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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800018742/ob6008sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800018742/ob6008Isup2.hkl
Contains datablock I

CCDC reference: 155834

Key indicators

  • Single-crystal X-ray study
  • T = 123 K
  • Mean [sigma](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




Comment top

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.

Experimental top

The title compound was obtained from an aqueous solution containing nickel nitrate, sodium dicyanamide and pyridyl-3-carboxylic acid.

Refinement top

All H atoms were observed in difference syntheses, however only those of the water ligands were allowed to refine freely.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Atom-numbering scheme for (I). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Crystal packing in (I), showing the extensive hydrogen bonding between complexes.
trans-Bis(pyridine-3-carboxylate)tetraaquonickel(II) top
Crystal data top
[Ni(C6H4NO2)2(H2O)4]F(000) = 388
Mr = 374.98Dx = 1.747 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
a = 14.0549 (7) ÅCell parameters from 5663 reflections
b = 6.8170 (2) Åθ = 2.7–27.8°
c = 8.4359 (4) ŵ = 1.41 mm1
β = 118.137 (2)°T = 123 K
V = 712.74 (5) Å3Rod, light blue
Z = 20.30 × 0.05 × 0.03 mm
Data collection top
Nonius KappaCCD
diffractometer
843 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
Graphite monochromatorθmax = 27.8°, θmin = 2.7°
Detector resolution: 9 pixels mm-1h = 1818
ϕ and ω scansk = 88
5664 measured reflectionsl = 1111
916 independent reflections
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.058H 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 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
[Ni(C6H4NO2)2(H2O)4]V = 712.74 (5) Å3
Mr = 374.98Z = 2
Monoclinic, C2/mMo Kα radiation
a = 14.0549 (7) ŵ = 1.41 mm1
b = 6.8170 (2) ÅT = 123 K
c = 8.4359 (4) Å0.30 × 0.05 × 0.03 mm
β = 118.137 (2)°
Data collection top
Nonius KappaCCD
diffractometer
843 reflections with I > 2σ(I)
5664 measured reflectionsRint = 0.050
916 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.058H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.37 e Å3
916 reflectionsΔρmin = 0.34 e Å3
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
xyzUiso*/Ueq
Ni10.00000.00000.50000.01259 (14)
O10.05577 (10)0.2183 (2)0.39281 (17)0.0189 (3)
H1A0.096 (2)0.161 (4)0.341 (3)0.051 (8)*
H1B0.096 (2)0.297 (4)0.468 (4)0.045 (8)*
N10.14602 (16)0.00000.7405 (3)0.0145 (4)
C20.1462 (2)0.00000.8993 (3)0.0150 (5)
H2A0.07870.00000.89960.018*
C30.2395 (2)0.00001.0634 (3)0.0146 (5)
C40.3381 (2)0.00001.0642 (3)0.0188 (5)
H4A0.40350.00001.17420.023*
C50.3393 (2)0.00000.9000 (3)0.0206 (6)
H5A0.40580.00000.89630.025*
C60.2428 (2)0.00000.7429 (3)0.0176 (5)
H6A0.24450.00000.63160.021*
C70.2301 (2)0.00001.2347 (3)0.0180 (5)
