Diaqua­bis(2-carboxy­benzoato-κO)nickel(II)

Xuan, Y.-W.; Wu, W.; Xie, D.-P.; Yuan, N.-X.

doi:10.1107/S1600536807064604

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m101

https://doi.org/10.1107/S1600536807064604

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Diaquabis(2-carboxybenzoato-κO)nickel(II)

Ya-Wen Xuan,^a ^* Wen Wu,^a Dong-Po Xie ^a and Nai-Xiang Yuan ^a

^aDepartment of Chemistry, Zhou Kou Normal University, Zhou Kou 466001, People's Republic of China
^*Correspondence e-mail: bookw@126.com

(Received 16 November 2007; accepted 30 November 2007; online 6 December 2007)

In the title compound, [Ni(C₈H₅O₄)₂(H₂O)₂], the Ni^II atom lies on an inversion centre and exhibits a square-planar geometry incorporating two phthalate and two water O atoms. The nickel complex is stabilized by intramolecular interactions involving water O atoms and H atoms of the phthalate groups. It forms one-dimensional zigzag chains along the b axis which are held together via π–π stacking interactions (3.647 Å) between the benzene rings of the phthalate groups. The adjacent chains are also hydrogen bonded, resulting in a three-dimensional supramolecular network.

Related literature

For related literature, see: Adiwidjaja & Küppers (1976 ).

Experimental

Crystal data

[Ni(C₈H₅O₄)₂(H₂O)₂]
M_r = 424.98
Monoclinic, P 2₁ /c
a = 8.3601 (17) Å
b = 14.439 (3) Å
c = 7.1005 (14) Å
β = 111.99 (3)°
V = 794.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.28 mm⁻¹
T = 291 (2) K
0.20 × 0.18 × 0.16 mm

Data collection

Rigaku R-AXIS IV diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.784, T_max = 0.821
2628 measured reflections
1416 independent reflections
1343 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.090
S = 1.07
1416 reflections
137 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5F⋯O4ⁱ	0.86 (2)	1.82 (2)	2.667 (3)	170 (5)
O5—H5E⋯O3ⁱⁱ	0.86 (2)	1.95 (2)	2.789 (3)	164 (4)
O3—H3E⋯O2	0.87 (2)	1.54 (2)	2.403 (3)	171 (5)
C2—H2A⋯O1	0.93	2.33	2.689 (3)	102
C5—H5A⋯O4	0.93	2.36	2.707 (3)	102
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: R-AXIS (Rigaku, 1996 ); cell refinement: R-AXIS; data reduction: R-AXIS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN (Molecular Structure Corporation, 1997 ); software used to prepare material for publication: TEXSAN.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807064604/pv2050sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064604/pv2050Isup2.hkl

checkCIF report

Comment top

The molecule of the title complex, (I) (Fig. 1), is centrosymmetric, which crystallizes in space group P2₁/c. Its structure may be described as one-dimensional zigzag chains (Fig. 2) lying parallel to the b-Axis. It exhibits π-π stacking interactions belonging to a face-to-face form with the distance 3.647 Å. A three dimensional network is thus formed by π-π stacking interaction of phthalates and hydrogen bonds; details of hydrogen-bonding parameters have been provided in the Table.

Related literature top

For related literature, see: Adiwidjaja & Küppers (1976).

Experimental top

Potassium hydrogen phthalate (0.2040 g, 1 mmol), and KOH (0.0560 g, 1 mmol) were dissolved in 50 ml EtOH/H₂O (V:V = 1:1). To this solution was added a solution of Ni(NO₃)₂.6H₂O (0.2901 g, 1 mmol) in 10 ml double-distilled water. The resulting solution was heated at 373 K for 96 h. After cooling to room temperature, blue crystals suitable for X-ray analysis were obtained in a yield up to 65.42%.

Structure description top

For related literature, see: Adiwidjaja & Küppers (1976).

