supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2470    [ doi:10.1107/S1600536807042730 ]

Diaquabis(malato-[kappa]2O,O')nickel(II)

H.-Q. Liu

Abstract top

In the title compound, [Ni(C6H5O5)2(H2O)2], the NiII atom, located on an inversion centre, is coordinated by four O atoms from two malate ligands and two water molecules in an octahedral geometry showing a very large axial distortion. The packing is governed by intermolecular O-H...O hydrogen bonds.

Comment top

Some hydroxypolycarboxylic acids are present in fruits and living cells and they also play an important role in biological processes (Kotsakis et al., 2003). Hydroxypolycarboxylic acids can act not only as hydrogen-bond acceptors but also as hydrogen-bond donors, depending on the number of deprotonated carboxyl group.

In this paper, we report the synthesis and crystal structure of the title compound, (I). The NiII atom, located on an inversion center, is coordinated by four O atoms from two malate ligands and two water molecules in an axially distorted octahedral geometry (Fig. 1, Table 1).

Intermolecular O—H···O hydrogen bonds (Table 2) help to consolidate the crystal packing.

Related literature top

For background, see: Kotsakis et al. (2003).

Experimental top

Malic acid (0.15 g, 1.01 mmol) and NiCl2·6H2O (0.028 g, 0.12 mmol), were added to a mixed solvent system of methanol and acetonitrile. The mixture was heated for six hours under reflux at 389 K with stirring. The resultant solution was filtered and placed in a closed container, into which diethyl ether was allowed to infuse. After a week, green blocks of (I) were recovered.

Refinement top

The water H atoms were located in a difference Fourier map and were refined as riding in their as-found relative positions with Uiso(H) = 1.2Ueq(O). The other H atoms were placed in calculated positions (C—H = 0.93–0.97 Å, O—H = 0.82–0.86 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(carrier). The maximum difference peak is 1.12Å from C3.

