Di-μ-iodido-bis-[acet-yl(4-methyl-2,6,7-trioxa-1-phosphabicyclo-[2.2.2]octa-ne)(N-nitroso-N-oxidoaniline-κO,O')rhodium(III)].

The title compound, [Rh(2)(C(6)H(5)N(2)O(2))(2)(C(2)H(3)O)(2)I(2)(C(5)H(9)O(3)P)(2)], contains a binuclear centrosymmetric Rh(III) dimer bridged by iodide anions, with respective Rh⋯Rh and I⋯I distances of 4.1437 (5) and 3.9144 (5) Å. The Rh(III) atom is in a distorted octa-hedral RhCI(2)O(2)P coordination with considerably different Rh-I distances to the bridging iodide anions. There are no classical hydrogen-bonding inter-actions observed for this complex.

Related literature

For the synthesis of similar Rh complexes and information on oxidative addition products, see: Basson et al. (1984 ▶; 1986a ▶,b ▶; 1987 ▶, 1992 ▶); Roodt & Steyn (2000 ▶); Smit et al. (1994 ▶); Steyn et al. (1992 ▶); Van Leewen & Roobeeck (1981 ▶).

Experimental

Crystal data

[Rh2(C6H5N2O2)2(C2H3O)2I2(C5H9O3P)2]

M = 1116.14

Monoclinic,

a = 10.055 (2) Å

b = 16.944 (3) Å

c = 11.149 (2) Å

β = 112.75 (3)°

V = 1751.7 (7) Å3

Z = 2

Mo Kα radiation

μ = 2.86 mm−1

T = 293 K

0.10 × 0.08 × 0.06 mm

Data collection

Bruker SMART CCD 1K diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.763, T max = 0.847

12035 measured reflections

4344 independent reflections

3129 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.075

S = 0.95

4344 reflections

220 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.93 e Å−3

Δρmin = −0.50 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809043050/wm2267sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043050/wm2267Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Rh2(C6H5N2O2)2(C2H3O)2I2(C5H9O3P)2]	F(000) = 1080
Mr = 1116.14	Dx = 2.116 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 859 reflections
a = 10.055 (2) Å	θ = 2.3–28.1°
b = 16.944 (3) Å	µ = 2.86 mm−1
c = 11.149 (2) Å	T = 293 K
β = 112.75 (3)°	Cuboid, brown-red
V = 1751.7 (7) Å3	0.10 × 0.08 × 0.06 mm
Z = 2

Bruker SMART CCD 1K diffractometer	4344 independent reflections
Radiation source: fine-focus sealed tube	3129 reflections with I > 2σ(I)
graphite	Rint = 0.051
ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→11
Tmin = 0.763, Tmax = 0.847	k = −22→14
12035 measured reflections	l = −12→14

Refinement on F2	1 restraint
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033	w = 1/[σ2(Fo2) + (0.0354P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.075	(Δ/σ)max < 0.001
S = 0.95	Δρmax = 0.93 e Å−3
4344 reflections	Δρmin = −0.49 e Å−3
220 parameters

Experimental. The intensity data were collected on a Bruker SMART CCD 1 K diffractometer using an exposure time of 20 s/frame. A total of 1315 frames were collected with a frame width of 0.3° covering up to θ = 28.29° with 99.8% completeness accomplished. The first 50 frames were recollected at the end of the data collection to check for decay; none was found.