Computing details top

Data collection: R-AXIS (Rigaku, 1996); cell refinement: R-AXIS (Rigaku, 1996); data reduction: R-AXIS (Rigaku, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN (Molecular Structure Corporation, 1997); software used to prepare material for publication: TEXSAN (Molecular Structure Corporation, 1997).

Figures top

	Fig. 1. A view of (I) with 30% probability ellipsoid.
	Fig. 2. Unit cell packing of (I) showing hydrogen-bonding interactions.

Diaquabis(2-carboxybenzoato-κO)nickel(II) top

Crystal data top

[Ni(C₈H₅O₄)₂(H₂O)₂]	F(000) = 436
M_r = 424.98	D_x = 1.776 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 132 reflections
a = 8.3601 (17) Å	θ = 2–25.1°
b = 14.439 (3) Å	µ = 1.28 mm⁻¹
c = 7.1005 (14) Å	T = 291 K
β = 111.99 (3)°	Block, green
V = 794.8 (3) Å³	0.20 × 0.18 × 0.16 mm
Z = 2

Data collection top

Rigaku R-AXIS-IV diffractometer	1416 independent reflections
Radiation source: fine-focus sealed tube	1343 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 0 pixels mm^-1	θ_max = 25.5°, θ_min = 2.6°
Oscillation frames scans	h = −10→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −17→17
T_min = 0.784, T_max = 0.821	l = 0→8
2628 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0412P)² + 0.5337P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1416 reflections	Δρ_max = 0.30 e Å⁻³
137 parameters	Δρ_min = −0.38 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.094 (6)

Crystal data top

[Ni(C₈H₅O₄)₂(H₂O)₂]	V = 794.8 (3) Å³
M_r = 424.98	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3601 (17) Å	µ = 1.28 mm⁻¹
b = 14.439 (3) Å	T = 291 K
c = 7.1005 (14) Å	0.20 × 0.18 × 0.16 mm
β = 111.99 (3)°

