Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042730/hb2529sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042730/hb2529Isup2.hkl |
CCDC reference: 664185
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.
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.
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.
For background, see: Kotsakis et al. (2003).
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).
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). |
[Ni(C6H5O5)2(H2O)2] | F(000) = 372 |
Mr = 360.90 | Dx = 1.890 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1171 reflections |
a = 8.4762 (5) Å | θ = 2.5–25.5° |
b = 7.4377 (4) Å | µ = 1.60 mm−1 |
c = 10.3117 (6) Å | T = 298 K |
β = 102.680 (1)° | Block, green |
V = 634.23 (6) Å3 | 0.28 × 0.25 × 0.18 mm |
Z = 2 |
Bruker APEXII CCD diffractometer | 1171 independent reflections |
Radiation source: fine-focus sealed tube | 1018 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
φ and ω scans | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→5 |
Tmin = 0.664, Tmax = 0.762 | k = −8→9 |
3133 measured reflections | l = −11→12 |
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)] = 0.021 | Hydrogen site location: difmap and geom |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0426P)2 + 0.0527P] where P = (Fo2 + 2Fc2)/3 |
1171 reflections | (Δ/σ)max < 0.001 |
97 parameters | Δρmax = 0.24 e Å−3 |
3 restraints | Δρmin = −0.20 e Å−3 |
[Ni(C6H5O5)2(H2O)2] | V = 634.23 (6) Å3 |
Mr = 360.90 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.4762 (5) Å | µ = 1.60 mm−1 |
b = 7.4377 (4) Å | T = 298 K |
c = 10.3117 (6) Å | 0.28 × 0.25 × 0.18 mm |
β = 102.680 (1)° |
Bruker APEXII CCD diffractometer | 1171 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1018 reflections with I > 2σ(I) |
Tmin = 0.664, Tmax = 0.762 | Rint = 0.016 |
3133 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 3 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.24 e Å−3 |
1171 reflections | Δρmin = −0.20 e Å−3 |
97 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.0000 | 0.0000 | 0.0000 | 0.02590 (14) | |
O1 | 0.16156 (16) | 0.12408 (17) | 0.13402 (12) | 0.0315 (3) | |
H1 | 0.1591 | 0.1089 | 0.2162 | 0.047* | |
O1W | −0.22841 (16) | 0.18371 (18) | 0.05033 (13) | 0.0382 (3) | |
H1W | −0.2138 | 0.2826 | 0.0843 | 0.057* | |
H2W | −0.2735 | 0.1242 | 0.0974 | 0.057* | |
O2 | 0.1701 (2) | 0.44803 (18) | −0.11539 (13) | 0.0406 (4) | |
O3 | 0.03754 (16) | 0.19406 (17) | −0.11125 (12) | 0.0329 (3) | |
O4 | 0.39452 (18) | 0.4001 (2) | 0.35137 (14) | 0.0438 (4) | |
O5 | 0.61196 (18) | 0.2846 (2) | 0.29611 (14) | 0.0490 (4) | |
H5 | 0.6515 | 0.2998 | 0.3753 | 0.074* | |
C1 | 0.1317 (2) | 0.3162 (2) | −0.05532 (17) | 0.0281 (4) | |
C2 | 0.2029 (2) | 0.3002 (2) | 0.09437 (17) | 0.0292 (4) | |
H2 | 0.1550 | 0.3919 | 0.1422 | 0.035* | |
C3 | 0.3842 (2) | 0.3234 (3) | 0.12309 (19) | 0.0351 (5) | |
H3A | 0.4314 | 0.2211 | 0.0872 | 0.042* | |
H3B | 0.4096 | 0.4301 | 0.0776 | 0.042* | |
C4 | 0.4609 (2) | 0.3402 (2) | 0.26915 (18) | 0.0311 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0297 (2) | 0.0300 (2) | 0.01576 (19) | −0.00928 (13) | 0.00016 (13) | 0.00256 (12) |
O1 | 0.0419 (7) | 0.0330 (7) | 0.0178 (6) | −0.0093 (6) | 0.0025 (5) | 0.0026 (5) |
O1W | 0.0401 (8) | 0.0379 (8) | 0.0383 (8) | −0.0043 (6) | 0.0123 (7) | −0.0047 (6) |
