Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027961/bi2194sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027961/bi2194Isup2.hkl |
CCDC reference: 1225689
All chemicals were used as purchased from Jinan Henghua Sci & Tec Co. Ltd. A mixture of NiCl2.6H2O (0.5 mmol), KOH (0.5 mmol), 2-pyrazine carboxylic acid (0.5 mmol), EtOH (8 ml) and H2O (8 ml) in a 25 ml Teflon-lined stainless steel autoclave was heated to 413 K for 2 d. On cooling to room temperature, red crystals were obtained in a yield of 36%. Elemental analysis calculated: C 37.15, H 3.10, N 17.34, Co 18.27%; found: C 37.12, H 3.12, N 17.38, Co 18.19%.
H atoms on C atoms were placed geometrically and refined as riding with C—H = 0.93 Å and Uiso(H)= 1.2Ueq(C). The H atoms of the water molecule were located from difference Fourier maps and were refined with distance restraints of O—H = 0.82 (1) Å and H···H = 1.35 (1) Å. The refined Flack parameter (Flack, 1983) from 907 Friedel pairs is 0.452 (15), indicating inversion twinning.
The title compound, [Co(C5H3N2O2)2(H2O)]n, is isostructural with its FeII and NiII analogues (Hao & Liu, 2007; Hao, Mu & Liu, 2007).
The CoII atom is coordinated in a bidentate fashion by two O and two N atoms from two independent pyrazine-2-carboxylate anions. The distorted octahedral coordination is completed by another N atom from a third pyrazine-2-carboxylate ligand, and by the O atom of a water molecule (Fig. 1). The Co—N and Co—O bond lengths are in the range 2.057 (2)–2.104 (2) and 2.0384 (17)–2.0723 (18) Å, respectively.
One pyrazine-2-carboxylate ligand coordinates to a neighboring CoII atom via its second N atom, leading to a polymeric structure with zigzag chains extending parallel to the b axis (Fig. 2). Hydrogen bonding between the water molecules stabilizes the structure.
For the isostructural FeII and NiII analogues, see: Hao & Liu (2007); Hao et al. (2007).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
[Co(C5H3N2O2)2(H2O)] | F(000) = 652 |
Mr = 323.13 | Dx = 1.871 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2198 reflections |
a = 8.0121 (10) Å | θ = 2.5–26.0° |
b = 9.5327 (10) Å | µ = 1.52 mm−1 |
c = 15.023 (2) Å | T = 298 K |
V = 1147.4 (2) Å3 | Block, red |
Z = 4 | 0.10 × 0.10 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 2064 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 26.0°, θmin = 2.5° |
ω scans | h = −8→9 |
5916 measured reflections | k = −11→10 |
