Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053755/ng2354sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053755/ng2354Isup2.hkl |
CCDC reference: 672629
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.025
- wR factor = 0.064
- Data-to-parameter ratio = 16.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Rh - Cl .. 7.39 su PLAT480_ALERT_4_C Long H...A H-Bond Reported H27 .. F24 .. 2.63 Ang.
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 1 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 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title complex was obtained during the attempted synthesis of the [Rh((N-4-FPh)Trop)CO(PPh3)] derivative, due to the excess of ligands oxidation of the Rh(I) centre occurred. On evaporation of the acetone; crystals suitable for X-Ray crystallography was obtained.
H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å and with Uiso(H) = 1.2 times Ueq(C aromatic).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. : Representation of the title compound (I), showing the numbering scheme and displacement ellipsoids (50% probability). |
[Rh(C13H9NOF)2Cl(C18H15P)] | Z = 2 |
Mr = 829.05 | F(000) = 844 |
Triclinic, P1 | Dx = 1.510 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4681 (4) Å | Cell parameters from 9643 reflections |
b = 10.5333 (5) Å | θ = 2.4–28.3° |
c = 19.5749 (9) Å | µ = 0.64 mm−1 |
α = 100.552 (2)° | T = 100 K |
β = 91.904 (2)° | Plate, red |
γ = 107.430 (2)° | 0.35 × 0.35 × 0.06 mm |
V = 1822.98 (14) Å3 |
Bruker SMART 1K CCD area-detector diffractometer | 7924 independent reflections |
Radiation source: fine-focus sealed tube | 7289 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
Detector resolution: 512 pixels mm-1 | θmax = 27.0°, θmin = 2.1° |
phi and ω scans | h = −11→12 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −13→13 |
Tmin = 0.808, Tmax = 0.963 | l = −24→24 |
50714 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0253P)2 + 1.3992P] where P = (Fo2 + 2Fc2)/3 |
7924 reflections | (Δ/σ)max = 0.001 |
478 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.63 e Å−3 |
[Rh(C13H9NOF)2Cl(C18H15P)] | γ = 107.430 (2)° |
Mr = 829.05 | V = 1822.98 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.4681 (4) Å | Mo Kα radiation |
b = 10.5333 (5) Å | µ = 0.64 mm−1 |
c = 19.5749 (9) Å | T = 100 K |
α = 100.552 (2)° | 0.35 × 0.35 × 0.06 mm |
β = 91.904 (2)° |
Bruker SMART 1K CCD area-detector diffractometer | 7924 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 7289 reflections with I > 2σ(I) |
Tmin = 0.808, Tmax = 0.963 | Rint = 0.039 |
50714 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.62 e Å−3 |
7924 reflections | Δρmin = −0.63 e Å−3 |
478 parameters |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Rh | 0.077509 (14) | 0.273280 (12) | 0.269392 (6) | 0.01352 (5) | |
Cl | −0.10642 (5) | 0.39378 (4) | 0.28114 (2) | 0.01912 (9) | |
P | 0.23870 (5) | 0.15092 (4) | 0.25259 (2) | 0.01517 (9) | |
F24 | 0.63836 (13) | 0.86999 (12) | 0.37281 (7) | 0.0363 (3) | |
O2 | −0.02742 (14) | 0.16654 (12) | 0.33902 (6) | 0.0188 (2) | |
O1 | 0.18050 (13) | 0.39257 (11) | 0.20541 (6) | 0.0155 (2) | |
