Tetra­aqua­bis[2-(2,4-dichloro­phen­oxy)acetato]nickel(II)

Chen, W.; Yuan, J.-W.; Lei, L.; Zeng, Q.-F.

doi:10.1107/S1600536809033662

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1148

doi:10.1107/S1600536809033662

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Tetraaquabis[2-(2,4-dichlorophenoxy)acetato]nickel(II)

Wu Chen,^a Ji-Wen Yuan,^a Lei Lei ^a and Qing-Fu Zeng ^a ^*

^aEngineering Research Center for Clean Production of Textile Dyeing and Printing, Ministry of Education, Wuhan 430073, People's Republic of China
^*Correspondence e-mail: qfzeng@wuse.edu.cn

(Received 23 August 2009; accepted 24 August 2009; online 29 August 2009)

In the title complex, [Ni(C₈H₅Cl₂O₃)₂(H₂O)₄], the Ni^II atom (site symmetry $[\overline{1}]$ ) adopts a slightly distorted NiO₆ octahedral coordination. An intramolecular O—H⋯O hydrogen bond helps to establish the conformation. In the crystal, further O—H⋯O hydrogen bonds link the molecules.

Related literature

For background, see: Cheng et al. (2006 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Ni(C₈H₅Cl₂O₃)₂(H₂O)₄]
M_r = 570.81
Monoclinic, P 2₁ /c
a = 16.860 (3) Å
b = 8.1370 (16) Å
c = 8.3010 (17) Å
β = 95.87 (3)°
V = 1132.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.38 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.683, T_max = 0.875
2134 measured reflections
1976 independent reflections
1596 reflections with I > 2σ(I)
R_int = 0.017
200 standard reflections every 3 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.214
S = 1.14
1976 reflections
154 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.86 e Å⁻³
Δρ_min = −1.97 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—O3	2.085 (5)
Ni1—O4	2.126 (4)
Ni1—O1	2.130 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2ⁱ	0.84 (5)	2.05 (7)	2.723 (7)	136 (8)
O1—H1B⋯O2	0.84 (3)	1.82 (5)	2.619 (7)	157 (7)
O3—H3A⋯O1ⁱ	0.85 (6)	2.44 (7)	3.217 (7)	153 (7)
O3—H3B⋯O6ⁱⁱ	0.846 (16)	2.34 (6)	2.980 (7)	133 (8)
Symmetry codes: (i) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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 global, I. DOI: 10.1107/S1600536809033662/hb5064sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033662/hb5064Isup2.hkl

checkCIF report

Comment top

There has been much research interest in acid metal complexes due to their molecular architectures and biological activities (e.g. Cheng et al., 2006). In this work, we report here the crystal structure of the title compound, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). The Ni^II atom is six-coordinated by two O atoms from the 2-(2,4-dichlorophenoxy)acetate and four O atoms from the water molecules, forming a slightly distorted octahedral coordination.

Related literature top

For background, see: Cheng et al. (2006). For reference structural data, see: Allen et al. (1987).

Experimental top

A mixture of 2-(2,4-dichlorophenoxy)acetic acid (440 mg, 2 mmol) and NiCl2.6H2O (1 mmol, 236 mg) in methanol (10 ml) was stirred for 3 h. After keeping the filtrate in air for 7 d, green blocks of (I) were formed.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 (I) showing 30% probability displacement ellipsoids. Atoms with the suffix A are generated by the symmetry operation (1–x, –y, 1–z).