Data collection top

Rigaku R-AXIS-IV diffractometer	1416 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1343 reflections with I > 2σ(I)
T_min = 0.784, T_max = 0.821	R_int = 0.030
2628 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	3 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.30 e Å⁻³
1416 reflections	Δρ_min = −0.38 e Å⁻³
137 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
Ni1	0.0000	0.0000	0.0000	0.0284 (2)
C1	0.7040 (3)	0.16274 (19)	0.2060 (4)	0.0391 (6)
H3A	0.7980	0.1236	0.2300	0.047*
C2	0.5426 (3)	0.12637 (17)	0.1689 (4)	0.0327 (6)
H2A	0.5285	0.0624	0.1650	0.039*
C3	0.3998 (3)	0.18327 (16)	0.1369 (3)	0.0266 (5)
C4	0.4213 (3)	0.28095 (16)	0.1374 (3)	0.0268 (5)
C5	0.5852 (3)	0.31545 (18)	0.1721 (4)	0.0362 (6)
H5A	0.6011	0.3792	0.1715	0.043*
C6	0.7252 (3)	0.25758 (19)	0.2075 (4)	0.0388 (6)
H4A	0.8338	0.2826	0.2323	0.047*
C7	0.2857 (3)	0.35548 (17)	0.1007 (4)	0.0328 (6)
C8	0.2350 (3)	0.13200 (17)	0.0993 (4)	0.0303 (5)
H3E	0.117 (6)	0.2779 (15)	0.110 (7)	0.094 (15)*
H5E	0.006 (4)	0.063 (2)	−0.329 (5)	0.065 (11)*
H5F	−0.132 (5)	−0.003 (2)	−0.378 (5)	0.084 (15)*
O1	0.2296 (2)	0.04720 (12)	0.0575 (3)	0.0388 (5)
O2	0.1034 (2)	0.17147 (13)	0.1107 (3)	0.0417 (5)
O3	0.1404 (2)	0.33670 (13)	0.1202 (3)	0.0416 (5)
O4	0.3147 (3)	0.43396 (12)	0.0568 (3)	0.0461 (5)
O5	−0.0588 (3)	0.02971 (16)	−0.2854 (3)	0.0514 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0268 (3)	0.0215 (3)	0.0385 (3)	−0.00561 (15)	0.0141 (2)	−0.00150 (16)
C1	0.0271 (13)	0.0423 (15)	0.0479 (16)	0.0051 (11)	0.0139 (11)	0.0009 (12)
C2	0.0332 (13)	0.0285 (12)	0.0370 (14)	0.0017 (10)	0.0136 (11)	0.0003 (10)
C3	0.0244 (11)	0.0286 (12)	0.0264 (12)	−0.0023 (9)	0.0091 (9)	0.0009 (9)
C4	0.0285 (12)	0.0278 (12)	0.0244 (11)	−0.0010 (9)	0.0101 (9)	−0.0014 (9)
C5	0.0338 (13)	0.0308 (12)	0.0417 (14)	−0.0072 (10)	0.0117 (11)	−0.0015 (10)
C6	0.0244 (12)	0.0467 (15)	0.0450 (16)	−0.0068 (11)	0.0127 (11)	−0.0037 (12)
C7	0.0322 (13)	0.0288 (13)	0.0327 (13)	0.0002 (10)	0.0068 (10)	−0.0029 (10)
C8	0.0273 (12)	0.0330 (13)	0.0311 (13)	0.0003 (10)	0.0114 (10)	0.0026 (10)
O1	0.0313 (10)	0.0299 (9)	0.0567 (12)	−0.0055 (7)	0.0187 (9)	−0.0027 (8)
O2	0.0301 (9)	0.0381 (10)	0.0631 (13)	−0.0014 (8)	0.0244 (9)	0.0017 (8)
O3	0.0369 (11)	0.0327 (10)	0.0602 (13)	0.0062 (8)	0.0240 (9)	−0.0020 (9)
O4	0.0421 (11)	0.0269 (9)	0.0613 (13)	0.0010 (8)	0.0102 (9)	0.0052 (8)
O5	0.048 (13)	0.0511 (13)	0.0440 (12)	−0.0266 (11)	0.0147 (10)	0.0008 (10)

Geometric parameters (Å, º) top

Ni1—O1ⁱ	1.9308 (18)	C4—C7	1.513 (3)
Ni1—O1	1.9308 (18)	C5—C6	1.382 (4)
Ni1—O5ⁱ	1.946 (2)	C5—H5A	0.9300
Ni1—O5	1.946 (2)	C6—H4A	0.9300
C1—C2	1.378 (4)	C7—O4	1.223 (3)
C1—C6	1.380 (4)	C7—O3	1.302 (3)
C1—H3A	0.9300	C8—O1	1.257 (3)
C2—C3	1.396 (3)	C8—O2	1.268 (3)
C2—H2A	0.9300	O3—H3E	0.87 (2)
C3—C4	1.422 (3)	O5—H5E	0.86 (2)
C3—C8	1.497 (3)	O5—H5F	0.86 (2)
C4—C5	1.391 (3)

O1ⁱ—Ni1—O1	180.00	C6—C5—C4	121.8 (2)
O1ⁱ—Ni1—O5ⁱ	89.20 (9)	C6—C5—H5A	119.1
O1—Ni1—O5ⁱ	90.80 (9)	C4—C5—H5A	119.1
O1ⁱ—Ni1—O5	90.80 (9)	C1—C6—C5	120.0 (2)
O1—Ni1—O5	89.20 (9)	C1—C6—H4A	120.0
O5ⁱ—Ni1—O5	180.00	C5—C6—H4A	120.0
C2—C1—C6	119.6 (2)	O4—C7—O3	120.1 (2)
C2—C1—H3A	120.2	O4—C7—C4	119.7 (2)
C6—C1—H3A	120.2	O3—C7—C4	120.1 (2)
C1—C2—C3	121.6 (2)	O1—C8—O2	119.8 (2)
C1—C2—H2A	119.2	O1—C8—C3	118.2 (2)
C3—C2—H2A	119.2	O2—C8—C3	121.9 (2)
C2—C3—C4	119.0 (2)	C8—O1—Ni1	109.8 (2)
C2—C3—C8	114.3 (2)	C7—O3—H3E	113 (3)
C4—C3—C8	126.7 (2)	Ni1—O5—H5E	123 (2)
C5—C4—C3	118.1 (2)	Ni1—O5—H5F	120 (3)
C5—C4—C7	113.6 (2)	H5E—O5—H5F	113 (4)
C3—C4—C7	128.3 (2)

