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The dirhodium complex bis(benzonitrile)tetrakis[μ-4-(diethylamino)benzoato-κ
2O:
O′]dirhodium(II)(
Rh—
Rh) benzonitrile disolvate, [Rh
2(C
11H
14NO
2)
4(C
7H
5N)
2]·2C
7H
5N, lies about an inversion centre. The dirhodium complex (methanol)tetrakis(μ-4-nitrobenzoato-κ
2O:
O′)(pyridine)dirhodium(II)(
Rh—
Rh) dichloromethane solvate, [Rh
2(C
7H
4NO
4)
4(C
5H
5N)(CH
4O)]·CH
2Cl
2, lies in a general position in the unit cell, but the complexes dimerize around an inversion centre
via O—H
O hydrogen bonding of the axial MeOH to a carboxylate O atom. In the latter crystal structure, π–π stacking interactions between the bridging 4-nitrobenzoate ligands and the axial pyridine ligand are observed between adjacent molecules.
Supporting information
CCDC references: 621273; 621274
Tetrakis(µ-acetato)bis(methanol)dirhodium was prepared according to the
literature procedure of Rempel et al. (1972).
p-Diethylaminobenzoic acid and p-nitrobenzoic acid were used as
received. Both complexes were prepared by a modification of the procedure
reported by Doyle et al. (1990) for tetrakis(µ-acetamidato)dirhodium.
For the preparation of compound (I), [Rh2(O2CMe)4(MeOH)2] (0.327 g,
0.65 mmol) and p-diethylaminobenzoic acid (2.95 g, 1.53 mmol) dissolved
in chlorobenzene (90 ml) were placed in a 200 ml round-bottomed flask. A
Soxhlet apparatus, in which sodium carboxylate (3 g) and molecular sieves (1 g) were mixed in a filter, was placed on the flask. The solution was refluxed
under an Ar atmosphere for 3 d. The resulting green precipitate was filtered
off, dissolved in CH2Cl2–PhCN (1:1 v/v), washed with
saturated aqueous NaHCO3 and water, and dried over MgSO4. Diffusion of
ethanol into the solution gave a reddish–purple precipitate.
Recrystallization from PhCN by slow diffusion of ethanol gave red crystals of
(I).
For the preparation of compound (II), [Rh2(O2CMe)4(MeOH)2] (1.019 g,
2.01 mmol) and p-nitrobenzoic acid (6.00 g, 35.9 mm mol) were reacted
in a similar method to (I). The resulting green precipitate was filtered off
and dissolved in PhCN–hexane (1:1 v/v). The solution was washed
with saturated aqueous NaHCO3 and water, and dried over MgSO4. Diffusion
of hexane gave a red precipitate. This was dissolved in CH2Cl2 and
pyridine was added until the colour of the solution changed to orange. The
solid obtained by the evaporation of this solution to dryness was
recrystallized from CH2Cl2 by slow diffusion of MeOH. Two types of
crystals were obtained in an almost 1:1 ratio; one was (II) and the other was
poor quality crystals of [Rh2(O2CC6H4NO2)2(py)2].
For compound (I), one diethylaminophenyl group is disordered over two sites.
Atoms C15A–C18A/C21A/C22A/N2A constitute
one group and atoms
C15B–C18B/C21B/C22B/N2B form the other,
sharing atoms C13, C14, C19 and C20. The occupancies of sets A and
B were refined and converged to 0.530 (1) and 0.470 (1), respectively.
For compound (II), the solvated dichloromethane molecule is disordered over
two sites, Cl1/Cl2/C35 and Cl3/Cl4/C36. The occupancies were refined and
converged to 0.672 (3) and 0.328 (3), respectively. The positional parameters of
the O-bound H atom in (I) [Should this be (II)?] were refined [Final
O—H = ?], with Uiso(H) = 1.5Ueq(O). All other H atoms
were placed in idealized positions and treated as riding atoms, with C—H
distances in the range 0.93–0.98 Å and with Uiso(H) =
1.2Ueq(C) or 1.5Ueq(C).
For both compounds, data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and TEXSAN.
(I) bis(benzonitrile)tetrakis[µ-
p-(diethylamino)benzoato-
κ2O,
O']dirhodium(II)(Rh—Rh) benzonitrile disolvate
top
Crystal data top
[Rh2(C11H14NO2)4(C7H5N)2]·2C7H5N | Z = 1 |
Mr = 1387.23 | F(000) = 718 |
TriclinicP1 | Dx = 1.368 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 10.049 (4) Å | Cell parameters from 3948 reflections |
b = 12.752 (6) Å | θ = 3.1–27.5° |
c = 13.479 (6) Å | µ = 0.55 mm−1 |
α = 98.641 (6)° | T = 296 K |
β = 90.781 (6)° | Block, dark-red |
γ = 99.424 (6)° | 0.20 × 0.10 × 0.10 mm |
V = 1683.3 (13) Å3 | |
Data collection top
Rigaku/MSC Mercury CCD area-detector diffractometer | 5661 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 14.62 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −10→13 |
13963 measured reflections | k = −14→16 |
7660 independent reflections | l = −16→17 |
Refinement top
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0391P)2] where P = (Fo2 + 2Fc2)/3 |
7660 reflections | (Δ/σ)max = 0.016 |
475 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.71 e Å−3 |
Crystal data top
[Rh2(C11H14NO2)4(C7H5N)2]·2C7H5N | γ = 99.424 (6)° |
Mr = 1387.23 | V = 1683.3 (13) Å3 |
TriclinicP1 | Z = 1 |
a = 10.049 (4) Å | Mo Kα radiation |
b = 12.752 (6) Å | µ = 0.55 mm−1 |
c = 13.479 (6) Å | T = 296 K |
α = 98.641 (6)° | 0.20 × 0.10 × 0.10 mm |
β = 90.781 (6)° | |
Data collection top
Rigaku/MSC Mercury CCD area-detector diffractometer | 5661 reflections with I > 2σ(I) |
13963 measured reflections | Rint = 0.046 |
7660 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.52 e Å−3 |
7660 reflections | Δρmin = −0.71 e Å−3 |
475 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Rh1 | 0.552152 (11) | 0.421492 (9) | 0.485928 (7) | 0.02236 (3) | |
O1 | 0.73006 (9) | 0.51287 (7) | 0.54496 (6) | 0.0303 (3) | |
O2 | 0.62944 (9) | 0.66036 (7) | 0.57133 (6) | 0.0299 (3) | |
C1 | 0.73019 (14) | 0.61217 (11) | 0.57619 (8) | 0.0251 (4) | |
C2 | 0.85701 (14) | 0.67764 (11) | 0.62264 (9) | 0.0271 (4) | |
C3 | 0.97393 (14) | 0.63500 (11) | 0.63393 (9) | 0.0308 (4) | |
H1 | 0.9753 | 0.5637 | 0.6069 | 0.037* | |
C4 | 1.08789 (15) | 0.69553 (12) | 0.68399 (9) | 0.0355 (5) | |
H2 | 1.1636 | 0.6637 | 0.6914 | 0.043* | |
C5 | 1.09239 (15) | 0.80456 (12) | 0.72428 (9) | 0.0347 (5) | |
C6 | 0.97561 (15) | 0.84857 (12) | 0.70855 (10) | 0.0379 (5) | |
H3 | 0.9755 | 0.9212 | 0.7310 | 0.045* | |
C7 | 0.86136 (14) | 0.78590 (11) | 0.66046 (9) | 0.0333 (4) | |
H4 | 0.7849 | 0.8169 | 0.6531 | 0.040* | |
N1 | 1.20521 (12) | 0.86475 (10) | 0.77475 (9) | 0.0448 (4) | |
C8 | 1.20818 (17) | 0.97993 (13) | 0.81210 (12) | 0.0588 (6) | |
H5 | 1.1692 | 1.0121 | 0.7603 | 0.071* | |
H6 | 1.3015 | 1.0148 | 0.8239 | 0.071* | |
C9 | 1.1340 (2) | 1.00218 (17) | 0.90689 (13) | 0.0874 (8) | |
H7 | 1.0413 | 0.9682 | 0.8961 | 0.131* | |
H8 | 1.1386 | 1.0784 | 0.9253 | 0.131* | |
H9 | 1.1748 | 0.9741 | 0.9598 | 0.131* | |
C10 | 1.31034 (16) | 0.81547 (15) | 0.81423 (11) | 0.0604 (6) | |
H10 | 1.3915 | 0.8689 | 0.8283 | 0.072* | |
H11 | 1.3306 | 0.7585 | 0.7634 | 0.072* | |
C11 | 1.2724 (2) | 0.76896 (18) | 0.90915 (12) | 0.1005 (9) | |
H12 | 1.2620 | 0.8261 | 0.9621 | 0.151* | |
H13 | 1.3422 | 0.7320 | 0.9284 | 0.151* | |
H14 | 1.1889 | 0.7194 | 0.8970 | 0.151* | |
O3 | 0.50002 (9) | 0.39384 (7) | 0.62665 (6) | 0.0285 (3) | |
O4 | 0.39815 (9) | 0.54064 (7) | 0.65149 (6) | 0.0296 (3) | |
C12 | 0.43364 (13) | 0.45797 (11) | 0.67920 (9) | 0.0270 (4) | |
C13 | 0.39445 (14) | 0.43526 (11) | 0.77973 (9) | 0.0320 (4) | |
C14 | 0.45205 (16) | 0.36432 (12) | 0.82801 (10) | 0.0399 (5) | |
