Tetra­aqua­bis­(N,N-dimethyl­formamide-κO)zinc(II) bis­[(2-{3-[2-(carboxyl­ato­meth­oxy-κ2O,O′)phen­yl]pyrazol-1-yl-κN2}acetato-κO)chloridozincate(II)]

Yang, J.; Shen, L.; Ji, C.; Shen, X.-F.; Yang, G.-W.

doi:10.1107/S1600536812023045

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m817

doi:10.1107/S1600536812023045

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Tetraaquabis(N,N-dimethylformamide-κO)zinc(II) bis[(2-{3-[2-(carboxylatomethoxy-κ²O,O′)phenyl]pyrazol-1-yl-κN²}acetato-κO)chloridozincate(II)]

Jie Yang,^a Lei Shen,^a Cheng Ji,^a Xiao-Feng Shen ^a and Gao-Weng Yang ^a ^*

^aDepartment of Chemistry & Materials Engineering, Jiangsu Laboratory of Advanced Functional Materials, Changshu Institute of Technology, Changshu 215500, Jiangsu, People's Republic of China
^*Correspondence e-mail: ygwsx@126.com

(Received 28 March 2012; accepted 20 May 2012; online 26 May 2012)

The asymmetric unit of the title compound, [Zn(C₃H₇NO)₂(H₂O)₄][Zn(C₁₃H₁₀N₂O₅)Cl]₂, is composed of a single anion and half a cation. The Zn^II atom in the monoanion has a distorted triganol–pyramidal geometry, being coordinated by three O atoms and one N atom from one 2-{3-[2-(carboxylatomethoxy)phenyl]pyrazol-1-yl}acetate ligand and one Cl atom. In the dication, the Zn^II atom is located on an inversion center and is coordinated by six O atoms in a slightly distorted octahedral geometry. In the crystal, the ions are linked by O—H⋯O hydrogen bonds, forming a two-dimensional network lying parallel to the ab plane. There are also C—H⋯O and C—H⋯Cl interactions present, which lead to the formation of a three-dimensional structure.

Related literature

For potential applications of pyrazole derivatives in advanced materials, see: Su et al. (2000 ); Tong et al. (2003 ). For the τ-descriptor of penta-coordinated metal atoms, see: Addison et al. (1984 ).

Experimental

Crystal data

[Zn(C₃H₇NO)₂(H₂O)₄][Zn(C₁₃H₁₀N₂O₅)Cl]₂
M_r = 1033.79
Triclinic, $[P \overline 1]$
a = 8.0040 (16) Å
b = 8.7276 (17) Å
c = 15.782 (3) Å
α = 90.06 (3)°
β = 101.22 (3)°
γ = 107.95 (3)°
V = 1026.6 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.95 mm⁻¹
T = 291 K
0.25 × 0.22 × 0.21 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.642, T_max = 0.686
10740 measured reflections
4704 independent reflections
3632 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.168
S = 1.07
4704 reflections
265 parameters
23 restraints
H-atom parameters constrained
Δρ_max = 1.99 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7B⋯O3ⁱ	0.96	1.83	2.710 (5)	151
O8—H8B⋯O2ⁱⁱ	0.96	2.21	2.941 (5)	132
O8—H8C⋯O5ⁱⁱⁱ	0.96	1.91	2.715 (5)	140
C2—H2A⋯Cl1^iv	0.93	2.79	3.668 (5)	159
C10—H10B⋯O5^v	0.97	2.59	3.511 (6)	159
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y-1, z; (iii) x+1, y, z; (iv) -x+1, -y+2, -z+1; (v) x+1, y+1, z.

Data collection: CrystalClear (Rigaku/MSC, 2001 ); 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) and CrystalStructure (Rigaku/MSC, 2004 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812023045/su2397sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023045/su2397Isup2.hkl

checkCIF report

Comment top

Coordination compounds containing a pyrazole group have been the subject of an intense research effort in recent years, owing to their unique structures and their potential applications in advanced materials (Su et al., 2000; Tong et al., 2003). Pyrazole-derived ligands, such as [3-(2-Carboxymethoxy-phenyl)-pyrazol-1-yl]-acetic acid, have been the subject of limited studies with metal ions, and no coordination complexes have been reported to date. The title ligand comprises N atoms of the pyrazole group and O atoms of the carboxylate, which should display flexible coordination behaviour.