2198 independent reflections | l = −18→9 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.055 | w = 1/[σ2(Fo2) + (0.0323P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2198 reflections | Δρmax = 0.80 e Å−3 |
190 parameters | Δρmin = −0.22 e Å−3 |
3 restraints | Absolute structure: Flack (1983), with 907 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.452 (15) |
[Co(C5H3N2O2)2(H2O)] | V = 1147.4 (2) Å3 |
Mr = 323.13 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.0121 (10) Å | µ = 1.52 mm−1 |
b = 9.5327 (10) Å | T = 298 K |
c = 15.023 (2) Å | 0.10 × 0.10 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 2064 reflections with I > 2σ(I) |
5916 measured reflections | Rint = 0.026 |
2198 independent reflections |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.055 | Δρmax = 0.80 e Å−3 |
S = 1.04 | Δρmin = −0.22 e Å−3 |
2198 reflections | Absolute structure: Flack (1983), with 907 Friedel pairs |
190 parameters | Absolute structure parameter: 0.452 (15) |
3 restraints |
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 | ||
Co1 | 0.42683 (4) | 0.36583 (3) | 0.409285 (19) | 0.01727 (9) | |
C1 | 0.6433 (3) | 0.5285 (3) | 0.51916 (18) | 0.0279 (6) | |
C2 | 0.4620 (3) | 0.5736 (3) | 0.54104 (17) | 0.0279 (6) | |
C3 | 0.4253 (4) | 0.6652 (3) | 0.60858 (18) | 0.0388 (7) | |
H3A | 0.5122 | 0.7030 | 0.6419 | 0.047* | |
C4 | 0.1419 (3) | 0.6488 (3) | 0.57852 (19) | 0.0363 (6) | |
H4A | 0.0320 | 0.6742 | 0.5902 | 0.044* | |
C5 | 0.1760 (3) | 0.5570 (3) | 0.51064 (18) | 0.0311 (6) | |
H5A | 0.0890 | 0.5208 | 0.4767 | 0.037* | |
C6 | 0.6842 (3) | 0.0674 (3) | 0.23679 (18) | 0.0291 (6) | |
H6A | 0.7913 | 0.0407 | 0.2200 | 0.035* | |
C7 | 0.3951 (3) | 0.0422 (3) | 0.22755 (17) | 0.0251 (6) | |
H7A | 0.3024 | −0.0040 | 0.2046 | 0.030* | |
C8 | 0.1943 (3) | 0.1916 (3) | 0.31693 (16) | 0.0229 (5) | |
C9 | 0.3723 (3) | 0.1454 (3) | 0.28905 (15) | 0.0226 (5) | |
C10 | 0.6630 (3) | 0.1690 (3) | 0.29927 (18) | 0.0274 (6) | |
H10A | 0.7555 | 0.2117 | 0.3249 | 0.033* | |
N1 | 0.3349 (3) | 0.5187 (2) | 0.49264 (13) | 0.0254 (5) | |
N2 | 0.2661 (3) | 0.7025 (3) | 0.62837 (17) | 0.0447 (7) | |
N3 | 0.5503 (3) | 0.0048 (2) | 0.19881 (13) | 0.0253 (5) | |
N4 | 0.5061 (3) | 0.2085 (2) | 0.32447 (14) | 0.0239 (5) | |
O1 | 0.7625 (2) | 0.5798 (3) | 0.55879 (15) | 0.0487 (6) | |
O2 | 0.6535 (2) | 0.43497 (18) | 0.45923 (11) | 0.0270 (4) | |
O3 | 0.1939 (2) | 0.29727 (18) | 0.36884 (11) | 0.0268 (4) | |
O4 | 0.0688 (2) | 0.13059 (19) | 0.29097 (11) | 0.0356 (4) | |
O5 | 0.4188 (3) | 0.23496 (19) | 0.51651 (12) | 0.0333 (4) | |
