metal-organic compounds
Poly[[hexaaqua(μ3-2,2′-bipyridine-4,4′,6,6′-tetracarboxylato-κ6O4:N,O6,O6′,N′:O4′)dinickel(II)] dihydrate]
aState Key Lab. Base of Novel Functional Materials and Preparation Science, Institute of Solid Materials Chemistry, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
*Correspondence e-mail: leikeweipublic@hotmail.com
In the title complex, {[Ni2(C14H4N2O8)(H2O)6]·2H2O}n, the two NiII atoms are located in different special positions (one on a twofold rotation axis and the second on a centre of symmetry) and have different distorted octahedral environments (one by two N atoms from a bipyridine unit, two O atoms from two water molecules and two O atoms from two carboxylate groups, and the second by four O atoms from four water molecules and two O atoms from two carboxylate groups). Thus, the environments of the NiII atoms may be denoted as NiN2O4 and NiO6. In the crystal, there exists an extensive network of classical O—H⋯O hydrogen bonds.
Experimental
Crystal data
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Refinement
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Data collection: RAPID-AUTO (Rigaku, 1998); cell RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); 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: SHELXL97.
Supporting information
10.1107/S1600536812043942/rk2355sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812043942/rk2355Isup2.hkl
A mixture of 6–(4,6–dicarboxypyridin–2–yl)pyridine–2,4–dicarboxylic acid (0.0332 g, 0.1 mmol), Ni(NO3)2.6H2O (0.0724 g, 0.3 mmol) and water (10 ml) was placed in a teflon–lined stainless steel vessel (25 ml) and heated at 443.15 K for 72 h, and then cooled to room temperature at a rate of 5/h (Al-Harbi, 2011). The resulting green single crystals were isolated by washing with DMF and dried in vacuo. Yield: 62.3%.
All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms (C—H = 0.93%A; N—H = 0.86Å; O—H = 0.82Å) and Uiso(H) values weren taken to be equal to 1.2 Ueq(C, N) and 1.5Ueq(O).
Data collection: RAPID-AUTO (Rigaku, 1998); cell
RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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: SHELXL97 (Sheldrick, 2008).Fig. 1. The structure of the title complex with the atom–numbering scheme. Displacement ellipsoids are drawn at 30% probability level. | |
Fig. 2. The three–dimensional structure of the title complex. The hydrogen bonds are indicated by dashed lines. |
[Ni2(C14H4N2O8)(H2O)6]·2H2O | F(000) = 604 |
Mr = 589.70 | Dx = 1.897 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yac | Cell parameters from 8794 reflections |
a = 7.3588 (8) Å | θ = 1.7–27.5° |
b = 11.8463 (13) Å | µ = 1.91 mm−1 |
c = 11.9942 (13) Å | T = 296 K |
β = 99.184 (1)° | Block, green |
V = 1032.19 (19) Å3 | 0.28 × 0.24 × 0.19 mm |
Z = 2 |
Rigaku R-AXIS RAPID diffractometer | 2365 independent reflections |
Radiation source: fine–focus sealed tube | 2248 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
Detector resolution: 0 pixels mm-1 | θmax = 27.5°, θmin = 1.7° |
ω scans | h = −9→8 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −15→14 |