F14 | −0.48903 (18) | −0.31325 (15) | 0.15354 (9) | 0.0599 (4) | |
N1 | −0.03774 (16) | 0.17037 (14) | 0.17478 (7) | 0.0163 (3) | |
N2 | 0.18529 (16) | 0.39043 (14) | 0.36101 (7) | 0.0155 (3) | |
C41 | 0.36683 (19) | 0.16472 (17) | 0.32757 (9) | 0.0172 (3) | |
C21 | 0.00897 (19) | 0.22668 (18) | 0.40479 (9) | 0.0178 (3) | |
C226 | 0.2743 (2) | 0.61971 (18) | 0.33940 (9) | 0.0194 (4) | |
H226 | 0.1770 | 0.6091 | 0.3202 | 0.023* | |
C24 | 0.1255 (2) | 0.4292 (2) | 0.54940 (9) | 0.0227 (4) | |
H24 | 0.1666 | 0.5060 | 0.5861 | 0.027* | |
C116 | −0.2632 (2) | 0.0362 (2) | 0.21465 (10) | 0.0245 (4) | |
H116 | −0.2582 | 0.1118 | 0.2507 | 0.029* | |
C12 | −0.00746 (19) | 0.23929 (17) | 0.12344 (9) | 0.0166 (3) | |
C25 | 0.0302 (2) | 0.3155 (2) | 0.56990 (9) | 0.0258 (4) | |
H25 | 0.0207 | 0.3223 | 0.6185 | 0.031* | |
C46 | 0.3023 (2) | 0.12251 (18) | 0.38602 (9) | 0.0201 (4) | |
H46 | 0.1971 | 0.0920 | 0.3857 | 0.024* | |
C27 | −0.0616 (2) | 0.1570 (2) | 0.45422 (10) | 0.0234 (4) | |
H27 | −0.1280 | 0.0688 | 0.4356 | 0.028* | |
C22 | 0.12562 (19) | 0.35789 (17) | 0.41819 (9) | 0.0163 (3) | |
C56 | 0.2348 (2) | −0.11511 (19) | 0.20036 (10) | 0.0261 (4) | |
H56 | 0.3302 | −0.0748 | 0.1863 | 0.031* | |
C23 | 0.1691 (2) | 0.44731 (18) | 0.48484 (9) | 0.0190 (3) | |
H23 | 0.2394 | 0.5331 | 0.4843 | 0.023* | |
C42 | 0.5211 (2) | 0.20584 (18) | 0.32832 (9) | 0.0203 (4) | |
H42 | 0.5666 | 0.2333 | 0.2886 | 0.024* | |
C224 | 0.5275 (2) | 0.75131 (19) | 0.36894 (10) | 0.0243 (4) | |
C52 | 0.0157 (2) | −0.09324 (19) | 0.25376 (10) | 0.0249 (4) | |
H52 | −0.0397 | −0.0384 | 0.2760 | 0.030* | |
C51 | 0.1532 (2) | −0.03287 (17) | 0.23153 (9) | 0.0202 (4) | |
C221 | 0.30347 (19) | 0.51321 (16) | 0.36373 (8) | 0.0157 (3) | |
C31 | 0.3499 (2) | 0.19638 (18) | 0.18167 (9) | 0.0194 (4) | |
C13 | −0.1042 (2) | 0.20736 (18) | 0.06111 (9) | 0.0221 (4) | |
H13 | −0.1985 | 0.1425 | 0.0616 | 0.027* | |
C11 | 0.12681 (19) | 0.35670 (17) | 0.14058 (9) | 0.0167 (3) | |
C45 | 0.3905 (2) | 0.12466 (19) | 0.44454 (10) | 0.0239 (4) | |
H45 | 0.3456 | 0.0970 | 0.4843 | 0.029* | |
C223 | 0.5605 (2) | 0.64715 (19) | 0.39194 (10) | 0.0260 (4) | |
H223 | 0.6592 | 0.6571 | 0.4090 | 0.031* | |
C32 | 0.4651 (2) | 0.31947 (19) | 0.19284 (10) | 0.0245 (4) | |
H32 | 0.4851 | 0.3784 | 0.2374 | 0.029* | |
C55 | 0.1765 (3) | −0.2557 (2) | 0.18998 (10) | 0.0334 (5) | |
H55 | 0.2318 | −0.3111 | 0.1683 | 0.040* | |
C15 | 0.0404 (3) | 0.3479 (2) | −0.01873 (10) | 0.0322 (5) | |
H15 | 0.0358 | 0.3604 | −0.0655 | 0.039* | |
C36 | 0.3158 (2) | 0.1156 (2) | 0.11458 (10) | 0.0261 (4) | |
H36 | 0.2340 | 0.0343 | 0.1056 | 0.031* | |
C26 | −0.0507 (2) | 0.1957 (2) | 0.52714 (10) | 0.0271 (4) | |
H26 | −0.1080 | 0.1287 | 0.5503 | 0.032* | |
C16 | 0.1687 (2) | 0.4232 (2) | 0.02335 (10) | 0.0293 (4) | |
H16 | 0.2431 | 0.4798 | 0.0012 | 0.035* | |
C225 | 0.3870 (2) | 0.74156 (19) | 0.34297 (10) | 0.0234 (4) | |
H225 | 0.3675 | 0.8160 | 0.3279 | 0.028* | |
C17 | 0.2049 (2) | 0.42846 (18) | 0.09351 (9) | 0.0211 (4) | |
H17 | 0.2987 | 0.4916 | 0.1124 | 0.025* | |
C43 | 0.6089 (2) | 0.20682 (19) | 0.38693 (10) | 0.0246 (4) | |
H43 | 0.7141 | 0.2349 | 0.3871 | 0.029* | |
C14 | −0.0825 (2) | 0.2557 (2) | 0.00036 (10) | 0.0271 (4) | |
