Crystal structure of fac

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Z. Kristallogr. NCS 230 (2015) 150-152 / DOI 10.1515/ncrs-2014-9013 © 2015 Walter de Gruyter GmbH, Berlin/Munich/Boston

Crystal structure of fac-(acetylacetonato-"2O,O')tricarbonyl(cyclohexyldiphenylphosphine-"P) rhenium(I), C26H28O5PRe Amanda-Lee Manicum*, Hendrik G. Visser, Ilana Engelbrecht and Andreas Roodt Department of Chemistry, University of the Free State, P.O. Box 339, Bloemfontein 9300, South Africa Received August 06, 2014, accepted March 13, 2015, available online March 19, 2015, CCDC no. 1267/4279

title complex, suitable for single X-ray diffractometry were collected. Yield = 33 mg, 51%. IR (KBr, cm–1): !CO(2014, 1907, 1879). Experimental details The H atoms were positioned geometrically and refined discemible using a riding model, with C–Hmethine = 0.98 Å; C–Hmethyl =0.96 Å; C–Haromatic = 0.93 Å. The H atom isotropic displacement parameters were fixed; Uiso(H) = 1.2Ueq(C) for aromatic and methine and Uiso(H) = 1.5Ueq(C) for methyl protons, allowing them to ride on the parent atom. The PPh2Cy ligand displays a structural disorder between one of the phenyl rings and the cyclohexyl ring, occupying two positions (A/B) with occupancies of 0.567(14)/0.433(14). In one case, the phenyl ring displays the dominant occupancy, in the other case, the cyclohexyl ring.

Abstract C26H28O5PRe, monoclinic, P21/n (no. 14), a = 11.752(5) Å, b = 12.417(4) Å, c = 17.185(5) Å, ' = 91.921(4)°, V = 2506.3 Å3, Z = 4, Rgt(F) = 0.0238, wRref(F2) = 0.054, T = 101 K. Table 1. Data collection and handling. Crystal: Wavelength: -: Diffractometer, scan mode: 2+max: N(hkl)measured, N(hkl)unique: Criterion for Iobs, N(hkl)gt: N(param)refined: Programs:

colourless cuboids, size 0.15$0.22$0.45 mm Mo K, radiation (0.71069 Å) 49.46 cm)1 Bruker APEX-II CCD, ! and " 56.22° 72764, 6093 Iobs > 2 &(Iobs), 5048 380 SADABS, SHELX, SIR97, DIAMOND, WinGX [9–13]

Source of material The starting complex fac-[Re(CO)3(H2O)(acac)] was prepared ac c o r d in g to a p ubl i she d proc e dure [6 ] . fac[Re(CO)3(H2O)(acac)] (39 mg; 0.1 mmol) was dissolved in MeOH (3ml) and cyclohexyldiphenylphosphine (PPh 2 Cy) (0.027 g; 0.1 mmol) dissolved in methanol (2 ml) was added and the solution was stirred for 6 hours at room temperature [8]. A white precipitate formed, which was crystallised by slow evaporation from dichloromethane/methanol. Colourless crystals of the

Discussion This study forms part of continuous research, which aims to determine structure and reactivity relationships of the rhenium(I) complexes particularly complexes bearing the fac-[Re(CO)3]+ synthon, for its application in radiopharmaceuticals. These rhenium complexes comprise of various coordinated ligands: combinations of mono- and bidentate ligands (OO'–, NO–, NN–, NS–, SS– and SO– donating) via the 2+1 mixed ligand approach, and tridentate ligands (combinations of N, O and S donor atoms) [1–4]. In the title compound, [Re(C5H7O2)(CO)3(PPh2Cy)], the coordination geometry around the rhenium is a distorted octahedron, consisting of three carbonyl ligands, a chelate '-diketonato moiety, acetylacetone (acac), and a monodentate cyclohexyl diphenylphosphine ligand (PPh2Cy) (see Figure). The octahedral distortion is observed in the slight deviation from 90°, with O5–Re1–O4 being the furthest outlier (85.28(8)°), which correlates well with similar acetylacetonate coordinated Re(I) complexes, ranging between 84.5(2)° and 85.9(2)°. All the bonding distances and angles are considered to be within the normal range [5–8]. The molecules pack in horizontal layers, in a head-to-tail fashion, across the ab-plane. Table 2. Atomic coordinates and displacement parameters (in Å2). Atom

Site Occ.

x

H(4A) H(4B) H(4C) H(6) H(8A) H(8B)

4e 4e 4e 4e 4e 4e

0.7148 0.8237 0.8236 0.8121 0.7513 0.7994

_____________

* Correspondence author (e-mail: [email protected])

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y )0.0112 )0.0072 0.0591 0.1045 0.3008 0.1806

z

Uiso

0.0985 0.1569 0.0770 0.2605 0.3889 0.3833

0.105 0.105 0.105 0.070 0.105 0.105

C26H28O5PRe

151

Table 2. continued.

Table 2. continued.

Atom

Site Occ.

x

H(8C) H(12) H(13) H(14) H(15) H(16) H(22A) H(23A) H(24A) H(25A) H(26A) H(21B) H(22B) H(22C) H(23B) H(23C) H(24B) H(24C) H(25B)

4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e

0.3932 0.4324 0.5057 0.5509 0.5090 0.2844 0.2168 0.2672 0.3853 0.4529 0.4575 0.3133 0.2218 0.2408 0.3761 0.3103 0.2151 0.4509

0.567 0.567 0.567 0.567 0.567 0.433 0.433 0.433 0.433 0.433 0.433 0.433 0.433

y 0.2005 0.0751 )0.1062 )0.2138 )0.1384 0.0420 0.0901 0.1189 0.2757 0.4036 0.3747 0.1999 0.0770 0.1724 0.1048 0.1176 0.2492 0.2815 0.3159

z

Uiso

Atom

Site Occ.

0.3977 0.0574 0.0352 0.1345 0.2550 0.2796 0.2960 0.4209 0.4893 0.4329 0.3081 0.3146 0.3036 0.3037 0.4295 0.4295 0.5024 0.4379 0.4319

0.105 0.076 0.099 0.102 0.095 0.069 0.065 0.069 0.060 0.064 0.057 0.045 0.050 0.050 0.060 0.060 0.072 0.072 0.076

H(25C) H(26B) H(26C) H(32B) H(33B) H(34B) H(35B) H(36B) H(32A) H(32C) H(35A) H(35C) H(34A) H(34C) H(33A) H(33C) H(36A) H(36C) H(31A)

4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e

x

0.433 0.3535 0.433 0.2997 0.433 0.4353 0.433 0.3122 0.433 0.1333 0.433 )0.0144 0.433 0.0167 0.433 0.1956 0.567 0.2026 0.567 0.2850 0.567 0.1194 0.567 0.0318 0.567 )0.0230 0.567 0.0056 0.567 0.0903 0.567 0.1518 0.567 0.1608 0.567 0.2229 0.567 0.3008

y

z

Uiso

0.4056 0.3689 0.3826 0.4006 0.4456 0.3193 0.1478 0.1027 0.3547 0.4026 0.1577 0.1094 0.2878 0.2822 0.4336 0.3635 0.1572 0.0772 0.2291

0.4318 0.3043 0.3073 0.1118 0.0573 0.0559 0.1090 0.1635 0.1931 0.1293 0.0280 0.0885 0.0515 0.1432 0.0936 0.0291 0.1953 0.1369 0.0729

0.076 0.051 0.051 0.058 0.083 0.099 0.094 0.087 0.058 0.058 0.079 0.079 0.091 0.091 0.075 0.075 0.064 0.064 0.048

Table 3. Atomic coordinates and displacement parameters (in Å2). Atom

Site Occ.

x

C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(11) C(12) C(13) C(14) C(15) C(16) O(1) O(2) O(3) O(4) O(5) P(1) Re(1) C(21A) C(22A) C(23A) C(24A) C(25A) C(26A) C(21B) C(22B) C(23B) C(24B) C(25B) C(26B) C(31B) C(32B) C(33B) C(34B) C(35B) C(36B) C(32A) C(35A) C(34A) C(33A) C(36A) C(31A)

4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e

0.5067(2) 0.4647(2) 0.1752(2) 0.5120(3) 0.3520(2) 0.0446(2) 0.7121(3) 0.4103(2) 0.1168(2) 0.7766(4) 0.0343(3) 0.1196(3) 0.7270(3) 0.1302(3) 0.1601(2) 0.7553(3) 0.1497(3) 0.2372(2) 0.7098(3) 0.2280(3) 0.2844(2) 0.7341(4) 0.2274(3) 0.3712(2) 0.4423(3) 0.0756(2) 0.1717(2) 0.4231(4) 0.0315(3) 0.0987(2) 0.4472(4) )0.0762(4) 0.0854(3) 0.4919(4) )0.1395(3) 0.1436(4) 0.5166(4) )0.0953(3) 0.2150(3) 0.4919(3) 0.0121(3) 0.2297(2) 0.4670(2) 0.5453(2) 0.1921(2) 0.4730(3) 0.3653(2) )0.0173(1) 0.7892(2) 0.4560(2) 0.0979(2) 0.6584(2) 0.1855(2) 0.1174(1) 0.6428(2) 0.3033(2) 0.2615(1) 0.41284(7) 0.21851(6) 0.18758(4) 0.575991(9) 0.332345(9) 0.146705(6) 0.375(1) 0.230(1) 0.2903(6) 0.305(1) 0.1537(9) 0.3238(7) 0.2647(9) 0.1708(8) 0.3980(7) 0.295(1) 0.264(1) 0.4386(6) 0.365(1) 0.3399(8) 0.4051(8) 0.4050(8) 0.3228(9) 0.3310(8) 0.384(2) 0.226(1) 0.2897(9) 0.299(2) 0.151(1) 0.323(1) 0.303(1) 0.151(1) 0.4111(9) 0.294(2) 0.255(2) 0.446(1) 0.373(2) 0.333(2) 0.413(1) 0.372(1) 0.336(1) 0.3241(9) 0.271(1) 0.247(1) 0.143(1) 0.252(1) 0.349(1) 0.1112(8) 0.146(1) 0.376(1) 0.079(1) 0.058(1) 0.301(2) 0.078(1) 0.077(1) 0.199(1) 0.1096(9) 0.183(1) 0.172(1) 0.142(1) 0.2271(9) 0.3466(9) 0.1389(7) 0.0906(8) 0.1652(8) 0.0812(8) 0.039(1) 0.277(1) 0.091(1) 0.126(1) 0.3628(9) 0.083(1) 0.1896(9) 0.150(1) 0.1421(9) 0.280(1) 0.235(1) 0.129(1)

0.567 0.567 0.567 0.567 0.567 0.567 0.433 0.433 0.433 0.433 0.433 0.433 0.433 0.433 0.433 0.433 0.433 0.433 0.567 0.567 0.567 0.567 0.567 0.567

y

z

U11

U22

U33

0.031(2) 0.047(2) 0.049(2) 0.067(3) 0.040(2) 0.047(2) 0.042(2) 0.079(3) 0.044(2) 0.081(3) 0.096(4) 0.080(3) 0.079(3) 0.057(2) 0.060(2) 0.090(2) 0.060(2) 0.044(1) 0.044(1) 0.0367(4) 0.03434(7) 0.064(7) 0.06(1) 0.053(6) 0.064(7) 0.071(8) 0.039(5) 0.044(7) 0.04(1) 0.063(8) 0.06(1) 0.10(1) 0.053(8) 0.028(6) 0.028(6) 0.056(9) 0.06(1) 0.048(7) 0.07(1) 0.034(5) 0.043(4) 0.049(5) 0.046(5) 0.029(5) 0.043(5)

0.041(2) 0.034(2) 0.034(2) 0.048(2) 0.038(2) 0.050(2) 0.044(2) 0.066(3) 0.036(2) 0.052(2) 0.059(3) 0.040(2) 0.042(2) 0.046(2) 0.038(1) 0.073(2) 0.059(2) 0.034(1) 0.045(1) 0.0339(4) 0.02844(6) 0.056(6) 0.07(1) 0.070(7) 0.056(6) 0.039(6) 0.053(6) 0.022(5) 0.04(1) 0.040(5) 0.07(1) 0.07(1) 0.044(5) 0.06(1) 0.064(6) 0.09(1) 0.12(2) 0.10(1) 0.07(1) 0.047(4) 0.067(6) 0.074(7) 0.053(6) 0.060(5) 0.038(4)

0.040(2) 0.046(2) 0.048(2) 0.097(3) 0.062(2) 0.078(3) 0.055(2) 0.062(2) 0.054(2) 0.058(2) 0.095(4) 0.139(5) 0.118(4) 0.069(2) 0.073(2) 0.042(1) 0.091(2) 0.052(1) 0.040(1) 0.0342(4) 0.03452(7) 0.030(5) 0.04(1) 0.051(5) 0.030(5) 0.050(9) 0.050(5) 0.048(8) 0.05(2) 0.049(7) 0.052(9) 0.027(7) 0.032(5) 0.041(8) 0.054(8) 0.06(1) 0.067(9) 0.09(1) 0.07(1) 0.063(7) 0.087(7) 0.10(1) 0.087(9) 0.071(8) 0.039(5)


U12 )0.001(1) )0.000(1) )0.000(1) 0.018(2) 0.003(1) 0.011(2) )0.011(2) )0.011(2) )0.010(1) )0.014(2) )0.023(3) )0.010(2) 0.011(2) 0.002(2) 0.011(1) )0.001(2) )0.019(1) 0.0070(9) )0.001(1) )0.0033(3) 0.00033(5) 0.014(5) )0.002(9) )0.002(5) 0.014(5) )0.010(6) )0.001(4) )0.015(5) )0.022(9) )0.001(5) 0.002(7) 0.035(9) 0.000(6) )0.009(6) 0.003(4) 0.001(7) 0.02(1) )0.019(8) )0.010(8) 0.004(3) )0.004(4) 0.014(5) 0.019(5) )0.009(3) 0.003(3)

U13 0.001(1) 0.001(2) 0.005(2) 0.024(2) 0.011(2) )0.010(2) )0.012(2) )0.028(2) 0.011(2) 0.021(2) 0.038(3) 0.049(3) 0.019(3) 0.006(2) 0.002(1) )0.016(1) 0.026(2) 0.008(1) )0.007(1) 0.0014(3) )0.00012(5) 0.010(4) 0.012(8) 0.013(4) 0.010(4) 0.005(6) 0.000(4) 0.005(5) 0.01(1) 0.020(6) 0.008(7) 0.008(8) 0.005(5) 0.001(5) 0.005(5) )0.018(7) )0.013(8) 0.004(6) )0.004(9) 0.001(4) )0.011(4) )0.032(6) )0.021(6) )0.006(5) 0.000(4)

U23 0.000(1) )0.001(1) )0.001(1) 0.011(2) 0.013(2) 0.019(2) 0.017(2) 0.025(2) )0.003(1) )0.016(2) )0.036(3) )0.019(3) 0.014(2) 0.001(2) )0.007(1) 0.007(1) )0.004(1) 0.0029(9) 0.0055(9) )0.0008(3) 0.00298(5) 0.002(4) )0.001(9) 0.010(4) 0.002(4) )0.002(5) )0.005(4) )0.002(5) 0.00(1) 0.005(4) 0.016(7) )0.007(7) )0.002(4) )0.007(6) )0.006(6) )0.016(8) )0.01(1) )0.038(8) 0.011(8) )0.014(4) )0.028(5) )0.035(6) )0.013(5) )0.006(4) )0.004(4)

152

C26H28O5PRe

Acknowledgments. Financial assistance from the University of the Free State is gratefully acknowledged. We also express our gratitude towards Ntembi, PETLabs Pharmaceuticals, SASOL, the South African National Research Foundation (SA-NRF/THRIP) and Head of the Chemistry Department, Prof A. Roodt. This work is based on the research supported in part by the National Research Foundations of South-Africa (Grant specific unique reference number (UID) 84913). The Grant holder acknowledges that opinions, findings and conclusions or recommendations expressed in any publication generated by the NRF supported research are that of the author(s) and that the NRF accepts no liability whatsoever in this regard.

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