Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807036744/dn2222sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807036744/dn2222Isup2.hkl |
CCDC reference: 657645
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.002 Å
- R factor = 0.028
- wR factor = 0.084
- Data-to-parameter ratio = 14.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.48
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1 (2) 1.87 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 3
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Preparation of [Co(H2MIA)2(H2O)2]: A heavy-walled prex tube containing a mixture of Co(OAc)2.6H2O (0.0285 g, 0.1 mmol), 2-methyl -1H-imidazole-4,5-dicarboxylic acid (0.034 g, 0.2 mmol), 0.65 mol/L NaOH solutions (0.3 ml) and H2O (2 ml) was frozen in liquid N2, sealed under vacuum and placed inside an oven at 150 °C. The red single crystals (I) suitable for X-ray analysis were then obtained after heating of 3 d. Yield: 0.026 g, 60%. Analysis, calculated for C12H14CoN4O10 (433.20): C 33.27, H 3.26, N 12.93%; found: C 33.12, H 3.36, N 12.90%.
All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and N—H = 0.86 Å with Uiso(H) = xUeq(C or N) where x=1.2 for C(aromatic) or N and 1.5 for methyl group.. H atoms of water molecule were located in difference Fourier maps and included in the subsequent refinement using restraints (O—H= 0.85 (1)Å and H···H= 1.39 (2) Å) with Uiso(H) = 1.5Ueq(O).In the final stage of refinement they coordinates were fixed.
Recently, our group (Nie et al., 2007) described the structure of diaquabis [2-methyl-1H-imidazole-4,5-dicarboxylato(1-)]cadmium (II) as a three-dimensional network of [Cd(H2MIA)2(H2O)2] molecules held together by hydrogen-bonding interactions. The present centrosymmetric Co complex is similiar to the Cd complex, but there are some differences in their structures.
The molecule of (I) is a discrete neutral monomer, in which the asymmetric unit contains one-half of the [Co(H2MIA)2(H2O)2] formula unit. The Co atom lies on a crystallographic inversion center and has a slightly distorted octahedral geometry. Two coordinated water molecules occupy the apical positions. The equatorial plane contains two bidentate 2-methyl-1H-imidazole-4,5-dicarboxylic acid monoanionic ligands which display a strong intramolecular O—H···O symmetrical hydrogen bond with a short O···O distance of 2.462 (2) Å (Fig. 1; Table 1). Similar strong intramolecular hydrogen bondings has been already reported with this ligand (Liu et al., 2004; Liu et al., 2006).
Owing to the location of the Co on an inversion center, the two chelate rings are coplanar, with a mean deviation 0.042 (2) Å, whereas in the Cd complex, the two chelate rings are shifted with a distance between the two planes of 0.5615 Å.. In the Cd complex, N—H···O hydrogen bonds link the molecules into chains which are further linked to a three-dimensional supramolecular framework via O—H···O hydrogen bonds whereas in the title complex, N—H···O hydrogen bonds (Table 1) link the molecules into a two-dimensional layers (Fig. 2). These layers are further linked through O—H···O (Table 1) involving the coordinated water O atoms and two carboxy O atoms to form a three-dimensional supramolecular framework. The Cd complex crystallizes in Monoclinic, space group P 21/c whereas the Co complex belongs to the orthorhombic, Pbca space group.