H14 | −0.1651 | 0.2202 | −0.0341 | 0.033* | |
C222 | 0.4466 (2) | 0.52674 (18) | 0.38975 (9) | 0.0210 (4) | |
H222 | 0.4666 | 0.4537 | 0.4060 | 0.025* | |
C54 | 0.0390 (3) | −0.3149 (2) | 0.21096 (10) | 0.0347 (5) | |
H54 | −0.0008 | −0.4111 | 0.2032 | 0.042* | |
C34 | 0.5184 (3) | 0.2719 (3) | 0.07349 (11) | 0.0379 (5) | |
H34 | 0.5779 | 0.2961 | 0.0369 | 0.045* | |
C44 | 0.5440 (2) | 0.16710 (19) | 0.44505 (10) | 0.0251 (4) | |
H44 | 0.6044 | 0.1689 | 0.4852 | 0.030* | |
C114 | −0.3806 (2) | −0.1929 (2) | 0.15728 (12) | 0.0373 (5) | |
C113 | −0.2799 (2) | −0.1844 (2) | 0.10845 (11) | 0.0326 (5) | |
H113 | −0.2876 | −0.2601 | 0.0720 | 0.039* | |
C112 | −0.1662 (2) | −0.06303 (18) | 0.11317 (10) | 0.0236 (4) | |
H112 | −0.0938 | −0.0556 | 0.0804 | 0.028* | |
C111 | −0.1585 (2) | 0.04800 (17) | 0.16608 (9) | 0.0193 (4) | |
C35 | 0.4009 (3) | 0.1537 (2) | 0.06111 (11) | 0.0346 (5) | |
H35 | 0.3779 | 0.0978 | 0.0157 | 0.041* | |
C115 | −0.3749 (2) | −0.0861 (2) | 0.21045 (11) | 0.0334 (5) | |
H115 | −0.4462 | −0.0957 | 0.2438 | 0.040* | |
C33 | 0.5504 (2) | 0.3561 (2) | 0.13909 (11) | 0.0332 (5) | |
H33 | 0.6305 | 0.4386 | 0.1472 | 0.040* | |
C53 | −0.0411 (3) | −0.2349 (2) | 0.24327 (10) | 0.0319 (5) | |
H53 | −0.1351 | −0.2761 | 0.2584 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh | 0.01308 (7) | 0.01306 (7) | 0.01213 (7) | 0.00142 (5) | −0.00088 (5) | 0.00165 (5) |
Cl | 0.0173 (2) | 0.0206 (2) | 0.0185 (2) | 0.00600 (16) | 0.00075 (15) | 0.00159 (15) |
P | 0.0166 (2) | 0.0136 (2) | 0.0138 (2) | 0.00334 (17) | −0.00083 (16) | 0.00194 (16) |
F24 | 0.0266 (6) | 0.0267 (6) | 0.0439 (7) | −0.0104 (5) | −0.0072 (5) | 0.0113 (5) |
O2 | 0.0186 (6) | 0.0192 (6) | 0.0148 (6) | 0.0003 (5) | −0.0003 (5) | 0.0035 (5) |
O1 | 0.0177 (6) | 0.0139 (5) | 0.0137 (6) | 0.0032 (5) | −0.0001 (4) | 0.0024 (4) |
F14 | 0.0449 (9) | 0.0368 (8) | 0.0716 (11) | −0.0232 (7) | 0.0016 (8) | 0.0066 (7) |
N1 | 0.0155 (7) | 0.0150 (7) | 0.0155 (7) | 0.0021 (6) | −0.0008 (5) | 0.0006 (5) |
N2 | 0.0146 (7) | 0.0149 (7) | 0.0149 (7) | 0.0022 (6) | −0.0023 (5) | 0.0020 (5) |
C41 | 0.0185 (8) | 0.0137 (8) | 0.0184 (8) | 0.0056 (7) | −0.0025 (7) | 0.0005 (6) |
C21 | 0.0145 (8) | 0.0213 (9) | 0.0178 (8) | 0.0058 (7) | −0.0005 (6) | 0.0046 (7) |
C226 | 0.0170 (8) | 0.0211 (9) | 0.0180 (8) | 0.0034 (7) | −0.0024 (7) | 0.0040 (7) |
C24 | 0.0233 (9) | 0.0288 (10) | 0.0169 (8) | 0.0124 (8) | −0.0010 (7) | 0.0005 (7) |
C116 | 0.0175 (9) | 0.0286 (10) | 0.0222 (9) | 0.0010 (8) | −0.0018 (7) | 0.0032 (7) |
C12 | 0.0182 (8) | 0.0161 (8) | 0.0154 (8) | 0.0072 (7) | 0.0016 (6) | −0.0001 (6) |
C25 | 0.0234 (10) | 0.0415 (11) | 0.0145 (8) | 0.0116 (9) | 0.0030 (7) | 0.0078 (8) |
C46 | 0.0189 (9) | 0.0197 (9) | 0.0208 (9) | 0.0056 (7) | 0.0000 (7) | 0.0030 (7) |
C27 | 0.0187 (9) | 0.0264 (9) | 0.0222 (9) | 0.0015 (7) | 0.0003 (7) | 0.0074 (7) |
C22 | 0.0144 (8) | 0.0190 (8) | 0.0167 (8) | 0.0069 (7) | −0.0003 (6) | 0.0041 (6) |
C56 | 0.0360 (11) | 0.0221 (9) | 0.0203 (9) | 0.0113 (8) | −0.0059 (8) | 0.0021 (7) |
C23 | 0.0190 (9) | 0.0189 (8) | 0.0183 (8) | 0.0062 (7) | −0.0010 (7) | 0.0022 (7) |
C42 | 0.0209 (9) | 0.0186 (8) | 0.0207 (9) | 0.0058 (7) | 0.0012 (7) | 0.0027 (7) |
