Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056152/sj2393sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056152/sj2393Isup2.hkl |
CCDC reference: 672659
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.004 Å
- R factor = 0.036
- wR factor = 0.068
- Data-to-parameter ratio = 20.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 500 Ang. PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.52 Ratio PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Rh - C10 .. 6.68 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 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 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
For the neutral 5-chloro-8-hydroxyquinoline ligand structure. see: Banerjee & Saha (1986). For an example of a β-diketonatorhodium(I)phosphine complex, see: Brink et al. (2007). For related quinolinatorhodium(I)phosphite complexes, see: Janse van Rensburg et al. (2005a,b, 2006a). For quinolinatorhodium(I)phosphine complexes, see Janse van Rensburg & Roodt (2006); Janse van Rensburg et al. (2006b). For related literature, see: Allen (2002); Domenicano et al. (1975); Hughes & Truter (1979); McCleverty & Wilkinson (1990); Otto et al. (2000); Tolman (1977).
Chemicals and solvents were obtained from Sigma-Aldrich and used as received. [RhCl(CO)2]2 was prepared according to the literature method (McCleverty & Wilkinson, 1990). [Rh(5ClOX)(CO)2] was synthesized by mixing solutions of 5-chloro-8-hydroxyquinoline, (5ClOX), (61.4 mg, 0.344 mmol) in DMF (1 ml) and [RhCl(CO)2]2 (60.9 mg, 0.156 mmol) in DMF (1 ml). Upon addition of ice water (30 ml) the product precipitated and was filtered. Ligand substitution on the complex [Rh(5ClOX)(CO)2] was performed by dissolving (50 mg, 0.148 mmol) in acetone (40 ml) followed by slow addition of P(4-ClC6H4)3 (55 mg, 0.163 mmol) in acetone (10 ml). Upon evaporation, crystals suitable for single-crystal X-ray crystallography were obtained (yield: 72 mg, 76%).
Spectroscopic data: 31P{H} NMR (CDCl3, 121.447 MHz, p.p.m.): 40.47 p.p.m. [1J(Rh—P) = 166 Hz]; IR (KBr) ν(CO): 1965 cm-1.
The H atoms were positioned geometrically and refined using a riding model with fixed C—H distances of 0.93 Å (CH) [Uiso(H) = 1.2Ueq].
The highest density peak is 0.68 located 0.95 Å from C10 and the deepest hole is -0.74 located at 0.56 Å from Rh.
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).
[Rh(C9H7ClNO)(C18H12Cl3P)(CO)] | F(000) = 1344 |
Mr = 675.11 | Dx = 1.67 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5536 reflections |
a = 9.558 (5) Å | θ = 2.5–28.1° |
b = 19.788 (5) Å | µ = 1.12 mm−1 |
c = 14.608 (5) Å | T = 100 K |
β = 103.670 (5)° | Cuboid, yellow |
