Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109054626/tr3058sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109054626/tr3058Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109054626/tr3058IIsup3.hkl |
CCDC references: 774023; 774024
Complexes (I) and (II) have been synthesized, and routinely characterized, as previously reported: (I) by reaction of excess triarylphosphine with [Co(CNCMe3)4H2O](ClO4)2 (Becker et al., 1986) and (II) by AgClO4 oxidation of (I) (Becker, 2000). X-ray quality crystals of (I), as the solvate [Co(CNCMe3)3{P(C6H4OMe-p)3}2]ClO4.2CH2Cl2, were obtained by slow evaporation of CH2Cl2/C6H12 solution at room temperature and the crystals of (II), also as a dichloromethane solvate [Co(CNCMe3)3{P(C6H4OMe-p)3}2](ClO4)2.2.08CH2Cl2, were obtained by diffusion of C6H12 into CH2Cl2 solution at room temperature.
For both compounds, all H atoms were refined using a riding model, with a C—H distance of 0.98Å and with Uiso(H) = 1.5Ueq(C). The highest residual peak for (I) was 1.614Å from atom Cl1 and for (II) was 0.900Å from atom C36. The methyl disorder of compound (I) seen on C31 was apparent in the structure, hence atoms C32A/C34A and atoms C32B/C33A where refined with complementary occupancies. The orientational disorder was refined over two positions using an EADP restraint (SHELXTL; Sheldrick, 2008); the final occupancy was 0.545 (5) for C32A/C34A and 0.454 (5) for C32B/C33A. The apparent solvent disorder in structure (II) was seen on dichloromethane atoms C58/C58A, and hence atoms Cl3A/Cl4A and Cl3B/Cl4B were refined with complementary occupancies. The orientational disorder was refined over two positions using bond length (DFIX) restraints [1.73 (2)Å] for the C—Cl bond lengths as well as EADP restraints for C58/C58A (SHELXTL; Sheldrick, 2008); the final occupancy was 0.489 (8) for Cl3A/Cl4A and 0.511 (8) for Cl3B/Cl4B. For satisfactory convergence it was also necessary to fix the coordinates of atoms C58, C58A, Cl4A and Cl4B during refinement. The further solvent disorder seen on C59 and C60A–D with its respective Cl atoms were refined with occupancies having been refined as a restrained linear sum of the free variables. These partial molecules have a sum of occupancies of 1.08 (CH2Cl2) (using a SUMP restraint), hence giving rise to discrepancies in the reported molecular weight and densities of the crystal.
Numerous tris(alkylisocyanide)bis(triarylphosphine)cobalt (I) perchlorate complexes, [Co(CNR)3(PR'3)2]ClO4, have been reported in the literature (Becker et al.,1986, 1991, 1995). Many, but not all, of these CoI complexes can be converted to the analogous five-coordinate CoII complexes, [Co(CNR)3(PR'3)2](ClO4)2, through oxidation with AgClO4 (Becker, 2000). Routine characterization has been reported for these complexes, but structural determinations are lacking. Coordination structures for both the CoI and CoII complexes are expected to be trigonal– bipyramidal. IR data for ν(–N≡C), in solution and solid state, suggest that the CoII complexes could have D3h symmetry for the CNR ligands (i.e. one band), while the CoI complexes may be distorted from idealized trigonal–bipyramidal coordination (i.e. two or three bands), but IR patterns are by no means conclusive for structural determination. There is disagreement in the literature over this assignment, however, particularly with respect to the interpretation of the quasi-reversible cyclic voltammograms (Hanzlik et al., 1980; Becker et al., 1995) which were later shown to be reversible (Ahmad et al., 2003).
A crystallographic investigation of these complexes seems merited for several reasons. Very few crystal structures are known for phosphine-substituted pentakis(organoisocyanide)cobalt(I) complexes, those few being with arylisocyanide, not alkylisocyanide, ligands, and, to our knowledge, no analogous structure for CoII has been reported. Five-coordination for both CoI and CoII complexes with identical ligands poses several questions: (i) are both coordination structures trigonal–bipyramidal, as usually assumed, and if so, (ii) are there any significant differences in coordination structure? Is one structure closer to idealized D3h Co site symmetry than the other, and if so, is it the CoI or the CoII complex? These questions can only be answered by a crystallographic study. [Co(CNCMe3)3{P(C6H4OMe-p)3}2]ClO4, (I), and [Co(CNCMe3)3{P(C6H4OMe-p)3}2](ClO4)2, (II), have been selected as an appropriate pair of complexes for this study.
Complex (I) is observed to crystallize in the hexagonal space group P63/m with six effectively equivalent molecules but three crystallographically independent structures in the unit cell. Where there is significant differences in bond lengths and angles quoted, the three independent values and/or average have been given. The molecular structure is shown in Figs. 1 and 2, with selected bond lengths and bond angles listed in Table 1. The site symmetry around the Co atom is effectively D3h (point group) symmetry. The entire Co(C≡ NC)3 moiety is planar with three equivalent Co—C bonds and C—Co—C bond angles of 120.000 (10)°, three almost equivalent C≡N bonds with Co—C≡ N bond angles close to the idealized 180.0° [averaging 179.16 (1)°] and three almost equivalent N—C bonds again with C≡N—C bond angles approaching 180° [averaging 177.97 (1)°]. This gives an effective σh through the entire Co(CNC)3 unit. The linear P—Co—P bonds are perpendicular to the CoC3 plane, forming the threefold rotation axis. Through the proper alignment of both the nine –CMe3 and six –C6H4OMe-p groups, the P1—Co1—P1 axis is also a crystallographic threefold rotation axis. The upper and lower P(C6H4OMe-p)3 rings are exactly eclipsed but are not properly 60° staggered (rather 43.8, 76.2° asymmetrically staggered) between the Co—C≡N bonds, preventing three σvs, and reducing the (point group) symmetry for the [Co(CNCMe3)3{P(C6H4OMe-p)3}2]+ cation overall to C3h. This is, nevertheless, still a very symmetrical ion.
The Co—P bond averaging 2.1783 (6) Å is shorter than that which is normally expected for a Co—P single bond [Cambridge Structural Database (CSD), Conquest 1.11, Allen, 2002], giving support for some degree of dπ→π* back-bonding, although less than the very short Co—P bond [i.e. 2.052 (5) Å] observed in HCo(PF3)4 (Frenz & Ibers, 1970). The averaged Co—C bond [1.826 (6) Å] is also quite short, supportive of the more extensive back-bonding expected to the organoisocyanide ligands. The perchlorate ion shows some distortion, with an average Cl—O bond length 1.416 (4) Å and average O—Cl—O bond angle 108.67 (5)°. There is no evidence for hydrogen bonding with either the ClO4- anion or the CH2Cl2 molecule.
Complex (II) is observed to crystallize in the monoclinic space group P21/n. The molecular structure is shown in Figs. 3 and 4, with selected bond lengths and bond angles listed in Table 2. The cation is best described as distorted trigonal–bipyramidal. The actual site symmetry around the Co atom is low, i.e. Cs. The CoC3 moiety appears to be approximately planar, in which case highest site symmetry is Cs, otherwise it is only C1. Three nonequivalent Co—C bonds form equatorial bond angles of 107.96 (11), 109.76 (10) and 142.27 (11)°, instead of the idealized 120.0°. The Co—C≡N bond angles [averaging 174.3 (2)°] and C≡N—C angles [averaging 177.5 (9)°], however, are reasonably close to linear. The C≡N bond lengths and N—C bond lengths appear normal for these bonds.
In structure (II) the averaged Co—P bond length of 2.2526 (7) Å is also rather short for a Co—P single bond, though not as shortened as seen for (I). Although the ionic radius for CoII is smaller than CoI, the Co2+ ion requires far less dπ→ π* electronic stabilization so the Co—P bond in (II) could be expected to be longer than in (I). The Co—C bond length is also shorter in (I) compared to (II), i.e. 1.826 (6) versus 1.888 (2) Å (averaged), while the C≡N bond lengths show slight increase [i.e. 1.159 (5) versus 1.145 (9) Å (averaged)] as would also be expected. A general insensitivity of the C≡N bond length to apparent bond order, however, has been observed (Cotton et al., 1965). The two perchlorate anions are nonequivalent and somewhat distorted. The averaged Cl—O bond length is 1.394 (8) Å in one, 1.406 (3) Å, in the other, but the averaged O—Cl—O bond angles are 109.4 (9) and 109.4 (8)°, respectively. Again there is no evidence for hydrogen bonding with either the ClO4- anions or the CH2Cl2 molecules in (II) as well as in (I). This may explain why the solvated CH2Cl2 is normally so readily lost shortly after preparation of these complexes.
In this pair of complexes, then, the IR data notwithstanding, the five-coordinate CoI complex, (I), has been shown to have rigorous trigonal–bipyramidal Co coordination (D3h) while the analogous five-coordinate CoII complex, (II), has distorted trigonal–bipyramidal coordination (Cs). Two disubstituted arylisocyanide CoI complexes from the literature show similarity with (I): [Co(CNC6H4NO2-p)3{PhP(OEt)2}2]ClO4 (III) (Graziani et al., 1976), and [Co(CNC6H4F-p)3{P(OCH3)3}2]BF4 (IV) (Loghry et al., 1978). Structural comparisons with these complexes are shown in Table 3. Although (III) and (IV) are clearly trigonal–bipyramidal structures, they do not exhibit the high level of coordination symmetry around the Co atom shown by (I). No analogous structures for disubstituted five-coordinate CoII organoisocyanide complexes could be found in the literature.
For related literature, see: Ahmad et al. (2003); Becker (2000); Becker & Barqawi (1995); Becker et al. (1986, 1991); Frenz & Ibers (1970); Graziani et al. (1976); Hanzlik et al. (1980); Loghry & Simonsen (1978).
