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Acta Cryst. (2008). E64, m2    [ doi:10.1107/S1600536807061296 ]

[mu]-Oxido-bis{chlorido[tris(2-pyridylmethyl)amine]chromium(III)} bis(hexafluoridophosphate)

S. Li, S.-B. Wang, F.-L. Zhang and K. Tang

Abstract top

The title compound, [Cr2Cl2O(C18H18N4)2](PF6)2, is isostructural with the VIII analogue. Each CrIII atom is chelated by the tetradentate tris(2-pyridylmethyl)amine ligand via four N atoms, and further coordinated by one Cl atom and one bridging O atom, giving a slightly distorted octahedral coordination geometry. The dinuclear complex is centrosymmetric, with the bridging O atom lying on a centre of inversion.

Comment top

A classical but nevertheless rapidly developing field of application for related metal-Schiff compounds is their use as catalysts in polymerization, oxidation reactions, and model examples for the interaction of metal ions within the active sites of enzymes (Butler & Carrano, 1991; Crans et al., 1989; Dey, 1974; Chen & Zubieta, 1990). In the dinuclear title compound (Fig. 1), each CrIII atom is chelated by the tetradentate ligand tris(2-pyridylmethyl)amine via four N atoms, and further coordinated by one Cl atom and one bridging O atom to give a slightly distorted octahedral coordination geometry.

Related literature top

For the isostructural VIII analogue, see: Tajika et al. (2005). For more general related literature, see: Butler & Carrano (1991); Crans et al. (1989); Dey (1974); Chen & Zubieta (1990).

Experimental top

A mixture of chromium(III) trichloride (1 mmol) and tris(2-pyridylmethyl)amine (1 mmol) in 20 ml me thanol was refluxed for two hours. After cooling, the solution was filtered and the filtrate was evaporated naturally at room temperature. Blue blocks of the title compound were obtained after a few days with a yield of 31%. Elemental analysis calculated: C 40.39, H 3.35, N 10.44%; found: C 40.35, H 3.39, N 10.42%.

Refinement top

All H atoms were placed in calculated positions with C—H = 0.93 or 0.97 Å and refined as riding with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure drawn with 30% probability displacement ellipsoids for the non-H atoms.
µ-Oxido-bis{chlorido[tris(2-pyridylmethyl)amine]chromium(III)} dihexafluoridophosphate top
Crystal data top
[Cr2Cl2O(C18H18N4)2](PF6)2Z = 1
Mr = 1061.57F000 = 536
Triclinic, P1Dx = 1.671 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.6107 (17) ÅCell parameters from 3877 reflections
b = 11.302 (2) Åθ = 3.0–25.5º
c = 12.798 (3) ŵ = 0.81 mm−1
α = 115.50 (3)ºT = 293 (2) K
β = 107.45 (3)ºBlock, blue
γ = 91.50 (3)º0.28 × 0.22 × 0.18 mm
V = 1054.8 (4) Å3
Data collection top
Bruker APEX II CCD
diffractometer		3877 independent reflections
Radiation source: fine-focus sealed tube3594 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 293(2) Kθmax = 25.5º
φ and ω scansθmin = 3.0º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −8→10
Tmin = 0.804, Tmax = 0.867k = −13→13
8686 measured reflectionsl = −15→15
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033  w = 1/[σ2(Fo2) + (0.0565P)2 + 0.3428P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.089(Δ/σ)max < 0.001
S = 1.00Δρmax = 0.51 e Å−3
3877 reflectionsΔρmin = −0.33 e Å−3
287 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.042 (3)
Secondary atom site location: difference Fourier map
Crystal data top
[Cr2Cl2O(C18H18N4)2](PF6)2γ = 91.50 (3)º
Mr = 1061.57V = 1054.8 (4) Å3
Triclinic, P1Z = 1
a = 8.6107 (17) ÅMo Kα
b = 11.302 (2) ŵ = 0.81 mm−1
c = 12.798 (3) ÅT = 293 (2) K
α = 115.50 (3)º0.28 × 0.22 × 0.18 mm
β = 107.45 (3)º
Data collection top
Bruker APEX II CCD
diffractometer		3877 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		3594 reflections with I > 2σ(I)
Tmin = 0.804, Tmax = 0.867Rint = 0.021
8686 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033287 parameters
wR(F2) = 0.089H-atom parameters constrained
S = 1.00Δρmax = 0.51 e Å−3
3877 reflectionsΔρmin = −0.33 e Å−3
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
Cr11.03745 (3)0.34679 (3)0.39271 (2)0.0408 (4)
C10.9871 (3)0.1897 (2)0.53070 (18)0.0447 (4)
H11.10180.19840.55730.054*
C20.8992 (3)0.1306 (2)0.5741 (2)0.0534 (5)
H20.95330.09980.62960.064*
C30.7284 (3)0.1173 (3)0.5340 (2)0.0605 (6)
H30.66620.07790.56260.073*
C40.6514 (3)0.1630 (2)0.4513 (2)0.0552 (5)
H40.53670.15370.42260.066*
C50.7464 (2)0.22306 (19)0.41135 (18)0.0425 (4)
C60.6721 (2)0.2874 (2)0.3310 (2)0.0490 (5)
H6A0.56430.23530.27300.059*
H6B0.65630.37570.38220.059*
C70.7467 (3)0.1753 (2)0.1450 (2)0.0573 (6)
H7A0.74430.20040.08110.069*
H7B0.63810.12530.12160.069*
C80.8712 (2)0.08565 (19)0.14924 (17)0.0414 (4)
C90.8351 (3)−0.0448 (2)0.0588 (2)0.0528 (5)
H90.7315−0.0793−0.00280.063*
C100.9546 (3)−0.1237 (2)0.0606 (2)0.0617 (6)
H100.9327−0.21190.00030.074*
C111.1069 (3)−0.0697 (2)0.1532 (2)0.0607 (6)
H111.1894−0.12080.15640.073*
C121.1346 (3)0.0605 (2)0.2404 (2)0.0526 (5)
H121.23740.09640.30280.063*
C130.7605 (3)0.4147 (2)0.23723 (19)0.0475 (5)
H13A0.74300.48810.30590.057*
H13B0.66510.39170.16390.057*
C140.9146 (3)0.4574 (2)0.21891 (17)0.0471 (5)
C150.9138 (4)0.5296 (2)0.1547 (2)0.0606 (6)
H150.81540.54820.11490.073*
C161.0629 (4)0.5734 (3)0.1512 (2)0.0728 (8)
H161.06500.62370.11000.087*
C171.2075 (4)0.5435 (3)0.2077 (3)0.0715 (7)
H171.30760.57210.20470.086*
C181.2007 (3)0.4704 (3)0.2686 (2)0.0610 (6)
H181.29780.44900.30690.073*
Cl11.31398 (6)0.35078 (6)0.48445 (5)0.05507 (17)
F10.5115 (2)0.90789 (16)0.13882 (17)0.0825 (5)
F20.4878 (2)0.8490 (2)0.27945 (15)0.0893 (5)
F30.5830 (3)0.6607 (2)0.1912 (2)0.1078 (7)
F40.7325 (2)0.8610 (2)0.24906 (17)0.0999 (6)
F50.6040 (2)0.72005 (19)0.04870 (17)0.0929 (6)
F60.36012 (19)0.71102 (16)0.08031 (14)0.0726 (4)
N11.0192 (2)0.13917 (16)0.23969 (15)0.0436 (4)
N21.0566 (2)0.42848 (18)0.27454 (16)0.0482 (4)
N30.91312 (19)0.23567 (15)0.45104 (15)0.0406 (3)
N40.7776 (2)0.29834 (16)0.26214 (15)0.0424 (4)
O11.00000.50000.50000.0420 (4)
P10.54870 (7)0.78424 (6)0.16549 (5)0.05276 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr10.0378 (11)0.0424 (10)0.0424 (10)0.0088 (8)0.0112 (8)0.0212 (8)
C10.0415 (10)0.0468 (10)0.0459 (10)0.0095 (8)0.0121 (8)0.0233 (8)
C20.0597 (14)0.0546 (12)0.0513 (12)0.0109 (10)0.0179 (10)0.0300 (10)
C30.0606 (14)0.0666 (14)0.0669 (14)0.0057 (11)0.0281 (11)0.0381 (12)
C40.0395 (11)0.0606 (13)0.0695 (14)0.0063 (9)0.0206 (10)0.0324 (11)
C50.0351 (9)0.0412 (9)0.0456 (10)0.0057 (7)0.0117 (8)0.0166 (8)
C60.0302 (9)0.0572 (12)0.0614 (12)0.0093 (8)0.0107 (8)0.0322 (10)
C70.0517 (13)0.0499 (12)0.0462 (11)0.0099 (9)−0.0011 (9)0.0127 (9)
C80.0424 (10)0.0438 (10)0.0403 (9)0.0052 (8)0.0153 (8)0.0207 (8)
C90.0562 (13)0.0484 (11)0.0497 (11)0.0027 (9)0.0185 (10)0.0189 (9)
C100.0769 (17)0.0441 (11)0.0634 (14)0.0138 (11)0.0334 (13)0.0178 (10)
C110.0653 (15)0.0551 (13)0.0714 (15)0.0256 (11)0.0342 (12)0.0297 (11)
C120.0460 (12)0.0572 (12)0.0570 (12)0.0167 (9)0.0199 (10)0.0265 (10)
C130.0504 (11)0.0490 (11)0.0410 (10)0.0162 (9)0.0097 (8)0.0224 (9)
C140.0599 (13)0.0426 (10)0.0358 (9)0.0112 (9)0.0152 (9)0.0162 (8)
C150.0864 (18)0.0503 (12)0.0451 (12)0.0140 (11)0.0197 (11)0.0237 (10)
C160.114 (2)0.0544 (13)0.0572 (14)0.0012 (14)0.0362 (15)0.0288 (12)
C170.084 (2)0.0710 (16)0.0683 (16)−0.0005 (14)0.0357 (14)0.0343 (13)
C180.0612 (14)0.0666 (14)0.0615 (14)0.0042 (11)0.0280 (11)0.0307 (12)
Cl10.0334 (3)0.0609 (3)0.0596 (3)0.0131 (2)0.0101 (2)0.0215 (2)
F10.0810 (11)0.0724 (10)0.0988 (12)0.0060 (8)0.0208 (9)0.0507 (9)
F20.0836 (12)0.1141 (14)0.0632 (9)0.0059 (10)0.0336 (8)0.0300 (9)
F30.1008 (15)0.1236 (16)0.163 (2)0.0524 (12)0.0641 (14)0.1074 (16)
F40.0483 (9)0.1549 (19)0.0854 (12)−0.0063 (10)0.0024 (8)0.0605 (12)
F50.0973 (13)0.0965 (12)0.0873 (12)0.0083 (10)0.0563 (10)0.0288 (10)
F60.0571 (9)0.0710 (9)0.0731 (9)−0.0042 (7)0.0144 (7)0.0248 (7)
N10.0425 (9)0.0456 (9)0.0444 (9)0.0116 (7)0.0164 (7)0.0210 (7)
N20.0526 (10)0.0497 (9)0.0451 (9)0.0087 (8)0.0187 (8)0.0231 (8)
N30.0348 (8)0.0421 (8)0.0447 (8)0.0082 (6)0.0125 (7)0.0205 (7)
N40.0376 (8)0.0442 (8)0.0411 (8)0.0101 (7)0.0077 (6)0.0195 (7)
O10.0384 (10)0.0430 (10)0.0424 (10)0.0081 (8)0.0119 (8)0.0190 (8)
P10.0429 (3)0.0665 (4)0.0529 (3)0.0075 (3)0.0151 (2)0.0321 (3)
Geometric parameters (Å, °) top
Cr1—O11.7986 (7)C9—H90.930
Cr1—N32.1206 (18)C10—C111.378 (4)
Cr1—N22.1238 (18)C10—H100.930
Cr1—N42.2370 (19)C11—C121.370 (3)
Cr1—N12.2814 (19)C11—H110.930
Cr1—Cl12.3070 (9)C12—N11.351 (3)