V = 2684.6 (18) Å3 | 0.12 × 0.08 × 0.06 mm |
Z = 4 |
Bruker X8 APEXII 4K Kappa CCD diffractometer | 6708 independent reflections |
Radiation source: fine-focus sealed tube | 4272 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.097 |
ω & ϕ scans | θmax = 28.4°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −12→12 |
Tmin = 0.877, Tmax = 0.946 | k = −26→26 |
39703 measured reflections | l = −19→19 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0221P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.068 | (Δ/σ)max < 0.001 |
S = 0.88 | Δρmax = 0.68 e Å−3 |
6708 reflections | Δρmin = −0.74 e Å−3 |
334 parameters |
[Rh(C9H7ClNO)(C18H12Cl3P)(CO)] | V = 2684.6 (18) Å3 |
Mr = 675.11 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.558 (5) Å | µ = 1.12 mm−1 |
b = 19.788 (5) Å | T = 100 K |
c = 14.608 (5) Å | 0.12 × 0.08 × 0.06 mm |
β = 103.670 (5)° |
Bruker X8 APEXII 4K Kappa CCD diffractometer | 6708 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 4272 reflections with I > 2σ(I) |
Tmin = 0.877, Tmax = 0.946 | Rint = 0.097 |
39703 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.68 e Å−3 |
6708 reflections | Δρmin = −0.74 e Å−3 |
334 parameters |
Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD diffractometer using an exposure time of 40 s/frame. A total of 1348 frames were collected with a frame width of 0.5° covering up to θ = 28.36° with 99.7% completeness accomplished. |
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 | ||
C1 | −0.1624 (4) | 0.04276 (15) | −0.0917 (2) | 0.0211 (7) | |
H1 | −0.2456 | 0.052 | −0.0713 | 0.025* | |
C2 | −0.1670 (4) | −0.00805 (15) | −0.1592 (2) | 0.0248 (8) | |
H2 | −0.2516 | −0.0319 | −0.1827 | 0.03* | |
C3 | −0.0468 (4) | −0.02217 (15) | −0.1899 (2) | 0.0240 (8) | |
H3 | −0.0498 | −0.0551 | −0.2358 | 0.029* | |
C4 | 0.0823 (4) | 0.01282 (14) | −0.15262 (19) | 0.0206 (7) | |
C5 | 0.2164 (4) | 0.00051 (15) | −0.1737 (2) | 0.0260 (8) | |
C6 | 0.3369 (4) | 0.03361 (16) | −0.1267 (2) | 0.0291 (8) | |
H6 | 0.4249 | 0.023 | −0.1398 | 0.035* | |
C7 | 0.3318 (4) | 0.08330 (16) | −0.0591 (2) | 0.0262 (8) | |
H7 | 0.4162 | 0.1048 | −0.0278 | 0.031* | |
C8 | 0.2036 (4) | 0.10045 (14) | −0.03872 (19) | 0.0189 (7) | |
C9 | 0.0780 (4) | 0.06354 (15) | −0.08460 (19) | 0.0183 (7) | |
C10 | −0.1950 (4) | 0.16063 (16) | 0.05666 (19) | 0.0214 (7) | |
C11 | −0.0802 (3) | 0.27579 (14) | 0.20064 (19) | 0.0143 (6) | |
C12 | −0.1370 (3) | 0.23426 (15) | 0.2598 (2) | 0.0188 (7) | |
H12 | −0.0998 | 0.191 | 0.2733 | 0.023* | |
C13 | −0.2469 (3) | 0.25576 (16) | 0.2985 (2) | 0.0215 (7) | |
H13 | −0.2825 | 0.228 | 0.3391 | 0.026* | |
C14 | −0.3032 (3) | 0.31923 (16) | 0.27585 (19) | 0.0194 (7) | |
