Chloro(1,5-cyclo­octa­diene)(tri­phenyl­phosphine)­rhodium(I)

Horn, Q.L.; Jones, D.S.; Evans, R.N.; Ogle, C.A.; Masterman, T.C.

doi:10.1107/S1600536802000077

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Chloro(1,5-cyclooctadiene)(triphenylphosphine)rhodium(I)

Q. L. Horn, D. S. Jones, R. N. Evans, C. A. Ogle and T. C. Masterman

The crystal and molecular structure of the title compound, [RhCl(C₈H₁₂){P(C₆H₅)₃}], has been determined by means of X-ray diffraction. Compounds of this nature are important because of their ability to act as homogenous hydrogenation catalysts and to serve as precursors for more elaborate compounds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802000077/wn6068sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802000077/wn6068Isup2.hkl Contains datablock I

CCDC reference: 180758

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.011 Å
R factor = 0.036
wR factor = 0.046
Data-to-parameter ratio = 10.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



DIFF_012  Alert A _diffrn_reflns_av_R_equivalents is missing
          R factor for symmetry-equivalent intensities.
          The following tests will not be performed
          RINTA

SHFSU_01  Alert A The absolute value of parameter shift to su ratio > 0.20
          Absolute value of the parameter shift to su ratio given   0.280
          Additional refinement cycles may be required.


 Alert Level C:



GOODF_01  Alert C The least squares goodness of fit parameter lies
          outside the range 0.80 <> 2.00
          Goodness of fit given =      2.180

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.25
         From the CIF: _reflns_number_total               3170
         Count of symmetry unique reflns         3152
         Completeness (_total/calc)            100.57%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured        18
         Fraction of Friedel pairs measured     0.006
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 2 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Computing details top

Data collection: KRISEL control software [Any reference?]; cell refinement: MolEN (Enraf-Nonius, 1990); data reduction: MolEN; program(s) used to solve structure: MolEN; program(s) used to refine structure: MolEN; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: Word Pad, IUCR CIF Template.

Cloro(1,5-Cyclooctadiene)Triphenylphosphiterhodium(I) top

Crystal data top

[RhCl(C₈H₁₂)(C₁₈H₁₅P)]	D_x = 1.50 Mg m⁻³
M_r = 508.84	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 17 reflections
a = 16.246 (3) Å	θ = 10.0–20.5°
b = 8.145 (2) Å	µ = 0.96 mm⁻¹
c = 16.992 (4) Å	T = 296 K
V = 2248 (1) Å³	Irregular, brown
Z = 4	0.29 × 0.28 × 0.28 mm
F(000) = 1040.0

Data collection top

Picker four-circle diffractometer	θ_max = 28.3°, θ_min = 1.0°
Radiation source: x-ray tube	h = 0→21
Grahpite monochromator	k = 0→10
ω–2θ scans	l = 0→22
3170 measured reflections	3 standard reflections every 120 min
3170 independent reflections	intensity decay: none
2839 reflections with I > 2σ(I)

Refinement top

Refinement on F	0 restraints
Least-squares matrix: full	0 constraints
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.046	Weighting scheme based on measured s.u.'s w = 4F²/[σ²(F²) + (0.03F²)²]
S = 2.18	(Δ/σ)_max = 0.28
2839 reflections	Δρ_max = 0.46 e Å⁻³
262 parameters	Δρ_min = −0.12 e Å⁻³

