The title complex, [Ni(C6H4NO2)2(H2O)4], consists of Ni atoms coordinated to two trans pyridylcarboxylate ligands, coordinated through the N atoms, and four water ligands. The Ni atom lies on a centre of symmetry. Extensive inter-complex hydrogen bonding occurs between the water ligands and the carboxylate groups, resulting in a three-dimensional network.
Supporting information
CCDC reference: 155833
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (C-C) = 0.002 Å
- R factor = 0.025
- wR factor = 0.058
- Data-to-parameter ratio = 13.3
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-4-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-4-carboxylate)tetraaquonickel(II)
top
Crystal data top
[Ni(C6H4NO2)2(H2O)4] | Z = 1 |
Mr = 374.98 | F(000) = 194 |
Triclinic, P1 | Dx = 1.822 Mg m−3 |
a = 6.2862 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 6.8598 (2) Å | Cell parameters from 3694 reflections |
c = 9.2394 (4) Å | θ = 2.4–28.3° |
α = 96.511 (3)° | µ = 1.47 mm−1 |
β = 104.929 (2)° | T = 123 K |
γ = 113.692 (3)° | Plate, blue |
V = 341.77 (2) Å3 | 0.18 × 0.13 × 0.05 mm |
Data collection top
Nonius KappaCCD diffractometer | 1626 independent reflections |
Radiation source: fine-focus sealed tube | 1558 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 9 pixels mm-1 | θmax = 28.3°, θmin = 2.4° |
ϕ and ω scans | h = −8→8 |
Absorption correction: integration (XPREP; Siemens, 1994) | k = −8→8 |
Tmin = 0.835, Tmax = 0.940 | l = −11→12 |
3694 measured 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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0023P)2 + 0.1806P] where P = (Fo2 + 2Fc2)/3 |
1626 reflections | (Δ/σ)max < 0.001 |
122 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.52 e Å−3 |
Crystal data top
[Ni(C6H4NO2)2(H2O)4] | γ = 113.692 (3)° |
Mr = 374.98 | V = 341.77 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.2862 (3) Å | Mo Kα radiation |
b = 6.8598 (2) Å | µ = 1.47 mm−1 |
c = 9.2394 (4) Å | T = 123 K |
α = 96.511 (3)° | 0.18 × 0.13 × 0.05 mm |
β = 104.929 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 1626 independent reflections |
Absorption correction: integration (XPREP; Siemens, 1994) | 1558 reflections with I > 2σ(I) |
Tmin = 0.835, Tmax = 0.940 | Rint = 0.029 |
3694 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | Δρmax = 0.34 e Å−3 |
1626 reflections | Δρmin = −0.52 e Å−3 |
122 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 | 0.5000 | 0.5000 | 0.5000 | 0.00985 (10) | |
O1 | 0.3201 (2) | 0.68358 (19) | 0.54174 (13) | 0.0133 (2) | |
H11 | 0.233 (4) | 0.716 (3) | 0.448 (2) | 0.022 (5)* | |
H12 | 0.406 (5) | 0.799 (4) | 0.603 (3) | 0.038 (7)* | |
O2 | 0.2785 (2) | 0.23654 (19) | 0.57230 (13) | 0.0146 (2) | |
H21 | 0.357 (5) | 0.179 (4) | 0.621 (3) | 0.031 (6)* | |
H22 | 0.169 (6) | 0.232 (5) | 0.609 (3) | 0.051 (8)* | |
N1 | 0.2618 (2) | 0.3588 (2) | 0.27200 (14) | 0.0115 (3) | |
C1 | 0.0173 (3) | 0.2869 (3) | 0.23226 (18) | 0.0146 (3) | |
H1A | −0.0535 | 0.2808 | 0.3119 | 0.017* | |
C2 | −0.1366 (3) | 0.2211 (2) | 0.08009 (18) | 0.0133 (3) | |
H2A | −0.3090 | 0.1709 | 0.0566 | 0.016* | |
C3 | −0.0356 (3) | 0.2294 (2) | −0.03765 (17) | 0.0113 (3) | |
