Acta Cryst. (2012). E68, m919 [ doi:10.1107/S1600536812024749 ]
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2N,O)nickel(II)In the title complex, [Ni(C6H5O2N2)2], the NiII atom is situated on an inversion centre and is coordinated in a square-planar geometry by four O atoms and two N atoms of the chelating ligands.
A mixture of NiCl2.6H2O (0.238 g, 1 mmol), Hmpca (0.304 g, 1 mmol) and distilled H2O (6 ml) was sealed in a 15 ml Teflon-lined stainless steel vessel, which was heated at 120°C for 3 days and then cooled to room temperature at a rate of 5°C/h. Red crystals were obtained, washed with ethanol (yield 43% based on Ni).
The H atoms of C atoms were positioned geometrically and refined with a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The water H atoms were located in difference Fourier maps, and were refined with distance restraints of O—H = 0.85±0.02 Å and H···H = 1.39±0.02 Å.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./ru2036fig1thm.gif)
| Fig. 1. A view of the molecular structure of (I) with the atom-labling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. |
![[Figure 2]](./ru2036fig2thm.gif)
| Fig. 2. Two dimensional layer sructure of (I) |
| [Ni(C6H5N2O2)2] | F(000) = 340 |
| Mr = 332.95 | Dx = 1.754 Mg m−3 Dm = 1.754 Mg m−3 Dm measured by not measured |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2220 reflections |
| a = 11.3098 (19) Å | θ = 1.3–24.1° |
| b = 7.6721 (11) Å | µ = 1.56 mm−1 |
| c = 7.5467 (10) Å | T = 298 K |
| β = 105.647 (2)° | Block, green |
| V = 630.56 (16) Å3 | 0.42 × 0.31 × 0.19 mm |
| Z = 2 |
| Bruker APEXII CCD diffractometer | 1105 independent reflections |
| Radiation source: fine-focus sealed tube | 827 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.057 |
| φ and ω scans | θmax = 25.0°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→10 |
| Tmin = 0.560, Tmax = 0.756 | k = −9→6 |
| 2875 measured reflections | l = −8→8 |
| 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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.176 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.121P)2 + 0.167P] where P = (Fo2 + 2Fc2)/3 |
| 1105 reflections | (Δ/σ)max < 0.001 |
| 97 parameters | Δρmax = 1.34 e Å−3 |
| 0 restraints | Δρmin = −1.37 e Å−3 |
| [Ni(C6H5N2O2)2] | V = 630.56 (16) Å3 |
| Mr = 332.95 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.3098 (19) Å | µ = 1.56 mm−1 |
| b = 7.6721 (11) Å | T = 298 K |
| c = 7.5467 (10) Å | 0.42 × 0.31 × 0.19 mm |
| β = 105.647 (2)° |
| Bruker APEXII CCD diffractometer | 1105 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 827 reflections with I > 2σ(I) |
| Tmin = 0.560, Tmax = 0.756 | Rint = 0.057 |