Tmin = 0.591, Tmax = 0.695 | l = −15→15 |
8794 measured reflections |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0255P)2 + 0.5729P] where P = (Fo2 + 2Fc2)/3 |
2365 reflections | (Δ/σ)max < 0.001 |
176 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
[Ni2(C14H4N2O8)(H2O)6]·2H2O | V = 1032.19 (19) Å3 |
Mr = 589.70 | Z = 2 |
Monoclinic, P2/n | Mo Kα radiation |
a = 7.3588 (8) Å | µ = 1.91 mm−1 |
b = 11.8463 (13) Å | T = 296 K |
c = 11.9942 (13) Å | 0.28 × 0.24 × 0.19 mm |
β = 99.184 (1)° |
Rigaku R-AXIS RAPID diffractometer | 2365 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2248 reflections with I > 2σ(I) |
Tmin = 0.591, Tmax = 0.695 | Rint = 0.038 |
8794 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.40 e Å−3 |
2365 reflections | Δρmin = −0.42 e Å−3 |
176 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 | ||
Ni1 | 0.2500 | 0.36726 (2) | 0.7500 | 0.01154 (8) | |
Ni2 | 0.0000 | 1.0000 | 1.0000 | 0.01064 (8) | |
O1 | −0.10038 (16) | 0.87338 (9) | 0.89420 (9) | 0.0161 (2) | |
O3 | 0.10695 (15) | 1.06255 (9) | 0.86383 (9) | 0.0145 (2) | |
H3A | 0.0846 | 1.1302 | 0.8571 | 0.022* | |
O2 | −0.33996 (15) | 0.76758 (9) | 0.92552 (9) | 0.0162 (2) | |
O4 | 0.23852 (15) | 0.90408 (10) | 1.03816 (9) | 0.0162 (2) | |
H4A | 0.3218 | 0.9436 | 1.0709 | 0.024* | |
O8 | 0.04444 (15) | 0.28697 (9) | 0.82901 (9) | 0.0152 (2) | |
C1 | 0.1670 (2) | 0.60269 (12) | 0.77858 (12) | 0.0118 (3) | |
N1 | 0.10800 (18) | 0.49784 (10) | 0.79747 (10) | 0.0110 (2) | |
C6 | −0.1837 (2) | 0.78123 (12) | 0.89848 (11) | 0.0112 (3) | |
C4 | −0.1418 (2) | 0.56825 (12) | 0.88022 (11) | 0.0112 (3) | |
H4C | −0.2463 | 0.5552 | 0.9130 | 0.013* | |
C2 | 0.0741 (2) | 0.69601 (13) | 0.81220 (12) | 0.0123 (3) | |
H2A | 0.1153 | 0.7688 | 0.8011 | 0.015* | |
C5 | −0.0391 (2) | 0.47890 (12) | 0.84663 (12) | 0.0112 (3) | |
C3 | −0.0820 (2) | 0.67854 (12) | 0.86283 (11) | 0.0108 (3) | |
O7 | −0.21194 (15) | 0.32298 (9) | 0.90173 (9) | 0.0157 (2) | |
O5 | 0.07941 (17) | 0.35897 (11) | 0.59723 (10) | 0.0201 (2) | |
H5A | 0.1245 | 0.3169 | 0.5548 | 0.030* | |
C7 | −0.0751 (2) | 0.35285 (12) | 0.86043 (12) | 0.0120 (3) | |
O6 | 0.02584 (17) | 0.96743 (11) | 0.64958 (10) | 0.0191 (2) | |
H6A | −0.015 (3) | 0.909 (2) | 0.6259 (19) | 0.031 (6)* | |
H6B | 0.114 (4) | 0.976 (2) | 0.621 (2) | 0.037 (7)* | |
H5B | −0.025 (4) | 0.352 (2) | 0.603 (2) | 0.043 (7)* | |
H4B | 0.240 (4) | 0.842 (2) | 1.059 (2) | 0.047 (8)* | |
H3B | 0.069 (3) | 1.031 (2) | 0.801 (2) | 0.035 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01010 (14) | 0.00796 (14) | 0.01721 (14) | 0.000 | 0.00415 (10) | 0.000 |
Ni2 | 0.01066 (15) | 0.00722 (14) | 0.01465 (14) | 0.00026 (9) | 0.00393 (10) | −0.00035 (9) |
O1 | 0.0192 (6) | 0.0099 (5) | 0.0203 (5) | −0.0022 (4) | 0.0067 (4) | −0.0040 (4) |
O3 | 0.0182 (6) | 0.0093 (5) | 0.0165 (5) | −0.0002 (4) | 0.0048 (4) | 0.0003 (4) |
O2 | 0.0151 (5) | 0.0139 (5) | 0.0209 (5) | 0.0015 (4) | 0.0067 (4) | 0.0015 (4) |
O4 | 0.0140 (5) | 0.0103 (5) | 0.0241 (5) | 0.0009 (4) | 0.0025 (4) | 0.0019 (4) |
