Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015227/ob6072sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015227/ob6072Isup2.hkl |
CCDC reference: 175338
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.014 Å
- Disorder in main residue
- R factor = 0.033
- wR factor = 0.082
- Data-to-parameter ratio = 12.7
checkCIF results
No syntax errors found
Alert Level B:
PLAT_111 Alert B ADDSYM detects (pseudo) centre of symmetry ... 86 Perc Fit PLAT_113 Alert B ADDSYM suggests Pseudo/New Spacegroup ........ C2/c
Alert Level C:
PLAT_301 Alert C Main Residue Disorder ........................ 12.00 Perc. PLAT_420 Alert C D-H Without Acceptor N1 - H1B ? General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 29.98 From the CIF: _reflns_number_total 2259 Count of symmetry unique reflns 2230 Completeness (_total/calc) 101.30% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 29 Fraction of Friedel pairs measured 0.013 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
0 Alert Level A = Potentially serious problem
2 Alert Level B = Potential problem
2 Alert Level C = Please check
The title compound was prepared by adapting the procedures described by Nagata et al. (1985) and Nagata & Kanamori (2001). Crystals of (I) were obtained by a spontaneous evaporation of an aqueous solution at room temperature.
Systematic absences showed the space group of either C2/c or Cc. The former case could not locate non-coordinating anions and water molecules successfully, whereas the latter case gave a satisfactory result (C2/c, R = 8.0%; Cc, R = 3.3%). Comparison of the two solutions revealed that the [CoCl2(tmd)2]+ moiety has a pseudosymmetry of inversion but that the non-coordinating Cl- and water lower the lattice symmetry down to Cc (Fig. 3). The Flack (1983) parameter [0.13 (3)] is also consistent with the absence of inversion symmetry. Disorder of the two C atoms (C3 and C7) was suggested by their highly anisotropic displacement parameters, so that two positions for each atom were calculated by moving along the direction of the largest eigenvalue of the displacement tensor, with a fixed site occupation factor of 0.5. H atoms bonded to C and N atoms were placed geometrically and refined using a riding model via the SHELXL97 HFIX/AFIX 23 facility. The displacement parameter was set as 1.2 times that of the parent atom. H atoms of water were refined with a fixed O—H distance and H—O—H angle via SHELXL97 DFIX facility.
Data collection: AFC-7R Diffractometer Control Software (Rigaku, 1999); cell refinement: AFC-7R Diffractometer Control Software; data reduction: AFC-7R Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[CoCl2(C4H12N2)2]Cl·H2O | F(000) = 752 |
Mr = 359.61 | Dx = 1.561 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