H15 | 0.5248 | 0.3372 | 0.7982 | 0.048* | 0.5339 (11) |
H16 | 0.5072 | 0.3204 | 0.7938 | 0.048* | 0.4661 (11) |
C15A | 0.4100 (3) | 0.3302 (2) | 0.91768 (17) | 0.0361 (9) | 0.5339 (11) |
H17 | 0.4492 | 0.2793 | 0.9450 | 0.043* | 0.5339 (11) |
C16A | 0.3041 (3) | 0.3773 (2) | 0.96514 (19) | 0.0398 (9) | 0.5339 (11) |
C17A | 0.2421 (3) | 0.4450 (2) | 0.91452 (18) | 0.0435 (9) | 0.5339 (11) |
H18 | 0.1702 | 0.4739 | 0.9439 | 0.052* | 0.5339 (11) |
C18A | 0.2823 (3) | 0.4708 (2) | 0.82403 (17) | 0.0339 (8) | 0.5339 (11) |
H19 | 0.2342 | 0.5127 | 0.7913 | 0.041* | 0.5339 (11) |
N2A | 0.2619 (3) | 0.3531 (2) | 1.05754 (16) | 0.0475 (8) | 0.5339 (11) |
C19 | 0.3612 (2) | 0.31944 (15) | 1.12892 (11) | 0.0650 (7) | |
H20 | 0.4541 | 0.3394 | 1.1110 | 0.078* | 0.5339 (11) |
H21 | 0.3508 | 0.3496 | 1.1983 | 0.078* | 0.5339 (11) |
H22 | 0.4576 | 0.3296 | 1.1191 | 0.078* | 0.4661 (11) |
H23 | 0.3512 | 0.3403 | 1.2003 | 0.078* | 0.4661 (11) |
C20 | 0.3171 (2) | 0.20260 (16) | 1.11041 (15) | 0.0956 (9) | |
H24 | 0.2213 | 0.1866 | 1.1175 | 0.143* | |
H25 | 0.3622 | 0.1702 | 1.1580 | 0.143* | |
H26 | 0.3389 | 0.1745 | 1.0436 | 0.143* | |
C21A | 0.1352 (3) | 0.3818 (3) | 1.0990 (2) | 0.0533 (11) | 0.5339 (11) |
H27 | 0.0688 | 0.3756 | 1.0446 | 0.064* | 0.5339 (11) |
H28 | 0.1001 | 0.3315 | 1.1435 | 0.064* | 0.5339 (11) |
C22A | 0.1556 (4) | 0.4916 (3) | 1.1547 (2) | 0.0847 (16) | 0.5339 (11) |
H29 | 0.2162 | 0.4966 | 1.2115 | 0.127* | 0.5339 (11) |
H30 | 0.0705 | 0.5088 | 1.1774 | 0.127* | 0.5339 (11) |
H31 | 0.1933 | 0.5413 | 1.1115 | 0.127* | 0.5339 (11) |
N3 | 0.63450 (11) | 0.26902 (9) | 0.45682 (7) | 0.0289 (3) | |
C23 | 0.65322 (14) | 0.18222 (11) | 0.44693 (9) | 0.0293 (4) | |
C24 | 0.67660 (15) | 0.07296 (11) | 0.43877 (9) | 0.0331 (4) | |
C25 | 0.58005 (17) | −0.01020 (12) | 0.39092 (11) | 0.0453 (5) | |
H32 | 0.5033 | 0.0049 | 0.3603 | 0.054* | |
C26 | 0.59831 (18) | −0.11516 (13) | 0.38887 (12) | 0.0548 (6) | |
H33 | 0.5334 | −0.1714 | 0.3576 | 0.066* | |
C27 | 0.71266 (18) | −0.13652 (13) | 0.43313 (12) | 0.0563 (6) | |
H34 | 0.7250 | −0.2074 | 0.4317 | 0.068* | |
C28 | 0.80813 (19) | −0.05491 (13) | 0.47898 (12) | 0.0576 (6) | |
H35 | 0.8850 | −0.0707 | 0.5088 | 0.069* | |
C29 | 0.79253 (16) | 0.05088 (12) | 0.48190 (11) | 0.0439 (5) | |
H36 | 0.8588 | 0.1064 | 0.5123 | 0.053* | |
N4 | 0.6152 (2) | 0.10310 (16) | 0.83623 (12) | 0.1085 (9) | |
C30 | 0.7048 (2) | 0.15151 (17) | 0.80061 (13) | 0.0774 (8) | |
C31 | 0.81370 (19) | 0.21005 (15) | 0.75547 (12) | 0.0598 (6) | |
C32 | 0.79204 (19) | 0.27358 (14) | 0.68501 (11) | 0.0564 (6) | |
H37 | 0.7041 | 0.2805 | 0.6682 | 0.068* | |
C33 | 0.89628 (19) | 0.32648 (15) | 0.63942 (13) | 0.0634 (7) | |
H38 | 0.8792 | 0.3681 | 0.5912 | 0.076* | |
C34 | 1.0263 (2) | 0.31881 (17) | 0.66409 (15) | 0.0834 (8) | |
H39 | 1.0980 | 0.3555 | 0.6335 | 0.100* | |
C35 | 1.0497 (2) | 0.25543 (18) | 0.73555 (16) | 0.0952 (9) | |
H40 | 1.1381 | 0.2503 | 0.7529 | 0.114* | |
C36 | 0.9460 (2) | 0.20057 (17) | 0.78068 (15) | 0.0834 (8) | |
H41 | 0.9630 | 0.1574 | 0.8276 | 0.100* | |
C15B | 0.4265 (3) | 0.3597 (2) | 0.9275 (2) | 0.0338 (10) | 0.4661 (11) |
H42 | 0.4729 | 0.3159 | 0.9593 | 0.041* | 0.4661 (11) |
C16B | 0.3402 (3) | 0.4130 (3) | 0.9840 (2) | 0.0349 (10) | 0.4661 (11) |
C17B | 0.2857 (3) | 0.4890 (3) | 0.9367 (2) | 0.0386 (10) | 0.4661 (11) |
H43 | 0.2271 | 0.5297 | 0.9708 | 0.046* | 0.4661 (11) |
C18B | 0.3196 (3) | 0.5029 (3) | 0.8395 (2) | 0.0356 (10) | 0.4661 (11) |
H44 | 0.2916 | 0.5593 | 0.8128 | 0.043* | 0.4661 (11) |
N2B | 0.3119 (3) | 0.4045 (2) | 1.08063 (17) | 0.0440 (9) | 0.4661 (11) |
C21B | 0.2207 (4) | 0.4668 (4) | 1.1357 (2) | 0.0716 (16) | 0.4661 (11) |
H45 | 0.2393 | 0.5399 | 1.1212 | 0.086* | 0.4661 (11) |
H46 | 0.2383 | 0.4695 | 1.2071 | 0.086* | 0.4661 (11) |
C22B | 0.0685 (5) | 0.4204 (4) | 1.1101 (3) | 0.105 (2) | 0.4661 (11) |
H47 | 0.0534 | 0.4051 | 1.0386 | 0.158* | 0.4661 (11) |
H48 | 0.0143 | 0.4722 | 1.1378 | 0.158* | 0.4661 (11) |
H49 | 0.0441 | 0.3554 | 1.1383 | 0.158* | 0.4661 (11) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh1 | 0.02241 (5) | 0.02235 (5) | 0.02284 (4) | 0.00427 (4) | 0.00088 (4) | 0.00454 (4) |
O1 | 0.0243 (5) | 0.0277 (5) | 0.0378 (5) | 0.0056 (4) | −0.0043 (4) | 0.0011 (4) |
O2 | 0.0252 (5) | 0.0266 (5) | 0.0369 (5) | 0.0035 (4) | −0.0029 (4) | 0.0031 (4) |
C1 | 0.0263 (7) | 0.0303 (7) | 0.0208 (6) | 0.0028 (6) | 0.0032 (5) | 0.0121 (5) |
C2 | 0.0231 (7) | 0.0326 (8) | 0.0254 (6) | 0.0003 (6) | −0.0001 (6) | 0.0082 (6) |
C3 | 0.0285 (8) | 0.0309 (8) | 0.0326 (7) | 0.0017 (7) | 0.0023 (6) | 0.0070 (6) |
C4 | 0.0240 (8) | 0.0456 (9) | 0.0384 (7) | 0.0041 (7) | −0.0019 (6) | 0.0138 (7) |
C5 | 0.0311 (8) | 0.0433 (9) | 0.0278 (6) | −0.0010 (7) | −0.0003 (6) | 0.0079 (6) |
C6 | 0.0340 (9) | 0.0349 (8) | 0.0403 (8) | −0.0005 (7) | −0.0049 (7) | −0.0007 (7) |
C7 | 0.0271 (8) | 0.0359 (8) | 0.0379 (7) | 0.0058 (7) | −0.0012 (6) | 0.0087 (6) |
N1 | 0.0305 (7) | 0.0505 (8) | 0.0468 (7) | −0.0048 (6) | −0.0131 (6) | 0.0007 (6) |
C8 | 0.0395 (10) | 0.0640 (12) | 0.0629 (10) | −0.0083 (9) | −0.0090 (9) | −0.0029 (9) |
C9 | 0.0949 (16) | 0.1037 (16) | 0.0595 (11) | 0.0295 (13) | −0.0153 (11) | −0.0124 (11) |
C10 | 0.0347 (9) | 0.0768 (13) | 0.0610 (10) | 0.0047 (9) | −0.0219 (8) | −0.0096 (9) |
C11 | 0.1241 (16) | 0.1501 (19) | 0.0428 (10) | 0.0803 (13) | −0.0129 (11) | 0.0031 (11) |
O3 | 0.0336 (5) | 0.0292 (5) | 0.0261 (4) | 0.0107 (4) | 0.0068 (4) | 0.0089 (4) |
O4 | 0.0349 (5) | 0.0336 (5) | 0.0241 (4) | 0.0113 (4) | 0.0080 (4) | 0.0100 (4) |
C12 | 0.0212 (7) | 0.0323 (8) | 0.0268 (6) | 0.0005 (6) | 0.0016 (6) | 0.0071 (6) |
C13 | 0.0334 (8) | 0.0367 (8) | 0.0286 (6) | 0.0099 (7) | 0.0073 (6) | 0.0087 (6) |
C14 | 0.0416 (9) | 0.0519 (9) | 0.0322 (7) | 0.0222 (7) | 0.0103 (6) | 0.0094 (7) |
C15A | 0.0499 (17) | 0.0332 (15) | 0.0307 (12) | 0.0169 (13) | 0.0175 (12) | 0.0107 (11) |
C16A | 0.0431 (17) | 0.0496 (18) | 0.0298 (13) | 0.0114 (14) | 0.0000 (12) | 0.0121 (12) |
C17A | 0.0442 (17) | 0.0597 (19) | 0.0333 (13) | 0.0252 (14) | 0.0177 (12) | 0.0094 (13) |
C18A | 0.0284 (15) | 0.0482 (16) | 0.0310 (12) | 0.0146 (13) | 0.0029 (11) | 0.0165 (12) |
N2A | 0.0528 (16) | 0.0617 (16) | 0.0360 (11) | 0.0198 (13) | 0.0207 (11) | 0.0203 (11) |
C19 | 0.0783 (13) | 0.0830 (13) | 0.0395 (8) | 0.0236 (11) | 0.0127 (9) | 0.0160 (9) |
C20 | 0.0970 (18) | 0.0988 (17) | 0.0777 (13) | −0.0187 (15) | 0.0234 (13) | 0.0080 (12) |
C21A | 0.058 (2) | 0.072 (2) | 0.0411 (15) | 0.0254 (17) | 0.0192 (14) | 0.0266 (14) |
C22A | 0.123 (3) | 0.082 (3) | 0.0554 (19) | 0.024 (3) | 0.034 (2) | 0.0206 (19) |
N3 | 0.0281 (7) | 0.0260 (6) | 0.0337 (6) | 0.0060 (5) | 0.0023 (5) | 0.0060 (5) |
C23 | 0.0275 (8) | 0.0317 (8) | 0.0293 (6) | 0.0049 (6) | 0.0041 (6) | 0.0059 (6) |
C24 | 0.0415 (9) | 0.0248 (7) | 0.0344 (7) | 0.0085 (7) | 0.0086 (7) | 0.0055 (6) |
C25 | 0.0421 (10) | 0.0408 (9) | 0.0525 (9) | 0.0112 (8) | 0.0047 (8) | 0.0008 (8) |
C26 | 0.0579 (12) | 0.0317 (9) | 0.0701 (10) | −0.0014 (8) | 0.0180 (9) | 0.0011 (8) |
C27 | 0.0694 (12) | 0.0296 (8) | 0.0776 (11) | 0.0173 (8) | 0.0287 (9) | 0.0210 (8) |
C28 | 0.0632 (12) | 0.0432 (9) | 0.0760 (11) | 0.0218 (9) | 0.0030 (9) | 0.0265 (8) |