| 2875 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.062 | H-atom parameters constrained |
| wR(F2) = 0.176 | Δρmax = 1.34 e Å−3 |
| S = 1.03 | Δρmin = −1.37 e Å−3 |
| 1105 reflections | Absolute structure: ? |
| 97 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.5000 | 0.5000 | 0.5000 | 0.0317 (4) | |
| N1 | 0.3510 (4) | 0.4618 (5) | 0.5844 (6) | 0.0312 (10) | |
| N2 | 0.1370 (5) | 0.4682 (6) | 0.6946 (7) | 0.0475 (13) | |
| O1 | 0.4846 (3) | 0.7385 (4) | 0.5791 (5) | 0.0412 (9) | |
| O2 | 0.3624 (4) | 0.9088 (5) | 0.6943 (5) | 0.0485 (10) | |
| C1 | 0.3918 (5) | 0.7680 (7) | 0.6395 (7) | 0.0355 (12) | |
| C2 | 0.3114 (5) | 0.6106 (6) | 0.6398 (6) | 0.0342 (12) | |
| C3 | 0.2062 (5) | 0.6111 (7) | 0.6967 (8) | 0.0463 (14) | |
| H3 | 0.1814 | 0.7151 | 0.7389 | 0.056* | |
| C4 | 0.2869 (4) | 0.3151 (7) | 0.5865 (7) | 0.0360 (12) | |
| H4 | 0.3148 | 0.2096 | 0.5523 | 0.043* | |
| C5 | 0.1780 (5) | 0.3214 (7) | 0.6401 (7) | 0.0404 (13) | |
| C6 | 0.1017 (5) | 0.1600 (8) | 0.6309 (8) | 0.0529 (15) | |
| H6A | 0.0434 | 0.1771 | 0.7011 | 0.079* | |
| H6B | 0.1541 | 0.0633 | 0.6806 | 0.079* | |
| H6C | 0.0588 | 0.1362 | 0.5051 | 0.079* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ni1 | 0.0421 (6) | 0.0079 (5) | 0.0502 (7) | −0.0023 (3) | 0.0210 (4) | −0.0035 (3) |
| N1 | 0.039 (2) | 0.016 (2) | 0.040 (2) | −0.0016 (17) | 0.0133 (18) | 0.0004 (16) |
| N2 | 0.052 (3) | 0.033 (3) | 0.062 (3) | −0.003 (2) | 0.023 (2) | −0.005 (2) |
| O1 | 0.053 (2) | 0.0154 (18) | 0.059 (2) | −0.0040 (16) | 0.0209 (18) | −0.0051 (17) |
| O2 | 0.067 (2) | 0.014 (2) | 0.068 (3) | 0.0046 (18) | 0.0242 (19) | −0.0060 (17) |
| C1 | 0.048 (3) | 0.016 (3) | 0.041 (3) | 0.000 (2) | 0.010 (2) | −0.001 (2) |
| C2 | 0.046 (3) | 0.019 (3) | 0.039 (3) | 0.001 (2) | 0.013 (2) | −0.004 (2) |
| C3 | 0.059 (4) | 0.026 (3) | 0.061 (3) | 0.004 (2) | 0.027 (3) | −0.007 (2) |
| C4 | 0.044 (3) | 0.016 (3) | 0.048 (3) | −0.001 (2) | 0.012 (2) | −0.002 (2) |
| C5 | 0.050 (3) | 0.030 (3) | 0.044 (3) | −0.007 (2) | 0.018 (2) | 0.001 (2) |
| C6 | 0.058 (3) | 0.037 (3) | 0.067 (4) | −0.015 (3) | 0.022 (3) | −0.003 (3) |
| Ni1—O1 | 1.947 (3) | C1—C2 | 1.512 (7) |
| Ni1—O1i | 1.947 (3) | C2—C3 | 1.370 (7) |
| Ni1—N1 | 1.977 (4) | C3—H3 | 0.9300 |
| Ni1—N1i | 1.977 (4) | C4—C5 | 1.397 (7) |
| N1—C2 | 1.335 (6) | C4—H4 | 0.9300 |
| N1—C4 | 1.341 (6) | C5—C6 | 1.501 (7) |
| N2—C5 | 1.325 (7) | C6—H6A | 0.9600 |
| N2—C3 | 1.345 (7) | C6—H6B | 0.9600 |
| O1—C1 | 1.272 (6) | C6—H6C | 0.9600 |
| O2—C1 | 1.233 (6) | ||
| O1—Ni1—O1i | 180.000 (1) | C3—C2—C1 | 124.9 (5) |
| O1—Ni1—N1 | 83.45 (16) | N2—C3—C2 | 123.1 (5) |
| O1i—Ni1—N1 | 96.55 (16) | N2—C3—H3 | 118.5 |
| O1—Ni1—N1i | 96.55 (16) | C2—C3—H3 | 118.5 |
