4'-Cyanophenyl-2,2':6',2''-terpyridine (cptpy) was employed as an N,N',N''-tridentate ligand to synthesize the compounds bis[4'-(4-cyanophenyl)-2,2':6',2''-terpyridine]cobalt(II) bis(tetrafluoridoborate) nitromethane solvate, [CoII(C22H14N4)2](BF4)2·CH3NO2, (I), and bis[4'-(4-cyanophenyl)-2,2':6',2''-terpyridine]cobalt(III) tris(tetrafluoridoborate) nitromethane sesquisolvate, [CoIII(C22H14N4)2](BF4)3·1.5CH3NO2, (II). In both complexes, the cobalt ions occupy a distorted octahedral geometry with two cptpy ligands in a meridional configuration. A greater distortion from octahedral geometry is observed in (I), which indicates a different steric consequence of the constrained ligand bite on the CoII and CoIII ions. The crystal structure of (I) features an interlocked sheet motif, which differs from the one-dimensional chain packing style present in (II). The lower dimensionality in (II) can be explained by the disturbance caused by the larger number of anions and solvent molecules involved in the crystal structure of (II). All atoms in (I) are on general positions, and the F atoms of one BF4- anion are disordered. In (II), one B atom is on an inversion center, necessitating disorder of the four attached F atoms, another B atom is on a twofold axis with ordered F atoms, and the C and N atoms of one nitromethane solvent molecule are on a twofold axis, causing disorder of the methyl H atoms. This relatively uncommon study of analogous CoII and CoIII complexes provides a better understanding of the effects of different oxidation states on coordination geometry and crystal packing.
Supporting information
CCDC references: 690179; 690180
4'-Cyanophenyl-2,2':6',2''-terpyridine was synthesized according to literature
procedures (Chamchoumis & Potvin, 1998; Constable et al.,
1990). For
the synthesis of (I), a solution of Co(BF4)2.6H2O (0.1 mmol) in methanol
(20 ml) was layered over a solution of cptpy (0.2 mmol) in dichloromethane (20 ml). Red needle-shaped crystals of (I) formed after one week at 278 K. Red
block-shaped crystals of (I) suitable for X-ray diffraction were obtained by
recrystallization from a nitromethane/diethyl ether system after one week at
313 K. Complex (II) was prepared by adding a tetrahydrofuran solution of
AgBF4 to a nitromethane solution of (I) [quantities of reagents?].
After one week at room temperature, orange crystals of (II) suitable for X-ray
diffraction were obtained. Oxidation by the AgI ion resulted in the
formation of the CoIII species from (I).
All H atoms were positioned geometrically and treated as riding [C—H = 0.95
and 0.98 Å, and Uiso(H) = 1.2Ueq(C)]. One BF4- anion
(containing B2) in (I) was disordered such that three of the F atoms were each
distributed over two positions with 50% occupancy. In (II) one BF4- anion
(containing B4) was disordered with all four F atoms statistically distributed
over two sites related by inversion symmetry. The methyl H atoms on one
nitromethane molecule (containing N10 and C46) were statistically disordered
over two sets of positions related by twofold rotation.
For both compounds, data collection: CrystalClear (Rigaku Corporation, 2001); cell refinement: CrystalClear (Rigaku Corporation, 2001). Data reduction: CrystalStructure (Rigaku Corporation, 2001) for (I); TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000) for (II). Program(s) used to solve structure: SIR97 (Altomare et al., 1994) for (I); SIR92 (Altomare et al., 1994) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: CrystalStructure (Rigaku Corporation, 2001) for (I); TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000) for (II). Software used to prepare material for publication: CrystalStructure (Rigaku Corporation, 2001) for (I); TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000) for (II).
(I) bis[4'-(4-cyanophenyl)-2,2':6',2''-terpyridine]cobalt(II)
bis(tetrafluoridoborate)
nitromethane solvate
top
Crystal data top
[Co(C22H14N4)2](BF4)2·CH3NO2 | F(000) = 1956.00 |
Mr = 962.34 | Dx = 1.552 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: C -2yc | Cell parameters from 4860 reflections |
a = 13.304 (13) Å | θ = 3.1–27.5° |
b = 12.125 (12) Å | µ = 0.51 mm−1 |
c = 27.30 (3) Å | T = 120 K |
β = 110.761 (12)° | Block, red |
V = 4118 (7) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 4 | |
Data collection top
Rigaku Mercury diffractometer | Rint = 0.056 |
Detector resolution: 7.31 pixels mm-1 | θmax = 27.5° |
ω scans | h = −11→17 |
23489 measured reflections | k = −15→15 |
8003 independent reflections | l = −35→35 |
6271 reflections with F2 > 2σ(F2) | |
Refinement top
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0976P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.070 | (Δ/σ)max < 0.001 |
wR(F2) = 0.169 | Δρmax = 1.13 e Å−3 |
S = 1.04 | Δρmin = −0.43 e Å−3 |
8003 reflections | Absolute structure: Flack (1983), 3285 Friedel pairs |
632 parameters | Absolute structure parameter: 0.026 (19) |
H-atom parameters constrained | |
Crystal data top
[Co(C22H14N4)2](BF4)2·CH3NO2 | V = 4118 (7) Å3 |
Mr = 962.34 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 13.304 (13) Å | µ = 0.51 mm−1 |
b = 12.125 (12) Å | T = 120 K |
c = 27.30 (3) Å | 0.20 × 0.20 × 0.10 mm |
β = 110.761 (12)° | |
Data collection top
Rigaku Mercury diffractometer | 6271 reflections with F2 > 2σ(F2) |
23489 measured reflections | Rint = 0.056 |
8003 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.070 | H-atom parameters constrained |
wR(F2) = 0.169 | Δρmax = 1.13 e Å−3 |
S = 1.04 | Δρmin = −0.43 e Å−3 |
8003 reflections | Absolute structure: Flack (1983), 3285 Friedel pairs |
632 parameters | Absolute structure parameter: 0.026 (19) |
Special details top
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement was performed using all reflections. The weighted R-factor
(wR) and goodness of fit (S) are based on F^2^.
R-factor (gt) are based on F. The threshold expression of
F^2^ > 2.0 σ(F^2^) is used only for calculating
R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.91661 (6) | 0.24303 (5) | 0.36935 (3) | 0.03026 (16) | |
F1 | 0.9936 (2) | −0.0648 (2) | 0.58424 (13) | 0.0515 (8) | |
F2 | 0.9909 (4) | 0.0583 (4) | 0.64513 (18) | 0.0949 (15) | |
F3 | 0.8384 (4) | −0.0294 (4) | 0.5993 (3) | 0.118 (2) | |
F4 | 0.9105 (4) | 0.1021 (3) | 0.5635 (2) | 0.0883 (15) | |
F5 | 0.8793 (9) | 0.2208 (19) | 0.7061 (3) | 0.120 (7) | 0.50 |
F6 | 0.8582 (8) | 0.3335 (12) | 0.7600 (9) | 0.109 (6) | 0.50 |
F7 | 0.8242 (11) | 0.1657 (17) | 0.7668 (9) | 0.169 (11) | 0.50 |
F8 | 0.7105 (3) | 0.2575 (3) | 0.70447 (15) | 0.0601 (11) | |
F9 | 0.8388 (11) | 0.245 (2) | 0.7844 (3) | 0.165 (11) | 0.50 |
F10 | 0.8748 (15) | 0.307 (2) | 0.7225 (13) | 0.254 (18) | 0.50 |
F11 | 0.8421 (11) | 0.1373 (13) | 0.7286 (12) | 0.187 (12) | 0.50 |
O1 | 0.6148 (6) | 0.2537 (4) | 0.5200 (2) | 0.080 (2) | |
O2 | 0.7191 (4) | 0.3928 (4) | 0.5257 (2) | 0.0738 (14) | |
N1 | 0.9913 (3) | 0.4008 (3) | 0.38735 (18) | 0.0407 (10) | |
N2 | 1.0126 (4) | 0.2289 (3) | 0.4447 (2) | 0.0342 (11) | |
N3 | 0.8744 (3) | 0.0838 (3) | 0.39044 (16) | 0.0316 (9) | |
N4 | 1.0294 (3) | 0.1764 (3) | 0.33722 (16) | 0.0315 (9) | |
N5 | 0.8273 (3) | 0.2282 (3) | 0.29211 (19) | 0.0296 (10) | |
N6 | 0.7655 (3) | 0.3110 (3) | 0.36453 (17) | 0.0339 (9) | |
N7 | 1.5792 (4) | 0.0508 (5) | 0.7683 (2) | 0.0658 (16) | |
N8 | 0.3523 (4) | −0.0829 (4) | −0.02878 (19) | 0.0515 (13) | |
N9 | 0.6898 (5) | 0.3110 (4) | 0.5441 (2) | 0.0553 (13) | |
C1 | 1.0849 (4) | 0.3074 (4) | 0.4682 (2) | 0.0352 (11) | |
C2 | 1.1641 (4) | 0.2917 (4) | 0.5160 (2) | 0.0339 (11) | |
C3 | 1.1691 (4) | 0.1909 (4) | 0.5415 (2) | 0.0375 (12) | |
C4 | 1.0928 (4) | 0.1114 (4) | 0.5185 (2) | 0.0342 (11) | |
C5 | 1.0162 (4) | 0.1298 (4) | 0.46995 (19) | 0.0312 (10) | |
C6 | 1.0693 (4) | 0.4100 (4) | 0.4368 (2) | 0.0337 (11) | |
C7 | 1.1244 (4) | 0.5069 (4) | 0.4540 (2) | 0.0418 (13) | |
C8 | 1.1012 (5) | 0.5964 (5) | 0.4211 (2) | 0.0547 (16) | |
C9 | 1.0240 (5) | 0.5896 (4) | 0.3723 (2) | 0.0503 (15) | |
C10 | 0.9718 (5) | 0.4901 (5) | 0.3572 (2) | 0.0498 (14) | |
C11 | 0.9350 (4) | 0.0503 (3) | 0.4394 (2) | 0.0319 (11) | |
C12 | 0.9217 (4) | −0.0555 (4) | 0.4572 (2) | 0.0349 (11) | |
C13 | 0.8477 (4) | −0.1260 (4) | 0.4249 (2) | 0.0373 (12) | |
C14 | 0.7853 (4) | −0.0922 (4) | 0.3754 (2) | 0.0380 (13) | |
C15 | 0.7986 (4) | 0.0149 (4) | 0.3599 (2) | 0.0385 (12) | |
C16 | 1.2574 (4) | 0.1660 (4) | 0.5929 (2) | 0.0338 (11) | |
C17 | 1.3586 (4) | 0.2151 (4) | 0.6048 (2) | 0.0390 (12) | |