O20.13636 (16)0.00001.2175 (2)0.0263 (4)
O30.31551 (15)0.00001.3817 (2)0.0234 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0109 (2)0.0136 (2)0.0092 (2)0.0000.00141 (18)0.000
O10.0185 (7)0.0198 (7)0.0153 (7)0.0041 (5)0.0055 (6)0.0011 (5)
N10.0149 (11)0.0140 (10)0.0117 (10)0.0000.0038 (8)0.000
C20.0142 (12)0.0139 (12)0.0145 (12)0.0000.0049 (10)0.000
C30.0183 (13)0.0082 (11)0.0130 (12)0.0000.0039 (10)0.000
C40.0145 (13)0.0176 (12)0.0163 (12)0.0000.0007 (10)0.000
C50.0127 (13)0.0252 (14)0.0220 (14)0.0000.0067 (11)0.000
C60.0165 (13)0.0194 (12)0.0159 (12)0.0000.0068 (11)0.000
C70.0253 (15)0.0111 (11)0.0138 (12)0.0000.0060 (11)0.000
O20.0265 (11)0.0341 (11)0.0203 (10)0.0000.0127 (9)0.000
O30.0277 (11)0.0196 (9)0.0119 (9)0.0000.0003 (8)0.000
Geometric parameters (Å, º) top
Ni1—O1i2.0775 (12)N1—C61.351 (3)
Ni1—O1ii2.0775 (12)C2—C31.387 (3)
Ni1—O1iii2.0775 (13)C3—C41.382 (4)
Ni1—O12.0775 (12)C3—C71.512 (3)
Ni1—N12.098 (2)C4—C51.394 (4)
Ni1—N1iii2.098 (2)C5—C61.378 (4)
O1—H1A0.95 (3)C7—O31.255 (3)
O1—H1B0.82 (3)C7—O21.256 (3)
N1—C21.339 (3)
O1i—Ni1—O1ii180.0 (8)Ni1—O1—H1B113.4 (18)
O1i—Ni1—O1iii88.48 (8)H1A—O1—H1B106 (2)
O1ii—Ni1—O1iii91.52 (8)C2—N1—C6117.3 (2)
O1—Ni1—N191.32 (5)C2—N1—Ni1120.46 (17)
O1—Ni1—O1i91.52 (8)C6—N1—Ni1122.25 (16)
O1ii—Ni1—O188.48 (8)N1—C2—C3123.6 (2)
O1iii—Ni1—O1180.00 (6)C4—C3—C2118.6 (2)
O1i—Ni1—N191.32 (5)C4—C3—C7122.3 (2)
O1ii—Ni1—N188.68 (5)C2—C3—C7119.1 (2)
O1iii—Ni1—N188.68 (5)C3—C4—C5118.5 (2)
O1i—Ni1—N1iii88.68 (5)C6—C5—C4119.2 (2)
O1ii—Ni1—N1iii91.32 (5)N1—C6—C5122.8 (2)
O1iii—Ni1—N1iii91.32 (5)O3—C7—O2125.2 (2)
O1—Ni1—N1iii88.68 (5)O3—C7—C3118.0 (2)
N1—Ni1—N1iii180.0O2—C7—C3116.7 (2)
Ni1—O1—H1A109.7 (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···AD—HH···AD···AD—H···A
O1—H1A···O2iv0.95 (3)1.77 (3)2.696 (2)161 (2)
O1—H1B···O3v0.82 (3)1.89 (3)2.708 (2)173 (3)
Symmetry codes: (iv) x, y, z1; (v) x+1/2, y+1/2, z+2.

Experimental details

Crystal data
Chemical formula[Ni(C6H4NO2)2(H2O)4]
Mr374.98
Crystal system, space groupMonoclinic, C2/m
Temperature (K)123
a, b, c (Å)14.0549 (7), 6.8170 (2), 8.4359 (4)
β (°) 118.137 (2)
V3)712.74 (5)
Z2
Radiation typeMo Kα
µ (mm1)1.41
Crystal size (mm)0.30 × 0.05 × 0.03
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5664, 916, 843
Rint0.050
(sin θ/λ)max1)0.657
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.058, 1.12
No. of reflections916
No. of parameters76
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.37, 0.34

Computer programs: COLLECT (Hooft, 1998), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.

Selected geometric parameters (Å, º) top
Ni1—O12.0775 (12)Ni1—N12.098 (2)
O1—Ni1—N191.32 (5)O1—Ni1—O1i91.52 (8)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O2ii0.95 (3)1.77 (3)2.696 (2)161 (2)
O1—H1B···O3iii0.82 (3)1.89 (3)2.708 (2)173 (3)
Symmetry codes: (ii) x, y, z1; (iii) x+1/2, y+1/2, z+2.
 

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