metal-organic compounds
cis-Tetrakis(μ-N-phenylacetamidato)-κ4N:O;κ4O:N-bis[(benzonitrile-κN)rhodium(II)](Rh—Rh)
aDepartment of Chemistry, East Tennessee State University, PO Box 70695, Johnson City, TN 37614, USA
*Correspondence e-mail: eaglec@etsu.edu
The complex molecule of the title compound, [Rh2{N(C6H5)COCH3}4(C6H5CN)2], exhibits crystallographically imposed centrosymmetry. The four acetamide ligands bridging the dirhodium core are arranged in a 2,2-cis manner, with two N atoms and two O atoms coordinating to the unique RhII atom cis to one another. The Neq—Rh—Rh—Oeq torsion angles on the acetamide bridges vary between 1.62 (4) and 1.78 (4)°. The Rh—Rh bond length is 2.4319 (3) Å. The axial nitrile ligand completes the distorted octahedral coordination sphere and shows a non-linear coordination with an Rh—N—C bond angle of 167.14 (15)°, while the N—C bond length is 1.135 (3) Å.
Experimental
Crystal data
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Data collection: CrystalClear-SM Auto (Rigaku, 2011); cell CrystalClear-SM Auto; data reduction: CrystalClear-SM Auto; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).
Supporting information
10.1107/S1600536813012828/mw2103sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813012828/mw2103Isup2.hkl
Approximately 10 mg of 2,2-cis-[Rh2(N(C6H5)COCH3)4] was dissolved in 18 mL of dichloromethane. 10 µL of benzonitrile was then added to this solution, via a gas tight syringe, turning the solution from a green to a light blue color. Crystals grew over a one week period via vapor diffusion with acetone. From the κ4N:O;κ4O:N rhodium(II)] with benzonitrile in each axial site.
compound 1 is an adduct of cis-tetrakis[µ-N-(phenyl)acetamidato]-H-atoms were included in calculated positions with C—H = 0.94 - 0.97 Å and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atom.
Atoms C22 and C23 exhibit slightly extended displacement perpendicular to the plane of the ring containing them. This is likely due to a combination of some rotational disorder about the N3-Rh1 bond and also due to normal stacking errors, as evidenced in similar displacement amplitudes in the adjacent ring (C5 to C10).
There are three strong reflections missing. They may have been low-angle reflections behind the beamstop shadow or the relections may have overloaded in the detector (even in the overload-correction mode).
Data collection: CrystalClear-SM Auto (Rigaku, 2011); cell
CrystalClear-SM Auto (Rigaku, 2011); data reduction: CrystalClear-SM Auto (Rigaku, 2011); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).Fig. 1. ORTEP of the title compound showing 30% probability ellipsoids. Hydrogen atoms are drawn as small spheres. | |
Fig. 2. Packing diagram for the title compound as seen along the b axis. |