C15 | −0.2514 (3) | 0.36159 (15) | 0.21715 (19) | 0.0205 (7) | |
H15 | −0.2921 | 0.404 | 0.2021 | 0.025* | |
C16 | −0.1378 (3) | 0.34030 (16) | 0.18070 (18) | 0.0189 (7) | |
H16 | −0.0996 | 0.3692 | 0.1427 | 0.023* | |
C21 | 0.2029 (3) | 0.22046 (14) | 0.24806 (19) | 0.0146 (6) | |
C22 | 0.3095 (3) | 0.17624 (14) | 0.2356 (2) | 0.0189 (7) | |
H22 | 0.3046 | 0.1575 | 0.1765 | 0.023* | |
C23 | 0.4229 (3) | 0.15985 (16) | 0.3101 (2) | 0.0235 (7) | |
H23 | 0.4941 | 0.1301 | 0.3016 | 0.028* | |
C24 | 0.4294 (3) | 0.18803 (15) | 0.3974 (2) | 0.0197 (7) | |
C25 | 0.3261 (3) | 0.23252 (15) | 0.4116 (2) | 0.0202 (7) | |
H25 | 0.3321 | 0.2514 | 0.4707 | 0.024* | |
C26 | 0.2132 (3) | 0.24863 (15) | 0.3365 (2) | 0.0183 (7) | |
H26 | 0.143 | 0.2788 | 0.3454 | 0.022* | |
C31 | 0.1206 (3) | 0.31427 (14) | 0.09282 (19) | 0.0170 (7) | |
C32 | 0.0440 (4) | 0.33531 (16) | 0.0045 (2) | 0.0246 (7) | |
H32 | −0.0355 | 0.3106 | −0.0273 | 0.029* | |
C33 | 0.0851 (4) | 0.39297 (17) | −0.0367 (2) | 0.0340 (9) | |
H33 | 0.0324 | 0.4077 | −0.0952 | 0.041* | |
C34 | 0.2040 (4) | 0.42767 (16) | 0.0099 (2) | 0.0267 (8) | |
C35 | 0.2825 (4) | 0.40741 (17) | 0.0963 (2) | 0.0359 (9) | |
H35 | 0.3643 | 0.4312 | 0.1267 | 0.043* | |
C36 | 0.2384 (4) | 0.35094 (17) | 0.1379 (2) | 0.0313 (8) | |
H36 | 0.2896 | 0.3376 | 0.1975 | 0.038* | |
N | −0.0451 (3) | 0.07802 (12) | −0.05580 (16) | 0.0179 (6) | |
O1 | 0.1899 (2) | 0.14853 (10) | 0.02175 (13) | 0.0211 (5) | |
O2 | −0.3131 (2) | 0.16127 (12) | 0.06297 (15) | 0.0329 (6) | |
P | 0.05603 (9) | 0.24118 (4) | 0.14644 (5) | 0.01512 (18) | |
Cl1 | −0.44424 (8) | 0.34634 (4) | 0.32268 (5) | 0.02688 (18) | |
Cl | 0.22850 (11) | −0.05749 (4) | −0.26151 (6) | 0.0387 (2) | |
Cl2 | 0.57460 (9) | 0.16895 (4) | 0.49090 (6) | 0.0322 (2) | |
Cl3 | 0.25882 (13) | 0.49923 (5) | −0.04213 (7) | 0.0507 (3) | |
Rh | −0.01248 (3) | 0.156302 (12) | 0.043330 (15) | 0.01617 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0222 (19) | 0.0186 (17) | 0.0196 (16) | −0.0004 (15) | −0.0007 (14) | 0.0037 (13) |
C2 | 0.032 (2) | 0.0150 (16) | 0.0213 (16) | −0.0053 (16) | −0.0052 (15) | 0.0011 (13) |
C3 | 0.042 (2) | 0.0131 (16) | 0.0145 (15) | −0.0019 (16) | 0.0023 (15) | −0.0019 (12) |
C4 | 0.038 (2) | 0.0090 (15) | 0.0145 (15) | −0.0037 (15) | 0.0057 (14) | 0.0019 (12) |
C5 | 0.045 (2) | 0.0142 (16) | 0.0249 (17) | −0.0032 (16) | 0.0201 (16) | −0.0040 (13) |
C6 | 0.038 (2) | 0.0186 (17) | 0.039 (2) | −0.0054 (17) | 0.0253 (18) | −0.0039 (15) |
C7 | 0.030 (2) | 0.0229 (18) | 0.0283 (18) | −0.0086 (16) | 0.0128 (16) | −0.0053 (14) |
C8 | 0.031 (2) | 0.0121 (15) | 0.0158 (15) | −0.0055 (14) | 0.0090 (14) | 0.0006 (12) |
C9 | 0.029 (2) | 0.0122 (15) | 0.0140 (14) | −0.0037 (14) | 0.0066 (14) | 0.0027 (12) |
