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Acta Cryst. (2008). E64, m1230    [ doi:10.1107/S1600536808027645 ]

Di-[mu]-chlorido-chlorido-1[kappa]Cl-([mu]-1-phenyl-3-phenyliminobut-1-enolato-1:2[kappa]3O:O,N)bis(1-phenyl-3-phenyliminobut-1-enolato)-1[kappa]2N,O;2[kappa]2N,O-dichromium(III) toluene disolvate

L. Tang and Z.-X. Li

Abstract top

In the title dichromium complex, [Cr2(C16H14NO)3Cl3]·2C7H8, each CrIII atom has a distorted octahedral coordination geometry. The complex molecule has three six-membered chelate rings formed by hydroxybutaneimine ligands and the two CrIII atoms are bridged by two Cl atoms and one O atom.

Comment top

In recent years organochromium complexes have received more and more attentions as heterogenous or homogeneous catalysts for olefin polymerization (MacAdams et al., 2005; Smith 2005; Jones et al., 2005). Previously, much research effort has been dedicated in the synthesis of half-sandwich chromium complexes as model systems for the unipol family of silica-supported chromium catalysts which can produce high density polyethylene (Theopold et al., 1998; Karol et al., 1972; Cole & Gibson, 1994). Recently, a number of non-cyclopentadienyl ligand have been investigated with a view to synthesizing high active, single site or well define olefin polymerizaton catalysts, which have provided new opportunities for the production of polymers with tailored structures and novel properties. Hence, our work aimed to synthesize the new chromium complex with β-diketiminato ligand. Here, we report the synthesis and structure of the first such species, [(Ph)NC(Ph)C(H)C(CH3)OCr]2(µ-Cl)2[µ-O(CH3)CC(H)(Ph)CN(Ph)] Cl.2C7H8.

The title complex crystallized in the monoclinic system and the structure consists of three six-membered chelate rings, as illustrated in Figure 1. Two unsymmetric chromium centres are in a distorted octahedral environment held together by one oxygen and two chloride bridges. The two Cr atoms are in distinct stereochemical environment. Atom Cr1 is coordinated by two β-diketiminato ligands, two bridging C1 (Clb) atoms and one bridging O atom (Ob); atom Cr2 is coordinated by one β-diketiminato ligand, one Cl atom, two Clb atoms and one Ob atom. In each chelate ring the bite angle is near optimal, the respective O—Cr—N angles being in the range 88.80 (10) to 99.22 (10)°.

The range of the Cr—O, Cr—N and Cr—Cl bonds lengths (Table 1) are 1.890–2.138, 2.016–2.019 and 2.3954–2.4145 Å, respectively. These are comparable to the bond lengths for the reported mononuclear chromium complexes with salicylaldiminato ligands (Gibson et al., 2000), which have Cr—O bond length of 1.947 (3) Å, Cr—N bond length of 2.074 (4) Å and Cr—Cl bond length of 2.320 (1) Å. In addition, the Cr—Cl distance for Cr1 atom bonded to one terminate Cl is somewhat shorter than those for Cr2 bonded to two Clb. The Cr—O distances for atoms bonded to Ob are longer than those for Cr bonded to β-diketiminato ligand.

Related literature top

For related literature, see: Abbati (2005); Ballem et al. (2004); Cole & Gibson (1994); Gibson et al. (2000); Jones et al. (2005); Karol et al. (1972); MacAdams et al. (2005); Smith (2005); Theopold (1998).

Experimental top

Reaction of CrCl3(THF)3 with equivalent lithium salt of β-diketiminate in dried tetrahydrofuran for 20 h at ambient temperature followed by evaporation of the solvent in vacuum to yield a crude product. To the crude product was added dried CH2Cl2, and the mixture was stirred for 10 min and then filtered. The filtrate was evaporated in vacuum to afford a solid residue, which was dissolved by toluene and layered with n-hexane. The brown crystals of the title compound were obtained in 62% yield.