a = 14.914 (5) Å | Cell parameters from 25 reflections |
b = 13.560 (6) Å | θ = 14.2–14.9° |
c = 8.994 (4) Å | µ = 1.64 mm−1 |
β = 122.75 (2)° | T = 296 K |
V = 1529.8 (11) Å3 | Prism, green |
Z = 4 | 0.20 × 0.20 × 0.20 mm |
Rigaku AFC-7R diffractometer | 2097 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 30.0°, θmin = 2.7° |
ω–2θ scans | h = 0→20 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→19 |
Tmin = 0.735, Tmax = 0.735 | l = −12→10 |
2259 measured reflections | 3 standard reflections every 60 min |
2259 independent reflections | intensity decay: 2.8% |
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)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0335P)2 + 2.6779P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2259 reflections | Δρmax = 1.00 e Å−3 |
178 parameters | Δρmin = −0.55 e Å−3 |
5 restraints | Absolute structure: (Flack, 1983), 29 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.13 (3) |
[CoCl2(C4H12N2)2]Cl·H2O | V = 1529.8 (11) Å3 |
Mr = 359.61 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 14.914 (5) Å | µ = 1.64 mm−1 |
b = 13.560 (6) Å | T = 296 K |
c = 8.994 (4) Å | 0.20 × 0.20 × 0.20 mm |
β = 122.75 (2)° |
Rigaku AFC-7R diffractometer | 2097 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
Tmin = 0.735, Tmax = 0.735 | 3 standard reflections every 60 min |
2259 measured reflections | intensity decay: 2.8% |
2259 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.082 | Δρmax = 1.00 e Å−3 |
S = 1.05 | Δρmin = −0.55 e Å−3 |
2259 reflections | Absolute structure: (Flack, 1983), 29 Friedel pairs |
178 parameters | Absolute structure parameter: 0.13 (3) |
5 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 | Occ. (<1) | |
Co | 0.42289 (14) | 0.25059 (5) | 0.0390 (2) | 0.02536 (10) | |
Cl1 | 0.30277 (14) | 0.18861 (11) | −0.2308 (2) | 0.0383 (3) | |
Cl2 | 0.54476 (14) | 0.30961 (12) | 0.3100 (2) | 0.0400 (3) | |
N1 | 0.4330 (4) | 0.1178 (4) | 0.1442 (7) | 0.0414 (12) | |
H1A | 0.4566 | 0.0757 | 0.0953 | 0.050* | |
H1B | 0.4847 | 0.1219 | 0.2597 | 0.050* | |
N2 | 0.3023 (4) | 0.2882 (4) | 0.0608 (6) | 0.0333 (10) | |
H2A | 0.2846 | 0.3502 | 0.0192 | 0.040* | |
H2B | 0.2472 | 0.2497 | −0.0158 | 0.040* | |
C1 | 0.3404 (7) | 0.0699 (5) | 0.1336 (11) | 0.0577 (19) | |
H1C | 0.3497 | −0.0010 | 0.1375 | 0.069* | |
H1D | 0.2765 | 0.0861 | 0.0207 | 0.069* | |
C2 | 0.3246 (9) | 0.1000 (6) | 0.2800 (13) | 0.086 (3) | |
H2C | 0.2519 | 0.0837 | 0.2419 | 0.103* | |
H2D | 0.3710 | 0.0591 | 0.3820 | 0.103* | |
C3A | 0.3418 (17) | 0.1945 (12) | 0.335 (2) | 0.057 (4) | 0.50 |
H3AA | 0.4187 | 0.2009 | 0.4085 | 0.068* | 0.50 |
H3AB | 0.3168 | 0.1991 | 0.4139 | 0.068* | 0.50 |
C3B | 0.2687 (8) | 0.1950 (8) | 0.2691 (11) | 0.0320 (19) | 0.50 |
H3BA | 0.1936 | 0.1868 | 0.1792 | 0.038* | 0.50 |