Tetraaquabis[2-(2,4-dichlorophenoxy)acetato]nickel(II) top

Crystal data top

[Ni(C₈H₅Cl₂O₃)₂(H₂O)₄]	F(000) = 580
M_r = 570.81	D_x = 1.673 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 16.860 (3) Å	θ = 9–12°
b = 8.1370 (16) Å	µ = 1.38 mm⁻¹
c = 8.3010 (17) Å	T = 293 K
β = 95.87 (3)°	Block, green
V = 1132.8 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	1596 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 25.2°, θ_min = 1.2°
ω/2θ scans	h = −20→20
Absorption correction: ψ scan (North et al., 1968)	k = −9→0
T_min = 0.683, T_max = 0.875	l = 0→9
2134 measured reflections	200 standard reflections every 3 reflections
1976 independent reflections	intensity decay: 1%

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.214	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ²(F_o²) + (0.1181P)² + 3.965P] where P = (F_o² + 2F_c²)/3
1976 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.86 e Å⁻³
6 restraints	Δρ_min = −1.97 e Å⁻³

Crystal data top

[Ni(C₈H₅Cl₂O₃)₂(H₂O)₄]	V = 1132.8 (4) Å³
M_r = 570.81	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.860 (3) Å	µ = 1.38 mm⁻¹
b = 8.1370 (16) Å	T = 293 K
c = 8.3010 (17) Å	0.30 × 0.20 × 0.10 mm
β = 95.87 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1596 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.017
T_min = 0.683, T_max = 0.875	200 standard reflections every 3 reflections
2134 measured reflections	intensity decay: 1%
1976 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	6 restraints
wR(F²) = 0.214	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	Δρ_max = 0.86 e Å⁻³
1976 reflections	Δρ_min = −1.97 e Å⁻³
154 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
C1	0.1103 (4)	0.1141 (9)	0.3299 (9)	0.0487 (17)
H1	0.0872	0.0160	0.3585	0.058*
C2	0.1780 (4)	0.4056 (8)	0.2486 (8)	0.0363 (14)
C3	0.1822 (4)	0.1110 (8)	0.2642 (9)	0.0454 (16)
H3	0.2076	0.0113	0.2504	0.054*
C4	0.0724 (4)	0.2598 (9)	0.3534 (9)	0.0458 (16)
C5	0.1072 (4)	0.4079 (8)	0.3131 (8)	0.0431 (15)
H5	0.0821	0.5072	0.3303	0.052*
C6	0.3693 (4)	0.0240 (7)	0.2247 (7)	0.0296 (12)
C7	0.2173 (4)	0.2580 (7)	0.2183 (8)	0.0345 (13)
C8	0.3201 (4)	0.1188 (8)	0.0942 (7)	0.0388 (15)
H8A	0.3533	0.1447	0.0088	0.047*
H8B	0.2770	0.0489	0.0479	0.047*
Cl1	−0.01949 (12)	0.2621 (3)	0.4316 (3)	0.0626 (6)
Cl2	0.22352 (11)	0.5880 (2)	0.1988 (3)	0.0557 (6)
H1A	0.418 (3)	−0.233 (12)	0.523 (6)	0.067*
H3A	0.452 (4)	−0.018 (10)	0.785 (6)	0.067*
H1B	0.436 (4)	−0.226 (11)	0.366 (3)	0.067*
H3B	0.3858 (7)	0.030 (11)	0.687 (9)	0.067*
Ni1	0.5000	0.0000	0.5000	0.0266 (4)
O1	0.4550 (3)	−0.2430 (5)	0.4624 (6)	0.0406 (11)
O2	0.3738 (3)	−0.1289 (5)	0.2003 (5)	0.0433 (11)
O3	0.4362 (3)	0.0347 (7)	0.6996 (6)	0.0503 (12)
O4	0.4045 (2)	0.0994 (5)	0.3429 (5)	0.0319 (9)
O6	0.2866 (3)	0.2687 (6)	0.1489 (6)	0.0420 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.053 (4)	0.039 (4)	0.052 (4)	−0.005 (3)	−0.005 (3)	−0.005 (3)
C2	0.038 (3)	0.029 (3)	0.041 (3)	−0.008 (3)	−0.002 (3)	0.005 (3)
C3	0.048 (4)	0.027 (3)	0.059 (4)	−0.002 (3)	−0.009 (3)	0.004 (3)
C4	0.049 (4)	0.046 (4)	0.040 (4)	−0.006 (3)	−0.006 (3)	0.002 (3)
C5	0.049 (4)	0.032 (3)	0.047 (4)	0.000 (3)	0.000 (3)	0.000 (3)
C6	0.039 (3)	0.018 (3)	0.032 (3)	0.001 (2)	0.006 (2)	−0.002 (2)
C7	0.037 (3)	0.029 (3)	0.036 (3)	0.004 (2)	−0.004 (2)	0.000 (2)
C8	0.046 (4)	0.035 (3)	0.034 (3)	0.006 (3)	−0.001 (3)	−0.009 (3)
Cl1	0.0543 (11)	0.0675 (13)	0.0680 (13)	−0.0061 (9)	0.0147 (9)	−0.0037 (10)
Cl2	0.0552 (11)	0.0276 (8)	0.0841 (14)	0.0013 (7)	0.0062 (9)	0.0059 (8)
Ni1	0.0369 (6)	0.0154 (5)	0.0270 (6)	0.0015 (4)	0.0017 (4)	0.0023 (4)
O1	0.058 (3)	0.028 (2)	0.035 (2)	0.000 (2)	−0.001 (2)	−0.0015 (19)
O2	0.066 (3)	0.031 (2)	0.032 (2)	−0.001 (2)	−0.003 (2)	−0.0056 (18)
O3	0.048 (3)	0.054 (3)	0.050 (3)	0.009 (2)	0.013 (2)	0.007 (2)
O4	0.043 (2)	0.0205 (19)	0.030 (2)	0.0092 (17)	−0.0054 (17)	−0.0048 (17)
O6	0.037 (2)	0.032 (2)	0.056 (3)	0.0010 (18)	−0.002 (2)	0.004 (2)

