (2000). For other metal complexes of dicarboxylate dianions and thiourea, see: Burrows et al. (2004); Ke et al. (2002); Zhang et al. (2000).

Experimental top

Zinc oxide (0.21 g, 2.5 mmol) was added to a stirred solution of 3-nitrophthalic acid (0.53 g, 2.5 mmol) in boiling water (20.0 ml) over a period of 40 min following which thiourea (0.30 g, 4 mmol) was added to the solution. After filtration, slow evaporation over a period of a week at room temperature provided colorless needle crystals of (I).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the structure of (I) showing the atom-numbering scheme and coordination environment for Zn atom; displacement ellipsoids were drawn at the 50% probability level [Symmetry codes: (i) -x + 1, -y + 1, -z + 1]. Only the major component of the disorder is shown.
	Fig. 2. The packing diagram of (I) showing the hydrogen-bonding interactions. For clarity, the minor components have been omitted.

Bis(µ-3-nitrophthalato-κ²O¹:O²)bis[(thiourea- κS)zinc] dihydrate top

Crystal data top

[Zn₂(C₈H₃NO₆)₂(CH₄N₂S)₄]·2H₂O	F(000) = 904
M_r = 889.49	D_x = 1.791 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6473 reflections
a = 7.661 (3) Å	θ = 1.8–27.9°
b = 18.999 (7) Å	µ = 1.79 mm⁻¹
c = 11.732 (4) Å	T = 294 K
β = 104.960 (6)°	Needle, colorless
V = 1649.7 (11) Å³	0.20 × 0.10 × 0.08 mm
Z = 2

Data collection top

Rigaku Saturn CCD area-detector diffractometer	3905 independent reflections
Radiation source: rotating anode	3018 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.030
Detector resolution: 28.571 pixels mm^-1	θ_max = 27.9°, θ_min = 2.1°
ω scans	h = −10→9
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −24→24
T_min = 0.803, T_max = 0.885	l = −15→15
13709 measured reflections

Refinement top

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.034P)²] where P = (F_o² + 2F_c²)/3
3905 reflections	(Δ/σ)_max = 0.001
245 parameters	Δρ_max = 0.35 e Å⁻³
19 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