H3BB | 0.2745 | 0.2041 | 0.3809 | 0.038* | 0.50 |
C4 | 0.3048 (6) | 0.2863 (5) | 0.2297 (9) | 0.0472 (16) | |
H4A | 0.3505 | 0.3397 | 0.3040 | 0.057* | |
H4B | 0.2335 | 0.3003 | 0.2015 | 0.057* | |
N3 | 0.4171 (4) | 0.3824 (3) | −0.0629 (6) | 0.0320 (9) | |
H3C | 0.3703 | 0.3776 | −0.1804 | 0.038* | |
H3D | 0.3883 | 0.4241 | −0.0221 | 0.038* | |
N4 | 0.5462 (4) | 0.2143 (4) | 0.0190 (6) | 0.0331 (10) | |
H4C | 0.5992 | 0.2562 | 0.0901 | 0.040* | |
H4D | 0.5676 | 0.1542 | 0.0682 | 0.040* | |
C5 | 0.5146 (6) | 0.4322 (4) | −0.0365 (9) | 0.0448 (13) | |
H5A | 0.5745 | 0.4176 | 0.0819 | 0.054* | |
H5B | 0.5034 | 0.5030 | −0.0443 | 0.054* | |
C6 | 0.5438 (7) | 0.4019 (5) | −0.1691 (11) | 0.0579 (16) | |
H6A | 0.4864 | 0.4265 | −0.2827 | 0.069* | |
H6B | 0.6062 | 0.4407 | −0.1386 | 0.069* | |
C7A | 0.564 (3) | 0.3123 (16) | −0.200 (4) | 0.106 (9) | 0.50 |
H7AA | 0.6399 | 0.3125 | −0.1520 | 0.127* | 0.50 |
H7AB | 0.5296 | 0.3097 | −0.3272 | 0.127* | 0.50 |
C7B | 0.5020 (7) | 0.3022 (9) | −0.2556 (12) | 0.0244 (19) | 0.50 |
H7BA | 0.4254 | 0.3028 | −0.3096 | 0.029* | 0.50 |
H7BB | 0.5141 | 0.2971 | −0.3509 | 0.029* | 0.50 |
C8 | 0.5428 (6) | 0.2105 (4) | −0.1508 (9) | 0.0436 (15) | |
H8A | 0.4734 | 0.1871 | −0.2449 | 0.052* | |
H8B | 0.5961 | 0.1643 | −0.1386 | 0.052* | |
Cl3 | 0.25888 (14) | 0.47305 (13) | 0.5027 (2) | 0.0576 (3) | |
O | 0.0882 (5) | 0.4928 (4) | 0.0955 (8) | 0.0846 (19) | |
H1WA | 0.138 (3) | 0.497 (7) | 0.199 (3) | 0.101* | |
H1WB | 0.111 (5) | 0.484 (7) | 0.031 (7) | 0.101* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.02508 (17) | 0.02802 (18) | 0.02302 (16) | 0.00227 (13) | 0.01304 (13) | 0.00186 (12) |
Cl1 | 0.0326 (7) | 0.0460 (7) | 0.0301 (7) | −0.0009 (6) | 0.0129 (6) | −0.0062 (6) |
Cl2 | 0.0357 (8) | 0.0487 (8) | 0.0289 (6) | 0.0007 (6) | 0.0130 (6) | −0.0048 (6) |
N1 | 0.053 (3) | 0.035 (2) | 0.045 (3) | 0.005 (2) | 0.033 (3) | 0.010 (2) |
N2 | 0.035 (3) | 0.033 (2) | 0.039 (3) | 0.0050 (17) | 0.025 (2) | 0.0056 (17) |
C1 | 0.083 (5) | 0.036 (3) | 0.083 (5) | −0.010 (3) | 0.064 (5) | 0.000 (3) |
C2 | 0.147 (9) | 0.064 (4) | 0.118 (7) | 0.031 (5) | 0.117 (7) | 0.034 (5) |
C3A | 0.082 (13) | 0.061 (9) | 0.043 (8) | 0.004 (8) | 0.043 (9) | 0.003 (7) |
C3B | 0.022 (4) | 0.056 (6) | 0.019 (3) | 0.004 (4) | 0.012 (3) | 0.004 (3) |
C4 | 0.060 (4) | 0.061 (4) | 0.039 (3) | −0.008 (3) | 0.039 (3) | −0.012 (3) |
N3 | 0.034 (2) | 0.0303 (19) | 0.034 (2) | 0.0063 (17) | 0.021 (2) | 0.0040 (17) |
N4 | 0.030 (3) | 0.036 (2) | 0.034 (3) | 0.0069 (17) | 0.018 (2) | 0.0050 (17) |
C5 | 0.058 (4) | 0.033 (2) | 0.063 (3) | −0.004 (2) | 0.046 (3) | 0.000 (2) |
C6 | 0.080 (4) | 0.049 (3) | 0.079 (4) | −0.013 (3) | 0.065 (4) | −0.005 (3) |
C7A | 0.18 (3) | 0.083 (14) | 0.122 (19) | 0.048 (17) | 0.13 (2) | 0.048 (13) |
