Aqua­(2,2′-bipyridine-κ2N,N′)[2-(3-thien­yl)malonato-κ2O,O′]zinc(II) dihydrate

Meng, C.-X.; Zheng, X.-G.; Fu, F.; Zhang, X.-N.; Zhang, P.

doi:10.1107/S1600536809047448

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages m1604-m1605

doi:10.1107/S1600536809047448

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Aqua(2,2′-bipyridine-κ²N,N′)[2-(3-thienyl)malonato-κ²O,O′]zinc(II) dihydrate

Cai-Xia Meng,^a Xue-Gang Zheng,^b Feng Fu,^a ^* Xiao-Ning Zhang ^a and Peng Zhang ^a

^aDepartment of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an University, Yan'an 716000, People's Republic of China, and ^bLanzhou Institute of Biological Products, Lanzhou 730046, People's Republic of China
^*Correspondence e-mail: chemfufeng@126.com

(Received 23 October 2009; accepted 10 November 2009; online 18 November 2009)

In the crystal structure of the title compound, [Zn(C₇H₄O₄S)(C₁₀H₈N₂)(H₂O)]·2H₂O, the Zn^II ion assumes a trigonal–bipyramidal coordination geometry completed by two N atoms from a 2,2′-bipyridine ligand, two O atoms from a 2-(3-thienyl)malonate anion and a water molecule. The S atom of the 2-(3-thienyl)malonate ligand is disordered over two sites with an occupancy ratio of 0.701 (5):0.299 (5). Intermolecular O—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For general background to organic heterocycles, see: Lin et al. (2008 ); Jin et al. (2001 ). For related thiophenemalonate complexes, see: He et al. (2009 ); Murray et al. (2008 ); Huang et al. (2009 ); Lim et al. (2006 ). For hydrogen-bonded rings in polymeric complexes, see: Eppel & Bernstein (2009 ); Etter (1990 ); Nichol & Clegg (2009 ).

Experimental

Crystal data

[Zn(C₇H₄O₄S)(C₁₀H₈N₂)(H₂O)]·2H₂O
M_r = 459.76
Orthorhombic, P b c a
a = 15.9978 (10) Å
b = 14.5647 (9) Å
c = 16.5889 (10) Å
V = 3865.3 (4) Å³
Z = 8
Mo Kα radiation
μ = 1.42 mm⁻¹
T = 293 K
0.15 × 0.10 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.843, T_max = 0.918
23919 measured reflections
4752 independent reflections
3107 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.094
S = 1.01
4752 reflections
273 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1	2.0001 (15)
Zn1—O3	2.0224 (15)
Zn1—O5	1.9596 (15)
Zn1—N1	2.1123 (18)
Zn1—N2	2.100 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H18⋯O7ⁱ	0.85	1.74	2.568 (2)	165
O5—H19⋯O4ⁱⁱ	0.85	1.83	2.618 (2)	155
O6—H20⋯O2	0.85	1.94	2.784 (2)	172
O6—H21⋯O4ⁱⁱⁱ	0.85	2.22	2.943 (2)	144
O6—H21⋯O3ⁱⁱⁱ	0.85	2.45	3.238 (2)	154
O7—H22⋯O2	0.85	2.04	2.847 (3)	158
O7—H22⋯O1	0.85	2.47	3.165 (2)	139
O7—H23⋯O6^iv	0.85	1.88	2.700 (3)	162
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809047448/xu2654sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809047448/xu2654Isup2.hkl

checkCIF report

Comment top

The nature of organic heterocycles are special enough to attract a lot of scientific researches (Lin et al., 2008; Jin et al., 2001). Because of the big radius of the S atom, its lone pair of electrons can be more easily delocalized with in the heterocycle, and the ligand exhibits good charge-transfer ability (He et al., 2009). However, its reaction mechanism is rather complicated to study, a small quantity of literatures about thiophenemalonic are reported, with thiophenemalonic acid researched even less (Murray et al., 2008; Huang et al., 2009; Lim et al., 2006). In this paper, we report the hydrothermal synthesis and structure of a new compound incorporating the thiophene-containing ligand3-thiophenecarboxylate with two kinds of hydrogen bond rings (Nichol et al., 2009; Etter, 1990; Eppel et al., 2009).

