trans-Diaqua­bis­(1H-imidazole-4-carboxyl­ato-κ2N3,O4)nickel(II)

Zheng, S.; Cai, S.; Fan, J.; Zhang, W.

doi:10.1107/S1600536811018824

metal-organic compounds

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Volume 67| Part 7| July 2011| Page m865

doi:10.1107/S1600536811018824

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trans-Diaquabis(1H-imidazole-4-carboxylato-κ²N³,O⁴)nickel(II)

Shengrun Zheng,^a Songliang Cai,^a Jun Fan ^a and Weiguang Zhang ^a ^*

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: wgzhang@scnu.edu.cn

(Received 24 April 2011; accepted 17 May 2011; online 11 June 2011)

In the title complex, [Ni(C₄H₃N₂O₂)₂(H₂O)₂], the Ni^II ion is located on an inversion center and shows a distorted octahedral geometry, defined by two N,O-bidentate 1H-imidazole-4-carboxylate ligands in the equatorial plane and two water molecules in the axial positions. Intermolecular N—H⋯O hydrogen bonds link the complex molecules into layers parallel to (10 $[\overline{2}]$ ), which are further linked into a three-dimensional supramolecular network through O—H⋯O hydrogen bonds.

Related literature

For general background to the design and synthesis of coordination polymers, see: Choi & Jeon (2003 ); Moulton & Zaworotko (2001 ); Roesky & Andruh (2003 ); Tao et al. (2000 ). For complexes with imidazole-4,5-dicarboxylic acid, see: Alkordi et al. (2009 ); Lu et al. (2009 ); Sun et al. (2005 ). For related structures, see: Gryz et al. (2007 ); Haggag (2005 ); Starosta & Leciejewicz (2006 ); Xu et al. (2008 ); Yin et al. (2009 ); Zheng et al. (2011 ).

Experimental

Crystal data

[Ni(C₄H₃N₂O₂)₂(H₂O)₂]
M_r = 316.91
Monoclinic, P 2₁ /c
a = 6.6123 (18) Å
b = 12.267 (3) Å
c = 7.239 (2) Å
β = 101.059 (3)°
V = 576.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.72 mm⁻¹
T = 298 K
0.48 × 0.36 × 0.32 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.493, T_max = 0.610
2878 measured reflections
1043 independent reflections
947 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.070
S = 1.07
1043 reflections
88 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O2ⁱ	0.86	2.16	2.942 (3)	152
N2—H2N⋯O1ⁱ	0.86	2.36	3.130 (2)	149
O1W—H1WA⋯O2ⁱⁱ	0.83	1.94	2.762 (2)	169
O1W—H1WB⋯O2ⁱⁱⁱ	0.84	1.94	2.7654 (19)	168
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536811018824/hy2425sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811018824/hy2425Isup2.hkl

checkCIF report

Comment top

The rational design and synthesis of coordination polymers have received extensive attention over the past decades (Moulton & Zaworotko, 2001; Roesky & Andruh, 2003). The choice of suitable ligands is an important factor that greatly affects the structure and stabilization of the coordination architecture (Choi & Jeon, 2003; Tao et al., 2000). Recently, our group has focused on constructing coordination polymers based on N-heterocyclic carboxylic acids (Zheng et al., 2011). 1H-Imidazole-4-carboxylic acid (H₂imc), which is recognized as efficient N/O donors exhibiting versatile coordination behaviors and potential hydrogen-bonding abilities, remains largely unexplored, compared with its analogue imidazole-4,5-dicarboxylic acid (Alkordi et al., 2009; Lu et al., 2009; Sun et al., 2005). A few of mononuclear complexes based on the H₂imc ligand have been reported (Gryz et al., 2007; Haggag, 2005; Starosta & Leciejewicz, 2006; Yin et al., 2009). In this work, we report the synthesis and structure of a new Ni^II complex, which was obtained by the solvothermal reaction of Ni(ClO₄)₂.6H₂O and H₂imc.

