Diaqua­bis­(1H-imidazole-4-carboxyl­ato-κ2N3,O)zinc

Shuai, W.; Cai, S.; Zheng, S.

doi:10.1107/S1600536811020800

metal-organic compounds

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Volume 67| Part 7| July 2011| Page m897

doi:10.1107/S1600536811020800

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Diaquabis(1H-imidazole-4-carboxylato-κ²N³,O)zinc

Wenlin Shuai,^a ^* Songliang Cai ^b and Shengrun Zheng ^b

^aGuangdong Test Center for Green Labelling, Guangzhou 510440, People's Republic of China, and ^bSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: S2371386@yahoo.com.cn

(Received 20 May 2011; accepted 30 May 2011; online 11 June 2011)

In the title compound, [Zn(C₄H₃N₂O₂)₂(H₂O)₂], the Zn^II ion is situated on a twofold rotation axis and exhibits a distorted octahedral coordination configuration. The equatorial plane contains two cis-oriented bidentate 1H-imidazole-4-carboxylate ligands and the axial positions are occupied by two coordinated water molecules. In the crystal structure, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into a three-dimensional supramolecular network. There are π–π interactions between the imidazole rings, with a centroid-to-centroid distance of 3.504 (3) Å.

Related literature

For general background, see: Yin et al. (2009 ); Zheng et al. (2011); Alkordi et al. (2009 ); Lu et al. (2009 ). For related structures, see: Haggag (2005 ); Starosta & Leciejewicz (2006 ); Gryz et al. (2007 ); Yin et al. (2009).

Experimental

Crystal data

[Zn(C₄H₃N₂O₂)₂(H₂O)₂]
M_r = 323.57
Orthorhombic, P c c n
a = 7.1399 (19) Å
b = 11.757 (3) Å
c = 13.508 (4) Å
V = 1133.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.20 mm⁻¹
T = 298 K
0.35 × 0.32 × 0.30 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.513, T_max = 0.558
5336 measured reflections
1037 independent reflections
913 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.066
S = 1.08
1037 reflections
95 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.86	1.93	2.784 (2)	174
O1W—H1WA⋯O2ⁱⁱ	0.83 (2)	2.04 (2)	2.850 (2)	167 (3)
O1W—H1WB⋯O2ⁱⁱⁱ	0.82 (2)	1.96 (2)	2.778 (2)	175 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y, z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2; data reduction: APEX2; 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811020800/cv5098sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020800/cv5098Isup2.hkl

checkCIF report

Comment top

Recently, we were interested in constructing coordination polymers based on N-heterocyclic carboxylic acids (Zheng et al., 2011). The imidazole-4-carboxylatic acid (H₂imc), which contains two N atoms of an imidazole group and one carboxylate group, remains largely unexplored, compared with its analogue imidazole-4,5-dicarboxylic acid (Alkordi et al., 2009; Lu et al., 2009). To date, only a few mononuclear complexes based on the H₂imc ligand have been documented (Haggag, 2005; Starosta & Leciejewicz, 2006; Gryz et al., 2007; Yin et al., 2009). For instance, Yin et al. (2009) reported the structure of a mononuclear complex [Cd(Himc)₂(H₂O)₂], which was prepared by the solvent evaporation method. Herein, we report a new Zn^II coordination polymer [Zn(Himc)₂(H₂O)₂], (I), which is isomorphous with the Cd^II analog.

The asymmetric unit of (I) contains a half of [Zn(Himc)₂(H₂O)₂] formula unit. The Zn^II ion exhibits a distorted octahedral geometry (Fig. 1), in which two cis-oriented bidentate chelating Himc^- ligands are located in the equatorial plane, forming two stable five-membered rings with metal ion, and the axial sites are occupied by two coordinated water molecules (Fig. 1). The Zn—O distances range from 2.1623 (17) to 2.1626 (14) Å and Zn—N bonds have the value of 2.0751 (16) Å. All Zn—O and Zn—N bond distances are shorter than those of Cd^II analog [the axial Cd—O, the equatorial Cd—O and Cd—N bond distances are 2.343 (2), 2.325 (2) and 2.274 (2) Å, respectively].