The molecular structure of the title complex is shown in Fig.1. The coordination geometry around Zn²⁺ ion is five-coordinated, with two N atoms from 2,2'-bipyridine ligand (N1, N2), two O atom from 3-thiophenecarboxylate ligand (O1,O3), and a coordinated water(O5). The equatorial positions are occupied by N2, O1 and O5, while N1, O3 are in axial positions, so the local coordination environment of Zn(II) can be described as a distorted trigonal bipyramidal environment (Table 1). The S1 and C6 atoms of the 3-thiophenemalonate ligand are disordered over two sites with refined occupancies of 0.701 (5) and 0.299 (5). The units are interconnected by two kinds of O–H···O hydrogen bonds rings (R₃³(12), R₄³(12)) to form a two-dimensional supramolecular network, in which the lattice water molecule acts as both hydrogen-bond donor and acceptor (Table 2). These hydrogen bonds rings contributes to the additional stability of the structure.

Related literature top

For ganeral background to organic heterocycles, see: Lin et al. (2008); Jin et al. (2001). For related thiophenemalonate complexes, see: He et al. (2009); Murray et al. (2008); Huang et al. (2009); Lim et al. (2006). For hydrogen-bonded rings in polymeric complexes, see: Eppel & Bernstein (2009); Etter (1990); Nichol & Clegg (2009).

For related literature, see:

Experimental top

A mixture of Zn(NO₃)₂.6H₂O (0.030 g, 0.1 mmol), 2,2'-bipyridine (0.008 g, 0.05 mmol), 3-thiophenemalonic acid (0.018 g, 0.1 mmol), NaOH (0.008 g, 0.2 mmol) and distilled water(10 ml) was sealed in a 25 ml Teflon-lined stainless autoclave and heated at 413 K for 72 h under autogenous pressure. After cooled at room temperature over 48 h, colorless crystals of the title compound suitable for X-ray analysis were obtained from the reaction mixture by filtration.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of title complex,with the atom-numbering scheme for the asymmetric unit, showing displacementellipsoids at the 50% probability level.

Aqua(2,2'-bipyridine-κ²N,N')[2-(3-thienyl)malonato- κ²O,O']zinc(II) dihydrate top

Crystal data top

[Zn(C₇H₄O₄S)(C₁₀H₈N₂)(H₂O)]·2H₂O	F(000) = 1888
M_r = 459.76	D_x = 1.580 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4757 reflections
a = 15.9978 (10) Å	θ = 2.3–28.3°
b = 14.5647 (9) Å	µ = 1.42 mm⁻¹
c = 16.5889 (10) Å	T = 293 K
V = 3865.3 (4) Å³	Prism, colorless
Z = 8	0.15 × 0.10 × 0.06 mm

Data collection top

Bruker SMART CCD diffractometer	4752 independent reflections
Radiation source: fine-focus sealed tube	3107 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→21
T_min = 0.843, T_max = 0.918	k = −19→19
23919 measured reflections	l = −13→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0445P)² + 0.5447P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.013
4752 reflections	Δρ_max = 0.29 e Å⁻³
273 parameters	Δρ_min = −0.39 e Å⁻³
1 restraint	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0056 (3)

Crystal data top

[Zn(C₇H₄O₄S)(C₁₀H₈N₂)(H₂O)]·2H₂O	V = 3865.3 (4) Å³
M_r = 459.76	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 15.9978 (10) Å	µ = 1.42 mm⁻¹
b = 14.5647 (9) Å	T = 293 K
c = 16.5889 (10) Å	0.15 × 0.10 × 0.06 mm

