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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010800992X/sq3135sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010800992X/sq3135Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010800992X/sq3135IIsup3.hkl
Contains datablock II

CCDC references: 690179; 690180

Comment top

[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 ππ 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 ππ 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 ππ 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 ππ 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.

Related literature top

For related literature, see: Alcock et al. (2000); Chamchoumis & Potvin (1998); Constable et al. (1990); Figgis et al. (1983); Galet et al. (2006); Gaspar et al. (2001); Hayami et al. (2005); Judge & Baker (1967); Kremer et al. (1982); Mutai et al. (2001); Scudder et al. (1999); Whittle et al. (1998); Yutaka et al. (2003).

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structures of the cobalt complexes in (I) and (II), showing the atom-labeling schemes and 50% probability displacement ellipsoids. For clarity, H atoms, BF4- anions and CH3NO2 molecules are not shown.
[Figure 2] Fig. 2. The intermolecular interaction scheme of the [Co(cptpy)2]2+ complexes in (I). The ππ interactions are indicated by double-headed arrows and C—H···π interactions are indicated by dashed lines.
[Figure 3] Fig. 3. Packing of the [Co(cptpy)3]3+ complexes in (II). Double-headed arrows indicate ππ interactions.
(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·CH3NO2F(000) = 1956.00
Mr = 962.34Dx = 1.552 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71070 Å
Hall symbol: C -2ycCell parameters from 4860 reflections
a = 13.304 (13) Åθ = 3.1–27.5°
b = 12.125 (12) ŵ = 0.51 mm1
c = 27.30 (3) ÅT = 120 K
β = 110.761 (12)°Block, red
V = 4118 (7) Å30.20 × 0.20 × 0.10 mm
Z = 4
Data collection top
Rigaku Mercury
diffractometer
Rint = 0.056
Detector resolution: 7.31 pixels mm-1θmax = 27.5°
ω scansh = 1117
23489 measured reflectionsk = 1515
8003 independent reflectionsl = 3535
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) = 0.169Δρmax = 1.13 e Å3
S = 1.04Δρmin = 0.43 e Å3
8003 reflectionsAbsolute structure: Flack (1983), 3285 Friedel pairs
632 parametersAbsolute structure parameter: 0.026 (19)
H-atom parameters constrained
Crystal data top
[Co(C22H14N4)2](BF4)2·CH3NO2V = 4118 (7) Å3
Mr = 962.34Z = 4
Monoclinic, CcMo Kα radiation
a = 13.304 (13) ŵ = 0.51 mm1
b = 12.125 (12) ÅT = 120 K
c = 27.30 (3) Å0.20 × 0.20 × 0.10 mm
β = 110.761 (12)°
Data collection top
Rigaku Mercury
diffractometer
6271 reflections with F2 > 2σ(F2)
23489 measured reflectionsRint = 0.056
8003 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.070H-atom parameters constrained
wR(F2) = 0.169Δρmax = 1.13 e Å3
S = 1.04Δρmin = 0.43 e Å3
8003 reflectionsAbsolute structure: Flack (1983), 3285 Friedel pairs
632 parametersAbsolute 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
xyzUiso*/UeqOcc. (<1)
Co10.91661 (6)0.24303 (5)0.36935 (3)0.03026 (16)
F10.9936 (2)0.0648 (2)0.58424 (13)0.0515 (8)
F20.9909 (4)0.0583 (4)0.64513 (18)0.0949 (15)
F30.8384 (4)0.0294 (4)0.5993 (3)0.118 (2)
F40.9105 (4)0.1021 (3)0.5635 (2)0.0883 (15)
F50.8793 (9)0.2208 (19)0.7061 (3)0.120 (7)0.50
F60.8582 (8)0.3335 (12)0.7600 (9)0.109 (6)0.50
F70.8242 (11)0.1657 (17)0.7668 (9)0.169 (11)0.50
F80.7105 (3)0.2575 (3)0.70447 (15)0.0601 (11)
F90.8388 (11)0.245 (2)0.7844 (3)0.165 (11)0.50
F100.8748 (15)0.307 (2)0.7225 (13)0.254 (18)0.50
F110.8421 (11)0.1373 (13)0.7286 (12)0.187 (12)0.50
O10.6148 (6)0.2537 (4)0.5200 (2)0.080 (2)
O20.7191 (4)0.3928 (4)0.5257 (2)0.0738 (14)
N10.9913 (3)0.4008 (3)0.38735 (18)0.0407 (10)
N21.0126 (4)0.2289 (3)0.4447 (2)0.0342 (11)
N30.8744 (3)0.0838 (3)0.39044 (16)0.0316 (9)
N41.0294 (3)0.1764 (3)0.33722 (16)0.0315 (9)
N50.8273 (3)0.2282 (3)0.29211 (19)0.0296 (10)
N60.7655 (3)0.3110 (3)0.36453 (17)0.0339 (9)
N71.5792 (4)0.0508 (5)0.7683 (2)0.0658 (16)
N80.3523 (4)0.0829 (4)0.02878 (19)0.0515 (13)
N90.6898 (5)0.3110 (4)0.5441 (2)0.0553 (13)
C11.0849 (4)0.3074 (4)0.4682 (2)0.0352 (11)
C21.1641 (4)0.2917 (4)0.5160 (2)0.0339 (11)
C31.1691 (4)0.1909 (4)0.5415 (2)0.0375 (12)
C41.0928 (4)0.1114 (4)0.5185 (2)0.0342 (11)
C51.0162 (4)0.1298 (4)0.46995 (19)0.0312 (10)
C61.0693 (4)0.4100 (4)0.4368 (2)0.0337 (11)
C71.1244 (4)0.5069 (4)0.4540 (2)0.0418 (13)
C81.1012 (5)0.5964 (5)0.4211 (2)0.0547 (16)
C91.0240 (5)0.5896 (4)0.3723 (2)0.0503 (15)
C100.9718 (5)0.4901 (5)0.3572 (2)0.0498 (14)
C110.9350 (4)0.0503 (3)0.4394 (2)0.0319 (11)
C120.9217 (4)0.0555 (4)0.4572 (2)0.0349 (11)
C130.8477 (4)0.1260 (4)0.4249 (2)0.0373 (12)
C140.7853 (4)0.0922 (4)0.3754 (2)0.0380 (13)
C150.7986 (4)0.0149 (4)0.3599 (2)0.0385 (12)
C161.2574 (4)0.1660 (4)0.5929 (2)0.0338 (11)
C171.3586 (4)0.2151 (4)0.6048 (2)0.0390 (12)
C181.4413 (4)0.1884 (5)0.6502 (2)0.0464 (14)
C191.4244 (4)0.1107 (5)0.6848 (2)0.0398 (13)
C201.3238 (4)0.0641 (5)0.6739 (2)0.0419 (13)
C211.2395 (4)0.0924 (4)0.6290 (2)0.0436 (13)
C221.5122 (5)0.0794 (5)0.7316 (2)0.0502 (15)
C230.8695 (4)0.1703 (4)0.2618 (2)0.0339 (11)
C240.8056 (4)0.1311 (4)0.2130 (2)0.0321 (11)
C250.6949 (4)0.1545 (4)0.1951 (2)0.0343 (11)
C260.6547 (4)0.2158 (4)0.2270 (2)0.0370 (12)
C270.7222 (4)0.2488 (4)0.27568 (19)0.0311 (11)
C280.9870 (4)0.1495 (4)0.2866 (2)0.0331 (11)
C291.0487 (4)0.1083 (4)0.2587 (2)0.0340 (11)
C301.1589 (4)0.0954 (4)0.2853 (2)0.0405 (12)
C311.2019 (4)0.1214 (4)0.3372 (2)0.0389 (12)
C321.1352 (4)0.1598 (4)0.3625 (2)0.0350 (11)
C330.6866 (4)0.3030 (3)0.3160 (2)0.0316 (10)
C340.5824 (4)0.3395 (4)0.3062 (2)0.0390 (12)
C350.5577 (4)0.3833 (4)0.3472 (2)0.0408 (13)
C360.6365 (4)0.3917 (4)0.3964 (2)0.0414 (13)
C370.7396 (4)0.3559 (4)0.4027 (2)0.0390 (12)
C380.6209 (4)0.1063 (4)0.14486 (19)0.0327 (11)
C390.6397 (5)0.0003 (4)0.1313 (2)0.0431 (13)
C400.5685 (5)0.0474 (4)0.0862 (2)0.0482 (14)