Special details top

Refinement. The structure for this molecule was refined several years ago using a mainframe computer. Because cycles of refinment on the mainframe were so time consuming, refinment on this molecule was stopped when the the largest ratio of the refinment shift to standard uncertaintly was equal to 0.28. The MolEN program which was used for refinment is no longer available for our use.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
RH1	0.63038 (3)	0.10595 (6)	0.11040 (3)	0.1662
CL1	0.6358 (1)	0.3708 (2)	0.1666 (1)	0.2107
P1	0.5951 (1)	0.2265 (2)	−0.00778 (9)	0.4970
C1	0.5787 (4)	−0.1265 (8)	0.0787 (4)	0.1847
C2	0.6643 (4)	−0.1261 (8)	0.0659 (4)	0.1950
C3	0.7016 (5)	0.0202 (9)	0.2130 (4)	0.2047
C4	0.6220 (5)	−0.0074 (9)	0.2301 (4)	0.2093
C5	0.5801 (5)	−0.176 (1)	0.2277 (4)	0.2223
C6	0.5343 (5)	−0.200 (1)	0.1477 (5)	0.2197
C7	0.7252 (5)	−0.2189 (9)	0.1175 (5)	0.2103
C8	0.7635 (5)	−0.108 (1)	0.1818 (5)	0.2273
C11	0.5088 (4)	0.3637 (7)	0.0064 (4)	0.1717
C12	0.4999 (5)	0.5114 (9)	−0.0334 (4)	0.2100
C13	0.4288 (5)	0.606 (1)	−0.0215 (5)	0.2197
C14	0.3689 (5)	0.555 (1)	0.0314 (5)	0.2287
C15	0.3774 (4)	0.407 (1)	0.0724 (4)	0.2097
C16	0.4479 (4)	0.3156 (9)	0.0597 (4)	0.1907
C21	0.5595 (4)	0.0923 (8)	−0.0877 (3)	0.1797
C22	0.4758 (4)	0.0788 (9)	−0.1080 (4)	0.1960
C23	0.4519 (5)	−0.034 (1)	−0.1636 (5)	0.2350
C24	0.5066 (6)	−0.135 (1)	−0.2020 (5)	0.2493
C25	0.5903 (6)	−0.122 (1)	−0.1824 (5)	0.2390
C26	0.6166 (5)	−0.0095 (9)	−0.1258 (4)	0.2083
C31	0.6738 (4)	0.3503 (8)	−0.0565 (4)	0.1733
C32	0.7407 (4)	0.4105 (9)	−0.0130 (4)	0.1963
C33	0.7992 (5)	0.5057 (9)	−0.0492 (4)	0.2100
C34	0.7954 (5)	0.543 (1)	−0.1297 (5)	0.2160
C35	0.7282 (5)	0.481 (1)	−0.1732 (5)	0.2173
C36	0.6696 (4)	0.386 (1)	−0.1364 (4)	0.2000
H1	0.542	0.548	−0.068	0.2414*
H2	0.422	0.705	−0.050	0.2516*
H3	0.322	0.622	0.040	0.2639*
H4	0.336	0.371	0.108	0.2414*
H5	0.455	0.216	0.088	0.2165*
H6	0.436	0.147	−0.084	0.2306*
H7	0.395	−0.043	−0.176	0.2735*
H8	0.488	−0.212	−0.240	0.2891*
H9	0.629	−0.189	−0.208	0.2779*
H10	0.673	−0.002	−0.113	0.2387*
H11	0.745	0.385	0.041	0.2279*
H12	0.844	0.548	−0.019	0.2387*
H13	0.837	0.608	−0.154	0.2466*
H14	0.723	0.505	−0.228	0.2516*
H15	0.625	0.344	−0.166	0.2306*
H16	0.542	−0.184	0.270	0.2591*
H17	0.621	−0.259	0.233	0.2591*
H18	0.528	−0.314	0.139	0.2566*
H19	0.482	−0.149	0.152	0.2566*
H20	0.768	−0.261	0.085	0.2414*
H21	0.697	−0.307	0.142	0.2414*
H22	0.781	−0.174	0.224	0.2615*
H23	0.809	−0.052	0.160	0.2615*
H24	0.546	−0.075	0.040	0.2135*
H25	0.685	−0.065	0.023	0.2251*
H26	0.722	0.129	0.221	0.2387*
H27	0.589	0.084	0.245	0.2466*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
RH1	0.0339 (2)	0.0227 (2)	0.0261 (2)	−0.0008 (2)	−0.0023 (2)	−0.0005 (2)
CL1	0.071 (1)	0.0277 (7)	0.0410 (7)	−0.0025 (9)	−0.0083 (9)	−0.0071 (6)
P1	0.0296 (7)	0.0251 (7)	0.0278 (7)	−0.0025 (7)	−0.0015 (7)	0.0002 (6)
C1	0.044 (3)	0.022 (3)	0.039 (3)	−0.006 (3)	−0.000 (3)	−0.002 (3)
C2	0.045 (3)	0.030 (3)	0.042 (3)	0.004 (3)	0.007 (3)	−0.008 (3)
C3	0.055 (4)	0.045 (4)	0.031 (3)	0.009 (4)	−0.008 (3)	0.009 (3)
C4	0.066 (4)	0.049 (4)	0.024 (3)	0.005 (4)	−0.007 (3)	0.010 (3)
C5	0.068 (5)	0.051 (4)	0.034 (3)	−0.007 (4)	0.005 (4)	0.012 (3)
C6	0.045 (4)	0.051 (4)	0.056 (4)	−0.018 (3)	0.000 (3)	0.019 (4)
C7	0.048 (4)	0.033 (3)	0.053 (4)	0.007 (3)	−0.004 (4)	0.001 (4)
C8	0.044 (4)	0.047 (4)	0.066 (4)	0.008 (4)	−0.011 (3)	0.000 (5)
C11	0.031 (3)	0.024 (3)	0.035 (3)	−0.001 (2)	−0.001 (3)	−0.003 (2)
C12	0.052 (4)	0.034 (3)	0.047 (4)	0.002 (3)	−0.002 (3)	0.000 (3)
C13	0.045 (3)	0.041 (4)	0.061 (4)	0.008 (4)	−0.002 (3)	0.009 (4)
C14	0.042 (3)	0.051 (4)	0.067 (5)	0.008 (4)	−0.009 (4)	−0.008 (4)
C15	0.036 (3)	0.049 (4)	0.049 (3)	0.007 (4)	0.002 (3)	−0.008 (3)
C16	0.036 (3)	0.038 (3)	0.035 (3)	0.002 (3)	0.002 (3)	−0.001 (3)
C21	0.038 (3)	0.030 (3)	0.030 (3)	−0.009 (3)	−0.003 (2)	0.003 (3)
C22	0.045 (3)	0.045 (4)	0.031 (3)	−0.009 (3)	−0.019 (3)	0.005 (3)
C23	0.062 (5)	0.055 (4)	0.055 (4)	−0.018 (4)	−0.016 (4)	−0.005 (4)
C24	0.081 (5)	0.060 (5)	0.051 (4)	−0.009 (5)	−0.013 (4)	−0.011 (4)
C25	0.074 (5)	0.057 (5)	0.048 (4)	−0.011 (5)	0.004 (4)	−0.022 (4)
C26	0.056 (4)	0.044 (3)	0.033 (3)	−0.004 (3)	0.000 (3)	−0.008 (3)
C31	0.030 (3)	0.029 (3)	0.032 (3)	−0.001 (3)	0.002 (3)	0.001 (3)
C32	0.037 (3)	0.030 (3)	0.052 (4)	−0.006 (3)	−0.000 (3)	−0.005 (3)
C33	0.048 (4)	0.042 (4)	0.043 (4)	−0.006 (3)	0.002 (3)	−0.003 (3)
C34	0.046 (4)	0.040 (4)	0.055 (4)	−0.005 (3)	0.006 (3)	0.005 (4)
C35	0.052 (4)	0.043 (4)	0.051 (4)	−0.013 (4)	0.011 (3)	0.006 (4)
C36	0.035 (3)	0.050 (4)	0.039 (3)	−0.012 (4)	0.002 (3)	0.006 (3)

Geometric parameters (Å, º) top

RH1—CL1	2.361 (2)	C34—C35	1.41 (1)
C11—C16	1.396 (9)	C7—C8	1.55 (1)
RH1—P1	2.308 (2)	C35—C36	1.38 (1)
C12—C13	1.40 (1)	C11—C12	1.388 (9)
RH1—C1	2.140 (6)	C1—H24	0.944
C13—C14	1.39 (1)	C2—H25	0.945
RH1—C2	2.109 (7)	C3—H26	0.956
C14—C15	1.40 (1)	C4—H27	0.952
RH1—C3	2.205 (7)	C5—H16	0.951
C15—C16	1.38 (1)	C5—H17	0.952
RH1—C4	2.238 (7)	C6—H18	0.946
C21—C22	1.406 (9)	C6—H19	0.949
P1—C11	1.809 (6)	C7—H21	0.948
C21—C26	1.40 (1)	C7—H20	0.952
P1—C21	1.837 (6)	C8—H22	0.940
C22—C23	1.37 (1)	C8—H23	0.944
P1—C31	1.827 (6)	C12—H1	0.950
C23—C24	1.38 (1)	C13—H2	0.947
C1—C2	1.41 (1)	C14—H3	0.949
C24—C25	1.40 (1)	C15—H4	0.951
C1—C6	1.50 (1)	C16—H5	0.950
C25—C26	1.39 (1)	C22—H6	0.945
C2—C7	1.52 (1)	C23—H7	0.951
C31—C32	1.402 (9)	C24—H8	0.950
C3—C4	1.34 (1)	C25—H9	0.939
C31—C36	1.390 (9)	C26—H10	0.944
C3—C8	1.54 (1	C32—H11	0.943
C32—C33	1.37 (1)	C33—H12	0.955
C4—C5	1.53 (1)	C34—H13	0.953
C33—C34	1.40 (1)	C35—H14	0.955
C5—C6	1.56 (1)	C36—H15	0.946

CL1—RH1—P1	88.44 (6)	H25—C2—C1	118.18
RH1—C1—C6	110.1 (5)	H25—C2—C7	118.33
CL1—RH1—C1	157.7 (2)	H26—C3—C4	117.25
C2—C1—C6	126.7 (6)	H26—C3—C8	116.75
CL1—RH1—C2	162.6 (2)	H27—C4—C3	117.94
RH1—C2—C1	71.9 (4)	H27—C4—C5	117.23
CL1—RH1—C3	87.1 (2)	H16—C5—H17	109.52
RH1—C2—C7	114.1 (5)	H16—C5—C4	109.29
CL1—RH1—C4	90.7 (2)	H16—C5—C6	109.83
C1—C2—C7	123.4 (6)	H17—C5—C4	108.88
P1—RH1—C1	93.4 (2)	H17—C5—C6	109.02
RH1—C3—C4	73.7 (4)	H18—C6—H19	110.18
P1—RH1—C2	97.7 (2)	H18—C6—C1	108.75
RH1—C3—C8	106.5 (5)	H18—C6—C5	108.09
P1—RH1—C3	162.3 (2)	H19—C6—C1	108.42
C4—C3—C8	126.1 (7)	H19—C6—C5	107.75
P1—RH1—C4	162.0 (2)	H21—C7—H20	109.59
RH1—C4—C3	71.1 (4)	H21—C7—C2	108.34
RH1—C4—C5	111.9 (4)	H21—C7—C8	109.03
C3—C4—C5	124.8 (7)	H20—C7—C2	108.63
C4—C5—C6	110.2 (6)	H20—C7—C8	109.03
C1—C6—C5	113.7 (6)	H22—C8—H23	109.79
C2—C7—C8	112.1 (6)	H22—C8—C3	108.77
C3—C8—C7	112.0 (6)	H22—C8—C7	109.04
RH1—P1—C11	109.8 (2)	H23—C8—C3	108.54
P1—C11—C12	123.4 (5)	H23—C8—C7	108.64
RH1—P1—C21	118.0 (2)	H1—C12—C11	119.91
P1—C11—C16	117.5 (5)	H1—C12—C13	120.64
RH1—P1—C31	117.1 (2)	H2—C13—C14	120.27
C12—C11—C16	119.1 (6)	H2—C13—C12	119.33
C11—P1—C21	102.8 (3)	H3—C14—C13	119.38
C11—C12—C13	119.3 (7)	H3—C14—C15	119.89
C11—P1—C31	105.2 (3)	H4—C15—C16	121.27
C12—C13—C14	120.6 (8)	H4—C15—C14	120.84
C21—P1—C31	102.4 (3)	H5—C16—C15	118.76
C13—C14—C15	120.6 (7)	H5—C16—C11	118.78
RH1—C1—C2	69.5 (4)	H6—C22—C23	119.77
C14—C15—C16	117.9 (7)	H6—C22—C21	120.63
C11—C16—C15	122.4 (6)	H7—C23—C22	118.60
P1—C31—C32	119.8 (5)	H7—C23—C24	118.48
P1—C21—C22	122.2 (5)	H8—C24—C23	120.80
P1—C31—C36	121.6 (5)	H8—C24—C25	121.29
P1—C21—C26	118.9 (5)	H9—C25—C26	119.72
C32—C31—C36	118.7 (6)	H9—C25—C24	119.64
C22—C21—C26	118.7 (6)	H10—C26—C25	119.9
C31—C32—C33	119.9 (6)	H10—C26—C21	119.8
C21—C22—C23	119.6 (7)	H11—C32—C33	120.6
C32—C33—C34	121.9 (7)	H11—C32—C31	119.53
C22—C23—C24	123.0 (8)	H12—C33—C32	119.40
C33—C34—C35	117.8 (7)	H12—C33—C34	118.65
C23—C24—C25	117.7 (8)	H13—C34—C33	120.79
C34—C35—C36	119.9 (7)	H13—C34—C35	121.36
C24—C25—C26	120.8 (8)	H14—C35—C36	119.77
C31—C36—C35	121.8 (6)	H14—C35—C34	120.37
C21—C26—C25	120.2 (7)	H15—C36—C35	119.43
H24—C1—C2	116.58	H15—C36—C31	118.76
H24—C1—C6	116.81

Rh-to-cod ligand distances and angles in the title compound and in some related structures. top

Compound	Rh—D1	Rh—D2	Cl—Rh—D1	Cl—Rh—D2	D1—Rh—D2
A	1.986 (6)	2.013 (6)	178.1 (2)	90.8 (2)	87.7 (3)
B	1.989 (5)	2.026 (5)	177.9 (2)	91.9 (2)	88.2 (2)
C	1.978 (5)	2.001 (5)	175.9 (2)	91.9 (1)	88.0 (2)
D	1.987 (8)	2.118 (6)	177.5 (5)	90.9 (3)	86.8 (4)
2	2.005 (7)	2.118 (7)	174.6 (2)	88.8 (2)	86.5 (4)
E	1.988 (6)	2.099 (7)	176.5 (4)	90.4 (3)	86.3 (4)
F	1.996 (9)	2.089 (7)	175.7 (3)	90.2 (2)	85.9 (4)
G	1.994 (4)	2.092 (4)	176.1 (1)	90.1 (1)	84.0 (2)

D1 and D2 are the mid-points of the two double bonds in cod.

A = Rh(cod)Cl(Et₃P═N(C₆H₄)CH₃)) (Imhoff et al., 1990).

B = RhCl(C₈H₁₂)(C₉H₁₆N₂) (Flörke et al., 1992).

C = RhCl(C₈H₁₂)(C₇H₁₂N₂) .1/2C₄H₈O₂ (Flörke et al., 1992).

D = RhCl(cod)P(p-C₆H₄F₃)₃ (Iglesias et al., 1987).

2 = Title compound RhCl(cod)P(C₆H₅)₃

E = RhCl(cod)P(C₆H₅)(o-tol) (Hubbard, 1988).

F = RhCl(cod)P(C₆H₅)(o-tol)₂ at 252K (Hubbard, 1988).

G = RhCl(cod)P(C₆H₅)(o-tol)₂ at 123K (Pinkerton, 1988).

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