Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680503970X/ci6711sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680503970X/ci6711Isup2.hkl |
CCDC reference: 296535
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.036
- wR factor = 0.098
- Data-to-parameter ratio = 11.9
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.638 0.883 Tmin(prime) and Tmax expected: 0.776 0.883 RR(prime) = 0.822 Please check that your absorption correction is appropriate. PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.82 PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT417_ALERT_2_C Short Inter D-H..H-D H7B .. H11B .. 2.11 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 5 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 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion
An aqueous solution (10 ml) of benzene-1,3,5-tricarboxylic acid (0.210 g), terephthalic acid (0.166 g) and piperazine hexahydrate (0.132 g) was mixed with an aqueous solution (5 ml) of cobalt nitrate hexahydrate (0.292 g) with continuous stirring. The mixture was sealed in a 40 ml Teflon-lined stainless steel vessel and heated at 453 K for 96 h under autogenous conditions. After cooling to room temperature, the resulting product was filtered off to obtain pale-red crystals of (I) (about 76.2% yield, based on the Co source). Spectroscopic analysis: IR (KBr, ν, cm−1): 3120, 2445, 2345, 1610, 1532, 1454, 1429, 1363, 1202, 1087, 754, 712, 542, 521, 459. Elemental analysis, calculated for C11H17N Co O10: C 34.54, H 4.48, N 3.66%; found: C 34.45, H 4.51, N 3.62%.
The water H atoms were located in a difference map, their bond lengths were set to ideal values [O—H = 0.85 (1) and H···H = 1.37 (2) Å] and they were refined using a riding model [Uiso(H) = 1.5Ueq(O)]. The remaining H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å and N—H = 0.90 Å, and with Uiso(H) = 1.2Ueq(C,N).
Data collection: APEX2 (Bruker, 1997); cell refinement: APEX2; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
(C4H12N2)[Co2(C9H3O6)2(H2O)6]·2H2O | Z = 1 |
Mr = 764.38 | F(000) = 394 |
Triclinic, P1 | Dx = 1.764 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1443 (11) Å | Cell parameters from 1224 reflections |
b = 10.5308 (16) Å | θ = 2.1–25.0° |
c = 10.5385 (16) Å | µ = 1.25 mm−1 |
α = 110.753 (2)° | T = 293 K |
β = 102.521 (2)° | Block, pale-red |
γ = 91.351 (2)° | 0.20 × 0.12 × 0.10 mm |
V = 719.40 (19) Å3 |
Bruker SMART APEX2 CCD area-detector diffractometer | 2503 independent reflections |
Radiation source: fine-focus sealed tube | 1957 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.638, Tmax = 0.883 | k = −12→12 |
3896 measured reflections | l = −8→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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0626P)2] where P = (Fo2 + 2Fc2)/3 |
2503 reflections | (Δ/σ)max = 0.001 |
211 parameters | Δρmax = 0.56 e Å−3 |
12 restraints | Δρmin = −0.56 e Å−3 |
(C4H12N2)[Co2(C9H3O6)2(H2O)6]·2H2O | γ = 91.351 (2)° |
Mr = 764.38 | V = 719.40 (19) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.1443 (11) Å | Mo Kα radiation |
b = 10.5308 (16) Å | µ = 1.25 mm−1 |
c = 10.5385 (16) Å | T = 293 K |
α = 110.753 (2)° | 0.20 × 0.12 × 0.10 mm |
β = 102.521 (2)° |
Bruker SMART APEX2 CCD area-detector diffractometer | 2503 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1957 reflections with I > 2σ(I) |
Tmin = 0.638, Tmax = 0.883 | Rint = 0.015 |
3896 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 12 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.56 e Å−3 |
2503 reflections | Δρmin = −0.56 e Å−3 |
211 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 | 0.0000 | 1.0000 | 0.0000 | 0.01768 (17) | |
Co2 | 0.0000 | 0.5000 | 0.5000 | 0.02347 (18) | |
O1 | 0.1519 (3) | 0.6995 (2) | 0.6363 (2) | 0.0266 (5) | |
O2 | 0.0267 (3) | 0.6506 (2) | 0.4138 (2) | 0.0288 (5) | |
O3 | 0.1060 (3) | 0.9742 (2) | 0.18822 (19) | 0.0241 (5) | |
O4 | 0.2732 (3) | 1.1785 (2) | 0.3085 (2) | 0.0289 (5) | |
O5 | 0.6055 (3) | 1.2898 (2) | 0.8111 (2) | 0.0322 (6) | |
O6 | 0.5058 (3) | 1.1671 (2) | 0.9223 (2) | 0.0291 (5) | |
O7 | 0.2534 (3) | 0.4354 (2) | 0.4549 (2) | 0.0356 (6) | |
H7A | 0.2522 | 0.3504 | 0.4100 | 0.053* | |
H7B | 0.3036 | 0.4780 | 0.4133 | 0.053* | |
O8 | 0.1637 (3) | 0.8460 (2) | −0.0887 (2) | 0.0249 (5) | |
H8A | 0.1686 | 0.8175 | −0.1740 | 0.037* | |
H8B | 0.2771 | 0.8528 | −0.0390 | 0.037* | |
O9 | 0.2139 (3) | 1.1639 (2) | 0.0473 (2) | 0.0225 (5) | |
H9A | 0.3049 | 1.1501 | 0.0054 | 0.034* | |
H9B | 0.2622 | 1.1769 | 0.1326 | 0.034* | |
C1 | 0.1986 (4) | 0.8720 (3) | 0.5422 (3) | 0.0187 (6) | |
C2 | 0.1654 (4) | 0.9058 (3) | 0.4244 (3) | 0.0183 (6) | |
H2 | 0.0936 | 0.8428 | 0.3398 | 0.022* | |
C3 | 0.2369 (4) | 1.0315 (3) | 0.4298 (3) | 0.0170 (6) | |
C4 | 0.3451 (4) | 1.1244 (3) | 0.5569 (3) | 0.0191 (6) | |
H4 | 0.3963 | 1.2084 | 0.5614 | 0.023* | |
C5 | 0.3778 (4) | 1.0939 (3) | 0.6769 (3) | 0.0178 (6) | |
C6 | 0.3053 (4) | 0.9673 (3) | 0.6696 (3) | 0.0196 (7) | |
H6 | 0.3277 | 0.9459 | 0.7496 | 0.024* | |
C7 | 0.1223 (4) | 0.7339 (3) | 0.5306 (3) | 0.0208 (7) | |
C8 | 0.2030 (4) | 1.0652 (3) | 0.3004 (3) | 0.0189 (6) | |
C9 | 0.5054 (4) | 1.1914 (3) | 0.8138 (3) | 0.0211 (7) | |
C10 | 0.8829 (5) | 0.5889 (3) | 0.0791 (3) | 0.0296 (8) | |
H10A | 0.7579 | 0.5663 | 0.0130 | 0.036* | |
H10B | 0.8703 | 0.6591 | 0.1652 | 0.036* | |
C11 | 0.9435 (5) | 0.4647 (3) | 0.1073 (3) | 0.0321 (8) | |
H11C | 1.0621 | 0.4892 | 0.1802 | 0.038* | |
H11D | 0.8450 | 0.4291 | 0.1401 | 0.038* | |
N1 | 0.9741 (4) | 0.3578 (3) | −0.0211 (3) | 0.0288 (6) | |
