Diaqua­bis(cyclo­hexa­necarboxyl­ato)zinc(II) monohydrate

Zhang, Y.-W.; Wang, L.-J.; Hou, J.; Zeng, Q.-F.

doi:10.1107/S1600536809033479

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1147

doi:10.1107/S1600536809033479

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Diaquabis(cyclohexanecarboxylato)zinc(II) monohydrate

Yue-Wu Zhang,^a Li-Jun Wang,^a Jian Hou ^a and Qing-Fu Zeng ^a ^*

^aEngineering Research Center for Clean Production of Textile Dyeing and Printing, Ministry of Education, Wuhan 430073, People's Republic of China
^*Correspondence e-mail: qfzeng@wuse.edu.cn

(Received 20 August 2009; accepted 22 August 2009; online 29 August 2009)

In the title compound, [Zn(C₇H₁₁O₂)₂(H₂O)₂]·H₂O, the Zn^II atom (site symmetry $[\overline{1}]$ ) is four-coordinated by two O atoms from the cyclohexanecarboxylate anions and two O atoms from the water molecules, forming a slightly distorted square-planar coordination. The O atom of the uncoordinated water molecule lies on a crysatllographic twofold rotation axis. In the crystal, the components are linked by O—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For background, see: Cheng et al. (2006 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Zn(C₇H₁₁O₂)₂(H₂O)₂]·H₂O
M_r = 373.75
Monoclinic, P 2/c
a = 15.9045 (16) Å
b = 4.9295 (6) Å
c = 11.5335 (16) Å
β = 91.585 (6)°
V = 903.89 (19) Å³
Z = 2
Mo Kα radiation
μ = 1.39 mm⁻¹
T = 296 K
0.28 × 0.25 × 0.22 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.698, T_max = 0.750
4764 measured reflections
1752 independent reflections
1436 reflections with I > 2σ(I)
R_int = 0.032
200 standard reflections every 3 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.158
S = 1.07
1752 reflections
114 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.00 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O2	1.961 (3)
Zn1—O3	1.977 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7⋯O1	0.834 (10)	1.99 (3)	2.699 (4)	142 (5)
O3—H3D⋯O1ⁱ	0.846 (10)	2.53 (7)	3.132 (6)	129 (8)
O3—H3C⋯O7ⁱⁱ	0.853 (10)	2.17 (2)	2.997 (5)	164 (6)
Symmetry codes: (i) $[x, -y+1, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+2, -z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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 global, I. DOI: 10.1107/S1600536809033479/hb5057sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033479/hb5057Isup2.hkl

checkCIF report

Comment top

There has been much research interest in acid metal complexes due to their molecular architectures and biological activities (e.g. Cheng et al., 2006). In this work, we report here the crystal structure of the title compound, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). The Zn^II atom is four-coordinated by two O atoms from the cyclohexanecarboxylate and two O atoms from the water molecules, forming a slightly distorted square-planar coordination (Table 1). In the crystal, O—H···O hydrogen bonds (Table 2) link the components.

Related literature top

For background, see: Cheng et al. (2006). For reference structural data, see: Allen et al. (1987).

Experimental top

A mixture of cyclohexanecarboxylic acid (256 mg, 2 mmol) and ZnNO₃.6H₂O (1 mmol, 297 mg) in methanol (10 ml) was stirred for 2 h. After keeping the filtrate in air for 6 d, colourless blocks of (I) were formed.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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. The molecular structure of (I) showing 30% probability displacement ellipsoids. Atoms with the suffix A are generated by the symmetry code (1–x, 1–y, –z).

Diaquabis(cyclohexanecarboxylato)zinc(II) monohydrate top

Crystal data top

[Zn(C₇H₁₁O₂)₂(H₂O)₂]·H₂O	F(000) = 396
M_r = 373.75	D_x = 1.373 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 25 reflections
a = 15.9045 (16) Å	θ = 9–12°
b = 4.9295 (6) Å	µ = 1.39 mm⁻¹
c = 11.5335 (16) Å	T = 296 K
β = 91.585 (6)°	Block, colorless
V = 903.89 (19) Å³	0.28 × 0.25 × 0.22 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	1436 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.032
Graphite monochromator	θ_max = 26.0°, θ_min = 2.6°
ω/2θ scans	h = −18→19
Absorption correction: ψ scan (North et al., 1968)	k = −6→6
T_min = 0.698, T_max = 0.750	l = −12→14
4764 measured reflections	200 standard reflections every 3 reflections
1752 independent reflections	intensity decay: 1%