In the crystal structure, intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) link the molecules into a three-dimensional supramolecular network, which demonstrate π–π interactions between the imidazole rings (Fig. 2) with the centroid-to-centroid distance of 3.504 (3) Å.

Related literature top

For general background, see: Yin et al. (2009); Zheng et al. (2011); Alkordi et al. (2009); Lu et al. (2009). For related structures, see: Haggag (2005); Starosta & Leciejewicz (2006); Gryz et al. (2007); Yin et al. (2009).

Experimental top

13.6 mg ZnCl₂ (0.10 mmol) and 16.8 mg H₂imc (0.20 mmol) were mixed in 6 ml EtOH/H₂O (1:1). The aqueous NaOH (0.20 M) solution was dropwise added to the above solution and the pH was adjusted to about 7. Then, the resulting mixture was sealed into a 10 ml Teflon-lined stainless-steel reactor, which was heated at 100°C for 48 h under autogenous pressure, and then slowly cooled to room temperature at a rate of 2°C/h. Colorless block crystals of (I) were isolated, washed with distilled water, and dried in air (yield: 56%). IR (KBr, n/cm^-1): 3382m, 3147 s, 2997w, 2941w, 2849w, 1688m, 1584 s, 15581m, 1462m, 1402w, 1395 s, 1237 s, 1094m, 1003 s, 931w, 847w, 820w, 793m, 713w, 656m, 610w, 494m.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); 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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level [symmetry code: (i) -x + 5/2, -y + 3/2, z.]
	Fig. 2. A portion of the crystal packing showing π–π interactions between the imidazole rings as dashed lines.

Diaquabis(1H-imidazole-4-carboxylato-κ²N³,O)zinc top

Crystal data top

[Zn(C₄H₃N₂O₂)₂(H₂O)₂]	D_x = 1.895 Mg m⁻³
M_r = 323.57	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pccn	Cell parameters from 2272 reflections
a = 7.1399 (19) Å	θ = 3.3–27.3°
b = 11.757 (3) Å	µ = 2.20 mm⁻¹
c = 13.508 (4) Å	T = 298 K
V = 1133.9 (5) Å³	Block, colourless
Z = 4	0.35 × 0.32 × 0.30 mm
F(000) = 656

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1037 independent reflections
Radiation source: fine-focus sealed tube	913 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 25.2°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→8
T_min = 0.513, T_max = 0.558	k = −8→14
5336 measured reflections	l = −14→16