C29 | 0.0446 (10) | 0.0347 (9) | 0.0560 (9) | 0.0137 (8) | 0.0001 (8) | 0.0114 (7) |
N4 | 0.1033 (16) | 0.1449 (18) | 0.0730 (11) | −0.0077 (14) | −0.0105 (11) | 0.0353 (11) |
C30 | 0.0810 (15) | 0.0991 (16) | 0.0507 (10) | 0.0080 (13) | −0.0138 (10) | 0.0164 (10) |
C31 | 0.0566 (12) | 0.0717 (13) | 0.0499 (9) | 0.0110 (10) | 0.0004 (9) | 0.0052 (9) |
C32 | 0.0569 (11) | 0.0647 (11) | 0.0470 (9) | 0.0179 (9) | −0.0052 (8) | −0.0007 (8) |
C33 | 0.0590 (12) | 0.0615 (12) | 0.0726 (11) | 0.0157 (10) | −0.0056 (10) | 0.0141 (9) |
C34 | 0.0599 (14) | 0.0911 (16) | 0.1027 (15) | 0.0137 (12) | 0.0121 (12) | 0.0239 (13) |
C35 | 0.0626 (14) | 0.1208 (18) | 0.1132 (16) | 0.0381 (13) | −0.0062 (13) | 0.0297 (14) |
C36 | 0.0853 (16) | 0.0913 (15) | 0.0850 (13) | 0.0277 (13) | −0.0004 (12) | 0.0360 (11) |
C15B | 0.046 (2) | 0.0218 (15) | 0.0393 (16) | 0.0142 (14) | −0.0093 (15) | 0.0139 (13) |
C16B | 0.042 (2) | 0.047 (2) | 0.0173 (13) | 0.0136 (16) | 0.0057 (13) | 0.0033 (13) |
C17B | 0.054 (2) | 0.0409 (18) | 0.0293 (15) | 0.0267 (15) | 0.0165 (14) | 0.0102 (14) |
C18B | 0.037 (2) | 0.0357 (18) | 0.0343 (16) | 0.0061 (16) | 0.0026 (15) | 0.0072 (14) |
N2B | 0.0512 (18) | 0.0590 (18) | 0.0262 (12) | 0.0158 (15) | 0.0095 (12) | 0.0129 (12) |
C21B | 0.091 (3) | 0.102 (3) | 0.0290 (17) | 0.031 (3) | 0.0257 (19) | 0.0138 (19) |
C22B | 0.077 (3) | 0.187 (5) | 0.075 (3) | 0.058 (3) | 0.027 (2) | 0.051 (3) |
Geometric parameters (Å, º) top
Rh1—Rh1i | 2.3920 (9) | C19—C20 | 1.465 (3) |
Rh1—O1 | 2.0463 (10) | C19—N2B | 1.492 (4) |
Rh1—O2i | 2.0276 (10) | C19—H20 | 0.9700 |
Rh1—O3 | 2.0407 (12) | C19—H21 | 0.9700 |
Rh1—O4i | 2.0318 (12) | C19—H22 | 0.9700 |
Rh1—N3 | 2.2194 (14) | C19—H23 | 0.9700 |
O1—C1 | 1.2728 (16) | C20—H24 | 0.9600 |
O2—C1 | 1.2732 (18) | C20—H25 | 0.9600 |
O2—Rh1i | 2.0276 (10) | C20—H26 | 0.9600 |
C1—C2 | 1.4784 (18) | C21A—C22A | 1.467 (4) |
C2—C3 | 1.389 (2) | C21A—H27 | 0.9700 |
C2—C7 | 1.391 (2) | C21A—H28 | 0.9700 |
C3—C4 | 1.3767 (18) | C22A—H29 | 0.9600 |
C3—H1 | 0.9300 | C22A—H30 | 0.9600 |
C4—C5 | 1.408 (2) | C22A—H31 | 0.9600 |
C4—H2 | 0.9300 | N3—C23 | 1.1415 (19) |
C5—N1 | 1.3691 (18) | C23—C24 | 1.439 (2) |
C5—C6 | 1.408 (2) | C24—C29 | 1.383 (2) |
C6—C7 | 1.3786 (19) | C24—C25 | 1.3865 (19) |
C6—H3 | 0.9300 | C25—C26 | 1.377 (2) |
C7—H4 | 0.9300 | C25—H32 | 0.9300 |
N1—C10 | 1.448 (2) | C26—C27 | 1.372 (3) |
N1—C8 | 1.475 (2) | C26—H33 | 0.9300 |
C8—C9 | 1.501 (2) | C27—C28 | 1.360 (2) |
C8—H5 | 0.9700 | C27—H34 | 0.9300 |
C8—H6 | 0.9700 | C28—C29 | 1.378 (2) |
C9—H7 | 0.9600 | C28—H35 | 0.9300 |
C9—H8 | 0.9600 | C29—H36 | 0.9300 |
C9—H9 | 0.9600 | N4—C30 | 1.158 (3) |
C10—C11 | 1.517 (3) | C30—C31 | 1.419 (3) |
C10—H10 | 0.9700 | C31—C32 | 1.374 (3) |
C10—H11 | 0.9700 | C31—C36 | 1.397 (3) |
C11—H12 | 0.9600 | C32—C33 | 1.357 (3) |
C11—H13 | 0.9600 | C32—H37 | 0.9300 |
C11—H14 | 0.9600 | C33—C34 | 1.366 (3) |
O3—C12 | 1.2778 (16) | C33—H38 | 0.9300 |
O4—C12 | 1.2712 (18) | C34—C35 | 1.388 (3) |
O4—Rh1i | 2.0318 (11) | C34—H39 | 0.9300 |
C12—C13 | 1.4731 (19) | C35—C36 | 1.361 (3) |
C13—C14 | 1.384 (2) | C35—H40 | 0.9300 |
C13—C18A | 1.391 (3) | C36—H41 | 0.9300 |
C13—C18B | 1.407 (4) | C15B—C16B | 1.359 (5) |
C14—C15B | 1.377 (3) | C15B—H42 | 0.9300 |
C14—C15A | 1.393 (3) | C16B—N2B | 1.354 (4) |
C14—H15 | 0.9300 | C16B—C17B | 1.412 (5) |
C14—H16 | 0.9300 | C17B—C18B | 1.388 (4) |
C15A—C16A | 1.420 (4) | C17B—H43 | 0.9300 |
C15A—H17 | 0.9300 | C18B—H44 | 0.9300 |
C16A—N2A | 1.383 (3) | N2B—C21B | 1.449 (5) |
C16A—C17A | 1.393 (4) | C21B—C22B | 1.561 (6) |
C17A—C18A | 1.360 (4) | C21B—H45 | 0.9700 |
C17A—H18 | 0.9300 | C21B—H46 | 0.9700 |
C18A—H19 | 0.9300 | C22B—H47 | 0.9600 |
N2A—C21A | 1.476 (4) | C22B—H48 | 0.9600 |
N2A—C19 | 1.531 (3) | C22B—H49 | 0.9600 |
| | | |
Rh1i—Rh1—O1 | 89.16 (4) | C20—C19—N2B | 129.38 (18) |
Rh1i—Rh1—O2i | 87.17 (4) | C20—C19—N2A | 99.70 (16) |
Rh1i—Rh1—O3 | 88.20 (3) | C20—C19—H20 | 111.8 |
Rh1i—Rh1—O4i | 88.11 (3) | N2B—C19—H20 | 94.1 |
Rh1i—Rh1—N3 | 175.93 (3) | N2A—C19—H20 | 111.8 |
O1—Rh1—O2i | 176.33 (4) | C20—C19—H21 | 111.8 |
O1—Rh1—O3 | 89.53 (4) | N2B—C19—H21 | 97.9 |
O1—Rh1—O4i | 89.30 (4) | N2A—C19—H21 | 111.8 |
O1—Rh1—N3 | 94.87 (5) | H20—C19—H21 | 109.6 |
O2i—Rh1—O3 | 90.51 (4) | C20—C19—H22 | 104.9 |
O2i—Rh1—O4i | 90.44 (4) | N2B—C19—H22 | 104.9 |
O2i—Rh1—N3 | 88.80 (5) | N2A—C19—H22 | 122.3 |
O3—Rh1—O4i | 176.14 (4) | H21—C19—H22 | 105.9 |
O3—Rh1—N3 | 91.29 (4) | C20—C19—H23 | 104.9 |
O4i—Rh1—N3 | 92.47 (4) | N2B—C19—H23 | 104.9 |
C1—O1—Rh1 | 117.60 (9) | N2A—C19—H23 | 116.9 |
C1—O2—Rh1i | 120.65 (8) | H20—C19—H23 | 110.9 |
O1—C1—O2 | 125.39 (11) | H22—C19—H23 | 105.8 |
O1—C1—C2 | 117.84 (13) | C19—C20—H24 | 109.5 |
O2—C1—C2 | 116.77 (12) | C19—C20—H25 | 109.5 |
C3—C2—C7 | 117.15 (12) | H24—C20—H25 | 109.5 |
C3—C2—C1 | 122.76 (12) | C19—C20—H26 | 109.5 |
C7—C2—C1 | 120.06 (13) | H24—C20—H26 | 109.5 |
C4—C3—C2 | 121.76 (13) | H25—C20—H26 | 109.5 |
C4—C3—H1 | 119.1 | C22A—C21A—N2A | 111.8 (3) |
C2—C3—H1 | 119.1 | C22A—C21A—H27 | 109.3 |
C3—C4—C5 | 121.48 (14) | N2A—C21A—H27 | 109.3 |
C3—C4—H2 | 119.3 | C22A—C21A—H28 | 109.3 |
C5—C4—H2 | 119.3 | N2A—C21A—H28 | 109.3 |
N1—C5—C6 | 121.94 (13) | H27—C21A—H28 | 107.9 |
N1—C5—C4 | 121.62 (14) | C23—N3—Rh1 | 166.99 (11) |
C6—C5—C4 | 116.44 (12) | N3—C23—C24 | 177.70 (13) |
C7—C6—C5 | 121.14 (14) | C29—C24—C25 | 120.24 (14) |
C7—C6—H3 | 119.4 | C29—C24—C23 | 120.02 (12) |
C5—C6—H3 | 119.4 | C25—C24—C23 | 119.69 (14) |
C6—C7—C2 | 121.94 (14) | C26—C25—C24 | 119.69 (16) |
C6—C7—H4 | 119.0 | C26—C25—H32 | 120.2 |
C2—C7—H4 | 119.0 | C24—C25—H32 | 120.2 |
C5—N1—C10 | 121.85 (14) | C27—C26—C25 | 119.73 (14) |
C5—N1—C8 | 120.05 (14) | C27—C26—H33 | 120.1 |
C10—N1—C8 | 116.48 (12) | C25—C26—H33 | 120.1 |
N1—C8—C9 | 114.46 (15) | C28—C27—C26 | 120.58 (16) |
N1—C8—H5 | 108.6 | C28—C27—H34 | 119.7 |
C9—C8—H5 | 108.6 | C26—C27—H34 | 119.7 |
N1—C8—H6 | 108.6 | C27—C28—C29 | 120.88 (17) |
C9—C8—H6 | 108.6 | C27—C28—H35 | 119.6 |
H5—C8—H6 | 107.6 | C29—C28—H35 | 119.6 |
C8—C9—H7 | 109.5 | C28—C29—C24 | 118.86 (14) |
C8—C9—H8 | 109.5 | C28—C29—H36 | 120.6 |
H7—C9—H8 | 109.5 | C24—C29—H36 | 120.6 |
C8—C9—H9 | 109.5 | N4—C30—C31 | 179.1 (2) |
H7—C9—H9 | 109.5 | C32—C31—C36 | 119.02 (18) |
H8—C9—H9 | 109.5 | C32—C31—C30 | 121.49 (18) |
N1—C10—C11 | 113.23 (15) | C36—C31—C30 | 119.46 (19) |
N1—C10—H10 | 108.9 | C33—C32—C31 | 121.34 (18) |
C11—C10—H10 | 108.9 | C33—C32—H37 | 119.3 |
N1—C10—H11 | 108.9 | C31—C32—H37 | 119.3 |
C11—C10—H11 | 108.9 | C32—C33—C34 | 120.26 (19) |
H10—C10—H11 | 107.7 | C32—C33—H38 | 119.9 |
C10—C11—H12 | 109.5 | C34—C33—H38 | 119.9 |
C10—C11—H13 | 109.5 | C33—C34—C35 | 119.0 (2) |
H12—C11—H13 | 109.5 | C33—C34—H39 | 120.5 |
C10—C11—H14 | 109.5 | C35—C34—H39 | 120.5 |
H12—C11—H14 | 109.5 | C36—C35—C34 | 121.3 (2) |
H13—C11—H14 | 109.5 | C36—C35—H40 | 119.3 |
C12—O3—Rh1 | 118.97 (9) | C34—C35—H40 | 119.3 |
C12—O4—Rh1i | 119.68 (8) | C35—C36—C31 | 119.0 (2) |
O4—C12—O3 | 125.02 (12) | C35—C36—H41 | 120.5 |
O4—C12—C13 | 116.87 (12) | C31—C36—H41 | 120.5 |
O3—C12—C13 | 118.11 (13) | C16B—C15B—C14 | 126.4 (3) |
