Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013253/cf6098sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013253/cf6098Isup2.hkl |
CCDC reference: 117501
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.048
- wR factor = 0.074
- Data-to-parameter ratio = 20.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
GOODF_01 Alert C The least squares goodness of fit parameter lies outside the range 0.80 <> 2.00 Goodness of fit given = 0.735
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound, (I), was prepared according to the reported procedure (Thomas et al., 1994). Layering dry hexane over a dichloromethane solution of the compound yielded single crystals suitable for X-ray diffraction.
Data collection: MolEN (Fair, 1990); cell refinement: MolEN; data reduction: MolEN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: PLATON.
Fig. 1. The title compound, (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. Packing diagram of the complex viewed down the b axis. |
[CoCl2(C32H38N11P3)] | Dx = 1.395 Mg m−3 |
Mr = 799.47 | Melting point: 221 dec K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 38.755 (3) Å | Cell parameters from 41 reflections |
b = 9.378 (3) Å | θ = 5.1–18.8° |
c = 22.043 (2) Å | µ = 0.76 mm−1 |
β = 108.19 (3)° | T = 293 K |
V = 7611 (3) Å3 | Prism, blue |
Z = 8 | 0.46 × 0.37 × 0.29 mm |
F(000) = 3304 |
Philips PW11100 diffractometer | 2983 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.062 |
Graphite monochromator | θmax = 28.0°, θmin = 3.0° |
θ–2θ scans | h = −51→48 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→12 |
Tmin = 0.673, Tmax = 0.803 | l = 0→29 |
9394 measured reflections | 1 standard reflections every 100 reflections |
9174 independent reflections | intensity decay: none |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.048 | |
wR(F2) = 0.074 | (Δ/σ)max = 0.001 |
S = 0.74 | Δρmax = 0.33 e Å−3 |
9174 reflections | Δρmin = −0.36 e Å−3 |
442 parameters |
[CoCl2(C32H38N11P3)] | V = 7611 (3) Å3 |
Mr = 799.47 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 38.755 (3) Å | µ = 0.76 mm−1 |
b = 9.378 (3) Å | T = 293 K |
c = 22.043 (2) Å | 0.46 × 0.37 × 0.29 mm |
β = 108.19 (3)° |
Philips PW11100 diffractometer | 2983 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.062 |
Tmin = 0.673, Tmax = 0.803 | 1 standard reflections every 100 reflections |
9394 measured reflections | intensity decay: none |
9174 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 0.74 | Δρmax = 0.33 e Å−3 |
9174 reflections | Δρmin = −0.36 e Å−3 |
442 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. |
x | y | z | Uiso*/Ueq | ||
Co | 0.107332 (15) | 0.08260 (6) | 0.64398 (2) | 0.03451 (16) | |
Cl1 | 0.14970 (3) | 0.15821 (13) | 0.73627 (5) | 0.0531 (3) | |
Cl2 | 0.06071 (3) | −0.05287 (13) | 0.65412 (6) | 0.0611 (4) | |
N5 | 0.14187 (8) | −0.0842 (4) | 0.62750 (14) | 0.0353 (9) | |
N4 | 0.15796 (8) | −0.0591 (3) | 0.58043 (14) | 0.0320 (9) | |
C13 | 0.18335 (11) | −0.1631 (5) | 0.5821 (2) | 0.0425 (12) | |
C14 | 0.18313 (11) | −0.2520 (5) | 0.6304 (2) | 0.0447 (12) | |
H14 | 0.1976 | −0.3325 | 0.6435 | 0.050* | |
C15 | 0.15756 (11) | −0.2015 (5) | 0.6568 (2) | 0.0379 (12) | |
C16 | 0.20494 (12) | −0.1613 (5) | 0.5363 (2) | 0.0620 (15) | |
H16A | 0.1976 | −0.0816 | 0.5079 | 0.050* | |
H16B | 0.2008 | −0.2481 | 0.5121 | 0.050* | |
H16C | 0.2303 | −0.1529 | 0.5597 | 0.050* | |
C17 | 0.14715 (12) | −0.2648 (5) | 0.7112 (2) | 0.0621 (15) | |
H17A | 0.1285 | −0.2078 | 0.7192 | 0.050* | |
H17B | 0.1680 | −0.2670 | 0.7487 | 0.050* | |
H17C | 0.1383 | −0.3601 | 0.7003 | 0.050* | |
P2 | 0.14202 (3) | 0.07504 (13) | 0.52784 (5) | 0.0301 (3) | |
N6 | 0.12074 (8) | −0.0100 (3) | 0.45962 (15) | 0.0359 (9) | |
N7 | 0.09186 (10) | −0.0971 (4) | 0.46213 (16) | 0.0538 (11) | |
C18 | 0.07513 (13) | −0.1289 (5) | 0.4023 (2) | 0.0599 (16) | |
C19 | 0.09191 (13) | −0.0699 (6) | 0.36077 (19) | 0.0630 (15) | |
H19 | 0.0851 | −0.0815 | 0.3167 | 0.050* | |
C20 | 0.12039 (12) | 0.0083 (5) | 0.3976 (2) | 0.0471 (13) | |
C21 | 0.04142 (14) | −0.2185 (6) | 0.3855 (2) | 0.105 (2) | |
H21A | 0.0363 | −0.2455 | 0.4238 | 0.050* | |
H21B | 0.0450 | −0.3026 | 0.3633 | 0.050* | |
H21C | 0.0214 | −0.1648 | 0.3585 | 0.050* | |
C22 | 0.14643 (13) | 0.0969 (6) | 0.37685 (19) | 0.0749 (17) | |
H22A | 0.1637 | 0.1393 | 0.4135 | 0.050* | |
H22B | 0.1335 | 0.1707 | 0.3487 | 0.050* | |
H22C | 0.1590 | 0.0381 | 0.3549 | 0.050* | |
N1 | 0.17303 (8) | 0.1696 (3) | 0.51749 (14) | 0.0321 (9) | |
P1 | 0.17412 (3) | 0.34171 (13) | 0.52595 (5) | 0.0332 (3) | |
N3 | 0.13776 (7) | 0.4112 (3) | 0.53470 (13) | 0.0317 (8) | |
P3 | 0.10493 (3) | 0.31585 (12) | 0.53502 (5) | 0.0306 (3) | |
N2 | 0.11321 (7) | 0.1508 (3) | 0.55672 (12) | 0.0269 (8) | |
N8 | 0.08363 (8) | 0.3769 (4) | 0.58572 (15) | 0.0368 (10) | |
N9 | 0.07925 (9) | 0.2867 (4) | 0.63302 (15) | 0.0379 (10) | |
C23 | 0.06250 (12) | 0.3661 (5) | 0.6638 (2) | 0.0477 (14) | |
C24 | 0.05621 (13) | 0.5042 (5) | 0.6393 (2) | 0.0606 (16) | |
H24 | 0.0449 | 0.5779 | 0.6541 | 0.050* | |
C25 | 0.06984 (12) | 0.5098 (5) | 0.5898 (2) | 0.0452 (13) | |
C26 | 0.05355 (12) | 0.3046 (5) | 0.7204 (2) | 0.0687 (16) | |
H26A | 0.0613 | 0.2069 | 0.7263 | 0.050* | |
H26B | 0.0278 | 0.3095 | 0.7129 | 0.050* | |
H26C | 0.0659 | 0.3583 | 0.7580 | 0.050* | |
C27 | 0.07229 (13) | 0.6285 (5) | 0.5467 (2) | 0.0753 (17) | |
H27A | 0.0843 | 0.5956 | 0.5172 | 0.050* | |
H27B | 0.0859 | 0.7057 | 0.5715 | 0.050* | |
H27C | 0.0483 | 0.6609 | 0.5234 | 0.050* | |
N10 | 0.07212 (8) | 0.3221 (3) | 0.46325 (14) | 0.0325 (9) | |
N11 | 0.08347 (9) | 0.3548 (4) | 0.41048 (16) | 0.0435 (10) | |
C28 | 0.05688 (13) | 0.3084 (5) | 0.3613 (2) | 0.0520 (14) | |
C29 | 0.02938 (12) | 0.2420 (5) | 0.3792 (2) | 0.0557 (14) | |
H29 | 0.0084 | 0.1999 | 0.3524 | 0.050* | |
C30 | 0.03948 (11) | 0.2512 (5) | 0.4435 (2) | 0.0448 (12) | |
C31 | 0.05900 (13) | 0.3244 (6) | 0.2954 (2) | 0.093 (2) | |
H31A | 0.0810 | 0.3735 | 0.2969 | 0.050* | |
H31B | 0.0385 | 0.3781 | 0.2700 | 0.050* | |
H31C | 0.0589 | 0.2318 | 0.2767 | 0.050* | |
C32 | 0.02140 (11) | 0.1944 (6) | 0.4894 (2) | 0.096 (2) | |
H32A | 0.0359 | 0.2168 | 0.5323 | 0.050* | |
H32B | 0.0189 | 0.0928 | 0.4847 | 0.050* | |
H32C | −0.0022 | 0.2371 | 0.4808 | 0.050* | |
C1 | 0.18243 (10) | 0.4223 (5) | 0.45740 (18) | 0.0364 (11) | |
C2 | 0.16117 (12) | 0.5368 (5) | 0.4268 (2) | 0.0543 (14) | |
H2 | 0.1430 | 0.5730 | 0.4418 | 0.050* | |
C3 | 0.16748 (13) | 0.5948 (6) | 0.3749 (2) | 0.0693 (16) | |
H3 | 0.1537 | 0.6726 | 0.3550 | 0.050* | |
C4 | 0.19313 (15) | 0.5432 (7) | 0.3512 (2) | 0.0757 (19) | |
H4 | 0.1965 | 0.5843 | 0.3150 | 0.050* | |
C5 | 0.21421 (13) | 0.4304 (6) | 0.3803 (2) | 0.0664 (16) | |
H5 | 0.2322 | 0.3952 | 0.3646 | 0.050* | |
C6 | 0.20845 (12) | 0.3699 (5) | 0.4329 (2) | 0.0518 (14) | |
H6 | 0.2224 | 0.2921 | 0.4524 | 0.050* | |
C7 | 0.21172 (10) | 0.3846 (4) | 0.59637 (19) | 0.0311 (11) | |
C8 | 0.24038 (11) | 0.4716 (5) | 0.59429 (19) | 0.0425 (12) | |
H8 | 0.2418 | 0.5057 | 0.5555 | 0.050* | |
C9 | 0.26703 (11) | 0.5068 (5) | 0.6514 (3) | 0.0593 (15) | |
H9 | 0.2859 | 0.5671 | 0.6506 | 0.050* | |
C10 | 0.26580 (12) | 0.4545 (6) | 0.7079 (2) | 0.0598 (16) | |
H10 | 0.2837 | 0.4792 | 0.7456 | 0.050* | |
C11 | 0.23810 (13) | 0.3652 (5) | 0.7097 (2) | 0.0578 (15) | |
H11 | 0.2376 | 0.3275 | 0.7485 | 0.050* | |
C12 | 0.21079 (11) | 0.3311 (5) | 0.6540 (2) | 0.0464 (13) | |
H12 | 0.1918 | 0.2719 | 0.6555 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0360 (3) | 0.0357 (4) | 0.0297 (3) | 0.0022 (4) | 0.0071 (3) | 0.0041 (3) |
Cl1 | 0.0518 (8) | 0.0597 (9) | 0.0373 (7) | 0.0056 (7) | −0.0010 (6) | −0.0052 (7) |
Cl2 | 0.0524 (8) | 0.0583 (10) | 0.0779 (9) | −0.0117 (7) | 0.0278 (7) | 0.0034 (8) |
N5 | 0.042 (2) | 0.036 (2) | 0.027 (2) | 0.008 (2) | 0.0108 (17) | 0.010 (2) |
N4 | 0.039 (2) | 0.026 (2) | 0.033 (2) | 0.0096 (19) | 0.0127 (17) | 0.0018 (18) |
C13 | 0.044 (3) | 0.029 (3) | 0.053 (3) | 0.009 (3) | 0.012 (3) | −0.005 (3) |
C14 | 0.057 (3) | 0.027 (3) | 0.045 (3) | 0.012 (3) | 0.008 (3) | 0.010 (3) |
C15 | 0.048 (3) | 0.028 (3) | 0.033 (3) | 0.003 (2) | 0.006 (2) | 0.001 (2) |
C16 | 0.071 (4) | 0.041 (3) | 0.081 (4) | 0.020 (3) | 0.034 (3) | 0.005 (3) |
C17 | 0.078 (4) | 0.055 (4) | 0.051 (3) | 0.015 (3) | 0.016 (3) | 0.012 (3) |
P2 | 0.0349 (7) | 0.0254 (7) | 0.0292 (6) | 0.0027 (7) | 0.0089 (5) | −0.0001 (6) |
N6 | 0.043 (2) | 0.034 (2) | 0.027 (2) | −0.010 (2) | 0.0057 (18) | −0.0031 (19) |
N7 | 0.068 (3) | 0.050 (3) | 0.040 (2) | −0.027 (2) | 0.012 (2) | −0.006 (2) |
C18 | 0.066 (4) | 0.066 (4) | 0.041 (3) | −0.036 (3) | 0.007 (3) | −0.010 (3) |
C19 | 0.084 (4) | 0.068 (4) | 0.033 (3) | −0.034 (4) | 0.013 (3) | −0.015 (3) |
C20 | 0.068 (4) | 0.045 (3) | 0.038 (3) | −0.010 (3) | 0.030 (3) | −0.007 (3) |
C21 | 0.114 (5) | 0.136 (6) | 0.053 (4) | −0.067 (5) | 0.007 (4) | 0.000 (4) |
C22 | 0.101 (4) | 0.098 (5) | 0.037 (3) | −0.020 (4) | 0.039 (3) | −0.015 (3) |
N1 | 0.030 (2) | 0.029 (2) | 0.039 (2) | −0.0011 (18) | 0.0124 (17) | 0.0049 (19) |
P1 | 0.0333 (7) | 0.0277 (7) | 0.0376 (7) | 0.0000 (6) | 0.0096 (6) | 0.0011 (6) |
N3 | 0.0275 (19) | 0.0236 (19) | 0.040 (2) | −0.0023 (19) | 0.0052 (16) | 0.0012 (19) |
P3 | 0.0298 (7) | 0.0298 (7) | 0.0312 (7) | 0.0061 (6) | 0.0079 (6) | 0.0025 (6) |
N2 | 0.0285 (19) | 0.028 (2) | 0.0255 (18) | −0.0002 (17) | 0.0097 (15) | 0.0013 (17) |
N8 | 0.049 (2) | 0.032 (2) | 0.033 (2) | 0.0124 (19) | 0.0172 (19) | 0.0042 (18) |
N9 | 0.044 (2) | 0.043 (3) | 0.027 (2) | 0.004 (2) | 0.0118 (18) | 0.006 (2) |
C23 | 0.054 (3) | 0.060 (4) | 0.035 (3) | 0.012 (3) | 0.021 (3) | 0.004 (3) |
C24 | 0.092 (4) | 0.044 (3) | 0.061 (4) | 0.037 (3) | 0.044 (3) | 0.007 (3) |
C25 | 0.057 (3) | 0.034 (3) | 0.049 (3) | 0.023 (3) | 0.021 (3) | 0.006 (3) |
C26 | 0.089 (4) | 0.074 (4) | 0.052 (3) | 0.020 (3) | 0.035 (3) | 0.003 (3) |
C27 | 0.118 (5) | 0.038 (4) | 0.077 (4) | 0.037 (3) | 0.043 (3) | 0.014 (3) |
N10 | 0.025 (2) | 0.041 (2) | 0.026 (2) | 0.0004 (19) | 0.0002 (17) | 0.0069 (19) |
N11 | 0.050 (2) | 0.051 (3) | 0.028 (2) | −0.002 (2) | 0.0102 (19) | 0.006 (2) |
C28 | 0.063 (4) | 0.063 (4) | 0.026 (3) | −0.005 (3) | 0.008 (3) | 0.006 (3) |
C29 | 0.044 (3) | 0.068 (4) | 0.042 (3) | −0.007 (3) | −0.005 (3) | 0.004 (3) |
C30 | 0.037 (3) | 0.063 (3) | 0.035 (3) | −0.003 (3) | 0.012 (2) | 0.008 (3) |
C31 | 0.107 (5) | 0.120 (5) | 0.043 (3) | −0.020 (4) | 0.011 (3) | 0.002 (4) |
C32 | 0.037 (3) | 0.166 (6) | 0.075 (4) | −0.035 (4) | 0.003 (3) | 0.020 (4) |
C1 | 0.035 (3) | 0.037 (3) | 0.037 (3) | −0.010 (3) | 0.012 (2) | 0.000 (3) |
C2 | 0.055 (3) | 0.051 (4) | 0.063 (4) | 0.002 (3) | 0.027 (3) | 0.017 (3) |
C3 | 0.072 (4) | 0.063 (4) | 0.068 (4) | 0.004 (3) | 0.015 (3) | 0.034 (4) |
C4 | 0.080 (4) | 0.094 (6) | 0.059 (4) | −0.020 (4) | 0.032 (3) | 0.028 (4) |
C5 | 0.075 (4) | 0.074 (4) | 0.064 (4) | −0.007 (4) | 0.043 (3) | 0.000 (4) |
C6 | 0.059 (3) | 0.048 (4) | 0.053 (3) | 0.005 (3) | 0.026 (3) | 0.007 (3) |
C7 | 0.024 (2) | 0.028 (3) | 0.039 (3) | 0.004 (2) | 0.007 (2) | −0.006 (2) |
C8 | 0.037 (3) | 0.046 (3) | 0.043 (3) | 0.005 (3) | 0.010 (2) | −0.005 (3) |
C9 | 0.026 (3) | 0.061 (4) | 0.085 (4) | −0.006 (3) | 0.009 (3) | −0.009 (3) |
C10 | 0.045 (3) | 0.073 (5) | 0.050 (3) | 0.006 (3) | −0.002 (3) | −0.018 (3) |
C11 | 0.060 (4) | 0.070 (4) | 0.038 (3) | 0.002 (3) | 0.008 (3) | 0.005 (3) |
C12 | 0.041 (3) | 0.055 (3) | 0.043 (3) | −0.007 (3) | 0.012 (2) | 0.002 (3) |
Co—N2 | 2.106 (3) | C23—C24 | 1.395 (6) |
Co—N5 | 2.162 (3) | C23—C26 | 1.512 (6) |
Co—N9 | 2.177 (3) | C24—C25 | 1.353 (5) |
Co—Cl2 | 2.2760 (13) | C24—H24 | 0.930 |
Co—Cl1 | 2.2917 (14) | C25—C27 | 1.487 (6) |
N5—C15 | 1.324 (5) | C26—H26A | 0.960 |
N5—N4 | 1.387 (4) | C26—H26B | 0.960 |
N4—C13 | 1.378 (4) | C26—H26C | 0.960 |
N4—P2 | 1.692 (3) | C27—H27A | 0.960 |
C13—C14 | 1.356 (5) | C27—H27B | 0.960 |
C13—C16 | 1.498 (5) | C27—H27C | 0.960 |
C14—C15 | 1.380 (5) | N10—C30 | 1.374 (4) |
C14—H14 | 0.930 | N10—N11 | 1.400 (4) |
C15—C17 | 1.501 (5) | N11—C28 | 1.315 (5) |
C16—H16A | 0.960 | C28—C29 | 1.394 (5) |
C16—H16B | 0.960 | C28—C31 | 1.488 (5) |
C16—H16C | 0.960 | C29—C30 | 1.350 (5) |
C17—H17A | 0.960 | C29—H29 | 0.930 |
C17—H17B | 0.960 | C30—C32 | 1.498 (5) |
C17—H17C | 0.960 | C31—H31A | 0.960 |
P2—N1 | 1.567 (3) | C31—H31B | 0.960 |
P2—N2 | 1.612 (3) | C31—H31C | 0.960 |
P2—N6 | 1.674 (3) | C32—H32A | 0.960 |
N6—C20 | 1.373 (5) | C32—H32B | 0.960 |
N6—N7 | 1.400 (4) | C32—H32C | 0.960 |
N7—C18 | 1.310 (5) | C1—C6 | 1.375 (5) |
C18—C19 | 1.392 (6) | C1—C2 | 1.393 (5) |
C18—C21 | 1.500 (6) | C2—C3 | 1.357 (6) |
C19—C20 | 1.363 (5) | C2—H2 | 0.930 |
C19—H19 | 0.930 | C3—C4 | 1.349 (6) |
C20—C22 | 1.485 (5) | C3—H3 | 0.930 |
C21—H21A | 0.960 | C4—C5 | 1.368 (6) |
C21—H21B | 0.960 | C4—H4 | 0.930 |
C21—H21C | 0.960 | C5—C6 | 1.370 (6) |
C22—H22A | 0.960 | C5—H5 | 0.930 |
C22—H22B | 0.960 | C6—H6 | 0.930 |
C22—H22C | 0.960 | C7—C12 | 1.376 (5) |
N1—P1 | 1.624 (3) | C7—C8 | 1.390 (5) |
P1—N3 | 1.618 (3) | C8—C9 | 1.396 (5) |
P1—C1 | 1.806 (4) | C8—H8 | 0.930 |
P1—C7 | 1.812 (4) | C9—C10 | 1.353 (6) |
N3—P3 | 1.557 (3) | C9—H9 | 0.930 |
P3—N2 | 1.622 (3) | C10—C11 | 1.372 (6) |
P3—N8 | 1.683 (3) | C10—H10 | 0.930 |
P3—N10 | 1.693 (3) | C11—C12 | 1.386 (5) |
N8—C25 | 1.370 (5) | C11—H11 | 0.930 |
N8—N9 | 1.394 (4) | C12—H12 | 0.930 |
N9—C23 | 1.308 (5) | ||
N2—Co—N5 | 79.45 (12) | N9—N8—P3 | 119.3 (3) |
N2—Co—N9 | 79.90 (12) | C23—N9—N8 | 103.8 (4) |
N5—Co—N9 | 158.67 (13) | C23—N9—Co | 139.0 (3) |
N2—Co—Cl2 | 125.08 (9) | N8—N9—Co | 116.3 (2) |
N5—Co—Cl2 | 99.48 (10) | N9—C23—C24 | 112.6 (4) |
N9—Co—Cl2 | 96.72 (10) | N9—C23—C26 | 119.3 (5) |
N2—Co—Cl1 | 117.71 (8) | C24—C23—C26 | 128.1 (5) |
N5—Co—Cl1 | 93.63 (9) | C25—C24—C23 | 106.4 (4) |
N9—Co—Cl1 | 91.23 (9) | C25—C24—H24 | 126.8 |
Cl2—Co—Cl1 | 117.15 (5) | C23—C24—H24 | 126.8 |
C15—N5—N4 | 105.1 (3) | C24—C25—N8 | 106.1 (4) |
C15—N5—Co | 137.2 (3) | C24—C25—C27 | 131.6 (4) |
N4—N5—Co | 116.7 (3) | N8—C25—C27 | 122.3 (4) |
C13—N4—N5 | 110.2 (3) | C23—C26—H26A | 109.5 |
C13—N4—P2 | 130.5 (3) | C23—C26—H26B | 109.5 |
N5—N4—P2 | 119.0 (3) | H26A—C26—H26B | 109.5 |
C14—C13—N4 | 106.0 (4) | C23—C26—H26C | 109.5 |
C14—C13—C16 | 132.7 (4) | H26A—C26—H26C | 109.5 |
N4—C13—C16 | 121.2 (4) | H26B—C26—H26C | 109.5 |
C13—C14—C15 | 107.5 (4) | C25—C27—H27A | 109.5 |
C13—C14—H14 | 126.2 | C25—C27—H27B | 109.5 |
C15—C14—H14 | 126.2 | H27A—C27—H27B | 109.5 |
N5—C15—C14 | 111.2 (4) | C25—C27—H27C | 109.5 |
N5—C15—C17 | 121.4 (4) | H27A—C27—H27C | 109.5 |
C14—C15—C17 | 127.4 (4) | H27B—C27—H27C | 109.5 |
C13—C16—H16A | 109.5 | C30—N10—N11 | 109.8 (3) |
C13—C16—H16B | 109.5 | C30—N10—P3 | 128.9 (3) |
H16A—C16—H16B | 109.5 | N11—N10—P3 | 116.4 (3) |
C13—C16—H16C | 109.5 | C28—N11—N10 | 104.2 (3) |
H16A—C16—H16C | 109.5 | N11—C28—C29 | 112.7 (4) |
H16B—C16—H16C | 109.5 | N11—C28—C31 | 120.3 (4) |
C15—C17—H17A | 109.5 | C29—C28—C31 | 127.0 (5) |
C15—C17—H17B | 109.5 | C30—C29—C28 | 105.8 (4) |
H17A—C17—H17B | 109.5 | C30—C29—H29 | 127.1 |
C15—C17—H17C | 109.5 | C28—C29—H29 | 127.1 |
H17A—C17—H17C | 109.5 | C29—C30—N10 | 107.5 (4) |
H17B—C17—H17C | 109.5 | C29—C30—C32 | 130.1 (5) |
N1—P2—N2 | 117.74 (17) | N10—C30—C32 | 122.4 (4) |
N1—P2—N6 | 108.91 (17) | C28—C31—H31A | 109.5 |
N2—P2—N6 | 110.91 (16) | C28—C31—H31B | 109.5 |
N1—P2—N4 | 112.83 (16) | H31A—C31—H31B | 109.5 |
N2—P2—N4 | 101.93 (16) | C28—C31—H31C | 109.5 |
N6—P2—N4 | 103.50 (16) | H31A—C31—H31C | 109.5 |
C20—N6—N7 | 110.7 (3) | H31B—C31—H31C | 109.5 |
C20—N6—P2 | 133.1 (3) | C30—C32—H32A | 109.5 |
N7—N6—P2 | 114.7 (3) | C30—C32—H32B | 109.5 |
C18—N7—N6 | 104.1 (4) | H32A—C32—H32B | 109.5 |
N7—C18—C19 | 112.7 (4) | C30—C32—H32C | 109.5 |
N7—C18—C21 | 119.7 (5) | H32A—C32—H32C | 109.5 |
C19—C18—C21 | 127.6 (5) | H32B—C32—H32C | 109.5 |
C20—C19—C18 | 106.2 (4) | C6—C1—C2 | 118.7 (4) |
C20—C19—H19 | 126.9 | C6—C1—P1 | 121.6 (4) |
C18—C19—H19 | 126.9 | C2—C1—P1 | 119.6 (3) |
C19—C20—N6 | 106.3 (4) | C3—C2—C1 | 118.8 (4) |
C19—C20—C22 | 128.2 (4) | C3—C2—H2 | 120.6 |
N6—C20—C22 | 125.5 (4) | C1—C2—H2 | 120.6 |
C18—C21—H21A | 109.5 | C4—C3—C2 | 122.2 (5) |
C18—C21—H21B | 109.5 | C4—C3—H3 | 118.9 |
H21A—C21—H21B | 109.5 | C2—C3—H3 | 118.9 |
C18—C21—H21C | 109.5 | C3—C4—C5 | 120.0 (5) |
H21A—C21—H21C | 109.5 | C3—C4—H4 | 120.0 |
H21B—C21—H21C | 109.5 | C5—C4—H4 | 120.0 |
C20—C22—H22A | 109.5 | C4—C5—C6 | 119.1 (5) |
C20—C22—H22B | 109.5 | C4—C5—H5 | 120.5 |
H22A—C22—H22B | 109.5 | C6—C5—H5 | 120.5 |
C20—C22—H22C | 109.5 | C5—C6—C1 | 121.2 (4) |
H22A—C22—H22C | 109.5 | C5—C6—H6 | 119.4 |
H22B—C22—H22C | 109.5 | C1—C6—H6 | 119.4 |
P2—N1—P1 | 122.6 (2) | C12—C7—C8 | 119.7 (4) |
N3—P1—N1 | 114.96 (17) | C12—C7—P1 | 117.6 (3) |
N3—P1—C1 | 108.69 (19) | C8—C7—P1 | 122.6 (3) |
N1—P1—C1 | 108.95 (19) | C7—C8—C9 | 118.9 (4) |
N3—P1—C7 | 107.80 (17) | C7—C8—H8 | 120.6 |
N1—P1—C7 | 107.72 (18) | C9—C8—H8 | 120.6 |
C1—P1—C7 | 108.55 (19) | C10—C9—C8 | 121.0 (4) |
P3—N3—P1 | 120.8 (2) | C10—C9—H9 | 119.5 |
N3—P3—N2 | 117.56 (17) | C8—C9—H9 | 119.5 |
N3—P3—N8 | 112.24 (17) | C9—C10—C11 | 120.0 (4) |
N2—P3—N8 | 102.80 (17) | C9—C10—H10 | 120.0 |
N3—P3—N10 | 110.61 (17) | C11—C10—H10 | 120.0 |
N2—P3—N10 | 109.28 (16) | C10—C11—C12 | 120.2 (4) |
N8—P3—N10 | 103.16 (16) | C10—C11—H11 | 119.9 |
P2—N2—P3 | 113.67 (18) | C12—C11—H11 | 119.9 |
P2—N2—Co | 120.84 (16) | C7—C12—C11 | 120.1 (4) |
P3—N2—Co | 119.41 (16) | C7—C12—H12 | 120.0 |
C25—N8—N9 | 111.2 (3) | C11—C12—H12 | 120.0 |
C25—N8—P3 | 129.4 (3) |
Experimental details
Crystal data | |
Chemical formula | [CoCl2(C32H38N11P3)] |
Mr | 799.47 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 38.755 (3), 9.378 (3), 22.043 (2) |
β (°) | 108.19 (3) |
V (Å3) | 7611 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.76 |
Crystal size (mm) | 0.46 × 0.37 × 0.29 |
Data collection | |
Diffractometer | Philips PW11100 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.673, 0.803 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9394, 9174, 2983 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.074, 0.74 |
No. of reflections | 9174 |
No. of parameters | 442 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.36 |
Computer programs: MolEN (Fair, 1990), MolEN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2000), PLATON.
Co—N2 | 2.106 (3) | P2—N2 | 1.612 (3) |
Co—N5 | 2.162 (3) | N1—P1 | 1.624 (3) |
Co—N9 | 2.177 (3) | P1—N3 | 1.618 (3) |
Co—Cl2 | 2.2760 (13) | N3—P3 | 1.557 (3) |
Co—Cl1 | 2.2917 (14) | P3—N2 | 1.622 (3) |
P2—N1 | 1.567 (3) | ||
N2—Co—N5 | 79.45 (12) | N9—Co—Cl1 | 91.23 (9) |
N2—Co—N9 | 79.90 (12) | Cl2—Co—Cl1 | 117.15 (5) |
N5—Co—N9 | 158.67 (13) | N1—P2—N2 | 117.74 (17) |
N2—Co—Cl2 | 125.08 (9) | P2—N1—P1 | 122.6 (2) |
N5—Co—Cl2 | 99.48 (10) | N3—P1—N1 | 114.96 (17) |
N9—Co—Cl2 | 96.72 (10) | P3—N3—P1 | 120.8 (2) |
N2—Co—Cl1 | 117.71 (8) | N3—P3—N2 | 117.56 (17) |
N5—Co—Cl1 | 93.63 (9) | P2—N2—P3 | 113.67 (18) |
Pyrazolyl derivatives containing main group elements, such as boron (pyrazolylborates) and phosphorus, have received much attention in recent years due to their varying modes of interaction with transition metals (Trofimenko, 1993; Parkin, 1995; Reger, 1996; Kitajima & Tolman, 1995). The pyrazole (pz) moiety also occurs in some drug molecules such as antipyrine and celecoxib. We have been studying the coordination behaviour of pyrazolylcyclotriphosphazenes towards transition metals. Previously, we reported the synthesis and characterization of a series of transition metal complexes derived from the cyclotriphosphazene (ctp) ligands, hexakis(3,5-dimethylpyrazole-1-yl)cyclotriphosphazene (hdpctp) (Thomas, Chandrasekhar, Pal et al., 1993; Thomas, Chandrasekhar, Scott et al., 1993), 2,2-diphenyl-4,4,6,6-tetrakis(3,5-dimethylpyrazol-1-yl)cyclotriphosphazene (tdpctp) (Thomas et al., 1994; Thomas, Tharmaraj et al., 1995), and 2,2-diphenyl-4,4,6,6-tetrakis(1-pyrazolyl)cyclotriphosphazene (tpctp) (Thomas, Chandrasekhar et al., 1995). The cyclotriphosphazene interaction varies with the nature of the transition metal in the tdpctp complexes. While the Cu—Nctp distance is longer, the Ni—Nctp distance is appreciably shorter and comparable to the Ni—Npz bond length. This discrepancy has prompted us to examine the crystal structure of the present cobalt complex, [tdpctp·CoCl2], (I).
The N3 donor set afforded by the potentially multidentate ligand, tdpctp, comprises of two non-geminal pyrazolyl N atoms and one cyclotriphosphazene skeletal N atom. The coordination geometry of the Co atom is best described as a trigonal bipyramid with slight distortion. The trigonal plane of the coordination polyhedron is derived from the two Cl- ions and a cyclotriphosphazene ring N atom. The two non-geminal pyrazole N atoms fill the axial postions. For the title cobalt complex, (I), and the nickel complex [tdpctp·NiCl2], (II) (Thomas et al., 1994), the M—Nctp and M—Npz bond distances are comparable [2.106 (3) and 2.170 (3) Å for (I), and 2.079 (3) and 2.085 (4) Å for (II), respectively] and the small differences may arise from the difference in the basicity of the cyclophosphazene and pyrazole N atoms. On the other hand, for the related copper and cobalt complexes, [tdpctp·CuCl2], (III) (Thomas, Chandrasekhar, Pal et al., 1993), and [tpctp·CoCl2], (IV) (Thomas et al., 1994), these M—Nctp and M—Npz bond distances exhibit anomalous differences [2.320 (5) and 1.979 (5) Å for (III), and 2.419 (3) and 2.050 (4) Å for (IV), respectively], which may be due to the axial elongation induced by a Jahn–Teller effect in the copper complex and the resultant reduced basicity from the absence of methyl substituents on the pyrazole nucleus in the cobalt complex. Another striking difference between cobalt complexes (I) and (IV) is the Npz—Co—Npz bond angle [158.67 (13) and 114.03 (14)° for (I) and (IV), respectively]. Although both the complexes have trigonal-bipyramidal geometry, the trigonal plane in (I) is composed of the Nctp atom and two Cl- ions, where as in (IV) it consists of two Npz atoms and a Cl- ion. This difference in the spatial arrangement is mainly attributed to the enhanced steric effect exerted by the methyl substituents in the tdpctp ligand. The Cl—M—Cl angles are within the normal trigonal range for the cobalt and nickel complexes, (I) and (II) [117.15 (5) and 114.77 (6)°, respectively], and the corresponding Cl—M—Cl angle in copper complex (III) is widened [132.21 (8) Å]; probably the structure is approaching a square-based pyramidal one. This conclusion is also arrived at by comparing the trigonal distortion parameters (τ; Addison et al., 1984), for which the values are 0.56, 0.53 and 0.45 for the complexes (I), (II) and (III), respectively. In the cyclophosphazene skeleton of (I), the P—N bond associated with the coordinating N atom is elongated [1.614(3 Å] and the adjacent P—N bond is shortened [1.564 (2) Å]. Even though a similar trend has been observed for the geminal N3P3X2Y4-type compounds (where X is an electron-withdrawing group; Chandrasekhar & Thomas, 1993), as well as in the related metal complexes (II), (III) and (IV), it is found that the metal interaction reinforces the effect. The P—N—P angles are normally around 120° and that for the N atom interacting with the metal is close to the value of the tetrahedral angle [113.67 (18) Å]. This indicates that the N atom undergoes a hydridization change from sp2 to sp3 due to the metal coordination. The cyclotriphosphazene ring significantly deviates from planarity, while pyrazole groups do not show any noteworthy distortions.