Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047903/bg2106sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047903/bg2106Isup2.hkl |
CCDC reference: 667122
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- H-atom completeness 97%
- Disorder in solvent or counterion
- R factor = 0.039
- wR factor = 0.121
- Data-to-parameter ratio = 14.0
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT430_ALERT_2_A Short Inter D...A Contact O11 .. O11' .. 2.20 Ang.
Author Response: They are parts of a disordered water molecule |
Alert level B PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.02 Ratio
Alert level C 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 ............ 0.50 Ratio PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.26 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C14 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C31 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 50.00 Perc. PLAT431_ALERT_2_C Short Inter HL..A Contact Cl2 .. O11 .. 3.24 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O3 .. C29 .. 2.92 Ang.
Alert level G FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C17 H28 Cl1 Co1 N7 O5.5 Atom count from the _atom_site data: C17 H27 Cl1 Co1 N7 O5.5 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 8 From the CIF: _chemical_formula_sum C17 H28 Cl Co N7 O5.50 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 136.00 136.00 0.00 H 224.00 216.00 8.00 Cl 8.00 8.00 0.00 Co 8.00 8.00 0.00 N 56.00 56.00 0.00 O 44.00 44.00 0.00 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 7 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 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The green colored Trans-Hydrogen dichlorobis(dimethylgloximato) cobaltate(III), H[Co(dmgH)2Cl2] was prepared by the method reported in the literature (Phor, et al., 1985). Using this complex, as the starting material, the cobaloxime: pyrazine-2-tert-butylcarboxamidopyrazinechlorocobaloxime viz., [Co(dmgH)2(t-BuPzAM)Cl] was prepared by adopting the method reported earlier (Vijayaraghavanan & Dayalan, 1992). Hydrogen dichlorobis (dimethylglyoximato)cobaltate(III) (0.01 mole) and 0.01 mole of Pyrazine-2-tert-butylcarboxamide were taken in about 60 ml of absolute alcohol and stirred for 1 hr, with warming over hot water bath, until the green colour due to dichlorocobaloxime was discharged to get the required brown colored complex. The resulting complex was filtered, washed with alcohol and dried in a vacuum desiccator. Crystals of the complex were grown in ethanol by slow evaporation.
Even though the unit cell satisfies orthorhombic metric conditions within the limits of s.u., Rint pointed clearly to a monoclinic symmetry (Rint ortho=0.59, Rintmono=0.027). The structure was solved and refined in P21/c. All the H atoms were located in a difference Fourier map. H atoms linked to carbon and oxygen atoms were relocated at idealized positions and allowed to ride with C—H(aromatic): 0.93A%, and 1.2UeqC; C—H(tertiary): 0.96A%, and 1.5UeqC; O—H: 0.82A%, and 1.5UeqO. N—H hydrogen distances were restrained (N—H:0.83 (1)) and refined isotropically. Ther disordered crystal water molecule is split into two equally populated sites (O11 and O11', with 50% occupancy each).
Dimethylglyoximatocobalt(III) complexes, generally known as cobaloximes, have been studied extensively as model compounds for vitamin-B12 (Trommel, et al., 2001; Ohkubo & Fukuzumi, 2005). Most of the work on cobaloximes include electron-transfer reactions (Dayalan & Vijayaraghavan,2001) and catalytic activity (Razavelt, et al., 2005) in solution. There are few literature evidences (Gupta, et al., 2000; Gupta, et al., 2001; Gupta, et al., 2004) relating the structural aspects of cobaloximes. We report here the synthesis, physical characterization and the crystal structure of a typical cobaloxime viz., pyrazine-2-tert-butylcarboxamidochlorocobaloxime. Figure 1 shows the ORTEP representation of the two independent molecules in the asymmetric unit, with 50% anisotropic ellipsoids. Figure 2 presents a packing diagram of the structure depicting the hydrogen bonding interactions. The geometry around the metal atom is octahedral; the bonds to chlorines and pyrazine N atoms are almost perpendicular to the mean glyoximate planes. The difference Fourier clearly shows one O—H group in each one of the glyoximate moieties attached to Co2, while in those attached to Co1, both hydrogen atoms are bound to only one of the glyoximate moieties. The planar glyoximate groups subtend dihedral angles of 7.76 (13)° (Co1) and 0.95 (13)° (Co2). There are strong intra molecular O—H···O hydrogen bonds linking the glyoximate moieties (Figure 2). There is one crystal water molecule per asymmetric unit (disordered into two positions O11, O11') hydrogen bonded to the chlorine atoms Cl2, attached to Co2. The corresponding water H atoms could not be located in the difference map and were not included in the model.
For related literature, see: Dayalan & Vijayaraghavan (2001); Gupta et al. (2000, 2001, 2004); Ohkubo & Fukuzumi (2005); Phor et al. (1985); Razavelt et al. (2005); Trommel et al. (2001); Vijayaraghavanan & Dayalan (1992).
Data collection: APEX2 (Bruker–Nonius, 2004); cell refinement: APEX2 and SAINT (Bruker–Nonius, 2004); data reduction: SAINT and XPREP (Bruker–Nonius, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-32 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Co(C4H7N2O2)2Cl(C9H13N3O)]·0.5H2O | F(000) = 2136 |
Mr = 521.84 | Dx = 1.434 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5042 reflections |
a = 11.4320 (2) Å | θ = 2.2–24.0° |
b = 15.8134 (4) Å | µ = 0.88 mm−1 |
c = 26.2781 (6) Å | T = 293 K |
β = 90.06 (2)° | Plate, brown |
V = 4750.52 (18) Å3 | 0.30 × 0.30 × 0.20 mm |
Z = 8 |
Bruker Kappa-APEXII CCD diffractometer | 8366 independent reflections |
Radiation source: fine-focus sealed tube | 7136 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω and φ scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −13→13 |
Tmin = 0.779, Tmax = 0.844 | k = −18→18 |
92600 measured reflections | l = −31→31 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0498P)2 + 4.9702P] where P = (Fo2 + 2Fc2)/3 |
8366 reflections | (Δ/σ)max < 0.001 |
599 parameters | Δρmax = 0.62 e Å−3 |
2 restraints | Δρmin = −0.48 e Å−3 |
[Co(C4H7N2O2)2Cl(C9H13N3O)]·0.5H2O | V = 4750.52 (18) Å3 |
Mr = 521.84 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.4320 (2) Å | µ = 0.88 mm−1 |
b = 15.8134 (4) Å | T = 293 K |
c = 26.2781 (6) Å | 0.30 × 0.30 × 0.20 mm |
β = 90.06 (2)° |
Bruker Kappa-APEXII CCD diffractometer | 8366 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 7136 reflections with I > 2σ(I) |
Tmin = 0.779, Tmax = 0.844 | Rint = 0.028 |
92600 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 2 restraints |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | Δρmax = 0.62 e Å−3 |
8366 reflections | Δρmin = −0.48 e Å−3 |
599 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 | Occ. (<1) | |
Co1 | 0.19069 (3) | 0.40860 (3) | 0.881531 (15) | 0.04025 (12) | |
Co2 | 0.68130 (3) | 0.16125 (2) | 0.932065 (14) | 0.03599 (12) | |
Cl1 | 0.29360 (7) | 0.49466 (5) | 0.93160 (3) | 0.0526 (2) | |
Cl2 | 0.84549 (7) | 0.18912 (6) | 0.97384 (4) | 0.0594 (2) | |
O1 | 0.2782 (2) | 0.27258 (15) | 0.94263 (10) | 0.0616 (6) | |
H1 | 0.3243 | 0.2754 | 0.9188 | 0.092* | |
O2 | −0.0168 (2) | 0.50395 (15) | 0.89776 (9) | 0.0575 (6) | |
H2 | 0.0129 | 0.5249 | 0.8723 | 0.086* | |
O3 | 0.3940 (2) | 0.31032 (17) | 0.86636 (11) | 0.0678 (7) | |
O4 | 0.1109 (2) | 0.55231 (16) | 0.82713 (10) | 0.0636 (7) | |
O5 | −0.1258 (3) | 0.4237 (2) | 0.72781 (11) | 0.0833 (9) | |
O6 | 0.7355 (2) | 0.29998 (16) | 0.86563 (10) | 0.0632 (7) | |
H6 | 0.7663 | 0.2588 | 0.8522 | 0.095* | |
O7 | 0.5523 (2) | 0.16829 (17) | 1.02569 (8) | 0.0594 (6) | |
O8 | 0.8124 (2) | 0.15686 (18) | 0.84180 (10) | 0.0649 (7) | |
O9 | 0.6362 (2) | 0.02904 (16) | 1.00172 (9) | 0.0615 (6) | |
H9A | 0.6060 | 0.0710 | 1.0145 | 0.092* | |
O10 | 0.4877 (2) | 0.20804 (16) | 0.74627 (8) | 0.0578 (6) | |
O11 | 0.0668 (6) | 0.0909 (6) | 0.9244 (4) | 0.131 (3) | 0.50 |
O11' | 0.0274 (10) | −0.0106 (12) | 0.9790 (4) | 0.248 (9) | 0.50 |
N1 | 0.1903 (2) | 0.32829 (16) | 0.93528 (10) | 0.0439 (6) | |
N2 | 0.0507 (2) | 0.44081 (16) | 0.91462 (10) | 0.0422 (6) | |
N3 | 0.1944 (3) | 0.49340 (18) | 0.83087 (10) | 0.0513 (7) | |
N4 | 0.3315 (2) | 0.37604 (19) | 0.84952 (11) | 0.0532 (7) | |
N5 | 0.1012 (2) | 0.33275 (16) | 0.83651 (9) | 0.0419 (6) | |
N6 | −0.0132 (2) | 0.22650 (19) | 0.76889 (10) | 0.0529 (7) | |
N7 | −0.1513 (3) | 0.2913 (2) | 0.69531 (11) | 0.0591 (8) | |
N8 | 0.5929 (2) | 0.21253 (17) | 0.98524 (9) | 0.0436 (6) | |
N9 | 0.6790 (2) | 0.27532 (16) | 0.90817 (10) | 0.0436 (6) | |
N10 | 0.7705 (2) | 0.11158 (18) | 0.87964 (10) | 0.0476 (6) | |
N11 | 0.6847 (2) | 0.04996 (16) | 0.95777 (10) | 0.0455 (6) | |
N12 | 0.53778 (19) | 0.13526 (14) | 0.89466 (8) | 0.0318 (5) | |
N13 | 0.3360 (2) | 0.09520 (17) | 0.84150 (10) | 0.0446 (6) | |
N14 | 0.3224 (3) | 0.1300 (2) | 0.74051 (10) | 0.0519 (7) | |
C1 | 0.1072 (3) | 0.3342 (2) | 0.96801 (12) | 0.0441 (7) | |
C2 | 0.0209 (3) | 0.3986 (2) | 0.95452 (12) | 0.0438 (7) | |
C3 | 0.1040 (4) | 0.2855 (3) | 1.01639 (15) | 0.0698 (11) | |
H3A | 0.1820 | 0.2693 | 1.0257 | 0.105* | |
H3B | 0.0569 | 0.2358 | 1.0119 | 0.105* | |
H3C | 0.0709 | 0.3200 | 1.0428 | 0.105* | |
C4 | −0.0885 (3) | 0.4132 (2) | 0.98398 (15) | 0.0599 (9) | |
H4A | −0.1238 | 0.4654 | 0.9732 | 0.090* | |
H4B | −0.0703 | 0.4164 | 1.0196 | 0.090* | |
H4C | −0.1419 | 0.3674 | 0.9781 | 0.090* | |
C5 | 0.2836 (4) | 0.4923 (2) | 0.80097 (13) | 0.0609 (10) | |
C6 | 0.3647 (3) | 0.4230 (3) | 0.81171 (15) | 0.0628 (10) | |
C7 | 0.3023 (5) | 0.5578 (3) | 0.76089 (17) | 0.0937 (16) | |
H7A | 0.2283 | 0.5815 | 0.7511 | 0.141* | |
H7B | 0.3386 | 0.5323 | 0.7318 | 0.141* | |
H7C | 0.3519 | 0.6017 | 0.7740 | 0.141* | |
C8 | 0.4763 (4) | 0.4079 (3) | 0.7832 (2) | 0.0947 (17) | |
H8A | 0.5262 | 0.3714 | 0.8028 | 0.142* | |
H8B | 0.5151 | 0.4608 | 0.7774 | 0.142* | |
H8C | 0.4589 | 0.3817 | 0.7511 | 0.142* | |
C9 | 0.1165 (3) | 0.2493 (2) | 0.83801 (12) | 0.0484 (7) | |
H9 | 0.1671 | 0.2261 | 0.8619 | 0.058* | |
C10 | 0.0583 (3) | 0.1969 (2) | 0.80457 (13) | 0.0526 (8) | |
H10 | 0.0694 | 0.1388 | 0.8071 | 0.063* | |
C11 | −0.0292 (3) | 0.3095 (2) | 0.76843 (12) | 0.0476 (7) | |
C12 | 0.0257 (3) | 0.3632 (2) | 0.80229 (12) | 0.0488 (8) | |
H12 | 0.0101 | 0.4209 | 0.8013 | 0.059* | |
C13 | −0.1088 (3) | 0.3476 (3) | 0.72809 (13) | 0.0569 (9) | |
C14 | −0.2259 (3) | 0.3111 (2) | 0.65050 (13) | 0.0567 (9) | |
C15 | −0.1623 (4) | 0.3724 (3) | 0.61602 (15) | 0.0743 (12) | |
H15A | −0.1484 | 0.4243 | 0.6339 | 0.111* | |
H15B | −0.2092 | 0.3834 | 0.5864 | 0.111* | |
H15C | −0.0889 | 0.3482 | 0.6058 | 0.111* | |
C16 | −0.2478 (5) | 0.2279 (3) | 0.62361 (19) | 0.0955 (17) | |
H16A | −0.1743 | 0.2019 | 0.6153 | 0.143* | |
H16B | −0.2913 | 0.2379 | 0.5929 | 0.143* | |
H16C | −0.2916 | 0.1910 | 0.6455 | 0.143* | |
C17 | −0.3399 (4) | 0.3488 (3) | 0.66804 (18) | 0.0834 (13) | |
H17A | −0.3253 | 0.4018 | 0.6847 | 0.125* | |
H17B | −0.3772 | 0.3108 | 0.6914 | 0.125* | |
H17C | −0.3901 | 0.3578 | 0.6392 | 0.125* | |
C18 | 0.5706 (3) | 0.2921 (2) | 0.98100 (12) | 0.0470 (7) | |
C19 | 0.6235 (3) | 0.32953 (19) | 0.93559 (13) | 0.0474 (8) | |
C20 | 0.5008 (4) | 0.3412 (3) | 1.01852 (15) | 0.0691 (11) | |
H20A | 0.4574 | 0.3030 | 1.0397 | 0.104* | |
H20B | 0.4476 | 0.3779 | 1.0008 | 0.104* | |
H20C | 0.5524 | 0.3745 | 1.0393 | 0.104* | |
C21 | 0.6167 (4) | 0.4217 (2) | 0.92368 (18) | 0.0730 (12) | |
H21A | 0.6423 | 0.4537 | 0.9527 | 0.110* | |
H21B | 0.5374 | 0.4365 | 0.9156 | 0.110* | |
H21C | 0.6661 | 0.4341 | 0.8951 | 0.110* | |
C22 | 0.7898 (3) | 0.0309 (2) | 0.88436 (15) | 0.0578 (9) | |
C23 | 0.7377 (3) | −0.0052 (2) | 0.92970 (15) | 0.0570 (9) | |
C24 | 0.8640 (4) | −0.0181 (3) | 0.84738 (19) | 0.0903 (15) | |
H24A | 0.8934 | 0.0195 | 0.8217 | 0.136* | |
H24B | 0.8176 | −0.0615 | 0.8317 | 0.136* | |
H24C | 0.9284 | −0.0436 | 0.8652 | 0.136* | |
C25 | 0.7458 (5) | −0.0962 (3) | 0.9446 (2) | 0.0982 (17) | |
H25A | 0.7551 | −0.1005 | 0.9808 | 0.147* | |
H25B | 0.8119 | −0.1216 | 0.9280 | 0.147* | |
H25C | 0.6757 | −0.1251 | 0.9344 | 0.147* | |
C26 | 0.4487 (3) | 0.09584 (19) | 0.91725 (11) | 0.0417 (7) | |
H26 | 0.4541 | 0.0815 | 0.9515 | 0.050* | |
C27 | 0.3490 (3) | 0.0762 (2) | 0.89058 (12) | 0.0487 (8) | |
H27 | 0.2885 | 0.0485 | 0.9074 | 0.058* | |
C28 | 0.4248 (2) | 0.13517 (18) | 0.81967 (10) | 0.0353 (6) | |
C29 | 0.5259 (2) | 0.15585 (18) | 0.84576 (10) | 0.0361 (6) | |
H29 | 0.5859 | 0.1843 | 0.8291 | 0.043* | |
C30 | 0.4141 (3) | 0.1617 (2) | 0.76477 (11) | 0.0416 (7) | |
C31 | 0.2904 (3) | 0.1486 (3) | 0.68706 (12) | 0.0613 (10) | |
C32 | 0.1821 (5) | 0.0962 (4) | 0.67658 (17) | 0.115 (2) | |
H32A | 0.2000 | 0.0374 | 0.6810 | 0.173* | |
H32B | 0.1563 | 0.1059 | 0.6423 | 0.173* | |
H32C | 0.1212 | 0.1122 | 0.6998 | 0.173* | |
C33 | 0.2628 (5) | 0.2417 (3) | 0.68204 (19) | 0.0954 (16) | |
H33A | 0.3333 | 0.2740 | 0.6864 | 0.143* | |
H33B | 0.2072 | 0.2577 | 0.7076 | 0.143* | |
H33C | 0.2306 | 0.2526 | 0.6489 | 0.143* | |
C34 | 0.3904 (5) | 0.1230 (3) | 0.65208 (15) | 0.0874 (14) | |
H34A | 0.4561 | 0.1596 | 0.6578 | 0.131* | |
H34B | 0.3656 | 0.1275 | 0.6173 | 0.131* | |
H34C | 0.4127 | 0.0656 | 0.6591 | 0.131* | |
H7 | −0.133 (3) | 0.2419 (10) | 0.6996 (15) | 0.064 (13)* | |
H14 | 0.278 (3) | 0.101 (2) | 0.7576 (13) | 0.061 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0387 (2) | 0.0422 (2) | 0.0398 (2) | 0.00500 (17) | −0.00959 (16) | −0.00484 (17) |
Co2 | 0.0374 (2) | 0.0339 (2) | 0.0367 (2) | −0.00246 (16) | −0.00596 (16) | 0.00130 (16) |
Cl1 | 0.0478 (4) | 0.0535 (5) | 0.0566 (5) | 0.0013 (3) | −0.0129 (3) | −0.0159 (4) |
Cl2 | 0.0508 (5) | 0.0577 (5) | 0.0696 (6) | −0.0058 (4) | −0.0235 (4) | −0.0023 (4) |
O1 | 0.0552 (14) | 0.0551 (14) | 0.0744 (16) | 0.0222 (11) | −0.0217 (12) | −0.0014 (12) |
O2 | 0.0526 (13) | 0.0568 (14) | 0.0630 (14) | 0.0199 (11) | −0.0130 (11) | 0.0055 (12) |
O3 | 0.0477 (13) | 0.0603 (16) | 0.095 (2) | 0.0139 (12) | −0.0015 (13) | −0.0215 (14) |
O4 | 0.0710 (16) | 0.0537 (14) | 0.0661 (16) | 0.0037 (13) | −0.0198 (13) | 0.0123 (12) |
O5 | 0.111 (2) | 0.070 (2) | 0.0687 (18) | 0.0054 (17) | −0.0454 (17) | −0.0072 (15) |
O6 | 0.0688 (16) | 0.0582 (15) | 0.0627 (15) | −0.0142 (12) | 0.0061 (12) | 0.0176 (12) |
O7 | 0.0679 (15) | 0.0744 (17) | 0.0360 (12) | −0.0099 (13) | 0.0003 (11) | 0.0040 (11) |
O8 | 0.0557 (14) | 0.0785 (18) | 0.0604 (15) | −0.0041 (13) | 0.0187 (12) | 0.0028 (13) |
O9 | 0.0762 (17) | 0.0552 (15) | 0.0531 (14) | −0.0011 (12) | −0.0038 (12) | 0.0200 (12) |
O10 | 0.0665 (15) | 0.0694 (16) | 0.0374 (11) | −0.0237 (13) | −0.0042 (10) | 0.0077 (11) |
O11 | 0.066 (4) | 0.161 (8) | 0.166 (8) | 0.018 (5) | 0.012 (5) | −0.038 (7) |
O11' | 0.166 (10) | 0.44 (2) | 0.134 (9) | 0.200 (13) | −0.060 (8) | −0.139 (12) |
N1 | 0.0445 (14) | 0.0398 (14) | 0.0472 (15) | 0.0094 (11) | −0.0192 (12) | −0.0065 (11) |
N2 | 0.0405 (13) | 0.0406 (14) | 0.0455 (14) | 0.0095 (11) | −0.0139 (11) | −0.0058 (12) |
N3 | 0.0568 (16) | 0.0513 (16) | 0.0457 (15) | −0.0060 (13) | −0.0103 (13) | −0.0003 (13) |
N4 | 0.0427 (15) | 0.0569 (17) | 0.0600 (18) | −0.0013 (13) | −0.0028 (13) | −0.0215 (14) |
N5 | 0.0407 (13) | 0.0473 (15) | 0.0375 (13) | 0.0019 (11) | −0.0045 (10) | −0.0027 (11) |
N6 | 0.0542 (16) | 0.0636 (19) | 0.0410 (14) | −0.0138 (14) | −0.0043 (12) | −0.0023 (13) |
N7 | 0.0677 (19) | 0.063 (2) | 0.0460 (16) | −0.0100 (17) | −0.0225 (14) | 0.0035 (15) |
N8 | 0.0456 (14) | 0.0493 (16) | 0.0359 (13) | −0.0056 (12) | −0.0085 (11) | −0.0029 (11) |
N9 | 0.0436 (14) | 0.0422 (14) | 0.0450 (14) | −0.0098 (11) | −0.0097 (11) | 0.0080 (12) |
N10 | 0.0363 (13) | 0.0548 (17) | 0.0518 (16) | 0.0003 (12) | 0.0005 (11) | −0.0042 (13) |
N11 | 0.0458 (14) | 0.0397 (14) | 0.0510 (15) | −0.0024 (12) | −0.0124 (12) | 0.0074 (12) |
N12 | 0.0373 (12) | 0.0282 (11) | 0.0300 (11) | 0.0003 (9) | 0.0012 (9) | −0.0014 (9) |
N13 | 0.0433 (14) | 0.0490 (15) | 0.0416 (14) | −0.0100 (12) | −0.0047 (11) | 0.0013 (12) |
N14 | 0.0562 (17) | 0.0667 (19) | 0.0327 (14) | −0.0186 (15) | −0.0074 (12) | 0.0015 (13) |
C1 | 0.0478 (17) | 0.0433 (17) | 0.0412 (16) | −0.0025 (14) | −0.0136 (14) | −0.0022 (13) |
C2 | 0.0418 (16) | 0.0423 (17) | 0.0473 (18) | −0.0019 (13) | −0.0070 (13) | −0.0116 (14) |
C3 | 0.074 (3) | 0.072 (3) | 0.063 (2) | −0.008 (2) | −0.0149 (19) | 0.019 (2) |
C4 | 0.051 (2) | 0.056 (2) | 0.072 (2) | −0.0057 (16) | 0.0080 (17) | −0.0145 (18) |
C5 | 0.076 (2) | 0.063 (2) | 0.0438 (18) | −0.021 (2) | −0.0018 (18) | −0.0100 (17) |
C6 | 0.063 (2) | 0.069 (2) | 0.057 (2) | −0.0193 (19) | 0.0118 (18) | −0.0249 (19) |
C7 | 0.128 (4) | 0.092 (3) | 0.061 (3) | −0.040 (3) | 0.009 (3) | 0.007 (2) |
C8 | 0.086 (3) | 0.094 (3) | 0.104 (4) | −0.027 (3) | 0.043 (3) | −0.038 (3) |
C9 | 0.0442 (17) | 0.0531 (19) | 0.0479 (18) | 0.0004 (14) | −0.0064 (14) | −0.0025 (15) |
C10 | 0.057 (2) | 0.0503 (19) | 0.0504 (19) | −0.0090 (16) | −0.0063 (15) | −0.0021 (15) |
C11 | 0.0481 (17) | 0.059 (2) | 0.0356 (16) | −0.0074 (15) | −0.0034 (13) | −0.0009 (14) |
C12 | 0.0498 (18) | 0.0533 (19) | 0.0431 (17) | 0.0009 (15) | −0.0093 (14) | −0.0014 (14) |
C13 | 0.060 (2) | 0.069 (3) | 0.0424 (18) | −0.0054 (18) | −0.0146 (15) | −0.0027 (17) |
C14 | 0.061 (2) | 0.066 (2) | 0.0433 (18) | −0.0154 (18) | −0.0194 (16) | 0.0015 (16) |
C15 | 0.077 (3) | 0.096 (3) | 0.050 (2) | −0.018 (2) | −0.0136 (19) | 0.012 (2) |
C16 | 0.129 (4) | 0.073 (3) | 0.084 (3) | −0.009 (3) | −0.062 (3) | −0.004 (2) |
C17 | 0.063 (3) | 0.113 (4) | 0.074 (3) | −0.010 (2) | −0.013 (2) | 0.016 (3) |
C18 | 0.0469 (17) | 0.0482 (19) | 0.0460 (17) | 0.0005 (14) | −0.0146 (14) | −0.0132 (14) |
C19 | 0.0480 (18) | 0.0355 (16) | 0.059 (2) | −0.0018 (13) | −0.0195 (15) | −0.0050 (14) |
C20 | 0.068 (2) | 0.071 (3) | 0.068 (2) | 0.008 (2) | −0.0103 (19) | −0.030 (2) |
C21 | 0.077 (3) | 0.040 (2) | 0.102 (3) | −0.0010 (18) | −0.031 (2) | 0.003 (2) |
C22 | 0.0475 (19) | 0.056 (2) | 0.070 (2) | 0.0124 (16) | −0.0085 (16) | −0.0154 (18) |
C23 | 0.055 (2) | 0.0414 (18) | 0.074 (2) | 0.0075 (15) | −0.0159 (18) | 0.0001 (17) |
C24 | 0.081 (3) | 0.092 (3) | 0.098 (3) | 0.033 (3) | 0.005 (3) | −0.028 (3) |
C25 | 0.125 (4) | 0.046 (2) | 0.123 (4) | 0.022 (3) | −0.014 (3) | 0.009 (3) |
C26 | 0.0469 (17) | 0.0436 (17) | 0.0345 (15) | −0.0086 (13) | −0.0014 (12) | 0.0052 (13) |
C27 | 0.0462 (17) | 0.057 (2) | 0.0426 (17) | −0.0170 (15) | −0.0008 (13) | 0.0082 (15) |
C28 | 0.0402 (15) | 0.0344 (14) | 0.0314 (14) | −0.0006 (12) | −0.0001 (11) | −0.0036 (11) |
C29 | 0.0375 (14) | 0.0396 (15) | 0.0311 (14) | −0.0031 (12) | 0.0015 (11) | −0.0021 (12) |
C30 | 0.0464 (17) | 0.0452 (17) | 0.0331 (15) | −0.0014 (14) | −0.0022 (13) | −0.0045 (13) |
C31 | 0.068 (2) | 0.083 (3) | 0.0332 (16) | −0.020 (2) | −0.0126 (15) | 0.0017 (17) |
C32 | 0.118 (4) | 0.170 (6) | 0.056 (3) | −0.081 (4) | −0.040 (3) | 0.016 (3) |
C33 | 0.110 (4) | 0.100 (4) | 0.077 (3) | 0.010 (3) | −0.027 (3) | 0.029 (3) |
C34 | 0.108 (4) | 0.115 (4) | 0.039 (2) | −0.018 (3) | 0.002 (2) | −0.012 (2) |
Co1—N4 | 1.888 (3) | C7—H7A | 0.9600 |
Co1—N3 | 1.890 (3) | C7—H7B | 0.9600 |
Co1—N2 | 1.892 (3) | C7—H7C | 0.9600 |
Co1—N1 | 1.899 (3) | C8—H8A | 0.9600 |
Co1—N5 | 1.970 (2) | C8—H8B | 0.9600 |
Co1—Cl1 | 2.2282 (9) | C8—H8C | 0.9600 |
Co2—N11 | 1.885 (3) | C9—C10 | 1.379 (5) |
Co2—N10 | 1.886 (3) | C9—H9 | 0.9300 |
Co2—N8 | 1.906 (3) | C10—H10 | 0.9300 |
Co2—N9 | 1.910 (3) | C11—C12 | 1.380 (5) |
Co2—N12 | 1.955 (2) | C11—C13 | 1.521 (5) |
Co2—Cl2 | 2.2177 (9) | C12—H12 | 0.9300 |
O1—N1 | 1.350 (3) | C14—C17 | 1.507 (6) |
O1—H1 | 0.8200 | C14—C15 | 1.513 (5) |
O2—N2 | 1.337 (3) | C14—C16 | 1.515 (6) |
O2—H2 | 0.8200 | C15—H15A | 0.9600 |
O3—N4 | 1.337 (4) | C15—H15B | 0.9600 |
O4—N3 | 1.337 (4) | C15—H15C | 0.9600 |
O5—C13 | 1.218 (5) | C16—H16A | 0.9600 |
O6—N9 | 1.349 (3) | C16—H16B | 0.9600 |
O6—H6 | 0.8200 | C16—H16C | 0.9600 |
O7—N8 | 1.355 (3) | C17—H17A | 0.9600 |
O8—N10 | 1.316 (4) | C17—H17B | 0.9600 |
O9—N11 | 1.323 (4) | C17—H17C | 0.9600 |
O9—H9A | 0.8200 | C18—C19 | 1.463 (5) |
O10—C30 | 1.218 (4) | C18—C20 | 1.488 (5) |
O11'—O11'i | 1.314 (19) | C19—C21 | 1.493 (5) |
N1—C1 | 1.286 (4) | C20—H20A | 0.9600 |
N2—C2 | 1.288 (4) | C20—H20B | 0.9600 |
N3—C5 | 1.288 (5) | C20—H20C | 0.9600 |
N4—C6 | 1.298 (5) | C21—H21A | 0.9600 |
N5—C9 | 1.331 (4) | C21—H21B | 0.9600 |
N5—C12 | 1.335 (4) | C21—H21C | 0.9600 |
N6—C11 | 1.326 (5) | C22—C23 | 1.449 (6) |
N6—C10 | 1.329 (4) | C22—C24 | 1.505 (5) |
N7—C13 | 1.330 (5) | C23—C25 | 1.495 (5) |
N7—C14 | 1.486 (4) | C24—H24A | 0.9600 |
N7—H7 | 0.82 (3) | C24—H24B | 0.9600 |
N8—C18 | 1.288 (4) | C24—H24C | 0.9600 |
N9—C19 | 1.287 (4) | C25—H25A | 0.9600 |
N10—C22 | 1.301 (5) | C25—H25B | 0.9600 |
N11—C23 | 1.293 (5) | C25—H25C | 0.9600 |
N12—C29 | 1.333 (3) | C26—C27 | 1.372 (4) |
N12—C26 | 1.334 (4) | C26—H26 | 0.9300 |
N13—C28 | 1.327 (4) | C27—H27 | 0.9300 |
N13—C27 | 1.333 (4) | C28—C29 | 1.382 (4) |
N14—C30 | 1.325 (4) | C28—C30 | 1.507 (4) |
N14—C31 | 1.480 (4) | C29—H29 | 0.9300 |
N14—H14 | 0.82 (3) | C31—C33 | 1.512 (6) |
C1—C2 | 1.461 (4) | C31—C32 | 1.514 (5) |
C1—C3 | 1.487 (5) | C31—C34 | 1.523 (6) |
C2—C4 | 1.490 (5) | C32—H32A | 0.9600 |
C3—H3A | 0.9600 | C32—H32B | 0.9600 |
C3—H3B | 0.9600 | C32—H32C | 0.9600 |
C3—H3C | 0.9600 | C33—H33A | 0.9600 |
C4—H4A | 0.9600 | C33—H33B | 0.9600 |
C4—H4B | 0.9600 | C33—H33C | 0.9600 |
C4—H4C | 0.9600 | C34—H34A | 0.9600 |
C5—C6 | 1.463 (6) | C34—H34B | 0.9600 |
C5—C7 | 1.492 (6) | C34—H34C | 0.9600 |
C6—C8 | 1.499 (6) | ||
N4—Co1—N3 | 81.95 (14) | N6—C10—C9 | 122.2 (3) |
N4—Co1—N2 | 179.10 (12) | N6—C10—H10 | 118.9 |
N3—Co1—N2 | 98.75 (12) | C9—C10—H10 | 118.9 |
N4—Co1—N1 | 98.70 (13) | N6—C11—C12 | 122.7 (3) |
N3—Co1—N1 | 176.55 (11) | N6—C11—C13 | 118.8 (3) |
N2—Co1—N1 | 80.55 (11) | C12—C11—C13 | 118.5 (3) |
N4—Co1—N5 | 90.50 (11) | N5—C12—C11 | 120.4 (3) |
N3—Co1—N5 | 91.20 (11) | N5—C12—H12 | 119.8 |
N2—Co1—N5 | 90.05 (10) | C11—C12—H12 | 119.8 |
N1—Co1—N5 | 92.18 (11) | O5—C13—N7 | 126.8 (3) |
N4—Co1—Cl1 | 88.85 (8) | O5—C13—C11 | 119.4 (3) |
N3—Co1—Cl1 | 88.31 (9) | N7—C13—C11 | 113.8 (3) |
N2—Co1—Cl1 | 90.61 (8) | N7—C14—C17 | 109.7 (3) |
N1—Co1—Cl1 | 88.33 (8) | N7—C14—C15 | 109.5 (3) |
N5—Co1—Cl1 | 179.23 (8) | C17—C14—C15 | 110.3 (4) |
N11—Co2—N10 | 82.07 (12) | N7—C14—C16 | 106.3 (3) |
N11—Co2—N8 | 98.34 (12) | C17—C14—C16 | 110.1 (4) |
N10—Co2—N8 | 179.22 (12) | C15—C14—C16 | 110.9 (4) |
N11—Co2—N9 | 178.16 (11) | C14—C15—H15A | 109.5 |
N10—Co2—N9 | 99.23 (12) | C14—C15—H15B | 109.5 |
N8—Co2—N9 | 80.34 (11) | H15A—C15—H15B | 109.5 |
N11—Co2—N12 | 90.04 (10) | C14—C15—H15C | 109.5 |
N10—Co2—N12 | 89.95 (10) | H15A—C15—H15C | 109.5 |
N8—Co2—N12 | 90.72 (10) | H15B—C15—H15C | 109.5 |
N9—Co2—N12 | 91.27 (10) | C14—C16—H16A | 109.5 |
N11—Co2—Cl2 | 89.49 (8) | C14—C16—H16B | 109.5 |
N10—Co2—Cl2 | 89.23 (8) | H16A—C16—H16B | 109.5 |
N8—Co2—Cl2 | 90.11 (8) | C14—C16—H16C | 109.5 |
N9—Co2—Cl2 | 89.22 (8) | H16A—C16—H16C | 109.5 |
N12—Co2—Cl2 | 179.11 (7) | H16B—C16—H16C | 109.5 |
N1—O1—H1 | 109.5 | C14—C17—H17A | 109.5 |
N2—O2—H2 | 109.5 | C14—C17—H17B | 109.5 |
N9—O6—H6 | 109.5 | H17A—C17—H17B | 109.5 |
N11—O9—H9A | 109.5 | C14—C17—H17C | 109.5 |
C1—N1—O1 | 120.1 (3) | H17A—C17—H17C | 109.5 |
C1—N1—Co1 | 116.8 (2) | H17B—C17—H17C | 109.5 |
O1—N1—Co1 | 122.7 (2) | N8—C18—C19 | 112.6 (3) |
C2—N2—O2 | 120.3 (3) | N8—C18—C20 | 123.9 (3) |
C2—N2—Co1 | 117.3 (2) | C19—C18—C20 | 123.5 (3) |
O2—N2—Co1 | 122.5 (2) | N9—C19—C18 | 113.0 (3) |
C5—N3—O4 | 122.0 (3) | N9—C19—C21 | 123.9 (4) |
C5—N3—Co1 | 116.0 (3) | C18—C19—C21 | 123.0 (3) |
O4—N3—Co1 | 122.0 (2) | C18—C20—H20A | 109.5 |
C6—N4—O3 | 122.8 (3) | C18—C20—H20B | 109.5 |
C6—N4—Co1 | 115.8 (3) | H20A—C20—H20B | 109.5 |
O3—N4—Co1 | 121.4 (2) | C18—C20—H20C | 109.5 |
C9—N5—C12 | 117.5 (3) | H20A—C20—H20C | 109.5 |
C9—N5—Co1 | 121.2 (2) | H20B—C20—H20C | 109.5 |
C12—N5—Co1 | 121.3 (2) | C19—C21—H21A | 109.5 |
C11—N6—C10 | 116.1 (3) | C19—C21—H21B | 109.5 |
C13—N7—C14 | 125.5 (3) | H21A—C21—H21B | 109.5 |
C13—N7—H7 | 117 (3) | C19—C21—H21C | 109.5 |
C14—N7—H7 | 117 (3) | H21A—C21—H21C | 109.5 |
C18—N8—O7 | 120.3 (3) | H21B—C21—H21C | 109.5 |
C18—N8—Co2 | 117.2 (2) | N10—C22—C23 | 113.2 (3) |
O7—N8—Co2 | 122.5 (2) | N10—C22—C24 | 122.6 (4) |
C19—N9—O6 | 120.5 (3) | C23—C22—C24 | 124.1 (4) |
C19—N9—Co2 | 116.8 (2) | N11—C23—C22 | 113.4 (3) |
O6—N9—Co2 | 122.6 (2) | N11—C23—C25 | 122.0 (4) |
C22—N10—O8 | 122.9 (3) | C22—C23—C25 | 124.6 (4) |
C22—N10—Co2 | 115.5 (3) | C22—C24—H24A | 109.5 |
O8—N10—Co2 | 121.5 (2) | C22—C24—H24B | 109.5 |
C23—N11—O9 | 121.7 (3) | H24A—C24—H24B | 109.5 |
C23—N11—Co2 | 115.7 (2) | C22—C24—H24C | 109.5 |
O9—N11—Co2 | 122.5 (2) | H24A—C24—H24C | 109.5 |
C29—N12—C26 | 117.8 (2) | H24B—C24—H24C | 109.5 |
C29—N12—Co2 | 121.22 (19) | C23—C25—H25A | 109.5 |
C26—N12—Co2 | 121.03 (19) | C23—C25—H25B | 109.5 |
C28—N13—C27 | 116.2 (3) | H25A—C25—H25B | 109.5 |
C30—N14—C31 | 125.2 (3) | C23—C25—H25C | 109.5 |
C30—N14—H14 | 116 (3) | H25A—C25—H25C | 109.5 |
C31—N14—H14 | 118 (3) | H25B—C25—H25C | 109.5 |
N1—C1—C2 | 112.8 (3) | N12—C26—C27 | 120.8 (3) |
N1—C1—C3 | 123.6 (3) | N12—C26—H26 | 119.6 |
C2—C1—C3 | 123.5 (3) | C27—C26—H26 | 119.6 |
N2—C2—C1 | 112.3 (3) | N13—C27—C26 | 122.3 (3) |
N2—C2—C4 | 124.4 (3) | N13—C27—H27 | 118.8 |
C1—C2—C4 | 123.3 (3) | C26—C27—H27 | 118.8 |
C1—C3—H3A | 109.5 | N13—C28—C29 | 122.5 (3) |
C1—C3—H3B | 109.5 | N13—C28—C30 | 119.0 (3) |
H3A—C3—H3B | 109.5 | C29—C28—C30 | 118.5 (3) |
C1—C3—H3C | 109.5 | N12—C29—C28 | 120.4 (3) |
H3A—C3—H3C | 109.5 | N12—C29—H29 | 119.8 |
H3B—C3—H3C | 109.5 | C28—C29—H29 | 119.8 |
C2—C4—H4A | 109.5 | O10—C30—N14 | 125.6 (3) |
C2—C4—H4B | 109.5 | O10—C30—C28 | 119.6 (3) |
H4A—C4—H4B | 109.5 | N14—C30—C28 | 114.8 (3) |
C2—C4—H4C | 109.5 | N14—C31—C33 | 109.1 (3) |
H4A—C4—H4C | 109.5 | N14—C31—C32 | 105.4 (3) |
H4B—C4—H4C | 109.5 | C33—C31—C32 | 110.3 (4) |
N3—C5—C6 | 113.3 (3) | N14—C31—C34 | 109.6 (3) |
N3—C5—C7 | 122.3 (4) | C33—C31—C34 | 111.3 (4) |
C6—C5—C7 | 124.4 (4) | C32—C31—C34 | 111.1 (4) |
N4—C6—C5 | 113.0 (3) | C31—C32—H32A | 109.5 |
N4—C6—C8 | 122.8 (4) | C31—C32—H32B | 109.5 |
C5—C6—C8 | 124.2 (4) | H32A—C32—H32B | 109.5 |
C5—C7—H7A | 109.5 | C31—C32—H32C | 109.5 |
C5—C7—H7B | 109.5 | H32A—C32—H32C | 109.5 |
H7A—C7—H7B | 109.5 | H32B—C32—H32C | 109.5 |
C5—C7—H7C | 109.5 | C31—C33—H33A | 109.5 |
H7A—C7—H7C | 109.5 | C31—C33—H33B | 109.5 |
H7B—C7—H7C | 109.5 | H33A—C33—H33B | 109.5 |
C6—C8—H8A | 109.5 | C31—C33—H33C | 109.5 |
C6—C8—H8B | 109.5 | H33A—C33—H33C | 109.5 |
H8A—C8—H8B | 109.5 | H33B—C33—H33C | 109.5 |
C6—C8—H8C | 109.5 | C31—C34—H34A | 109.5 |
H8A—C8—H8C | 109.5 | C31—C34—H34B | 109.5 |
H8B—C8—H8C | 109.5 | H34A—C34—H34B | 109.5 |
N5—C9—C10 | 120.9 (3) | C31—C34—H34C | 109.5 |
N5—C9—H9 | 119.5 | H34A—C34—H34C | 109.5 |
C10—C9—H9 | 119.5 | H34B—C34—H34C | 109.5 |
N4—Co1—N1—C1 | 176.3 (2) | Co1—N1—C1—C3 | −170.2 (3) |
N2—Co1—N1—C1 | −3.2 (2) | O2—N2—C2—C1 | −178.1 (2) |
N5—Co1—N1—C1 | −92.9 (2) | Co1—N2—C2—C1 | 2.5 (3) |
Cl1—Co1—N1—C1 | 87.7 (2) | O2—N2—C2—C4 | 1.8 (4) |
N4—Co1—N1—O1 | 2.8 (2) | Co1—N2—C2—C4 | −177.6 (2) |
N2—Co1—N1—O1 | −176.6 (2) | N1—C1—C2—N2 | −5.0 (4) |
N5—Co1—N1—O1 | 93.7 (2) | C3—C1—C2—N2 | 170.5 (3) |
Cl1—Co1—N1—O1 | −85.7 (2) | N1—C1—C2—C4 | 175.1 (3) |
N3—Co1—N2—C2 | −176.5 (2) | C3—C1—C2—C4 | −9.4 (5) |
N1—Co1—N2—C2 | 0.1 (2) | O4—N3—C5—C6 | 179.6 (3) |
N5—Co1—N2—C2 | 92.3 (2) | Co1—N3—C5—C6 | 1.3 (4) |
Cl1—Co1—N2—C2 | −88.1 (2) | O4—N3—C5—C7 | 1.7 (5) |
N3—Co1—N2—O2 | 4.2 (2) | Co1—N3—C5—C7 | −176.7 (3) |
N1—Co1—N2—O2 | −179.2 (2) | O3—N4—C6—C5 | −178.6 (3) |
N5—Co1—N2—O2 | −87.0 (2) | Co1—N4—C6—C5 | −0.9 (4) |
Cl1—Co1—N2—O2 | 92.6 (2) | O3—N4—C6—C8 | 0.2 (5) |
N4—Co1—N3—C5 | −1.4 (2) | Co1—N4—C6—C8 | 177.9 (3) |
N2—Co1—N3—C5 | 178.0 (2) | N3—C5—C6—N4 | −0.3 (4) |
N5—Co1—N3—C5 | −91.7 (3) | C7—C5—C6—N4 | 177.6 (3) |
Cl1—Co1—N3—C5 | 87.7 (2) | N3—C5—C6—C8 | −179.1 (4) |
N4—Co1—N3—O4 | −179.7 (2) | C7—C5—C6—C8 | −1.1 (6) |
N2—Co1—N3—O4 | −0.3 (2) | C12—N5—C9—C10 | 1.4 (5) |
N5—Co1—N3—O4 | 89.9 (2) | Co1—N5—C9—C10 | −176.5 (2) |
Cl1—Co1—N3—O4 | −90.7 (2) | C11—N6—C10—C9 | −2.5 (5) |
N3—Co1—N4—C6 | 1.2 (2) | N5—C9—C10—N6 | 1.5 (5) |
N1—Co1—N4—C6 | −175.3 (2) | C10—N6—C11—C12 | 0.9 (5) |
N5—Co1—N4—C6 | 92.4 (3) | C10—N6—C11—C13 | 179.2 (3) |
Cl1—Co1—N4—C6 | −87.2 (2) | C9—N5—C12—C11 | −3.0 (5) |
N3—Co1—N4—O3 | 179.0 (2) | Co1—N5—C12—C11 | 174.9 (2) |
N1—Co1—N4—O3 | 2.4 (2) | N6—C11—C12—N5 | 2.0 (5) |
N5—Co1—N4—O3 | −89.9 (2) | C13—C11—C12—N5 | −176.4 (3) |
Cl1—Co1—N4—O3 | 90.5 (2) | C14—N7—C13—O5 | 2.0 (7) |
N4—Co1—N5—C9 | 64.1 (3) | C14—N7—C13—C11 | −176.5 (3) |
N3—Co1—N5—C9 | 146.1 (3) | N6—C11—C13—O5 | 178.7 (4) |
N2—Co1—N5—C9 | −115.2 (3) | C12—C11—C13—O5 | −2.9 (5) |
N1—Co1—N5—C9 | −34.6 (3) | N6—C11—C13—N7 | −2.6 (5) |
N4—Co1—N5—C12 | −113.8 (3) | C12—C11—C13—N7 | 175.8 (3) |
N3—Co1—N5—C12 | −31.8 (3) | C13—N7—C14—C17 | −63.4 (5) |
N2—Co1—N5—C12 | 67.0 (3) | C13—N7—C14—C15 | 57.7 (5) |
N1—Co1—N5—C12 | 147.5 (3) | C13—N7—C14—C16 | 177.6 (4) |
N11—Co2—N8—C18 | −179.6 (2) | O7—N8—C18—C19 | 178.8 (2) |
N9—Co2—N8—C18 | 1.8 (2) | Co2—N8—C18—C19 | −2.4 (3) |
N12—Co2—N8—C18 | −89.4 (2) | O7—N8—C18—C20 | −0.2 (4) |
Cl2—Co2—N8—C18 | 90.9 (2) | Co2—N8—C18—C20 | 178.7 (2) |
N11—Co2—N8—O7 | −0.7 (2) | O6—N9—C19—C18 | −178.2 (2) |
N9—Co2—N8—O7 | −179.4 (2) | Co2—N9—C19—C18 | −0.4 (3) |
N12—Co2—N8—O7 | 89.4 (2) | O6—N9—C19—C21 | −0.3 (5) |
Cl2—Co2—N8—O7 | −90.2 (2) | Co2—N9—C19—C21 | 177.6 (3) |
N10—Co2—N9—C19 | 180.0 (2) | N8—C18—C19—N9 | 1.8 (4) |
N8—Co2—N9—C19 | −0.7 (2) | C20—C18—C19—N9 | −179.3 (3) |
N12—Co2—N9—C19 | 89.8 (2) | N8—C18—C19—C21 | −176.2 (3) |
Cl2—Co2—N9—C19 | −90.9 (2) | C20—C18—C19—C21 | 2.7 (5) |
N10—Co2—N9—O6 | −2.2 (2) | O8—N10—C22—C23 | 178.4 (3) |
N8—Co2—N9—O6 | 177.1 (2) | Co2—N10—C22—C23 | 0.2 (4) |
N12—Co2—N9—O6 | −92.4 (2) | O8—N10—C22—C24 | 1.1 (5) |
Cl2—Co2—N9—O6 | 86.9 (2) | Co2—N10—C22—C24 | −177.1 (3) |
N11—Co2—N10—C22 | 1.0 (2) | O9—N11—C23—C22 | −177.1 (3) |
N9—Co2—N10—C22 | 179.7 (2) | Co2—N11—C23—C22 | 2.8 (4) |
N12—Co2—N10—C22 | −89.0 (2) | O9—N11—C23—C25 | 1.1 (5) |
Cl2—Co2—N10—C22 | 90.6 (2) | Co2—N11—C23—C25 | −178.9 (3) |
N11—Co2—N10—O8 | −177.2 (2) | N10—C22—C23—N11 | −2.0 (4) |
N9—Co2—N10—O8 | 1.5 (2) | C24—C22—C23—N11 | 175.2 (4) |
N12—Co2—N10—O8 | 92.8 (2) | N10—C22—C23—C25 | 179.9 (4) |
Cl2—Co2—N10—O8 | −87.6 (2) | C24—C22—C23—C25 | −2.9 (6) |
N10—Co2—N11—C23 | −2.2 (2) | C29—N12—C26—C27 | 1.0 (4) |
N8—Co2—N11—C23 | 178.5 (2) | Co2—N12—C26—C27 | −178.6 (2) |
N12—Co2—N11—C23 | 87.7 (2) | C28—N13—C27—C26 | −0.5 (5) |
Cl2—Co2—N11—C23 | −91.5 (2) | N12—C26—C27—N13 | −0.2 (5) |
N10—Co2—N11—O9 | 177.8 (2) | C27—N13—C28—C29 | 0.3 (4) |
N8—Co2—N11—O9 | −1.6 (2) | C27—N13—C28—C30 | −177.6 (3) |
N12—Co2—N11—O9 | −92.3 (2) | C26—N12—C29—C28 | −1.2 (4) |
Cl2—Co2—N11—O9 | 88.5 (2) | Co2—N12—C29—C28 | 178.5 (2) |
N11—Co2—N12—C29 | −132.3 (2) | N13—C28—C29—N12 | 0.5 (4) |
N10—Co2—N12—C29 | −50.2 (2) | C30—C28—C29—N12 | 178.5 (3) |
N8—Co2—N12—C29 | 129.4 (2) | C31—N14—C30—O10 | −2.8 (6) |
N9—Co2—N12—C29 | 49.0 (2) | C31—N14—C30—C28 | 178.0 (3) |
N11—Co2—N12—C26 | 47.4 (2) | N13—C28—C30—O10 | 170.2 (3) |
N10—Co2—N12—C26 | 129.4 (2) | C29—C28—C30—O10 | −7.9 (4) |
N8—Co2—N12—C26 | −51.0 (2) | N13—C28—C30—N14 | −10.6 (4) |
N9—Co2—N12—C26 | −131.3 (2) | C29—C28—C30—N14 | 171.4 (3) |
O1—N1—C1—C2 | 178.9 (2) | C30—N14—C31—C33 | −63.1 (5) |
Co1—N1—C1—C2 | 5.3 (3) | C30—N14—C31—C32 | 178.6 (4) |
O1—N1—C1—C3 | 3.4 (5) | C30—N14—C31—C34 | 59.0 (5) |
Symmetry code: (i) −x, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3 | 0.82 | 1.69 | 2.476 (4) | 161 |
O2—H2···O4 | 0.82 | 1.69 | 2.483 (4) | 162 |
O6—H6···O8 | 0.82 | 1.72 | 2.507 (4) | 161 |
O9—H9A···O7 | 0.82 | 1.68 | 2.483 (4) | 165 |
Experimental details
Crystal data | |
Chemical formula | [Co(C4H7N2O2)2Cl(C9H13N3O)]·0.5H2O |
Mr | 521.84 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.4320 (2), 15.8134 (4), 26.2781 (6) |
β (°) | 90.06 (2) |
V (Å3) | 4750.52 (18) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.30 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Bruker Kappa-APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.779, 0.844 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 92600, 8366, 7136 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.121, 1.17 |
No. of reflections | 8366 |
No. of parameters | 599 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.62, −0.48 |
Computer programs: APEX2 (Bruker–Nonius, 2004), APEX2 and SAINT (Bruker–Nonius, 2004), SAINT and XPREP (Bruker–Nonius, 2004), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-32 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3 | 0.82 | 1.69 | 2.476 (4) | 161.3 |
O2—H2···O4 | 0.82 | 1.69 | 2.483 (4) | 162.1 |
O6—H6···O8 | 0.82 | 1.72 | 2.507 (4) | 160.9 |
O9—H9A···O7 | 0.82 | 1.68 | 2.483 (4) | 164.7 |
Dimethylglyoximatocobalt(III) complexes, generally known as cobaloximes, have been studied extensively as model compounds for vitamin-B12 (Trommel, et al., 2001; Ohkubo & Fukuzumi, 2005). Most of the work on cobaloximes include electron-transfer reactions (Dayalan & Vijayaraghavan,2001) and catalytic activity (Razavelt, et al., 2005) in solution. There are few literature evidences (Gupta, et al., 2000; Gupta, et al., 2001; Gupta, et al., 2004) relating the structural aspects of cobaloximes. We report here the synthesis, physical characterization and the crystal structure of a typical cobaloxime viz., pyrazine-2-tert-butylcarboxamidochlorocobaloxime. Figure 1 shows the ORTEP representation of the two independent molecules in the asymmetric unit, with 50% anisotropic ellipsoids. Figure 2 presents a packing diagram of the structure depicting the hydrogen bonding interactions. The geometry around the metal atom is octahedral; the bonds to chlorines and pyrazine N atoms are almost perpendicular to the mean glyoximate planes. The difference Fourier clearly shows one O—H group in each one of the glyoximate moieties attached to Co2, while in those attached to Co1, both hydrogen atoms are bound to only one of the glyoximate moieties. The planar glyoximate groups subtend dihedral angles of 7.76 (13)° (Co1) and 0.95 (13)° (Co2). There are strong intra molecular O—H···O hydrogen bonds linking the glyoximate moieties (Figure 2). There is one crystal water molecule per asymmetric unit (disordered into two positions O11, O11') hydrogen bonded to the chlorine atoms Cl2, attached to Co2. The corresponding water H atoms could not be located in the difference map and were not included in the model.