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0809P)² + 1.216P] where P = (F_o² + 2F_c²)/3
1752 reflections	(Δ/σ)_max = 0.003
114 parameters	Δρ_max = 1.00 e Å⁻³
4 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Zn(C₇H₁₁O₂)₂(H₂O)₂]·H₂O	V = 903.89 (19) Å³
M_r = 373.75	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 15.9045 (16) Å	µ = 1.39 mm⁻¹
b = 4.9295 (6) Å	T = 296 K
c = 11.5335 (16) Å	0.28 × 0.25 × 0.22 mm
β = 91.585 (6)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1436 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.032
T_min = 0.698, T_max = 0.750	200 standard reflections every 3 reflections
4764 measured reflections	intensity decay: 1%
1752 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	4 restraints
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 1.00 e Å⁻³
1752 reflections	Δρ_min = −0.37 e Å⁻³
114 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
C1	0.2156 (3)	0.3294 (12)	−0.0060 (4)	0.0586 (12)
H1A	0.2463	0.2824	−0.0747	0.070*
H1B	0.2126	0.5256	−0.0017	0.070*
C2	0.1273 (3)	0.2162 (13)	−0.0177 (4)	0.0711 (14)
H2A	0.0988	0.2966	−0.0847	0.085*
H2B	0.1301	0.0218	−0.0300	0.085*
C3	0.0779 (3)	0.2734 (13)	0.0889 (5)	0.0743 (15)
H3A	0.0709	0.4676	0.0980	0.089*
H3B	0.0226	0.1917	0.0810	0.089*
C4	0.1236 (3)	0.1592 (16)	0.1934 (5)	0.0832 (18)
H4A	0.1264	−0.0367	0.1864	0.100*
H4B	0.0925	0.2017	0.2622	0.100*
C5	0.2124 (3)	0.2720 (13)	0.2071 (4)	0.0661 (14)
H5A	0.2095	0.4653	0.2221	0.079*
H5B	0.2405	0.1867	0.2733	0.079*
C6	0.2630 (2)	0.2234 (9)	0.0999 (3)	0.0427 (9)
H6	0.2708	0.0274	0.0908	0.051*
C7	0.3485 (2)	0.3560 (8)	0.1063 (4)	0.0455 (9)
H7	0.475 (3)	0.722 (8)	0.205 (3)	0.058 (14)*
O1	0.3660 (3)	0.5302 (7)	0.1802 (4)	0.0755 (11)
O2	0.39946 (17)	0.2822 (6)	0.0283 (3)	0.0549 (8)
O3	0.4282 (3)	0.7551 (8)	−0.0904 (4)	0.0718 (10)
O7	0.5000	0.8302 (10)	0.2500	0.0775 (16)
Zn1	0.5000	0.5000	0.0000	0.0492 (3)
H3D	0.384 (3)	0.71 (2)	−0.127 (5)	0.18 (5)*
H3C	0.457 (3)	0.852 (11)	−0.136 (4)	0.076 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.045 (2)	0.085 (4)	0.046 (2)	−0.007 (2)	−0.0019 (18)	0.005 (2)
C2	0.048 (3)	0.097 (4)	0.067 (3)	−0.012 (3)	−0.011 (2)	−0.006 (3)
C3	0.037 (2)	0.094 (4)	0.092 (4)	−0.003 (2)	0.000 (2)	−0.010 (3)
C4	0.057 (3)	0.120 (5)	0.075 (3)	−0.017 (3)	0.026 (3)	0.004 (4)
C5	0.053 (3)	0.101 (4)	0.045 (2)	−0.002 (3)	0.005 (2)	0.002 (2)
C6	0.0374 (19)	0.046 (2)	0.045 (2)	−0.0065 (16)	0.0017 (16)	−0.0002 (17)
C7	0.041 (2)	0.041 (2)	0.054 (2)	−0.0016 (17)	−0.0066 (18)	0.0067 (19)
O1	0.065 (2)	0.074 (3)	0.086 (3)	−0.0155 (18)	−0.0144 (19)	−0.0217 (19)
O2	0.0323 (14)	0.0504 (17)	0.083 (2)	−0.0060 (12)	0.0125 (14)	0.0045 (15)
O3	0.060 (2)	0.066 (2)	0.089 (3)	−0.0020 (18)	−0.004 (2)	0.012 (2)
O7	0.047 (3)	0.041 (3)	0.143 (5)	0.000	−0.008 (3)	0.000
Zn1	0.0317 (4)	0.0478 (4)	0.0684 (5)	−0.0007 (3)	0.0066 (3)	0.0097 (3)

Geometric parameters (Å, º) top

C1—C6	1.511 (6)	C5—H5A	0.9700
C1—C2	1.513 (6)	C5—H5B	0.9700
C1—H1A	0.9700	C6—C7	1.509 (5)
C1—H1B	0.9700	C6—H6	0.9800
C2—C3	1.503 (7)	C7—O1	1.236 (5)
C2—H2A	0.9700	C7—O2	1.281 (5)
C2—H2B	0.9700	Zn1—O2	1.961 (3)
C3—C4	1.500 (8)	Zn1—O3	1.977 (4)
C3—H3A	0.9700	O3—H3D	0.846 (10)
C3—H3B	0.9700	O3—H3C	0.853 (10)
C4—C5	1.521 (7)	O7—H7	0.834 (10)
C4—H4A	0.9700	Zn1—O2ⁱ	1.961 (3)
C4—H4B	0.9700	Zn1—O3ⁱ	1.977 (4)
C5—C6	1.513 (6)

