Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, [RhBr(C18H15P)2(CO)], can be characterized as a rhodium(I) Vaska-type compound based only on the spectroscopic [νKBr(CO), 31P] data. A low-temperature X-ray crystallographic analysis shows that the compound possesses a crystallographically imposed centre of symmetry with a statistically disordered Br atom and CO group. The essentially different occupancies for the Br atom and the CO group [0.283 (2) and 0.717 (2), respectively] suggest that the compound exists as a mixture of rhodium(0), rhodium(I) and rhodium(II) complexes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806014619/cv2038sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536806014619/cv2038Isup2.hkl
Contains datablock I

CCDC reference: 608591

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.002 Å
  • Disorder in main residue
  • R factor = 0.018
  • wR factor = 0.047
  • Data-to-parameter ratio = 19.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.04 PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms .. ? PLAT213_ALERT_2_C Atom Br has ADP max/min Ratio ............. 4.00 prolat PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.18 Ratio PLAT301_ALERT_3_C Main Residue Disorder ......................... 8.00 Perc.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2004); software used to prepare material for publication: SHELXL97.

trans-Bromocarbonylbis(triphenylphosphine)rhodium top
Crystal data top
[RhBr(C18H15P)2(CO)]Z = 1
Mr = 712.84F(000) = 360.9
Triclinic, P1Dx = 1.472 Mg m3
Hall symbol: -p 1Mo Kα radiation, λ = 0.71073 Å
a = 9.1519 (4) ÅCell parameters from 8332 reflections
b = 9.5797 (5) Åθ = 2.6–28.3°
c = 10.2796 (5) ŵ = 1.36 mm1
α = 73.040 (2)°T = 100 K
β = 89.016 (2)°Plate, yellow
γ = 69.567 (2)°0.37 × 0.12 × 0.07 mm
V = 804.19 (7) Å3
Data collection top
Bruker APEX 24K CCD area-detector
diffractometer
4011 independent reflections
Radiation source: fine-focus sealed tube3855 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
Detector resolution: 512 x 512 pixels mm-1θmax = 28.3°, θmin = 2.4°
φ and ω scansh = 1212
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
k = 1212
Tmin = 0.762, Tmax = 0.877l = 1313
21423 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)] = 0.018Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.047H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0192P)2 + 0.4097P]
where P = (Fo2 + 2Fc2)/3
4011 reflections(Δ/σ)max = 0.001
206 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.54 e Å3
Special details top

Experimental. Spectral data: 1H NMR (CDCl3, 300 MHz): 7.68 (m, 12H), 7.48 (m, 6H), 7.35 (m, 12H); 31P NMR (CDCl3, 75 MHz): 30.11 (d, 1J 133.67 Hz). IR νKBr(CO): 1969 (s) cm-1.

