Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032795/xu2285sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032795/xu2285Isup2.hkl |
CCDC reference: 657559
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.
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.
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).
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).
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.
[Ni(C10H8N2)(H2O)4](C8H10O4) | F(000) = 960 |
Mr = 457.12 | Dx = 1.514 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2378 reflections |
a = 11.9151 (16) Å | θ = 1.6–25.0° |
b = 24.642 (4) Å | µ = 1.02 mm−1 |
c = 7.5556 (9) Å | T = 298 K |
β = 115.313 (2)° | Block, green |
V = 2005.4 (5) Å3 | 0.28 × 0.27 × 0.26 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1811 independent reflections |
Radiation source: fine-focus sealed tube | 1619 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 25.2°, θmin = 1.6° |
Absorption correction: multi-scan SADABS (Bruker, 1997) | h = −14→11 |
Tmin = 0.762, Tmax = 0.771 | k = −29→29 |
5087 measured reflections | l = −3→9 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-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 parameters | Δρmax = 0.81 e Å−3 |
8 restraints | Δρmin = −0.60 e Å−3 |
[Ni(C10H8N2)(H2O)4](C8H10O4) | V = 2005.4 (5) Å3 |
Mr = 457.12 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.9151 (16) Å | µ = 1.02 mm−1 |
b = 24.642 (4) Å | T = 298 K |
c = 7.5556 (9) Å | 0.28 × 0.27 × 0.26 mm |
β = 115.313 (2)° |
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 = 0.771 | Rint = 0.024 |
5087 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 8 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.81 e Å−3 |
1811 reflections | Δρmin = −0.60 e Å−3 |
129 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.5000 | 0.35801 (2) | 0.2500 | 0.0293 (2) | |
O1W | 0.3653 (3) | 0.30106 (12) | 0.1394 (4) | 0.0564 (8) | |
H1W | 0.3677 | 0.2717 | 0.1897 | 0.085* | |
H2W | 0.3167 | 0.3006 | 0.0243 | 0.085* | |
O2W | 0.4852 (2) | 0.35990 (11) | 0.5128 (4) | 0.0464 (7) | |
H3W | 0.4164 | 0.3521 | 0.5339 | 0.070* | |
H4W | 0.5565 | 0.3538 | 0.6170 | 0.070* | |
N1 | 0.6216 (3) | 0.42334 (13) | 0.3502 (4) | 0.0414 (7) | |
C1 | 0.5681 (4) | 0.47248 (16) | 0.3031 (6) | 0.0492 (10) | |
C2 | 0.6395 (6) | 0.5193 (2) | 0.3525 (9) | 0.0786 (16) | |
H2 | 0.6013 | 0.5531 | 0.3180 | 0.094* | |
C3 | 0.7648 (7) | 0.5161 (3) | 0.4509 (10) | 0.097 (2) | |
H3 | 0.8130 | 0.5474 | 0.4839 | 0.117* | |
C4 | 0.8184 (5) | 0.4668 (3) | 0.5002 (9) | 0.0854 (18) | |
H4 | 0.9042 | 0.4638 | 0.5679 | 0.102* | |
C5 | 0.7448 (4) | 0.4204 (2) | 0.4495 (6) | 0.0585 (11) | |
H5 | 0.7823 | 0.3866 | 0.4855 | 0.070* | |
C6 | 0.2126 (3) | 0.32072 (17) | 0.6345 (5) | 0.0441 (9) | |
O1 | 0.3097 (2) | 0.34452 (14) | 0.6550 (4) | 0.0558 (8) | |
O2 | 0.1963 (3) | 0.30016 (12) | 0.7729 (4) | 0.0537 (8) | |
C7 | 0.0998 (5) | 0.3329 (4) | 0.4395 (8) | 0.0738 (19) | 0.50 |
H7 | 0.0849 | 0.3720 | 0.4190 | 0.089* | 0.50 |
C8 | 0.1280 (8) | 0.3070 (5) | 0.2776 (10) | 0.0738 (19) | 0.50 |
H8A | 0.1610 | 0.2709 | 0.3196 | 0.089* | 0.50 |
H8B | 0.1924 | 0.3282 | 0.2636 | 0.089* | 0.50 |
C9 | −0.0169 (7) | 0.3026 (6) | 0.4245 (12) | 0.0738 (19) | 0.50 |
H9A | 0.0035 | 0.2646 | 0.4540 | 0.089* | 0.50 |