The molecular structure of the title compound is shown in Fig. 1. In the dication atom Zn1 is located on an inversion center. It is coordinated by four O atoms from four water molecules and two O atoms from two DMF molecules, forming a slightly distorted octahedron.

In the monoanion atom Zn2 is coordinated by one nitrogen atom (N1) from the pyrazolyl, three oxygen atoms (O1, O2, O4) from the carboxylate groups and one chlorine atom, leading to a highly distorted trigonal bipyramidal geometry [the τ factor is 0.69; for perfect SP τ = 0, while for perfect TBP τ = 1.0 (Addison et al., 1984). The ligand is chelated to the zinc(II) atom through a carboxylate bridge (O2, O4), a phenoxide group (O1) and a pyrazole nitrogen atom (N1) to form one five-membered and two six-membered chelate rings.

In the crystal, the ions are linked by O-H···O hydrogen-bonds, to form a two-dimensional network lying parallel to (001). There are also C-H···O and C-H···Cl interactions present leading to the formation of a three-dimensional structure (Table 1 and Fig. 2).

Related literature top

Forpotential applications of pyrazole derivatives in advanced materials, see: Su et al. (2000); Tong et al. (2003). For the τ-descriptor of penta-coordinated metal atoms, see: Addison et al. (1984).

Experimental top

The title compound was synthesized by the reaction of [3-(2-Carboxymethoxy-phenyl)-pyrazol-1-yl]-acetic acid (0.0552 g, 0.2 mmol) and ZnCl₂^.4H₂O (0.0209 mg, 0.1 mmol) in DMF (5 mL). The mixture was sealed in a 25 ml Teflon lined stainless steel container, which was heated at 363 K for 48 h and then cooled to room temperature. Colourless block-like crystals were obtained in ca. 64% yield based on Zn. Analysis, found: C, 28.55; H, 4.08; N, 24.57%. calculated: C, 28.57; H, 4.04; N, 24.55%.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalClear (Rigaku/MSC, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and CrystalStructure (Rigaku/MSC, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure for title compound, showing the atom numbering. Displacement ellipsoids are drawn at the 30% probability level [symmetry code: (a) = -x+2, -y, -z].
	Fig. 2. A view along the a axis of the crystal packing of the title compound, with the hydrogen bonds shown as dashed lines - see Table 1 for details.

Tetraaquabis(N,N-dimethylformamide-κO)zinc(II) bis[(2-{3-[2-(carboxylatomethoxy-κ²O,O')phenyl]pyrazol-1- yl-κN²}acetato-κO)chloridozincate(II)] top

Crystal data top

[Zn(C₃H₇NO)₂(H₂O)₄][Zn(C₁₃H₁₀N₂O₅)Cl]₂	Z = 1
M_r = 1033.79	F(000) = 528
Triclinic, P1	D_x = 1.672 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0040 (16) Å	Cell parameters from 10740 reflections
b = 8.7276 (17) Å	θ = 3.1–27.5°
c = 15.782 (3) Å	µ = 1.95 mm⁻¹
α = 90.06 (3)°	T = 291 K
β = 101.22 (3)°	Block, colourless
γ = 107.95 (3)°	0.25 × 0.22 × 0.21 mm
V = 1026.6 (3) Å³

Data collection top

Rigaku Mercury diffractometer	4704 independent reflections
Radiation source: fine-focus sealed tube	3632 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.642, T_max = 0.686	k = −11→11
10740 measured reflections	l = −20→20

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
4704 reflections	(Δ/σ)_max < 0.001
265 parameters	Δρ_max = 1.99 e Å⁻³
23 restraints	Δρ_min = −0.73 e Å⁻³

Crystal data top

[Zn(C₃H₇NO)₂(H₂O)₄][Zn(C₁₃H₁₀N₂O₅)Cl]₂	γ = 107.95 (3)°
M_r = 1033.79	V = 1026.6 (3) Å³
Triclinic, P1	Z = 1
a = 8.0040 (16) Å	Mo Kα radiation
b = 8.7276 (17) Å	µ = 1.95 mm⁻¹
c = 15.782 (3) Å	T = 291 K
α = 90.06 (3)°	0.25 × 0.22 × 0.21 mm
β = 101.22 (3)°

