Crystal structure of carbonyl(2-oxopyridin-1(2H)-olato-k2O,O′)(triphenylarsine-κAs)rhodium(I), C24H19AsNO3Rh

Mohammed A. Elmakki; Orbett T. Alexander; Johan A. Venter; Andreas Roodt

doi:10.1515/ncrs-2020-0490

Open Access Published by De Gruyter (O) December 10, 2020

Crystal structure of carbonyl(2-oxopyridin-1(2H)-olato-k²O,O′)(triphenylarsine-κAs)rhodium(I), C₂₄H₁₉AsNO₃Rh

Mohammed A. Elmakki , Orbett T. Alexander , Johan A. Venter and Andreas Roodt

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2020-0490

Abstract

C₂₄H₁₉AsNO₃Rh, triclinic, P1‾ (no. 2), a = 9.1358(5) Å, b = 9.6478(6) Å, c = 12.4509(7) Å, α = 92.303(2)°, β = 106.281(2)°, γ = 99.137(2)°, V = 1035.89(1) Å³, Z = 2, R_gt(F) = 0.0336, wR_ref(F²) = 0.0900, T = 100 K.

CCDC no.: 2039781

The molecular structure is shown in the Figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:	Yellow plate
Size	0.25 × 0.18 × 0.05 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	2.44 mm⁻¹
Diffractometer, scan mode:	Bruker APEX-II, φ and ω
θ_max, completeness:	28.3°, 99 %
N(hkl)_measured, N(hkl)_unique, R_int:	13050, 5046, 0.052
Criterion for I_obs, N(hkl)_gt:	I_obs > 2 σ(I_obs), 4283
N(param)_refined:	271
Programs:	SHELX [1], Bruker [2], Diamond [3], OLEX2 [4]

Table 2:

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

Atom	x	y	z	U_iso*/U_eq
As1	0.34390 (3)	0.29682 (3)	0.68910 (2)	0.01458 (9)
C1	−0.0073 (3)	0.2082 (3)	0.9250 (2)	0.0159 (6)
C2	−0.0990 (4)	0.1868 (4)	0.9968 (3)	0.0216 (7)
H2	−0.096246	0.106811	1.038937	0.026*
C3	−0.1927 (4)	0.2794 (4)	1.0074 (3)	0.0228 (7)
H3	−0.254851	0.264685	1.057015	0.027*
C4	−0.1972 (4)	0.3968 (4)	0.9444 (3)	0.0215 (6)
H4	−0.264618	0.460778	0.949425	0.026*
C5	−0.1043 (4)	0.4182 (3)	0.8763 (3)	0.0197 (6)
H5	−0.106210	0.497969	0.833899	0.024*
C6	0.3112 (4)	0.0396 (4)	0.8152 (3)	0.0245 (7)
C7	0.4641 (3)	0.4813 (3)	0.7527 (2)	0.0158 (6)
C8	0.5769 (4)	0.5467 (3)	0.7066 (3)	0.0195 (6)
H8	0.591718	0.503615	0.641396	0.023*
C9	0.6679 (4)	0.6757 (4)	0.7567 (3)	0.0221 (7)
H9	0.743827	0.721223	0.724948	0.027*
C10	0.6476 (4)	0.7374 (3)	0.8527 (3)	0.0225 (7)
H10	0.710298	0.824772	0.887129	0.027*
C11	0.5357 (4)	0.6713 (4)	0.8985 (3)	0.0234 (7)
H11	0.522575	0.713399	0.964706	0.028*
C12	0.4426 (4)	0.5441 (3)	0.8482 (3)	0.0187 (6)
H12	0.364669	0.500332	0.878926	0.022*
C13	0.4939 (3)	0.2123 (3)	0.6375 (3)	0.0168 (6)
C14	0.6020 (4)	0.1499 (3)	0.7128 (3)	0.0224 (7)
H14	0.598476	0.144413	0.788066	0.027*
C15	0.7154 (4)	0.0955 (4)	0.6785 (3)	0.0287 (8)
H15	0.788727	0.052146	0.729902	0.034*
C16	0.7208 (4)	0.1049 (4)	0.5689 (3)	0.0311 (8)
H16	0.799203	0.069223	0.545710	0.037*
C17	0.6133 (4)	0.1656 (4)	0.4931 (3)	0.0274 (8)
H17	0.617064	0.170712	0.417814	0.033*
C18	0.4992 (4)	0.2195 (3)	0.5275 (3)	0.0201 (6)
H18	0.424950	0.261156	0.475562	0.024*
C19	0.2027 (3)	0.3333 (3)	0.5494 (2)	0.0161 (6)
C20	0.0878 (4)	0.2215 (4)	0.4912 (3)	0.0223 (7)
H20	0.081445	0.132005	0.520383	0.027*
C21	−0.0172 (4)	0.2407 (4)	0.3907 (3)	0.0269 (7)
H21	−0.094072	0.163763	0.350405	0.032*
C22	−0.0102 (4)	0.3715 (4)	0.3490 (3)	0.0242 (7)
H22	−0.083031	0.384688	0.280597	0.029*
C23	0.1031 (4)	0.4835 (4)	0.4071 (3)	0.0218 (6)
H23	0.107648	0.573354	0.378367	0.026*
C24	0.2102 (4)	0.4645 (3)	0.5073 (3)	0.0187 (6)
H24	0.288163	0.541137	0.546844	0.022*
N1	−0.0074 (3)	0.3254 (3)	0.8681 (2)	0.0211 (6)
O1	0.0812 (3)	0.1168 (2)	0.91090 (19)	0.0209 (5)
O2	0.0869 (3)	0.3463 (2)	0.80385 (18)	0.0194 (5)
O3	0.3684 (4)	−0.0581 (3)	0.8221 (3)	0.0394 (7)
Rh1	0.21129 (3)	0.18715 (2)	0.80716 (2)	0.01565 (8)

Source of material

[Rh(hopo)(CO)₂] (hopo=2-oxopyridineN-oxide) was synthesized according to the method described previously [5]. [Rh(opo)(CO)(AsPh₃)] was synthesized by dissolving [Rh(hopo)(CO)₂] (0.0210 g, 0.0780 mmol) in 5 cm³ of acetone. Triphenylarsine (0.0239 g, 0.0780 mmol) was added to the aforementioned solution with stirring. Some ice water was added dropwise to precipitate the product. Yellow plate crystals were obtained from recrystallization in acetone and a few drops of water.

IR: ν_CO 1954 cm⁻¹. ¹H NMR (400 MHz, CD₂Cl₂) δ 8.11 (d, J = 6.2 Hz, 1H), 7.77 (s, 1H), 7.67 (d, J = 6.7 Hz, 15H), 7.56 (d, J = 7.5 Hz, 1H), 7.52 – 7.43 (m, 15H), 7.18 (t, J = 7.5 Hz, 1H), 7.00 (d, J = 8.9 Hz, 1H), 6.76 (d, J = 8.7 Hz, 1H), 6.60 (s, 1H), 6.49 (t, J = 6.3 Hz, 1H).

Experimental details

All H-atoms were positioned on geometrically idealized positions and refined using the riding model with fixed C–H distances for aromatic C–H of 0.93 Å (C–H) [U_iso (H)=1.2 U_eq]. The graphics were obtained using the DIAMOND [3] program with 50% probability ellipsoids.

Comment

The carbonylation of methanol using a rhodium complex as catalyst is an industrial relevant reaction to produce acetic acid. One of the carbonyl ligands in the precursor [Rh(BID)(CO)₂] complexes (BID = different monocharged bidentate ligands such as cupferrate and 2-oxopyridine N-oxide, etc.) is substituted by tertiary phosphine ligands (PX₃) to form [Rh(BID)(CO)(PX₃)] complexes. These complexes have been studied intensively for a potential application in catalytic hydroformylation, hydrogenation, carbonylation, and decarbonylation [6], [7], [8], [9], [10], [11], [12], [13].

The coordination mode in the title complex is similar to the complexes reported previously [14], [15]. In this structure, the ligands are coordinated to rhodium in a distorted square planar geometry. This distortion of the O1-Rh-O2 bond angle from 90° is indicated by the small bite angle of 79.87(2)° of the five membered ring as well as the As1-Rh1-C6, As1-Rh1-O2 and C6-Rh1-O1, angles of 92.37(2), 91.89(2) and 95.89(3)°, respectively. The Rh1-O1, Rh1-O2, Rh1-As1 and Rh1-C6 bond distances are 2.0532(1), 2.0442(1), 2.3377(1) and 1.8010(1) Å, respectively. The lengthening of Rh-O1 compared to Rh-O2 is due to the strong trans influence of the As atom. Phenyl hydrogen atoms in the figure are omitted for clarity (see the figure).

Corresponding author: Mohammed A. Elmakki, Department of ChemistryUniversity of the Free State, Bloemfontein, 9301, South Africa, E-mail: azeez77777@gmail.com

Funding source: University of the Free State

Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: The authors would like to thank the University of the Free State for financial support.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2020-09-23

Accepted: 2020-10-21

Published Online: 2020-12-10

Published in Print: 2021-01-26

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