H9B | −0.0411 | 0.3169 | 0.5227 | 0.089* | 0.50 |
C7' | 0.1074 (6) | 0.3070 (4) | 0.4328 (7) | 0.0738 (19) | 0.50 |
H7' | 0.0935 | 0.2679 | 0.4108 | 0.089* | 0.50 |
C8' | 0.1261 (8) | 0.3360 (5) | 0.2670 (11) | 0.0738 (19) | 0.50 |
H8'1 | 0.1909 | 0.3175 | 0.2450 | 0.089* | 0.50 |
H8'2 | 0.1537 | 0.3729 | 0.3074 | 0.089* | 0.50 |
C9' | −0.0073 (7) | 0.3375 (5) | 0.4261 (12) | 0.0738 (19) | 0.50 |
H9'1 | −0.0272 | 0.3229 | 0.5285 | 0.089* | 0.50 |
H9'2 | 0.0157 | 0.3752 | 0.4582 | 0.089* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0283 (3) | 0.0319 (3) | 0.0221 (3) | 0.000 | 0.0055 (2) | 0.000 |
O1W | 0.0597 (17) | 0.0521 (16) | 0.0330 (14) | −0.0236 (14) | −0.0035 (13) | 0.0093 (12) |
O2W | 0.0352 (13) | 0.0742 (19) | 0.0267 (13) | 0.0003 (12) | 0.0104 (11) | 0.0033 (12) |
N1 | 0.0452 (18) | 0.0455 (18) | 0.0326 (16) | −0.0096 (14) | 0.0157 (14) | −0.0065 (13) |
C1 | 0.075 (3) | 0.038 (2) | 0.042 (2) | −0.0087 (19) | 0.032 (2) | −0.0033 (16) |
C2 | 0.113 (5) | 0.046 (3) | 0.087 (4) | −0.023 (3) | 0.052 (4) | −0.012 (3) |
C3 | 0.111 (5) | 0.075 (4) | 0.106 (5) | −0.057 (4) | 0.046 (4) | −0.030 (4) |
C4 | 0.064 (3) | 0.109 (5) | 0.074 (4) | −0.044 (3) | 0.022 (3) | −0.024 (3) |
C5 | 0.045 (2) | 0.076 (3) | 0.049 (2) | −0.016 (2) | 0.0145 (19) | −0.012 (2) |
C6 | 0.0335 (19) | 0.059 (2) | 0.0286 (19) | −0.0039 (17) | 0.0026 (15) | 0.0038 (16) |
O1 | 0.0368 (15) | 0.090 (2) | 0.0324 (14) | −0.0174 (14) | 0.0067 (12) | 0.0066 (14) |
O2 | 0.0452 (15) | 0.0683 (19) | 0.0330 (14) | −0.0215 (14) | 0.0028 (12) | 0.0082 (13) |
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) |
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) |
Ni1—O1W | 2.024 (3) | C6—O2 | 1.250 (5) |
Ni1—O1Wi | 2.024 (3) | C6—C7' | 1.540 (2) |
Ni1—O2Wi | 2.068 (3) | C6—C7 | 1.540 (2) |
Ni1—O2W | 2.068 (3) | C7—C8 | 1.538 (2) |
Ni1—N1 | 2.080 (3) | C7—C9 | 1.540 (2) |
Ni1—N1i | 2.080 (3) | C7—H7 | 0.9800 |
O1W—H1W | 0.8112 | C8—C9ii | 1.539 (2) |
O1W—H2W | 0.8133 | C8—H8A | 0.9700 |
O2W—H3W | 0.9183 | C8—H8B | 0.9700 |
O2W—H4W | 0.8902 | C9—C8ii | 1.539 (2) |
N1—C5 | 1.335 (5) | C9—H9A | 0.9700 |
N1—C1 | 1.344 (5) | C9—H9B | 0.9700 |
C1—C2 | 1.388 (6) | C7'—C8' | 1.538 (2) |
C1—C1i | 1.471 (9) | C7'—C9' | 1.541 (2) |
C2—C3 | 1.355 (9) | C7'—H7' | 0.9800 |
C2—H2 | 0.9300 | C8'—C9'ii | 1.539 (2) |
C3—C4 | 1.350 (9) | C8'—H8'1 | 0.9700 |
C3—H3 | 0.9300 | C8'—H8'2 | 0.9700 |
C4—C5 | 1.391 (7) | C9'—C8'ii | 1.539 (2) |
C4—H4 | 0.9300 | C9'—H9'1 | 0.9700 |
C5—H5 | 0.9300 | C9'—H9'2 | 0.9700 |
C6—O1 | 1.247 (5) | ||
O1W—Ni1—O1Wi | 92.22 (18) | O1—C6—C7' | 123.1 (4) |
O1W—Ni1—O2Wi | 89.87 (11) | O2—C6—C7' | 112.8 (4) |
O1Wi—Ni1—O2Wi | 91.93 (11) | O1—C6—C7 | 114.3 (4) |
O1W—Ni1—O2W | 91.93 (11) | O2—C6—C7 | 119.7 (4) |
O1Wi—Ni1—O2W | 89.87 (11) | C8—C7—C9 | 103.8 (8) |
O2Wi—Ni1—O2W | 177.41 (16) | C8—C7—C6 | 106.4 (5) |
O1W—Ni1—N1 | 173.17 (13) | C9—C7—C6 | 111.5 (5) |
O1Wi—Ni1—N1 | 94.61 (13) | C8—C7—H7 | 111.6 |
O2Wi—Ni1—N1 | 89.99 (11) | C9—C7—H7 | 111.6 |
O2W—Ni1—N1 | 88.01 (11) | C6—C7—H7 | 111.6 |
O1W—Ni1—N1i | 94.61 (13) | C7—C8—C9ii | 115.6 (6) |
O1Wi—Ni1—N1i | 173.17 (13) | C7—C8—H8A | 108.4 |
O2Wi—Ni1—N1i | 88.01 (11) | C9ii—C8—H8A | 108.4 |
O2W—Ni1—N1i | 89.98 (11) | C7—C8—H8B | 108.4 |
N1—Ni1—N1i | 78.57 (18) | C9ii—C8—H8B | 108.4 |