C410.4841 (4)0.0140 (4)0.0536 (2)0.0384 (12)
C420.4685 (5)0.1231 (4)0.0653 (2)0.0416 (13)
C430.5382 (4)0.1677 (5)0.1114 (2)0.0433 (13)
C440.4099 (4)0.0390 (4)0.0062 (2)0.0424 (13)
C450.7466 (6)0.2862 (6)0.6000 (2)0.0622 (18)
B10.9282 (5)0.0141 (5)0.5972 (2)0.0426 (15)
B20.8179 (5)0.2396 (6)0.7338 (2)0.0449 (16)
H21.21470.34830.53160.041*
H41.09330.04390.53620.041*
H71.17770.51170.48800.050*
H81.13920.66360.43230.066*
H91.00670.65140.34940.060*
H100.91850.48510.32310.060*
H120.96420.07790.49170.042*
H130.83950.19810.43650.045*
H140.73410.14060.35230.046*
H150.75240.04010.32650.046*
H171.37010.26710.58130.047*
H181.50970.22210.65830.056*
H201.31270.01210.69750.050*
H211.16990.06260.62250.052*
H240.83580.08950.19220.039*
H260.58070.23490.21520.044*
H291.01660.08970.22260.041*
H301.20360.06860.26750.049*
H311.27690.11330.35580.047*
H321.16510.17500.39900.042*
H340.52930.33450.27210.047*
H350.48660.40760.34170.049*
H360.62070.42120.42510.050*
H370.79430.36390.43610.047*
H390.70070.04030.15290.052*
H400.57780.12180.07770.058*
H420.41140.16570.04220.050*
H430.52880.24190.12010.052*
H45A0.71450.32880.62120.075*
H45B0.82260.30590.60980.075*
H45C0.74030.20720.60620.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0292 (3)0.0317 (3)0.0299 (2)0.0003 (3)0.0106 (2)0.0018 (3)
F10.059 (2)0.0513 (19)0.0524 (19)0.0036 (16)0.0294 (17)0.0012 (16)
F20.110 (3)0.101 (3)0.070 (2)0.004 (3)0.028 (2)0.016 (2)
F30.094 (3)0.070 (3)0.225 (6)0.019 (2)0.099 (4)0.020 (3)
F40.131 (4)0.057 (2)0.105 (3)0.017 (2)0.077 (3)0.013 (2)
F50.039 (6)0.29 (2)0.034 (4)0.065 (10)0.009 (3)0.035 (8)
F60.030 (4)0.100 (9)0.194 (17)0.016 (5)0.036 (8)0.101 (11)
F70.063 (7)0.179 (16)0.25 (2)0.022 (11)0.040 (13)0.202 (18)
F80.036 (2)0.097 (3)0.042 (2)0.0088 (18)0.0060 (16)0.0158 (19)
F90.056 (8)0.41 (3)0.022 (4)0.060 (16)0.003 (4)0.028 (9)
F100.091 (15)0.29 (2)0.29 (3)0.091 (19)0.047 (16)0.24 (2)
F110.051 (8)0.095 (9)0.34 (2)0.021 (6)0.025 (12)0.134 (14)
O10.116 (5)0.056 (3)0.052 (3)0.016 (3)0.007 (3)0.011 (2)
O20.070 (3)0.073 (3)0.086 (3)0.017 (2)0.037 (2)0.030 (2)
N10.038 (2)0.042 (2)0.045 (2)0.001 (2)0.019 (2)0.003 (2)
N20.046 (3)0.025 (2)0.038 (2)0.001 (2)0.023 (2)0.0021 (19)
N30.027 (2)0.033 (2)0.032 (2)0.0019 (18)0.0057 (18)0.0019 (18)
N40.032 (2)0.029 (2)0.033 (2)0.0050 (18)0.0109 (18)0.0018 (18)
N50.024 (2)0.032 (2)0.033 (2)0.0034 (19)0.011 (2)0.0045 (19)
N60.036 (2)0.029 (2)0.041 (2)0.0042 (19)0.020 (2)0.0024 (19)
N70.042 (3)0.101 (4)0.051 (3)0.004 (3)0.012 (2)0.004 (3)
N80.057 (3)0.044 (2)0.040 (2)0.003 (2)0.000 (2)0.009 (2)
N90.068 (3)0.053 (3)0.049 (3)0.011 (3)0.025 (2)0.015 (2)
C10.040 (3)0.030 (2)0.045 (3)0.005 (2)0.028 (2)0.009 (2)
C20.033 (2)0.030 (2)0.039 (2)0.009 (2)0.012 (2)0.008 (2)
C30.025 (2)0.043 (3)0.041 (2)0.001 (2)0.007 (2)0.005 (2)
C40.036 (3)0.033 (2)0.036 (2)0.002 (2)0.015 (2)0.005 (2)
C50.033 (2)0.028 (2)0.033 (2)0.001 (2)0.012 (2)0.002 (2)
C60.030 (2)0.030 (2)0.051 (3)0.002 (2)0.026 (2)0.000 (2)
C70.047 (3)0.029 (2)0.058 (3)0.009 (2)0.028 (2)0.005 (2)
C80.069 (4)0.042 (3)0.069 (4)0.008 (3)0.043 (3)0.003 (3)
C90.058 (4)0.030 (2)0.075 (4)0.004 (2)0.037 (3)0.014 (3)
C100.050 (3)0.046 (3)0.061 (3)0.015 (2)0.029 (3)0.019 (3)
C110.033 (2)0.029 (2)0.039 (2)0.005 (2)0.019 (2)0.003 (2)
C120.039 (3)0.031 (2)0.035 (2)0.002 (2)0.013 (2)0.005 (2)
C130.036 (3)0.035 (2)0.041 (2)0.004 (2)0.014 (2)0.011 (2)
C140.044 (3)0.031 (2)0.037 (3)0.004 (2)0.011 (2)0.002 (2)
C150.037 (3)0.037 (2)0.040 (2)0.001 (2)0.011 (2)0.007 (2)
C160.032 (2)0.034 (2)0.037 (2)0.001 (2)0.014 (2)0.009 (2)
C170.043 (3)0.041 (2)0.035 (2)0.007 (2)0.017 (2)0.005 (2)
C180.038 (3)0.058 (3)0.045 (3)0.009 (2)0.018 (2)0.016 (2)
C190.036 (3)0.055 (3)0.020 (2)0.002 (2)0.000 (2)0.004 (2)
C200.040 (3)0.051 (3)0.031 (2)0.006 (2)0.009 (2)0.004 (2)
C210.043 (3)0.046 (3)0.045 (3)0.010 (2)0.018 (2)0.005 (2)
C220.044 (3)0.057 (3)0.047 (3)0.002 (3)0.012 (3)0.004 (2)
C230.037 (2)0.029 (2)0.037 (2)0.002 (2)0.013 (2)0.002 (2)
C240.034 (2)0.030 (2)0.039 (2)0.002 (2)0.021 (2)0.004 (2)
C250.036 (3)0.032 (2)0.031 (2)0.010 (2)0.007 (2)0.005 (2)
C260.035 (3)0.037 (2)0.034 (2)0.002 (2)0.007 (2)0.000 (2)
C270.033 (2)0.032 (2)0.030 (2)0.004 (2)0.014 (2)0.011 (2)
C280.031 (2)0.029 (2)0.035 (2)0.003 (2)0.005 (2)0.004 (2)
C290.037 (3)0.037 (2)0.032 (2)0.005 (2)0.016 (2)0.010 (2)
C300.043 (3)0.041 (2)0.045 (3)0.006 (2)0.025 (2)0.008 (2)
C310.032 (3)0.038 (2)0.047 (3)0.002 (2)0.013 (2)0.001 (2)
C320.033 (2)0.029 (2)0.041 (2)0.006 (2)0.011 (2)0.002 (2)
C330.030 (2)0.024 (2)0.039 (2)0.001 (2)0.011 (2)0.003 (2)
C340.037 (3)0.036 (2)0.047 (2)0.003 (2)0.018 (2)0.003 (2)
C350.037 (3)0.029 (2)0.061 (3)0.001 (2)0.023 (2)0.002 (2)
C360.046 (3)0.035 (2)0.050 (3)0.003 (2)0.026 (3)0.004 (2)
C370.049 (3)0.026 (2)0.044 (3)0.007 (2)0.019 (2)0.004 (2)
C380.034 (2)0.035 (2)0.028 (2)0.004 (2)0.010 (2)0.004 (2)
C390.048 (3)0.043 (3)0.034 (2)0.004 (2)0.009 (2)0.002 (2)
C400.061 (4)0.037 (3)0.046 (3)0.001 (2)0.019 (3)0.002 (2)
C410.048 (3)0.034 (2)0.026 (2)0.008 (2)0.005 (2)0.001 (2)
C420.050 (3)0.041 (3)0.031 (2)0.004 (2)0.011 (2)0.001 (2)
C430.037 (3)0.048 (3)0.042 (3)0.003 (2)0.011 (2)0.011 (2)
C440.049 (3)0.042 (3)0.038 (3)0.004 (2)0.017 (2)0.002 (2)
C450.070 (4)0.075 (4)0.042 (3)0.002 (3)0.021 (3)0.003 (3)
B10.047 (3)0.048 (3)0.038 (3)0.019 (3)0.023 (2)0.006 (2)
B20.032 (3)0.059 (4)0.039 (3)0.006 (3)0.007 (2)0.015 (3)
Geometric parameters (Å, º) top
Co1—N12.132 (4)C18—C191.408 (9)
Co1—N22.007 (4)C19—C201.385 (8)
Co1—N32.146 (4)C19—C221.442 (7)
Co1—N42.147 (5)C20—C211.378 (7)
Co1—N52.028 (4)C23—C241.385 (6)
Co1—N62.133 (4)C23—C281.488 (7)
F1—B11.420 (8)C24—C251.406 (7)
F2—B11.385 (7)C25—C261.388 (8)
F3—B11.326 (10)C25—C381.495 (6)
F4—B11.375 (8)C26—C271.373 (6)
F5—F101.15 (4)C27—C331.494 (8)
F5—F111.37 (3)C28—C291.396 (8)
F5—B21.317 (15)C29—C301.397 (7)
F6—F91.33 (3)C30—C311.362 (7)
F6—F101.17 (4)C31—C321.385 (9)
F6—B21.350 (17)C33—C341.389 (7)
F7—F91.06 (3)C34—C351.380 (9)
F7—F111.20 (4)C35—C361.384 (7)
F7—B21.25 (2)C36—C371.390 (9)
F8—B21.385 (7)C38—C391.391 (8)
F9—B21.310 (12)C38—C431.374 (7)
F10—B21.23 (3)C39—C401.384 (7)
F11—B21.303 (19)C40—C411.378 (7)
O1—N91.204 (8)C41—C421.394 (8)
O2—N91.235 (8)C41—C441.467 (7)
N1—C61.384 (6)C42—C431.381 (7)
N1—C101.328 (7)C2—H20.950
N2—C11.343 (6)C4—H40.950
N2—C51.378 (6)C7—H70.950
N3—C111.355 (5)C8—H80.950
N3—C151.347 (6)C9—H90.950
N4—C281.334 (6)C10—H100.950
N4—C321.344 (6)C12—H120.950
N5—C231.350 (8)C13—H130.950
N5—C271.332 (7)C14—H140.950
N6—C331.372 (5)C15—H150.950
N6—C371.324 (8)C17—H170.950
N7—C221.134 (7)C18—H180.950
N8—C441.125 (6)C20—H200.950
N9—C451.474 (8)C21—H210.950
C1—C21.370 (6)C24—H240.950
C1—C61.484 (7)C26—H260.950
C2—C31.396 (8)C29—H290.950
C3—C41.379 (7)C30—H300.950
C3—C161.507 (6)C31—H310.950
C4—C51.374 (6)C32—H320.950
C5—C111.467 (6)C34—H340.950
C6—C71.376 (7)C35—H350.950
C7—C81.372 (8)C36—H360.950
C8—C91.367 (8)C37—H370.950
C9—C101.380 (8)C39—H390.950
C11—C121.406 (7)C40—H400.950
C12—C131.365 (6)C42—H420.950
C13—C141.373 (6)C43—H430.950
C14—C151.397 (7)C45—H45A0.980
C16—C171.401 (8)C45—H45B0.980
C16—C211.412 (8)C45—H45C0.980
C17—C181.374 (6)
N1—Co1—N276.41 (17)N6—C33—C27114.2 (4)
N1—Co1—N3152.98 (16)N6—C33—C34122.1 (5)
N1—Co1—N495.49 (19)C27—C33—C34123.7 (4)
N1—Co1—N5111.88 (17)C33—C34—C35118.5 (4)
N1—Co1—N691.12 (18)C34—C35—C36119.9 (5)
N2—Co1—N377.31 (16)C35—C36—C37118.1 (6)
N2—Co1—N495.9 (2)N6—C37—C36123.6 (4)
N2—Co1—N5169.48 (18)C25—C38—C39119.1 (4)
N2—Co1—N6109.9 (2)C25—C38—C43120.7 (4)
N3—Co1—N493.34 (17)C39—C38—C43120.2 (4)
N3—Co1—N594.96 (16)C38—C39—C40119.3 (5)
N3—Co1—N691.93 (17)C39—C40—C41119.7 (5)
N4—Co1—N577.21 (18)C40—C41—C42121.2 (4)
N4—Co1—N6154.20 (15)C40—C41—C44118.2 (5)
N5—Co1—N677.19 (19)C42—C41—C44120.6 (4)
F10—F5—F11115 (2)C41—C42—C43118.4 (4)
F10—F5—B259.3 (17)C38—C43—C42120.9 (5)
F11—F5—B258.1 (12)N8—C44—C41177.1 (6)
F9—F6—F10110 (2)F1—B1—F2106.2 (5)
F9—F6—B258.4 (10)F1—B1—F3112.6 (5)
F10—F6—B257.8 (17)F1—B1—F4109.3 (6)
F9—F7—F11126 (2)F2—B1—F3111.3 (7)
F9—F7—B268.4 (15)F2—B1—F4103.6 (5)
F11—F7—B264.2 (16)F3—B1—F4113.2 (5)
F6—F9—F7122 (2)F5—B2—F6103.8 (13)
F6—F9—B261.4 (12)F5—B2—F7113.1 (14)
F7—F9—B262.6 (16)F5—B2—F8114.7 (6)
F5—F10—F6130 (3)F5—B2—F9132.2 (9)
F5—F10—B267.2 (18)F5—B2—F1053.5 (19)
F6—F10—B269 (2)F5—B2—F1162.9 (17)
F5—F11—F7113.2 (18)F6—B2—F7108.2 (14)
F5—F11—B259.1 (11)F6—B2—F8108.0 (7)
F7—F11—B259.8 (15)F6—B2—F960.2 (16)
Co1—N1—C6115.1 (3)F6—B2—F1053.6 (19)
Co1—N1—C10128.0 (3)F6—B2—F11142.6 (10)
C6—N1—C10116.9 (4)F7—B2—F8108.7 (8)
Co1—N2—C1121.1 (3)F7—B2—F949.1 (17)
Co1—N2—C5118.9 (3)F7—B2—F10140.3 (14)
C1—N2—C5119.2 (4)F7—B2—F1155.9 (19)
Co1—N3—C11114.4 (3)F8—B2—F9113.1 (9)
Co1—N3—C15127.0 (3)F8—B2—F10110.6 (12)
C11—N3—C15118.5 (4)F8—B2—F11109.3 (8)
Co1—N4—C28114.5 (3)F9—B2—F10108.2 (19)
Co1—N4—C32127.0 (3)F9—B2—F11101 (2)
C28—N4—C32118.5 (5)F10—B2—F11114.1 (19)
Co1—N5—C23117.7 (3)C1—C2—H2120.6
Co1—N5—C27119.4 (4)C3—C2—H2120.6
C23—N5—C27120.4 (4)C3—C4—H4120.0
Co1—N6—C33114.4 (3)C5—C4—H4120.0
Co1—N6—C37127.8 (3)C6—C7—H7120.6
C33—N6—C37117.8 (4)C8—C7—H7120.6
O1—N9—O2124.2 (5)C7—C8—H8119.8
O1—N9—C45118.0 (6)C9—C8—H8119.8
O2—N9—C45117.7 (5)C8—C9—H9121.0
N2—C1—C2122.4 (4)C10—C9—H9121.0
N2—C1—C6112.9 (4)N1—C10—H10118.0
C2—C1—C6124.8 (4)C9—C10—H10118.0
C1—C2—C3118.8 (4)C11—C12—H12120.1
C2—C3—C4119.2 (4)C13—C12—H12120.1
C2—C3—C16121.5 (4)C12—C13—H13120.2
C4—C3—C16119.3 (4)C14—C13—H13120.1
C3—C4—C5120.0 (4)C13—C14—H14120.7
N2—C5—C4120.4 (4)C15—C14—H14120.7
N2—C5—C11113.6 (3)N3—C15—H15118.8
C4—C5—C11126.0 (4)C14—C15—H15118.8
N1—C6—C1113.5 (4)C16—C17—H17119.8
N1—C6—C7121.7 (4)C18—C17—H17119.8
C1—C6—C7124.8 (4)C17—C18—H18120.1
C6—C7—C8118.9 (5)C19—C18—H18120.1
C7—C8—C9120.5 (5)C19—C20—H20119.7
C8—C9—C10117.9 (5)C21—C20—H20119.7
N1—C10—C9124.1 (5)C16—C21—H21120.2
N3—C11—C5115.2 (4)C20—C21—H21120.2
N3—C11—C12120.8 (4)C23—C24—H24120.8
C5—C11—C12124.0 (4)C25—C24—H24120.8
C11—C12—C13119.8 (4)C25—C26—H26120.1
C12—C13—C14119.7 (5)C27—C26—H26120.1
C13—C14—C15118.6 (4)C28—C29—H29121.1
N3—C15—C14122.4 (4)C30—C29—H29121.1
C3—C16—C17119.9 (5)C29—C30—H30120.3
C3—C16—C21120.5 (4)C31—C30—H30120.3
C17—C16—C21119.5 (4)C30—C31—H31120.4
C16—C17—C18120.4 (5)C32—C31—H31120.4
C17—C18—C19119.7 (5)N4—C32—H32118.9
C18—C19—C20120.1 (4)C31—C32—H32118.9
C18—C19—C22119.8 (5)C33—C34—H34120.8
C20—C19—C22120.1 (5)C35—C34—H34120.8
C19—C20—C21120.6 (5)C34—C35—H35120.0
C16—C21—C20119.5 (5)C36—C35—H35120.0
N7—C22—C19177.2 (7)C35—C36—H36121.0
N5—C23—C24121.3 (5)C37—C36—H36120.9
N5—C23—C28114.1 (4)N6—C37—H37118.2
C24—C23—C28124.6 (5)C36—C37—H37118.2
C23—C24—C25118.4 (5)C38—C39—H39120.3
C24—C25—C26118.6 (4)C40—C39—H39120.3
C24—C25—C38120.5 (5)C39—C40—H40120.1
C26—C25—C38120.7 (5)C41—C40—H40120.1
C25—C26—C27119.8 (5)C41—C42—H42120.8
N5—C27—C26121.3 (5)C43—C42—H42120.8
N5—C27—C33113.8 (4)C38—C43—H43119.5
C26—C27—C33124.8 (5)C42—C43—H43119.5
N4—C28—C23114.9 (5)N9—C45—H45A109.5
N4—C28—C29122.6 (4)N9—C45—H45B109.5
C23—C28—C29122.5 (4)N9—C45—H45C109.5
C28—C29—C30117.9 (4)H45A—C45—H45B109.5
C29—C30—C31119.5 (6)H45A—C45—H45C109.5
C30—C31—C32119.3 (5)H45B—C45—H45C109.5
N4—C32—C31122.2 (4)
N1—Co1—N2—C19.5 (5)F5—F11—B2—F7151.5 (12)
N1—Co1—N2—C5179.0 (5)F5—F11—B2—F8108.5 (8)
N2—Co1—N1—C65.0 (4)F5—F11—B2—F9131.9 (11)
N2—Co1—N1—C10174.7 (6)F5—F11—B2—F1015.9 (18)
N1—Co1—N3—C1118.5 (6)F7—F11—B2—F5151.5 (12)
N1—Co1—N3—C15164.1 (4)F7—F11—B2—F675 (2)
N3—Co1—N1—C618.7 (7)F7—F11—B2—F8100.0 (12)
N3—Co1—N1—C10161.0 (5)F7—F11—B2—F919.6 (12)
N1—Co1—N4—C28116.9 (3)F7—F11—B2—F10135.6 (18)
N1—Co1—N4—C3263.1 (4)Co1—N1—C6—C10.6 (6)
N4—Co1—N1—C689.8 (4)Co1—N1—C6—C7180.0 (4)
N4—Co1—N1—C1090.5 (6)Co1—N1—C10—C9179.6 (6)
N1—Co1—N5—C23102.2 (4)C6—N1—C10—C90.0 (9)
N1—Co1—N5—C2795.3 (4)C10—N1—C6—C1179.1 (6)
N5—Co1—N1—C6168.2 (4)C10—N1—C6—C70.3 (8)
N5—Co1—N1—C1012.1 (6)Co1—N2—C1—C2168.0 (5)
N1—Co1—N6—C33117.0 (3)Co1—N2—C1—C611.8 (7)
N1—Co1—N6—C3765.2 (4)Co1—N2—C5—C4169.6 (4)
N6—Co1—N1—C6115.1 (4)Co1—N2—C5—C118.4 (7)
N6—Co1—N1—C1064.5 (6)C1—N2—C5—C40.1 (7)
N2—Co1—N3—C114.9 (4)C1—N2—C5—C11178.2 (5)
N2—Co1—N3—C15177.8 (5)C5—N2—C1—C21.6 (10)
N3—Co1—N2—C1176.9 (5)C5—N2—C1—C6178.7 (5)
N3—Co1—N2—C57.3 (4)Co1—N3—C11—C52.0 (6)
N2—Co1—N4—C28166.3 (3)Co1—N3—C11—C12175.4 (4)
N2—Co1—N4—C3213.8 (4)Co1—N3—C15—C14172.8 (4)
N4—Co1—N2—C184.8 (5)C11—N3—C15—C144.5 (9)
N4—Co1—N2—C584.8 (5)C15—N3—C11—C5179.6 (5)
N2—Co1—N5—C2338.7 (15)C15—N3—C11—C122.2 (8)
N2—Co1—N5—C27123.8 (12)Co1—N4—C28—C230.2 (5)
N5—Co1—N2—C1133.5 (11)Co1—N4—C28—C29177.9 (3)
N5—Co1—N2—C536.1 (16)Co1—N4—C32—C31176.6 (3)
N2—Co1—N6—C33167.1 (3)C28—N4—C32—C313.4 (7)
N2—Co1—N6—C3710.7 (5)C32—N4—C28—C23179.9 (3)
N6—Co1—N2—C195.7 (5)C32—N4—C28—C292.1 (7)
N6—Co1—N2—C594.7 (4)Co1—N5—C23—C24162.6 (4)
N3—Co1—N4—C2888.7 (3)Co1—N5—C23—C2814.9 (6)
N3—Co1—N4—C3291.4 (4)Co1—N5—C27—C26164.6 (4)
N4—Co1—N3—C1190.5 (4)Co1—N5—C27—C3311.7 (5)
N4—Co1—N3—C1586.9 (4)C23—N5—C27—C262.6 (8)
N3—Co1—N5—C2381.0 (4)C23—N5—C27—C33173.7 (4)
N3—Co1—N5—C2781.6 (3)C27—N5—C23—C240.3 (6)
N5—Co1—N3—C11167.9 (4)C27—N5—C23—C28177.2 (4)
N5—Co1—N3—C159.5 (5)Co1—N6—C33—C270.5 (5)
N3—Co1—N6—C3389.9 (3)Co1—N6—C33—C34177.7 (4)
N3—Co1—N6—C3787.9 (4)Co1—N6—C37—C36175.7 (4)
N6—Co1—N3—C11114.8 (4)C33—N6—C37—C362.0 (7)
N6—Co1—N3—C1567.8 (5)C37—N6—C33—C27178.5 (4)
N4—Co1—N5—C2311.4 (3)C37—N6—C33—C340.3 (6)
N4—Co1—N5—C27173.9 (4)N2—C1—C2—C30.7 (10)
N5—Co1—N4—C285.7 (3)N2—C1—C6—N16.6 (8)
N5—Co1—N4—C32174.3 (4)N2—C1—C6—C7172.7 (6)
N4—Co1—N6—C3311.9 (6)C2—C1—C6—N1173.2 (6)
N4—Co1—N6—C37170.3 (4)C2—C1—C6—C77.5 (10)
N6—Co1—N4—C2812.8 (5)C6—C1—C2—C3179.6 (6)
N6—Co1—N4—C32167.2 (4)C1—C2—C3—C41.6 (9)
N5—Co1—N6—C334.8 (3)C1—C2—C3—C16176.9 (6)
N5—Co1—N6—C37177.4 (4)C2—C3—C4—C53.0 (9)
N6—Co1—N5—C23171.8 (4)C2—C3—C16—C1729.2 (9)
N6—Co1—N5—C279.3 (3)C2—C3—C16—C21151.6 (6)
F10—F5—F11—F710 (2)C4—C3—C16—C17149.3 (6)
F10—F5—F11—B217.1 (15)C4—C3—C16—C2129.9 (8)
F11—F5—F10—F612 (2)C16—C3—C4—C5175.5 (5)
F11—F5—F10—B216.9 (15)C3—C4—C5—N22.2 (9)
F10—F5—B2—F619.5 (17)C3—C4—C5—C11175.7 (6)
F10—F5—B2—F7136.4 (18)N2—C5—C11—N33.8 (7)
F10—F5—B2—F898.1 (16)N2—C5—C11—C12178.9 (5)
F10—F5—B2—F982 (2)C4—C5—C11—N3174.1 (5)
F10—F5—B2—F11161.9 (18)C4—C5—C11—C123.1 (10)
B2—F5—F10—F629.3 (18)N1—C6—C7—C80.0 (10)
F11—F5—B2—F6142.5 (13)C1—C6—C7—C8179.2 (6)
F11—F5—B2—F725.5 (14)C6—C7—C8—C90.6 (11)
F11—F5—B2—F899.9 (12)C7—C8—C9—C100.8 (12)
F11—F5—B2—F980 (2)C8—C9—C10—N10.6 (12)
F11—F5—B2—F10161.9 (18)N3—C11—C12—C130.6 (9)
B2—F5—F11—F726.7 (11)C5—C11—C12—C13176.5 (5)
F9—F6—F10—F52 (2)C11—C12—C13—C141.3 (9)
F9—F6—F10—B226.6 (13)C12—C13—C14—C150.8 (9)
F10—F6—F9—F712 (2)C13—C14—C15—N33.8 (10)
F10—F6—F9—B226.4 (13)C3—C16—C17—C18176.5 (5)
F9—F6—B2—F5131.1 (12)C3—C16—C21—C20174.9 (5)
F9—F6—B2—F710.7 (13)C17—C16—C21—C204.3 (9)
F9—F6—B2—F8106.8 (11)C21—C16—C17—C182.7 (9)
F9—F6—B2—F10150.5 (17)C16—C17—C18—C190.4 (9)
F9—F6—B2—F1168 (3)C17—C18—C19—C202.0 (9)
B2—F6—F9—F714.3 (14)C17—C18—C19—C22177.6 (6)
F10—F6—B2—F519.4 (16)C18—C19—C20—C210.3 (9)
F10—F6—B2—F7139.8 (17)C22—C19—C20—C21179.2 (6)
F10—F6—B2—F8102.7 (15)C19—C20—C21—C162.8 (9)
F10—F6—B2—F9150.5 (17)N5—C23—C24—C251.0 (8)
F10—F6—B2—F1183 (3)N5—C23—C28—N49.5 (6)
B2—F6—F10—F529.0 (18)N5—C23—C28—C29168.6 (4)
F9—F7—F11—F54 (2)C24—C23—C28—N4167.9 (5)
F9—F7—F11—B230.2 (18)C24—C23—C28—C2914.0 (8)
F11—F7—F9—F615 (2)C28—C23—C24—C25178.2 (5)
F11—F7—F9—B229.1 (18)C23—C24—C25—C260.1 (6)
F9—F7—B2—F5126.7 (14)C23—C24—C25—C38174.8 (5)
F9—F7—B2—F612.3 (14)C24—C25—C26—C272.3 (8)
F9—F7—B2—F8104.7 (12)C24—C25—C38—C3936.5 (8)
F9—F7—B2—F1067 (3)C24—C25—C38—C43140.9 (6)
F9—F7—B2—F11154.2 (15)C26—C25—C38—C39138.3 (6)
B2—F7—F9—F614.1 (15)C26—C25—C38—C4344.3 (8)
F11—F7—B2—F527.5 (12)C38—C25—C26—C27172.6 (5)
F11—F7—B2—F6141.9 (12)C25—C26—C27—N53.6 (8)
F11—F7—B2—F8101.0 (10)C25—C26—C27—C33172.3 (5)
F11—F7—B2—F9154.2 (15)N5—C27—C33—N66.9 (6)
F11—F7—B2—F1088 (3)N5—C27—C33—C34174.9 (5)
B2—F7—F11—F526.5 (11)C26—C27—C33—N6169.3 (5)
F6—F9—B2—F581 (2)C26—C27—C33—C348.9 (8)
F6—F9—B2—F7166.5 (15)N4—C28—C29—C300.1 (6)
F6—F9—B2—F898.3 (9)C23—C28—C29—C30177.9 (4)
F6—F9—B2—F1024.6 (16)C28—C29—C30—C310.9 (8)
F6—F9—B2—F11144.9 (11)C29—C30—C31—C320.3 (6)
F7—F9—B2—F585 (2)C30—C31—C32—N42.5 (8)
F7—F9—B2—F6166.5 (15)N6—C33—C34—C351.3 (8)
F7—F9—B2—F895.3 (14)C27—C33—C34—C35176.8 (4)
F7—F9—B2—F10141.8 (18)C33—C34—C35—C361.2 (8)
F7—F9—B2—F1121.5 (14)C34—C35—C36—C370.4 (8)
F5—F10—B2—F6156.3 (18)C35—C36—C37—N62.1 (8)
F5—F10—B2—F783 (3)C25—C38—C39—C40176.8 (6)
F5—F10—B2—F8106.1 (11)C25—C38—C43—C42178.9 (6)
F5—F10—B2—F9129.6 (15)C39—C38—C43—C423.8 (10)
F5—F10—B2—F1118 (2)C43—C38—C39—C405.8 (10)
F6—F10—B2—F5156.3 (18)C38—C39—C40—C414.0 (10)
F6—F10—B2—F774 (3)C39—C40—C41—C420.3 (8)
F6—F10—B2—F897.7 (13)C39—C40—C41—C44179.6 (6)
F6—F10—B2—F926.7 (18)C40—C41—C42—C431.8 (10)
F6—F10—B2—F11138.7 (16)C44—C41—C42—C43177.5 (6)
F5—F11—B2—F677 (2)C41—C42—C43—C380.0 (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)3·1.5CH3NO2F(000) = 4368.00
Mr = 1079.67Dx = 1.572 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.7107 Å
Hall symbol: -C 2ycCell parameters from 6774 reflections
a = 37.80 (2) Åθ = 3.1–27.5°
b = 10.748 (6) ŵ = 0.48 mm1
c = 22.99 (1) ÅT = 110 K
β = 102.388 (9)°Chip, orange
V = 9123 (8) Å30.30 × 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-1Rint = 0.072
ω scansθmax = 27.5°
Absorption correction: multi-scan
(Jacobson, 1998)
h = 4848
Tmin = 0.789, Tmax = 0.976k = 1313
35412 measured reflectionsl = 2929
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) = 0.238Δρmax = 1.03 e Å3
S = 1.17Δρmin = 0.62 e Å3
10280 reflectionsExtinction correction: SHELXL97, Fc^*^=kFc[1+0.001xFc^2^λ^3^/sin(2θ)]^-1/4^
688 parametersExtinction coefficient: 0.0000
H-atom parameters constrained
Crystal data top
[Co(C22H14N4)2](BF4)3·1.5CH3NO2V = 9123 (8) Å3
Mr = 1079.67Z = 8
Monoclinic, C2/cMo Kα radiation
a = 37.80 (2) ŵ = 0.48 mm1
b = 10.748 (6) ÅT = 110 K
c = 22.99 (1) Å0.30 × 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 = 0.976Rint = 0.072
35412 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.096688 parameters
wR(F2) = 0.238H-atom parameters constrained
S = 1.17Δρmax = 1.03 e Å3
10280 reflectionsΔρmin = 0.62 e Å3
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
xyzUiso*/UeqOcc. (<1)
Co10.64391 (2)0.03735 (5)0.55080 (3)0.0247 (2)
F10.7397 (1)0.3556 (4)0.3515 (2)0.073 (1)
F20.73854 (9)0.5222 (3)0.2913 (1)0.0424 (7)
F30.6920 (1)0.4848 (3)0.3384 (2)0.0562 (9)
F40.6998 (1)0.3627 (4)0.2637 (2)0.079 (1)
F50.68683 (8)0.6159 (3)0.4994 (1)0.0375 (7)
F60.68523 (8)0.4351 (3)0.5501 (1)0.0378 (7)
F70.64203 (8)0.4743 (3)0.4664 (1)0.0409 (7)
F80.64212 (8)0.5840 (3)0.5508 (1)0.0399 (7)
F90.4895 (1)0.1393 (4)0.1995 (2)0.063 (1)
F100.4717 (1)0.2869 (4)0.2581 (2)0.063 (1)
F110.5016 (2)0.003 (1)0.4394 (4)0.082 (3)0.50
F120.5358 (2)0.0656 (8)0.4979 (3)0.057 (2)0.50
F130.5044 (3)0.096 (1)0.5319 (7)0.116 (4)0.50
F140.4764 (2)0.1008 (6)0.4750 (3)0.045 (2)0.50
O10.6145 (1)0.6320 (4)0.2984 (2)0.058 (1)
O20.6020 (1)0.4827 (4)0.2341 (2)0.0474 (10)
O30.5256 (1)0.6683 (5)0.2819 (2)0.073 (1)
N10.6195 (1)0.0584 (3)0.6018 (2)0.0268 (8)
N20.6810 (1)0.0758 (3)0.5784 (2)0.0256 (8)
N30.6787 (1)0.1010 (3)0.5068 (2)0.0256 (8)
N40.6573 (1)0.1621 (4)0.6128 (2)0.0266 (8)
N50.60793 (9)0.1522 (3)0.5205 (2)0.0232 (7)
N60.6198 (1)0.0559 (3)0.4821 (2)0.0278 (8)
N70.8738 (2)0.6595 (5)0.6880 (3)0.061 (1)
N80.4410 (1)0.7848 (5)0.3378 (2)0.050 (1)
N90.6033 (1)0.5252 (4)0.2836 (2)0.039 (1)
N100.50000.7237 (8)0.25000.057 (2)
C10.7116 (1)0.0695 (4)0.5569 (2)0.0253 (9)
C20.7393 (1)0.1530 (4)0.5762 (2)0.0265 (9)
C30.7360 (1)0.2414 (4)0.6195 (2)0.0257 (9)
C40.7034 (1)0.2468 (4)0.6404 (2)0.0281 (9)
C50.6761 (1)0.1620 (4)0.6181 (2)0.0265 (9)
C60.7099 (1)0.0327 (4)0.5140 (2)0.0263 (9)
C70.7368 (1)0.0599 (4)0.4835 (2)0.0294 (10)
C80.7320 (1)0.1619 (4)0.4456 (2)0.0303 (10)
C90.7007 (1)0.2320 (4)0.4385 (2)0.0295 (10)
C100.6747 (1)0.1984 (4)0.4699 (2)0.0287 (9)
C110.6397 (1)0.1535 (4)0.6317 (2)0.0278 (9)
C120.6263 (1)0.2297 (4)0.6702 (2)0.034 (1)
C130.5910 (1)0.2097 (5)0.6779 (2)0.035 (1)
C140.5706 (1)0.1146 (5)0.6480 (2)0.035 (1)
C150.5857 (1)0.0399 (4)0.6103 (2)0.0301 (10)
C160.7660 (1)0.3299 (4)0.6422 (2)0.0268 (9)
C170.8018 (1)0.2948 (5)0.6429 (2)0.035 (1)
C180.8297 (1)0.3783 (5)0.6603 (3)0.039 (1)
C190.8224 (1)0.4989 (5)0.6770 (2)0.036 (1)
C200.7872 (1)0.5327 (4)0.6799 (2)0.035 (1)
C210.7589 (1)0.4476 (4)0.6623 (2)0.0306 (10)
C220.8515 (2)0.5896 (5)0.6860 (3)0.045 (1)
C230.6072 (1)0.2604 (4)0.5503 (2)0.0258 (9)
C240.5825 (1)0.3515 (4)0.5254 (2)0.0283 (9)
C250.5598 (1)0.3340 (4)0.4699 (2)0.0271 (9)
C260.5623 (1)0.2219 (4)0.4396 (2)0.0291 (10)
C270.5865 (1)0.1324 (4)0.4668 (2)0.0281 (9)
C280.6349 (1)0.2630 (4)0.6054 (2)0.0263 (9)
C290.6393 (1)0.3581 (5)0.6466 (2)0.033 (1)
C300.6680 (1)0.3508 (5)0.6962 (2)0.035 (1)
C310.6910 (1)0.2501 (5)0.7022 (2)0.036 (1)
C320.6848 (1)0.1555 (5)0.6607 (2)0.032 (1)
C330.5928 (1)0.0077 (4)0.4443 (2)0.0285 (9)
C340.5733 (1)0.0453 (5)0.3927 (2)0.034 (1)
C350.5810 (2)0.1690 (5)0.3804 (3)0.042 (1)
C360.6075 (2)0.2326 (5)0.4191 (2)0.039 (1)
C370.6267 (1)0.1745 (4)0.4694 (2)0.032 (1)
C380.5338 (1)0.4320 (4)0.4428 (2)0.0280 (9)
C390.5390 (1)0.5558 (4)0.4602 (2)0.032 (1)
C400.5146 (2)0.6472 (5)0.4351 (3)0.039 (1)
C410.4849 (1)0.6144 (5)0.3903 (2)0.034 (1)
C420.4787 (2)0.4911 (5)0.3721 (3)0.043 (1)
C430.5032 (1)0.4008 (5)0.3985 (3)0.039 (1)
C440.4605 (1)0.7106 (5)0.3618 (3)0.039 (1)
C450.5920 (2)0.4489 (6)0.3284 (3)0.057 (2)
C460.50000.8609 (9)0.25000.079 (3)
B10.7175 (2)0.4309 (5)0.3112 (3)0.032 (1)
B20.6640 (1)0.5270 (5)0.5167 (3)0.031 (1)
B30.50000.2117 (9)0.25000.039 (2)
B40.50000.00000.50000.068 (3)
H20.76050.15080.56020.0316*
H40.70020.30730.66890.0335*
H70.75800.01030.48840.0351*
H80.75020.18380.42470.0365*
H90.69710.30170.41250.0352*
H100.65320.24650.46490.0348*
H120.64080.29450.69110.0404*
H130.58120.26230.70370.0417*
H140.54660.09960.65310.0422*
H150.57180.02660.59000.0359*
H170.80690.21300.63140.0427*
H180.85390.35390.66080.0460*
H200.78240.61300.69390.0417*
H210.73490.47010.66390.0364*
H240.58120.42680.54670.0340*
H260.54750.20770.40120.0348*
H290.62310.42700.64150.0395*
H300.67170.41490.72540.0418*
H310.71120.24570.73500.0435*
H320.70010.08440.66610.0389*
H340.55530.00070.36620.0408*
H350.56770.20890.34550.0508*
H360.61280.31660.41120.0461*
H370.64520.21910.49590.0378*
H390.55960.57810.48990.0382*
H400.51800.73110.44810.0470*
H420.45790.46930.34230.0506*
H430.49920.31630.38640.0467*
H45A0.59460.49480.36430.0681*
H45B0.56730.42590.31460.0681*
H45C0.60650.37620.33520.0681*
H46A0.50040.89030.28910.0937*0.50
H46B0.52080.89030.23730.0937*0.50
H46C0.47880.89030.22360.0937*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0235 (3)0.0248 (3)0.0269 (3)0.0023 (2)0.0076 (2)0.0035 (3)
F10.041 (2)0.089 (3)0.096 (3)0.019 (2)0.029 (2)0.062 (3)
F20.050 (2)0.041 (2)0.036 (2)0.009 (1)0.009 (1)0.007 (1)
F30.057 (2)0.051 (2)0.070 (2)0.008 (2)0.034 (2)0.001 (2)
F40.104 (3)0.088 (3)0.051 (2)0.052 (3)0.031 (2)0.036 (2)
F50.033 (1)0.032 (1)0.050 (2)0.000 (1)0.013 (1)0.007 (1)
F60.034 (2)0.040 (2)0.040 (2)0.005 (1)0.009 (1)0.008 (1)
F70.043 (2)0.037 (2)0.040 (2)0.002 (1)0.004 (1)0.003 (1)
F80.042 (2)0.038 (2)0.044 (2)0.002 (1)0.020 (1)0.004 (1)
F90.069 (2)0.073 (2)0.039 (2)0.003 (2)0.003 (2)0.007 (2)
F100.040 (2)0.086 (3)0.068 (3)0.010 (2)0.023 (2)0.002 (2)
F110.038 (4)0.126 (8)0.075 (6)0.019 (5)0.000 (4)0.037 (6)
F120.032 (3)0.091 (5)0.047 (4)0.009 (3)0.010 (3)0.016 (4)
F130.103 (9)0.087 (8)0.15 (1)0.015 (7)0.010 (9)0.027 (8)
F140.029 (3)0.042 (3)0.062 (4)0.000 (3)0.004 (3)0.016 (3)
O10.070 (3)0.043 (2)0.062 (3)0.011 (2)0.014 (2)0.017 (2)
O20.060 (3)0.049 (2)0.035 (2)0.015 (2)0.015 (2)0.012 (2)
O30.055 (3)0.088 (4)0.065 (3)0.006 (3)0.009 (2)0.010 (3)
N10.027 (2)0.029 (2)0.025 (2)0.001 (2)0.007 (1)0.001 (2)
N20.020 (2)0.029 (2)0.029 (2)0.002 (1)0.008 (1)0.002 (2)
N30.026 (2)0.025 (2)0.025 (2)0.000 (2)0.004 (1)0.000 (2)
N40.031 (2)0.028 (2)0.023 (2)0.001 (2)0.009 (2)0.002 (2)
N50.019 (2)0.025 (2)0.025 (2)0.000 (1)0.004 (1)0.003 (2)
N60.027 (2)0.026 (2)0.032 (2)0.001 (2)0.010 (2)0.002 (2)
