Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037579/at2358sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037579/at2358Isup2.hkl |
CCDC reference: 660056
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.015 Å
- R factor = 0.075
- wR factor = 0.213
- Data-to-parameter ratio = 19.2
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low .... 38 Perc.
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.141 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.14 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.69 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.59 Ratio PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.56 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for C14 - C15 .. 5.50 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C14 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C20 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C30 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C11 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C19 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C27 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl1 PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 15 PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2A ... ? PLAT420_ALERT_2_C D-H Without Acceptor N4 - H4A ... ?
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.688 Tmax scaled 0.208 Tmin scaled 0.203 PLAT793_ALERT_1_G Check the Absolute Configuration of N2 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of N4 = ... S PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1 (9) 4.01 PLAT794_ALERT_5_G Check Predicted Bond Valency for Co2 (9) 4.00 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 24
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 16 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 11 ALERT type 2 Indicator that the structure model may be wrong or deficient 6 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
3,5-Dibromosalicylaldehyde (0.2 mmol, 56.0 mg), N-cyclohexyl-1,3-diaminopropane (0.2 mmol, 31.0 mg), and Cu(ClO4)·7H2O (0.1 mmol, 39.0 mg) were dissolved in a methanol solution (20 ml). The mixture was stirred for half an hour at room temperature, giving a brown solution. After allowing the solution to stand in air for a week, brown block-like crystals were formed.
H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å, N—H = 0.91 Å, and with Uiso(H) set at 1.2Ueq(C,N). The ration of observed/unique reflections is low (38%), and the value of Rint is 0.14, due to the poor quality of the diffraction.
Cobalt complexes with Schiff base ligands have received much attention in recent years (Sacconi et al., 1965; Zakrzewski & Sacconi, 1968). Some of the complexes have been found to have pharmacological and antitumor properties (Hodnett et al., 1971; Hodnett & Dunn, 1972; Takeuchi et al., 1998). We have recently reported a few transition metal complexes (Diao, Huang et al., 2007; Diao, Shu et al., 2007; Diao, 2007a,b). As an extension of the work on the crystal structures of such complexes, we report herein the crystal structure of the title complex.
The complex is a centrosymmetric mononuclear Schiff base cobalt(III) complex, which consists of a cobalt(III) cation and a perchlorate anion. The Co atom is hexacoordinated by two O and four N atoms from two Schiff base ligands, forming an octahedral geometry (Fig. 1).
For related literature, see: Diao (2007a,b); Diao, Huang et al. (2007); Diao, Shu et al. (2007); Hodnett & Dunn (1972); Hodnett et al. (1971); Sacconi et al. (1965); Takeuchi et al. (1998); Zakrzewski & Sacconi (1968).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Co(C16H21Br2N2O)2]ClO4 | F(000) = 1976 |
Mr = 992.72 | Dx = 1.781 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1447 reflections |
a = 16.208 (3) Å | θ = 2.3–24.5° |
b = 12.801 (3) Å | µ = 4.90 mm−1 |
c = 18.060 (4) Å | T = 298 K |
β = 98.91 (3)° | Block, brown |
V = 3701.8 (14) Å3 | 0.33 × 0.32 × 0.32 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 8354 independent reflections |
Radiation source: fine-focus sealed tube | 3168 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.142 |
ω scans | θmax = 27.5°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −21→21 |
Tmin = 0.295, Tmax = 0.303 | k = −16→16 |
30784 measured reflections | l = −22→23 |
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)] = 0.075 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.213 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0821P)2] where P = (Fo2 + 2Fc2)/3 |
8354 reflections | (Δ/σ)max < 0.001 |
436 parameters | Δρmax = 1.12 e Å−3 |
24 restraints | Δρmin = −0.76 e Å−3 |
[Co(C16H21Br2N2O)2]ClO4 | V = 3701.8 (14) Å3 |
Mr = 992.72 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.208 (3) Å | µ = 4.90 mm−1 |
b = 12.801 (3) Å | T = 298 K |
c = 18.060 (4) Å | 0.33 × 0.32 × 0.32 mm |
β = 98.91 (3)° |
Bruker SMART CCD area-detector diffractometer | 8354 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 3168 reflections with I > 2σ(I) |
Tmin = 0.295, Tmax = 0.303 | Rint = 0.142 |
30784 measured reflections |
R[F2 > 2σ(F2)] = 0.075 | 24 restraints |
wR(F2) = 0.213 | H-atom parameters constrained |
S = 0.96 | Δρmax = 1.12 e Å−3 |
8354 reflections | Δρmin = −0.76 e Å−3 |
436 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 | 0.0388 (4) | |
Co2 | 0.0000 | 0.0000 | 0.5000 | 0.0351 (4) | |
Br1 | 0.15360 (8) | 0.79302 (11) | 0.28990 (8) | 0.0947 (5) | |
Br2 | 0.23554 (7) | 0.37506 (9) | 0.36766 (7) | 0.0779 (4) | |
Br3 | 0.40645 (7) | 0.02431 (11) | 0.36755 (8) | 0.0917 (5) | |
Br4 | 0.06878 (8) | 0.13017 (10) | 0.26659 (6) | 0.0795 (4) | |
Cl1 | 0.35696 (18) | 0.8654 (3) | 0.67797 (19) | 0.0731 (9) | |
O1 | 0.3871 (4) | 0.4778 (4) | 0.4574 (3) | 0.0465 (16) | |
O2 | 0.0500 (4) | 0.0608 (4) | 0.4218 (3) | 0.0443 (15) | |
O3 | 0.3804 (8) | 0.8974 (11) | 0.6126 (7) | 0.175 (5) | |
O4 | 0.2889 (8) | 0.9120 (11) | 0.6912 (7) | 0.174 (5) | |
O5 | 0.4137 (12) | 0.9087 (15) | 0.7300 (11) | 0.256 (8) | |
O6 | 0.3674 (9) | 0.7618 (13) | 0.6982 (9) | 0.206 (6) | |
N1 | 0.4761 (5) | 0.6429 (6) | 0.5224 (4) | 0.0442 (19) | |
N2 | 0.4722 (5) | 0.4576 (6) | 0.5999 (4) | 0.052 (2) | |
H2A | 0.5201 | 0.4265 | 0.6224 | 0.062* | |
N3 | 0.1045 (4) | 0.0001 (5) | 0.5661 (4) | 0.0374 (17) | |
N4 | −0.0236 (4) | 0.1438 (6) | 0.5369 (4) | 0.0453 (19) | |
H4A | −0.0719 | 0.1322 | 0.5553 | 0.054* | |
C1 | 0.3510 (5) | 0.6588 (7) | 0.4321 (5) | 0.044 (2) | |
C2 | 0.3363 (6) | 0.5496 (8) | 0.4234 (5) | 0.046 (2) | |
C3 | 0.2619 (6) | 0.5196 (7) | 0.3778 (6) | 0.053 (3) | |
C4 | 0.2069 (6) | 0.5910 (9) | 0.3389 (5) | 0.059 (3) | |
H4 | 0.1574 | 0.5690 | 0.3101 | 0.071* | |
C5 | 0.2281 (7) | 0.6968 (9) | 0.3443 (6) | 0.064 (3) | |
C6 | 0.2971 (6) | 0.7307 (8) | 0.3913 (6) | 0.054 (3) | |
H6 | 0.3083 | 0.8019 | 0.3963 | 0.064* | |
C7 | 0.4161 (6) | 0.6962 (7) | 0.4881 (5) | 0.045 (2) | |
H7 | 0.4144 | 0.7666 | 0.5006 | 0.054* | |
C8 | 0.5282 (6) | 0.6920 (8) | 0.5894 (5) | 0.056 (3) | |
H8A | 0.5066 | 0.7610 | 0.5976 | 0.068* | |
H8B | 0.5851 | 0.7000 | 0.5798 | 0.068* | |
C9 | 0.5282 (8) | 0.6267 (9) | 0.6591 (6) | 0.078 (4) | |
H9A | 0.5209 | 0.6726 | 0.7003 | 0.094* | |
H9B | 0.5823 | 0.5933 | 0.6715 | 0.094* | |
C10 | 0.4603 (7) | 0.5423 (8) | 0.6518 (6) | 0.070 (3) | |
H10A | 0.4586 | 0.5125 | 0.7010 | 0.084* | |
H10B | 0.4066 | 0.5749 | 0.6352 | 0.084* | |
C11 | 0.4077 (6) | 0.3707 (7) | 0.5978 (5) | 0.046 (2) | |
H11 | 0.4015 | 0.3405 | 0.5474 | 0.055* | |
C12 | 0.4408 (7) | 0.2828 (8) | 0.6527 (6) | 0.071 (3) | |
H12A | 0.4481 | 0.3086 | 0.7038 | 0.085* | |
H12B | 0.4945 | 0.2585 | 0.6422 | 0.085* | |
C13 | 0.3771 (9) | 0.1920 (8) | 0.6434 (7) | 0.089 (4) | |
H13A | 0.3740 | 0.1624 | 0.5936 | 0.107* | |
H13B | 0.3958 | 0.1376 | 0.6795 | 0.107* | |
C14 | 0.2907 (10) | 0.2297 (12) | 0.6549 (8) | 0.114 (6) | |
H14A | 0.2515 | 0.1720 | 0.6475 | 0.136* | |
H14B | 0.2928 | 0.2549 | 0.7058 | 0.136* | |
C15 | 0.2627 (8) | 0.3127 (10) | 0.6025 (8) | 0.090 (4) | |
H15A | 0.2078 | 0.3356 | 0.6107 | 0.108* | |
H15B | 0.2575 | 0.2854 | 0.5519 | 0.108* | |
C16 | 0.3215 (6) | 0.4068 (8) | 0.6094 (7) | 0.076 (3) | |
H16A | 0.3007 | 0.4589 | 0.5721 | 0.091* | |
H16B | 0.3242 | 0.4382 | 0.6586 | 0.091* | |
C17 | 0.1947 (6) | 0.0204 (6) | 0.4686 (5) | 0.044 (2) | |
C18 | 0.1278 (6) | 0.0523 (7) | 0.4124 (5) | 0.045 (2) | |
C19 | 0.1514 (6) | 0.0796 (7) | 0.3438 (5) | 0.048 (2) | |
C20 | 0.2327 (8) | 0.0718 (8) | 0.3306 (6) | 0.070 (3) | |
H20 | 0.2460 | 0.0901 | 0.2840 | 0.084* | |
C21 | 0.2949 (6) | 0.0365 (8) | 0.3870 (7) | 0.060 (3) | |
C22 | 0.2758 (6) | 0.0135 (7) | 0.4557 (6) | 0.053 (3) | |
H22 | 0.3177 | −0.0070 | 0.4942 | 0.064* | |
C23 | 0.1772 (5) | 0.0054 (7) | 0.5443 (5) | 0.045 (2) | |
H23 | 0.2233 | −0.0012 | 0.5816 | 0.054* | |
C24 | 0.1034 (6) | 0.0094 (7) | 0.6471 (5) | 0.049 (2) | |
H24A | 0.1603 | 0.0145 | 0.6731 | 0.059* | |
H24B | 0.0785 | −0.0530 | 0.6647 | 0.059* | |
C25 | 0.0551 (7) | 0.1031 (8) | 0.6650 (5) | 0.061 (3) | |
H25A | 0.0881 | 0.1397 | 0.7064 | 0.073* | |
H25B | 0.0048 | 0.0788 | 0.6825 | 0.073* | |
C26 | 0.0299 (7) | 0.1804 (8) | 0.6032 (5) | 0.063 (3) | |
H26A | 0.0020 | 0.2381 | 0.6237 | 0.076* | |
H26B | 0.0805 | 0.2079 | 0.5879 | 0.076* | |
C27 | −0.0514 (5) | 0.2239 (6) | 0.4777 (5) | 0.040 (2) | |
H27 | −0.0680 | 0.1866 | 0.4303 | 0.048* | |
C28 | −0.1276 (6) | 0.2791 (8) | 0.4964 (6) | 0.063 (3) | |
H28A | −0.1133 | 0.3175 | 0.5430 | 0.076* | |
H28B | −0.1703 | 0.2283 | 0.5030 | 0.076* | |
C29 | −0.1616 (8) | 0.3557 (10) | 0.4322 (7) | 0.095 (4) | |
H29A | −0.1818 | 0.3163 | 0.3871 | 0.113* | |
H29B | −0.2081 | 0.3948 | 0.4460 | 0.113* | |
C30 | −0.0944 (10) | 0.4309 (10) | 0.4163 (8) | 0.105 (5) | |
H30A | −0.1159 | 0.4736 | 0.3733 | 0.126* | |
H30B | −0.0796 | 0.4768 | 0.4590 | 0.126* | |
C31 | −0.0177 (8) | 0.3742 (9) | 0.4010 (7) | 0.083 (4) | |
H31A | 0.0250 | 0.4245 | 0.3938 | 0.100* | |
H31B | −0.0311 | 0.3338 | 0.3553 | 0.100* | |
C32 | 0.0156 (6) | 0.3016 (8) | 0.4656 (6) | 0.067 (3) | |
H32A | 0.0644 | 0.2648 | 0.4542 | 0.080* | |
H32B | 0.0320 | 0.3421 | 0.5109 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0420 (10) | 0.0357 (10) | 0.0374 (10) | 0.0002 (8) | 0.0021 (8) | −0.0028 (8) |
Co2 | 0.0375 (9) | 0.0342 (9) | 0.0329 (10) | 0.0023 (7) | 0.0031 (7) | −0.0017 (8) |
Br1 | 0.0855 (9) | 0.0993 (10) | 0.0913 (10) | 0.0441 (8) | −0.0112 (8) | 0.0101 (8) |
Br2 | 0.0671 (8) | 0.0720 (8) | 0.0864 (9) | −0.0146 (6) | −0.0138 (6) | −0.0125 (7) |
Br3 | 0.0655 (8) | 0.1031 (11) | 0.1179 (12) | −0.0095 (7) | 0.0496 (8) | −0.0105 (8) |
Br4 | 0.0935 (9) | 0.0932 (9) | 0.0530 (7) | 0.0052 (7) | 0.0156 (6) | 0.0266 (7) |
Cl1 | 0.0549 (18) | 0.088 (2) | 0.077 (2) | 0.0211 (16) | 0.0111 (16) | 0.0037 (18) |
O1 | 0.053 (4) | 0.039 (4) | 0.046 (4) | −0.002 (3) | 0.000 (3) | 0.000 (3) |
O2 | 0.052 (4) | 0.046 (4) | 0.036 (4) | 0.000 (3) | 0.009 (3) | 0.005 (3) |
O3 | 0.189 (8) | 0.200 (9) | 0.152 (8) | 0.061 (7) | 0.080 (7) | 0.013 (7) |
O4 | 0.147 (7) | 0.231 (9) | 0.156 (8) | 0.089 (7) | 0.065 (6) | 0.045 (7) |
O5 | 0.248 (11) | 0.246 (11) | 0.256 (11) | −0.018 (9) | −0.018 (9) | −0.007 (9) |
O6 | 0.214 (9) | 0.169 (9) | 0.239 (10) | −0.003 (8) | 0.040 (8) | 0.021 (8) |
N1 | 0.042 (5) | 0.041 (5) | 0.050 (5) | 0.002 (4) | 0.007 (4) | −0.008 (4) |
N2 | 0.067 (5) | 0.040 (5) | 0.048 (5) | 0.001 (4) | 0.008 (4) | 0.001 (4) |
N3 | 0.042 (4) | 0.032 (4) | 0.035 (4) | 0.007 (3) | −0.004 (3) | −0.006 (3) |
N4 | 0.048 (5) | 0.051 (5) | 0.034 (4) | 0.005 (4) | −0.001 (4) | −0.007 (4) |
C1 | 0.041 (5) | 0.044 (6) | 0.047 (6) | 0.007 (5) | 0.010 (5) | −0.001 (5) |
C2 | 0.049 (6) | 0.050 (6) | 0.039 (6) | −0.002 (5) | 0.008 (5) | −0.004 (5) |
C3 | 0.048 (6) | 0.051 (7) | 0.059 (7) | −0.002 (5) | 0.001 (5) | 0.000 (5) |
C4 | 0.046 (6) | 0.088 (9) | 0.043 (6) | −0.002 (6) | 0.000 (5) | −0.013 (6) |
C5 | 0.062 (7) | 0.066 (8) | 0.062 (8) | 0.030 (6) | 0.006 (6) | 0.014 (6) |
C6 | 0.056 (7) | 0.041 (6) | 0.065 (7) | 0.015 (5) | 0.016 (6) | 0.002 (5) |
C7 | 0.044 (6) | 0.033 (5) | 0.060 (7) | −0.001 (5) | 0.016 (5) | −0.010 (5) |
C8 | 0.062 (7) | 0.052 (7) | 0.052 (7) | 0.001 (5) | −0.001 (5) | −0.016 (5) |
C9 | 0.105 (10) | 0.073 (8) | 0.054 (8) | −0.006 (7) | 0.002 (7) | −0.022 (6) |
C10 | 0.095 (9) | 0.075 (8) | 0.045 (7) | −0.012 (7) | 0.026 (6) | −0.012 (6) |
C11 | 0.055 (6) | 0.045 (6) | 0.036 (5) | −0.005 (5) | 0.004 (4) | 0.014 (5) |
C12 | 0.089 (8) | 0.054 (7) | 0.064 (7) | −0.015 (6) | −0.004 (6) | 0.011 (6) |
C13 | 0.153 (13) | 0.038 (7) | 0.066 (8) | −0.009 (8) | −0.014 (9) | 0.010 (6) |
C14 | 0.141 (14) | 0.101 (12) | 0.118 (12) | −0.083 (11) | 0.078 (11) | −0.030 (10) |
C15 | 0.085 (9) | 0.072 (9) | 0.119 (12) | −0.022 (7) | 0.036 (8) | 0.015 (9) |
C16 | 0.052 (7) | 0.073 (8) | 0.107 (10) | 0.011 (6) | 0.026 (7) | 0.003 (7) |
C17 | 0.056 (6) | 0.032 (5) | 0.043 (6) | 0.003 (4) | 0.006 (5) | −0.003 (4) |
C18 | 0.063 (7) | 0.028 (5) | 0.044 (6) | −0.002 (5) | 0.007 (5) | −0.006 (4) |
C19 | 0.065 (7) | 0.050 (6) | 0.035 (6) | −0.004 (5) | 0.019 (5) | 0.006 (5) |
C20 | 0.091 (9) | 0.069 (8) | 0.064 (8) | −0.012 (7) | 0.052 (7) | −0.007 (6) |
C21 | 0.046 (6) | 0.066 (7) | 0.071 (8) | −0.011 (5) | 0.018 (6) | −0.002 (6) |
C22 | 0.049 (6) | 0.040 (6) | 0.072 (8) | −0.008 (5) | 0.017 (5) | −0.015 (5) |
C23 | 0.031 (5) | 0.042 (6) | 0.058 (7) | −0.007 (4) | −0.005 (5) | −0.002 (5) |
C24 | 0.055 (6) | 0.053 (6) | 0.037 (6) | 0.010 (5) | −0.003 (5) | 0.003 (5) |
C25 | 0.081 (8) | 0.061 (7) | 0.036 (6) | 0.013 (6) | −0.009 (5) | −0.008 (5) |
C26 | 0.082 (8) | 0.054 (7) | 0.048 (7) | 0.017 (6) | −0.006 (6) | −0.013 (5) |
C27 | 0.051 (6) | 0.029 (5) | 0.041 (6) | 0.001 (4) | 0.006 (4) | −0.007 (4) |
C28 | 0.061 (7) | 0.067 (7) | 0.066 (7) | 0.007 (6) | 0.023 (6) | −0.011 (6) |
C29 | 0.103 (10) | 0.096 (11) | 0.084 (10) | 0.060 (9) | 0.012 (8) | 0.005 (8) |
C30 | 0.143 (14) | 0.055 (9) | 0.112 (12) | 0.016 (9) | 0.003 (10) | 0.040 (8) |
C31 | 0.100 (10) | 0.064 (8) | 0.082 (9) | −0.022 (7) | 0.001 (8) | 0.022 (7) |
C32 | 0.070 (8) | 0.065 (8) | 0.063 (7) | −0.018 (6) | 0.006 (6) | 0.008 (6) |
Co1—O1 | 1.894 (6) | C11—C12 | 1.541 (12) |
Co1—O1i | 1.894 (6) | C11—H11 | 0.9800 |
Co1—N1 | 1.926 (7) | C12—C13 | 1.546 (14) |
Co1—N1i | 1.926 (7) | C12—H12A | 0.9700 |
Co1—N2i | 2.002 (7) | C12—H12B | 0.9700 |
Co1—N2 | 2.002 (7) | C13—C14 | 1.526 (17) |
Co2—O2ii | 1.900 (6) | C13—H13A | 0.9700 |
Co2—O2 | 1.900 (6) | C13—H13B | 0.9700 |
Co2—N3ii | 1.915 (7) | C14—C15 | 1.449 (18) |
Co2—N3 | 1.915 (7) | C14—H14A | 0.9700 |
Co2—N4ii | 2.014 (7) | C14—H14B | 0.9700 |
Co2—N4 | 2.014 (7) | C15—C16 | 1.529 (15) |
Br1—C5 | 1.889 (9) | C15—H15A | 0.9700 |
Br2—C3 | 1.901 (9) | C15—H15B | 0.9700 |
Br3—C21 | 1.900 (10) | C16—H16A | 0.9700 |
Br4—C19 | 1.891 (10) | C16—H16B | 0.9700 |
Cl1—O4 | 1.309 (11) | C17—C22 | 1.372 (12) |
Cl1—O5 | 1.330 (18) | C17—C18 | 1.425 (12) |
Cl1—O3 | 1.359 (12) | C17—C23 | 1.452 (13) |
Cl1—O6 | 1.380 (15) | C18—C19 | 1.397 (12) |
O1—C2 | 1.319 (10) | C19—C20 | 1.379 (13) |
O2—C18 | 1.303 (10) | C20—C21 | 1.394 (14) |
N1—C7 | 1.268 (10) | C20—H20 | 0.9300 |
N1—C8 | 1.503 (11) | C21—C22 | 1.358 (14) |
N2—C10 | 1.465 (12) | C22—H22 | 0.9300 |
N2—C11 | 1.522 (11) | C23—H23 | 0.9300 |
N2—H2A | 0.9100 | C24—C25 | 1.495 (12) |
N3—C23 | 1.300 (10) | C24—H24A | 0.9700 |
N3—C24 | 1.470 (11) | C24—H24B | 0.9700 |
N4—C26 | 1.443 (11) | C25—C26 | 1.500 (13) |
N4—C27 | 1.500 (10) | C25—H25A | 0.9700 |
N4—H4A | 0.9100 | C25—H25B | 0.9700 |
C1—C6 | 1.397 (12) | C26—H26A | 0.9700 |
C1—C2 | 1.423 (12) | C26—H26B | 0.9700 |
C1—C7 | 1.427 (12) | C27—C28 | 1.507 (12) |
C2—C3 | 1.405 (12) | C27—C32 | 1.513 (12) |
C3—C4 | 1.389 (13) | C27—H27 | 0.9800 |
C4—C5 | 1.397 (14) | C28—C29 | 1.553 (14) |
C4—H4 | 0.9300 | C28—H28A | 0.9700 |
C5—C6 | 1.368 (13) | C28—H28B | 0.9700 |
C6—H6 | 0.9300 | C29—C30 | 1.513 (17) |
C7—H7 | 0.9300 | C29—H29A | 0.9700 |
C8—C9 | 1.510 (14) | C29—H29B | 0.9700 |
C8—H8A | 0.9700 | C30—C31 | 1.501 (16) |
C8—H8B | 0.9700 | C30—H30A | 0.9700 |
C9—C10 | 1.534 (14) | C30—H30B | 0.9700 |
C9—H9A | 0.9700 | C31—C32 | 1.523 (14) |
C9—H9B | 0.9700 | C31—H31A | 0.9700 |
C10—H10A | 0.9700 | C31—H31B | 0.9700 |
C10—H10B | 0.9700 | C32—H32A | 0.9700 |
C11—C16 | 1.518 (12) | C32—H32B | 0.9700 |
O1—Co1—O1i | 180.00 (16) | C13—C12—H12A | 110.0 |
O1—Co1—N1 | 90.8 (3) | C11—C12—H12B | 110.0 |
O1i—Co1—N1 | 89.2 (3) | C13—C12—H12B | 110.0 |
O1—Co1—N1i | 89.2 (3) | H12A—C12—H12B | 108.4 |
O1i—Co1—N1i | 90.8 (3) | C14—C13—C12 | 111.0 (10) |
N1—Co1—N1i | 180.000 (1) | C14—C13—H13A | 109.4 |
O1—Co1—N2i | 90.7 (3) | C12—C13—H13A | 109.4 |
O1i—Co1—N2i | 89.3 (3) | C14—C13—H13B | 109.4 |
N1—Co1—N2i | 90.7 (3) | C12—C13—H13B | 109.4 |
N1i—Co1—N2i | 89.3 (3) | H13A—C13—H13B | 108.0 |
O1—Co1—N2 | 89.3 (3) | C15—C14—C13 | 110.1 (10) |
O1i—Co1—N2 | 90.7 (3) | C15—C14—H14A | 109.6 |
N1—Co1—N2 | 89.3 (3) | C13—C14—H14A | 109.6 |
N1i—Co1—N2 | 90.7 (3) | C15—C14—H14B | 109.6 |
N2i—Co1—N2 | 180.000 (2) | C13—C14—H14B | 109.6 |
O2ii—Co2—O2 | 180.000 (1) | H14A—C14—H14B | 108.2 |
O2ii—Co2—N3ii | 91.4 (3) | C14—C15—C16 | 113.4 (11) |
O2—Co2—N3ii | 88.6 (3) | C14—C15—H15A | 108.9 |
O2ii—Co2—N3 | 88.6 (3) | C16—C15—H15A | 108.9 |
O2—Co2—N3 | 91.4 (3) | C14—C15—H15B | 108.9 |
N3ii—Co2—N3 | 180.000 (1) | C16—C15—H15B | 108.9 |
O2ii—Co2—N4ii | 89.8 (3) | H15A—C15—H15B | 107.7 |
O2—Co2—N4ii | 90.2 (3) | C11—C16—C15 | 108.9 (9) |
N3ii—Co2—N4ii | 89.3 (3) | C11—C16—H16A | 109.9 |
N3—Co2—N4ii | 90.7 (3) | C15—C16—H16A | 109.9 |
O2ii—Co2—N4 | 90.2 (3) | C11—C16—H16B | 109.9 |
O2—Co2—N4 | 89.8 (3) | C15—C16—H16B | 109.9 |
N3ii—Co2—N4 | 90.7 (3) | H16A—C16—H16B | 108.3 |
N3—Co2—N4 | 89.3 (3) | C22—C17—C18 | 122.8 (9) |
N4ii—Co2—N4 | 180.0 (4) | C22—C17—C23 | 118.9 (9) |
O4—Cl1—O5 | 101.0 (11) | C18—C17—C23 | 118.0 (8) |
O4—Cl1—O3 | 112.3 (8) | O2—C18—C19 | 119.9 (9) |
O5—Cl1—O3 | 103.5 (11) | O2—C18—C17 | 125.2 (8) |
O4—Cl1—O6 | 117.5 (9) | C19—C18—C17 | 114.9 (9) |
O5—Cl1—O6 | 99.8 (10) | C20—C19—C18 | 122.4 (10) |
O3—Cl1—O6 | 118.8 (9) | C20—C19—Br4 | 118.9 (8) |
C2—O1—Co1 | 125.3 (6) | C18—C19—Br4 | 118.7 (8) |
C18—O2—Co2 | 126.5 (6) | C19—C20—C21 | 120.0 (9) |
C7—N1—C8 | 117.5 (8) | C19—C20—H20 | 120.0 |
C7—N1—Co1 | 124.9 (6) | C21—C20—H20 | 120.0 |
C8—N1—Co1 | 117.4 (6) | C22—C21—C20 | 119.8 (10) |
C10—N2—C11 | 113.5 (8) | C22—C21—Br3 | 120.6 (9) |
C10—N2—Co1 | 116.5 (6) | C20—C21—Br3 | 119.6 (9) |
C11—N2—Co1 | 115.1 (5) | C21—C22—C17 | 120.1 (10) |
C10—N2—H2A | 103.1 | C21—C22—H22 | 120.0 |
C11—N2—H2A | 103.1 | C17—C22—H22 | 120.0 |
Co1—N2—H2A | 103.1 | N3—C23—C17 | 127.7 (8) |
C23—N3—C24 | 116.7 (7) | N3—C23—H23 | 116.2 |
C23—N3—Co2 | 124.5 (6) | C17—C23—H23 | 116.2 |
C24—N3—Co2 | 118.3 (6) | N3—C24—C25 | 111.6 (7) |
C26—N4—C27 | 116.5 (7) | N3—C24—H24A | 109.3 |
C26—N4—Co2 | 116.8 (6) | C25—C24—H24A | 109.3 |
C27—N4—Co2 | 116.1 (5) | N3—C24—H24B | 109.3 |
C26—N4—H4A | 101.0 | C25—C24—H24B | 109.3 |
C27—N4—H4A | 101.0 | H24A—C24—H24B | 108.0 |
Co2—N4—H4A | 101.0 | C24—C25—C26 | 117.3 (8) |
C6—C1—C2 | 120.6 (9) | C24—C25—H25A | 108.0 |
C6—C1—C7 | 119.0 (9) | C26—C25—H25A | 108.0 |
C2—C1—C7 | 120.0 (8) | C24—C25—H25B | 108.0 |
O1—C2—C3 | 120.0 (8) | C26—C25—H25B | 108.0 |
O1—C2—C1 | 123.5 (8) | H25A—C25—H25B | 107.2 |
C3—C2—C1 | 116.5 (9) | N4—C26—C25 | 117.6 (8) |
C4—C3—C2 | 122.9 (9) | N4—C26—H26A | 107.9 |
C4—C3—Br2 | 118.3 (8) | C25—C26—H26A | 107.9 |
C2—C3—Br2 | 118.8 (7) | N4—C26—H26B | 107.9 |
C3—C4—C5 | 118.1 (9) | C25—C26—H26B | 107.9 |
C3—C4—H4 | 120.9 | H26A—C26—H26B | 107.2 |
C5—C4—H4 | 120.9 | N4—C27—C28 | 109.1 (7) |
C6—C5—C4 | 121.3 (9) | N4—C27—C32 | 114.1 (7) |
C6—C5—Br1 | 120.8 (9) | C28—C27—C32 | 110.8 (8) |
C4—C5—Br1 | 117.8 (8) | N4—C27—H27 | 107.5 |
C5—C6—C1 | 120.2 (9) | C28—C27—H27 | 107.5 |
C5—C6—H6 | 119.9 | C32—C27—H27 | 107.5 |
C1—C6—H6 | 119.9 | C27—C28—C29 | 109.7 (8) |
N1—C7—C1 | 126.4 (8) | C27—C28—H28A | 109.7 |
N1—C7—H7 | 116.8 | C29—C28—H28A | 109.7 |
C1—C7—H7 | 116.8 | C27—C28—H28B | 109.7 |
N1—C8—C9 | 111.5 (8) | C29—C28—H28B | 109.7 |
N1—C8—H8A | 109.3 | H28A—C28—H28B | 108.2 |
C9—C8—H8A | 109.3 | C30—C29—C28 | 111.1 (10) |
N1—C8—H8B | 109.3 | C30—C29—H29A | 109.4 |
C9—C8—H8B | 109.3 | C28—C29—H29A | 109.4 |
H8A—C8—H8B | 108.0 | C30—C29—H29B | 109.4 |
C8—C9—C10 | 114.3 (9) | C28—C29—H29B | 109.4 |
C8—C9—H9A | 108.7 | H29A—C29—H29B | 108.0 |
C10—C9—H9A | 108.7 | C31—C30—C29 | 111.6 (10) |
C8—C9—H9B | 108.7 | C31—C30—H30A | 109.3 |
C10—C9—H9B | 108.7 | C29—C30—H30A | 109.3 |
H9A—C9—H9B | 107.6 | C31—C30—H30B | 109.3 |
N2—C10—C9 | 114.3 (9) | C29—C30—H30B | 109.3 |
N2—C10—H10A | 108.7 | H30A—C30—H30B | 108.0 |
C9—C10—H10A | 108.7 | C30—C31—C32 | 111.1 (10) |
N2—C10—H10B | 108.7 | C30—C31—H31A | 109.4 |
C9—C10—H10B | 108.7 | C32—C31—H31A | 109.4 |
H10A—C10—H10B | 107.6 | C30—C31—H31B | 109.4 |
C16—C11—N2 | 114.7 (8) | C32—C31—H31B | 109.4 |
C16—C11—C12 | 111.7 (8) | H31A—C31—H31B | 108.0 |
N2—C11—C12 | 110.4 (7) | C27—C32—C31 | 109.5 (8) |
C16—C11—H11 | 106.5 | C27—C32—H32A | 109.8 |
N2—C11—H11 | 106.5 | C31—C32—H32A | 109.8 |
C12—C11—H11 | 106.5 | C27—C32—H32B | 109.8 |
C11—C12—C13 | 108.6 (8) | C31—C32—H32B | 109.8 |
C11—C12—H12A | 110.0 | H32A—C32—H32B | 108.2 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co(C16H21Br2N2O)2]ClO4 |
Mr | 992.72 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 16.208 (3), 12.801 (3), 18.060 (4) |
β (°) | 98.91 (3) |
V (Å3) | 3701.8 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.90 |
Crystal size (mm) | 0.33 × 0.32 × 0.32 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.295, 0.303 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30784, 8354, 3168 |
Rint | 0.142 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.075, 0.213, 0.96 |
No. of reflections | 8354 |
No. of parameters | 436 |
No. of restraints | 24 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.12, −0.76 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
Cobalt complexes with Schiff base ligands have received much attention in recent years (Sacconi et al., 1965; Zakrzewski & Sacconi, 1968). Some of the complexes have been found to have pharmacological and antitumor properties (Hodnett et al., 1971; Hodnett & Dunn, 1972; Takeuchi et al., 1998). We have recently reported a few transition metal complexes (Diao, Huang et al., 2007; Diao, Shu et al., 2007; Diao, 2007a,b). As an extension of the work on the crystal structures of such complexes, we report herein the crystal structure of the title complex.
The complex is a centrosymmetric mononuclear Schiff base cobalt(III) complex, which consists of a cobalt(III) cation and a perchlorate anion. The Co atom is hexacoordinated by two O and four N atoms from two Schiff base ligands, forming an octahedral geometry (Fig. 1).