Ni1—O1W—H1W | 124.2 | H8A—C8—H8B | 107.5 |
Ni1—O1W—H2W | 121.8 | C8ii—C9—C7 | 113.9 (6) |
H1W—O1W—H2W | 110.8 | C8ii—C9—H9A | 108.8 |
Ni1—O2W—H3W | 127.6 | C7—C9—H9A | 108.8 |
Ni1—O2W—H4W | 113.8 | C8ii—C9—H9B | 108.8 |
H3W—O2W—H4W | 113.4 | C7—C9—H9B | 108.8 |
C5—N1—C1 | 118.8 (4) | H9A—C9—H9B | 107.7 |
C5—N1—Ni1 | 126.2 (3) | C8'—C7'—C6 | 111.3 (5) |
C1—N1—Ni1 | 115.0 (3) | C8'—C7'—C9' | 100.5 (8) |
N1—C1—C2 | 120.8 (5) | C6—C7'—C9' | 105.1 (5) |
N1—C1—C1i | 115.6 (2) | C8'—C7'—H7' | 113.0 |
C2—C1—C1i | 123.6 (3) | C6—C7'—H7' | 113.0 |
C3—C2—C1 | 120.2 (5) | C9'—C7'—H7' | 113.0 |
C3—C2—H2 | 119.9 | C7'—C8'—C9'ii | 112.9 (6) |
C1—C2—H2 | 119.9 | C7'—C8'—H8'1 | 109.0 |
C4—C3—C2 | 119.0 (5) | C9'ii—C8'—H8'1 | 109.0 |
C4—C3—H3 | 120.5 | C7'—C8'—H8'2 | 109.0 |
C2—C3—H3 | 120.5 | C9'ii—C8'—H8'2 | 109.0 |
C3—C4—C5 | 119.7 (5) | H8'1—C8'—H8'2 | 107.8 |
C3—C4—H4 | 120.1 | C8'ii—C9'—C7' | 117.5 (7) |
C5—C4—H4 | 120.1 | C8'ii—C9'—H9'1 | 107.9 |
N1—C5—C4 | 121.5 (5) | C7'—C9'—H9'1 | 107.9 |
N1—C5—H5 | 119.3 | C8'ii—C9'—H9'2 | 107.9 |
C4—C5—H5 | 119.3 | C7'—C9'—H9'2 | 107.9 |
O1—C6—O2 | 123.7 (3) | H9'1—C9'—H9'2 | 107.2 |
O1Wi—Ni1—N1—C5 | 0.8 (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—C5 | 90.5 (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—C1 | 178.9 (3) | C7'—C6—C7—C9 | 63.3 (12) |
O2Wi—Ni1—N1—C1 | 86.9 (3) | C9—C7—C8—C9ii | 48.8 (10) |
O2W—Ni1—N1—C1 | −91.4 (3) | C6—C7—C8—C9ii | 166.6 (9) |
N1i—Ni1—N1—C1 | −1.1 (2) | C8—C7—C9—C8ii | −58.2 (10) |
C5—N1—C1—C2 | 1.5 (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—C1i | 2.8 (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—C3 | 179.9 (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—C5 | 0.1 (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—C4 | 176.3 (4) | C8'—C7'—C9'—C8'ii | 58.9 (10) |
C3—C4—C5—N1 | 0.9 (8) | C6—C7'—C9'—C8'ii | 174.6 (10) |
O1—C6—C7—C8 | 67.9 (9) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2iii | 0.81 | 2.00 | 2.759 (4) | 157 |
O1W—H2W···O2iv | 0.81 | 1.83 | 2.637 (4) | 175 |
O2W—H3W···O1 | 0.92 | 1.87 | 2.754 (4) | 162 |
O2W—H4W···O1v | 0.89 | 1.79 | 2.678 (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. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C10H8N2)(H2O)4](C8H10O4) |
Mr | 457.12 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 11.9151 (16), 24.642 (4), 7.5556 (9) |
β (°) | 115.313 (2) |
V (Å3) | 2005.4 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.02 |
Crystal size (mm) | 0.28 × 0.27 × 0.26 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan SADABS (Bruker, 1997) |
Tmin, Tmax | 0.762, 0.771 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5087, 1811, 1619 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.130, 1.04 |
No. of reflections | 1811 |
No. of parameters | 129 |
No. of restraints | 8 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.81, −0.60 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2001), SHELXTL and DIAMOND (Brandenburg, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2i | 0.81 | 2.00 | 2.759 (4) | 157 |
O1W—H2W···O2ii | 0.81 | 1.83 | 2.637 (4) | 175 |
O2W—H3W···O1 | 0.92 | 1.87 | 2.754 (4) | 162 |
O2W—H4W···O1iii | 0.89 | 1.79 | 2.678 (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. |
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).