O2 | 0.0631 (10) | 0.0318 (7) | 0.0247 (7) | −0.0091 (7) | 0.0052 (7) | 0.0041 (6) |
O3 | 0.0375 (7) | 0.0379 (7) | 0.0206 (7) | −0.0083 (6) | 0.0001 (6) | 0.0029 (5) |
O4 | 0.0424 (8) | 0.0591 (10) | 0.0299 (8) | 0.0064 (7) | 0.0083 (6) | −0.0017 (7) |
O5 | 0.0381 (8) | 0.0670 (11) | 0.0379 (9) | 0.0049 (8) | −0.0003 (7) | −0.0145 (7) |
C1 | 0.0321 (10) | 0.0296 (10) | 0.0229 (9) | 0.0010 (8) | 0.0064 (8) | 0.0012 (7) |
C2 | 0.0352 (10) | 0.0286 (10) | 0.0233 (9) | −0.0024 (8) | 0.0055 (8) | −0.0001 (7) |
C3 | 0.0363 (11) | 0.0426 (11) | 0.0263 (10) | −0.0050 (9) | 0.0066 (8) | −0.0012 (8) |
C4 | 0.0353 (10) | 0.0294 (10) | 0.0283 (10) | −0.0061 (8) | 0.0066 (8) | −0.0004 (7) |
Ni1—O3 | 1.9134 (12) | O3—C1 | 1.262 (2) |
Ni1—O3i | 1.9134 (12) | O4—C4 | 1.202 (2) |
Ni1—O1i | 1.9509 (12) | O5—C4 | 1.316 (2) |
Ni1—O1 | 1.9509 (12) | O5—H5 | 0.8200 |
Ni1—O1W | 2.5151 (13) | C1—C2 | 1.534 (2) |
Ni1—O1Wi | 2.5151 (13) | C2—C3 | 1.510 (3) |
O1—C2 | 1.438 (2) | C2—H2 | 0.9800 |
O1—H1 | 0.8600 | C3—C4 | 1.509 (3) |
O1W—H1W | 0.8126 | C3—H3A | 0.9700 |
O1W—H2W | 0.8117 | C3—H3B | 0.9700 |
O2—C1 | 1.241 (2) | ||
O3—Ni1—O3i | 180.0 | C1—O3—Ni1 | 116.15 (11) |
O3—Ni1—O1i | 96.63 (5) | C4—O5—H5 | 109.4 |
O3i—Ni1—O1i | 83.37 (5) | O2—C1—O3 | 123.34 (17) |
O3—Ni1—O1 | 83.37 (5) | O2—C1—C2 | 118.40 (16) |
O3i—Ni1—O1 | 96.63 (5) | O3—C1—C2 | 118.26 (15) |
O1i—Ni1—O1 | 180.0 | O1—C2—C3 | 110.43 (16) |
O3—Ni1—O1W | 87.18 (5) | O1—C2—C1 | 106.89 (14) |
O3i—Ni1—O1W | 92.82 (5) | C3—C2—C1 | 110.30 (15) |
O1i—Ni1—O1W | 87.17 (5) | O1—C2—H2 | 109.7 |
O1—Ni1—O1W | 92.83 (5) | C3—C2—H2 | 109.7 |
O1—Ni1—O1Wi | 87.18 (5) | C1—C2—H2 | 109.7 |
O1i—Ni1—O1Wi | 92.82 (5) | C4—C3—C2 | 113.71 (16) |
O3i—Ni1—O1Wi | 87.17 (5) | C4—C3—H3A | 108.8 |
O3—Ni1—O1Wi | 92.83 (5) | C2—C3—H3A | 108.8 |
O1W—Ni1—O1Wi | 180.0 | C4—C3—H3B | 108.8 |
C2—O1—Ni1 | 113.97 (10) | C2—C3—H3B | 108.8 |
C2—O1—H1 | 117.4 | H3A—C3—H3B | 107.7 |
Ni1—O1—H1 | 118.1 | O4—C4—O5 | 123.53 (19) |
Ni1—O1W—H1W | 122.0 | O4—C4—C3 | 124.69 (18) |
Ni1—O1W—H2W | 108.1 | O5—C4—C3 | 111.76 (16) |
H1W—O1W—H2W | 106.4 |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2ii | 0.86 | 1.77 | 2.6245 (17) | 172 |
O1W—H1W···O2iii | 0.81 | 2.05 | 2.8374 (19) | 163 |
O1W—H2W···O4iv | 0.81 | 2.08 | 2.843 (2) | 156 |
O5—H5···O1Wv | 0.82 | 1.87 | 2.6835 (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. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C6H5O5)2(H2O)2] |
Mr | 360.90 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 8.4762 (5), 7.4377 (4), 10.3117 (6) |
β (°) | 102.680 (1) |
V (Å3) | 634.23 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.60 |
Crystal size (mm) | 0.28 × 0.25 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.664, 0.762 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3133, 1171, 1018 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.061, 1.02 |
No. of reflections | 1171 |
No. of parameters | 97 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.20 |
Computer programs: APEX2 (Bruker, ????), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.86 | 1.77 | 2.6245 (17) | 172 |
O1W—H1W···O2ii | 0.81 | 2.05 | 2.8374 (19) | 163 |
O1W—H2W···O4iii | 0.81 | 2.08 | 2.843 (2) | 156 |
O5—H5···O1Wiv | 0.82 | 1.87 | 2.6835 (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. |
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.