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0338P)² + 0.618P] where P = (F_o² + 2F_c²)/3
1037 reflections	(Δ/σ)_max < 0.001
95 parameters	Δρ_max = 0.29 e Å⁻³
2 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Zn(C₄H₃N₂O₂)₂(H₂O)₂]	V = 1133.9 (5) Å³
M_r = 323.57	Z = 4
Orthorhombic, Pccn	Mo Kα radiation
a = 7.1399 (19) Å	µ = 2.20 mm⁻¹
b = 11.757 (3) Å	T = 298 K
c = 13.508 (4) Å	0.35 × 0.32 × 0.30 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1037 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	913 reflections with I > 2σ(I)
T_min = 0.513, T_max = 0.558	R_int = 0.021
5336 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	2 restraints
wR(F²) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.29 e Å⁻³
1037 reflections	Δρ_min = −0.33 e Å⁻³
95 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	1.2500	0.7500	0.37215 (2)	0.02665 (15)
N1	1.0565 (2)	0.81059 (14)	0.47393 (11)	0.0263 (4)
N2	0.8608 (2)	0.87069 (15)	0.58685 (12)	0.0318 (4)
H2	0.8123	0.8836	0.6440	0.038*
C2	0.9100 (3)	0.86538 (16)	0.42860 (13)	0.0229 (4)
C1	0.9084 (3)	0.87026 (16)	0.31884 (14)	0.0229 (4)
C3	0.7885 (3)	0.90319 (19)	0.49823 (15)	0.0291 (4)
H3	0.6781	0.9433	0.4875	0.035*
C4	1.0207 (3)	0.81514 (18)	0.56937 (14)	0.0322 (5)
H4	1.0966	0.7838	0.6182	0.039*
O1	1.04760 (19)	0.82909 (12)	0.27495 (9)	0.0304 (3)
O2	0.76821 (19)	0.91520 (13)	0.27745 (10)	0.0303 (4)
O1W	1.0979 (2)	0.59370 (14)	0.34656 (12)	0.0356 (4)
H1WA	1.150 (4)	0.550 (2)	0.3077 (18)	0.062 (9)*
H1WB	0.989 (3)	0.595 (3)	0.328 (2)	0.072 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0242 (2)	0.0358 (2)	0.0200 (2)	0.00824 (13)	0.000	0.000
N1	0.0267 (9)	0.0336 (10)	0.0187 (8)	0.0059 (7)	0.0010 (7)	0.0021 (7)
N2	0.0338 (10)	0.0426 (11)	0.0189 (8)	0.0024 (8)	0.0070 (7)	−0.0012 (7)
C2	0.0220 (10)	0.0252 (10)	0.0214 (10)	0.0008 (8)	0.0003 (8)	0.0002 (8)
C1	0.0246 (10)	0.0238 (10)	0.0205 (9)	−0.0028 (8)	−0.0016 (8)	0.0009 (8)
C3	0.0254 (10)	0.0344 (11)	0.0275 (11)	0.0040 (9)	0.0007 (9)	−0.0018 (9)
C4	0.0344 (12)	0.0421 (13)	0.0203 (10)	0.0044 (9)	−0.0009 (9)	0.0046 (9)
O1	0.0283 (8)	0.0434 (9)	0.0194 (7)	0.0063 (6)	0.0021 (6)	−0.0011 (6)
O2	0.0249 (8)	0.0433 (9)	0.0227 (7)	0.0044 (6)	−0.0045 (6)	0.0051 (6)
O1W	0.0264 (8)	0.0386 (9)	0.0417 (9)	0.0049 (7)	−0.0033 (7)	−0.0108 (7)

Geometric parameters (Å, º) top

Zn1—N1	2.0751 (16)	N2—H2	0.8600
Zn1—N1ⁱ	2.0751 (16)	C2—C3	1.354 (3)
Zn1—O1	2.1626 (14)	C2—C1	1.484 (3)
Zn1—O1ⁱ	2.1626 (14)	C1—O1	1.255 (2)
Zn1—O1Wⁱ	2.1623 (17)	C1—O2	1.262 (2)
Zn1—O1W	2.1623 (17)	C3—H3	0.9300
N1—C4	1.315 (2)	C4—H4	0.9300
N1—C2	1.373 (2)	O1W—H1WA	0.828 (17)
N2—C4	1.336 (3)	O1W—H1WB	0.818 (18)
N2—C3	1.358 (3)

N1—Zn1—N1ⁱ	97.01 (9)	C4—N2—H2	126.1
N1—Zn1—O1	79.04 (6)	C3—N2—H2	126.1
N1ⁱ—Zn1—O1	174.10 (5)	C3—C2—N1	109.40 (16)
N1—Zn1—O1ⁱ	174.10 (5)	C3—C2—C1	132.55 (17)
N1ⁱ—Zn1—O1ⁱ	79.04 (6)	N1—C2—C1	118.02 (15)
O1—Zn1—O1ⁱ	105.24 (7)	O1—C1—O2	125.47 (17)
N1—Zn1—O1Wⁱ	98.53 (7)	O1—C1—C2	116.81 (15)
N1ⁱ—Zn1—O1Wⁱ	93.64 (7)	O2—C1—C2	117.71 (16)
O1—Zn1—O1Wⁱ	82.71 (6)	C2—C3—N2	106.05 (18)
O1ⁱ—Zn1—O1Wⁱ	86.15 (6)	C2—C3—H3	127.0
N1—Zn1—O1W	93.64 (7)	N2—C3—H3	127.0
N1ⁱ—Zn1—O1W	98.54 (7)	N1—C4—N2	111.05 (18)
O1—Zn1—O1W	86.15 (6)	N1—C4—H4	124.5
O1ⁱ—Zn1—O1W	82.71 (6)	N2—C4—H4	124.5
O1Wⁱ—Zn1—O1W	161.60 (9)	C1—O1—Zn1	114.11 (11)
C4—N1—C2	105.65 (16)	Zn1—O1W—H1WA	114 (2)
C4—N1—Zn1	142.45 (15)	Zn1—O1W—H1WB	121 (2)
C2—N1—Zn1	111.89 (12)	H1WA—O1W—H1WB	104 (3)
C4—N2—C3	107.84 (17)