For both compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-NT (Bruker, 2005); data reduction: SAINT-NT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
[Co(C5H9N)3(C21H21O3P)2]ClO4·2(CH2Cl2) | Dx = 1.332 Mg m−3 |
Mr = 1282.32 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P63/m | Cell parameters from 7171 reflections |
Hall symbol: -P 6c | θ = 2.6–28.3° |
a = 21.7568 (3) Å | µ = 0.58 mm−1 |
c = 23.3983 (6) Å | T = 173 K |
V = 9591.9 (3) Å3 | Hexagonal, yellow |
Z = 6 | 0.38 × 0.38 × 0.1 mm |
F(000) = 4020 |
CCD area detector diffractometer | 4167 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.058 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 26.0°, θmin = 1.1° |
Tmin = 0.809, Tmax = 0.944 | h = −25→24 |
46534 measured reflections | k = −26→26 |
6456 independent reflections | l = −27→28 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0695P)2 + 16.3243P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.152 | (Δ/σ)max = 0.001 |
S = 0.97 | Δρmax = 1.07 e Å−3 |
6456 reflections | Δρmin = −0.58 e Å−3 |
390 parameters |
[Co(C5H9N)3(C21H21O3P)2]ClO4·2(CH2Cl2) | Z = 6 |
Mr = 1282.32 | Mo Kα radiation |
Hexagonal, P63/m | µ = 0.58 mm−1 |
a = 21.7568 (3) Å | T = 173 K |
c = 23.3983 (6) Å | 0.38 × 0.38 × 0.1 mm |
V = 9591.9 (3) Å3 |
CCD area detector diffractometer | 6456 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4167 reflections with I > 2σ(I) |
Tmin = 0.809, Tmax = 0.944 | Rint = 0.058 |
46534 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0695P)2 + 16.3243P] where P = (Fo2 + 2Fc2)/3 |
6456 reflections | Δρmax = 1.07 e Å−3 |
390 parameters | Δρmin = −0.58 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.57951 (16) | 0.28994 (16) | 0.62264 (12) | 0.0221 (6) | |
C2 | 0.52705 (17) | 0.30234 (17) | 0.64370 (14) | 0.0275 (7) | |
H2 | 0.5358 | 0.3295 | 0.6776 | 0.033* | |
C3 | 0.46170 (18) | 0.27565 (18) | 0.61607 (14) | 0.0310 (7) | |
H3 | 0.4267 | 0.2855 | 0.6304 | 0.037* | |
C4 | 0.44879 (17) | 0.23489 (17) | 0.56771 (14) | 0.0298 (8) | |
C5 | 0.49963 (18) | 0.21963 (19) | 0.54749 (15) | 0.0334 (8) | |
H5 | 0.4897 | 0.1899 | 0.515 | 0.04* | |
C6 | 0.56455 (17) | 0.24743 (17) | 0.57442 (13) | 0.0280 (7) | |
H6 | 0.5994 | 0.2374 | 0.5599 | 0.034* | |
O1 | 0.38749 (13) | 0.20628 (14) | 0.53635 (11) | 0.0432 (7) | |
C7 | 0.3371 (2) | 0.2278 (2) | 0.55046 (17) | 0.0472 (10) | |
H7A | 0.3211 | 0.2142 | 0.59 | 0.071* | |
H7B | 0.2963 | 0.2046 | 0.5246 | 0.071* | |
H7C | 0.3594 | 0.2794 | 0.5465 | 0.071* | |
C8 | 0.7582 (2) | 0.3524 (2) | 0.75 | 0.0211 (9) | |
N1 | 0.8165 (2) | 0.3648 (2) | 0.75 | 0.0304 (9) | |
C9 | 0.8899 (2) | 0.3808 (3) | 0.75 | 0.0289 (10) | |
C10 | 0.9359 (3) | 0.4616 (3) | 0.75 | 0.0457 (14) | |
H10A | 0.9188 | 0.4815 | 0.7205 | 0.069* | 0.5 |
H10B | 0.9853 | 0.4751 | 0.742 | 0.069* | 0.5 |
H10C | 0.9331 | 0.4801 | 0.7875 | 0.069* | 0.5 |
C11 | 0.9005 (2) | 0.3484 (2) | 0.69623 (16) | 0.0439 (10) | |
H11A | 0.8695 | 0.2968 | 0.6974 | 0.066* | |
H11B | 0.9501 | 0.36 | 0.6938 | 0.066* | |
H11C | 0.8887 | 0.3676 | 0.6627 | 0.066* | |
P1 | 0.6667 | 0.3333 | 0.65677 (5) | 0.0182 (3) | |
Co1 | 0.6667 | 0.3333 | 0.75 | 0.0175 (2) | |
C12 | 0.06759 (15) | 0.08358 (15) | 0.62508 (12) | 0.0194 (6) | |
C13 | 0.09576 (16) | 0.08764 (17) | 0.57080 (13) | 0.0255 (7) | |
H13 | 0.0804 | 0.0455 | 0.5492 | 0.031* | |
C14 | 0.14572 (17) | 0.15222 (18) | 0.54803 (13) | 0.0279 (7) | |
H14 | 0.1638 | 0.1543 | 0.5107 | 0.033* | |
C15 | 0.16947 (17) | 0.21403 (17) | 0.57956 (14) | 0.0263 (7) | |
C16 | 0.14373 (17) | 0.21131 (17) | 0.63387 (14) | 0.0275 (7) | |
H16 | 0.1605 | 0.2533 | 0.656 | 0.033* | |
C17 | 0.09276 (17) | 0.14608 (16) | 0.65579 (13) | 0.0239 (7) | |
H17 | 0.0746 | 0.1443 | 0.693 | 0.029* | |
O2 | 0.21914 (13) | 0.27510 (12) | 0.55329 (10) | 0.0358 (6) | |
C18 | 0.2456 (2) | 0.33995 (19) | 0.58458 (17) | 0.0448 (10) | |
H18A | 0.2065 | 0.3486 | 0.5931 | 0.067* | |
H18B | 0.2815 | 0.3793 | 0.5617 | 0.067* | |
H18C | 0.267 | 0.3364 | 0.6204 | 0.067* | |
C19 | −0.0561 (2) | −0.0970 (2) | 0.75 | 0.0200 (9) | |
N2 | −0.0908 (2) | −0.1582 (2) | 0.75 | 0.0259 (8) | |
C20 | −0.1388 (2) | −0.2345 (2) | 0.75 | 0.0286 (10) | |
C21 | −0.2137 (3) | −0.2461 (3) | 0.75 | 0.0411 (13) | |
H21A | −0.2176 | −0.2158 | 0.7792 | 0.062* | 0.5 |
H21B | −0.2475 | −0.296 | 0.7585 | 0.062* | 0.5 |
H21C | −0.2243 | −0.2339 | 0.7124 | 0.062* | 0.5 |
C22 | −0.1240 (2) | −0.2645 (2) | 0.69642 (16) | 0.0420 (9) | |
H22A | −0.1313 | −0.2424 | 0.6626 | 0.063* | |
H22B | −0.1564 | −0.3159 | 0.695 | 0.063* | |
H22C | −0.0749 | −0.2546 | 0.6972 | 0.063* | |
P2 | 0 | 0 | 0.65699 (5) | 0.0164 (3) | |
Co2 | 0 | 0 | 0.75 | 0.0161 (2) | |
C23 | 0.37638 (16) | 0.62157 (16) | 0.62489 (12) | 0.0227 (7) | |
C24 | 0.36941 (17) | 0.56103 (17) | 0.65066 (14) | 0.0277 (7) | |
H24 | 0.3424 | 0.5442 | 0.6848 | 0.033* | |
C25 | 0.40075 (18) | 0.52423 (18) | 0.62799 (14) | 0.0297 (7) | |
H25 | 0.3952 | 0.4828 | 0.6463 | 0.036* | |
C26 | 0.44008 (18) | 0.54894 (18) | 0.57828 (14) | 0.0301 (8) | |
C27 | 0.4482 (2) | 0.6098 (2) | 0.55204 (14) | 0.0359 (8) | |
H27 | 0.4755 | 0.6268 | 0.5181 | 0.043* | |
C28 | 0.41658 (18) | 0.64566 (18) | 0.57524 (14) | 0.0300 (7) | |
H28 | 0.4224 | 0.6873 | 0.557 | 0.036* | |
O3 | 0.47361 (15) | 0.51787 (14) | 0.55222 (10) | 0.0417 (6) | |
C29 | 0.4710 (2) | 0.4579 (2) | 0.57982 (17) | 0.0443 (10) | |
H29A | 0.4892 | 0.4708 | 0.6189 | 0.066* | |
H29B | 0.5003 | 0.4431 | 0.5585 | 0.066* | |
H29C | 0.4219 | 0.4187 | 0.5809 | 0.066* | |
C30 | 0.3115 (2) | 0.7374 (2) | 0.75 | 0.0221 (9) | |
C31 | 0.2790 (3) | 0.8378 (3) | 0.75 | 0.0531 (10) | |
C32A | 0.2012 (6) | 0.8071 (6) | 0.75 | 0.0531 (10) | 0.544 (5) |
H32A | 0.181 | 0.7775 | 0.7159 | 0.08* | 0.272 (3) |
H32B | 0.1899 | 0.8454 | 0.7497 | 0.08* | 0.544 (5) |
H32C | 0.181 | 0.778 | 0.7843 | 0.08* | 0.272 (3) |
C34A | 0.3141 (4) | 0.8853 (4) | 0.6974 (4) | 0.0531 (10) | 0.544 (5) |
H34A | 0.3651 | 0.902 | 0.6977 | 0.08* | 0.544 (5) |
H34B | 0.3067 | 0.9261 | 0.6987 | 0.08* | 0.544 (5) |
H34C | 0.2928 | 0.858 | 0.6625 | 0.08* | 0.544 (5) |
C33A | 0.2323 (5) | 0.8255 (5) | 0.6979 (4) | 0.0531 (10) | 0.456 (5) |
H33A | 0.2602 | 0.8333 | 0.6631 | 0.08* | 0.456 (5) |
H33B | 0.2141 | 0.8586 | 0.6988 | 0.08* | 0.456 (5) |
H33C | 0.1924 | 0.7767 | 0.6984 | 0.08* | 0.456 (5) |
C32B | 0.3453 (7) | 0.9029 (7) | 0.75 | 0.0531 (10) | 0.456 (5) |
H32D | 0.3714 | 0.9062 | 0.7149 | 0.08* | 0.228 (3) |
H32E | 0.3733 | 0.9043 | 0.7833 | 0.08* | 0.228 (3) |
H32F | 0.3365 | 0.9429 | 0.7518 | 0.08* | 0.456 (5) |
N3 | 0.2961 (2) | 0.7814 (2) | 0.75 | 0.0307 (9) | |
P3 | 0.3333 | 0.6667 | 0.65694 (5) | 0.0186 (3) | |
Co3 | 0.3333 | 0.6667 | 0.75 | 0.0178 (2) | |
C35 | 0.2752 (2) | 0.3176 (2) | 0.42498 (17) | 0.0466 (10) | |
H35A | 0.2622 | 0.3383 | 0.3927 | 0.056* | |
H35B | 0.246 | 0.3151 | 0.4583 | 0.056* | |
Cl2 | 0.25520 (7) | 0.23061 (6) | 0.40648 (4) | 0.0574 (3) | |
Cl3 | 0.36438 (6) | 0.37316 (7) | 0.44143 (5) | 0.0644 (3) | |
Cl1 | 0.00736 (8) | 0.65908 (7) | 0.75 | 0.0453 (4) | |
O4 | 0.0645 (3) | 0.6441 (3) | 0.75 | 0.0901 (18) | |
O5 | 0.0351 (2) | 0.7339 (2) | 0.75 | 0.0631 (12) | |
O6 | −0.0306 (3) | 0.6302 (2) | 0.69993 (19) | 0.1110 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0243 (16) | 0.0231 (16) | 0.0173 (15) | 0.0107 (13) | −0.0006 (12) | 0.0031 (12) |
C2 | 0.0286 (17) | 0.0302 (18) | 0.0240 (16) | 0.0148 (15) | −0.0021 (14) | −0.0036 (14) |
C3 | 0.0269 (17) | 0.0345 (19) | 0.0336 (18) | 0.0169 (15) | −0.0009 (14) | 0.0016 (15) |
C4 | 0.0243 (17) | 0.0277 (17) | 0.0308 (18) | 0.0079 (14) | −0.0043 (14) | 0.0052 (14) |
C5 | 0.0341 (19) | 0.0339 (19) | 0.0277 (18) | 0.0138 (16) | −0.0085 (15) | −0.0087 (15) |
C6 | 0.0280 (17) | 0.0324 (18) | 0.0231 (16) | 0.0147 (15) | −0.0005 (14) | −0.0033 (14) |
O1 | 0.0312 (14) | 0.0484 (16) | 0.0458 (15) | 0.0167 (12) | −0.0178 (12) | −0.0082 (13) |
C7 | 0.031 (2) | 0.061 (3) | 0.048 (2) | 0.022 (2) | −0.0100 (18) | 0.010 (2) |
C8 | 0.025 (2) | 0.024 (2) | 0.014 (2) | 0.0119 (19) | 0 | 0 |
N1 | 0.028 (2) | 0.044 (2) | 0.024 (2) | 0.022 (2) | 0 | 0 |
C9 | 0.020 (2) | 0.038 (3) | 0.032 (3) | 0.017 (2) | 0 | 0 |
C10 | 0.042 (3) | 0.038 (3) | 0.051 (3) | 0.015 (3) | 0 | 0 |
C11 | 0.035 (2) | 0.059 (3) | 0.043 (2) | 0.027 (2) | 0.0016 (17) | −0.0089 (19) |
P1 | 0.0197 (4) | 0.0197 (4) | 0.0153 (6) | 0.0098 (2) | 0 | 0 |
Co1 | 0.0196 (3) | 0.0196 (3) | 0.0135 (5) | 0.00978 (16) | 0 | 0 |
C12 | 0.0201 (15) | 0.0214 (15) | 0.0166 (14) | 0.0103 (13) | −0.0009 (12) | 0.0028 (12) |
C13 | 0.0263 (16) | 0.0271 (17) | 0.0199 (15) | 0.0111 (14) | 0.0005 (13) | −0.0014 (13) |
C14 | 0.0257 (17) | 0.0334 (18) | 0.0174 (15) | 0.0094 (15) | 0.0045 (13) | 0.0019 (14) |
C15 | 0.0240 (16) | 0.0263 (17) | 0.0250 (16) | 0.0100 (14) | 0.0007 (13) | 0.0078 (13) |
C16 | 0.0296 (17) | 0.0212 (16) | 0.0283 (17) | 0.0101 (14) | −0.0017 (14) | −0.0006 (13) |
C17 | 0.0297 (17) | 0.0240 (16) | 0.0189 (15) | 0.0141 (14) | 0.0047 (13) | 0.0026 (13) |
O2 | 0.0367 (14) | 0.0255 (12) | 0.0316 (13) | 0.0053 (11) | 0.0078 (11) | 0.0060 (10) |
C18 | 0.049 (2) | 0.0244 (19) | 0.042 (2) | 0.0040 (17) | 0.0051 (18) | 0.0067 (16) |
C19 | 0.024 (2) | 0.028 (3) | 0.0110 (19) | 0.015 (2) | 0 | 0 |
N2 | 0.030 (2) | 0.023 (2) | 0.0210 (19) | 0.0103 (18) | 0 | 0 |
C20 | 0.027 (2) | 0.020 (2) | 0.033 (3) | 0.007 (2) | 0 | 0 |
C21 | 0.029 (3) | 0.037 (3) | 0.047 (3) | 0.009 (2) | 0 | 0 |
C22 | 0.045 (2) | 0.035 (2) | 0.042 (2) | 0.0170 (18) | −0.0009 (17) | −0.0116 (17) |
P2 | 0.0193 (4) | 0.0193 (4) | 0.0107 (6) | 0.0097 (2) | 0 | 0 |
Co2 | 0.0190 (3) | 0.0190 (3) | 0.0102 (4) | 0.00950 (16) | 0 | 0 |
C23 | 0.0243 (16) | 0.0275 (17) | 0.0187 (15) | 0.0147 (14) | −0.0010 (12) | −0.0026 (13) |
C24 | 0.0294 (17) | 0.0282 (17) | 0.0248 (16) | 0.0139 (15) | 0.0088 (14) | 0.0039 (14) |