Refinement top

H atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined in the riding-model approximation, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). For one of the toluene molecules, atoms C56–C62 were refined isotropically to avoid abnormal deformation of the displacement ellipsoids.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-NT (Bruker, 2003); data reduction: SAINT-NT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound with atom labels. Displacement ellipsoids are shown at the 50% probability level. H atoms not involved in hydrogen bonding have been omitted for clarity.
Di-µ-chlorido-chlorido-1κCl-(µ-1-phenyl-3-phenyliminobut-1-enolato- 1:2κ3O:O,N)bis(1-phenyl-3-phenyliminobut-1-enolato)-1κ2N,O;2κ2N,O- dichromium(III) toluene disolvate top
Crystal data top
[Cr2(C16H14NO)3Cl3]·2(C7H8)F(000) = 2296
Mr = 1103.46Dx = 1.299 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5147 reflections
a = 17.829 (4) Åθ = 2.3–26.0°
b = 12.644 (3) ŵ = 0.57 mm−1
c = 25.038 (5) ÅT = 293 K
β = 90.90 (3)°Block, blue
V = 5643 (2) Å30.45 × 0.42 × 0.08 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		9904 independent reflections
Radiation source: fine-focus sealed tube7777 reflections with I > 2σ(I)
graphiteRint = 0.024
Detector resolution: 8 pixels mm-1θmax = 25.0°, θmin = 1.6°
φ and ω scansh = −21→19
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −14→14
Tmin = 0.772, Tmax = 0.955l = −29→27
28782 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0908P)2 + 4.1962P]
where P = (Fo2 + 2Fc2)/3
9904 reflections(Δ/σ)max = 0.014
611 parametersΔρmax = 0.88 e Å−3
0 restraintsΔρmin = −0.50 e Å−3
Crystal data top
[Cr2(C16H14NO)3Cl3]·2(C7H8)V = 5643 (2) Å3
Mr = 1103.46Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.829 (4) ŵ = 0.57 mm−1
b = 12.644 (3) ÅT = 293 K
c = 25.038 (5) Å0.45 × 0.42 × 0.08 mm
β = 90.90 (3)°
Data collection top
Bruker SMART APEX CCD
diffractometer		9904 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		7777 reflections with I > 2σ(I)
Tmin = 0.772, Tmax = 0.955Rint = 0.024
28782 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.153Δρmax = 0.88 e Å−3
S = 1.02Δρmin = −0.50 e Å−3
9904 reflectionsAbsolute structure: ?
611 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cr10.21300 (3)0.47166 (4)0.408402 (18)0.03352 (14)
Cr20.27644 (3)0.57522 (4)0.506694 (18)0.03328 (14)
Cl10.21103 (4)0.65638 (6)0.43236 (3)0.04033 (19)
Cl20.34183 (4)0.47921 (6)0.43935 (3)0.04182 (19)
Cl30.08908 (4)0.46873 (7)0.38655 (3)0.0484 (2)
C10.23621 (17)0.7543 (3)0.57680 (12)0.0412 (7)
C20.2849 (2)0.7659 (3)0.61958 (16)0.0660 (11)
H2A0.30200.70670.63810.079*
C30.3084 (3)0.8663 (4)0.63509 (18)0.0749 (12)
H3A0.34050.87360.66450.090*
C40.2857 (2)0.9530 (3)0.60827 (17)0.0663 (11)
H4A0.30161.01980.61920.080*
C50.2388 (3)0.9422 (3)0.56473 (17)0.0680 (11)
H5A0.22331.00190.54580.082*
C60.2142 (2)0.8428 (3)0.54864 (15)0.0582 (9)
H6A0.18290.83600.51880.070*
C70.14930 (17)0.6124 (2)0.57870 (12)0.0397 (7)
C80.11773 (17)0.5134 (2)0.56223 (12)0.0401 (7)
H8A0.07680.49080.58180.048*
C90.13845 (16)0.4473 (2)0.52229 (11)0.0345 (6)
C100.09372 (16)0.3508 (2)0.51082 (11)0.0362 (6)
C110.01696 (17)0.3492 (3)0.52023 (13)0.0436 (7)
H11A−0.00660.40970.53290.052*
C12−0.02463 (19)0.2581 (3)0.51088 (15)0.0533 (9)
H12A−0.07580.25780.51740.064*
C130.0094 (2)0.1683 (3)0.49198 (15)0.0581 (9)
H13A−0.01860.10730.48590.070*
C140.0855 (2)0.1689 (3)0.48209 (15)0.0545 (9)
H14A0.10860.10850.46900.065*
C150.12709 (19)0.2591 (2)0.49162 (13)0.0447 (7)
H15A0.17830.25870.48510.054*
C160.1053 (2)0.6699 (3)0.62084 (15)0.0586 (10)
H16A0.13010.73520.62970.088*
H16B0.10240.62660.65220.088*
H16C0.05570.68440.60740.088*
C170.2615 (2)0.5963 (3)0.31358 (12)0.0480 (8)
C180.3346 (3)0.6290 (4)0.31626 (18)0.0795 (13)
H18A0.37180.58470.33000.095*
C190.3523 (4)0.7303 (4)0.2979 (2)0.1081 (13)
H19A0.40160.75420.29900.130*
C200.2965 (4)0.7934 (4)0.2784 (2)0.1081 (13)
H20A0.30850.86110.26670.130*
C210.2244 (4)0.7616 (4)0.2753 (2)0.1081 (13)
H21A0.18760.80570.26090.130*
C220.2064 (3)0.6625 (3)0.29382 (16)0.0691 (11)
H22A0.15670.64010.29300.083*
C230.2389 (2)0.4162 (3)0.29538 (12)0.0454 (8)
C240.2233 (2)0.3093 (3)0.30801 (13)0.0531 (9)
H24A0.21490.26320.27960.064*
C250.21957 (18)0.2683 (3)0.35811 (13)0.0434 (7)
C260.2115 (2)0.1529 (3)0.36700 (14)0.0489 (8)
C270.1626 (3)0.0931 (3)0.33530 (18)0.0660 (11)
H27A0.13510.12560.30800.079*
C280.1548 (3)−0.0142 (4)0.3441 (2)0.0922 (16)
H28A0.1216−0.05370.32320.111*
C290.1962 (4)−0.0620 (4)0.3841 (3)0.0997 (19)
H29A0.1911−0.13420.39010.120*
C300.2453 (4)−0.0041 (4)0.4152 (2)0.0882 (16)
H30A0.2737−0.03730.44180.106*
C310.2525 (3)0.1036 (3)0.40705 (16)0.0644 (10)
H31A0.28510.14290.42860.077*
C320.2546 (3)0.4401 (3)0.23774 (14)0.0646 (11)
H32A0.26480.51430.23380.097*
H32B0.21170.42140.21610.097*
H32C0.29730.40010.22660.097*
C330.29759 (18)0.4312 (3)0.59879 (13)0.0461 (8)
C340.2772 (2)0.3323 (3)0.58094 (16)0.0595 (10)
H34A0.29390.30760.54820.071*
C350.2313 (3)0.2693 (4)0.6126 (2)0.0780 (13)
H35A0.21680.20250.60070.094*
C360.2076 (3)0.3055 (4)0.6607 (2)0.0845 (15)
H36A0.17630.26350.68110.101*
C370.2289 (3)0.4015 (4)0.67933 (19)0.0834 (14)
H37A0.21310.42490.71250.100*
C380.2750 (2)0.4654 (3)0.64824 (15)0.0637 (10)
H38A0.29040.53110.66100.076*
C390.41098 (18)0.5142 (3)0.56965 (13)0.0449 (7)
C400.45142 (18)0.5924 (3)0.54261 (14)0.0484 (8)
H40A0.50350.58760.54380.058*
C410.42037 (17)0.6754 (3)0.51448 (12)0.0419 (7)
C420.46498 (18)0.7627 (3)0.49090 (14)0.0482 (8)
C430.4312 (2)0.8270 (4)0.45372 (19)0.0743 (12)
H43A0.38150.81470.44380.089*
C440.4693 (3)0.9097 (4)0.4307 (2)0.0987 (18)
H44A0.44540.95250.40550.118*
C450.5421 (3)0.9286 (4)0.4450 (2)0.0965 (17)
H45A0.56720.98630.43080.116*
C460.5781 (3)0.8632 (4)0.4801 (2)0.0844 (14)
H46A0.62860.87440.48830.101*
C470.5405 (2)0.7801 (4)0.50358 (17)0.0681 (11)
H47A0.56540.73600.52770.082*
C480.4557 (2)0.4393 (3)0.60547 (16)0.0628 (10)
H48A0.42220.38980.62170.094*
H48B0.48140.47920.63280.094*
H48C0.49160.40180.58450.094*
C490.0647 (5)0.5239 (7)0.1550 (4)0.164 (3)
H49A0.05970.51980.11680.246*
H49B0.11570.54080.16450.246*
H49C0.03210.57800.16820.246*
C500.0444 (3)0.4211 (5)0.1787 (3)0.0977 (17)
C510.0247 (4)0.3390 (7)0.1478 (2)0.112 (2)
H51A0.02470.34670.11080.135*
C520.0043 (4)0.2433 (7)0.1698 (4)0.129 (3)
H52A−0.01110.18800.14770.154*
C530.0067 (4)0.2295 (6)0.2237 (4)0.125 (2)
H53A−0.00650.16510.23880.150*
C540.0288 (3)0.3123 (6)0.2550 (2)0.1031 (18)
H54A0.03130.30400.29190.124*
C550.0473 (3)0.4063 (5)0.2333 (2)0.0929 (16)
H55A0.06230.46180.25540.111*
C560.4330 (7)0.1718 (10)0.3302 (5)0.223 (5)*
H56A0.45700.19890.36190.335*
H56B0.45700.10720.31980.335*
H56C0.38110.15850.33700.335*
C570.4390 (10)0.2464 (16)0.2888 (8)0.270 (7)*
C580.4135 (5)0.2281 (7)0.2416 (4)0.146 (3)*
H58A0.38660.16670.23400.175*
C590.4269 (7)0.3020 (10)0.2023 (5)0.204 (4)*
H59A0.41220.28380.16770.245*
C600.4589 (7)0.3970 (10)0.2085 (5)0.202 (4)*
H60A0.46210.45030.18310.242*
C610.4871 (8)0.3998 (12)0.2620 (6)0.238 (6)*
H61A0.51410.46010.27140.286*
C620.4798 (7)0.3256 (11)0.3018 (5)0.204 (5)*
H62A0.50270.33250.33530.245*
N10.21138 (13)0.6510 (2)0.55977 (10)0.0375 (6)
N20.24170 (14)0.4922 (2)0.33154 (10)0.0388 (6)
N30.33750 (14)0.5026 (2)0.56454 (10)0.0404 (6)
O10.19941 (11)0.46256 (15)0.49295 (8)0.0342 (4)
O20.22622 (12)0.32403 (17)0.40153 (8)0.0431 (5)
O30.34883 (11)0.68544 (17)0.50624 (8)0.0418 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr10.0333 (3)0.0352 (3)0.0322 (3)0.00034 (19)0.00170 (19)−0.00150 (19)
Cr20.0289 (2)0.0363 (3)0.0347 (3)−0.00178 (19)0.00146 (18)−0.00088 (19)
Cl10.0445 (4)0.0358 (4)0.0407 (4)0.0034 (3)−0.0004 (3)0.0010 (3)
Cl20.0317 (4)0.0513 (5)0.0426 (4)0.0041 (3)0.0033 (3)−0.0048 (3)
Cl30.0361 (4)0.0611 (5)0.0481 (5)−0.0016 (3)−0.0026 (3)−0.0037 (4)
C10.0397 (17)0.0437 (18)0.0404 (17)−0.0063 (14)0.0076 (13)−0.0102 (14)
C20.081 (3)0.058 (2)0.059 (2)−0.003 (2)−0.017 (2)−0.0103 (19)
C30.082 (3)0.073 (3)0.069 (3)−0.013 (2)−0.018 (2)−0.026 (2)
C40.076 (3)0.055 (2)0.068 (3)−0.023 (2)0.017 (2)−0.023 (2)
C50.087 (3)0.047 (2)0.070 (3)−0.011 (2)0.005 (2)−0.0064 (19)
C60.068 (2)0.049 (2)0.058 (2)−0.0079 (18)−0.0078 (18)−0.0062 (17)
C70.0355 (16)0.0445 (17)0.0392 (16)−0.0005 (13)0.0038 (13)−0.0034 (13)
C80.0351 (16)0.0433 (17)0.0421 (17)−0.0044 (13)0.0079 (13)−0.0024 (13)
C90.0310 (15)0.0357 (15)0.0367 (15)−0.0001 (12)0.0008 (12)0.0059 (12)
C100.0375 (16)0.0369 (16)0.0344 (15)−0.0038 (12)0.0010 (12)0.0027 (12)
C110.0376 (16)0.0443 (18)0.0490 (18)0.0005 (14)0.0014 (14)−0.0017 (14)
C120.0365 (17)0.059 (2)0.064 (2)−0.0107 (16)0.0010 (15)−0.0046 (18)
C130.060 (2)0.049 (2)0.065 (2)−0.0183 (18)0.0014 (18)−0.0055 (18)
C140.063 (2)0.0377 (18)0.063 (2)−0.0036 (16)0.0074 (18)−0.0066 (16)
C150.0446 (18)0.0408 (17)0.0491 (18)−0.0009 (14)0.0087 (14)0.0005 (14)
C160.055 (2)0.061 (2)0.061 (2)−0.0106 (18)0.0220 (18)−0.0201 (18)
C170.064 (2)0.0453 (19)0.0346 (16)−0.0054 (16)0.0088 (15)−0.0008 (14)
C180.080 (3)0.087 (3)0.072 (3)−0.031 (3)0.002 (2)0.015 (2)
C190.170 (4)0.068 (2)0.086 (2)−0.028 (2)0.015 (2)0.0124 (16)
C200.170 (4)0.068 (2)0.086 (2)−0.028 (2)0.015 (2)0.0124 (16)
C210.170 (4)0.068 (2)0.086 (2)−0.028 (2)0.015 (2)0.0124 (16)
C220.096 (3)0.058 (2)0.054 (2)0.014 (2)0.013 (2)0.0062 (19)
C230.055 (2)0.0488 (19)0.0330 (16)0.0010 (15)0.0031 (14)−0.0039 (14)
C240.077 (2)0.0429 (19)0.0395 (18)−0.0013 (17)0.0032 (17)−0.0075 (15)
C250.0463 (18)0.0396 (17)0.0445 (18)0.0027 (14)0.0041 (14)−0.0038 (14)
C260.060 (2)0.0368 (17)0.0500 (19)0.0048 (15)0.0112 (16)−0.0040 (14)
C270.080 (3)0.044 (2)0.075 (3)−0.0032 (19)0.003 (2)−0.0066 (19)
C280.115 (4)0.050 (3)0.112 (4)−0.017 (3)0.012 (3)−0.013 (3)
C290.152 (6)0.040 (2)0.108 (4)0.002 (3)0.036 (4)0.005 (3)
C300.127 (4)0.063 (3)0.075 (3)0.038 (3)0.021 (3)0.020 (2)
C310.083 (3)0.052 (2)0.058 (2)0.017 (2)0.006 (2)0.0038 (18)
C320.096 (3)0.059 (2)0.0390 (19)−0.001 (2)0.0133 (19)−0.0038 (17)
C330.0395 (18)0.051 (2)0.0470 (18)0.0001 (14)−0.0058 (14)0.0124 (15)
C340.063 (2)0.049 (2)0.066 (2)−0.0008 (18)−0.0135 (19)0.0114 (18)
C350.080 (3)0.059 (3)0.094 (4)−0.018 (2)−0.025 (3)0.030 (2)
C360.070 (3)0.095 (4)0.088 (4)−0.014 (3)−0.002 (3)0.047 (3)
C370.091 (3)0.095 (4)0.065 (3)0.002 (3)0.018 (2)0.031 (3)
C380.073 (3)0.068 (3)0.050 (2)0.001 (2)0.0061 (19)0.0129 (18)
C390.0404 (18)0.0509 (19)0.0432 (17)0.0038 (15)−0.0040 (14)−0.0023 (15)
C400.0321 (17)0.058 (2)0.055 (2)−0.0017 (15)0.0003 (14)0.0015 (16)
C410.0354 (17)0.0493 (18)0.0411 (17)−0.0060 (14)0.0038 (13)−0.0084 (14)
C420.0377 (17)0.052 (2)0.055 (2)−0.0071 (15)0.0067 (15)−0.0041 (16)
C430.054 (2)0.079 (3)0.090 (3)−0.011 (2)0.004 (2)0.029 (2)
C440.070 (3)0.101 (4)0.126 (4)−0.015 (3)0.007 (3)0.057 (3)
C450.070 (3)0.092 (4)0.128 (5)−0.030 (3)0.021 (3)0.034 (3)
C460.054 (2)0.096 (4)0.104 (4)−0.032 (2)0.006 (2)0.010 (3)
C470.050 (2)0.075 (3)0.079 (3)−0.020 (2)−0.0023 (19)0.004 (2)
C480.047 (2)0.075 (3)0.066 (2)0.0061 (18)−0.0123 (18)0.017 (2)
C490.140 (7)0.155 (7)0.199 (9)0.009 (6)0.009 (6)0.068 (7)
C500.074 (3)0.116 (5)0.103 (4)0.008 (3)0.006 (3)0.010 (4)
C510.096 (4)0.161 (7)0.079 (4)0.017 (4)−0.008 (3)−0.030 (4)
C520.097 (5)0.143 (7)0.146 (7)−0.007 (5)−0.007 (5)−0.054 (6)
C530.100 (5)0.121 (6)0.154 (7)−0.011 (4)0.011 (5)0.021 (5)
C540.088 (4)0.139 (6)0.082 (4)−0.007 (4)−0.001 (3)−0.004 (4)
C550.080 (3)0.117 (5)0.081 (4)−0.001 (3)−0.001 (3)−0.013 (3)
N10.0358 (13)0.0391 (14)0.0375 (13)−0.0026 (11)0.0019 (10)−0.0053 (11)
N20.0412 (14)0.0399 (14)0.0354 (13)0.0011 (11)0.0043 (11)0.0020 (11)
N30.0364 (14)0.0446 (15)0.0401 (14)−0.0021 (11)−0.0006 (11)0.0026 (11)
O10.0310 (10)0.0366 (11)0.0349 (10)−0.0027 (8)0.0024 (8)−0.0012 (8)
O20.0527 (13)0.0382 (12)0.0383 (11)0.0014 (10)0.0014 (10)−0.0013 (9)
O30.0320 (11)0.0425 (12)0.0510 (12)−0.0053 (9)0.0011 (9)−0.0003 (10)
Geometric parameters (Å, °) top
Cr1—O21.890 (2)C29—H29A0.9300
Cr1—N22.016 (2)C30—C311.383 (6)
Cr1—O12.138 (2)C30—H30A0.9300
Cr1—Cl32.2680 (10)C31—H31A0.9300
Cr1—Cl12.4116 (10)C32—H32A0.9600
Cr1—Cl22.4145 (10)C32—H32B0.9600
Cr2—O31.900 (2)C32—H32C0.9600
Cr2—O12.005 (2)C33—C341.374 (5)
Cr2—N32.019 (3)C33—C381.378 (5)
Cr2—N12.019 (2)C33—N31.441 (4)
Cr2—Cl22.3954 (10)C34—C351.398 (6)
Cr2—Cl12.4101 (10)C34—H34A0.9300
C1—C21.376 (5)C35—C361.363 (7)
C1—C61.376 (5)C35—H35A0.9300
C1—N11.441 (4)C36—C371.353 (7)
C2—C31.390 (6)C36—H36A0.9300
C2—H2A0.9300C37—C381.397 (6)
C3—C41.345 (6)C37—H37A0.9300
C3—H3A0.9300C38—H38A0.9300
C4—C51.370 (6)C39—N31.322 (4)
C4—H4A0.9300C39—C401.404 (5)
C5—C61.389 (5)C39—C481.520 (5)
C5—H5A0.9300C40—C411.375 (5)
C6—H6A0.9300C40—H40A0.9300
C7—N11.306 (4)C41—O31.295 (4)
C7—C81.431 (4)C41—C421.489 (5)
C7—C161.511 (4)C42—C431.369 (5)
C8—C91.359 (4)C42—C471.396 (5)
C8—H8A0.9300C43—C441.378 (6)
C9—O11.335 (3)C43—H43A0.9300
C9—C101.484 (4)C44—C451.362 (7)
C10—C151.391 (4)C44—H44A0.9300
C10—C111.392 (4)C45—C461.360 (7)
C11—C121.388 (5)C45—H45A0.9300
C11—H11A0.9300C46—C471.383 (6)
C12—C131.376 (5)C46—H46A0.9300
C12—H12A0.9300C47—H47A0.9300
C13—C141.382 (5)C48—H48A0.9600
C13—H13A0.9300C48—H48B0.9600
C14—C151.380 (5)C48—H48C0.9600
C14—H14A0.9300C49—C501.478 (9)
C15—H15A0.9300C49—H49A0.9600
C16—H16A0.9600C49—H49B0.9600
C16—H16B0.9600C49—H49C0.9600
C16—H16C0.9600C50—C511.339 (9)
C17—C181.367 (6)C50—C551.378 (8)
C17—C221.376 (6)C51—C521.381 (10)
C17—N21.437 (4)C51—H51A0.9300
C18—C191.399 (7)C52—C531.361 (10)
C18—H18A0.9300C52—H52A0.9300
C19—C201.360 (9)C53—C541.363 (9)
C19—H19A0.9300C53—H53A0.9300
C20—C211.347 (9)C54—C551.350 (8)
C20—H20A0.9300C54—H54A0.9300
C21—C221.376 (6)C55—H55A0.9300
C21—H21A0.9300C56—C571.406 (18)
C22—H22A0.9300C56—H56A0.9600
C23—N21.321 (4)C56—H56B0.9600
C23—C241.416 (5)C56—H56C0.9600
C23—C321.505 (5)C57—C621.277 (18)
C24—C251.360 (5)C57—C581.280 (18)
C24—H24A0.9300C58—C591.381 (13)
C25—O21.299 (4)C58—H58A0.9300
C25—C261.484 (5)C59—C601.337 (14)
C26—C311.381 (5)C59—H59A0.9300
C26—C271.392 (5)C60—C611.423 (15)
C27—C281.382 (6)C60—H60A0.9300
C27—H27A0.9300C61—C621.375 (15)
C28—C291.375 (8)C61—H61A0.9300
C28—H28A0.9300C62—H62A0.9300
C29—C301.373 (8)
O2—Cr1—N290.36 (10)C31—C30—H30A119.9
O2—Cr1—O193.05 (8)C26—C31—C30120.1 (5)
N2—Cr1—O1170.66 (9)C26—C31—H31A119.9
O2—Cr1—Cl394.83 (7)C30—C31—H31A119.9
N2—Cr1—Cl391.88 (8)C23—C32—H32A109.5
O1—Cr1—Cl396.49 (7)C23—C32—H32B109.5
O2—Cr1—Cl1168.99 (7)H32A—C32—H32B109.5
N2—Cr1—Cl196.76 (8)C23—C32—H32C109.5
O1—Cr1—Cl178.67 (6)H32A—C32—H32C109.5
Cl3—Cr1—Cl193.32 (3)H32B—C32—H32C109.5
O2—Cr1—Cl287.07 (7)C34—C33—C38119.9 (3)
N2—Cr1—Cl292.68 (8)C34—C33—N3120.4 (3)
O1—Cr1—Cl278.83 (6)C38—C33—N3119.5 (3)
Cl3—Cr1—Cl2175.05 (3)C33—C34—C35119.2 (4)
Cl1—Cr1—Cl284.22 (3)C33—C34—H34A120.4
O3—Cr2—O1169.72 (9)C35—C34—H34A120.4
O3—Cr2—N388.80 (10)C36—C35—C34120.1 (4)
O1—Cr2—N399.22 (10)C36—C35—H35A119.9
O3—Cr2—N193.04 (10)C34—C35—H35A119.9
O1—Cr2—N192.94 (9)C37—C36—C35121.1 (4)
N3—Cr2—N193.02 (11)C37—C36—H36A119.4
O3—Cr2—Cl291.68 (7)C35—C36—H36A119.4
O1—Cr2—Cl281.88 (6)C36—C37—C38119.4 (5)
N3—Cr2—Cl290.66 (8)C36—C37—H37A120.3
N1—Cr2—Cl2174.07 (7)C38—C37—H37A120.3
O3—Cr2—Cl190.21 (7)C33—C38—C37120.1 (4)
O1—Cr2—Cl181.26 (6)C33—C38—H38A119.9
N3—Cr2—Cl1175.20 (8)C37—C38—H38A119.9
N1—Cr2—Cl191.73 (8)N3—C39—C40123.1 (3)
Cl2—Cr2—Cl184.67 (3)N3—C39—C48119.8 (3)
Cr2—Cl1—Cr176.77 (3)C40—C39—C48117.0 (3)
Cr2—Cl2—Cr176.99 (3)C41—C40—C39125.4 (3)
C2—C1—C6118.9 (3)C41—C40—H40A117.3
C2—C1—N1120.9 (3)C39—C40—H40A117.3
C6—C1—N1120.1 (3)O3—C41—C40123.0 (3)
C1—C2—C3119.9 (4)O3—C41—C42113.3 (3)
C1—C2—H2A120.0C40—C41—C42123.8 (3)
C3—C2—H2A120.0C43—C42—C47118.3 (3)
C4—C3—C2121.2 (4)C43—C42—C41118.6 (3)
C4—C3—H3A119.4C47—C42—C41123.1 (3)
C2—C3—H3A119.4C42—C43—C44121.3 (4)
C3—C4—C5119.4 (4)C42—C43—H43A119.3
C3—C4—H4A120.3C44—C43—H43A119.3
C5—C4—H4A120.3C45—C44—C43119.8 (5)
C4—C5—C6120.4 (4)C45—C44—H44A120.1
C4—C5—H5A119.8C43—C44—H44A120.1
C6—C5—H5A119.8C46—C45—C44120.1 (4)
C1—C6—C5120.1 (4)C46—C45—H45A119.9
C1—C6—H6A120.0C44—C45—H45A119.9
C5—C6—H6A120.0C45—C46—C47120.6 (4)
N1—C7—C8123.7 (3)C45—C46—H46A119.7
N1—C7—C16121.7 (3)C47—C46—H46A119.7
C8—C7—C16114.6 (3)C46—C47—C42119.7 (4)
C9—C8—C7129.8 (3)C46—C47—H47A120.2
C9—C8—H8A115.1C42—C47—H47A120.2
C7—C8—H8A115.1C39—C48—H48A109.5
O1—C9—C8123.3 (3)C39—C48—H48B109.5
O1—C9—C10116.9 (2)H48A—C48—H48B109.5
C8—C9—C10119.8 (3)C39—C48—H48C109.5
C15—C10—C11118.3 (3)H48A—C48—H48C109.5
C15—C10—C9121.4 (3)H48B—C48—H48C109.5
C11—C10—C9120.4 (3)C50—C49—H49A109.5
C12—C11—C10120.5 (3)C50—C49—H49B109.5
C12—C11—H11A119.8H49A—C49—H49B109.5
C10—C11—H11A119.8C50—C49—H49C109.5
C13—C12—C11120.4 (3)H49A—C49—H49C109.5
C13—C12—H12A119.8H49B—C49—H49C109.5
C11—C12—H12A119.8C51—C50—C55118.4 (6)
C12—C13—C14119.8 (3)C51—C50—C49120.8 (7)
C12—C13—H13A120.1C55—C50—C49120.8 (7)
C14—C13—H13A120.1C50—C51—C52121.1 (6)
C15—C14—C13120.0 (3)C50—C51—H51A119.5
C15—C14—H14A120.0C52—C51—H51A119.5
C13—C14—H14A120.0C53—C52—C51120.3 (7)