H1A | 0.8612 | 0.3291 | −0.0857 | 0.035* | |
H1B | 1.0165 | 0.2857 | −0.0010 | 0.035* | |
O11 | 0.4461 (4) | 0.5031 (3) | 0.2864 (3) | 0.0631 (9) | |
H11A | 0.4503 | 0.5576 | 0.2435 | 0.095* | |
H11B | 0.5514 | 0.5066 | 0.3442 | 0.095* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0185 (3) | 0.0199 (3) | 0.0140 (3) | −0.0025 (2) | −0.0002 (2) | 0.0082 (2) |
Co2 | 0.0272 (3) | 0.0197 (3) | 0.0211 (3) | −0.0054 (3) | 0.0012 (3) | 0.0079 (3) |
O1 | 0.0365 (13) | 0.0242 (12) | 0.0194 (11) | −0.0059 (10) | 0.0034 (9) | 0.0109 (9) |
O2 | 0.0387 (13) | 0.0219 (12) | 0.0217 (11) | −0.0096 (10) | 0.0006 (10) | 0.0078 (10) |
O3 | 0.0295 (12) | 0.0258 (12) | 0.0142 (10) | −0.0051 (10) | −0.0026 (9) | 0.0093 (9) |
O4 | 0.0418 (14) | 0.0233 (13) | 0.0207 (11) | −0.0086 (10) | 0.0014 (10) | 0.0112 (10) |
O5 | 0.0306 (13) | 0.0300 (13) | 0.0275 (12) | −0.0142 (11) | −0.0088 (10) | 0.0108 (11) |
O6 | 0.0195 (11) | 0.0478 (15) | 0.0166 (11) | −0.0076 (10) | −0.0033 (9) | 0.0131 (10) |
O7 | 0.0348 (13) | 0.0239 (13) | 0.0484 (14) | −0.0004 (10) | 0.0128 (11) | 0.0123 (11) |
O8 | 0.0216 (11) | 0.0336 (13) | 0.0159 (10) | 0.0039 (10) | 0.0003 (9) | 0.0072 (9) |
O9 | 0.0190 (11) | 0.0303 (13) | 0.0182 (10) | −0.0033 (9) | 0.0016 (8) | 0.0109 (9) |
C1 | 0.0168 (15) | 0.0197 (16) | 0.0198 (15) | −0.0009 (12) | 0.0041 (12) | 0.0077 (13) |
C2 | 0.0169 (15) | 0.0202 (16) | 0.0158 (14) | −0.0002 (12) | 0.0006 (12) | 0.0062 (12) |
C3 | 0.0145 (14) | 0.0225 (16) | 0.0153 (14) | 0.0007 (12) | 0.0033 (11) | 0.0086 (12) |
C4 | 0.0166 (15) | 0.0189 (15) | 0.0232 (15) | −0.0022 (12) | 0.0034 (12) | 0.0105 (13) |
C5 | 0.0119 (14) | 0.0226 (16) | 0.0175 (14) | −0.0010 (12) | 0.0019 (11) | 0.0068 (13) |
C6 | 0.0179 (15) | 0.0260 (17) | 0.0173 (14) | −0.0005 (13) | 0.0040 (12) | 0.0111 (13) |
C7 | 0.0207 (15) | 0.0213 (16) | 0.0181 (15) | −0.0019 (13) | 0.0026 (12) | 0.0061 (13) |
C8 | 0.0168 (15) | 0.0230 (17) | 0.0175 (15) | 0.0028 (13) | 0.0048 (12) | 0.0077 (13) |
C9 | 0.0142 (14) | 0.0249 (17) | 0.0210 (15) | −0.0013 (13) | 0.0002 (12) | 0.0072 (13) |
C10 | 0.0264 (17) | 0.0300 (19) | 0.0260 (17) | −0.0041 (14) | −0.0003 (14) | 0.0069 (15) |
C11 | 0.039 (2) | 0.0311 (19) | 0.0225 (16) | −0.0068 (16) | 0.0004 (14) | 0.0107 (15) |
N1 | 0.0329 (15) | 0.0219 (15) | 0.0269 (14) | −0.0048 (12) | −0.0044 (12) | 0.0106 (12) |
O11 | 0.0496 (18) | 0.077 (2) | 0.071 (2) | −0.0133 (16) | −0.0056 (15) | 0.0500 (18) |
Co1—O3 | 2.0787 (19) | O9—H9B | 0.85 |
Co1—O3i | 2.0787 (19) | C1—C2 | 1.383 (4) |
Co1—O8 | 2.088 (2) | C1—C6 | 1.399 (4) |
Co1—O8i | 2.088 (2) | C1—C7 | 1.495 (4) |
Co1—O9 | 2.1210 (19) | C2—C3 | 1.385 (4) |
Co1—O9i | 2.1210 (19) | C2—H2 | 0.93 |
Co2—O7 | 2.041 (2) | C3—C4 | 1.391 (4) |
Co2—O7ii | 2.041 (2) | C3—C8 | 1.500 (4) |
