Diaqua­bis­[4-(4H-1,2,4-triazol-4-yl)benzoato-κ2O,O′]nickel(II)

Xu, S.; Shao, W.; Yu, M.; Gong, G.

doi:10.1107/S1600536811016643

metal-organic compounds

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Volume 67| Part 6| June 2011| Page m728

doi:10.1107/S1600536811016643

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Diaquabis[4-(4H-1,2,4-triazol-4-yl)benzoato-κ²O,O′]nickel(II)

Shuzhi Xu,^a ^* Wenxin Shao,^a Miao Yu ^a and Guihua Gong ^a

^aJilin Business and Technology College, Changchun 130062, People's Republic of China
^*Correspondence e-mail: chemxusz@yahoo.cn

(Received 27 April 2011; accepted 3 May 2011; online 7 May 2011)

In the title compound, [Ni(C₉H₆N₃O₂)₂(H₂O)₂], the Ni^II atom lies on a twofold rotation axis and is six-coordinated by two bidentate chelating 4-(1,2,4-triazol-4-yl)benzoate ligands and two water molecules in a distorted octahedral geometry. Intermolecular O—H⋯N hydrogen bonds link the complex molecules into a two-dimensional network parallel to (010).

Related literature

For general background to the structures and applications of metal complexes, see: Mahata et al. (2009 ); Perry et al. (2004 ); Qin et al. (2005 ); Shi et al. (2009 ). For a related structure, see: Zhu (2010 ).

Experimental

Crystal data

[Ni(C₉H₆N₃O₂)₂(H₂O)₂]
M_r = 471.06
Monoclinic, C 2/c
a = 13.5194 (6) Å
b = 9.8480 (5) Å
c = 14.3234 (7) Å
β = 112.293 (1)°
V = 1764.47 (15) Å³
Z = 4
Mo Kα radiation
μ = 1.16 mm⁻¹
T = 296 K
0.28 × 0.24 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.72, T_max = 0.82
4732 measured reflections
1744 independent reflections
1662 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.084
S = 1.13
1744 reflections
147 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—O1	2.1507 (14)
Ni1—O2	2.1240 (14)
Ni1—O3	2.0453 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯N2ⁱ	0.78 (2)	2.06 (2)	2.836 (2)	172 (3)
O3—H3A⋯N3ⁱⁱ	0.79 (2)	1.99 (2)	2.768 (2)	169 (3)
Symmetry codes: (i) $[-x, y, -z+{\script{3\over 2}}]$ ; (ii) $[x+1, -y, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811016643/hy2427sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016643/hy2427Isup2.hkl

checkCIF report

Comment top

The construction of novel coordination complexes is the current interest in the field of supramolecular chemistry and crystal engineering stemming from their potential applications as functional materials, as well as their intriguing variety of architectures and topologies (Perry et al., 2004; Qin et al., 2005). Heterocyclic carboxylates have often been used as mono-, bi- or multi-dentate ligands to bind transition metal centers, leading to the formation of moderately robust metal–organic coordination frameworks (Mahata et al., 2009; Shi et al., 2009). In this contribution, we selected 4-(1,2,4-triazol-4-yl)benzoic acid (Htyb) as an organic carboxylate ligand, generating the title compound, which is reported here.

In the title compound, the Ni^II atom lies on a twofold rotation axis and adopts a distorted octahedral coordination geometry, being coordinated by four carboxylate O atoms from two tyb ligands and two water molecules (Fig. 1, Table 1). The Ni—O bond lengths and the O—Ni—O bond angles are in the normal range (Zhu, 2010). Intermolecular O—H···N hydrogen bonds (Table 2) stabilize the structure and give a two-dimensional network (Fig. 2).

Related literature top

For general background to the structures and applications of metal complexes, see: Mahata et al. (2009); Perry et al. (2004); Qin et al. (2005); Shi et al. (2009). For a related structure, see: Zhu (2010).

Experimental top

The synthesis was performed under hydrothermal conditions. A mixture of Ni(CH₃COO)₂.4H₂O (0.2 mmol, 0.05 g), 4-(1,2,4-triazol-4-yl)benzoic acid (0.4 mmol, 0.075 g), NaOH (0.4 mmol, 0.016 g) and H₂O (15 ml) in a 25 ml stainless steel reactor with a Teflon liner was heated from 293 to 443 K in 2 h and a constant temperature was maintained at 443 K for 72 h. After the mixture was cooled to 298 K, green crystals of the title compound were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) 1-x, y, 3/2-z.]
	Fig. 2. View of the layer structure in the title compound, built by O—H···N hydrogen bonds (dashed lines).