C7B | 0.016 (4) | 0.044 (5) | 0.017 (4) | 0.002 (4) | 0.011 (3) | −0.001 (4) |
C8 | 0.050 (4) | 0.040 (3) | 0.055 (4) | 0.009 (2) | 0.038 (4) | 0.000 (3) |
Cl3 | 0.0700 (9) | 0.0500 (6) | 0.0695 (8) | −0.0165 (7) | 0.0487 (8) | −0.0096 (7) |
O | 0.092 (4) | 0.067 (3) | 0.123 (5) | 0.031 (3) | 0.077 (4) | 0.042 (4) |
Co—Cl1 | 2.2582 (19) | C4—H4A | 0.9700 |
Co—Cl2 | 2.2571 (19) | C4—H4B | 0.9700 |
Co—N1 | 2.002 (5) | N3—H3C | 0.9000 |
Co—N2 | 1.978 (4) | N3—H3D | 0.9000 |
Co—N3 | 1.989 (4) | N3—C5 | 1.501 (7) |
Co—N4 | 2.003 (4) | N4—H4C | 0.9000 |
N1—H1A | 0.9000 | N4—H4D | 0.9000 |
N1—H1B | 0.9000 | N4—C8 | 1.501 (7) |
N1—C1 | 1.482 (8) | C5—H5A | 0.9700 |
N2—H2A | 0.9000 | C5—H5B | 0.9700 |
N2—H2B | 0.9000 | C5—C6 | 1.531 (8) |
N2—C4 | 1.500 (7) | C6—H6A | 0.9700 |
C1—H1C | 0.9700 | C6—H6B | 0.9700 |
C1—H1D | 0.9700 | C6—C7A | 1.32 (2) |
C1—C2 | 1.513 (9) | C6—C7B | 1.516 (13) |
C2—H2C | 0.9700 | C7A—H7AA | 0.9700 |
C2—H2D | 0.9700 | C7A—H7AB | 0.9700 |
C2—C3A | 1.346 (18) | C7A—C8 | 1.53 (2) |
C2—C3B | 1.509 (14) | C7B—H7BA | 0.9700 |
C3A—H3AA | 0.9700 | C7B—H7BB | 0.9700 |
C3A—H3AB | 0.9700 | C7B—C8 | 1.477 (13) |
C3A—C4 | 1.476 (17) | C8—H8A | 0.9700 |
C3B—H3BA | 0.9700 | C8—H8B | 0.9700 |
C3B—H3BB | 0.9700 | O—H1WA | 0.82 (5) |
C3B—C4 | 1.468 (13) | O—H1WB | 0.83 (8) |
Co···C1 | 3.062 (8) | N1···C4 | 3.325 (9) |
Co···C4 | 3.090 (7) | N1···N4 | 2.808 (7) |
Co···C5 | 3.066 (6) | N1···Oiii | 3.086 (8) |
Co···C8 | 3.116 (7) | N2···C1 | 3.018 (8) |
Cl1···N1 | 2.997 (6) | N2···C2 | 3.130 (10) |
Cl1···N2 | 2.953 (5) | N2···N3 | 2.804 (6) |
Cl1···C1 | 3.414 (8) | N2···Cl3iv | 3.288 (5) |
Cl1···N3 | 3.051 (5) | C1···C4 | 3.184 (10) |
Cl1···N4 | 3.086 (5) | C3A···C7Bv | 3.450 (19) |
Cl1···N4i | 3.482 (5) | C3B···C7Avi | 3.21 (3) |
Cl1···C7B | 3.459 (10) | N3···N4 | 2.813 (7) |
Cl1···C8 | 3.262 (8) | N3···C7A | 3.18 (3) |
Cl2···N1 | 3.013 (5) | N3···C7B | 2.857 (11) |
Cl2···N2 | 3.068 (5) | N3···C8 | 3.343 (8) |
Cl2···N2ii | 3.497 (5) | N3···Cl3iv | 3.356 (5) |
Cl2···C4 | 3.260 (8) | N4···C5 | 2.992 (8) |
Cl2···N3 | 2.990 (5) | N4···C6 | 3.045 (9) |
Cl2···N4 | 2.930 (5) | N4···Oiii | 3.070 (8) |
Cl2···C5 | 3.341 (7) | C5···C8 | 3.277 (9) |
N1···N2 | 2.849 (7) | Cl3···O | 3.143 (6) |
N1···C3A | 2.895 (19) | Cl3···Ovii | 3.113 (6) |
N1···C3B | 3.368 (11) | ||
Cl1—Co—Cl2 | 178.83 (8) | N2—C4—H4A | 108.0 |
Cl1—Co—N1 | 89.22 (16) | N2—C4—H4B | 108.0 |
Cl1—Co—N2 | 88.11 (15) | C3A—C4—H4A | 108.0 |
Cl1—Co—N3 | 91.62 (14) | C3A—C4—H4B | 108.0 |
Cl1—Co—N4 | 92.61 (15) | C3B—C4—H4A | 132.5 |
Cl2—Co—N1 | 89.85 (17) | C3B—C4—H4B | 74.5 |
Cl2—Co—N2 | 92.61 (15) | H4A—C4—H4B | 107.2 |
Cl2—Co—N3 | 89.30 (14) | Co—N3—H3C | 106.8 |
Cl2—Co—N4 | 86.68 (14) | Co—N3—H3D | 106.8 |
N1—Co—N2 | 91.4 (2) | Co—N3—C5 | 122.3 (4) |
N1—Co—N3 | 178.4 (3) | H3C—N3—H3D | 106.6 |