C25 | 0.0360 (19) | 0.0276 (17) | 0.0278 (18) | 0.0178 (15) | 0.0047 (15) | 0.0014 (14) |
C26 | 0.0361 (19) | 0.0344 (19) | 0.0252 (17) | 0.0216 (16) | 0.0024 (15) | −0.0046 (14) |
C27 | 0.046 (2) | 0.047 (2) | 0.0228 (17) | 0.0295 (19) | 0.0154 (15) | 0.0067 (15) |
C28 | 0.041 (2) | 0.0327 (18) | 0.0230 (17) | 0.0232 (16) | 0.0044 (15) | 0.0022 (14) |
O3 | 0.0588 (17) | 0.0491 (16) | 0.0345 (14) | 0.0401 (14) | 0.0144 (12) | 0.0033 (12) |
C29 | 0.061 (3) | 0.051 (2) | 0.041 (2) | 0.042 (2) | 0.0080 (19) | 0.0021 (19) |
C30 | 0.024 (2) | 0.027 (2) | 0.014 (2) | 0.012 (2) | 0 | 0 |
C31 | 0.058 (2) | 0.042 (2) | 0.071 (3) | 0.034 (2) | 0 | 0 |
C32A | 0.058 (2) | 0.042 (2) | 0.071 (3) | 0.034 (2) | 0 | 0 |
C34A | 0.058 (2) | 0.042 (2) | 0.071 (3) | 0.034 (2) | 0 | 0 |
C33A | 0.058 (2) | 0.042 (2) | 0.071 (3) | 0.034 (2) | 0 | 0 |
C32B | 0.058 (2) | 0.042 (2) | 0.071 (3) | 0.034 (2) | 0 | 0 |
N3 | 0.040 (2) | 0.030 (2) | 0.028 (2) | 0.022 (2) | 0 | 0 |
P3 | 0.0206 (4) | 0.0206 (4) | 0.0147 (6) | 0.0103 (2) | 0 | 0 |
Co3 | 0.0197 (3) | 0.0197 (3) | 0.0139 (5) | 0.00985 (16) | 0 | 0 |
C35 | 0.057 (3) | 0.050 (2) | 0.036 (2) | 0.030 (2) | 0.0070 (19) | 0.0071 (18) |
Cl2 | 0.0823 (8) | 0.0566 (7) | 0.0363 (5) | 0.0369 (6) | −0.0018 (5) | −0.0034 (5) |
Cl3 | 0.0580 (7) | 0.0611 (7) | 0.0575 (7) | 0.0173 (6) | −0.0048 (5) | 0.0179 (6) |
Cl1 | 0.0661 (9) | 0.0437 (8) | 0.0333 (7) | 0.0329 (7) | 0 | 0 |
O4 | 0.112 (5) | 0.092 (4) | 0.107 (4) | 0.081 (4) | 0 | 0 |
O5 | 0.069 (3) | 0.039 (2) | 0.085 (3) | 0.030 (2) | 0 | 0 |
O6 | 0.156 (4) | 0.082 (3) | 0.100 (3) | 0.063 (3) | −0.074 (3) | −0.032 (2) |
Co1—C8i | 1.820 (4) | C20—C22 | 1.521 (4) |
Co2—C19ii | 1.834 (4) | C20—C22iv | 1.521 (4) |
Co3—C30iii | 1.824 (5) | C21—H21A | 0.98 |
P1—Co1 | 2.1814 (13) | C21—H21B | 0.98 |
P2—Co2 | 2.1762 (12) | C21—H21C | 0.98 |
P3—Co3 | 2.1774 (13) | C22—H22A | 0.98 |
C8—N1 | 1.157 (6) | C22—H22B | 0.98 |
C19—N2 | 1.158 (6) | C22—H22C | 0.98 |
C30—N3 | 1.162 (6) | P2—C12vi | 1.831 (3) |
N1—C9 | 1.455 (6) | P2—C12ii | 1.831 (3) |
N2—C20 | 1.453 (6) | Co2—C19ii | 1.834 (4) |
N3—C31 | 1.449 (7) | Co2—C19vi | 1.834 (4) |
C1—C2 | 1.388 (4) | Co2—P2iv | 2.1762 (12) |
C1—C6 | 1.390 (4) | C23—C24 | 1.386 (4) |
C1—P1 | 1.826 (3) | C23—C28 | 1.389 (4) |
C2—C3 | 1.397 (5) | C23—P3 | 1.822 (3) |
C2—H2 | 0.95 | C24—C25 | 1.390 (4) |
C3—C4 | 1.377 (5) | C24—H24 | 0.95 |
C3—H3 | 0.95 | C25—C26 | 1.384 (5) |
C4—O1 | 1.369 (4) | C25—H25 | 0.95 |
C4—C5 | 1.387 (5) | C26—O3 | 1.362 (4) |
C5—C6 | 1.380 (5) | C26—C27 | 1.388 (5) |
C5—H5 | 0.95 | C27—C28 | 1.384 (5) |
C6—H6 | 0.95 | C27—H27 | 0.95 |
O1—C7 | 1.429 (5) | C28—H28 | 0.95 |
C7—H7A | 0.98 | O3—C29 | 1.432 (4) |
C7—H7B | 0.98 | C29—H29A | 0.98 |
C7—H7C | 0.98 | C29—H29B | 0.98 |
C8—Co1 | 1.820 (4) | C29—H29C | 0.98 |
C9—C11 | 1.515 (4) | C30—Co3 | 1.824 (5) |
C9—C11iv | 1.515 (4) | C31—C32B | 1.429 (15) |
C9—C10 | 1.527 (7) | C31—C32A | 1.478 (13) |
C10—H10A | 0.98 | C31—C33Aiv | 1.523 (10) |
C10—H10B | 0.98 | C31—C33A | 1.523 (10) |
C10—H10C | 0.98 | C31—C34Aiv | 1.541 (9) |
C11—H11A | 0.98 | C31—C34A | 1.541 (9) |
C11—H11B | 0.98 | C32A—H32A | 0.98 |
C11—H11C | 0.98 | C32A—H32B | 0.98 |
P1—C1v | 1.826 (3) | C32A—H32C | 0.98 |
P1—C1i | 1.826 (3) | C34A—H34A | 0.98 |
Co1—C8v | 1.820 (4) | C34A—H34B | 0.98 |
Co1—P1iv | 2.1814 (13) | C34A—H34C | 0.98 |
C12—C17 | 1.386 (4) | C33A—H33A | 0.98 |
C12—C13 | 1.394 (4) | C33A—H33B | 0.98 |
C12—P2 | 1.831 (3) | C33A—H33C | 0.98 |
C13—C14 | 1.383 (4) | C32B—H32D | 0.98 |
C13—H13 | 0.95 | C32B—H32E | 0.98 |
C14—C15 | 1.388 (5) | C32B—H32F | 0.98 |
C14—H14 | 0.95 | P3—C23vii | 1.822 (3) |
C15—O2 | 1.369 (4) | P3—C23iii | 1.822 (3) |
C15—C16 | 1.378 (5) | Co3—C30vii | 1.824 (5) |
C16—C17 | 1.390 (4) | Co3—P3iv | 2.1774 (13) |
C16—H16 | 0.95 | C35—Cl3 | 1.741 (4) |
C17—H17 | 0.95 | C35—Cl2 | 1.772 (4) |
O2—C18 | 1.430 (4) | C35—H35A | 0.99 |
C18—H18A | 0.98 | C35—H35B | 0.99 |
C18—H18B | 0.98 | Cl1—O6iv | 1.389 (4) |
C18—H18C | 0.98 | Cl1—O4 | 1.434 (5) |
C19—Co2 | 1.834 (4) | Cl1—O5 | 1.426 (4) |
C20—C21 | 1.518 (7) | Cl1—O6 | 1.389 (4) |
N1—C8—Co1 | 179.7 (4) | H22A—C22—H22C | 109.5 |
N2—C19—Co2 | 179.2 (4) | H22B—C22—H22C | 109.5 |
N3—C30—Co3 | 178.6 (4) | C12vi—P2—C12 | 104.51 (11) |
C8—N1—C9 | 179.7 (5) | C12vi—P2—C12ii | 104.51 (11) |
C19—N2—C20 | 175.8 (4) | C12—P2—C12ii | 104.51 (11) |
C30—N3—C31 | 178.4 (5) | C12vi—P2—Co2 | 114.06 (9) |
C8—Co1—C8i | 120.0000 (10) | C12—P2—Co2 | 114.06 (9) |
C8—Co1—C8v | 120.000 (2) | C12ii—P2—Co2 | 114.06 (9) |
C19ii—Co2—C19 | 120.0000 (10) | C19ii—Co2—C19vi | 120.0000 (10) |
C30—Co3—C30iii | 120.0000 (10) | C19—Co2—C19vi | 120 |
P1iv—Co1—P1 | 180.0000 (10) | C19ii—Co2—P2 | 90 |
P2—Co2—P2iv | 180 | C19—Co2—P2 | 90 |
P3iv—Co3—P3 | 180 | C19vi—Co2—P2 | 90 |
C2—C1—C6 | 118.4 (3) | C19ii—Co2—P2iv | 90 |
C2—C1—P1 | 119.1 (2) | C19—Co2—P2iv | 90 |
C6—C1—P1 | 122.4 (2) | C19vi—Co2—P2iv | 90 |
C1—C2—C3 | 121.3 (3) | C24—C23—C28 | 118.1 (3) |
C1—C2—H2 | 119.3 | C24—C23—P3 | 119.4 (2) |
C3—C2—H2 | 119.3 | C28—C23—P3 | 122.5 (2) |
C4—C3—C2 | 119.0 (3) | C23—C24—C25 | 121.9 (3) |
C4—C3—H3 | 120.5 | C23—C24—H24 | 119 |
C2—C3—H3 | 120.5 | C25—C24—H24 | 119 |
O1—C4—C3 | 124.9 (3) | C26—C25—C24 | 118.9 (3) |
O1—C4—C5 | 114.9 (3) | C26—C25—H25 | 120.6 |
C3—C4—C5 | 120.3 (3) | C24—C25—H25 | 120.6 |
C6—C5—C4 | 120.2 (3) | O3—C26—C25 | 124.3 (3) |
C6—C5—H5 | 119.9 | O3—C26—C27 | 115.6 (3) |
C4—C5—H5 | 119.9 | C25—C26—C27 | 120.1 (3) |
C5—C6—C1 | 120.7 (3) | C28—C27—C26 | 120.2 (3) |
C5—C6—H6 | 119.7 | C28—C27—H27 | 119.9 |
C1—C6—H6 | 119.7 | C26—C27—H27 | 119.9 |
C4—O1—C7 | 117.3 (3) | C27—C28—C23 | 120.8 (3) |
O1—C7—H7A | 109.5 | C27—C28—H28 | 119.6 |
O1—C7—H7B | 109.5 | C23—C28—H28 | 119.6 |
H7A—C7—H7B | 109.5 | C26—O3—C29 | 117.7 (3) |
O1—C7—H7C | 109.5 | O3—C29—H29A | 109.5 |
H7A—C7—H7C | 109.5 | O3—C29—H29B | 109.5 |
H7B—C7—H7C | 109.5 | H29A—C29—H29B | 109.5 |
N1—C9—C11 | 107.0 (3) | O3—C29—H29C | 109.5 |
N1—C9—C11iv | 107.0 (3) | H29A—C29—H29C | 109.5 |
C11—C9—C11iv | 112.3 (4) | H29B—C29—H29C | 109.5 |
N1—C9—C10 | 106.6 (4) | N3—C31—C32B | 106.3 (7) |
C11—C9—C10 | 111.8 (3) | N3—C31—C32A | 109.8 (6) |
C11iv—C9—C10 | 111.8 (3) | C32B—C31—C32A | 143.9 (8) |
C9—C10—H10A | 109.5 | N3—C31—C33Aiv | 106.4 (4) |
C9—C10—H10B | 109.5 | C32B—C31—C33Aiv | 115.3 (5) |
H10A—C10—H10B | 109.5 | C32A—C31—C33Aiv | 53.6 (4) |
C9—C10—H10C | 109.5 | N3—C31—C33A | 106.4 (4) |
H10A—C10—H10C | 109.5 | C32B—C31—C33A | 115.3 (5) |
H10B—C10—H10C | 109.5 | C32A—C31—C33A | 53.6 (4) |
C9—C11—H11A | 109.5 | C33Aiv—C31—C33A | 106.3 (9) |
C9—C11—H11B | 109.5 | N3—C31—C34Aiv | 108.5 (4) |
H11A—C11—H11B | 109.5 | C32B—C31—C34Aiv | 54.5 (4) |
C9—C11—H11C | 109.5 | C32A—C31—C34Aiv | 112.0 (5) |
H11A—C11—H11C | 109.5 | C33Aiv—C31—C34Aiv | 62.8 (5) |
H11B—C11—H11C | 109.5 | C33A—C31—C34Aiv | 145.1 (6) |
C1v—P1—C1i | 102.31 (12) | N3—C31—C34A | 108.5 (4) |
C1v—P1—C1 | 102.31 (12) | C32B—C31—C34A | 54.5 (4) |
C1i—P1—C1 | 102.31 (12) | C32A—C31—C34A | 112.0 (5) |
C1v—P1—Co1 | 115.93 (10) | C33Aiv—C31—C34A | 145.1 (6) |
C1i—P1—Co1 | 115.93 (10) | C33A—C31—C34A | 62.8 (5) |
C1—P1—Co1 | 115.93 (10) | C34Aiv—C31—C34A | 105.9 (7) |
C8i—Co1—C8v | 120.000 (2) | C31—C32A—H32A | 109.5 |
C8—Co1—P1iv | 90 | C31—C32A—H32B | 109.5 |
C8i—Co1—P1iv | 90 | H32A—C32A—H32B | 109.5 |
C8v—Co1—P1iv | 90 | C31—C32A—H32C | 109.5 |
C8—Co1—P1 | 90 | H32A—C32A—H32C | 109.5 |
C8i—Co1—P1 | 90 | H32B—C32A—H32C | 109.5 |
C8v—Co1—P1 | 90 | C31—C34A—H34A | 109.5 |
C17—C12—C13 | 117.7 (3) | C31—C34A—H34B | 109.5 |
C17—C12—P2 | 119.4 (2) | H34A—C34A—H34B | 109.5 |
C13—C12—P2 | 122.9 (2) | C31—C34A—H34C | 109.5 |
C14—C13—C12 | 120.9 (3) | H34A—C34A—H34C | 109.5 |
C14—C13—H13 | 119.6 | H34B—C34A—H34C | 109.5 |
C12—C13—H13 | 119.6 | C31—C33A—H33A | 109.5 |
C13—C14—C15 | 120.2 (3) | C31—C33A—H33B | 109.5 |
C13—C14—H14 | 119.9 | C31—C33A—H33C | 109.5 |
C15—C14—H14 | 119.9 | C31—C32B—H32D | 109.5 |
O2—C15—C16 | 124.2 (3) | C31—C32B—H32E | 109.5 |
O2—C15—C14 | 115.6 (3) | H32D—C32B—H32E | 109.5 |
C16—C15—C14 | 120.2 (3) | C31—C32B—H32F | 109.5 |
C15—C16—C17 | 118.9 (3) | H32D—C32B—H32F | 109.5 |
C15—C16—H16 | 120.5 | H32E—C32B—H32F | 109.5 |
C17—C16—H16 | 120.5 | C23vii—P3—C23iii | 104.24 (11) |
C12—C17—C16 | 122.2 (3) | C23vii—P3—C23 | 104.24 (12) |
C12—C17—H17 | 118.9 | C23iii—P3—C23 | 104.24 (12) |
C16—C17—H17 | 118.9 | C23vii—P3—Co3 | 114.30 (10) |
C15—O2—C18 | 117.4 (3) | C23iii—P3—Co3 | 114.30 (10) |
O2—C18—H18A | 109.5 | C23—P3—Co3 | 114.30 (10) |
O2—C18—H18B | 109.5 | C30—Co3—C30vii | 120.0000 (10) |
H18A—C18—H18B | 109.5 | C30iii—Co3—C30vii | 120.0000 (10) |
O2—C18—H18C | 109.5 | C30—Co3—P3iv | 90 |
H18A—C18—H18C | 109.5 | C30iii—Co3—P3iv | 90 |
H18B—C18—H18C | 109.5 | C30vii—Co3—P3iv | 90 |
N2—C20—C21 | 106.8 (4) | C30—Co3—P3 | 90 |
N2—C20—C22 | 107.7 (3) | C30iii—Co3—P3 | 90 |
C21—C20—C22 | 111.6 (3) | C30vii—Co3—P3 | 90 |
N2—C20—C22iv | 107.7 (3) | Cl3—C35—Cl2 | 112.8 (2) |
C21—C20—C22iv | 111.6 (3) | Cl3—C35—H35A | 109 |
C22—C20—C22iv | 111.0 (4) | Cl2—C35—H35A | 109 |
C20—C21—H21A | 109.5 | Cl3—C35—H35B | 109 |
C20—C21—H21B | 109.5 | Cl2—C35—H35B | 109 |
H21A—C21—H21B | 109.5 | H35A—C35—H35B | 107.8 |
C20—C21—H21C | 109.5 | O6—Cl1—O6iv | 115.0 (5) |
H21A—C21—H21C | 109.5 | O5—Cl1—O4 | 109.8 (3) |
H21B—C21—H21C | 109.5 | O6—Cl1—O4 | 106.5 (2) |
C20—C22—H22A | 109.5 | O6—Cl1—O5 | 109.4 (2) |
C20—C22—H22B | 109.5 | O6iv—Cl1—O5 | 109.4 (2) |
H22A—C22—H22B | 109.5 | O6iv—Cl1—O4 | 106.5 (2) |
C20—C22—H22C | 109.5 | ||
C6—C1—C2—C3 | −2.8 (5) | C17—C12—P2—C12ii | −150.7 (3) |
P1—C1—C2—C3 | 174.2 (3) | C13—C12—P2—C12ii | 28.9 (3) |
C1—C2—C3—C4 | 1.5 (5) | C17—C12—P2—Co2 | −25.5 (3) |
C2—C3—C4—O1 | −179.2 (3) | C13—C12—P2—Co2 | 154.1 (2) |
C2—C3—C4—C5 | 1.2 (5) | C12vi—P2—Co2—C19ii | −45.55 (16) |