Geometric parameters (Å, º) top

C1—C4	1.369 (10)	C7—O6	1.358 (8)
C1—C3	1.381 (11)	C8—O6	1.437 (7)
C1—H1	0.9300	C8—H8A	0.9700
C2—C5	1.358 (10)	C8—H8B	0.9700
C2—C7	1.407 (9)	Ni1—O3	2.085 (5)
C2—Cl2	1.740 (6)	Ni1—O3ⁱ	2.085 (5)
C3—C7	1.403 (9)	Ni1—O4	2.126 (4)
C3—H3	0.9300	Ni1—O4ⁱ	2.126 (4)
C4—C5	1.396 (10)	Ni1—O1ⁱ	2.130 (4)
C4—Cl1	1.741 (8)	Ni1—O1	2.130 (4)
C5—H5	0.9300	O1—H1A	0.841 (10)
C6—O4	1.253 (7)	O1—H1B	0.840 (10)
C6—O2	1.265 (7)	O3—H3A	0.844 (10)
C6—C8	1.508 (8)	O3—H3B	0.847 (10)

C4—C1—C3	120.9 (7)	C6—C8—H8B	108.7
C4—C1—H1	119.6	H8A—C8—H8B	107.6
C3—C1—H1	119.6	O3—Ni1—O3ⁱ	180.0
C5—C2—C7	122.1 (6)	O3—Ni1—O4	90.93 (19)
C5—C2—Cl2	120.6 (5)	O3ⁱ—Ni1—O4	89.07 (18)
C7—C2—Cl2	117.3 (5)	O3—Ni1—O4ⁱ	89.07 (18)
C1—C3—C7	120.2 (6)	O3ⁱ—Ni1—O4ⁱ	90.93 (18)
C1—C3—H3	119.9	O4—Ni1—O4ⁱ	180.0
C7—C3—H3	119.9	O3—Ni1—O1ⁱ	87.9 (2)
C1—C4—C5	120.0 (7)	O3ⁱ—Ni1—O1ⁱ	92.1 (2)
C1—C4—Cl1	120.5 (6)	O4—Ni1—O1ⁱ	88.46 (16)
C5—C4—Cl1	119.5 (6)	O4ⁱ—Ni1—O1ⁱ	91.54 (16)
C2—C5—C4	119.4 (6)	O3—Ni1—O1	92.1 (2)
C2—C5—H5	120.3	O3ⁱ—Ni1—O1	87.9 (2)
C4—C5—H5	120.3	O4—Ni1—O1	91.54 (16)
O4—C6—O2	125.2 (5)	O4ⁱ—Ni1—O1	88.46 (16)
O4—C6—C8	119.6 (5)	O1ⁱ—Ni1—O1	180.0
O2—C6—C8	115.2 (5)	Ni1—O1—H1A	96 (7)
O6—C7—C3	125.1 (6)	Ni1—O1—H1B	94 (6)
O6—C7—C2	117.5 (5)	H1A—O1—H1B	108.9 (18)
C3—C7—C2	117.4 (6)	Ni1—O3—H3A	117 (6)
O6—C8—C6	114.4 (5)	Ni1—O3—H3B	119 (6)
O6—C8—H8A	108.7	H3A—O3—H3B	108.4 (18)
C6—C8—H8A	108.7	C6—O4—Ni1	124.2 (4)
O6—C8—H8B	108.7	C7—O6—C8	117.5 (5)