Data collection top

Bruker SMART CCD diffractometer	4752 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3107 reflections with I > 2σ(I)
T_min = 0.843, T_max = 0.918	R_int = 0.045
23919 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	1 restraint
wR(F²) = 0.094	H-atom parameters constrained
S = 1.01	Δρ_max = 0.29 e Å⁻³
4752 reflections	Δρ_min = −0.39 e Å⁻³
273 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	0.006504 (15)	0.702960 (16)	0.153476 (15)	0.03795 (11)
S1A	0.1680 (2)	0.8323 (2)	−0.04031 (12)	0.0838 (10)	0.701 (5)
C6A	0.1110 (9)	0.9380 (17)	−0.0371 (9)	0.086 (5)	0.701 (5)
H6AA	0.0975	0.9781	−0.0788	0.103*	0.701 (5)
S1B	0.1113 (9)	0.9171 (14)	−0.0430 (7)	0.104 (4)	0.299 (5)
C6B	0.1633 (18)	0.8181 (18)	−0.0295 (10)	0.100 (11)	0.299 (5)
H6BA	0.1852	0.7779	−0.0676	0.120*	0.299 (5)
O1	0.11079 (10)	0.71831 (9)	0.21860 (10)	0.0469 (4)
O2	0.21138 (11)	0.80238 (11)	0.27006 (12)	0.0647 (5)
O3	−0.03265 (9)	0.82628 (10)	0.19487 (10)	0.0453 (4)
O4	−0.00902 (9)	0.96587 (11)	0.23639 (12)	0.0595 (5)
O5	−0.06263 (9)	0.61837 (11)	0.21667 (11)	0.0582 (5)
H18	−0.1147	0.6295	0.2189	0.087*
H19	−0.0547	0.5646	0.2351	0.087*
N1	0.06793 (11)	0.61120 (12)	0.07465 (11)	0.0416 (4)
N2	−0.05051 (12)	0.73028 (13)	0.04201 (13)	0.0491 (5)
C1	0.01571 (12)	0.89209 (14)	0.20888 (13)	0.0376 (5)
C2	0.14652 (14)	0.79424 (14)	0.23075 (14)	0.0406 (5)
C3	0.10954 (12)	0.88032 (14)	0.19092 (13)	0.0375 (5)
H3	0.1390	0.9340	0.2123	0.045*
C4	0.12234 (12)	0.87804 (15)	0.10066 (14)	0.0426 (5)
C5	0.09144 (18)	0.9444 (2)	0.04875 (19)	0.0722 (8)
H5	0.0695	1.0000	0.0670	0.087*
C7	0.16463 (17)	0.81237 (18)	0.05892 (17)	0.0561 (7)
H7	0.1929	0.7608	0.0830	0.067*
C8	0.12881 (14)	0.55364 (16)	0.09565 (16)	0.0515 (6)
H8	0.1428	0.5489	0.1499	0.062*
C9	0.17174 (16)	0.50113 (19)	0.04116 (19)	0.0639 (7)
H9	0.2145	0.4623	0.0578	0.077*
C10	0.14997 (19)	0.5074 (2)	−0.0387 (2)	0.0747 (9)
H10	0.1778	0.4723	−0.0771	0.090*
C11	0.08674 (18)	0.5659 (2)	−0.06165 (17)	0.0659 (7)
H11	0.0713	0.5706	−0.1156	0.079*
C12	0.04632 (14)	0.61766 (16)	−0.00342 (14)	0.0455 (6)
C13	−0.02145 (15)	0.68297 (17)	−0.02135 (15)	0.0478 (6)
C14	−0.05387 (19)	0.6973 (2)	−0.09774 (17)	0.0738 (9)
H14	−0.0336	0.6638	−0.1413	0.089*
C15	−0.1155 (2)	0.7605 (3)	−0.1090 (2)	0.0865 (10)
H15	−0.1378	0.7699	−0.1601	0.104*
C16	−0.1442 (2)	0.8096 (2)	−0.0452 (2)	0.0820 (10)
H16	−0.1855	0.8539	−0.0520	0.098*
C17	−0.11076 (18)	0.79227 (18)	0.0303 (2)	0.0716 (9)
H17	−0.1310	0.8249	0.0744	0.086*
