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

Abstract

In the title complex, [Ni(C₈H₅Cl₂O₃)₂(H₂O)₄], the Ni^II atom (site symmetry ) 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,

• a = 16.860 (3) Å

• b = 8.1370 (16) Å

• c = 8.3010 (17) Å

• β = 95.87 (3)°

• V = 1132.8 (4) ų

• 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[F ² > 2σ(F ²)] = 0.071

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

The water H atoms were located in a difference map and their positions were refined with the restraint O—H = 0.83 (1)Å. The other H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C).

Figures

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).

Crystal data

[Ni(C8H5Cl2O3)2(H2O)4]	F(000) = 580
Mr = 570.81	Dx = 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

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

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)] = 0.071	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(Fo2) + (0.1181P)2 + 3.965P] where P = (Fo2 + 2Fc2)/3
1976 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.86 e Å−3
6 restraints	Δρmin = −1.97 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
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

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.