Carbonyl­(tri­phenyl­arsine)(tropolonato)­rhodium(I)

The title complex, [Rh(C₇H₅O₂)(C₁₈H₁₅As)(CO)], has a distorted square-planar geometry. The most important bond distances and angles include Rh—C = 1.788 (10) Å, Rh—O(trans to CO) = 2.039 (6) Å, Rh—O(trans to As) = 2.059 (6) Å, Rh—As = 2.3507 (13) Å, O—Rh—O = 78.1 (2)° and O—C—C—O = 3.4 (12)°. The short interplanar distances between the tropolonate ligands [3.57 (5) Å] and phenyl groups [3.51 (5) Å] of neighbouring mol­ecules indicate π–π stacking interactions, which stabilize the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.016 Å
• R factor = 0.070
• wR factor = 0.186
• Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT331_ALERT_2_C Small Average Phenyl C-C Dist.   C11    -C16           1.37 Ang.
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         16
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 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
   1 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMAR-NT (Siemens, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SHELXTL (Siemens, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97.

Carbonyl(triphenylarsine)(tropolonato)rhodium(I).

Crystal data

[Rh(C7H5O2)(C18H15As)(CO)]	Z = 2
Mr = 558.25	F(000) = 556
Triclinic, P1	Dx = 1.656 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71069 Å
a = 8.996 (5) Å	Cell parameters from 1266 reflections
b = 9.387 (5) Å	θ = 2.5–22.1°
c = 14.137 (5) Å	µ = 2.25 mm^−1
α = 96.550 (5)°	T = 295 K
β = 103.623 (5)°	Block, orange
γ = 101.722 (5)°	0.15 × 0.14 × 0.08 mm
V = 1119.5 (9) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4552 independent reflections
Radiation source: fine-focus sealed tube	2446 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
Detector resolution: 512 x 512 pixels mm^-1	θmax = 26.4°, θmin = 1.5°
ω scans	h = −11→10
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −11→11
Tmin = 0.729, Tmax = 0.840	l = −17→17
7120 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.070	Hydrogen site location: riding model
wR(F^2) = 0.186	H-atom parameters constrained
S = 0.92	w = 1/[σ^2(Fo^2) + (0.1006P)^2] where P = (Fo^2 + 2Fc^2)/3
4552 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 1.63 e Å^−3
0 restraints	Δρmin = −1.49 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Rh	0.72494 (9)	0.27339 (8)	0.15166 (5)	0.0396 (3)
As1	0.81952 (10)	0.14315 (10)	0.27619 (6)	0.0373 (3)
C25	0.5613 (14)	−0.2951 (13)	0.1995 (10)	0.074 (3)
H25	0.5224	−0.3658	0.1424	0.088*
O12	0.6714 (7)	0.4182 (7)	0.0571 (5)	0.0466 (16)
C01	0.5413 (12)	0.1385 (12)	0.1119 (7)	0.049 (3)
C13	1.2913 (13)	0.1962 (13)	0.2791 (9)	0.068 (3)
H13	1.3659	0.2657	0.2623	0.082*
C24	0.5410 (14)	−0.3296 (13)	0.2895 (12)	0.079 (4)
H24	0.4867	−0.4242	0.2916	0.094*
C34	0.8531 (16)	0.4206 (12)	0.5830 (8)	0.065 (3)
H34	0.8563	0.4753	0.6429	0.078*
C22	0.6779 (12)	−0.0911 (11)	0.3705 (8)	0.052 (3)
H22	0.7174	−0.0210	0.4279	0.062*
C1	0.9347 (12)	0.5323 (11)	0.1306 (6)	0.043 (2)
C16	1.0721 (13)	−0.0075 (12)	0.3273 (8)	0.059 (3)
H16	0.9968	−0.0785	0.3422	0.071*
C11	1.0323 (11)	0.1129 (10)	0.2914 (6)	0.042 (2)
C31	0.8385 (10)	0.2540 (9)	0.4044 (6)	0.033 (2)
C7	1.0781 (12)	0.6310 (11)	0.1412 (8)	0.055 (3)
H7	1.1620	0.6161	0.1887	0.066*
C32	0.9600 (13)	0.2624 (11)	0.4864 (7)	0.055 (3)
H32	1.0373	0.2112	0.4825	0.065*
C35	0.7352 (15)	0.4117 (13)	0.5018 (10)	0.070 (3)
H35	0.6564	0.4605	0.5064	0.084*
O11	0.9316 (8)	0.4302 (7)	0.1864 (5)	0.0519 (18)
O01	0.4199 (9)	0.0565 (9)	0.0850 (6)	0.072 (2)
C21	0.7014 (10)	−0.0529 (9)	0.2818 (7)	0.036 (2)
C23	0.5981 (13)	−0.2291 (13)	0.3748 (10)	0.070 (3)
H23	0.5831	−0.2540	0.4342	0.084*
C2	0.7840 (12)	0.5255 (11)	0.0596 (6)	0.042 (2)
C26	0.6402 (13)	−0.1543 (11)	0.1968 (8)	0.057 (3)
H26	0.6517	−0.1281	0.1370	0.069*
C14	1.3339 (13)	0.0793 (13)	0.3181 (8)	0.063 (3)
H14	1.4373	0.0700	0.3287	0.076*
C15	1.2250 (14)	−0.0227 (14)	0.3411 (9)	0.070 (3)
H15	1.2529	−0.1036	0.3663	0.084*
C33	0.9668 (16)	0.3482 (13)	0.5754 (8)	0.068 (3)
H33	1.0506	0.3559	0.6302	0.081*
C36	0.7287 (13)	0.3331 (11)	0.4134 (7)	0.052 (3)
H36	0.6485	0.3329	0.3581	0.062*
C5	1.0228 (13)	0.8014 (12)	0.0231 (8)	0.056 (3)
H5	1.0724	0.8790	−0.0025	0.068*
C12	1.1385 (13)	0.2127 (12)	0.2643 (8)	0.059 (3)
H12	1.1093	0.2911	0.2362	0.071*
C6	1.1169 (13)	0.7484 (11)	0.0926 (8)	0.056 (3)
H6	1.2229	0.7973	0.1105	0.067*
C3	0.7594 (12)	0.6341 (12)	0.0011 (7)	0.056 (3)
H3	0.6550	0.6232	−0.0335	0.067*