C224 | 0.0226 (9) | 0.0197 (9) | 0.0229 (9) | −0.0042 (7) | −0.0017 (7) | 0.0039 (7) |
C52 | 0.0294 (10) | 0.0190 (9) | 0.0222 (9) | 0.0023 (8) | −0.0062 (8) | 0.0046 (7) |
C51 | 0.0269 (10) | 0.0135 (8) | 0.0175 (8) | 0.0043 (7) | −0.0074 (7) | 0.0016 (6) |
C221 | 0.0165 (8) | 0.0146 (8) | 0.0124 (8) | 0.0019 (6) | 0.0000 (6) | −0.0010 (6) |
C31 | 0.0197 (9) | 0.0235 (9) | 0.0177 (8) | 0.0093 (7) | 0.0036 (7) | 0.0068 (7) |
C13 | 0.0230 (9) | 0.0199 (9) | 0.0206 (9) | 0.0049 (7) | −0.0036 (7) | 0.0010 (7) |
C11 | 0.0188 (8) | 0.0145 (8) | 0.0174 (8) | 0.0074 (7) | 0.0000 (6) | 0.0013 (6) |
C45 | 0.0258 (10) | 0.0257 (9) | 0.0200 (9) | 0.0071 (8) | 0.0005 (7) | 0.0061 (7) |
C223 | 0.0161 (9) | 0.0258 (10) | 0.0316 (10) | 0.0029 (7) | −0.0056 (7) | 0.0017 (8) |
C32 | 0.0235 (10) | 0.0259 (10) | 0.0253 (9) | 0.0078 (8) | 0.0030 (7) | 0.0080 (8) |
C55 | 0.0573 (15) | 0.0217 (10) | 0.0224 (10) | 0.0181 (10) | −0.0103 (9) | 0.0000 (8) |
C15 | 0.0453 (13) | 0.0347 (11) | 0.0169 (9) | 0.0114 (10) | −0.0014 (8) | 0.0080 (8) |
C36 | 0.0309 (11) | 0.0285 (10) | 0.0211 (9) | 0.0126 (8) | 0.0009 (8) | 0.0052 (8) |
C26 | 0.0220 (10) | 0.0367 (11) | 0.0221 (9) | 0.0037 (8) | 0.0044 (7) | 0.0139 (8) |
C16 | 0.0388 (12) | 0.0278 (10) | 0.0208 (9) | 0.0068 (9) | 0.0065 (8) | 0.0089 (8) |
C225 | 0.0254 (10) | 0.0195 (9) | 0.0239 (9) | 0.0030 (7) | −0.0014 (7) | 0.0081 (7) |
C17 | 0.0237 (9) | 0.0174 (8) | 0.0206 (9) | 0.0047 (7) | 0.0024 (7) | 0.0030 (7) |
C43 | 0.0175 (9) | 0.0245 (9) | 0.0295 (10) | 0.0053 (7) | −0.0023 (7) | 0.0027 (8) |
C14 | 0.0347 (11) | 0.0263 (10) | 0.0192 (9) | 0.0106 (9) | −0.0066 (8) | 0.0013 (7) |
C222 | 0.0191 (9) | 0.0177 (8) | 0.0246 (9) | 0.0055 (7) | −0.0030 (7) | 0.0017 (7) |
C54 | 0.0603 (15) | 0.0148 (9) | 0.0238 (10) | 0.0060 (9) | −0.0147 (10) | 0.0038 (7) |
C34 | 0.0384 (13) | 0.0561 (14) | 0.0294 (11) | 0.0215 (11) | 0.0171 (9) | 0.0204 (10) |
C44 | 0.0251 (10) | 0.0265 (10) | 0.0231 (9) | 0.0085 (8) | −0.0058 (7) | 0.0041 (7) |
C114 | 0.0273 (11) | 0.0273 (11) | 0.0439 (13) | −0.0104 (9) | −0.0058 (9) | 0.0073 (9) |
C113 | 0.0337 (12) | 0.0208 (10) | 0.0336 (11) | −0.0009 (8) | −0.0073 (9) | −0.0011 (8) |
C112 | 0.0239 (10) | 0.0199 (9) | 0.0225 (9) | 0.0024 (7) | −0.0027 (7) | 0.0008 (7) |
C111 | 0.0177 (9) | 0.0182 (8) | 0.0184 (8) | 0.0010 (7) | −0.0035 (7) | 0.0031 (7) |
C35 | 0.0460 (13) | 0.0426 (12) | 0.0201 (10) | 0.0208 (11) | 0.0070 (9) | 0.0065 (9) |
C115 | 0.0196 (10) | 0.0410 (12) | 0.0318 (11) | −0.0038 (9) | 0.0011 (8) | 0.0102 (9) |
C33 | 0.0259 (11) | 0.0371 (12) | 0.0389 (12) | 0.0068 (9) | 0.0074 (9) | 0.0180 (9) |
C53 | 0.0406 (12) | 0.0219 (10) | 0.0263 (10) | −0.0013 (9) | −0.0109 (9) | 0.0090 (8) |
Rh—O1 | 2.0054 (12) | C52—C51 | 1.390 (3) |
Rh—O2 | 2.0225 (12) | C52—C53 | 1.399 (3) |
Rh—N2 | 2.0233 (13) | C52—H52 | 0.9500 |
Rh—N1 | 2.0536 (14) | C221—C222 | 1.389 (2) |
Rh—P | 2.2704 (4) | C31—C36 | 1.397 (3) |
Rh—Cl | 2.4373 (4) | C31—C32 | 1.397 (3) |
P—C31 | 1.8175 (18) | C13—C14 | 1.375 (3) |
P—C51 | 1.8220 (18) | C13—H13 | 0.9500 |
P—C41 | 1.8290 (17) | C11—C17 | 1.390 (3) |
F24—C224 | 1.358 (2) | C45—C44 | 1.385 (3) |
O2—C21 | 1.311 (2) | C45—H45 | 0.9500 |
O1—C11 | 1.295 (2) | C223—C222 | 1.390 (3) |
F14—C114 | 1.359 (2) | C223—H223 | 0.9500 |
N1—C12 | 1.334 (2) | C32—C33 | 1.388 (3) |
N1—C111 | 1.422 (2) | C32—H32 | 0.9500 |
N2—C22 | 1.325 (2) | C55—C54 | 1.377 (3) |
N2—C221 | 1.425 (2) | C55—H55 | 0.9500 |
C41—C42 | 1.392 (2) | C15—C16 | 1.378 (3) |
C41—C46 | 1.396 (3) | C15—C14 | 1.387 (3) |
C21—C27 | 1.389 (3) | C15—H15 | 0.9500 |
C21—C22 | 1.460 (2) | C36—C35 | 1.386 (3) |
C226—C225 | 1.390 (3) | C36—H36 | 0.9500 |
C226—C221 | 1.391 (2) | C26—H26 | 0.9500 |
C226—H226 | 0.9500 | C16—C17 | 1.392 (3) |
C24—C23 | 1.371 (3) | C16—H16 | 0.9500 |
C24—C25 | 1.401 (3) | C225—H225 | 0.9500 |
C24—H24 | 0.9500 | C17—H17 | 0.9500 |
C116—C115 | 1.387 (3) | C43—C44 | 1.383 (3) |
C116—C111 | 1.391 (3) | C43—H43 | 0.9500 |
C116—H116 | 0.9500 | C14—H14 | 0.9500 |
C12—C13 | 1.425 (2) | C222—H222 | 0.9500 |
C12—C11 | 1.461 (2) | C54—C53 | 1.381 (3) |
C25—C26 | 1.368 (3) | C54—H54 | 0.9500 |
C25—H25 | 0.9500 | C34—C35 | 1.375 (3) |
C46—C45 | 1.387 (2) | C34—C33 | 1.387 (3) |
C46—H46 | 0.9500 | C34—H34 | 0.9500 |
C27—C26 | 1.402 (3) | C44—H44 | 0.9500 |
C27—H27 | 0.9500 | C114—C113 | 1.368 (3) |
C22—C23 | 1.429 (2) | C114—C115 | 1.373 (3) |
C56—C55 | 1.389 (3) | C113—C112 | 1.389 (3) |
C56—C51 | 1.399 (3) | C113—H113 | 0.9500 |
C56—H56 | 0.9500 | C112—C111 | 1.395 (3) |
C23—H23 | 0.9500 | C112—H112 | 0.9500 |
C42—C43 | 1.391 (3) | C35—H35 | 0.9500 |
C42—H42 | 0.9500 | C115—H115 | 0.9500 |
C224—C223 | 1.372 (3) | C33—H33 | 0.9500 |
C224—C225 | 1.376 (3) | C53—H53 | 0.9500 |
O1—Rh—O2 | 175.41 (5) | C36—C31—P | 121.33 (15) |
O1—Rh—N2 | 98.36 (5) | C32—C31—P | 119.58 (14) |
O2—Rh—N2 | 78.32 (5) | C14—C13—C12 | 130.19 (19) |
O1—Rh—N1 | 78.62 (5) | C14—C13—H13 | 114.9 |
O2—Rh—N1 | 104.41 (5) | C12—C13—H13 | 114.9 |
N2—Rh—N1 | 174.43 (5) | O1—C11—C17 | 117.59 (16) |
O1—Rh—P | 90.79 (3) | O1—C11—C12 | 116.25 (15) |
O2—Rh—P | 92.63 (4) | C17—C11—C12 | 126.09 (15) |
N2—Rh—P | 94.69 (4) | C44—C45—C46 | 120.07 (18) |
N1—Rh—P | 90.06 (4) | C44—C45—H45 | 120.0 |
O1—Rh—Cl | 89.39 (3) | C46—C45—H45 | 120.0 |
O2—Rh—Cl | 87.39 (4) | C224—C223—C222 | 118.55 (17) |
N2—Rh—Cl | 89.02 (4) | C224—C223—H223 | 120.7 |
N1—Rh—Cl | 86.27 (4) | C222—C223—H223 | 120.7 |
P—Rh—Cl | 176.222 (15) | C33—C32—C31 | 120.28 (18) |
C31—P—C51 | 106.84 (8) | C33—C32—H32 | 119.9 |
C31—P—C41 | 107.47 (8) | C31—C32—H32 | 119.9 |
C51—P—C41 | 99.36 (8) | C54—C55—C56 | 120.3 (2) |
C31—P—Rh | 110.08 (6) | C54—C55—H55 | 119.8 |
C51—P—Rh | 115.27 (6) | C56—C55—H55 | 119.8 |
C41—P—Rh | 116.88 (6) | C16—C15—C14 | 126.52 (19) |
C21—O2—Rh | 115.43 (11) | C16—C15—H15 | 116.7 |
C11—O1—Rh | 116.17 (11) | C14—C15—H15 | 116.7 |
C12—N1—C111 | 121.24 (14) | C35—C36—C31 | 120.2 (2) |
C12—N1—Rh | 114.11 (11) | C35—C36—H36 | 119.9 |
C111—N1—Rh | 123.71 (11) | C31—C36—H36 | 119.9 |
C22—N2—C221 | 121.41 (14) | C25—C26—C27 | 129.62 (18) |
C22—N2—Rh | 116.04 (11) | C25—C26—H26 | 115.2 |
C221—N2—Rh | 121.79 (11) | C27—C26—H26 | 115.2 |
C42—C41—C46 | 118.87 (16) | C15—C16—C17 | 129.42 (19) |
C42—C41—P | 124.62 (14) | C15—C16—H16 | 115.3 |
C46—C41—P | 116.38 (13) | C17—C16—H16 | 115.3 |
O2—C21—C27 | 117.17 (16) | C224—C225—C226 | 118.08 (17) |
O2—C21—C22 | 115.86 (15) | C224—C225—H225 | 121.0 |