C14—C13—C18A | 115.90 (16) | C16B—C15B—H42 | 116.8 |
C14—C13—C18B | 116.21 (17) | C14—C15B—H42 | 116.8 |
C14—C13—C12 | 122.34 (13) | N2B—C16B—C15B | 125.9 (3) |
C18A—C13—C12 | 120.99 (16) | N2B—C16B—C17B | 119.3 (3) |
C18B—C13—C12 | 119.96 (18) | C15B—C16B—C17B | 114.6 (3) |
C15B—C14—C13 | 119.02 (19) | C18B—C17B—C16B | 120.2 (3) |
C13—C14—C15A | 125.33 (18) | C18B—C17B—H43 | 119.9 |
C13—C14—H15 | 117.3 | C16B—C17B—H43 | 119.9 |
C15A—C14—H15 | 117.3 | C17B—C18B—C13 | 122.6 (3) |
C15B—C14—H16 | 120.5 | C17B—C18B—H44 | 118.7 |
C13—C14—H16 | 120.5 | C13—C18B—H44 | 118.7 |
C15A—C14—H16 | 112.1 | C16B—N2B—C21B | 122.0 (3) |
C14—C15A—C16A | 116.5 (2) | C16B—N2B—C19 | 119.6 (3) |
C14—C15A—H17 | 121.8 | C21B—N2B—C19 | 117.9 (2) |
C16A—C15A—H17 | 121.8 | N2B—C21B—C22B | 113.6 (3) |
N2A—C16A—C17A | 121.6 (3) | N2B—C21B—H45 | 108.8 |
N2A—C16A—C15A | 120.2 (3) | C22B—C21B—H45 | 108.8 |
C17A—C16A—C15A | 118.1 (2) | N2B—C21B—H46 | 108.9 |
C18A—C17A—C16A | 122.8 (3) | C22B—C21B—H46 | 108.9 |
C18A—C17A—H18 | 118.6 | H45—C21B—H46 | 107.7 |
C16A—C17A—H18 | 118.6 | C21B—C22B—H47 | 109.5 |
C17A—C18A—C13 | 121.0 (3) | C21B—C22B—H48 | 109.5 |
C17A—C18A—H19 | 119.5 | H47—C22B—H48 | 109.5 |
C13—C18A—H19 | 119.5 | C21B—C22B—H49 | 109.5 |
C16A—N2A—C21A | 121.5 (3) | H47—C22B—H49 | 109.5 |
C16A—N2A—C19 | 119.5 (2) | H48—C22B—H49 | 109.5 |
C21A—N2A—C19 | 117.6 (2) | | |
| | | |
O1—Rh1—Rh1i—O2 | −0.15 (4) | C14—C15A—C16A—N2A | −176.0 (2) |
O3—Rh1—Rh1i—O4 | −1.13 (3) | C14—C15A—C16A—C17A | 6.1 (3) |
O4i—Rh1—O1—C1 | 89.17 (9) | N2A—C16A—C17A—C18A | 179.5 (2) |
O3—Rh1—O1—C1 | −87.15 (9) | C15A—C16A—C17A—C18A | −2.6 (4) |
N3—Rh1—O1—C1 | −178.41 (9) | C16A—C17A—C18A—C13 | −4.0 (4) |
Rh1i—Rh1—O1—C1 | 1.06 (8) | C14—C13—C18A—C17A | 6.4 (3) |
Rh1—O1—C1—O2 | −2.01 (16) | C12—C13—C18A—C17A | 176.57 (19) |
Rh1—O1—C1—C2 | 177.59 (8) | C17A—C16A—N2A—C21A | 10.9 (4) |
Rh1i—O2—C1—O1 | 1.89 (16) | C15A—C16A—N2A—C21A | −167.0 (2) |
Rh1i—O2—C1—C2 | −177.72 (8) | C17A—C16A—N2A—C19 | −155.2 (2) |
O1—C1—C2—C3 | −0.51 (18) | C15A—C16A—N2A—C19 | 27.0 (3) |
O2—C1—C2—C3 | 179.13 (12) | C16A—N2A—C19—C20 | −100.5 (2) |
O1—C1—C2—C7 | −178.23 (11) | C21A—N2A—C19—C20 | 92.9 (2) |
O2—C1—C2—C7 | 1.41 (17) | C16A—N2A—C21A—C22A | −86.5 (3) |
C7—C2—C3—C4 | 2.65 (19) | C19—N2A—C21A—C22A | 79.8 (3) |
C1—C2—C3—C4 | −175.13 (12) | O2i—Rh1—N3—C23 | −36.5 (4) |
C2—C3—C4—C5 | −1.5 (2) | O4i—Rh1—N3—C23 | −126.9 (4) |
C3—C4—C5—N1 | 179.51 (13) | O3—Rh1—N3—C23 | 53.9 (4) |
C3—C4—C5—C6 | −1.4 (2) | O1—Rh1—N3—C23 | 143.6 (4) |
N1—C5—C6—C7 | −177.84 (13) | C29—C24—C25—C26 | 1.8 (2) |
C4—C5—C6—C7 | 3.1 (2) | C23—C24—C25—C26 | −175.74 (14) |
C5—C6—C7—C2 | −2.0 (2) | C24—C25—C26—C27 | −0.8 (2) |
C3—C2—C7—C6 | −0.9 (2) | C25—C26—C27—C28 | 0.0 (3) |
C1—C2—C7—C6 | 176.90 (12) | C26—C27—C28—C29 | −0.1 (3) |
C6—C5—N1—C10 | 163.30 (14) | C27—C28—C29—C24 | 1.1 (2) |
C4—C5—N1—C10 | −17.7 (2) | C25—C24—C29—C28 | −1.9 (2) |
C6—C5—N1—C8 | −1.7 (2) | C23—C24—C29—C28 | 175.59 (14) |
C4—C5—N1—C8 | 177.37 (13) | C36—C31—C32—C33 | 0.3 (3) |
C5—N1—C8—C9 | 78.16 (19) | C30—C31—C32—C33 | −177.67 (17) |
C10—N1—C8—C9 | −87.58 (18) | C31—C32—C33—C34 | −1.0 (3) |
C5—N1—C10—C11 | −75.91 (18) | C32—C33—C34—C35 | 0.6 (3) |
C8—N1—C10—C11 | 89.55 (17) | C33—C34—C35—C36 | 0.4 (3) |
O2i—Rh1—O3—C12 | −85.58 (9) | C34—C35—C36—C31 | −1.1 (3) |
O1—Rh1—O3—C12 | 90.76 (9) | C32—C31—C36—C35 | 0.7 (3) |
N3—Rh1—O3—C12 | −174.38 (9) | C30—C31—C36—C35 | 178.76 (18) |
Rh1i—Rh1—O3—C12 | 1.58 (8) | C13—C14—C15B—C16B | 5.4 (4) |
Rh1i—O4—C12—O3 | −0.13 (16) | C14—C15B—C16B—N2B | 177.2 (3) |
Rh1i—O4—C12—C13 | 179.94 (8) | C14—C15B—C16B—C17B | −7.9 (4) |
Rh1—O3—C12—O4 | −1.23 (16) | N2B—C16B—C17B—C18B | 176.4 (3) |
Rh1—O3—C12—C13 | 178.70 (8) | C15B—C16B—C17B—C18B | 1.2 (4) |
O4—C12—C13—C14 | −164.63 (12) | C16B—C17B—C18B—C13 | 7.8 (5) |
O3—C12—C13—C14 | 15.44 (18) | C14—C13—C18B—C17B | −10.2 (4) |
O4—C12—C13—C18A | 25.9 (2) | C12—C13—C18B—C17B | −176.6 (2) |
O3—C12—C13—C18A | −154.05 (16) | C15B—C16B—N2B—C21B | 178.4 (3) |
O4—C12—C13—C18B | 0.9 (2) | C17B—C16B—N2B—C21B | 3.7 (5) |
O3—C12—C13—C18B | −179.06 (17) | C15B—C16B—N2B—C19 | −9.5 (5) |
C18B—C13—C14—C15B | 3.8 (3) | C17B—C16B—N2B—C19 | 175.9 (2) |
C12—C13—C14—C15B | 169.83 (18) | C20—C19—N2B—C16B | −70.6 (4) |
C18A—C13—C14—C15A | −2.7 (2) | C20—C19—N2B—C21B | 101.9 (3) |
C12—C13—C14—C15A | −172.64 (16) | C16B—N2B—C21B—C22B | 78.9 (4) |
C13—C14—C15A—C16A | −3.6 (3) | C19—N2B—C21B—C22B | −93.4 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
(II) (methanol)tetrakis(µ-
p-nitrobenzoato-
κ2O,
O')(pyridine)dirhodium(II)(Rh—Rh) dichloromethane
solvate, [Rh
2(C
7H
4NO
4)
4(C
2H
4O)(C
5H
5N)]·CH
2Cl
2 top
Crystal data top
[Rh2(C7H4NO4)4(C2H4O)(C5H5N)]·CH2Cl2 | Z = 2 |
Mr = 1066.34 | F(000) = 1064 |
TriclinicP1 | Dx = 1.806 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 12.750 (6) Å | Cell parameters from 5195 reflections |
b = 13.290 (4) Å | θ = 3.0–27.5° |
c = 14.773 (5) Å | µ = 1.06 mm−1 |
α = 96.55 (3)° | T = 113 K |
β = 109.42 (1)° | Block, dark-red |
γ = 118.43 (1)° | 0.30 × 0.10 × 0.10 mm |
V = 1961.0 (13) Å3 | |
Data collection top
Rigaku/MSC Mercury CCD area-detector diffractometer | 6931 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 14.62 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −16→16 |
16189 measured reflections | k = −17→13 |
8932 independent reflections | l = −12→19 |
Refinement top
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0533P)2 + 2.6928P] where P = (Fo2 + 2Fc2)/3 |
8932 reflections | (Δ/σ)max = 0.001 |
577 parameters | Δρmax = 0.82 e Å−3 |
0 restraints | Δρmin = −1.05 e Å−3 |
Crystal data top
[Rh2(C7H4NO4)4(C2H4O)(C5H5N)]·CH2Cl2 | γ = 118.43 (1)° |
Mr = 1066.34 | V = 1961.0 (13) Å3 |
TriclinicP1 | Z = 2 |
a = 12.750 (6) Å | Mo Kα radiation |
b = 13.290 (4) Å | µ = 1.06 mm−1 |
c = 14.773 (5) Å | T = 113 K |
α = 96.55 (3)° | 0.30 × 0.10 × 0.10 mm |
β = 109.42 (1)° | |
Data collection top
Rigaku/MSC Mercury CCD area-detector diffractometer | 6931 reflections with I > 2σ(I) |
16189 measured reflections | Rint = 0.047 |
8932 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.82 e Å−3 |
8932 reflections | Δρmin = −1.05 e Å−3 |
577 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Rh1 | 0.65481 (3) | 0.45721 (2) | 0.28436 (2) | 0.01313 (9) | |
Rh2 | 0.48824 (3) | 0.39051 (2) | 0.34454 (2) | 0.01327 (9) | |
O1 | 0.6812 (3) | 0.6242 (2) | 0.3173 (2) | 0.0196 (6) | |
O2 | 0.5260 (3) | 0.5609 (2) | 0.3755 (2) | 0.0220 (6) | |
O3 | 0.8234 (3) | 1.2025 (3) | 0.4742 (3) | 0.0353 (8) | |
O4 | 0.6737 (3) | 1.1383 (3) | 0.5294 (2) | 0.0309 (7) | |
O5 | 0.7915 (3) | 0.5082 (2) | 0.4296 (2) | 0.0183 (6) | |
O6 | 0.6337 (3) | 0.4434 (3) | 0.4852 (2) | 0.0206 (6) | |
O7 | 1.2647 (3) | 0.7855 (3) | 0.9301 (2) | 0.0316 (7) | |
O8 | 1.1089 (3) | 0.7131 (3) | 0.9790 (2) | 0.0321 (7) | |
O9 | 0.6176 (3) | 0.2860 (2) | 0.2560 (2) | 0.0195 (6) | |
O10 | 0.4603 (3) | 0.2251 (2) | 0.3126 (2) | 0.0230 (6) | |
O11 | 0.4497 (4) | −0.3047 (3) | 0.1239 (3) | 0.0368 (8) | |
O12 | 0.3019 (3) | −0.3563 (3) | 0.1814 (3) | 0.0318 (8) | |
O13 | 0.5075 (3) | 0.4038 (2) | 0.1432 (2) | 0.0180 (6) | |
O14 | 0.3514 (3) | 0.3426 (3) | 0.2010 (2) | 0.0246 (6) | |
