supplementary materials


bq2376 scheme

Acta Cryst. (2012). E68, m1393    [ doi:10.1107/S160053681204322X ]

Tetraaquabis(6-chloropyridine-3-carboxylato-[kappa]O)nickel(II) tetrahydrate

Q.-H. Xia, Z.-F. Guo, L. Liu, J.-Q. Lv and B. Li

Abstract top

In the title compound, [Ni(C6H3ClNO2)2(H2O)4]·4H2O, the NiII ion is located on an inversion centre and is octahedrally coordinated by four O atoms from four water molecules in the equatorial plane and two O atoms of two 6-chloro-3-carboxylate ligands in axial positions. There are also four lattice water molecules present. The organic ligands are bound to the NiII ion in a monodentate manner through a carboxylate O atom. There is one strong intramolecular O-H...O hydrogen bond and six intermolecular O-H...O and O-H...N hydrogen-bonding interactions in the packing, resulting in a complex three-dimensional network structure.

Comment top

The asymmetric unit of the title complex, contains a half of NiII ion lying on a crystallographic inversion center, 6-chloropyridine-3-carboxylate anion, two coordinated water molecules and two lattice water molecules (Fig. 1). The NiII ion is six-coordinated within a octahedral, NiO6 coordination geometry. Six coordination arises from two 6-chloropyridine-3-carboxylate ligands in the apical positions [Ni—O = 2.0335 (12) Å] and four water molecules in the equatorial plane [Ni—O = 2.0742 (16) Å and 2.0814 (12) Å]. The bond angles around the Ni center lie within the range 88.8–91.2° for the formally cis pairs of ligating atoms. The 6-chloropyridine-3-carboxylate carboxylate ligands are bound to the NiII ion in a monodentate mode through a carboxylate O atom. There is one strong intramolecular hydrogen bond of type O—H···O, formed by coordinated water atom OW2 and uncoordinated carboxylate atom O2, as well as six strong intermolecular hydrogen bonds of O—H···O type and one of O—H···N type in the packing of the title compound forming a three-dimensional supramolecular structure (Fig.2).

Related literature top

For background to complexes based on 6-chloronicotinic acid, see: Long et al. (2007); Li et al. (2006).

Experimental top

All commercially obtained reagent grade chemicals were used without further purification. A mixture of nickelous sulfate hexahydrate (0.5698 g) and 6-chloronicotinic acid (0.1701 g) were added into 20 ml water and with 20 drops of 0.1 mol/L sodium hydroxide solution, and then stirred for 1 h. Finally, 10 ml 95% ethanol carefully layered above-mentioned solution in glass tube. After 1 days, green crystals of the title complex were collected.

Refinement top

H atoms bonded to C atoms were introduced in calculated positions and refined using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms. H atoms belonging to water molecules were found in difference Fourier maps.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, with 50% probability displacement ellipsoids for non-H atoms. Symmetry codes: (A) -x, -y, 1 - z.
[Figure 2] Fig. 2. Crystal packing diagram for the title compound. All atoms are shown as isotropic spheres of arbitrary size. H atoms bonded to C atoms are omitted for clarity. The H-bonding interactions are shown as yellow dashed lines.
Tetraaquabis(6-chloropyridine-3-carboxylato-κO)nickel(II) tetrahydrate top
Crystal data top
[Ni(C6H3ClNO2)2(H2O)4]·4H2OZ = 1
Mr = 515.91F(000) = 266
Triclinic, P1Dx = 1.630 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.0245 (14) ÅCell parameters from 4651 reflections
b = 7.3436 (15) Åθ = 3.1–27.5°
c = 11.547 (2) ŵ = 1.24 mm1
α = 86.35 (3)°T = 293 K
β = 77.78 (3)°Block, green
γ = 64.55 (3)°0.39 × 0.29 × 0.16 mm
V = 525.4 (2) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2371 independent reflections
Radiation source: fine-focus sealed tube2170 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 89
Tmin = 0.754, Tmax = 0.862k = 99
5167 measured reflectionsl = 1414
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.076 w = 1/[σ2(Fo2) + (0.0344P)2 + 0.1122P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2371 reflectionsΔρmax = 0.47 e Å3
134 parametersΔρmin = 0.41 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.115 (6)
Crystal data top
[Ni(C6H3ClNO2)2(H2O)4]·4H2Oγ = 64.55 (3)°
Mr = 515.91V = 525.4 (2) Å3
Triclinic, P1Z = 1
a = 7.0245 (14) ÅMo Kα radiation
b = 7.3436 (15) ŵ = 1.24 mm1
c = 11.547 (2) ÅT = 293 K
α = 86.35 (3)°0.39 × 0.29 × 0.16 mm
β = 77.78 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2371 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
2170 reflections with I > 2σ(I)
Tmin = 0.754, Tmax = 0.862Rint = 0.049
5167 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.076Δρmax = 0.47 e Å3
S = 1.06Δρmin = 0.41 e Å3
2371 reflectionsAbsolute structure: ?
134 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.49297 (8)0.29064 (8)1.14788 (4)0.04615 (15)
Ni0.00000.00000.50000.02619 (12)
O10.1088 (2)0.0624 (2)0.65419 (10)0.0345 (3)
O20.1079 (2)0.1909 (2)0.76064 (10)0.0369 (3)
OW10.1737 (2)0.2994 (2)0.44232 (11)0.0438 (3)
H1WB0.21960.39610.48380.066*
H1WA0.13100.33100.38970.066*
OW20.27477 (19)0.0432 (2)0.42777 (10)0.0354 (3)
H2WB0.28840.12610.46800.053*
H2WA0.23660.09780.36680.053*
OW30.3330 (2)0.3218 (2)0.55701 (12)0.0476 (3)
H3WB0.24300.35390.61680.071*
H3WA0.44860.25390.57470.071*
OW40.0265 (2)0.5912 (2)0.73619 (11)0.0475 (3)
H4WB0.07880.46820.74630.071*
H4WA0.02080.64570.79920.071*
N0.1923 (2)0.2769 (2)1.04439 (11)0.0334 (3)
C10.3679 (3)0.2457 (3)1.02767 (14)0.0316 (3)
C20.4551 (3)0.1812 (3)0.92311 (15)0.0362 (4)
H2A0.58000.16260.91590.043*
C30.3501 (3)0.1457 (3)0.83059 (14)0.0347 (4)
H3A0.40230.10030.75930.042*
C40.1653 (2)0.1777 (2)0.84378 (13)0.0273 (3)
C50.0943 (3)0.2442 (3)0.95247 (13)0.0312 (3)
H5A0.02820.26730.96200.037*
C60.0457 (2)0.1415 (2)0.74546 (13)0.0270 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0594 (3)0.0454 (3)0.0361 (2)0.0180 (2)0.0256 (2)0.00447 (19)
Ni0.03131 (17)0.03082 (19)0.02103 (16)0.01728 (13)0.00745 (11)0.00611 (10)
O10.0433 (6)0.0454 (8)0.0255 (5)0.0280 (6)0.0117 (5)0.0114 (5)