Diaquabis[4-(4H-1,2,4-triazol-4-yl)benzoato- κ²O,O']nickel(II) top

Crystal data top

[Ni(C₉H₆N₃O₂)₂(H₂O)₂]	F(000) = 968
M_r = 471.06	D_x = 1.773 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1744 reflections
a = 13.5194 (6) Å	θ = 1.0–26.0°
b = 9.8480 (5) Å	µ = 1.16 mm⁻¹
c = 14.3234 (7) Å	T = 296 K
β = 112.293 (1)°	Block, green
V = 1764.47 (15) Å³	0.28 × 0.24 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1744 independent reflections
Radiation source: fine-focus sealed tube	1662 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −16→16
T_min = 0.72, T_max = 0.82	k = −12→9
4732 measured reflections	l = −14→17

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) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0345P)² + 4.2534P] where P = (F_o² + 2F_c²)/3
1744 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.31 e Å⁻³
2 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Ni(C₉H₆N₃O₂)₂(H₂O)₂]	V = 1764.47 (15) Å³
M_r = 471.06	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.5194 (6) Å	µ = 1.16 mm⁻¹
b = 9.8480 (5) Å	T = 296 K
c = 14.3234 (7) Å	0.28 × 0.24 × 0.22 mm
β = 112.293 (1)°

Data collection top

Bruker APEXII CCD diffractometer	1744 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1662 reflections with I > 2σ(I)
T_min = 0.72, T_max = 0.82	R_int = 0.021
4732 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	2 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.31 e Å⁻³
1744 reflections	Δρ_min = −0.45 e Å⁻³
147 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.30391 (16)	0.07262 (19)	0.68990 (15)	0.0139 (4)
C2	0.18541 (15)	0.0695 (2)	0.66363 (15)	0.0144 (4)
C3	0.12703 (16)	0.1900 (2)	0.64420 (15)	0.0164 (4)
H3	0.1616	0.2723	0.6465	0.020*
C4	0.01757 (15)	0.1882 (2)	0.62145 (15)	0.0164 (4)
H4	−0.0217	0.2684	0.6074	0.020*
C5	−0.03212 (15)	0.0645 (2)	0.62014 (15)	0.0132 (4)
C6	0.02504 (16)	−0.0562 (2)	0.64143 (16)	0.0167 (4)
H6	−0.0092	−0.1381	0.6416	0.020*
C7	0.13424 (16)	−0.0531 (2)	0.66248 (16)	0.0163 (4)
H7	0.1732	−0.1336	0.6759	0.020*
C8	−0.21097 (15)	0.1595 (2)	0.60494 (15)	0.0157 (4)
H8	−0.1890	0.2466	0.6290	0.019*
C9	−0.21064 (16)	−0.0489 (2)	0.55868 (16)	0.0178 (4)
H9	−0.1883	−0.1332	0.5450	0.021*
N1	−0.14499 (13)	0.05953 (17)	0.59661 (12)	0.0136 (4)
N2	−0.30914 (13)	0.11583 (19)	0.57442 (13)	0.0176 (4)
N3	−0.30856 (13)	−0.01823 (19)	0.54433 (13)	0.0188 (4)
O1	0.35080 (11)	0.18546 (14)	0.69937 (11)	0.0162 (3)
O2	0.35618 (11)	−0.03741 (15)	0.70360 (11)	0.0184 (3)
O3	0.50303 (12)	0.10080 (19)	0.89291 (12)	0.0248 (4)
Ni1	0.5000	0.07701 (4)	0.7500	0.01674 (14)
H3A	0.5529 (17)	0.080 (3)	0.9416 (16)	0.025*
H3B	0.4511 (17)	0.113 (3)	0.903 (2)	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0112 (10)	0.0169 (10)	0.0139 (9)	−0.0001 (7)	0.0050 (8)	−0.0002 (7)
C2	0.0097 (10)	0.0186 (10)	0.0148 (9)	0.0000 (7)	0.0045 (8)	−0.0001 (7)
C3	0.0125 (9)	0.0150 (10)	0.0218 (10)	−0.0022 (8)	0.0066 (8)	0.0014 (8)
C4	0.0114 (9)	0.0149 (10)	0.0221 (10)	0.0024 (7)	0.0056 (8)	0.0033 (8)
C5	0.0073 (9)	0.0189 (10)	0.0132 (9)	−0.0003 (7)	0.0038 (7)	−0.0006 (7)
C6	0.0122 (10)	0.0153 (10)	0.0229 (11)	−0.0022 (8)	0.0069 (8)	−0.0005 (8)
C7	0.0124 (10)	0.0142 (9)	0.0229 (10)	0.0018 (8)	0.0075 (8)	0.0003 (8)
C8	0.0104 (9)	0.0193 (10)	0.0174 (10)	0.0019 (8)	0.0053 (8)	0.0006 (8)
C9	0.0135 (10)	0.0188 (10)	0.0204 (10)	−0.0034 (8)	0.0056 (8)	−0.0026 (8)
N1	0.0087 (8)	0.0164 (8)	0.0156 (8)	−0.0013 (6)	0.0045 (7)	−0.0001 (6)
N2	0.0110 (8)	0.0230 (9)	0.0183 (9)	−0.0001 (7)	0.0049 (7)	0.0005 (7)
N3	0.0118 (8)	0.0232 (9)	0.0203 (9)	−0.0025 (7)	0.0047 (7)	−0.0003 (7)
O1	0.0089 (6)	0.0161 (7)	0.0231 (7)	−0.0010 (5)	0.0054 (6)	0.0001 (6)
O2	0.0091 (6)	0.0164 (7)	0.0293 (8)	0.0008 (6)	0.0070 (6)	0.0005 (6)
O3	0.0090 (7)	0.0468 (10)	0.0188 (8)	0.0075 (7)	0.0054 (6)	0.0057 (7)
Ni1	0.0100 (2)	0.0175 (2)	0.0222 (2)	0.000	0.00558 (16)	0.000

