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In diaquatetra-μ-acetamidato-κ4N:O;κ4O:N-dirhodium(II,III) hexafluorophosphate, [Rh2(C2H4NO)4(H2O)2]PF6, and diaquatetra-μ-acetamidato-κ4N:O;κ4O:N-dirhodium(II,III)hexafluorophosphate dihydrate, [Rh2(C2H4NO)4(H2O)2]PF6·2H2O, the cations and anions lie on inversion centers. Diaquatetra-μ-propionamidato-κ4N:O;κ4O:N-dirhodium(II,III) hexafluorophosphate dihydrate, [Rh2(C3H6NO)4(H2O)2]PF6·2H2O, and diaquatetra-μ-butyramidato-κ4N:O;κ4O:N-dirhodium(II,III) hexafluorophosphate, [Rh2(C4H8NO)4(H2O)2]PF6, crystallize with two crystallographically independent complexes that lie on inversion centers. In all of the structures, the dirhodium units are hydrogen bonded to one another. The hydrogen-bonded networks vary with the alkyl substituents.
Supporting information
CCDC references: 616107; 616108; 616109; 616110
[Rh2(acam)4(H2O)2]·6H2O was synthesized according to a published method (Doyle et al., 1990). Compounds (I) and (II) were prepared by a modification of the method of Baranovskii et al. (1986) for [Rh2(acam)4(H2O)2]ClO4. To an aqueous solution (50 ml) of [Rh2(acam)4(H2O)2]·6H2O (0.751 g, 1.29 mmol) at 353 K, Ag2SO4 (0.200 g, 0.64 mmol) was added and the mixture was stirred for 10 min. The solution was cooled to 273 K and the precipitate was filtered off. NH4PF6 (10.1 g, 62.1 mmol) was added to the brown filtrate and left for 20 h to give brown crystals of (II) (yield 0.612 g, 72%). The crystals gradually lost their water of crystallization. The crystals of (I) were obtained by slow evaporation of an aqueous solution of (II). Analysis calculated for C8H20F6N4O6PRh2: C 15.52, H 3.26, N 9.05%; found: C 15.42, H 3.12, N 8.74%. Compound (III) was prepared in a similar manner to (II). [Rh2(CH3CO2)4(CH3OH)2] (0.515 g, 1.02 mmol) was heated at 363 K for 1 h under reduced pressure. An excess of propionamide (3.60 g, 49.3 mmol) and toluene (76 ml) were added to it. The suspension of the mixture was refluxed for seven days under an Ar atmosphere equipped with a Soxhlet extractor in which the extraction thimble contained sodium carbonate and molecular sieves (3 Å). The resulting blue–purple solution was distilled to remove the solvent and amide. The residual amide was sublimed from the resulting blue–purple powder. An aqueous solution (60 ml) of Ag2SO4 (0.16 g, 0.51 mmol) was added and stirred for 12 h at 323 K. A gray precipitate was filtered off, and NH4PF6 (10.5 g, 64.5 mmol) was added. After the solution had been left to stand for several days, X-ray quality crystals of (III) were obtained (yield 0.318 g, 44%). Analysis calculated for C12H32F6N4O8PRh2: C 20.27, H 4.54, N 7.88%; found: C 20.05, H 4.25, N 7.77%. Compound (IV) was also prepared in a similar manner to (II). Starting from [Rh2(CH3CO2)4(CH3OH)2] (0.502 g, 0.992 mmol) and butyramide (3.35 g, 35.2 mmol), a brown powder of (IV) was obtained (0.291 g, 40%). X-ray quality crystals were obtained by slow diffusion of n-hexane into a dichloromethane solution. Analysis calculated for C16H36F6N4O6PRh2: C 26.28, H 4.96, N 7.66%; found: C 26.51, H 4.89, N 8.06%.
One ethyl group in (III) is disordered. Atoms C11 and C12 were refined with isotropic displacement parameters by splitting at two sites with the occupancies of the two sets of atoms, A and B, as 0.50. In (IV), one disordered methyl C atom, C16, was refined by splitting at two sites with the occupancies as 0.75 and 1/4, respectively. Four of the six F atoms in (IV) are also disordered. Atoms F3, F4, F5 and F6 were refined by splitting at two sites with the occupancies of the two sets of atoms, A and B, as 0.60 and 0.40, respectively. H atoms on O atoms were refined freely. All other H atoms were placed in idealized positions and treated as riding atoms with C—H distances in the range 0.98–0.99 Å and N—H distances of 0.88 Å.
For all compounds, data collection: CrystalClear (Molecular Structure Corporation & Rigaku Corporation, 2001); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 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) diaquatetra-µ-acetamidato-
κ4N:
O;
κ4O:
N-dirhodium(II,III) hexafluorophosphate
top
Crystal data top
[Rh2(C2H4NO)4(H2O)2]PF6 | Z = 1 |
Mr = 619.07 | F(000) = 303 |
Triclinic, P1 | Dx = 2.226 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 6.631 (3) Å | Cell parameters from 1576 reflections |
b = 7.719 (4) Å | θ = 3.5–27.5° |
c = 9.645 (4) Å | µ = 1.97 mm−1 |
α = 92.014 (5)° | T = 118 K |
β = 92.205 (5)° | Platelet, brown |
γ = 110.471 (7)° | 0.10 × 0.10 × 0.03 mm |
V = 461.6 (4) Å3 | |
Data collection top
Rigaku/MSC Mercury CCD diffractometer | 2096 independent reflections |
Graphite monochromator | 1903 reflections with I > 2σ(I) |
Detector resolution: 14.62 pixels mm-1 | Rint = 0.026 |
ω scans | θmax = 27.5°, θmin = 3.5° |
Absorption correction: integration (NUMABS; Higashi, 1999) | h = −8→8 |
Tmin = 0.751, Tmax = 0.940 | k = −10→7 |
3818 measured reflections | l = −12→12 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0246P)2 + 0.4628P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2096 reflections | Δρmax = 0.48 e Å−3 |
133 parameters | Δρmin = −0.64 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0080 (14) |
Crystal data top
[Rh2(C2H4NO)4(H2O)2]PF6 | γ = 110.471 (7)° |
Mr = 619.07 | V = 461.6 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.631 (3) Å | Mo Kα radiation |
b = 7.719 (4) Å | µ = 1.97 mm−1 |
c = 9.645 (4) Å | T = 118 K |
α = 92.014 (5)° | 0.10 × 0.10 × 0.03 mm |
β = 92.205 (5)° | |
Data collection top
Rigaku/MSC Mercury CCD diffractometer | 2096 independent reflections |
Absorption correction: integration (NUMABS; Higashi, 1999) | 1903 reflections with I > 2σ(I) |
Tmin = 0.751, Tmax = 0.940 | Rint = 0.026 |
3818 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.48 e Å−3 |
2096 reflections | Δρmin = −0.64 e Å−3 |