O6	0.30803 (11)	0.96079 (13)	0.28178 (15)	0.0902 (7)
H20	0.2790	0.9120	0.2835	0.135*
H21	0.3574	0.9424	0.2919	0.135*
O7	0.27699 (11)	0.62083 (13)	0.27671 (16)	0.0973 (8)
H22	0.2451	0.6675	0.2774	0.146*
H23	0.2433	0.5767	0.2851	0.146*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.03884 (16)	0.03100 (15)	0.04402 (17)	−0.00086 (10)	−0.00143 (11)	−0.00347 (11)
S1A	0.0931 (16)	0.102 (2)	0.0563 (9)	−0.0365 (14)	0.0254 (9)	−0.0082 (10)
C6A	0.053 (5)	0.109 (11)	0.096 (9)	0.016 (5)	0.005 (5)	0.048 (7)
S1B	0.113 (6)	0.124 (8)	0.076 (4)	−0.004 (4)	0.021 (3)	0.031 (3)
C6B	0.078 (12)	0.041 (8)	0.18 (3)	−0.002 (8)	0.059 (12)	0.034 (10)
O1	0.0499 (9)	0.0316 (8)	0.0592 (10)	0.0009 (7)	−0.0149 (8)	0.0001 (7)
O2	0.0510 (10)	0.0531 (11)	0.0899 (14)	−0.0023 (8)	−0.0338 (10)	0.0044 (9)
O3	0.0337 (8)	0.0366 (9)	0.0655 (11)	−0.0017 (7)	0.0039 (8)	−0.0123 (8)
O4	0.0452 (9)	0.0363 (9)	0.0968 (14)	0.0014 (7)	0.0116 (9)	−0.0224 (9)
O5	0.0435 (9)	0.0411 (9)	0.0899 (13)	0.0012 (7)	0.0131 (9)	0.0187 (9)
N1	0.0401 (10)	0.0402 (10)	0.0446 (11)	−0.0004 (8)	0.0010 (8)	−0.0022 (9)
N2	0.0494 (12)	0.0404 (11)	0.0574 (13)	0.0018 (9)	−0.0142 (10)	0.0001 (10)
C1	0.0366 (11)	0.0317 (11)	0.0444 (13)	0.0000 (9)	0.0015 (9)	−0.0017 (10)
C2	0.0382 (12)	0.0396 (12)	0.0442 (13)	0.0046 (10)	−0.0028 (10)	−0.0005 (10)
C3	0.0322 (11)	0.0307 (11)	0.0497 (13)	−0.0019 (9)	−0.0042 (10)	−0.0026 (10)
C4	0.0318 (11)	0.0440 (13)	0.0518 (14)	−0.0058 (9)	0.0033 (10)	0.0081 (11)
C5	0.0660 (17)	0.077 (2)	0.073 (2)	0.0156 (15)	0.0104 (15)	0.0262 (16)
C7	0.0586 (16)	0.0536 (16)	0.0560 (17)	−0.0071 (12)	0.0175 (13)	−0.0004 (13)
C8	0.0479 (13)	0.0487 (14)	0.0579 (16)	0.0061 (11)	−0.0070 (12)	−0.0047 (12)
C9	0.0522 (15)	0.0572 (17)	0.082 (2)	0.0089 (12)	0.0002 (15)	−0.0139 (15)
C10	0.0691 (19)	0.080 (2)	0.075 (2)	0.0102 (16)	0.0159 (17)	−0.0264 (17)
C11	0.0748 (18)	0.078 (2)	0.0450 (15)	−0.0004 (16)	0.0044 (13)	−0.0155 (14)
C12	0.0455 (13)	0.0467 (14)	0.0441 (14)	−0.0095 (11)	0.0024 (11)	−0.0032 (11)
C13	0.0495 (13)	0.0500 (15)	0.0439 (14)	−0.0112 (11)	−0.0053 (11)	0.0067 (11)
C14	0.0690 (19)	0.104 (2)	0.0487 (17)	−0.0068 (17)	−0.0068 (15)	0.0143 (16)
C15	0.081 (2)	0.101 (3)	0.077 (2)	−0.011 (2)	−0.0295 (19)	0.034 (2)
C16	0.070 (2)	0.063 (2)	0.113 (3)	0.0004 (15)	−0.042 (2)	0.0220 (19)
C17	0.0668 (18)	0.0556 (17)	0.092 (2)	0.0114 (14)	−0.0271 (17)	−0.0064 (15)
O6	0.0429 (11)	0.0615 (12)	0.166 (2)	0.0055 (9)	−0.0057 (12)	−0.0011 (13)
O7	0.0408 (10)	0.0598 (13)	0.191 (2)	0.0105 (9)	−0.0077 (13)	0.0120 (14)