O15 | 0.0097 (3) | 0.1383 (3) | −0.3450 (2) | 0.0351 (8) | |
O16 | −0.1368 (3) | 0.0902 (3) | −0.2881 (2) | 0.0289 (7) | |
O17 | 0.3274 (3) | 0.3247 (3) | 0.4007 (2) | 0.0180 (6) | |
H1 | 0.331 (5) | 0.349 (4) | 0.444 (4) | 0.027* | |
N1 | 0.7357 (4) | 1.1217 (3) | 0.4882 (3) | 0.0237 (8) | |
N2 | 1.1473 (4) | 0.7256 (3) | 0.9124 (3) | 0.0236 (8) | |
N3 | 0.3914 (4) | −0.2804 (3) | 0.1650 (3) | 0.0225 (8) | |
N4 | −0.0212 (3) | 0.1375 (3) | −0.2746 (3) | 0.0211 (7) | |
N5 | 0.8072 (3) | 0.5171 (3) | 0.2266 (2) | 0.0126 (6) | |
C1 | 0.6140 (4) | 0.6407 (3) | 0.3568 (3) | 0.0167 (8) | |
C2 | 0.6431 (4) | 0.7659 (3) | 0.3880 (3) | 0.0168 (8) | |
C3 | 0.7495 (4) | 0.8627 (3) | 0.3828 (3) | 0.0200 (8) | |
H2 | 0.8020 | 0.8485 | 0.3569 | 0.024* | |
C4 | 0.7802 (4) | 0.9790 (4) | 0.4147 (3) | 0.0237 (9) | |
H3 | 0.8527 | 1.0449 | 0.4107 | 0.028* | |
C5 | 0.7026 (4) | 0.9971 (3) | 0.4527 (3) | 0.0173 (8) | |
C6 | 0.5973 (4) | 0.9037 (4) | 0.4603 (3) | 0.0205 (8) | |
H4 | 0.5466 | 0.9189 | 0.4877 | 0.025* | |
C7 | 0.5674 (4) | 0.7876 (4) | 0.4270 (3) | 0.0191 (8) | |
H5 | 0.4945 | 0.7219 | 0.4309 | 0.023* | |
C8 | 0.7537 (4) | 0.4958 (3) | 0.4991 (3) | 0.0152 (8) | |
C9 | 0.8570 (4) | 0.5497 (3) | 0.6067 (3) | 0.0172 (8) | |
C10 | 0.9918 (4) | 0.6106 (3) | 0.6299 (3) | 0.0168 (8) | |
H6 | 1.0180 | 0.6128 | 0.5766 | 0.020* | |
C11 | 1.0873 (4) | 0.6678 (3) | 0.7296 (3) | 0.0195 (8) | |
H7 | 1.1791 | 0.7092 | 0.7458 | 0.023* | |
C12 | 1.0463 (4) | 0.6636 (3) | 0.8059 (3) | 0.0197 (8) | |
C13 | 0.9121 (4) | 0.6013 (3) | 0.7851 (3) | 0.0187 (8) | |
H8 | 0.8862 | 0.5984 | 0.8386 | 0.022* | |
C14 | 0.8179 (4) | 0.5440 (3) | 0.6848 (3) | 0.0187 (8) | |
H9 | 0.7260 | 0.5004 | 0.6688 | 0.022* | |
C15 | 0.5283 (4) | 0.2072 (3) | 0.2751 (3) | 0.0172 (8) | |
C16 | 0.4987 (4) | 0.0815 (3) | 0.2501 (3) | 0.0179 (8) | |
C17 | 0.5565 (5) | 0.0485 (4) | 0.1980 (4) | 0.0283 (10) | |
H10 | 0.6191 | 0.1071 | 0.1804 | 0.034* | |
C18 | 0.5228 (5) | −0.0700 (4) | 0.1717 (4) | 0.0280 (10) | |
H11 | 0.5632 | −0.0929 | 0.1374 | 0.034* | |
C19 | 0.4299 (4) | −0.1541 (3) | 0.1961 (3) | 0.0195 (8) | |
C20 | 0.3714 (4) | −0.1232 (4) | 0.2477 (3) | 0.0217 (9) | |
H12 | 0.3077 | −0.1826 | 0.2640 | 0.026* | |
C21 | 0.4067 (4) | −0.0047 (3) | 0.2753 (3) | 0.0209 (9) | |
H13 | 0.3680 | 0.0180 | 0.3116 | 0.025* | |
C22 | 0.3891 (4) | 0.3558 (3) | 0.1317 (3) | 0.0169 (8) | |
C23 | 0.2829 (4) | 0.3072 (3) | 0.0256 (3) | 0.0177 (8) | |
C24 | 0.3151 (4) | 0.3186 (3) | −0.0560 (3) | 0.0183 (8) | |
H14 | 0.4057 | 0.3637 | −0.0436 | 0.022* | |
C25 | 0.2158 (4) | 0.2645 (3) | −0.1543 (3) | 0.0181 (8) | |
H15 | 0.2368 | 0.2724 | −0.2102 | 0.022* | |
C26 | 0.0846 (4) | 0.1982 (3) | −0.1699 (3) | 0.0181 (8) | |
C27 | 0.0493 (4) | 0.1890 (4) | −0.0914 (3) | 0.0218 (9) | |
H16 | −0.0416 | 0.1462 | −0.1045 | 0.026* | |
C28 | 0.1493 (4) | 0.2436 (4) | 0.0072 (3) | 0.0219 (9) | |
H17 | 0.1272 | 0.2378 | 0.0626 | 0.026* | |
C29 | 0.9372 (4) | 0.5897 (3) | 0.2916 (3) | 0.0158 (8) | |
H18 | 0.9626 | 0.6144 | 0.3624 | 0.019* | |
C30 | 1.0343 (4) | 0.6290 (3) | 0.2587 (3) | 0.0198 (8) | |
H19 | 1.1255 | 0.6799 | 0.3060 | 0.024* | |
C31 | 0.9966 (4) | 0.5929 (4) | 0.1540 (3) | 0.0231 (9) | |
H20 | 1.0615 | 0.6193 | 0.1290 | 0.028* | |
C32 | 0.8629 (4) | 0.5181 (3) | 0.0884 (3) | 0.0187 (8) | |
H21 | 0.8345 | 0.4920 | 0.0172 | 0.022* | |
C33 | 0.7709 (4) | 0.4814 (3) | 0.1266 (3) | 0.0172 (8) | |
H22 | 0.6790 | 0.4294 | 0.0809 | 0.021* | |
C34 | 0.2082 (5) | 0.2092 (4) | 0.3509 (4) | 0.0328 (11) | |
H23 | 0.1619 | 0.2007 | 0.2799 | 0.049* | |
H24 | 0.1512 | 0.1997 | 0.3847 | 0.049* | |
H25 | 0.2285 | 0.1468 | 0.3536 | 0.049* | |
Cl1 | 0.8365 (3) | 0.0287 (2) | 0.1603 (2) | 0.0666 (9) | 0.672 (3) |
Cl2 | 0.7855 (3) | −0.0314 (2) | −0.0540 (2) | 0.0672 (8) | 0.672 (3) |
C35 | 0.7184 (10) | −0.0394 (8) | 0.0300 (10) | 0.069 (3) | 0.672 (3) |
H26 | 0.6537 | −0.1257 | 0.0177 | 0.083* | 0.672 (3) |
H27 | 0.6688 | 0.0005 | 0.0162 | 0.083* | 0.672 (3) |
Cl3 | 0.8996 (6) | 0.0533 (5) | 0.0948 (5) | 0.075 (2) | 0.328 (3) |
Cl4 | 0.6120 (7) | −0.1059 (5) | −0.0202 (4) | 0.0692 (18) | 0.328 (3) |
C36 | 0.754 (2) | −0.0111 (19) | −0.0202 (16) | 0.046 (5)* | 0.328 (3) |
H28 | 0.7489 | 0.0558 | −0.0401 | 0.055* | 0.328 (3) |
H29 | 0.7629 | −0.0538 | −0.0735 | 0.055* | 0.328 (3) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh1 | 0.01197 (17) | 0.01514 (15) | 0.01285 (17) | 0.00688 (13) | 0.00705 (13) | 0.00426 (12) |
Rh2 | 0.01196 (16) | 0.01534 (15) | 0.01294 (16) | 0.00685 (13) | 0.00706 (13) | 0.00429 (12) |
O1 | 0.0211 (15) | 0.0187 (13) | 0.0275 (16) | 0.0116 (12) | 0.0180 (14) | 0.0086 (12) |
O2 | 0.0287 (17) | 0.0204 (14) | 0.0328 (17) | 0.0160 (13) | 0.0248 (15) | 0.0143 (13) |
O3 | 0.038 (2) | 0.0186 (15) | 0.045 (2) | 0.0106 (15) | 0.0219 (18) | 0.0076 (14) |
O4 | 0.0260 (18) | 0.0267 (16) | 0.0365 (19) | 0.0163 (14) | 0.0113 (16) | −0.0016 (14) |
O5 | 0.0109 (14) | 0.0258 (14) | 0.0125 (14) | 0.0060 (12) | 0.0056 (12) | 0.0057 (11) |
O6 | 0.0157 (15) | 0.0312 (15) | 0.0162 (15) | 0.0117 (13) | 0.0094 (13) | 0.0106 (12) |
O7 | 0.0174 (17) | 0.0325 (17) | 0.0234 (17) | 0.0049 (14) | 0.0015 (14) | 0.0030 (14) |
O8 | 0.036 (2) | 0.0429 (19) | 0.0140 (16) | 0.0205 (16) | 0.0106 (15) | 0.0062 (14) |
O9 | 0.0206 (15) | 0.0181 (13) | 0.0279 (16) | 0.0114 (12) | 0.0174 (14) | 0.0100 (12) |
O10 | 0.0225 (16) | 0.0151 (13) | 0.0356 (18) | 0.0077 (12) | 0.0216 (15) | 0.0068 (12) |
O11 | 0.042 (2) | 0.0254 (16) | 0.047 (2) | 0.0192 (16) | 0.0256 (19) | 0.0030 (15) |
O12 | 0.0347 (19) | 0.0203 (15) | 0.038 (2) | 0.0119 (14) | 0.0178 (17) | 0.0118 (14) |
O13 | 0.0138 (14) | 0.0243 (14) | 0.0155 (14) | 0.0097 (12) | 0.0071 (12) | 0.0074 (12) |
O14 | 0.0126 (15) | 0.0380 (17) | 0.0138 (15) | 0.0090 (13) | 0.0048 (13) | 0.0041 (13) |
O15 | 0.0231 (18) | 0.057 (2) | 0.0162 (17) | 0.0184 (16) | 0.0076 (15) | 0.0021 (15) |
O16 | 0.0121 (15) | 0.0347 (17) | 0.0247 (17) | 0.0072 (13) | 0.0034 (13) | 0.0007 (14) |
O17 | 0.0170 (15) | 0.0198 (14) | 0.0184 (16) | 0.0084 (12) | 0.0119 (13) | 0.0048 (12) |
N1 | 0.0210 (19) | 0.0224 (17) | 0.0209 (19) | 0.0115 (16) | 0.0043 (16) | 0.0022 (15) |
N2 | 0.028 (2) | 0.0216 (17) | 0.0162 (18) | 0.0125 (16) | 0.0069 (16) | 0.0043 (14) |
N3 | 0.0205 (19) | 0.0176 (16) | 0.0223 (19) | 0.0090 (15) | 0.0055 (16) | 0.0025 (14) |
N4 | 0.0195 (19) | 0.0218 (17) | 0.0193 (19) | 0.0108 (15) | 0.0076 (16) | 0.0040 (15) |
N5 | 0.0120 (16) | 0.0128 (14) | 0.0135 (16) | 0.0069 (13) | 0.0058 (14) | 0.0054 (12) |
C1 | 0.017 (2) | 0.0229 (19) | 0.015 (2) | 0.0125 (17) | 0.0084 (17) | 0.0078 (16) |
C2 | 0.015 (2) | 0.0225 (19) | 0.0124 (19) | 0.0104 (17) | 0.0050 (16) | 0.0062 (16) |
C3 | 0.019 (2) | 0.0194 (19) | 0.024 (2) | 0.0111 (17) | 0.0125 (18) | 0.0031 (17) |
C4 | 0.021 (2) | 0.021 (2) | 0.024 (2) | 0.0088 (18) | 0.0107 (19) | 0.0044 (17) |
C5 | 0.019 (2) | 0.0169 (18) | 0.0117 (19) | 0.0103 (16) | 0.0030 (16) | 0.0002 (15) |
C6 | 0.020 (2) | 0.027 (2) | 0.018 (2) | 0.0165 (18) | 0.0076 (18) | 0.0062 (17) |
C7 | 0.015 (2) | 0.0212 (19) | 0.020 (2) | 0.0099 (17) | 0.0077 (17) | 0.0073 (17) |
