Literature DB >> 22199629

[(1,2,5,6-η)-Cyclo-octa-1,5-diene]bis-(1-isopropyl-3-methyl-imidazolin-2-yl-idene)rhodium(I) tetra-fluorido-borate.

Gary S Nichol, Jonathan Rajaseelan, David P Walton, Edward Rajaseelan.   

Abstract

In the title compound, [Rh(C(8)H(12))(C(7)H(12)N(2))(2)]BF(4), the square-planar Rh complex cation and the BF(4) (-) anion are both bis-ected by a crystallographic twofold rotation axis. The Rh and B atoms lie on this axis and all others are in general positions. In the crystal, two unique C-H⋯F hydrogen-bonding inter-actions are present, which involve both imidazolin-2-yl-idene H atoms. They form two separate C(5) motifs, the combination of which is a rippled hydrogen-bonded sheet structure in the ab plane.

Entities:  

Year:  2011        PMID： 22199629      PMCID： PMC3238752          DOI： 10.1107/S1600536811049890

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For the structure and dynamics of related N-heterocyclic carbene rhodium and iridium complexes, see: Chianese et al. (2003 ▶); Köcher & Herrmann (1997 ▶); Leung et al. (2006 ▶); Nichol et al. (2009 ▶, 2010 ▶); Herrmann et al. (2006 ▶). For the catalytic properties of these complexes, see: Albrecht et al. (2002 ▶); Frey et al. (2006 ▶); Gnanamgari et al. (2007 ▶); Voutchkova et al. (2008 ▶).

Experimental

Crystal data

[Rh(C8H12)(C7H12N2)2]BF4 M = 546.27 Orthorhombic, a = 11.7508 (6) Å b = 11.9283 (6) Å c = 17.3129 (9) Å V = 2426.7 (2) Å3 Z = 4 Mo Kα radiation μ = 0.75 mm−1 T = 100 K 0.38 × 0.37 × 0.37 mm

