Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040717/om6278sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040717/om6278Isup2.hkl |
CCDC reference: 296630
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.031
- wR factor = 0.074
- Data-to-parameter ratio = 19.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.04
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 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 0 ALERT type 4 Improvement, methodology, query or suggestion
[Rh(NBD)Cl]2 (NBD = norbornadiene) was kindly provided by Dr A. Muller (University of the Free State). All other chemicals were used as received. A solution of 1,2-bis(diphenylphosphino)ethane (0.50 g, 1.25 mmol) in dichloromethane (5 ml) was slowly added to a solution of [Rh(NBD)Cl]2 (0.145 g, 0.31 mmol) in dichloromethane (5 ml). After stirring for 1 h a solution of NaBPh4 (0.22 g, 0.64 mmol) in ethanol (5 ml) was added. The resulting mixture was stirred for 4 h and filtered. The volatiles were removed in vacuo. The residue was taken up in acetone, filtered, and the solvent was removed in vacuo to give the title compound as a yellow powder. Recrystallization from dichloromethane afforded crystals suitable for X-ray diffraction. All analytical data were in agreement with the literature (Faraone, 1975).
The aromatic and methylene H atoms were placed in geometrically idealized positions (C—H = 0.95 and 0.99 Å, respectively) and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).
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: WinGX (Farrugia, 1999).
[Rh(C26H24P2)2](C24H20B) | F(000) = 2536 |
Mr = 1218.9 | Dx = 1.33 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 977 reflections |
a = 17.010 (2) Å | θ = 2.6–28.2° |
b = 16.560 (2) Å | µ = 0.43 mm−1 |
c = 22.142 (3) Å | T = 173 K |
β = 102.642 (2)° | Cuboid, yellow |
V = 6086.0 (13) Å3 | 0.2 × 0.2 × 0.19 mm |
Z = 4 |
Bruker SMART CCD 1K diffractometer | 5664 reflections with I > 2σ(I) |
ω scans | Rint = 0.037 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | θmax = 28°, θmin = 1.7° |
Tmin = 0.919, Tmax = 0.923 | h = −19→22 |
20334 measured reflections | k = −19→21 |
7320 independent reflections | l = −29→27 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0346P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.074 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.39 e Å−3 |
7320 reflections | Δρmin = −0.37 e Å−3 |
371 parameters |
[Rh(C26H24P2)2](C24H20B) | V = 6086.0 (13) Å3 |
Mr = 1218.9 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.010 (2) Å | µ = 0.43 mm−1 |
b = 16.560 (2) Å | T = 173 K |
c = 22.142 (3) Å | 0.2 × 0.2 × 0.19 mm |
β = 102.642 (2)° |
Bruker SMART CCD 1K diffractometer | 7320 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 5664 reflections with I > 2σ(I) |