C27—C21—C22 | 126.89 (16) | C226—C225—H225 | 121.0 |
C225—C226—C221 | 120.30 (16) | C11—C17—C16 | 130.78 (18) |
C225—C226—H226 | 119.9 | C11—C17—H17 | 114.6 |
C221—C226—H226 | 119.9 | C16—C17—H17 | 114.6 |
C23—C24—C25 | 130.34 (18) | C44—C43—C42 | 120.41 (18) |
C23—C24—H24 | 114.8 | C44—C43—H43 | 119.8 |
C25—C24—H24 | 114.8 | C42—C43—H43 | 119.8 |
C115—C116—C111 | 119.92 (18) | C13—C14—C15 | 130.39 (19) |
C115—C116—H116 | 120.0 | C13—C14—H14 | 114.8 |
C111—C116—H116 | 120.0 | C15—C14—H14 | 114.8 |
N1—C12—C13 | 122.74 (16) | C221—C222—C223 | 119.97 (17) |
N1—C12—C11 | 113.09 (14) | C221—C222—H222 | 120.0 |
C13—C12—C11 | 123.96 (16) | C223—C222—H222 | 120.0 |
C26—C25—C24 | 126.70 (17) | C55—C54—C53 | 120.14 (19) |
C26—C25—H25 | 116.6 | C55—C54—H54 | 119.9 |
C24—C25—H25 | 116.6 | C53—C54—H54 | 119.9 |
C45—C46—C41 | 120.61 (17) | C35—C34—C33 | 120.3 (2) |
C45—C46—H46 | 119.7 | C35—C34—H34 | 119.8 |
C41—C46—H46 | 119.7 | C33—C34—H34 | 119.8 |
C21—C27—C26 | 130.54 (18) | C43—C44—C45 | 119.78 (17) |
C21—C27—H27 | 114.7 | C43—C44—H44 | 120.1 |
C26—C27—H27 | 114.7 | C45—C44—H44 | 120.1 |
N2—C22—C23 | 122.05 (16) | F14—C114—C113 | 118.4 (2) |
N2—C22—C21 | 113.11 (15) | F14—C114—C115 | 118.8 (2) |
C23—C22—C21 | 124.78 (16) | C113—C114—C115 | 122.80 (19) |
C55—C56—C51 | 120.1 (2) | C114—C113—C112 | 118.70 (19) |
C55—C56—H56 | 119.9 | C114—C113—H113 | 120.7 |
C51—C56—H56 | 119.9 | C112—C113—H113 | 120.7 |
C24—C23—C22 | 130.33 (18) | C113—C112—C111 | 119.88 (19) |
C24—C23—H23 | 114.8 | C113—C112—H112 | 120.1 |
C22—C23—H23 | 114.8 | C111—C112—H112 | 120.1 |
C43—C42—C41 | 120.25 (17) | C116—C111—C112 | 119.95 (17) |
C43—C42—H42 | 119.9 | C116—C111—N1 | 118.97 (16) |
C41—C42—H42 | 119.9 | C112—C111—N1 | 120.87 (17) |
F24—C224—C223 | 118.36 (17) | C34—C35—C36 | 120.3 (2) |
F24—C224—C225 | 118.60 (17) | C34—C35—H35 | 119.9 |
C223—C224—C225 | 123.04 (17) | C36—C35—H35 | 119.9 |
C51—C52—C53 | 119.88 (19) | C114—C115—C116 | 118.7 (2) |
C51—C52—H52 | 120.1 | C114—C115—H115 | 120.6 |
C53—C52—H52 | 120.1 | C116—C115—H115 | 120.6 |
C52—C51—C56 | 119.27 (17) | C34—C33—C32 | 119.8 (2) |
C52—C51—P | 120.79 (14) | C34—C33—H33 | 120.1 |
C56—C51—P | 119.46 (15) | C32—C33—H33 | 120.1 |
C222—C221—C226 | 120.02 (16) | C54—C53—C52 | 120.2 (2) |
C222—C221—N2 | 120.75 (15) | C54—C53—H53 | 119.9 |
C226—C221—N2 | 119.22 (15) | C52—C53—H53 | 119.9 |
C36—C31—C32 | 118.92 (17) | ||
O1—Rh—P—C31 | −10.46 (7) | C41—P—C51—C52 | 98.78 (15) |
O2—Rh—P—C31 | 172.59 (7) | Rh—P—C51—C52 | −26.99 (16) |
N2—Rh—P—C31 | −108.92 (8) | C31—P—C51—C56 | 38.42 (16) |
N1—Rh—P—C31 | 68.16 (8) | C41—P—C51—C56 | −73.15 (15) |
O1—Rh—P—C51 | −131.37 (7) | Rh—P—C51—C56 | 161.08 (12) |
O2—Rh—P—C51 | 51.68 (7) | C225—C226—C221—C222 | −2.0 (3) |
N2—Rh—P—C51 | 130.17 (7) | C225—C226—C221—N2 | 178.53 (16) |
N1—Rh—P—C51 | −52.75 (7) | C22—N2—C221—C222 | 74.0 (2) |
O1—Rh—P—C41 | 112.47 (7) | Rh—N2—C221—C222 | −116.35 (15) |
O2—Rh—P—C41 | −64.48 (7) | C22—N2—C221—C226 | −106.50 (18) |
N2—Rh—P—C41 | 14.01 (8) | Rh—N2—C221—C226 | 63.10 (19) |
N1—Rh—P—C41 | −168.91 (8) | C51—P—C31—C36 | 25.98 (17) |
N2—Rh—O2—C21 | 7.17 (11) | C41—P—C31—C36 | 131.85 (15) |
N1—Rh—O2—C21 | −167.84 (11) | Rh—P—C31—C36 | −99.86 (14) |
P—Rh—O2—C21 | 101.42 (11) | C51—P—C31—C32 | −158.86 (14) |
Cl—Rh—O2—C21 | −82.36 (11) | C41—P—C31—C32 | −53.00 (16) |
N2—Rh—O1—C11 | −172.10 (11) | Rh—P—C31—C32 | 75.29 (15) |
N1—Rh—O1—C11 | 3.14 (11) | N1—C12—C13—C14 | −171.02 (18) |
P—Rh—O1—C11 | 93.05 (11) | C11—C12—C13—C14 | 14.7 (3) |
Cl—Rh—O1—C11 | −83.18 (11) | Rh—O1—C11—C17 | −173.25 (12) |
O1—Rh—N1—C12 | −10.19 (11) | Rh—O1—C11—C12 | 3.86 (18) |
O2—Rh—N1—C12 | 166.28 (11) | N1—C12—C11—O1 | −12.5 (2) |
P—Rh—N1—C12 | −100.98 (12) | C13—C12—C11—O1 | 162.26 (16) |
Cl—Rh—N1—C12 | 79.95 (12) | N1—C12—C11—C17 | 164.28 (16) |
O1—Rh—N1—C111 | −179.21 (14) | C13—C12—C11—C17 | −20.9 (3) |
O2—Rh—N1—C111 | −2.74 (14) | C41—C46—C45—C44 | −0.9 (3) |
P—Rh—N1—C111 | 90.00 (13) | F24—C224—C223—C222 | 178.37 (17) |
Cl—Rh—N1—C111 | −89.08 (13) | C225—C224—C223—C222 | −0.8 (3) |
O1—Rh—N2—C22 | 166.48 (12) | C36—C31—C32—C33 | −4.3 (3) |
O2—Rh—N2—C22 | −10.30 (12) | P—C31—C32—C33 | −179.58 (15) |
P—Rh—N2—C22 | −102.03 (12) | C51—C56—C55—C54 | −0.7 (3) |
Cl—Rh—N2—C22 | 77.23 (12) | C32—C31—C36—C35 | 3.7 (3) |
O1—Rh—N2—C221 | −3.65 (13) | P—C31—C36—C35 | 178.93 (15) |
O2—Rh—N2—C221 | 179.57 (13) | C24—C25—C26—C27 | −1.3 (4) |
P—Rh—N2—C221 | 87.84 (12) | C21—C27—C26—C25 | 2.1 (4) |
Cl—Rh—N2—C221 | −92.90 (12) | C14—C15—C16—C17 | −1.7 (4) |
C31—P—C41—C42 | 1.24 (17) | F24—C224—C225—C226 | −179.86 (16) |
C51—P—C41—C42 | 112.31 (16) | C223—C224—C225—C226 | −0.7 (3) |
Rh—P—C41—C42 | −123.03 (14) | C221—C226—C225—C224 | 2.1 (3) |
C31—P—C41—C46 | −174.68 (13) | O1—C11—C17—C16 | −172.75 (18) |
C51—P—C41—C46 | −63.60 (15) | C12—C11—C17—C16 | 10.5 (3) |
Rh—P—C41—C46 | 61.05 (14) | C15—C16—C17—C11 | 2.9 (4) |
Rh—O2—C21—C27 | 179.52 (12) | C41—C42—C43—C44 | 0.0 (3) |
Rh—O2—C21—C22 | −3.39 (18) | C12—C13—C14—C15 | 1.2 (4) |
C111—N1—C12—C13 | 9.2 (3) | C16—C15—C14—C13 | −6.3 (4) |
Rh—N1—C12—C13 | −160.07 (13) | C226—C221—C222—C223 | 0.5 (3) |
C111—N1—C12—C11 | −175.88 (15) | N2—C221—C222—C223 | 179.92 (16) |
Rh—N1—C12—C11 | 14.80 (18) | C224—C223—C222—C221 | 0.9 (3) |
C23—C24—C25—C26 | −4.6 (3) | C56—C55—C54—C53 | −0.8 (3) |
C42—C41—C46—C45 | 1.6 (3) | C42—C43—C44—C45 | 0.7 (3) |
P—C41—C46—C45 | 177.74 (14) | C46—C45—C44—C43 | −0.2 (3) |
O2—C21—C27—C26 | −177.45 (18) | F14—C114—C113—C112 | −178.12 (19) |
C22—C21—C27—C26 | 5.8 (3) | C115—C114—C113—C112 | 0.6 (3) |
C221—N2—C22—C23 | 4.2 (2) | C114—C113—C112—C111 | −1.4 (3) |
Rh—N2—C22—C23 | −166.00 (12) | C115—C116—C111—C112 | 0.1 (3) |
C221—N2—C22—C21 | −178.46 (14) | C115—C116—C111—N1 | −174.69 (17) |
Rh—N2—C22—C21 | 11.38 (18) | C113—C112—C111—C116 | 1.1 (3) |
O2—C21—C22—N2 | −5.2 (2) | C113—C112—C111—N1 | 175.79 (17) |
C27—C21—C22—N2 | 171.53 (17) | C12—N1—C111—C116 | −126.67 (18) |
O2—C21—C22—C23 | 172.07 (15) | Rh—N1—C111—C116 | 41.6 (2) |
C27—C21—C22—C23 | −11.2 (3) | C12—N1—C111—C112 | 58.6 (2) |
C25—C24—C23—C22 | 3.1 (3) | Rh—N1—C111—C112 | −133.17 (15) |
N2—C22—C23—C24 | −176.69 (17) | C33—C34—C35—C36 | −1.8 (3) |
C21—C22—C23—C24 | 6.3 (3) | C31—C36—C35—C34 | −0.7 (3) |
C46—C41—C42—C43 | −1.1 (3) | F14—C114—C115—C116 | 179.30 (19) |
P—C41—C42—C43 | −176.91 (13) | C113—C114—C115—C116 | 0.6 (3) |
C53—C52—C51—C56 | −1.5 (3) | C111—C116—C115—C114 | −0.9 (3) |