C8 | 0.015 (2) | 0.0140 (17) | 0.019 (2) | 0.0084 (16) | 0.0086 (17) | 0.0069 (15) |
C9 | 0.018 (2) | 0.0160 (18) | 0.019 (2) | 0.0084 (16) | 0.0093 (18) | 0.0086 (16) |
C10 | 0.018 (2) | 0.0194 (18) | 0.017 (2) | 0.0111 (17) | 0.0100 (17) | 0.0090 (16) |
C11 | 0.017 (2) | 0.0193 (19) | 0.021 (2) | 0.0082 (17) | 0.0084 (18) | 0.0089 (17) |
C12 | 0.023 (2) | 0.0161 (18) | 0.017 (2) | 0.0107 (17) | 0.0058 (18) | 0.0045 (16) |
C13 | 0.022 (2) | 0.0230 (19) | 0.017 (2) | 0.0132 (18) | 0.0132 (18) | 0.0067 (16) |
C14 | 0.015 (2) | 0.0189 (19) | 0.023 (2) | 0.0081 (16) | 0.0094 (18) | 0.0101 (17) |
C15 | 0.016 (2) | 0.0178 (18) | 0.015 (2) | 0.0067 (16) | 0.0079 (17) | 0.0043 (15) |
C16 | 0.018 (2) | 0.0190 (18) | 0.021 (2) | 0.0107 (17) | 0.0116 (18) | 0.0064 (16) |
C17 | 0.031 (3) | 0.021 (2) | 0.040 (3) | 0.013 (2) | 0.026 (2) | 0.0102 (19) |
C18 | 0.030 (3) | 0.020 (2) | 0.039 (3) | 0.0124 (19) | 0.023 (2) | 0.0047 (19) |
C19 | 0.017 (2) | 0.0150 (18) | 0.020 (2) | 0.0060 (16) | 0.0048 (17) | 0.0039 (16) |
C20 | 0.016 (2) | 0.0186 (19) | 0.023 (2) | 0.0042 (17) | 0.0093 (18) | 0.0054 (17) |
C21 | 0.021 (2) | 0.0204 (19) | 0.025 (2) | 0.0110 (18) | 0.0156 (19) | 0.0075 (17) |
C22 | 0.018 (2) | 0.0185 (18) | 0.015 (2) | 0.0096 (17) | 0.0091 (17) | 0.0053 (15) |
C23 | 0.016 (2) | 0.0200 (18) | 0.017 (2) | 0.0098 (17) | 0.0084 (17) | 0.0044 (16) |
C24 | 0.016 (2) | 0.0217 (19) | 0.018 (2) | 0.0095 (17) | 0.0094 (17) | 0.0087 (16) |
C25 | 0.019 (2) | 0.0202 (19) | 0.015 (2) | 0.0101 (17) | 0.0087 (17) | 0.0053 (16) |
C26 | 0.014 (2) | 0.0170 (18) | 0.016 (2) | 0.0061 (16) | 0.0039 (17) | 0.0020 (15) |
C27 | 0.015 (2) | 0.028 (2) | 0.021 (2) | 0.0100 (18) | 0.0096 (18) | 0.0076 (18) |
C28 | 0.021 (2) | 0.031 (2) | 0.018 (2) | 0.0138 (19) | 0.0122 (19) | 0.0095 (18) |
C29 | 0.016 (2) | 0.0156 (17) | 0.0131 (19) | 0.0082 (16) | 0.0048 (16) | 0.0038 (15) |
C30 | 0.016 (2) | 0.0190 (19) | 0.024 (2) | 0.0098 (17) | 0.0084 (18) | 0.0072 (17) |
C31 | 0.024 (2) | 0.024 (2) | 0.031 (3) | 0.0151 (19) | 0.019 (2) | 0.0120 (19) |
C32 | 0.023 (2) | 0.0212 (19) | 0.018 (2) | 0.0128 (17) | 0.0126 (18) | 0.0078 (16) |
C33 | 0.018 (2) | 0.0180 (18) | 0.018 (2) | 0.0114 (16) | 0.0079 (17) | 0.0055 (16) |
C34 | 0.024 (3) | 0.024 (2) | 0.040 (3) | 0.004 (2) | 0.016 (2) | 0.010 (2) |
Cl1 | 0.0632 (17) | 0.0462 (13) | 0.090 (2) | 0.0339 (12) | 0.0299 (15) | 0.0151 (13) |
Cl2 | 0.0725 (19) | 0.0584 (15) | 0.082 (2) | 0.0366 (14) | 0.0384 (17) | 0.0419 (14) |
C35 | 0.025 (5) | 0.029 (4) | 0.116 (10) | 0.003 (4) | 0.018 (6) | −0.002 (5) |
Cl3 | 0.071 (4) | 0.049 (3) | 0.096 (5) | 0.033 (3) | 0.028 (4) | 0.019 (3) |
Cl4 | 0.085 (5) | 0.058 (3) | 0.061 (4) | 0.037 (3) | 0.032 (3) | 0.020 (3) |
Geometric parameters (Å, º) top
Rh1—Rh2 | 2.3937 (10) | C10—H6 | 0.9500 |
Rh1—O1 | 2.051 (3) | C11—C12 | 1.387 (6) |
Rh1—O5 | 2.039 (3) | C11—H7 | 0.9500 |
Rh1—O9 | 2.050 (3) | C12—C13 | 1.397 (6) |
Rh1—O13 | 2.042 (3) | C13—C14 | 1.380 (6) |
Rh1—N5 | 2.218 (3) | C13—H8 | 0.9500 |
Rh2—O2 | 2.037 (3) | C14—H9 | 0.9500 |
Rh2—O6 | 2.028 (3) | C15—C16 | 1.495 (5) |
Rh2—O10 | 2.022 (3) | C16—C21 | 1.392 (5) |
Rh2—O14 | 2.030 (3) | C16—C17 | 1.393 (5) |
Rh2—O17 | 2.291 (3) | C17—C18 | 1.385 (6) |
O1—C1 | 1.268 (4) | C17—H10 | 0.9500 |
O2—C1 | 1.264 (4) | C18—C19 | 1.377 (6) |
O3—N1 | 1.227 (5) | C18—H11 | 0.9500 |
O4—N1 | 1.224 (5) | C19—C20 | 1.380 (6) |
O5—C8 | 1.267 (4) | C20—C21 | 1.381 (5) |
O6—C8 | 1.270 (5) | C20—H12 | 0.9500 |
O7—N2 | 1.225 (5) | C21—H13 | 0.9500 |
O8—N2 | 1.231 (5) | C22—C23 | 1.494 (5) |
O9—C15 | 1.272 (4) | C23—C28 | 1.399 (6) |
O10—C15 | 1.265 (5) | C23—C24 | 1.399 (5) |
O11—N3 | 1.230 (5) | C24—C25 | 1.380 (5) |
O12—N3 | 1.234 (4) | C24—H14 | 0.9500 |
O13—C22 | 1.266 (5) | C25—C26 | 1.386 (5) |
O14—C22 | 1.264 (5) | C25—H15 | 0.9500 |
O15—N4 | 1.227 (4) | C26—C27 | 1.375 (5) |
O16—N4 | 1.225 (4) | C27—C28 | 1.385 (6) |
O17—C34 | 1.409 (5) | C27—H16 | 0.9500 |
O17—H1 | 0.65 (5) | C28—H17 | 0.9500 |
N1—C5 | 1.479 (5) | C29—C30 | 1.372 (6) |
N2—C12 | 1.469 (5) | C29—H18 | 0.9500 |
N3—C19 | 1.469 (5) | C30—C31 | 1.403 (6) |
N4—C26 | 1.467 (5) | C30—H19 | 0.9500 |
N5—C33 | 1.341 (5) | C31—C32 | 1.378 (6) |
N5—C29 | 1.344 (5) | C31—H20 | 0.9500 |
C1—C2 | 1.497 (5) | C32—C33 | 1.375 (5) |
C2—C3 | 1.390 (5) | C32—H21 | 0.9500 |
C2—C7 | 1.394 (5) | C33—H22 | 0.9500 |
C3—C4 | 1.377 (5) | C34—H23 | 0.9800 |
C3—H2 | 0.9500 | C34—H24 | 0.9800 |
C4—C5 | 1.385 (6) | C34—H25 | 0.9800 |
C4—H3 | 0.9500 | Cl1—C35 | 1.780 (12) |
C5—C6 | 1.378 (6) | Cl2—C35 | 1.713 (12) |
C6—C7 | 1.383 (5) | C35—H26 | 0.9900 |
C6—H4 | 0.9500 | C35—H27 | 0.9900 |
C7—H5 | 0.9500 | Cl3—C36 | 1.77 (2) |
C8—C9 | 1.491 (5) | Cl4—C36 | 1.64 (2) |
C9—C10 | 1.396 (5) | C36—H28 | 0.9900 |
C9—C14 | 1.398 (5) | C36—H29 | 0.9900 |
C10—C11 | 1.379 (6) | | |
| | | |
N2···C32i | 3.177 (6) | N4···C30ii | 3.172 (7) |
C11···C29i | 3.252 (7) | O16···C30ii | 3.230 (5) |
O7···C33i | 3.320 (6) | C25···C33ii | 3.270 (7) |
O8···C32i | 3.340 (7) | O15···C29ii | 3.289 (6) |
C12···C31i | 3.342 (7) | C25···N5ii | 3.310 (6) |
C11···N5i | 3.347 (7) | N4···C29ii | 3.323 (5) |
C13···C31i | 3.394 (8) | C27···C31ii | 3.386 (7) |
C10···C29i | 3.399 (7) | C26···C31ii | 3.403 (8) |
N2···C33i | 3.430 (7) | C26···C30ii | 3.459 (7) |
C12···C30i | 3.433 (6) | C24···C33ii | 3.464 (6) |
C12···C32i | 3.454 (7) | C26···C32ii | 3.484 (6) |
C13···C30i | 3.477 (7) | C27···C32ii | 3.491 (6) |
O7···C32i | 3.493 (5) | O15···C30ii | 3.568 (7) |
C11···C30i | 3.536 (6) | C26···C29ii | 3.581 (6) |
N2···C31i | 3.564 (5) | | |
| | | |
O5—Rh1—O13 | 175.59 (10) | C10—C11—H7 | 120.7 |
O5—Rh1—O9 | 90.76 (12) | C12—C11—H7 | 120.7 |
O13—Rh1—O9 | 89.73 (12) | C11—C12—C13 | 122.2 (4) |
O5—Rh1—O1 | 88.89 (12) | C11—C12—N2 | 119.0 (4) |
O13—Rh1—O1 | 90.28 (12) | C13—C12—N2 | 118.8 (4) |
O9—Rh1—O1 | 175.46 (10) | C14—C13—C12 | 118.3 (4) |
O5—Rh1—N5 | 92.70 (12) | C14—C13—H8 | 120.8 |
O13—Rh1—N5 | 91.66 (12) | C12—C13—H8 | 120.8 |
O9—Rh1—N5 | 91.74 (10) | C13—C14—C9 | 120.4 (4) |
O1—Rh1—N5 | 92.80 (10) | C13—C14—H9 | 119.8 |
O5—Rh1—Rh2 | 87.95 (8) | C9—C14—H9 | 119.8 |
O13—Rh1—Rh2 | 87.69 (8) | O10—C15—O9 | 125.8 (3) |
O9—Rh1—Rh2 | 87.86 (8) | O10—C15—C16 | 116.4 (3) |
O1—Rh1—Rh2 | 87.61 (8) | O9—C15—C16 | 117.8 (3) |
N5—Rh1—Rh2 | 179.23 (9) | C21—C16—C17 | 119.9 (4) |
O10—Rh2—O6 | 90.41 (12) | C21—C16—C15 | 118.9 (3) |
O10—Rh2—O14 | 90.05 (13) | C17—C16—C15 | 121.1 (3) |
O6—Rh2—O14 | 176.52 (11) | C18—C17—C16 | 120.0 (4) |
O10—Rh2—O2 | 176.70 (11) | C18—C17—H10 | 120.0 |
O6—Rh2—O2 | 88.83 (12) | C16—C17—H10 | 120.0 |
O14—Rh2—O2 | 90.52 (13) | C19—C18—C17 | 119.1 (4) |
O10—Rh2—O17 | 91.18 (10) | C19—C18—H11 | 120.5 |
O6—Rh2—O17 | 92.37 (11) | C17—C18—H11 | 120.5 |
O14—Rh2—O17 | 91.07 (12) | C18—C19—C20 | 121.9 (4) |
O2—Rh2—O17 | 92.06 (10) | C18—C19—N3 | 118.7 (4) |
O10—Rh2—Rh1 | 88.33 (8) | C20—C19—N3 | 119.4 (3) |
O6—Rh2—Rh1 | 88.05 (8) | C19—C20—C21 | 119.0 (4) |
O14—Rh2—Rh1 | 88.51 (9) | C19—C20—H12 | 120.5 |
O2—Rh2—Rh1 | 88.43 (8) | C21—C20—H12 | 120.5 |
O17—Rh2—Rh1 | 179.36 (8) | C20—C21—C16 | 120.2 (4) |
C1—O1—Rh1 | 119.2 (2) | C20—C21—H13 | 119.9 |
C1—O2—Rh2 | 119.1 (2) | C16—C21—H13 | 119.9 |
C8—O5—Rh1 | 119.0 (3) | O14—C22—O13 | 126.5 (4) |
C8—O6—Rh2 | 119.4 (2) | O14—C22—C23 | 116.6 (3) |
C15—O9—Rh1 | 118.4 (2) | O13—C22—C23 | 117.0 (3) |
C15—O10—Rh2 | 119.5 (2) | C28—C23—C24 | 119.7 (4) |
C22—O13—Rh1 | 118.7 (2) | C28—C23—C22 | 119.5 (3) |
C22—O14—Rh2 | 118.5 (3) | C24—C23—C22 | 120.7 (4) |
C34—O17—Rh2 | 122.0 (3) | C25—C24—C23 | 120.2 (4) |
C34—O17—H1 | 109 (5) | C25—C24—H14 | 119.9 |
Rh2—O17—H1 | 128 (5) | C23—C24—H14 | 119.9 |
O4—N1—O3 | 123.8 (4) | C24—C25—C26 | 118.5 (4) |
O4—N1—C5 | 118.1 (3) | C24—C25—H15 | 120.7 |
O3—N1—C5 | 118.1 (4) | C26—C25—H15 | 120.7 |
O7—N2—O8 | 123.6 (4) | C27—C26—C25 | 122.8 (4) |
O7—N2—C12 | 118.5 (3) | C27—C26—N4 | 118.6 (4) |
O8—N2—C12 | 117.9 (4) | C25—C26—N4 | 118.6 (4) |
O11—N3—O12 | 123.6 (3) | C26—C27—C28 | 118.5 (4) |
O11—N3—C19 | 118.3 (3) | C26—C27—H16 | 120.8 |
O12—N3—C19 | 118.1 (3) | C28—C27—H16 | 120.8 |
O16—N4—O15 | 122.7 (4) | C27—C28—C23 | 120.2 (4) |
O16—N4—C26 | 118.5 (3) | C27—C28—H17 | 119.9 |
O15—N4—C26 | 118.8 (3) | C23—C28—H17 | 119.9 |
C33—N5—C29 | 119.2 (3) | N5—C29—C30 | 122.0 (4) |
C33—N5—Rh1 | 120.5 (3) | N5—C29—H18 | 119.0 |
C29—N5—Rh1 | 120.3 (3) | C30—C29—H18 | 119.0 |
O2—C1—O1 | 125.6 (4) | C29—C30—C31 | 119.0 (4) |
O2—C1—C2 | 116.2 (3) | C29—C30—H19 | 120.5 |
O1—C1—C2 | 118.1 (3) | C31—C30—H19 | 120.5 |
C3—C2—C7 | 119.2 (4) | C32—C31—C30 | 118.4 (4) |
C3—C2—C1 | 120.4 (3) | C32—C31—H20 | 120.8 |
C7—C2—C1 | 120.3 (3) | C30—C31—H20 | 120.8 |
C4—C3—C2 | 121.0 (4) | C33—C32—C31 | 119.7 (4) |
C4—C3—H2 | 119.5 | C33—C32—H21 | 120.2 |
C2—C3—H2 | 119.5 | C31—C32—H21 | 120.2 |
C3—C4—C5 | 118.2 (4) | N5—C33—C32 | 121.8 (4) |
C3—C4—H3 | 120.9 | N5—C33—H22 | 119.1 |
C5—C4—H3 | 120.9 | C32—C33—H22 | 119.1 |
C6—C5—C4 | 122.5 (4) | O17—C34—H23 | 109.5 |
C6—C5—N1 | 118.8 (4) | O17—C34—H24 | 109.5 |
C4—C5—N1 | 118.6 (4) | H23—C34—H24 | 109.5 |
C5—C6—C7 | 118.4 (4) | O17—C34—H25 | 109.5 |
C5—C6—H4 | 120.8 | H23—C34—H25 | 109.5 |
C7—C6—H4 | 120.8 | H24—C34—H25 | 109.5 |
C6—C7—C2 | 120.6 (4) | Cl2—C35—Cl1 | 114.6 (6) |
C6—C7—H5 | 119.7 | Cl2—C35—H26 | 108.6 |
C2—C7—H5 | 119.7 | Cl1—C35—H26 | 108.6 |
O5—C8—O6 | 125.2 (4) | Cl2—C35—H27 | 108.6 |
O5—C8—C9 | 118.4 (3) | Cl1—C35—H27 | 108.6 |
O6—C8—C9 | 116.3 (3) | H26—C35—H27 | 107.6 |
C10—C9—C14 | 120.0 (4) | Cl4—C36—Cl3 | 117.2 (14) |
C10—C9—C8 | 120.6 (3) | Cl4—C36—H28 | 108.0 |
C14—C9—C8 | 119.3 (3) | Cl3—C36—H28 | 108.0 |
C11—C10—C9 | 120.4 (4) | Cl4—C36—H29 | 108.0 |
C11—C10—H6 | 119.8 | Cl3—C36—H29 | 108.0 |
C9—C10—H6 | 119.8 | H28—C36—H29 | 107.2 |
C10—C11—C12 | 118.6 (4) | | |
| | | |
O5—Rh1—Rh2—O10 | −91.09 (12) | N1—C5—C6—C7 | −179.9 (3) |
O13—Rh1—Rh2—O10 | 89.57 (12) | C5—C6—C7—C2 | 0.8 (6) |
O9—Rh1—Rh2—O10 | −0.25 (12) | C3—C2—C7—C6 | 0.1 (6) |
O1—Rh1—Rh2—O10 | 179.94 (12) | C1—C2—C7—C6 | 177.1 (4) |
O5—Rh1—Rh2—O6 | −0.61 (10) | Rh1—O5—C8—O6 | 6.7 (5) |
O13—Rh1—Rh2—O6 | −179.96 (11) | Rh1—O5—C8—C9 | −171.2 (2) |
O9—Rh1—Rh2—O6 | 90.22 (12) | Rh2—O6—C8—O5 | −7.5 (5) |
O1—Rh1—Rh2—O6 | −89.59 (12) | Rh2—O6—C8—C9 | 170.4 (2) |
O5—Rh1—Rh2—O14 | 178.82 (11) | O5—C8—C9—C10 | −1.0 (5) |
O13—Rh1—Rh2—O14 | −0.52 (11) | O6—C8—C9—C10 | −179.1 (3) |
O9—Rh1—Rh2—O14 | −90.34 (13) | O5—C8—C9—C14 | 175.8 (3) |
O1—Rh1—Rh2—O14 | 89.85 (12) | O6—C8—C9—C14 | −2.3 (5) |
O5—Rh1—Rh2—O2 | 88.26 (12) | C14—C9—C10—C11 | −1.5 (5) |
O13—Rh1—Rh2—O2 | −91.08 (12) | C8—C9—C10—C11 | 175.4 (3) |
O9—Rh1—Rh2—O2 | 179.10 (12) | C9—C10—C11—C12 | −0.2 (5) |
O1—Rh1—Rh2—O2 | −0.71 (11) | C10—C11—C12—C13 | 1.5 (6) |
O5—Rh1—O1—C1 | −86.1 (3) | C10—C11—C12—N2 | −179.2 (3) |
O13—Rh1—O1—C1 | 89.5 (3) | O7—N2—C12—C11 | 4.5 (5) |
N5—Rh1—O1—C1 | −178.8 (3) | O8—N2—C12—C11 | −174.6 (4) |
Rh2—Rh1—O1—C1 | 1.8 (3) | O7—N2—C12—C13 | −176.2 (4) |
O6—Rh2—O2—C1 | 87.9 (3) | O8—N2—C12—C13 | 4.7 (5) |
O14—Rh2—O2—C1 | −88.7 (3) | C11—C12—C13—C14 | −1.1 (6) |
O17—Rh2—O2—C1 | −179.8 (3) | N2—C12—C13—C14 | 179.6 (3) |
Rh1—Rh2—O2—C1 | −0.2 (3) | C12—C13—C14—C9 | −0.6 (5) |
O9—Rh1—O5—C8 | −90.4 (3) | C10—C9—C14—C13 | 1.9 (5) |
O1—Rh1—O5—C8 | 85.1 (3) | C8—C9—C14—C13 | −175.0 (3) |
N5—Rh1—O5—C8 | 177.9 (3) | Rh2—O10—C15—O9 | 1.2 (6) |
Rh2—Rh1—O5—C8 | −2.5 (3) | Rh2—O10—C15—C16 | −177.9 (3) |
O10—Rh2—O6—C8 | 92.3 (3) | Rh1—O9—C15—O10 | −1.5 (5) |
O2—Rh2—O6—C8 | −84.5 (3) | Rh1—O9—C15—C16 | 177.6 (3) |
O17—Rh2—O6—C8 | −176.5 (3) | O10—C15—C16—C21 | −4.3 (6) |
Rh1—Rh2—O6—C8 | 4.0 (3) | O9—C15—C16—C21 | 176.5 (4) |
O5—Rh1—O9—C15 | 88.8 (3) | O10—C15—C16—C17 | 172.6 (4) |
O13—Rh1—O9—C15 | −86.8 (3) | O9—C15—C16—C17 | −6.6 (6) |
N5—Rh1—O9—C15 | −178.4 (3) | C21—C16—C17—C18 | −0.3 (7) |
Rh2—Rh1—O9—C15 | 0.9 (3) | C15—C16—C17—C18 | −177.1 (4) |
O6—Rh2—O10—C15 | −88.4 (3) | C16—C17—C18—C19 | 1.3 (7) |
O14—Rh2—O10—C15 | 88.2 (3) | C17—C18—C19—C20 | −1.3 (7) |
O17—Rh2—O10—C15 | 179.3 (3) | C17—C18—C19—N3 | 178.0 (4) |
Rh1—Rh2—O10—C15 | −0.3 (3) | O11—N3—C19—C18 | 4.4 (6) |
O9—Rh1—O13—C22 | 86.4 (3) | O12—N3—C19—C18 | −175.4 (4) |
O1—Rh1—O13—C22 | −89.0 (3) | O11—N3—C19—C20 | −176.3 (4) |
N5—Rh1—O13—C22 | 178.2 (3) | O12—N3—C19—C20 | 4.0 (6) |
Rh2—Rh1—O13—C22 | −1.4 (3) | C18—C19—C20—C21 | 0.3 (7) |
O10—Rh2—O14—C22 | −85.7 (3) | N3—C19—C20—C21 | −179.0 (4) |
O2—Rh2—O14—C22 | 91.1 (3) | C19—C20—C21—C16 | 0.8 (6) |
O17—Rh2—O14—C22 | −176.9 (3) | C17—C16—C21—C20 | −0.8 (7) |
Rh1—Rh2—O14—C22 | 2.6 (3) | C15—C16—C21—C20 | 176.1 (4) |
O10—Rh2—O17—C34 | −40.0 (3) | Rh2—O14—C22—O13 | −4.8 (5) |
O6—Rh2—O17—C34 | −130.5 (3) | Rh2—O14—C22—C23 | 173.6 (2) |
O14—Rh2—O17—C34 | 50.1 (3) | Rh1—O13—C22—O14 | 4.2 (5) |
O2—Rh2—O17—C34 | 140.6 (3) | Rh1—O13—C22—C23 | −174.2 (2) |
O5—Rh1—N5—C33 | 165.0 (3) | O14—C22—C23—C28 | −4.3 (5) |
O13—Rh1—N5—C33 | −15.7 (3) | O13—C22—C23—C28 | 174.3 (3) |
O9—Rh1—N5—C33 | 74.1 (3) | O14—C22—C23—C24 | 179.3 (3) |
O1—Rh1—N5—C33 | −106.0 (3) | O13—C22—C23—C24 | −2.0 (5) |
O5—Rh1—N5—C29 | −15.0 (3) | C28—C23—C24—C25 | −1.9 (6) |
O13—Rh1—N5—C29 | 164.4 (3) | C22—C23—C24—C25 | 174.5 (3) |
O9—Rh1—N5—C29 | −105.8 (3) | C23—C24—C25—C26 | −0.6 (6) |
O1—Rh1—N5—C29 | 74.0 (3) | C24—C25—C26—C27 | 3.2 (6) |
Rh2—O2—C1—O1 | 1.8 (5) | C24—C25—C26—N4 | −178.2 (3) |
Rh2—O2—C1—C2 | −175.9 (2) | O16—N4—C26—C27 | 6.5 (5) |
Rh1—O1—C1—O2 | −2.6 (5) | O15—N4—C26—C27 | −174.9 (4) |
Rh1—O1—C1—C2 | 175.0 (2) | O16—N4—C26—C25 | −172.2 (3) |
O2—C1—C2—C3 | 171.6 (4) | O15—N4—C26—C25 | 6.4 (5) |
O1—C1—C2—C3 | −6.3 (6) | C25—C26—C27—C28 | −3.1 (6) |
O2—C1—C2—C7 | −5.3 (5) | N4—C26—C27—C28 | 178.3 (3) |
O1—C1—C2—C7 | 176.8 (4) | C26—C27—C28—C23 | 0.5 (6) |
C7—C2—C3—C4 | −0.7 (6) | C24—C23—C28—C27 | 2.0 (6) |
C1—C2—C3—C4 | −177.7 (4) | C22—C23—C28—C27 | −174.5 (4) |
C2—C3—C4—C5 | 0.4 (6) | C33—N5—C29—C30 | 0.3 (5) |
C3—C4—C5—C6 | 0.5 (6) | Rh1—N5—C29—C30 | −179.7 (3) |
C3—C4—C5—N1 | 179.3 (4) | N5—C29—C30—C31 | 0.3 (5) |
O4—N1—C5—C6 | 4.9 (5) | C29—C30—C31—C32 | −0.6 (5) |
O3—N1—C5—C6 | −174.8 (4) | C30—C31—C32—C33 | 0.2 (6) |
O4—N1—C5—C4 | −174.0 (4) | C29—N5—C33—C32 | −0.8 (5) |
O3—N1—C5—C4 | 6.3 (6) | Rh1—N5—C33—C32 | 179.3 (3) |
C4—C5—C6—C7 | −1.0 (6) | C31—C32—C33—N5 | 0.5 (6) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O17—H1···O2iii | 0.65 (5) | 2.42 (5) | 2.963 (4) | 143 (6) |
Symmetry code: (iii) −x+1, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Rh2(C11H14NO2)4(C7H5N)2]·2C7H5N | [Rh2(C7H4NO4)4(C2H4O)(C5H5N)]·CH2Cl2 |
Mr | 1387.23 | 1066.34 |
Crystal system, space group | TriclinicP1 | TriclinicP1 |
Temperature (K) | 296 | 113 |
a, b, c (Å) | 10.049 (4), 12.752 (6), 13.479 (6) | 12.750 (6), 13.290 (4), 14.773 (5) |
α, β, γ (°) | 98.641 (6), 90.781 (6), 99.424 (6) | 96.55 (3), 109.42 (1), 118.43 (1) |
V (Å3) | 1683.3 (13) | 1961.0 (13) |
Z | 1 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.55 | 1.06 |
Crystal size (mm) | 0.20 × 0.10 × 0.10 | 0.30 × 0.10 × 0.10 |
|
Data collection |
Diffractometer | Rigaku/MSC Mercury CCD area-detector diffractometer | Rigaku/MSC Mercury CCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13963, 7660, 5661 | 16189, 8932, 6931 |
Rint | 0.046 | 0.047 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.104, 1.05 | 0.047, 0.116, 1.05 |
No. of reflections | 7660 | 8932 |
No. of parameters | 475 | 577 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.52, −0.71 | 0.82, −1.05 |
Selected bond lengths (Å) for (I) topRh1—Rh1i | 2.3920 (9) | Rh1—O3 | 2.0407 (12) |
Rh1—O1 | 2.0463 (10) | Rh1—O4i | 2.0318 (12) |
Rh1—O2i | 2.0276 (10) | Rh1—N3 | 2.2194 (14) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Dihedral angles (°) in the p-diaminobenzoate ligand for (I) topO2C | C6H4 | NC2 | O2C–C6H4 | C6H4–NC2 |
O1/C1/O2 | C2–C7 | C8/N1/C10 | 3.83 (14) | 16.54 (16) |
O3/C12/O4 | C13–C18 | C19/N2/C21 | 20.28 (17)a | 22.8 (2)a |
| | | 11.27 (18)b | 6.7 (3)b |
Notes: (a) Site A. (b) Site B. |
Selected bond lengths (Å) for (II) topRh1—Rh2 | 2.3937 (10) | Rh2—O2 | 2.037 (3) |
Rh1—O1 | 2.051 (3) | Rh2—O6 | 2.028 (3) |
Rh1—O5 | 2.039 (3) | Rh2—O10 | 2.022 (3) |
Rh1—O9 | 2.050 (3) | Rh2—O14 | 2.030 (3) |
Rh1—O13 | 2.042 (3) | Rh2—O17 | 2.291 (3) |
Rh1—N5 | 2.218 (3) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O17—H1···O2i | 0.65 (5) | 2.42 (5) | 2.963 (4) | 143 (6) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Dihedral angles (°) in the p-nitrobenzoate ligand for (II) topO2C | C6H4 | NO2 | O2C–C6H4 | C6H4–NO2 |
O1/C1/O2 | C2–C7 | O3/N1/O4 | 7.1 (4) | 5.8 (4) |
O5/C8/O6 | C9–C14 | O7/N2/O8 | 6.2 (2) | 4.5 (2) |
O9/C15/O10 | C16–C21 | O11/N3/O12 | 6.4 (4) | 4.7 (4) |
O13/C22/O14 | C23–C28 | O15/N4/O16 | 7.1 (3) | 6.4 (2) |
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Paddlewheel dimetal complexes have been attracted much attention in recent years, because they are useful modules to make assembled frameworks. Among such paddlewheel complexes, metal–metal single-bonded dirhodium(II) complexes are interesting examples that change their highest occupied molecular orbitals (HOMOs) depending on their bridging and axial ligands (Kawamura et al., 1989, 1998). For example, the HOMOs of such compounds with carboxylate bridges are π* orbitals, but amidate-bridged ones have a δ* HOMO. We have studied assembled structures with paddlewheel dirhodium cationic radicals constructed by π–π stacking interactions between odd electron densities on the bridging ligands (Kawamura et al., 1993, 2000) or by connection with axial linker ligands (Yang et al., 2000, 2001, 2006; Takazaki et al., 2003; Fuma et al., 2004). Substituted benzoates are interesting bridging ligands, the donor ability and stacking pattern of which are changed with their substituents. In this paper, we report the crystal structures of two novel dirhodium complexes with p-substituted benzoate bridges, [Rh2(O2CC6H4NEt2)4(PhCN)2]·2PhCN, (I), and [Rh2(O2CC6H4NO2)4(MeOH)(py)]·CH2Cl2, (II).
In the structure of (I), the rhodium complex lies on a crystallographic inversion centre, there is also one benzonitrile solvent molecule in the asymmetric unit. The O—Rh—Rh—O torsion angles are close to 0°. In one of the two independent bridging ligands, four of the six phenyl C atoms, the N atom and one ethyl group are disordered over two sets of sites, labelled A and B. In both disordered sites, the phenyl groups are slightly tilted from the CO2 plane (Table 2). The C2N moiety of the amino group does not deviate much from the C6H4 plane. The ethyl groups of the diethylamino substituent point toward opposite sides of the phenyl ring for the A site and towards the same side for the B site. For the other bridging ligand, the C2N, C6H4 and CO2 moieties are nearly coplanar and the ethyl groups of the amino substituent point towards the same side of the phenyl ring. The near-planarity of the diethylaminobenzoate group suggests that it has a significant quinoid character. This is also reflected in the bond-length pattern of the ligand [average distances are: C2—C3 and C2—C7 1.390 (2) Å; C3—C4 and C6—C7 1.378 (2) Å; C4—C5 and C5—C6 1.408 (2) Å]. The axial positions are occupied by benzonitrile molecules, with almost straight Rh1—Rh1—N3 and the slightly bent Rh1—N3—C23 angles. The Rh—Rh distance of 2.3920 (9) Å is very close to the values observed for dirhodium complexes bridged by benzoate or its derivatives and axially bonded by N-donors [2.3882 (4)–2.4037 (4) Å; Castro et al., 2002; Cotton & Thompson, 1984; Cotton et al., 2002; Hikichi et al., 2003; Mehmet & Tocher, 1991]. In the crystal structure of (I), π–π stacking interactions are not observed.
In the structure of (II), there is one independent molecule in the asymmetric unit with a disordered dichloromethane molecule. The Rh2O8 skeleton is in a nearly complete eclipsed conformation, as was found for (I). The bridging nitrobenzoate ligands are almost planar: dihedral angles between the O2C and phenyl groups and between the phenyl and NO2 groups for each ligand are close to 0° (Table 5). The axial sites are occupied by one MeOH and one pyridine ligand. Only two dirhodium compounds with an N and an O atom at the axial positions have been reported to date (Cogne et al., 1987, 1989). The pyridine ring is slightly tilted from the plane of the nearer carboxylate groups, with a torsion angle between them of ca 15°. The Rh—Rh distance [2.3936 (10) Å] is very similar to that of (I).
In the crystal structure of (II), the MeOH ligand donates an H atom to an O atom of the bridging carboxylate [O2i; Fig. 3 and Table 4; symmetry code: (ii) Should this be (i)? 1 - x, 1 - y, 1 - z]. This type of hydrogen bonding has also been observed in some paddlewheel complexes with axial alcohol ligands (Rao et al., 1983; Noinville et al., 1993; Agterberg et al., 1997). Strong π–π stacking interactions between p-nitrobenzoate and pyridine are observed between the complex molecules at (x, y, z) and (1 - x, 1 - y, -z), and between those at (x, y, z) and (2 - x, 1 - y, 1 - z) (Fig. 3). In the former pair, representative short contacts are as follows: N2···C32ii 3.177 (6), C11···C29ii 3.252 (7), O7···C33ii 3.320 (6), C12···C31ii 3.342 (7) and C13···C31ii 3.394 (8) Å [symmetry code: (ii) 1 - x, 1 - y, -z]. In the latter pair, very similar contacts are observed: N4···C30iii 3.172 (7), C25···C33iii 3.270 (7), O16···C30iii 3.230 (5), C27···C31iii 3.386 (7) and C26···C31iii 3.403 (8) Å [symmetry code: (iii) 2 - x, 1 - y, 1 - z]. These interactions result in the nitrobenzoate ligands sandwiching the pyridine.