Data collection

Bruker Kappa APEXII DUO CCD diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.763, T max = 0.771 234794 measured reflections 14018 independent reflections 10241 reflections with I > 2σ(I) R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.020 wR(F 2) = 0.059 S = 1.13 14018 reflections 218 parameters All H-atom parameters refined Δρmax = 1.55 e Å−3 Δρmin = −0.92 e Å−3 Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶). Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811049890/fj2478sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811049890/fj2478Isup2.hkl Supplementary material file. DOI: 10.1107/S1600536811049890/fj2478Isup3.cdx Additional supplementary materials: crystallographic information; 3D view; checkCIF report
[Rh(C8H12)(C7H12N2)2]BF4F(000) = 1128
Mr = 546.27Dx = 1.495 Mg m−3
Orthorhombic, PccnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 9624 reflections
a = 11.7508 (6) Åθ = 4.2–51.7°
b = 11.9283 (6) ŵ = 0.75 mm−1
c = 17.3129 (9) ÅT = 100 K
V = 2426.7 (2) Å3Block, yellow
Z = 40.38 × 0.37 × 0.37 mm
Bruker Kappa APEXII DUO CCD diffractometer14018 independent reflections
Radiation source: fine-focus sealed tube with Miracol optics10241 reflections with I > 2σ(I)
graphiteRint = 0.033
φ and ω scansθmax = 52.3°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −26→25
Tmin = 0.763, Tmax = 0.771k = −26→26
234794 measured reflectionsl = −37→38
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Hydrogen site location: difference Fourier map
wR(F2) = 0.059All H-atom parameters refined
S = 1.13w = 1/[σ2(Fo2) + (0.0182P)2 + 0.6772P] where P = (Fo2 + 2Fc2)/3
14018 reflections(Δ/σ)max = 0.002
218 parametersΔρmax = 1.55 e Å−3
0 restraintsΔρmin = −0.92 e Å−3
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.
xyzUiso*/Ueq
Rh10.75000.25000.507678 (3)0.01052 (1)
N10.56243 (4)0.20105 (4)0.38873 (3)0.01399 (6)
N20.66738 (4)0.05648 (4)0.40496 (3)0.01512 (6)
C10.65651 (4)0.16534 (4)0.42664 (3)0.01295 (6)
C20.51512 (5)0.11598 (5)0.34425 (4)0.01757 (8)
H20.4526 (10)0.1269 (10)0.3143 (7)0.022 (3)*
C30.58158 (5)0.02502 (5)0.35458 (4)0.01811 (8)
H30.5769 (10)−0.0434 (10)0.3364 (7)0.028 (3)*
C40.51719 (5)0.31568 (5)0.39338 (3)0.01602 (7)
H40.5633 (9)0.3517 (9)0.4313 (6)0.019 (3)*
C50.53212 (7)0.37474 (6)0.31623 (4)0.02376 (11)
H5A0.4910 (11)0.3362 (11)0.2772 (7)0.030 (3)*
H5B0.6089 (11)0.3778 (11)0.3028 (8)0.031 (3)*
H5C0.5034 (11)0.4517 (11)0.3183 (8)0.035 (3)*
C60.39373 (6)0.31435 (7)0.41936 (5)0.02579 (12)
H6A0.3478 (11)0.2754 (11)0.3834 (8)0.028 (3)*
H6B0.3635 (11)0.3876 (11)0.4230 (8)0.035 (3)*
H6C0.3844 (12)0.2775 (12)0.4678 (9)0.033 (3)*
C70.75478 (6)−0.02030 (5)0.43195 (4)0.02033 (9)
H7A0.8005 (10)0.0166 (10)0.4689 (7)0.024 (3)*
H7B0.7196 (11)−0.0845 (12)0.4540 (8)0.031 (3)*
H7C0.8014 (11)−0.0430 (11)0.3906 (8)0.032 (3)*
C80.61291 (5)0.22486 (5)0.59096 (3)0.01603 (7)
H80.5433 (10)0.2098 (10)0.5610 (7)0.021 (3)*
C90.68830 (5)0.13645 (5)0.60051 (3)0.01646 (8)
H90.6691 (10)0.0669 (10)0.5751 (7)0.025 (3)*
C100.77717 (6)0.12488 (6)0.66365 (4)0.01943 (9)
H10A0.7517 (9)0.1609 (11)0.7107 (8)0.023 (3)*
H10B0.7852 (10)0.0442 (11)0.6775 (7)0.026 (3)*
C110.89369 (5)0.16926 (6)0.63829 (4)0.01888 (9)
H11A0.9440 (9)0.1813 (9)0.6833 (7)0.020 (2)*
H11B0.9335 (10)0.1111 (10)0.6049 (7)0.023 (3)*
B10.75000.75000.29593 (6)0.01705 (12)
F10.76439 (5)0.84479 (5)0.24966 (3)0.03003 (10)
F20.65419 (4)0.76347 (4)0.34218 (3)0.02659 (9)
U11U22U33U12U13U23
Rh10.01063 (2)0.00980 (2)0.01114 (2)−0.00124 (1)0.0000.000
N10.01412 (14)0.01361 (14)0.01424 (15)0.00070 (11)−0.00193 (11)−0.00109 (12)
N20.01684 (16)0.01164 (14)0.01689 (16)0.00010 (12)−0.00365 (13)−0.00144 (12)
C10.01345 (15)0.01194 (15)0.01347 (16)−0.00035 (12)−0.00093 (12)−0.00044 (12)
C20.01794 (19)0.01713 (19)0.0176 (2)−0.00031 (15)−0.00510 (16)−0.00262 (15)
C30.0211 (2)0.01475 (18)0.0185 (2)−0.00131 (16)−0.00536 (17)−0.00293 (15)
C40.01615 (18)0.01608 (18)0.01583 (18)0.00398 (14)−0.00011 (14)−0.00123 (14)
C50.0321 (3)0.0195 (2)0.0197 (2)0.0075 (2)0.0032 (2)0.00306 (19)
C60.0185 (2)0.0318 (3)0.0270 (3)0.0065 (2)0.0043 (2)−0.0023 (2)
C70.0218 (2)0.01268 (16)0.0265 (3)0.00234 (17)−0.0073 (2)−0.00142 (16)
C80.01421 (17)0.01788 (18)0.01599 (18)−0.00244 (14)0.00177 (14)−0.00026 (15)
C90.01790 (19)0.01465 (17)0.01685 (19)−0.00334 (15)0.00120 (15)0.00176 (14)
C100.0215 (2)0.0200 (2)0.0168 (2)−0.00095 (18)−0.00002 (17)0.00507 (17)
C110.0179 (2)0.0210 (2)0.0178 (2)0.00064 (17)−0.00287 (16)0.00310 (17)
B10.0149 (3)0.0145 (3)0.0218 (3)0.0006 (2)0.0000.000
F10.0346 (3)0.0235 (2)0.0320 (2)0.00074 (18)0.00329 (18)0.01073 (17)
F20.01926 (17)0.02301 (19)0.0375 (3)0.00023 (13)0.00938 (16)−0.00171 (16)
Rh1—C12.0482 (5)C6—H6A0.946 (13)
Rh1—C1i2.0482 (5)C6—H6B0.946 (14)
Rh1—C82.1826 (6)C6—H6C0.952 (15)
Rh1—C8i2.1826 (6)C7—H7A0.944 (12)
Rh1—C92.2233 (6)C7—H7B0.950 (14)
Rh1—C9i2.2233 (6)C7—H7C0.941 (13)
N1—C11.3544 (7)C8—H80.985 (12)
N1—C21.3899 (7)C8—C91.3872 (9)
N1—C41.4692 (7)C8—C11i1.5074 (9)
N2—C11.3577 (7)C9—H90.965 (12)
N2—C31.3850 (7)C9—C101.5181 (9)
N2—C71.4532 (8)C10—H10A0.968 (13)
C2—H20.909 (11)C10—H10B0.997 (13)
C2—C31.3487 (9)C10—C111.5322 (9)
C3—H30.877 (12)C11—C8i1.5075 (9)
C4—H40.954 (11)C11—H11A0.989 (11)
C4—C51.5202 (9)C11—H11B1.017 (12)
C4—C61.5190 (9)B1—F11.3960 (8)
C5—H5A0.950 (13)B1—F1ii1.3960 (8)
C5—H5B0.933 (13)B1—F21.3908 (8)
C5—H5C0.979 (14)B1—F2ii1.3909 (8)
C1—Rh1—C1i93.53 (3)C4—C6—H6A110.8 (8)
C1—Rh1—C889.36 (2)C4—C6—H6B111.7 (8)
C1i—Rh1—C8i89.36 (2)C4—C6—H6C112.0 (8)
C1—Rh1—C8i156.36 (2)H6A—C6—H6B106.4 (11)
C1i—Rh1—C8156.36 (2)H6A—C6—H6C106.7 (11)
C1—Rh1—C991.14 (2)H6B—C6—H6C108.9 (11)
C1i—Rh1—C9166.03 (2)N2—C7—H7A109.0 (7)
C1i—Rh1—C9i91.14 (2)N2—C7—H7B109.3 (8)
C1—Rh1—C9i166.03 (2)N2—C7—H7C110.4 (8)
C8—Rh1—C8i97.31 (3)H7A—C7—H7B110.6 (11)
C8—Rh1—C936.69 (2)H7A—C7—H7C108.6 (11)
C8i—Rh1—C981.19 (2)H7B—C7—H7C109.0 (11)
C8i—Rh1—C9i36.69 (2)Rh1—C8—H8106.8 (7)
C8—Rh1—C9i81.19 (2)Rh1—C8—C973.25 (3)
C9—Rh1—C9i87.42 (3)Rh1—C8—C11i106.38 (4)
C1—N1—C2111.43 (5)H8—C8—C9117.0 (7)
C1—N1—C4124.16 (5)H8—C8—C11i113.3 (7)
C2—N1—C4124.41 (5)C9—C8—C11i127.23 (5)
C1—N2—C3111.39 (5)Rh1—C9—C870.06 (3)
C1—N2—C7125.48 (5)Rh1—C9—H9105.7 (7)
