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The title complex, [Ni(C6H4NO2)2(H2O)4], consists of an Ni atom coordinated to two trans pyridinecarboxylate ligands, coordinated through the N atoms, and four water ligands. The Ni atom lies on a site of 2/m symmetry, and the pyridinecarboxylate ligand lies on a mirror plane. Extensive inter-complex hydrogen bonding occurs between the water ligands and the carboxylate groups, resulting in a three-dimensional network.
Supporting information
CCDC reference: 155834
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (C-C) = 0.004 Å
- R factor = 0.032
- wR factor = 0.058
- Data-to-parameter ratio = 12.1
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
The title compound was obtained from an aqueous solution containing nickel
nitrate, sodium dicyanamide and pyridyl-3-carboxylic acid.
All H atoms were observed in difference syntheses, however only those of the
water ligands were allowed to refine freely.
Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
trans-Bis(pyridine-3-carboxylate)tetraaquonickel(II)
top
Crystal data top
[Ni(C6H4NO2)2(H2O)4] | F(000) = 388 |
Mr = 374.98 | Dx = 1.747 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
a = 14.0549 (7) Å | Cell parameters from 5663 reflections |
b = 6.8170 (2) Å | θ = 2.7–27.8° |
c = 8.4359 (4) Å | µ = 1.41 mm−1 |
β = 118.137 (2)° | T = 123 K |
V = 712.74 (5) Å3 | Rod, light blue |
Z = 2 | 0.30 × 0.05 × 0.03 mm |
Data collection top
Nonius KappaCCD diffractometer | 843 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 27.8°, θmin = 2.7° |
Detector resolution: 9 pixels mm-1 | h = −18→18 |
ϕ and ω scans | k = −8→8 |
5664 measured reflections | l = −11→11 |
916 independent reflections | |
Refinement top
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0108P)2 + 1.0314P] where P = (Fo2 + 2Fc2)/3 |
916 reflections | (Δ/σ)max < 0.001 |
76 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
[Ni(C6H4NO2)2(H2O)4] | V = 712.74 (5) Å3 |
Mr = 374.98 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 14.0549 (7) Å | µ = 1.41 mm−1 |
b = 6.8170 (2) Å | T = 123 K |
c = 8.4359 (4) Å | 0.30 × 0.05 × 0.03 mm |
β = 118.137 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 843 reflections with I > 2σ(I) |
5664 measured reflections | Rint = 0.050 |
916 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.37 e Å−3 |
916 reflections | Δρmin = −0.34 e Å−3 |
76 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. All hydrogen atoms were found, however only those of the water
ligands were allowed to refine freely. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.0000 | 0.0000 | 0.5000 | 0.01259 (14) | |
O1 | 0.05577 (10) | 0.2183 (2) | 0.39281 (17) | 0.0189 (3) | |
H1A | 0.096 (2) | 0.161 (4) | 0.341 (3) | 0.051 (8)* | |
H1B | 0.096 (2) | 0.297 (4) | 0.468 (4) | 0.045 (8)* | |
N1 | 0.14602 (16) | 0.0000 | 0.7405 (3) | 0.0145 (4) | |
C2 | 0.1462 (2) | 0.0000 | 0.8993 (3) | 0.0150 (5) | |
H2A | 0.0787 | 0.0000 | 0.8996 | 0.018* | |
C3 | 0.2395 (2) | 0.0000 | 1.0634 (3) | 0.0146 (5) | |
C4 | 0.3381 (2) | 0.0000 | 1.0642 (3) | 0.0188 (5) | |
H4A | 0.4035 | 0.0000 | 1.1742 | 0.023* | |
C5 | 0.3393 (2) | 0.0000 | 0.9000 (3) | 0.0206 (6) | |
H5A | 0.4058 | 0.0000 | 0.8963 | 0.025* | |
C6 | 0.2428 (2) | 0.0000 | 0.7429 (3) | 0.0176 (5) | |
H6A | 0.2445 | 0.0000 | 0.6316 | 0.021* | |
C7 | 0.2301 (2) | 0.0000 | 1.2347 (3) | 0.0180 (5) | |
O2 | 0.13636 (16) | 0.0000 | 1.2175 (2) | 0.0263 (4) | |
O3 | 0.31551 (15) | 0.0000 | 1.3817 (2) | 0.0234 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0109 (2) | 0.0136 (2) | 0.0092 (2) | 0.000 | 0.00141 (18) | 0.000 |
O1 | 0.0185 (7) | 0.0198 (7) | 0.0153 (7) | −0.0041 (5) | 0.0055 (6) | −0.0011 (5) |
N1 | 0.0149 (11) | 0.0140 (10) | 0.0117 (10) | 0.000 | 0.0038 (8) | 0.000 |
C2 | 0.0142 (12) | 0.0139 (12) | 0.0145 (12) | 0.000 | 0.0049 (10) | 0.000 |
C3 | 0.0183 (13) | 0.0082 (11) | 0.0130 (12) | 0.000 | 0.0039 (10) | 0.000 |
C4 | 0.0145 (13) | 0.0176 (12) | 0.0163 (12) | 0.000 | 0.0007 (10) | 0.000 |
C5 | 0.0127 (13) | 0.0252 (14) | 0.0220 (14) | 0.000 | 0.0067 (11) | 0.000 |
C6 | 0.0165 (13) | 0.0194 (12) | 0.0159 (12) | 0.000 | 0.0068 (11) | 0.000 |
C7 | 0.0253 (15) | 0.0111 (11) | 0.0138 (12) | 0.000 | 0.0060 (11) | 0.000 |