133 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 | |
Rh1 | 0.57195 (4) | 0.38189 (3) | 0.46797 (2) | 0.00767 (10) | |
N1 | 0.3919 (4) | 0.3470 (3) | 0.2932 (3) | 0.0112 (5) | |
H1 | 0.3913 | 0.2589 | 0.2326 | 0.013* | |
O1 | 0.2539 (3) | 0.5704 (3) | 0.3481 (2) | 0.0107 (4) | |
N2 | 0.8082 (4) | 0.5800 (3) | 0.3886 (3) | 0.0102 (5) | |
H2 | 0.9145 | 0.5511 | 0.3549 | 0.012* | |
O2 | 0.6732 (3) | 0.8068 (3) | 0.4369 (2) | 0.0100 (4) | |
O3 | 0.7148 (4) | 0.1685 (3) | 0.3915 (3) | 0.0147 (5) | |
H3 | 0.705 (6) | 0.154 (5) | 0.314 (4) | 0.022* | |
H4 | 0.690 (6) | 0.064 (6) | 0.410 (4) | 0.022* | |
C1 | 0.2743 (5) | 0.4465 (4) | 0.2623 (3) | 0.0114 (6) | |
C2 | 0.1560 (5) | 0.4228 (5) | 0.1224 (3) | 0.0180 (7) | |
H5 | 0.0086 | 0.4193 | 0.1348 | 0.027* | |
H6 | 0.1514 | 0.3068 | 0.0753 | 0.027* | |
H7 | 0.2310 | 0.5269 | 0.0661 | 0.027* | |
C3 | 0.8175 (5) | 0.7519 (4) | 0.3825 (3) | 0.0103 (6) | |
C4 | 0.9905 (5) | 0.8888 (4) | 0.3087 (3) | 0.0147 (6) | |
H8 | 0.9309 | 0.9121 | 0.2197 | 0.022* | |
H9 | 1.1058 | 0.8398 | 0.2921 | 0.022* | |
H10 | 1.0490 | 1.0048 | 0.3657 | 0.022* | |
P1 | 0.5000 | 0.0000 | 0.0000 | 0.0155 (2) | |
F1 | 0.6361 (3) | 0.1854 (3) | 0.0930 (2) | 0.0263 (5) | |
F2 | 0.5098 (4) | 0.1187 (3) | −0.1327 (2) | 0.0334 (5) | |
F3 | 0.2813 (3) | 0.0270 (3) | 0.0398 (2) | 0.0338 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh1 | 0.00802 (13) | 0.00665 (13) | 0.00928 (13) | 0.00371 (9) | 0.00082 (8) | 0.00067 (8) |
N1 | 0.0119 (12) | 0.0104 (12) | 0.0108 (12) | 0.0035 (10) | −0.0002 (10) | −0.0018 (10) |
O1 | 0.0096 (10) | 0.0110 (10) | 0.0119 (10) | 0.0043 (8) | 0.0001 (8) | 0.0008 (8) |
N2 | 0.0082 (11) | 0.0111 (12) | 0.0124 (12) | 0.0046 (10) | 0.0018 (10) | 0.0009 (10) |
O2 | 0.0110 (10) | 0.0095 (10) | 0.0110 (10) | 0.0050 (8) | 0.0035 (8) | 0.0023 (8) |
O3 | 0.0220 (12) | 0.0105 (11) | 0.0153 (11) | 0.0097 (10) | 0.0056 (10) | 0.0024 (9) |
C1 | 0.0090 (14) | 0.0113 (14) | 0.0123 (14) | 0.0014 (12) | 0.0001 (11) | 0.0027 (11) |
C2 | 0.0215 (17) | 0.0207 (17) | 0.0133 (15) | 0.0099 (14) | −0.0037 (13) | −0.0004 (13) |
C3 | 0.0099 (14) | 0.0106 (14) | 0.0091 (14) | 0.0023 (11) | −0.0011 (11) | 0.0006 (11) |
C4 | 0.0146 (15) | 0.0119 (14) | 0.0179 (16) | 0.0045 (12) | 0.0046 (13) | 0.0030 (12) |
P1 | 0.0169 (6) | 0.0168 (6) | 0.0119 (5) | 0.0045 (5) | 0.0038 (5) | −0.0014 (4) |
F1 | 0.0277 (11) | 0.0227 (11) | 0.0206 (11) | −0.0004 (9) | 0.0024 (9) | −0.0076 (9) |
F2 | 0.0461 (14) | 0.0289 (12) | 0.0194 (11) | 0.0056 (11) | −0.0016 (10) | 0.0075 (9) |
F3 | 0.0216 (11) | 0.0412 (13) | 0.0399 (13) | 0.0135 (10) | 0.0068 (10) | −0.0114 (11) |
Geometric parameters (Å, º) top
Rh1—Rh1i | 2.4085 (10) | O3—H4 | 0.80 (4) |
Rh1—O1i | 2.029 (2) | C1—C2 | 1.507 (4) |
Rh1—O2i | 2.040 (2) | C2—H5 | 0.9800 |
Rh1—O3 | 2.284 (2) | C2—H6 | 0.9800 |
Rh1—N1 | 1.983 (3) | C2—H7 | 0.9800 |
Rh1—N2 | 1.969 (3) | C3—C4 | 1.486 (4) |
N1—C1 | 1.305 (4) | C4—H8 | 0.9800 |
N1—H1 | 0.8800 | C4—H9 | 0.9800 |
O1—C1 | 1.290 (3) | C4—H10 | 0.9800 |
N2—C3 | 1.311 (4) | P1—F2 | 1.591 (2) |
N2—H2 | 0.8800 | P1—F3 | 1.594 (2) |
O2—C3 | 1.295 (3) | P1—F1 | 1.616 (2) |
O3—H3 | 0.75 (4) | | |
| | | |
N2—Rh1—N1 | 90.78 (11) | O1—C1—C2 | 116.4 (2) |
N2—Rh1—O1i | 89.50 (10) | N1—C1—C2 | 121.2 (3) |
N1—Rh1—O1i | 176.04 (8) | C1—C2—H5 | 109.5 |
N2—Rh1—O2i | 175.07 (8) | C1—C2—H6 | 109.5 |
N1—Rh1—O2i | 91.67 (10) | H5—C2—H6 | 109.5 |
O1i—Rh1—O2i | 87.75 (9) | C1—C2—H7 | 109.5 |
N2—Rh1—O3 | 90.09 (10) | H5—C2—H7 | 109.5 |
N1—Rh1—O3 | 91.48 (9) | H6—C2—H7 | 109.5 |
O1i—Rh1—O3 | 92.47 (8) | O2—C3—N2 | 121.3 (3) |
O2i—Rh1—O3 | 94.13 (9) | O2—C3—C4 | 117.8 (2) |
N2—Rh1—Rh1i | 86.58 (7) | N2—C3—C4 | 120.9 (2) |
N1—Rh1—Rh1i | 85.73 (7) | C3—C4—H8 | 109.5 |
O1i—Rh1—Rh1i | 90.35 (6) | C3—C4—H9 | 109.5 |
O2i—Rh1—Rh1i | 89.33 (6) | H8—C4—H9 | 109.5 |
O3—Rh1—Rh1i | 175.62 (7) | C3—C4—H10 | 109.5 |
C1—N1—Rh1 | 124.1 (2) | H8—C4—H10 | 109.5 |
C1—N1—H1 | 117.9 | H9—C4—H10 | 109.5 |
Rh1—N1—H1 | 117.9 | F2ii—P1—F2 | 180.00 (16) |
C1—O1—Rh1i | 117.31 (18) | F2ii—P1—F3 | 89.77 (12) |
C3—N2—Rh1 | 124.32 (19) | F2—P1—F3 | 90.23 (12) |
C3—N2—H2 | 117.8 | F3—P1—F3ii | 180.0 |
Rh1—N2—H2 | 117.8 | F2ii—P1—F1 | 89.49 (11) |
C3—O2—Rh1i | 118.31 (18) | F2—P1—F1 | 90.51 (11) |
Rh1—O3—H3 | 112 (3) | F3—P1—F1 | 89.89 (11) |
Rh1—O3—H4 | 131 (3) | F3ii—P1—F1 | 90.11 (11) |
H3—O3—H4 | 98 (4) | F1—P1—F1ii | 180.00 (11) |
O1—C1—N1 | 122.4 (3) | | |
| | | |
N2—Rh1—N1—C1 | −83.8 (2) | Rh1i—O1—C1—N1 | 3.7 (4) |
O2i—Rh1—N1—C1 | 91.9 (2) | Rh1i—O1—C1—C2 | −175.8 (2) |
O3—Rh1—N1—C1 | −173.9 (2) | Rh1—N1—C1—O1 | −4.6 (4) |
Rh1i—Rh1—N1—C1 | 2.7 (2) | Rh1—N1—C1—C2 | 174.8 (2) |
N1—Rh1—N2—C3 | 81.3 (2) | Rh1i—O2—C3—N2 | −0.3 (4) |
O1i—Rh1—N2—C3 | −94.8 (2) | Rh1i—O2—C3—C4 | 177.7 (2) |
O3—Rh1—N2—C3 | 172.7 (2) | Rh1—N2—C3—O2 | 3.9 (4) |
Rh1i—Rh1—N2—C3 | −4.4 (2) | Rh1—N2—C3—C4 | −174.0 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H4···O2iii | 0.80 (4) | 1.97 (4) | 2.760 (3) | 170 (4) |
O3—H3···F1 | 0.75 (4) | 2.20 (4) | 2.924 (3) | 162 (4) |
N1—H1···F1 | 0.88 | 2.35 | 3.064 (3) | 138 |
N1—H1···F3 | 0.88 | 2.44 | 3.285 (3) | 162 |
N2—H2···O1iv | 0.88 | 2.21 | 3.022 (3) | 154 |
Symmetry codes: (iii) x, y−1, z; (iv) x+1, y, z. |
(II) diaquatetra-µ-acetamidato-
κ4N:
O;
κ4O:
N-dirhodium(II,III) hexafluorophosphate dihydrate
top
Crystal data top
[Rh2(C2H4NO)4(H2O)2]PF6·2H2O | F(000) = 646 |
Mr = 655.10 | Dx = 2.152 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ybc | Cell parameters from 3400 reflections |
a = 11.6900 (17) Å | θ = 3.2–27.5° |
b = 11.5700 (13) Å | µ = 1.81 mm−1 |
c = 7.9800 (13) Å | T = 118 K |
β = 110.510 (6)° | Block, brown |
V = 1010.9 (3) Å3 | 0.30 × 0.30 × 0.15 mm |
Z = 2 | |
Data collection top
Rigaku/MSC Mercury CCD diffractometer | 2308 independent reflections |
Graphite monochromator | 2208 reflections with I > 2σ(I) |
Detector resolution: 14.62 pixels mm-1 | Rint = 0.026 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: integration (NUMABS; Higashi, 1999) | h = −15→12 |
Tmin = 0.712, Tmax = 0.828 | k = −15→12 |
7888 measured reflections | l = −10→10 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | w = 1/[σ2(Fo2) + (0.0199P)2 + 1.4706P] where P = (Fo2 + 2Fc2)/3 |
2308 reflections | (Δ/σ)max < 0.001 |
151 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.60 e Å−3 |
Crystal data top
[Rh2(C2H4NO)4(H2O)2]PF6·2H2O | V = 1010.9 (3) Å3 |
Mr = 655.10 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.6900 (17) Å | µ = 1.81 mm−1 |
b = 11.5700 (13) Å | T = 118 K |
c = 7.9800 (13) Å | 0.30 × 0.30 × 0.15 mm |
β = 110.510 (6)° | |
Data collection top
Rigaku/MSC Mercury CCD diffractometer | 2308 independent reflections |
Absorption correction: integration (NUMABS; Higashi, 1999) | 2208 reflections with I > 2σ(I) |
Tmin = 0.712, Tmax = 0.828 | Rint = 0.026 |
7888 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | Δρmax = 0.48 e Å−3 |
2308 reflections | Δρmin = −0.60 e Å−3 |
151 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 | |
Rh1 | 0.455494 (16) | 0.594804 (16) | 0.48006 (2) | 0.00878 (7) | |
N1 | 0.30983 (18) | 0.51921 (19) | 0.5034 (3) | 0.0126 (4) | |
H1 | 0.2470 | 0.5629 | 0.4976 | 0.015* | |
O1 | 0.39136 (15) | 0.33911 (15) | 0.5480 (2) | 0.0125 (4) | |
N2 | 0.53624 (18) | 0.61223 (19) | 0.7411 (3) | 0.0120 (4) | |
H2 | 0.5290 | 0.6791 | 0.7889 | 0.014* | |
O2 | 0.61337 (16) | 0.43007 (16) | 0.7904 (2) | 0.0125 (4) | |
O3 | 0.37215 (18) | 0.77161 (16) | 0.4414 (3) | 0.0158 (4) | |
H3 | 0.370 (3) | 0.818 (3) | 0.535 (5) | 0.032 (10)* | |
H4 | 0.309 (4) | 0.778 (4) | 0.364 (6) | 0.039 (11)* | |
C1 | 0.3017 (2) | 0.4083 (2) | 0.5267 (3) | 0.0126 (5) | |
C2 | 0.1850 (2) | 0.3545 (3) | 0.5276 (4) | 0.0197 (6) | |
H5 | 0.1449 | 0.3143 | 0.4139 | 0.030* | |
H6 | 0.1308 | 0.4149 | 0.5430 | 0.030* | |
H7 | 0.2032 | 0.2991 | 0.6264 | 0.030* | |
C3 | 0.5994 (2) | 0.5319 (2) | 0.8476 (3) | 0.0114 (5) | |
C4 | 0.6575 (2) | 0.5537 (2) | 1.0446 (3) | 0.0144 (5) | |
H8 | 0.6294 | 0.4954 | 1.1105 | 0.022* | |
H9 | 0.6346 | 0.6308 | 1.0727 | 0.022* | |
H10 | 0.7466 | 0.5490 | 1.0792 | 0.022* | |
O4 | 0.1546 (2) | 0.8112 (2) | 0.1609 (3) | 0.0278 (5) | |
H11 | 0.131 (4) | 0.757 (5) | 0.115 (7) | 0.058 (17)* | |
H12 | 0.116 (5) | 0.840 (5) | 0.214 (7) | 0.070 (17)* | |
P1 | 0.0000 | 0.5000 | 0.0000 | 0.0197 (2) | |
F1 | 0.07901 (17) | 0.59909 (17) | −0.0516 (3) | 0.0354 (5) | |
F2 | 0.12194 (17) | 0.43281 (19) | 0.1082 (3) | 0.0377 (5) | |
F3 | 0.0082 (2) | 0.5694 (2) | 0.1758 (3) | 0.0399 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh1 | 0.01300 (10) | 0.00600 (11) | 0.00798 (11) | 0.00051 (7) | 0.00449 (7) | 0.00004 (7) |
N1 | 0.0125 (9) | 0.0136 (11) | 0.0130 (11) | 0.0003 (8) | 0.0058 (8) | −0.0003 (9) |
O1 | 0.0160 (8) | 0.0082 (9) | 0.0146 (9) | −0.0010 (7) | 0.0069 (7) | 0.0002 (7) |
N2 | 0.0166 (10) | 0.0088 (10) | 0.0109 (10) | 0.0004 (8) | 0.0051 (8) | −0.0012 (8) |
O2 | 0.0176 (8) | 0.0102 (9) | 0.0093 (9) | 0.0008 (7) | 0.0042 (7) | −0.0009 (7) |
O3 | 0.0208 (9) | 0.0105 (9) | 0.0136 (9) | 0.0046 (7) | 0.0031 (8) | −0.0014 (8) |
C1 | 0.0146 (11) | 0.0149 (13) | 0.0085 (12) | −0.0017 (9) | 0.0043 (9) | −0.0005 (10) |
C2 | 0.0188 (13) | 0.0206 (15) | 0.0210 (15) | −0.0040 (11) | 0.0084 (11) | 0.0015 (12) |
C3 | 0.0135 (11) | 0.0113 (12) | 0.0112 (12) | −0.0019 (9) | 0.0065 (9) | −0.0005 (10) |
C4 | 0.0199 (12) | 0.0114 (12) | 0.0114 (12) | 0.0009 (9) | 0.0050 (10) | −0.0008 (10) |
O4 | 0.0229 (11) | 0.0304 (14) | 0.0288 (13) | −0.0022 (10) | 0.0075 (10) | −0.0049 (11) |
P1 | 0.0199 (5) | 0.0217 (6) | 0.0185 (5) | −0.0020 (4) | 0.0081 (4) | −0.0005 (4) |
F1 | 0.0353 (10) | 0.0329 (11) | 0.0428 (12) | −0.0094 (8) | 0.0196 (9) | 0.0041 (9) |
F2 | 0.0276 (9) | 0.0475 (13) | 0.0378 (12) | 0.0100 (9) | 0.0112 (8) | 0.0156 (10) |
F3 | 0.0527 (12) | 0.0429 (13) | 0.0283 (11) | −0.0055 (10) | 0.0195 (9) | −0.0118 (10) |
Geometric parameters (Å, º) top
Rh1—Rh1i | 2.4010 (4) | C1—C2 | 1.502 (3) |
Rh1—O1i | 2.0299 (17) | C2—H5 | 0.9800 |
Rh1—O2i | 2.0425 (18) | C2—H6 | 0.9800 |
Rh1—O3 | 2.2402 (19) | C2—H7 | 0.9800 |
Rh1—N1 | 1.980 (2) | C3—C4 | 1.499 (3) |
Rh1—N2 | 1.973 (2) | C4—H8 | 0.9800 |
N1—C1 | 1.305 (3) | C4—H9 | 0.9800 |
N1—H1 | 0.8800 | C4—H10 | 0.9800 |
O1—C1 | 1.282 (3) | O4—H11 | 0.72 (5) |
N2—C3 | 1.301 (3) | O4—H12 | 0.80 (6) |
N2—H2 | 0.8800 | P1—F2 | 1.5873 (18) |
O2—C3 | 1.294 (3) | P1—F3 | 1.590 (2) |
O3—H3 | 0.93 (4) | P1—F1 | 1.6135 (18) |
O3—H4 | 0.78 (4) | | |
| | | |
N2—Rh1—N1 | 93.15 (9) | O1—C1—C2 | 116.3 (2) |
N2—Rh1—O1i | 87.93 (8) | N1—C1—C2 | 121.3 (2) |
N1—Rh1—O1i | 175.85 (8) | C1—C2—H5 | 109.5 |
N2—Rh1—O2i | 174.67 (8) | C1—C2—H6 | 109.5 |
N1—Rh1—O2i | 90.20 (8) | H5—C2—H6 | 109.5 |
O1i—Rh1—O2i | 88.44 (7) | C1—C2—H7 | 109.5 |
N2—Rh1—O3 | 94.36 (8) | H5—C2—H7 | 109.5 |
N1—Rh1—O3 | 93.98 (8) | H6—C2—H7 | 109.5 |
O1i—Rh1—O3 | 89.93 (7) | O2—C3—N2 | 122.2 (2) |
O2i—Rh1—O3 | 89.53 (7) | O2—C3—C4 | 117.2 (2) |
N2—Rh1—Rh1i | 85.91 (6) | N2—C3—C4 | 120.6 (2) |
N1—Rh1—Rh1i | 86.04 (7) | C3—C4—H8 | 109.5 |
O1i—Rh1—Rh1i | 90.04 (5) | C3—C4—H9 | 109.5 |
O2i—Rh1—Rh1i | 90.19 (5) | H8—C4—H9 | 109.5 |
O3—Rh1—Rh1i | 179.73 (5) | C3—C4—H10 | 109.5 |
C1—N1—Rh1 | 123.76 (17) | H8—C4—H10 | 109.5 |
C1—N1—H1 | 118.1 | H9—C4—H10 | 109.5 |
Rh1—N1—H1 | 118.1 | H11—O4—H12 | 116 (5) |
C1—O1—Rh1i | 117.52 (16) | F2ii—P1—F2 | 180.0 |
C3—N2—Rh1 | 124.66 (18) | F2ii—P1—F3 | 89.89 (12) |
C3—N2—H2 | 117.7 | F2—P1—F3 | 90.11 (12) |
Rh1—N2—H2 | 117.7 | F3—P1—F3ii | 180.0 |
C3—O2—Rh1i | 116.71 (16) | F2—P1—F1ii | 89.91 (10) |
Rh1—O3—H3 | 123 (2) | F3—P1—F1ii | 89.81 (11) |
Rh1—O3—H4 | 116 (3) | F2—P1—F1 | 90.09 (10) |
H3—O3—H4 | 107 (4) | F3—P1—F1 | 90.19 (11) |
O1—C1—N1 | 122.4 (2) | F1ii—P1—F1 | 180.0 |
| | | |
N2—Rh1—N1—C1 | −86.6 (2) | Rh1i—O1—C1—N1 | −5.9 (3) |
O2i—Rh1—N1—C1 | 89.2 (2) | Rh1i—O1—C1—C2 | 173.31 (17) |
O3—Rh1—N1—C1 | 178.8 (2) | Rh1—N1—C1—O1 | 4.5 (4) |