N1—Co—N4 | 89.0 (2) | H3C—N3—C5 | 106.8 |
N2—Co—N3 | 89.94 (18) | H3D—N3—C5 | 106.8 |
N2—Co—N4 | 179.1 (3) | Co—N4—H4C | 106.1 |
N3—Co—N4 | 89.59 (18) | Co—N4—H4D | 106.1 |
Co—N1—H1A | 106.8 | Co—N4—C8 | 124.9 (4) |
Co—N1—H1B | 106.8 | H4C—N4—H4D | 106.3 |
Co—N1—C1 | 122.3 (4) | H4C—N4—C8 | 106.1 |
H1A—N1—H1B | 106.6 | H4D—N4—C8 | 106.1 |
H1A—N1—C1 | 106.8 | N3—C5—H5A | 108.6 |
H1B—N1—C1 | 106.8 | N3—C5—H5B | 108.6 |
Co—N2—H2A | 106.1 | N3—C5—C6 | 114.5 (5) |
Co—N2—H2B | 106.1 | H5A—C5—H5B | 107.6 |
Co—N2—C4 | 124.8 (4) | H5A—C5—C6 | 108.6 |
H2A—N2—H2B | 106.3 | H5B—C5—C6 | 108.6 |
H2A—N2—C4 | 106.1 | C5—C6—H6A | 105.5 |
H2B—N2—C4 | 106.1 | C5—C6—H6B | 105.5 |
N1—C1—H1C | 108.8 | C5—C6—C7A | 127.2 (10) |
N1—C1—H1D | 108.8 | C5—C6—C7B | 115.3 (5) |
N1—C1—C2 | 113.8 (7) | H6A—C6—H6B | 106.1 |
H1C—C1—H1D | 107.7 | H6A—C6—C7A | 105.5 |
H1C—C1—C2 | 108.8 | H6A—C6—C7B | 83.3 |
H1D—C1—C2 | 108.8 | H6B—C6—C7A | 105.5 |
C1—C2—H2C | 107.6 | H6B—C6—C7B | 134.0 |
C1—C2—H2D | 107.6 | C6—C7A—H7AA | 104.3 |
C1—C2—C3A | 119.0 (8) | C6—C7A—H7AB | 104.3 |
C1—C2—C3B | 120.9 (7) | C6—C7A—C8 | 131.7 (15) |
H2C—C2—H2D | 107.0 | H7AA—C7A—H7AB | 105.6 |
H2C—C2—C3A | 107.6 | H7AA—C7A—C8 | 104.3 |
H2C—C2—C3B | 72.5 | H7AB—C7A—C8 | 104.3 |
H2D—C2—C3A | 107.6 | C6—C7B—H7BA | 107.2 |
H2D—C2—C3B | 129.5 | C6—C7B—H7BB | 107.2 |
C2—C3A—H3AA | 104.9 | C6—C7B—C8 | 120.7 (8) |
C2—C3A—H3AB | 104.9 | H7BA—C7B—H7BB | 106.8 |
C2—C3A—C4 | 129.7 (13) | H7BA—C7B—C8 | 107.2 |
H3AA—C3A—H3AB | 105.8 | H7BB—C7B—C8 | 107.2 |
H3AA—C3A—C4 | 104.9 | N4—C8—C7A | 111.3 (10) |
H3AB—C3A—C4 | 104.9 | N4—C8—C7B | 113.3 (5) |
C2—C3B—H3BA | 107.7 | N4—C8—H8A | 109.4 |
C2—C3B—H3BB | 107.7 | N4—C8—H8B | 109.4 |
C2—C3B—C4 | 118.3 (8) | C7A—C8—H8A | 109.4 |
H3BA—C3B—H3BB | 107.1 | C7A—C8—H8B | 109.4 |
H3BA—C3B—C4 | 107.7 | C7B—C8—H8A | 80.9 |
H3BB—C3B—C4 | 107.7 | C7B—C8—H8B | 130.2 |
N2—C4—C3A | 117.2 (7) | H8A—C8—H8B | 108.0 |
N2—C4—C3B | 116.6 (6) | H1WA—O—H1WB | 109 (7) |
Co—N1—C1—C2 | −86.0 (7) | N1—C1—C2—C3B | 81.6 (11) |
Co—N2—C4—C3A | −51.0 (12) | N2—Co—N1—C1 | 26.0 (5) |
Co—N2—C4—C3B | −91.9 (8) | N2—Co—N3—C5 | 148.9 (4) |
Co—N3—C5—C6 | 85.2 (6) | C1—C2—C3A—C4 | 47 (2) |
Co—N4—C8—C7A | 85.4 (14) | C1—C2—C3B—C4 | −50.9 (13) |
Co—N4—C8—C7B | 52.6 (8) | C2—C3A—C4—N2 | −38 (2) |
Cl1—Co—N1—C1 | −62.1 (5) | C2—C3B—C4—N2 | 57.6 (11) |
Cl1—Co—N2—C4 | 144.9 (5) | N3—Co—N2—C4 | −123.5 (5) |
Cl1—Co—N3—C5 | −123.0 (4) | N3—Co—N4—C8 | −60.6 (5) |
Cl1—Co—N4—C8 | 31.0 (4) | N3—C5—C6—C7A | −58 (2) |
Cl2—Co—N1—C1 | 118.6 (5) | N3—C5—C6—C7B | −23.4 (9) |
Cl2—Co—N2—C4 | −34.2 (5) | N4—Co—N1—C1 | −154.7 (5) |
Cl2—Co—N3—C5 | 56.3 (4) | N4—Co—N3—C5 | −30.4 (4) |
Cl2—Co—N4—C8 | −149.9 (5) | C5—C6—C7A—C8 | 15 (4) |
N1—Co—N2—C4 | 55.7 (5) | C5—C6—C7B—C8 | −67.6 (10) |
N1—Co—N4—C8 | 120.2 (5) | C6—C7A—C8—N4 | −30 (4) |
N1—C1—C2—C3A | 38.8 (15) | C6—C7B—C8—N4 | 47.7 (9) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x+1/2, y−1/2, z; (iv) x, −y+1, z−1/2; (v) x, y, z+1; (vi) x−1/2, −y+1/2, z+1/2; (vii) x, −y+1, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [CoCl2(C4H12N2)2]Cl·H2O |
Mr | 359.61 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 296 |
a, b, c (Å) | 14.914 (5), 13.560 (6), 8.994 (4) |
β (°) | 122.75 (2) |
V (Å3) | 1529.8 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.64 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.735, 0.735 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2259, 2259, 2097 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.082, 1.05 |
No. of reflections | 2259 |
No. of parameters | 178 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.00, −0.55 |
Absolute structure | (Flack, 1983), 29 Friedel pairs |
Absolute structure parameter | 0.13 (3) |
Computer programs: AFC-7R Diffractometer Control Software (Rigaku, 1999), AFC-7R Diffractometer Control Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
Co—Cl1 | 2.2582 (19) | Co—N2 | 1.978 (4) |
Co—Cl2 | 2.2571 (19) | Co—N3 | 1.989 (4) |
Co—N1 | 2.002 (5) | Co—N4 | 2.003 (4) |
Cl1—Co—Cl2 | 178.83 (8) | Cl2—Co—N4 | 86.68 (14) |
Cl1—Co—N1 | 89.22 (16) | N1—Co—N2 | 91.4 (2) |
Cl1—Co—N2 | 88.11 (15) | N1—Co—N3 | 178.4 (3) |
Cl1—Co—N3 | 91.62 (14) | N1—Co—N4 | 89.0 (2) |
Cl1—Co—N4 | 92.61 (15) | N2—Co—N3 | 89.94 (18) |
Cl2—Co—N1 | 89.85 (17) | N2—Co—N4 | 179.1 (3) |
Cl2—Co—N2 | 92.61 (15) | N3—Co—N4 | 89.59 (18) |
Cl2—Co—N3 | 89.30 (14) |
1,4-Butanediamine (tmd: putrescin or tetramethylenediamine) is a biogenic diamine. The interaction between transition metals and tmd is of interest from the viewpoint of bioinorganic chemistry (Gasowska et al., 2000). However, only a few structures have been reported for transition metal complexes of tmd (Sato et al., 1974; Shimoi et al., 1988; Kurachi & Ohba, 1992). We report here the structure of the title compound, trans-[CoIIICl2(tmd)2]Cl·H2O, (I).
The complex cation (Fig. 1) has a pseudosymmetry of inversion and thus the conformations of the seven-membered chelate rings are almost identical. One of the C atoms of the two tmd chelates (C3 and C7, respectively) is disordered with equal occupancy factors. The C3b and C7a positions correspond to the twist-chair conformation of the cycloheptane ring, and the C3a and C7b positions to the twist-boat conformation (Fig. 2), though the observed conformations deviate from the ideal conformations to a considerable extent (Hendrickson, 1961).
The Co—N bond distances range from 1.978 (4) to 2.003 (4) Å and are comparable with those found in [Co(NO2)2(tmd)2]NO3 (Shimoi et al., 1988). The bite angles of the seven-membered chelate rings are 91.4 (2) and 89.59 (18)° and are also normal.