C14—C15—C10121.1 (3)C53—C52—H52A119.9
C14—C15—H15A119.4C51—C52—H52A119.9
C10—C15—H15A119.4C52—C53—C54118.4 (7)
C7—C16—H16A109.5C52—C53—H53A120.8
C7—C16—H16B109.5C54—C53—H53A120.8
H16A—C16—H16B109.5C55—C54—C53121.0 (6)
C7—C16—H16C109.5C55—C54—H54A119.5
H16A—C16—H16C109.5C53—C54—H54A119.5
H16B—C16—H16C109.5C54—C55—C50120.8 (6)
C18—C17—C22120.5 (4)C54—C55—H55A119.6
C18—C17—N2120.0 (4)C50—C55—H55A119.6
C22—C17—N2119.5 (3)C57—C56—H56A109.5
C17—C18—C19118.7 (5)C57—C56—H56B109.5
C17—C18—H18A120.6H56A—C56—H56B109.5
C19—C18—H18A120.6C57—C56—H56C109.5
C20—C19—C18119.2 (6)H56A—C56—H56C109.5
C20—C19—H19A120.4H56B—C56—H56C109.5
C18—C19—H19A120.4C62—C57—C58124.8 (19)
C21—C20—C19122.4 (6)C62—C57—C56112.8 (19)
C21—C20—H20A118.8C58—C57—C56121.9 (18)
C19—C20—H20A118.8C57—C58—C59118.1 (14)
C20—C21—C22118.7 (6)C57—C58—H58A120.9
C20—C21—H21A120.6C59—C58—H58A120.9
C22—C21—H21A120.6C60—C59—C58127.1 (13)
C21—C22—C17120.4 (5)C60—C59—H59A116.5
C21—C22—H22A119.8C58—C59—H59A116.5
C17—C22—H22A119.8C59—C60—C61106.0 (13)
N2—C23—C24123.1 (3)C59—C60—H60A127.0
N2—C23—C32120.3 (3)C61—C60—H60A127.0
C24—C23—C32116.5 (3)C62—C61—C60128.9 (15)
C25—C24—C23125.6 (3)C62—C61—H61A115.5
C25—C24—H24A117.2C60—C61—H61A115.5
C23—C24—H24A117.2C57—C62—C61114.2 (17)
O2—C25—C24124.0 (3)C57—C62—H62A122.9
O2—C25—C26114.6 (3)C61—C62—H62A122.9
C24—C25—C26121.3 (3)C7—N1—C1119.3 (2)
C31—C26—C27119.3 (4)C7—N1—Cr2124.1 (2)
C31—C26—C25120.1 (3)C1—N1—Cr2116.61 (18)
C27—C26—C25120.6 (3)C23—N2—C17117.3 (3)
C28—C27—C26120.4 (5)C23—N2—Cr1123.6 (2)
C28—C27—H27A119.8C17—N2—Cr1118.95 (19)
C26—C27—H27A119.8C39—N3—C33120.6 (3)
C29—C28—C27119.6 (5)C39—N3—Cr2122.8 (2)
C29—C28—H28A120.2C33—N3—Cr2116.5 (2)
C27—C28—H28A120.2C9—O1—Cr2124.71 (18)
C30—C29—C28120.5 (5)C9—O1—Cr1131.18 (18)
C30—C29—H29A119.7Cr2—O1—Cr192.51 (8)
C28—C29—H29A119.7C25—O2—Cr1127.0 (2)
C29—C30—C31120.1 (5)C41—O3—Cr2126.5 (2)
C29—C30—H30A119.9
O3—Cr2—Cl1—Cr1135.75 (7)C62—C57—C58—C59−4(2)
O1—Cr2—Cl1—Cr1−38.50 (6)C56—C57—C58—C59−174.9 (13)
N3—Cr2—Cl1—Cr157.7 (9)C57—C58—C59—C60−6(2)
N1—Cr2—Cl1—Cr1−131.20 (7)C58—C59—C60—C619.1 (19)
Cl2—Cr2—Cl1—Cr144.08 (3)C59—C60—C61—C62−4(2)
O2—Cr1—Cl1—Cr2−5.8 (4)C58—C57—C62—C618(3)
N2—Cr1—Cl1—Cr2−135.71 (8)C56—C57—C62—C61179.7 (12)
O1—Cr1—Cl1—Cr236.05 (6)C60—C61—C62—C57−4(2)
Cl3—Cr1—Cl1—Cr2132.00 (4)C8—C7—N1—C1176.5 (3)
Cl2—Cr1—Cl1—Cr2−43.69 (3)C16—C7—N1—C1−4.2 (5)
O3—Cr2—Cl2—Cr1−134.02 (7)C8—C7—N1—Cr2−3.1 (4)
O1—Cr2—Cl2—Cr137.94 (6)C16—C7—N1—Cr2176.3 (3)
N3—Cr2—Cl2—Cr1137.16 (8)C2—C1—N1—C792.6 (4)
N1—Cr2—Cl2—Cr18.7 (8)C6—C1—N1—C7−90.6 (4)
Cl1—Cr2—Cl2—Cr1−43.97 (3)C2—C1—N1—Cr2−87.8 (3)
O2—Cr1—Cl2—Cr2−129.28 (7)C6—C1—N1—Cr289.0 (3)
N2—Cr1—Cl2—Cr2140.50 (8)O3—Cr2—N1—C7−178.3 (3)
O1—Cr1—Cl2—Cr2−35.58 (6)O1—Cr2—N1—C710.1 (3)
Cl3—Cr1—Cl2—Cr2−16.5 (4)N3—Cr2—N1—C7−89.4 (3)
Cl1—Cr1—Cl2—Cr243.97 (3)Cl2—Cr2—N1—C739.0 (9)
C6—C1—C2—C32.8 (6)Cl1—Cr2—N1—C791.4 (2)
N1—C1—C2—C3179.6 (4)O3—Cr2—N1—C12.1 (2)
C1—C2—C3—C4−1.4 (7)O1—Cr2—N1—C1−169.5 (2)
C2—C3—C4—C5−0.4 (7)N3—Cr2—N1—C191.1 (2)
C3—C4—C5—C60.7 (7)Cl2—Cr2—N1—C1−140.6 (7)
C2—C1—C6—C5−2.5 (6)Cl1—Cr2—N1—C1−88.2 (2)
N1—C1—C6—C5−179.3 (3)C24—C23—N2—C17177.2 (3)
C4—C5—C6—C10.8 (6)C32—C23—N2—C17−1.2 (5)
N1—C7—C8—C9−7.6 (6)C24—C23—N2—Cr1−7.1 (5)
C16—C7—C8—C9173.1 (3)C32—C23—N2—Cr1174.5 (3)
C7—C8—C9—O15.6 (5)C18—C17—N2—C23−93.7 (4)
C7—C8—C9—C10−176.5 (3)C22—C17—N2—C2386.4 (4)
O1—C9—C10—C1529.8 (4)C18—C17—N2—Cr190.5 (4)
C8—C9—C10—C15−148.3 (3)C22—C17—N2—Cr1−89.5 (3)
O1—C9—C10—C11−151.6 (3)O2—Cr1—N2—C2320.3 (3)
C8—C9—C10—C1130.3 (4)O1—Cr1—N2—C23131.8 (5)
C15—C10—C11—C120.4 (5)Cl3—Cr1—N2—C23−74.6 (3)
C9—C10—C11—C12−178.3 (3)Cl1—Cr1—N2—C23−168.2 (3)
C10—C11—C12—C13−0.3 (5)Cl2—Cr1—N2—C23107.4 (3)
C11—C12—C13—C14−0.2 (6)O2—Cr1—N2—C17−164.2 (2)
C12—C13—C14—C150.5 (6)O1—Cr1—N2—C17−52.6 (7)
C13—C14—C15—C10−0.4 (5)Cl3—Cr1—N2—C17101.0 (2)
C11—C10—C15—C140.0 (5)Cl1—Cr1—N2—C177.4 (2)
C9—C10—C15—C14178.6 (3)Cl2—Cr1—N2—C17−77.1 (2)
C22—C17—C18—C19−0.8 (6)C40—C39—N3—C33−171.2 (3)
N2—C17—C18—C19179.2 (4)C48—C39—N3—C3310.0 (5)
C17—C18—C19—C200.5 (8)C40—C39—N3—Cr212.6 (5)
C18—C19—C20—C21−1.0 (9)C48—C39—N3—Cr2−166.2 (3)
C19—C20—C21—C221.7 (9)C34—C33—N3—C39−100.1 (4)
C20—C21—C22—C17−2.0 (7)C38—C33—N3—C3984.7 (4)
C18—C17—C22—C211.6 (6)C34—C33—N3—Cr276.3 (4)
N2—C17—C22—C21−178.5 (4)C38—C33—N3—Cr2−98.9 (3)
N2—C23—C24—C25−9.6 (6)O3—Cr2—N3—C39−28.1 (3)
C32—C23—C24—C25168.9 (4)O1—Cr2—N3—C39145.4 (2)
C23—C24—C25—O23.7 (6)N1—Cr2—N3—C39−121.1 (3)
C23—C24—C25—C26−172.9 (4)Cl2—Cr2—N3—C3963.6 (3)
O2—C25—C26—C31−39.0 (5)Cl1—Cr2—N3—C3950.0 (11)
C24—C25—C26—C31137.9 (4)O3—Cr2—N3—C33155.5 (2)
O2—C25—C26—C27140.9 (3)O1—Cr2—N3—C33−30.9 (2)
C24—C25—C26—C27−42.2 (5)N1—Cr2—N3—C3362.6 (2)
C31—C26—C27—C280.6 (6)Cl2—Cr2—N3—C33−112.8 (2)
C25—C26—C27—C28−179.3 (4)Cl1—Cr2—N3—C33−126.3 (9)
C26—C27—C28—C29−0.8 (7)C8—C9—O1—Cr26.5 (4)
C27—C28—C29—C300.0 (8)C10—C9—O1—Cr2−171.47 (18)
C28—C29—C30—C311.0 (8)C8—C9—O1—Cr1−126.1 (3)
C27—C26—C31—C300.4 (6)C10—C9—O1—Cr155.9 (3)
C25—C26—C31—C30−179.7 (4)O3—Cr2—O1—C9−137.3 (5)
C29—C30—C31—C26−1.2 (7)N3—Cr2—O1—C981.7 (2)
C38—C33—C34—C352.5 (5)N1—Cr2—O1—C9−11.8 (2)
N3—C33—C34—C35−172.7 (3)Cl2—Cr2—O1—C9171.0 (2)
C33—C34—C35—C36−0.6 (6)Cl1—Cr2—O1—C9−103.1 (2)
C34—C35—C36—C37−1.2 (7)O3—Cr2—O1—Cr19.0 (5)
C35—C36—C37—C381.1 (8)N3—Cr2—O1—Cr1−131.98 (9)
C34—C33—C38—C37−2.6 (6)N1—Cr2—O1—Cr1134.48 (9)
N3—C33—C38—C37172.6 (4)Cl2—Cr2—O1—Cr1−42.63 (6)
C36—C37—C38—C330.8 (7)Cl1—Cr2—O1—Cr143.18 (6)
N3—C39—C40—C4110.4 (6)O2—Cr1—O1—C9−88.2 (2)
C48—C39—C40—C41−170.7 (3)N2—Cr1—O1—C9160.5 (5)
C39—C40—C41—O3−5.9 (5)Cl3—Cr1—O1—C97.0 (2)
C39—C40—C41—C42173.6 (3)Cl1—Cr1—O1—C999.1 (2)
O3—C41—C42—C43−15.5 (5)Cl2—Cr1—O1—C9−174.6 (2)
C40—C41—C42—C43165.0 (4)O2—Cr1—O1—Cr2129.10 (9)
O3—C41—C42—C47166.7 (3)N2—Cr1—O1—Cr217.8 (6)
C40—C41—C42—C47−12.8 (5)Cl3—Cr1—O1—Cr2−135.68 (6)
C47—C42—C43—C44−2.6 (7)Cl1—Cr1—O1—Cr2−43.58 (6)
C41—C42—C43—C44179.5 (5)Cl2—Cr1—O1—Cr242.69 (6)
C42—C43—C44—C45−0.1 (9)C24—C25—O2—Cr120.0 (5)
C43—C44—C45—C463.0 (10)C26—C25—O2—Cr1−163.2 (2)
C44—C45—C46—C47−3.2 (9)N2—Cr1—O2—C25−27.0 (3)
C45—C46—C47—C420.5 (8)O1—Cr1—O2—C25161.7 (3)
C43—C42—C47—C462.3 (6)Cl3—Cr1—O2—C2564.9 (3)
C41—C42—C47—C46−179.9 (4)Cl1—Cr1—O2—C25−157.4 (3)
C55—C50—C51—C523.0 (9)Cl2—Cr1—O2—C25−119.7 (3)
C49—C50—C51—C52−178.9 (7)C40—C41—O3—Cr2−23.6 (4)
C50—C51—C52—C53−2.5 (11)C42—C41—O3—Cr2156.8 (2)
C51—C52—C53—C540.6 (11)O1—Cr2—O3—C41−107.4 (5)
C52—C53—C54—C550.6 (10)N3—Cr2—O3—C4134.2 (2)
C53—C54—C55—C50−0.1 (9)N1—Cr2—O3—C41127.1 (2)
C51—C50—C55—C54−1.8 (9)Cl2—Cr2—O3—C41−56.5 (2)
C49—C50—C55—C54−179.9 (6)Cl1—Cr2—O3—C41−141.1 (2)
Acknowledgements top

The authors are grateful for financial support by the National Natural Science Foundation of China.

references
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