catena-Poly[[(ethane­diol-κ² O,O′)zinc]-μ-oxalato-κ⁴ O ¹,O ²:O ^1′,O ^2′]

Abstract

In the title complex, [Zn(C₂O₄)(C₂H₆O₂)]_n, the Zn^II ion is in a distorted octa­hedral environment formed by two O atoms from an ethyl­ene glycol mol­ecule and four O atoms from two oxalate anions. The oxalate anions link the Zn^II ions, forming a zigzag chain along [010]. The zigzag chains are extended into a three-dimensional network by O—H⋯O hydrogen bonds.

Related literature  

For related structures of complexes with oxalates, see: Jin & Lin (2011 ▶); Shen & Lush (2012 ▶).

Experimental  

Crystal data  

• [Zn(C₂O₄)(C₂H₆O₂)]

• M _r = 215.46

• Orthorhombic,

• a = 7.6411 (15) Å

• b = 9.3603 (19) Å

• c = 19.589 (4) Å

• V = 1401.1 (5) ų

• Z = 8

• Mo Kα radiation

• μ = 3.49 mm⁻¹

• T = 293 K

• 0.26 × 0.25 × 0.24 mm

Data collection  

• Rigaku SCXmini CCD diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.464, T _max = 0.488

• 11048 measured reflections

• 1258 independent reflections

• 1064 reflections with I > 2σ(I)

• R _int = 0.068

Refinement  

• R[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 0.133

• S = 0.97

• 1258 reflections

• 108 parameters

• 2 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.41 e Å⁻³

• Δρ_min = −0.29 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); 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: XP in SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg & Putz, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O1i	0.82 (1)	1.88 (2)	2.689 (5)	170 (7)
O6—H6⋯O2ii	0.82 (1)	1.91 (2)	2.717 (5)	169 (6)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Oxalate is a very useful ligand for constructing coordination polymers (Shen & Lush, 2012) and it can be obtained as the degradation of some organic ligands (Jin & Lin, 2011). In this paper, we obtained the oxalate ligand by the oxidation of ethylene glycol in situ by solvothermal method. In the title compound, the Zn^II ion is in a distorted octahedral environment formed by two O atoms from a chelate ethylene glycol molecule and four O atoms from two different oxalate anions (Fig. 1). The oxalate anions link the Zn^II ions, leading to a zigzag chain structure along [0 1 0] (Fig. 2). The zigzag chains are extended into a three-dimensional structure by O—H···O hydrogen bonds (Fig. 3 and Table 1).

Experimental

A mixture of Zn(NO₃)₂.6H₂O (0.148 g, 0.5 mmol) and concentrated sulfuric acid (0.5 ml) in ethylene glycol (10 ml) was placed in a 23 ml Teflon-lined stainless steel reactor and heated at 383 K for 48 h. After cooling to room temperature over a period of 48 h, colorless crystals suitable for X-ray analysis were obtained.

Refinement

C-bound H atoms were placed at calculated positions and refined as riding atoms, with C—H = 0.97 Å and with U_iso(H) = 1.2U_eq(C). H atoms on O atoms were located in a difference Fourier map and refined isotropically, with a distance restraint of O—H = 0.82 (1) Å.

Figures

Fig. 1.

The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) 1/2-x, -1/2+y, z.]

Fig. 2.

The one-dimensional zigzag chain in the title compound.

Fig. 3.

Crystal packing of the title compound. Dashed lines denote hydrogen bonds.

Crystal data

[Zn(C2O4)(C2H6O2)]	F(000) = 864
Mr = 215.46	Dx = 2.043 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 11377 reflections
a = 7.6411 (15) Å	θ = 3.0–27.6°
b = 9.3603 (19) Å	µ = 3.49 mm−1
c = 19.589 (4) Å	T = 293 K
V = 1401.1 (5) Å3	Block, colorless
Z = 8	0.26 × 0.25 × 0.24 mm

Data collection

Rigaku SCXmini CCD diffractometer	1258 independent reflections
Radiation source: fine-focus sealed tube	1064 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
ω scans	θmax = 25.2°, θmin = 3.4°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −9→9
Tmin = 0.464, Tmax = 0.488	k = −11→11
11048 measured reflections	l = −23→23