C4	0.8630 (15)	0.7545 (12)	−0.0143 (8)	0.064 (3)
H4	0.8170	0.8122	−0.0563	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh	0.0335 (5)	0.0414 (5)	0.0388 (5)	0.0063 (4)	0.0008 (3)	0.0088 (3)
As1	0.0302 (5)	0.0390 (6)	0.0410 (6)	0.0078 (4)	0.0049 (4)	0.0106 (4)
C25	0.059 (8)	0.046 (7)	0.101 (10)	0.003 (6)	0.007 (7)	0.000 (7)
O12	0.033 (4)	0.046 (4)	0.059 (4)	0.004 (3)	0.008 (3)	0.021 (3)
C01	0.041 (6)	0.053 (6)	0.053 (6)	0.003 (5)	0.012 (5)	0.018 (5)
C13	0.048 (7)	0.067 (8)	0.102 (10)	0.016 (6)	0.029 (7)	0.041 (7)
C24	0.054 (8)	0.046 (7)	0.136 (13)	0.006 (6)	0.021 (8)	0.034 (8)
C34	0.082 (9)	0.040 (7)	0.057 (7)	−0.016 (6)	0.019 (7)	0.000 (5)
C22	0.043 (6)	0.049 (6)	0.054 (6)	0.004 (5)	0.001 (5)	0.006 (5)
C1	0.048 (6)	0.045 (6)	0.037 (5)	0.019 (5)	0.007 (5)	0.004 (4)
C16	0.043 (6)	0.060 (7)	0.084 (8)	0.023 (6)	0.018 (6)	0.025 (6)
C11	0.033 (5)	0.046 (6)	0.041 (5)	0.003 (4)	0.003 (4)	0.011 (4)
C31	0.029 (5)	0.029 (5)	0.038 (5)	0.004 (4)	0.003 (4)	0.014 (4)
C7	0.039 (6)	0.050 (6)	0.063 (7)	0.000 (5)	−0.004 (5)	0.014 (5)
C32	0.061 (7)	0.042 (6)	0.051 (6)	−0.002 (5)	0.009 (5)	0.010 (5)
C35	0.071 (9)	0.064 (8)	0.083 (9)	0.019 (7)	0.035 (8)	0.008 (7)
O11	0.047 (4)	0.042 (4)	0.051 (4)	0.001 (3)	−0.015 (3)	0.020 (3)
O01	0.037 (4)	0.079 (6)	0.085 (6)	−0.002 (4)	0.003 (4)	0.011 (5)
C21	0.022 (4)	0.031 (5)	0.054 (6)	0.006 (4)	0.006 (4)	0.011 (4)
C23	0.051 (7)	0.062 (8)	0.086 (9)	−0.008 (6)	0.009 (7)	0.023 (7)
C2	0.043 (6)	0.051 (6)	0.033 (5)	0.017 (5)	0.007 (4)	0.009 (4)
C26	0.056 (7)	0.050 (7)	0.065 (7)	0.016 (6)	0.017 (6)	0.004 (6)
C14	0.033 (6)	0.074 (8)	0.086 (8)	0.020 (6)	0.014 (6)	0.021 (7)
C15	0.059 (8)	0.066 (8)	0.092 (9)	0.025 (7)	0.021 (7)	0.023 (7)
C33	0.075 (9)	0.062 (8)	0.043 (6)	−0.011 (7)	−0.002 (6)	0.006 (6)
C36	0.050 (6)	0.060 (7)	0.048 (6)	0.016 (6)	0.016 (5)	0.008 (5)
C5	0.045 (6)	0.054 (7)	0.070 (7)	0.004 (5)	0.018 (6)	0.019 (6)
C12	0.051 (7)	0.057 (7)	0.077 (8)	0.017 (6)	0.024 (6)	0.024 (6)
C6	0.046 (6)	0.049 (6)	0.066 (7)	−0.005 (5)	0.013 (6)	0.014 (5)
C3	0.041 (6)	0.072 (8)	0.058 (7)	0.021 (6)	0.005 (5)	0.032 (6)
C4	0.084 (9)	0.049 (7)	0.069 (7)	0.026 (7)	0.021 (7)	0.028 (6)

Geometric parameters (Å, º)

Rh—C01	1.788 (10)	C16—H16	0.9300
Rh—O11	2.039 (6)	C11—C12	1.352 (13)
Rh—O12	2.059 (6)	C31—C36	1.370 (13)
Rh—As1	2.3507 (13)	C31—C32	1.375 (13)
As1—C31	1.936 (9)	C7—C6	1.393 (13)
As1—C21	1.949 (8)	C7—H7	0.9300
As1—C11	1.957 (9)	C32—C33	1.396 (15)
C25—C26	1.377 (15)	C32—H32	0.9300
C25—C24	1.392 (17)	C35—C36	1.360 (14)
C25—H25	0.9300	C35—H35	0.9300
O12—C2	1.266 (11)	C21—C26	1.366 (13)
C01—O01	1.151 (11)	C23—H23	0.9300
C13—C14	1.366 (15)	C2—C3	1.403 (12)
C13—C12	1.384 (15)	C26—H26	0.9300
C13—H13	0.9300	C14—C15	1.350 (14)
C24—C23	1.363 (17)	C14—H14	0.9300
C24—H24	0.9300	C15—H15	0.9300
C34—C35	1.348 (16)	C33—H33	0.9300
C34—C33	1.356 (16)	C36—H36	0.9300
C34—H34	0.9300	C5—C6	1.349 (14)
C22—C23	1.363 (14)	C5—C4	1.368 (15)
C22—C21	1.394 (13)	C5—H5	0.9300
C22—H22	0.9300	C12—H12	0.9300
C1—O11	1.309 (10)	C6—H6	0.9300
C1—C7	1.392 (13)	C3—C4	1.385 (14)
C1—C2	1.470 (13)	C3—H3	0.9300
C16—C11	1.368 (13)	C4—H4	0.9300
C16—C15	1.382 (15)
C01—Rh—O11	175.7 (3)	C31—C32—H32	120.2
C01—Rh—O12	98.3 (4)	C33—C32—H32	120.2
O11—Rh—O12	78.1 (2)	C34—C35—C36	121.7 (12)
C01—Rh—As1	90.9 (3)	C34—C35—H35	119.2
O11—Rh—As1	92.89 (17)	C36—C35—H35	119.2
O12—Rh—As1	170.15 (18)	C1—O11—Rh	114.9 (6)
C31—As1—C21	102.9 (4)	C26—C21—C22	119.6 (9)
C31—As1—C11	101.7 (4)	C26—C21—As1	119.1 (7)
C21—As1—C11	101.7 (4)	C22—C21—As1	121.3 (7)
C31—As1—Rh	109.7 (2)	C24—C23—C22	118.2 (11)
C21—As1—Rh	120.8 (3)	C24—C23—H23	120.9
C11—As1—Rh	117.6 (3)	C22—C23—H23	120.9
C26—C25—C24	118.6 (12)	O12—C2—C3	120.5 (9)
C26—C25—H25	120.7	O12—C2—C1	116.0 (8)
C24—C25—H25	120.7	C3—C2—C1	123.5 (9)
C2—O12—Rh	115.6 (6)	C21—C26—C25	120.1 (11)
O01—C01—Rh	177.0 (10)	C21—C26—H26	119.9
C14—C13—C12	120.8 (10)	C25—C26—H26	119.9
C14—C13—H13	119.6	C15—C14—C13	119.5 (10)
C12—C13—H13	119.6	C15—C14—H14	120.2
C23—C24—C25	122.1 (11)	C13—C14—H14	120.2
C23—C24—H24	118.9	C14—C15—C16	120.3 (11)
C25—C24—H24	118.9	C14—C15—H15	119.8
C35—C34—C33	118.6 (11)	C16—C15—H15	119.8
C35—C34—H34	120.7	C34—C33—C32	121.0 (11)
C33—C34—H34	120.7	C34—C33—H33	119.5
C23—C22—C21	121.3 (10)	C32—C33—H33	119.5
C23—C22—H22	119.3	C35—C36—C31	121.0 (10)
C21—C22—H22	119.3	C35—C36—H36	119.5
O11—C1—C7	118.0 (9)	C31—C36—H36	119.5
O11—C1—C2	115.1 (8)	C6—C5—C4	127.8 (10)
C7—C1—C2	126.9 (9)	C6—C5—H5	116.1
C11—C16—C15	119.6 (10)	C4—C5—H5	116.1
C11—C16—H16	120.2	C11—C12—C13	118.9 (10)
C15—C16—H16	120.2	C11—C12—H12	120.5
C12—C11—C16	120.7 (10)	C13—C12—H12	120.5
C12—C11—As1	118.4 (7)	C5—C6—C7	129.2 (10)
C16—C11—As1	120.9 (7)	C5—C6—H6	115.4
C36—C31—C32	118.0 (9)	C7—C6—H6	115.4
C36—C31—As1	118.5 (7)	C4—C3—C2	131.5 (10)
C32—C31—As1	123.5 (7)	C4—C3—H3	114.3
C1—C7—C6	130.7 (10)	C2—C3—H3	114.3
C1—C7—H7	114.6	C5—C4—C3	129.7 (10)
C6—C7—H7	114.6	C5—C4—H4	115.2
C31—C32—C33	119.7 (11)	C3—C4—H4	115.2
C01—Rh—As1—C31	−110.7 (4)	C11—As1—C21—C26	−87.2 (8)
O11—Rh—As1—C31	71.4 (3)	Rh—As1—C21—C26	45.1 (8)
C01—Rh—As1—C21	8.7 (4)	C31—As1—C21—C22	−11.9 (8)
C01—Rh—As1—C11	133.9 (5)	C11—As1—C21—C22	93.1 (8)
O11—Rh—As1—C11	−44.1 (4)	Rh—As1—C21—C22	−134.5 (7)
C01—Rh—O12—C2	−174.4 (7)	C25—C24—C23—C22	−0.2 (19)
O11—Rh—O12—C2	3.3 (6)	C21—C22—C23—C24	−0.2 (17)
C26—C25—C24—C23	−0.8 (19)	Rh—O12—C2—C3	−177.5 (7)
C15—C16—C11—C12	3.6 (17)	Rh—O12—C2—C1	−1.1 (10)
C15—C16—C11—As1	−177.3 (9)	O11—C1—C2—O12	−3.4 (12)
C31—As1—C11—C12	−92.0 (8)	C7—C1—C2—O12	174.0 (9)
C21—As1—C11—C12	162.0 (8)	O11—C1—C2—C3	172.9 (9)
Rh—As1—C11—C12	27.7 (9)	C7—C1—C2—C3	−9.7 (16)
C31—As1—C11—C16	88.9 (9)	C22—C21—C26—C25	−2.7 (15)
C21—As1—C11—C16	−17.1 (9)	As1—C21—C26—C25	177.6 (8)
Rh—As1—C11—C16	−151.3 (8)	C24—C25—C26—C21	2.3 (17)
C21—As1—C31—C36	−94.0 (7)	C12—C13—C14—C15	1 (2)
C11—As1—C31—C36	160.9 (7)	C13—C14—C15—C16	−1.3 (19)
Rh—As1—C31—C36	35.7 (7)	C11—C16—C15—C14	−0.9 (19)
C21—As1—C31—C32	88.6 (8)	C35—C34—C33—C32	−2.0 (16)
C11—As1—C31—C32	−16.4 (8)	C31—C32—C33—C34	1.7 (16)
Rh—As1—C31—C32	−141.6 (7)	C34—C35—C36—C31	3.0 (17)
O11—C1—C7—C6	179.6 (11)	C32—C31—C36—C35	−3.2 (14)
C2—C1—C7—C6	2.3 (18)	As1—C31—C36—C35	179.3 (8)
C36—C31—C32—C33	0.9 (14)	C16—C11—C12—C13	−4.0 (17)
As1—C31—C32—C33	178.2 (7)	As1—C11—C12—C13	177.0 (9)
C33—C34—C35—C36	−0.3 (17)	C14—C13—C12—C11	1.6 (19)
C7—C1—O11—Rh	−171.4 (7)	C4—C5—C6—C7	3 (2)
C2—C1—O11—Rh	6.2 (10)	C1—C7—C6—C5	2 (2)
O12—Rh—O11—C1	−5.2 (6)	O12—C2—C3—C4	−175.1 (11)
As1—Rh—O11—C1	178.7 (6)	C1—C2—C3—C4	8.8 (18)
C23—C22—C21—C26	1.7 (15)	C6—C5—C4—C3	−7 (2)
C23—C22—C21—As1	−178.6 (8)	C2—C3—C4—C5	1 (2)
C31—As1—C21—C26	167.8 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O11	0.93	2.30	3.152 (13)	152