O8 | 0.0136 (5) | 0.0090 (5) | 0.0239 (5) | 0.0007 (4) | 0.0059 (4) | 0.0014 (4) |
C1 | 0.0120 (7) | 0.0097 (7) | 0.0135 (6) | −0.0012 (5) | 0.0020 (5) | 0.0007 (5) |
N1 | 0.0108 (6) | 0.0092 (6) | 0.0131 (6) | −0.0003 (4) | 0.0025 (5) | −0.0002 (4) |
C6 | 0.0130 (7) | 0.0107 (7) | 0.0097 (6) | 0.0016 (5) | 0.0015 (5) | 0.0008 (5) |
C4 | 0.0098 (7) | 0.0124 (7) | 0.0114 (6) | −0.0002 (5) | 0.0018 (5) | 0.0010 (5) |
C2 | 0.0138 (7) | 0.0092 (7) | 0.0140 (6) | −0.0012 (5) | 0.0023 (5) | 0.0005 (5) |
C5 | 0.0106 (7) | 0.0107 (7) | 0.0119 (6) | −0.0004 (5) | 0.0005 (5) | 0.0008 (5) |
C3 | 0.0112 (7) | 0.0100 (7) | 0.0109 (6) | 0.0003 (5) | 0.0001 (5) | −0.0010 (5) |
O7 | 0.0127 (5) | 0.0124 (5) | 0.0227 (5) | −0.0007 (4) | 0.0049 (4) | 0.0029 (4) |
O5 | 0.0117 (6) | 0.0275 (7) | 0.0217 (6) | −0.0010 (5) | 0.0045 (4) | −0.0089 (5) |
C7 | 0.0111 (7) | 0.0103 (7) | 0.0139 (6) | 0.0001 (5) | −0.0004 (5) | 0.0012 (5) |
O6 | 0.0156 (6) | 0.0219 (6) | 0.0210 (6) | −0.0053 (5) | 0.0061 (5) | −0.0033 (5) |
Ni1—N1i | 1.9996 (12) | O8—C7 | 1.2769 (18) |
Ni1—N1 | 1.9996 (12) | C1—N1 | 1.3468 (18) |
Ni1—O5 | 2.0516 (12) | C1—C2 | 1.393 (2) |
Ni1—O5i | 2.0516 (12) | C1—C1i | 1.493 (3) |
Ni1—O8 | 2.1327 (11) | N1—C5 | 1.3317 (19) |
Ni1—O8i | 2.1327 (11) | C6—C3 | 1.525 (2) |
Ni2—O1 | 2.0265 (11) | C4—C5 | 1.397 (2) |
Ni2—O1ii | 2.0265 (11) | C4—C3 | 1.405 (2) |
Ni2—O3ii | 2.0607 (10) | C4—H4C | 0.9300 |
Ni2—O3 | 2.0607 (10) | C2—C3 | 1.398 (2) |
Ni2—O4ii | 2.0796 (11) | C2—H2A | 0.9300 |
Ni2—O4 | 2.0796 (11) | C5—C7 | 1.530 (2) |
O1—C6 | 1.2570 (18) | O7—C7 | 1.2427 (19) |
O3—H3A | 0.8200 | O5—H5A | 0.8200 |
O3—H3B | 0.85 (2) | O5—H5B | 0.78 (3) |
O2—C6 | 1.2541 (18) | O6—H6A | 0.79 (3) |
O4—H4A | 0.8200 | O6—H6B | 0.79 (3) |
O4—H4B | 0.78 (3) | ||
N1i—Ni1—N1 | 78.65 (7) | H3A—O3—H3B | 108.0 |
N1i—Ni1—O5 | 93.20 (5) | Ni2—O4—H4A | 109.5 |
N1—Ni1—O5 | 91.05 (5) | Ni2—O4—H4B | 124 (2) |
N1i—Ni1—O5i | 91.05 (5) | H4A—O4—H4B | 114.4 |
N1—Ni1—O5i | 93.20 (5) | C7—O8—Ni1 | 115.42 (9) |
O5—Ni1—O5i | 174.51 (7) | N1—C1—C2 | 119.82 (13) |
N1i—Ni1—O8 | 155.70 (5) | N1—C1—C1i | 112.73 (8) |
N1—Ni1—O8 | 77.21 (5) | C2—C1—C1i | 127.45 (8) |
O5—Ni1—O8 | 89.96 (5) | C5—N1—C1 | 122.43 (12) |
O5i—Ni1—O8 | 87.60 (5) | C5—N1—Ni1 | 119.63 (10) |
N1i—Ni1—O8i | 77.21 (5) | C1—N1—Ni1 | 117.94 (10) |
N1—Ni1—O8i | 155.70 (5) | O2—C6—O1 | 126.58 (14) |
O5—Ni1—O8i | 87.60 (5) | O2—C6—C3 | 118.75 (13) |
O5i—Ni1—O8i | 89.96 (5) | O1—C6—C3 | 114.64 (13) |
O8—Ni1—O8i | 127.03 (6) | C5—C4—C3 | 117.70 (13) |
O1—Ni2—O1ii | 180.00 (4) | C5—C4—H4C | 121.1 |
O1—Ni2—O3ii | 94.76 (4) | C3—C4—H4C | 121.1 |
O1ii—Ni2—O3ii | 85.24 (4) | C1—C2—C3 | 118.91 (13) |
O1—Ni2—O3 | 85.24 (4) | C1—C2—H2A | 120.5 |
O1ii—Ni2—O3 | 94.76 (4) | C3—C2—H2A | 120.5 |
O3ii—Ni2—O3 | 180.000 (1) | N1—C5—C4 | 121.05 (13) |
O1—Ni2—O4ii | 93.22 (5) | N1—C5—C7 | 112.28 (12) |
O1ii—Ni2—O4ii | 86.78 (5) | C4—C5—C7 | 126.67 (13) |
O3ii—Ni2—O4ii | 87.43 (4) | C2—C3—C4 | 120.06 (13) |
O3—Ni2—O4ii | 92.57 (4) | C2—C3—C6 | 118.55 (13) |
O1—Ni2—O4 | 86.78 (5) | C4—C3—C6 | 121.39 (13) |
O1ii—Ni2—O4 | 93.22 (5) | Ni1—O5—H5A | 109.5 |
O3ii—Ni2—O4 | 92.57 (4) | Ni1—O5—H5B | 113.3 (19) |