Refinement

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ2(Fo2) + (0.1P)2 + 0.250P] where P = (Fo2 + 2Fc2)/3
1258 reflections	(Δ/σ)max = 0.001
108 parameters	Δρmax = 0.41 e Å−3
2 restraints	Δρmin = −0.29 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.43052 (8)	0.45088 (6)	0.86776 (3)	0.0252 (3)
O1	0.2638 (5)	0.5709 (3)	0.80505 (17)	0.0313 (9)
O2	0.4012 (4)	0.6358 (4)	0.92671 (16)	0.0261 (8)
O3	0.2619 (5)	0.8446 (4)	0.92532 (17)	0.0307 (9)
O4	0.1094 (5)	0.7728 (4)	0.80610 (17)	0.0324 (9)
O5	0.6647 (5)	0.5109 (5)	0.8235 (2)	0.0382 (9)
O6	0.6152 (5)	0.3630 (5)	0.93473 (19)	0.0360 (9)
C1	0.3000 (6)	0.7272 (5)	0.9006 (2)	0.0226 (10)
C2	0.2171 (6)	0.6879 (5)	0.8305 (2)	0.0234 (11)
C3	0.7851 (8)	0.4251 (8)	0.9253 (3)	0.0510 (18)
H3A	0.8742	0.3650	0.9457	0.061*
H3B	0.7902	0.5187	0.9465	0.061*
C4	0.8139 (9)	0.4373 (8)	0.8507 (3)	0.0516 (18)
H4A	0.9202	0.4906	0.8414	0.062*
H4B	0.8245	0.3433	0.8303	0.062*
H6	0.597 (7)	0.368 (7)	0.9757 (8)	0.045 (18)*
H5	0.690 (9)	0.520 (8)	0.7831 (11)	0.06 (2)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Zn1	0.0290 (4)	0.0245 (4)	0.0222 (4)	−0.0007 (2)	0.0003 (2)	0.0003 (2)
O1	0.042 (2)	0.0265 (19)	0.0256 (19)	0.0090 (16)	−0.0116 (16)	−0.0070 (16)
O2	0.0293 (18)	0.0275 (19)	0.0213 (17)	0.0034 (15)	−0.0039 (14)	−0.0025 (15)
O3	0.037 (2)	0.029 (2)	0.0263 (18)	0.0066 (16)	−0.0081 (16)	−0.0075 (16)
O4	0.042 (2)	0.035 (2)	0.0207 (18)	0.0090 (17)	−0.0090 (15)	−0.0024 (17)
O5	0.031 (2)	0.057 (2)	0.026 (2)	−0.0013 (19)	0.0066 (18)	0.0115 (19)
O6	0.037 (2)	0.047 (2)	0.024 (2)	0.0084 (18)	−0.0009 (17)	0.0094 (19)
C1	0.026 (3)	0.023 (2)	0.019 (2)	−0.005 (2)	0.002 (2)	0.001 (2)
C2	0.030 (3)	0.023 (3)	0.018 (2)	0.001 (2)	−0.005 (2)	−0.002 (2)
C3	0.032 (3)	0.086 (5)	0.035 (3)	0.011 (3)	−0.001 (3)	0.009 (3)
C4	0.036 (4)	0.081 (5)	0.037 (3)	0.001 (3)	0.003 (3)	0.011 (3)

Geometric parameters (Å, º)

Zn1—O5	2.066 (4)	O5—C4	1.434 (7)
Zn1—O4i	2.081 (3)	O5—H5	0.82 (1)
Zn1—O2	2.092 (3)	O6—C3	1.434 (8)
Zn1—O6	2.095 (4)	O6—H6	0.82 (1)
Zn1—O1	2.096 (3)	C1—C2	1.557 (6)
Zn1—O3i	2.103 (3)	C3—C4	1.482 (8)
O1—C2	1.255 (5)	C3—H3A	0.9700
O2—C1	1.262 (6)	C3—H3B	0.9700
O3—C1	1.236 (6)	C4—H4A	0.9700
O4—C2	1.239 (6)	C4—H4B	0.9700
O5—Zn1—O4i	95.80 (15)	C3—O6—Zn1	111.7 (3)
O5—Zn1—O2	95.72 (15)	C3—O6—H6	105 (4)
O4i—Zn1—O2	165.25 (15)	Zn1—O6—H6	118 (4)
O5—Zn1—O6	77.65 (15)	O3—C1—O2	126.0 (4)
O4i—Zn1—O6	98.49 (16)	O3—C1—C2	117.4 (4)
O2—Zn1—O6	92.94 (15)	O2—C1—C2	116.5 (4)
O5—Zn1—O1	97.75 (15)	O4—C2—O1	126.5 (4)
O4i—Zn1—O1	90.01 (13)	O4—C2—C1	117.3 (4)
O2—Zn1—O1	79.34 (12)	O1—C2—C1	116.2 (4)
O6—Zn1—O1	170.66 (16)	O6—C3—C4	107.0 (5)
O5—Zn1—O3i	163.54 (15)	O6—C3—H3A	110.3
O4i—Zn1—O3i	80.20 (13)	C4—C3—H3A	110.3
O2—Zn1—O3i	91.17 (13)	O6—C3—H3B	110.3
O6—Zn1—O3i	87.11 (16)	C4—C3—H3B	110.3
O1—Zn1—O3i	98.21 (15)	H3A—C3—H3B	108.6
C2—O1—Zn1	114.1 (3)	O5—C4—C3	106.5 (5)
C1—O2—Zn1	113.8 (3)	O5—C4—H4A	110.4
C1—O3—Zn1ii	112.0 (3)	C3—C4—H4A	110.4
C2—O4—Zn1ii	112.8 (3)	O5—C4—H4B	110.4
C4—O5—Zn1	113.7 (3)	C3—C4—H4B	110.4
C4—O5—H5	103 (5)	H4A—C4—H4B	108.6
Zn1—O5—H5	130 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O1iii	0.82 (1)	1.88 (2)	2.689 (5)	170 (7)
O6—H6···O2iv	0.82 (1)	1.91 (2)	2.717 (5)	169 (6)

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