Geometric parameters (Å, º) top

C1—O1	1.261 (2)	C7—H7	0.9300
C1—O2	1.268 (2)	C8—N2	1.303 (3)
C1—C2	1.501 (3)	C8—N1	1.364 (3)
C1—Ni1	2.458 (2)	C8—H8	0.9300
C2—C7	1.388 (3)	C9—N3	1.296 (3)
C2—C3	1.394 (3)	C9—N1	1.363 (3)
C3—C4	1.389 (3)	C9—H9	0.9300
C3—H3	0.9300	N2—N3	1.390 (3)
C4—C5	1.388 (3)	O3—H3A	0.79 (2)
C4—H4	0.9300	O3—H3B	0.78 (2)
C5—C6	1.387 (3)	Ni1—O1	2.1507 (14)
C5—N1	1.433 (2)	Ni1—O2	2.1240 (14)
C6—C7	1.391 (3)	Ni1—O3	2.0453 (16)
C6—H6	0.9300

O1—C1—O2	120.58 (18)	C9—N3—N2	107.32 (17)
O1—C1—C2	119.38 (17)	C1—O1—Ni1	88.14 (11)
O2—C1—C2	120.03 (17)	C1—O2—Ni1	89.16 (12)
O1—C1—Ni1	61.01 (10)	Ni1—O3—H3A	123 (2)
O2—C1—Ni1	59.79 (10)	Ni1—O3—H3B	122 (2)
C2—C1—Ni1	174.50 (14)	H3A—O3—H3B	114 (3)
C7—C2—C3	119.77 (18)	O3—Ni1—O3ⁱ	166.84 (11)
C7—C2—C1	120.05 (18)	O3—Ni1—O2	92.43 (6)
C3—C2—C1	120.14 (17)	O3ⁱ—Ni1—O2	94.54 (6)
C4—C3—C2	120.52 (18)	O3—Ni1—O2ⁱ	94.54 (6)
C4—C3—H3	119.7	O3ⁱ—Ni1—O2ⁱ	92.43 (6)
C2—C3—H3	119.7	O2—Ni1—O2ⁱ	115.92 (8)
C5—C4—C3	118.77 (18)	O3—Ni1—O1ⁱ	86.88 (6)
C5—C4—H4	120.6	O3ⁱ—Ni1—O1ⁱ	86.60 (6)
C3—C4—H4	120.6	O2—Ni1—O1ⁱ	177.55 (6)
C6—C5—C4	121.53 (18)	O2ⁱ—Ni1—O1ⁱ	61.82 (6)
C6—C5—N1	118.50 (17)	O3—Ni1—O1	86.60 (6)
C4—C5—N1	119.97 (17)	O3ⁱ—Ni1—O1	86.88 (6)
C5—C6—C7	119.07 (18)	O2—Ni1—O1	61.82 (6)
C5—C6—H6	120.5	O2ⁱ—Ni1—O1	177.55 (6)
C7—C6—H6	120.5	O1ⁱ—Ni1—O1	120.45 (8)
C2—C7—C6	120.32 (19)	O3—Ni1—C1	87.82 (6)
C2—C7—H7	119.8	O3ⁱ—Ni1—C1	92.41 (6)
C6—C7—H7	119.8	O2—Ni1—C1	31.05 (6)
N2—C8—N1	110.45 (18)	O2ⁱ—Ni1—C1	146.94 (6)
N2—C8—H8	124.8	O1ⁱ—Ni1—C1	151.16 (6)
N1—C8—H8	124.8	O1—Ni1—C1	30.85 (6)
N3—C9—N1	110.64 (19)	O3—Ni1—C1ⁱ	92.41 (6)
N3—C9—H9	124.7	O3ⁱ—Ni1—C1ⁱ	87.82 (6)
N1—C9—H9	124.7	O2—Ni1—C1ⁱ	146.94 (6)
C9—N1—C8	104.57 (17)	O2ⁱ—Ni1—C1ⁱ	31.05 (6)
C9—N1—C5	126.49 (17)	O1ⁱ—Ni1—C1ⁱ	30.85 (6)
C8—N1—C5	128.93 (17)	O1—Ni1—C1ⁱ	151.16 (6)
C8—N2—N3	107.02 (16)	C1—Ni1—C1ⁱ	177.99 (9)

O1—C1—C2—C7	−173.79 (19)	N1—C9—N3—N2	−0.5 (2)
O2—C1—C2—C7	5.3 (3)	C8—N2—N3—C9	0.4 (2)
O1—C1—C2—C3	3.7 (3)	O2—C1—O1—Ni1	−5.41 (19)
O2—C1—C2—C3	−177.18 (18)	C2—C1—O1—Ni1	173.72 (16)
C7—C2—C3—C4	−1.4 (3)	O1—C1—O2—Ni1	5.47 (19)
C1—C2—C3—C4	−178.94 (18)	C2—C1—O2—Ni1	−173.65 (16)
C2—C3—C4—C5	1.1 (3)	C1—O2—Ni1—O3	81.70 (12)
C3—C4—C5—C6	0.3 (3)	C1—O2—Ni1—O3ⁱ	−87.13 (12)
C3—C4—C5—N1	−179.81 (17)	C1—O2—Ni1—O2ⁱ	177.95 (13)
C4—C5—C6—C7	−1.4 (3)	C1—O1—Ni1—O3	−91.44 (12)
N1—C5—C6—C7	178.78 (18)	C1—O1—Ni1—O3ⁱ	100.00 (12)
C3—C2—C7—C6	0.4 (3)	C1—O1—Ni1—O2	3.15 (11)
C1—C2—C7—C6	177.89 (18)	C1—O1—Ni1—O1ⁱ	−175.80 (12)
C5—C6—C7—C2	1.0 (3)	O1—C1—Ni1—O3	87.02 (12)
N3—C9—N1—C8	0.4 (2)	O2—C1—Ni1—O3	−98.36 (12)
N3—C9—N1—C5	−178.76 (17)	O1—C1—Ni1—O3ⁱ	−79.81 (12)
N2—C8—N1—C9	−0.1 (2)	O2—C1—Ni1—O3ⁱ	94.80 (12)
N2—C8—N1—C5	178.99 (18)	O1—C1—Ni1—O2	−174.61 (19)
C6—C5—N1—C9	−24.4 (3)	O1—C1—Ni1—O2ⁱ	−178.00 (10)
C4—C5—N1—C9	155.7 (2)	O2—C1—Ni1—O2ⁱ	−3.4 (2)
C6—C5—N1—C8	156.7 (2)	O1—C1—Ni1—O1ⁱ	7.5 (2)
C4—C5—N1—C8	−23.2 (3)	O2—C1—Ni1—O1ⁱ	−177.86 (11)
N1—C8—N2—N3	−0.2 (2)	O2—C1—Ni1—O1	174.61 (19)

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
O3—H3B···N2ⁱⁱ	0.78 (2)	2.06 (2)	2.836 (2)	172 (3)
O3—H3A···N3ⁱⁱⁱ	0.79 (2)	1.99 (2)	2.768 (2)	169 (3)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₉H₆N₃O₂)₂(H₂O)₂]
M_r	471.06
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	13.5194 (6), 9.8480 (5), 14.3234 (7)
β (°)	112.293 (1)
V (Å³)	1764.47 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.16
Crystal size (mm)	0.28 × 0.24 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.72, 0.82
No. of measured, independent and observed [I > 2σ(I)] reflections	4732, 1744, 1662
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.084, 1.13
No. of reflections	1744
No. of parameters	147
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)	0.31, −0.45

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Selected bond lengths (Å) top

Ni1—O1	2.1507 (14)	Ni1—O3	2.0453 (16)
Ni1—O2	2.1240 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···N2ⁱ	0.78 (2)	2.06 (2)	2.836 (2)	172 (3)
O3—H3A···N3ⁱⁱ	0.79 (2)	1.99 (2)	2.768 (2)	169 (3)

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

Acknowledgements

We thank Jilin Business and Technology College for supporting this work.

References

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