O20.0415 (6)0.0468 (8)0.0335 (6)0.0283 (6)0.0127 (5)0.0120 (5)
OW10.0630 (8)0.0321 (7)0.0362 (6)0.0166 (6)0.0186 (6)0.0031 (5)
OW20.0389 (6)0.0457 (8)0.0303 (5)0.0251 (6)0.0116 (5)0.0085 (5)
OW30.0432 (7)0.0526 (9)0.0462 (7)0.0186 (7)0.0140 (6)0.0092 (6)
OW40.0700 (9)0.0437 (9)0.0328 (6)0.0308 (7)0.0047 (6)0.0033 (6)
N0.0412 (8)0.0352 (9)0.0235 (6)0.0162 (6)0.0076 (6)0.0065 (5)
C10.0383 (8)0.0279 (9)0.0266 (7)0.0102 (7)0.0114 (6)0.0018 (6)
C20.0357 (8)0.0462 (11)0.0326 (8)0.0224 (8)0.0093 (7)0.0054 (7)
C30.0387 (9)0.0428 (11)0.0264 (7)0.0224 (8)0.0052 (7)0.0061 (7)
C40.0313 (7)0.0262 (8)0.0241 (7)0.0125 (6)0.0053 (6)0.0036 (6)
C50.0347 (8)0.0342 (10)0.0263 (7)0.0166 (7)0.0067 (6)0.0062 (6)
C60.0330 (8)0.0245 (8)0.0232 (7)0.0119 (6)0.0066 (6)0.0037 (6)
Geometric parameters (Å, º) top
Cl—C11.7369 (16)OW1—H1WB0.8140
Ni—O1i2.0335 (12)OW1—H1WA0.8174
Ni—O12.0335 (12)C4—C51.389 (2)
Ni—OW12.0742 (16)C4—C31.392 (2)
Ni—OW1i2.0742 (16)C2—C31.374 (2)
Ni—OW22.0814 (12)C2—H2A0.9300
Ni—OW2i2.0814 (12)N—C51.339 (2)
O1—C61.2607 (18)C5—H5A0.9300
C6—O21.2550 (19)C3—H3A0.9300
C6—C41.496 (2)OW4—H4WB0.8210
C1—N1.321 (2)OW4—H4WA0.8080
C1—C21.386 (2)OW3—H3WB0.8000
OW2—H2WB0.8378OW3—H3WA0.8121
OW2—H2WA0.8252
O1i—Ni—O1180.00 (2)Ni—OW2—H2WB112.2
O1i—Ni—OW188.84 (6)Ni—OW2—H2WA97.3
O1—Ni—OW191.16 (6)H2WB—OW2—H2WA108.5
O1i—Ni—OW1i91.16 (6)Ni—OW1—H1WB126.3
O1—Ni—OW1i88.84 (6)Ni—OW1—H1WA114.0
OW1—Ni—OW1i180.0H1WB—OW1—H1WA108.8
O1i—Ni—OW293.00 (5)C5—C4—C3117.46 (14)
O1—Ni—OW287.00 (5)C5—C4—C6120.79 (14)
OW1—Ni—OW287.71 (6)C3—C4—C6121.74 (14)
OW1i—Ni—OW292.29 (6)C3—C2—C1117.44 (15)
O1i—Ni—OW2i87.00 (5)C3—C2—H2A121.3
O1—Ni—OW2i93.00 (5)C1—C2—H2A121.3
OW1—Ni—OW2i92.29 (6)C1—N—C5116.77 (14)
OW1i—Ni—OW2i87.71 (6)N—C5—C4123.71 (15)
OW2—Ni—OW2i180.00 (3)N—C5—H5A118.1
C6—O1—Ni128.83 (10)C4—C5—H5A118.1
O2—C6—O1125.72 (14)C2—C3—C4119.83 (15)
O2—C6—C4117.79 (14)C2—C3—H3A120.1
O1—C6—C4116.49 (13)C4—C3—H3A120.1
N—C1—C2124.78 (14)H4WB—OW4—H4WA110.3
N—C1—Cl115.91 (13)H3WB—OW3—H3WA107.9
C2—C1—Cl119.31 (13)
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW2—H2WA···O2i0.831.832.6401 (18)167
OW1—H1WB···OW3ii0.812.072.869 (2)167
OW1—H1WA···OW4iii0.821.972.7915 (19)179
OW4—H4WA···Niv0.812.142.850 (2)147
OW3—H3WB···OW4v0.801.992.763 (2)163
OW3—H3WA···OW2vi0.812.212.933 (2)149
OW2—H2WB···OW30.841.982.819 (2)177
OW4—H4WB···O20.821.972.764 (2)162
Symmetry codes: (i) x, y, z+1; (ii) x, y1, z; (iii) x, y1, z+1; (iv) x, y1, z+2; (v) x, y+1, z; (vi) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW2—H2WA···O2i0.831.832.6401 (18)166.5
OW1—H1WB···OW3ii0.812.072.869 (2)166.7
OW1—H1WA···OW4iii0.821.972.7915 (19)179.4
OW4—H4WA···Niv0.812.142.850 (2)146.9
OW3—H3WB···OW4v0.801.992.763 (2)162.7
OW3—H3WA···OW2vi0.812.212.933 (2)148.8
OW2—H2WB···OW30.841.982.819 (2)177.2
OW4—H4WB···O20.821.972.764 (2)162.0
Symmetry codes: (i) x, y, z+1; (ii) x, y1, z; (iii) x, y1, z+1; (iv) x, y1, z+2; (v) x, y+1, z; (vi) x+1, y, z+1.
Acknowledgements top

This work was supported by the National Natural Science (No.21207117) and Zhejiang Provincial Municipal Science and Technology Project (2008 C12055).

references
References top

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Li, F.-H., Yin, H.-D., Sun, L., Zhao, Q. & Liu, W.-L. (2006). Acta Cryst. E62, m1117–m1118.

Long, S., Siegler, M. & Li, T. (2007). Acta Cryst. E63, o279–o281.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.