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Acta Cryst. (2009). E65, m1708    [ doi:10.1107/S1600536809051204 ]

Tetraaquabis[3-(4-pyridyl)benzoato-[kappa]N]nickel(II)

Q.-X. Wang, M.-H. Zeng and S. W. Ng

Abstract top

The NiII atom in the title compound, [Ni(C12H8NO2)2(H2O)4], exists in an all-trans octahedral coordination environment. The 3-(4-pyridyl)benzoate ligand binds to Ni atom through the pyridyl N atom; the pyridine and benzene rings are oriented at a dihedral angle of 26.27 (10)°. Adjacent complexes are linked by O-H...O hydrogen bonds, forming a three-dimensional network. The metal atom lies on a special position of 2 site symmetry in the crystal structure.

Related literature top

The 3-(pyridin-4-yl)benzoate unit is fairly rigid like the nicotinate unit, which also forms a similar zwitterionic nickel derivative; see: Batten & Harris (2001).

Experimental top

3-(Pyridin-4-yl)benzoic acid was purchased from a chemical supplier. The reagent (0.199 g, 1 mmol) and sodium hydroxide (0.040 g, 1 mmol) were mixed with nickel(II) nitrate hexahydrate (0.150 g, 0.5 mmol) in water (10 ml). The mixture was placed in a 15 ml Teflon-lined autoclave and heated at 423 K for 48 h. The autoclave was cooled over 12 h at a rate of 5 K an hour. Green crystals were isolated by hand (yield ca 60% based on Ni).