Data collection top

Rigaku Mercury diffractometer	4704 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3632 reflections with I > 2σ(I)
T_min = 0.642, T_max = 0.686	R_int = 0.051
10740 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	23 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 1.07	Δρ_max = 1.99 e Å⁻³
4704 reflections	Δρ_min = −0.73 e Å⁻³
265 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
Zn2	0.28061 (6)	0.71444 (5)	0.29770 (3)	0.0271 (2)
Cl1	0.04523 (14)	0.78125 (14)	0.32248 (8)	0.0415 (4)
O1	0.2909 (4)	0.5528 (3)	0.41252 (18)	0.0343 (9)
O2	0.3455 (4)	0.8648 (4)	0.20287 (18)	0.0371 (9)
O3	0.5276 (4)	1.0071 (5)	0.1224 (2)	0.0509 (13)
O4	0.2013 (4)	0.4924 (3)	0.24461 (19)	0.0365 (9)
O5	0.0503 (4)	0.2338 (4)	0.2575 (2)	0.0459 (11)
N1	0.5313 (4)	0.8109 (4)	0.3703 (2)	0.0283 (10)
N2	0.6622 (4)	0.9126 (4)	0.3366 (2)	0.0301 (10)
C1	0.7964 (5)	1.0017 (5)	0.3987 (3)	0.0361 (12)
C2	0.7530 (6)	0.9617 (5)	0.4766 (3)	0.0350 (12)
C3	0.5845 (5)	0.8392 (4)	0.4578 (2)	0.0249 (11)
C4	0.4840 (5)	0.7501 (5)	0.5203 (3)	0.0277 (11)
C5	0.5382 (6)	0.8039 (5)	0.6081 (3)	0.0336 (12)
C6	0.4588 (7)	0.7199 (6)	0.6715 (3)	0.0413 (16)
C7	0.3213 (7)	0.5759 (6)	0.6478 (3)	0.0432 (16)
C8	0.2595 (6)	0.5178 (5)	0.5621 (3)	0.0348 (12)
C9	0.3411 (5)	0.6049 (5)	0.4985 (2)	0.0273 (11)
C10	0.6618 (6)	0.9009 (6)	0.2440 (3)	0.0398 (14)
C11	0.4999 (5)	0.9281 (5)	0.1858 (3)	0.0339 (12)
C12	0.1551 (5)	0.4021 (4)	0.3845 (3)	0.0281 (11)
C13	0.1363 (6)	0.3744 (5)	0.2887 (3)	0.0348 (12)
Zn1	1.00000	0.00000	0.00000	0.0325 (2)
O6	1.0708 (8)	0.2476 (5)	−0.0070 (4)	0.094 (2)
O7	0.7437 (5)	−0.0088 (7)	0.0101 (2)	0.0810 (19)
O8	1.0867 (5)	0.0342 (4)	0.13520 (19)	0.0494 (11)
N3	1.2254 (6)	0.4929 (5)	−0.0348 (3)	0.0660 (18)
C14	1.1206 (6)	0.3353 (5)	−0.0562 (3)	0.101 (3)
C15	1.3142 (14)	0.5932 (12)	0.0394 (5)	0.117 (4)
C16	1.2371 (14)	0.5717 (13)	−0.1167 (5)	0.127 (5)
H1A	0.90130	1.07770	0.39000	0.0430*
H2A	0.82010	1.00570	0.53090	0.0420*
H5A	0.63130	0.90010	0.62420	0.0400*
H6A	0.49700	0.75920	0.72910	0.0500*
H7A	0.26940	0.51700	0.69030	0.0520*
H8A	0.16510	0.42230	0.54690	0.0420*
H10A	0.66620	0.79470	0.22870	0.0480*
H10B	0.76960	0.97980	0.23300	0.0480*
H12A	0.04210	0.40420	0.39730	0.0340*
H12B	0.18820	0.31550	0.41460	0.0340*
H7B	0.66940	−0.02460	−0.04690	0.1210*
H7C	0.74740	0.09090	0.03730	0.1210*
H8B	1.21120	0.04140	0.15010	0.0740*
H8C	1.07190	0.13250	0.15470	0.0740*