The asymmetric unit contains a half of [Ni(Himc)₂(H₂O)₂] formula unit, with the Ni^II ion lying on an inversion center. The Ni^II ion exhibits a distorted octahedral geometry, in which two 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 Ni—O distances range from 2.0764 (13) to 2.0947 (17) Å and Ni—N bonds have the value of 2.0502 (17) Å, which are similar to the reported Ni^II complexes with imidazole-based carboxylate ligands (Xu et al., 2008).

In the crystal, each complex molecule is joined to four adjacent ones via N2–H2···O1ⁱⁱ and N2–H2···O2ⁱⁱ hydrogen bonds between the imidazole N—H group and carboxylate O atoms (Table 1) [symmetry code: (ii) x + 1, -y + 1/2, z + 1/2], generating a two-dimensional hydrogen-bonded sheet parallel to (1 0 2) (Fig. 2). These sheets are further linked by O—H···O hydrogen bonds involving the coordinated water molecules (O1W) and carboxylate O atoms (O2), resulting in a three-dimensional supramolecular network (Fig. 3).

Related literature top

For general background to the design and synthesis of coordination polymers, see: Choi & Jeon (2003); Moulton & Zaworotko (2001); Roesky & Andruh (2003); Tao et al. (2000). For complexes with imidazole-4,5-dicarboxylic acid, see: Alkordi et al. (2009); Lu et al. (2009); Sun et al. (2005). For related structures, see: Gryz et al. (2007); Haggag (2005); Starosta & Leciejewicz (2006); Xu et al. (2008); Yin et al. (2009); Zheng et al. (2011).

Experimental top

A mixture of Ni(ClO₄)₂.6H₂O (41.9 mg, 0.10 mmol), H₂imc (11.2 mg, 0.10 mmol), NaOH (4.0 mg, 0.10 mmol) and EtOH/H2O (v/v 1:1, 6 ml) was sealed in a 10 ml Teflon-lined stainless-steel reactor, which was heated to 100°C for 48 h under autogenous pressure, and then slowly cooled to room temperature at a rate of 5°C h^-1. Pale green block crystals of the title compound were isolated, washed with distilled water and dried in air (yield: 78%). IR (KBr, cm^-1): 3340 s, 2923 m, 2853 w, 2350 w, 1598 s, 1461 m, 1427 w, 1402 w, 1357 m, 1287 w, 1260 w, 1091 s, 1039 m, 854 w, 806 w, 723 m, 655 w, 544 m, 456w.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 the title compound, with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) 1 - x, -y, -z.]
	Fig. 2. The crystal packing of the title compound, showing the two-dimensional hydrogen-bonded network. Hydrogen bonds are shown as dashed lines. [Symmetry code: (ii) x + 1, -y + 1/2, z + 1/2.]
	Fig. 3. The crystal packing of the title compound, showing the three-dimensional hydrogen-bonded network. Hydrogen bonds are shown as dashed lines.

trans-Diaquabis(1H-imidazole-4-carboxylato- κ²N³,O⁴)nickel(II) top

Crystal data top

[Ni(C₄H₃N₂O₂)₂(H₂O)₂]	F(000) = 324
M_r = 316.91	D_x = 1.826 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1803 reflections
a = 6.6123 (18) Å	θ = 3.1–27.8°
b = 12.267 (3) Å	µ = 1.72 mm⁻¹
c = 7.239 (2) Å	T = 298 K
β = 101.059 (3)°	Block, pale green
V = 576.2 (3) Å³	0.48 × 0.36 × 0.32 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1043 independent reflections
Radiation source: fine-focus sealed tube	947 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.2°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.493, T_max = 0.610	k = −14→14
2878 measured reflections	l = −8→7

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0415P)² + 0.1301P] where P = (F_o² + 2F_c²)/3
1043 reflections	(Δ/σ)_max < 0.001
88 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Ni(C₄H₃N₂O₂)₂(H₂O)₂]	V = 576.2 (3) Å³
M_r = 316.91	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6123 (18) Å	µ = 1.72 mm⁻¹
b = 12.267 (3) Å	T = 298 K
c = 7.239 (2) Å	0.48 × 0.36 × 0.32 mm
β = 101.059 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1043 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	947 reflections with I > 2σ(I)
T_min = 0.493, T_max = 0.610	R_int = 0.027
2878 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.07	Δρ_max = 0.25 e Å⁻³
1043 reflections	Δρ_min = −0.42 e Å⁻³
88 parameters

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

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.0000	0.0000	0.02288 (16)
N1	0.7437 (3)	0.09727 (13)	0.1157 (2)	0.0289 (4)
C3	0.8498 (3)	0.26678 (17)	0.1929 (3)	0.0331 (5)
H2	0.8537	0.3422	0.2070	0.040*
C4	0.9370 (3)	0.09539 (18)	0.2052 (3)	0.0401 (6)
H4	1.0157	0.0325	0.2312	0.048*
C2	0.6866 (3)	0.20552 (15)	0.1070 (3)	0.0226 (4)
N2	1.0046 (3)	0.19580 (17)	0.2536 (3)	0.0411 (5)
H2N	1.1260	0.2125	0.3132	0.049*
O2	0.4160 (2)	0.32925 (10)	−0.0090 (2)	0.0322 (4)
O1	0.3604 (2)	0.15166 (10)	−0.0480 (2)	0.0270 (3)
O1W	0.4100 (3)	−0.00996 (9)	0.2616 (2)	0.0307 (4)
C1	0.4750 (3)	0.23191 (17)	0.0111 (2)	0.0225 (4)
H1WA	0.4644	−0.0632	0.3236	0.027*
H1WB	0.4254	0.0483	0.3241	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0221 (3)	0.0146 (2)	0.0284 (2)	0.00075 (12)	−0.00422 (15)	−0.00212 (12)
N1	0.0249 (10)	0.0224 (9)	0.0348 (9)	0.0037 (7)	−0.0057 (7)	−0.0029 (7)
C3	0.0268 (11)	0.0294 (11)	0.0410 (12)	−0.0075 (9)	0.0013 (9)	−0.0092 (9)
C4	0.0267 (13)	0.0401 (13)	0.0473 (13)	0.0096 (10)	−0.0089 (10)	−0.0050 (10)
C2	0.0213 (10)	0.0200 (9)	0.0249 (9)	−0.0018 (7)	−0.0001 (8)	−0.0020 (7)
N2	0.0179 (9)	0.0548 (12)	0.0455 (11)	−0.0031 (8)	−0.0066 (8)	−0.0147 (9)
O2	0.0348 (9)	0.0188 (7)	0.0385 (9)	0.0048 (6)	−0.0037 (6)	0.0020 (5)
O1	0.0211 (7)	0.0199 (7)	0.0348 (7)	0.0010 (6)	−0.0076 (6)	−0.0025 (6)
O1W	0.0403 (10)	0.0188 (7)	0.0306 (8)	0.0027 (6)	0.0008 (7)	−0.0008 (5)
C1	0.0243 (11)	0.0214 (11)	0.0204 (9)	0.0008 (7)	0.0008 (8)	0.0003 (7)

Geometric parameters (Å, º) top

Ni1—N1	2.0502 (17)	C4—N2	1.334 (3)
Ni1—O1	2.0764 (13)	C4—H4	0.9300
Ni1—O1W	2.0947 (17)	C2—C1	1.473 (3)
N1—C4	1.318 (3)	N2—H2N	0.8600
N1—C2	1.379 (3)	O2—C1	1.256 (2)
C3—N2	1.352 (3)	O1—C1	1.266 (2)
C3—C2	1.363 (3)	O1W—H1WA	0.83
C3—H2	0.9300	O1W—H1WB	0.84

