Diaqua­bis­(2-hy­droxy-5-meth­oxy­benzoato-κO1)zinc

Li, T.; Tang, L.-R.; Yang, L.; Huang, B.

doi:10.1107/S1600536811030893

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page m1262

doi:10.1107/S1600536811030893

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Diaquabis(2-hydroxy-5-methoxybenzoato-κO¹)zinc

Tao Li,^a ^* Li-Rong Tang,^b Lin Yang ^a and Biao Huang ^b

^aSchool of Life Sciences, Fujian Agriculture and Forestry University, Fuzhou, Fujian 350002, People's Republic of China, and ^bMaterial Engineering College, Fujian Agriculture and Forestry University, Fuzhou, Fujian 350002, People's Republic of China
^*Correspondence e-mail: ltdl@sina.com

(Received 20 July 2011; accepted 1 August 2011; online 17 August 2011)

The title compound, [Zn(C₈H₇O₄)₂(H₂O)₂], has been synthesized by hydrothermal methods. The Zn^II atom, whose symmetry element is a twofold axis, is four coordinated by two O atoms from 5-methoxysalicylate anions and two aqua O atoms in a distorted tetrahedral geometry. In the crystal, molecules are linked into a layer by O—H⋯O hydrogen bonds, which stabilize the packing.

Related literature

For coordination polymers constructed by hydrogen bonds, see: Li et al. (2006 ); Jiang et al. (2011 ). For the structure of the complex with 5-methoxysalicylate ligands and its analogues, see: Púčeková-Repická et al. (2007 ); Valigura et al. (2006 ).

Experimental

Crystal data

[Zn(C₈H₇O₄)₂(H₂O)₂]
M_r = 435.67
Monoclinic, C 2/c
a = 25.113 (4) Å
b = 5.5065 (6) Å
c = 12.648 (3) Å
β = 97.845 (12)°
V = 1732.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 173 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury CCD/AFC diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ) T_min = 0.745, T_max = 0.752
6403 measured reflections
1986 independent reflections
1837 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.082
S = 1.08
1986 reflections
136 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1⋯O1	0.87 (3)	1.76 (3)	2.5771 (19)	155 (2)
O4—H4A⋯O2ⁱ	0.73 (3)	1.93 (3)	2.643 (2)	169 (3)
O4—H4B⋯O5ⁱⁱ	0.84 (3)	1.97 (3)	2.790 (2)	167 (3)
Symmetry codes: (i) $[-x, y+1, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2007); 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 DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811030893/zk2017sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030893/zk2017Isup2.hkl

checkCIF report

Comment top

Generally, the self-assembly of inorganic metal species and organic ligands can be achieved by the use of noncovalent contacts. Among the noncovalent contacts, hydrogen bonds have the great influence in determining the geometry of the obtained metal complexes (Li et al. 2006; Jiang et al. 2011). In the other hand, the reactions of transition metal ions with 5-MeOsal ligands and its analogues are relatively rare (Valigura et al., 2006; Púčeková-Repická et al.,2007). In this paper we present results of hydrothermal reactions of ZnCl₂ and 5-MeOsal ligand. Title Compound was isolated as molecular complex and the intermolecular O—H—O hydrogen bonds in (I) together with intramolecular O—H—O hydrogen bonds promote the molecules into two-dimensional structure.