O3—Ni2—O4 | 87.43 (4) | H5A—O5—H5B | 119.4 |
O4ii—Ni2—O4 | 180.0 | O7—C7—O8 | 125.72 (14) |
C6—O1—Ni2 | 138.47 (10) | O7—C7—C5 | 119.10 (13) |
Ni2—O3—H3A | 109.5 | O8—C7—C5 | 115.18 (13) |
Ni2—O3—H3B | 115.5 (17) | H6A—O6—H6B | 105 (2) |
Symmetry codes: (i) −x+1/2, y, −z+3/2; (ii) −x, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O6 | 0.85 (2) | 1.95 (2) | 2.7821 (16) | 169 (2) |
O3—H3A···O8iii | 0.82 | 1.90 | 2.7189 (16) | 174 |
O4—H4A···O6iv | 0.82 | 1.95 | 2.7697 (17) | 178 |
O4—H4B···O7v | 0.78 (3) | 2.03 (3) | 2.7997 (16) | 172 (3) |
O5—H5A···O2vi | 0.82 | 1.90 | 2.6891 (16) | 162 |
O5—H5B···O7vii | 0.78 (3) | 1.96 (3) | 2.7395 (17) | 172 (3) |
O6—H6A···O2vii | 0.79 (3) | 2.03 (3) | 2.8096 (17) | 170 (2) |
Symmetry codes: (iii) x, y+1, z; (iv) x+1/2, −y+2, z+1/2; (v) −x, −y+1, −z+2; (vi) x+1/2, −y+1, z−1/2; (vii) −x−1/2, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Ni2(C14H4N2O8)(H2O)6]·2H2O |
Mr | 589.70 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 296 |
a, b, c (Å) | 7.3588 (8), 11.8463 (13), 11.9942 (13) |
β (°) | 99.184 (1) |
V (Å3) | 1032.19 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.91 |
Crystal size (mm) | 0.28 × 0.24 × 0.19 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.591, 0.695 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8794, 2365, 2248 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.062, 1.06 |
No. of reflections | 2365 |
No. of parameters | 176 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.42 |
Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O6 | 0.85 (2) | 1.95 (2) | 2.7821 (16) | 169 (2) |
O3—H3A···O8i | 0.82 | 1.90 | 2.7189 (16) | 174.4 |
O4—H4A···O6ii | 0.82 | 1.95 | 2.7697 (17) | 177.8 |
O4—H4B···O7iii | 0.78 (3) | 2.03 (3) | 2.7997 (16) | 172 (3) |
O5—H5A···O2iv | 0.82 | 1.90 | 2.6891 (16) | 161.9 |
O5—H5B···O7v | 0.78 (3) | 1.96 (3) | 2.7395 (17) | 172 (3) |
O6—H6A···O2v | 0.79 (3) | 2.03 (3) | 2.8096 (17) | 170 (2) |
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, −y+2, z+1/2; (iii) −x, −y+1, −z+2; (iv) x+1/2, −y+1, z−1/2; (v) −x−1/2, y, −z+3/2. |
Acknowledgements
This project was sponsored by the K. C. Wong Magna Fund in Ningbo University, the Talent Fund of Ningbo Municipal Natural Science Foundation (No. 2010 A610187) and the Talent Fund of Ningbo University (No. Xkl09070).
References
Al-Harbi, T. (2011). J. Alloys Compd, 509, 387–390. CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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The complex structure is shown in Fig. 1. In the title complex two Ni atoms are placed in two different special positions: Ni1 - on 2–fold axis and Ni2 - in centre of symmetry. These atoms have different environment: Ni1 is coordinated by two N atoms of dipyridine moiety, two O atoms from water molecules and two O atoms from two carboxylate moieties; Ni2 is coordinated only by six O atoms: four O from four water molecules and two O from two carboxylate moieties.
In the crystal structure there is the wide net of classical O—H···O type H–bonds (Table 1, Fig. 2), which stabilize crystal packing.