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Acta Cryst. (2007). E63, m2110    [ doi:10.1107/S1600536807032795 ]

Tetraaqua(2,2'-bipyridine-[kappa]2N,N')nickel(II) cyclohexane-1,4-dicarboxylate

M. Yu, S.-X. Liu, L.-H. Xie, R.-G. Cao and Y.-H. Ren

Abstract top

In the title compound, [Ni(C10H8N2)(H2O)4](C8H10O4), the NiII ion is located on a twofold rotation axis and has a distorted octahedral geometry formed by a chelating 2,2'-bipyridine ligand and four water molecules. The disordered cyclohexane-1,4-dicarboxylate dianion is located across another twofold rotation axis and adopts a boat conformation. O-H...O hydrogen bonding between the complex cation and the cyclohexane-1,4-dicarboxylate dianion helps to stabilize the crystal structure.

Comment top

Cyclohexane-1,4-dicarboxylic acid (H2chdc) is a flexible ligand for constructing functional metal-organic frameworks (Qi et al., 2003; Kurmoo et al., 2003, 2006; Rao et al., 2007). As part of investigation on cyclohexane-1,4-dicarboxylate complexes (Yu et al., 2006, 2007), we present here the crystal structure of the title NiII complex.

The crystal of the NiII compound consists of [Ni(2,2'-bpy)(H2O)4]2+ cations and cyclohexane-1,4-dicarboxylate dianions. The complex cation and conter-dianion are located on individual twofold rotation axis. In the cation, Ni atom coordinates with two N atoms from a 2,2'-bpy ligand and four water molecules in a distorted octahedral geometry (Figure 1). The chdc anion is disordered and it has been modeled at two positions with their occupancies set to be 0.5. Hydrogen bonding (Table 1) between coordinated water molecules of the complex cations and carboxyl O atoms of chdc anions results in a double layer supra-molecular structure along ac plane (Figure 2, Figure 3).

Related literature top

For related metal complexes with the cyclohexane-1,4-dicarboxylate ligand, see: Kurmoo et al. (2006, 2003); Qi et al. (2003); Rao et al. (2007); Yu et al. (2006, 2007).

Experimental top

NiCl2.6H2O (0.6 mmol, 0.143 g) and H2chdc (0.6 mmol, 0.103 g) were dissolved in 18 ml water. Then an ethanol solution (8 ml) of 2,2'-bipyridine (0.6 mmol, 0.094 g) was mixed with the solution. The pH value of the solution was adjusted to 7.0 with diluted NaOH solution. The mixture was then refluxed at 363 K for 12 h. The filtrate was kept under room temperature for about two weeks. Single crystals of the title compound were obtained from the filtrate yield.