C4 | 0.2166 (3) | 0.2947 (2) | 0.00326 (18) | 0.0127 (3) | |
H4A | 0.2911 | 0.2962 | −0.0742 | 0.015* | |
C5 | 0.3569 (3) | 0.3571 (2) | 0.15742 (17) | 0.0125 (3) | |
H5A | 0.5287 | 0.4009 | 0.1839 | 0.015* | |
C6 | −0.1921 (3) | 0.1762 (2) | −0.20519 (18) | 0.0127 (3) | |
O3 | −0.4223 (2) | 0.08506 (19) | −0.23781 (13) | 0.0176 (2) | |
O4 | −0.0777 (2) | 0.2321 (2) | −0.29873 (13) | 0.0183 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.00868 (14) | 0.01290 (15) | 0.00829 (15) | 0.00532 (11) | 0.00296 (10) | 0.00170 (10) |
O1 | 0.0129 (5) | 0.0160 (6) | 0.0113 (5) | 0.0083 (5) | 0.0023 (4) | 0.0013 (4) |
O2 | 0.0127 (5) | 0.0171 (6) | 0.0164 (6) | 0.0071 (5) | 0.0069 (5) | 0.0072 (4) |
N1 | 0.0113 (6) | 0.0131 (6) | 0.0103 (6) | 0.0059 (5) | 0.0033 (5) | 0.0024 (5) |
C1 | 0.0133 (7) | 0.0178 (8) | 0.0141 (7) | 0.0071 (6) | 0.0069 (6) | 0.0033 (6) |
C2 | 0.0102 (7) | 0.0133 (7) | 0.0156 (8) | 0.0053 (6) | 0.0042 (6) | 0.0011 (6) |
C3 | 0.0129 (7) | 0.0079 (7) | 0.0127 (7) | 0.0051 (6) | 0.0028 (6) | 0.0023 (5) |
C4 | 0.0139 (7) | 0.0126 (7) | 0.0129 (7) | 0.0062 (6) | 0.0060 (6) | 0.0034 (6) |
C5 | 0.0101 (7) | 0.0150 (7) | 0.0132 (7) | 0.0063 (6) | 0.0041 (6) | 0.0031 (6) |
C6 | 0.0147 (7) | 0.0106 (7) | 0.0134 (7) | 0.0076 (6) | 0.0030 (6) | 0.0019 (5) |
O3 | 0.0124 (5) | 0.0210 (6) | 0.0161 (6) | 0.0065 (5) | 0.0019 (4) | 0.0036 (4) |
O4 | 0.0177 (6) | 0.0286 (7) | 0.0129 (6) | 0.0131 (5) | 0.0065 (5) | 0.0071 (5) |
Geometric parameters (Å, º) top
Ni1—O1 | 2.0669 (11) | C1—C2 | 1.386 (2) |
Ni1—O1i | 2.0669 (11) | C1—H1A | 0.9500 |
Ni1—N1i | 2.0890 (13) | C2—C3 | 1.389 (2) |
Ni1—N1 | 2.0891 (13) | C2—H2A | 0.9500 |
Ni1—O2i | 2.0932 (11) | C3—C4 | 1.392 (2) |
Ni1—O2 | 2.0932 (11) | C3—C6 | 1.515 (2) |
O1—H11 | 1.00 (2) | C4—C5 | 1.379 (2) |
O1—H12 | 0.80 (3) | C4—H4A | 0.9500 |
O2—H21 | 0.83 (3) | C5—H5A | 0.9500 |
O2—H22 | 0.83 (3) | C6—O3 | 1.2575 (19) |
N1—C1 | 1.342 (2) | C6—O4 | 1.2591 (19) |
N1—C5 | 1.344 (2) | | |
| | | |
O1—Ni1—O1i | 180.0 | C1—N1—C5 | 117.60 (13) |
O1—Ni1—N1i | 88.10 (5) | C1—N1—Ni1 | 122.94 (10) |
O1i—Ni1—N1i | 91.90 (5) | C5—N1—Ni1 | 119.18 (10) |
O1—Ni1—N1 | 91.90 (5) | N1—C1—C2 | 122.89 (14) |
O1i—Ni1—N1 | 88.10 (5) | N1—C1—H1A | 118.6 |
N1i—Ni1—N1 | 180.0 | C2—C1—H1A | 118.6 |
O1—Ni1—O2i | 86.76 (5) | C1—C2—C3 | 119.19 (15) |
O1i—Ni1—O2i | 93.24 (5) | C1—C2—H2A | 120.4 |
N1i—Ni1—O2i | 90.76 (5) | C3—C2—H2A | 120.4 |
N1—Ni1—O2i | 89.24 (5) | C2—C3—C4 | 117.91 (14) |
O1—Ni1—O2 | 93.24 (5) | C2—C3—C6 | 121.39 (14) |
O1i—Ni1—O2 | 86.76 (5) | C4—C3—C6 | 120.68 (14) |
N1i—Ni1—O2 | 89.24 (5) | C5—C4—C3 | 119.29 (14) |
N1—Ni1—O2 | 90.76 (5) | C5—C4—H4A | 120.4 |
O2i—Ni1—O2 | 180.000 (1) | C3—C4—H4A | 120.4 |
Ni1—O1—H11 | 114.6 (12) | N1—C5—C4 | 123.00 (14) |
Ni1—O1—H12 | 114.8 (18) | N1—C5—H5A | 118.5 |
H11—O1—H12 | 106 (2) | C4—C5—H5A | 118.5 |
Ni1—O2—H21 | 112.3 (16) | O3—C6—O4 | 126.02 (15) |
Ni1—O2—H22 | 126.5 (19) | O3—C6—C3 | 117.62 (14) |
H21—O2—H22 | 109 (2) | O4—C6—C3 | 116.34 (14) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O4ii | 1.00 (2) | 1.64 (2) | 2.634 (2) | 177 (2) |
O1—H12···O3iii | 0.80 (2) | 2.00 (3) | 2.793 (2) | 172 (2) |