Geometric parameters (Å, º) top

Zn1—O1	2.0001 (15)	C3—H3	0.9800
Zn1—O3	2.0224 (15)	C4—C7	1.361 (3)
Zn1—O5	1.9596 (15)	C4—C5	1.386 (3)
Zn1—N1	2.1123 (18)	C5—H5	0.9317
Zn1—N2	2.100 (2)	C7—H7	0.9630
S1A—C7	1.672 (3)	C8—C9	1.369 (3)
S1A—C6A	1.79 (2)	C8—H8	0.9300
C6A—C5	1.461 (16)	C9—C10	1.373 (4)
C6A—H6AA	0.9300	C9—H9	0.9300
S1B—C6B	1.68 (3)	C10—C11	1.376 (4)
S1B—C5	1.606 (14)	C10—H10	0.9300
C6B—C7	1.469 (17)	C11—C12	1.385 (3)
C6B—H6BA	0.9300	C11—H11	0.9300
O1—C2	1.261 (2)	C12—C13	1.473 (3)
O2—C2	1.231 (3)	C13—C14	1.385 (3)
O3—C1	1.254 (2)	C14—C15	1.361 (4)
O4—C1	1.233 (2)	C14—H14	0.9300
O5—H18	0.8499	C15—C16	1.358 (5)
O5—H19	0.8500	C15—H15	0.9300
N1—C8	1.331 (3)	C16—C17	1.385 (4)
N1—C12	1.344 (3)	C16—H16	0.9300
N2—C17	1.335 (3)	C17—H17	0.9300
N2—C13	1.340 (3)	O6—H20	0.8499
C1—C3	1.540 (3)	O6—H21	0.8501
C2—C3	1.536 (3)	O7—H22	0.8500
C3—C4	1.512 (3)	O7—H23	0.8501

O5—Zn1—O1	104.60 (7)	C4—C5—C6A	119.0 (9)
O5—Zn1—O3	101.65 (6)	C4—C5—S1B	110.2 (6)
O1—Zn1—O3	88.61 (6)	C6A—C5—S1B	10.7 (17)
O5—Zn1—N2	110.18 (7)	C4—C5—H5	122.6
O1—Zn1—N2	144.76 (7)	C6A—C5—H5	116.9
O3—Zn1—N2	89.78 (7)	S1B—C5—H5	126.7
O5—Zn1—N1	101.30 (7)	C4—C7—S1A	113.3 (2)
O1—Zn1—N1	90.98 (7)	C4—C7—C6B	117.4 (11)
O3—Zn1—N1	156.38 (7)	S1A—C7—C6B	7.3 (11)
N2—Zn1—N1	77.11 (7)	C4—C7—H7	124.8
C7—S1A—C6A	95.9 (5)	S1A—C7—H7	121.8
C5—C6A—S1A	101.1 (10)	C6B—C7—H7	117.7
C5—C6A—H6AA	129.4	N1—C8—C9	123.1 (2)
S1A—C6A—H6AA	129.4	N1—C8—H8	118.5
C6B—S1B—C5	100.6 (10)	C9—C8—H8	118.5
S1B—C6B—C7	100.9 (15)	C8—C9—C10	118.2 (3)
S1B—C6B—H6BA	129.5	C8—C9—H9	120.9
C7—C6B—H6BA	129.5	C10—C9—H9	120.9
C2—O1—Zn1	124.22 (14)	C9—C10—C11	119.7 (3)
C1—O3—Zn1	123.42 (13)	C9—C10—H10	120.2
Zn1—O5—H18	117.2	C11—C10—H10	120.2
Zn1—O5—H19	133.4	C10—C11—C12	119.1 (3)
H18—O5—H19	107.9	C10—C11—H11	120.4
C8—N1—C12	119.0 (2)	C12—C11—H11	120.4
C8—N1—Zn1	125.22 (16)	N1—C12—C11	120.9 (2)
C12—N1—Zn1	115.63 (15)	N1—C12—C13	115.4 (2)
C17—N2—C13	119.0 (2)	C11—C12—C13	123.7 (2)
C17—N2—Zn1	124.7 (2)	N2—C13—C14	120.7 (2)
C13—N2—Zn1	116.26 (16)	N2—C13—C12	115.4 (2)
O4—C1—O3	122.49 (19)	C14—C13—C12	123.9 (3)
O4—C1—C3	118.79 (18)	C15—C14—C13	119.9 (3)
O3—C1—C3	118.73 (18)	C15—C14—H14	120.0
O2—C2—O1	123.4 (2)	C13—C14—H14	120.0
O2—C2—C3	118.29 (19)	C16—C15—C14	119.6 (3)
O1—C2—C3	118.20 (19)	C16—C15—H15	120.2
C4—C3—C2	110.86 (17)	C14—C15—H15	120.2
C4—C3—C1	109.04 (17)	C15—C16—C17	118.6 (3)
C2—C3—C1	112.53 (17)	C15—C16—H16	120.7
C4—C3—H3	108.1	C17—C16—H16	120.7
C2—C3—H3	108.1	N2—C17—C16	122.2 (3)
C1—C3—H3	108.1	N2—C17—H17	118.9
C7—C4—C5	110.6 (2)	C16—C17—H17	118.9
C7—C4—C3	125.9 (2)	H20—O6—H21	103.8
C5—C4—C3	123.5 (2)	H22—O7—H23	102.8