[Zn₂(C₈H₃NO₆)₂(CH₄N₂S)₄]·2H₂O	V = 1649.7 (11) Å³
M_r = 889.49	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.661 (3) Å	µ = 1.79 mm⁻¹
b = 18.999 (7) Å	T = 294 K
c = 11.732 (4) Å	0.20 × 0.10 × 0.08 mm
β = 104.960 (6)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	3905 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	3018 reflections with I > 2σ(I)
T_min = 0.803, T_max = 0.885	R_int = 0.030
13709 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	19 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.00	Δρ_max = 0.35 e Å⁻³
3905 reflections	Δρ_min = −0.50 e Å⁻³
245 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.26375 (3)	0.465538 (10)	0.296748 (17)	0.01321 (7)
S1	0.38057 (7)	0.46840 (2)	0.13467 (4)	0.02084 (11)
S2	−0.04728 (6)	0.45989 (2)	0.25699 (4)	0.01749 (11)
O1	0.55143 (16)	0.59210 (7)	0.30902 (11)	0.0204 (3)
O2	0.31823 (16)	0.55754 (6)	0.37813 (10)	0.0161 (3)
O3	0.61945 (17)	0.59897 (6)	0.57337 (11)	0.0174 (3)
O4	0.69068 (19)	0.69389 (7)	0.68684 (11)	0.0275 (3)
O5	0.06166 (18)	0.73729 (7)	0.13145 (11)	0.0259 (3)
O6	0.18545 (19)	0.63506 (7)	0.17013 (12)	0.0265 (3)
N1	0.2512 (2)	0.41575 (8)	−0.07518 (13)	0.0231 (4)
H1A	0.3054	0.4533	−0.0982	0.028*
H1B	0.1905	0.3849	−0.1292	0.028*
N2	0.1825 (2)	0.35129 (8)	0.07208 (13)	0.0197 (3)
H2A	0.1903	0.3450	0.1493	0.024*
H2B	0.1214	0.3201	0.0188	0.024*
N3	−0.0126 (14)	0.3943 (6)	0.4644 (9)	0.0311 (18)	0.53 (3)
H3A	0.0835	0.3710	0.4527	0.037*	0.53 (3)
H3B	−0.0499	0.3863	0.5300	0.037*	0.53 (3)
N4	−0.2513 (9)	0.4699 (6)	0.4019 (7)	0.0212 (14)	0.53 (3)
H4A	−0.3110	0.4987	0.3440	0.025*	0.53 (3)
H4B	−0.2931	0.4628	0.4660	0.025*	0.53 (3)
N3'	0.0236 (16)	0.4119 (6)	0.4809 (8)	0.0223 (17)	0.47 (3)
H3'A	0.1369	0.4041	0.4753	0.027*	0.47 (3)
H3'B	−0.0070	0.4010	0.5478	0.027*	0.47 (3)
N4'	−0.2637 (8)	0.4451 (9)	0.3977 (8)	0.0306 (19)	0.47 (3)
H4'A	−0.3495	0.4646	0.3389	0.037*	0.47 (3)
H4'B	−0.2890	0.4336	0.4661	0.037*	0.47 (3)
N5	0.1667 (2)	0.69621 (8)	0.19691 (13)	0.0187 (3)
C1	0.4272 (2)	0.60353 (9)	0.35579 (15)	0.0139 (4)
C2	0.3923 (2)	0.67846 (9)	0.38999 (15)	0.0121 (3)
C3	0.2711 (2)	0.72277 (9)	0.31257 (15)	0.0149 (4)
C4	0.2396 (2)	0.79171 (9)	0.33902 (17)	0.0191 (4)
H4	0.1577	0.8191	0.2847	0.023*
C5	0.3301 (2)	0.81947 (9)	0.44617 (16)	0.0198 (4)
H5	0.3125	0.8661	0.4646	0.024*
C6	0.4482 (2)	0.77666 (9)	0.52632 (16)	0.0164 (4)
H6	0.5074	0.7948	0.5997	0.020*
C7	0.4805 (2)	0.70735 (9)	0.49987 (15)	0.0134 (4)
C8	0.6076 (2)	0.66467 (9)	0.59491 (15)	0.0148 (4)
C9	0.2607 (2)	0.40643 (9)	0.03736 (16)	0.0173 (4)
C10	−0.1008 (2)	0.43850 (10)	0.38726 (16)	0.0185 (4)
O7	0.83935 (17)	0.67482 (7)	0.28846 (11)	0.0237 (3)
H7A	0.7478	0.6517	0.2960	0.036*
H7B	0.8098	0.7152	0.2584	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01454 (11)	0.01171 (11)	0.01271 (12)	−0.00086 (7)	0.00228 (8)	−0.00136 (8)
S1	0.0248 (2)	0.0223 (3)	0.0178 (2)	−0.00789 (18)	0.0096 (2)	−0.00637 (19)
S2	0.0157 (2)	0.0219 (2)	0.0154 (2)	−0.00093 (17)	0.00484 (18)	0.00302 (18)
O1	0.0182 (6)	0.0195 (7)	0.0255 (7)	−0.0014 (5)	0.0091 (6)	−0.0084 (5)
O2	0.0224 (7)	0.0112 (6)	0.0149 (7)	−0.0049 (5)	0.0050 (6)	−0.0018 (5)
O3	0.0208 (6)	0.0130 (6)	0.0164 (7)	0.0030 (5)	0.0009 (6)	−0.0008 (5)
O4	0.0386 (8)	0.0150 (7)	0.0194 (7)	−0.0019 (6)	−0.0098 (6)	−0.0017 (5)
O5	0.0258 (7)	0.0248 (8)	0.0217 (7)	0.0036 (6)	−0.0035 (6)	0.0052 (6)
O6	0.0362 (8)	0.0194 (7)	0.0201 (7)	0.0019 (6)	0.0005 (6)	−0.0040 (6)
N1	0.0316 (9)	0.0216 (9)	0.0154 (8)	−0.0012 (7)	0.0050 (7)	−0.0003 (6)
N2	0.0248 (8)	0.0211 (8)	0.0117 (8)	−0.0058 (6)	0.0019 (7)	−0.0046 (6)
N3	0.031 (3)	0.030 (3)	0.035 (3)	0.010 (3)	0.014 (2)	0.015 (3)
N4	0.024 (2)	0.021 (3)	0.024 (2)	−0.0007 (18)	0.0156 (18)	0.004 (2)
N3'	0.038 (4)	0.019 (3)	0.015 (3)	0.003 (3)	0.017 (3)	0.004 (2)
N4'	0.016 (2)	0.054 (5)	0.021 (2)	−0.014 (3)	0.0036 (18)	0.010 (3)
N5	0.0186 (8)	0.0204 (9)	0.0166 (8)	−0.0025 (6)	0.0033 (7)	0.0021 (6)
C1	0.0146 (8)	0.0140 (9)	0.0108 (9)	−0.0005 (6)	−0.0011 (7)	−0.0004 (6)
C2	0.0119 (8)	0.0105 (8)	0.0158 (9)	−0.0018 (6)	0.0072 (7)	−0.0004 (6)
C3	0.0153 (8)	0.0156 (9)	0.0135 (9)	−0.0025 (7)	0.0034 (7)	0.0003 (7)
C4	0.0184 (9)	0.0168 (9)	0.0212 (10)	0.0036 (7)	0.0033 (8)	0.0050 (7)
C5	0.0232 (9)	0.0113 (9)	0.0253 (10)	0.0020 (7)	0.0070 (8)	−0.0012 (7)
C6	0.0169 (8)	0.0141 (9)	0.0186 (9)	−0.0013 (7)	0.0050 (8)	−0.0021 (7)
C7	0.0124 (8)	0.0126 (9)	0.0157 (9)	−0.0009 (6)	0.0044 (7)	0.0010 (7)
C8	0.0153 (8)	0.0131 (9)	0.0164 (9)	−0.0021 (6)	0.0047 (8)	0.0006 (7)
C9	0.0166 (9)	0.0184 (10)	0.0164 (9)	0.0040 (7)	0.0032 (8)	−0.0018 (7)
C10	0.0225 (9)	0.0170 (9)	0.0163 (10)	−0.0086 (7)	0.0054 (8)	−0.0047 (7)
O7	0.0227 (7)	0.0188 (7)	0.0303 (8)	0.0006 (5)	0.0083 (6)	0.0061 (6)