| O1i—Ni1—N1i | 83.45 (16) | N1—C4—C5 | 119.7 (5) |
| N1—Ni1—N1i | 180.0 | N1—C4—H4 | 120.1 |
| C2—N1—C4 | 119.1 (4) | C5—C4—H4 | 120.1 |
| C2—N1—Ni1 | 111.2 (3) | N2—C5—C4 | 122.0 (5) |
| C4—N1—Ni1 | 129.7 (4) | N2—C5—C6 | 118.1 (5) |
| C5—N2—C3 | 116.4 (5) | C4—C5—C6 | 119.9 (5) |
| C1—O1—Ni1 | 115.3 (3) | C5—C6—H6A | 109.5 |
| O2—C1—O1 | 126.8 (5) | C5—C6—H6B | 109.5 |
| O2—C1—C2 | 118.9 (4) | H6A—C6—H6B | 109.5 |
| O1—C1—C2 | 114.4 (4) | C5—C6—H6C | 109.5 |
| N1—C2—C3 | 119.6 (5) | H6A—C6—H6C | 109.5 |
| N1—C2—C1 | 115.5 (4) | H6B—C6—H6C | 109.5 |
| O1—Ni1—N1—C2 | 3.6 (3) | Ni1—N1—C2—C1 | −4.3 (5) |
| O1i—Ni1—N1—C2 | −176.4 (3) | O2—C1—C2—N1 | −177.9 (4) |
| N1i—Ni1—N1—C2 | −75 (100) | O1—C1—C2—N1 | 2.7 (6) |
| O1—Ni1—N1—C4 | −178.8 (5) | O2—C1—C2—C3 | 0.1 (8) |
| O1i—Ni1—N1—C4 | 1.2 (5) | O1—C1—C2—C3 | −179.3 (5) |
| N1i—Ni1—N1—C4 | 102 (100) | C5—N2—C3—C2 | 2.5 (9) |
| O1i—Ni1—O1—C1 | −153 (100) | N1—C2—C3—N2 | −2.2 (9) |
| N1—Ni1—O1—C1 | −2.3 (3) | C1—C2—C3—N2 | 179.9 (5) |
| N1i—Ni1—O1—C1 | 177.7 (3) | C2—N1—C4—C5 | 2.2 (7) |
| Ni1—O1—C1—O2 | −178.9 (4) | Ni1—N1—C4—C5 | −175.2 (3) |
| Ni1—O1—C1—C2 | 0.5 (5) | C3—N2—C5—C4 | −0.4 (8) |
| C4—N1—C2—C3 | −0.3 (7) | C3—N2—C5—C6 | −178.4 (5) |
| Ni1—N1—C2—C3 | 177.6 (4) | N1—C4—C5—N2 | −1.9 (8) |
| C4—N1—C2—C1 | 177.8 (4) | N1—C4—C5—C6 | 176.0 (5) |
| Symmetry code: (i) −x+1, −y+1, −z+1. |
We gratefully acknowledge the Scientific Research Program Funded by Shaanxi Provincial Education Department (Nos. 11 J K0578 and 2010 J K882), the Natural Science Foundation of Shaanxi Province (No. 2010JQ2007) and the Open Foundation of the Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education.
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Since the mononuclear complex [Cu(mpca)2(H2O)3H2O](Hmpca = 2-methylpyrazine-5-carboxylic acid) was reported by Leciejewicz, many complexes based on the Hmpca have been prepared. The complex of Hmpca have been extensively investigated and have often been considered for practical use as a class of functional materials. In this paper, we report on the synthesis and characterization of [Ni(mpca)2]n.
Single-crystal analysis shows the complex crystallizes in monoclinic space group P21/c and exists as a two-dimensional geometry. As shown in Figure 1, Ni1 is four-coordinated by two oxygen atoms and two nitrogen atoms from two mpca- ligands, displaying a square planar coordination geometry with Ni1—O1 = 1.947 (3) Å and Ni1—N1 = 1.977 (4) Å. The weak coordiantion between Ni1 and O2, which from the adjacent mpca- igand, result in the formation of a distorted octahedral geometry for nickle atom (Ni1—O2=2.509 (2) Å). Then the complex is further extend into a two-dimensional layer structure, see Figure 2.