C53—C52—C51—P | −173.49 (14) | C35—C34—C33—C32 | 1.2 (3) |
C55—C56—C51—C52 | 1.9 (3) | C31—C32—C33—C34 | 1.9 (3) |
C55—C56—C51—P | 173.95 (14) | C55—C54—C53—C52 | 1.1 (3) |
C31—P—C51—C52 | −149.65 (14) | C51—C52—C53—C54 | 0.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C116—H116···Cl | 0.95 | 2.83 | 3.579 (2) | 137 |
C17—H17···F14i | 0.95 | 2.39 | 3.325 (2) | 167 |
C27—H27···F24ii | 0.95 | 2.63 | 3.541 (2) | 162 |
Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | [Rh(C13H9NOF)2Cl(C18H15P)] |
Mr | 829.05 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 9.4681 (4), 10.5333 (5), 19.5749 (9) |
α, β, γ (°) | 100.552 (2), 91.904 (2), 107.430 (2) |
V (Å3) | 1822.98 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.35 × 0.35 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.808, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 50714, 7924, 7289 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.064, 1.05 |
No. of reflections | 7924 |
No. of parameters | 478 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.63 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg Putz, 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
C116—H116···Cl | 0.95 | 2.83 | 3.579 (2) | 137.0 |
C17—H17···F14i | 0.95 | 2.39 | 3.325 (2) | 167.3 |
C27—H27···F24ii | 0.95 | 2.63 | 3.541 (2) | 162.2 |
Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y−1, z. |
Rhodium(III) complexes play a vital role in catalytic processes applied in industry today (Crous et al., 2005; Otto & Roodt, 2004), with rhodium systems being investigated for a wide variety of catalytic activities (Roodt et al., 2003; Otto & Roodt, 2002). The title complex, (I), is a possible by-product in these systems where diketonato or acetato ligands might be in use. A similar system have been reported for O,O-diketonato Rh(III) complexes (Das et al., 2002), however the coordination mode differs with one of the diketonato oxygen atoms coordinated via an apical position. The title complex is the first example of a N,O-bidentate Rh(III) complex with a triphenylphosphane and halogen moiety, see Fig. 1.
The distortion of the octahedral geometry about the Rh(III) metal centre can be observed from the slight deviation from linearity of the O—Rh—O and N—Rh—N bond angles of the complex, see Table 1. A significant distortion of the cycloheptatriene moeities is observed as these units are twisted away from the apical triphenylphosphane ligand. The distortion of the seven membered rings are also evidant in the torsion angles of the bidentate ligand, Table 1, which differ by 7 ° for the respective units. The free ligand had a similar but smaller torsional change for the O—C—C—N unit (Steyl, 2007).
The effect of weak intra- and intermolecular interactions play a significant role in determining the packing mode of the title complex. Weak intra- and intermolecular hydrogen bonds are formed in the system with the halogen atoms contributing to the solid state ordering, see Table 2. Intercalation is observed between symmetry associated cycloheptatriene rings; C11···C17 and C11···C17 [-x, 1 - y, -z] and C21···C27 and C21···C27 [-x, 1 - y, 1 - z], in the order of 3.282 (2) and 3.534 (6) Å respectively.