C6—C1—C2—C3	−1.4 (4)	C3—C4—C7—O4	−161.9 (2)
C1—C2—C3—C4	1.7 (4)	C5—C4—C7—O3	−161.5 (2)
C1—C2—C3—C8	−179.9 (2)	C3—C4—C7—O3	19.7 (4)
C2—C3—C4—C5	−0.6 (3)	C2—C3—C8—O1	−14.6 (3)
C8—C3—C4—C5	−178.9 (2)	C4—C3—C8—O1	163.7 (2)
C2—C3—C4—C7	178.1 (2)	C2—C3—C8—O2	164.6 (2)
C8—C3—C4—C7	−0.1 (4)	C4—C3—C8—O2	−17.1 (4)
C3—C4—C5—C6	−0.7 (4)	O2—C8—O1—Ni1	4.3 (3)
C7—C4—C5—C6	−179.6 (2)	C3—C8—O1—Ni1	−176.50 (16)
C2—C1—C6—C5	0.1 (4)	O5ⁱ—Ni1—O1—C8	−89.48 (18)
C4—C5—C6—C1	1.0 (4)	O5—Ni1—O1—C8	90.52 (18)
C5—C4—C7—O4	16.9 (3)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5F···O4ⁱⁱ	0.86 (2)	1.82 (2)	2.667 (3)	170 (5)
O5—H5E···O3ⁱⁱⁱ	0.86 (2)	1.95 (2)	2.789 (3)	164 (4)
O3—H3E···O2	0.87 (2)	1.54 (2)	2.403 (3)	171 (5)
C2—H2A···O1	0.93	2.33	2.689 (3)	102
C5—H5A···O4	0.93	2.36	2.707 (3)	102

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(C₈H₅O₄)₂(H₂O)₂]
M_r	424.98
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	8.3601 (17), 14.439 (3), 7.1005 (14)
β (°)	111.99 (3)
V (Å³)	794.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.28
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS-IV
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.784, 0.821
No. of measured, independent and observed [I > 2σ(I)] reflections	2628, 1416, 1343
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.090, 1.07
No. of reflections	1416
No. of parameters	137
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.38

Computer programs: R-AXIS (Rigaku, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), TEXSAN (Molecular Structure Corporation, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5F···O4ⁱ	0.86 (2)	1.82 (2)	2.667 (3)	170 (5)
O5—H5E···O3ⁱⁱ	0.86 (2)	1.95 (2)	2.789 (3)	164 (4)
O3—H3E···O2	0.87 (2)	1.54 (2)	2.403 (3)	171 (5)
C2—H2A···O1	0.93	2.33	2.689 (3)	102.2
C5—H5A···O4	0.93	2.36	2.707 (3)	101.8

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

Acknowledgements

The authors thank the Natural Science Foundation of Henan Province and the Key Discipline Foundation of Zhoukou Normal University for financial support of this research.

References

Adiwidjaja, G. & Küppers, H. (1976). Acta Cryst. B32, 1571–1574. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Molecular Structure Corporation (1997). TEXSAN. Version 1.7. MSC, The Woodlands, Texas, USA. Google Scholar
Rigaku (1996). R-AXIS. Rigaku Corporation, Akishima-shi, Tokyo 196-8666, Japan. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar