Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104011102/fa1061sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104011102/fa1061Isup2.hkl |
CCDC reference: 245856
The title compound, (I), was synthesized by dissolving [Rh(TropNO2)(CO)2] (10 mg, 0.031 mmol) in the minimum amount of hexane (40 ml), adding 1.1 equivalents of PPh3 (9 mg, 0.034) and allowing crystallization to occur under slow evaporation (ca 1 d). νCO: 1983 cm−1; 1H NMR (CDCl3, 300 MHz): 8.2 (m); 31P NMR (CDCl3, 121.497 MHz): 49.197 (d) 1J(Rh—P) 173.9 Hz.
All H atoms were positioned geometrically (C—H = 0.93 Å) and allowed to ride on their parent atoms, with Uiso(H) values of 1.2Ueq of the parent atom.
Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus and XPREP (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: SHELXL97.
[Rh(C7H4NO4)(C18H15P)(CO)] | Z = 2 |
Mr = 559.30 | F(000) = 564 |
Triclinic, P1 | Dx = 1.592 Mg m−3 Dm = 1.60 Mg m−3 Dm measured by Flotation in aqueous KI |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 9.3078 (19) Å | Cell parameters from 1631 reflections |
b = 10.329 (2) Å | θ = 2–21° |
c = 12.898 (3) Å | µ = 0.84 mm−1 |
α = 93.51 (3)° | T = 293 K |
β = 105.33 (3)° | Plate, brown |
γ = 100.75 (3)° | 0.17 × 0.11 × 0.05 mm |
V = 1166.9 (5) Å3 |
Brukr SMART CCD 1K area detector diffractometer | 3988 independent reflections |
Radiation source: fine-focus sealed tube | 2582 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 8.5 pixels mm-1 | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −12→8 |
Tmin = 0.871, Tmax = 0.959 | l = −15→15 |
7136 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0469P)2] where P = (Fo2 + 2Fc2)/3 |
3988 reflections | (Δ/σ)max = 0.002 |
307 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.59 e Å−3 |
[Rh(C7H4NO4)(C18H15P)(CO)] | γ = 100.75 (3)° |
Mr = 559.30 | V = 1166.9 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.3078 (19) Å | Mo Kα radiation |
b = 10.329 (2) Å | µ = 0.84 mm−1 |
c = 12.898 (3) Å | T = 293 K |
α = 93.51 (3)° | 0.17 × 0.11 × 0.05 mm |
β = 105.33 (3)° |
Brukr SMART CCD 1K area detector diffractometer | 3988 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 2582 reflections with I > 2σ(I) |
Tmin = 0.871, Tmax = 0.959 | Rint = 0.050 |
7136 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.55 e Å−3 |
3988 reflections | Δρmin = −0.59 e Å−3 |
307 parameters |
Experimental. First 80 frames repeated after collection for monitoring possible decay. |