Refinement top

H atoms on water molecules were located in a difference Fourier map and refined as ringing in their as-found relative positions, Uiso(H) = 1.5Ueq(O). The others H atoms were placed in calculated positions and refined in the riding model approximation with C—H = 0.93 or 0.97 Å and Uiso(H) = 1.2Ueq(C). The cyclohexane ring of chdc anion is disordered, and the disorder was modeled as two components. The occupancies of both components were set to be 1/2, and the geometries of the two components were restrained with C—C = 1.54 Å. The displacement parameters of C atoms of the disordered cyclohexane ring were restrained to be equal.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level. The chdc anion is disordered at two positions with one part shown with open bonds.
[Figure 2] Fig. 2. Perspective view of the two-dimensional double layer along b axis. Hydrogen bonds are represented by pink dashed lines.
[Figure 3] Fig. 3. Side view of the double layer.
Tetraaqua(2,2'-bipyridine-κ2N,N')nickel(II) cyclohexane-1,4-dicarboxylate top
Crystal data top
[Ni(C10H8N2)(H2O)4](C8H10O4)F(000) = 960
Mr = 457.12Dx = 1.514 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2378 reflections
a = 11.9151 (16) Åθ = 1.6–25.0°
b = 24.642 (4) ŵ = 1.02 mm−1
c = 7.5556 (9) ÅT = 298 K
β = 115.313 (2)°Block, green
V = 2005.4 (5) Å30.28 × 0.27 × 0.26 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		1811 independent reflections
Radiation source: fine-focus sealed tube1619 reflections with I > 2σ(I)
graphiteRint = 0.024
φ and ω scansθmax = 25.2°, θmin = 1.6°
Absorption correction: multi-scan
SADABS (Bruker, 1997)		h = −14→11
Tmin = 0.762, Tmax = 0.771k = −29→29
5087 measured reflectionsl = −3→9
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0627P)2 + 7.6283P]
where P = (Fo2 + 2Fc2)/3
1811 reflections(Δ/σ)max < 0.001
129 parametersΔρmax = 0.81 e Å−3
8 restraintsΔρmin = −0.60 e Å−3
Crystal data top
[Ni(C10H8N2)(H2O)4](C8H10O4)V = 2005.4 (5) Å3
Mr = 457.12Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.9151 (16) ŵ = 1.02 mm−1
b = 24.642 (4) ÅT = 298 K
c = 7.5556 (9) Å0.28 × 0.27 × 0.26 mm
β = 115.313 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1811 independent reflections
Absorption correction: multi-scan
SADABS (Bruker, 1997)		1619 reflections with I > 2σ(I)
Tmin = 0.762, Tmax = 0.771Rint = 0.024
5087 measured reflectionsθmax = 25.2°
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.130Δρmax = 0.81 e Å−3
S = 1.04Δρmin = −0.60 e Å−3
1811 reflectionsAbsolute structure: ?
129 parametersFlack parameter: ?
8 restraintsRogers parameter: ?
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
xyzUiso*/UeqOcc. (<1)
Ni10.50000.35801 (2)0.25000.0293 (2)
O1W0.3653 (3)0.30106 (12)0.1394 (4)0.0564 (8)
H1W0.36770.27170.18970.085*
H2W0.31670.30060.02430.085*
O2W0.4852 (2)0.35990 (11)0.5128 (4)0.0464 (7)
H3W0.41640.35210.53390.070*
H4W0.55650.35380.61700.070*
N10.6216 (3)0.42334 (13)0.3502 (4)0.0414 (7)
C10.5681 (4)0.47248 (16)0.3031 (6)0.0492 (10)
C20.6395 (6)0.5193 (2)0.3525 (9)0.0786 (16)
H20.60130.55310.31800.094*
C30.7648 (7)0.5161 (3)0.4509 (10)0.097 (2)
H30.81300.54740.48390.117*
C40.8184 (5)0.4668 (3)0.5002 (9)0.0854 (18)
H40.90420.46380.56790.102*
C50.7448 (4)0.4204 (2)0.4495 (6)0.0585 (11)
H50.78230.38660.48550.070*
C60.2126 (3)0.32072 (17)0.6345 (5)0.0441 (9)
O10.3097 (2)0.34452 (14)0.6550 (4)0.0558 (8)
O20.1963 (3)0.30016 (12)0.7729 (4)0.0537 (8)
C70.0998 (5)0.3329 (4)0.4395 (8)0.0738 (19)0.50
H70.08490.37200.41900.089*0.50
C80.1280 (8)0.3070 (5)0.2776 (10)0.0738 (19)0.50
H8A0.16100.27090.31960.089*0.50
H8B0.19240.32820.26360.089*0.50
C9−0.0169 (7)0.3026 (6)0.4245 (12)0.0738 (19)0.50
H9A0.00350.26460.45400.089*0.50
H9B−0.04110.31690.52270.089*0.50
C7'0.1074 (6)0.3070 (4)0.4328 (7)0.0738 (19)0.50
H7'0.09350.26790.41080.089*0.50
C8'0.1261 (8)0.3360 (5)0.2670 (11)0.0738 (19)0.50
H8'10.19090.31750.24500.089*0.50
H8'20.15370.37290.30740.089*0.50
C9'−0.0073 (7)0.3375 (5)0.4261 (12)0.0738 (19)0.50
H9'1−0.02720.32290.52850.089*0.50
H9'20.01570.37520.45820.089*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0283 (3)0.0319 (3)0.0221 (3)0.0000.0055 (2)0.000
O1W0.0597 (17)0.0521 (16)0.0330 (14)−0.0236 (14)−0.0035 (13)0.0093 (12)
O2W0.0352 (13)0.0742 (19)0.0267 (13)0.0003 (12)0.0104 (11)0.0033 (12)
N10.0452 (18)0.0455 (18)0.0326 (16)−0.0096 (14)0.0157 (14)−0.0065 (13)
C10.075 (3)0.038 (2)0.042 (2)−0.0087 (19)0.032 (2)−0.0033 (16)
C20.113 (5)0.046 (3)0.087 (4)−0.023 (3)0.052 (4)−0.012 (3)
C30.111 (5)0.075 (4)0.106 (5)−0.057 (4)0.046 (4)−0.030 (4)
C40.064 (3)0.109 (5)0.074 (4)−0.044 (3)0.022 (3)−0.024 (3)
C50.045 (2)0.076 (3)0.049 (2)−0.016 (2)0.0145 (19)−0.012 (2)
C60.0335 (19)0.059 (2)0.0286 (19)−0.0039 (17)0.0026 (15)0.0038 (16)
O10.0368 (15)0.090 (2)0.0324 (14)−0.0174 (14)0.0067 (12)0.0066 (14)
O20.0452 (15)0.0683 (19)0.0330 (14)−0.0215 (14)0.0028 (12)0.0082 (13)
C70.0413 (16)0.130 (6)0.0346 (16)−0.009 (3)0.0013 (14)0.011 (2)
C80.0413 (16)0.130 (6)0.0346 (16)−0.009 (3)0.0013 (14)0.011 (2)
C90.0413 (16)0.130 (6)0.0346 (16)−0.009 (3)0.0013 (14)0.011 (2)
C7'0.0413 (16)0.130 (6)0.0346 (16)−0.009 (3)0.0013 (14)0.011 (2)
C8'0.0413 (16)0.130 (6)0.0346 (16)−0.009 (3)0.0013 (14)0.011 (2)
C9'0.0413 (16)0.130 (6)0.0346 (16)−0.009 (3)0.0013 (14)0.011 (2)
Geometric parameters (Å, °) top
Ni1—O1W2.024 (3)C6—O21.250 (5)
Ni1—O1Wi2.024 (3)C6—C7'1.540 (2)
Ni1—O2Wi2.068 (3)C6—C71.540 (2)
Ni1—O2W2.068 (3)C7—C81.538 (2)
Ni1—N12.080 (3)C7—C91.540 (2)
Ni1—N1i2.080 (3)C7—H70.9800
O1W—H1W0.8112C8—C9ii1.539 (2)
O1W—H2W0.8133C8—H8A0.9700
O2W—H3W0.9183C8—H8B0.9700
O2W—H4W0.8902C9—C8ii1.539 (2)
N1—C51.335 (5)C9—H9A0.9700
N1—C11.344 (5)C9—H9B0.9700
C1—C21.388 (6)C7'—C8'1.538 (2)
C1—C1i1.471 (9)C7'—C9'1.541 (2)
C2—C31.355 (9)C7'—H7'0.9800
C2—H20.9300C8'—C9'ii1.539 (2)
C3—C41.350 (9)C8'—H8'10.9700
C3—H30.9300C8'—H8'20.9700
C4—C51.391 (7)C9'—C8'ii1.539 (2)
C4—H40.9300C9'—H9'10.9700
C5—H50.9300C9'—H9'20.9700
C6—O11.247 (5)
O1W—Ni1—O1Wi92.22 (18)O1—C6—C7'123.1 (4)
O1W—Ni1—O2Wi89.87 (11)O2—C6—C7'112.8 (4)
O1Wi—Ni1—O2Wi91.93 (11)O1—C6—C7114.3 (4)
O1W—Ni1—O2W91.93 (11)O2—C6—C7119.7 (4)
O1Wi—Ni1—O2W89.87 (11)C8—C7—C9103.8 (8)
O2Wi—Ni1—O2W177.41 (16)C8—C7—C6106.4 (5)
O1W—Ni1—N1173.17 (13)C9—C7—C6111.5 (5)
O1Wi—Ni1—N194.61 (13)C8—C7—H7111.6
O2Wi—Ni1—N189.99 (11)C9—C7—H7111.6
O2W—Ni1—N188.01 (11)C6—C7—H7111.6
O1W—Ni1—N1i94.61 (13)C7—C8—C9ii115.6 (6)
O1Wi—Ni1—N1i173.17 (13)C7—C8—H8A108.4
O2Wi—Ni1—N1i88.01 (11)C9ii—C8—H8A108.4
O2W—Ni1—N1i89.98 (11)C7—C8—H8B108.4
N1—Ni1—N1i78.57 (18)C9ii—C8—H8B108.4
Ni1—O1W—H1W124.2H8A—C8—H8B107.5
Ni1—O1W—H2W121.8C8ii—C9—C7113.9 (6)
H1W—O1W—H2W110.8C8ii—C9—H9A108.8
Ni1—O2W—H3W127.6C7—C9—H9A108.8
Ni1—O2W—H4W113.8C8ii—C9—H9B108.8
H3W—O2W—H4W113.4C7—C9—H9B108.8
C5—N1—C1118.8 (4)H9A—C9—H9B107.7
C5—N1—Ni1126.2 (3)C8'—C7'—C6111.3 (5)
C1—N1—Ni1115.0 (3)C8'—C7'—C9'100.5 (8)
N1—C1—C2120.8 (5)C6—C7'—C9'105.1 (5)
N1—C1—C1i115.6 (2)C8'—C7'—H7'113.0
C2—C1—C1i123.6 (3)C6—C7'—H7'113.0
C3—C2—C1120.2 (5)C9'—C7'—H7'113.0
C3—C2—H2119.9C7'—C8'—C9'ii112.9 (6)
C1—C2—H2119.9C7'—C8'—H8'1109.0
C4—C3—C2119.0 (5)C9'ii—C8'—H8'1109.0
C4—C3—H3120.5C7'—C8'—H8'2109.0
C2—C3—H3120.5C9'ii—C8'—H8'2109.0
C3—C4—C5119.7 (5)H8'1—C8'—H8'2107.8
C3—C4—H4120.1C8'ii—C9'—C7'117.5 (7)
C5—C4—H4120.1C8'ii—C9'—H9'1107.9
N1—C5—C4121.5 (5)C7'—C9'—H9'1107.9
N1—C5—H5119.3C8'ii—C9'—H9'2107.9
C4—C5—H5119.3C7'—C9'—H9'2107.9
O1—C6—O2123.7 (3)H9'1—C9'—H9'2107.2
O1Wi—Ni1—N1—C50.8 (3)O2—C6—C7—C8−128.8 (7)
O2Wi—Ni1—N1—C5−91.1 (3)C7'—C6—C7—C8−49.2 (11)
O2W—Ni1—N1—C590.5 (3)O1—C6—C7—C9−179.6 (8)
N1i—Ni1—N1—C5−179.1 (4)O2—C6—C7—C9−16.3 (11)
O1Wi—Ni1—N1—C1178.9 (3)C7'—C6—C7—C963.3 (12)
O2Wi—Ni1—N1—C186.9 (3)C9—C7—C8—C9ii48.8 (10)
O2W—Ni1—N1—C1−91.4 (3)C6—C7—C8—C9ii166.6 (9)
N1i—Ni1—N1—C1−1.1 (2)C8—C7—C9—C8ii−58.2 (10)
C5—N1—C1—C21.5 (6)C6—C7—C9—C8ii−172.3 (9)
Ni1—N1—C1—C2−176.7 (4)O1—C6—C7'—C8'−11.3 (11)
C5—N1—C1—C1i−179.0 (4)O2—C6—C7'—C8'176.3 (7)
Ni1—N1—C1—C1i2.8 (5)C7—C6—C7'—C8'64.2 (13)
N1—C1—C2—C3−0.6 (8)O1—C6—C7'—C9'−119.2 (8)
C1i—C1—C2—C3179.9 (5)O2—C6—C7'—C9'68.4 (8)
C1—C2—C3—C4−0.2 (10)C7—C6—C7'—C9'−43.7 (10)
C2—C3—C4—C50.1 (10)C6—C7'—C8'—C9'ii−163.0 (9)
C1—N1—C5—C4−1.6 (6)C9'—C7'—C8'—C9'ii−52.0 (10)
Ni1—N1—C5—C4176.3 (4)C8'—C7'—C9'—C8'ii58.9 (10)
C3—C4—C5—N10.9 (8)C6—C7'—C9'—C8'ii174.6 (10)
O1—C6—C7—C867.9 (9)
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2iii0.812.002.759 (4)157
O1W—H2W···O2iv0.811.832.637 (4)175
O2W—H3W···O10.921.872.754 (4)162
O2W—H4W···O1v0.891.792.678 (4)173
Symmetry codes: (iii) −x+1/2, −y+1/2, −z+1; (iv) x, y, z−1; (v) −x+1, y, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2i0.812.002.759 (4)157
O1W—H2W···O2ii0.811.832.637 (4)175
O2W—H3W···O10.921.872.754 (4)162
O2W—H4W···O1iii0.891.792.678 (4)173
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x, y, z−1; (iii) −x+1, y, −z+3/2.
Acknowledgements top