H14A	1.08940	0.28160	−0.11290	0.1510*
H15A	1.30250	0.53170	0.08960	0.1750*
H15B	1.26260	0.67830	0.04230	0.1750*
H15C	1.43890	0.63880	0.03760	0.1750*
H16A	1.17280	0.49420	−0.16430	0.1900*
H16B	1.36070	0.61470	−0.12100	0.1900*
H16C	1.18550	0.65770	−0.11810	0.1900*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn2	0.0249 (3)	0.0290 (3)	0.0234 (3)	0.0051 (2)	0.0009 (2)	0.0017 (2)
Cl1	0.0314 (5)	0.0477 (7)	0.0473 (7)	0.0147 (5)	0.0092 (5)	−0.0004 (5)
O1	0.0401 (16)	0.0295 (15)	0.0255 (14)	0.0018 (12)	0.0031 (12)	0.0017 (12)
O2	0.0267 (14)	0.0531 (19)	0.0271 (15)	0.0065 (13)	0.0048 (12)	0.0146 (14)
O3	0.0330 (17)	0.083 (3)	0.0349 (18)	0.0130 (17)	0.0115 (14)	0.0271 (17)
O4	0.0455 (17)	0.0321 (16)	0.0290 (15)	0.0076 (13)	0.0084 (13)	−0.0017 (12)
O5	0.0502 (19)	0.0320 (17)	0.0456 (19)	−0.0007 (14)	0.0089 (15)	−0.0144 (14)
N1	0.0214 (15)	0.0339 (18)	0.0270 (17)	0.0061 (14)	0.0030 (13)	0.0041 (14)
N2	0.0237 (16)	0.0361 (19)	0.0286 (18)	0.0079 (14)	0.0033 (14)	0.0075 (14)
C1	0.025 (2)	0.033 (2)	0.040 (2)	−0.0009 (17)	−0.0014 (18)	0.0049 (19)
C2	0.029 (2)	0.034 (2)	0.034 (2)	0.0038 (17)	−0.0023 (17)	−0.0019 (18)
C3	0.0261 (18)	0.0230 (18)	0.0244 (19)	0.0099 (15)	−0.0013 (15)	0.0002 (15)
C4	0.0262 (19)	0.029 (2)	0.028 (2)	0.0126 (16)	−0.0004 (16)	0.0002 (16)
C5	0.039 (2)	0.036 (2)	0.024 (2)	0.0140 (18)	−0.0012 (17)	−0.0048 (17)
C6	0.046 (3)	0.053 (3)	0.026 (2)	0.019 (2)	0.0041 (19)	−0.004 (2)
C7	0.046 (3)	0.058 (3)	0.030 (2)	0.017 (2)	0.017 (2)	0.013 (2)
C8	0.035 (2)	0.037 (2)	0.031 (2)	0.0090 (19)	0.0075 (18)	0.0018 (18)
C9	0.029 (2)	0.032 (2)	0.0230 (19)	0.0133 (17)	0.0040 (16)	0.0000 (16)
C10	0.029 (2)	0.056 (3)	0.035 (2)	0.012 (2)	0.0103 (18)	0.013 (2)
C11	0.029 (2)	0.045 (2)	0.026 (2)	0.0102 (19)	0.0038 (17)	0.0036 (18)
C12	0.0272 (19)	0.0220 (19)	0.032 (2)	0.0034 (15)	0.0057 (16)	0.0013 (16)
C13	0.031 (2)	0.034 (2)	0.040 (2)	0.0138 (18)	0.0027 (18)	−0.0043 (19)
Zn1	0.0342 (4)	0.0339 (4)	0.0301 (4)	0.0116 (3)	0.0071 (3)	0.0034 (3)
O6	0.133 (4)	0.050 (3)	0.098 (4)	0.022 (3)	0.030 (3)	0.031 (2)
O7	0.050 (2)	0.177 (5)	0.0319 (19)	0.058 (3)	0.0093 (17)	0.007 (2)
O8	0.070 (2)	0.061 (2)	0.0268 (16)	0.0414 (19)	−0.0013 (15)	−0.0040 (15)
N3	0.073 (3)	0.039 (2)	0.090 (4)	0.014 (2)	0.032 (3)	0.002 (2)
C14	0.116 (5)	0.069 (4)	0.113 (5)	0.017 (4)	0.031 (4)	0.004 (4)
C15	0.168 (8)	0.130 (7)	0.066 (5)	0.082 (6)	0.001 (5)	−0.018 (5)
C16	0.157 (9)	0.163 (9)	0.052 (5)	0.049 (7)	0.005 (5)	0.022 (5)