C3—N2—C7123.10 (5)Rh1—C9—C10110.59 (4)
Rh1—C1—N1127.93 (4)C8—C9—H9116.7 (7)
Rh1—C1—N2127.62 (4)C8—C9—C10126.46 (6)
N1—C1—N2104.10 (4)H9—C9—C10114.2 (7)
N1—C2—H2122.4 (7)C9—C10—H10A110.7 (7)
N1—C2—C3106.40 (5)C9—C10—H10B109.0 (7)
H2—C2—C3131.2 (7)C9—C10—C11112.14 (5)
N2—C3—C2106.68 (5)H10A—C10—H10B104.8 (11)
N2—C3—H3121.6 (8)H10A—C10—C11111.3 (7)
C2—C3—H3131.7 (8)H10B—C10—C11108.6 (7)
N1—C4—H4104.6 (7)C8i—C11—C10113.53 (5)
N1—C4—C5109.96 (5)C8i—C11—H11A109.7 (7)
N1—C4—C6110.61 (5)C8i—C11—H11B106.6 (7)
H4—C4—C5109.3 (7)C10—C11—H11A111.0 (7)
H4—C4—C6110.0 (7)C10—C11—H11B109.8 (7)
C5—C4—C6112.04 (6)H11A—C11—H11B105.8 (9)
C4—C5—H5A110.0 (8)F1—B1—F1ii109.97 (9)
C4—C5—H5B110.4 (8)F1—B1—F2109.56 (3)
C4—C5—H5C111.2 (8)F1ii—B1—F2109.02 (3)
H5A—C5—H5B109.5 (11)F1ii—B1—F2ii109.56 (3)
H5A—C5—H5C107.7 (11)F1—B1—F2ii109.02 (3)
H5B—C5—H5C107.9 (11)F2—B1—F2ii109.70 (9)
C2—N1—C1—Rh1−173.45 (4)C2—N1—C4—C656.65 (8)
C2—N1—C1—N20.13 (6)C1—Rh1—C8—C992.76 (4)
C4—N1—C1—Rh17.28 (8)C1i—Rh1—C8—C9−169.87 (5)
C4—N1—C1—N2−179.14 (5)C1i—Rh1—C8—C11i−45.11 (7)
C3—N2—C1—Rh1173.54 (4)C1—Rh1—C8—C11i−142.49 (4)
C3—N2—C1—N1−0.07 (6)C8i—Rh1—C8—C9−64.50 (3)
C7—N2—C1—Rh1−4.70 (8)C8i—Rh1—C8—C11i60.26 (4)
C7—N2—C1—N1−178.31 (6)C9i—Rh1—C8—C9−97.57 (4)
C1i—Rh1—C1—N1−83.65 (5)C9—Rh1—C8—C11i124.75 (6)
C1i—Rh1—C1—N2104.22 (5)C9i—Rh1—C8—C11i27.19 (4)
C8—Rh1—C1—N172.88 (5)Rh1—C8—C9—C10101.36 (6)
C8i—Rh1—C1—N1179.85 (5)C11i—C8—C9—Rh1−98.12 (6)
C8—Rh1—C1—N2−99.26 (5)C11i—C8—C9—C103.25 (9)
C8i—Rh1—C1—N27.72 (8)C1—Rh1—C9—C8−87.40 (4)
C9—Rh1—C1—N1109.52 (5)C1i—Rh1—C9—C8163.01 (8)
C9i—Rh1—C1—N125.66 (11)C1—Rh1—C9—C10149.98 (4)
C9—Rh1—C1—N2−62.61 (5)C1i—Rh1—C9—C1040.40 (11)
C9i—Rh1—C1—N2−146.48 (8)C8i—Rh1—C9—C8115.05 (4)
C1—N1—C2—C3−0.15 (7)C8—Rh1—C9—C10−122.61 (6)
C4—N1—C2—C3179.12 (5)C8i—Rh1—C9—C10−7.56 (4)
N1—C2—C3—N20.09 (7)C9i—Rh1—C9—C878.69 (3)
C1—N2—C3—C2−0.01 (7)C9i—Rh1—C9—C10−43.92 (4)
C7—N2—C3—C2178.27 (6)Rh1—C9—C10—C11−13.94 (7)
C1—N1—C4—C5111.55 (6)C8—C9—C10—C11−93.84 (7)
C1—N1—C4—C6−124.17 (6)C9—C10—C11—C8i39.69 (8)
C2—N1—C4—C5−67.63 (8)
D—H···AD—HH···AD···AD—H···A
C2—H2···F1iii0.909 (11)2.496 (11)3.3975 (8)171.4 (10)
C3—H3···F2iv0.877 (12)2.478 (12)3.2415 (8)145.9 (11)
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
C2—H2⋯F1i0.909 (11)2.496 (11)3.3975 (8)171.4 (10)
C3—H3⋯F2ii0.877 (12)2.478 (12)3.2415 (8)145.9 (11)

Symmetry codes: (i) ; (ii) .

  2 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  [(1,2,5,6-η)-1,5-Cyclo-octa-diene](1-isopropyl-3-methyl-imidazolin-2-yl-idene)(triphenyl-phosphine)iridium(I) tetra-fluorido-borate dichloro-methane solvate.

Authors:  Gary S Nichol; Daniel Stasiw; Laura J Anna; Edward Rajaseelan
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2010-08-18
  2 in total
  1 in total

1.  [2-Butyl-4-(4-tert-butyl-benz-yl)-1,2,4-triazol-3-yl-idene]chlorido[(1,2,5,6-η)-cyclo-octa-1,5-diene]iridium(I).

Authors:  Gary S Nichol; David P Walton; Laura J Anna; Edward Rajaseelan
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2012-01-14
  1 in total

北京卡尤迪生物科技股份有限公司 © 2022-2023.