O1—C4—C5—C6 | 177.9 (3) | C12—P2—Co2—C19ii | 74.45 (16) |
C3—C4—C5—C6 | −2.5 (5) | C12ii—P2—Co2—C19ii | −165.55 (16) |
C4—C5—C6—C1 | 1.2 (5) | C12vi—P2—Co2—C19 | 74.45 (16) |
C2—C1—C6—C5 | 1.4 (5) | C12—P2—Co2—C19 | −165.55 (16) |
P1—C1—C6—C5 | −175.4 (3) | C12ii—P2—Co2—C19 | −45.55 (16) |
C3—C4—O1—C7 | 8.5 (5) | C12vi—P2—Co2—C19vi | −165.55 (16) |
C5—C4—O1—C7 | −171.9 (3) | C12—P2—Co2—C19vi | −45.55 (16) |
C2—C1—P1—C1v | 170.9 (2) | C12ii—P2—Co2—C19vi | 74.45 (16) |
C6—C1—P1—C1v | −12.3 (3) | C28—C23—C24—C25 | −0.6 (5) |
C2—C1—P1—C1i | −83.4 (3) | P3—C23—C24—C25 | 179.7 (3) |
C6—C1—P1—C1i | 93.4 (2) | C23—C24—C25—C26 | 0.1 (5) |
C2—C1—P1—Co1 | 43.7 (3) | C24—C25—C26—O3 | 179.5 (3) |
C6—C1—P1—Co1 | −139.5 (2) | C24—C25—C26—C27 | 0.4 (5) |
C1v—P1—Co1—C8 | 41.50 (17) | O3—C26—C27—C28 | −179.6 (3) |
C1i—P1—Co1—C8 | −78.50 (17) | C25—C26—C27—C28 | −0.4 (6) |
C1—P1—Co1—C8 | 161.50 (17) | C26—C27—C28—C23 | −0.1 (6) |
C1v—P1—Co1—C8i | −78.50 (17) | C24—C23—C28—C27 | 0.6 (5) |
C1i—P1—Co1—C8i | 161.50 (17) | P3—C23—C28—C27 | −179.7 (3) |
C1—P1—Co1—C8i | 41.50 (17) | C25—C26—O3—C29 | −3.5 (5) |
C1v—P1—Co1—C8v | 161.50 (17) | C27—C26—O3—C29 | 175.7 (3) |
C1i—P1—Co1—C8v | 41.50 (17) | C24—C23—P3—C23vii | −88.9 (3) |
C1—P1—Co1—C8v | −78.50 (17) | C28—C23—P3—C23vii | 91.4 (2) |
C17—C12—C13—C14 | −1.7 (5) | C24—C23—P3—C23iii | 162.1 (3) |
P2—C12—C13—C14 | 178.7 (2) | C28—C23—P3—C23iii | −17.6 (3) |
C12—C13—C14—C15 | 1.1 (5) | C24—C23—P3—Co3 | 36.6 (3) |
C13—C14—C15—O2 | 179.7 (3) | C28—C23—P3—Co3 | −143.1 (2) |
C13—C14—C15—C16 | 0.4 (5) | C23vii—P3—Co3—C30 | −76.20 (17) |
O2—C15—C16—C17 | 179.4 (3) | C23iii—P3—Co3—C30 | 43.80 (17) |
C14—C15—C16—C17 | −1.4 (5) | C23—P3—Co3—C30 | 163.80 (17) |
C13—C12—C17—C16 | 0.7 (5) | C23vii—P3—Co3—C30iii | 43.80 (17) |
P2—C12—C17—C16 | −179.6 (2) | C23iii—P3—Co3—C30iii | 163.80 (17) |
C15—C16—C17—C12 | 0.8 (5) | C23—P3—Co3—C30iii | −76.20 (17) |
C16—C15—O2—C18 | −0.1 (5) | C23vii—P3—Co3—C30vii | 163.80 (17) |
C14—C15—O2—C18 | −179.3 (3) | C23iii—P3—Co3—C30vii | −76.20 (17) |
C17—C12—P2—C12vi | 99.7 (3) | C23—P3—Co3—C30vii | 43.80 (17) |
C13—C12—P2—C12vi | −80.6 (2) |
Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −x+y, −x, z; (iii) −y+1, x−y+1, z; (iv) x, y, −z+3/2; (v) −y+1, x−y, z; (vi) −y, x−y, z; (vii) −x+y, −x+1, z. |
[Co(C5H9N)3(C21H21O3P)2](ClO4)2·2CH2Cl2 | F(000) = 2876 |
Mr = 1381.77 | Dx = 1.324 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7487 reflections |
a = 12.3461 (3) Å | θ = 2.2–28.3° |
b = 19.7566 (5) Å | µ = 0.59 mm−1 |
c = 28.4452 (7) Å | T = 173 K |
β = 92.818 (2)° | Block, red |
V = 6929.9 (3) Å3 | 0.43 × 0.31 × 0.22 mm |
Z = 4 |
CCD area detector diffractometer | 11549 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.056 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 28°, θmin = 1.3° |
Tmin = 0.787, Tmax = 0.882 | h = −11→16 |
93953 measured reflections | k = −26→25 |
16738 independent reflections | l = −37→37 |
Refinement on F2 | 40 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.0551P)2 + 6.8607P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.146 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.55 e Å−3 |
16738 reflections | Δρmin = −0.41 e Å−3 |
848 parameters |
[Co(C5H9N)3(C21H21O3P)2](ClO4)2·2CH2Cl2 | V = 6929.9 (3) Å3 |
Mr = 1381.77 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.3461 (3) Å | µ = 0.59 mm−1 |
b = 19.7566 (5) Å | T = 173 K |
c = 28.4452 (7) Å | 0.43 × 0.31 × 0.22 mm |
β = 92.818 (2)° |
CCD area detector diffractometer | 16738 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 11549 reflections with I > 2σ(I) |
Tmin = 0.787, Tmax = 0.882 | Rint = 0.056 |
93953 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 40 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.55 e Å−3 |
16738 reflections | Δρmin = −0.41 e Å−3 |
848 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Co1 | 0.68257 (3) | 0.259635 (17) | 0.140563 (11) | 0.02421 (9) | |
P1 | 0.85415 (5) | 0.23994 (3) | 0.12087 (2) | 0.02777 (14) | |
P2 | 0.50954 (5) | 0.28107 (3) | 0.15757 (2) | 0.02748 (14) | |
O1 | 0.4094 (2) | 0.21261 (12) | 0.35471 (8) | 0.0583 (7) | |
O2 | 0.20341 (19) | 0.11000 (13) | 0.04109 (9) | 0.0597 (7) | |
O3 | 0.4076 (2) | 0.57047 (11) | 0.11887 (7) | 0.0536 (6) | |
O4 | 1.0815 (2) | 0.49649 (11) | 0.07796 (9) | 0.0562 (6) | |
O5 | 0.8796 (2) | 0.04875 (13) | −0.04040 (10) | 0.0678 (7) | |
O6 | 1.1209 (2) | 0.09637 (17) | 0.26965 (10) | 0.0819 (10) | |
O7 | −0.0955 (3) | 0.3014 (2) | 0.41746 (11) | 0.1155 (14) | |
O8 | 0.0778 (3) | 0.3012 (2) | 0.39321 (12) | 0.1180 (14) | |
O9 | 0.0473 (3) | 0.27277 (19) | 0.46977 (13) | 0.1079 (12) | |
O10 | 0.0230 (4) | 0.37957 (15) | 0.44613 (16) | 0.1213 (15) | |
O11 | 0.7607 (4) | 0.4690 (2) | 0.23018 (16) | 0.1434 (19) | |
O12 | 0.9313 (2) | 0.51768 (19) | 0.23011 (11) | 0.0897 (10) | |
O13 | 0.7955 (3) | 0.57446 (19) | 0.26319 (11) | 0.0992 (11) | |
O14 | 0.7914 (3) | 0.55936 (17) | 0.18250 (10) | 0.0876 (9) | |
Cl1 | 0.01292 (7) | 0.31316 (4) | 0.43069 (3) | 0.0501 (2) | |
Cl2 | 0.81796 (7) | 0.52868 (4) | 0.22679 (3) | 0.0495 (2) | |
N1 | 0.62505 (19) | 0.11146 (11) | 0.12094 (8) | 0.0328 (5) | |
N2 | 0.65614 (19) | 0.34645 (12) | 0.05362 (7) | 0.0347 (5) | |
N3 | 0.7585 (2) | 0.27935 (13) | 0.24208 (8) | 0.0404 (6) | |
C1 | 0.4785 (2) | 0.26315 (14) | 0.21791 (9) | 0.0310 (5) | |
C2 | 0.5114 (2) | 0.20180 (14) | 0.23851 (10) | 0.0352 (6) | |
H2 | 0.5507 | 0.1702 | 0.2209 | 0.042* | |
C3 | 0.4874 (2) | 0.18675 (15) | 0.28396 (10) | 0.0410 (7) | |
H3 | 0.5105 | 0.145 | 0.2976 | 0.049* | |
C4 | 0.4295 (3) | 0.23258 (16) | 0.31005 (10) | 0.0417 (7) | |
C5 | 0.3979 (3) | 0.29366 (16) | 0.29062 (10) | 0.0439 (7) | |
H5 | 0.3597 | 0.3254 | 0.3086 | 0.053* | |
C6 | 0.4220 (2) | 0.30883 (15) | 0.24459 (10) | 0.0389 (6) | |
H6 | 0.3995 | 0.3509 | 0.2312 | 0.047* | |
C7 | 0.3501 (4) | 0.2581 (2) | 0.38304 (14) | 0.0797 (14) | |
H7A | 0.3866 | 0.3022 | 0.3843 | 0.12* | |
H7B | 0.347 | 0.2398 | 0.4149 | 0.12* | |
H7C | 0.2764 | 0.2636 | 0.3692 | 0.12* | |
C8 | 0.4127 (2) | 0.23227 (14) | 0.12155 (9) | 0.0320 (6) | |
C9 | 0.4234 (3) | 0.22742 (17) | 0.07336 (10) | 0.0455 (7) | |
H9 | 0.4802 | 0.2514 | 0.0593 | 0.055* | |
C10 | 0.3533 (3) | 0.18846 (17) | 0.04526 (11) | 0.0474 (8) | |
H10 | 0.361 | 0.1866 | 0.0122 | 0.057* | |
C11 | 0.2724 (2) | 0.15241 (16) | 0.06547 (11) | 0.0437 (7) | |
C12 | 0.2592 (3) | 0.15734 (19) | 0.11281 (12) | 0.0560 (9) | |
H12 | 0.202 | 0.1334 | 0.1265 | 0.067* | |
C13 | 0.3289 (2) | 0.19710 (17) | 0.14114 (11) | 0.0472 (8) | |
H13 | 0.319 | 0.2001 | 0.174 | 0.057* | |
C14 | 0.2238 (3) | 0.0958 (2) | −0.00678 (13) | 0.0690 (11) | |
H14A | 0.2148 | 0.1373 | −0.0255 | 0.103* | |
H14B | 0.1727 | 0.0614 | −0.019 | 0.103* | |
H14C | 0.2981 | 0.079 | −0.0088 | 0.103* | |
C15 | 0.4757 (2) | 0.36890 (13) | 0.14731 (9) | 0.0296 (5) | |
C16 | 0.5510 (2) | 0.41826 (14) | 0.16158 (10) | 0.0368 (6) | |
H16 | 0.6172 | 0.4051 | 0.1773 | 0.044* | |
C17 | 0.5308 (3) | 0.48593 (15) | 0.15319 (10) | 0.0408 (7) | |
H17 | 0.5825 | 0.5191 | 0.1634 | 0.049* | |
C18 | 0.4347 (3) | 0.50511 (14) | 0.12976 (9) | 0.0388 (7) | |
C19 | 0.3590 (3) | 0.45655 (15) | 0.11535 (10) | 0.0404 (7) | |
H19 | 0.2929 | 0.4699 | 0.0995 | 0.048* | |
C20 | 0.3792 (2) | 0.38927 (14) | 0.12399 (10) | 0.0356 (6) | |
H20 | 0.327 | 0.3563 | 0.114 | 0.043* | |
C21 | 0.4878 (4) | 0.62149 (17) | 0.12987 (13) | 0.0702 (12) | |
H21A | 0.5065 | 0.6209 | 0.1637 | 0.105* | |
H21B | 0.4586 | 0.666 | 0.1209 | 0.105* | |
H21C | 0.5528 | 0.6123 | 0.1125 | 0.105* | |
C22 | 0.9221 (2) | 0.31767 (13) | 0.10681 (9) | 0.0312 (5) | |
C23 | 0.9010 (2) | 0.37584 (15) | 0.13202 (10) | 0.0374 (6) | |
H23 | 0.8499 | 0.374 | 0.1559 | 0.045* | |
C24 | 0.9522 (2) | 0.43644 (15) | 0.12348 (10) | 0.0387 (6) | |
H24 | 0.9365 | 0.4756 | 0.1413 | 0.046* | |
C25 | 1.0259 (2) | 0.43966 (15) | 0.08895 (10) | 0.0398 (7) | |
C26 | 1.0483 (3) | 0.38193 (17) | 0.06327 (13) | 0.0612 (10) | |
H26 | 1.0997 | 0.384 | 0.0395 | 0.073* | |
C27 | 0.9968 (3) | 0.32162 (16) | 0.07200 (12) | 0.0523 (9) | |
H27 | 1.0125 | 0.2826 | 0.0541 | 0.063* | |
C28 | 1.0597 (3) | 0.55627 (18) | 0.10414 (16) | 0.0666 (11) | |
H28A | 0.983 | 0.5684 | 0.0993 | 0.1* | |
H28B | 1.1048 | 0.5935 | 0.0934 | 0.1* | |
H28C | 1.0763 | 0.548 | 0.1377 | 0.1* | |
C29 | 0.8627 (2) | 0.18404 (13) | 0.07071 (9) | 0.0324 (6) | |
C30 | 0.9434 (3) | 0.13528 (18) | 0.06889 (13) | 0.0539 (9) | |
H30 | 0.9971 | 0.1324 | 0.0939 | 0.065* | |
C31 | 0.9470 (3) | 0.09095 (19) | 0.03146 (15) | 0.0640 (11) | |
H31 | 1.0024 | 0.0576 | 0.0311 | 0.077* | |
C32 | 0.8705 (3) | 0.09494 (16) | −0.00533 (11) | 0.0465 (8) | |
C33 | 0.7906 (3) | 0.14317 (16) | −0.00476 (10) | 0.0487 (8) | |
H33 | 0.7386 | 0.1467 | −0.0304 | 0.058* | |
C34 | 0.7859 (3) | 0.18657 (16) | 0.03328 (10) | 0.0451 (8) | |
H34 | 0.729 | 0.2189 | 0.0338 | 0.054* | |
C35 | 0.7954 (4) | 0.0470 (2) | −0.07718 (13) | 0.0821 (14) | |
H35A | 0.7251 | 0.0403 | −0.0633 | 0.123* | |
H35B | 0.8091 | 0.0096 | −0.0988 | 0.123* | |
H35C | 0.7947 | 0.0899 | −0.0945 | 0.123* | |
C36 | 0.9381 (2) | 0.19975 (15) | 0.16688 (9) | 0.0355 (6) | |
C37 | 0.9041 (3) | 0.13940 (18) | 0.18639 (12) | 0.0524 (9) | |
H37 | 0.836 | 0.1208 | 0.1762 | 0.063* | |
C38 | 0.9668 (3) | 0.1061 (2) | 0.22006 (14) | 0.0657 (11) | |
H38 | 0.9427 | 0.0644 | 0.2325 | 0.079* | |
C39 | 1.0662 (3) | 0.1334 (2) | 0.23604 (12) | 0.0578 (10) | |
C40 | 1.0996 (2) | 0.1944 (2) | 0.21841 (11) | 0.0517 (8) | |
H40 | 1.1658 | 0.2141 | 0.2301 | 0.062* | |
C41 | 1.0364 (2) | 0.22721 (16) | 0.18343 (10) | 0.0402 (7) | |
H41 | 1.0607 | 0.2687 | 0.1708 | 0.048* | |
C42 | 1.2229 (4) | 0.1226 (4) | 0.2875 (2) | 0.127 (3) | |
H42A | 1.2709 | 0.1291 | 0.2614 | 0.191* | |
H42B | 1.2563 | 0.0905 | 0.3102 | 0.191* | |
H42C | 1.2115 | 0.166 | 0.3031 | 0.191* | |
C43 | 0.7289 (2) | 0.26853 (14) | 0.20416 (9) | 0.0323 (6) | |
C44 | 0.6470 (2) | 0.16677 (14) | 0.12926 (8) | 0.0299 (5) | |
C45 | 0.6616 (2) | 0.30927 (13) | 0.08462 (9) | 0.0307 (5) | |
C46 | 0.6531 (3) | 0.39462 (15) | 0.01432 (10) | 0.0410 (7) | |
C47 | 0.7213 (3) | 0.3633 (2) | −0.02354 (11) | 0.0606 (10) | |
H47A | 0.7961 | 0.3575 | −0.011 | 0.091* | |
H47B | 0.7204 | 0.3931 | −0.0511 | 0.091* | |
H47C | 0.691 | 0.3191 | −0.0328 | 0.091* | |
C48 | 0.5346 (3) | 0.40141 (18) | −0.00238 (11) | 0.0507 (8) | |
H48A | 0.5072 | 0.3573 | −0.0133 | 0.076* | |
H48B | 0.5283 | 0.4341 | −0.0283 | 0.076* | |
H48C | 0.4922 | 0.4172 | 0.0237 | 0.076* | |
C49 | 0.6993 (4) | 0.46024 (19) | 0.03341 (14) | 0.0718 (12) | |
H49A | 0.6548 | 0.4767 | 0.0586 | 0.108* | |
H49B | 0.6995 | 0.4939 | 0.0081 | 0.108* | |
H49C | 0.7737 | 0.4528 | 0.046 | 0.108* | |
C50 | 0.5953 (2) | 0.04203 (13) | 0.10785 (10) | 0.0362 (6) | |
C51 | 0.6943 (3) | −0.00155 (17) | 0.11717 (14) | 0.0584 (9) | |
H51A | 0.7524 | 0.0137 | 0.0974 | 0.088* | |
H51B | 0.6764 | −0.0488 | 0.1098 | 0.088* | |
H51C | 0.7186 | 0.0022 | 0.1504 | 0.088* | |
C52 | 0.5592 (3) | 0.04302 (17) | 0.05593 (11) | 0.0562 (9) | |
H52A | 0.4971 | 0.0735 | 0.0511 | 0.084* | |
H52B | 0.5383 | −0.0028 | 0.0458 | 0.084* | |
H52C | 0.6191 | 0.0589 | 0.0374 | 0.084* | |
C53 | 0.5034 (3) | 0.02117 (19) | 0.13816 (13) | 0.0608 (10) | |
H53A | 0.5273 | 0.0245 | 0.1715 | 0.091* | |
H53B | 0.4825 | −0.0256 | 0.1308 | 0.091* | |
H53C | 0.4411 | 0.0511 | 0.1318 | 0.091* | |
C54 | 0.7997 (3) | 0.29097 (17) | 0.29064 (10) | 0.0486 (8) | |
C55 | 0.7164 (3) | 0.3319 (2) | 0.31506 (12) | 0.0622 (10) | |
H55A | 0.7072 | 0.3758 | 0.2994 | 0.093* | |
H55B | 0.7406 | 0.3388 | 0.348 | 0.093* | |
H55C | 0.6471 | 0.3076 | 0.3136 | 0.093* | |
C56 | 0.8160 (5) | 0.2215 (2) | 0.31198 (13) | 0.0860 (15) | |
H56A | 0.7465 | 0.1975 | 0.3115 | 0.129* | |
H56B | 0.8448 | 0.2259 | 0.3446 | 0.129* | |
H56C | 0.8674 | 0.1958 | 0.2937 | 0.129* | |
C57 | 0.9048 (3) | 0.3301 (3) | 0.28810 (13) | 0.0792 (13) | |
H57A | 0.957 | 0.3034 | 0.2711 | 0.119* | |
H57B | 0.9345 | 0.3393 | 0.32 | 0.119* | |
H57C | 0.8908 | 0.373 | 0.2716 | 0.119* | |
C58 | 0.6802 | 0.2026 | 0.4236 | 0.140 (3) | 0.489 (8) |
H58A | 0.7314 | 0.2384 | 0.4145 | 0.21* | 0.489 (8) |
H58B | 0.6467 | 0.1833 | 0.3942 | 0.21* | 0.489 (8) |
Cl3A | 0.7552 (6) | 0.1376 (4) | 0.4540 (4) | 0.267 (7) | 0.489 (8) |
Cl4A | 0.5903 | 0.2357 | 0.4517 | 0.144 (2) | 0.489 (8) |
C58A | 0.6802 | 0.2026 | 0.4236 | 0.140 (3) | 0.511 (8) |
H58C | 0.6424 | 0.1939 | 0.3927 | 0.21* | 0.511 (8) |
H58D | 0.7431 | 0.2324 | 0.4186 | 0.21* | 0.511 (8) |
Cl3B | 0.7242 (4) | 0.1265 (2) | 0.44896 (13) | 0.0987 (14) | 0.511 (8) |
Cl4B | 0.5902 | 0.2428 | 0.462 | 0.120 (2) | 0.511 (8) |
C59 | 0.538 (2) | 0.4671 (14) | 0.3261 (13) | 0.094 (10) | 0.164 (3) |
H59A | 0.5737 | 0.5114 | 0.3318 | 0.113* | 0.164 (3) |
H59B | 0.5773 | 0.4435 | 0.3014 | 0.113* | 0.164 (3) |
Cl9A | 0.4103 (5) | 0.4808 (4) | 0.3059 (4) | 0.103 (3) | 0.164 (3) |
Cl9B | 0.5493 (5) | 0.4187 (3) | 0.3784 (2) | 0.070 (2) | 0.164 (3) |
Cl5A | 0.1850 (7) | 0.4127 (5) | 0.2062 (3) | 0.0751 (13) | 0.291 (7) |
C60A | 0.1346 (15) | 0.4396 (14) | 0.2581 (7) | 0.105 (8)* | 0.291 (7) |
H60A | 0.095 | 0.4016 | 0.2721 | 0.126* | 0.291 (7) |
H60B | 0.0817 | 0.4763 | 0.2511 | 0.126* | 0.291 (7) |
Cl6A | 0.2342 (7) | 0.4694 (7) | 0.3002 (4) | 0.0783 (9) | 0.291 (7) |
Cl5B | 0.155 (2) | 0.4135 (19) | 0.2086 (7) | 0.0751 (13) | 0.079 (3) |
C60B | 0.165 (4) | 0.4669 (14) | 0.2589 (8) | 0.041 (9)* | 0.079 (3) |
H60C | 0.2296 | 0.4965 | 0.2576 | 0.049* | 0.079 (3) |
H60D | 0.0998 | 0.4959 | 0.2601 | 0.049* | 0.079 (3) |
Cl6B | 0.1764 (12) | 0.4144 (10) | 0.3087 (5) | 0.0783 (9) | 0.079 (3) |
Cl5C | 0.2073 (6) | 0.4426 (5) | 0.2086 (3) | 0.0751 (13) | 0.183 (3) |
C60C | 0.149 (3) | 0.3804 (13) | 0.2389 (7) | 0.083 (11)* | 0.183 (3) |
H60E | 0.073 | 0.3763 | 0.2268 | 0.1* | 0.183 (3) |
H60F | 0.186 | 0.3375 | 0.2313 | 0.1* | 0.183 (3) |
Cl6C | 0.1491 (5) | 0.3869 (4) | 0.2977 (3) | 0.0783 (9) | 0.183 (3) |
Cl5D | 0.1602 (6) | 0.3936 (4) | 0.2201 (3) | 0.0751 (13) | 0.358 (7) |
C60D | 0.1424 (9) | 0.4309 (7) | 0.2745 (5) | 0.060 (3)* | 0.358 (7) |
H60G | 0.1186 | 0.3961 | 0.2968 | 0.072* | 0.358 (7) |
H60H | 0.0846 | 0.4655 | 0.2711 | 0.072* | 0.358 (7) |
Cl6D | 0.2645 (5) | 0.4699 (5) | 0.2982 (3) | 0.0783 (9) | 0.358 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.02695 (17) | 0.02599 (18) | 0.01963 (15) | −0.00013 (13) | 0.00066 (12) | 0.00018 (12) |
P1 | 0.0281 (3) | 0.0292 (3) | 0.0262 (3) | 0.0003 (3) | 0.0029 (2) | 0.0009 (2) |
P2 | 0.0272 (3) | 0.0294 (3) | 0.0258 (3) | 0.0000 (3) | 0.0015 (2) | −0.0006 (2) |
O1 | 0.0768 (17) | 0.0562 (14) | 0.0449 (12) | 0.0095 (12) | 0.0327 (12) | 0.0145 (11) |
O2 | 0.0484 (14) | 0.0684 (17) | 0.0620 (15) | −0.0245 (12) | 0.0007 (11) | −0.0219 (12) |
O3 | 0.0862 (18) | 0.0310 (12) | 0.0420 (12) | 0.0012 (11) | −0.0133 (11) | 0.0059 (9) |
O4 | 0.0634 (15) | 0.0400 (13) | 0.0676 (15) | −0.0176 (11) | 0.0260 (12) | −0.0059 (11) |
O5 | 0.0758 (18) | 0.0539 (15) | 0.0750 (17) | 0.0028 (13) | 0.0154 (14) | −0.0362 (13) |
O6 | 0.0421 (14) | 0.123 (3) | 0.0790 (19) | −0.0055 (15) | −0.0173 (13) | 0.0555 (18) |
O7 | 0.074 (2) | 0.206 (4) | 0.0654 (19) | −0.035 (2) | −0.0111 (16) | −0.016 (2) |
O8 | 0.095 (3) | 0.184 (4) | 0.076 (2) | 0.035 (3) | 0.0207 (19) | −0.017 (2) |
O9 | 0.117 (3) | 0.097 (3) | 0.107 (3) | 0.022 (2) | −0.018 (2) | 0.045 (2) |
O10 | 0.162 (4) | 0.0427 (18) | 0.156 (4) | 0.019 (2) | −0.032 (3) | −0.025 (2) |
O11 | 0.163 (4) | 0.100 (3) | 0.159 (4) | −0.078 (3) | −0.081 (3) | 0.048 (3) |
O12 | 0.0536 (17) | 0.123 (3) | 0.092 (2) | 0.0248 (17) | 0.0000 (15) | −0.0176 (19) |
O13 | 0.101 (2) | 0.121 (3) | 0.077 (2) | 0.026 (2) | 0.0240 (18) | −0.0389 (19) |
O14 | 0.106 (2) | 0.090 (2) | 0.0649 (18) | 0.0191 (19) | −0.0150 (17) | 0.0006 (16) |
Cl1 | 0.0668 (5) | 0.0409 (4) | 0.0411 (4) | 0.0082 (4) | −0.0127 (4) | −0.0096 (3) |
Cl2 | 0.0491 (4) | 0.0511 (5) | 0.0479 (4) | 0.0046 (4) | −0.0024 (3) | −0.0133 (3) |
N1 | 0.0378 (13) | 0.0275 (13) | 0.0329 (11) | −0.0014 (10) | −0.0002 (9) | −0.0013 (9) |
N2 | 0.0413 (13) | 0.0340 (13) | 0.0289 (11) | 0.0071 (10) | 0.0039 (9) | 0.0045 (9) |
N3 | 0.0451 (14) | 0.0473 (15) | 0.0285 (12) | −0.0021 (11) | −0.0017 (10) | −0.0023 (10) |
C1 | 0.0292 (13) | 0.0353 (14) | 0.0290 (12) | −0.0021 (11) | 0.0065 (10) | 0.0008 (10) |
C2 | 0.0366 (15) | 0.0316 (15) | 0.0386 (14) | 0.0021 (11) | 0.0120 (11) | 0.0001 (11) |
C3 | 0.0459 (17) | 0.0351 (16) | 0.0433 (16) | 0.0033 (13) | 0.0136 (13) | 0.0094 (12) |
C4 | 0.0447 (17) | 0.0454 (17) | 0.0362 (15) | 0.0003 (14) | 0.0151 (12) | 0.0067 (12) |
C5 | 0.0474 (18) | 0.0439 (18) | 0.0418 (16) | 0.0113 (14) | 0.0176 (13) | 0.0003 (13) |
C6 | 0.0421 (16) | 0.0387 (16) | 0.0366 (14) | 0.0080 (13) | 0.0079 (12) | 0.0032 (12) |
C7 | 0.111 (4) | 0.080 (3) | 0.053 (2) | 0.029 (3) | 0.050 (2) | 0.020 (2) |
C8 | 0.0285 (13) | 0.0302 (14) | 0.0371 (14) | −0.0001 (11) | −0.0018 (11) | −0.0033 (11) |
C9 | 0.0480 (18) | 0.054 (2) | 0.0341 (15) | −0.0174 (15) | −0.0032 (13) | 0.0033 (13) |
C10 | 0.0467 (18) | 0.057 (2) | 0.0374 (15) | −0.0152 (15) | −0.0071 (13) | −0.0040 (14) |
C11 | 0.0320 (15) | 0.0454 (18) | 0.0529 (18) | −0.0035 (13) | −0.0053 (13) | −0.0128 (14) |
C12 | 0.0405 (18) | 0.071 (2) | 0.058 (2) | −0.0249 (17) | 0.0141 (15) | −0.0160 (17) |
C13 | 0.0355 (16) | 0.062 (2) | 0.0446 (17) | −0.0098 (15) | 0.0120 (13) | −0.0143 (15) |
C14 | 0.070 (3) | 0.075 (3) | 0.061 (2) | −0.028 (2) | −0.0091 (19) | −0.022 (2) |
C15 | 0.0310 (13) | 0.0314 (14) | 0.0265 (12) | 0.0012 (11) | 0.0038 (10) | −0.0009 (10) |
C16 | 0.0380 (15) | 0.0362 (16) | 0.0358 (14) | 0.0006 (12) | −0.0032 (12) | −0.0048 (11) |
C17 | 0.0511 (18) | 0.0371 (16) | 0.0337 (14) | −0.0079 (13) | −0.0026 (13) | −0.0067 (12) |
C18 | 0.0579 (19) | 0.0331 (15) | 0.0252 (12) | 0.0023 (13) | −0.0001 (12) | 0.0009 (11) |
C19 | 0.0436 (17) | 0.0402 (17) | 0.0365 (14) | 0.0052 (13) | −0.0059 (12) | 0.0050 (12) |
C20 | 0.0358 (15) | 0.0336 (15) | 0.0371 (14) | −0.0010 (12) | −0.0014 (11) | 0.0018 (11) |
C21 | 0.120 (4) | 0.0320 (18) | 0.057 (2) | −0.015 (2) | −0.017 (2) | 0.0041 (15) |
C22 | 0.0325 (14) | 0.0322 (14) | 0.0291 (12) | −0.0052 (11) | 0.0043 (10) | −0.0011 (10) |
C23 | 0.0404 (16) | 0.0393 (16) | 0.0338 (14) | −0.0050 (12) | 0.0139 (12) | −0.0067 (11) |
C24 | 0.0425 (16) | 0.0329 (15) | 0.0415 (15) | −0.0069 (12) | 0.0102 (12) | −0.0104 (12) |
C25 | 0.0399 (16) | 0.0379 (16) | 0.0422 (15) | −0.0110 (13) | 0.0076 (12) | −0.0020 (12) |
C26 | 0.074 (2) | 0.048 (2) | 0.065 (2) | −0.0177 (18) | 0.0473 (19) | −0.0115 (16) |
C27 | 0.065 (2) | 0.0362 (17) | 0.059 (2) | −0.0113 (15) | 0.0350 (17) | −0.0138 (14) |
C28 | 0.068 (2) | 0.0375 (19) | 0.096 (3) | −0.0166 (17) | 0.027 (2) | −0.0113 (19) |
C29 | 0.0351 (14) | 0.0293 (14) | 0.0336 (13) | 0.0001 (11) | 0.0091 (11) | −0.0031 (10) |
C30 | 0.0330 (16) | 0.051 (2) | 0.076 (2) | 0.0089 (14) | −0.0100 (15) | −0.0268 (17) |
C31 | 0.0383 (18) | 0.055 (2) | 0.098 (3) | 0.0111 (16) | −0.0017 (18) | −0.041 (2) |
C32 | 0.0546 (19) | 0.0357 (16) | 0.0508 (18) | −0.0061 (14) | 0.0183 (15) | −0.0153 (13) |
C33 | 0.077 (2) | 0.0417 (18) | 0.0278 (14) | 0.0139 (16) | 0.0021 (14) | −0.0030 (12) |
C34 | 0.064 (2) | 0.0418 (17) | 0.0291 (13) | 0.0223 (15) | −0.0002 (13) | 0.0004 (12) |
C35 | 0.145 (4) | 0.055 (2) | 0.046 (2) | 0.005 (3) | −0.002 (2) | −0.0212 (18) |
C36 | 0.0288 (13) | 0.0450 (17) | 0.0327 (13) | 0.0027 (12) | 0.0002 (11) | 0.0050 (12) |
C37 | 0.0361 (17) | 0.059 (2) | 0.061 (2) | −0.0074 (15) | −0.0115 (14) | 0.0238 (17) |
C38 | 0.0417 (19) | 0.077 (3) | 0.077 (3) | −0.0084 (18) | −0.0124 (17) | 0.042 (2) |
C39 | 0.0315 (16) | 0.087 (3) | 0.054 (2) | 0.0003 (17) | −0.0045 (14) | 0.0297 (19) |
C40 | 0.0307 (15) | 0.081 (3) | 0.0430 (17) | −0.0077 (16) | −0.0031 (13) | 0.0101 (16) |
C41 | 0.0322 (15) | 0.0523 (19) | 0.0362 (14) | −0.0055 (13) | 0.0033 (11) | 0.0029 (13) |
C42 | 0.047 (2) | 0.208 (7) | 0.122 (4) | −0.029 (3) | −0.041 (3) | 0.099 (5) |
C43 | 0.0319 (14) | 0.0370 (15) | 0.0278 (13) | −0.0018 (11) | −0.0009 (10) | −0.0026 (11) |
C44 | 0.0280 (13) | 0.0375 (16) | 0.0241 (11) | 0.0015 (11) | 0.0007 (10) | 0.0015 (10) |
C45 | 0.0328 (14) | 0.0318 (14) | 0.0278 (12) | 0.0030 (11) | 0.0051 (10) | 0.0012 (10) |
C46 | 0.0506 (18) | 0.0402 (17) | 0.0324 (14) | 0.0093 (13) | 0.0050 (12) | 0.0156 (12) |
C47 | 0.064 (2) | 0.079 (3) | 0.0412 (17) | 0.0259 (19) | 0.0189 (16) | 0.0265 (17) |
C48 | 0.053 (2) | 0.057 (2) | 0.0425 (17) | 0.0194 (16) | 0.0038 (14) | 0.0152 (15) |
C49 | 0.101 (3) | 0.049 (2) | 0.064 (2) | −0.012 (2) | −0.007 (2) | 0.0209 (18) |
C50 | 0.0468 (17) | 0.0236 (14) | 0.0382 (14) | −0.0027 (12) | 0.0024 (12) | −0.0008 (11) |
C51 | 0.059 (2) | 0.0357 (18) | 0.079 (3) | 0.0098 (16) | −0.0074 (18) | −0.0077 (17) |
C52 | 0.087 (3) | 0.0368 (18) | 0.0431 (17) | −0.0058 (17) | −0.0097 (17) | −0.0057 (14) |
C53 | 0.065 (2) | 0.057 (2) | 0.062 (2) | −0.0250 (18) | 0.0157 (18) | −0.0084 (17) |
C54 | 0.064 (2) | 0.055 (2) | 0.0254 (13) | −0.0064 (16) | −0.0111 (13) | −0.0056 (13) |
C55 | 0.082 (3) | 0.068 (2) | 0.0372 (17) | −0.009 (2) | 0.0052 (17) | −0.0157 (16) |
C56 | 0.146 (5) | 0.069 (3) | 0.0390 (19) | 0.018 (3) | −0.030 (2) | −0.0042 (18) |
C57 | 0.064 (3) | 0.126 (4) | 0.046 (2) | −0.025 (3) | −0.0131 (18) | −0.014 (2) |
C58 | 0.205 (8) | 0.112 (5) | 0.110 (5) | −0.030 (5) | 0.076 (5) | 0.011 (4) |
Cl3A | 0.098 (4) | 0.143 (5) | 0.570 (18) | 0.020 (4) | 0.113 (6) | 0.135 (7) |
Cl4A | 0.120 (4) | 0.141 (5) | 0.168 (4) | 0.025 (3) | −0.027 (3) | 0.043 (3) |
C58A | 0.205 (8) | 0.112 (5) | 0.110 (5) | −0.030 (5) | 0.076 (5) | 0.011 (4) |
Cl3B | 0.093 (3) | 0.095 (2) | 0.110 (3) | −0.0008 (19) | 0.0289 (17) | 0.0129 (17) |
Cl4B | 0.181 (5) | 0.110 (3) | 0.075 (2) | −0.002 (3) | 0.055 (2) | 0.0062 (18) |
C59 | 0.058 (16) | 0.049 (15) | 0.17 (3) | −0.001 (12) | −0.010 (18) | 0.018 (17) |
Cl9A | 0.053 (4) | 0.059 (4) | 0.194 (10) | −0.014 (3) | −0.019 (5) | 0.017 (5) |
Cl9B | 0.050 (3) | 0.089 (5) | 0.074 (4) | −0.013 (3) | 0.013 (3) | −0.030 (3) |
Cl5A | 0.055 (2) | 0.097 (4) | 0.073 (2) | 0.012 (2) | −0.0045 (16) | −0.007 (2) |
Cl6A | 0.042 (2) | 0.1016 (15) | 0.0905 (14) | 0.002 (2) | −0.0019 (19) | −0.0184 (11) |
Cl5B | 0.055 (2) | 0.097 (4) | 0.073 (2) | 0.012 (2) | −0.0045 (16) | −0.007 (2) |
Cl6B | 0.042 (2) | 0.1016 (15) | 0.0905 (14) | 0.002 (2) | −0.0019 (19) | −0.0184 (11) |
Cl5C | 0.055 (2) | 0.097 (4) | 0.073 (2) | 0.012 (2) | −0.0045 (16) | −0.007 (2) |
Cl6C | 0.042 (2) | 0.1016 (15) | 0.0905 (14) | 0.002 (2) | −0.0019 (19) | −0.0184 (11) |
Cl5D | 0.055 (2) | 0.097 (4) | 0.073 (2) | 0.012 (2) | −0.0045 (16) | −0.007 (2) |
Cl6D | 0.042 (2) | 0.1016 (15) | 0.0905 (14) | 0.002 (2) | −0.0019 (19) | −0.0184 (11) |
Co1—C45 | 1.876 (3) | C30—C31 | 1.381 (5) |
Co1—C43 | 1.879 (3) | C30—H30 | 0.95 |
Co1—C44 | 1.910 (3) | C31—C32 | 1.377 (5) |
Co1—P1 | 2.2515 (7) | C31—H31 | 0.95 |
Co1—P2 | 2.2536 (7) | C32—C33 | 1.372 (5) |
C44—N1 | 1.148 (3) | C33—C34 | 1.384 (4) |
C45—N2 | 1.147 (3) | C33—H33 | 0.95 |
C43—N3 | 1.142 (3) | C34—H34 | 0.95 |
N1—C50 | 1.463 (3) | C35—H35A | 0.98 |
N2—C46 | 1.467 (3) | C35—H35B | 0.98 |
N3—C54 | 1.466 (3) | C35—H35C | 0.98 |
P1—C22 | 1.804 (3) | C36—C37 | 1.389 (4) |
P1—C29 | 1.811 (3) | C36—C41 | 1.390 (4) |
P1—C36 | 1.812 (3) | C37—C38 | 1.370 (4) |
P2—C15 | 1.805 (3) | C37—H37 | 0.95 |
P2—C1 | 1.812 (3) | C38—C39 | 1.397 (5) |
P2—C8 | 1.813 (3) | C38—H38 | 0.95 |
O1—C4 | 1.365 (3) | C39—C40 | 1.376 (5) |
O1—C7 | 1.432 (4) | C40—C41 | 1.394 (4) |
O2—C11 | 1.360 (3) | C40—H40 | 0.95 |
O2—C14 | 1.425 (4) | C41—H41 | 0.95 |
O3—C18 | 1.366 (3) | C42—H42A | 0.98 |
O3—C21 | 1.436 (4) | C42—H42B | 0.98 |
O4—C25 | 1.360 (3) | C42—H42C | 0.98 |
O4—C28 | 1.429 (4) | C46—C49 | 1.507 (5) |
O5—C32 | 1.361 (3) | C46—C48 | 1.521 (4) |
O5—C35 | 1.438 (5) | C46—C47 | 1.530 (4) |
O6—C39 | 1.358 (4) | C47—H47A | 0.98 |
O6—C42 | 1.431 (5) | C47—H47B | 0.98 |
O7—Cl1 | 1.392 (3) | C47—H47C | 0.98 |
O8—Cl1 | 1.385 (3) | C48—H48A | 0.98 |
O9—Cl1 | 1.416 (3) | C48—H48B | 0.98 |
O10—Cl1 | 1.387 (3) | C48—H48C | 0.98 |
O11—Cl2 | 1.380 (3) | C49—H49A | 0.98 |
O12—Cl2 | 1.415 (3) | C49—H49B | 0.98 |
O13—Cl2 | 1.412 (3) | C49—H49C | 0.98 |
O14—Cl2 | 1.422 (3) | C50—C51 | 1.508 (4) |
C1—C6 | 1.389 (4) | C50—C53 | 1.515 (4) |
C1—C2 | 1.398 (4) | C50—C52 | 1.522 (4) |
C2—C3 | 1.373 (4) | C51—H51A | 0.98 |
C2—H2 | 0.95 | C51—H51B | 0.98 |
C3—C4 | 1.391 (4) | C51—H51C | 0.98 |
C3—H3 | 0.95 | C52—H52A | 0.98 |
C4—C5 | 1.376 (4) | C52—H52B | 0.98 |
C5—C6 | 1.390 (4) | C52—H52C | 0.98 |
C5—H5 | 0.95 | C53—H53A | 0.98 |
C6—H6 | 0.95 | C53—H53B | 0.98 |
C7—H7A | 0.98 | C53—H53C | 0.98 |
C7—H7B | 0.98 | C54—C55 | 1.505 (5) |
C7—H7C | 0.98 | C54—C56 | 1.511 (5) |
C8—C13 | 1.385 (4) | C54—C57 | 1.515 (5) |
C8—C9 | 1.387 (4) | C55—H55A | 0.98 |
C9—C10 | 1.383 (4) | C55—H55B | 0.98 |
C9—H9 | 0.95 | C55—H55C | 0.98 |
C10—C11 | 1.376 (4) | C56—H56A | 0.98 |
C10—H10 | 0.95 | C56—H56B | 0.98 |
C11—C12 | 1.368 (5) | C56—H56C | 0.98 |
C12—C13 | 1.392 (4) | C57—H57A | 0.98 |
C12—H12 | 0.95 | C57—H57B | 0.98 |
C13—H13 | 0.95 | C57—H57C | 0.98 |
C14—H14A | 0.98 | C58—Cl4A | 1.5437 |
C14—H14B | 0.98 | C58—Cl3A | 1.782 (8) |
C14—H14C | 0.98 | C58—H58A | 0.99 |
C15—C20 | 1.394 (4) | C58—H58B | 0.99 |
C15—C16 | 1.394 (4) | C58A—Cl3B | 1.744 (4) |
C16—C17 | 1.378 (4) | C58A—Cl4B | 1.7836 |
C16—H16 | 0.95 | C58A—H58C | 0.99 |
C17—C18 | 1.385 (4) | C58A—H58D | 0.99 |
C17—H17 | 0.95 | C59—Cl9A | 1.67 (3) |
C18—C19 | 1.387 (4) | C59—Cl9B | 1.77 (3) |
C19—C20 | 1.372 (4) | C59—H59A | 0.99 |
C19—H19 | 0.95 | C59—H59B | 0.99 |
C20—H20 | 0.95 | Cl9A—Cl6D | 1.815 (9) |
C21—H21A | 0.98 | Cl9A—Cl6A | 2.184 (11) |
C21—H21B | 0.98 | Cl5A—C60A | 1.714 (16) |
C21—H21C | 0.98 | C60A—Cl6A | 1.775 (16) |
C22—C23 | 1.386 (4) | C60A—H60A | 0.99 |
C22—C27 | 1.388 (4) | C60A—H60B | 0.99 |
C23—C24 | 1.381 (4) | Cl5B—C60B | 1.777 (19) |
C23—H23 | 0.95 | C60B—Cl6B | 1.755 (19) |
C24—C25 | 1.373 (4) | C60B—H60C | 0.99 |
C24—H24 | 0.95 | C60B—H60D | 0.99 |
C25—C26 | 1.390 (4) | Cl5C—C60C | 1.680 (18) |
C26—C27 | 1.379 (4) | C60C—Cl6C | 1.678 (18) |
C26—H26 | 0.95 | C60C—H60E | 0.99 |
C27—H27 | 0.95 | C60C—H60F | 0.99 |
C28—H28A | 0.98 | Cl5D—C60D | 1.737 (12) |
C28—H28B | 0.98 | C60D—Cl6D | 1.794 (11) |
C28—H28C | 0.98 | C60D—H60G | 0.99 |
C29—C30 | 1.389 (4) | C60D—H60H | 0.99 |
C29—C34 | 1.391 (4) | ||
N1—C44—Co1 | 177.8 (2) | C32—C33—H33 | 120.1 |
N2—C45—Co1 | 170.8 (2) | C34—C33—H33 | 120.1 |
N3—C43—Co1 | 174.5 (3) | C33—C34—C29 | 121.6 (3) |
C43—N3—C54 | 177.7 (3) | C33—C34—H34 | 119.2 |
C44—N1—C50 | 177.0 (3) | C29—C34—H34 | 119.2 |
C45—N2—C46 | 178.0 (3) | O5—C35—H35A | 109.5 |
C45—Co1—C43 | 142.25 (12) | O5—C35—H35B | 109.5 |
C45—Co1—C44 | 109.77 (11) | H35A—C35—H35B | 109.5 |
C43—Co1—C44 | 107.97 (11) | O5—C35—H35C | 109.5 |
C43—Co1—P1 | 90.57 (8) | H35A—C35—H35C | 109.5 |
C44—Co1—P1 | 90.19 (8) | H35B—C35—H35C | 109.5 |
C45—Co1—P1 | 88.37 (8) | C37—C36—C41 | 118.4 (3) |
C43—Co1—P2 | 91.31 (8) | C37—C36—P1 | 119.4 (2) |
C44—Co1—P2 | 90.25 (8) | C41—C36—P1 | 122.2 (2) |
C45—Co1—P2 | 89.49 (8) | C38—C37—C36 | 121.4 (3) |
P1—Co1—P2 | 177.84 (3) | C38—C37—H37 | 119.3 |
C22—P1—C29 | 107.38 (12) | C36—C37—H37 | 119.3 |
C22—P1—C36 | 106.11 (13) | C37—C38—C39 | 119.9 (3) |
C29—P1—C36 | 104.39 (13) | C37—C38—H38 | 120 |
C22—P1—Co1 | 111.19 (9) | C39—C38—H38 | 120 |
C29—P1—Co1 | 113.14 (9) | O6—C39—C40 | 125.5 (3) |
C36—P1—Co1 | 114.06 (9) | O6—C39—C38 | 114.8 (3) |
C15—P2—C1 | 106.43 (12) | C40—C39—C38 | 119.7 (3) |
C15—P2—C8 | 106.18 (12) | C39—C40—C41 | 120.0 (3) |
C1—P2—C8 | 105.49 (13) | C39—C40—H40 | 120 |
C15—P2—Co1 | 111.13 (9) | C41—C40—H40 | 120 |
C1—P2—Co1 | 114.42 (9) | C36—C41—C40 | 120.6 (3) |
C8—P2—Co1 | 112.61 (9) | C36—C41—H41 | 119.7 |
C4—O1—C7 | 117.6 (3) | C40—C41—H41 | 119.7 |
C11—O2—C14 | 118.2 (3) | O6—C42—H42A | 109.5 |
C18—O3—C21 | 117.1 (3) | O6—C42—H42B | 109.5 |
C25—O4—C28 | 116.9 (2) | H42A—C42—H42B | 109.5 |
C32—O5—C35 | 117.8 (3) | O6—C42—H42C | 109.5 |
C39—O6—C42 | 117.0 (3) | H42A—C42—H42C | 109.5 |
O7—Cl1—O9 | 111.4 (2) | H42B—C42—H42C | 109.5 |
O8—Cl1—O7 | 110.4 (2) | N2—C46—C49 | 106.8 (2) |
O8—Cl1—O9 | 110.3 (2) | N2—C46—C48 | 106.4 (2) |
O8—Cl1—O10 | 111.0 (3) | C49—C46—C48 | 112.2 (3) |
O10—Cl1—O7 | 108.3 (3) | N2—C46—C47 | 106.2 (2) |
O10—Cl1—O9 | 105.4 (2) | C49—C46—C47 | 113.0 (3) |
O11—Cl2—O12 | 111.9 (3) | C48—C46—C47 | 111.7 (3) |
O11—Cl2—O13 | 112.1 (3) | C46—C47—H47A | 109.5 |
O11—Cl2—O14 | 109.2 (2) | C46—C47—H47B | 109.5 |
O12—Cl2—O14 | 108.0 (2) | H47A—C47—H47B | 109.5 |
O13—Cl2—O12 | 106.2 (2) | C46—C47—H47C | 109.5 |
O13—Cl2—O14 | 109.4 (2) | H47A—C47—H47C | 109.5 |
C6—C1—C2 | 118.5 (2) | H47B—C47—H47C | 109.5 |
C6—C1—P2 | 121.7 (2) | C46—C48—H48A | 109.5 |
C2—C1—P2 | 119.7 (2) | C46—C48—H48B | 109.5 |
C3—C2—C1 | 120.7 (3) | H48A—C48—H48B | 109.5 |
C3—C2—H2 | 119.6 | C46—C48—H48C | 109.5 |
C1—C2—H2 | 119.6 | H48A—C48—H48C | 109.5 |
C2—C3—C4 | 120.1 (3) | H48B—C48—H48C | 109.5 |
C2—C3—H3 | 119.9 | C46—C49—H49A | 109.5 |
C4—C3—H3 | 119.9 | C46—C49—H49B | 109.5 |
O1—C4—C5 | 124.5 (3) | H49A—C49—H49B | 109.5 |
O1—C4—C3 | 115.5 (3) | C46—C49—H49C | 109.5 |
C5—C4—C3 | 120.0 (3) | H49A—C49—H49C | 109.5 |
C4—C5—C6 | 119.9 (3) | H49B—C49—H49C | 109.5 |
C4—C5—H5 | 120.1 | N1—C50—C51 | 107.4 (2) |
C6—C5—H5 | 120.1 | N1—C50—C53 | 107.2 (2) |
C1—C6—C5 | 120.7 (3) | C51—C50—C53 | 111.6 (3) |
C1—C6—H6 | 119.6 | N1—C50—C52 | 107.0 (2) |
C5—C6—H6 | 119.6 | C51—C50—C52 | 112.0 (3) |
O1—C7—H7A | 109.5 | C53—C50—C52 | 111.4 (3) |
O1—C7—H7B | 109.5 | C50—C51—H51A | 109.5 |
H7A—C7—H7B | 109.5 | C50—C51—H51B | 109.5 |
O1—C7—H7C | 109.5 | H51A—C51—H51B | 109.5 |
H7A—C7—H7C | 109.5 | C50—C51—H51C | 109.5 |
H7B—C7—H7C | 109.5 | H51A—C51—H51C | 109.5 |
C13—C8—C9 | 118.2 (3) | H51B—C51—H51C | 109.5 |
C13—C8—P2 | 121.6 (2) | C50—C52—H52A | 109.5 |
C9—C8—P2 | 120.2 (2) | C50—C52—H52B | 109.5 |
C10—C9—C8 | 121.5 (3) | H52A—C52—H52B | 109.5 |
C10—C9—H9 | 119.3 | C50—C52—H52C | 109.5 |
C8—C9—H9 | 119.3 | H52A—C52—H52C | 109.5 |
C11—C10—C9 | 119.6 (3) | H52B—C52—H52C | 109.5 |
C11—C10—H10 | 120.2 | C50—C53—H53A | 109.5 |
C9—C10—H10 | 120.2 | C50—C53—H53B | 109.5 |
O2—C11—C12 | 116.4 (3) | H53A—C53—H53B | 109.5 |
O2—C11—C10 | 123.7 (3) | C50—C53—H53C | 109.5 |
C12—C11—C10 | 119.9 (3) | H53A—C53—H53C | 109.5 |
C11—C12—C13 | 120.7 (3) | H53B—C53—H53C | 109.5 |
C11—C12—H12 | 119.7 | N3—C54—C55 | 107.8 (3) |
C13—C12—H12 | 119.7 | N3—C54—C56 | 105.6 (3) |
C8—C13—C12 | 120.2 (3) | C55—C54—C56 | 112.5 (3) |
C8—C13—H13 | 119.9 | N3—C54—C57 | 107.0 (3) |
C12—C13—H13 | 119.9 | C55—C54—C57 | 110.7 (3) |
O2—C14—H14A | 109.5 | C56—C54—C57 | 112.7 (4) |
O2—C14—H14B | 109.5 | C54—C55—H55A | 109.5 |
H14A—C14—H14B | 109.5 | C54—C55—H55B | 109.5 |
O2—C14—H14C | 109.5 | H55A—C55—H55B | 109.5 |
H14A—C14—H14C | 109.5 | C54—C55—H55C | 109.5 |
H14B—C14—H14C | 109.5 | H55A—C55—H55C | 109.5 |
C20—C15—C16 | 118.6 (3) | H55B—C55—H55C | 109.5 |
C20—C15—P2 | 122.7 (2) | C54—C56—H56A | 109.5 |
C16—C15—P2 | 118.7 (2) | C54—C56—H56B | 109.5 |
C17—C16—C15 | 121.1 (3) | H56A—C56—H56B | 109.5 |
C17—C16—H16 | 119.5 | C54—C56—H56C | 109.5 |
C15—C16—H16 | 119.5 | H56A—C56—H56C | 109.5 |
C16—C17—C18 | 119.4 (3) | H56B—C56—H56C | 109.5 |
C16—C17—H17 | 120.3 | C54—C57—H57A | 109.5 |
C18—C17—H17 | 120.3 | C54—C57—H57B | 109.5 |
O3—C18—C17 | 124.2 (3) | H57A—C57—H57B | 109.5 |
O3—C18—C19 | 115.7 (3) | C54—C57—H57C | 109.5 |
C17—C18—C19 | 120.1 (3) | H57A—C57—H57C | 109.5 |
C20—C19—C18 | 120.2 (3) | H57B—C57—H57C | 109.5 |
C20—C19—H19 | 119.9 | Cl4A—C58—Cl3A | 115.0 (3) |
C18—C19—H19 | 119.9 | Cl4A—C58—H58A | 108.5 |
C19—C20—C15 | 120.6 (3) | Cl3A—C58—H58A | 108.5 |
C19—C20—H20 | 119.7 | Cl4A—C58—H58B | 108.5 |
C15—C20—H20 | 119.7 | Cl3A—C58—H58B | 108.5 |
O3—C21—H21A | 109.5 | H58A—C58—H58B | 107.5 |
O3—C21—H21B | 109.5 | Cl3B—C58A—Cl4B | 108.73 (13) |
H21A—C21—H21B | 109.5 | Cl3B—C58A—H58C | 109.9 |
O3—C21—H21C | 109.5 | Cl4B—C58A—H58C | 109.9 |
H21A—C21—H21C | 109.5 | Cl3B—C58A—H58D | 109.9 |
H21B—C21—H21C | 109.5 | Cl4B—C58A—H58D | 109.9 |
C23—C22—C27 | 118.1 (3) | H58C—C58A—H58D | 108.3 |
C23—C22—P1 | 119.3 (2) | Cl9A—C59—Cl9B | 114.3 (18) |
C27—C22—P1 | 122.6 (2) | Cl9A—C59—H59A | 108.7 |
C24—C23—C22 | 121.9 (2) | Cl9B—C59—H59A | 108.7 |
C24—C23—H23 | 119 | Cl9A—C59—H59B | 108.7 |
C22—C23—H23 | 119 | Cl9B—C59—H59B | 108.7 |
C25—C24—C23 | 119.4 (3) | H59A—C59—H59B | 107.6 |
C25—C24—H24 | 120.3 | C59—Cl9A—Cl6D | 159.1 (12) |
C23—C24—H24 | 120.3 | C59—Cl9A—Cl6A | 157.9 (12) |
O4—C25—C24 | 124.2 (3) | Cl6D—Cl9A—Cl6A | 2.9 (5) |
O4—C25—C26 | 116.2 (3) | Cl5A—C60A—Cl6A | 114.6 (11) |
C24—C25—C26 | 119.6 (3) | Cl5A—C60A—H60A | 108.6 |
C27—C26—C25 | 120.6 (3) | Cl6A—C60A—H60A | 108.6 |
C27—C26—H26 | 119.7 | Cl5A—C60A—H60B | 108.6 |
C25—C26—H26 | 119.7 | Cl6A—C60A—H60B | 108.6 |
C26—C27—C22 | 120.4 (3) | H60A—C60A—H60B | 107.6 |
C26—C27—H27 | 119.8 | C60A—Cl6A—Cl9A | 137.5 (8) |
C22—C27—H27 | 119.8 | Cl6B—C60B—Cl5B | 107.3 (14) |
O4—C28—H28A | 109.5 | Cl6B—C60B—H60C | 110.3 |
O4—C28—H28B | 109.5 | Cl5B—C60B—H60C | 110.3 |
H28A—C28—H28B | 109.5 | Cl6B—C60B—H60D | 110.3 |
O4—C28—H28C | 109.5 | Cl5B—C60B—H60D | 110.3 |
H28A—C28—H28C | 109.5 | H60C—C60B—H60D | 108.5 |
H28B—C28—H28C | 109.5 | Cl6C—C60C—Cl5C | 118.5 (14) |
C30—C29—C34 | 117.3 (3) | Cl6C—C60C—H60E | 107.7 |
C30—C29—P1 | 121.5 (2) | Cl5C—C60C—H60E | 107.7 |
C34—C29—P1 | 121.2 (2) | Cl6C—C60C—H60F | 107.7 |
C31—C30—C29 | 121.3 (3) | Cl5C—C60C—H60F | 107.7 |
C31—C30—H30 | 119.4 | H60E—C60C—H60F | 107.1 |
C29—C30—H30 | 119.4 | Cl5D—C60D—Cl6D | 112.0 (7) |
C32—C31—C30 | 120.2 (3) | Cl5D—C60D—H60G | 109.2 |
C32—C31—H31 | 119.9 | Cl6D—C60D—H60G | 109.2 |
C30—C31—H31 | 119.9 | Cl5D—C60D—H60H | 109.2 |
O5—C32—C33 | 124.0 (3) | Cl6D—C60D—H60H | 109.2 |
O5—C32—C31 | 116.1 (3) | H60G—C60D—H60H | 107.9 |
C33—C32—C31 | 119.8 (3) | C60D—Cl6D—Cl9A | 155.0 (7) |
C32—C33—C34 | 119.8 (3) | ||
C45—Co1—P1—C22 | 51.80 (12) | O3—C18—C19—C20 | 179.1 (3) |
C43—Co1—P1—C22 | −90.46 (12) | C17—C18—C19—C20 | −0.4 (4) |
C44—Co1—P1—C22 | 161.57 (12) | C18—C19—C20—C15 | 0.1 (4) |
C45—Co1—P1—C29 | −69.14 (13) | C16—C15—C20—C19 | −0.1 (4) |
C43—Co1—P1—C29 | 148.61 (13) | P2—C15—C20—C19 | −177.4 (2) |
C44—Co1—P1—C29 | 40.63 (12) | C29—P1—C22—C23 | 160.9 (2) |
C45—Co1—P1—C36 | 171.73 (14) | C36—P1—C22—C23 | −87.9 (2) |
C43—Co1—P1—C36 | 29.48 (14) | Co1—P1—C22—C23 | 36.7 (3) |
C44—Co1—P1—C36 | −78.50 (13) | C29—P1—C22—C27 | −20.2 (3) |
C45—Co1—P2—C15 | −45.19 (12) | C36—P1—C22—C27 | 91.0 (3) |
C43—Co1—P2—C15 | 97.06 (12) | Co1—P1—C22—C27 | −144.5 (3) |
C44—Co1—P2—C15 | −154.95 (11) | C27—C22—C23—C24 | −0.2 (5) |
C45—Co1—P2—C1 | −165.75 (13) | P1—C22—C23—C24 | 178.7 (2) |
C43—Co1—P2—C1 | −23.50 (13) | C22—C23—C24—C25 | 0.2 (5) |
C44—Co1—P2—C1 | 84.49 (12) | C28—O4—C25—C24 | −0.7 (5) |
C45—Co1—P2—C8 | 73.80 (13) | C28—O4—C25—C26 | −179.8 (4) |
C43—Co1—P2—C8 | −143.95 (13) | C23—C24—C25—O4 | −179.4 (3) |
C44—Co1—P2—C8 | −35.96 (12) | C23—C24—C25—C26 | −0.3 (5) |
C15—P2—C1—C6 | 9.9 (3) | O4—C25—C26—C27 | 179.5 (4) |
C8—P2—C1—C6 | −102.6 (2) | C24—C25—C26—C27 | 0.4 (6) |
Co1—P2—C1—C6 | 133.1 (2) | C25—C26—C27—C22 | −0.4 (6) |
C15—P2—C1—C2 | −170.4 (2) | C23—C22—C27—C26 | 0.3 (5) |
C8—P2—C1—C2 | 77.1 (2) | P1—C22—C27—C26 | −178.6 (3) |
Co1—P2—C1—C2 | −47.2 (2) | C22—P1—C29—C30 | 95.9 (3) |
C6—C1—C2—C3 | 0.6 (4) | C36—P1—C29—C30 | −16.4 (3) |
P2—C1—C2—C3 | −179.1 (2) | Co1—P1—C29—C30 | −141.0 (2) |
C1—C2—C3—C4 | 0.3 (5) | C22—P1—C29—C34 | −86.6 (3) |
C7—O1—C4—C5 | 0.8 (5) | C36—P1—C29—C34 | 161.0 (2) |
C7—O1—C4—C3 | 179.9 (4) | Co1—P1—C29—C34 | 36.5 (3) |
C2—C3—C4—O1 | 179.6 (3) | C34—C29—C30—C31 | −0.2 (5) |
C2—C3—C4—C5 | −1.3 (5) | P1—C29—C30—C31 | 177.3 (3) |
O1—C4—C5—C6 | −179.6 (3) | C29—C30—C31—C32 | 0.8 (6) |
C3—C4—C5—C6 | 1.4 (5) | C35—O5—C32—C33 | −5.1 (5) |
C2—C1—C6—C5 | −0.5 (4) | C35—O5—C32—C31 | 174.1 (4) |
P2—C1—C6—C5 | 179.2 (2) | C30—C31—C32—O5 | −179.3 (3) |
C4—C5—C6—C1 | −0.5 (5) | C30—C31—C32—C33 | 0.1 (6) |
C15—P2—C8—C13 | −106.3 (3) | O5—C32—C33—C34 | 177.9 (3) |
C1—P2—C8—C13 | 6.4 (3) | C31—C32—C33—C34 | −1.4 (5) |
Co1—P2—C8—C13 | 131.9 (2) | C32—C33—C34—C29 | 2.0 (5) |
C15—P2—C8—C9 | 76.0 (3) | C30—C29—C34—C33 | −1.1 (5) |
C1—P2—C8—C9 | −171.3 (2) | P1—C29—C34—C33 | −178.7 (3) |
Co1—P2—C8—C9 | −45.8 (3) | C22—P1—C36—C37 | 177.6 (3) |
C13—C8—C9—C10 | −0.3 (5) | C29—P1—C36—C37 | −69.1 (3) |
P2—C8—C9—C10 | 177.5 (3) | Co1—P1—C36—C37 | 54.8 (3) |
C8—C9—C10—C11 | −1.4 (5) | C22—P1—C36—C41 | −2.6 (3) |
C14—O2—C11—C12 | −171.2 (3) | C29—P1—C36—C41 | 110.6 (3) |
C14—O2—C11—C10 | 7.7 (5) | Co1—P1—C36—C41 | −125.4 (2) |
C9—C10—C11—O2 | −176.4 (3) | C41—C36—C37—C38 | −2.1 (5) |
C9—C10—C11—C12 | 2.5 (5) | P1—C36—C37—C38 | 177.7 (3) |
O2—C11—C12—C13 | 177.1 (3) | C36—C37—C38—C39 | 1.2 (6) |
C10—C11—C12—C13 | −1.8 (6) | C42—O6—C39—C40 | −1.2 (7) |
C9—C8—C13—C12 | 1.0 (5) | C42—O6—C39—C38 | −179.5 (5) |
P2—C8—C13—C12 | −176.7 (3) | C37—C38—C39—O6 | 179.5 (4) |
C11—C12—C13—C8 | 0.0 (6) | C37—C38—C39—C40 | 1.1 (6) |
C1—P2—C15—C20 | −99.9 (2) | O6—C39—C40—C41 | 179.3 (4) |
C8—P2—C15—C20 | 12.1 (3) | C38—C39—C40—C41 | −2.5 (6) |
Co1—P2—C15—C20 | 134.9 (2) | C37—C36—C41—C40 | 0.7 (5) |
C1—P2—C15—C16 | 82.8 (2) | P1—C36—C41—C40 | −179.1 (2) |
C8—P2—C15—C16 | −165.2 (2) | C39—C40—C41—C36 | 1.6 (5) |
Co1—P2—C15—C16 | −42.4 (2) | Cl9B—C59—Cl9A—Cl6D | −18 (5) |
C20—C15—C16—C17 | 0.4 (4) | Cl9B—C59—Cl9A—Cl6A | −11 (5) |
P2—C15—C16—C17 | 177.8 (2) | Cl5A—C60A—Cl6A—Cl9A | −1 (3) |
C15—C16—C17—C18 | −0.7 (4) | C59—Cl9A—Cl6A—C60A | −114 (4) |
C21—O3—C18—C17 | 4.3 (4) | Cl6D—Cl9A—Cl6A—C60A | 4 (13) |
C21—O3—C18—C19 | −175.1 (3) | Cl5D—C60D—Cl6D—Cl9A | −27 (2) |
C16—C17—C18—O3 | −178.7 (3) | C59—Cl9A—Cl6D—C60D | −80 (5) |
C16—C17—C18—C19 | 0.7 (4) | Cl6A—Cl9A—Cl6D—C60D | −148 (15) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Co(C5H9N)3(C21H21O3P)2]ClO4·2(CH2Cl2) | [Co(C5H9N)3(C21H21O3P)2](ClO4)2·2CH2Cl2 |
Mr | 1282.32 | 1381.77 |
Crystal system, space group | Hexagonal, P63/m | Monoclinic, P21/n |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 21.7568 (3), 21.7568 (3), 23.3983 (6) | 12.3461 (3), 19.7566 (5), 28.4452 (7) |
α, β, γ (°) | 90, 90, 120 | 90, 92.818 (2), 90 |
V (Å3) | 9591.9 (3) | 6929.9 (3) |
Z | 6 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.58 | 0.59 |
Crystal size (mm) | 0.38 × 0.38 × 0.1 | 0.43 × 0.31 × 0.22 |
Data collection | ||
Diffractometer | CCD area detector | CCD area detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.809, 0.944 | 0.787, 0.882 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 46534, 6456, 4167 | 93953, 16738, 11549 |
Rint | 0.058 | 0.056 |
(sin θ/λ)max (Å−1) | 0.617 | 0.661 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.152, 0.97 | 0.051, 0.146, 1.06 |
No. of reflections | 6456 | 16738 |
No. of parameters | 390 | 848 |
No. of restraints | 0 | 40 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0695P)2 + 16.3243P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0551P)2 + 6.8607P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.07, −0.58 | 0.55, −0.41 |
Computer programs: APEX2 (Bruker, 2005), SAINT-NT (Bruker, 2005), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Co1—C8i | 1.820 (4) | C30—N3 | 1.162 (6) |
Co2—C19ii | 1.834 (4) | N1—C9 | 1.455 (6) |
Co3—C30iii | 1.824 (5) | N2—C20 | 1.453 (6) |
P1—Co1 | 2.1814 (13) | N3—C31 | 1.449 (7) |
P2—Co2 | 2.1762 (12) | Cl1—O4 | 1.434 (5) |
P3—Co3 | 2.1774 (13) | Cl1—O5 | 1.426 (4) |
C8—N1 | 1.157 (6) | Cl1—O6 | 1.389 (4) |
C19—N2 | 1.158 (6) | ||
N1—C8—Co1 | 179.7 (4) | P1v—Co1—P1 | 180.0000 (10) |
N2—C19—Co2 | 179.2 (4) | P2—Co2—P2v | 180 |
N3—C30—Co3 | 178.6 (4) | P3v—Co3—P3 | 180 |
C8—N1—C9 | 179.7 (5) | C8—Co1—P1v | 90 |
C19—N2—C20 | 175.8 (4) | C19—Co2—P2 | 90 |
C30—N3—C31 | 178.4 (5) | C30—Co3—P3 | 90 |
C8—Co1—C8iv | 120.000 (2) | O5—Cl1—O4 | 109.8 (3) |
C19ii—Co2—C19 | 120.0000 (10) | O6—Cl1—O4 | 106.5 (2) |
C30—Co3—C30iii | 120.0000 (10) | O6—Cl1—O5 | 109.4 (2) |
Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −x+y, −x, z; (iii) −y+1, x−y+1, z; (iv) −y+1, x−y, z; (v) x, y, −z+3/2. |
Co1—C45 | 1.876 (3) | N3—C54 | 1.466 (3) |
Co1—C43 | 1.879 (3) | O7—Cl1 | 1.392 (3) |
Co1—C44 | 1.910 (3) | O8—Cl1 | 1.385 (3) |
Co1—P1 | 2.2515 (7) | O9—Cl1 | 1.416 (3) |
Co1—P2 | 2.2536 (7) | O10—Cl1 | 1.387 (3) |
C44—N1 | 1.148 (3) | O11—Cl2 | 1.380 (3) |
C45—N2 | 1.147 (3) | O12—Cl2 | 1.415 (3) |
C43—N3 | 1.142 (3) | O13—Cl2 | 1.412 (3) |
N1—C50 | 1.463 (3) | O14—Cl2 | 1.422 (3) |
N2—C46 | 1.467 (3) | ||
N1—C44—Co1 | 177.8 (2) | C45—Co1—P2 | 89.49 (8) |
N2—C45—Co1 | 170.8 (2) | P1—Co1—P2 | 177.84 (3) |
N3—C43—Co1 | 174.5 (3) | O7—Cl1—O9 | 111.4 (2) |
C43—N3—C54 | 177.7 (3) | O8—Cl1—O7 | 110.4 (2) |
C44—N1—C50 | 177.0 (3) | O8—Cl1—O9 | 110.3 (2) |
C45—N2—C46 | 178.0 (3) | O8—Cl1—O10 | 111.0 (3) |
C45—Co1—C43 | 142.25 (12) | O10—Cl1—O7 | 108.3 (3) |
C45—Co1—C44 | 109.77 (11) | O10—Cl1—O9 | 105.4 (2) |
C43—Co1—C44 | 107.97 (11) | O11—Cl2—O12 | 111.9 (3) |
C43—Co1—P1 | 90.57 (8) | O11—Cl2—O13 | 112.1 (3) |
C44—Co1—P1 | 90.19 (8) | O11—Cl2—O14 | 109.2 (2) |
C45—Co1—P1 | 88.37 (8) | O12—Cl2—O14 | 108.0 (2) |
C43—Co1—P2 | 91.31 (8) | O13—Cl2—O12 | 106.2 (2) |
C44—Co1—P2 | 90.25 (8) | O13—Cl2—O14 | 109.4 (2) |
Parameter | (I) | (III) | (IV) |
Co—C (Å) | 1.825 (6) | 1.78 (1) | 1.85 (1) |
1.81 (2) | 1.83 (1) | ||
C≡N (Å) | 1.159 (5) | 1.16 (2) | 1.17 (2) |
1.17 (2) | 1.14 (2) | ||
Co—P (Å) | 2.1784 (12) | 2.18 (1) | 2.137 (3) |
C—Co—C (°) | 120.0 (2) | 105.0 (5) | 115.7 (5) |
125.5 (7) | 122.2 (4) | ||
Co—C≡N (°) | 179.2 (1) | 176 (1) | 176 (1) |
177(1.5) | 180 | ||
178 (1) | |||
.C≡N—C (°) | 178.0 (1) | 171 (2) | 178 (1) |
172 (2) | 180 | ||
P—Co—P (°) | 180.00 (3) | 178.4 (2) | 179.7 (4) |
Identification of compounds: [Co(CNC6H4NO2-p)3{PhP(OEt)2}2]ClO4, (III), and [Co(CNC6H4F-p)3{P(OMe)3}2]BF4, (IV) |
Numerous tris(alkylisocyanide)bis(triarylphosphine)cobalt (I) perchlorate complexes, [Co(CNR)3(PR'3)2]ClO4, have been reported in the literature (Becker et al.,1986, 1991, 1995). Many, but not all, of these CoI complexes can be converted to the analogous five-coordinate CoII complexes, [Co(CNR)3(PR'3)2](ClO4)2, through oxidation with AgClO4 (Becker, 2000). Routine characterization has been reported for these complexes, but structural determinations are lacking. Coordination structures for both the CoI and CoII complexes are expected to be trigonal– bipyramidal. IR data for ν(–N≡C), in solution and solid state, suggest that the CoII complexes could have D3h symmetry for the CNR ligands (i.e. one band), while the CoI complexes may be distorted from idealized trigonal–bipyramidal coordination (i.e. two or three bands), but IR patterns are by no means conclusive for structural determination. There is disagreement in the literature over this assignment, however, particularly with respect to the interpretation of the quasi-reversible cyclic voltammograms (Hanzlik et al., 1980; Becker et al., 1995) which were later shown to be reversible (Ahmad et al., 2003).
A crystallographic investigation of these complexes seems merited for several reasons. Very few crystal structures are known for phosphine-substituted pentakis(organoisocyanide)cobalt(I) complexes, those few being with arylisocyanide, not alkylisocyanide, ligands, and, to our knowledge, no analogous structure for CoII has been reported. Five-coordination for both CoI and CoII complexes with identical ligands poses several questions: (i) are both coordination structures trigonal–bipyramidal, as usually assumed, and if so, (ii) are there any significant differences in coordination structure? Is one structure closer to idealized D3h Co site symmetry than the other, and if so, is it the CoI or the CoII complex? These questions can only be answered by a crystallographic study. [Co(CNCMe3)3{P(C6H4OMe-p)3}2]ClO4, (I), and [Co(CNCMe3)3{P(C6H4OMe-p)3}2](ClO4)2, (II), have been selected as an appropriate pair of complexes for this study.
Complex (I) is observed to crystallize in the hexagonal space group P63/m with six effectively equivalent molecules but three crystallographically independent structures in the unit cell. Where there is significant differences in bond lengths and angles quoted, the three independent values and/or average have been given. The molecular structure is shown in Figs. 1 and 2, with selected bond lengths and bond angles listed in Table 1. The site symmetry around the Co atom is effectively D3h (point group) symmetry. The entire Co(C≡ NC)3 moiety is planar with three equivalent Co—C bonds and C—Co—C bond angles of 120.000 (10)°, three almost equivalent C≡N bonds with Co—C≡ N bond angles close to the idealized 180.0° [averaging 179.16 (1)°] and three almost equivalent N—C bonds again with C≡N—C bond angles approaching 180° [averaging 177.97 (1)°]. This gives an effective σh through the entire Co(CNC)3 unit. The linear P—Co—P bonds are perpendicular to the CoC3 plane, forming the threefold rotation axis. Through the proper alignment of both the nine –CMe3 and six –C6H4OMe-p groups, the P1—Co1—P1 axis is also a crystallographic threefold rotation axis. The upper and lower P(C6H4OMe-p)3 rings are exactly eclipsed but are not properly 60° staggered (rather 43.8, 76.2° asymmetrically staggered) between the Co—C≡N bonds, preventing three σvs, and reducing the (point group) symmetry for the [Co(CNCMe3)3{P(C6H4OMe-p)3}2]+ cation overall to C3h. This is, nevertheless, still a very symmetrical ion.
The Co—P bond averaging 2.1783 (6) Å is shorter than that which is normally expected for a Co—P single bond [Cambridge Structural Database (CSD), Conquest 1.11, Allen, 2002], giving support for some degree of dπ→π* back-bonding, although less than the very short Co—P bond [i.e. 2.052 (5) Å] observed in HCo(PF3)4 (Frenz & Ibers, 1970). The averaged Co—C bond [1.826 (6) Å] is also quite short, supportive of the more extensive back-bonding expected to the organoisocyanide ligands. The perchlorate ion shows some distortion, with an average Cl—O bond length 1.416 (4) Å and average O—Cl—O bond angle 108.67 (5)°. There is no evidence for hydrogen bonding with either the ClO4- anion or the CH2Cl2 molecule.
Complex (II) is observed to crystallize in the monoclinic space group P21/n. The molecular structure is shown in Figs. 3 and 4, with selected bond lengths and bond angles listed in Table 2. The cation is best described as distorted trigonal–bipyramidal. The actual site symmetry around the Co atom is low, i.e. Cs. The CoC3 moiety appears to be approximately planar, in which case highest site symmetry is Cs, otherwise it is only C1. Three nonequivalent Co—C bonds form equatorial bond angles of 107.96 (11), 109.76 (10) and 142.27 (11)°, instead of the idealized 120.0°. The Co—C≡N bond angles [averaging 174.3 (2)°] and C≡N—C angles [averaging 177.5 (9)°], however, are reasonably close to linear. The C≡N bond lengths and N—C bond lengths appear normal for these bonds.
In structure (II) the averaged Co—P bond length of 2.2526 (7) Å is also rather short for a Co—P single bond, though not as shortened as seen for (I). Although the ionic radius for CoII is smaller than CoI, the Co2+ ion requires far less dπ→ π* electronic stabilization so the Co—P bond in (II) could be expected to be longer than in (I). The Co—C bond length is also shorter in (I) compared to (II), i.e. 1.826 (6) versus 1.888 (2) Å (averaged), while the C≡N bond lengths show slight increase [i.e. 1.159 (5) versus 1.145 (9) Å (averaged)] as would also be expected. A general insensitivity of the C≡N bond length to apparent bond order, however, has been observed (Cotton et al., 1965). The two perchlorate anions are nonequivalent and somewhat distorted. The averaged Cl—O bond length is 1.394 (8) Å in one, 1.406 (3) Å, in the other, but the averaged O—Cl—O bond angles are 109.4 (9) and 109.4 (8)°, respectively. Again there is no evidence for hydrogen bonding with either the ClO4- anions or the CH2Cl2 molecules in (II) as well as in (I). This may explain why the solvated CH2Cl2 is normally so readily lost shortly after preparation of these complexes.
In this pair of complexes, then, the IR data notwithstanding, the five-coordinate CoI complex, (I), has been shown to have rigorous trigonal–bipyramidal Co coordination (D3h) while the analogous five-coordinate CoII complex, (II), has distorted trigonal–bipyramidal coordination (Cs). Two disubstituted arylisocyanide CoI complexes from the literature show similarity with (I): [Co(CNC6H4NO2-p)3{PhP(OEt)2}2]ClO4 (III) (Graziani et al., 1976), and [Co(CNC6H4F-p)3{P(OCH3)3}2]BF4 (IV) (Loghry et al., 1978). Structural comparisons with these complexes are shown in Table 3. Although (III) and (IV) are clearly trigonal–bipyramidal structures, they do not exhibit the high level of coordination symmetry around the Co atom shown by (I). No analogous structures for disubstituted five-coordinate CoII organoisocyanide complexes could be found in the literature.