Diaqua­bis(4-formyl­benzoato-κO)zinc(II)

Deng, Z.-P.; Gao, S.; Huo, L.-H.; Ng, S.W.

doi:10.1107/S1600536808003152

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page m447

doi:10.1107/S1600536808003152

Open

access

Diaquabis(4-formylbenzoato-κO)zinc(II)

Zhao-Peng Deng,^a Shan Gao,^a Li-Hua Huo ^a and Seik Weng Ng ^b ^*

^aSchool of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 11 January 2008; accepted 28 January 2008; online 6 February 2008)

The Zn^II atom in the title compound, [Zn(C₈H₅O₃)₂(H₂O)₂], which lies on a twofold rotation axis, is coordinated by two monodentate carboxylate groups and two water molecules in a tetrahedral geometry; the geometry is distorted towards octahedral owing to two long Zn⋯O_carbonyl contacts [2.512 (2) Å]. Hydrogen-bonding interactions give rise to a three-dimensional network. The formyl group is disordered approximately equally over two positions.

Related literature

A pseudo-polymorph of the title compound containing a solvent water molecule exists in a P2/c modification, which features zinc in an unambiguous tetrahedral coordination geometry; see Deng et al. (2006 ).

Experimental

Crystal data

[Zn(C₈H₅O₃)₂(H₂O)₂]
M_r = 399.64
Monoclinic, C 2/c
a = 27.537 (1) Å
b = 5.0039 (2) Å
c = 12.0930 (6) Å
β = 110.039 (2)°
V = 1565.4 (1) Å³
Z = 4
Mo Kα radiation
μ = 1.61 mm⁻¹
T = 295 (2) K
0.34 × 0.26 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.532, T_max = 0.760
7203 measured reflections
1785 independent reflections
1448 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.082
S = 1.09
1785 reflections
132 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1W	1.983 (2)
Zn1—O1	2.005 (2)
Zn1—O2	2.512 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O1ⁱ	0.84 (1)	1.93 (1)	2.761 (2)	174 (3)
O1W—H1W2⋯O2ⁱⁱ	0.84 (1)	1.88 (1)	2.720 (2)	174 (3)
Symmetry codes: (i) $[-x+1, y-1, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808003152/bt2669sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808003152/bt2669Isup2.hkl

checkCIF report

Comment top

A pseuodpolymorph of the title compound containing a solvent water molecule was isolated from the reaction of zinc acetate and 4-formylbenzoic acid in the presence of sodium hydroxide (Deng et al., 2006). The reaction with pyridine in place of sodium hydroxide yielded the title polymorph.

Related literature top

A pseudopolymorph of the title compound containing a solvent water molecule exists in a P2/c modification, which features zinc in an unambiguous tetrahedral coordination geometry; see Deng et al. (2006).

Experimental top

Zinc diacetate dihydrate (2.2 g, 10 mmol) was added to anaqueous solution of 4-formylbenzoic acid (3.0 g, 20 mmol) that has earlier been treated with 1 ml pyridine to give a pH of 6. The solution was allowed to evaporate at room temperature; colorless prismatic crystals separated from the filtered solution after several days. C&N elemental analysis. Calc. C₁₆H₁₄O₈Zn: C 48.08, H3.53%. Found: C 48.06, H 3.56%.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. Anisotropic displacement parameter plot of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms as spheres of arbitrary radius.

Diaquabis(4-formylbenzoato-κO)zinc(II) top

Crystal data top

[Zn(C₈H₅O₃)₂(H₂O)₂]	F(000) = 816
M_r = 399.64	D_x = 1.696 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5776 reflections
a = 27.537 (1) Å	θ = 3.2–27.5°
b = 5.0039 (2) Å	µ = 1.61 mm⁻¹
c = 12.0930 (6) Å	T = 295 K
β = 110.039 (2)°	Block, colorless
V = 1565.4 (1) Å³	0.34 × 0.26 × 0.18 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1785 independent reflections
Radiation source: fine-focus sealed tube	1448 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −35→35
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −6→6
T_min = 0.532, T_max = 0.760	l = −15→15
7203 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0444P)² + 0.5739P] where P = (F_o² + 2F_c²)/3
1785 reflections	(Δ/σ)_max = 0.001
132 parameters	Δρ_max = 0.59 e Å⁻³
3 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

[Zn(C₈H₅O₃)₂(H₂O)₂]	V = 1565.4 (1) Å³
M_r = 399.64	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 27.537 (1) Å	µ = 1.61 mm⁻¹
b = 5.0039 (2) Å	T = 295 K
c = 12.0930 (6) Å	0.34 × 0.26 × 0.18 mm
β = 110.039 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1785 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1448 reflections with I > 2σ(I)
T_min = 0.532, T_max = 0.760	R_int = 0.034
7203 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	3 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.59 e Å⁻³
1785 reflections	Δρ_min = −0.38 e Å⁻³
132 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.5000	0.07300 (7)	0.7500	0.03500 (15)
O1W	0.52887 (7)	−0.2045 (3)	0.67306 (15)	0.0420 (4)
O1	0.44080 (6)	0.3312 (3)	0.69827 (13)	0.0347 (4)
O2	0.46297 (6)	0.2522 (3)	0.54394 (14)	0.0396 (4)
O3	0.28940 (13)	1.2782 (7)	0.2481 (3)	0.0537 (13)	0.508 (5)
O3'	0.25060 (16)	1.2320 (10)	0.3707 (4)	0.0757 (18)	0.492 (5)
H1W1	0.5398 (10)	−0.346 (3)	0.7104 (19)	0.051 (8)*
H1W2	0.5313 (11)	−0.208 (5)	0.6055 (12)	0.062 (9)*
C1	0.43534 (8)	0.3714 (4)	0.59025 (19)	0.0299 (5)
C2	0.39595 (8)	0.5736 (4)	0.52428 (18)	0.0283 (4)
C3	0.35743 (9)	0.6552 (5)	0.5675 (2)	0.0396 (5)
H3	0.3554	0.5809	0.6363	0.048*
C4	0.32199 (9)	0.8489 (6)	0.5070 (2)	0.0444 (6)
H4	0.2963	0.9046	0.5357	0.053*
C5	0.32469 (8)	0.9588 (4)	0.4047 (2)	0.0348 (5)
C6	0.36283 (9)	0.8759 (5)	0.3612 (2)	0.0373 (5)
H6	0.3645	0.9485	0.2919	0.045*
C7	0.39830 (9)	0.6846 (5)	0.4219 (2)	0.0358 (5)
H7	0.4240	0.6303	0.3932	0.043*
C8	0.28767 (9)	1.1697 (5)	0.3399 (2)	0.0460 (6)
H8	0.2621	1.2233	0.3691	0.055*	0.508 (5)
H8'	0.2924	1.2551	0.2760	0.055*	0.492 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0384 (2)	0.02089 (19)	0.0487 (3)	0.000	0.01878 (17)	0.000
O1W	0.0676 (11)	0.0278 (8)	0.0359 (10)	0.0119 (8)	0.0247 (8)	0.0052 (7)
O1	0.0445 (9)	0.0313 (8)	0.0266 (8)	−0.0005 (7)	0.0101 (6)	0.0054 (6)
O2	0.0460 (9)	0.0351 (8)	0.0355 (9)	0.0121 (7)	0.0111 (7)	−0.0003 (7)
O3	0.051 (2)	0.055 (2)	0.052 (2)	0.0156 (17)	0.0141 (17)	0.0215 (19)
O3'	0.058 (3)	0.086 (4)	0.079 (3)	0.036 (2)	0.019 (2)	0.008 (3)
C1	0.0335 (11)	0.0244 (10)	0.0276 (11)	−0.0051 (8)	0.0051 (8)	−0.0011 (8)
C2	0.0318 (10)	0.0251 (10)	0.0264 (10)	−0.0022 (8)	0.0078 (8)	−0.0022 (9)
C3	0.0413 (12)	0.0478 (13)	0.0338 (13)	0.0033 (11)	0.0180 (10)	0.0055 (10)
C4	0.0356 (12)	0.0557 (15)	0.0458 (15)	0.0093 (11)	0.0190 (10)	−0.0025 (12)
C5	0.0314 (11)	0.0341 (12)	0.0337 (12)	0.0016 (9)	0.0044 (9)	−0.0032 (10)
C6	0.0418 (12)	0.0386 (12)	0.0322 (12)	0.0061 (10)	0.0135 (9)	0.0093 (10)
C7	0.0417 (12)	0.0366 (11)	0.0342 (12)	0.0106 (10)	0.0196 (10)	0.0037 (10)
C8	0.0368 (13)	0.0432 (13)	0.0497 (16)	0.0091 (11)	0.0043 (11)	−0.0036 (12)

Geometric parameters (Å, º) top

Zn1—O1w	1.983 (2)	C2—C3	1.395 (3)
Zn1—O1wⁱ	1.983 (2)	C3—C4	1.392 (4)
Zn1—O1ⁱ	2.005 (2)	C3—H3	0.9300
Zn1—O1	2.005 (2)	C4—C5	1.379 (4)
Zn1—O2	2.512 (2)	C4—H4	0.9300
O1W—H1W1	0.84 (1)	C5—C6	1.389 (3)
O1W—H1W2	0.84 (1)	C5—C8	1.490 (3)
O1—C1	1.279 (3)	C6—C7	1.385 (3)
O2—C1	1.241 (3)	C6—H6	0.9300
O3—C8	1.251 (4)	C7—H7	0.9300
O3'—C8	1.240 (5)	C8—H8	0.9300
C1—C2	1.498 (3)	C8—H8'	0.9300
C2—C7	1.379 (3)

O1W—Zn1—O1Wⁱ	91.11 (10)	C5—C4—H4	119.8
O1W—Zn1—O1ⁱ	100.59 (7)	C3—C4—H4	119.8
O1Wⁱ—Zn1—O1ⁱ	135.95 (7)	C4—C5—C6	120.0 (2)
O1W—Zn1—O1	135.95 (7)	C4—C5—C8	121.1 (2)
O1Wⁱ—Zn1—O1	100.59 (7)	C6—C5—C8	118.9 (2)
O1ⁱ—Zn1—O1	99.75 (9)	C7—C6—C5	119.6 (2)
Zn1—O1W—H1W1	117.8 (17)	C7—C6—H6	120.2
Zn1—O1W—H1W2	130.4 (17)	C5—C6—H6	120.2
H1W1—O1W—H1W2	111.8 (16)	C2—C7—C6	120.8 (2)
C1—O1—Zn1	102.62 (13)	C2—C7—H7	119.6
O2—C1—O1	120.65 (19)	C6—C7—H7	119.6
O2—C1—C2	121.9 (2)	O3—C8—O3'	116.3 (3)
O1—C1—C2	117.42 (19)	O3—C8—C5	123.1 (3)
C7—C2—C3	119.6 (2)	O3'—C8—C5	120.4 (3)
C7—C2—C1	120.14 (19)	O3—C8—H8	118.4
C3—C2—C1	120.2 (2)	C5—C8—H8	118.4
C4—C3—C2	119.5 (2)	O3'—C8—H8'	119.8
C4—C3—H3	120.2	C5—C8—H8'	119.8
C2—C3—H3	120.2	H8—C8—H8'	121.5
C5—C4—C3	120.4 (2)

O1W—Zn1—O1—C1	−27.75 (17)	C3—C4—C5—C6	0.1 (4)
O1Wⁱ—Zn1—O1—C1	−130.56 (13)	C3—C4—C5—C8	−178.9 (2)
O1ⁱ—Zn1—O1—C1	88.73 (13)	C4—C5—C6—C7	−0.6 (4)
Zn1—O1—C1—O2	2.0 (2)	C8—C5—C6—C7	178.5 (2)
Zn1—O1—C1—C2	−175.83 (14)	C3—C2—C7—C6	−0.1 (3)
O2—C1—C2—C7	−17.2 (3)	C1—C2—C7—C6	−178.6 (2)
O1—C1—C2—C7	160.7 (2)	C5—C6—C7—C2	0.6 (4)
O2—C1—C2—C3	164.4 (2)	C4—C5—C8—O3	178.6 (3)
O1—C1—C2—C3	−17.8 (3)	C6—C5—C8—O3	−0.5 (4)
C7—C2—C3—C4	−0.3 (4)	C4—C5—C8—O3'	−7.0 (5)
C1—C2—C3—C4	178.2 (2)	C6—C5—C8—O3'	173.9 (3)
C2—C3—C4—C5	0.3 (4)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1ⁱⁱ	0.84 (1)	1.93 (1)	2.761 (2)	174 (3)
O1W—H1W2···O2ⁱⁱⁱ	0.84 (1)	1.88 (1)	2.720 (2)	174 (3)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₈H₅O₃)₂(H₂O)₂]
M_r	399.64
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	27.537 (1), 5.0039 (2), 12.0930 (6)
β (°)	110.039 (2)
V (Å³)	1565.4 (1)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.61
Crystal size (mm)	0.34 × 0.26 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.532, 0.760
No. of measured, independent and observed [I > 2σ(I)] reflections	7203, 1785, 1448
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.082, 1.09
No. of reflections	1785
No. of parameters	132
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.38

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Selected bond lengths (Å) top

Zn1—O1w	1.983 (2)	Zn1—O2	2.512 (2)
Zn1—O1	2.005 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1ⁱ	0.84 (1)	1.93 (1)	2.761 (2)	174 (3)
O1W—H1W2···O2ⁱⁱ	0.84 (1)	1.88 (1)	2.720 (2)	174 (3)

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

Acknowledgements

We thank the Heilongjiang Province Natural Science Foundation (No. B200501), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (No. 1054G036), Heilongjiang University and the University of Malaya for supporting this work.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Deng, Z.-P., Gao, S., Huo, L.-H. & Zhao, H. (2006). Acta Cryst. E62, m3524–m3526. Web of Science CSD CrossRef IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). 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
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar