(Acetyl­acetonato-κ2O,O′)carbon­yl[2-(diphenyl­phosphino)pyridine-κP]rhodium(I)

Coetzee, M.; Purcell, W.; Visser, H.G.; Venter, J.A.

doi:10.1107/S1600536807058886

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(Acetylacetonato-κ²O,O′)carbonyl[2-(diphenylphosphino)pyridine-κP]rhodium(I)

M. Coetzee, W. Purcell, H. G. Visser and J. A. Venter

The title complex, [Rh(C₅H₇O₂)(C₁₇H₁₄NP)(CO)], adopts a square-planar geometry, with bite angles around the rhodium(I) centre varying between 85.28 (7) and 93.59 (8)°. The two phenyl rings and the one pyridine ring of the phosphine ligand are arranged in a face on/edge on orientation, with dihedral angles between the planes formed by these rings ranging between 66.55 (7) and 80.50 (7)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807058886/ng2373sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807058886/ng2373Isup2.hkl Contains datablock I

CCDC reference: 672760

checkCIF report

Key indicators

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.003 Å
R factor = 0.026
wR factor = 0.065
Data-to-parameter ratio = 19.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT147_ALERT_1_C su on Symmetry Constrained Cell Angle(s) .......          ?
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)  Rh1    -   C6      ..       8.16 su

   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

   2 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The title compound (I) contains a rhodium(I) centre which is surrounded by two oxygen atoms of the acac ligand, a carbon atom of the carbonyl ligand and a phosphorous atom of the P(Pyr)(Ph)₂ ligand. The Rh1–C6 bonding distance is 1.810 (2) Å while the Rh1–O1 and Rh1–O2 distances are 2.0700 (15) and 2.0343 (15) Å respectively. The Rh1–P1 bonding distance is 2.2302 (8) Å.

The bite angles around the rhodium(I) centre vary between 85.28 (7) and 93.59 (8)°. All the bonding distances and angles fall in the expected range for similar complexes (Wajda-Hermanowicz et al. 2006, Drommi et al. 1995, Brink et al. 2007a, Brink et al. 2007b).

The P(Pyr)(Ph)₂ ligand is behaving as a monodentate ligand in (I), although several cases have been reported where it behaves as a bridging (Farr et al. 1983; Cotton & Matusz, 1988; Marsh, 1997) or a bidentate ligand (Clarke et al. 2001).

Related literature top

For the synthesis of [Rh(acac)(CO)₂], see: Leipoldt et al. (1978). For metal complexes of the ligand, see: Clarke et al. (2001); Cotton & Matusz (1988); Farr et al. (1983); Marsh (1997). For similar complexes, see: Brink et al. (2007a,b); Drommi et al. (1995); Wajda-Hermanowicz et al. (2006).

Experimental top

[Rh(acac)(CO)₂] (Leipoldt et al.,1978) (0.0109 g, 0.042 mmol) was dissolved in methanol (5 ml). 2-(Diphenylphosphino)pyridine (0.0111 g, 0.042 mmol) was added to this solution. The solution was stirred until a yellow precipitate formed. The product, (I), was dissolved in 5 ml diethyl ether and filtered. Yellow crystals were obtained after 24 h in 70% yield. ³¹P NMR (CDCl₃, p.p.m..): [δ, ¹J(Rh–P) = 177.09 Hz] IR ν(Rh—CO) 1963 cm^-1.

Computing details top

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: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. View of (I) (50% probability displacement ellipsoids)

(Acetylacetonato-κ²O,O')carbonyl[2- (diphenylphosphino)pyridine-κP]rhodium(I) top

Crystal data top

[Rh(C₅H₇O₂)(C₁₇H₁₄NP)(CO)]	F(000) = 1000
M_r = 493.29	D_x = 1.554 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 8227 reflections
a = 8.822 (5) Å	θ = 2.3–28.2°
b = 17.782 (5) Å	µ = 0.91 mm⁻¹
c = 13.798 (5) Å	T = 150 K
β = 103.027 (5)°	Cuboid, yellow
V = 2108.8 (15) Å³	0.19 × 0.18 × 0.06 mm
Z = 4

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	4522 reflections with I > 2σ(I)
ω and ϕ scans	R_int = 0.034
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 28.3°, θ_min = 2.5°
T_min = 0.846, T_max = 0.947	h = −11→11
24055 measured reflections	k = −23→23
5248 independent reflections	l = −18→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.026	w = 1/[σ²(F_o²) + (0.0253P)² + 1.8318P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.46 e Å⁻³
5248 reflections	Δρ_min = −0.39 e Å⁻³
266 parameters

Crystal data top

[Rh(C₅H₇O₂)(C₁₇H₁₄NP)(CO)]	V = 2108.8 (15) Å³
M_r = 493.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.822 (5) Å	µ = 0.91 mm⁻¹
b = 17.782 (5) Å	T = 150 K
c = 13.798 (5) Å	0.19 × 0.18 × 0.06 mm
β = 103.027 (5)°

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	5248 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	4522 reflections with I > 2σ(I)
T_min = 0.846, T_max = 0.947	R_int = 0.034
24055 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.05	Δρ_max = 0.46 e Å⁻³
5248 reflections	Δρ_min = −0.39 e Å⁻³
266 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Rh1	0.413043 (18)	0.130551 (9)	0.345080 (11)	0.01678 (5)
P2	0.45125 (6)	0.07735 (3)	0.20616 (4)	0.01570 (10)
O3	0.5393 (2)	0.26775 (9)	0.27114 (12)	0.0325 (4)
O1	0.38355 (18)	0.18126 (8)	0.47462 (10)	0.0244 (3)
O2	0.32107 (17)	0.03483 (8)	0.38876 (10)	0.0234 (3)
C6	0.4920 (2)	0.21458 (12)	0.30102 (15)	0.0227 (4)
C26	0.2370 (2)	−0.00915 (12)	0.06995 (14)	0.0207 (4)
H26	0.2259	0.0327	0.0285	0.025*
N1	0.7625 (2)	0.09914 (12)	0.25525 (15)	0.0325 (4)
C16	0.2750 (2)	0.18390 (12)	0.08777 (15)	0.0233 (4)
H16	0.207	0.1765	0.1295	0.028*
C11	0.4094 (2)	0.14104 (11)	0.10007 (14)	0.0184 (4)
C21	0.3381 (2)	−0.00670 (11)	0.16307 (14)	0.0177 (4)
C25	0.1530 (3)	−0.07393 (13)	0.03899 (16)	0.0257 (5)
H25	0.0856	−0.0754	−0.0234	0.031*
C4	0.3242 (3)	0.20150 (15)	0.63005 (17)	0.0366 (6)
H4A	0.2795	0.2492	0.6065	0.055*
H4B	0.4284	0.2089	0.6681	0.055*
H4C	0.2628	0.1785	0.6712	0.055*
C13	0.4763 (3)	0.20638 (14)	−0.03672 (16)	0.0307 (5)
H13	0.5441	0.2141	−0.0785	0.037*
C23	0.2679 (3)	−0.13384 (12)	0.19316 (17)	0.0265 (5)
H23	0.2778	−0.1758	0.2344	0.032*
C32	0.6925 (2)	−0.02201 (12)	0.18125 (15)	0.0237 (4)
H32	0.6153	−0.0558	0.1518	0.028*
C12	0.5094 (3)	0.15155 (12)	0.03682 (16)	0.0238 (4)
H12	0.5982	0.122	0.0435	0.029*
C33	0.8482 (3)	−0.04076 (14)	0.19355 (17)	0.0318 (5)
H33	0.8767	−0.0875	0.1732	0.038*
C15	0.2423 (3)	0.23717 (14)	0.01422 (17)	0.0313 (5)
H15	0.1515	0.2654	0.0059	0.038*
C22	0.3524 (2)	−0.06947 (12)	0.22521 (16)	0.0223 (4)
H22	0.4187	−0.068	0.288	0.027*
C31	0.6531 (2)	0.04760 (11)	0.21339 (13)	0.0177 (4)
C34	0.9600 (3)	0.01062 (16)	0.23621 (17)	0.0351 (6)
H34	1.0651	−0.001	0.2455	0.042*
C35	0.9140 (3)	0.07956 (16)	0.26490 (18)	0.0363 (6)
H35	0.9904	0.1144	0.2922	0.044*
C14	0.3433 (3)	0.24935 (14)	−0.04791 (17)	0.0318 (5)
H14	0.3216	0.2863	−0.0968	0.038*
C5	0.2152 (3)	−0.05386 (14)	0.48055 (18)	0.0378 (6)
H5A	0.1784	−0.0764	0.4163	0.057*
H5C	0.1316	−0.0515	0.5146	0.057*
H5B	0.2984	−0.0836	0.5186	0.057*
C3	0.2732 (2)	0.02422 (13)	0.46823 (15)	0.0246 (4)
C24	0.1681 (3)	−0.13612 (13)	0.09948 (17)	0.0279 (5)
H24	0.1119	−0.1796	0.0779	0.034*
C1	0.3270 (3)	0.15107 (13)	0.54241 (15)	0.0250 (5)
C2	0.2724 (3)	0.07777 (14)	0.54181 (16)	0.0292 (5)
H2	0.2315	0.0631	0.5954	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.01685 (8)	0.01675 (8)	0.01773 (8)	−0.00021 (6)	0.00598 (6)	−0.00119 (6)
P2	0.0140 (2)	0.0158 (2)	0.0174 (2)	0.00126 (19)	0.00381 (18)	−0.00040 (18)
O3	0.0433 (10)	0.0230 (8)	0.0357 (9)	−0.0072 (7)	0.0184 (8)	−0.0026 (7)
O1	0.0303 (8)	0.0234 (8)	0.0216 (7)	0.0005 (6)	0.0107 (6)	−0.0030 (6)
O2	0.0252 (8)	0.0230 (8)	0.0225 (7)	−0.0038 (6)	0.0065 (6)	0.0010 (6)
C6	0.0253 (11)	0.0223 (11)	0.0224 (10)	−0.0011 (9)	0.0092 (8)	−0.0074 (8)
C26	0.0201 (10)	0.0229 (10)	0.0201 (9)	0.0001 (8)	0.0067 (8)	−0.0011 (8)
N1	0.0227 (10)	0.0404 (12)	0.0334 (10)	−0.0032 (9)	0.0045 (8)	−0.0052 (9)
C16	0.0193 (10)	0.0274 (11)	0.0235 (10)	0.0035 (9)	0.0055 (8)	0.0036 (8)
C11	0.0194 (10)	0.0172 (10)	0.0174 (9)	0.0007 (8)	0.0019 (7)	−0.0006 (7)
C21	0.0143 (9)	0.0184 (10)	0.0216 (9)	0.0005 (7)	0.0067 (7)	−0.0034 (7)
C25	0.0222 (11)	0.0316 (12)	0.0235 (10)	−0.0044 (9)	0.0053 (8)	−0.0068 (9)
C4	0.0488 (15)	0.0415 (15)	0.0224 (11)	0.0116 (12)	0.0141 (11)	−0.0012 (10)
C13	0.0347 (13)	0.0338 (13)	0.0264 (11)	0.0016 (10)	0.0126 (10)	0.0060 (9)
C23	0.0272 (11)	0.0194 (10)	0.0346 (11)	−0.0021 (9)	0.0107 (9)	0.0014 (9)
C32	0.0224 (10)	0.0237 (11)	0.0268 (10)	0.0034 (9)	0.0091 (8)	0.0019 (8)
C12	0.0236 (11)	0.0234 (11)	0.0253 (10)	0.0041 (8)	0.0075 (9)	0.0010 (8)
C33	0.0311 (12)	0.0352 (13)	0.0329 (12)	0.0154 (10)	0.0154 (10)	0.0079 (10)
C15	0.0263 (12)	0.0311 (13)	0.0346 (12)	0.0090 (10)	0.0030 (10)	0.0048 (10)
C22	0.0193 (10)	0.0225 (11)	0.0255 (10)	0.0013 (8)	0.0055 (8)	0.0000 (8)
C31	0.0153 (9)	0.0229 (10)	0.0153 (8)	0.0030 (8)	0.0041 (7)	0.0021 (7)
C34	0.0176 (11)	0.0613 (17)	0.0276 (11)	0.0098 (11)	0.0072 (9)	0.0128 (11)
C35	0.0215 (12)	0.0533 (16)	0.0319 (12)	−0.0077 (11)	0.0014 (10)	−0.0033 (11)
C14	0.0353 (13)	0.0288 (12)	0.0298 (11)	0.0039 (10)	0.0041 (10)	0.0094 (9)
C5	0.0445 (15)	0.0348 (14)	0.0333 (12)	−0.0097 (12)	0.0075 (11)	0.0100 (10)
C3	0.0193 (10)	0.0294 (12)	0.0237 (10)	−0.0011 (9)	0.0021 (8)	0.0077 (9)
C24	0.0254 (11)	0.0250 (11)	0.0356 (12)	−0.0068 (9)	0.0113 (9)	−0.0094 (9)
C1	0.0234 (11)	0.0316 (12)	0.0205 (10)	0.0082 (9)	0.0059 (8)	0.0017 (8)
C2	0.0332 (12)	0.0358 (13)	0.0211 (10)	0.0019 (10)	0.0112 (9)	0.0068 (9)

Geometric parameters (Å, º) top

Rh1—C6	1.810 (2)	C13—C12	1.390 (3)
Rh1—O2	2.0345 (15)	C13—H13	0.93
Rh1—O1	2.0701 (15)	C23—C22	1.383 (3)
Rh1—P2	2.2303 (8)	C23—C24	1.391 (3)
P2—C21	1.821 (2)	C23—H23	0.93
P2—C11	1.821 (2)	C32—C31	1.385 (3)
P2—C31	1.839 (2)	C32—C33	1.386 (3)
O3—C6	1.147 (3)	C32—H32	0.93
O1—C1	1.274 (3)	C12—H12	0.93
O2—C3	1.275 (2)	C33—C34	1.376 (4)
C26—C25	1.384 (3)	C33—H33	0.93
C26—C21	1.390 (3)	C15—C14	1.386 (3)
C26—H26	0.93	C15—H15	0.93
N1—C35	1.359 (3)	C22—H22	0.93
N1—C31	1.361 (3)	C34—C35	1.377 (4)
C16—C15	1.371 (3)	C34—H34	0.93
C16—C11	1.387 (3)	C35—H35	0.93
C16—H16	0.93	C14—H14	0.93
C11—C12	1.386 (3)	C5—C3	1.502 (3)
C21—C22	1.396 (3)	C5—H5A	0.96
C25—C24	1.374 (3)	C5—H5C	0.96
C25—H25	0.93	C5—H5B	0.96
C4—C1	1.510 (3)	C3—C2	1.393 (3)
C4—H4A	0.96	C24—H24	0.93
C4—H4B	0.96	C1—C2	1.389 (3)
C4—H4C	0.96	C2—H2	0.93
C13—C14	1.379 (3)

C6—Rh1—O2	177.68 (7)	C31—C32—H32	120.4
C6—Rh1—O1	93.62 (8)	C33—C32—H32	120.4
O2—Rh1—O1	88.42 (6)	C11—C12—C13	119.7 (2)
C6—Rh1—P2	85.26 (6)	C11—C12—H12	120.1
O2—Rh1—P2	92.71 (5)	C13—C12—H12	120.1
O1—Rh1—P2	178.43 (4)	C34—C33—C32	119.2 (2)
C21—P2—C11	104.54 (9)	C34—C33—H33	120.4
C21—P2—C31	103.56 (9)	C32—C33—H33	120.4
C11—P2—C31	103.93 (9)	C16—C15—C14	120.5 (2)
C21—P2—Rh1	116.79 (6)	C16—C15—H15	119.7
C11—P2—Rh1	112.61 (7)	C14—C15—H15	119.7
C31—P2—Rh1	114.05 (6)	C23—C22—C21	119.8 (2)
C1—O1—Rh1	126.64 (14)	C23—C22—H22	120.1
C3—O2—Rh1	127.61 (14)	C21—C22—H22	120.1
O3—C6—Rh1	178.4 (2)	N1—C31—C32	122.19 (19)
C25—C26—C21	119.9 (2)	N1—C31—P2	114.48 (15)
C25—C26—H26	120	C32—C31—P2	123.32 (16)
C21—C26—H26	120	C33—C34—C35	119.0 (2)
C35—N1—C31	117.2 (2)	C33—C34—H34	120.5
C15—C16—C11	120.1 (2)	C35—C34—H34	120.5
C15—C16—H16	119.9	N1—C35—C34	123.2 (2)
C11—C16—H16	119.9	N1—C35—H35	118.4
C12—C11—C16	119.75 (19)	C34—C35—H35	118.4
C12—C11—P2	123.20 (16)	C13—C14—C15	119.6 (2)
C16—C11—P2	116.91 (15)	C13—C14—H14	120.2
C26—C21—C22	119.56 (19)	C15—C14—H14	120.2
C26—C21—P2	121.18 (15)	C3—C5—H5A	109.5
C22—C21—P2	119.26 (15)	C3—C5—H5C	109.5
C24—C25—C26	120.7 (2)	H5A—C5—H5C	109.5
C24—C25—H25	119.7	C3—C5—H5B	109.5
C26—C25—H25	119.7	H5A—C5—H5B	109.5
C1—C4—H4A	109.5	H5C—C5—H5B	109.5
C1—C4—H4B	109.5	O2—C3—C2	125.6 (2)
H4A—C4—H4B	109.5	O2—C3—C5	114.9 (2)
C1—C4—H4C	109.5	C2—C3—C5	119.4 (2)
H4A—C4—H4C	109.5	C25—C24—C23	119.7 (2)
H4B—C4—H4C	109.5	C25—C24—H24	120.1
C14—C13—C12	120.2 (2)	C23—C24—H24	120.1
C14—C13—H13	119.9	O1—C1—C2	125.7 (2)
C12—C13—H13	119.9	O1—C1—C4	114.7 (2)
C22—C23—C24	120.3 (2)	C2—C1—C4	119.6 (2)
C22—C23—H23	119.9	C1—C2—C3	125.94 (19)
C24—C23—H23	119.9	C1—C2—H2	117
C31—C32—C33	119.3 (2)	C3—C2—H2	117

Experimental details

Crystal data
Chemical formula	[Rh(C₅H₇O₂)(C₁₇H₁₄NP)(CO)]
M_r	493.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	8.822 (5), 17.782 (5), 13.798 (5)
β (°)	103.027 (5)
V (Å³)	2108.8 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.19 × 0.18 × 0.06

Data collection
Diffractometer	Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.846, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	24055, 5248, 4522
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.065, 1.05
No. of reflections	5248
No. of parameters	266
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.39

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

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