Rh1i—Rh1—N1—C1 | −0.9 (2) | Rh1—N1—C1—C2 | −174.64 (19) |
N1—Rh1—N2—C3 | 83.1 (2) | Rh1i—O2—C3—N2 | 5.5 (3) |
O1i—Rh1—N2—C3 | −92.9 (2) | Rh1i—O2—C3—C4 | −175.63 (16) |
O3—Rh1—N2—C3 | 177.4 (2) | Rh1—N2—C3—O2 | −1.3 (3) |
Rh1i—Rh1—N2—C3 | −2.7 (2) | Rh1—N2—C3—C4 | 179.89 (17) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2iii | 0.93 (4) | 1.86 (4) | 2.778 (3) | 168 (3) |
O3—H4···O4 | 0.78 (4) | 2.00 (4) | 2.774 (3) | 173 (4) |
O4—H11···F1 | 0.72 (5) | 2.22 (6) | 2.937 (4) | 170 (5) |
O4—H12···F1iv | 0.80 (6) | 2.18 (6) | 2.923 (3) | 156 (5) |
N1—H1···O4iv | 0.88 | 2.44 | 3.213 (3) | 146 |
N2—H2···O1iii | 0.88 | 2.27 | 3.073 (3) | 152 |
N2—H2···O3iv | 0.88 | 2.59 | 3.192 (3) | 126 |
Symmetry codes: (iii) −x+1, y+1/2, −z+3/2; (iv) x, −y+3/2, z+1/2. |
(III) Diaquatetra-µ-propionamidato-
κ4N:
O;
κ4O:
N-dirhodium(II,III) hexafluorophosphate dihydrate
top
Crystal data top
[Rh2(C3H6NO)4(H2O)2]PF6·2H2O | Z = 2 |
Mr = 711.21 | F(000) = 710 |
Triclinic, P1 | Dx = 1.879 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 8.980 (2) Å | Cell parameters from 4209 reflections |
b = 11.866 (3) Å | θ = 3.1–27.5° |
c = 12.682 (4) Å | µ = 1.46 mm−1 |
α = 87.696 (10)° | T = 118 K |
β = 85.095 (8)° | Prism, brown |
γ = 69.032 (6)° | 0.30 × 0.10 × 0.10 mm |
V = 1257.2 (6) Å3 | |
Data collection top
Rigaku/MSC Mercury CCD diffractometer | 5685 independent reflections |
Graphite monochromator | 5122 reflections with I > 2σ(I) |
Detector resolution: 14.62 pixels mm-1 | Rint = 0.023 |
ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: integration (NUMABS; Higashi, 1999) | h = −11→11 |
Tmin = 0.619, Tmax = 0.773 | k = −13→15 |
10284 measured reflections | l = −12→16 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.065 | w = 1/[σ2(Fo2) + (0.0334P)2 + 1.006P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
5685 reflections | Δρmax = 0.66 e Å−3 |
327 parameters | Δρmin = −0.76 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0026 (5) |
Crystal data top
[Rh2(C3H6NO)4(H2O)2]PF6·2H2O | γ = 69.032 (6)° |
Mr = 711.21 | V = 1257.2 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.980 (2) Å | Mo Kα radiation |
b = 11.866 (3) Å | µ = 1.46 mm−1 |
c = 12.682 (4) Å | T = 118 K |
α = 87.696 (10)° | 0.30 × 0.10 × 0.10 mm |
β = 85.095 (8)° | |
Data collection top
Rigaku/MSC Mercury CCD diffractometer | 5685 independent reflections |
Absorption correction: integration (NUMABS; Higashi, 1999) | 5122 reflections with I > 2σ(I) |
Tmin = 0.619, Tmax = 0.773 | Rint = 0.023 |
10284 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.065 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.66 e Å−3 |
5685 reflections | Δρmin = −0.76 e Å−3 |
327 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 | 0.11442 (2) | 0.531040 (15) | −0.010445 (14) | 0.01051 (7) | |
N1 | −0.0139 (3) | 0.67297 (17) | 0.07682 (17) | 0.0142 (4) | |
H1 | 0.0321 | 0.7235 | 0.0931 | 0.017* | |
O1 | −0.2332 (2) | 0.61961 (14) | 0.09746 (14) | 0.0146 (4) | |
N2 | 0.0206 (3) | 0.62028 (18) | −0.13831 (16) | 0.0140 (4) | |
H2 | 0.0750 | 0.6581 | −0.1766 | 0.017* | |
O2 | −0.1985 (2) | 0.56676 (15) | −0.12242 (14) | 0.0152 (4) | |
Rh2 | 0.46169 (2) | 0.496401 (15) | 0.411805 (14) | 0.01095 (7) | |
N3 | 0.6549 (3) | 0.53348 (18) | 0.36174 (17) | 0.0145 (4) | |
H3 | 0.6776 | 0.5369 | 0.2931 | 0.017* | |
O3 | 0.7278 (2) | 0.54617 (15) | 0.52664 (14) | 0.0153 (4) | |
N4 | 0.3340 (3) | 0.67008 (18) | 0.42799 (17) | 0.0152 (4) | |
H4 | 0.2785 | 0.7080 | 0.3750 | 0.018* | |
O4 | 0.4061 (2) | 0.68285 (15) | 0.59292 (14) | 0.0159 (4) | |
O5 | 0.3312 (2) | 0.58223 (16) | −0.04169 (16) | 0.0164 (4) | |
H5 | 0.370 (4) | 0.607 (3) | 0.009 (3) | 0.025* | |
H6 | 0.323 (4) | 0.632 (3) | −0.090 (3) | 0.025* | |
O6 | 0.4001 (3) | 0.4963 (2) | 0.24462 (16) | 0.0241 (4) | |
H7 | 0.345 (5) | 0.471 (3) | 0.218 (3) | 0.036* | |
H8 | 0.406 (4) | 0.553 (3) | 0.209 (3) | 0.036* | |
O7 | 0.7473 (3) | 0.26084 (18) | 0.20635 (16) | 0.0217 (4) | |
H9 | 0.785 (4) | 0.186 (3) | 0.199 (3) | 0.033* | |
H10 | 0.694 (5) | 0.272 (3) | 0.254 (3) | 0.033* | |
O8 | 0.4439 (2) | 0.67316 (17) | 0.11793 (16) | 0.0190 (4) | |
H11 | 0.533 (4) | 0.668 (3) | 0.109 (3) | 0.028* | |
H12 | 0.399 (4) | 0.743 (3) | 0.131 (3) | 0.028* | |
C1 | −0.1621 (3) | 0.6954 (2) | 0.11132 (19) | 0.0136 (5) | |
C2 | −0.2609 (3) | 0.8112 (2) | 0.1657 (2) | 0.0175 (5) | |
H13 | −0.1913 | 0.8396 | 0.2057 | 0.021* | |
H14 | −0.3422 | 0.7969 | 0.2168 | 0.021* | |
C3 | −0.3440 (4) | 0.9079 (2) | 0.0855 (3) | 0.0305 (7) | |
H15 | −0.2634 | 0.9246 | 0.0368 | 0.046* | |
H16 | −0.4101 | 0.9820 | 0.1228 | 0.046* | |
H17 | −0.4119 | 0.8793 | 0.0454 | 0.046* | |
C4 | −0.1169 (3) | 0.6265 (2) | −0.16929 (19) | 0.0131 (5) | |
C5 | −0.1873 (3) | 0.7036 (2) | −0.2625 (2) | 0.0175 (5) | |
H18 | −0.2018 | 0.6521 | −0.3173 | 0.021* | |
H19 | −0.1123 | 0.7423 | −0.2936 | 0.021* | |
C6 | −0.3488 (4) | 0.8014 (2) | −0.2304 (3) | 0.0279 (6) | |
H20 | −0.4204 | 0.7638 | −0.1944 | 0.042* | |
H21 | −0.3963 | 0.8448 | −0.2937 | 0.042* | |
H22 | −0.3328 | 0.8582 | −0.1825 | 0.042* | |
C7 | 0.7497 (3) | 0.5530 (2) | 0.4248 (2) | 0.0150 (5) | |
C8 | 0.8895 (3) | 0.5878 (2) | 0.3832 (2) | 0.0183 (5) | |
H23 | 0.8928 | 0.5928 | 0.3050 | 0.022* | |
H24 | 0.9899 | 0.5244 | 0.4031 | 0.022* | |
C9 | 0.8795 (4) | 0.7085 (3) | 0.4265 (2) | 0.0321 (7) | |
H25 | 0.7769 | 0.7704 | 0.4113 | 0.048* | |
H26 | 0.9672 | 0.7312 | 0.3928 | 0.048* | |
H27 | 0.8880 | 0.7013 | 0.5032 | 0.048* | |
C10 | 0.3266 (3) | 0.7322 (2) | 0.5125 (2) | 0.0163 (5) | |
C11A | 0.2451 (9) | 0.8690 (6) | 0.5168 (6) | 0.0181 (17)* | 0.50 |
H28A | 0.1595 | 0.8940 | 0.4671 | 0.022* | 0.50 |
H29A | 0.1937 | 0.8914 | 0.5889 | 0.022* | 0.50 |
C12A | 0.3529 (9) | 0.9369 (6) | 0.4902 (6) | 0.0332 (15)* | 0.50 |
H30A | 0.4090 | 0.9124 | 0.4205 | 0.050* | 0.50 |
H31A | 0.4311 | 0.9198 | 0.5436 | 0.050* | 0.50 |
H32A | 0.2902 | 1.0235 | 0.4891 | 0.050* | 0.50 |
C11B | 0.2111 (8) | 0.8600 (5) | 0.5216 (5) | 0.0137 (15)* | 0.50 |
H28B | 0.1351 | 0.8679 | 0.5846 | 0.016* | 0.50 |
H29B | 0.1494 | 0.8828 | 0.4581 | 0.016* | 0.50 |
C12B | 0.3078 (10) | 0.9433 (7) | 0.5317 (7) | 0.0393 (17)* | 0.50 |
H30B | 0.3831 | 0.9344 | 0.4692 | 0.059* | 0.50 |
H31B | 0.3670 | 0.9209 | 0.5954 | 0.059* | 0.50 |
H32B | 0.2344 | 1.0273 | 0.5369 | 0.059* | 0.50 |
P1 | 0.10150 (8) | 0.96146 (6) | 0.19677 (6) | 0.01790 (15) | |
F1 | 0.2926 (2) | 0.91799 (15) | 0.18054 (18) | 0.0403 (5) | |
F2 | 0.0845 (2) | 1.08120 (14) | 0.13045 (14) | 0.0312 (4) | |
F3 | 0.0986 (3) | 0.89178 (16) | 0.09252 (15) | 0.0366 (5) | |
F4 | 0.1173 (2) | 0.83972 (14) | 0.26363 (15) | 0.0316 (4) | |
F5 | 0.1047 (2) | 1.02849 (15) | 0.30243 (14) | 0.0330 (4) | |
F6 | −0.0896 (2) | 1.00336 (14) | 0.21468 (17) | 0.0342 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh1 | 0.01059 (10) | 0.01053 (10) | 0.01128 (10) | −0.00457 (7) | −0.00204 (7) | 0.00007 (7) |
N1 | 0.0165 (11) | 0.0133 (9) | 0.0150 (10) | −0.0079 (8) | −0.0014 (8) | −0.0014 (8) |
O1 | 0.0129 (9) | 0.0131 (8) | 0.0176 (9) | −0.0044 (7) | −0.0006 (7) | −0.0028 (6) |
N2 | 0.0147 (10) | 0.0150 (10) | 0.0132 (10) | −0.0066 (8) | −0.0001 (8) | 0.0007 (8) |
O2 | 0.0154 (9) | 0.0161 (8) | 0.0163 (9) | −0.0080 (7) | −0.0048 (7) | 0.0039 (7) |
Rh2 | 0.01211 (11) | 0.01268 (10) | 0.00880 (10) | −0.00511 (7) | −0.00187 (7) | 0.00032 (7) |
N3 | 0.0162 (11) | 0.0180 (10) | 0.0096 (10) | −0.0069 (8) | −0.0002 (8) | 0.0017 (8) |
O3 | 0.0154 (9) | 0.0186 (8) | 0.0130 (9) | −0.0078 (7) | 0.0000 (7) | 0.0011 (7) |
N4 | 0.0169 (11) | 0.0148 (10) | 0.0127 (10) | −0.0040 (8) | −0.0035 (8) | 0.0020 (8) |
O4 | 0.0199 (9) | 0.0140 (8) | 0.0125 (9) | −0.0042 (7) | −0.0026 (7) | 0.0003 (6) |
O5 | 0.0152 (9) | 0.0191 (9) | 0.0181 (10) | −0.0098 (7) | −0.0032 (8) | 0.0030 (7) |
O6 | 0.0350 (12) | 0.0354 (11) | 0.0141 (10) | −0.0261 (10) | −0.0098 (9) | 0.0065 (8) |
O7 | 0.0232 (11) | 0.0179 (9) | 0.0200 (10) | −0.0044 (8) | 0.0055 (8) | 0.0015 (8) |
O8 | 0.0148 (9) | 0.0176 (9) | 0.0247 (10) | −0.0062 (8) | 0.0012 (8) | −0.0034 (7) |
C1 | 0.0180 (12) | 0.0135 (11) | 0.0101 (11) | −0.0062 (9) | −0.0027 (9) | 0.0008 (8) |
C2 | 0.0177 (13) | 0.0163 (12) | 0.0187 (13) | −0.0069 (10) | 0.0024 (10) | −0.0034 (9) |
C3 | 0.0320 (17) | 0.0172 (13) | 0.0334 (17) | 0.0003 (12) | 0.0044 (14) | 0.0024 (11) |
C4 | 0.0171 (12) | 0.0112 (10) | 0.0104 (11) | −0.0041 (9) | −0.0018 (9) | −0.0007 (8) |
C5 | 0.0204 (13) | 0.0194 (12) | 0.0146 (12) | −0.0088 (10) | −0.0067 (10) | 0.0046 (9) |
C6 | 0.0225 (15) | 0.0210 (13) | 0.0376 (18) | −0.0037 (11) | −0.0097 (13) | 0.0072 (12) |
C7 | 0.0153 (12) | 0.0126 (11) | 0.0157 (12) | −0.0034 (9) | −0.0008 (10) | 0.0002 (9) |
C8 | 0.0179 (13) | 0.0271 (13) | 0.0132 (12) | −0.0120 (11) | −0.0029 (10) | 0.0038 (10) |
C9 | 0.046 (2) | 0.0412 (17) | 0.0226 (15) | −0.0328 (16) | 0.0028 (14) | 0.0000 (13) |
C10 | 0.0162 (12) | 0.0161 (11) | 0.0162 (12) | −0.0054 (10) | −0.0004 (10) | 0.0007 (9) |
P1 | 0.0180 (3) | 0.0134 (3) | 0.0222 (4) | −0.0057 (2) | −0.0003 (3) | 0.0002 (2) |
F1 | 0.0177 (9) | 0.0250 (9) | 0.0768 (15) | −0.0066 (7) | 0.0065 (9) | −0.0134 (9) |
F2 | 0.0449 (11) | 0.0207 (8) | 0.0301 (10) | −0.0153 (8) | −0.0004 (8) | 0.0056 (7) |
F3 | 0.0577 (13) | 0.0308 (9) | 0.0279 (10) | −0.0231 (9) | −0.0026 (9) | −0.0081 (7) |
F4 | 0.0378 (11) | 0.0218 (8) | 0.0372 (10) | −0.0127 (7) | −0.0095 (8) | 0.0116 (7) |
F5 | 0.0472 (12) | 0.0301 (9) | 0.0250 (9) | −0.0171 (8) | −0.0046 (8) | −0.0039 (7) |
F6 | 0.0196 (9) | 0.0201 (8) | 0.0623 (13) | −0.0067 (7) | −0.0014 (9) | −0.0011 (8) |
Geometric parameters (Å, º) top
Rh1—Rh1i | 2.4105 (6) | C3—H16 | 0.9800 |
Rh1—O1i | 2.0356 (17) | C3—H17 | 0.9800 |
Rh1—O2i | 2.0469 (18) | C4—C5 | 1.504 (3) |
Rh1—O5 | 2.2388 (19) | C5—C6 | 1.532 (4) |
Rh1—N1 | 1.983 (2) | C5—H18 | 0.9900 |
Rh1—N2 | 1.979 (2) | C5—H19 | 0.9900 |
N1—C1 | 1.300 (3) | C6—H20 | 0.9800 |
N1—H1 | 0.8800 | C6—H21 | 0.9800 |
O1—C1 | 1.300 (3) | C6—H22 | 0.9800 |
N2—C4 | 1.304 (3) | C7—C8 | 1.504 (4) |
N2—H2 | 0.8800 | C8—C9 | 1.524 (4) |
O2—C4 | 1.287 (3) | C8—H23 | 0.9900 |
Rh2—Rh2ii | 2.4095 (7) | C8—H24 | 0.9900 |
Rh2—O3ii | 2.0289 (18) | C9—H25 | 0.9800 |
Rh2—O4ii | 2.0318 (17) | C9—H26 | 0.9800 |
Rh2—O6 | 2.237 (2) | C9—H27 | 0.9800 |
Rh2—N3 | 1.985 (2) | C10—C11B | 1.502 (6) |
Rh2—N4 | 1.977 (2) | C10—C11A | 1.524 (7) |
N3—C7 | 1.301 (3) | C11A—C12A | 1.477 (10) |
N3—H3 | 0.8800 | C11A—H28A | 0.9900 |
O3—C7 | 1.294 (3) | C11A—H29A | 0.9900 |
N4—C10 | 1.309 (3) | C12A—H30A | 0.9800 |
N4—H4 | 0.8800 | C12A—H31A | 0.9800 |
O4—C10 | 1.292 (3) | C12A—H32A | 0.9800 |
O5—H5 | 0.86 (4) | C11B—C12B | 1.546 (10) |
O5—H6 | 0.82 (4) | C11B—H28B | 0.9900 |
O6—H7 | 0.76 (4) | C11B—H29B | 0.9900 |
O6—H8 | 0.81 (4) | C12B—H30B | 0.9800 |
O7—H9 | 0.84 (4) | C12B—H31B | 0.9800 |
O7—H10 | 0.72 (4) | C12B—H32B | 0.9800 |
O8—H11 | 0.77 (4) | P1—F2 | 1.5874 (17) |
O8—H12 | 0.80 (4) | P1—F5 | 1.5931 (18) |
C1—C2 | 1.500 (3) | P1—F3 | 1.5942 (18) |
C2—C3 | 1.528 (4) | P1—F1 | 1.6027 (19) |
C2—H13 | 0.9900 | P1—F6 | 1.6052 (19) |
C2—H14 | 0.9900 | P1—F4 | 1.6129 (17) |
C3—H15 | 0.9800 | | |
| | | |
N2—Rh1—N1 | 89.53 (9) | O2—C4—N2 | 122.0 (2) |
N2—Rh1—O1i | 90.82 (8) | O2—C4—C5 | 116.7 (2) |
N1—Rh1—O1i | 175.82 (8) | N2—C4—C5 | 121.3 (2) |
N2—Rh1—O2i | 175.76 (8) | C4—C5—C6 | 111.5 (2) |
N1—Rh1—O2i | 90.82 (8) | C4—C5—H18 | 109.3 |
O1i—Rh1—O2i | 88.53 (7) | C6—C5—H18 | 109.3 |
N2—Rh1—O5 | 91.26 (8) | C4—C5—H19 | 109.3 |
N1—Rh1—O5 | 96.62 (8) | C6—C5—H19 | 109.3 |
O1i—Rh1—O5 | 87.54 (7) | H18—C5—H19 | 108.0 |
O2i—Rh1—O5 | 92.90 (7) | C5—C6—H20 | 109.5 |
N2—Rh1—Rh1i | 86.51 (6) | C5—C6—H21 | 109.5 |
N1—Rh1—Rh1i | 87.01 (6) | H20—C6—H21 | 109.5 |
O1i—Rh1—Rh1i | 88.86 (5) | C5—C6—H22 | 109.5 |
O2i—Rh1—Rh1i | 89.28 (5) | H20—C6—H22 | 109.5 |
O5—Rh1—Rh1i | 175.73 (5) | H21—C6—H22 | 109.5 |
C1—N1—Rh1 | 123.60 (17) | O3—C7—N3 | 122.1 (2) |