Geometric parameters (Å, º) top

Zn2—Cl1	2.2373 (14)	C1—C2	1.359 (7)
Zn2—O1	2.302 (3)	C2—C3	1.416 (6)
Zn2—O2	2.029 (3)	C3—C4	1.466 (6)
Zn2—O4	1.973 (3)	C4—C5	1.403 (7)
Zn2—N1	2.027 (3)	C4—C9	1.409 (6)
Zn1—O6	2.067 (4)	C5—C6	1.380 (7)
Zn1—O7	2.066 (4)	C6—C7	1.385 (7)
Zn1—O8	2.102 (3)	C7—C8	1.384 (7)
Zn1—O6ⁱ	2.067 (4)	C8—C9	1.401 (6)
Zn1—O7ⁱ	2.066 (4)	C10—C11	1.519 (7)
Zn1—O8ⁱ	2.102 (3)	C12—C13	1.502 (7)
O1—C9	1.372 (4)	C1—H1A	0.9300
O1—C12	1.427 (5)	C2—H2A	0.9300
O2—C11	1.271 (5)	C5—H5A	0.9300
O3—C11	1.233 (6)	C6—H6A	0.9300
O4—C13	1.276 (5)	C7—H7A	0.9300
O5—C13	1.252 (5)	C8—H8A	0.9300
O6—C14	1.132 (7)	C10—H10B	0.9700
O7—H7B	0.9600	C10—H10A	0.9700
O7—H7C	0.9600	C12—H12B	0.9700
O8—H8C	0.9600	C12—H12A	0.9700
O8—H8B	0.9600	C14—H14A	0.9600
N1—N2	1.347 (5)	C15—H15A	0.9600
N1—C3	1.362 (4)	C15—H15B	0.9600
N2—C1	1.339 (6)	C15—H15C	0.9600
N2—C10	1.464 (6)	C16—H16A	0.9600
N3—C15	1.390 (10)	C16—H16B	0.9600
N3—C16	1.470 (10)	C16—H16C	0.9600
N3—C14	1.374 (6)