H51 | 0.501 (2) | 0.219 (3) | 0.5471 (17) | 0.041 (10)* | |
H52 | 0.344 (3) | 0.179 (3) | 0.527 (2) | 0.067 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01816 (14) | 0.01545 (14) | 0.01821 (14) | 0.00010 (13) | 0.00071 (13) | −0.00059 (13) |
C1 | 0.0271 (13) | 0.0267 (14) | 0.0297 (14) | 0.0013 (11) | −0.0016 (11) | 0.0032 (11) |
C2 | 0.0294 (16) | 0.0273 (13) | 0.0271 (13) | −0.0015 (11) | −0.0007 (11) | 0.0022 (11) |
C3 | 0.0341 (15) | 0.0380 (16) | 0.0443 (18) | −0.0030 (14) | −0.0049 (14) | −0.0150 (12) |
C4 | 0.0303 (13) | 0.0336 (15) | 0.0449 (16) | 0.0038 (12) | 0.0041 (12) | −0.0077 (14) |
C5 | 0.0264 (14) | 0.0285 (14) | 0.0384 (16) | −0.0029 (11) | −0.0033 (12) | 0.0001 (11) |
C6 | 0.0240 (14) | 0.0298 (14) | 0.0333 (15) | 0.0011 (11) | −0.0001 (11) | −0.0042 (12) |
C7 | 0.0265 (15) | 0.0234 (12) | 0.0253 (12) | 0.0009 (10) | −0.0018 (11) | −0.0023 (10) |
C8 | 0.0221 (13) | 0.0243 (12) | 0.0222 (13) | 0.0001 (10) | 0.0014 (10) | 0.0025 (10) |
C9 | 0.0263 (12) | 0.0220 (12) | 0.0196 (11) | −0.0010 (11) | −0.0008 (9) | 0.0026 (10) |
C10 | 0.0229 (13) | 0.0283 (15) | 0.0309 (14) | 0.0003 (11) | −0.0014 (11) | −0.0033 (11) |
N1 | 0.0261 (11) | 0.0218 (11) | 0.0281 (11) | −0.0007 (9) | −0.0004 (9) | −0.0001 (9) |
N2 | 0.0410 (15) | 0.0440 (15) | 0.0492 (15) | 0.0038 (12) | 0.0048 (12) | −0.0184 (12) |
N3 | 0.0282 (12) | 0.0228 (10) | 0.0248 (10) | −0.0014 (10) | −0.0011 (9) | −0.0007 (8) |
N4 | 0.0246 (11) | 0.0221 (11) | 0.0251 (12) | 0.0006 (9) | 0.0011 (9) | 0.0032 (9) |
O1 | 0.0305 (11) | 0.0535 (13) | 0.0620 (14) | −0.0047 (10) | −0.0088 (10) | −0.0188 (11) |
O2 | 0.0270 (9) | 0.0237 (9) | 0.0303 (10) | 0.0020 (8) | −0.0022 (8) | −0.0017 (8) |
O3 | 0.0246 (9) | 0.0272 (10) | 0.0285 (9) | 0.0015 (8) | 0.0031 (7) | −0.0033 (8) |
O4 | 0.0255 (9) | 0.0383 (10) | 0.0432 (10) | −0.0059 (11) | 0.0014 (9) | −0.0096 (9) |
O5 | 0.0331 (10) | 0.0326 (10) | 0.0341 (10) | −0.0102 (10) | −0.0081 (10) | 0.0126 (8) |
Co1—O5 | 2.0384 (17) | C5—H5A | 0.930 |
Co1—N1 | 2.057 (2) | C6—N3 | 1.354 (3) |
Co1—N4 | 2.068 (2) | C6—C10 | 1.359 (4) |
Co1—O3 | 2.0687 (17) | C6—H6A | 0.930 |
Co1—O2 | 2.0723 (18) | C7—C9 | 1.362 (4) |
Co1—N3i | 2.104 (2) | C7—N3 | 1.364 (3) |
C1—O1 | 1.227 (3) | C7—H7A | 0.930 |
C1—O2 | 1.270 (3) | C8—O4 | 1.226 (3) |
C1—C2 | 1.550 (4) | C8—O3 | 1.274 (3) |
C2—N1 | 1.357 (3) | C8—C9 | 1.550 (3) |
C2—C3 | 1.371 (4) | C9—N4 | 1.339 (3) |
C3—N2 | 1.357 (4) | C10—N4 | 1.366 (3) |
C3—H3A | 0.930 | C10—H10A | 0.930 |
C4—N2 | 1.346 (4) | N3—Co1ii | 2.104 (2) |
C4—C5 | 1.371 (4) | O5—H51 | 0.82 (1) |
C4—H4A | 0.930 | O5—H52 | 0.82 (1) |
C5—N1 | 1.352 (3) | ||
O5—Co1—N1 | 86.63 (8) | N3—C6—C10 | 120.4 (2) |
O5—Co1—N4 | 93.02 (8) | N3—C6—H6A | 119.8 |
N1—Co1—N4 | 176.88 (9) | C10—C6—H6A | 119.8 |
O5—Co1—O3 | 90.59 (8) | C9—C7—N3 | 121.7 (2) |
N1—Co1—O3 | 94.56 (8) | C9—C7—H7A | 119.1 |
N4—Co1—O3 | 82.34 (7) | N3—C7—H7A | 119.1 |
O5—Co1—O2 | 86.35 (8) | O4—C8—O3 | 124.6 (2) |
N1—Co1—O2 | 82.42 (8) | O4—C8—C9 | 122.3 (2) |
N4—Co1—O2 | 100.65 (8) | O3—C8—C9 | 113.1 (2) |
O3—Co1—O2 | 175.81 (7) | N4—C9—C7 | 119.1 (2) |
O5—Co1—N3i | 176.49 (9) | N4—C9—C8 | 120.1 (2) |
N1—Co1—N3i | 93.15 (8) | C7—C9—C8 | 120.8 (2) |
N4—Co1—N3i | 87.39 (8) | C6—C10—N4 | 120.2 (2) |
O3—Co1—N3i | 92.92 (8) | C6—C10—H10A | 119.9 |
O2—Co1—N3i | 90.15 (8) | N4—C10—H10A | 119.9 |
O1—C1—O2 | 125.0 (3) | C5—N1—C2 | 119.7 (2) |
O1—C1—C2 | 121.0 (2) | C5—N1—Co1 | 130.57 (18) |
O2—C1—C2 | 113.9 (2) | C2—N1—Co1 | 109.32 (17) |
N1—C2—C3 | 118.8 (2) | C4—N2—C3 | 118.3 (2) |
N1—C2—C1 | 118.9 (2) | C6—N3—C7 | 118.3 (2) |
C3—C2—C1 | 122.3 (2) | C6—N3—Co1ii | 122.25 (17) |
N2—C3—C2 | 122.0 (3) | C7—N3—Co1ii | 119.24 (16) |
N2—C3—H3A | 119.0 | C9—N4—C10 | 120.2 (2) |
C2—C3—H3A | 119.0 | C9—N4—Co1 | 108.97 (16) |
N2—C4—C5 | 120.6 (3) | C10—N4—Co1 | 130.79 (17) |
N2—C4—H4A | 119.7 | C1—O2—Co1 | 115.09 (16) |
C5—C4—H4A | 119.7 | C8—O3—Co1 | 115.28 (15) |
N1—C5—C4 | 120.6 (3) | Co1—O5—H51 | 122.1 (19) |
N1—C5—H5A | 119.7 | Co1—O5—H52 | 125 (2) |
C4—C5—H5A | 119.7 | H51—O5—H52 | 111.4 (17) |
O1—C1—C2—N1 | 177.0 (2) | C10—C6—N3—C7 | −2.7 (4) |
O2—C1—C2—N1 | −4.0 (3) | C10—C6—N3—Co1ii | 172.10 (19) |
O1—C1—C2—C3 | −4.1 (4) | C9—C7—N3—C6 | 3.8 (4) |
O2—C1—C2—C3 | 174.8 (2) | C9—C7—N3—Co1ii | −171.17 (18) |
N1—C2—C3—N2 | 0.0 (4) | C7—C9—N4—C10 | −0.3 (4) |
C1—C2—C3—N2 | −178.9 (3) | C8—C9—N4—C10 | −179.3 (2) |
N2—C4—C5—N1 | 0.1 (4) | C7—C9—N4—Co1 | 176.90 (18) |
N3—C7—C9—N4 | −2.3 (4) | C8—C9—N4—Co1 | −2.1 (3) |
N3—C7—C9—C8 | 176.6 (2) | C6—C10—N4—C9 | 1.3 (4) |
O4—C8—C9—N4 | −174.9 (2) | C6—C10—N4—Co1 | −175.16 (18) |
O3—C8—C9—N4 | 4.9 (3) | O5—Co1—N4—C9 | 89.80 (17) |
O4—C8—C9—C7 | 6.2 (4) | O3—Co1—N4—C9 | −0.39 (16) |
O3—C8—C9—C7 | −174.1 (2) | O2—Co1—N4—C9 | 176.64 (16) |
N3—C6—C10—N4 | 0.2 (4) | N3i—Co1—N4—C9 | −93.69 (16) |
C4—C5—N1—C2 | −1.3 (4) | O5—Co1—N4—C10 | −93.4 (2) |
C4—C5—N1—Co1 | 170.45 (19) | O3—Co1—N4—C10 | 176.4 (2) |
C3—C2—N1—C5 | 1.3 (4) | O2—Co1—N4—C10 | −6.6 (2) |
C1—C2—N1—C5 | −179.9 (2) | N3i—Co1—N4—C10 | 83.1 (2) |
C3—C2—N1—Co1 | −172.1 (2) | O1—C1—O2—Co1 | 177.7 (2) |