Co2—O2ii | 2.111 (2) | C4—C5 | 1.386 (4) |
Co2—O2 | 2.111 (2) | C4—H4 | 0.93 |
Co2—O1ii | 2.175 (2) | C5—C6 | 1.389 (4) |
Co2—O1 | 2.175 (2) | C5—C9 | 1.517 (4) |
Co2—C7ii | 2.480 (3) | C6—H6 | 0.93 |
Co2—C7 | 2.480 (3) | C10—N1iii | 1.489 (4) |
O1—C7 | 1.266 (3) | C10—C11 | 1.494 (5) |
O2—C7 | 1.262 (3) | C10—H10A | 0.97 |
O3—C8 | 1.267 (3) | C10—H10B | 0.97 |
O4—C8 | 1.251 (3) | C11—N1 | 1.486 (4) |
O5—C9 | 1.256 (4) | C11—H11C | 0.97 |
O6—C9 | 1.258 (4) | C11—H11D | 0.97 |
O7—H7A | 0.85 | N1—C10iii | 1.489 (4) |
O7—H7B | 0.85 | N1—H1A | 0.90 |
O8—H8A | 0.85 | N1—H1B | 0.90 |
O8—H8B | 0.85 | O11—H11A | 0.85 |
O9—H9A | 0.85 | O11—H11B | 0.85 |
O3—Co1—O3i | 180.0 | Co1—O9—H9A | 119.0 |
O3—Co1—O8 | 87.26 (8) | Co1—O9—H9B | 99.1 |
O3i—Co1—O8 | 92.74 (8) | H9A—O9—H9B | 107.7 |
O3—Co1—O8i | 92.74 (8) | C2—C1—C6 | 119.2 (3) |
O3i—Co1—O8i | 87.26 (8) | C2—C1—C7 | 119.5 (3) |
O8—Co1—O8i | 180.000 (1) | C6—C1—C7 | 121.3 (3) |
O3—Co1—O9 | 93.22 (8) | C1—C2—C3 | 121.4 (3) |
O3i—Co1—O9 | 86.78 (8) | C1—C2—H2 | 119.3 |
O8—Co1—O9 | 95.51 (8) | C3—C2—H2 | 119.3 |
O8i—Co1—O9 | 84.49 (8) | C2—C3—C4 | 118.7 (3) |
O3—Co1—O9i | 86.78 (8) | C2—C3—C8 | 120.6 (3) |
O3i—Co1—O9i | 93.22 (8) | C4—C3—C8 | 120.6 (3) |
O8—Co1—O9i | 84.49 (8) | C5—C4—C3 | 121.0 (3) |
O8i—Co1—O9i | 95.51 (8) | C5—C4—H4 | 119.5 |
O9—Co1—O9i | 180.00 (11) | C3—C4—H4 | 119.5 |
O7—Co2—O7ii | 180.00 (14) | C4—C5—C6 | 119.5 (3) |
O7—Co2—O2ii | 90.77 (9) | C4—C5—C9 | 121.2 (3) |
O7ii—Co2—O2ii | 89.23 (9) | C6—C5—C9 | 119.1 (3) |
O7—Co2—O2 | 89.23 (9) | C5—C6—C1 | 120.1 (3) |
O7ii—Co2—O2 | 90.77 (9) | C5—C6—H6 | 119.9 |
O2ii—Co2—O2 | 180.0 | C1—C6—H6 | 119.9 |
O7—Co2—O1ii | 90.37 (9) | O2—C7—O1 | 119.6 (3) |
O7ii—Co2—O1ii | 89.63 (9) | O2—C7—C1 | 119.5 (3) |
O2ii—Co2—O1ii | 61.26 (8) | O1—C7—C1 | 120.9 (2) |
O2—Co2—O1ii | 118.74 (8) | O2—C7—Co2 | 58.34 (15) |
O7—Co2—O1 | 89.63 (9) | O1—C7—Co2 | 61.25 (15) |
O7ii—Co2—O1 | 90.37 (9) | C1—C7—Co2 | 177.1 (2) |
O2ii—Co2—O1 | 118.74 (8) | O4—C8—O3 | 124.2 (3) |
O2—Co2—O1 | 61.26 (8) | O4—C8—C3 | 118.9 (2) |
O1ii—Co2—O1 | 180.00 (8) | O3—C8—C3 | 116.9 (3) |
O7—Co2—C7ii | 91.33 (9) | O5—C9—O6 | 124.3 (3) |
O7ii—Co2—C7ii | 88.67 (9) | O5—C9—C5 | 118.1 (3) |
O2ii—Co2—C7ii | 30.58 (9) | O6—C9—C5 | 117.5 (3) |
O2—Co2—C7ii | 149.42 (9) | N1iii—C10—C11 | 111.0 (3) |
O1ii—Co2—C7ii | 30.69 (8) | N1iii—C10—H10A | 109.4 |
O1—Co2—C7ii | 149.31 (8) | C11—C10—H10A | 109.4 |
O7—Co2—C7 | 88.67 (9) | N1iii—C10—H10B | 109.4 |
O7ii—Co2—C7 | 91.33 (9) | C11—C10—H10B | 109.4 |
O2ii—Co2—C7 | 149.42 (9) | H10A—C10—H10B | 108.0 |
O2—Co2—C7 | 30.58 (9) | N1—C11—C10 | 110.7 (3) |
O1ii—Co2—C7 | 149.31 (8) | N1—C11—H11C | 109.5 |
O1—Co2—C7 | 30.69 (8) | C10—C11—H11C | 109.5 |
C7ii—Co2—C7 | 180.0 | N1—C11—H11D | 109.5 |
C7—O1—Co2 | 88.06 (17) | C10—C11—H11D | 109.5 |
C7—O2—Co2 | 91.08 (18) | H11C—C11—H11D | 108.1 |
C8—O3—Co1 | 125.94 (19) | C11—N1—C10iii | 111.1 (2) |
Co2—O7—H7A | 116.6 | C11—N1—H1A | 109.4 |
Co2—O7—H7B | 114.5 | C10iii—N1—H1A | 109.4 |
H7A—O7—H7B | 107.5 | C11—N1—H1B | 109.4 |
Co1—O8—H8A | 124.2 | C10iii—N1—H1B | 109.4 |
Co1—O8—H8B | 114.2 | H1A—N1—H1B | 108.0 |
H8A—O8—H8B | 108.2 | H11A—O11—H11B | 113.6 |
O7—Co2—O1—C7 | 88.03 (18) | Co2—O1—C7—O2 | 2.2 (3) |
O7ii—Co2—O1—C7 | −91.97 (18) | Co2—O1—C7—C1 | −177.9 (3) |
O2ii—Co2—O1—C7 | 178.70 (17) | C2—C1—C7—O2 | −0.8 (4) |
O2—Co2—O1—C7 | −1.30 (17) | C6—C1—C7—O2 | −179.9 (3) |
C7ii—Co2—O1—C7 | 180.000 (1) | C2—C1—C7—O1 | 179.3 (3) |
O7—Co2—O2—C7 | −88.70 (19) | C6—C1—C7—O1 | 0.1 (4) |
O7ii—Co2—O2—C7 | 91.30 (19) | O7—Co2—C7—O2 | 90.73 (19) |
O1ii—Co2—O2—C7 | −178.70 (17) | O7ii—Co2—C7—O2 | −89.27 (19) |
O1—Co2—O2—C7 | 1.30 (17) | O2ii—Co2—C7—O2 | 180.000 (1) |
C7ii—Co2—O2—C7 | 180.000 (1) | O1ii—Co2—C7—O2 | 2.2 (3) |
O8—Co1—O3—C8 | 120.4 (2) | O1—Co2—C7—O2 | −177.8 (3) |
O8i—Co1—O3—C8 | −59.6 (2) | O7—Co2—C7—O1 | −91.51 (17) |
O9—Co1—O3—C8 | 25.1 (2) | O7ii—Co2—C7—O1 | 88.49 (17) |
O9i—Co1—O3—C8 | −154.9 (2) | O2ii—Co2—C7—O1 | −2.2 (3) |
C6—C1—C2—C3 | 0.5 (4) | O2—Co2—C7—O1 | 177.8 (3) |
C7—C1—C2—C3 | −178.6 (3) | O1ii—Co2—C7—O1 | 180.000 (2) |
C1—C2—C3—C4 | 0.4 (4) | Co1—O3—C8—O4 | −10.9 (4) |
C1—C2—C3—C8 | 178.7 (3) | Co1—O3—C8—C3 | 170.14 (18) |
C2—C3—C4—C5 | −1.4 (4) | C2—C3—C8—O4 | −178.5 (3) |
C8—C3—C4—C5 | −179.7 (3) | C4—C3—C8—O4 | −0.2 (4) |
C3—C4—C5—C6 | 1.5 (4) | C2—C3—C8—O3 | 0.5 (4) |
C3—C4—C5—C9 | 176.4 (3) | C4—C3—C8—O3 | 178.7 (3) |
C4—C5—C6—C1 | −0.6 (4) | C4—C5—C9—O5 | −11.3 (4) |
C9—C5—C6—C1 | −175.5 (3) | C6—C5—C9—O5 | 163.6 (3) |
C2—C1—C6—C5 | −0.5 (4) | C4—C5—C9—O6 | 169.7 (3) |
C7—C1—C6—C5 | 178.7 (3) | C6—C5—C9—O6 | −15.5 (4) |
Co2—O2—C7—O1 | −2.3 (3) | N1iii—C10—C11—N1 | −56.1 (4) |
Co2—O2—C7—C1 | 177.8 (2) | C10—C11—N1—C10iii | 56.1 (4) |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x, −y+1, −z+1; (iii) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O5iv | 0.90 | 1.86 | 2.751 (4) | 168 |
N1—H1B···O9v | 0.90 | 2.03 | 2.880 (4) | 157 |
N1—H1B···O8vi | 0.90 | 2.42 | 3.011 (4) | 124 |
O7—H7A···O4vii | 0.85 | 1.78 | 2.622 (3) | 173 |
O7—H7B···O11 | 0.85 | 1.93 | 2.733 (4) | 157 |
O8—H8A···O1viii | 0.85 | 1.91 | 2.740 (3) | 162 |
O8—H8B···O6ix | 0.85 | 1.83 | 2.657 (3) | 166 |
O9—H9A···O6viii | 0.85 | 1.87 | 2.703 (3) | 165 |
O9—H9B···O4 | 0.85 | 1.83 | 2.640 (3) | 158 |
O11—H11A···O5ix | 0.85 | 1.91 | 2.722 (4) | 158 |
O11—H11B···O7x | 0.85 | 2.14 | 2.934 (4) | 156 |
Symmetry codes: (iv) x, y−1, z−1; (v) x+1, y−1, z; (vi) −x+1, −y+1, −z; (vii) x, y−1, z; (viii) x, y, z−1; (ix) −x+1, −y+2, −z+1; (x) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C4H12N2)[Co2(C9H3O6)2(H2O)6]·2H2O |
Mr | 764.38 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.1443 (11), 10.5308 (16), 10.5385 (16) |
α, β, γ (°) | 110.753 (2), 102.521 (2), 91.351 (2) |
V (Å3) | 719.40 (19) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.20 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX2 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.638, 0.883 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3896, 2503, 1957 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.598 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.098, 1.01 |
No. of reflections | 2503 |
No. of parameters | 211 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.56, −0.56 |
Computer programs: APEX2 (Bruker, 1997), APEX2, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O5i | 0.90 | 1.86 | 2.751 (4) | 168 |
N1—H1B···O9ii | 0.90 | 2.03 | 2.880 (4) | 157 |
N1—H1B···O8iii | 0.90 | 2.42 | 3.011 (4) | 124 |
O7—H7A···O4iv | 0.85 | 1.78 | 2.622 (3) | 173 |
O7—H7B···O11 | 0.85 | 1.93 | 2.733 (4) | 157 |
O8—H8A···O1v | 0.85 | 1.91 | 2.740 (3) | 162 |
O8—H8B···O6vi | 0.85 | 1.83 | 2.657 (3) | 166 |
O9—H9A···O6v | 0.85 | 1.87 | 2.703 (3) | 165 |
O9—H9B···O4 | 0.85 | 1.83 | 2.640 (3) | 158 |
O11—H11A···O5vi | 0.85 | 1.91 | 2.722 (4) | 158 |
O11—H11B···O7vii | 0.85 | 2.14 | 2.934 (4) | 156 |
Symmetry codes: (i) x, y−1, z−1; (ii) x+1, y−1, z; (iii) −x+1, −y+1, −z; (iv) x, y−1, z; (v) x, y, z−1; (vi) −x+1, −y+2, −z+1; (vii) −x+1, −y+1, −z+1. |
Benzene-1,3,5-tricarboxylate (BTC) usually plays the role of a bridging ligand in metal complexes. We present here the crystal structure of the title CoII complex, [(C18H18Co2O18)2−]n.n[C4H12N2]2+.2nH2O, (I). This determination corrects a previous report which formulated this compound as [C18H20Co2O18]n.n[C4H10N2].2nH2O, (II) (Chen & Liu, 2004). In compound (II), the C—O bond lengths [1.251 and 1.262 Å] of the uncoordinated carboxyl groups clearly indicate proton transfer from them to a piperazine ring, resulting in a [C4H12N2]2+ cation. However, in (II), the components were reported as neutral. In (I), the proton transfer is taken into account, and the protons are assigned to the piperazine ring.
Compound (I) contains two independent CoII atoms, which are located at the centres of different centrosymmetric CoO6 octahedra (Fig. 1). Each BTC ligand bridges two CoII atoms to form a polymeric zigzag chain, and these are further linked via O—H···O hydrogen bonds to form a three-dimensional network (Table 1). The two carboxylate groups of the BTC ligand coordinate to CoII atoms, one in a monodentate fashion and the other in a bidentate chelating fashion. The third carboxylate group is not coordinated to CoII. The packing of the chains forms quadrilateral pores, which are occupied by C4H12N2]2+ cations and free water molecules (Fig. 2).