Cl1—Zn2—O1	94.96 (9)	C3—C4—C5	119.3 (4)
Cl1—Zn2—O2	99.10 (11)	C4—C5—C6	122.6 (4)
Cl1—Zn2—O4	110.29 (11)	C5—C6—C7	118.8 (4)
Cl1—Zn2—N1	122.65 (10)	C6—C7—C8	121.3 (4)
O1—Zn2—O2	164.05 (13)	C7—C8—C9	119.1 (4)
O1—Zn2—O4	74.99 (11)	O1—C9—C4	116.2 (3)
O1—Zn2—N1	75.37 (12)	O1—C9—C8	122.5 (4)
O2—Zn2—O4	106.75 (13)	C4—C9—C8	121.2 (3)
O2—Zn2—N1	90.64 (13)	N2—C10—C11	114.2 (4)
O4—Zn2—N1	120.51 (14)	O2—C11—C10	119.1 (4)
O7—Zn1—O7ⁱ	180.00	O2—C11—O3	124.1 (4)
O7—Zn1—O8ⁱ	89.06 (15)	O3—C11—C10	116.8 (4)
O6ⁱ—Zn1—O8	90.8 (2)	O1—C12—C13	108.3 (3)
O7ⁱ—Zn1—O8	89.06 (15)	O4—C13—O5	124.6 (4)
O8—Zn1—O8ⁱ	180.00	O5—C13—C12	115.8 (4)
O6ⁱ—Zn1—O7ⁱ	90.4 (2)	O4—C13—C12	119.6 (4)
O6ⁱ—Zn1—O8ⁱ	89.2 (2)	C2—C1—H1A	126.00
O7ⁱ—Zn1—O8ⁱ	90.94 (15)	N2—C1—H1A	126.00
O7—Zn1—O8	90.94 (15)	C1—C2—H2A	127.00
O6ⁱ—Zn1—O7	89.6 (2)	C3—C2—H2A	127.00
O6—Zn1—O7	90.4 (2)	C6—C5—H5A	119.00
O6—Zn1—O8	89.2 (2)	C4—C5—H5A	119.00
O6—Zn1—O6ⁱ	180.00	C5—C6—H6A	121.00
O6—Zn1—O7ⁱ	89.6 (2)	C7—C6—H6A	121.00
O6—Zn1—O8ⁱ	90.8 (2)	C8—C7—H7A	119.00
Zn2—O1—C12	106.2 (2)	C6—C7—H7A	119.00
C9—O1—C12	120.6 (3)	C7—C8—H8A	120.00
Zn2—O1—C9	125.9 (2)	C9—C8—H8A	120.00
Zn2—O2—C11	127.5 (3)	N2—C10—H10A	109.00
Zn2—O4—C13	119.3 (3)	C11—C10—H10B	109.00
Zn1—O6—C14	135.3 (5)	H10A—C10—H10B	108.00
H7B—O7—H7C	109.00	N2—C10—H10B	109.00
Zn1—O7—H7C	110.00	C11—C10—H10A	109.00
Zn1—O7—H7B	109.00	C13—C12—H12A	110.00
H8B—O8—H8C	109.00	O1—C12—H12B	110.00
Zn1—O8—H8B	109.00	O1—C12—H12A	110.00
Zn1—O8—H8C	109.00	C13—C12—H12B	110.00
N2—N1—C3	106.0 (3)	H12A—C12—H12B	108.00
Zn2—N1—C3	129.2 (3)	O6—C14—N3	123.6 (5)
Zn2—N1—N2	120.7 (2)	O6—C14—H14A	111.00
N1—N2—C1	111.5 (3)	N3—C14—H14A	125.00
N1—N2—C10	121.0 (3)	N3—C15—H15A	109.00
C1—N2—C10	126.8 (4)	N3—C15—H15B	110.00
C14—N3—C16	106.6 (5)	N3—C15—H15C	109.00
C14—N3—C15	138.4 (6)	H15A—C15—H15B	109.00
C15—N3—C16	115.0 (6)	H15A—C15—H15C	109.00
N2—C1—C2	108.2 (4)	H15B—C15—H15C	109.00
C1—C2—C3	105.7 (4)	N3—C16—H16A	109.00
N1—C3—C2	108.6 (3)	N3—C16—H16B	109.00
N1—C3—C4	124.3 (3)	N3—C16—H16C	109.00
C2—C3—C4	127.0 (3)	H16A—C16—H16B	110.00
C3—C4—C9	123.7 (4)	H16A—C16—H16C	110.00
C5—C4—C9	116.9 (4)	H16B—C16—H16C	109.00