C1—C2—N1—Co1 | 6.8 (3) | C2—C1—O2—Co1 | −1.2 (3) |
O5—Co1—N1—C5 | −91.2 (2) | O5—Co1—O2—C1 | −83.30 (18) |
O3—Co1—N1—C5 | −0.9 (2) | N1—Co1—O2—C1 | 3.78 (18) |
O2—Co1—N1—C5 | −178.0 (2) | N4—Co1—O2—C1 | −175.68 (18) |
N3i—Co1—N1—C5 | 92.3 (2) | N3i—Co1—O2—C1 | 96.94 (18) |
O5—Co1—N1—C2 | 81.21 (17) | O4—C8—O3—Co1 | 174.82 (19) |
O3—Co1—N1—C2 | 171.53 (16) | C9—C8—O3—Co1 | −4.9 (3) |
O2—Co1—N1—C2 | −5.55 (16) | O5—Co1—O3—C8 | −89.72 (18) |
N3i—Co1—N1—C2 | −95.29 (16) | N1—Co1—O3—C8 | −176.38 (17) |
C5—C4—N2—C3 | 1.1 (5) | N4—Co1—O3—C8 | 3.24 (17) |
C2—C3—N2—C4 | −1.2 (4) | N3i—Co1—O3—C8 | 90.22 (18) |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H52···O2iii | 0.82 (1) | 1.88 (1) | 2.697 (3) | 172 (3) |
O5—H51···O3iv | 0.82 (1) | 2.00 (1) | 2.814 (3) | 172 (3) |
Symmetry codes: (iii) x−1/2, −y+1/2, −z+1; (iv) x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co(C5H3N2O2)2(H2O)] |
Mr | 323.13 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 8.0121 (10), 9.5327 (10), 15.023 (2) |
V (Å3) | 1147.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.52 |
Crystal size (mm) | 0.10 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5916, 2198, 2064 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.055, 1.04 |
No. of reflections | 2198 |
No. of parameters | 190 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.80, −0.22 |
Absolute structure | Flack (1983), with 907 Friedel pairs |
Absolute structure parameter | 0.452 (15) |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H52···O2i | 0.82 (1) | 1.88 (1) | 2.697 (3) | 172 (3) |
O5—H51···O3ii | 0.82 (1) | 2.00 (1) | 2.814 (3) | 172 (3) |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, −y+1/2, −z+1. |
The title compound, [Co(C5H3N2O2)2(H2O)]n, is isostructural with its FeII and NiII analogues (Hao & Liu, 2007; Hao, Mu & Liu, 2007).
The CoII atom is coordinated in a bidentate fashion by two O and two N atoms from two independent pyrazine-2-carboxylate anions. The distorted octahedral coordination is completed by another N atom from a third pyrazine-2-carboxylate ligand, and by the O atom of a water molecule (Fig. 1). The Co—N and Co—O bond lengths are in the range 2.057 (2)–2.104 (2) and 2.0384 (17)–2.0723 (18) Å, respectively.
One pyrazine-2-carboxylate ligand coordinates to a neighboring CoII atom via its second N atom, leading to a polymeric structure with zigzag chains extending parallel to the b axis (Fig. 2). Hydrogen bonding between the water molecules stabilizes the structure.