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.

	x	y	z	Uiso*/Ueq
C6	0.3530 (9)	0.3279 (4)	0.4556 (7)	0.0389 (18)
C5	0.3479 (11)	0.2939 (5)	0.5784 (8)	0.053 (2)
H1A	0.4329	0.3102	0.6522	0.064*
H1B	0.2637	0.314	0.5908	0.064*
C4	0.4801 (10)	0.2932 (5)	0.4347 (9)	0.050 (2)
H2A	0.4849	0.3154	0.3563	0.06*
H2B	0.568	0.3073	0.5072	0.06*
C7	0.3688 (11)	0.4178 (5)	0.4674 (9)	0.060 (3)
H5A	0.4549	0.431	0.5408	0.091*
H5B	0.2867	0.4399	0.479	0.091*
H5C	0.3747	0.4389	0.3897	0.091*
O1	0.1009 (7)	0.0872 (4)	0.5202 (7)	0.0698 (19)
C1	0.1039 (9)	0.0605 (5)	0.4219 (9)	0.045 (2)
C2	−0.0248 (11)	0.0383 (7)	0.3093 (10)	0.074 (3)
H9A	−0.0107	−0.0129	0.279	0.111*
H9B	−0.0418	0.0763	0.2412	0.111*
H9C	−0.1064	0.0366	0.3338	0.111*
I	0.43362 (5)	−0.00049 (3)	0.64352 (4)	0.03779 (16)
Rh	0.29476 (7)	0.04485 (4)	0.40073 (6)	0.03779 (16)
P	0.3320 (2)	0.17126 (11)	0.43763 (19)	0.0342 (4)
O2	0.2452 (6)	−0.0699 (3)	0.3412 (5)	0.0382 (12)
N1	0.1775 (7)	−0.0076 (4)	0.1406 (6)	0.0433 (16)
O3	0.2017 (6)	0.0583 (3)	0.2034 (5)	0.0413 (13)
N2	0.1995 (7)	−0.0702 (3)	0.2114 (6)	0.0366 (14)
C11	0.1793 (8)	−0.1465 (4)	0.1476 (7)	0.0355 (17)
O6	0.4702 (6)	0.2079 (3)	0.4228 (6)	0.0495 (14)
O4	0.2045 (6)	0.2201 (3)	0.3337 (5)	0.0511 (15)
O5	0.3416 (7)	0.2073 (3)	0.5719 (5)	0.0535 (16)
C15	0.2426 (11)	−0.2819 (5)	0.1644 (10)	0.061 (3)
H010	0.292	−0.3249	0.2131	0.073*
C16	0.2521 (10)	−0.2091 (5)	0.2224 (8)	0.050 (2)
H011	0.3069	−0.2026	0.3107	0.061*
C13	0.0867 (11)	−0.2264 (6)	−0.0368 (10)	0.068 (3)
H012	0.0298	−0.2321	−0.1248	0.082*
C12	0.0962 (10)	−0.1545 (5)	0.0197 (8)	0.058 (2)
H013	0.0463	−0.1114	−0.0288	0.07*
C14	0.1587 (11)	−0.2907 (6)	0.0322 (10)	0.065 (3)
H014	0.1518	−0.3393	−0.0083	0.078*
C3	0.2178 (10)	0.3068 (4)	0.3415 (9)	0.051 (2)
H01A	0.1346	0.3297	0.3522	0.061*
H01B	0.2222	0.3275	0.262	0.061*

	U11	U22	U33	U12	U13	U23
C6	0.059 (5)	0.025 (4)	0.037 (4)	0.005 (4)	0.022 (4)	0.005 (3)
C5	0.086 (7)	0.039 (5)	0.042 (5)	0.001 (4)	0.033 (5)	−0.008 (4)
C4	0.064 (6)	0.030 (4)	0.064 (6)	−0.013 (4)	0.034 (5)	−0.010 (4)
C7	0.097 (8)	0.035 (5)	0.056 (6)	0.003 (5)	0.036 (5)	0.007 (4)
O1	0.070 (5)	0.070 (5)	0.085 (5)	0.003 (4)	0.047 (4)	−0.006 (4)
C1	0.050 (5)	0.040 (5)	0.053 (5)	0.010 (4)	0.027 (4)	0.004 (4)
C2	0.060 (7)	0.091 (8)	0.076 (7)	0.000 (6)	0.032 (6)	0.008 (6)
I	0.0466 (3)	0.0360 (2)	0.0325 (2)	0.00276 (18)	0.01725 (17)	0.00362 (16)
Rh	0.0466 (3)	0.0360 (2)	0.0325 (2)	0.00276 (18)	0.01725 (17)	0.00362 (16)
P	0.0421 (11)	0.0291 (10)	0.0324 (10)	0.0012 (8)	0.0155 (8)	0.0015 (8)
O2	0.058 (3)	0.024 (2)	0.035 (3)	−0.008 (2)	0.021 (3)	−0.002 (2)
N1	0.043 (4)	0.051 (4)	0.029 (3)	0.001 (3)	0.007 (3)	0.005 (3)
O3	0.054 (3)	0.024 (3)	0.044 (3)	0.001 (2)	0.017 (3)	0.007 (2)
N2	0.046 (4)	0.028 (3)	0.035 (3)	−0.003 (3)	0.015 (3)	0.001 (3)
C11	0.040 (4)	0.030 (4)	0.038 (4)	−0.004 (3)	0.017 (3)	−0.006 (3)
O6	0.051 (3)	0.032 (3)	0.076 (4)	−0.004 (3)	0.036 (3)	−0.007 (3)
O4	0.056 (4)	0.030 (3)	0.052 (3)	0.009 (3)	0.004 (3)	0.002 (3)
O5	0.100 (5)	0.032 (3)	0.038 (3)	−0.001 (3)	0.038 (3)	0.000 (2)
C15	0.078 (7)	0.039 (5)	0.064 (6)	0.004 (5)	0.025 (5)	−0.002 (4)
C16	0.067 (6)	0.038 (4)	0.041 (5)	0.002 (4)	0.016 (4)	−0.006 (4)
C13	0.071 (7)	0.066 (7)	0.053 (6)	−0.016 (5)	0.008 (5)	−0.022 (5)
C12	0.062 (6)	0.055 (6)	0.041 (5)	0.002 (5)	0.001 (4)	−0.005 (4)
C14	0.067 (7)	0.053 (6)	0.079 (7)	−0.021 (5)	0.033 (6)	−0.030 (5)
C3	0.072 (6)	0.026 (4)	0.054 (5)	0.010 (4)	0.022 (5)	0.003 (4)

C6—C5	1.504 (10)	Rh—P	2.186 (2)
C6—C4	1.504 (11)	Rh—Ii	3.0511 (9)
C6—C3	1.502 (12)	P—O6	1.588 (6)
C6—C7	1.533 (10)	P—O5	1.585 (5)
C5—O5	1.468 (9)	P—O4	1.589 (5)
C5—H1A	0.97	O2—N2	1.339 (7)
C5—H1B	0.97	N1—O3	1.290 (8)
C4—O6	1.451 (8)	N1—N2	1.289 (8)
C4—H2A	0.97	N2—C11	1.451 (9)
C4—H2B	0.97	C11—C12	1.352 (10)
C7—H5A	0.96	C11—C16	1.374 (11)
C7—H5B	0.96	O4—C3	1.474 (9)
C7—H5C	0.96	C15—C16	1.379 (11)
O1—C1	1.196 (10)	C15—C14	1.394 (13)
C1—C2	1.461 (13)	C15—H010	0.93
C1—Rh	2.040 (8)	C16—H011	0.93
C2—H9A	0.96	C13—C14	1.368 (14)
C2—H9B	0.96	C13—C12	1.358 (12)
C2—H9C	0.96	C13—H012	0.93
I—Rh	2.6351 (8)	C12—H013	0.93
I—Rhi	3.0511 (9)	C14—H014	0.93
Rh—O3	2.044 (5)	C3—H01A	0.97
Rh—O2	2.052 (5)	C3—H01B	0.97
C5—C6—C4	108.7 (7)	C1—Rh—Ii	172.7 (2)
C5—C6—C3	110.0 (7)	O3—Rh—Ii	85.36 (16)
C4—C6—C3	108.7 (7)	O2—Rh—Ii	80.51 (15)
C5—C6—C7	110.0 (6)	P—Rh—Ii	99.96 (6)
C4—C6—C7	109.6 (7)	I—Rh—Ii	86.70 (2)
C3—C6—C7	109.8 (6)	O6—P—O5	102.2 (3)
O5—C5—C6	110.7 (6)	O6—P—O4	102.2 (3)
O5—C5—H1A	109.5	O5—P—O4	103.0 (3)
C6—C5—H1A	109.5	O6—P—Rh	117.2 (2)
O5—C5—H1B	109.5	O5—P—Rh	120.0 (2)
C6—C5—H1B	109.5	O4—P—Rh	110.0 (2)
H1A—C5—H1B	108.1	N2—O2—Rh	107.0 (4)
O6—C4—C6	111.8 (6)	O3—N1—N2	115.4 (6)
O6—C4—H2A	109.3	N1—O3—Rh	113.5 (4)
C6—C4—H2A	109.3	N1—N2—O2	124.3 (6)
O6—C4—H2B	109.3	N1—N2—C11	118.3 (6)
C6—C4—H2B	109.3	O2—N2—C11	117.3 (6)
H2A—C4—H2B	107.9	C12—C11—C16	122.0 (7)
C6—C7—H5A	109.5	C12—C11—N2	121.2 (7)
C6—C7—H5B	109.5	C16—C11—N2	116.7 (7)
H5A—C7—H5B	109.5	C4—O6—P	114.3 (5)
C6—C7—H5C	109.5	C3—O4—P	116.6 (5)
H5A—C7—H5C	109.5	C5—O5—P	114.7 (4)
H5B—C7—H5C	109.5	C16—C15—C14	119.7 (9)
O1—C1—C2	123.8 (9)	C16—C15—H010	120.2
O1—C1—Rh	120.9 (7)	C14—C15—H010	120.2
C2—C1—Rh	115.3 (7)	C11—C16—C15	118.8 (8)
C1—C2—H9A	109.5	C11—C16—H011	120.6
C1—C2—H9B	109.5	C15—C16—H011	120.6
H9A—C2—H9B	109.5	C14—C13—C12	121.8 (9)
C1—C2—H9C	109.5	C14—C13—H012	119.1
H9A—C2—H9C	109.5	C12—C13—H012	119.1
H9B—C2—H9C	109.5	C11—C12—C13	118.9 (9)
Rh—I—Rhi	93.30 (2)	C11—C12—H013	120.6
C1—Rh—O3	92.9 (3)	C13—C12—H013	120.6
C1—Rh—O2	92.2 (3)	C13—C14—C15	118.8 (8)
O3—Rh—O2	78.74 (19)	C13—C14—H014	120.6
C1—Rh—P	87.2 (2)	C15—C14—H014	120.6
O3—Rh—P	93.85 (14)	O4—C3—C6	108.6 (6)
O2—Rh—P	172.54 (15)	O4—C3—H01A	110
C1—Rh—I	93.9 (2)	C6—C3—H01A	110
O3—Rh—I	168.12 (14)	O4—C3—H01B	110
O2—Rh—I	91.25 (14)	C6—C3—H01B	110
P—Rh—I	96.21 (6)	H01A—C3—H01B	108.4

C1—Rh	2.040 (8)
I—Rh	2.6351 (8)
Rh—O3	2.044 (5)
Rh—O2	2.052 (5)
Rh—P	2.186 (2)
Rh—Ii	3.0511 (9)

Rh—I—Rhi	93.30 (2)
C1—Rh—O3	92.9 (3)
C1—Rh—O2	92.2 (3)
O3—Rh—O2	78.74 (19)
O2—Rh—P	172.54 (15)
C1—Rh—I	93.9 (2)
O3—Rh—I	168.12 (14)
C1—Rh—Ii	172.7 (2)

Symmetry code: (i) .