Refinement top

Carbon-bound hydrogen atoms were generated geometrically and were constrained to ride on their parent atoms [C–H = 0.95 Å; Uiso(H) =1.2Ueq(C)]. The water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of O–H 0.84±0.01 Å; their temperature factors were refined.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of Ni(H2O)4(C12H2NO2)2 at the 70% probability level; hydrogen atoms are drawn as sphere of arbitrary radius.
Tetraaquabis[3-(4-pyridyl)benzoato-κN]nickel(II) top
Crystal data top
[Ni(C12H8NO2)2(H2O)4]F(000) = 1096
Mr = 527.16Dx = 1.597 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 996 reflections
a = 24.564 (3) Åθ = 3.0–26.9°
b = 7.0520 (8) ŵ = 0.94 mm−1
c = 13.781 (2) ÅT = 173 K
β = 113.325 (2)°Prism, green
V = 2192.1 (4) Å30.47 × 0.31 × 0.08 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer		2360 independent reflections
Radiation source: fine-focus sealed tube1977 reflections with I > 2σ(I)
graphiteRint = 0.023
φ and ω scansθmax = 27.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→31
Tmin = 0.666, Tmax = 0.929k = −8→8
5587 measured reflectionsl = −17→10
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0539P)2 + 0.5684P]
where P = (Fo2 + 2Fc2)/3
2360 reflections(Δ/σ)max = 0.001
175 parametersΔρmax = 0.38 e Å−3
4 restraintsΔρmin = −0.27 e Å−3
Crystal data top
[Ni(C12H8NO2)2(H2O)4]V = 2192.1 (4) Å3
Mr = 527.16Z = 4
Monoclinic, C2/cMo Kα radiation
a = 24.564 (3) ŵ = 0.94 mm−1
b = 7.0520 (8) ÅT = 173 K
c = 13.781 (2) Å0.47 × 0.31 × 0.08 mm
β = 113.325 (2)°
Data collection top
Bruker APEXII
diffractometer		1977 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		Rint = 0.023
Tmin = 0.666, Tmax = 0.929θmax = 27.0°
5587 measured reflectionsStandard reflections: 0
2360 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090Δρmax = 0.38 e Å−3
S = 1.09Δρmin = −0.27 e Å−3
2360 reflectionsAbsolute structure: ?
175 parametersFlack parameter: ?
4 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.50000.30069 (5)0.75000.01561 (13)
N10.58142 (7)0.3092 (2)0.73473 (13)0.0179 (3)
O10.90563 (6)0.2232 (2)0.96391 (12)0.0266 (3)
O20.96160 (6)0.29413 (19)0.87580 (12)0.0242 (3)
O1W0.46891 (6)0.0848 (2)0.64084 (11)0.0199 (3)
O2W0.53247 (6)0.5047 (2)0.86819 (11)0.0208 (3)
C10.91223 (9)0.2740 (3)0.88189 (16)0.0197 (4)
C20.85662 (8)0.3156 (3)0.78537 (16)0.0172 (4)
C30.85969 (8)0.3652 (3)0.69003 (17)0.0208 (4)
H30.89700.37320.68450.025*
C40.80768 (8)0.4029 (3)0.60302 (16)0.0220 (4)
H40.80960.43660.53770.026*
C50.75295 (8)0.3919 (3)0.61016 (15)0.0205 (4)
H50.71780.41880.55000.025*
C60.74932 (8)0.3414 (3)0.70535 (15)0.0176 (4)
C70.80178 (8)0.3043 (3)0.79252 (16)0.0173 (4)
H70.80000.27060.85800.021*
C80.69121 (8)0.3288 (3)0.71474 (16)0.0173 (4)
C90.68658 (8)0.3575 (3)0.81138 (16)0.0198 (4)
H90.72100.38560.87270.024*
C100.63215 (9)0.3452 (3)0.81801 (16)0.0205 (4)
H100.63050.36320.88510.025*
C110.58576 (9)0.2824 (3)0.64134 (16)0.0199 (4)
H11A0.55050.25660.58110.024*
C120.63867 (8)0.2903 (3)0.62852 (16)0.0198 (4)
H12A0.63920.26940.56080.024*
H110.4524 (11)0.124 (4)0.5786 (11)0.048 (9)*
H120.4935 (8)0.004 (3)0.6396 (17)0.023 (6)*
H210.5473 (10)0.452 (3)0.9275 (11)0.030 (7)*
H220.5096 (10)0.591 (3)0.869 (2)0.043 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.01032 (18)0.0186 (2)0.0183 (2)0.0000.00608 (14)0.000
N10.0125 (7)0.0184 (8)0.0222 (9)−0.0001 (6)0.0061 (7)0.0022 (7)
O10.0189 (7)0.0361 (9)0.0215 (8)−0.0012 (6)0.0043 (6)0.0023 (6)
O20.0118 (7)0.0227 (8)0.0362 (9)0.0008 (5)0.0077 (6)0.0012 (6)
O1W0.0155 (7)0.0222 (8)0.0216 (8)0.0010 (6)0.0071 (6)−0.0019 (6)
O2W0.0156 (7)0.0225 (8)0.0226 (8)0.0028 (6)0.0056 (6)−0.0022 (6)
C10.0154 (9)0.0154 (9)0.0259 (11)−0.0002 (7)0.0056 (8)−0.0042 (8)
C20.0149 (9)0.0145 (9)0.0214 (10)−0.0026 (7)0.0064 (8)−0.0045 (8)
C30.0149 (9)0.0215 (10)0.0294 (11)−0.0027 (8)0.0122 (8)−0.0026 (8)
C40.0212 (10)0.0277 (11)0.0202 (10)−0.0032 (8)0.0115 (8)−0.0003 (9)
C50.0158 (9)0.0234 (10)0.0206 (10)−0.0007 (8)0.0054 (8)−0.0002 (8)
C60.0135 (9)0.0176 (9)0.0223 (10)−0.0020 (7)0.0078 (8)−0.0033 (7)