A single-crystal X-ray diffraction study of (I) reveals a discrete coordination complex that crystallizes in the space group C2/c. Coordination of the Zn atoms in (I) is a slightly distorted tetrahedral geometry with each Zn atom bonding to four oxygen atoms, in which two from the monodentate 5-MeOSal ligands and two from the waters (Fig.1). Further inspection into the structure reveals that there are O—H—O intramolecular and intermolecular hydrogen bonds. (Table 1). As described in Figure 2, the intramolecular hydrogen bonds from hydroxyl hydrogen atom of the 5-MeOsal anions to the coordinated carboxylate oxygen atoms O3—H—O1 with the distance of 2.577 (1) Å, then create six-memberedrings(O₂C₃H), and stabilize the structure. The mean deviation from the planes C(2)—C(3)—C(4)—C(5)—C(6)-(7), and O(1)—H(13)—O(3)—C(3)—C(2)—C(1)are 0.0032 and 0.0229 Å,respectively. Furthermore the dihedral angles between planes is 0.9°, indicating a planar structure for this ligand. Furthermore the uncoordinated oxygen atoms of the carboxyl group and methoxy group of the 5-MeOsal anions(O2, O5) are hydrogen bonded with the hydrogen atoms of coordinated water with the distances of 2.643 (2) and 2.790 (2) Å, respectively. As a result every coordinated water molecule is connected by two oxygen atoms through hydrogen bonds and the isolated units are to be form a 2-D layer. A prospective view of the structure packing from a direction is presented in Fig. 3.

Related literature top

For coordination polymers constructed by hydrogen bonds, see: Li et al. (2006); Jiang et al. (2011). For the structure of the complex with 5-methoxysalicylate ligands and its analogues, see: Púčeková-Repická et al. (2007); Valigura et al. (2006).

Experimental top

The title compound was hydrothermally synthesized under autogenous pressure. A mixture of ZnCl₂ (68 mg, 0.5 mmol), 5-MeOsal (84 mg, 0.5 mmol), and H₂O (6 ml) was sealed in a stainless reactor with Teflon liner, which was heated to 358 K for two days. After slow cooling to room temperature, prism pale yellow crystals were obtained as a major phase by filtration, which were washed with distilled water, and finally dried in air(65% yield).Anal. calc. for C₁₆H₁₈O₁₀Zn: C, 44.11; H, 4.16; O, 36.72%; Found: C, 44.32; H, 4.15; O, 36.23%. IR (KBr pellet):3448(w), 3290(w), 2839(w), 2615(w), 1661(s), 1616(s), 1486(s), 1428(s), 1223(s), 1188(s), 1033(m), 824(m), 788(m), 761(m), 678(m), 555(m), 464(w).

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Displacement ellipsoids are drawn at the 30% probability level. (-x, y, -z + 1/2)
	Fig. 2. The intramolecular and intermoleclar hydrogen bonds (the dashed lines) in title compound. Symmetry codes: (A)x, -y + 2, z + 1/2; (B)x, -y + 1, z + 1/2.
	Fig. 3. The 2-D layer of title compound by O—H—O interactions (black dash lines) viewed from a direction.

Diaquabis(2-hydroxy-5-methoxybenzoato-κO¹)zinc(II) top

Crystal data top

[Zn(C₈H₇O₄)₂(H₂O)₂]	F(000) = 896
M_r = 435.67	D_x = 1.670 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2689 reflections
a = 25.113 (4) Å	θ = 2.1–27.5°
b = 5.5065 (6) Å	µ = 1.47 mm⁻¹
c = 12.648 (3) Å	T = 173 K
β = 97.845 (12)°	Prism, pale yellow
V = 1732.7 (5) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku Mercury CCD/AFC diffractometer	1986 independent reflections
Radiation source: fine-focus sealed tube	1837 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −31→32
T_min = 0.745, T_max = 0.752	k = −7→7
6403 measured reflections	l = −16→15

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0494P)²] where P = (F_o² + 2F_c²)/3
1986 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

[Zn(C₈H₇O₄)₂(H₂O)₂]	V = 1732.7 (5) Å³
M_r = 435.67	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 25.113 (4) Å	µ = 1.47 mm⁻¹
b = 5.5065 (6) Å	T = 173 K
c = 12.648 (3) Å	0.20 × 0.20 × 0.20 mm
β = 97.845 (12)°

Data collection top

Rigaku Mercury CCD/AFC diffractometer	1986 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	1837 reflections with I > 2σ(I)
T_min = 0.745, T_max = 0.752	R_int = 0.027
6403 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.27 e Å⁻³
1986 reflections	Δρ_min = −0.69 e Å⁻³
136 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
Zn1	0.0000	0.94430 (5)	0.2500	0.03390 (13)
O1	0.07205 (5)	0.8141 (2)	0.23289 (10)	0.0398 (3)
O2	0.01520 (5)	0.6023 (2)	0.12225 (11)	0.0379 (3)
O3	0.17146 (5)	0.6892 (3)	0.27805 (10)	0.0433 (3)
O4	0.02830 (7)	1.1674 (3)	0.36768 (14)	0.0556 (4)
O5	0.12868 (6)	−0.0192 (3)	−0.03081 (11)	0.0432 (3)
C1	0.06216 (6)	0.6401 (3)	0.16527 (12)	0.0294 (3)
C2	0.10816 (6)	0.4881 (3)	0.14311 (13)	0.0269 (3)
C3	0.15997 (7)	0.5201 (3)	0.19989 (13)	0.0301 (3)
C4	0.20140 (7)	0.3720 (4)	0.17747 (14)	0.0358 (4)
H4	0.2364	0.3946	0.2153	0.043*
C5	0.19295 (7)	0.1916 (3)	0.10108 (14)	0.0355 (4)
H5	0.2219	0.0912	0.0866	0.043*
C6	0.09982 (6)	0.3065 (3)	0.06567 (12)	0.0297 (3)
H6	0.0651	0.2848	0.0266	0.036*
C7	0.14159 (7)	0.1582 (3)	0.04532 (12)	0.0307 (3)
C8	0.17070 (8)	−0.1737 (4)	−0.05639 (16)	0.0470 (5)
H8A	0.1989	−0.0751	−0.0818	0.070*
H8B	0.1562	−0.2881	−0.1123	0.070*
H8C	0.1859	−0.2639	0.0074	0.070*
H1	0.1412 (11)	0.767 (5)	0.275 (2)	0.065 (8)*
H4A	0.0164 (10)	1.283 (5)	0.378 (2)	0.052 (7)*
H4B	0.0570 (12)	1.135 (6)	0.407 (2)	0.081 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02475 (17)	0.03398 (19)	0.0432 (2)	0.000	0.00526 (12)	0.000
O1	0.0334 (6)	0.0375 (7)	0.0492 (7)	−0.0006 (5)	0.0087 (5)	−0.0142 (5)
O2	0.0256 (6)	0.0363 (6)	0.0511 (7)	0.0028 (5)	0.0025 (5)	−0.0042 (5)
O3	0.0319 (7)	0.0497 (8)	0.0462 (7)	−0.0039 (6)	−0.0015 (6)	−0.0164 (6)
O4	0.0486 (9)	0.0465 (9)	0.0660 (10)	0.0189 (8)	−0.0124 (8)	−0.0210 (8)
O5	0.0393 (7)	0.0429 (7)	0.0464 (8)	0.0083 (6)	0.0020 (6)	−0.0165 (6)
C1	0.0283 (8)	0.0280 (8)	0.0330 (8)	−0.0011 (7)	0.0081 (6)	0.0022 (6)
C2	0.0244 (8)	0.0279 (7)	0.0288 (8)	−0.0005 (7)	0.0051 (6)	0.0021 (6)
C3	0.0277 (8)	0.0338 (8)	0.0287 (8)	−0.0039 (7)	0.0027 (6)	−0.0002 (6)
C4	0.0237 (8)	0.0458 (9)	0.0366 (8)	0.0012 (8)	−0.0002 (7)	0.0002 (7)
C5	0.0279 (8)	0.0418 (9)	0.0372 (8)	0.0090 (7)	0.0053 (7)	0.0016 (7)
C6	0.0251 (7)	0.0330 (8)	0.0302 (7)	−0.0006 (6)	0.0015 (6)	−0.0004 (6)
C7	0.0321 (8)	0.0309 (8)	0.0291 (7)	0.0017 (7)	0.0045 (6)	−0.0003 (6)
C8	0.0519 (12)	0.0448 (11)	0.0466 (10)	0.0112 (9)	0.0155 (9)	−0.0063 (8)