O1—Cr1i1.7986 (7)C12—H120.930
C1—N31.341 (3)C13—N41.482 (3)
C1—C21.369 (3)C13—C141.516 (3)
C1—H10.930C13—H13A0.970
C2—C31.386 (4)C13—H13B0.970
C2—H20.930C14—N21.345 (3)
C3—C41.376 (4)C14—C151.383 (3)
C3—H30.930C15—C161.384 (4)
C4—C51.382 (3)C15—H150.930
C4—H40.930C16—C171.371 (4)
C5—N31.352 (3)C16—H160.930
C5—C61.506 (3)C17—C181.369 (4)
C6—N41.479 (3)C17—H170.930
C6—H6A0.970C18—N21.351 (3)
C6—H6B0.970C18—H180.930
C7—N41.483 (3)F1—P11.5939 (17)
C7—C81.499 (3)F2—P11.5803 (18)
C7—H7A0.970F3—P11.582 (2)
C7—H7B0.970F4—P11.5859 (18)
C8—N11.342 (3)F5—P11.5804 (18)
C8—C91.379 (3)F6—P11.6129 (17)
C9—C101.380 (4)
O1—Cr1—N391.01 (5)N1—C12—H12118.5
O1—Cr1—N292.46 (5)C11—C12—H12118.5
N3—Cr1—N2154.67 (7)N4—C13—C14110.48 (16)
O1—Cr1—N491.36 (6)N4—C13—H13A109.6
N3—Cr1—N478.03 (7)C14—C13—H13A109.6
N2—Cr1—N476.81 (7)N4—C13—H13B109.6
O1—Cr1—N1166.58 (5)C14—C13—H13B109.6
N3—Cr1—N181.87 (7)H13A—C13—H13B108.1
N2—Cr1—N189.30 (7)N2—C14—C15120.7 (2)
N4—Cr1—N176.09 (7)N2—C14—C13116.67 (18)
O1—Cr1—Cl1103.29 (5)C15—C14—C13122.5 (2)
N3—Cr1—Cl1104.03 (5)C14—C15—C16118.4 (3)
N2—Cr1—Cl199.56 (6)C14—C15—H15120.8
N4—Cr1—Cl1165.11 (5)C16—C15—H15120.8
N1—Cr1—Cl189.52 (6)C17—C16—C15120.8 (2)
N3—C1—C2122.1 (2)C17—C16—H16119.6
N3—C1—H1118.9C15—C16—H16119.6
C2—C1—H1119.0C16—C17—C18118.2 (3)
C3—C2—C1118.8 (2)C16—C17—H17120.9
C3—C2—H2120.6C18—C17—H17120.9
C1—C2—H2120.6N2—C18—C17121.8 (3)
C2—C3—C4119.4 (2)N2—C18—H18119.1
C2—C3—H3120.3C17—C18—H18119.1
C4—C3—H3120.3C12—N1—C8117.79 (18)
C3—C4—C5119.3 (2)C12—N1—Cr1126.02 (15)
C3—C4—H4120.4C8—N1—Cr1115.61 (13)
C5—C4—H4120.4C14—N2—C18120.1 (2)
N3—C5—C4120.95 (19)C14—N2—Cr1114.45 (14)
N3—C5—C6116.79 (18)C18—N2—Cr1124.62 (17)
C4—C5—C6122.07 (19)C1—N3—C5119.42 (18)
N4—C6—C5112.19 (16)C1—N3—Cr1125.22 (14)
N4—C6—H6A109.2C5—N3—Cr1115.07 (13)
C5—C6—H6A109.2C6—N4—C7112.30 (18)
N4—C6—H6B109.2C6—N4—C13112.63 (16)
C5—C6—H6B109.2C7—N4—C13109.74 (17)
H6A—C6—H6B107.9C6—N4—Cr1105.11 (12)
N4—C7—C8114.97 (17)C7—N4—Cr1112.78 (13)
N4—C7—H7A108.5C13—N4—Cr1103.96 (12)
C8—C7—H7A108.5Cr1—O1—Cr1i180.0
N4—C7—H7B108.5F5—P1—F390.59 (12)
C8—C7—H7B108.5F5—P1—F2178.06 (11)
H7A—C7—H7B107.5F3—P1—F290.59 (13)
N1—C8—C9122.2 (2)F5—P1—F490.15 (11)
N1—C8—C7117.57 (17)F3—P1—F491.62 (13)
C9—C8—C7120.13 (19)F2—P1—F491.35 (11)
C10—C9—C8119.3 (2)F5—P1—F189.58 (11)
C10—C9—H9120.4F3—P1—F1179.22 (11)
C8—C9—H9120.4F2—P1—F189.22 (11)
C11—C10—C9118.9 (2)F4—P1—F189.14 (11)
C11—C10—H10120.5F5—P1—F690.19 (10)
C9—C10—H10120.5F3—P1—F690.39 (12)
C10—C11—C12118.9 (2)F2—P1—F688.26 (10)
C10—C11—H11120.6F4—P1—F6177.95 (11)
C12—C11—H11120.6F1—P1—F688.85 (10)
N1—C12—C11122.9 (2)
Symmetry codes: (i) −x+2, −y+1, −z+1.
Acknowledgements top

The authors are grateful for financial support from Henan University (grant No.05YBGG013).

references
References top

Bruker (2001). SADABS, SAINT-Plus and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Butler, A. & Carrano, C. J. (1991). Chem. Rev. 109, 61–105.

Chen, Q. & Zubieta, I. (1990). Inorg. Chem. 29, 1456–1458.

Crans, D., Bunch, R. L. & Theisen, L. A. (1989). J. Am. Chem. Soc. 111, 7597–7601.

Dey, K. J. (1974). Sci. Ind. Res. 33, 76–97.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Tajika, Y., Tsuge, K. & Sasaki, Y. (2005). Dalton Trans. pp. 1438–1447.