O2 | 0.0265 (11) | 0.0341 (11) | 0.0203 (10) | 0.000 | 0.0127 (9) | 0.000 |
O3 | 0.0277 (11) | 0.0196 (9) | 0.0119 (9) | 0.000 | 0.0003 (8) | 0.000 |
Geometric parameters (Å, º) top
Ni1—O1i | 2.0775 (12) | N1—C6 | 1.351 (3) |
Ni1—O1ii | 2.0775 (12) | C2—C3 | 1.387 (3) |
Ni1—O1iii | 2.0775 (13) | C3—C4 | 1.382 (4) |
Ni1—O1 | 2.0775 (12) | C3—C7 | 1.512 (3) |
Ni1—N1 | 2.098 (2) | C4—C5 | 1.394 (4) |
Ni1—N1iii | 2.098 (2) | C5—C6 | 1.378 (4) |
O1—H1A | 0.95 (3) | C7—O3 | 1.255 (3) |
O1—H1B | 0.82 (3) | C7—O2 | 1.256 (3) |
N1—C2 | 1.339 (3) | | |
| | | |
O1i—Ni1—O1ii | 180.0 (8) | Ni1—O1—H1B | 113.4 (18) |
O1i—Ni1—O1iii | 88.48 (8) | H1A—O1—H1B | 106 (2) |
O1ii—Ni1—O1iii | 91.52 (8) | C2—N1—C6 | 117.3 (2) |
O1—Ni1—N1 | 91.32 (5) | C2—N1—Ni1 | 120.46 (17) |
O1—Ni1—O1i | 91.52 (8) | C6—N1—Ni1 | 122.25 (16) |
O1ii—Ni1—O1 | 88.48 (8) | N1—C2—C3 | 123.6 (2) |
O1iii—Ni1—O1 | 180.00 (6) | C4—C3—C2 | 118.6 (2) |
O1i—Ni1—N1 | 91.32 (5) | C4—C3—C7 | 122.3 (2) |
O1ii—Ni1—N1 | 88.68 (5) | C2—C3—C7 | 119.1 (2) |
O1iii—Ni1—N1 | 88.68 (5) | C3—C4—C5 | 118.5 (2) |
O1i—Ni1—N1iii | 88.68 (5) | C6—C5—C4 | 119.2 (2) |
O1ii—Ni1—N1iii | 91.32 (5) | N1—C6—C5 | 122.8 (2) |
O1iii—Ni1—N1iii | 91.32 (5) | O3—C7—O2 | 125.2 (2) |
O1—Ni1—N1iii | 88.68 (5) | O3—C7—C3 | 118.0 (2) |
N1—Ni1—N1iii | 180.0 | O2—C7—C3 | 116.7 (2) |
Ni1—O1—H1A | 109.7 (16) | | |
Symmetry codes: (i) x, −y, z; (ii) −x, y, −z+1; (iii) −x, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2iv | 0.95 (3) | 1.77 (3) | 2.696 (2) | 161 (2) |
O1—H1B···O3v | 0.82 (3) | 1.89 (3) | 2.708 (2) | 173 (3) |
Symmetry codes: (iv) x, y, z−1; (v) −x+1/2, −y+1/2, −z+2. |
Experimental details
Crystal data |
Chemical formula | [Ni(C6H4NO2)2(H2O)4] |
Mr | 374.98 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 123 |
a, b, c (Å) | 14.0549 (7), 6.8170 (2), 8.4359 (4) |
β (°) | 118.137 (2) |
V (Å3) | 712.74 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.41 |
Crystal size (mm) | 0.30 × 0.05 × 0.03 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5664, 916, 843 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.657 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.058, 1.12 |
No. of reflections | 916 |
No. of parameters | 76 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.34 |
Selected geometric parameters (Å, º) topNi1—O1 | 2.0775 (12) | Ni1—N1 | 2.098 (2) |
| | | |
O1—Ni1—N1 | 91.32 (5) | O1—Ni1—O1i | 91.52 (8) |
Symmetry code: (i) x, −y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2ii | 0.95 (3) | 1.77 (3) | 2.696 (2) | 161 (2) |
O1—H1B···O3iii | 0.82 (3) | 1.89 (3) | 2.708 (2) | 173 (3) |
Symmetry codes: (ii) x, y, z−1; (iii) −x+1/2, −y+1/2, −z+2. |
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A number of novel new coordination polymers which contain bridging pyridylcarboxylate ligands and display interesting physical properties have been reported recently (Lin et al., 1998; Evans, Xiong et al., 1999; Evans, Wang et al., 1999; Evans & Lin, 2000). However, if the ligands coordinate only in a monodentate fashion, the possibility of participating in hydrogen bonding-networks arises. We report here the structure of NiL2(H2O)4 (L is pyridyl-3-carboxylate), (I), in which such a hydrogen-bonded network is found.
The structure of (I) is isomorphous with the previously reported cobalt(II) (Anagnostopoulos et al., 1969; Waizumi et al., 1998) and zinc(II) (Cotton et al., 1991; Cingi et al., 1971; Sabirov et al., 1984) analogues. It consists of mononuclear nickel complexes containing two trans nitrogen-bound pyridyl-3-carboxylate ligands and four water ligands (Fig. 1). The octahedrally coordinated Ni atom (Table 1) lies on a site of 2/m symmetry, while the pyridylcarboxylate ligand lies on a mirror plane and is thus rigidly planar.
As expected, there is extensive hydrogen bonding between the water ligands and the uncoordinated carboxylate groups, giving rise to a complex three-dimensional network (Fig. 2). Each carboxylate O atom is hydrogen bonded to two separate water ligands (Table 2), and each water ligand hydrogen bonds to two separate carboxylates. Each complex thus participates in 16 O—H···O intermolecular hydrogen bonds to six neighbouring complexes.