[Rh2(C8H8NO)4(C7H5N)2] | F(000) = 964.00 |
Mr = 948.69 | Dx = 1.476 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2yn | Cell parameters from 20104 reflections |
a = 10.2115 (7) Å | θ = 3.2–27.5° |
b = 9.9667 (7) Å | µ = 0.82 mm−1 |
c = 21.3672 (16) Å | T = 223 K |
β = 100.971 (7)° | Prism, red |
V = 2134.9 (3) Å3 | 0.49 × 0.35 × 0.16 mm |
Z = 2 |
Rigaku XtaLAB mini diffractometer | 4413 reflections with F2 > 2σ(F2) |
Detector resolution: 6.827 pixels mm-1 | Rint = 0.023 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | h = −13→13 |
Tmin = 0.689, Tmax = 0.880 | k = −12→12 |
21686 measured reflections | l = −27→27 |
4872 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0268P)2 + 0.9991P] where P = (Fo2 + 2Fc2)/3 |
4872 reflections | (Δ/σ)max = 0.005 |
264 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Primary atom site location: structure-invariant direct methods |
[Rh2(C8H8NO)4(C7H5N)2] | V = 2134.9 (3) Å3 |
Mr = 948.69 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.2115 (7) Å | µ = 0.82 mm−1 |
b = 9.9667 (7) Å | T = 223 K |
c = 21.3672 (16) Å | 0.49 × 0.35 × 0.16 mm |
β = 100.971 (7)° |
Rigaku XtaLAB mini diffractometer | 4872 independent reflections |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | 4413 reflections with F2 > 2σ(F2) |
Tmin = 0.689, Tmax = 0.880 | Rint = 0.023 |
21686 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.39 e Å−3 |
4872 reflections | Δρmin = −0.34 e Å−3 |
264 parameters |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Rh1 | 0.987101 (12) | 0.041420 (12) | 0.552011 (5) | 0.02306 (5) | |
O1 | 1.07504 (13) | −0.13034 (12) | 0.59283 (5) | 0.0343 (3) | |
O2 | 0.80499 (13) | −0.05051 (13) | 0.53865 (6) | 0.0347 (3) | |
N1 | 0.89591 (14) | 0.20483 (14) | 0.50448 (7) | 0.0279 (3) | |
N2 | 1.17358 (13) | 0.12274 (14) | 0.55998 (6) | 0.0267 (3) | |
N3 | 0.95315 (16) | 0.11158 (17) | 0.64638 (7) | 0.0365 (4) | |
C1 | 1.12289 (18) | −0.21431 (17) | 0.55768 (8) | 0.0311 (4) | |
C3 | 0.75803 (17) | −0.10896 (17) | 0.48590 (8) | 0.0299 (4) | |
C5 | 0.83771 (17) | 0.30448 (18) | 0.53903 (8) | 0.0321 (4) | |
C11 | 1.23573 (16) | 0.18266 (18) | 0.61898 (8) | 0.0292 (4) | |
C18 | 0.89020 (19) | 0.24259 (19) | 0.74055 (8) | 0.0358 (4) | |
C17 | 0.92479 (19) | 0.16727 (19) | 0.68819 (8) | 0.0356 (4) | |
C16 | 1.2654 (2) | 0.1039 (2) | 0.67331 (9) | 0.0400 (5) | |
C2 | 1.2038 (3) | −0.3258 (2) | 0.59377 (10) | 0.0456 (5) | |
C13 | 1.3258 (3) | 0.3739 (3) | 0.68191 (11) | 0.0509 (6) | |
C4 | 0.61698 (19) | −0.1591 (3) | 0.48041 (10) | 0.0445 (5) | |
C19 | 0.7609 (3) | 0.2429 (3) | 0.75172 (11) | 0.0524 (6) | |
C14 | 1.3553 (2) | 0.2951 (3) | 0.73554 (10) | 0.0512 (6) | |
C10 | 0.9057 (3) | 0.4201 (3) | 0.55934 (13) | 0.0560 (7) | |
C6 | 0.7144 (2) | 0.2840 (3) | 0.55464 (12) | 0.0545 (6) | |