C7—S1A—C6A—C5	−2.2 (10)	C7—C4—C5—C6A	−3.1 (10)
C5—S1B—C6B—C7	−1.9 (17)	C3—C4—C5—C6A	177.0 (9)
O5—Zn1—O1—C2	−136.45 (18)	C7—C4—C5—S1B	3.7 (7)
O3—Zn1—O1—C2	−34.78 (18)	C3—C4—C5—S1B	−176.2 (7)
N2—Zn1—O1—C2	52.9 (2)	S1A—C6A—C5—C4	3.4 (13)
N1—Zn1—O1—C2	121.60 (18)	S1A—C6A—C5—S1B	−33 (5)
O5—Zn1—O3—C1	139.19 (18)	C6B—S1B—C5—C4	−0.9 (14)
O1—Zn1—O3—C1	34.56 (18)	C6B—S1B—C5—C6A	145 (6)
N2—Zn1—O3—C1	−110.24 (19)	C5—C4—C7—S1A	1.1 (3)
N1—Zn1—O3—C1	−54.7 (3)	C3—C4—C7—S1A	−179.0 (2)
O5—Zn1—N1—C8	−72.87 (18)	C5—C4—C7—C6B	−5.5 (12)
O1—Zn1—N1—C8	32.23 (18)	C3—C4—C7—C6B	174.4 (12)
O3—Zn1—N1—C8	121.0 (2)	C6A—S1A—C7—C4	0.8 (7)
N2—Zn1—N1—C8	178.76 (19)	C6A—S1A—C7—C6B	127 (10)
O5—Zn1—N1—C12	111.89 (16)	S1B—C6B—C7—C4	4.5 (18)
O1—Zn1—N1—C12	−143.01 (15)	S1B—C6B—C7—S1A	−52 (9)
O3—Zn1—N1—C12	−54.3 (2)	C12—N1—C8—C9	1.0 (3)
N2—Zn1—N1—C12	3.51 (15)	Zn1—N1—C8—C9	−174.14 (18)
O5—Zn1—N2—C17	82.5 (2)	N1—C8—C9—C10	−0.9 (4)
O1—Zn1—N2—C17	−107.2 (2)	C8—C9—C10—C11	0.4 (4)
O3—Zn1—N2—C17	−19.9 (2)	C9—C10—C11—C12	0.2 (4)
N1—Zn1—N2—C17	179.9 (2)	C8—N1—C12—C11	−0.4 (3)
O5—Zn1—N2—C13	−99.53 (17)	Zn1—N1—C12—C11	175.18 (18)
O1—Zn1—N2—C13	70.9 (2)	C8—N1—C12—C13	−179.9 (2)
O3—Zn1—N2—C13	158.13 (17)	Zn1—N1—C12—C13	−4.4 (2)
N1—Zn1—N2—C13	−2.06 (16)	C10—C11—C12—N1	−0.2 (4)
Zn1—O3—C1—O4	−177.78 (18)	C10—C11—C12—C13	179.4 (2)
Zn1—O3—C1—C3	2.3 (3)	C17—N2—C13—C14	−0.7 (4)
Zn1—O1—C2—O2	−178.94 (18)	Zn1—N2—C13—C14	−178.78 (19)
Zn1—O1—C2—C3	−2.1 (3)	C17—N2—C13—C12	178.6 (2)
O2—C2—C3—C4	107.2 (2)	Zn1—N2—C13—C12	0.5 (3)
O1—C2—C3—C4	−69.8 (2)	N1—C12—C13—N2	2.6 (3)
O2—C2—C3—C1	−130.3 (2)	C11—C12—C13—N2	−176.9 (2)
O1—C2—C3—C1	52.6 (3)	N1—C12—C13—C14	−178.2 (2)
O4—C1—C3—C4	−109.2 (2)	C11—C12—C13—C14	2.3 (4)
O3—C1—C3—C4	70.7 (2)	N2—C13—C14—C15	0.5 (4)
O4—C1—C3—C2	127.4 (2)	C12—C13—C14—C15	−178.7 (3)
O3—C1—C3—C2	−52.7 (3)	C13—C14—C15—C16	0.6 (5)
C2—C3—C4—C7	−3.5 (3)	C14—C15—C16—C17	−1.4 (5)
C1—C3—C4—C7	−127.9 (2)	C13—N2—C17—C16	−0.2 (4)
C2—C3—C4—C5	176.4 (2)	Zn1—N2—C17—C16	177.8 (2)
C1—C3—C4—C5	52.0 (3)	C15—C16—C17—N2	1.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H18···O7ⁱ	0.85	1.74	2.568 (2)	165
O5—H19···O4ⁱⁱ	0.85	1.83	2.618 (2)	155
O6—H20···O2	0.85	1.94	2.784 (2)	172
O6—H21···O4ⁱⁱⁱ	0.85	2.22	2.943 (2)	144
O6—H21···O3ⁱⁱⁱ	0.85	2.45	3.238 (2)	154
O7—H22···O2	0.85	2.04	2.847 (3)	158
O7—H22···O1	0.85	2.47	3.165 (2)	139
O7—H23···O6^iv	0.85	1.88	2.700 (3)	162

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

Experimental details

Crystal data
Chemical formula	[Zn(C₇H₄O₄S)(C₁₀H₈N₂)(H₂O)]·2H₂O
M_r	459.76
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	15.9978 (10), 14.5647 (9), 16.5889 (10)
V (Å³)	3865.3 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.42
Crystal size (mm)	0.15 × 0.10 × 0.06

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.843, 0.918
No. of measured, independent and observed [I > 2σ(I)] reflections	23919, 4752, 3107
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.094, 1.01
No. of reflections	4752
No. of parameters	273
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.39

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—O1	2.0001 (15)	Zn1—N1	2.1123 (18)
Zn1—O3	2.0224 (15)	Zn1—N2	2.100 (2)
Zn1—O5	1.9596 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H18···O7ⁱ	0.85	1.74	2.568 (2)	164.8
O5—H19···O4ⁱⁱ	0.85	1.83	2.618 (2)	154.5
O6—H20···O2	0.85	1.94	2.784 (2)	171.5
O6—H21···O4ⁱⁱⁱ	0.85	2.22	2.943 (2)	143.6
O6—H21···O3ⁱⁱⁱ	0.85	2.45	3.238 (2)	154.4
O7—H22···O2	0.85	2.04	2.847 (3)	158.0
O7—H22···O1	0.85	2.47	3.165 (2)	139.1
O7—H23···O6^iv	0.85	1.88	2.700 (3)	162.1

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

Acknowledgements

This work was supported financially by the Natural Science Foundation of Shaanxi Provinces of China (SJ08B11).

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