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 | 0.67529 (5) | 0.03586 (4) | 0.72435 (4) | 0.04218 (18) | |
P1 | 0.79140 (15) | 0.22016 (13) | 0.83881 (11) | 0.0360 (3) | |
O12 | 0.5576 (5) | −0.1251 (4) | 0.6111 (3) | 0.0623 (11) | |
O11 | 0.4530 (4) | 0.0629 (4) | 0.6871 (3) | 0.0540 (10) | |
C31 | 0.7541 (6) | 0.3714 (5) | 0.7798 (4) | 0.0397 (13) | |
O01 | 0.9579 (5) | −0.0657 (4) | 0.7787 (5) | 0.0920 (16) | |
C11 | 0.9984 (6) | 0.2449 (5) | 0.8844 (4) | 0.0373 (13) | |
C26 | 0.6957 (6) | 0.1187 (5) | 1.0091 (4) | 0.0494 (15) | |
H26 | 0.6895 | 0.0363 | 0.9730 | 0.059* | |
C16 | 1.0790 (6) | 0.2496 (6) | 0.9905 (5) | 0.0531 (16) | |
H16 | 1.0286 | 0.2468 | 1.0440 | 0.064* | |
C01 | 0.8490 (7) | −0.0204 (6) | 0.7566 (5) | 0.0601 (17) | |
C1 | 0.3522 (7) | −0.0335 (5) | 0.6287 (4) | 0.0474 (14) | |
C32 | 0.8688 (6) | 0.4798 (5) | 0.7821 (4) | 0.0489 (15) | |
H32 | 0.9695 | 0.4781 | 0.8168 | 0.059* | |
C21 | 0.7379 (5) | 0.2333 (5) | 0.9647 (4) | 0.0399 (13) | |
C22 | 0.7433 (6) | 0.3544 (6) | 1.0182 (4) | 0.0482 (15) | |
H22 | 0.7701 | 0.4319 | 0.9882 | 0.058* | |
C33 | 0.8349 (7) | 0.5906 (5) | 0.7334 (5) | 0.0556 (16) | |
H33 | 0.9123 | 0.6630 | 0.7355 | 0.067* | |
C12 | 1.0781 (6) | 0.2508 (5) | 0.8069 (5) | 0.0536 (16) | |
H12 | 1.0249 | 0.2471 | 0.7344 | 0.064* | |
C36 | 0.6041 (6) | 0.3766 (6) | 0.7272 (4) | 0.0501 (15) | |
H36 | 0.5259 | 0.3043 | 0.7237 | 0.060* | |
C25 | 0.6627 (7) | 0.1272 (7) | 1.1080 (5) | 0.0660 (19) | |
H25 | 0.6363 | 0.0502 | 1.1386 | 0.079* | |
C6 | 0.0698 (8) | −0.1302 (7) | 0.5591 (5) | 0.0720 (19) | |
H6 | −0.0223 | −0.1091 | 0.5614 | 0.086* | |
C5 | 0.0570 (9) | −0.2485 (7) | 0.5033 (5) | 0.067 (2) | |
O52 | −0.1209 (7) | −0.4346 (6) | 0.4023 (5) | 0.121 (2) | |
C3 | 0.3247 (8) | −0.2565 (6) | 0.5166 (4) | 0.0625 (18) | |
H3 | 0.3813 | −0.3099 | 0.4914 | 0.075* | |
O51 | −0.2082 (8) | −0.2774 (8) | 0.4646 (6) | 0.135 (3) | |
N5 | −0.1016 (9) | −0.3272 (8) | 0.4540 (5) | 0.092 (2) | |
C7 | 0.1975 (7) | −0.0355 (6) | 0.6134 (5) | 0.0641 (17) | |
H7 | 0.1771 | 0.0398 | 0.6452 | 0.077* | |
C15 | 1.2361 (7) | 0.2586 (7) | 1.0190 (5) | 0.072 (2) | |
H15 | 1.2901 | 0.2605 | 1.0911 | 0.087* | |
C13 | 1.2325 (7) | 0.2619 (6) | 0.8346 (6) | 0.0618 (17) | |
H13 | 1.2837 | 0.2677 | 0.7816 | 0.074* | |
C24 | 0.6688 (8) | 0.2468 (7) | 1.1601 (5) | 0.0661 (18) | |
H24 | 0.6454 | 0.2512 | 1.2258 | 0.079* | |
C4 | 0.1689 (9) | −0.3047 (7) | 0.4814 (5) | 0.070 (2) | |
H4 | 0.1364 | −0.3853 | 0.4373 | 0.085* | |
C2 | 0.4129 (8) | −0.1408 (5) | 0.5840 (4) | 0.0503 (15) | |
C14 | 1.3106 (7) | 0.2645 (7) | 0.9400 (6) | 0.072 (2) | |
H14 | 1.4154 | 0.2703 | 0.9588 | 0.087* | |
C23 | 0.7090 (7) | 0.3615 (6) | 1.1170 (5) | 0.0591 (17) | |
H23 | 0.7133 | 0.4434 | 1.1534 | 0.071* | |
C34 | 0.6858 (8) | 0.5925 (6) | 0.6819 (5) | 0.0605 (17) | |
H34 | 0.6630 | 0.6658 | 0.6477 | 0.073* | |
C35 | 0.5703 (7) | 0.4875 (6) | 0.6805 (5) | 0.0595 (17) | |
H35 | 0.4696 | 0.4913 | 0.6480 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh | 0.0440 (3) | 0.0401 (3) | 0.0419 (3) | 0.0078 (2) | 0.0126 (2) | 0.00090 (19) |
P1 | 0.0310 (8) | 0.0376 (8) | 0.0399 (8) | 0.0056 (6) | 0.0117 (7) | 0.0051 (6) |
O12 | 0.059 (3) | 0.055 (3) | 0.064 (3) | 0.015 (2) | 0.006 (2) | −0.016 (2) |
O11 | 0.045 (2) | 0.046 (2) | 0.063 (3) | 0.010 (2) | 0.004 (2) | −0.007 (2) |
C31 | 0.042 (3) | 0.041 (3) | 0.038 (3) | 0.008 (3) | 0.015 (3) | 0.000 (3) |
O01 | 0.063 (3) | 0.063 (3) | 0.153 (5) | 0.027 (3) | 0.028 (3) | 0.005 (3) |
C11 | 0.032 (3) | 0.038 (3) | 0.040 (3) | 0.004 (2) | 0.010 (3) | 0.001 (3) |
C26 | 0.057 (4) | 0.038 (3) | 0.053 (4) | 0.003 (3) | 0.019 (3) | 0.011 (3) |
C16 | 0.039 (4) | 0.074 (4) | 0.050 (4) | 0.017 (3) | 0.017 (3) | 0.004 (3) |
C01 | 0.057 (4) | 0.042 (4) | 0.083 (5) | 0.012 (3) | 0.021 (4) | −0.003 (3) |
C1 | 0.045 (4) | 0.041 (4) | 0.046 (3) | 0.004 (3) | −0.001 (3) | 0.007 (3) |
C32 | 0.044 (4) | 0.047 (4) | 0.054 (4) | 0.007 (3) | 0.014 (3) | 0.005 (3) |
C21 | 0.026 (3) | 0.048 (4) | 0.043 (3) | 0.000 (2) | 0.010 (3) | 0.005 (3) |
C22 | 0.048 (4) | 0.044 (4) | 0.053 (4) | −0.001 (3) | 0.025 (3) | 0.004 (3) |
C33 | 0.063 (4) | 0.037 (4) | 0.065 (4) | 0.002 (3) | 0.018 (4) | 0.008 (3) |
C12 | 0.037 (3) | 0.064 (4) | 0.060 (4) | 0.006 (3) | 0.016 (3) | 0.014 (3) |
C36 | 0.038 (3) | 0.054 (4) | 0.057 (4) | 0.008 (3) | 0.014 (3) | 0.006 (3) |
C25 | 0.084 (5) | 0.064 (5) | 0.060 (4) | 0.013 (4) | 0.034 (4) | 0.026 (4) |
C6 | 0.056 (5) | 0.080 (5) | 0.065 (5) | 0.004 (4) | 0.000 (4) | 0.002 (4) |
C5 | 0.073 (5) | 0.070 (5) | 0.033 (4) | −0.022 (4) | −0.005 (4) | 0.013 (4) |
O52 | 0.120 (5) | 0.090 (4) | 0.099 (4) | −0.046 (4) | −0.011 (4) | −0.005 (4) |
C3 | 0.086 (5) | 0.050 (4) | 0.041 (4) | 0.008 (4) | 0.007 (4) | −0.013 (3) |
O51 | 0.076 (5) | 0.164 (7) | 0.125 (6) | −0.044 (5) | 0.010 (4) | −0.006 (5) |
N5 | 0.090 (6) | 0.095 (6) | 0.051 (4) | −0.045 (5) | −0.007 (4) | 0.016 (4) |
C7 | 0.048 (4) | 0.061 (4) | 0.069 (4) | 0.007 (3) | −0.002 (4) | −0.010 (3) |
C15 | 0.049 (4) | 0.103 (6) | 0.059 (4) | 0.023 (4) | 0.002 (4) | 0.004 (4) |
C13 | 0.040 (4) | 0.070 (4) | 0.078 (5) | 0.005 (3) | 0.025 (4) | 0.002 (4) |
C24 | 0.087 (5) | 0.073 (5) | 0.047 (4) | 0.020 (4) | 0.031 (4) | 0.010 (4) |
C4 | 0.094 (6) | 0.053 (4) | 0.035 (4) | −0.020 (4) | −0.004 (4) | −0.008 (3) |
C2 | 0.072 (5) | 0.038 (3) | 0.033 (3) | 0.006 (3) | 0.006 (3) | −0.001 (3) |
C14 | 0.031 (4) | 0.087 (5) | 0.097 (6) | 0.017 (3) | 0.013 (4) | 0.000 (4) |
C23 | 0.065 (4) | 0.057 (4) | 0.055 (4) | 0.006 (3) | 0.023 (3) | −0.008 (3) |
C34 | 0.072 (5) | 0.045 (4) | 0.066 (4) | 0.020 (4) | 0.016 (4) | 0.015 (3) |
C35 | 0.047 (4) | 0.059 (4) | 0.073 (4) | 0.019 (3) | 0.010 (3) | 0.012 (4) |
Rh—C01 | 1.775 (7) | C12—H12 | 0.9300 |
Rh—O12 | 2.068 (4) | C36—C35 | 1.376 (7) |
Rh—O11 | 2.072 (4) | C36—H36 | 0.9300 |
Rh—P1 | 2.2397 (17) | C25—C24 | 1.354 (8) |
P1—C11 | 1.823 (5) | C25—H25 | 0.9300 |
P1—C21 | 1.824 (5) | C6—C5 | 1.349 (9) |
P1—C31 | 1.830 (5) | C6—C7 | 1.379 (8) |
O12—C2 | 1.274 (7) | C6—H6 | 0.9300 |
O11—C1 | 1.275 (6) | C5—C4 | 1.365 (9) |
C31—C32 | 1.388 (7) | C5—N5 | 1.496 (9) |
C31—C36 | 1.395 (7) | O52—N5 | 1.217 (9) |
O01—C01 | 1.170 (6) | C3—C4 | 1.382 (9) |
C11—C16 | 1.369 (7) | C3—C2 | 1.410 (7) |
C11—C12 | 1.391 (7) | C3—H3 | 0.9300 |
C26—C21 | 1.383 (7) | O51—N5 | 1.234 (9) |
C26—C25 | 1.390 (8) | C7—H7 | 0.9300 |
C26—H26 | 0.9300 | C15—C14 | 1.375 (8) |
C16—C15 | 1.393 (7) | C15—H15 | 0.9300 |
C16—H16 | 0.9300 | C13—C14 | 1.357 (8) |
C1—C7 | 1.397 (8) | C13—H13 | 0.9300 |
C1—C2 | 1.486 (8) | C24—C23 | 1.370 (8) |
C32—C33 | 1.386 (7) | C24—H24 | 0.9300 |
C32—H32 | 0.9300 | C4—H4 | 0.9300 |
C21—C22 | 1.377 (7) | C14—H14 | 0.9300 |
C22—C23 | 1.396 (7) | C23—H23 | 0.9300 |
C22—H22 | 0.9300 | C34—C35 | 1.372 (8) |
C33—C34 | 1.375 (8) | C34—H34 | 0.9300 |
C33—H33 | 0.9300 | C35—H35 | 0.9300 |
C12—C13 | 1.367 (7) | ||
C01—Rh—O12 | 94.6 (2) | C31—C36—H36 | 119.6 |
C01—Rh—O11 | 168.7 (2) | C24—C25—C26 | 120.4 (5) |
O12—Rh—O11 | 77.09 (16) | C24—C25—H25 | 119.8 |
C01—Rh—P1 | 89.3 (2) | C26—C25—H25 | 119.8 |
O12—Rh—P1 | 175.38 (13) | C5—C6—C7 | 130.4 (7) |
O11—Rh—P1 | 99.41 (12) | C5—C6—H6 | 114.8 |
C11—P1—C21 | 103.5 (2) | C7—C6—H6 | 114.8 |
C11—P1—C31 | 105.0 (2) | C6—C5—C4 | 128.9 (7) |
C21—P1—C31 | 103.8 (2) | C6—C5—N5 | 116.1 (8) |
C11—P1—Rh | 114.45 (17) | C4—C5—N5 | 114.9 (8) |
C21—P1—Rh | 116.08 (17) | C4—C3—C2 | 131.5 (7) |
C31—P1—Rh | 112.74 (18) | C4—C3—H3 | 114.3 |
C2—O12—Rh | 115.5 (4) | C2—C3—H3 | 114.3 |