Cl1—Zn2—O1—C9	−69.9 (3)	Zn2—N1—N2—C10	−29.1 (5)
Cl1—Zn2—O1—C12	79.9 (2)	C3—N1—N2—C1	1.0 (4)
O4—Zn2—O1—C9	−179.6 (4)	Zn2—N1—N2—C1	160.1 (3)
O4—Zn2—O1—C12	−29.8 (2)	N2—N1—C3—C4	−177.7 (4)
N1—Zn2—O1—C9	52.6 (3)	C3—N1—N2—C10	171.8 (4)
N1—Zn2—O1—C12	−157.7 (3)	Zn2—N1—C3—C2	−156.8 (3)
Cl1—Zn2—O2—C11	150.2 (3)	Zn2—N1—C3—C4	25.6 (6)
O4—Zn2—O2—C11	−95.3 (4)	N2—N1—C3—C2	−0.1 (4)
N1—Zn2—O2—C11	27.0 (4)	N1—N2—C10—C11	61.6 (5)
Cl1—Zn2—O4—C13	−66.6 (4)	C1—N2—C10—C11	−129.1 (4)
O1—Zn2—O4—C13	23.2 (3)	C10—N2—C1—C2	−171.6 (4)
O2—Zn2—O4—C13	−173.3 (3)	N1—N2—C1—C2	−1.4 (5)
N1—Zn2—O4—C13	85.7 (4)	C15—N3—C14—O6	6.5 (13)
Cl1—Zn2—N1—N2	−111.0 (3)	C16—N3—C14—O6	−171.4 (7)
Cl1—Zn2—N1—C3	42.7 (4)	N2—C1—C2—C3	1.3 (5)
O1—Zn2—N1—N2	162.5 (3)	C1—C2—C3—N1	−0.7 (5)
O1—Zn2—N1—C3	−43.8 (3)	C1—C2—C3—C4	176.8 (4)
O2—Zn2—N1—N2	−9.8 (3)	N1—C3—C4—C5	−171.2 (4)
O2—Zn2—N1—C3	143.9 (3)	N1—C3—C4—C9	13.3 (6)
O4—Zn2—N1—N2	100.2 (3)	C2—C3—C4—C5	11.7 (7)
O4—Zn2—N1—C3	−106.1 (3)	C2—C3—C4—C9	−163.8 (4)
O7ⁱ—Zn1—O6—C14	60.2 (8)	C3—C4—C9—O1	−3.7 (6)
O8ⁱ—Zn1—O6—C14	−30.8 (8)	C3—C4—C5—C6	−175.1 (5)
O7—Zn1—O6—C14	−119.8 (8)	C9—C4—C5—C6	0.7 (7)
O8—Zn1—O6—C14	149.3 (8)	C5—C4—C9—C8	−0.9 (6)
C12—O1—C9—C4	176.1 (4)	C3—C4—C9—C8	174.6 (4)
C9—O1—C12—C13	−177.2 (4)	C5—C4—C9—O1	−179.3 (4)
C12—O1—C9—C8	−2.2 (6)	C4—C5—C6—C7	0.7 (8)
Zn2—O1—C12—C13	31.1 (4)	C5—C6—C7—C8	−1.8 (8)
Zn2—O1—C9—C4	−38.1 (5)	C6—C7—C8—C9	1.6 (8)
Zn2—O1—C9—C8	143.6 (4)	C7—C8—C9—O1	178.1 (4)
Zn2—O2—C11—O3	173.3 (3)	C7—C8—C9—C4	−0.2 (7)
Zn2—O2—C11—C10	−4.1 (6)	N2—C10—C11—O2	−42.3 (6)
Zn2—O4—C13—O5	165.2 (4)	N2—C10—C11—O3	140.2 (4)
Zn2—O4—C13—C12	−12.3 (6)	O1—C12—C13—O4	−16.5 (6)
Zn1—O6—C14—N3	−152.5 (5)	O1—C12—C13—O5	165.7 (4)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O3ⁱⁱ	0.96	1.83	2.710 (5)	151
O8—H8B···O2ⁱⁱⁱ	0.96	2.21	2.941 (5)	132
O8—H8C···O5^iv	0.96	1.91	2.715 (5)	140
C2—H2A···Cl1^v	0.93	2.79	3.668 (5)	159
C10—H10B···O5^vi	0.97	2.59	3.511 (6)	159

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

Experimental details

Crystal data
Chemical formula	[Zn(C₃H₇NO)₂(H₂O)₄][Zn(C₁₃H₁₀N₂O₅)Cl]₂
M_r	1033.79
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	8.0040 (16), 8.7276 (17), 15.782 (3)
α, β, γ (°)	90.06 (3), 101.22 (3), 107.95 (3)
V (Å³)	1026.6 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.95
Crystal size (mm)	0.25 × 0.22 × 0.21

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.642, 0.686
No. of measured, independent and observed [I > 2σ(I)] reflections	10740, 4704, 3632
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.168, 1.07
No. of reflections	4704
No. of parameters	265
No. of restraints	23
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.99, −0.73

Computer programs: CrystalClear (Rigaku/MSC, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and CrystalStructure (Rigaku/MSC, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O3ⁱ	0.96	1.83	2.710 (5)	151
O8—H8B···O2ⁱⁱ	0.96	2.21	2.941 (5)	132
O8—H8C···O5ⁱⁱⁱ	0.96	1.91	2.715 (5)	140
C2—H2A···Cl1^iv	0.93	2.79	3.668 (5)	159
C10—H10B···O5^v	0.97	2.59	3.511 (6)	159

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

Acknowledgements

This work was supported by the Foundation of Suzhou Science and Technology of Jiangsu Province of China (SYN201015) and the Key Laboratory of Advanced Functioal Materials of Jiangsu Province of China (No. 10KFJJ002).

References

Addison, A. W., Rao, T. N., Reedijk, J., Van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2001). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Su, W. P., Hong, M. C., Weng, J. B., Cao, R. & Lu, S. F. (2000). Angew. Chem. Int. Ed. 39, 2911–2914. Web of Science CrossRef CAS Google Scholar
Tong, M. L., Chen, X. M. & Batten, S. R. (2003). J. Am. Chem. Soc. 125, 16170–16171. Web of Science CSD CrossRef PubMed CAS Google Scholar

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