For related literature, see: Nie et al. (2007); Liu et al. (2004); Liu et al. (2006).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[Co(C6H5N2O4)2(H2O)2] | F(000) = 884 |
Mr = 433.20 | Dx = 1.805 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3494 reflections |
a = 6.8261 (8) Å | θ = 2.9–28.1° |
b = 13.9705 (16) Å | µ = 1.14 mm−1 |
c = 16.7173 (19) Å | T = 291 K |
V = 1594.2 (3) Å3 | Block, red |
Z = 4 | 0.38 × 0.18 × 0.16 mm |
Bruker SMART CCD area-detector diffractometer | 1825 independent reflections |
Radiation source: fine-focus sealed tube | 1459 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
φ and ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.673, Tmax = 0.839 | k = −17→18 |
10909 measured reflections | l = −20→21 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.4264P] where P = (Fo2 + 2Fc2)/3 |
1825 reflections | (Δ/σ)max < 0.001 |
128 parameters | Δρmax = 0.33 e Å−3 |
3 restraints | Δρmin = −0.33 e Å−3 |
[Co(C6H5N2O4)2(H2O)2] | V = 1594.2 (3) Å3 |
Mr = 433.20 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 6.8261 (8) Å | µ = 1.14 mm−1 |
b = 13.9705 (16) Å | T = 291 K |
c = 16.7173 (19) Å | 0.38 × 0.18 × 0.16 mm |
Bruker SMART CCD area-detector diffractometer | 1825 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1459 reflections with I > 2σ(I) |
Tmin = 0.673, Tmax = 0.839 | Rint = 0.025 |
10909 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 3 restraints |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.33 e Å−3 |
1825 reflections | Δρmin = −0.33 e Å−3 |
128 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 | ||
Co1 | 0.5000 | 0.5000 | 0.5000 | 0.02327 (13) | |
O1 | 0.4610 (2) | 0.37350 (9) | 0.87496 (7) | 0.0384 (3) | |
O2 | 0.5322 (2) | 0.52489 (10) | 0.84444 (8) | 0.0353 (3) | |
O3 | 0.5701 (2) | 0.62758 (8) | 0.72576 (7) | 0.0354 (3) | |
H3 | 0.545 (3) | 0.5850 (17) | 0.7866 (15) | 0.053* | |
O4 | 0.5556 (2) | 0.60690 (8) | 0.59313 (7) | 0.0321 (3) | |
O5 | 0.7904 (2) | 0.46448 (11) | 0.49466 (6) | 0.0356 (3) | |
H1W | 0.8536 | 0.4646 | 0.4530 | 0.053* | |
H2W | 0.8482 | 0.4340 | 0.5309 | 0.053* | |
N1 | 0.47986 (19) | 0.41778 (10) | 0.60525 (8) | 0.0234 (3) | |
N2 | 0.4548 (2) | 0.32451 (10) | 0.71031 (8) | 0.0273 (3) | |
H2 | 0.4385 | 0.2738 | 0.7387 | 0.033* | |
C1 | 0.4181 (4) | 0.24506 (13) | 0.57651 (11) | 0.0446 (5) | |
H1A | 0.4148 | 0.2657 | 0.5218 | 0.067* | |
H1B | 0.2958 | 0.2152 | 0.5900 | 0.067* | |
H1C | 0.5228 | 0.2000 | 0.5837 | 0.067* | |
C2 | 0.4504 (3) | 0.32885 (12) | 0.62924 (10) | 0.0269 (4) | |
C3 | 0.4899 (2) | 0.41492 (12) | 0.73939 (10) | 0.0232 (3) | |
C4 | 0.5065 (2) | 0.47207 (13) | 0.67325 (10) | 0.0228 (3) | |
C5 | 0.4943 (2) | 0.43642 (13) | 0.82581 (10) | 0.0268 (4) | |
C6 | 0.5460 (2) | 0.57575 (12) | 0.66241 (10) | 0.0248 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0353 (2) | 0.0211 (2) | 0.0134 (2) | −0.00068 (12) | −0.00038 (11) | 0.00064 (11) |