Tmin = 0.919, Tmax = 0.923 | Rint = 0.037 |
20334 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.39 e Å−3 |
7320 reflections | Δρmin = −0.37 e Å−3 |
371 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. |
x | y | z | Uiso*/Ueq | ||
Rh | 0.5 | 0.210290 (12) | 0.25 | 0.01656 (6) | |
P1 | 0.60831 (3) | 0.21762 (3) | 0.33360 (2) | 0.01846 (10) | |
P2 | 0.60083 (3) | 0.19785 (3) | 0.19581 (2) | 0.01893 (11) | |
B | 1 | 0.18014 (19) | 0.25 | 0.0239 (7) | |
C1 | 0.70401 (11) | 0.20313 (12) | 0.30841 (8) | 0.0240 (4) | |
H1A | 0.7484 | 0.2307 | 0.3375 | 0.029* | |
H1B | 0.717 | 0.1449 | 0.3081 | 0.029* | |
C2 | 0.69502 (11) | 0.23827 (12) | 0.24348 (8) | 0.0231 (4) | |
H2A | 0.7414 | 0.2224 | 0.2258 | 0.028* | |
H2B | 0.6927 | 0.298 | 0.2449 | 0.028* | |
C11 | 0.62503 (11) | 0.31524 (11) | 0.37331 (8) | 0.0211 (4) | |
C12 | 0.57851 (11) | 0.38199 (11) | 0.35073 (8) | 0.0237 (4) | |
H12 | 0.54 | 0.378 | 0.3127 | 0.028* | |
C13 | 0.58751 (12) | 0.45474 (12) | 0.38305 (9) | 0.0301 (5) | |
H13 | 0.5549 | 0.4999 | 0.3674 | 0.036* | |
C14 | 0.64446 (13) | 0.46082 (13) | 0.43824 (10) | 0.0340 (5) | |
H14 | 0.6501 | 0.5099 | 0.461 | 0.041* | |
C15 | 0.69311 (13) | 0.39566 (13) | 0.46028 (9) | 0.0327 (5) | |
H15 | 0.733 | 0.4005 | 0.4975 | 0.039* | |
C16 | 0.68371 (12) | 0.32331 (12) | 0.42813 (9) | 0.0272 (4) | |
H16 | 0.7174 | 0.2788 | 0.4434 | 0.033* | |
C21 | 0.61418 (11) | 0.14513 (11) | 0.39716 (8) | 0.0202 (4) | |
C22 | 0.58604 (11) | 0.16495 (12) | 0.44973 (8) | 0.0246 (4) | |
H22 | 0.5697 | 0.2188 | 0.4554 | 0.03* | |
C23 | 0.58163 (12) | 0.10643 (13) | 0.49404 (9) | 0.0329 (5) | |
H23 | 0.5622 | 0.1205 | 0.5297 | 0.039* | |
C24 | 0.60530 (13) | 0.02833 (13) | 0.48639 (10) | 0.0358 (5) | |
H24 | 0.6024 | −0.0113 | 0.5169 | 0.043* | |
C25 | 0.63324 (13) | 0.00751 (12) | 0.43453 (10) | 0.0331 (5) | |
H25 | 0.6493 | −0.0465 | 0.4292 | 0.04* | |
C26 | 0.63792 (12) | 0.06543 (12) | 0.39007 (9) | 0.0269 (4) | |
H26 | 0.6574 | 0.0508 | 0.3545 | 0.032* | |
C31 | 0.59659 (10) | 0.24128 (12) | 0.11921 (8) | 0.0205 (4) | |
C32 | 0.60500 (12) | 0.19528 (12) | 0.06835 (8) | 0.0262 (4) | |
H32 | 0.6158 | 0.1391 | 0.0732 | 0.031* | |
C33 | 0.59763 (13) | 0.23108 (13) | 0.01044 (9) | 0.0325 (5) | |
H33 | 0.6044 | 0.1995 | −0.0239 | 0.039* | |
C34 | 0.58051 (13) | 0.31255 (13) | 0.00287 (9) | 0.0340 (5) | |
H34 | 0.5745 | 0.3367 | −0.0368 | 0.041* | |
C35 | 0.57211 (12) | 0.35894 (13) | 0.05311 (9) | 0.0318 (5) | |
H35 | 0.5605 | 0.415 | 0.048 | 0.038* | |
C36 | 0.58072 (11) | 0.32323 (12) | 0.11090 (9) | 0.0251 (4) | |
H36 | 0.5757 | 0.3554 | 0.1454 | 0.03* | |
C41 | 0.62362 (11) | 0.09177 (11) | 0.18519 (8) | 0.0219 (4) | |
C42 | 0.69990 (12) | 0.06444 (13) | 0.18070 (9) | 0.0312 (5) | |
H42 | 0.7439 | 0.1011 | 0.1867 | 0.037* | |
C43 | 0.71161 (13) | −0.01574 (13) | 0.16752 (10) | 0.0351 (5) | |
H43 | 0.7639 | −0.0338 | 0.1651 | 0.042* | |
C44 | 0.64847 (14) | −0.06981 (13) | 0.15781 (9) | 0.0364 (5) | |
H44 | 0.657 | −0.1247 | 0.1484 | 0.044* | |
C45 | 0.57261 (13) | −0.04367 (13) | 0.16181 (10) | 0.0365 (5) | |
H45 | 0.5286 | −0.0803 | 0.1543 | 0.044* | |
C46 | 0.56082 (12) | 0.03631 (12) | 0.17683 (9) | 0.0279 (4) | |
H46 | 0.5091 | 0.0533 | 0.1814 | 0.034* | |
C51 | 0.95218 (11) | 0.12619 (12) | 0.29323 (8) | 0.0268 (4) | |
C52 | 0.91287 (13) | 0.05376 (13) | 0.27359 (10) | 0.0369 (5) | |
H52 | 0.9183 | 0.0315 | 0.2352 | 0.044* | |
C53 | 0.86607 (14) | 0.01280 (15) | 0.30791 (12) | 0.0466 (6) | |
H53 | 0.8397 | −0.0359 | 0.2925 | 0.056* | |
C54 | 0.85794 (14) | 0.04268 (16) | 0.36412 (12) | 0.0487 (7) | |
H54 | 0.827 | 0.0142 | 0.3881 | 0.058* | |
C55 | 0.89486 (13) | 0.11399 (16) | 0.38529 (10) | 0.0437 (6) | |
H55 | 0.8892 | 0.1353 | 0.4239 | 0.052* | |
C56 | 0.94063 (12) | 0.15513 (14) | 0.35026 (9) | 0.0328 (5) | |
H56 | 0.9651 | 0.2048 | 0.3655 | 0.039* | |
C61 | 0.92764 (11) | 0.23343 (12) | 0.20644 (8) | 0.0259 (4) | |
C62 | 0.90545 (13) | 0.31106 (13) | 0.22108 (10) | 0.0354 (5) | |
H62 | 0.9353 | 0.3363 | 0.2575 | 0.043* | |
C63 | 0.84109 (14) | 0.35315 (14) | 0.18439 (12) | 0.0443 (6) | |
H63 | 0.8285 | 0.4061 | 0.1959 | 0.053* | |
C64 | 0.79592 (14) | 0.31836 (16) | 0.13173 (11) | 0.0453 (6) | |
H64 | 0.7528 | 0.3472 | 0.1063 | 0.054* | |
C65 | 0.81422 (13) | 0.24073 (16) | 0.11629 (10) | 0.0408 (6) | |
H65 | 0.7829 | 0.2155 | 0.0805 | 0.049* | |
C66 | 0.87833 (12) | 0.19953 (13) | 0.15305 (9) | 0.0304 (5) | |
H66 | 0.8894 | 0.1461 | 0.1417 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh | 0.01558 (10) | 0.02155 (11) | 0.01242 (10) | 0 | 0.00278 (7) | 0 |
P1 | 0.0175 (2) | 0.0229 (3) | 0.0144 (2) | −0.00038 (19) | 0.00202 (18) | 0.00064 (19) |
P2 | 0.0179 (2) | 0.0243 (3) | 0.0149 (2) | −0.00110 (19) | 0.00441 (18) | 0.00034 (19) |
B | 0.0272 (17) | 0.0238 (16) | 0.0204 (15) | 0 | 0.0045 (13) | 0 |
C1 | 0.0178 (9) | 0.0321 (11) | 0.0219 (9) | 0.0003 (8) | 0.0037 (7) | 0.0009 (8) |
C2 | 0.0201 (10) | 0.0282 (10) | 0.0216 (9) | −0.0027 (8) | 0.0057 (8) | −0.0010 (8) |
C11 | 0.0211 (10) | 0.0244 (10) | 0.0184 (9) | −0.0043 (8) | 0.0057 (7) | 0.0003 (7) |
C12 | 0.0222 (10) | 0.0277 (11) | 0.0208 (9) | −0.0019 (8) | 0.0035 (8) | 0.0013 (8) |
C13 | 0.0305 (12) | 0.0246 (11) | 0.0368 (12) | 0.0004 (9) | 0.0110 (9) | 0.0021 (9) |
C14 | 0.0386 (13) | 0.0290 (12) | 0.0368 (12) | −0.0096 (10) | 0.0133 (10) | −0.0093 (9) |
C15 | 0.0334 (12) | 0.0373 (12) | 0.0252 (10) | −0.0101 (10) | 0.0016 (9) | −0.0058 (9) |
C16 | 0.0256 (11) | 0.0281 (11) | 0.0254 (10) | −0.0025 (8) | 0.0004 (8) | 0.0010 (8) |
C21 | 0.0177 (9) | 0.0228 (10) | 0.0177 (9) | −0.0016 (7) | −0.0013 (7) | 0.0010 (7) |
C22 | 0.0233 (10) | 0.0281 (11) | 0.0219 (9) | 0.0024 (8) | 0.0038 (8) | 0.0035 (8) |
C23 | 0.0322 (12) | 0.0438 (13) | 0.0238 (10) | 0.0023 (10) | 0.0088 (9) | 0.0097 (9) |
C24 | 0.0357 (13) | 0.0342 (13) | 0.0356 (12) | −0.0028 (10) | 0.0036 (10) | 0.0177 (10) |
C25 | 0.0335 (12) | 0.0213 (11) | 0.0403 (12) | −0.0002 (9) | −0.0009 (10) | 0.0042 (9) |
C26 | 0.0267 (11) | 0.0268 (11) | 0.0250 (10) | −0.0019 (8) | 0.0010 (8) | −0.0024 (8) |
C31 | 0.0159 (9) | 0.0288 (10) | 0.0171 (8) | −0.0016 (8) | 0.0045 (7) | 0.0014 (8) |
C32 | 0.0282 (11) | 0.0297 (12) | 0.0214 (9) | −0.0027 (8) | 0.0072 (8) | −0.0015 (8) |
C33 | 0.0380 (12) | 0.0410 (13) | 0.0205 (10) | −0.0050 (10) | 0.0107 (9) | −0.0037 (9) |
C34 | 0.0351 (12) | 0.0464 (14) | 0.0205 (10) | −0.0042 (10) | 0.0060 (9) | 0.0074 (9) |
C35 | 0.0333 (12) | 0.0315 (12) | 0.0300 (11) | 0.0012 (9) | 0.0057 (9) | 0.0078 (9) |
C36 | 0.0237 (10) | 0.0298 (11) | 0.0224 (9) | 0.0001 (8) | 0.0061 (8) | −0.0016 (8) |
C41 | 0.0224 (10) | 0.0249 (10) | 0.0192 (9) | 0.0015 (8) | 0.0059 (8) | 0.0025 (8) |
C42 | 0.0275 (11) | 0.0343 (12) | 0.0346 (11) | 0.0012 (9) | 0.0128 (9) | 0.0003 (9) |
C43 | 0.0321 (12) | 0.0418 (13) | 0.0348 (12) | 0.0107 (10) | 0.0146 (10) | −0.0016 (10) |
C44 | 0.0472 (14) | 0.0281 (12) | 0.0322 (11) | 0.0099 (10) | 0.0051 (10) | −0.0022 (9) |
C45 | 0.0353 (13) | 0.0272 (12) | 0.0428 (13) | −0.0010 (9) | −0.0008 (10) | 0.0019 (10) |
C46 | 0.0245 (11) | 0.0281 (11) | 0.0313 (11) | 0.0029 (8) | 0.0061 (9) | 0.0052 (9) |
C51 | 0.0227 (10) | 0.0305 (11) | 0.0246 (10) | 0.0036 (8) | −0.0008 (8) | 0.0067 (8) |
C52 | 0.0370 (13) | 0.0339 (13) | 0.0357 (12) | −0.0038 (10) | −0.0012 (10) | 0.0090 (10) |
C53 | 0.0367 (14) | 0.0401 (14) | 0.0569 (16) | −0.0065 (11) | −0.0033 (12) | 0.0207 (12) |
C54 | 0.0253 (12) | 0.0616 (17) | 0.0586 (16) | 0.0028 (12) | 0.0078 (11) | 0.0340 (14) |
C55 | 0.0331 (13) | 0.0643 (17) | 0.0360 (12) | 0.0116 (12) | 0.0125 (10) | 0.0160 (12) |
C56 | 0.0261 (11) | 0.0415 (13) | 0.0309 (11) | 0.0045 (9) | 0.0064 (9) | 0.0067 (10) |
C61 | 0.0257 (11) | 0.0310 (11) | 0.0227 (9) | −0.0004 (8) | 0.0092 (8) | 0.0048 (8) |
C62 | 0.0338 (13) | 0.0320 (12) | 0.0409 (12) | 0.0034 (9) | 0.0088 (10) | 0.0041 (10) |
C63 | 0.0367 (14) | 0.0366 (13) | 0.0640 (16) | 0.0094 (11) | 0.0204 (13) | 0.0190 (12) |
C64 | 0.0260 (12) | 0.0627 (17) | 0.0499 (15) | 0.0083 (11) | 0.0141 (11) | 0.0360 (13) |
C65 | 0.0244 (12) | 0.0700 (18) | 0.0278 (11) | −0.0042 (11) | 0.0056 (9) | 0.0155 (11) |
C66 | 0.0244 (11) | 0.0429 (13) | 0.0248 (10) | −0.0022 (9) | 0.0071 (8) | 0.0039 (9) |
Rh—P2 | 2.3076 (5) | C32—C33 | 1.393 (3) |
Rh—P2i | 2.3076 (5) | C32—H32 | 0.95 |
Rh—P1i | 2.3114 (5) | C33—C34 | 1.383 (3) |
Rh—P1 | 2.3114 (5) | C33—H33 | 0.95 |
P1—C11 | 1.8326 (19) | C34—C35 | 1.385 (3) |
P1—C21 | 1.8358 (18) | C34—H34 | 0.95 |
P1—C1 | 1.8484 (18) | C35—C36 | 1.388 (3) |
P2—C41 | 1.8253 (19) | C35—H35 | 0.95 |
P2—C31 | 1.8290 (18) | C36—H36 | 0.95 |
P2—C2 | 1.8410 (18) | C41—C46 | 1.390 (3) |
B—C61ii | 1.644 (3) | C41—C42 | 1.398 (3) |
B—C61 | 1.644 (3) | C42—C43 | 1.383 (3) |
B—C51ii | 1.648 (3) | C42—H42 | 0.95 |
B—C51 | 1.648 (3) | C43—C44 | 1.379 (3) |
C1—C2 | 1.527 (2) | C43—H43 | 0.95 |
C1—H1A | 0.99 | C44—C45 | 1.382 (3) |
C1—H1B | 0.99 | C44—H44 | 0.95 |
C2—H2A | 0.99 | C45—C46 | 1.391 (3) |
C2—H2B | 0.99 | C45—H45 | 0.95 |
C11—C12 | 1.387 (3) | C46—H46 | 0.95 |
C11—C16 | 1.399 (3) | C51—C52 | 1.396 (3) |
C12—C13 | 1.393 (3) | C51—C56 | 1.404 (3) |
C12—H12 | 0.95 | C52—C53 | 1.392 (3) |
C13—C14 | 1.387 (3) | C52—H52 | 0.95 |
C13—H13 | 0.95 | C53—C54 | 1.374 (4) |
C14—C15 | 1.382 (3) | C53—H53 | 0.95 |
C14—H14 | 0.95 | C54—C55 | 1.371 (3) |
C15—C16 | 1.385 (3) | C54—H54 | 0.95 |
C15—H15 | 0.95 | C55—C56 | 1.392 (3) |
C16—H16 | 0.95 | C55—H55 | 0.95 |
C21—C22 | 1.391 (2) | C56—H56 | 0.95 |
C21—C26 | 1.399 (3) | C61—C62 | 1.398 (3) |
C22—C23 | 1.393 (3) | C61—C66 | 1.408 (3) |
C22—H22 | 0.95 | C62—C63 | 1.398 (3) |
C23—C24 | 1.376 (3) | C62—H62 | 0.95 |
C23—H23 | 0.95 | C63—C64 | 1.375 (3) |
C24—C25 | 1.379 (3) | C63—H63 | 0.95 |
C24—H24 | 0.95 | C64—C65 | 1.383 (3) |
C25—C26 | 1.389 (3) | C64—H64 | 0.95 |
C25—H25 | 0.95 | C65—C66 | 1.389 (3) |
C26—H26 | 0.95 | C65—H65 | 0.95 |
C31—C36 | 1.388 (3) | C66—H66 | 0.95 |
C31—C32 | 1.393 (2) | ||
P2—Rh—P2i | 169.75 (3) | C36—C31—C32 | 118.62 (17) |
P2—Rh—P1i | 98.110 (18) | C36—C31—P2 | 118.32 (13) |
P2i—Rh—P1i | 82.432 (18) | C32—C31—P2 | 122.99 (15) |
P2—Rh—P1 | 82.432 (18) | C31—C32—C33 | 120.46 (19) |
P2i—Rh—P1 | 98.110 (18) | C31—C32—H32 | 119.8 |
P1i—Rh—P1 | 173.98 (3) | C33—C32—H32 | 119.8 |
C11—P1—C21 | 103.44 (8) | C34—C33—C32 | 120.06 (18) |
C11—P1—C1 | 101.82 (8) | C34—C33—H33 | 120 |
C21—P1—C1 | 104.05 (8) | C32—C33—H33 | 120 |
C11—P1—Rh | 116.32 (6) | C33—C34—C35 | 120.00 (18) |
C21—P1—Rh | 118.67 (6) | C33—C34—H34 | 120 |
C1—P1—Rh | 110.59 (6) | C35—C34—H34 | 120 |
C41—P2—C31 | 103.03 (8) | C34—C35—C36 | 119.7 (2) |
C41—P2—C2 | 103.95 (9) | C34—C35—H35 | 120.1 |
C31—P2—C2 | 103.97 (8) | C36—C35—H35 | 120.1 |
C41—P2—Rh | 110.85 (6) | C35—C36—C31 | 121.13 (18) |
C31—P2—Rh | 124.34 (6) | C35—C36—H36 | 119.4 |
C2—P2—Rh | 108.78 (6) | C31—C36—H36 | 119.4 |
C61ii—B—C61 | 115.1 (2) | C46—C41—C42 | 118.35 (18) |
C61ii—B—C51ii | 103.31 (9) | C46—C41—P2 | 118.32 (14) |
C61—B—C51ii | 110.57 (9) | C42—C41—P2 | 123.17 (15) |
C61ii—B—C51 | 110.57 (9) | C43—C42—C41 | 120.29 (19) |
C61—B—C51 | 103.31 (9) | C43—C42—H42 | 119.9 |
C51ii—B—C51 | 114.4 (2) | C41—C42—H42 | 119.9 |
C2—C1—P1 | 108.74 (13) | C44—C43—C42 | 120.9 (2) |
C2—C1—H1A | 109.9 | C44—C43—H43 | 119.6 |