C70.0156 (9)0.0179 (9)0.0187 (9)0.0002 (7)0.0071 (8)0.0002 (8)
C80.0149 (9)0.0163 (9)0.0205 (10)0.0014 (7)0.0069 (8)0.0024 (7)
C90.0130 (9)0.0242 (10)0.0204 (10)0.0011 (8)0.0047 (8)0.0004 (8)
C100.0175 (9)0.0255 (10)0.0198 (10)0.0014 (8)0.0090 (8)0.0003 (8)
C110.0139 (9)0.0237 (10)0.0210 (10)−0.0004 (8)0.0057 (8)0.0008 (8)
C120.0167 (10)0.0230 (10)0.0196 (10)−0.0007 (8)0.0071 (8)−0.0007 (8)
Geometric parameters (Å, °) top
Ni1—O1W2.0627 (14)C3—C41.388 (3)
Ni1—O1Wi2.0627 (14)C3—H30.9500
Ni1—O2W2.0811 (14)C4—C51.389 (3)
Ni1—O2Wi2.0811 (14)C4—H40.9500
Ni1—N1i2.0931 (16)C5—C61.396 (3)
Ni1—N12.0931 (16)C5—H50.9500
N1—C101.342 (3)C6—C71.395 (3)
N1—C111.346 (2)C6—C81.486 (3)
O1—C11.256 (3)C7—H70.9500
O2—C11.256 (2)C8—C121.392 (3)
O1W—H110.838 (10)C8—C91.396 (3)
O1W—H120.834 (10)C9—C101.378 (3)
O2W—H210.840 (10)C9—H90.9500
O2W—H220.833 (10)C10—H100.9500
C1—C21.511 (3)C11—C121.380 (3)
C2—C31.390 (3)C11—H11A0.9500
C2—C71.391 (3)C12—H12A0.9500
O1W—Ni1—O1Wi84.85 (8)C4—C3—C2119.26 (17)
O1W—Ni1—O2W176.09 (6)C4—C3—H3120.4
O1Wi—Ni1—O2W91.32 (6)C2—C3—H3120.4
O1W—Ni1—O2Wi91.32 (6)C3—C4—C5120.92 (18)
O1Wi—Ni1—O2Wi176.09 (6)C3—C4—H4119.5
O2W—Ni1—O2Wi92.51 (8)C5—C4—H4119.5
O1W—Ni1—N1i90.11 (6)C4—C5—C6120.31 (18)
O1Wi—Ni1—N1i92.32 (6)C4—C5—H5119.8
O2W—Ni1—N1i89.24 (6)C6—C5—H5119.8
O2Wi—Ni1—N1i88.48 (6)C7—C6—C5118.45 (17)
O1W—Ni1—N192.32 (6)C7—C6—C8120.35 (17)
O1Wi—Ni1—N190.11 (6)C5—C6—C8121.19 (17)
O2W—Ni1—N188.48 (6)C2—C7—C6121.21 (18)
O2Wi—Ni1—N189.24 (6)C2—C7—H7119.4
N1i—Ni1—N1176.71 (9)C6—C7—H7119.4
C10—N1—C11116.48 (16)C12—C8—C9116.40 (17)
C10—N1—Ni1121.33 (13)C12—C8—C6122.37 (18)
C11—N1—Ni1122.18 (13)C9—C8—C6121.23 (17)
Ni1—O1W—H11113 (2)C10—C9—C8120.12 (18)
Ni1—O1W—H12117.0 (16)C10—C9—H9119.9
H11—O1W—H12105 (2)C8—C9—H9119.9
Ni1—O2W—H21109.7 (18)N1—C10—C9123.49 (18)
Ni1—O2W—H22117.8 (19)N1—C10—H10118.3
H21—O2W—H22110 (2)C9—C10—H10118.3
O1—C1—O2124.36 (19)N1—C11—C12123.49 (19)
O1—C1—C2116.99 (17)N1—C11—H11A118.3
O2—C1—C2118.65 (18)C12—C11—H11A118.3
C3—C2—C7119.85 (18)C11—C12—C8120.03 (19)
C3—C2—C1120.82 (17)C11—C12—H12A120.0
C7—C2—C1119.32 (18)C8—C12—H12A120.0
O1W—Ni1—N1—C10−144.22 (15)C3—C2—C7—C60.1 (3)
O1Wi—Ni1—N1—C10−59.36 (15)C1—C2—C7—C6−179.93 (17)
O2W—Ni1—N1—C1031.96 (15)C5—C6—C7—C2−0.4 (3)
O2Wi—Ni1—N1—C10124.49 (15)C8—C6—C7—C2−179.88 (17)
O1W—Ni1—N1—C1136.93 (15)C7—C6—C8—C12−154.18 (19)
O1Wi—Ni1—N1—C11121.79 (15)C5—C6—C8—C1226.4 (3)
O2W—Ni1—N1—C11−146.89 (15)C7—C6—C8—C926.6 (3)
O2Wi—Ni1—N1—C11−54.36 (15)C5—C6—C8—C9−152.89 (19)
O1—C1—C2—C3−177.38 (18)C12—C8—C9—C100.6 (3)
O2—C1—C2—C33.5 (3)C6—C8—C9—C10179.95 (18)
O1—C1—C2—C72.7 (3)C11—N1—C10—C90.8 (3)
O2—C1—C2—C7−176.42 (17)Ni1—N1—C10—C9−178.14 (15)
C7—C2—C3—C40.0 (3)C8—C9—C10—N1−1.1 (3)
C1—C2—C3—C4−179.89 (18)C10—N1—C11—C120.0 (3)
C2—C3—C4—C50.1 (3)Ni1—N1—C11—C12178.89 (14)
C3—C4—C5—C6−0.4 (3)N1—C11—C12—C8−0.4 (3)
C4—C5—C6—C70.5 (3)C9—C8—C12—C110.1 (3)
C4—C5—C6—C8179.99 (18)C6—C8—C12—C11−179.22 (18)
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H11···O1ii0.84 (1)1.88 (1)2.682 (2)160 (3)
O1w—H12···O2iii0.83 (1)1.91 (1)2.734 (2)170 (2)
O2w—H21···O1iv0.84 (1)1.93 (1)2.732 (2)159 (2)
O2w—H22···O2v0.83 (1)1.88 (1)2.711 (2)177 (3)
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+3/2, y−1/2, −z+3/2; (iv) −x+3/2, −y+1/2, −z+2; (v) x−1/2, y+1/2, z.
Table 1
Selected geometric parameters (Å) top
Ni1—O1W2.0627 (14)Ni1—N12.0931 (16)
Ni1—O2W2.0811 (14)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H11···O1i0.84 (1)1.88 (1)2.682 (2)160 (3)
O1w—H12···O2ii0.83 (1)1.91 (1)2.734 (2)170 (2)
O2w—H21···O1iii0.84 (1)1.93 (1)2.732 (2)159 (2)
O2w—H22···O2iv0.83 (1)1.88 (1)2.711 (2)177 (3)
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) −x+3/2, −y+1/2, −z+2; (iv) x−1/2, y+1/2, z.
Acknowledgements top

This work was supported by the Guangxi Graduate Education Innovation Program (2009106020703M44) and the University of Malaya.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Batten, S. R. & Harris, A. R. (2001). Acta Cryst. E57, m9–m11.

Bruker (2004). APEX2 and SAINT. Bruker AXS inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2009). publCIF. In preparation.