O1 | 0.0641 (9) | 0.0341 (7) | 0.0171 (6) | 0.0043 (6) | 0.0036 (6) | 0.0033 (5) |
O2 | 0.0582 (9) | 0.0314 (7) | 0.0163 (6) | 0.0004 (6) | −0.0036 (5) | −0.0031 (5) |
O3 | 0.0631 (9) | 0.0227 (6) | 0.0205 (6) | −0.0040 (6) | −0.0022 (6) | −0.0050 (5) |
O4 | 0.0538 (8) | 0.0232 (6) | 0.0194 (6) | −0.0038 (6) | −0.0007 (5) | 0.0001 (5) |
O5 | 0.0367 (7) | 0.0506 (8) | 0.0195 (6) | 0.0070 (7) | 0.0023 (5) | 0.0063 (5) |
N1 | 0.0350 (7) | 0.0204 (7) | 0.0148 (7) | −0.0014 (5) | −0.0013 (5) | −0.0008 (5) |
N2 | 0.0412 (8) | 0.0223 (7) | 0.0186 (7) | −0.0018 (6) | 0.0003 (6) | 0.0027 (5) |
C1 | 0.0819 (15) | 0.0254 (9) | 0.0265 (10) | −0.0102 (10) | −0.0024 (10) | −0.0040 (7) |
C2 | 0.0389 (9) | 0.0228 (8) | 0.0189 (8) | −0.0005 (7) | −0.0004 (7) | −0.0001 (6) |
C3 | 0.0296 (8) | 0.0220 (8) | 0.0180 (8) | 0.0015 (6) | −0.0002 (6) | −0.0005 (6) |
C4 | 0.0304 (8) | 0.0215 (8) | 0.0166 (8) | 0.0004 (6) | −0.0004 (6) | −0.0015 (6) |
C5 | 0.0328 (9) | 0.0292 (10) | 0.0185 (9) | 0.0053 (6) | −0.0004 (6) | −0.0004 (7) |
C6 | 0.0344 (8) | 0.0216 (8) | 0.0186 (8) | 0.0010 (6) | −0.0007 (6) | −0.0019 (6) |
Co1—O5 | 2.0453 (14) | O5—H2W | 0.8386 |
Co1—O5i | 2.0453 (14) | N1—C2 | 1.321 (2) |
Co1—N1i | 2.1057 (14) | N1—C4 | 1.379 (2) |
Co1—N1 | 2.1057 (14) | N2—C2 | 1.357 (2) |
Co1—O4i | 2.1904 (12) | N2—C3 | 1.374 (2) |
Co1—O4 | 2.1904 (12) | N2—H2 | 0.8600 |
O1—C5 | 1.225 (2) | C1—C2 | 1.482 (2) |
O2—C5 | 1.301 (2) | C1—H1A | 0.9600 |
O2—H3 | 1.28 (2) | C1—H1B | 0.9600 |
O3—C6 | 1.2933 (19) | C1—H1C | 0.9600 |
O3—H3 | 1.19 (2) | C3—C4 | 1.368 (2) |
O4—C6 | 1.239 (2) | C3—C5 | 1.476 (2) |
O5—H1W | 0.8190 | C4—C6 | 1.485 (2) |
O5—Co1—O5i | 180.0 | C2—N2—C3 | 108.42 (14) |
O5—Co1—N1i | 91.87 (5) | C2—N2—H2 | 125.8 |
O5i—Co1—N1i | 88.13 (5) | C3—N2—H2 | 125.8 |
O5—Co1—N1 | 88.13 (5) | C2—C1—H1A | 109.5 |
O5i—Co1—N1 | 91.87 (5) | C2—C1—H1B | 109.5 |
N1i—Co1—N1 | 180.0 | H1A—C1—H1B | 109.5 |
O5—Co1—O4i | 88.36 (5) | C2—C1—H1C | 109.5 |
O5i—Co1—O4i | 91.64 (5) | H1A—C1—H1C | 109.5 |
N1i—Co1—O4i | 77.84 (5) | H1B—C1—H1C | 109.5 |
N1—Co1—O4i | 102.16 (5) | N1—C2—N2 | 110.00 (15) |
O5—Co1—O4 | 91.64 (5) | N1—C2—C1 | 125.79 (15) |
O5i—Co1—O4 | 88.36 (5) | N2—C2—C1 | 124.21 (16) |
N1i—Co1—O4 | 102.16 (5) | C4—C3—N2 | 105.35 (14) |
N1—Co1—O4 | 77.84 (5) | C4—C3—C5 | 132.11 (17) |
O4i—Co1—O4 | 180.000 (1) | N2—C3—C5 | 122.46 (16) |
C5—O2—H3 | 117.1 (11) | C3—C4—N1 | 109.54 (15) |
C6—O3—H3 | 113.7 (11) | C3—C4—C6 | 133.06 (15) |
C6—O4—Co1 | 114.58 (10) | N1—C4—C6 | 117.40 (14) |
Co1—O5—H1W | 123.2 | O1—C5—O2 | 123.94 (16) |
Co1—O5—H2W | 123.2 | O1—C5—C3 | 120.47 (16) |
H1W—O5—H2W | 111.5 | O2—C5—C3 | 115.58 (15) |
C2—N1—C4 | 106.68 (14) | O4—C6—O3 | 124.21 (15) |
C2—N1—Co1 | 140.96 (12) | O4—C6—C4 | 117.79 (14) |
C4—N1—Co1 | 112.35 (11) | O3—C6—C4 | 118.00 (14) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 1.19 (2) | 1.28 (2) | 2.4619 (18) | 168 (2) |
O5—H1W···O2ii | 0.82 | 1.98 | 2.7920 (18) | 171 |
O5—H2W···O1iii | 0.84 | 1.95 | 2.7789 (17) | 172 |