P1—C1—H1A | 109.9 | C42—C43—H43 | 119.6 |
C2—C1—H1B | 109.9 | C43—C44—C45 | 119.5 (2) |
P1—C1—H1B | 109.9 | C43—C44—H44 | 120.2 |
H1A—C1—H1B | 108.3 | C45—C44—H44 | 120.2 |
C1—C2—P2 | 107.25 (12) | C44—C45—C46 | 119.9 (2) |
C1—C2—H2A | 110.3 | C44—C45—H45 | 120 |
P2—C2—H2A | 110.3 | C46—C45—H45 | 120 |
C1—C2—H2B | 110.3 | C41—C46—C45 | 120.94 (19) |
P2—C2—H2B | 110.3 | C41—C46—H46 | 119.5 |
H2A—C2—H2B | 108.5 | C45—C46—H46 | 119.5 |
C12—C11—C16 | 118.62 (17) | C52—C51—C56 | 114.96 (19) |
C12—C11—P1 | 120.90 (14) | C52—C51—B | 123.26 (18) |
C16—C11—P1 | 120.46 (15) | C56—C51—B | 121.42 (18) |
C11—C12—C13 | 120.94 (18) | C53—C52—C51 | 122.8 (2) |
C11—C12—H12 | 119.5 | C53—C52—H52 | 118.6 |
C13—C12—H12 | 119.5 | C51—C52—H52 | 118.6 |
C14—C13—C12 | 119.51 (19) | C54—C53—C52 | 120.1 (2) |
C14—C13—H13 | 120.2 | C54—C53—H53 | 119.9 |
C12—C13—H13 | 120.2 | C52—C53—H53 | 119.9 |
C15—C14—C13 | 120.21 (19) | C55—C54—C53 | 119.4 (2) |
C15—C14—H14 | 119.9 | C55—C54—H54 | 120.3 |
C13—C14—H14 | 119.9 | C53—C54—H54 | 120.3 |
C14—C15—C16 | 120.07 (19) | C54—C55—C56 | 120.1 (2) |
C14—C15—H15 | 120 | C54—C55—H55 | 120 |
C16—C15—H15 | 120 | C56—C55—H55 | 120 |
C15—C16—C11 | 120.58 (19) | C55—C56—C51 | 122.7 (2) |
C15—C16—H16 | 119.7 | C55—C56—H56 | 118.7 |
C11—C16—H16 | 119.7 | C51—C56—H56 | 118.7 |
C22—C21—C26 | 118.50 (17) | C62—C61—C66 | 114.83 (19) |
C22—C21—P1 | 121.07 (14) | C62—C61—B | 124.27 (18) |
C26—C21—P1 | 119.96 (14) | C66—C61—B | 120.69 (19) |
C21—C22—C23 | 120.44 (19) | C61—C62—C63 | 122.7 (2) |
C21—C22—H22 | 119.8 | C61—C62—H62 | 118.6 |
C23—C22—H22 | 119.8 | C63—C62—H62 | 118.6 |
C24—C23—C22 | 120.32 (19) | C64—C63—C62 | 120.3 (2) |
C24—C23—H23 | 119.8 | C64—C63—H63 | 119.8 |
C22—C23—H23 | 119.8 | C62—C63—H63 | 119.8 |
C23—C24—C25 | 120.06 (18) | C63—C64—C65 | 119.0 (2) |
C23—C24—H24 | 120 | C63—C64—H64 | 120.5 |
C25—C24—H24 | 120 | C65—C64—H64 | 120.5 |
C24—C25—C26 | 120.06 (19) | C64—C65—C66 | 120.1 (2) |
C24—C25—H25 | 120 | C64—C65—H65 | 119.9 |
C26—C25—H25 | 120 | C66—C65—H65 | 119.9 |
C25—C26—C21 | 120.61 (19) | C65—C66—C61 | 122.9 (2) |
C25—C26—H26 | 119.7 | C65—C66—H66 | 118.5 |
C21—C26—H26 | 119.7 | C61—C66—H66 | 118.5 |
P2—Rh—P1—C11 | 111.92 (7) | C41—P2—C31—C32 | 3.46 (18) |
P2i—Rh—P1—C11 | −78.41 (7) | C2—P2—C31—C32 | 111.68 (17) |
P2—Rh—P1—C21 | −123.62 (7) | Rh—P2—C31—C32 | −123.45 (15) |
P2i—Rh—P1—C21 | 46.06 (7) | C36—C31—C32—C33 | 0.0 (3) |
P2—Rh—P1—C1 | −3.55 (7) | P2—C31—C32—C33 | 177.10 (15) |
P2i—Rh—P1—C1 | 166.12 (7) | C31—C32—C33—C34 | −1.1 (3) |
P2i—Rh—P2—C41 | −0.88 (6) | C32—C33—C34—C35 | 1.2 (3) |
P1i—Rh—P2—C41 | −93.20 (6) | C33—C34—C35—C36 | −0.2 (3) |
P1—Rh—P2—C41 | 92.85 (7) | C34—C35—C36—C31 | −0.9 (3) |
P2i—Rh—P2—C31 | 122.64 (8) | C32—C31—C36—C35 | 0.9 (3) |
P1i—Rh—P2—C31 | 30.33 (8) | P2—C31—C36—C35 | −176.25 (15) |
P1—Rh—P2—C31 | −143.62 (8) | C31—P2—C41—C46 | −100.49 (15) |
P2i—Rh—P2—C2 | −114.59 (7) | C2—P2—C41—C46 | 151.28 (15) |
P1i—Rh—P2—C2 | 153.09 (7) | Rh—P2—C41—C46 | 34.56 (16) |
P1—Rh—P2—C2 | −20.86 (7) | C31—P2—C41—C42 | 74.84 (18) |
C11—P1—C1—C2 | −91.40 (14) | C2—P2—C41—C42 | −33.39 (18) |
C21—P1—C1—C2 | 161.31 (13) | Rh—P2—C41—C42 | −150.11 (15) |
Rh—P1—C1—C2 | 32.83 (14) | C46—C41—C42—C43 | 0.7 (3) |
P1—C1—C2—P2 | −49.41 (15) | P2—C41—C42—C43 | −174.59 (15) |
C41—P2—C2—C1 | −71.28 (14) | C41—C42—C43—C44 | 0.8 (3) |
C31—P2—C2—C1 | −178.81 (13) | C42—C43—C44—C45 | −0.5 (3) |
Rh—P2—C2—C1 | 46.87 (14) | C43—C44—C45—C46 | −1.4 (3) |
C21—P1—C11—C12 | −136.86 (15) | C42—C41—C46—C45 | −2.6 (3) |
C1—P1—C11—C12 | 115.38 (15) | P2—C41—C46—C45 | 172.91 (15) |
Rh—P1—C11—C12 | −4.91 (17) | C44—C45—C46—C41 | 3.0 (3) |
C21—P1—C11—C16 | 41.36 (17) | C61ii—B—C51—C52 | −152.97 (19) |
C1—P1—C11—C16 | −66.40 (16) | C61—B—C51—C52 | 83.4 (2) |
Rh—P1—C11—C16 | 173.31 (13) | C51ii—B—C51—C52 | −36.86 (16) |
C16—C11—C12—C13 | −2.6 (3) | C61ii—B—C51—C56 | 34.3 (2) |
P1—C11—C12—C13 | 175.68 (14) | C61—B—C51—C56 | −89.32 (19) |
C11—C12—C13—C14 | 0.8 (3) | C51ii—B—C51—C56 | 150.44 (19) |
C12—C13—C14—C15 | 1.4 (3) | C56—C51—C52—C53 | −0.4 (3) |
C13—C14—C15—C16 | −1.7 (3) | B—C51—C52—C53 | −173.49 (19) |
C14—C15—C16—C11 | −0.2 (3) | C51—C52—C53—C54 | −1.0 (3) |
C12—C11—C16—C15 | 2.3 (3) | C52—C53—C54—C55 | 1.4 (4) |
P1—C11—C16—C15 | −175.99 (15) | C53—C54—C55—C56 | −0.5 (3) |
C11—P1—C21—C22 | 34.82 (17) | C54—C55—C56—C51 | −0.9 (3) |
C1—P1—C21—C22 | 140.90 (15) | C52—C51—C56—C55 | 1.3 (3) |
Rh—P1—C21—C22 | −95.73 (15) | B—C51—C56—C55 | 174.56 (17) |
C11—P1—C21—C26 | −153.13 (15) | C61ii—B—C61—C62 | −27.67 (15) |
C1—P1—C21—C26 | −47.06 (16) | C51ii—B—C61—C62 | −144.24 (19) |
Rh—P1—C21—C26 | 76.31 (16) | C51—B—C61—C62 | 93.0 (2) |
C26—C21—C22—C23 | −0.1 (3) | C61ii—B—C61—C66 | 157.96 (18) |
P1—C21—C22—C23 | 172.03 (15) | C51ii—B—C61—C66 | 41.4 (2) |
C21—C22—C23—C24 | 0.2 (3) | C51—B—C61—C66 | −81.41 (19) |
C22—C23—C24—C25 | −0.3 (3) | C66—C61—C62—C63 | −2.2 (3) |
C23—C24—C25—C26 | 0.3 (3) | B—C61—C62—C63 | −176.89 (17) |
C24—C25—C26—C21 | −0.3 (3) | C61—C62—C63—C64 | 0.6 (3) |
C22—C21—C26—C25 | 0.2 (3) | C62—C63—C64—C65 | 1.1 (3) |
P1—C21—C26—C25 | −172.08 (15) | C63—C64—C65—C66 | −1.2 (3) |
C41—P2—C31—C36 | −179.48 (15) | C64—C65—C66—C61 | −0.5 (3) |
C2—P2—C31—C36 | −71.26 (16) | C62—C61—C66—C65 | 2.2 (3) |
Rh—P2—C31—C36 | 53.62 (17) | B—C61—C66—C65 | 177.05 (16) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Rh(C26H24P2)2](C24H20B) |
Mr | 1218.9 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 17.010 (2), 16.560 (2), 22.142 (3) |
β (°) | 102.642 (2) |
V (Å3) | 6086.0 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.43 |
Crystal size (mm) | 0.2 × 0.2 × 0.19 |