C4—C1—C3—C7	−0.9 (11)	O4—C6—C8—O6	−28.4 (8)
C3—C1—C4—C5	−1.0 (11)	O2—C6—C8—O6	154.2 (6)
C3—C1—C4—Cl1	178.4 (5)	O2—C6—O4—Ni1	14.9 (9)
C7—C2—C5—C4	1.0 (10)	C8—C6—O4—Ni1	−162.2 (4)
Cl2—C2—C5—C4	−179.3 (5)	O3—Ni1—O4—C6	−122.0 (5)
C1—C4—C5—C2	0.9 (10)	O3ⁱ—Ni1—O4—C6	58.0 (5)
Cl1—C4—C5—C2	−178.5 (5)	O4ⁱ—Ni1—O4—C6	76 (100)
C1—C3—C7—O6	−178.2 (6)	O1ⁱ—Ni1—O4—C6	150.1 (5)
C1—C3—C7—C2	2.7 (10)	O1—Ni1—O4—C6	−29.9 (5)
C5—C2—C7—O6	178.0 (6)	C3—C7—O6—C8	10.6 (9)
Cl2—C2—C7—O6	−1.6 (8)	C2—C7—O6—C8	−170.3 (5)
C5—C2—C7—C3	−2.8 (10)	C6—C8—O6—C7	−83.3 (7)
Cl2—C2—C7—C3	177.5 (5)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱⁱ	0.84 (5)	2.05 (7)	2.723 (7)	136 (8)
O1—H1B···O2	0.84 (3)	1.82 (5)	2.619 (7)	157 (7)
O3—H3A···O1ⁱⁱ	0.85 (6)	2.44 (7)	3.217 (7)	153 (7)
O3—H3B···O6ⁱⁱⁱ	0.85 (2)	2.34 (6)	2.980 (7)	133 (8)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₈H₅Cl₂O₃)₂(H₂O)₄]
M_r	570.81
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	16.860 (3), 8.1370 (16), 8.3010 (17)
β (°)	95.87 (3)
V (Å³)	1132.8 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.38
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.683, 0.875
No. of measured, independent and observed [I > 2σ(I)] reflections	2134, 1976, 1596
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.214, 1.14
No. of reflections	1976
No. of parameters	154
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.86, −1.97

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—O3	2.085 (5)	Ni1—O1	2.130 (4)
Ni1—O4	2.126 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱ	0.84 (5)	2.05 (7)	2.723 (7)	136 (8)
O1—H1B···O2	0.84 (3)	1.82 (5)	2.619 (7)	157 (7)
O3—H3A···O1ⁱ	0.85 (6)	2.44 (7)	3.217 (7)	153 (7)
O3—H3B···O6ⁱⁱ	0.846 (16)	2.34 (6)	2.980 (7)	133 (8)

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

Acknowledgements

The project was supported by the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, Educational Commission of Hubei Province (D20091703) and the Natural Science Foundation of Hubei Province (2008CDB038).

References

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