Geometric parameters (Å, º) top

Zn1—O4	1.9852 (15)	C2—C6	1.395 (2)
Zn1—O4ⁱ	1.9852 (15)	C2—C3	1.409 (2)
Zn1—O1	1.9854 (13)	C3—C4	1.382 (2)
Zn1—O1ⁱ	1.9854 (13)	C4—C5	1.382 (3)
O1—C1	1.286 (2)	C4—H4	0.9500
O2—C1	1.247 (2)	C5—C7	1.395 (2)
O3—C3	1.360 (2)	C5—H5	0.9500
O3—H1	0.87 (3)	C6—C7	1.381 (2)
O4—H4A	0.73 (3)	C6—H6	0.9500
O4—H4B	0.84 (3)	C8—H8A	0.9800
O5—C7	1.379 (2)	C8—H8B	0.9800
O5—C8	1.427 (2)	C8—H8C	0.9800
C1—C2	1.484 (2)

O4—Zn1—O4ⁱ	103.54 (11)	C4—C3—C2	119.37 (16)
O4—Zn1—O1	93.83 (6)	C3—C4—C5	121.33 (15)
O4ⁱ—Zn1—O1	112.34 (7)	C3—C4—H4	119.3
O4—Zn1—O1ⁱ	112.34 (7)	C5—C4—H4	119.3
O4ⁱ—Zn1—O1ⁱ	93.83 (6)	C4—C5—C7	119.43 (16)
O1—Zn1—O1ⁱ	137.66 (7)	C4—C5—H5	120.3
C1—O1—Zn1	104.20 (10)	C7—C5—H5	120.3
C3—O3—H1	102.2 (17)	C7—C6—C2	120.63 (14)
Zn1—O4—H4A	125 (2)	C7—C6—H6	119.7
Zn1—O4—H4B	120 (2)	C2—C6—H6	119.7
H4A—O4—H4B	115 (3)	O5—C7—C6	115.91 (14)
C7—O5—C8	118.04 (15)	O5—C7—C5	124.02 (15)
O2—C1—O1	120.00 (15)	C6—C7—C5	120.07 (15)
O2—C1—C2	122.53 (15)	O5—C8—H8A	109.5
O1—C1—C2	117.46 (14)	O5—C8—H8B	109.5
C6—C2—C3	119.16 (15)	H8A—C8—H8B	109.5
C6—C2—C1	119.38 (14)	O5—C8—H8C	109.5
C3—C2—C1	121.45 (15)	H8A—C8—H8C	109.5
O3—C3—C4	117.55 (15)	H8B—C8—H8C	109.5
O3—C3—C2	123.07 (16)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O1	0.87 (3)	1.76 (3)	2.5771 (19)	155 (2)
O4—H4A···O2ⁱⁱ	0.73 (3)	1.93 (3)	2.643 (2)	169 (3)
O4—H4B···O5ⁱⁱⁱ	0.84 (3)	1.97 (3)	2.790 (2)	167 (3)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₈H₇O₄)₂(H₂O)₂]
M_r	435.67
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	25.113 (4), 5.5065 (6), 12.648 (3)
β (°)	97.845 (12)
V (Å³)	1732.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.47
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Mercury CCD/AFC diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2007)
T_min, T_max	0.745, 0.752
No. of measured, independent and observed [I > 2σ(I)] reflections	6403, 1986, 1837
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.082, 1.08
No. of reflections	1986
No. of parameters	136
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.69

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O1	0.87 (3)	1.76 (3)	2.5771 (19)	155 (2)
O4—H4A···O2ⁱ	0.73 (3)	1.93 (3)	2.643 (2)	169 (3)
O4—H4B···O5ⁱⁱ	0.84 (3)	1.97 (3)	2.790 (2)	167 (3)

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

Acknowledgements

This work was supported by a grant from the National Science Foundation of China (30771682).

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