N70.060 (3)0.067 (4)0.053 (3)0.030 (3)0.009 (3)0.010 (3)
N80.049 (3)0.046 (3)0.052 (3)0.018 (2)0.007 (2)0.006 (2)
N90.047 (3)0.036 (2)0.035 (2)0.002 (2)0.008 (2)0.007 (2)
N100.052 (4)0.068 (5)0.046 (4)0.00000.003 (3)0.0000
C10.023 (2)0.028 (2)0.027 (2)0.001 (2)0.009 (2)0.001 (2)
C20.024 (2)0.026 (2)0.031 (2)0.002 (2)0.011 (2)0.001 (2)
C30.026 (2)0.022 (2)0.029 (2)0.000 (2)0.007 (2)0.000 (2)
C40.029 (2)0.029 (2)0.026 (2)0.002 (2)0.007 (2)0.002 (2)
C50.028 (2)0.026 (2)0.028 (2)0.000 (2)0.010 (2)0.001 (2)
C60.026 (2)0.026 (2)0.027 (2)0.000 (2)0.005 (2)0.001 (2)
C70.028 (2)0.032 (2)0.030 (2)0.004 (2)0.010 (2)0.002 (2)
C80.031 (2)0.032 (2)0.029 (2)0.005 (2)0.010 (2)0.000 (2)
C90.031 (2)0.027 (2)0.030 (2)0.001 (2)0.008 (2)0.002 (2)
C100.029 (2)0.024 (2)0.033 (2)0.002 (2)0.006 (2)0.005 (2)
C110.023 (2)0.032 (2)0.029 (2)0.001 (2)0.008 (2)0.004 (2)
C120.035 (3)0.029 (2)0.039 (3)0.004 (2)0.011 (2)0.009 (2)
C130.031 (2)0.041 (3)0.034 (3)0.001 (2)0.011 (2)0.005 (2)
C140.029 (2)0.039 (3)0.040 (3)0.000 (2)0.013 (2)0.008 (2)
C150.024 (2)0.032 (2)0.035 (2)0.002 (2)0.008 (2)0.001 (2)
C160.026 (2)0.027 (2)0.028 (2)0.004 (2)0.006 (2)0.000 (2)
C170.030 (2)0.034 (2)0.042 (3)0.002 (2)0.007 (2)0.004 (2)
C180.027 (2)0.044 (3)0.044 (3)0.004 (2)0.008 (2)0.005 (2)
C190.037 (3)0.043 (3)0.030 (2)0.013 (2)0.009 (2)0.006 (2)
C200.042 (3)0.029 (2)0.034 (3)0.004 (2)0.009 (2)0.002 (2)
C210.030 (2)0.030 (2)0.033 (2)0.001 (2)0.009 (2)0.000 (2)
C220.048 (3)0.046 (3)0.040 (3)0.014 (3)0.006 (2)0.016 (3)
C230.023 (2)0.029 (2)0.026 (2)0.002 (2)0.008 (2)0.001 (2)
C240.030 (2)0.026 (2)0.030 (2)0.003 (2)0.008 (2)0.001 (2)
C250.024 (2)0.025 (2)0.033 (2)0.000 (2)0.008 (2)0.002 (2)
C260.023 (2)0.031 (2)0.034 (2)0.000 (2)0.007 (2)0.001 (2)
C270.026 (2)0.029 (2)0.030 (2)0.001 (2)0.010 (2)0.000 (2)
C280.023 (2)0.029 (2)0.029 (2)0.001 (2)0.010 (2)0.004 (2)
C290.029 (2)0.039 (3)0.031 (2)0.001 (2)0.007 (2)0.003 (2)
C300.036 (3)0.039 (3)0.031 (3)0.002 (2)0.008 (2)0.002 (2)
C310.031 (2)0.045 (3)0.030 (3)0.001 (2)0.002 (2)0.001 (2)
C320.029 (2)0.039 (3)0.029 (2)0.006 (2)0.006 (2)0.008 (2)
C330.031 (2)0.026 (2)0.031 (2)0.002 (2)0.010 (2)0.001 (2)
C340.039 (3)0.034 (3)0.028 (2)0.009 (2)0.004 (2)0.001 (2)
C350.045 (3)0.040 (3)0.040 (3)0.000 (2)0.006 (2)0.011 (2)
C360.048 (3)0.031 (2)0.039 (3)0.008 (2)0.013 (2)0.001 (2)
C370.036 (3)0.026 (2)0.035 (3)0.005 (2)0.013 (2)0.003 (2)
C380.023 (2)0.031 (2)0.029 (2)0.002 (2)0.004 (2)0.008 (2)
C390.031 (2)0.027 (2)0.038 (3)0.004 (2)0.004 (2)0.002 (2)
C400.045 (3)0.026 (2)0.049 (3)0.004 (2)0.013 (2)0.004 (2)
C410.035 (2)0.033 (2)0.036 (3)0.012 (2)0.012 (2)0.007 (2)
C420.039 (3)0.043 (3)0.042 (3)0.008 (2)0.001 (2)0.000 (2)
C430.038 (3)0.031 (3)0.045 (3)0.006 (2)0.000 (2)0.005 (2)
C440.036 (3)0.035 (3)0.045 (3)0.009 (2)0.009 (2)0.004 (2)
C450.083 (5)0.046 (3)0.044 (3)0.012 (3)0.017 (3)0.001 (3)
C460.106 (10)0.045 (5)0.077 (8)0.00000.002 (7)0.0000
B10.035 (3)0.031 (3)0.031 (3)0.002 (2)0.010 (2)0.002 (2)
B20.028 (3)0.026 (3)0.039 (3)0.003 (2)0.010 (2)0.005 (2)
B30.035 (4)0.053 (5)0.031 (4)0.00000.016 (3)0.0000
B40.061 (7)0.074 (8)0.055 (7)0.015 (6)0.020 (5)0.022 (6)
Geometric parameters (Å, º) top
Co1—N11.937 (4)C13—C141.375 (7)
Co1—N21.860 (4)C13—H130.951
Co1—N31.946 (4)C14—C151.392 (8)
Co1—N41.944 (4)C14—H140.951
Co1—N51.857 (3)C15—H150.949
Co1—N61.927 (4)C16—C171.400 (7)
F1—B11.371 (7)C16—C211.393 (7)
F2—B11.401 (7)C17—C181.376 (7)
F3—B11.383 (8)C17—H170.950
F4—B11.365 (7)C18—C191.396 (8)
F5—B21.401 (6)C18—H180.949
F6—B21.394 (6)C19—C201.398 (8)
F7—B21.391 (6)C19—C221.449 (8)
F8—B21.396 (7)C20—C211.397 (7)
F9—B31.384 (6)C20—H200.951
F10—B31.385 (7)C21—H210.950
F11—F13i1.25 (2)C23—C241.388 (6)
F11—B41.409 (10)C23—C281.462 (6)
F12—F131.59 (2)C24—C251.390 (6)
F12—B41.536 (7)C24—H240.951
F13—F141.49 (1)C25—C261.405 (7)
F13—B41.26 (1)C25—C381.485 (6)
F14—B41.442 (6)C26—C271.382 (6)
O1—N91.244 (6)C26—H260.951
O2—N91.217 (6)C27—C331.474 (7)
O3—N101.233 (6)C28—C291.378 (7)
N1—C111.370 (6)C29—C301.397 (6)
N1—C151.345 (6)C29—H290.952
N2—C11.355 (7)C30—C311.378 (7)
N2—C51.342 (6)C30—H300.951
N3—C61.369 (6)C31—C321.380 (7)
N3—C101.335 (6)C31—H310.951
N4—C281.365 (6)C32—H320.951
N4—C321.342 (6)C33—C341.377 (6)
N5—C231.353 (6)C34—C351.402 (8)
N5—C271.340 (5)C34—H340.950
N6—C331.372 (6)C35—C361.372 (7)
N6—C371.346 (6)C35—H350.951
N7—C221.122 (8)C36—C371.376 (7)
N8—C441.145 (7)C36—H360.950
N9—C451.451 (9)C37—H370.952
N10—C461.47 (1)C38—C391.390 (6)
C1—C21.379 (6)C38—C431.408 (7)
C1—C61.469 (6)C39—C401.385 (7)
C2—C31.400 (7)C39—H390.950
C2—H20.950C40—C411.395 (7)
C3—C41.416 (7)C40—H400.951
C3—C161.488 (6)C41—C421.395 (7)
C4—C51.389 (6)C41—C441.446 (7)
C4—H40.950C42—C431.388 (7)
C5—C111.476 (7)C42—H420.952
C6—C71.385 (7)C43—H430.952
C7—C81.387 (7)C45—H45A0.948
C7—H70.949C45—H45B0.951
C8—C91.381 (7)C45—H45C0.949
C8—H80.951C46—H46A0.950
C9—C101.387 (7)C46—H46Aii0.950
C9—H90.949C46—H46B0.950
C10—H100.951C46—H46Bii0.950
C11—C121.379 (7)C46—H46C0.950
C12—C131.399 (8)C46—H46Cii0.950
C12—H120.951
F1···C32iii2.931 (7)F14···C40vii3.291 (8)
F1···C31iii3.326 (7)F14···N8vii3.383 (8)
F1···C1iii3.382 (6)O1···C36vi3.195 (7)
F1···C6iii3.481 (6)O1···C35vi3.280 (8)
F2···C3iii3.137 (5)O1···C18iii3.392 (7)
F2···C2iii3.296 (6)O1···C30v3.418 (8)
F2···C21iv3.318 (6)O2···C29v3.190 (7)
F2···C30v3.354 (6)O2···C13iv3.197 (6)
F2···C4iii3.411 (5)O2···C12iv3.314 (7)
F2···C31v3.439 (6)O2···C30v3.333 (7)
F2···C32iii3.449 (6)O3···C35vi3.246 (7)
F2···C20iv3.457 (7)N7···C13viii3.130 (7)
F3···C17iii3.362 (6)N7···C12viii3.347 (8)
F3···C2iii3.415 (6)N7···C45ix3.421 (9)
F4···C4iv3.126 (6)N8···C15x3.236 (7)
F4···C12iv3.439 (6)N8···C28x3.434 (8)
F4···C30v3.540 (7)N8···C29x3.486 (8)
F5···C37vi3.169 (6)N8···C23x3.489 (8)
F5···C3vi3.349 (5)N8···C14x3.594 (7)
F5···C7iii3.401 (6)C7···C9iii3.462 (6)
F5···C2vi3.423 (5)C7···C8iii3.487 (7)
F5···C4vi3.492 (6)C7···C21ix3.598 (7)
F5···C36vi3.560 (6)C8···C20ix3.145 (7)
F6···C7iii3.202 (6)C8···C8iii3.199 (9)
F6···C8iii3.280 (6)C8···C21ix3.456 (7)
F6···C21vi3.595 (5)C8···C9iii3.460 (6)
F7···C36vi3.492 (6)C8···C19ix3.572 (7)
F8···C37vi3.179 (6)C9···C22ix3.464 (7)
F8···C5vi3.263 (5)C9···C20ix3.570 (7)
F8···C4vi3.296 (5)C12···C22xi3.565 (8)
F8···C11vi3.392 (6)C17···C31viii3.546 (8)
F8···C12vi3.551 (6)C18···C36ix3.500 (8)
F9···C46vii3.20 (1)C23···C44x3.597 (8)
F9···C14iv3.525 (7)C24···C44x3.407 (8)
F12···C40vii3.429 (9)C24···C41x3.536 (8)
F14···C44vii3.250 (9)C37···B2vii3.578 (7)
N1—Co1—N282.4 (2)N5—C27—C33110.9 (4)
N1—Co1—N3164.6 (2)C26—C27—C33128.0 (4)
N1—Co1—N490.4 (2)N4—C28—C23113.7 (4)
N1—Co1—N5100.0 (2)N4—C28—C29121.6 (4)
N1—Co1—N690.9 (2)C23—C28—C29124.7 (4)
N2—Co1—N382.2 (2)C28—C29—C30118.5 (4)
N2—Co1—N498.2 (2)C28—C29—H29120.8
N2—Co1—N5177.4 (2)C30—C29—H29120.7
N2—Co1—N697.4 (2)C29—C30—C31119.3 (5)
N3—Co1—N492.3 (2)C29—C30—H30120.4
N3—Co1—N595.3 (2)C31—C30—H30120.3
N3—Co1—N690.6 (2)C30—C31—C32119.9 (4)
N4—Co1—N582.6 (2)C30—C31—H31120.1
N4—Co1—N6164.4 (2)C32—C31—H31120.0
N5—Co1—N681.9 (2)N4—C32—C31121.0 (4)
F13i—F11—B456.0 (8)N4—C32—H32119.5
F13—F12—B447.3 (5)C31—C32—H32119.5
F11i—F13—F12109.6 (10)N6—C33—C27112.6 (4)
F11i—F13—F14108.5 (9)N6—C33—C34121.8 (4)
F11i—F13—B468.5 (8)C27—C33—C34125.6 (4)
F12—F13—F1492.3 (9)C33—C34—C35118.1 (4)
F12—F13—B464.1 (7)C33—C34—H34121.0
F14—F13—B462.5 (6)C35—C34—H34121.0
F13—F14—B450.6 (5)C34—C35—C36119.7 (5)
Co1—N1—C11114.3 (3)C34—C35—H35120.3
Co1—N1—C15126.8 (3)C36—C35—H35120.1
C11—N1—C15118.9 (4)C35—C36—C37120.0 (5)
Co1—N2—C1118.9 (3)C35—C36—H36120.2
Co1—N2—C5118.7 (3)C37—C36—H36119.9
C1—N2—C5122.4 (4)N6—C37—C36121.3 (4)
Co1—N3—C6114.2 (3)N6—C37—H37119.3
Co1—N3—C10127.6 (3)C36—C37—H37119.4
C6—N3—C10118.2 (4)C25—C38—C39121.2 (4)
Co1—N4—C28113.6 (3)C25—C38—C43120.2 (4)
Co1—N4—C32126.8 (3)C39—C38—C43118.6 (4)
C28—N4—C32119.6 (4)C38—C39—C40121.3 (4)
Co1—N5—C23118.3 (3)C38—C39—H39119.4
Co1—N5—C27119.2 (3)C40—C39—H39119.3
C23—N5—C27121.9 (4)C39—C40—C41119.0 (4)
Co1—N6—C33114.6 (3)C39—C40—H40120.6
Co1—N6—C37126.2 (3)C41—C40—H40120.4
C33—N6—C37119.2 (4)C40—C41—C42121.3 (5)
O1—N9—O2123.0 (5)C40—C41—C44119.2 (4)
O1—N9—C45117.5 (5)C42—C41—C44119.6 (4)
O2—N9—C45119.5 (5)C41—C42—C43118.6 (5)
O3—N10—O3ii122.3 (8)C41—C42—H42120.7
O3—N10—C46118.9 (4)C43—C42—H42120.7
O3ii—N10—C46118.9 (4)C38—C43—C42121.2 (5)
N2—C1—C2120.0 (4)C38—C43—H43119.4
N2—C1—C6111.3 (4)C42—C43—H43119.4
C2—C1—C6128.7 (5)N8—C44—C41178.0 (6)
C1—C2—C3119.5 (5)N9—C45—H45A109.4
C1—C2—H2120.2N9—C45—H45B109.3
C3—C2—H2120.3N9—C45—H45C109.4
C2—C3—C4119.1 (4)H45A—C45—H45B109.5
C2—C3—C16120.3 (4)H45A—C45—H45C109.7
C4—C3—C16120.6 (4)H45B—C45—H45C109.5
C3—C4—C5118.7 (4)N10—C46—H46A109.4
C3—C4—H4120.7N10—C46—H46Aii109.4
C5—C4—H4120.6N10—C46—H46B109.4
N2—C5—C4120.3 (4)N10—C46—H46Bii109.4
N2—C5—C11111.8 (4)N10—C46—H46C109.4
C4—C5—C11128.0 (4)N10—C46—H46Cii109.4
N3—C6—C1113.2 (4)H46A—C46—H46Aii141.2
N3—C6—C7122.3 (4)H46A—C46—H46B109.5
C1—C6—C7124.5 (4)H46A—C46—H46Bii56.3
C6—C7—C8118.1 (4)H46A—C46—H46C109.5
C6—C7—H7120.9H46A—C46—H46Cii56.3
C8—C7—H7120.9H46Aii—C46—H46B56.3
C7—C8—C9120.0 (5)H46Aii—C46—H46Bii109.5
C7—C8—H8120.1H46Aii—C46—H46C56.3
C9—C8—H8119.9H46Aii—C46—H46Cii109.5
C8—C9—C10118.7 (4)H46B—C46—H46Bii141.2
C8—C9—H9120.7H46B—C46—H46C109.5
C10—C9—H9120.7H46B—C46—H46Cii56.3
N3—C10—C9122.7 (4)H46Bii—C46—H46C56.3
N3—C10—H10118.6H46Bii—C46—H46Cii109.5
C9—C10—H10118.7H46C—C46—H46Cii141.2
N1—C11—C5112.7 (4)F1—B1—F2109.1 (4)
N1—C11—C12121.5 (4)F1—B1—F3109.0 (5)
C5—C11—C12125.8 (4)F1—B1—F4110.3 (5)
C11—C12—C13118.8 (4)F2—B1—F3110.7 (4)
C11—C12—H12120.6F2—B1—F4109.2 (5)
C13—C12—H12120.6F3—B1—F4108.5 (5)
C12—C13—C14120.0 (5)F5—B2—F6108.8 (4)
C12—C13—H13120.1F5—B2—F7109.6 (4)
C14—C13—H13120.0F5—B2—F8109.6 (4)
C13—C14—C15118.5 (5)F6—B2—F7109.8 (4)
C13—C14—H14120.8F6—B2—F8110.1 (4)
C15—C14—H14120.6F7—B2—F8108.9 (4)
N1—C15—C14122.3 (4)F9—B3—F9ii111.6 (7)
N1—C15—H15119.0F9—B3—F10110.5 (2)
C14—C15—H15118.7F9—B3—F10ii107.8 (2)
C3—C16—C17119.7 (4)F9ii—B3—F10107.8 (2)
C3—C16—C21120.7 (4)F9ii—B3—F10ii110.5 (2)
C17—C16—C21119.7 (4)F10—B3—F10ii108.6 (7)
C16—C17—C18120.3 (5)F11—B4—F11i180.0
C16—C17—H17120.0F11—B4—F1275.6 (4)
C18—C17—H17119.7F11—B4—F12i104.4 (4)
C17—C18—C19120.2 (5)F11—B4—F13124.5 (8)
C17—C18—H18119.9F11—B4—F13i55.5 (8)
C19—C18—H18119.9F11—B4—F1477.0 (5)
C18—C19—C20120.0 (5)F11—B4—F14i103.0 (5)
C18—C19—C22118.5 (5)F11i—B4—F12104.4 (4)
C20—C19—C22121.3 (5)F11i—B4—F12i75.6 (4)
C19—C20—C21119.5 (5)F11i—B4—F1355.5 (8)
C19—C20—H20120.2F11i—B4—F13i124.5 (8)
C21—C20—H20120.3F11i—B4—F14103.0 (5)
C16—C21—C20120.1 (5)F11i—B4—F14i77.0 (5)
C16—C21—H21119.9F12—B4—F12i180.0
C20—C21—H21120.0F12—B4—F1368.6 (7)
N7—C22—C19174.2 (7)F12—B4—F13i111.4 (7)
N5—C23—C24119.0 (4)F12—B4—F1496.7 (4)
N5—C23—C28111.5 (4)F12—B4—F14i83.3 (4)
C24—C23—C28129.5 (4)F12i—B4—F13111.4 (7)
C23—C24—C25120.7 (4)F12i—B4—F13i68.6 (7)
C23—C24—H24119.6F12i—B4—F1483.3 (4)
C25—C24—H24119.7F12i—B4—F14i96.7 (4)
C24—C25—C26118.6 (4)F13—B4—F13i180.0
C24—C25—C38120.8 (4)F13—B4—F1466.9 (6)
C26—C25—C38120.6 (4)F13—B4—F14i113.1 (6)
C25—C26—C27118.8 (4)F13i—B4—F14113.1 (6)
C25—C26—H26120.7F13i—B4—F14i66.9 (6)
C27—C26—H26120.5F14—B4—F14i180.0
N5—C27—C26121.1 (4)
Co1—N1—C11—C50.1 (5)N5—Co1—N1—C150.2 (4)
Co1—N1—C11—C12179.4 (4)N5—Co1—N2—C113 (3)
Co1—N1—C15—C14179.8 (4)N5—Co1—N2—C5165 (3)
Co1—N2—C1—C2179.3 (3)N5—Co1—N3—C6175.6 (3)
Co1—N2—C1—C60.8 (5)N5—Co1—N3—C101.7 (4)
Co1—N2—C5—C4179.1 (3)N5—Co1—N4—C281.8 (3)
Co1—N2—C5—C112.2 (5)N5—Co1—N4—C32179.8 (4)
Co1—N3—C6—C14.2 (5)N5—Co1—N6—C336.3 (4)
Co1—N3—C6—C7176.3 (3)N5—Co1—N6—C37172.5 (5)
Co1—N3—C10—C9176.7 (3)N5—C23—C24—C252.4 (7)
Co1—N4—C28—C234.3 (5)N5—C23—C28—C29176.2 (5)
Co1—N4—C28—C29177.0 (4)N5—C27—C26—C251.2 (7)
Co1—N4—C32—C31178.8 (4)N5—C27—C33—N62.6 (6)
Co1—N5—C23—C24174.3 (4)N5—C27—C33—C34174.7 (5)
Co1—N5—C23—C283.8 (5)N6—Co1—N1—C1198.4 (3)
Co1—N5—C27—C26172.5 (4)N6—Co1—N1—C1582.1 (4)
Co1—N5—C27—C338.2 (5)N6—Co1—N2—C187.1 (3)
Co1—N6—C33—C273.6 (5)N6—Co1—N2—C591.8 (3)
Co1—N6—C33—C34179.0 (4)N6—Co1—N3—C693.7 (3)
Co1—N6—C37—C36179.4 (4)N6—Co1—N3—C1083.5 (4)
F11—F13i—F12i—B452.7 (7)N6—Co1—N4—C283.4 (9)
F11—F13i—F14i—B452.4 (8)N6—Co1—N4—C32174.5 (6)
F11—F13i—B4—F1253.7 (7)N6—Co1—N5—C23179.8 (4)
F11—F13i—B4—F12i126.3 (7)N6—Co1—N5—C278.3 (4)
F11—F13i—B4—F1453.9 (8)N6—C33—C27—C26178.2 (5)
F11—F13i—B4—F14i126.1 (8)N6—C33—C34—C352.2 (8)
F11—B4—F12—F13136.7 (8)N6—C37—C36—C350.7 (9)
F11—B4—F12i—F13i43.3 (8)N7—C22—C19—C1869 (6)
F11—B4—F13—F1253.7 (7)N7—C22—C19—C20105 (6)
F11—B4—F13—F1453.9 (8)N8—C44—C41—C40148 (17)
F11—B4—F13i—F12i126.3 (7)N8—C44—C41—C4230 (17)
F11—B4—F13i—F14i126.1 (8)C1—N2—C5—C42.1 (6)
F11—B4—F14—F13136.9 (8)C1—N2—C5—C11176.7 (4)
F11—B4—F14i—F13i43.1 (8)C1—C2—C3—C43.0 (6)
F12—F13—F11i—B450.3 (7)C1—C2—C3—C16178.1 (4)
F12—F13—F14—B459.1 (6)C1—C6—N3—C10178.3 (4)
F12—F13—B4—F14107.6 (6)C1—C6—C7—C8178.0 (4)
F12—F13—B4—F14i72.4 (6)C2—C1—N2—C50.5 (6)
F12—B4—F11—F13i129.2 (8)C2—C1—C6—C72.0 (7)
F12—B4—F11i—F1350.8 (8)C2—C3—C4—C51.5 (6)
F12—B4—F13—F14107.6 (6)C2—C3—C16—C1728.6 (7)
F12—B4—F13i—F14i72.4 (6)C2—C3—C16—C21150.7 (5)
F12—B4—F14—F1363.3 (8)C3—C2—C1—C6177.7 (4)
F12—B4—F14i—F13i116.7 (8)C3—C4—C5—C11177.5 (4)
F13—F11i—B4—F1449.7 (8)C3—C16—C17—C18175.9 (5)
F13—F11i—B4—F14i130.3 (8)C3—C16—C21—C20175.9 (5)
F13—F12—B4—F1462.0 (7)C4—C3—C16—C17152.5 (5)
F13—F12—B4—F14i118.0 (7)C4—C3—C16—C2128.2 (7)
F13—F14—B4—F14i81.8C4—C5—C11—C120.6 (8)
F14—F13—F11i—B449.1 (7)C5—N2—C1—C6179.7 (4)
F14—F13—F12—B457.8 (5)C5—C4—C3—C16179.6 (4)
N1—Co1—N2—C1177.1 (3)C5—C11—N1—C15179.7 (4)
N1—Co1—N2—C51.8 (3)C5—C11—C12—C13179.6 (4)
N1—Co1—N3—C62.0 (8)C6—N3—C10—C90.5 (6)
N1—Co1—N3—C10179.3 (5)C6—C7—C8—C91.0 (7)
N1—Co1—N4—C2898.2 (3)C7—C6—N3—C101.3 (6)
N1—Co1—N4—C3279.7 (4)C7—C8—C9—C100.3 (7)
N1—Co1—N5—C2390.3 (4)C11—N1—C15—C140.7 (7)
N1—Co1—N5—C2797.8 (4)C11—C12—C13—C140.8 (7)
N1—Co1—N6—C33106.2 (4)C12—C11—N1—C150.1 (7)
N1—Co1—N6—C3772.5 (4)C12—C13—C14—C150.0 (7)
N1—C11—C5—N21.2 (5)C16—C17—C18—C190.5 (8)
N1—C11—C5—C4179.9 (4)C16—C21—C20—C190.3 (8)
N1—C11—C12—C130.8 (7)C17—C16—C21—C203.4 (7)
N1—C15—C14—C130.7 (7)C17—C18—C19—C204.3 (8)
N2—Co1—N1—C111.0 (3)C17—C18—C19—C22170.5 (5)
N2—Co1—N1—C15179.5 (4)C18—C17—C16—C213.4 (8)
N2—Co1—N3—C63.7 (3)C18—C19—C20—C214.2 (8)
N2—Co1—N3—C10179.1 (4)C21—C20—C19—C22170.4 (5)
N2—Co1—N4—C28179.4 (3)C23—N5—C27—C260.9 (7)
N2—Co1—N4—C322.7 (5)C23—N5—C27—C33179.9 (4)
N2—Co1—N5—C23106 (3)C23—C24—C25—C260.4 (7)
N2—Co1—N5—C2765 (3)C23—C24—C25—C38179.1 (5)
N2—Co1—N6—C33171.3 (4)C23—C28—N4—C32177.6 (4)
N2—Co1—N6—C3710.0 (5)C23—C28—C29—C30177.3 (5)
N2—C1—C2—C32.1 (6)C24—C23—N5—C272.7 (7)
N2—C1—C6—N32.3 (5)C24—C23—C28—C296.0 (9)
N2—C1—C6—C7178.2 (4)C24—C25—C26—C271.4 (7)
N2—C5—C4—C31.0 (6)C24—C25—C38—C3922.2 (8)
N2—C5—C11—C12179.2 (4)C24—C25—C38—C43158.1 (5)
N3—Co1—N1—C112.7 (8)C25—C24—C23—C28175.3 (5)
N3—Co1—N1—C15177.8 (5)C25—C26—C27—C33177.9 (5)
N3—Co1—N2—C12.5 (3)C25—C38—C39—C40179.8 (5)
N3—Co1—N2—C5178.6 (3)C25—C38—C43—C42179.4 (5)
N3—Co1—N4—C2896.9 (3)C26—C25—C38—C39157.2 (5)
N3—Co1—N4—C3285.1 (4)C26—C25—C38—C4322.4 (8)
N3—Co1—N5—C2390.4 (4)C26—C27—C33—C344.5 (9)
N3—Co1—N5—C2781.5 (4)C27—N5—C23—C28175.4 (4)
N3—Co1—N6—C3389.1 (4)C27—C26—C25—C38179.1 (5)
N3—Co1—N6—C3792.2 (4)C27—C33—N6—C37175.2 (5)
N3—C6—C1—C2177.6 (4)C27—C33—C34—C35174.9 (5)
N3—C6—C7—C81.5 (7)C28—N4—C32—C311.0 (8)
N3—C10—C9—C80.0 (7)C28—C29—C30—C310.5 (8)
N4—Co1—N1—C1197.2 (3)C29—C28—N4—C321.1 (7)
N4—Co1—N1—C1582.3 (4)C29—C30—C31—C322.5 (8)
N4—Co1—N2—C193.6 (3)C33—N6—C37—C360.7 (8)
N4—Co1—N2—C587.5 (3)C33—C34—C35—C360.7 (9)
N4—Co1—N3—C6101.6 (3)C34—C33—N6—C372.2 (8)
N4—Co1—N3—C1081.1 (4)C34—C35—C36—C370.6 (9)
N4—Co1—N5—C231.2 (4)C38—C39—C40—C412.0 (9)
N4—Co1—N5—C27173.1 (4)C38—C43—C42—C410.2 (9)
N4—Co1—N6—C3311.5 (9)C39—C38—C43—C420.3 (9)
N4—Co1—N6—C37167.2 (6)C39—C40—C41—C422.5 (9)
N4—C28—C23—N55.1 (6)C39—C40—C41—C44176.8 (6)
N4—C28—C23—C24172.7 (5)C40—C39—C38—C430.6 (8)
N4—C28—C29—C301.3 (8)C40—C41—C42—C431.6 (9)
N4—C32—C31—C302.8 (8)C43—C42—C41—C44177.6 (6)
N5—Co1—N1—C11179.7 (3)C43—C42—C41—C44177.6 (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, z1/2; (v) x, y+1, z1/2; (vi) x, y+1, z; (vii) x, y1, z; (viii) x+3/2, y1/2, z+3/2; (ix) x+3/2, y1/2, 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
Mr962.341079.67
Crystal system, space groupMonoclinic, CcMonoclinic, C2/c
Temperature (K)120110
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)
V3)4118 (7)9123 (8)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.510.48
Crystal size (mm)0.20 × 0.20 × 0.100.30 × 0.07 × 0.05
Data collection
DiffractometerRigaku Mercury
diffractometer
Rigaku Mercury
diffractometer
Absorption correctionMulti-scan
(Jacobson, 1998)
Tmin, Tmax0.789, 0.976
No. of measured, independent and
observed reflections
23489, 8003, 6271 [F2 > 2σ(F2)]35412, 10280, 7454 [I > 2σ(I)]
Rint0.0560.072
(sin θ/λ)max1)0.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.169, 1.04 0.096, 0.238, 1.17
No. of reflections800310280
No. of parameters632688
No. of restraints??
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.13, 0.431.03, 0.62
Absolute structureFlack (1983), 3285 Friedel pairs?
Absolute structure parameter0.026 (19)?

Computer programs: CrystalClear (Rigaku Corporation, 2001), CrystalStructure (Rigaku Corporation, 2001), TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000), SIR97 (Altomare et al., 1994), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008).

Selected geometric parameters (Å, º) for (I) top
Co1—N12.132 (4)Co1—N42.147 (5)
Co1—N22.007 (4)Co1—N52.028 (4)
Co1—N32.146 (4)Co1—N62.133 (4)
N1—Co1—N276.41 (17)N2—Co1—N5169.48 (18)
N1—Co1—N3152.98 (16)N4—Co1—N577.21 (18)
N1—Co1—N5111.88 (17)N4—Co1—N6154.20 (15)
N2—Co1—N377.31 (16)N5—Co1—N677.19 (19)
Selected geometric parameters (Å, º) for (II) top
Co1—N11.937 (4)Co1—N41.944 (4)
Co1—N21.860 (4)Co1—N51.857 (3)
Co1—N31.946 (4)Co1—N61.927 (4)
N1—Co1—N282.4 (2)N2—Co1—N5177.4 (2)
N1—Co1—N3164.6 (2)N4—Co1—N582.6 (2)
N1—Co1—N5100.0 (2)N4—Co1—N6164.4 (2)
N2—Co1—N382.2 (2)N5—Co1—N681.9 (2)
 

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