N1ⁱ—Ni1—N1	180.00 (10)	N2—C3—H2	127.0
N1ⁱ—Ni1—O1ⁱ	80.58 (6)	C2—C3—H2	127.0
N1—Ni1—O1ⁱ	99.42 (6)	N1—C4—N2	110.96 (19)
N1ⁱ—Ni1—O1	99.42 (6)	N1—C4—H4	124.5
N1—Ni1—O1	80.58 (6)	N2—C4—H4	124.5
O1ⁱ—Ni1—O1	180.00 (8)	C3—C2—N1	108.92 (18)
N1ⁱ—Ni1—O1Wⁱ	90.11 (7)	C3—C2—C1	133.68 (19)
N1—Ni1—O1Wⁱ	89.89 (7)	N1—C2—C1	117.39 (16)
O1ⁱ—Ni1—O1Wⁱ	90.53 (5)	C4—N2—C3	108.32 (18)
O1—Ni1—O1Wⁱ	89.47 (5)	C4—N2—H2N	125.8
N1ⁱ—Ni1—O1W	89.89 (7)	C3—N2—H2N	125.8
N1—Ni1—O1W	90.11 (7)	C1—O1—Ni1	114.94 (12)
O1ⁱ—Ni1—O1W	89.47 (5)	Ni1—O1W—H1WA	111.4
O1—Ni1—O1W	90.53 (5)	Ni1—O1W—H1WB	114.2
O1Wⁱ—Ni1—O1W	180.00 (11)	H1WA—O1W—H1WB	112.4
C4—N1—C2	105.70 (17)	O2—C1—O1	123.19 (17)
C4—N1—Ni1	143.40 (15)	O2—C1—C2	120.62 (18)
C2—N1—Ni1	110.80 (13)	O1—C1—C2	116.20 (17)
N2—C3—C2	106.10 (18)

O1ⁱ—Ni1—N1—C4	−2.4 (3)	C4—N1—C2—C1	179.45 (17)
O1—Ni1—N1—C4	177.6 (3)	Ni1—N1—C2—C1	−3.3 (2)
O1Wⁱ—Ni1—N1—C4	−92.9 (3)	N1—C4—N2—C3	−0.2 (3)
O1W—Ni1—N1—C4	87.1 (3)	C2—C3—N2—C4	0.2 (2)
O1ⁱ—Ni1—N1—C2	−177.92 (12)	N1ⁱ—Ni1—O1—C1	179.42 (13)
O1—Ni1—N1—C2	2.08 (12)	N1—Ni1—O1—C1	−0.58 (13)
O1Wⁱ—Ni1—N1—C2	91.56 (13)	O1Wⁱ—Ni1—O1—C1	−90.55 (13)
O1W—Ni1—N1—C2	−88.44 (13)	O1W—Ni1—O1—C1	89.45 (13)
C2—N1—C4—N2	0.2 (2)	Ni1—O1—C1—O2	178.85 (13)
Ni1—N1—C4—N2	−175.53 (18)	Ni1—O1—C1—C2	−1.03 (19)
N2—C3—C2—N1	−0.1 (2)	C3—C2—C1—O2	2.5 (3)
N2—C3—C2—C1	−179.5 (2)	N1—C2—C1—O2	−176.88 (16)
C4—N1—C2—C3	0.0 (2)	C3—C2—C1—O1	−177.7 (2)
Ni1—N1—C2—C3	177.21 (13)	N1—C2—C1—O1	3.0 (2)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O2ⁱⁱ	0.86	2.16	2.942 (3)	152
N2—H2N···O1ⁱⁱ	0.86	2.36	3.130 (2)	149
O1W—H1WA···O2ⁱⁱⁱ	0.83	1.94	2.762 (2)	169
O1W—H1WB···O2^iv	0.84	1.94	2.7654 (19)	168

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

Experimental details

Crystal data
Chemical formula	[Ni(C₄H₃N₂O₂)₂(H₂O)₂]
M_r	316.91
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	6.6123 (18), 12.267 (3), 7.239 (2)
β (°)	101.059 (3)
V (Å³)	576.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.72
Crystal size (mm)	0.48 × 0.36 × 0.32

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.493, 0.610
No. of measured, independent and observed [I > 2σ(I)] reflections	2878, 1043, 947
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.070, 1.07
No. of reflections	1043
No. of parameters	88
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.42

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O2ⁱ	0.86	2.16	2.942 (3)	152
N2—H2N···O1ⁱ	0.86	2.36	3.130 (2)	149
O1W—H1WA···O2ⁱⁱ	0.83	1.94	2.762 (2)	169
O1W—H1WB···O2ⁱⁱⁱ	0.84	1.94	2.7654 (19)	168

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

Acknowledgements

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

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