C8 | 0.7233 (3) | 0.4990 (3) | 0.60496 (15) | 0.0680 (8) | |
C12 | 1.2654 (2) | 0.31854 (19) | 0.62366 (10) | 0.0409 (5) | |
C7 | 0.6577 (3) | 0.3819 (3) | 0.58741 (15) | 0.0697 (8) | |
C20 | 0.7314 (3) | 0.3185 (3) | 0.80154 (11) | 0.0544 (6) | |
C9 | 0.8477 (3) | 0.5177 (3) | 0.59178 (17) | 0.0758 (9) | |
C21 | 0.8268 (3) | 0.3914 (3) | 0.83920 (11) | 0.0561 (6) | |
C23 | 0.9875 (3) | 0.3163 (3) | 0.77885 (11) | 0.0611 (7) | |
C15 | 1.3258 (3) | 0.1600 (3) | 0.73092 (10) | 0.0504 (6) | |
C22 | 0.9550 (3) | 0.3898 (4) | 0.82871 (13) | 0.0771 (9) | |
H9 | 1.2446 | 0.0119 | 0.6710 | 0.0480* | |
H10A | 1.2502 | −0.2924 | 0.6346 | 0.0548* | |
H10B | 1.2682 | −0.3583 | 0.5694 | 0.0548* | |
H10C | 1.1450 | −0.3986 | 0.6006 | 0.0548* | |
H11 | 1.3466 | 0.4658 | 0.6845 | 0.0611* | |
H12A | 0.5704 | −0.1511 | 0.4366 | 0.0534* | |
H12B | 0.5714 | −0.1059 | 0.5077 | 0.0534* | |
H12C | 0.6184 | −0.2524 | 0.4934 | 0.0534* | |
H13 | 0.6941 | 0.1923 | 0.7258 | 0.0629* | |
H14 | 1.3950 | 0.3329 | 0.7749 | 0.0614* | |
H15 | 0.9920 | 0.4335 | 0.5512 | 0.0672* | |
H16 | 0.6684 | 0.2034 | 0.5431 | 0.0653* | |
H17 | 0.6834 | 0.5662 | 0.6259 | 0.0816* | |
H18 | 1.2446 | 0.3735 | 0.5874 | 0.0491* | |
H19 | 0.5733 | 0.3671 | 0.5976 | 0.0836* | |
H20 | 0.6439 | 0.3191 | 0.8093 | 0.0653* | |
H21 | 0.8946 | 0.5972 | 0.6048 | 0.0910* | |
H22 | 0.8052 | 0.4431 | 0.8726 | 0.0674* | |
H23 | 1.0753 | 0.3168 | 0.7713 | 0.0733* | |
H24 | 1.3468 | 0.1053 | 0.7673 | 0.0604* | |
H25 | 1.0215 | 0.4391 | 0.8556 | 0.0926* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh1 | 0.03062 (7) | 0.02261 (7) | 0.01845 (7) | −0.00433 (5) | 0.01099 (5) | −0.00399 (5) |
O1 | 0.0538 (8) | 0.0259 (6) | 0.0250 (6) | −0.0002 (6) | 0.0122 (6) | 0.0003 (5) |
O2 | 0.0396 (7) | 0.0403 (7) | 0.0290 (6) | −0.0155 (6) | 0.0184 (6) | −0.0093 (6) |
N1 | 0.0307 (7) | 0.0264 (7) | 0.0280 (7) | −0.0011 (6) | 0.0087 (6) | −0.0042 (6) |
N2 | 0.0292 (7) | 0.0268 (7) | 0.0249 (7) | −0.0039 (6) | 0.0076 (6) | −0.0035 (6) |
N3 | 0.0406 (9) | 0.0419 (9) | 0.0298 (8) | −0.0058 (7) | 0.0140 (7) | −0.0090 (7) |
C1 | 0.0376 (9) | 0.0251 (8) | 0.0308 (9) | −0.0041 (7) | 0.0066 (7) | −0.0008 (7) |
C3 | 0.0331 (9) | 0.0286 (9) | 0.0299 (9) | −0.0061 (7) | 0.0110 (7) | −0.0026 (7) |
C5 | 0.0323 (9) | 0.0307 (9) | 0.0332 (9) | 0.0018 (7) | 0.0058 (7) | −0.0056 (7) |
C11 | 0.0264 (8) | 0.0335 (9) | 0.0275 (8) | 0.0006 (7) | 0.0048 (7) | −0.0063 (7) |
C18 | 0.0435 (10) | 0.0405 (10) | 0.0264 (9) | 0.0037 (9) | 0.0148 (8) | −0.0042 (8) |
C17 | 0.0404 (10) | 0.0399 (10) | 0.0288 (9) | −0.0032 (8) | 0.0122 (8) | −0.0030 (8) |
C16 | 0.0450 (11) | 0.0423 (11) | 0.0320 (10) | −0.0012 (9) | 0.0056 (8) | −0.0006 (8) |
C2 | 0.0604 (13) | 0.0352 (10) | 0.0380 (11) | 0.0072 (10) | 0.0009 (10) | 0.0021 (9) |
C13 | 0.0508 (12) | 0.0414 (11) | 0.0555 (13) | 0.0017 (10) | −0.0027 (10) | −0.0205 (11) |
C4 | 0.0353 (10) | 0.0559 (13) | 0.0456 (11) | −0.0143 (9) | 0.0161 (9) | −0.0126 (10) |
C19 | 0.0440 (12) | 0.0684 (15) | 0.0484 (12) | −0.0031 (11) | 0.0178 (10) | −0.0126 (11) |
C14 | 0.0416 (11) | 0.0692 (15) | 0.0384 (11) | 0.0033 (11) | −0.0034 (9) | −0.0232 (11) |
C10 | 0.0430 (12) | 0.0450 (12) | 0.0852 (18) | −0.0103 (10) | 0.0256 (12) | −0.0277 (12) |
C6 | 0.0380 (11) | 0.0518 (13) | 0.0778 (16) | −0.0093 (10) | 0.0219 (11) | −0.0282 (12) |
C8 | 0.0578 (15) | 0.0585 (15) | 0.091 (2) | 0.0060 (13) | 0.0224 (14) | −0.0397 (15) |
C12 | 0.0458 (11) | 0.0316 (10) | 0.0411 (11) | 0.0026 (8) | −0.0025 (9) | −0.0056 (8) |
C7 | 0.0437 (13) | 0.0741 (18) | 0.098 (2) | −0.0029 (13) | 0.0304 (13) | −0.0401 (17) |
C20 | 0.0491 (13) | 0.0688 (16) | 0.0534 (13) | 0.0122 (12) | 0.0301 (11) | −0.0022 (12) |
C9 | 0.0659 (17) | 0.0508 (15) | 0.116 (3) | −0.0130 (13) | 0.0304 (17) | −0.0484 (16) |
C21 | 0.0731 (16) | 0.0614 (15) | 0.0411 (12) | 0.0123 (13) | 0.0293 (11) | −0.0113 (11) |
C23 | 0.0485 (13) | 0.0875 (19) | 0.0526 (14) | −0.0088 (13) | 0.0233 (11) | −0.0350 (14) |
C15 | 0.0527 (13) | 0.0667 (15) | 0.0285 (10) | 0.0033 (11) | −0.0003 (9) | −0.0007 (10) |
C22 | 0.0711 (17) | 0.103 (3) | 0.0626 (16) | −0.0158 (17) | 0.0259 (14) | −0.0519 (17) |
Rh1—Rh1i | 2.4319 (3) | C6—C7 | 1.390 (4) |
Rh1—O1 | 2.0493 (12) | C8—C7 | 1.362 (4) |
Rh1—O2 | 2.0438 (14) | C8—C9 | 1.365 (5) |
Rh1—N1 | 2.0472 (14) | C20—C21 | 1.351 (4) |
Rh1—N2 | 2.0466 (14) | C21—C22 | 1.369 (5) |
Rh1—N3 | 2.2229 (16) | C23—C22 | 1.385 (4) |
O1—C1 | 1.282 (3) | C16—H9 | 0.940 |
O2—C3 | 1.278 (2) | C2—H10A | 0.970 |
N1—C1i | 1.309 (3) | C2—H10B | 0.970 |
N1—C5 | 1.432 (3) | C2—H10C | 0.970 |
N2—C3i | 1.315 (3) | C13—H11 | 0.940 |
N2—C11 | 1.430 (2) | C4—H12A | 0.970 |
N3—C17 | 1.135 (3) | C4—H12B | 0.970 |
C1—C2 | 1.507 (3) | C4—H12C | 0.970 |
C3—C4 | 1.508 (3) | C19—H13 | 0.940 |
C5—C10 | 1.373 (3) | C14—H14 | 0.940 |
C5—C6 | 1.378 (3) | C10—H15 | 0.940 |
C11—C16 | 1.386 (3) | C6—H16 | 0.940 |
C11—C12 | 1.387 (3) | C8—H17 | 0.940 |
C18—C17 | 1.446 (3) | C12—H18 | 0.940 |
C18—C19 | 1.386 (3) | C7—H19 | 0.940 |
C18—C23 | 1.374 (3) | C20—H20 | 0.940 |
C16—C15 | 1.385 (3) | C9—H21 | 0.940 |
C13—C14 | 1.374 (4) | C21—H22 | 0.940 |
C13—C12 | 1.393 (3) | C23—H23 | 0.940 |
C19—C20 | 1.383 (4) | C15—H24 | 0.940 |
C14—C15 | 1.380 (4) | C22—H25 | 0.940 |
C10—C9 | 1.390 (5) | ||
Rh1i—Rh1—O1 | 89.45 (4) | C19—C20—C21 | 120.9 (3) |
Rh1i—Rh1—O2 | 88.51 (4) | C10—C9—C8 | 120.6 (3) |
Rh1i—Rh1—N1 | 86.26 (5) | C20—C21—C22 | 120.0 (3) |
Rh1i—Rh1—N2 | 87.11 (4) | C18—C23—C22 | 119.3 (3) |
Rh1i—Rh1—N3 | 176.96 (5) | C16—C15—C14 | 120.8 (2) |
O1—Rh1—O2 | 89.90 (5) | C21—C22—C23 | 120.6 (3) |
O1—Rh1—N1 | 175.42 (5) | C11—C16—H9 | 119.8 |
O1—Rh1—N2 | 88.28 (6) | C15—C16—H9 | 119.8 |
O1—Rh1—N3 | 90.46 (6) | C1—C2—H10A | 109.5 |
O2—Rh1—N1 | 88.37 (6) | C1—C2—H10B | 109.5 |
O2—Rh1—N2 | 175.28 (6) | C1—C2—H10C | 109.5 |
O2—Rh1—N3 | 88.45 (6) | H10A—C2—H10B | 109.5 |
N1—Rh1—N2 | 93.12 (6) | H10A—C2—H10C | 109.5 |
N1—Rh1—N3 | 93.73 (6) | H10B—C2—H10C | 109.5 |
N2—Rh1—N3 | 95.92 (6) | C14—C13—H11 | 119.7 |
Rh1—O1—C1 | 118.76 (10) | C12—C13—H11 | 119.7 |
Rh1—O2—C3 | 120.41 (13) | C3—C4—H12A | 109.5 |
Rh1—N1—C1i | 121.73 (12) | C3—C4—H12B | 109.5 |
Rh1—N1—C5 | 119.35 (11) | C3—C4—H12C | 109.5 |
C1i—N1—C5 | 118.55 (14) | H12A—C4—H12B | 109.5 |
Rh1—N2—C3i | 120.96 (11) | H12A—C4—H12C | 109.5 |
Rh1—N2—C11 | 119.25 (11) | H12B—C4—H12C | 109.5 |
C3i—N2—C11 | 119.44 (14) | C18—C19—H13 | 120.4 |
Rh1—N3—C17 | 167.14 (15) | C20—C19—H13 | 120.4 |
O1—C1—N1i | 123.29 (16) | C13—C14—H14 | 120.4 |
O1—C1—C2 | 114.51 (16) | C15—C14—H14 | 120.4 |
N1i—C1—C2 | 122.20 (17) | C5—C10—H15 | 119.7 |
O2—C3—N2i | 122.80 (16) | C9—C10—H15 | 119.8 |
O2—C3—C4 | 114.33 (17) | C5—C6—H16 | 119.8 |
N2i—C3—C4 | 122.86 (16) | C7—C6—H16 | 119.8 |
N1—C5—C10 | 120.72 (18) | C7—C8—H17 | 120.4 |
N1—C5—C6 | 120.67 (17) | C9—C8—H17 | 120.4 |
C10—C5—C6 | 118.6 (2) | C11—C12—H18 | 119.9 |
N2—C11—C16 | 119.43 (16) | C13—C12—H18 | 119.9 |
N2—C11—C12 | 121.70 (16) | C6—C7—H19 | 119.7 |
C16—C11—C12 | 118.85 (17) | C8—C7—H19 | 119.7 |
C17—C18—C19 | 121.03 (18) | C19—C20—H20 | 119.6 |
C17—C18—C23 | 118.9 (2) | C21—C20—H20 | 119.6 |
C19—C18—C23 | 120.1 (2) | C10—C9—H21 | 119.7 |
N3—C17—C18 | 178.0 (2) | C8—C9—H21 | 119.7 |
C11—C16—C15 | 120.3 (2) | C20—C21—H22 | 120.0 |
C14—C13—C12 | 120.6 (2) | C22—C21—H22 | 120.0 |
C18—C19—C20 | 119.2 (2) | C18—C23—H23 | 120.4 |
C13—C14—C15 | 119.2 (2) | C22—C23—H23 | 120.4 |
C5—C10—C9 | 120.5 (3) | C16—C15—H24 | 119.6 |
C5—C6—C7 | 120.4 (2) | C14—C15—H24 | 119.6 |
C7—C8—C9 | 119.2 (3) | C21—C22—H25 | 119.7 |
C11—C12—C13 | 120.28 (19) | C23—C22—H25 | 119.7 |
C6—C7—C8 | 120.7 (3) | ||
O1—Rh1—Rh1i—O2i | −90.08 (4) | N1—Rh1—Rh1i—O1i | 1.62 (4) |
O1—Rh1—Rh1i—N1i | −1.62 (4) | N1—Rh1—Rh1i—O2i | 91.54 (4) |
O1—Rh1—Rh1i—N2i | 91.69 (4) | N1—Rh1—Rh1i—N2i | −86.68 (4) |
O2—Rh1—Rh1i—O1i | 90.08 (4) | N2—Rh1—Rh1i—O1i | −91.69 (4) |
O2—Rh1—Rh1i—N1i | −91.54 (4) | N2—Rh1—Rh1i—O2i | −1.78 (4) |
O2—Rh1—Rh1i—N2i | 1.78 (4) | N2—Rh1—Rh1i—N1i | 86.68 (4) |
Symmetry code: (i) −x+2, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Rh2(C8H8NO)4(C7H5N)2] |
Mr | 948.69 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 223 |
a, b, c (Å) | 10.2115 (7), 9.9667 (7), 21.3672 (16) |
β (°) | 100.971 (7) |
V (Å3) | 2134.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.82 |
Crystal size (mm) | 0.49 × 0.35 × 0.16 |
Data collection | |
Diffractometer | Rigaku XtaLAB mini diffractometer |
Absorption correction | Multi-scan (REQAB; Rigaku, 1998) |
Tmin, Tmax | 0.689, 0.880 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 21686, 4872, 4413 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.054, 1.03 |
No. of reflections | 4872 |
No. of parameters | 264 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.34 |
Computer programs: CrystalClear-SM Auto (Rigaku, 2011), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2010).
Acknowledgements
We thank Dr Lee Daniels of Rigaku Americas for his training on the Rigaku XtaLAB diffractometer and his extended help in the completion of the
Support was provided by a Start Up Grant from ETSU. We thank Johnson Matthey for their generous loan of rhodium trichloride.References
Bear, J. L. & Kadish, K. M. (1987). Inorg. Chem. 26, 830–836. CrossRef Web of Science Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Eagle, C. T., Farrar, D. G., Holder, G. N., Pennington, W. T. & Bailey, R. D. (2000). J. Organomet. Chem. 596, 90–94. Web of Science CrossRef CAS Google Scholar
Eagle, C. T., Kpogo, K. K., Zink, L. C. & Smith, A. E. (2012). Acta Cryst. E68, m877. CSD CrossRef IUCr Journals Google Scholar
Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2011). CrystalClear-SM Auto. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Previous papers report the structures of the related complexes 2,2-cis-Rh2[N(C6H5)COCH3]4.2DMSO (Bear et al. 1987), 2,2-trans-Rh2[N(C6H5)COCH3]4.2NCC6H5 (2) (Eagle et al., 2000) and 2,2-trans-Rh2[N(C9H11)COCH3]4.2NCC6H5 (3) (Eagle et al., 2012). The numbering scheme of the title compound was adapted from that of compound 2.
The axial rhodium-nitrogen-carbon bond angle for 1, 167.14 (15)°, (Fig. 1) is distinctly non-linear which is different from those found in 2 (178.5 (5)° and 169.3 (5)°) and 3 (180°; imposed by space group symmetry). The axial carbon-nitrogen bond length in 1 is 1.135 (3) Å which is comparable to the corresponding distances found in 2 (1.135 (8) and 1.145 (8) Å) and slightly longer than that in 3 (1.106 (6) Å). Compound 1 has pseudo four-fold symmetry with torsion angles on each acetamide bridge varying between 1.62 (4)° and 1.78 (4)°. These can be compared to the range of 9.03° and 11.89° in 2 and 1.12 (9)° in 3. A packing diagram of the structure is shown in Fig. 2 and indicates that van der Waals forces hold the molecules of 1 together.
The infrared absorption spectrum of 1 showed bands at 2359 and 2320 cm-1 attributable to carbon-nitrogen bond stretching modes. The corresponding band for uncomplexed benzonitrile appears at 2228 cm-1. This indicates that there is a shortening of the carbon-nitrogen bond and a stronger σ-interaction to the rhodium metal compared to the π-back-bonding which occurs upon complexation with cis-tetrakis[µ-N-(phenyl)acetamidato]-κ4N:O;κ4O:N rhodium(II)].