C1—O11—Rh | 115.6 (4) | O52—N5—O51 | 122.7 (8) |
C32—C31—C36 | 118.4 (5) | O52—N5—C5 | 119.3 (9) |
C32—C31—P1 | 123.0 (4) | O51—N5—C5 | 117.9 (9) |
C36—C31—P1 | 118.5 (4) | C6—C7—C1 | 130.9 (7) |
C16—C11—C12 | 118.1 (5) | C6—C7—H7 | 114.6 |
C16—C11—P1 | 123.4 (4) | C1—C7—H7 | 114.6 |
C12—C11—P1 | 118.4 (4) | C14—C15—C16 | 119.6 (6) |
C21—C26—C25 | 119.8 (6) | C14—C15—H15 | 120.2 |
C21—C26—H26 | 120.1 | C16—C15—H15 | 120.2 |
C25—C26—H26 | 120.1 | C14—C13—C12 | 119.6 (6) |
C11—C16—C15 | 120.5 (5) | C14—C13—H13 | 120.2 |
C11—C16—H16 | 119.7 | C12—C13—H13 | 120.2 |
C15—C16—H16 | 119.7 | C25—C24—C23 | 120.8 (6) |
O01—C01—Rh | 175.4 (5) | C25—C24—H24 | 119.6 |
O11—C1—C7 | 120.4 (6) | C23—C24—H24 | 119.6 |
O11—C1—C2 | 115.0 (5) | C5—C4—C3 | 127.9 (6) |
C7—C1—C2 | 124.5 (6) | C5—C4—H4 | 116.0 |
C33—C32—C31 | 120.8 (5) | C3—C4—H4 | 116.0 |
C33—C32—H32 | 119.6 | O12—C2—C3 | 118.6 (6) |
C31—C32—H32 | 119.6 | O12—C2—C1 | 115.8 (5) |
C22—C21—C26 | 119.3 (5) | C3—C2—C1 | 125.6 (6) |
C22—C21—P1 | 121.7 (4) | C13—C14—C15 | 120.5 (6) |
C26—C21—P1 | 119.0 (4) | C13—C14—H14 | 119.7 |
C21—C22—C23 | 120.3 (5) | C15—C14—H14 | 119.7 |
C21—C22—H22 | 119.8 | C24—C23—C22 | 119.4 (6) |
C23—C22—H22 | 119.8 | C24—C23—H23 | 120.3 |
C34—C33—C32 | 119.4 (5) | C22—C23—H23 | 120.3 |
C34—C33—H33 | 120.3 | C33—C34—C35 | 120.8 (6) |
C32—C33—H33 | 120.3 | C33—C34—H34 | 119.6 |
C13—C12—C11 | 121.7 (6) | C35—C34—H34 | 119.6 |
C13—C12—H12 | 119.2 | C36—C35—C34 | 119.8 (6) |
C11—C12—H12 | 119.2 | C36—C35—H35 | 120.1 |
C35—C36—C31 | 120.7 (5) | C34—C35—H35 | 120.1 |
C35—C36—H36 | 119.6 | ||
C01—Rh—P1—C11 | 12.3 (3) | P1—C21—C22—C23 | −176.8 (4) |
O11—Rh—P1—C11 | −175.0 (2) | C31—C32—C33—C34 | −0.2 (9) |
C01—Rh—P1—C21 | −108.2 (3) | C16—C11—C12—C13 | −0.5 (8) |
O11—Rh—P1—C21 | 64.5 (2) | P1—C11—C12—C13 | −176.4 (5) |
C01—Rh—P1—C31 | 132.2 (3) | C32—C31—C36—C35 | −1.1 (8) |
O11—Rh—P1—C31 | −55.0 (2) | P1—C31—C36—C35 | −179.3 (4) |
C01—Rh—O12—C2 | 164.2 (4) | C21—C26—C25—C24 | 1.3 (10) |
O11—Rh—O12—C2 | −8.1 (4) | C7—C6—C5—C4 | −3.2 (12) |
C01—Rh—O11—C1 | −34.3 (13) | C7—C6—C5—N5 | 180.0 (6) |
O12—Rh—O11—C1 | 9.0 (3) | C6—C5—N5—O52 | 179.7 (6) |
P1—Rh—O11—C1 | −174.1 (3) | C4—C5—N5—O52 | 2.4 (9) |
C11—P1—C31—C32 | −4.6 (5) | C6—C5—N5—O51 | 2.2 (9) |
C21—P1—C31—C32 | 103.7 (5) | C4—C5—N5—O51 | −175.1 (7) |
Rh—P1—C31—C32 | −129.8 (4) | C5—C6—C7—C1 | −1.1 (12) |
C11—P1—C31—C36 | 173.5 (4) | O11—C1—C7—C6 | −176.5 (6) |
C21—P1—C31—C36 | −78.2 (5) | C2—C1—C7—C6 | 1.3 (10) |
Rh—P1—C31—C36 | 48.2 (5) | C11—C16—C15—C14 | 0.9 (10) |
C21—P1—C11—C16 | 9.1 (5) | C11—C12—C13—C14 | 1.4 (9) |
C31—P1—C11—C16 | 117.6 (5) | C26—C25—C24—C23 | −0.7 (10) |
Rh—P1—C11—C16 | −118.2 (4) | C6—C5—C4—C3 | 4.0 (11) |
C21—P1—C11—C12 | −175.2 (4) | N5—C5—C4—C3 | −179.1 (6) |
C31—P1—C11—C12 | −66.7 (5) | C2—C3—C4—C5 | 0.9 (11) |
Rh—P1—C11—C12 | 57.5 (4) | Rh—O12—C2—C3 | −172.9 (4) |
C12—C11—C16—C15 | −0.7 (8) | Rh—O12—C2—C1 | 6.3 (6) |
P1—C11—C16—C15 | 175.0 (5) | C4—C3—C2—O12 | 174.4 (6) |
Rh—O11—C1—C7 | 169.5 (4) | C4—C3—C2—C1 | −4.8 (10) |
Rh—O11—C1—C2 | −8.5 (6) | O11—C1—C2—O12 | 1.5 (7) |
C36—C31—C32—C33 | 0.0 (8) | C7—C1—C2—O12 | −176.4 (5) |
P1—C31—C32—C33 | 178.1 (4) | O11—C1—C2—C3 | −179.3 (5) |
C25—C26—C21—C22 | −1.4 (8) | C7—C1—C2—C3 | 2.7 (9) |
C25—C26—C21—P1 | 176.5 (4) | C12—C13—C14—C15 | −1.3 (10) |
C11—P1—C21—C22 | 82.7 (5) | C16—C15—C14—C13 | 0.1 (10) |
C31—P1—C21—C22 | −26.7 (5) | C25—C24—C23—C22 | 0.3 (10) |
Rh—P1—C21—C22 | −151.0 (4) | C21—C22—C23—C24 | −0.4 (9) |
C11—P1—C21—C26 | −95.1 (4) | C32—C33—C34—C35 | 1.5 (9) |
C31—P1—C21—C26 | 155.4 (4) | C31—C36—C35—C34 | 2.4 (9) |
Rh—P1—C21—C26 | 31.1 (5) | C33—C34—C35—C36 | −2.6 (10) |
C26—C21—C22—C23 | 1.0 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C36—H36···O11 | 0.93 | 2.44 | 3.234 (7) | 143 |
C6—H6···O51 | 0.93 | 2.25 | 2.671 (9) | 107 |
C4—H4···O52 | 0.93 | 2.27 | 2.673 (9) | 106 |
C33—H33···O01i | 0.93 | 2.75 | 3.483 (7) | 136 |
C34—H34···O12i | 0.93 | 2.55 | 3.438 (7) | 159 |
C34—H34···O51ii | 0.93 | 2.96 | 3.473 (9) | 116 |
C6—H6···O01iii | 0.93 | 2.87 | 3.337 (9) | 112 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Rh(C7H4NO4)(C18H15P)(CO)] |
Mr | 559.30 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.3078 (19), 10.329 (2), 12.898 (3) |
α, β, γ (°) | 93.51 (3), 105.33 (3), 100.75 (3) |
V (Å3) | 1166.9 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.84 |
Crystal size (mm) | 0.17 × 0.11 × 0.05 |
Data collection | |
Diffractometer | Brukr SMART CCD 1K area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.871, 0.959 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7136, 3988, 2582 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.107, 1.00 |
No. of reflections | 3988 |
No. of parameters | 307 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.59 |
Computer programs: SMART-NT (Bruker, 1998), SAINT-Plus (Bruker, 1999), SAINT-Plus and XPREP (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg & Berndt, 2001), SHELXL97.