N2—H2···O3iv | 0.86 | 2.13 | 2.9564 (18) | 162 |
Symmetry codes: (ii) −x+3/2, −y+1, z−1/2; (iii) x+1/2, y, −z+3/2; (iv) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C6H5N2O4)2(H2O)2] |
Mr | 433.20 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 291 |
a, b, c (Å) | 6.8261 (8), 13.9705 (16), 16.7173 (19) |
V (Å3) | 1594.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.14 |
Crystal size (mm) | 0.38 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.673, 0.839 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10909, 1825, 1459 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.084, 1.08 |
No. of reflections | 1825 |
No. of parameters | 128 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.33 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 1.19 (2) | 1.28 (2) | 2.4619 (18) | 168 (2) |
O5—H1W···O2i | 0.82 | 1.98 | 2.7920 (18) | 170.5 |
O5—H2W···O1ii | 0.84 | 1.95 | 2.7789 (17) | 172.2 |
N2—H2···O3iii | 0.86 | 2.13 | 2.9564 (18) | 161.5 |
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x+1/2, y, −z+3/2; (iii) −x+1, y−1/2, −z+3/2. |
Recently, our group (Nie et al., 2007) described the structure of diaquabis [2-methyl-1H-imidazole-4,5-dicarboxylato(1-)]cadmium (II) as a three-dimensional network of [Cd(H2MIA)2(H2O)2] molecules held together by hydrogen-bonding interactions. The present centrosymmetric Co complex is similiar to the Cd complex, but there are some differences in their structures.
The molecule of (I) is a discrete neutral monomer, in which the asymmetric unit contains one-half of the [Co(H2MIA)2(H2O)2] formula unit. The Co atom lies on a crystallographic inversion center and has a slightly distorted octahedral geometry. Two coordinated water molecules occupy the apical positions. The equatorial plane contains two bidentate 2-methyl-1H-imidazole-4,5-dicarboxylic acid monoanionic ligands which display a strong intramolecular O—H···O symmetrical hydrogen bond with a short O···O distance of 2.462 (2) Å (Fig. 1; Table 1). Similar strong intramolecular hydrogen bondings has been already reported with this ligand (Liu et al., 2004; Liu et al., 2006).
Owing to the location of the Co on an inversion center, the two chelate rings are coplanar, with a mean deviation 0.042 (2) Å, whereas in the Cd complex, the two chelate rings are shifted with a distance between the two planes of 0.5615 Å.. In the Cd complex, N—H···O hydrogen bonds link the molecules into chains which are further linked to a three-dimensional supramolecular framework via O—H···O hydrogen bonds whereas in the title complex, N—H···O hydrogen bonds (Table 1) link the molecules into a two-dimensional layers (Fig. 2). These layers are further linked through O—H···O (Table 1) involving the coordinated water O atoms and two carboxy O atoms to form a three-dimensional supramolecular framework. The Cd complex crystallizes in Monoclinic, space group P 21/c whereas the Co complex belongs to the orthorhombic, Pbca space group.