Computing details top

Data collection: APEX2 (Bruker, ????); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Non-H atoms are shown as 50% probability displacement ellipsoids. Atoms marked with a ' are generated by the symmetry operation (−x, −y, −z).
Diaquabis(malato-κ2O,O')nickel(II) top
Crystal data top
[Ni(C6H5O5)2(H2O)2]F000 = 372
Mr = 360.90Dx = 1.890 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1171 reflections
a = 8.4762 (5) Åθ = 2.5–25.5º
b = 7.4377 (4) ŵ = 1.60 mm−1
c = 10.3117 (6) ÅT = 298 (2) K
β = 102.680 (1)ºBlock, green
V = 634.23 (6) Å30.28 × 0.25 × 0.18 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer		1171 independent reflections
Radiation source: fine-focus sealed tube1018 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.016
T = 298(2) Kθmax = 25.5º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→5
Tmin = 0.664, Tmax = 0.762k = −8→9
3133 measured reflectionsl = −11→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difmap and geom
R[F2 > 2σ(F2)] = 0.021H-atom parameters constrained
wR(F2) = 0.061  w = 1/[σ2(Fo2) + (0.0426P)2 + 0.0527P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
1171 reflectionsΔρmax = 0.24 e Å−3
97 parametersΔρmin = −0.20 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni(C6H5O5)2(H2O)2]V = 634.23 (6) Å3
Mr = 360.90Z = 2
Monoclinic, P21/cMo Kα
a = 8.4762 (5) ŵ = 1.60 mm−1
b = 7.4377 (4) ÅT = 298 (2) K
c = 10.3117 (6) Å0.28 × 0.25 × 0.18 mm
β = 102.680 (1)º
Data collection top
Bruker APEXII CCD
diffractometer		1171 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1018 reflections with I > 2σ(I)
Tmin = 0.664, Tmax = 0.762Rint = 0.016
3133 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0213 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 1.02Δρmax = 0.24 e Å−3
1171 reflectionsΔρmin = −0.20 e Å−3
97 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.00000.00000.00000.02590 (14)
O10.16156 (16)0.12408 (17)0.13402 (12)0.0315 (3)
H10.15910.10890.21620.047*
O1W−0.22841 (16)0.18371 (18)0.05033 (13)0.0382 (3)
H1W−0.21380.28260.08430.057*
H2W−0.27350.12420.09740.057*
O20.1701 (2)0.44803 (18)−0.11539 (13)0.0406 (4)
O30.03754 (16)0.19406 (17)−0.11125 (12)0.0329 (3)
O40.39452 (18)0.4001 (2)0.35137 (14)0.0438 (4)
O50.61196 (18)0.2846 (2)0.29611 (14)0.0490 (4)
H50.65150.29980.37530.074*
C10.1317 (2)0.3162 (2)−0.05532 (17)0.0281 (4)
C20.2029 (2)0.3002 (2)0.09437 (17)0.0292 (4)
H20.15500.39190.14220.035*
C30.3842 (2)0.3234 (3)0.12309 (19)0.0351 (5)
H3A0.43140.22110.08720.042*
H3B0.40960.43010.07760.042*
C40.4609 (2)0.3402 (2)0.26915 (18)0.0311 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0297 (2)0.0300 (2)0.01576 (19)−0.00928 (13)0.00016 (13)0.00256 (12)
O10.0419 (7)0.0330 (7)0.0178 (6)−0.0093 (6)0.0025 (5)0.0026 (5)
O1W0.0401 (8)0.0379 (8)0.0383 (8)−0.0043 (6)0.0123 (7)−0.0047 (6)
O20.0631 (10)0.0318 (7)0.0247 (7)−0.0091 (7)0.0052 (7)0.0041 (6)
O30.0375 (7)0.0379 (7)0.0206 (7)−0.0083 (6)0.0001 (6)0.0029 (5)
O40.0424 (8)0.0591 (10)0.0299 (8)0.0064 (7)0.0083 (6)−0.0017 (7)
O50.0381 (8)0.0670 (11)0.0379 (9)0.0049 (8)−0.0003 (7)−0.0145 (7)
C10.0321 (10)0.0296 (10)0.0229 (9)0.0010 (8)0.0064 (8)0.0012 (7)
C20.0352 (10)0.0286 (10)0.0233 (9)−0.0024 (8)0.0055 (8)−0.0001 (7)
C30.0363 (11)0.0426 (11)0.0263 (10)−0.0050 (9)0.0066 (8)−0.0012 (8)
C40.0353 (10)0.0294 (10)0.0283 (10)−0.0061 (8)0.0066 (8)−0.0004 (7)
Geometric parameters (Å, °) top
Ni1—O31.9134 (12)O3—C11.262 (2)
Ni1—O3i1.9134 (12)O4—C41.202 (2)
Ni1—O1i1.9509 (12)O5—C41.316 (2)
Ni1—O11.9509 (12)O5—H50.8200
Ni1—O1W2.5151 (13)C1—C21.534 (2)
Ni1—O1Wi2.5151 (13)C2—C31.510 (3)
O1—C21.438 (2)C2—H20.9800
O1—H10.8600C3—C41.509 (3)
O1W—H1W0.8126C3—H3A0.9700
O1W—H2W0.8117C3—H3B0.9700
O2—C11.241 (2)
O3—Ni1—O3i180.0C1—O3—Ni1116.15 (11)
O3—Ni1—O1i96.63 (5)C4—O5—H5109.4
O3i—Ni1—O1i83.37 (5)O2—C1—O3123.34 (17)
O3—Ni1—O183.37 (5)O2—C1—C2118.40 (16)
O3i—Ni1—O196.63 (5)O3—C1—C2118.26 (15)
O1i—Ni1—O1180.0O1—C2—C3110.43 (16)
O3—Ni1—O1W87.18 (5)O1—C2—C1106.89 (14)
O3i—Ni1—O1W92.82 (5)C3—C2—C1110.30 (15)
O1i—Ni1—O1W87.17 (5)O1—C2—H2109.7
O1—Ni1—O1W92.83 (5)C3—C2—H2109.7
O1—Ni1—O1Wi87.18 (5)C1—C2—H2109.7
O1i—Ni1—O1Wi92.82 (5)C4—C3—C2113.71 (16)
O3i—Ni1—O1Wi87.17 (5)C4—C3—H3A108.8
O3—Ni1—O1Wi92.83 (5)C2—C3—H3A108.8
O1W—Ni1—O1Wi180.0C4—C3—H3B108.8
C2—O1—Ni1113.97 (10)C2—C3—H3B108.8
C2—O1—H1117.4H3A—C3—H3B107.7
Ni1—O1—H1118.1O4—C4—O5123.53 (19)
Ni1—O1W—H1W122.0O4—C4—C3124.69 (18)
Ni1—O1W—H2W108.1O5—C4—C3111.76 (16)
H1W—O1W—H2W106.4
Symmetry codes: (i) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2ii0.861.772.6245 (17)172
O1W—H1W···O2iii0.812.052.8374 (19)163
O1W—H2W···O4iv0.812.082.843 (2)156
O5—H5···O1Wv0.821.872.6835 (19)171
Symmetry codes: (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z; (iv) −x, y−1/2, −z+1/2; (v) x+1, −y+1/2, z+1/2.
Table 1
Selected geometric parameters (Å) top
Ni1—O31.9134 (12)Ni1—O1W2.5151 (13)
Ni1—O11.9509 (12)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.861.772.6245 (17)172
O1W—H1W···O2ii0.812.052.8374 (19)163
O1W—H2W···O4iii0.812.082.843 (2)156
O5—H5···O1Wiv0.821.872.6835 (19)171
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, −y+1, −z; (iii) −x, y−1/2, −z+1/2; (iv) x+1, −y+1/2, z+1/2.
Acknowledgements top

The author is grateful to the Natural Science Foundation of Guangdong Province (grant No. M203066) for financial support.

references
References top

Bruker (1998). SAINT and SHELXTL. Bruker AXS Inc, Madison, Wisconsin, USA. Please check year 1998 or 1999? APEXII instrument requires APEX2 software rather than SMART - please complete APEX2 reference below.

Bruker (????). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Kotsakis, N., Raptopoulou, C. P., Tangoulis, V., Terzis, A., Giapintzakis, J. & Salifoglou, A. (2003). Inorg. Chem. 42, 22–31.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.