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

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 > 2sigma(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*/UeqOcc. (<1)
Rh0.50000.00000.50000.01169 (4)
P0.51567 (3)0.20414 (3)0.69633 (3)0.01267 (7)
C310.60990 (13)0.18920 (14)0.84385 (12)0.0150 (2)
C110.32540 (14)0.21141 (14)0.74499 (12)0.0160 (2)
C120.29214 (15)0.25401 (15)0.88053 (13)0.0177 (2)
H120.36820.27840.95070.021*
C210.62559 (16)0.40332 (15)0.69401 (13)0.0188 (2)
C320.62014 (15)0.04582 (16)0.83738 (13)0.0204 (2)
H320.57810.03930.75950.024*
C360.67359 (16)0.31624 (16)0.96180 (13)0.0215 (3)
H360.66840.41300.96720.026*
C130.14530 (16)0.26016 (17)0.91116 (14)0.0236 (3)
H130.12260.28631.00160.028*
C220.78850 (17)0.45225 (17)0.69448 (14)0.0261 (3)
H220.83940.38580.70170.031*
C140.03292 (16)0.22734 (19)0.80679 (16)0.0281 (3)
H140.06450.23320.82760.034*
C260.5514 (2)0.50360 (17)0.68120 (16)0.0311 (3)
H260.44310.47270.68000.037*
C330.69295 (17)0.02891 (18)0.94667 (15)0.0265 (3)
H330.70020.06700.94120.032*
C160.21037 (16)0.17588 (18)0.64093 (14)0.0261 (3)
H160.23100.14530.55020.031*
C250.6398 (3)0.6506 (2)0.6701 (2)0.0468 (5)
H250.58970.71690.66080.056*
C340.75439 (16)0.15451 (19)1.06328 (14)0.0267 (3)
H340.80220.14281.13650.032*
C150.06518 (17)0.1858 (2)0.67177 (16)0.0319 (3)
H150.01010.16470.60200.038*
C350.74476 (17)0.29776 (19)1.07107 (14)0.0272 (3)
H350.78600.38211.14970.033*
C230.8749 (2)0.5994 (2)0.68420 (17)0.0398 (4)
H230.98330.63110.68500.048*
C240.8004 (3)0.69856 (19)0.67278 (19)0.0477 (5)
H240.85840.79750.66690.057*
O10.2387 (5)0.1954 (5)0.5970 (5)0.0330 (13)0.717 (2)
C10.3282 (6)0.1286 (5)0.5619 (4)0.0324 (8)0.717 (2)
Br0.27493 (14)0.17121 (15)0.58152 (13)0.0160 (3)0.283 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rh0.01082 (7)0.01196 (7)0.01031 (6)0.00325 (5)0.00168 (4)0.00160 (4)
P0.01220 (14)0.01350 (14)0.01164 (13)0.00555 (11)0.00082 (11)0.00167 (11)
C310.0113 (5)0.0198 (6)0.0135 (5)0.0061 (5)0.0014 (4)0.0039 (4)
C110.0140 (5)0.0169 (6)0.0175 (6)0.0075 (5)0.0019 (4)0.0034 (4)
C120.0178 (6)0.0187 (6)0.0177 (6)0.0079 (5)0.0028 (5)0.0055 (5)
C210.0237 (6)0.0143 (6)0.0148 (5)0.0044 (5)0.0000 (5)0.0022 (4)
C320.0192 (6)0.0204 (6)0.0205 (6)0.0065 (5)0.0015 (5)0.0054 (5)
C360.0205 (6)0.0241 (7)0.0175 (6)0.0094 (5)0.0007 (5)0.0010 (5)
C130.0231 (7)0.0286 (7)0.0233 (6)0.0134 (6)0.0102 (5)0.0097 (5)
C220.0232 (7)0.0268 (7)0.0228 (7)0.0000 (6)0.0028 (5)0.0104 (6)
C140.0176 (6)0.0378 (8)0.0352 (8)0.0154 (6)0.0086 (6)0.0139 (6)
C260.0401 (9)0.0203 (7)0.0345 (8)0.0144 (6)0.0013 (7)0.0060 (6)
C330.0242 (7)0.0301 (7)0.0296 (7)0.0096 (6)0.0005 (6)0.0157 (6)
C160.0208 (6)0.0401 (8)0.0180 (6)0.0155 (6)0.0005 (5)0.0039 (6)
C250.0733 (14)0.0198 (8)0.0478 (11)0.0166 (9)0.0032 (9)0.0110 (7)
C340.0199 (6)0.0435 (9)0.0200 (6)0.0099 (6)0.0007 (5)0.0161 (6)
C150.0193 (7)0.0493 (10)0.0291 (7)0.0168 (7)0.0019 (6)0.0091 (7)
C350.0235 (7)0.0369 (8)0.0148 (6)0.0087 (6)0.0029 (5)0.0011 (5)
C230.0368 (9)0.0366 (9)0.0285 (8)0.0139 (7)0.0101 (7)0.0166 (7)
C240.0688 (13)0.0198 (8)0.0358 (9)0.0104 (8)0.0140 (9)0.0124 (7)
O10.036 (2)0.0299 (18)0.0182 (14)0.0023 (15)0.0091 (12)0.0026 (9)
C10.039 (2)0.0307 (19)0.0196 (14)0.0132 (16)0.0007 (14)0.0041 (12)
Br0.0115 (6)0.0167 (5)0.0128 (4)0.0034 (5)0.0079 (4)0.0051 (3)
Geometric parameters (Å, º) top
Rh—C11.861 (6)C13—H130.9300
Rh—C1i1.861 (6)C22—C231.389 (2)
Rh—P2.3302 (3)C22—H220.9300
Rh—Pi2.3302 (3)C14—C151.385 (2)
Rh—Bri2.4533 (13)C14—H140.9300
Rh—Br2.4533 (13)C26—C251.395 (2)
P—C111.8225 (12)C26—H260.9300
P—C311.8225 (12)C33—C341.382 (2)
P—C211.8273 (13)C33—H330.9300
C31—C321.3914 (18)C16—C151.3898 (19)
C31—C361.3997 (17)C16—H160.9300
C11—C121.3932 (17)C25—C241.376 (3)
C11—C161.3944 (18)C25—H250.9300
C12—C131.3923 (18)C34—C351.385 (2)
C12—H120.9300C34—H340.9300
C21—C261.3902 (19)C15—H150.9300
C21—C221.3977 (19)C35—H350.9300
C32—C331.3928 (18)C23—C241.379 (3)
C32—H320.9300C23—H230.9300
C36—C351.3925 (19)C24—H240.9300
C36—H360.9300O1—C10.985 (7)
C13—C141.387 (2)C1—Br0.592 (6)
C1—Rh—C1i180.0 (2)C14—C13—C12120.02 (12)
C1—Rh—P88.75 (11)C14—C13—H13120.0
C1i—Rh—P91.25 (10)C12—C13—H13120.0
C1—Rh—Pi91.25 (11)C23—C22—C21120.53 (15)
C1i—Rh—Pi88.75 (10)C23—C22—H22119.7
P—Rh—Pi180.0C21—C22—H22119.7
C1—Rh—Bri179.45 (11)C15—C14—C13120.25 (12)
C1i—Rh—Bri0.55 (11)C15—C14—H14119.9
P—Rh—Bri90.95 (3)C13—C14—H14119.9
Pi—Rh—Bri89.05 (3)C21—C26—C25119.90 (16)
C1—Rh—Br0.55 (11)C21—C26—H26120.1
C1i—Rh—Br179.45 (11)C25—C26—H26120.1
P—Rh—Br89.05 (3)C34—C33—C32120.10 (14)
Pi—Rh—Br90.95 (3)C34—C33—H33120.0
Bri—Rh—Br180.000 (1)C32—C33—H33120.0
C11—P—C31105.88 (5)C15—C16—C11120.53 (13)
C11—P—C21103.26 (6)C15—C16—H16119.7
C31—P—C21103.64 (6)C11—C16—H16119.7
C11—P—Rh113.54 (4)C24—C25—C26120.78 (17)
C31—P—Rh111.77 (4)C24—C25—H25119.6
C21—P—Rh117.56 (4)C26—C25—H25119.6
C32—C31—C36119.10 (12)C33—C34—C35119.98 (13)
C32—C31—P118.27 (9)C33—C34—H34120.0
C36—C31—P122.62 (10)C35—C34—H34120.0
C12—C11—C16119.24 (11)C14—C15—C16119.77 (13)
C12—C11—P122.89 (9)C14—C15—H15120.1
C16—C11—P117.86 (10)C16—C15—H15120.1
C13—C12—C11120.15 (12)C34—C35—C36120.35 (13)
C13—C12—H12119.9C34—C35—H35119.8
C11—C12—H12119.9C36—C35—H35119.8
C26—C21—C22118.86 (13)C24—C23—C22120.15 (17)
C26—C21—P122.00 (11)C24—C23—H23119.9
C22—C21—P118.95 (10)C22—C23—H23119.9
C31—C32—C33120.48 (13)C25—C24—C23119.76 (15)
C31—C32—H32119.8C25—C24—H24120.1
C33—C32—H32119.8C23—C24—H24120.1
C35—C36—C31119.98 (13)Br—C1—Rh177.7 (5)
C35—C36—H36120.0O1—C1—Rh178.6 (5)
C31—C36—H36120.0
C1—Rh—P—C1140.51 (12)C11—P—C21—C22163.99 (10)
C1i—Rh—P—C11139.49 (12)C31—P—C21—C2253.71 (11)
Bri—Rh—P—C11139.03 (5)Rh—P—C21—C2270.15 (11)
Br—Rh—P—C1140.97 (5)C36—C31—C32—C330.08 (19)
C1—Rh—P—C3179.19 (12)P—C31—C32—C33179.12 (10)
C1i—Rh—P—C31100.81 (12)C32—C31—C36—C350.56 (19)
Bri—Rh—P—C31101.27 (5)P—C31—C36—C35179.73 (10)
Br—Rh—P—C3178.73 (5)C11—C12—C13—C141.5 (2)
C1—Rh—P—C21161.15 (12)C26—C21—C22—C230.9 (2)
C1i—Rh—P—C2118.85 (12)P—C21—C22—C23175.98 (12)
Bri—Rh—P—C2118.39 (6)C12—C13—C14—C151.1 (2)
Br—Rh—P—C21161.61 (6)C22—C21—C26—C250.5 (2)
C11—P—C31—C32106.11 (10)P—C21—C26—C25175.42 (13)
C21—P—C31—C32145.56 (10)C31—C32—C33—C340.6 (2)
Rh—P—C31—C3218.00 (11)C12—C11—C16—C151.3 (2)
C11—P—C31—C3674.72 (11)P—C11—C16—C15177.26 (12)
C21—P—C31—C3633.61 (12)C21—C26—C25—C240.5 (3)
Rh—P—C31—C36161.18 (9)C32—C33—C34—C350.5 (2)
C31—P—C11—C1220.45 (12)C13—C14—C15—C160.5 (2)
C21—P—C11—C1288.14 (11)C11—C16—C15—C141.7 (2)
Rh—P—C11—C12143.45 (9)C33—C34—C35—C360.1 (2)
C31—P—C11—C16161.03 (11)C31—C36—C35—C340.7 (2)
C21—P—C11—C1690.37 (12)C21—C22—C23—C240.3 (2)
Rh—P—C11—C1638.04 (12)C26—C25—C24—C231.1 (3)
C16—C11—C12—C130.29 (19)C22—C23—C24—C250.7 (3)
P—C11—C12—C13178.79 (10)O1—C1—Br—Rh146 (13)
C11—P—C21—C2621.06 (13)P—Rh—Br—C157 (11)
C31—P—C21—C26131.34 (12)Pi—Rh—Br—C1123 (11)
Rh—P—C21—C26104.80 (11)
Symmetry code: (i) x+1, y, z+1.
Comparative X-ray data for [Rh(X)CO(PPh3)2] complexes top
XRh—XRh—CCODisorderSpace group
Cla2.3561.8471.126NP21/c
Clb2.4051.9870.739YP1
Clc2.3711.8101.143NP21/n
Cld2.3811.7591.143YP-1
Cle2.3831.7611.150YPbca
Brf2.4531.8620.984YP-1
Ig2.6841.8071.140NP21/n
Notes: (a) (Muir & Ibers, 1969); (b) (Del Pra et al., 1979); (c) (Ceriotti et al., 1983); (d) (Chen et al., 1991); (e) (Dunbar & Haefner, 1992); (f) this work; (g) (Basson et al., 1990).
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds