Carbon­yl(3,7-dichloro­tropolonato)(triphenyl­phosphine)rhodium(I)

The title compound, [Rh(C₇H₃Cl₂O₂)(C₁₈H₁₅P)(CO)], is a rhodium(I) derivative of chlorinated tropolonate. It crystallizes with a nearly square-planar geometry about the rhodium(I) metal centre. The most important bond distances and angles include: Rh-O(trans P) = 2.086 (2) Å, Rh-O(trans carbon­yl) = 2.056 (2) Å, Rh-P = 2.2377 (8) Å, Rh-C(carbon­yl) = 1.809 (2) Å, O-Rh-O = 76.60 (6)° and O-C-C-O = -3.0 (3)°.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.027
• wR factor = 0.061
• Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) .        500 Ang.
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Rh     -   C01     ..       7.63 su
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

   1 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

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

Carbonyl(3,7-dichlorotropolonato)(triphenylphosphine)rhodium(I)

Crystal data

[Rh(C7H3Cl2O2)(C18H15P)(CO)]	F(000) = 1168
Mr = 583.18	Dx = 1.665 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2yn	Cell parameters from 7376 reflections
a = 8.823 (5) Å	θ = 2.3–28.2°
b = 17.662 (5) Å	µ = 1.06 mm^−1
c = 15.563 (5) Å	T = 100 K
β = 106.450 (5)°	Plate, yellow
V = 2325.9 (17) Å^3	0.18 × 0.10 × 0.03 mm
Z = 4

Data collection

Bruker SMART 4K CCD area-detector diffractometer	5065 independent reflections
Radiation source: fine-focus sealed tube	4322 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 512 x 512 pixels mm^-1	θmax = 27.0°, θmin = 2.7°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −22→12
Tmin = 0.882, Tmax = 0.97	l = −19→18
16578 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)] = 0.027	Hydrogen site location: calc
wR(F^2) = 0.061	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0234P)^2 + 1.6672P] where P = (Fo^2 + 2Fc^2)/3
5065 reflections	(Δ/σ)max = 0.001
298 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

Experimental. First 80 frames repeated after data collection to control a crystal stability

¹H NMR (CDCl₃, 300 MHz): δ 7.85 (m, 2H), 7.71 (m, 7H), 7.41 (m, 9H); ³¹P NMR (CDCl₃, 242.6 MHz): δ 48.12 (d, ¹J_Rh–P 174.4 Hz); ¹³C NMR (CDCl₃, 242.6 MHz): δ 176.5 (s, CO), 136.9 (s), 134.4 (s), 132.2 (s), 130.6 (s), 128.4 (s), 127.7 (d), 120.3 (s).

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 (Ų)

	x	y	z	Uiso*/Ueq
Rh	0.43393 (2)	0.363881 (9)	0.306253 (11)	0.01063 (6)
Cl3	0.37593 (8)	0.26276 (3)	0.58760 (4)	0.02242 (14)
Cl7	0.24575 (8)	0.59751 (3)	0.40212 (4)	0.02535 (15)
P	0.47114 (7)	0.41700 (3)	0.18327 (4)	0.01033 (12)
O1	0.36047 (19)	0.45985 (8)	0.35770 (10)	0.0145 (3)
O01	0.5251 (2)	0.21800 (9)	0.24117 (11)	0.0229 (4)
O2	0.39171 (19)	0.32583 (8)	0.42427 (10)	0.0147 (3)
C4	0.2400 (3)	0.39295 (14)	0.60655 (16)	0.0194 (5)
H4	0.2258	0.3654	0.6546	0.023*
C31	0.3594 (3)	0.50448 (12)	0.15024 (15)	0.0122 (4)
C36	0.3846 (3)	0.56448 (12)	0.21184 (15)	0.0145 (5)
H36	0.4591	0.5596	0.2674	0.017*
C5	0.1862 (3)	0.46688 (14)	0.60004 (16)	0.0215 (5)
H5	0.1367	0.4819	0.6427	0.026*
C21	0.6756 (3)	0.44363 (12)	0.19273 (14)	0.0118 (4)
C12	0.2706 (3)	0.31800 (12)	0.06505 (15)	0.0153 (5)
H12	0.2048	0.3245	0.1018	0.018*
C2	0.3395 (3)	0.37555 (12)	0.46925 (15)	0.0136 (5)
C11	0.4150 (3)	0.35694 (12)	0.08383 (14)	0.0122 (4)
C22	0.7962 (3)	0.39152 (13)	0.22996 (15)	0.0160 (5)
H22	0.7709	0.3443	0.2485	0.019*
C01	0.4902 (3)	0.27504 (13)	0.26616 (15)	0.0150 (5)
C24	0.9920 (3)	0.48082 (14)	0.21319 (16)	0.0185 (5)
H24	1.0973	0.4937	0.2211	0.022*
C35	0.2989 (3)	0.63096 (13)	0.19002 (16)	0.0182 (5)
H35	0.3168	0.6707	0.2308	0.022*
C33	0.1604 (3)	0.57952 (13)	0.04618 (16)	0.0179 (5)
H33	0.0851	0.5846	−0.0091	0.022*
C3	0.3122 (3)	0.35419 (13)	0.55158 (15)	0.0159 (5)
C32	0.2471 (3)	0.51232 (13)	0.06723 (15)	0.0145 (5)
H32	0.2300	0.4730	0.0259	0.017*
C7	0.2562 (3)	0.51520 (13)	0.46462 (16)	0.0166 (5)
C34	0.1862 (3)	0.63849 (13)	0.10737 (17)	0.0195 (5)
H34	0.1283	0.6830	0.0932	0.023*
C15	0.4695 (3)	0.29597 (14)	−0.04314 (17)	0.0222 (5)
H15	0.5365	0.2877	−0.0788	0.027*
C6	0.1969 (3)	0.52145 (14)	0.53770 (16)	0.0205 (5)
H6	0.1587	0.5691	0.5463	0.025*
C25	0.8729 (3)	0.53252 (13)	0.17516 (16)	0.0172 (5)
H25	0.8988	0.5797	0.1568	0.021*
C26	0.7157 (3)	0.51403 (12)	0.16439 (15)	0.0149 (5)
H26	0.6367	0.5486	0.1382	0.018*
C14	0.3260 (3)	0.25846 (13)	−0.06107 (16)	0.0213 (5)
H14	0.2967	0.2252	−0.1093	0.026*
C16	0.5127 (3)	0.34618 (13)	0.02881 (16)	0.0164 (5)
H16	0.6075	0.3726	0.0400	0.020*
C1	0.3178 (3)	0.45172 (12)	0.42981 (15)	0.0133 (5)
C23	0.9532 (3)	0.40986 (14)	0.23935 (16)	0.0184 (5)
H23	1.0324	0.3747	0.2631	0.022*
C13	0.2259 (3)	0.26984 (13)	−0.00815 (16)	0.0178 (5)
H13	0.1288	0.2452	−0.0216	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh	0.01193 (10)	0.01076 (9)	0.00965 (9)	0.00044 (7)	0.00377 (7)	0.00048 (6)
Cl3	0.0320 (4)	0.0196 (3)	0.0180 (3)	0.0016 (2)	0.0108 (3)	0.0045 (2)
Cl7	0.0396 (4)	0.0141 (3)	0.0245 (3)	0.0055 (3)	0.0126 (3)	−0.0004 (2)
P	0.0095 (3)	0.0111 (3)	0.0105 (3)	−0.0004 (2)	0.0030 (2)	0.0002 (2)
O1	0.0181 (9)	0.0129 (8)	0.0133 (8)	0.0018 (6)	0.0060 (7)	0.0001 (6)
O01	0.0342 (11)	0.0149 (8)	0.0209 (9)	0.0053 (7)	0.0101 (8)	0.0002 (7)
O2	0.0199 (9)	0.0127 (8)	0.0131 (8)	0.0032 (6)	0.0074 (7)	0.0015 (6)
C4	0.0189 (13)	0.0280 (13)	0.0118 (12)	0.0004 (10)	0.0053 (10)	−0.0006 (10)
C31	0.0093 (11)	0.0139 (11)	0.0148 (12)	0.0002 (9)	0.0057 (9)	0.0028 (9)
C36	0.0146 (12)	0.0161 (11)	0.0139 (12)	−0.0013 (9)	0.0059 (9)	0.0015 (9)
C5	0.0190 (13)	0.0315 (14)	0.0131 (12)	0.0033 (11)	0.0033 (10)	−0.0055 (10)
C21	0.0101 (11)	0.0159 (11)	0.0099 (11)	−0.0022 (9)	0.0036 (9)	−0.0027 (8)
C12	0.0149 (12)	0.0156 (11)	0.0151 (12)	0.0014 (9)	0.0040 (10)	0.0024 (9)
C2	0.0107 (11)	0.0154 (11)	0.0133 (11)	−0.0007 (9)	0.0013 (9)	−0.0009 (9)
C11	0.0140 (11)	0.0112 (10)	0.0097 (11)	0.0014 (9)	0.0003 (9)	0.0011 (8)
C22	0.0172 (12)	0.0158 (11)	0.0151 (12)	−0.0001 (9)	0.0047 (10)	−0.0011 (9)
C01	0.0177 (12)	0.0173 (12)	0.0105 (11)	−0.0005 (9)	0.0048 (10)	0.0043 (9)
C24	0.0131 (12)	0.0295 (13)	0.0141 (12)	−0.0057 (10)	0.0060 (10)	−0.0063 (10)
C35	0.0215 (13)	0.0155 (11)	0.0198 (13)	−0.0023 (10)	0.0095 (10)	−0.0004 (9)
C33	0.0153 (12)	0.0232 (12)	0.0157 (12)	0.0032 (10)	0.0051 (10)	0.0092 (9)
C3	0.0149 (12)	0.0169 (11)	0.0142 (12)	−0.0010 (9)	0.0015 (9)	0.0003 (9)
C32	0.0140 (12)	0.0171 (11)	0.0133 (12)	−0.0014 (9)	0.0055 (9)	0.0011 (9)
C7	0.0183 (13)	0.0147 (11)	0.0144 (12)	0.0016 (9)	0.0006 (10)	−0.0013 (9)
C34	0.0201 (13)	0.0150 (11)	0.0265 (14)	0.0053 (10)	0.0118 (11)	0.0070 (10)
C15	0.0256 (14)	0.0273 (13)	0.0166 (13)	−0.0018 (11)	0.0107 (11)	−0.0044 (10)
C6	0.0195 (13)	0.0226 (13)	0.0180 (13)	0.0047 (10)	0.0031 (10)	−0.0065 (10)
C25	0.0172 (12)	0.0212 (12)	0.0155 (12)	−0.0076 (10)	0.0083 (10)	−0.0019 (9)
C26	0.0159 (12)	0.0161 (11)	0.0125 (12)	−0.0003 (9)	0.0037 (10)	0.0003 (9)
C14	0.0266 (14)	0.0191 (12)	0.0152 (13)	−0.0011 (10)	0.0008 (11)	−0.0059 (9)
C16	0.0166 (12)	0.0163 (11)	0.0163 (12)	−0.0028 (9)	0.0047 (10)	0.0004 (9)
C1	0.0100 (11)	0.0154 (11)	0.0134 (11)	−0.0018 (9)	0.0016 (9)	−0.0019 (9)
C23	0.0137 (12)	0.0242 (13)	0.0168 (12)	0.0030 (10)	0.0036 (10)	−0.0028 (10)
C13	0.0160 (12)	0.0157 (11)	0.0169 (12)	−0.0036 (9)	−0.0029 (10)	0.0004 (9)

Geometric parameters (Å, º)

Rh—C01	1.809 (2)	C11—C16	1.390 (3)
Rh—O1	2.0563 (16)	C22—C23	1.390 (3)
Rh—O2	2.0860 (16)	C22—H22	0.9300
Rh—P	2.2377 (8)	C24—C23	1.390 (3)
Cl3—C3	1.749 (2)	C24—C25	1.391 (3)
Cl7—C7	1.737 (2)	C24—H24	0.9300
P—C11	1.825 (2)	C35—C34	1.392 (3)
P—C31	1.827 (2)	C35—H35	0.9300
P—C21	1.829 (2)	C33—C34	1.386 (3)
O1—C1	1.289 (3)	C33—C32	1.400 (3)
O01—C01	1.153 (3)	C33—H33	0.9300
O2—C2	1.287 (3)	C32—H32	0.9300
C4—C5	1.383 (3)	C7—C6	1.384 (3)
C4—C3	1.383 (3)	C7—C1	1.419 (3)
C4—H4	0.9300	C34—H34	0.9300
C31—C32	1.394 (3)	C15—C14	1.385 (4)
C31—C36	1.404 (3)	C15—C16	1.394 (3)
C36—C35	1.386 (3)	C15—H15	0.9300
C36—H36	0.9300	C6—H6	0.9300
C5—C6	1.390 (4)	C25—C26	1.388 (3)
C5—H5	0.9300	C25—H25	0.9300
C21—C26	1.398 (3)	C26—H26	0.9300
C21—C22	1.402 (3)	C14—C13	1.383 (4)
C12—C13	1.387 (3)	C14—H14	0.9300
C12—C11	1.404 (3)	C16—H16	0.9300
C12—H12	0.9300	C23—H23	0.9300
C2—C3	1.420 (3)	C13—H13	0.9300
C2—C1	1.469 (3)
C01—Rh—O1	175.37 (8)	C36—C35—C34	120.3 (2)
C01—Rh—O2	99.15 (8)	C36—C35—H35	119.8
O1—Rh—O2	76.60 (6)	C34—C35—H35	119.8
C01—Rh—P	87.00 (7)	C34—C33—C32	120.2 (2)
O1—Rh—P	97.25 (5)	C34—C33—H33	119.9
O2—Rh—P	173.85 (4)	C32—C33—H33	119.9
C11—P—C31	104.94 (10)	C4—C3—C2	130.7 (2)
C11—P—C21	104.04 (10)	C4—C3—Cl3	114.91 (19)
C31—P—C21	104.28 (10)	C2—C3—Cl3	114.39 (17)
C11—P—Rh	114.27 (8)	C31—C32—C33	119.9 (2)
C31—P—Rh	113.39 (8)	C31—C32—H32	120.0
C21—P—Rh	114.78 (7)	C33—C32—H32	120.0
C1—O1—Rh	116.69 (14)	C6—C7—C1	130.7 (2)
C2—O2—Rh	116.08 (14)	C6—C7—Cl7	114.88 (18)
C5—C4—C3	129.1 (2)	C1—C7—Cl7	114.38 (18)
C5—C4—H4	115.5	C33—C34—C35	119.9 (2)
C3—C4—H4	115.5	C33—C34—H34	120.0
C32—C31—C36	119.5 (2)	C35—C34—H34	120.0
C32—C31—P	121.99 (17)	C14—C15—C16	119.5 (2)
C36—C31—P	118.53 (17)	C14—C15—H15	120.3
C35—C36—C31	120.1 (2)	C16—C15—H15	120.3
C35—C36—H36	119.9	C7—C6—C5	129.4 (2)
C31—C36—H36	119.9	C7—C6—H6	115.3
C4—C5—C6	128.0 (2)	C5—C6—H6	115.3
C4—C5—H5	116.0	C26—C25—C24	120.4 (2)
C6—C5—H5	116.0	C26—C25—H25	119.8
C26—C21—C22	118.9 (2)	C24—C25—H25	119.8
C26—C21—P	122.37 (17)	C25—C26—C21	120.3 (2)
C22—C21—P	118.69 (17)	C25—C26—H26	119.8
C13—C12—C11	120.1 (2)	C21—C26—H26	119.8
C13—C12—H12	119.9	C13—C14—C15	120.8 (2)
C11—C12—H12	119.9	C13—C14—H14	119.6
O2—C2—C3	119.2 (2)	C15—C14—H14	119.6
O2—C2—C1	115.0 (2)	C11—C16—C15	120.4 (2)
C3—C2—C1	125.8 (2)	C11—C16—H16	119.8
C16—C11—C12	119.3 (2)	C15—C16—H16	119.8
C16—C11—P	122.34 (17)	O1—C1—C7	118.8 (2)
C12—C11—P	118.28 (17)	O1—C1—C2	115.5 (2)
C23—C22—C21	120.5 (2)	C7—C1—C2	125.7 (2)
C23—C22—H22	119.7	C22—C23—C24	120.0 (2)
C21—C22—H22	119.7	C22—C23—H23	120.0
O01—C01—Rh	179.2 (2)	C24—C23—H23	120.0
C23—C24—C25	119.8 (2)	C14—C13—C12	119.8 (2)
C23—C24—H24	120.1	C14—C13—H13	120.1
C25—C24—H24	120.1	C12—C13—H13	120.1
C01—Rh—P—C11	35.65 (11)	C31—C36—C35—C34	0.6 (3)
O1—Rh—P—C11	−142.51 (9)	C5—C4—C3—C2	−6.3 (4)
C01—Rh—P—C31	155.85 (11)	C5—C4—C3—Cl3	175.5 (2)
O1—Rh—P—C31	−22.31 (9)	O2—C2—C3—C4	−171.3 (2)
C01—Rh—P—C21	−84.43 (11)	C1—C2—C3—C4	10.6 (4)
O1—Rh—P—C21	97.41 (9)	O2—C2—C3—Cl3	6.9 (3)
O2—Rh—O1—C1	−3.49 (15)	C1—C2—C3—Cl3	−171.26 (18)
P—Rh—O1—C1	176.47 (15)	C36—C31—C32—C33	−0.3 (3)
C01—Rh—O2—C2	−176.41 (16)	P—C31—C32—C33	177.71 (17)
O1—Rh—O2—C2	1.73 (15)	C34—C33—C32—C31	0.4 (3)
C11—P—C31—C32	5.6 (2)	C32—C33—C34—C35	0.1 (4)
C21—P—C31—C32	114.72 (19)	C36—C35—C34—C33	−0.6 (4)
Rh—P—C31—C32	−119.74 (18)	C1—C7—C6—C5	2.5 (5)
C11—P—C31—C36	−176.33 (18)	Cl7—C7—C6—C5	179.3 (2)
C21—P—C31—C36	−67.25 (19)	C4—C5—C6—C7	3.4 (4)
Rh—P—C31—C36	58.29 (19)	C23—C24—C25—C26	0.9 (3)
C32—C31—C36—C35	−0.2 (3)	C24—C25—C26—C21	0.8 (3)
P—C31—C36—C35	−178.28 (18)	C22—C21—C26—C25	−1.6 (3)
C3—C4—C5—C6	−2.5 (4)	P—C21—C26—C25	178.24 (18)
C11—P—C21—C26	100.68 (19)	C16—C15—C14—C13	−0.5 (4)
C31—P—C21—C26	−9.1 (2)	C12—C11—C16—C15	−1.4 (3)
Rh—P—C21—C26	−133.72 (17)	P—C11—C16—C15	175.82 (18)
C11—P—C21—C22	−79.47 (19)	C14—C15—C16—C11	1.9 (4)
C31—P—C21—C22	170.79 (18)	Rh—O1—C1—C7	−175.83 (16)
Rh—P—C21—C22	46.13 (19)	Rh—O1—C1—C2	4.6 (2)
Rh—O2—C2—C3	−178.30 (16)	C6—C7—C1—O1	177.2 (2)
Rh—O2—C2—C1	0.0 (2)	Cl7—C7—C1—O1	0.4 (3)
C13—C12—C11—C16	−0.5 (3)	C6—C7—C1—C2	−3.2 (4)
C13—C12—C11—P	−177.87 (17)	Cl7—C7—C1—C2	179.95 (18)
C31—P—C11—C16	103.04 (19)	O2—C2—C1—O1	−3.0 (3)
C21—P—C11—C16	−6.2 (2)	C3—C2—C1—O1	175.2 (2)
Rh—P—C11—C16	−132.14 (17)	O2—C2—C1—C7	177.4 (2)
C31—P—C11—C12	−79.70 (19)	C3—C2—C1—C7	−4.4 (4)
C21—P—C11—C12	171.04 (17)	C21—C22—C23—C24	1.1 (4)
Rh—P—C11—C12	45.12 (19)	C25—C24—C23—C22	−1.9 (3)
C26—C21—C22—C23	0.6 (3)	C15—C14—C13—C12	−1.5 (4)
P—C21—C22—C23	−179.22 (18)	C11—C12—C13—C14	2.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O2^i	0.93	2.38	3.301 (3)	171
C34—H34···O2^ii	0.93	2.54	3.387 (3)	152

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1/2, y+1/2, −z+1/2.