C18 | 1.4413 (4) | 0.1884 (5) | 0.6502 (2) | 0.0464 (14) | |
C19 | 1.4244 (4) | 0.1107 (5) | 0.6848 (2) | 0.0398 (13) | |
C20 | 1.3238 (4) | 0.0641 (5) | 0.6739 (2) | 0.0419 (13) | |
C21 | 1.2395 (4) | 0.0924 (4) | 0.6290 (2) | 0.0436 (13) | |
C22 | 1.5122 (5) | 0.0794 (5) | 0.7316 (2) | 0.0502 (15) | |
C23 | 0.8695 (4) | 0.1703 (4) | 0.2618 (2) | 0.0339 (11) | |
C24 | 0.8056 (4) | 0.1311 (4) | 0.2130 (2) | 0.0321 (11) | |
C25 | 0.6949 (4) | 0.1545 (4) | 0.1951 (2) | 0.0343 (11) | |
C26 | 0.6547 (4) | 0.2158 (4) | 0.2270 (2) | 0.0370 (12) | |
C27 | 0.7222 (4) | 0.2488 (4) | 0.27568 (19) | 0.0311 (11) | |
C28 | 0.9870 (4) | 0.1495 (4) | 0.2866 (2) | 0.0331 (11) | |
C29 | 1.0487 (4) | 0.1083 (4) | 0.2587 (2) | 0.0340 (11) | |
C30 | 1.1589 (4) | 0.0954 (4) | 0.2853 (2) | 0.0405 (12) | |
C31 | 1.2019 (4) | 0.1214 (4) | 0.3372 (2) | 0.0389 (12) | |
C32 | 1.1352 (4) | 0.1598 (4) | 0.3625 (2) | 0.0350 (11) | |
C33 | 0.6866 (4) | 0.3030 (3) | 0.3160 (2) | 0.0316 (10) | |
C34 | 0.5824 (4) | 0.3395 (4) | 0.3062 (2) | 0.0390 (12) | |
C35 | 0.5577 (4) | 0.3833 (4) | 0.3472 (2) | 0.0408 (13) | |
C36 | 0.6365 (4) | 0.3917 (4) | 0.3964 (2) | 0.0414 (13) | |
C37 | 0.7396 (4) | 0.3559 (4) | 0.4027 (2) | 0.0390 (12) | |
C38 | 0.6209 (4) | 0.1063 (4) | 0.14486 (19) | 0.0327 (11) | |
C39 | 0.6397 (5) | −0.0003 (4) | 0.1313 (2) | 0.0431 (13) | |
C40 | 0.5685 (5) | −0.0474 (4) | 0.0862 (2) | 0.0482 (14) | |
C41 | 0.4841 (4) | 0.0140 (4) | 0.0536 (2) | 0.0384 (12) | |
C42 | 0.4685 (5) | 0.1231 (4) | 0.0653 (2) | 0.0416 (13) | |
C43 | 0.5382 (4) | 0.1677 (5) | 0.1114 (2) | 0.0433 (13) | |
C44 | 0.4099 (4) | −0.0390 (4) | 0.0062 (2) | 0.0424 (13) | |
C45 | 0.7466 (6) | 0.2862 (6) | 0.6000 (2) | 0.0622 (18) | |
B1 | 0.9282 (5) | 0.0141 (5) | 0.5972 (2) | 0.0426 (15) | |
B2 | 0.8179 (5) | 0.2396 (6) | 0.7338 (2) | 0.0449 (16) | |
H2 | 1.2147 | 0.3483 | 0.5316 | 0.041* | |
H4 | 1.0933 | 0.0439 | 0.5362 | 0.041* | |
H7 | 1.1777 | 0.5117 | 0.4880 | 0.050* | |
H8 | 1.1392 | 0.6636 | 0.4323 | 0.066* | |
H9 | 1.0067 | 0.6514 | 0.3494 | 0.060* | |
H10 | 0.9185 | 0.4851 | 0.3231 | 0.060* | |
H12 | 0.9642 | −0.0779 | 0.4917 | 0.042* | |
H13 | 0.8395 | −0.1981 | 0.4365 | 0.045* | |
H14 | 0.7341 | −0.1406 | 0.3523 | 0.046* | |
H15 | 0.7524 | 0.0401 | 0.3265 | 0.046* | |
H17 | 1.3701 | 0.2671 | 0.5813 | 0.047* | |
H18 | 1.5097 | 0.2221 | 0.6583 | 0.056* | |
H20 | 1.3127 | 0.0121 | 0.6975 | 0.050* | |
H21 | 1.1699 | 0.0626 | 0.6225 | 0.052* | |
H24 | 0.8358 | 0.0895 | 0.1922 | 0.039* | |
H26 | 0.5807 | 0.2349 | 0.2152 | 0.044* | |
H29 | 1.0166 | 0.0897 | 0.2226 | 0.041* | |
H30 | 1.2036 | 0.0686 | 0.2675 | 0.049* | |
H31 | 1.2769 | 0.1133 | 0.3558 | 0.047* | |
H32 | 1.1651 | 0.1750 | 0.3990 | 0.042* | |
H34 | 0.5293 | 0.3345 | 0.2721 | 0.047* | |
H35 | 0.4866 | 0.4076 | 0.3417 | 0.049* | |
H36 | 0.6207 | 0.4212 | 0.4251 | 0.050* | |
H37 | 0.7943 | 0.3639 | 0.4361 | 0.047* | |
H39 | 0.7007 | −0.0403 | 0.1529 | 0.052* | |
H40 | 0.5778 | −0.1218 | 0.0777 | 0.058* | |
H42 | 0.4114 | 0.1657 | 0.0422 | 0.050* | |
H43 | 0.5288 | 0.2419 | 0.1201 | 0.052* | |
H45A | 0.7145 | 0.3288 | 0.6212 | 0.075* | |
H45B | 0.8226 | 0.3059 | 0.6098 | 0.075* | |
H45C | 0.7403 | 0.2072 | 0.6062 | 0.075* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0292 (3) | 0.0317 (3) | 0.0299 (2) | 0.0003 (3) | 0.0106 (2) | 0.0018 (3) |
F1 | 0.059 (2) | 0.0513 (19) | 0.0524 (19) | −0.0036 (16) | 0.0294 (17) | 0.0012 (16) |
F2 | 0.110 (3) | 0.101 (3) | 0.070 (2) | 0.004 (3) | 0.028 (2) | −0.016 (2) |
F3 | 0.094 (3) | 0.070 (3) | 0.225 (6) | −0.019 (2) | 0.099 (4) | −0.020 (3) |
F4 | 0.131 (4) | 0.057 (2) | 0.105 (3) | 0.017 (2) | 0.077 (3) | 0.013 (2) |
F5 | 0.039 (6) | 0.29 (2) | 0.034 (4) | 0.065 (10) | 0.009 (3) | −0.035 (8) |
F6 | 0.030 (4) | 0.100 (9) | 0.194 (17) | −0.016 (5) | 0.036 (8) | −0.101 (11) |
F7 | 0.063 (7) | 0.179 (16) | 0.25 (2) | 0.022 (11) | 0.040 (13) | 0.202 (18) |
F8 | 0.036 (2) | 0.097 (3) | 0.042 (2) | 0.0088 (18) | 0.0060 (16) | −0.0158 (19) |
F9 | 0.056 (8) | 0.41 (3) | 0.022 (4) | 0.060 (16) | 0.003 (4) | −0.028 (9) |
F10 | 0.091 (15) | 0.29 (2) | 0.29 (3) | −0.091 (19) | −0.047 (16) | 0.24 (2) |
F11 | 0.051 (8) | 0.095 (9) | 0.34 (2) | 0.021 (6) | −0.025 (12) | −0.134 (14) |
O1 | 0.116 (5) | 0.056 (3) | 0.052 (3) | −0.016 (3) | 0.007 (3) | 0.011 (2) |
O2 | 0.070 (3) | 0.073 (3) | 0.086 (3) | 0.017 (2) | 0.037 (2) | 0.030 (2) |
N1 | 0.038 (2) | 0.042 (2) | 0.045 (2) | −0.001 (2) | 0.019 (2) | 0.003 (2) |
N2 | 0.046 (3) | 0.025 (2) | 0.038 (2) | 0.001 (2) | 0.023 (2) | 0.0021 (19) |
N3 | 0.027 (2) | 0.033 (2) | 0.032 (2) | −0.0019 (18) | 0.0057 (18) | −0.0019 (18) |
N4 | 0.032 (2) | 0.029 (2) | 0.033 (2) | −0.0050 (18) | 0.0109 (18) | −0.0018 (18) |
N5 | 0.024 (2) | 0.032 (2) | 0.033 (2) | 0.0034 (19) | 0.011 (2) | 0.0045 (19) |
N6 | 0.036 (2) | 0.029 (2) | 0.041 (2) | −0.0042 (19) | 0.020 (2) | −0.0024 (19) |
N7 | 0.042 (3) | 0.101 (4) | 0.051 (3) | 0.004 (3) | 0.012 (2) | 0.004 (3) |
N8 | 0.057 (3) | 0.044 (2) | 0.040 (2) | 0.003 (2) | 0.000 (2) | −0.009 (2) |
N9 | 0.068 (3) | 0.053 (3) | 0.049 (3) | 0.011 (3) | 0.025 (2) | 0.015 (2) |
C1 | 0.040 (3) | 0.030 (2) | 0.045 (3) | −0.005 (2) | 0.028 (2) | −0.009 (2) |
C2 | 0.033 (2) | 0.030 (2) | 0.039 (2) | −0.009 (2) | 0.012 (2) | −0.008 (2) |
C3 | 0.025 (2) | 0.043 (3) | 0.041 (2) | −0.001 (2) | 0.007 (2) | −0.005 (2) |
C4 | 0.036 (3) | 0.033 (2) | 0.036 (2) | −0.002 (2) | 0.015 (2) | 0.005 (2) |
C5 | 0.033 (2) | 0.028 (2) | 0.033 (2) | 0.001 (2) | 0.012 (2) | 0.002 (2) |
C6 | 0.030 (2) | 0.030 (2) | 0.051 (3) | −0.002 (2) | 0.026 (2) | 0.000 (2) |
C7 | 0.047 (3) | 0.029 (2) | 0.058 (3) | −0.009 (2) | 0.028 (2) | −0.005 (2) |
C8 | 0.069 (4) | 0.042 (3) | 0.069 (4) | −0.008 (3) | 0.043 (3) | −0.003 (3) |
C9 | 0.058 (4) | 0.030 (2) | 0.075 (4) | 0.004 (2) | 0.037 (3) | 0.014 (3) |
C10 | 0.050 (3) | 0.046 (3) | 0.061 (3) | 0.015 (2) | 0.029 (3) | 0.019 (3) |
C11 | 0.033 (2) | 0.029 (2) | 0.039 (2) | 0.005 (2) | 0.019 (2) | 0.003 (2) |
C12 | 0.039 (3) | 0.031 (2) | 0.035 (2) | 0.002 (2) | 0.013 (2) | 0.005 (2) |
C13 | 0.036 (3) | 0.035 (2) | 0.041 (2) | −0.004 (2) | 0.014 (2) | 0.011 (2) |
C14 | 0.044 (3) | 0.031 (2) | 0.037 (3) | −0.004 (2) | 0.011 (2) | 0.002 (2) |
C15 | 0.037 (3) | 0.037 (2) | 0.040 (2) | −0.001 (2) | 0.011 (2) | 0.007 (2) |
C16 | 0.032 (2) | 0.034 (2) | 0.037 (2) | −0.001 (2) | 0.014 (2) | −0.009 (2) |
C17 | 0.043 (3) | 0.041 (2) | 0.035 (2) | −0.007 (2) | 0.017 (2) | −0.005 (2) |
C18 | 0.038 (3) | 0.058 (3) | 0.045 (3) | −0.009 (2) | 0.018 (2) | −0.016 (2) |
C19 | 0.036 (3) | 0.055 (3) | 0.020 (2) | 0.002 (2) | −0.000 (2) | −0.004 (2) |
C20 | 0.040 (3) | 0.051 (3) | 0.031 (2) | 0.006 (2) | 0.009 (2) | 0.004 (2) |
C21 | 0.043 (3) | 0.046 (3) | 0.045 (3) | −0.010 (2) | 0.018 (2) | −0.005 (2) |
C22 | 0.044 (3) | 0.057 (3) | 0.047 (3) | 0.002 (3) | 0.012 (3) | −0.004 (2) |
C23 | 0.037 (2) | 0.029 (2) | 0.037 (2) | 0.002 (2) | 0.013 (2) | 0.002 (2) |
C24 | 0.034 (2) | 0.030 (2) | 0.039 (2) | 0.002 (2) | 0.021 (2) | 0.004 (2) |
C25 | 0.036 (3) | 0.032 (2) | 0.031 (2) | −0.010 (2) | 0.007 (2) | 0.005 (2) |
C26 | 0.035 (3) | 0.037 (2) | 0.034 (2) | 0.002 (2) | 0.007 (2) | 0.000 (2) |
C27 | 0.033 (2) | 0.032 (2) | 0.030 (2) | 0.004 (2) | 0.014 (2) | 0.011 (2) |
C28 | 0.031 (2) | 0.029 (2) | 0.035 (2) | 0.003 (2) | 0.005 (2) | 0.004 (2) |
C29 | 0.037 (3) | 0.037 (2) | 0.032 (2) | 0.005 (2) | 0.016 (2) | 0.010 (2) |
C30 | 0.043 (3) | 0.041 (2) | 0.045 (3) | 0.006 (2) | 0.025 (2) | 0.008 (2) |
C31 | 0.032 (3) | 0.038 (2) | 0.047 (3) | −0.002 (2) | 0.013 (2) | 0.001 (2) |
C32 | 0.033 (2) | 0.029 (2) | 0.041 (2) | −0.006 (2) | 0.011 (2) | −0.002 (2) |
C33 | 0.030 (2) | 0.024 (2) | 0.039 (2) | −0.001 (2) | 0.011 (2) | −0.003 (2) |
C34 | 0.037 (3) | 0.036 (2) | 0.047 (2) | −0.003 (2) | 0.018 (2) | 0.003 (2) |
C35 | 0.037 (3) | 0.029 (2) | 0.061 (3) | −0.001 (2) | 0.023 (2) | 0.002 (2) |
C36 | 0.046 (3) | 0.035 (2) | 0.050 (3) | −0.003 (2) | 0.026 (3) | −0.004 (2) |
C37 | 0.049 (3) | 0.026 (2) | 0.044 (3) | −0.007 (2) | 0.019 (2) | −0.004 (2) |
C38 | 0.034 (2) | 0.035 (2) | 0.028 (2) | −0.004 (2) | 0.010 (2) | 0.004 (2) |
C39 | 0.048 (3) | 0.043 (3) | 0.034 (2) | 0.004 (2) | 0.009 (2) | 0.002 (2) |
C40 | 0.061 (4) | 0.037 (3) | 0.046 (3) | 0.001 (2) | 0.019 (3) | −0.002 (2) |
C41 | 0.048 (3) | 0.034 (2) | 0.026 (2) | −0.008 (2) | 0.005 (2) | 0.001 (2) |
C42 | 0.050 (3) | 0.041 (3) | 0.031 (2) | 0.004 (2) | 0.011 (2) | −0.001 (2) |
C43 | 0.037 (3) | 0.048 (3) | 0.042 (3) | −0.003 (2) | 0.011 (2) | −0.011 (2) |
C44 | 0.049 (3) | 0.042 (3) | 0.038 (3) | 0.004 (2) | 0.017 (2) | 0.002 (2) |
C45 | 0.070 (4) | 0.075 (4) | 0.042 (3) | −0.002 (3) | 0.021 (3) | 0.003 (3) |
B1 | 0.047 (3) | 0.048 (3) | 0.038 (3) | −0.019 (3) | 0.023 (2) | −0.006 (2) |
B2 | 0.032 (3) | 0.059 (4) | 0.039 (3) | 0.006 (3) | 0.007 (2) | −0.015 (3) |
Geometric parameters (Å, º) top
Co1—N1 | 2.132 (4) | C18—C19 | 1.408 (9) |
Co1—N2 | 2.007 (4) | C19—C20 | 1.385 (8) |
Co1—N3 | 2.146 (4) | C19—C22 | 1.442 (7) |
Co1—N4 | 2.147 (5) | C20—C21 | 1.378 (7) |
Co1—N5 | 2.028 (4) | C23—C24 | 1.385 (6) |
Co1—N6 | 2.133 (4) | C23—C28 | 1.488 (7) |
F1—B1 | 1.420 (8) | C24—C25 | 1.406 (7) |
F2—B1 | 1.385 (7) | C25—C26 | 1.388 (8) |
F3—B1 | 1.326 (10) | C25—C38 | 1.495 (6) |
F4—B1 | 1.375 (8) | C26—C27 | 1.373 (6) |
F5—F10 | 1.15 (4) | C27—C33 | 1.494 (8) |
F5—F11 | 1.37 (3) | C28—C29 | 1.396 (8) |
F5—B2 | 1.317 (15) | C29—C30 | 1.397 (7) |
F6—F9 | 1.33 (3) | C30—C31 | 1.362 (7) |
F6—F10 | 1.17 (4) | C31—C32 | 1.385 (9) |
F6—B2 | 1.350 (17) | C33—C34 | 1.389 (7) |
F7—F9 | 1.06 (3) | C34—C35 | 1.380 (9) |
F7—F11 | 1.20 (4) | C35—C36 | 1.384 (7) |
F7—B2 | 1.25 (2) | C36—C37 | 1.390 (9) |
F8—B2 | 1.385 (7) | C38—C39 | 1.391 (8) |
F9—B2 | 1.310 (12) | C38—C43 | 1.374 (7) |
F10—B2 | 1.23 (3) | C39—C40 | 1.384 (7) |
F11—B2 | 1.303 (19) | C40—C41 | 1.378 (7) |
O1—N9 | 1.204 (8) | C41—C42 | 1.394 (8) |
O2—N9 | 1.235 (8) | C41—C44 | 1.467 (7) |
N1—C6 | 1.384 (6) | C42—C43 | 1.381 (7) |
N1—C10 | 1.328 (7) | C2—H2 | 0.950 |
N2—C1 | 1.343 (6) | C4—H4 | 0.950 |
N2—C5 | 1.378 (6) | C7—H7 | 0.950 |
N3—C11 | 1.355 (5) | C8—H8 | 0.950 |
N3—C15 | 1.347 (6) | C9—H9 | 0.950 |
N4—C28 | 1.334 (6) | C10—H10 | 0.950 |
N4—C32 | 1.344 (6) | C12—H12 | 0.950 |
N5—C23 | 1.350 (8) | C13—H13 | 0.950 |
N5—C27 | 1.332 (7) | C14—H14 | 0.950 |
N6—C33 | 1.372 (5) | C15—H15 | 0.950 |
N6—C37 | 1.324 (8) | C17—H17 | 0.950 |
N7—C22 | 1.134 (7) | C18—H18 | 0.950 |
N8—C44 | 1.125 (6) | C20—H20 | 0.950 |
N9—C45 | 1.474 (8) | C21—H21 | 0.950 |
C1—C2 | 1.370 (6) | C24—H24 | 0.950 |
C1—C6 | 1.484 (7) | C26—H26 | 0.950 |
C2—C3 | 1.396 (8) | C29—H29 | 0.950 |
C3—C4 | 1.379 (7) | C30—H30 | 0.950 |
C3—C16 | 1.507 (6) | C31—H31 | 0.950 |
C4—C5 | 1.374 (6) | C32—H32 | 0.950 |
C5—C11 | 1.467 (6) | C34—H34 | 0.950 |
C6—C7 | 1.376 (7) | C35—H35 | 0.950 |
C7—C8 | 1.372 (8) | C36—H36 | 0.950 |
C8—C9 | 1.367 (8) | C37—H37 | 0.950 |
C9—C10 | 1.380 (8) | C39—H39 | 0.950 |
C11—C12 | 1.406 (7) | C40—H40 | 0.950 |
C12—C13 | 1.365 (6) | C42—H42 | 0.950 |
C13—C14 | 1.373 (6) | C43—H43 | 0.950 |
C14—C15 | 1.397 (7) | C45—H45A | 0.980 |
C16—C17 | 1.401 (8) | C45—H45B | 0.980 |
C16—C21 | 1.412 (8) | C45—H45C | 0.980 |
C17—C18 | 1.374 (6) | | |
| | | |
N1—Co1—N2 | 76.41 (17) | N6—C33—C27 | 114.2 (4) |
N1—Co1—N3 | 152.98 (16) | N6—C33—C34 | 122.1 (5) |
N1—Co1—N4 | 95.49 (19) | C27—C33—C34 | 123.7 (4) |
N1—Co1—N5 | 111.88 (17) | C33—C34—C35 | 118.5 (4) |
N1—Co1—N6 | 91.12 (18) | C34—C35—C36 | 119.9 (5) |
N2—Co1—N3 | 77.31 (16) | C35—C36—C37 | 118.1 (6) |
N2—Co1—N4 | 95.9 (2) | N6—C37—C36 | 123.6 (4) |
N2—Co1—N5 | 169.48 (18) | C25—C38—C39 | 119.1 (4) |
N2—Co1—N6 | 109.9 (2) | C25—C38—C43 | 120.7 (4) |
N3—Co1—N4 | 93.34 (17) | C39—C38—C43 | 120.2 (4) |
N3—Co1—N5 | 94.96 (16) | C38—C39—C40 | 119.3 (5) |
N3—Co1—N6 | 91.93 (17) | C39—C40—C41 | 119.7 (5) |
N4—Co1—N5 | 77.21 (18) | C40—C41—C42 | 121.2 (4) |
N4—Co1—N6 | 154.20 (15) | C40—C41—C44 | 118.2 (5) |
N5—Co1—N6 | 77.19 (19) | C42—C41—C44 | 120.6 (4) |
F10—F5—F11 | 115 (2) | C41—C42—C43 | 118.4 (4) |
F10—F5—B2 | 59.3 (17) | C38—C43—C42 | 120.9 (5) |
F11—F5—B2 | 58.1 (12) | N8—C44—C41 | 177.1 (6) |
F9—F6—F10 | 110 (2) | F1—B1—F2 | 106.2 (5) |
F9—F6—B2 | 58.4 (10) | F1—B1—F3 | 112.6 (5) |
F10—F6—B2 | 57.8 (17) | F1—B1—F4 | 109.3 (6) |
F9—F7—F11 | 126 (2) | F2—B1—F3 | 111.3 (7) |
F9—F7—B2 | 68.4 (15) | F2—B1—F4 | 103.6 (5) |
F11—F7—B2 | 64.2 (16) | F3—B1—F4 | 113.2 (5) |
F6—F9—F7 | 122 (2) | F5—B2—F6 | 103.8 (13) |
F6—F9—B2 | 61.4 (12) | F5—B2—F7 | 113.1 (14) |
F7—F9—B2 | 62.6 (16) | F5—B2—F8 | 114.7 (6) |
F5—F10—F6 | 130 (3) | F5—B2—F9 | 132.2 (9) |
F5—F10—B2 | 67.2 (18) | F5—B2—F10 | 53.5 (19) |
F6—F10—B2 | 69 (2) | F5—B2—F11 | 62.9 (17) |
F5—F11—F7 | 113.2 (18) | F6—B2—F7 | 108.2 (14) |
F5—F11—B2 | 59.1 (11) | F6—B2—F8 | 108.0 (7) |
F7—F11—B2 | 59.8 (15) | F6—B2—F9 | 60.2 (16) |
Co1—N1—C6 | 115.1 (3) | F6—B2—F10 | 53.6 (19) |
Co1—N1—C10 | 128.0 (3) | F6—B2—F11 | 142.6 (10) |
C6—N1—C10 | 116.9 (4) | F7—B2—F8 | 108.7 (8) |
Co1—N2—C1 | 121.1 (3) | F7—B2—F9 | 49.1 (17) |
Co1—N2—C5 | 118.9 (3) | F7—B2—F10 | 140.3 (14) |
C1—N2—C5 | 119.2 (4) | F7—B2—F11 | 55.9 (19) |
Co1—N3—C11 | 114.4 (3) | F8—B2—F9 | 113.1 (9) |
Co1—N3—C15 | 127.0 (3) | F8—B2—F10 | 110.6 (12) |
C11—N3—C15 | 118.5 (4) | F8—B2—F11 | 109.3 (8) |
Co1—N4—C28 | 114.5 (3) | F9—B2—F10 | 108.2 (19) |
Co1—N4—C32 | 127.0 (3) | F9—B2—F11 | 101 (2) |
C28—N4—C32 | 118.5 (5) | F10—B2—F11 | 114.1 (19) |
Co1—N5—C23 | 117.7 (3) | C1—C2—H2 | 120.6 |
Co1—N5—C27 | 119.4 (4) | C3—C2—H2 | 120.6 |
C23—N5—C27 | 120.4 (4) | C3—C4—H4 | 120.0 |
Co1—N6—C33 | 114.4 (3) | C5—C4—H4 | 120.0 |
Co1—N6—C37 | 127.8 (3) | C6—C7—H7 | 120.6 |
C33—N6—C37 | 117.8 (4) | C8—C7—H7 | 120.6 |
O1—N9—O2 | 124.2 (5) | C7—C8—H8 | 119.8 |
O1—N9—C45 | 118.0 (6) | C9—C8—H8 | 119.8 |
O2—N9—C45 | 117.7 (5) | C8—C9—H9 | 121.0 |
N2—C1—C2 | 122.4 (4) | C10—C9—H9 | 121.0 |
N2—C1—C6 | 112.9 (4) | N1—C10—H10 | 118.0 |
C2—C1—C6 | 124.8 (4) | C9—C10—H10 | 118.0 |
C1—C2—C3 | 118.8 (4) | C11—C12—H12 | 120.1 |
C2—C3—C4 | 119.2 (4) | C13—C12—H12 | 120.1 |
C2—C3—C16 | 121.5 (4) | C12—C13—H13 | 120.2 |
C4—C3—C16 | 119.3 (4) | C14—C13—H13 | 120.1 |
C3—C4—C5 | 120.0 (4) | C13—C14—H14 | 120.7 |
N2—C5—C4 | 120.4 (4) | C15—C14—H14 | 120.7 |
N2—C5—C11 | 113.6 (3) | N3—C15—H15 | 118.8 |
C4—C5—C11 | 126.0 (4) | C14—C15—H15 | 118.8 |
N1—C6—C1 | 113.5 (4) | C16—C17—H17 | 119.8 |
N1—C6—C7 | 121.7 (4) | C18—C17—H17 | 119.8 |
C1—C6—C7 | 124.8 (4) | C17—C18—H18 | 120.1 |
C6—C7—C8 | 118.9 (5) | C19—C18—H18 | 120.1 |
C7—C8—C9 | 120.5 (5) | C19—C20—H20 | 119.7 |
C8—C9—C10 | 117.9 (5) | C21—C20—H20 | 119.7 |
N1—C10—C9 | 124.1 (5) | C16—C21—H21 | 120.2 |
N3—C11—C5 | 115.2 (4) | C20—C21—H21 | 120.2 |
N3—C11—C12 | 120.8 (4) | C23—C24—H24 | 120.8 |
C5—C11—C12 | 124.0 (4) | C25—C24—H24 | 120.8 |
C11—C12—C13 | 119.8 (4) | C25—C26—H26 | 120.1 |
C12—C13—C14 | 119.7 (5) | C27—C26—H26 | 120.1 |
C13—C14—C15 | 118.6 (4) | C28—C29—H29 | 121.1 |
N3—C15—C14 | 122.4 (4) | C30—C29—H29 | 121.1 |
C3—C16—C17 | 119.9 (5) | C29—C30—H30 | 120.3 |
C3—C16—C21 | 120.5 (4) | C31—C30—H30 | 120.3 |
C17—C16—C21 | 119.5 (4) | C30—C31—H31 | 120.4 |
C16—C17—C18 | 120.4 (5) | C32—C31—H31 | 120.4 |
C17—C18—C19 | 119.7 (5) | N4—C32—H32 | 118.9 |
C18—C19—C20 | 120.1 (4) | C31—C32—H32 | 118.9 |
C18—C19—C22 | 119.8 (5) | C33—C34—H34 | 120.8 |
C20—C19—C22 | 120.1 (5) | C35—C34—H34 | 120.8 |
C19—C20—C21 | 120.6 (5) | C34—C35—H35 | 120.0 |
C16—C21—C20 | 119.5 (5) | C36—C35—H35 | 120.0 |
N7—C22—C19 | 177.2 (7) | C35—C36—H36 | 121.0 |
N5—C23—C24 | 121.3 (5) | C37—C36—H36 | 120.9 |
N5—C23—C28 | 114.1 (4) | N6—C37—H37 | 118.2 |
C24—C23—C28 | 124.6 (5) | C36—C37—H37 | 118.2 |
C23—C24—C25 | 118.4 (5) | C38—C39—H39 | 120.3 |
C24—C25—C26 | 118.6 (4) | C40—C39—H39 | 120.3 |
C24—C25—C38 | 120.5 (5) | C39—C40—H40 | 120.1 |
C26—C25—C38 | 120.7 (5) | C41—C40—H40 | 120.1 |
C25—C26—C27 | 119.8 (5) | C41—C42—H42 | 120.8 |
N5—C27—C26 | 121.3 (5) | C43—C42—H42 | 120.8 |
N5—C27—C33 | 113.8 (4) | C38—C43—H43 | 119.5 |
C26—C27—C33 | 124.8 (5) | C42—C43—H43 | 119.5 |
N4—C28—C23 | 114.9 (5) | N9—C45—H45A | 109.5 |
N4—C28—C29 | 122.6 (4) | N9—C45—H45B | 109.5 |
C23—C28—C29 | 122.5 (4) | N9—C45—H45C | 109.5 |
C28—C29—C30 | 117.9 (4) | H45A—C45—H45B | 109.5 |
C29—C30—C31 | 119.5 (6) | H45A—C45—H45C | 109.5 |
C30—C31—C32 | 119.3 (5) | H45B—C45—H45C | 109.5 |
N4—C32—C31 | 122.2 (4) | | |
| | | |
N1—Co1—N2—C1 | −9.5 (5) | F5—F11—B2—F7 | −151.5 (12) |
N1—Co1—N2—C5 | −179.0 (5) | F5—F11—B2—F8 | 108.5 (8) |
N2—Co1—N1—C6 | 5.0 (4) | F5—F11—B2—F9 | −131.9 (11) |
N2—Co1—N1—C10 | −174.7 (6) | F5—F11—B2—F10 | −15.9 (18) |
N1—Co1—N3—C11 | −18.5 (6) | F7—F11—B2—F5 | 151.5 (12) |
N1—Co1—N3—C15 | 164.1 (4) | F7—F11—B2—F6 | 75 (2) |
N3—Co1—N1—C6 | 18.7 (7) | F7—F11—B2—F8 | −100.0 (12) |
N3—Co1—N1—C10 | −161.0 (5) | F7—F11—B2—F9 | 19.6 (12) |
N1—Co1—N4—C28 | −116.9 (3) | F7—F11—B2—F10 | 135.6 (18) |
N1—Co1—N4—C32 | 63.1 (4) | Co1—N1—C6—C1 | −0.6 (6) |
N4—Co1—N1—C6 | −89.8 (4) | Co1—N1—C6—C7 | −180.0 (4) |
N4—Co1—N1—C10 | 90.5 (6) | Co1—N1—C10—C9 | 179.6 (6) |
N1—Co1—N5—C23 | 102.2 (4) | C6—N1—C10—C9 | −0.0 (9) |
N1—Co1—N5—C27 | −95.3 (4) | C10—N1—C6—C1 | 179.1 (6) |
N5—Co1—N1—C6 | −168.2 (4) | C10—N1—C6—C7 | −0.3 (8) |
N5—Co1—N1—C10 | 12.1 (6) | Co1—N2—C1—C2 | −168.0 (5) |
N1—Co1—N6—C33 | 117.0 (3) | Co1—N2—C1—C6 | 11.8 (7) |
N1—Co1—N6—C37 | −65.2 (4) | Co1—N2—C5—C4 | 169.6 (4) |
N6—Co1—N1—C6 | 115.1 (4) | Co1—N2—C5—C11 | −8.4 (7) |
N6—Co1—N1—C10 | −64.5 (6) | C1—N2—C5—C4 | −0.1 (7) |
N2—Co1—N3—C11 | −4.9 (4) | C1—N2—C5—C11 | −178.2 (5) |
N2—Co1—N3—C15 | 177.8 (5) | C5—N2—C1—C2 | 1.6 (10) |
N3—Co1—N2—C1 | 176.9 (5) | C5—N2—C1—C6 | −178.7 (5) |
N3—Co1—N2—C5 | 7.3 (4) | Co1—N3—C11—C5 | 2.0 (6) |
N2—Co1—N4—C28 | 166.3 (3) | Co1—N3—C11—C12 | −175.4 (4) |
N2—Co1—N4—C32 | −13.8 (4) | Co1—N3—C15—C14 | 172.8 (4) |
N4—Co1—N2—C1 | 84.8 (5) | C11—N3—C15—C14 | −4.5 (9) |
N4—Co1—N2—C5 | −84.8 (5) | C15—N3—C11—C5 | 179.6 (5) |
N2—Co1—N5—C23 | −38.7 (15) | C15—N3—C11—C12 | 2.2 (8) |
N2—Co1—N5—C27 | 123.8 (12) | Co1—N4—C28—C23 | −0.2 (5) |
N5—Co1—N2—C1 | 133.5 (11) | Co1—N4—C28—C29 | 177.9 (3) |
N5—Co1—N2—C5 | −36.1 (16) | Co1—N4—C32—C31 | −176.6 (3) |
N2—Co1—N6—C33 | −167.1 (3) | C28—N4—C32—C31 | 3.4 (7) |
N2—Co1—N6—C37 | 10.7 (5) | C32—N4—C28—C23 | 179.9 (3) |
N6—Co1—N2—C1 | −95.7 (5) | C32—N4—C28—C29 | −2.1 (7) |
N6—Co1—N2—C5 | 94.7 (4) | Co1—N5—C23—C24 | 162.6 (4) |
N3—Co1—N4—C28 | 88.7 (3) | Co1—N5—C23—C28 | −14.9 (6) |
N3—Co1—N4—C32 | −91.4 (4) | Co1—N5—C27—C26 | −164.6 (4) |
N4—Co1—N3—C11 | 90.5 (4) | Co1—N5—C27—C33 | 11.7 (5) |
N4—Co1—N3—C15 | −86.9 (4) | C23—N5—C27—C26 | −2.6 (8) |
N3—Co1—N5—C23 | −81.0 (4) | C23—N5—C27—C33 | 173.7 (4) |
N3—Co1—N5—C27 | 81.6 (3) | C27—N5—C23—C24 | 0.3 (6) |
N5—Co1—N3—C11 | 167.9 (4) | C27—N5—C23—C28 | −177.2 (4) |
N5—Co1—N3—C15 | −9.5 (5) | Co1—N6—C33—C27 | −0.5 (5) |
N3—Co1—N6—C33 | −89.9 (3) | Co1—N6—C33—C34 | 177.7 (4) |
N3—Co1—N6—C37 | 87.9 (4) | Co1—N6—C37—C36 | −175.7 (4) |
N6—Co1—N3—C11 | −114.8 (4) | C33—N6—C37—C36 | 2.0 (7) |
N6—Co1—N3—C15 | 67.8 (5) | C37—N6—C33—C27 | −178.5 (4) |
N4—Co1—N5—C23 | 11.4 (3) | C37—N6—C33—C34 | −0.3 (6) |
N4—Co1—N5—C27 | 173.9 (4) | N2—C1—C2—C3 | −0.7 (10) |
N5—Co1—N4—C28 | −5.7 (3) | N2—C1—C6—N1 | −6.6 (8) |
N5—Co1—N4—C32 | 174.3 (4) | N2—C1—C6—C7 | 172.7 (6) |
N4—Co1—N6—C33 | 11.9 (6) | C2—C1—C6—N1 | 173.2 (6) |
N4—Co1—N6—C37 | −170.3 (4) | C2—C1—C6—C7 | −7.5 (10) |
N6—Co1—N4—C28 | −12.8 (5) | C6—C1—C2—C3 | 179.6 (6) |
N6—Co1—N4—C32 | 167.2 (4) | C1—C2—C3—C4 | −1.6 (9) |
N5—Co1—N6—C33 | 4.8 (3) | C1—C2—C3—C16 | 176.9 (6) |
N5—Co1—N6—C37 | −177.4 (4) | C2—C3—C4—C5 | 3.0 (9) |
N6—Co1—N5—C23 | −171.8 (4) | C2—C3—C16—C17 | −29.2 (9) |
N6—Co1—N5—C27 | −9.3 (3) | C2—C3—C16—C21 | 151.6 (6) |
F10—F5—F11—F7 | −10 (2) | C4—C3—C16—C17 | 149.3 (6) |
F10—F5—F11—B2 | 17.1 (15) | C4—C3—C16—C21 | −29.9 (8) |
F11—F5—F10—F6 | 12 (2) | C16—C3—C4—C5 | −175.5 (5) |
F11—F5—F10—B2 | −16.9 (15) | C3—C4—C5—N2 | −2.2 (9) |
F10—F5—B2—F6 | −19.5 (17) | C3—C4—C5—C11 | 175.7 (6) |
F10—F5—B2—F7 | −136.4 (18) | N2—C5—C11—N3 | 3.8 (7) |
F10—F5—B2—F8 | 98.1 (16) | N2—C5—C11—C12 | −178.9 (5) |
F10—F5—B2—F9 | −82 (2) | C4—C5—C11—N3 | −174.1 (5) |
F10—F5—B2—F11 | −161.9 (18) | C4—C5—C11—C12 | 3.1 (10) |
B2—F5—F10—F6 | 29.3 (18) | N1—C6—C7—C8 | 0.0 (10) |
F11—F5—B2—F6 | 142.5 (13) | C1—C6—C7—C8 | −179.2 (6) |
F11—F5—B2—F7 | 25.5 (14) | C6—C7—C8—C9 | 0.6 (11) |
F11—F5—B2—F8 | −99.9 (12) | C7—C8—C9—C10 | −0.8 (12) |
F11—F5—B2—F9 | 80 (2) | C8—C9—C10—N1 | 0.6 (12) |
F11—F5—B2—F10 | 161.9 (18) | N3—C11—C12—C13 | 0.6 (9) |
B2—F5—F11—F7 | −26.7 (11) | C5—C11—C12—C13 | −176.5 (5) |
F9—F6—F10—F5 | −2 (2) | C11—C12—C13—C14 | −1.3 (9) |
F9—F6—F10—B2 | 26.6 (13) | C12—C13—C14—C15 | −0.8 (9) |
F10—F6—F9—F7 | −12 (2) | C13—C14—C15—N3 | 3.8 (10) |
F10—F6—F9—B2 | −26.4 (13) | C3—C16—C17—C18 | −176.5 (5) |
F9—F6—B2—F5 | −131.1 (12) | C3—C16—C21—C20 | 174.9 (5) |
F9—F6—B2—F7 | −10.7 (13) | C17—C16—C21—C20 | −4.3 (9) |
F9—F6—B2—F8 | 106.8 (11) | C21—C16—C17—C18 | 2.7 (9) |
F9—F6—B2—F10 | −150.5 (17) | C16—C17—C18—C19 | 0.4 (9) |
F9—F6—B2—F11 | −68 (3) | C17—C18—C19—C20 | −2.0 (9) |
B2—F6—F9—F7 | 14.3 (14) | C17—C18—C19—C22 | 177.6 (6) |
F10—F6—B2—F5 | 19.4 (16) | C18—C19—C20—C21 | 0.3 (9) |
F10—F6—B2—F7 | 139.8 (17) | C22—C19—C20—C21 | −179.2 (6) |
F10—F6—B2—F8 | −102.7 (15) | C19—C20—C21—C16 | 2.8 (9) |
F10—F6—B2—F9 | 150.5 (17) | N5—C23—C24—C25 | 1.0 (8) |
F10—F6—B2—F11 | 83 (3) | N5—C23—C28—N4 | 9.5 (6) |
B2—F6—F10—F5 | −29.0 (18) | N5—C23—C28—C29 | −168.6 (4) |
F9—F7—F11—F5 | −4 (2) | C24—C23—C28—N4 | −167.9 (5) |
F9—F7—F11—B2 | −30.2 (18) | C24—C23—C28—C29 | 14.0 (8) |
F11—F7—F9—F6 | 15 (2) | C28—C23—C24—C25 | 178.2 (5) |
F11—F7—F9—B2 | 29.1 (18) | C23—C24—C25—C26 | 0.1 (6) |
F9—F7—B2—F5 | 126.7 (14) | C23—C24—C25—C38 | −174.8 (5) |
F9—F7—B2—F6 | 12.3 (14) | C24—C25—C26—C27 | −2.3 (8) |
F9—F7—B2—F8 | −104.7 (12) | C24—C25—C38—C39 | 36.5 (8) |
F9—F7—B2—F10 | 67 (3) | C24—C25—C38—C43 | −140.9 (6) |
F9—F7—B2—F11 | 154.2 (15) | C26—C25—C38—C39 | −138.3 (6) |
B2—F7—F9—F6 | −14.1 (15) | C26—C25—C38—C43 | 44.3 (8) |
F11—F7—B2—F5 | −27.5 (12) | C38—C25—C26—C27 | 172.6 (5) |
F11—F7—B2—F6 | −141.9 (12) | C25—C26—C27—N5 | 3.6 (8) |
F11—F7—B2—F8 | 101.0 (10) | C25—C26—C27—C33 | −172.3 (5) |
F11—F7—B2—F9 | −154.2 (15) | N5—C27—C33—N6 | −6.9 (6) |
F11—F7—B2—F10 | −88 (3) | N5—C27—C33—C34 | 174.9 (5) |
B2—F7—F11—F5 | 26.5 (11) | C26—C27—C33—N6 | 169.3 (5) |
F6—F9—B2—F5 | 81 (2) | C26—C27—C33—C34 | −8.9 (8) |
F6—F9—B2—F7 | 166.5 (15) | N4—C28—C29—C30 | −0.1 (6) |
F6—F9—B2—F8 | −98.3 (9) | C23—C28—C29—C30 | 177.9 (4) |
F6—F9—B2—F10 | 24.6 (16) | C28—C29—C30—C31 | 0.9 (8) |
F6—F9—B2—F11 | 144.9 (11) | C29—C30—C31—C32 | 0.3 (6) |
F7—F9—B2—F5 | −85 (2) | C30—C31—C32—N4 | −2.5 (8) |
F7—F9—B2—F6 | −166.5 (15) | N6—C33—C34—C35 | −1.3 (8) |
F7—F9—B2—F8 | 95.3 (14) | C27—C33—C34—C35 | 176.8 (4) |
F7—F9—B2—F10 | −141.8 (18) | C33—C34—C35—C36 | 1.2 (8) |
F7—F9—B2—F11 | −21.5 (14) | C34—C35—C36—C37 | 0.4 (8) |
F5—F10—B2—F6 | 156.3 (18) | C35—C36—C37—N6 | −2.1 (8) |
F5—F10—B2—F7 | 83 (3) | C25—C38—C39—C40 | 176.8 (6) |
F5—F10—B2—F8 | −106.1 (11) | C25—C38—C43—C42 | −178.9 (6) |
F5—F10—B2—F9 | 129.6 (15) | C39—C38—C43—C42 | 3.8 (10) |
F5—F10—B2—F11 | 18 (2) | C43—C38—C39—C40 | −5.8 (10) |
F6—F10—B2—F5 | −156.3 (18) | C38—C39—C40—C41 | 4.0 (10) |
F6—F10—B2—F7 | −74 (3) | C39—C40—C41—C42 | −0.3 (8) |
F6—F10—B2—F8 | 97.7 (13) | C39—C40—C41—C44 | −179.6 (6) |
F6—F10—B2—F9 | −26.7 (18) | C40—C41—C42—C43 | −1.8 (10) |
F6—F10—B2—F11 | −138.7 (16) | C44—C41—C42—C43 | 177.5 (6) |
F5—F11—B2—F6 | −77 (2) | C41—C42—C43—C38 | 0.0 (10) |
(II) bis[4'-(4-cyanophenyl)-2,2':6',2''-terpyridine]cobalt(III)
tris(tetrafluoridoborate)
nitromethane sesquisolvate
top
Crystal data top
[Co(C22H14N4)2](BF4)3·1.5CH3NO2 | F(000) = 4368.00 |
Mr = 1079.67 | Dx = 1.572 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -C 2yc | Cell parameters from 6774 reflections |
a = 37.80 (2) Å | θ = 3.1–27.5° |
b = 10.748 (6) Å | µ = 0.48 mm−1 |
c = 22.99 (1) Å | T = 110 K |
β = 102.388 (9)° | Chip, orange |
V = 9123 (8) Å3 | 0.30 × 0.07 × 0.05 mm |
Z = 8 | |
Data collection top
Rigaku Mercury diffractometer | 7454 reflections with I > 2σ(I) |
Detector resolution: 14.71 pixels mm-1 | Rint = 0.072 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (Jacobson, 1998) | h = −48→48 |
Tmin = 0.789, Tmax = 0.976 | k = −13→13 |
35412 measured reflections | l = −29→29 |
10280 independent reflections | |
Refinement top
Refinement on F2 | w = 1/[σ^2^(Fo^2^) + (0.1193P)^2^] whereP = (Fo^2^ + 2Fc^2^)/3 |
R[F2 > 2σ(F2)] = 0.096 | (Δ/σ)max = −0.001 |
wR(F2) = 0.238 | Δρmax = 1.03 e Å−3 |
S = 1.17 | Δρmin = −0.62 e Å−3 |
10280 reflections | Extinction correction: SHELXL97, Fc^*^=kFc[1+0.001xFc^2^λ^3^/sin(2θ)]^-1/4^ |
688 parameters | Extinction coefficient: 0.0000 |
H-atom parameters constrained | |
Crystal data top
[Co(C22H14N4)2](BF4)3·1.5CH3NO2 | V = 9123 (8) Å3 |
Mr = 1079.67 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 37.80 (2) Å | µ = 0.48 mm−1 |
b = 10.748 (6) Å | T = 110 K |
c = 22.99 (1) Å | 0.30 × 0.07 × 0.05 mm |
β = 102.388 (9)° | |
Data collection top
Rigaku Mercury diffractometer | 10280 independent reflections |
Absorption correction: multi-scan (Jacobson, 1998) | 7454 reflections with I > 2σ(I) |
Tmin = 0.789, Tmax = 0.976 | Rint = 0.072 |
35412 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.096 | 688 parameters |
wR(F2) = 0.238 | H-atom parameters constrained |
S = 1.17 | Δρmax = 1.03 e Å−3 |
10280 reflections | Δρmin = −0.62 e Å−3 |
Special details top
Refinement. Refinement was carried out using all reflections. The weighted R-factor
(wR) and goodness of fit (S) are based on F^2^.
R-factor (gt) are based on F. The threshold expression of
F^2^ > 2.0 σ(F^2^) is used only for calculating
R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.64391 (2) | 0.03735 (5) | 0.55080 (3) | 0.0247 (2) | |
F1 | 0.7397 (1) | 0.3556 (4) | 0.3515 (2) | 0.073 (1) | |
F2 | 0.73854 (9) | 0.5222 (3) | 0.2913 (1) | 0.0424 (7) | |
F3 | 0.6920 (1) | 0.4848 (3) | 0.3384 (2) | 0.0562 (9) | |
F4 | 0.6998 (1) | 0.3627 (4) | 0.2637 (2) | 0.079 (1) | |
F5 | 0.68683 (8) | 0.6159 (3) | 0.4994 (1) | 0.0375 (7) | |
F6 | 0.68523 (8) | 0.4351 (3) | 0.5501 (1) | 0.0378 (7) | |
F7 | 0.64203 (8) | 0.4743 (3) | 0.4664 (1) | 0.0409 (7) | |
F8 | 0.64212 (8) | 0.5840 (3) | 0.5508 (1) | 0.0399 (7) | |
F9 | 0.4895 (1) | 0.1393 (4) | 0.1995 (2) | 0.063 (1) | |
F10 | 0.4717 (1) | 0.2869 (4) | 0.2581 (2) | 0.063 (1) | |
F11 | 0.5016 (2) | 0.003 (1) | 0.4394 (4) | 0.082 (3) | 0.50 |
F12 | 0.5358 (2) | −0.0656 (8) | 0.4979 (3) | 0.057 (2) | 0.50 |
F13 | 0.5044 (3) | −0.096 (1) | 0.5319 (7) | 0.116 (4) | 0.50 |
F14 | 0.4764 (2) | −0.1008 (6) | 0.4750 (3) | 0.045 (2) | 0.50 |
O1 | 0.6145 (1) | 0.6320 (4) | 0.2984 (2) | 0.058 (1) | |
O2 | 0.6020 (1) | 0.4827 (4) | 0.2341 (2) | 0.0474 (10) | |
O3 | 0.5256 (1) | 0.6683 (5) | 0.2819 (2) | 0.073 (1) | |
N1 | 0.6195 (1) | −0.0584 (3) | 0.6018 (2) | 0.0268 (8) | |
N2 | 0.6810 (1) | −0.0758 (3) | 0.5784 (2) | 0.0256 (8) | |
N3 | 0.6787 (1) | 0.1010 (3) | 0.5068 (2) | 0.0256 (8) | |
N4 | 0.6573 (1) | 0.1621 (4) | 0.6128 (2) | 0.0266 (8) | |
N5 | 0.60793 (9) | 0.1522 (3) | 0.5205 (2) | 0.0232 (7) | |
N6 | 0.6198 (1) | −0.0559 (3) | 0.4821 (2) | 0.0278 (8) | |
N7 | 0.8738 (2) | −0.6595 (5) | 0.6880 (3) | 0.061 (1) | |
N8 | 0.4410 (1) | 0.7848 (5) | 0.3378 (2) | 0.050 (1) | |
N9 | 0.6033 (1) | 0.5252 (4) | 0.2836 (2) | 0.039 (1) | |
N10 | 0.5000 | 0.7237 (8) | 0.2500 | 0.057 (2) | |
C1 | 0.7116 (1) | −0.0695 (4) | 0.5569 (2) | 0.0253 (9) | |
C2 | 0.7393 (1) | −0.1530 (4) | 0.5762 (2) | 0.0265 (9) | |
C3 | 0.7360 (1) | −0.2414 (4) | 0.6195 (2) | 0.0257 (9) | |
C4 | 0.7034 (1) | −0.2468 (4) | 0.6404 (2) | 0.0281 (9) | |
C5 | 0.6761 (1) | −0.1620 (4) | 0.6181 (2) | 0.0265 (9) | |
C6 | 0.7099 (1) | 0.0327 (4) | 0.5140 (2) | 0.0263 (9) | |
C7 | 0.7368 (1) | 0.0599 (4) | 0.4835 (2) | 0.0294 (10) | |
C8 | 0.7320 (1) | 0.1619 (4) | 0.4456 (2) | 0.0303 (10) | |
C9 | 0.7007 (1) | 0.2320 (4) | 0.4385 (2) | 0.0295 (10) | |
C10 | 0.6747 (1) | 0.1984 (4) | 0.4699 (2) | 0.0287 (9) | |
C11 | 0.6397 (1) | −0.1535 (4) | 0.6317 (2) | 0.0278 (9) | |
C12 | 0.6263 (1) | −0.2297 (4) | 0.6702 (2) | 0.034 (1) | |
C13 | 0.5910 (1) | −0.2097 (5) | 0.6779 (2) | 0.035 (1) | |
C14 | 0.5706 (1) | −0.1146 (5) | 0.6480 (2) | 0.035 (1) | |
C15 | 0.5857 (1) | −0.0399 (4) | 0.6103 (2) | 0.0301 (10) | |
C16 | 0.7660 (1) | −0.3299 (4) | 0.6422 (2) | 0.0268 (9) | |
C17 | 0.8018 (1) | −0.2948 (5) | 0.6429 (2) | 0.035 (1) | |
C18 | 0.8297 (1) | −0.3783 (5) | 0.6603 (3) | 0.039 (1) | |
C19 | 0.8224 (1) | −0.4989 (5) | 0.6770 (2) | 0.036 (1) | |
C20 | 0.7872 (1) | −0.5327 (4) | 0.6799 (2) | 0.035 (1) | |
C21 | 0.7589 (1) | −0.4476 (4) | 0.6623 (2) | 0.0306 (10) | |
C22 | 0.8515 (2) | −0.5896 (5) | 0.6860 (3) | 0.045 (1) | |
C23 | 0.6072 (1) | 0.2604 (4) | 0.5503 (2) | 0.0258 (9) | |
C24 | 0.5825 (1) | 0.3515 (4) | 0.5254 (2) | 0.0283 (9) | |
C25 | 0.5598 (1) | 0.3340 (4) | 0.4699 (2) | 0.0271 (9) | |
C26 | 0.5623 (1) | 0.2219 (4) | 0.4396 (2) | 0.0291 (10) | |
C27 | 0.5865 (1) | 0.1324 (4) | 0.4668 (2) | 0.0281 (9) | |
C28 | 0.6349 (1) | 0.2630 (4) | 0.6054 (2) | 0.0263 (9) | |
C29 | 0.6393 (1) | 0.3581 (5) | 0.6466 (2) | 0.033 (1) | |
C30 | 0.6680 (1) | 0.3508 (5) | 0.6962 (2) | 0.035 (1) | |
C31 | 0.6910 (1) | 0.2501 (5) | 0.7022 (2) | 0.036 (1) | |
C32 | 0.6848 (1) | 0.1555 (5) | 0.6607 (2) | 0.032 (1) | |
C33 | 0.5928 (1) | 0.0077 (4) | 0.4443 (2) | 0.0285 (9) | |
C34 | 0.5733 (1) | −0.0453 (5) | 0.3927 (2) | 0.034 (1) | |
C35 | 0.5810 (2) | −0.1690 (5) | 0.3804 (3) | 0.042 (1) | |
C36 | 0.6075 (2) | −0.2326 (5) | 0.4191 (2) | 0.039 (1) | |
C37 | 0.6267 (1) | −0.1745 (4) | 0.4694 (2) | 0.032 (1) | |
C38 | 0.5338 (1) | 0.4320 (4) | 0.4428 (2) | 0.0280 (9) | |
C39 | 0.5390 (1) | 0.5558 (4) | 0.4602 (2) | 0.032 (1) | |
C40 | 0.5146 (2) | 0.6472 (5) | 0.4351 (3) | 0.039 (1) | |
C41 | 0.4849 (1) | 0.6144 (5) | 0.3903 (2) | 0.034 (1) | |
C42 | 0.4787 (2) | 0.4911 (5) | 0.3721 (3) | 0.043 (1) | |
C43 | 0.5032 (1) | 0.4008 (5) | 0.3985 (3) | 0.039 (1) | |
C44 | 0.4605 (1) | 0.7106 (5) | 0.3618 (3) | 0.039 (1) | |
C45 | 0.5920 (2) | 0.4489 (6) | 0.3284 (3) | 0.057 (2) | |
C46 | 0.5000 | 0.8609 (9) | 0.2500 | 0.079 (3) | |
B1 | 0.7175 (2) | 0.4309 (5) | 0.3112 (3) | 0.032 (1) | |
B2 | 0.6640 (1) | 0.5270 (5) | 0.5167 (3) | 0.031 (1) | |
B3 | 0.5000 | 0.2117 (9) | 0.2500 | 0.039 (2) | |
B4 | 0.5000 | 0.0000 | 0.5000 | 0.068 (3) | |
H2 | 0.7605 | −0.1508 | 0.5602 | 0.0316* | |
H4 | 0.7002 | −0.3073 | 0.6689 | 0.0335* | |
H7 | 0.7580 | 0.0103 | 0.4884 | 0.0351* | |
H8 | 0.7502 | 0.1838 | 0.4247 | 0.0365* | |
H9 | 0.6971 | 0.3017 | 0.4125 | 0.0352* | |
H10 | 0.6532 | 0.2465 | 0.4649 | 0.0348* | |
H12 | 0.6408 | −0.2945 | 0.6911 | 0.0404* | |
H13 | 0.5812 | −0.2623 | 0.7037 | 0.0417* | |
H14 | 0.5466 | −0.0996 | 0.6531 | 0.0422* | |
H15 | 0.5718 | 0.0266 | 0.5900 | 0.0359* | |
H17 | 0.8069 | −0.2130 | 0.6314 | 0.0427* | |
H18 | 0.8539 | −0.3539 | 0.6608 | 0.0460* | |
H20 | 0.7824 | −0.6130 | 0.6939 | 0.0417* | |
H21 | 0.7349 | −0.4701 | 0.6639 | 0.0364* | |
H24 | 0.5812 | 0.4268 | 0.5467 | 0.0340* | |
H26 | 0.5475 | 0.2077 | 0.4012 | 0.0348* | |
H29 | 0.6231 | 0.4270 | 0.6415 | 0.0395* | |
H30 | 0.6717 | 0.4149 | 0.7254 | 0.0418* | |
H31 | 0.7112 | 0.2457 | 0.7350 | 0.0435* | |
H32 | 0.7001 | 0.0844 | 0.6661 | 0.0389* | |
H34 | 0.5553 | 0.0007 | 0.3662 | 0.0408* | |
H35 | 0.5677 | −0.2089 | 0.3455 | 0.0508* | |
H36 | 0.6128 | −0.3166 | 0.4112 | 0.0461* | |
H37 | 0.6452 | −0.2191 | 0.4959 | 0.0378* | |
H39 | 0.5596 | 0.5781 | 0.4899 | 0.0382* | |
H40 | 0.5180 | 0.7311 | 0.4481 | 0.0470* | |
H42 | 0.4579 | 0.4693 | 0.3423 | 0.0506* | |
H43 | 0.4992 | 0.3163 | 0.3864 | 0.0467* | |
H45A | 0.5946 | 0.4948 | 0.3643 | 0.0681* | |
H45B | 0.5673 | 0.4259 | 0.3146 | 0.0681* | |
H45C | 0.6065 | 0.3762 | 0.3352 | 0.0681* | |
H46A | 0.5004 | 0.8903 | 0.2891 | 0.0937* | 0.50 |
H46B | 0.5208 | 0.8903 | 0.2373 | 0.0937* | 0.50 |
H46C | 0.4788 | 0.8903 | 0.2236 | 0.0937* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0235 (3) | 0.0248 (3) | 0.0269 (3) | 0.0023 (2) | 0.0076 (2) | 0.0035 (3) |
F1 | 0.041 (2) | 0.089 (3) | 0.096 (3) | 0.019 (2) | 0.029 (2) | 0.062 (3) |
F2 | 0.050 (2) | 0.041 (2) | 0.036 (2) | −0.009 (1) | 0.009 (1) | 0.007 (1) |
F3 | 0.057 (2) | 0.051 (2) | 0.070 (2) | 0.008 (2) | 0.034 (2) | −0.001 (2) |
F4 | 0.104 (3) | 0.088 (3) | 0.051 (2) | −0.052 (3) | 0.031 (2) | −0.036 (2) |
F5 | 0.033 (1) | 0.032 (1) | 0.050 (2) | 0.000 (1) | 0.013 (1) | 0.007 (1) |
F6 | 0.034 (2) | 0.040 (2) | 0.040 (2) | 0.005 (1) | 0.009 (1) | 0.008 (1) |
F7 | 0.043 (2) | 0.037 (2) | 0.040 (2) | −0.002 (1) | 0.004 (1) | −0.003 (1) |
F8 | 0.042 (2) | 0.038 (2) | 0.044 (2) | 0.002 (1) | 0.020 (1) | −0.004 (1) |
F9 | 0.069 (2) | 0.073 (2) | 0.039 (2) | 0.003 (2) | −0.003 (2) | −0.007 (2) |
F10 | 0.040 (2) | 0.086 (3) | 0.068 (3) | 0.010 (2) | 0.023 (2) | −0.002 (2) |
F11 | 0.038 (4) | 0.126 (8) | 0.075 (6) | 0.019 (5) | 0.000 (4) | −0.037 (6) |
F12 | 0.032 (3) | 0.091 (5) | 0.047 (4) | −0.009 (3) | 0.010 (3) | −0.016 (4) |
F13 | 0.103 (9) | 0.087 (8) | 0.15 (1) | −0.015 (7) | 0.010 (9) | 0.027 (8) |
F14 | 0.029 (3) | 0.042 (3) | 0.062 (4) | 0.000 (3) | 0.004 (3) | 0.016 (3) |
O1 | 0.070 (3) | 0.043 (2) | 0.062 (3) | −0.011 (2) | 0.014 (2) | −0.017 (2) |
O2 | 0.060 (3) | 0.049 (2) | 0.035 (2) | −0.015 (2) | 0.015 (2) | −0.012 (2) |
O3 | 0.055 (3) | 0.088 (4) | 0.065 (3) | 0.006 (3) | −0.009 (2) | 0.010 (3) |
N1 | 0.027 (2) | 0.029 (2) | 0.025 (2) | 0.001 (2) | 0.007 (1) | 0.001 (2) |
N2 | 0.020 (2) | 0.029 (2) | 0.029 (2) | 0.002 (1) | 0.008 (1) | 0.002 (2) |
N3 | 0.026 (2) | 0.025 (2) | 0.025 (2) | 0.000 (2) | 0.004 (1) | 0.000 (2) |
N4 | 0.031 (2) | 0.028 (2) | 0.023 (2) | 0.001 (2) | 0.009 (2) | 0.002 (2) |
N5 | 0.019 (2) | 0.025 (2) | 0.025 (2) | 0.000 (1) | 0.004 (1) | 0.003 (2) |
N6 | 0.027 (2) | 0.026 (2) | 0.032 (2) | −0.001 (2) | 0.010 (2) | 0.002 (2) |
N7 | 0.060 (3) | 0.067 (4) | 0.053 (3) | 0.030 (3) | 0.009 (3) | 0.010 (3) |
N8 | 0.049 (3) | 0.046 (3) | 0.052 (3) | 0.018 (2) | 0.007 (2) | 0.006 (2) |
N9 | 0.047 (3) | 0.036 (2) | 0.035 (2) | 0.002 (2) | 0.008 (2) | −0.007 (2) |
N10 | 0.052 (4) | 0.068 (5) | 0.046 (4) | 0.0000 | −0.003 (3) | 0.0000 |
C1 | 0.023 (2) | 0.028 (2) | 0.027 (2) | −0.001 (2) | 0.009 (2) | −0.001 (2) |
C2 | 0.024 (2) | 0.026 (2) | 0.031 (2) | 0.002 (2) | 0.011 (2) | −0.001 (2) |
C3 | 0.026 (2) | 0.022 (2) | 0.029 (2) | 0.000 (2) | 0.007 (2) | 0.000 (2) |
C4 | 0.029 (2) | 0.029 (2) | 0.026 (2) | −0.002 (2) | 0.007 (2) | 0.002 (2) |
C5 | 0.028 (2) | 0.026 (2) | 0.028 (2) | 0.000 (2) | 0.010 (2) | −0.001 (2) |
C6 | 0.026 (2) | 0.026 (2) | 0.027 (2) | 0.000 (2) | 0.005 (2) | −0.001 (2) |
C7 | 0.028 (2) | 0.032 (2) | 0.030 (2) | 0.004 (2) | 0.010 (2) | 0.002 (2) |
C8 | 0.031 (2) | 0.032 (2) | 0.029 (2) | −0.005 (2) | 0.010 (2) | 0.000 (2) |
C9 | 0.031 (2) | 0.027 (2) | 0.030 (2) | −0.001 (2) | 0.008 (2) | 0.002 (2) |
C10 | 0.029 (2) | 0.024 (2) | 0.033 (2) | 0.002 (2) | 0.006 (2) | −0.005 (2) |
C11 | 0.023 (2) | 0.032 (2) | 0.029 (2) | 0.001 (2) | 0.008 (2) | 0.004 (2) |
C12 | 0.035 (3) | 0.029 (2) | 0.039 (3) | 0.004 (2) | 0.011 (2) | 0.009 (2) |
C13 | 0.031 (2) | 0.041 (3) | 0.034 (3) | −0.001 (2) | 0.011 (2) | 0.005 (2) |
C14 | 0.029 (2) | 0.039 (3) | 0.040 (3) | 0.000 (2) | 0.013 (2) | 0.008 (2) |
C15 | 0.024 (2) | 0.032 (2) | 0.035 (2) | 0.002 (2) | 0.008 (2) | 0.001 (2) |
C16 | 0.026 (2) | 0.027 (2) | 0.028 (2) | 0.004 (2) | 0.006 (2) | 0.000 (2) |
C17 | 0.030 (2) | 0.034 (2) | 0.042 (3) | 0.002 (2) | 0.007 (2) | 0.004 (2) |
C18 | 0.027 (2) | 0.044 (3) | 0.044 (3) | 0.004 (2) | 0.008 (2) | 0.005 (2) |
C19 | 0.037 (3) | 0.043 (3) | 0.030 (2) | 0.013 (2) | 0.009 (2) | 0.006 (2) |
C20 | 0.042 (3) | 0.029 (2) | 0.034 (3) | 0.004 (2) | 0.009 (2) | 0.002 (2) |
C21 | 0.030 (2) | 0.030 (2) | 0.033 (2) | 0.001 (2) | 0.009 (2) | 0.000 (2) |
C22 | 0.048 (3) | 0.046 (3) | 0.040 (3) | 0.014 (3) | 0.006 (2) | 0.016 (3) |
C23 | 0.023 (2) | 0.029 (2) | 0.026 (2) | 0.002 (2) | 0.008 (2) | 0.001 (2) |
C24 | 0.030 (2) | 0.026 (2) | 0.030 (2) | 0.003 (2) | 0.008 (2) | 0.001 (2) |
C25 | 0.024 (2) | 0.025 (2) | 0.033 (2) | 0.000 (2) | 0.008 (2) | 0.002 (2) |
C26 | 0.023 (2) | 0.031 (2) | 0.034 (2) | 0.000 (2) | 0.007 (2) | 0.001 (2) |
C27 | 0.026 (2) | 0.029 (2) | 0.030 (2) | −0.001 (2) | 0.010 (2) | 0.000 (2) |
C28 | 0.023 (2) | 0.029 (2) | 0.029 (2) | −0.001 (2) | 0.010 (2) | 0.004 (2) |
C29 | 0.029 (2) | 0.039 (3) | 0.031 (2) | −0.001 (2) | 0.007 (2) | −0.003 (2) |
C30 | 0.036 (3) | 0.039 (3) | 0.031 (3) | 0.002 (2) | 0.008 (2) | −0.002 (2) |
C31 | 0.031 (2) | 0.045 (3) | 0.030 (3) | −0.001 (2) | 0.002 (2) | 0.001 (2) |
C32 | 0.029 (2) | 0.039 (3) | 0.029 (2) | 0.006 (2) | 0.006 (2) | 0.008 (2) |
C33 | 0.031 (2) | 0.026 (2) | 0.031 (2) | 0.002 (2) | 0.010 (2) | 0.001 (2) |
C34 | 0.039 (3) | 0.034 (3) | 0.028 (2) | 0.009 (2) | 0.004 (2) | 0.001 (2) |
C35 | 0.045 (3) | 0.040 (3) | 0.040 (3) | 0.000 (2) | 0.006 (2) | −0.011 (2) |
C36 | 0.048 (3) | 0.031 (2) | 0.039 (3) | 0.008 (2) | 0.013 (2) | 0.001 (2) |
C37 | 0.036 (3) | 0.026 (2) | 0.035 (3) | 0.005 (2) | 0.013 (2) | 0.003 (2) |
C38 | 0.023 (2) | 0.031 (2) | 0.029 (2) | 0.002 (2) | 0.004 (2) | 0.008 (2) |
C39 | 0.031 (2) | 0.027 (2) | 0.038 (3) | 0.004 (2) | 0.004 (2) | 0.002 (2) |
C40 | 0.045 (3) | 0.026 (2) | 0.049 (3) | 0.004 (2) | 0.013 (2) | 0.004 (2) |
C41 | 0.035 (2) | 0.033 (2) | 0.036 (3) | 0.012 (2) | 0.012 (2) | 0.007 (2) |
C42 | 0.039 (3) | 0.043 (3) | 0.042 (3) | 0.008 (2) | 0.001 (2) | 0.000 (2) |
C43 | 0.038 (3) | 0.031 (3) | 0.045 (3) | 0.006 (2) | 0.000 (2) | −0.005 (2) |
C44 | 0.036 (3) | 0.035 (3) | 0.045 (3) | 0.009 (2) | 0.009 (2) | 0.004 (2) |
C45 | 0.083 (5) | 0.046 (3) | 0.044 (3) | −0.012 (3) | 0.017 (3) | −0.001 (3) |
C46 | 0.106 (10) | 0.045 (5) | 0.077 (8) | 0.0000 | 0.002 (7) | 0.0000 |
B1 | 0.035 (3) | 0.031 (3) | 0.031 (3) | 0.002 (2) | 0.010 (2) | 0.002 (2) |
B2 | 0.028 (3) | 0.026 (3) | 0.039 (3) | 0.003 (2) | 0.010 (2) | 0.005 (2) |
B3 | 0.035 (4) | 0.053 (5) | 0.031 (4) | 0.0000 | 0.016 (3) | 0.0000 |
B4 | 0.061 (7) | 0.074 (8) | 0.055 (7) | −0.015 (6) | −0.020 (5) | 0.022 (6) |
Geometric parameters (Å, º) top
Co1—N1 | 1.937 (4) | C13—C14 | 1.375 (7) |
Co1—N2 | 1.860 (4) | C13—H13 | 0.951 |
Co1—N3 | 1.946 (4) | C14—C15 | 1.392 (8) |
Co1—N4 | 1.944 (4) | C14—H14 | 0.951 |
Co1—N5 | 1.857 (3) | C15—H15 | 0.949 |
Co1—N6 | 1.927 (4) | C16—C17 | 1.400 (7) |
F1—B1 | 1.371 (7) | C16—C21 | 1.393 (7) |
F2—B1 | 1.401 (7) | C17—C18 | 1.376 (7) |
F3—B1 | 1.383 (8) | C17—H17 | 0.950 |
F4—B1 | 1.365 (7) | C18—C19 | 1.396 (8) |
F5—B2 | 1.401 (6) | C18—H18 | 0.949 |
F6—B2 | 1.394 (6) | C19—C20 | 1.398 (8) |
F7—B2 | 1.391 (6) | C19—C22 | 1.449 (8) |
F8—B2 | 1.396 (7) | C20—C21 | 1.397 (7) |
F9—B3 | 1.384 (6) | C20—H20 | 0.951 |
F10—B3 | 1.385 (7) | C21—H21 | 0.950 |
F11—F13i | 1.25 (2) | C23—C24 | 1.388 (6) |
F11—B4 | 1.409 (10) | C23—C28 | 1.462 (6) |
F12—F13 | 1.59 (2) | C24—C25 | 1.390 (6) |
F12—B4 | 1.536 (7) | C24—H24 | 0.951 |
F13—F14 | 1.49 (1) | C25—C26 | 1.405 (7) |
F13—B4 | 1.26 (1) | C25—C38 | 1.485 (6) |
F14—B4 | 1.442 (6) | C26—C27 | 1.382 (6) |
O1—N9 | 1.244 (6) | C26—H26 | 0.951 |
O2—N9 | 1.217 (6) | C27—C33 | 1.474 (7) |
O3—N10 | 1.233 (6) | C28—C29 | 1.378 (7) |
N1—C11 | 1.370 (6) | C29—C30 | 1.397 (6) |
N1—C15 | 1.345 (6) | C29—H29 | 0.952 |
N2—C1 | 1.355 (7) | C30—C31 | 1.378 (7) |
N2—C5 | 1.342 (6) | C30—H30 | 0.951 |
N3—C6 | 1.369 (6) | C31—C32 | 1.380 (7) |
N3—C10 | 1.335 (6) | C31—H31 | 0.951 |
N4—C28 | 1.365 (6) | C32—H32 | 0.951 |
N4—C32 | 1.342 (6) | C33—C34 | 1.377 (6) |
N5—C23 | 1.353 (6) | C34—C35 | 1.402 (8) |
N5—C27 | 1.340 (5) | C34—H34 | 0.950 |
N6—C33 | 1.372 (6) | C35—C36 | 1.372 (7) |
N6—C37 | 1.346 (6) | C35—H35 | 0.951 |
N7—C22 | 1.122 (8) | C36—C37 | 1.376 (7) |
N8—C44 | 1.145 (7) | C36—H36 | 0.950 |
N9—C45 | 1.451 (9) | C37—H37 | 0.952 |
N10—C46 | 1.47 (1) | C38—C39 | 1.390 (6) |
C1—C2 | 1.379 (6) | C38—C43 | 1.408 (7) |
C1—C6 | 1.469 (6) | C39—C40 | 1.385 (7) |
C2—C3 | 1.400 (7) | C39—H39 | 0.950 |
C2—H2 | 0.950 | C40—C41 | 1.395 (7) |
C3—C4 | 1.416 (7) | C40—H40 | 0.951 |
C3—C16 | 1.488 (6) | C41—C42 | 1.395 (7) |
C4—C5 | 1.389 (6) | C41—C44 | 1.446 (7) |
C4—H4 | 0.950 | C42—C43 | 1.388 (7) |
C5—C11 | 1.476 (7) | C42—H42 | 0.952 |
C6—C7 | 1.385 (7) | C43—H43 | 0.952 |
C7—C8 | 1.387 (7) | C45—H45A | 0.948 |
C7—H7 | 0.949 | C45—H45B | 0.951 |
C8—C9 | 1.381 (7) | C45—H45C | 0.949 |
C8—H8 | 0.951 | C46—H46A | 0.950 |
C9—C10 | 1.387 (7) | C46—H46Aii | 0.950 |
C9—H9 | 0.949 | C46—H46B | 0.950 |
C10—H10 | 0.951 | C46—H46Bii | 0.950 |
C11—C12 | 1.379 (7) | C46—H46C | 0.950 |
C12—C13 | 1.399 (8) | C46—H46Cii | 0.950 |
C12—H12 | 0.951 | | |
| | | |
F1···C32iii | 2.931 (7) | F14···C40vii | 3.291 (8) |
F1···C31iii | 3.326 (7) | F14···N8vii | 3.383 (8) |
F1···C1iii | 3.382 (6) | O1···C36vi | 3.195 (7) |
F1···C6iii | 3.481 (6) | O1···C35vi | 3.280 (8) |
F2···C3iii | 3.137 (5) | O1···C18iii | 3.392 (7) |
F2···C2iii | 3.296 (6) | O1···C30v | 3.418 (8) |
F2···C21iv | 3.318 (6) | O2···C29v | 3.190 (7) |
F2···C30v | 3.354 (6) | O2···C13iv | 3.197 (6) |
F2···C4iii | 3.411 (5) | O2···C12iv | 3.314 (7) |
F2···C31v | 3.439 (6) | O2···C30v | 3.333 (7) |
F2···C32iii | 3.449 (6) | O3···C35vi | 3.246 (7) |
F2···C20iv | 3.457 (7) | N7···C13viii | 3.130 (7) |
F3···C17iii | 3.362 (6) | N7···C12viii | 3.347 (8) |
F3···C2iii | 3.415 (6) | N7···C45ix | 3.421 (9) |
F4···C4iv | 3.126 (6) | N8···C15x | 3.236 (7) |
F4···C12iv | 3.439 (6) | N8···C28x | 3.434 (8) |
F4···C30v | 3.540 (7) | N8···C29x | 3.486 (8) |
F5···C37vi | 3.169 (6) | N8···C23x | 3.489 (8) |
F5···C3vi | 3.349 (5) | N8···C14x | 3.594 (7) |
F5···C7iii | 3.401 (6) | C7···C9iii | 3.462 (6) |
F5···C2vi | 3.423 (5) | C7···C8iii | 3.487 (7) |
F5···C4vi | 3.492 (6) | C7···C21ix | 3.598 (7) |
F5···C36vi | 3.560 (6) | C8···C20ix | 3.145 (7) |
F6···C7iii | 3.202 (6) | C8···C8iii | 3.199 (9) |
F6···C8iii | 3.280 (6) | C8···C21ix | 3.456 (7) |
F6···C21vi | 3.595 (5) | C8···C9iii | 3.460 (6) |
F7···C36vi | 3.492 (6) | C8···C19ix | 3.572 (7) |
F8···C37vi | 3.179 (6) | C9···C22ix | 3.464 (7) |
F8···C5vi | 3.263 (5) | C9···C20ix | 3.570 (7) |
F8···C4vi | 3.296 (5) | C12···C22xi | 3.565 (8) |
F8···C11vi | 3.392 (6) | C17···C31viii | 3.546 (8) |
F8···C12vi | 3.551 (6) | C18···C36ix | 3.500 (8) |
F9···C46vii | 3.20 (1) | C23···C44x | 3.597 (8) |
F9···C14iv | 3.525 (7) | C24···C44x | 3.407 (8) |
F12···C40vii | 3.429 (9) | C24···C41x | 3.536 (8) |
F14···C44vii | 3.250 (9) | C37···B2vii | 3.578 (7) |
| | | |
N1—Co1—N2 | 82.4 (2) | N5—C27—C33 | 110.9 (4) |
N1—Co1—N3 | 164.6 (2) | C26—C27—C33 | 128.0 (4) |
N1—Co1—N4 | 90.4 (2) | N4—C28—C23 | 113.7 (4) |
N1—Co1—N5 | 100.0 (2) | N4—C28—C29 | 121.6 (4) |
N1—Co1—N6 | 90.9 (2) | C23—C28—C29 | 124.7 (4) |
N2—Co1—N3 | 82.2 (2) | C28—C29—C30 | 118.5 (4) |
N2—Co1—N4 | 98.2 (2) | C28—C29—H29 | 120.8 |
N2—Co1—N5 | 177.4 (2) | C30—C29—H29 | 120.7 |
N2—Co1—N6 | 97.4 (2) | C29—C30—C31 | 119.3 (5) |
N3—Co1—N4 | 92.3 (2) | C29—C30—H30 | 120.4 |
N3—Co1—N5 | 95.3 (2) | C31—C30—H30 | 120.3 |
N3—Co1—N6 | 90.6 (2) | C30—C31—C32 | 119.9 (4) |
N4—Co1—N5 | 82.6 (2) | C30—C31—H31 | 120.1 |
N4—Co1—N6 | 164.4 (2) | C32—C31—H31 | 120.0 |
N5—Co1—N6 | 81.9 (2) | N4—C32—C31 | 121.0 (4) |
F13i—F11—B4 | 56.0 (8) | N4—C32—H32 | 119.5 |
F13—F12—B4 | 47.3 (5) | C31—C32—H32 | 119.5 |
F11i—F13—F12 | 109.6 (10) | N6—C33—C27 | 112.6 (4) |
F11i—F13—F14 | 108.5 (9) | N6—C33—C34 | 121.8 (4) |
F11i—F13—B4 | 68.5 (8) | C27—C33—C34 | 125.6 (4) |
F12—F13—F14 | 92.3 (9) | C33—C34—C35 | 118.1 (4) |
F12—F13—B4 | 64.1 (7) | C33—C34—H34 | 121.0 |
F14—F13—B4 | 62.5 (6) | C35—C34—H34 | 121.0 |
F13—F14—B4 | 50.6 (5) | C34—C35—C36 | 119.7 (5) |
Co1—N1—C11 | 114.3 (3) | C34—C35—H35 | 120.3 |
Co1—N1—C15 | 126.8 (3) | C36—C35—H35 | 120.1 |
C11—N1—C15 | 118.9 (4) | C35—C36—C37 | 120.0 (5) |
Co1—N2—C1 | 118.9 (3) | C35—C36—H36 | 120.2 |
Co1—N2—C5 | 118.7 (3) | C37—C36—H36 | 119.9 |
C1—N2—C5 | 122.4 (4) | N6—C37—C36 | 121.3 (4) |
Co1—N3—C6 | 114.2 (3) | N6—C37—H37 | 119.3 |
Co1—N3—C10 | 127.6 (3) | C36—C37—H37 | 119.4 |
C6—N3—C10 | 118.2 (4) | C25—C38—C39 | 121.2 (4) |
Co1—N4—C28 | 113.6 (3) | C25—C38—C43 | 120.2 (4) |
Co1—N4—C32 | 126.8 (3) | C39—C38—C43 | 118.6 (4) |
C28—N4—C32 | 119.6 (4) | C38—C39—C40 | 121.3 (4) |
Co1—N5—C23 | 118.3 (3) | C38—C39—H39 | 119.4 |
Co1—N5—C27 | 119.2 (3) | C40—C39—H39 | 119.3 |
C23—N5—C27 | 121.9 (4) | C39—C40—C41 | 119.0 (4) |
Co1—N6—C33 | 114.6 (3) | C39—C40—H40 | 120.6 |
Co1—N6—C37 | 126.2 (3) | C41—C40—H40 | 120.4 |
C33—N6—C37 | 119.2 (4) | C40—C41—C42 | 121.3 (5) |
O1—N9—O2 | 123.0 (5) | C40—C41—C44 | 119.2 (4) |
O1—N9—C45 | 117.5 (5) | C42—C41—C44 | 119.6 (4) |
O2—N9—C45 | 119.5 (5) | C41—C42—C43 | 118.6 (5) |
O3—N10—O3ii | 122.3 (8) | C41—C42—H42 | 120.7 |
O3—N10—C46 | 118.9 (4) | C43—C42—H42 | 120.7 |
O3ii—N10—C46 | 118.9 (4) | C38—C43—C42 | 121.2 (5) |
N2—C1—C2 | 120.0 (4) | C38—C43—H43 | 119.4 |
N2—C1—C6 | 111.3 (4) | C42—C43—H43 | 119.4 |
C2—C1—C6 | 128.7 (5) | N8—C44—C41 | 178.0 (6) |
C1—C2—C3 | 119.5 (5) | N9—C45—H45A | 109.4 |
C1—C2—H2 | 120.2 | N9—C45—H45B | 109.3 |
C3—C2—H2 | 120.3 | N9—C45—H45C | 109.4 |
C2—C3—C4 | 119.1 (4) | H45A—C45—H45B | 109.5 |
C2—C3—C16 | 120.3 (4) | H45A—C45—H45C | 109.7 |
C4—C3—C16 | 120.6 (4) | H45B—C45—H45C | 109.5 |
C3—C4—C5 | 118.7 (4) | N10—C46—H46A | 109.4 |
C3—C4—H4 | 120.7 | N10—C46—H46Aii | 109.4 |
C5—C4—H4 | 120.6 | N10—C46—H46B | 109.4 |
N2—C5—C4 | 120.3 (4) | N10—C46—H46Bii | 109.4 |
N2—C5—C11 | 111.8 (4) | N10—C46—H46C | 109.4 |
C4—C5—C11 | 128.0 (4) | N10—C46—H46Cii | 109.4 |
N3—C6—C1 | 113.2 (4) | H46A—C46—H46Aii | 141.2 |
N3—C6—C7 | 122.3 (4) | H46A—C46—H46B | 109.5 |
C1—C6—C7 | 124.5 (4) | H46A—C46—H46Bii | 56.3 |
C6—C7—C8 | 118.1 (4) | H46A—C46—H46C | 109.5 |
C6—C7—H7 | 120.9 | H46A—C46—H46Cii | 56.3 |
C8—C7—H7 | 120.9 | H46Aii—C46—H46B | 56.3 |
C7—C8—C9 | 120.0 (5) | H46Aii—C46—H46Bii | 109.5 |
C7—C8—H8 | 120.1 | H46Aii—C46—H46C | 56.3 |
C9—C8—H8 | 119.9 | H46Aii—C46—H46Cii | 109.5 |
C8—C9—C10 | 118.7 (4) | H46B—C46—H46Bii | 141.2 |
C8—C9—H9 | 120.7 | H46B—C46—H46C | 109.5 |
C10—C9—H9 | 120.7 | H46B—C46—H46Cii | 56.3 |
N3—C10—C9 | 122.7 (4) | H46Bii—C46—H46C | 56.3 |
N3—C10—H10 | 118.6 | H46Bii—C46—H46Cii | 109.5 |
C9—C10—H10 | 118.7 | H46C—C46—H46Cii | 141.2 |
N1—C11—C5 | 112.7 (4) | F1—B1—F2 | 109.1 (4) |
N1—C11—C12 | 121.5 (4) | F1—B1—F3 | 109.0 (5) |
C5—C11—C12 | 125.8 (4) | F1—B1—F4 | 110.3 (5) |
C11—C12—C13 | 118.8 (4) | F2—B1—F3 | 110.7 (4) |
C11—C12—H12 | 120.6 | F2—B1—F4 | 109.2 (5) |
C13—C12—H12 | 120.6 | F3—B1—F4 | 108.5 (5) |
C12—C13—C14 | 120.0 (5) | F5—B2—F6 | 108.8 (4) |
C12—C13—H13 | 120.1 | F5—B2—F7 | 109.6 (4) |
C14—C13—H13 | 120.0 | F5—B2—F8 | 109.6 (4) |
C13—C14—C15 | 118.5 (5) | F6—B2—F7 | 109.8 (4) |
C13—C14—H14 | 120.8 | F6—B2—F8 | 110.1 (4) |
C15—C14—H14 | 120.6 | F7—B2—F8 | 108.9 (4) |
N1—C15—C14 | 122.3 (4) | F9—B3—F9ii | 111.6 (7) |
N1—C15—H15 | 119.0 | F9—B3—F10 | 110.5 (2) |
C14—C15—H15 | 118.7 | F9—B3—F10ii | 107.8 (2) |
C3—C16—C17 | 119.7 (4) | F9ii—B3—F10 | 107.8 (2) |
C3—C16—C21 | 120.7 (4) | F9ii—B3—F10ii | 110.5 (2) |
C17—C16—C21 | 119.7 (4) | F10—B3—F10ii | 108.6 (7) |
C16—C17—C18 | 120.3 (5) | F11—B4—F11i | 180.0 |
C16—C17—H17 | 120.0 | F11—B4—F12 | 75.6 (4) |
C18—C17—H17 | 119.7 | F11—B4—F12i | 104.4 (4) |
C17—C18—C19 | 120.2 (5) | F11—B4—F13 | 124.5 (8) |
C17—C18—H18 | 119.9 | F11—B4—F13i | 55.5 (8) |
C19—C18—H18 | 119.9 | F11—B4—F14 | 77.0 (5) |
C18—C19—C20 | 120.0 (5) | F11—B4—F14i | 103.0 (5) |
C18—C19—C22 | 118.5 (5) | F11i—B4—F12 | 104.4 (4) |
C20—C19—C22 | 121.3 (5) | F11i—B4—F12i | 75.6 (4) |
C19—C20—C21 | 119.5 (5) | F11i—B4—F13 | 55.5 (8) |
C19—C20—H20 | 120.2 | F11i—B4—F13i | 124.5 (8) |
C21—C20—H20 | 120.3 | F11i—B4—F14 | 103.0 (5) |
C16—C21—C20 | 120.1 (5) | F11i—B4—F14i | 77.0 (5) |
C16—C21—H21 | 119.9 | F12—B4—F12i | 180.0 |
C20—C21—H21 | 120.0 | F12—B4—F13 | 68.6 (7) |
N7—C22—C19 | 174.2 (7) | F12—B4—F13i | 111.4 (7) |
N5—C23—C24 | 119.0 (4) | F12—B4—F14 | 96.7 (4) |
N5—C23—C28 | 111.5 (4) | F12—B4—F14i | 83.3 (4) |
C24—C23—C28 | 129.5 (4) | F12i—B4—F13 | 111.4 (7) |
C23—C24—C25 | 120.7 (4) | F12i—B4—F13i | 68.6 (7) |
C23—C24—H24 | 119.6 | F12i—B4—F14 | 83.3 (4) |
C25—C24—H24 | 119.7 | F12i—B4—F14i | 96.7 (4) |
C24—C25—C26 | 118.6 (4) | F13—B4—F13i | 180.0 |
C24—C25—C38 | 120.8 (4) | F13—B4—F14 | 66.9 (6) |
C26—C25—C38 | 120.6 (4) | F13—B4—F14i | 113.1 (6) |
C25—C26—C27 | 118.8 (4) | F13i—B4—F14 | 113.1 (6) |
C25—C26—H26 | 120.7 | F13i—B4—F14i | 66.9 (6) |
C27—C26—H26 | 120.5 | F14—B4—F14i | 180.0 |
N5—C27—C26 | 121.1 (4) | | |
| | | |
Co1—N1—C11—C5 | −0.1 (5) | N5—Co1—N1—C15 | −0.2 (4) |
Co1—N1—C11—C12 | 179.4 (4) | N5—Co1—N2—C1 | 13 (3) |
Co1—N1—C15—C14 | 179.8 (4) | N5—Co1—N2—C5 | −165 (3) |
Co1—N2—C1—C2 | −179.3 (3) | N5—Co1—N3—C6 | −175.6 (3) |
Co1—N2—C1—C6 | 0.8 (5) | N5—Co1—N3—C10 | 1.7 (4) |
Co1—N2—C5—C4 | −179.1 (3) | N5—Co1—N4—C28 | 1.8 (3) |
Co1—N2—C5—C11 | 2.2 (5) | N5—Co1—N4—C32 | 179.8 (4) |
Co1—N3—C6—C1 | −4.2 (5) | N5—Co1—N6—C33 | 6.3 (4) |
Co1—N3—C6—C7 | 176.3 (3) | N5—Co1—N6—C37 | −172.5 (5) |
Co1—N3—C10—C9 | −176.7 (3) | N5—C23—C24—C25 | −2.4 (7) |
Co1—N4—C28—C23 | −4.3 (5) | N5—C23—C28—C29 | −176.2 (5) |
Co1—N4—C28—C29 | 177.0 (4) | N5—C27—C26—C25 | −1.2 (7) |
Co1—N4—C32—C31 | −178.8 (4) | N5—C27—C33—N6 | −2.6 (6) |
Co1—N5—C23—C24 | 174.3 (4) | N5—C27—C33—C34 | 174.7 (5) |
Co1—N5—C23—C28 | −3.8 (5) | N6—Co1—N1—C11 | 98.4 (3) |
Co1—N5—C27—C26 | −172.5 (4) | N6—Co1—N1—C15 | −82.1 (4) |
Co1—N5—C27—C33 | 8.2 (5) | N6—Co1—N2—C1 | 87.1 (3) |
Co1—N6—C33—C27 | −3.6 (5) | N6—Co1—N2—C5 | −91.8 (3) |
Co1—N6—C33—C34 | 179.0 (4) | N6—Co1—N3—C6 | −93.7 (3) |
Co1—N6—C37—C36 | 179.4 (4) | N6—Co1—N3—C10 | 83.5 (4) |
F11—F13i—F12i—B4 | 52.7 (7) | N6—Co1—N4—C28 | −3.4 (9) |
F11—F13i—F14i—B4 | −52.4 (8) | N6—Co1—N4—C32 | 174.5 (6) |
F11—F13i—B4—F12 | 53.7 (7) | N6—Co1—N5—C23 | 179.8 (4) |
F11—F13i—B4—F12i | −126.3 (7) | N6—Co1—N5—C27 | −8.3 (4) |
F11—F13i—B4—F14 | −53.9 (8) | N6—C33—C27—C26 | 178.2 (5) |
F11—F13i—B4—F14i | 126.1 (8) | N6—C33—C34—C35 | 2.2 (8) |
F11—B4—F12—F13 | −136.7 (8) | N6—C37—C36—C35 | 0.7 (9) |
F11—B4—F12i—F13i | −43.3 (8) | N7—C22—C19—C18 | −69 (6) |
F11—B4—F13—F12 | 53.7 (7) | N7—C22—C19—C20 | 105 (6) |
F11—B4—F13—F14 | −53.9 (8) | N8—C44—C41—C40 | 148 (17) |
F11—B4—F13i—F12i | 126.3 (7) | N8—C44—C41—C42 | −30 (17) |
F11—B4—F13i—F14i | −126.1 (8) | C1—N2—C5—C4 | 2.1 (6) |
F11—B4—F14—F13 | 136.9 (8) | C1—N2—C5—C11 | −176.7 (4) |
F11—B4—F14i—F13i | 43.1 (8) | C1—C2—C3—C4 | 3.0 (6) |
F12—F13—F11i—B4 | 50.3 (7) | C1—C2—C3—C16 | −178.1 (4) |
F12—F13—F14—B4 | −59.1 (6) | C1—C6—N3—C10 | 178.3 (4) |
F12—F13—B4—F14 | 107.6 (6) | C1—C6—C7—C8 | −178.0 (4) |
F12—F13—B4—F14i | −72.4 (6) | C2—C1—N2—C5 | −0.5 (6) |
F12—B4—F11—F13i | −129.2 (8) | C2—C1—C6—C7 | 2.0 (7) |
F12—B4—F11i—F13 | −50.8 (8) | C2—C3—C4—C5 | −1.5 (6) |
F12—B4—F13—F14 | −107.6 (6) | C2—C3—C16—C17 | 28.6 (7) |
F12—B4—F13i—F14i | −72.4 (6) | C2—C3—C16—C21 | −150.7 (5) |
F12—B4—F14—F13 | 63.3 (8) | C3—C2—C1—C6 | 177.7 (4) |
F12—B4—F14i—F13i | 116.7 (8) | C3—C4—C5—C11 | 177.5 (4) |
F13—F11i—B4—F14 | 49.7 (8) | C3—C16—C17—C18 | −175.9 (5) |
F13—F11i—B4—F14i | −130.3 (8) | C3—C16—C21—C20 | 175.9 (5) |
F13—F12—B4—F14 | −62.0 (7) | C4—C3—C16—C17 | −152.5 (5) |
F13—F12—B4—F14i | 118.0 (7) | C4—C3—C16—C21 | 28.2 (7) |
F13—F14—B4—F14i | −81.8 | C4—C5—C11—C12 | 0.6 (8) |
F14—F13—F11i—B4 | −49.1 (7) | C5—N2—C1—C6 | 179.7 (4) |
F14—F13—F12—B4 | 57.8 (5) | C5—C4—C3—C16 | 179.6 (4) |
N1—Co1—N2—C1 | 177.1 (3) | C5—C11—N1—C15 | −179.7 (4) |
N1—Co1—N2—C5 | −1.8 (3) | C5—C11—C12—C13 | −179.6 (4) |
N1—Co1—N3—C6 | 2.0 (8) | C6—N3—C10—C9 | 0.5 (6) |
N1—Co1—N3—C10 | 179.3 (5) | C6—C7—C8—C9 | −1.0 (7) |
N1—Co1—N4—C28 | −98.2 (3) | C7—C6—N3—C10 | −1.3 (6) |
N1—Co1—N4—C32 | 79.7 (4) | C7—C8—C9—C10 | 0.3 (7) |
N1—Co1—N5—C23 | 90.3 (4) | C11—N1—C15—C14 | −0.7 (7) |
N1—Co1—N5—C27 | −97.8 (4) | C11—C12—C13—C14 | −0.8 (7) |
N1—Co1—N6—C33 | 106.2 (4) | C12—C11—N1—C15 | −0.1 (7) |
N1—Co1—N6—C37 | −72.5 (4) | C12—C13—C14—C15 | 0.0 (7) |
N1—C11—C5—N2 | −1.2 (5) | C16—C17—C18—C19 | 0.5 (8) |
N1—C11—C5—C4 | −179.9 (4) | C16—C21—C20—C19 | −0.3 (8) |
N1—C11—C12—C13 | 0.8 (7) | C17—C16—C21—C20 | −3.4 (7) |
N1—C15—C14—C13 | 0.7 (7) | C17—C18—C19—C20 | −4.3 (8) |
N2—Co1—N1—C11 | 1.0 (3) | C17—C18—C19—C22 | 170.5 (5) |
N2—Co1—N1—C15 | −179.5 (4) | C18—C17—C16—C21 | 3.4 (8) |
N2—Co1—N3—C6 | 3.7 (3) | C18—C19—C20—C21 | 4.2 (8) |
N2—Co1—N3—C10 | −179.1 (4) | C21—C20—C19—C22 | −170.4 (5) |
N2—Co1—N4—C28 | 179.4 (3) | C23—N5—C27—C26 | −0.9 (7) |
N2—Co1—N4—C32 | −2.7 (5) | C23—N5—C27—C33 | 179.9 (4) |
N2—Co1—N5—C23 | −106 (3) | C23—C24—C25—C26 | 0.4 (7) |
N2—Co1—N5—C27 | 65 (3) | C23—C24—C25—C38 | −179.1 (5) |
N2—Co1—N6—C33 | −171.3 (4) | C23—C28—N4—C32 | 177.6 (4) |
N2—Co1—N6—C37 | 10.0 (5) | C23—C28—C29—C30 | −177.3 (5) |
N2—C1—C2—C3 | −2.1 (6) | C24—C23—N5—C27 | 2.7 (7) |
N2—C1—C6—N3 | 2.3 (5) | C24—C23—C28—C29 | 6.0 (9) |
N2—C1—C6—C7 | −178.2 (4) | C24—C25—C26—C27 | 1.4 (7) |
N2—C5—C4—C3 | −1.0 (6) | C24—C25—C38—C39 | 22.2 (8) |
N2—C5—C11—C12 | 179.2 (4) | C24—C25—C38—C43 | −158.1 (5) |
N3—Co1—N1—C11 | 2.7 (8) | C25—C24—C23—C28 | 175.3 (5) |
N3—Co1—N1—C15 | −177.8 (5) | C25—C26—C27—C33 | 177.9 (5) |
N3—Co1—N2—C1 | −2.5 (3) | C25—C38—C39—C40 | −179.8 (5) |
N3—Co1—N2—C5 | 178.6 (3) | C25—C38—C43—C42 | −179.4 (5) |
N3—Co1—N4—C28 | 96.9 (3) | C26—C25—C38—C39 | −157.2 (5) |
N3—Co1—N4—C32 | −85.1 (4) | C26—C25—C38—C43 | 22.4 (8) |
N3—Co1—N5—C23 | −90.4 (4) | C26—C27—C33—C34 | −4.5 (9) |
N3—Co1—N5—C27 | 81.5 (4) | C27—N5—C23—C28 | −175.4 (4) |
N3—Co1—N6—C33 | −89.1 (4) | C27—C26—C25—C38 | −179.1 (5) |
N3—Co1—N6—C37 | 92.2 (4) | C27—C33—N6—C37 | 175.2 (5) |
N3—C6—C1—C2 | −177.6 (4) | C27—C33—C34—C35 | −174.9 (5) |
N3—C6—C7—C8 | 1.5 (7) | C28—N4—C32—C31 | −1.0 (8) |
N3—C10—C9—C8 | 0.0 (7) | C28—C29—C30—C31 | 0.5 (8) |
N4—Co1—N1—C11 | −97.2 (3) | C29—C28—N4—C32 | −1.1 (7) |
N4—Co1—N1—C15 | 82.3 (4) | C29—C30—C31—C32 | −2.5 (8) |
N4—Co1—N2—C1 | −93.6 (3) | C33—N6—C37—C36 | 0.7 (8) |
N4—Co1—N2—C5 | 87.5 (3) | C33—C34—C35—C36 | −0.7 (9) |
N4—Co1—N3—C6 | 101.6 (3) | C34—C33—N6—C37 | −2.2 (8) |
N4—Co1—N3—C10 | −81.1 (4) | C34—C35—C36—C37 | −0.6 (9) |
N4—Co1—N5—C23 | 1.2 (4) | C38—C39—C40—C41 | −2.0 (9) |
N4—Co1—N5—C27 | 173.1 (4) | C38—C43—C42—C41 | 0.2 (9) |
N4—Co1—N6—C33 | 11.5 (9) | C39—C38—C43—C42 | 0.3 (9) |
N4—Co1—N6—C37 | −167.2 (6) | C39—C40—C41—C42 | 2.5 (9) |
N4—C28—C23—N5 | 5.1 (6) | C39—C40—C41—C44 | −176.8 (6) |
N4—C28—C23—C24 | −172.7 (5) | C40—C39—C38—C43 | 0.6 (8) |
N4—C28—C29—C30 | 1.3 (8) | C40—C41—C42—C43 | −1.6 (9) |
N4—C32—C31—C30 | 2.8 (8) | C43—C42—C41—C44 | 177.6 (6) |
N5—Co1—N1—C11 | −179.7 (3) | C43—C42—C41—C44 | 177.6 (6) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y, −z+1/2; (iii) −x+3/2, −y+1/2, −z+1; (iv) x, −y, z−1/2; (v) x, −y+1, z−1/2; (vi) x, y+1, z; (vii) x, y−1, z; (viii) −x+3/2, y−1/2, −z+3/2; (ix) −x+3/2, −y−1/2, −z+1; (x) −x+1, −y+1, −z+1; (xi) −x+3/2, y+1/2, −z+3/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Co(C22H14N4)2](BF4)2·CH3NO2 | [Co(C22H14N4)2](BF4)3·1.5CH3NO2 |
Mr | 962.34 | 1079.67 |
Crystal system, space group | Monoclinic, Cc | Monoclinic, C2/c |
Temperature (K) | 120 | 110 |
a, b, c (Å) | 13.304 (13), 12.125 (12), 27.30 (3) | 37.80 (2), 10.748 (6), 22.99 (1) |
β (°) | 110.761 (12) | 102.388 (9) |
V (Å3) | 4118 (7) | 9123 (8) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.51 | 0.48 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 | 0.30 × 0.07 × 0.05 |
|
Data collection |
Diffractometer | Rigaku Mercury diffractometer | Rigaku Mercury diffractometer |
Absorption correction | – | Multi-scan (Jacobson, 1998) |
Tmin, Tmax | – | 0.789, 0.976 |
No. of measured, independent and observed reflections | 23489, 8003, 6271 [F2 > 2σ(F2)] | 35412, 10280, 7454 [I > 2σ(I)] |
Rint | 0.056 | 0.072 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.070, 0.169, 1.04 | 0.096, 0.238, 1.17 |
No. of reflections | 8003 | 10280 |
No. of parameters | 632 | 688 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.13, −0.43 | 1.03, −0.62 |
Absolute structure | Flack (1983), 3285 Friedel pairs | ? |
Absolute structure parameter | 0.026 (19) | ? |
Selected geometric parameters (Å, º) for (I) topCo1—N1 | 2.132 (4) | Co1—N4 | 2.147 (5) |
Co1—N2 | 2.007 (4) | Co1—N5 | 2.028 (4) |
Co1—N3 | 2.146 (4) | Co1—N6 | 2.133 (4) |
| | | |
N1—Co1—N2 | 76.41 (17) | N2—Co1—N5 | 169.48 (18) |
N1—Co1—N3 | 152.98 (16) | N4—Co1—N5 | 77.21 (18) |
N1—Co1—N5 | 111.88 (17) | N4—Co1—N6 | 154.20 (15) |
N2—Co1—N3 | 77.31 (16) | N5—Co1—N6 | 77.19 (19) |
Selected geometric parameters (Å, º) for (II) topCo1—N1 | 1.937 (4) | Co1—N4 | 1.944 (4) |
Co1—N2 | 1.860 (4) | Co1—N5 | 1.857 (3) |
Co1—N3 | 1.946 (4) | Co1—N6 | 1.927 (4) |
| | | |
N1—Co1—N2 | 82.4 (2) | N2—Co1—N5 | 177.4 (2) |
N1—Co1—N3 | 164.6 (2) | N4—Co1—N5 | 82.6 (2) |
N1—Co1—N5 | 100.0 (2) | N4—Co1—N6 | 164.4 (2) |
N2—Co1—N3 | 82.2 (2) | N5—Co1—N6 | 81.9 (2) |
[Co(tpy)2]2+ (tpy is terpyridine) and its derivatives have been attracting much attention because of their considerable variety of spin-crossover (SCO) behaviors (Judge & Baker, 1967; Kremer et al., 1982). The introduction of substituents into the 4'-positions of the terpyridines leads to properties with potential application in luminescence (Alcock et al., 2000), photochemistry (Yutaka et al., 2003), construction of multi-metallic arrays (Mutai et al., 2001) and enhancement of SCO characteristics (Gaspar et al., 2001; Hayami et al., 2005). We have designed the 4'-cyanophenyl-substituted ligand and prepared the first two cobalt complexes of this family, (I) and (II). These complexes could potentially be used as building blocks for new multinuclear supramolecular complexes with versatile physicochemical properties via bridging through the cyano groups in the molecule. Relatively few studies of the CoIII complexes with such ligands have been carried out (Yutaka et al., 2003). Figgis et al. (1983) observed significant changes in metal–ligand distance between CoII and CoIII complexes of unsubstituted terpyridine, but there is no comparative information on 4'-substituted terpyridine species. The present crystallographic study is intended to contribute to a better understanding of the comparative coordination geometry dependent on the oxidation state of the metal center.
The structure analysis confirms the bis-meridional configuration for both complex cations (Fig. 1). In complex (I), the Co—N distances (Table 1) are significantly longer than those observed in low spin (LS) CoII species [1.873 (11)–1.971 (13) Å (Alcock et al., 2000) and 1.849 (6)–1.956 (6) Å (Galet et al., 2006)] and are comparable to those of high spin (HS) CoII species [2.018 (2)–2.180 (3) Å (Galet et al., 2006) and 2.075 (5)–2.189 (3) Å (Takusagawa et al., 1986)], representing a characteristic feature of the HS state. The Co—N distances of (II) (Table 2) are close to those reported in [Co(tpy)2]Cl3 [1.853 (7)–1.937 (7) Å; Figgis et al., 1983], suggesting an LS state for (II). In both complexes, the Co—Ncentral distances are shorter than the Co—Nterminal distances, characterizing a compression along the N2—Co—N5 central axis. This compression indicates the steric effect of the constrained cptpy ligand bite on the metal center in the two complexes.
Furthermore, the Nterminal—Co—Nterminal bite angles for the terpyridyl chelates in (I) (Table 1) fall in the range reported for the CoII complexes of 4'-aryl-substituted terpyridines (Yutaka et al., 2003; Alcock et al., 2000; Whittle et al., 1998) and deviate considerably from ideal octahedral geometry. In (II), the bite angles are about 10° larger (Table 2). The terpyridyl units of the ligands are approximately planar. The N—C—C—N torsion angles of the two pyridyl rings of (I) [3.9 (8)–9.4 (7)° {3.8</span>(7)–9.5 (6)°?}] are markedly larger than those observed for (II) [1.2 (5)–5.1 (6)° {please check values; torsion angles for (II) not supplied in CIF}]. Thus, it can be seen that the coordination environment around the CoIII ion has a more ideal octahedral geometry than that observed in the CoII complex.
The phenyl rings of the cptpy ligands in each case are twisted significantly with respect to the terpyridyl units. The dihedral angles between the mean planes of the phenyl ring and terpyridyl unit are 33.8 (1) and 46.3 (2)° in (I) versus the much lower 18.8 (2) and 26.3 (1)° in (II). Since such twisting is especially sensitive to intermolecular interactions (Brock & Minton, 1989), it reveals the influence from the crystal packing effects in (I) and (II).
In (I), two types of interactions between terminal pyridyl rings of mutually adjacent molecules, namely offset π–π interactions [the nearest C—C distance is 3.376 (7) Å] and edge-to-face C—H···π interactions [C···π = 3.684 (7) Å {dihedral angle?}], operate in concert (Fig. 2). As is observed in [M(tpy)2]2+ complexes where the ratio of anions to cations is 2:1 (Scudder et al., 1999), the interactions involving anions and solvent molecules do not in general disrupt the motif of (I). Each terminal pyridyl ring of a ligand participates in these interactions with its adjacent molecules, thus forming a layer of interlocked cations. The layers stack through offset π–π interactions [with nearest C—C distances of 3.460 (9) and 3.618 (8) Å] between the phenyl rings and the central pyridyl rings of adjacent molecules [with dihedral angles of 3.4 (2) and 10.2 (2)°], as well as C—H···π interactions [C···π = 3.307 (9) Å and C—H···π = 31.9 (2)°] between the phenyl rings of adjacent molecules. As a result of the distortion of phenyl–terpyridyl unit, alternating layers in the stack are rotated by 45°. This packing motif is also observed in [Cu(terpy)2](PF6)2 (Scudder et al., 1999).
The crystal packing of (II) is disrupted compared with that in (I) by the greater number of BF4- ions and CH3NO2 molecules, which hinder the formation of C—H···π interactions between the terminal pyridyl rings. The complex cations are linked by π–π interactions to form a one-dimensional supramolecular chain similar to those seen in biphenyl-substituted species (Alcock et al., 2000) (Fig. 3). A two-dimensional layer is built by π–π interactions between terminal pyridyl rings of adjacent chains [3.199 (9) Å] and stabilized by C—H···π interactions between terminal pyridyl and phenyl rings [3.546 (8) Å and 46.5 (2)°]. As a result, the N2—Co—N5 central axes of molecules in adjacent layers are approximately perpendicular to each other, showing a visual crossover grid.
The difference in packing patterns between (I) and (II) may be attributed to the number of anions and solvent molecules. The larger ionic radius of CoII and greater distortion from octahedral geometry make it possible to build a different packing style of higher dimensionality involving fewer anions and solvent molecules as compared with the situation with CoIII. Given the sensitivity of the crystal packing to the number, charge and size of the constituent ions a the number of solvent molecules, it will be necessary to conduct more comparative studies of this type in order to obtain more relevant and precise conclusions.