C6—C1—C2	112.6 (4)	C6—C5—H5A	109.3
C6—C1—H1A	109.1	C4—C5—H5A	109.3
C2—C1—H1A	109.1	C6—C5—H5B	109.3
C6—C1—H1B	109.1	C4—C5—H5B	109.3
C2—C1—H1B	109.1	H5A—C5—H5B	107.9
H1A—C1—H1B	107.8	C7—C6—C1	108.6 (3)
C3—C2—C1	111.3 (4)	C7—C6—C5	113.0 (4)
C3—C2—H2A	109.4	C1—C6—C5	110.0 (4)
C1—C2—H2A	109.4	C7—C6—H6	108.4
C3—C2—H2B	109.4	C1—C6—H6	108.4
C1—C2—H2B	109.4	C5—C6—H6	108.4
H2A—C2—H2B	108.0	O1—C7—O2	123.1 (4)
C4—C3—C2	109.5 (4)	O1—C7—C6	121.4 (4)
C4—C3—H3A	109.8	O2—C7—C6	115.5 (4)
C2—C3—H3A	109.8	C7—O2—Zn1	119.8 (3)
C4—C3—H3B	109.8	Zn1—O3—H3D	123 (6)
C2—C3—H3B	109.8	Zn1—O3—H3C	112 (4)
H3A—C3—H3B	108.2	H3D—O3—H3C	107.5 (17)
C3—C4—C5	112.0 (5)	O2—Zn1—O2ⁱ	180.0
C3—C4—H4A	109.2	O2—Zn1—O3	88.54 (15)
C5—C4—H4A	109.2	O2ⁱ—Zn1—O3	91.46 (15)
C3—C4—H4B	109.2	O2—Zn1—O3ⁱ	91.46 (15)
C5—C4—H4B	109.2	O2ⁱ—Zn1—O3ⁱ	88.54 (15)
H4A—C4—H4B	107.9	O3—Zn1—O3ⁱ	180.0
C6—C5—C4	111.7 (4)

C6—C1—C2—C3	56.4 (6)	C5—C6—C7—O1	−14.3 (6)
C1—C2—C3—C4	−56.7 (7)	C1—C6—C7—O2	−69.8 (5)
C2—C3—C4—C5	57.1 (7)	C5—C6—C7—O2	167.9 (4)
C3—C4—C5—C6	−56.2 (7)	O1—C7—O2—Zn1	−13.6 (6)
C2—C1—C6—C7	−177.8 (4)	C6—C7—O2—Zn1	164.1 (3)
C2—C1—C6—C5	−53.7 (6)	C7—O2—Zn1—O2ⁱ	115 (24)
C4—C5—C6—C7	174.6 (5)	C7—O2—Zn1—O3	−79.1 (3)
C4—C5—C6—C1	53.1 (6)	C7—O2—Zn1—O3ⁱ	100.9 (3)
C1—C6—C7—O1	107.9 (5)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O1	0.83 (1)	1.99 (3)	2.699 (4)	142 (5)
O3—H3D···O1ⁱⁱ	0.85 (1)	2.53 (7)	3.132 (6)	129 (8)
O3—H3C···O7ⁱⁱⁱ	0.85 (1)	2.17 (2)	2.997 (5)	164 (6)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₇H₁₁O₂)₂(H₂O)₂]·H₂O
M_r	373.75
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	296
a, b, c (Å)	15.9045 (16), 4.9295 (6), 11.5335 (16)
β (°)	91.585 (6)
V (Å³)	903.89 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.39
Crystal size (mm)	0.28 × 0.25 × 0.22

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.698, 0.750
No. of measured, independent and observed [I > 2σ(I)] reflections	4764, 1752, 1436
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.158, 1.07
No. of reflections	1752
No. of parameters	114
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.00, −0.37

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—O2

1.961 (3)

Zn1—O3

1.977 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O1	0.834 (10)	1.99 (3)	2.699 (4)	142 (5)
O3—H3D···O1ⁱ	0.846 (10)	2.53 (7)	3.132 (6)	129 (8)
O3—H3C···O7ⁱⁱ	0.853 (10)	2.17 (2)	2.997 (5)	164 (6)

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

Acknowledgements

The project was supported by the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, Educational Commission of Hubei Province (D20091703) and the Natural Science Foundation of Hubei Province (2008CDB038).

References

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