Data collection | |
Diffractometer | Bruker SMART CCD 1K diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.919, 0.923 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20334, 7320, 5664 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.074, 1.04 |
No. of reflections | 7320 |
No. of parameters | 371 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.37 |
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), WinGX (Farrugia, 1999).
Rh—P2 | 2.3076 (5) | P2—C2 | 1.8410 (18) |
Rh—P1 | 2.3114 (5) | B—C61 | 1.644 (3) |
P1—C11 | 1.8326 (19) | B—C51 | 1.648 (3) |
P1—C21 | 1.8358 (18) | C1—C2 | 1.527 (2) |
P1—C1 | 1.8484 (18) | ||
P2—Rh—P2i | 169.75 (3) | P1i—Rh—P1 | 173.98 (3) |
P2—Rh—P1i | 98.110 (18) | C61ii—B—C61 | 115.1 (2) |
P2—Rh—P1 | 82.432 (18) | C61ii—B—C51ii | 103.31 (9) |
P1—C1—C2—P2 | −49.41 (15) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+2, y, −z+1/2. |
The lipophilic bis-chelated 1:2 MI diphosphine complexes [M(dppe)2]X (where M = Au, Ag and Cu, dppe = Ph2P(CH2)2PPh2 and X is a non-coordinating anion) exhibit antitumour activity against a range of tumour models [see Berners-Price et al. (1990), Berners-Price, Bowen, Galettis et al. (1999) and Berners-Price, Bowen, Hambley & Healy (1999) for examples]. Since the dppe ligand is itself cytotoxic (Mirabelli et al., 1987), albeit less potent than [M(dppe)2]X, it has been suggested that the phosphine is the antitumour agent and the role of the metal may largely be to protect the phosphine and deliver it to target sites. Conversely, the RhI complex [RhCl(PPh3)dppe] and the complexes [M'Cl2(dppe)], where M' is PtII, PdII and NiII, are all inactive. In this work, we sought to test the antitumor activity and various propositions for explaining this activity by examination of the [M(dppe)2]X class of compounds. We report here the preparation and structure of [Rh(dppe)2][BPh4], (I). Though initial tests on compound (I) seem to indicate that the complex is inactive, we will communicate the biological data elsewhere.
The structure of (I) does not show any unexpected features. The coordination around the Rh atom is approximately square planar, the distortion being due to the twofold crystallographic symmetry. This distortion can be seen from the dihedral angle of 12.67 (2)° between the planes defined by P1/Rh/P2 and P1i/Rh/P2i [symmetry code: (i) 1 − x, y, 1/2 − z]. In each phosphine the two aliphatic C atoms bridging the two phosphorus atoms are not equally positioned on either side of the appropriate P/Rh/P plane. The dominating feature of the five-membered chelate ring is the staggered conformation about the C—C bond. The bite angle of the dppe ligands in the title compound is 82.43 (2)°. This value compares well with other cationic rhodium–dppe complexes reported in literature.