N1ⁱ—Zn1—N1—C4	−5.0 (2)	C3—C2—C1—O2	−1.8 (3)
O1—Zn1—N1—C4	179.4 (3)	N1—C2—C1—O2	176.18 (18)
O1ⁱ—Zn1—N1—C4	42.6 (7)	N1—C2—C3—N2	−0.3 (2)
O1Wⁱ—Zn1—N1—C4	−99.8 (2)	C1—C2—C3—N2	177.80 (19)
O1W—Zn1—N1—C4	94.1 (3)	C4—N2—C3—C2	0.0 (2)
N1ⁱ—Zn1—N1—C2	175.82 (16)	C2—N1—C4—N2	−0.6 (2)
O1—Zn1—N1—C2	0.25 (13)	Zn1—N1—C4—N2	−179.84 (17)
O1ⁱ—Zn1—N1—C2	−136.6 (5)	C3—N2—C4—N1	0.4 (3)
O1Wⁱ—Zn1—N1—C2	81.05 (14)	O2—C1—O1—Zn1	−176.15 (15)
O1W—Zn1—N1—C2	−85.11 (14)	C2—C1—O1—Zn1	3.9 (2)
C4—N1—C2—C3	0.6 (2)	N1—Zn1—O1—C1	−2.39 (14)
Zn1—N1—C2—C3	−179.92 (14)	N1ⁱ—Zn1—O1—C1	−50.7 (6)
C4—N1—C2—C1	−177.86 (17)	O1ⁱ—Zn1—O1—C1	173.43 (15)
Zn1—N1—C2—C1	1.6 (2)	O1Wⁱ—Zn1—O1—C1	−102.60 (14)
C3—C2—C1—O1	178.1 (2)	O1W—Zn1—O1—C1	92.07 (14)
N1—C2—C1—O1	−3.9 (2)

Symmetry code: (i) −x+5/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱⁱ	0.86	1.93	2.784 (2)	174
O1W—H1WA···O2ⁱⁱⁱ	0.83 (2)	2.04 (2)	2.850 (2)	167 (3)
O1W—H1WB···O2^iv	0.82 (2)	1.96 (2)	2.778 (2)	175 (3)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₄H₃N₂O₂)₂(H₂O)₂]
M_r	323.57
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	298
a, b, c (Å)	7.1399 (19), 11.757 (3), 13.508 (4)
V (Å³)	1133.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.20
Crystal size (mm)	0.35 × 0.32 × 0.30

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.513, 0.558
No. of measured, independent and observed [I > 2σ(I)] reflections	5336, 1037, 913
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.066, 1.08
No. of reflections	1037
No. of parameters	95
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.33

Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.86	1.93	2.784 (2)	173.6
O1W—H1WA···O2ⁱⁱ	0.828 (17)	2.039 (18)	2.850 (2)	167 (3)
O1W—H1WB···O2ⁱⁱⁱ	0.818 (18)	1.962 (19)	2.778 (2)	175 (3)

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

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (grant No. 21003053) and the Natural Science Foundation of Guang Dong (grant No. 10451063101004667).

References

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