O2—H21···O3iv | 0.83 (3) | 2.00 (3) | 2.825 (2) | 171 (2) |
O2—H22···O4v | 0.83 (3) | 1.96 (3) | 2.786 (2) | 178 (3) |
C1—H1A···O1vi | 0.95 | 2.47 | 3.381 (2) | 160 |
Symmetry codes: (ii) −x, −y+1, −z; (iii) x+1, y+1, z+1; (iv) x+1, y, z+1; (v) x, y, z+1; (vi) −x, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Ni(C6H4NO2)2(H2O)4] |
Mr | 374.98 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 123 |
a, b, c (Å) | 6.2862 (3), 6.8598 (2), 9.2394 (4) |
α, β, γ (°) | 96.511 (3), 104.929 (2), 113.692 (3) |
V (Å3) | 341.77 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.47 |
Crystal size (mm) | 0.18 × 0.13 × 0.05 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Integration (XPREP; Siemens, 1994) |
Tmin, Tmax | 0.835, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3694, 1626, 1558 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.666 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.058, 1.15 |
No. of reflections | 1626 |
No. of parameters | 122 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.52 |
Selected geometric parameters (Å, º) topNi1—O1 | 2.0669 (11) | Ni1—O2 | 2.0932 (11) |
Ni1—N1 | 2.0891 (13) | | |
| | | |
O1—Ni1—N1 | 91.90 (5) | N1—Ni1—O2 | 90.76 (5) |
O1—Ni1—O2 | 93.24 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O4i | 1.00 (2) | 1.64 (2) | 2.634 (2) | 177 (2) |
O1—H12···O3ii | 0.80 (2) | 2.00 (3) | 2.793 (2) | 172 (2) |
O2—H21···O3iii | 0.83 (3) | 2.00 (3) | 2.825 (2) | 171 (2) |
O2—H22···O4iv | 0.83 (3) | 1.96 (3) | 2.786 (2) | 178 (3) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x+1, y+1, z+1; (iii) x+1, y, z+1; (iv) x, y, z+1. |
Pyridylcarboxylate ligands have recently been used in the construction of novel new coordination polymers with interesting microporous and non-linear optical properties (Lin et al., 1998; Evans, Xiong et al., 1999; Evans, Wang et al., 1999; Evans & Lin, 2000). A feature of this class of bridging ligand is the presence of two different coordinating functionalities – a pyridyl group and a carboxylate group. The ligands also offer the possibility of participating in hydrogen-bonding networks if monodentate coordination occurs. We report here the structure of NiL2(H2O)4 (L is pyridyl-4-carboxylate), (I), in which such a hydrogen-bonded network is found.
The structure of (I) is isomorphous with the previously reported manganese(II) (Hauptmann et al., 2000), iron(II) (Liu et al., 1999), cobalt(II) (Waizumi et al., 1998), copper(II) (Okabe et al., 1993; Waizumi et al., 1998), zinc(II) (Cingi et al., 1971) and cadmium(II) (Cingi et al., 1971) structures. It consists of mononuclear nickel complexes in which the metal ion is coordinated to the N atoms of two trans pyridyl-4-carboxylate ligands, and to four water ligands (Fig. 1). The octahedrally coordinated Ni atom (Table 1) lies on a centre of symmetry. The carboxylate group of the ligand is twisted slightly from the plane of the pyridyl group [the angle between the two planes is 13.93 (8)°].
Extensive hydrogen bonding between the water ligands and the uncoordinated carboxylate groups generates 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 is thus connected to six neighbours via 16 O—H···O hydrogen bonds.