This work was supported by the National Science Foundation of China (grant No. 20571014), the Scientific Research Foundation for Returned Overseas Chinese Scholars, the Ministry of Education and the Analysis and Testing Foundation of Northeast Normal University.

references
References top

Brandenburg, K. (1998). DIAMOND. Version 2.1. Crystal Impact GbR, Bonn, Germany.

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2001). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Kurmoo, M., Kumagai, H., Akita-Tanaka, M., Inoue, K. & Takagi, S. (2006). Inorg. Chem. 45, 1627–1637.

Kurmoo, M., Kumagai, H., Hughes, S. M. & Kepert, C. J. (2003). Inorg. Chem. 42, 6709–6722.

Qi, Y. J., Wang, Y. H., Hu, C. W., Cao, M. H., Mao, L. & Wang, E. B. (2003). Inorg. Chem. 42, 8519–8523.

Rao, K. P., Thirumurugan, A. & Rao, C. N. R. (2007). Chem. Eur. J. 13, 3193–3201.

Yu, M., Liu, S. X., Zhang, C. D., Gao, B., Sun, C. Y., Wang, C. L. & Cheng, H. Y. (2006). Chem. Res. Chin. Univ. 22, 415–418.

Yu, M., Xie, L. H., Liu, S. X., Wang, C. L., Cheng, H. Y., Ren, Y. H. & Su, Z. M. (2007). Inorg. Chim. Acta, 360, 3108–3112.