Geometric parameters (Å, º) top

Zn1—O3ⁱ	1.9801 (13)	N4—H4'A	0.9136
Zn1—O2	1.9839 (13)	N4—H4'B	1.1135
Zn1—S1	2.3018 (8)	N3'—C10	1.353 (8)
Zn1—S2	2.3093 (10)	N3'—H3A	1.0006
S1—C9	1.7295 (18)	N3'—H3B	1.0258
S2—C10	1.730 (2)	N3'—H3'A	0.9000
O1—C1	1.234 (2)	N3'—H3'B	0.8999
O2—C1	1.282 (2)	N4'—C10	1.291 (6)
O3—C8	1.281 (2)	N4'—H4A	1.2029
O3—Zn1ⁱ	1.9801 (13)	N4'—H4B	0.9480
O4—C8	1.234 (2)	N4'—H4'A	0.9001
O5—N5	1.2359 (19)	N4'—H4'B	0.9000
O6—N5	1.222 (2)	N5—C3	1.475 (2)
N1—C9	1.315 (2)	C1—C2	1.521 (2)
N1—H1A	0.9000	C2—C3	1.400 (2)
N1—H1B	0.9000	C2—C7	1.403 (2)
N2—C9	1.322 (2)	C3—C4	1.382 (3)
N2—H2A	0.9000	C4—C5	1.374 (3)
N2—H2B	0.9001	C4—H4	0.9300
N3—C10	1.290 (7)	C5—C6	1.387 (2)
N3—H3A	0.9000	C5—H5	0.9300
N3—H3B	0.8999	C6—C7	1.390 (2)
N3—H3'A	1.1353	C6—H6	0.9300
N3—H3'B	0.9767	C7—C8	1.513 (2)
N4—C10	1.348 (6)	O7—H7A	0.8510
N4—H4A	0.8999	O7—H7B	0.8508
N4—H4B	0.9000

O3ⁱ—Zn1—O2	100.25 (5)	H4B—N4'—H4'A	102.4
O3ⁱ—Zn1—S1	117.10 (4)	C10—N4'—H4'B	119.8
O2—Zn1—S1	107.36 (4)	H4A—N4'—H4'B	124.7
O3ⁱ—Zn1—S2	111.37 (4)	H4'A—N4'—H4'B	120.0
O2—Zn1—S2	102.48 (4)	O6—N5—O5	122.81 (15)
S1—Zn1—S2	115.80 (2)	O6—N5—C3	119.35 (14)
C9—S1—Zn1	106.01 (7)	O5—N5—C3	117.84 (15)
C10—S2—Zn1	107.45 (6)	O1—C1—O2	126.07 (16)
C1—O2—Zn1	124.72 (12)	O1—C1—C2	119.37 (15)
C8—O3—Zn1ⁱ	119.48 (11)	O2—C1—C2	114.56 (15)
C9—N1—H1A	119.8	C3—C2—C7	116.24 (15)
C9—N1—H1B	120.2	C3—C2—C1	121.59 (15)
H1A—N1—H1B	120.0	C7—C2—C1	122.16 (14)
C9—N2—H2A	119.8	C4—C3—C2	123.32 (16)
C9—N2—H2B	120.2	C4—C3—N5	116.51 (15)
H2A—N2—H2B	120.0	C2—C3—N5	120.16 (15)
C10—N3—H3A	120.9	C5—C4—C3	119.54 (16)
C10—N3—H3B	119.0	C5—C4—H4	120.2
H3A—N3—H3B	120.0	C3—C4—H4	120.2
C10—N3—H3'A	107.6	C4—C5—C6	118.80 (17)
H3B—N3—H3'A	117.8	C4—C5—H5	120.6
C10—N3—H3'B	119.9	C6—C5—H5	120.6
H3A—N3—H3'B	113.0	C5—C6—C7	121.77 (17)
H3'A—N3—H3'B	94.8	C5—C6—H6	119.1
C10—N4—H4A	117.3	C7—C6—H6	119.1
C10—N4—H4B	122.7	C6—C7—C2	120.30 (16)
H4A—N4—H4B	120.0	C6—C7—C8	117.45 (16)
C10—N4—H4'A	113.7	C2—C7—C8	122.22 (15)
H4B—N4—H4'A	105.2	O4—C8—O3	124.33 (16)
C10—N4—H4'B	101.0	O4—C8—C7	119.46 (16)
H4A—N4—H4'B	135.9	O3—C8—C7	116.20 (15)
H4'A—N4—H4'B	100.1	N1—C9—N2	120.25 (17)
C10—N3'—H3A	108.0	N1—C9—S1	116.95 (14)
C10—N3'—H3B	105.1	N2—C9—S1	122.79 (14)
H3A—N3'—H3B	100.6	N3—C10—N4'	109.9 (6)
C10—N3'—H3'A	119.5	N3—C10—N4	120.6 (6)
H3B—N3'—H3'A	130.1	N4'—C10—N3'	117.1 (6)
C10—N3'—H3'B	120.5	N4—C10—N3'	120.6 (6)
H3A—N3'—H3'B	110.8	N3—C10—S2	124.9 (5)
H3'A—N3'—H3'B	120.0	N4'—C10—S2	121.1 (4)
C10—N4'—H4A	101.6	N4—C10—S2	114.5 (4)
C10—N4'—H4B	124.1	N3'—C10—S2	121.8 (5)
H4A—N4'—H4B	92.1	H7A—O7—H7B	111.7
C10—N4'—H4'A	120.0

O3ⁱ—Zn1—S1—C9	91.23 (8)	C2—C3—C4—C5	0.0 (3)
O2—Zn1—S1—C9	−157.10 (7)	N5—C3—C4—C5	178.91 (16)
S2—Zn1—S1—C9	−43.36 (7)	C3—C4—C5—C6	−1.5 (3)
O3ⁱ—Zn1—S2—C10	29.72 (8)	C4—C5—C6—C7	1.7 (3)
O2—Zn1—S2—C10	−76.68 (8)	C5—C6—C7—C2	−0.3 (3)
S1—Zn1—S2—C10	166.81 (7)	C5—C6—C7—C8	−178.29 (16)
O3ⁱ—Zn1—O2—C1	110.95 (13)	C3—C2—C7—C6	−1.1 (2)
S1—Zn1—O2—C1	−11.84 (13)	C1—C2—C7—C6	178.24 (16)
S2—Zn1—O2—C1	−134.26 (12)	C3—C2—C7—C8	176.76 (15)
Zn1—O2—C1—O1	−22.5 (2)	C1—C2—C7—C8	−3.9 (2)
Zn1—O2—C1—C2	156.42 (11)	Zn1ⁱ—O3—C8—O4	13.0 (2)
O1—C1—C2—C3	91.4 (2)	Zn1ⁱ—O3—C8—C7	−166.24 (11)
O2—C1—C2—C3	−87.6 (2)	C6—C7—C8—O4	−6.8 (2)
O1—C1—C2—C7	−87.9 (2)	C2—C7—C8—O4	175.24 (17)
O2—C1—C2—C7	93.14 (19)	C6—C7—C8—O3	172.46 (16)
C7—C2—C3—C4	1.3 (3)	C2—C7—C8—O3	−5.5 (2)
C1—C2—C3—C4	−178.07 (16)	Zn1—S1—C9—N1	154.73 (13)
C7—C2—C3—N5	−177.58 (15)	Zn1—S1—C9—N2	−25.98 (16)
C1—C2—C3—N5	3.1 (2)	Zn1—S2—C10—N3	−38.9 (8)
O6—N5—C3—C4	−178.06 (17)	Zn1—S2—C10—N4'	166.3 (9)
O5—N5—C3—C4	1.2 (2)	Zn1—S2—C10—N4	143.9 (5)
O6—N5—C3—C2	0.9 (2)	Zn1—S2—C10—N3'	−16.2 (6)
O5—N5—C3—C2	−179.85 (16)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O4ⁱⁱ	0.85	2.03	2.870 (2)	169
O7—H7A···O1	0.85	1.92	2.769 (2)	175
N4′—H4′B···O2ⁱⁱⁱ	0.90	1.91	2.768 (9)	160
N4′—H4′A···O1^iv	0.90	2.54	3.182 (15)	129
N3′—H3′B···O7ⁱ	0.90	2.48	3.110 (8)	128
N3′—H3′A···O3ⁱ	0.90	2.09	2.971 (12)	166
N4—H4B···O2ⁱⁱⁱ	0.90	1.93	2.807 (8)	165
N4—H4A···O1^iv	0.90	2.05	2.830 (8)	144
N3—H3B···O7ⁱ	0.90	2.59	3.147 (8)	121
N3—H3A···O3ⁱ	0.90	2.44	3.159 (10)	137
N2—H2B···O5^v	0.90	2.23	3.119 (2)	168
N2—H2A···O4ⁱ	0.90	2.04	2.874 (2)	153
N1—H1B···O7^vi	0.90	2.15	2.968 (2)	151

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z+1; (iv) x−1, y, z; (v) −x, −y+1, −z; (vi) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Zn₂(C₈H₃NO₆)₂(CH₄N₂S)₄]·2H₂O
M_r	889.49
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	7.661 (3), 18.999 (7), 11.732 (4)
β (°)	104.960 (6)
V (Å³)	1649.7 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.79
Crystal size (mm)	0.20 × 0.10 × 0.08

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.803, 0.885
No. of measured, independent and observed [I > 2σ(I)] reflections	13709, 3905, 3018
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.064, 1.00
No. of reflections	3905
No. of parameters	245
No. of restraints	19
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.50

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O4ⁱ	0.85	2.03	2.870 (2)	169.1
O7—H7A···O1	0.85	1.92	2.769 (2)	174.8
N4'—H4'B···O2ⁱⁱ	0.90	1.91	2.768 (9)	159.9
N4'—H4'A···O1ⁱⁱⁱ	0.90	2.54	3.182 (15)	129.2
N3'—H3'B···O7^iv	0.90	2.48	3.110 (8)	127.6
N3'—H3'A···O3^iv	0.90	2.09	2.971 (12)	166.4
N4—H4B···O2ⁱⁱ	0.90	1.93	2.807 (8)	165.2
N4—H4A···O1ⁱⁱⁱ	0.90	2.05	2.830 (8)	144.3
N3—H3B···O7^iv	0.90	2.59	3.147 (8)	120.7
N3—H3A···O3^iv	0.90	2.44	3.159 (10)	136.9
N2—H2B···O5^v	0.90	2.23	3.119 (2)	168.0
N2—H2A···O4^iv	0.90	2.04	2.874 (2)	153.2
N1—H1B···O7^vi	0.90	2.15	2.968 (2)	151.2

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z; (vi) −x+1, −y+1, −z.

Acknowledgements

The authors thank Tianjin Polytechnic University for financial support.

References

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