C10 | 0.030 (2) | 0.0153 (16) | 0.0162 (15) | 0.0012 (17) | −0.0008 (14) | −0.0030 (13) |
C11 | 0.0139 (16) | 0.0131 (15) | 0.0139 (14) | −0.0017 (13) | −0.0006 (12) | −0.0025 (11) |
C12 | 0.0174 (18) | 0.0145 (16) | 0.0241 (16) | 0.0012 (14) | 0.0038 (14) | 0.0029 (13) |
C13 | 0.0219 (19) | 0.0223 (17) | 0.0203 (16) | −0.0057 (15) | 0.0050 (14) | 0.0018 (13) |
C14 | 0.0148 (17) | 0.0262 (17) | 0.0162 (15) | −0.0019 (14) | 0.0017 (13) | −0.0061 (13) |
C15 | 0.0260 (19) | 0.0152 (16) | 0.0189 (16) | 0.0042 (14) | 0.0026 (14) | −0.0022 (12) |
C16 | 0.0247 (17) | 0.0170 (15) | 0.0144 (14) | −0.0057 (16) | 0.0033 (12) | −0.0019 (13) |
C21 | 0.0162 (17) | 0.0114 (15) | 0.0154 (15) | −0.0008 (13) | 0.0019 (12) | 0.0023 (11) |
C22 | 0.0228 (18) | 0.0154 (16) | 0.0188 (15) | 0.0000 (14) | 0.0058 (13) | −0.0034 (12) |
C23 | 0.0232 (18) | 0.0142 (15) | 0.0317 (17) | 0.0053 (16) | 0.0038 (14) | −0.0033 (14) |
C24 | 0.0173 (18) | 0.0180 (16) | 0.0222 (16) | −0.0057 (14) | 0.0015 (14) | 0.0076 (13) |
C25 | 0.0227 (19) | 0.0233 (18) | 0.0143 (15) | 0.0000 (15) | 0.0040 (13) | 0.0000 (13) |
C26 | 0.0173 (17) | 0.0158 (16) | 0.0228 (16) | 0.0025 (14) | 0.0064 (13) | 0.0002 (13) |
C31 | 0.0221 (18) | 0.0128 (15) | 0.0183 (15) | 0.0008 (14) | 0.0091 (13) | −0.0004 (12) |
C32 | 0.0297 (19) | 0.0237 (18) | 0.0196 (15) | −0.0088 (16) | 0.0046 (14) | −0.0001 (14) |
C33 | 0.046 (3) | 0.034 (2) | 0.0207 (18) | −0.0048 (19) | 0.0046 (17) | 0.0100 (15) |
C34 | 0.036 (2) | 0.0156 (17) | 0.0323 (19) | −0.0041 (16) | 0.0157 (17) | 0.0097 (14) |
C35 | 0.033 (2) | 0.028 (2) | 0.041 (2) | −0.0162 (18) | −0.0041 (17) | 0.0070 (16) |
C36 | 0.032 (2) | 0.0269 (19) | 0.0283 (17) | −0.0092 (18) | −0.0065 (15) | 0.0109 (15) |
N | 0.0257 (16) | 0.0123 (13) | 0.0137 (12) | −0.0017 (12) | 0.0003 (11) | 0.0014 (10) |
O1 | 0.0287 (13) | 0.0174 (11) | 0.0198 (10) | −0.0066 (11) | 0.0111 (9) | −0.0057 (9) |
O2 | 0.0242 (14) | 0.0392 (15) | 0.0337 (13) | −0.0024 (13) | 0.0037 (11) | −0.0060 (12) |
P | 0.0190 (4) | 0.0113 (4) | 0.0148 (4) | −0.0008 (3) | 0.0034 (3) | −0.0005 (3) |
Cl1 | 0.0214 (4) | 0.0336 (5) | 0.0269 (4) | 0.0015 (4) | 0.0080 (3) | −0.0069 (4) |
Cl | 0.0581 (7) | 0.0247 (5) | 0.0409 (5) | −0.0090 (5) | 0.0271 (5) | −0.0160 (4) |
Cl2 | 0.0282 (5) | 0.0343 (5) | 0.0284 (4) | 0.0036 (4) | −0.0046 (4) | 0.0078 (4) |
Cl3 | 0.0676 (8) | 0.0303 (5) | 0.0560 (6) | −0.0130 (5) | 0.0181 (6) | 0.0206 (5) |
Rh | 0.02153 (13) | 0.01224 (11) | 0.01413 (11) | −0.00259 (12) | 0.00298 (9) | −0.00139 (10) |
C1—N | 1.319 (4) | C15—H15 | 0.93 |
C1—C2 | 1.401 (4) | C16—H16 | 0.93 |
C1—H1 | 0.93 | C21—C22 | 1.387 (4) |
C2—C3 | 1.357 (5) | C21—C26 | 1.389 (4) |
C2—H2 | 0.93 | C21—P | 1.833 (3) |
C3—C4 | 1.408 (4) | C22—C23 | 1.381 (4) |
C3—H3 | 0.93 | C22—H22 | 0.93 |
C4—C5 | 1.409 (5) | C23—C24 | 1.379 (4) |
C4—C9 | 1.420 (4) | C23—H23 | 0.93 |
C5—C6 | 1.361 (5) | C24—C25 | 1.375 (4) |
C5—Cl | 1.745 (3) | C24—Cl2 | 1.744 (3) |
C6—C7 | 1.403 (4) | C25—C26 | 1.382 (4) |
C6—H6 | 0.93 | C25—H25 | 0.93 |
C7—C8 | 1.370 (5) | C26—H26 | 0.93 |
C7—H7 | 0.93 | C31—C36 | 1.371 (4) |
C8—O1 | 1.326 (3) | C31—C32 | 1.388 (4) |
C8—C9 | 1.430 (4) | C31—P | 1.820 (3) |
C9—N | 1.370 (4) | C32—C33 | 1.390 (4) |
C10—O2 | 1.154 (4) | C32—H32 | 0.93 |
C10—Rh | 1.803 (4) | C33—C34 | 1.364 (5) |
C11—C12 | 1.392 (4) | C33—H33 | 0.93 |
C11—C16 | 1.393 (4) | C34—C35 | 1.368 (4) |
C11—P | 1.811 (3) | C34—Cl3 | 1.746 (3) |
C12—C13 | 1.372 (4) | C35—C36 | 1.384 (4) |
C12—H12 | 0.93 | C35—H35 | 0.93 |
C13—C14 | 1.376 (4) | C36—H36 | 0.93 |
C13—H13 | 0.93 | N—Rh | 2.093 (2) |
C14—C15 | 1.373 (4) | O1—Rh | 2.038 (2) |
C14—Cl1 | 1.734 (3) | P—Rh | 2.2478 (9) |
C15—C16 | 1.383 (4) | ||
N—C1—C2 | 122.8 (3) | C23—C22—C21 | 120.5 (3) |
N—C1—H1 | 118.6 | C23—C22—H22 | 119.7 |
C2—C1—H1 | 118.6 | C21—C22—H22 | 119.7 |
C3—C2—C1 | 119.5 (3) | C24—C23—C22 | 119.3 (3) |
C3—C2—H2 | 120.2 | C24—C23—H23 | 120.4 |
C1—C2—H2 | 120.2 | C22—C23—H23 | 120.4 |
C2—C3—C4 | 120.2 (3) | C25—C24—C23 | 121.4 (3) |
C2—C3—H3 | 119.9 | C25—C24—Cl2 | 119.2 (2) |
C4—C3—H3 | 119.9 | C23—C24—Cl2 | 119.4 (2) |
C3—C4—C5 | 126.2 (3) | C24—C25—C26 | 118.8 (3) |
C3—C4—C9 | 116.8 (3) | C24—C25—H25 | 120.6 |
C5—C4—C9 | 117.0 (3) | C26—C25—H25 | 120.6 |
C6—C5—C4 | 120.8 (3) | C25—C26—C21 | 121.1 (3) |
C6—C5—Cl | 119.5 (3) | C25—C26—H26 | 119.5 |
C4—C5—Cl | 119.8 (3) | C21—C26—H26 | 119.5 |
C5—C6—C7 | 121.8 (3) | C36—C31—C32 | 118.7 (3) |
C5—C6—H6 | 119.1 | C36—C31—P | 122.5 (2) |
C7—C6—H6 | 119.1 | C32—C31—P | 118.7 (2) |
C8—C7—C6 | 120.5 (3) | C31—C32—C33 | 120.6 (3) |
C8—C7—H7 | 119.7 | C31—C32—H32 | 119.7 |
C6—C7—H7 | 119.7 | C33—C32—H32 | 119.7 |
O1—C8—C7 | 123.8 (3) | C34—C33—C32 | 119.0 (3) |
O1—C8—C9 | 118.4 (3) | C34—C33—H33 | 120.5 |
C7—C8—C9 | 117.8 (3) | C32—C33—H33 | 120.5 |
N—C9—C4 | 122.1 (3) | C33—C34—C35 | 121.6 (3) |
N—C9—C8 | 115.9 (3) | C33—C34—Cl3 | 119.4 (3) |
C4—C9—C8 | 121.9 (3) | C35—C34—Cl3 | 118.9 (3) |
O2—C10—Rh | 177.4 (3) | C34—C35—C36 | 118.9 (3) |
C12—C11—C16 | 118.5 (3) | C34—C35—H35 | 120.5 |
C12—C11—P | 118.3 (2) | C36—C35—H35 | 120.5 |
C16—C11—P | 123.0 (2) | C31—C36—C35 | 121.2 (3) |
C13—C12—C11 | 121.4 (3) | C31—C36—H36 | 119.4 |
C13—C12—H12 | 119.3 | C35—C36—H36 | 119.4 |
C11—C12—H12 | 119.3 | C1—N—C9 | 118.6 (3) |
C12—C13—C14 | 118.6 (3) | C1—N—Rh | 129.8 (2) |
C12—C13—H13 | 120.7 | C9—N—Rh | 111.65 (19) |
C14—C13—H13 | 120.7 | C8—O1—Rh | 113.82 (19) |
C15—C14—C13 | 121.9 (3) | C11—P—C31 | 103.86 (14) |
C15—C14—Cl1 | 119.1 (2) | C11—P—C21 | 102.88 (13) |
C13—C14—Cl1 | 119.0 (2) | C31—P—C21 | 104.69 (14) |
C14—C15—C16 | 119.1 (3) | C11—P—Rh | 116.73 (10) |
C14—C15—H15 | 120.4 | C31—P—Rh | 112.33 (10) |
C16—C15—H15 | 120.4 | C21—P—Rh | 114.94 (10) |
C15—C16—C11 | 120.4 (3) | C10—Rh—O1 | 176.92 (11) |
C15—C16—H16 | 119.8 | C10—Rh—N | 96.90 (12) |
C11—C16—H16 | 119.8 | O1—Rh—N | 80.15 (9) |
C22—C21—C26 | 118.9 (3) | C10—Rh—P | 91.62 (10) |
C22—C21—P | 118.7 (2) | O1—Rh—P | 91.33 (6) |
C26—C21—P | 122.4 (2) | N—Rh—P | 171.45 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl | 0.93 | 2.77 | 3.132 (4) | 104 |
C22—H22···O1 | 0.93 | 2.27 | 3.111 (4) | 149 |
Experimental details
Crystal data | |
Chemical formula | [Rh(C9H7ClNO)(C18H12Cl3P)(CO)] |
Mr | 675.11 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 9.558 (5), 19.788 (5), 14.608 (5) |
β (°) | 103.670 (5) |
V (Å3) | 2684.6 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.12 |
Crystal size (mm) | 0.12 × 0.08 × 0.06 |
Data collection | |
Diffractometer | Bruker X8 APEXII 4K Kappa CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.877, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 39703, 6708, 4272 |
Rint | 0.097 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.068, 0.88 |
No. of reflections | 6708 |
No. of parameters | 334 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.68, −0.74 |
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).
C10—O2 | 1.154 (4) | O1—Rh | 2.038 (2) |
C10—Rh | 1.803 (4) | P—Rh | 2.2478 (9) |
N—Rh | 2.093 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl | 0.93 | 2.77 | 3.132 (4) | 104 |
C22—H22···O1 | 0.93 | 2.27 | 3.111 (4) | 149.3 |
System | N···O | C—O(hydroxyl) | Endocyclic ring angle 〈 C7—C8—C9 |
Rh(OXCl)COP(4-ClPh)3(i) | 2.659 (9) | 1.326 (3) | 117.8 (3) |
OXCl(ii) | 2.747 (7) | 1.346 (7) | 119.6 (5) |
OX(ii) | 2.742 (4) | 1.367 (5) | 121.4 (4) |
(i) This work; (OXCl) = 5-chloro-8-hydroxyquinoline and (4-ClC6H4) = p-chlorophenyl; (ii) Banerjee & Saha (1986); (OX) = 8-hydroxyquinoline. |
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Bonding of bidentate ligands to transition metals is a well known concept. One of the most common bidentate examples are probably the β-diketones, e.g. acetylacetone, with 42 entries in the CSD for Rh(I) complexes alone [Cambridge Structural Database, Version 5.28, May 2007 (Allen, 2002)]. Bidentate ligands with different donor atoms such as 8-hydroxyquinoline and its derivatives also form chelating ring systems with transition metals, via the N, O donor atoms. To date there are six 8-hydroxylquinolinatorhodium(I) complexes deposited in the CSD.
In the title compound [Rh(C9H7ClNO)(CO){P(C6H4Cl)3}], the fused ring system of the bidentate ligand is almost planar, with an r.m.s. deviation from planarity of 0.0423 Å and a dihedral angle of 4.87 (16) Å between the benzene and pyridine rings. The 5'-chloro substituent, the O-donor atom and the metal centre are essentially in the plane of the quinoline system, displaced by 0.124 (3) Å, 0.081 (3) Å and 0.065 (3) Å respectively. The rhodium metal centre is slightly displaced from the coordination plane by 0.014 (1) Å (r.m.s of fitted atoms = 0.0007 Å). The N···O bite distance is 2.659 (9) Å and the N—Rh—O bite angle is 80.15 (9)°. The Rh—P bond distance is 2.2478 (9) Å, while the C8—O1 bond distance is 1.326 (3) Å and the endocyclic angle at C7—C8—C9 = 117.8 (3)°. These are comparable to the average distances for rhodium(I)quinolinato complexes reported previously (Janse van Rensburg et al., 2005a,b, 2006, a,b, Janse van Rensburg & Roodt, 2006).
The metal-carbonyl is slightly bent with a Rh—C10—O2 bond angle of 177.4 (3)°, and a C10—O2 bond distance of 1.154 (4) Å, also comparable with previous reported rhodium(I)quinolinol complexes. Phosphine ligand substitution occurred trans to the N-donor atom which is the stronger σ-donor. Phosphine substituent arrangement is in such a way that one of the phenyl rings is cis to the carbonyl, reflected by the C10—Rh—P—C11 torsion angle of 1.86 (14)°. The steric behavior of the ligand at the metal centre was determined by calculating the effective cone angle as described previously (Tolman, 1977; Otto et al., 2000). A value of 165° was obtained.
Short intramolecular contacts are present between C3···Cl with C3—H···Cl = 104° and C3···Cl = 3.132 (4) Å and beween C22···O1 with C22—H···O1 = 149.3° and C22···O1 = 3.111 (4) Å. The familiar quinoline ligand to ligand stacking fashion for these type of compounds is also present, stabilized with a π-stacking distance of 3.26 Å between the palnes defined by the C1···C9, N atoms of adjacent quinoline ligands; in addition, there are two Rh···H contacts (3.388 Å) and two Cl···O contacts (3.489 Å).
Banerjee and Saha reported the effects on bond lengths and angles of the free 5'-chloro moiety versus that of the free 8-hydroxyquinoline ligand (Banarjee & Saha, 1986). In this article we compare these to the rhodium bonded 5-chloro-8-hydroxyquinoline title compound (Table 1). There is a ca 0.1 Å decrease in the N···O bite distance of the title compound, 2.659 (9) Å, when compared to that of the free ligand. Chelation of 5-chloro-8-hydroxyquinoline to the metal centre shortens the C8—O1 bond distance by ca 0.04 Å, compared to the neutral 8-hydroxyquinolines (Hughes & Truter, 1979).
A decrease is also noted in the C6—C7—C8 ring angle when comparing the title compound with the free 5-chloro-8-hydroxyquinoline and unsubstituted 8-hydroxyquinoline, (117.8 (3)°, 119.6 (5)° and 121.4 (4)°), respectively. Thus the smaller the endocyclic ring angle, the stronger conjugation is observed between the benzene and the oxygen (O1) (Banerjee & Saha, 1986; Domenicano et al., 1975).