Rh—C01 | 1.775 (7) | O11—C1 | 1.275 (6) |
Rh—O12 | 2.068 (4) | O01—C01 | 1.170 (6) |
Rh—O11 | 2.072 (4) | C5—N5 | 1.496 (9) |
Rh—P1 | 2.2397 (17) | O52—N5 | 1.217 (9) |
O12—C2 | 1.274 (7) | O51—N5 | 1.234 (9) |
C01—Rh—O12 | 94.6 (2) | O12—Rh—P1 | 175.38 (13) |
C01—Rh—O11 | 168.7 (2) | O11—Rh—P1 | 99.41 (12) |
O12—Rh—O11 | 77.09 (16) | O01—C01—Rh | 175.4 (5) |
C01—Rh—P1 | 89.3 (2) | O52—N5—O51 | 122.7 (8) |
C4—C5—N5—O52 | 2.4 (9) | O11—C1—C2—O12 | 1.5 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C36—H36···O11 | 0.93 | 2.44 | 3.234 (7) | 143 |
C6—H6···O51 | 0.93 | 2.25 | 2.671 (9) | 107 |
C4—H4···O52 | 0.93 | 2.27 | 2.673 (9) | 106 |
C33—H33···O01i | 0.93 | 2.75 | 3.483 (7) | 136 |
C34—H34···O12i | 0.93 | 2.55 | 3.438 (7) | 159 |
C34—H34···O51ii | 0.93 | 2.96 | 3.473 (9) | 116 |
C6—H6···O01iii | 0.93 | 2.87 | 3.337 (9) | 112 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z; (iii) x−1, y, z. |
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Although 5-nitrotropolone-type compounds are known for main group elements (Kubo et al., 2001a, 2001b; Dittes et al., 1996), very few transition metal complexes have been investigated to date. As part of our investigation into the role of functionalized tropolones (Steyl & Roodt, 2003) in rhodium(I) complexes, we present the first crystal structure of 5-nitrotropolone to be characterized for a transition group element.
The title compound, (I), crystallizes in the triclinic space group P1, with Rh—O bond distances of 2.072 (4) and 2.068 (4) Å, and an O—Rh—O bite angle of 77.09 (16)°. The effective and Tolman angles observed for the triphenylphosphine ligand, 159 and 155°, respectively, correspond well to observed cone angles (Tolman, 1977; Simanko et al., 2000). The carbonyl C atom is slightly displaced by 0.299 (7) Å above the plane defined by atoms Rh, P1, O12 and O11. The shortest intermolecular contact [H36···H13(x − 1, y, z) = 2.504 (1) Å] illustrates the generally efficient packing in the unit cell. However, high anisotropy is observed for the nitro moiety lying on the periphery of the molecule and is considered to be the result of locally weak packing forces allowing for high flexibility of the nitro group.
Intramolecular hydrogen bonding is observed between the nitro moiety and the troponoid H atoms (C6—H6.·O51 and C4—H4.·O52; see Table 2]. A further weak intramolecular hydrogen-bonding interaction is observed (C36—H36.·O11). A clearly defined bifurcated hydrogen bond is observed [C34—H34···O12(x, 1 + y, z)/O51(1 + x, 1 + y, z)], with the H atom lying in the plane defined by the donor/acceptor atoms (see Fig. 2). The carbonyl O atom is involved in two weak intermolecular hydrogen bonds, C6—H6.·O01(x − 1, y, z) and C33—H33.·O01 (x, 1 + y, z), which might be the cause of the slight deviation from linearity of the Rh—C—O moiety [bond angle = 175.4 (5)°].
Of further interest is the similarity of the Rh—O bond distances (Table 1), in spite of the presence of different trans moieties (P versus CO); this configuration is similar to that? generally observed in square planar rhodium(I) complexes (Leipoldt et al., 1980; Steyl et al., 2001). The distortion from square planar geometry can, in part, be attributed to the strong symmetry observed in the functionalized tropolone (O12—C2 and O11—C1) bond distances (Gilli et al., 1989; Bertolasi et al., 1991), as well as the out-of-plane distortion of the carbonyl moiety (O1/C1/Rh; Table 1). Strong hydrogen-bonding interactions are observed for the PhNO2 group, with closely related torsion angles for the C4—C5—N5—O52 moiety of (I). A host of nitrophenyl compounds have been characterized in the solid state, and of particular interest are the similarities between these nitrophenyl compounds (Andre et al., 1997a; Andre et al., 1997b) and (I) in the nitro moiety conformation, confirming the `aromatic' nature of the troponoid system.
In conclusion, the observed symmetry in the nitrotropolone moiety is attributed to both strong intramolecular and weak intermolecular hydrogen bonding with neighbouring nitrotropolone moieties. This is probably the cause of the distorted square planar geometry at the rhodium metal center.