C1—N1—H1 | 118.2 | O3—C7—C8 | 116.1 (2) |
Rh1—N1—H1 | 118.2 | N3—C7—C8 | 121.7 (2) |
C1—O1—Rh1i | 119.00 (15) | C7—C8—C9 | 112.0 (2) |
C4—N2—Rh1 | 124.00 (17) | C7—C8—H23 | 109.2 |
C4—N2—H2 | 118.0 | C9—C8—H23 | 109.2 |
Rh1—N2—H2 | 118.0 | C7—C8—H24 | 109.2 |
C4—O2—Rh1i | 118.08 (16) | C9—C8—H24 | 109.2 |
N4—Rh2—N3 | 91.03 (9) | H23—C8—H24 | 107.9 |
N4—Rh2—O3ii | 90.32 (8) | C8—C9—H25 | 109.5 |
N3—Rh2—O3ii | 175.65 (8) | C8—C9—H26 | 109.5 |
N4—Rh2—O4ii | 175.72 (8) | H25—C9—H26 | 109.5 |
N3—Rh2—O4ii | 89.88 (8) | C8—C9—H27 | 109.5 |
O3ii—Rh2—O4ii | 88.47 (7) | H25—C9—H27 | 109.5 |
N4—Rh2—O6 | 92.44 (9) | H26—C9—H27 | 109.5 |
N3—Rh2—O6 | 90.30 (8) | O4—C10—N4 | 121.4 (2) |
O3ii—Rh2—O6 | 93.77 (8) | O4—C10—C11B | 118.6 (3) |
O4ii—Rh2—O6 | 91.74 (8) | N4—C10—C11B | 119.7 (3) |
N4—Rh2—Rh2ii | 86.42 (6) | O4—C10—C11A | 115.4 (3) |
N3—Rh2—Rh2ii | 86.36 (6) | N4—C10—C11A | 122.6 (3) |
O3ii—Rh2—Rh2ii | 89.60 (5) | C12A—C11A—C10 | 114.6 (6) |
O4ii—Rh2—Rh2ii | 89.47 (5) | C12A—C11A—H28A | 108.6 |
O6—Rh2—Rh2ii | 176.45 (6) | C10—C11A—H28A | 108.6 |
C7—N3—Rh2 | 123.66 (18) | C12A—C11A—H29A | 108.6 |
C7—N3—H3 | 118.2 | C10—C11A—H29A | 108.6 |
Rh2—N3—H3 | 118.2 | H28A—C11A—H29A | 107.6 |
C7—O3—Rh2ii | 118.20 (16) | C11A—C12A—H30A | 109.5 |
C10—N4—Rh2 | 124.14 (18) | C11A—C12A—H31A | 109.5 |
C10—N4—H4 | 117.9 | H30A—C12A—H31A | 109.5 |
Rh2—N4—H4 | 117.9 | C11A—C12A—H32A | 109.5 |
C10—O4—Rh2ii | 118.52 (15) | H30A—C12A—H32A | 109.5 |
Rh1—O5—H5 | 121 (2) | H31A—C12A—H32A | 109.5 |
Rh1—O5—H6 | 113 (2) | C10—C11B—C12B | 108.2 (5) |
H5—O5—H6 | 106 (3) | C10—C11B—H28B | 110.0 |
Rh2—O6—H7 | 134 (3) | C12B—C11B—H28B | 110.0 |
Rh2—O6—H8 | 114 (3) | C10—C11B—H29B | 110.0 |
H7—O6—H8 | 107 (4) | C12B—C11B—H29B | 110.0 |
H9—O7—H10 | 106 (4) | H28B—C11B—H29B | 108.4 |
H11—O8—H12 | 103 (3) | F2—P1—F5 | 90.00 (10) |
N1—C1—O1 | 121.3 (2) | F2—P1—F3 | 91.25 (10) |
N1—C1—C2 | 121.9 (2) | F5—P1—F3 | 178.75 (10) |
O1—C1—C2 | 116.8 (2) | F2—P1—F1 | 90.82 (11) |
C1—C2—C3 | 110.8 (2) | F5—P1—F1 | 89.81 (11) |
C1—C2—H13 | 109.5 | F3—P1—F1 | 90.17 (11) |
C3—C2—H13 | 109.5 | F2—P1—F6 | 90.13 (10) |
C1—C2—H14 | 109.5 | F5—P1—F6 | 89.90 (11) |
C3—C2—H14 | 109.5 | F3—P1—F6 | 90.10 (11) |
H13—C2—H14 | 108.1 | F1—P1—F6 | 179.01 (12) |
C2—C3—H15 | 109.5 | F2—P1—F4 | 179.45 (11) |
C2—C3—H16 | 109.5 | F5—P1—F4 | 90.34 (10) |
H15—C3—H16 | 109.5 | F3—P1—F4 | 88.40 (10) |
C2—C3—H17 | 109.5 | F1—P1—F4 | 89.62 (10) |
H15—C3—H17 | 109.5 | F6—P1—F4 | 89.44 (10) |
H16—C3—H17 | 109.5 | | |
| | | |
N2—Rh1—N1—C1 | 83.2 (2) | Rh1i—O2—C4—N2 | 4.2 (3) |
O2i—Rh1—N1—C1 | −92.5 (2) | Rh1i—O2—C4—C5 | −176.20 (15) |
O5—Rh1—N1—C1 | 174.5 (2) | Rh1—N2—C4—O2 | −5.2 (3) |
Rh1i—Rh1—N1—C1 | −3.3 (2) | Rh1—N2—C4—C5 | 175.24 (17) |
N1—Rh1—N2—C4 | −84.0 (2) | O2—C4—C5—C6 | 61.3 (3) |
O1i—Rh1—N2—C4 | 91.82 (19) | N2—C4—C5—C6 | −119.1 (3) |
O5—Rh1—N2—C4 | 179.38 (19) | Rh2ii—O3—C7—N3 | −0.1 (3) |
Rh1i—Rh1—N2—C4 | 3.02 (19) | Rh2ii—O3—C7—C8 | 178.57 (16) |
N4—Rh2—N3—C7 | 83.9 (2) | Rh2—N3—C7—O3 | 2.1 (3) |
O4ii—Rh2—N3—C7 | −92.0 (2) | Rh2—N3—C7—C8 | −176.44 (17) |
O6—Rh2—N3—C7 | 176.3 (2) | O3—C7—C8—C9 | −57.1 (3) |
Rh2ii—Rh2—N3—C7 | −2.48 (19) | N3—C7—C8—C9 | 121.5 (3) |
N3—Rh2—N4—C10 | −85.6 (2) | Rh2ii—O4—C10—N4 | −2.1 (3) |
O3ii—Rh2—N4—C10 | 90.3 (2) | Rh2ii—O4—C10—C11B | 171.5 (3) |
O6—Rh2—N4—C10 | −175.9 (2) | Rh2ii—O4—C10—C11A | −173.7 (3) |
Rh2ii—Rh2—N4—C10 | 0.7 (2) | Rh2—N4—C10—O4 | 0.7 (4) |
Rh1—N1—C1—O1 | 5.6 (3) | Rh2—N4—C10—C11B | −172.9 (3) |
Rh1—N1—C1—C2 | −172.41 (18) | Rh2—N4—C10—C11A | 171.7 (4) |
Rh1i—O1—C1—N1 | −4.6 (3) | O4—C10—C11A—C12A | 78.0 (6) |
Rh1i—O1—C1—C2 | 173.50 (16) | N4—C10—C11A—C12A | −93.4 (6) |
N1—C1—C2—C3 | 88.6 (3) | O4—C10—C11B—C12B | 66.6 (6) |
O1—C1—C2—C3 | −89.5 (3) | N4—C10—C11B—C12B | −119.7 (5) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H6···O7iii | 0.82 (4) | 1.91 (4) | 2.706 (3) | 164 (3) |
O5—H5···O8 | 0.86 (4) | 1.89 (4) | 2.755 (3) | 176 (3) |
O6—H7···O2i | 0.76 (4) | 2.04 (4) | 2.789 (3) | 168 (4) |
O6—H8···O8 | 0.81 (4) | 1.90 (4) | 2.711 (3) | 173 (4) |
O7—H10···O4ii | 0.72 (4) | 2.07 (4) | 2.775 (3) | 163 (4) |
O7—H9···F6iv | 0.84 (4) | 2.07 (4) | 2.879 (3) | 164 (3) |
O8—H11···O1v | 0.77 (4) | 1.97 (4) | 2.729 (3) | 168 (4) |
O8—H12···F1 | 0.80 (4) | 2.05 (4) | 2.845 (3) | 173 (3) |
N1—H1···F3 | 0.88 | 2.28 | 3.123 (3) | 161 |
N2—H2···O7iii | 0.88 | 2.14 | 2.963 (3) | 155 |
N4—H4···F4 | 0.88 | 2.26 | 3.120 (3) | 168 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x+1, y−1, z; (v) x+1, y, z. |
(IV) Diaquatetra-µ-butyramidato-
κ4N:
O;
κ4O:
N-dirhodium(II,III) hexafluorophosphate
top
Crystal data top
[Rh2(C4H8NO)4(H2O)2]PF6 | Z = 2 |
Mr = 731.28 | F(000) = 734 |
Triclinic, P1 | Dx = 1.831 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 9.1037 (4) Å | Cell parameters from 4238 reflections |
b = 11.0653 (1) Å | θ = 3.0–27.5° |
c = 14.0104 (5) Å | µ = 1.38 mm−1 |
α = 73.667 (10)° | T = 173 K |
β = 82.14 (1)° | Needle, brown |
γ = 79.49 (1)° | 0.35 × 0.10 × 0.03 mm |
V = 1326.18 (11) Å3 | |
Data collection top
Rigaku/MSC Mercury CCD diffractometer | 6014 independent reflections |
Graphite monochromator | 5456 reflections with I > 2σ(I) |
Detector resolution: 14.62 pixels mm-1 | Rint = 0.028 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: integration (NUMABS; Higashi, 1999) | h = −11→11 |
Tmin = 0.643, Tmax = 0.960 | k = −14→9 |
10813 measured reflections | l = −18→15 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | w = 1/[σ2(Fo2) + 2.8905P] where P = (Fo2 + 2Fc2)/3 |
6014 reflections | (Δ/σ)max = 0.012 |
373 parameters | Δρmax = 0.75 e Å−3 |
0 restraints | Δρmin = −0.71 e Å−3 |
Crystal data top
[Rh2(C4H8NO)4(H2O)2]PF6 | γ = 79.49 (1)° |
Mr = 731.28 | V = 1326.18 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.1037 (4) Å | Mo Kα radiation |
b = 11.0653 (1) Å | µ = 1.38 mm−1 |
c = 14.0104 (5) Å | T = 173 K |
α = 73.667 (10)° | 0.35 × 0.10 × 0.03 mm |
β = 82.14 (1)° | |
Data collection top
Rigaku/MSC Mercury CCD diffractometer | 6014 independent reflections |
Absorption correction: integration (NUMABS; Higashi, 1999) | 5456 reflections with I > 2σ(I) |
Tmin = 0.643, Tmax = 0.960 | Rint = 0.028 |
10813 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.17 | Δρmax = 0.75 e Å−3 |
6014 reflections | Δρmin = −0.71 e Å−3 |
373 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 | 0.525743 (12) | 0.440873 (9) | 0.083607 (7) | 0.01391 (3) | |
N1 | 0.67886 (13) | 0.32883 (10) | 0.02144 (8) | 0.0189 (3) | |
H1 | 0.7345 | 0.2665 | 0.0610 | 0.023* | |
O1 | 0.63301 (11) | 0.43408 (8) | −0.13841 (7) | 0.0196 (3) | |
N2 | 0.37071 (13) | 0.34021 (10) | 0.07784 (8) | 0.0185 (3) | |
H2 | 0.3492 | 0.2799 | 0.1315 | 0.022* | |
O2 | 0.32283 (11) | 0.44407 (8) | −0.08122 (7) | 0.0191 (3) | |
Rh2 | 0.568158 (12) | 0.531738 (9) | 0.419427 (7) | 0.01345 (3) | |
N3 | 0.38044 (13) | 0.53100 (10) | 0.36252 (8) | 0.0176 (3) | |
H3 | 0.3805 | 0.5505 | 0.2971 | 0.021* | |
O3 | 0.24720 (11) | 0.47677 (8) | 0.51333 (7) | 0.0195 (3) | |
N4 | 0.50328 (13) | 0.70877 (9) | 0.43074 (8) | 0.0182 (3) | |
H4 | 0.5332 | 0.7710 | 0.3814 | 0.022* | |
O4 | 0.37024 (11) | 0.65349 (8) | 0.58142 (7) | 0.0182 (3) | |
O5 | 0.57577 (14) | 0.31717 (9) | 0.23751 (7) | 0.0296 (3) | |
H5 | 0.588 (2) | 0.3327 (15) | 0.2841 (13) | 0.039* | |
H6 | 0.611 (2) | 0.2485 (15) | 0.2391 (13) | 0.039* | |
O6 | 0.71106 (13) | 0.58714 (9) | 0.27117 (7) | 0.0270 (3) | |
H7 | 0.703 (2) | 0.5731 (15) | 0.2192 (13) | 0.035* | |
H8 | 0.725 (2) | 0.6466 (15) | 0.2613 (13) | 0.035* | |
C1 | 0.70341 (16) | 0.34094 (12) | −0.07522 (10) | 0.0181 (3) | |
C2 | 0.81406 (18) | 0.24454 (13) | −0.11606 (11) | 0.0266 (4) | |
H9 | 0.8709 | 0.1862 | −0.0614 | 0.032* | |
H10 | 0.8864 | 0.2893 | −0.1670 | 0.032* | |
C3 | 0.7371 (2) | 0.16745 (15) | −0.16256 (13) | 0.0431 (5) | |
H11 | 0.6821 | 0.2261 | −0.2181 | 0.052* | |
H12 | 0.8145 | 0.1088 | −0.1911 | 0.052* | |
C4 | 0.6293 (2) | 0.09114 (17) | −0.09000 (17) | 0.0608 (7) | |
H13 | 0.5831 | 0.0441 | −0.1246 | 0.079* | |
H14 | 0.5512 | 0.1486 | −0.0622 | 0.079* | |
H15 | 0.6834 | 0.0309 | −0.0358 | 0.079* | |
C5 | 0.29788 (16) | 0.35696 (11) | −0.00003 (10) | 0.0196 (4) | |
C6 | 0.18137 (18) | 0.27681 (13) | −0.00091 (11) | 0.0292 (4) | |
H16 | 0.2310 | 0.2038 | −0.0271 | 0.035* | |
H17 | 0.1075 | 0.3284 | −0.0478 | 0.035* | |
C7 | 0.09713 (18) | 0.22543 (14) | 0.10006 (12) | 0.0322 (4) | |
H18 | 0.0308 | 0.1676 | 0.0927 | 0.039* | |
H19 | 0.1705 | 0.1748 | 0.1477 | 0.039* | |
C8 | 0.0038 (2) | 0.32857 (18) | 0.14293 (16) | 0.0497 (6) | |
H20 | 0.0695 | 0.3826 | 0.1551 | 0.065* | |
H21 | −0.0511 | 0.2896 | 0.2060 | 0.065* | |
H22 | −0.0677 | 0.3805 | 0.0956 | 0.065* | |
C9 | 0.25585 (16) | 0.50280 (11) | 0.41758 (10) | 0.0175 (3) | |
C10 | 0.12011 (17) | 0.49483 (14) | 0.37170 (11) | 0.0263 (4) | |
H23 | 0.1387 | 0.5226 | 0.2981 | 0.032* | |
H24 | 0.0342 | 0.5539 | 0.3922 | 0.032* | |
C11 | 0.07939 (19) | 0.36063 (15) | 0.40197 (13) | 0.0356 (5) | |
H25 | 0.0585 | 0.3336 | 0.4755 | 0.043* | |
H26 | −0.0132 | 0.3617 | 0.3719 | 0.043* | |
C12 | 0.2030 (2) | 0.26489 (16) | 0.36932 (16) | 0.0476 (6) | |
H27 | 0.2367 | 0.2985 | 0.2988 | 0.062* | |
H28 | 0.1649 | 0.1848 | 0.3781 | 0.062* | |
H29 | 0.2875 | 0.2494 | 0.4099 | 0.062* | |
C13 | 0.42016 (16) | 0.73909 (11) | 0.50553 (10) | 0.0178 (3) | |
C14 | 0.36866 (19) | 0.87469 (12) | 0.50818 (11) | 0.0261 (4) | |
H30 | 0.4198 | 0.9318 | 0.4509 | 0.031* | |
H31 | 0.3960 | 0.8872 | 0.5704 | 0.031* | |
C15 | 0.1988 (2) | 0.90910 (15) | 0.50356 (13) | 0.0373 (5) | |
H32A | 0.1489 | 0.8566 | 0.5642 | 0.045* | 0.75 |
H33A | 0.1688 | 0.9994 | 0.5044 | 0.045* | 0.75 |
H32B | 0.1612 | 0.9914 | 0.5198 | 0.045* | 0.25 |
H33B | 0.1461 | 0.8422 | 0.5504 | 0.045* | 0.25 |
C16A | 0.1426 (3) | 0.8900 (2) | 0.4122 (2) | 0.0457 (8) | 0.75 |
H36A | 0.0335 | 0.9145 | 0.4143 | 0.059* | 0.75 |
H34A | 0.1685 | 0.8001 | 0.4118 | 0.059* | 0.75 |
H35A | 0.1897 | 0.9429 | 0.3515 | 0.059* | 0.75 |
C16B | 0.1771 (7) | 0.9183 (6) | 0.3944 (5) | 0.0246 (13)* | 0.25 |
H36B | 0.0701 | 0.9407 | 0.3843 | 0.032* | 0.25 |
H34B | 0.2158 | 0.8360 | 0.3800 | 0.032* | 0.25 |
H35B | 0.2317 | 0.9840 | 0.3495 | 0.032* | 0.25 |
P1 | 0.75849 (5) | 0.96188 (4) | 0.23061 (3) | 0.03291 (12) | |
F1 | 0.67662 (15) | 0.86228 (9) | 0.20496 (10) | 0.0648 (4) | |
F2 | 0.82988 (17) | 1.06696 (12) | 0.25652 (11) | 0.0995 (5) | |
F3A | 0.6646 (3) | 0.94023 (17) | 0.33111 (15) | 0.0866 (7) | 0.60 |
F4A | 0.8746 (3) | 0.8425 (3) | 0.2770 (2) | 0.1014 (11) | 0.60 |
F5A | 0.8616 (3) | 0.9730 (2) | 0.12567 (15) | 0.0673 (8) | 0.60 |
F6A | 0.6478 (3) | 1.07459 (17) | 0.17736 (19) | 0.0779 (9) | 0.60 |
F3B | 0.7017 (5) | 0.9210 (4) | 0.3457 (3) | 0.1074 (15) | 0.40 |
F4B | 0.9058 (5) | 0.8797 (4) | 0.2479 (4) | 0.1072 (16) | 0.40 |
F5B | 0.7930 (6) | 1.0208 (4) | 0.1204 (3) | 0.1084 (18) | 0.40 |
F6B | 0.5945 (4) | 1.0591 (3) | 0.2210 (4) | 0.1213 (17) | 0.40 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh1 | 0.01807 (5) | 0.01412 (4) | 0.01013 (4) | −0.00311 (3) | −0.00105 (4) | −0.00381 (3) |
N1 | 0.0206 (6) | 0.0179 (5) | 0.0168 (5) | 0.0003 (4) | −0.0033 (5) | −0.0035 (4) |
O1 | 0.0247 (5) | 0.0203 (4) | 0.0128 (4) | −0.0003 (4) | 0.0002 (4) | −0.0057 (3) |
N2 | 0.0230 (6) | 0.0181 (5) | 0.0143 (5) | −0.0083 (4) | −0.0009 (5) | −0.0014 (4) |
O2 | 0.0242 (5) | 0.0190 (4) | 0.0163 (4) | −0.0087 (3) | −0.0023 (4) | −0.0046 (3) |
Rh2 | 0.01733 (5) | 0.01336 (4) | 0.00985 (4) | −0.00368 (3) | 0.00065 (4) | −0.00340 (3) |
N3 | 0.0230 (6) | 0.0176 (4) | 0.0134 (5) | −0.0033 (4) | −0.0034 (4) | −0.0049 (4) |
O3 | 0.0188 (5) | 0.0251 (4) | 0.0144 (4) | −0.0041 (4) | −0.0002 (4) | −0.0049 (3) |
N4 | 0.0246 (6) | 0.0126 (4) | 0.0167 (5) | −0.0046 (4) | 0.0016 (5) | −0.0036 (4) |
O4 | 0.0239 (5) | 0.0151 (4) | 0.0145 (4) | −0.0028 (4) | 0.0011 (4) | −0.0038 (3) |
O5 | 0.0539 (7) | 0.0207 (4) | 0.0136 (4) | 0.0008 (5) | −0.0091 (5) | −0.0047 (3) |
O6 | 0.0417 (6) | 0.0264 (4) | 0.0171 (4) | −0.0165 (4) | 0.0044 (4) | −0.0086 (3) |
C1 | 0.0186 (6) | 0.0170 (5) | 0.0193 (6) | −0.0038 (5) | 0.0005 (5) | −0.0062 (4) |
C2 | 0.0270 (8) | 0.0249 (6) | 0.0244 (7) | 0.0028 (6) | 0.0039 (6) | −0.0083 (5) |
C3 | 0.0644 (12) | 0.0328 (7) | 0.0366 (8) | 0.0113 (8) | −0.0208 (8) | −0.0201 (6) |
C4 | 0.0573 (12) | 0.0496 (8) | 0.0927 (13) | −0.0113 (8) | −0.0187 (10) | −0.0388 (8) |
C5 | 0.0217 (7) | 0.0169 (5) | 0.0231 (6) | −0.0055 (5) | 0.0001 (5) | −0.0093 (4) |
C6 | 0.0367 (8) | 0.0320 (6) | 0.0264 (7) | −0.0185 (6) | −0.0043 (6) | −0.0108 (5) |
C7 | 0.0318 (7) | 0.0367 (7) | 0.0307 (8) | −0.0209 (6) | −0.0048 (7) | −0.0020 (6) |
C8 | 0.0285 (9) | 0.0702 (10) | 0.0578 (11) | −0.0125 (8) | 0.0020 (9) | −0.0284 (8) |
C9 | 0.0199 (6) | 0.0157 (5) | 0.0178 (6) | −0.0012 (5) | −0.0004 (5) | −0.0077 (4) |
C10 | 0.0225 (7) | 0.0392 (7) | 0.0206 (6) | −0.0045 (6) | −0.0065 (6) | −0.0115 (5) |
C11 | 0.0349 (8) | 0.0484 (8) | 0.0313 (8) | −0.0224 (6) | 0.0003 (7) | −0.0145 (6) |
C12 | 0.0563 (11) | 0.0349 (8) | 0.0578 (11) | −0.0111 (8) | −0.0119 (9) | −0.0162 (7) |
C13 | 0.0204 (6) | 0.0156 (5) | 0.0186 (6) | −0.0025 (5) | −0.0046 (5) | −0.0052 (4) |
C14 | 0.0403 (9) | 0.0158 (5) | 0.0221 (7) | −0.0048 (6) | 0.0028 (6) | −0.0070 (5) |
C15 | 0.0430 (10) | 0.0296 (7) | 0.0349 (8) | 0.0125 (7) | −0.0008 (8) | −0.0138 (6) |
C16A | 0.0350 (13) | 0.0521 (13) | 0.0471 (14) | 0.0020 (11) | −0.0065 (11) | −0.0125 (11) |
P1 | 0.0429 (2) | 0.02863 (17) | 0.0293 (2) | −0.01534 (16) | 0.00271 (18) | −0.00758 (15) |
F1 | 0.0912 (8) | 0.0363 (5) | 0.0794 (7) | −0.0233 (5) | −0.0280 (6) | −0.0172 (5) |
F2 | 0.1424 (9) | 0.1161 (7) | 0.0728 (8) | −0.1051 (5) | 0.0078 (7) | −0.0318 (6) |
F3A | 0.1373 (15) | 0.0574 (9) | 0.0677 (10) | −0.0576 (9) | 0.0844 (10) | −0.0376 (8) |
F4A | 0.0685 (16) | 0.116 (2) | 0.0902 (18) | 0.0127 (15) | −0.0352 (13) | 0.0162 (16) |
F5A | 0.0610 (13) | 0.0873 (13) | 0.0463 (11) | −0.0127 (11) | 0.0302 (10) | −0.0216 (10) |
F6A | 0.0957 (18) | 0.0227 (8) | 0.0916 (17) | 0.0177 (10) | −0.0039 (15) | 0.0045 (10) |
F3B | 0.194 (4) | 0.120 (2) | 0.0370 (17) | −0.104 (2) | 0.019 (2) | −0.0317 (15) |
F4B | 0.049 (2) | 0.136 (2) | 0.155 (3) | 0.036 (2) | −0.015 (2) | −0.095 (2) |
F5B | 0.212 (5) | 0.086 (2) | 0.0282 (17) | −0.057 (3) | −0.004 (2) | 0.0028 (16) |
F6B | 0.051 (2) | 0.0843 (18) | 0.262 (4) | 0.0237 (17) | −0.048 (2) | −0.1047 (19) |
Geometric parameters (Å, º) top
Rh1—Rh1i | 2.4026 (3) | C7—C8 | 1.509 (3) |
Rh1—O1i | 2.0389 (10) | C7—H18 | 0.9900 |
Rh1—O2i | 2.0314 (10) | C7—H19 | 0.9900 |
Rh1—O5 | 2.2608 (10) | C8—H20 | 0.9800 |
Rh1—N1 | 1.9706 (12) | C8—H21 | 0.9800 |
Rh1—N2 | 1.9735 (13) | C8—H22 | 0.9800 |
N1—C1 | 1.3146 (18) | C9—C10 | 1.496 (2) |
N1—H1 | 0.8800 | C10—C11 | 1.525 (2) |
O1—C1 | 1.2875 (15) | C10—H23 | 0.9900 |
N2—C5 | 1.3051 (19) | C10—H24 | 0.9900 |
N2—H2 | 0.8800 | C11—C12 | 1.515 (3) |
O2—C5 | 1.2912 (15) | C11—H25 | 0.9900 |
Rh2—Rh2ii | 2.4064 (3) | C11—H26 | 0.9900 |
Rh2—O3ii | 2.0118 (11) | C12—H27 | 0.9800 |
Rh2—O4ii | 2.0268 (9) | C12—H28 | 0.9800 |
Rh2—O6 | 2.2844 (10) | C12—H29 | 0.9800 |
Rh2—N3 | 1.9843 (13) | C13—C14 | 1.4974 (18) |
Rh2—N4 | 1.9845 (11) | C14—C15 | 1.529 (3) |
N3—C9 | 1.3165 (18) | C14—H30 | 0.9900 |
N3—H3 | 0.8800 | C14—H31 | 0.9900 |
O3—C9 | 1.2849 (16) | C15—C16A | 1.522 (4) |
N4—C13 | 1.2928 (18) | C15—C16B | 1.542 (7) |
N4—H4 | 0.8800 | C15—H32A | 0.9900 |
O4—C13 | 1.3011 (15) | C15—H33A | 0.9900 |
O5—H5 | 0.75 (2) | C15—H32B | 0.9900 |
O5—H6 | 0.766 (16) | C15—H33B | 0.9900 |
O6—H7 | 0.801 (19) | C16A—H36A | 0.9800 |
O6—H8 | 0.664 (17) | C16A—H34A | 0.9800 |
C1—C2 | 1.508 (2) | C16A—H35A | 0.9800 |
C2—C3 | 1.516 (3) | C16B—H36B | 0.9800 |
C2—H9 | 0.9900 | C16B—H34B | 0.9800 |
C2—H10 | 0.9900 | C16B—H35B | 0.9800 |
C3—C4 | 1.502 (3) | P1—F4B | 1.485 (4) |
C3—H11 | 0.9900 | P1—F5B | 1.512 (3) |
C3—H12 | 0.9900 | P1—F3A | 1.525 (2) |
C4—H13 | 0.9800 | P1—F6A | 1.534 (2) |
C4—H14 | 0.9800 | P1—F4A | 1.575 (3) |
C4—H15 | 0.9800 | P1—F2 | 1.5760 (16) |
C5—C6 | 1.505 (2) | P1—F1 | 1.5797 (14) |
C6—C7 | 1.524 (2) | P1—F3B | 1.587 (3) |
C6—H16 | 0.9900 | P1—F5A | 1.619 (2) |
C6—H17 | 0.9900 | P1—F6B | 1.671 (4) |
| | | |
N1—Rh1—N2 | 90.39 (5) | C7—C8—H21 | 109.5 |
N1—Rh1—O2i | 91.24 (5) | H20—C8—H21 | 109.5 |
N2—Rh1—O2i | 175.47 (4) | C7—C8—H22 | 109.5 |
N1—Rh1—O1i | 175.99 (4) | H20—C8—H22 | 109.5 |
N2—Rh1—O1i | 90.43 (4) | H21—C8—H22 | 109.5 |
O2i—Rh1—O1i | 87.66 (4) | O3—C9—N3 | 121.41 (14) |
N1—Rh1—O5 | 90.73 (4) | O3—C9—C10 | 117.06 (12) |
N2—Rh1—O5 | 91.25 (4) | N3—C9—C10 | 121.49 (12) |
O2i—Rh1—O5 | 92.95 (4) | C9—C10—C11 | 112.59 (12) |
O1i—Rh1—O5 | 93.18 (4) | C9—C10—H23 | 109.1 |
N1—Rh1—Rh1i | 86.25 (3) | C11—C10—H23 | 109.1 |
N2—Rh1—Rh1i | 86.22 (3) | C9—C10—H24 | 109.1 |
O2i—Rh1—Rh1i | 89.67 (3) | C11—C10—H24 | 109.1 |
O1i—Rh1—Rh1i | 89.88 (3) | H23—C10—H24 | 107.8 |
O5—Rh1—Rh1i | 176.05 (3) | C12—C11—C10 | 112.43 (14) |
C1—N1—Rh1 | 124.39 (9) | C12—C11—H25 | 109.1 |
C1—N1—H1 | 117.8 | C10—C11—H25 | 109.1 |
Rh1—N1—H1 | 117.8 | C12—C11—H26 | 109.1 |
C1—O1—Rh1i | 117.81 (9) | C10—C11—H26 | 109.1 |
C5—N2—Rh1 | 124.52 (9) | H25—C11—H26 | 107.8 |
C5—N2—H2 | 117.7 | C11—C12—H27 | 109.5 |
Rh1—N2—H2 | 117.7 | C11—C12—H28 | 109.5 |
C5—O2—Rh1i | 118.25 (10) | H27—C12—H28 | 109.5 |
N3—Rh2—N4 | 92.26 (5) | C11—C12—H29 | 109.5 |
N3—Rh2—O3ii | 175.64 (4) | H27—C12—H29 | 109.5 |
N4—Rh2—O3ii | 89.16 (5) | H28—C12—H29 | 109.5 |
N3—Rh2—O4ii | 88.47 (4) | N4—C13—O4 | 121.91 (12) |
N4—Rh2—O4ii | 175.84 (4) | N4—C13—C14 | 122.35 (11) |
O3ii—Rh2—O4ii | 89.82 (4) | O4—C13—C14 | 115.67 (12) |
N3—Rh2—O6 | 97.03 (4) | C13—C14—C15 | 110.74 (14) |
N4—Rh2—O6 | 95.30 (4) | C13—C14—H30 | 109.5 |
O3ii—Rh2—O6 | 86.94 (4) | C15—C14—H30 | 109.5 |
O4ii—Rh2—O6 | 88.67 (4) | C13—C14—H31 | 109.5 |
N3—Rh2—Rh2ii | 86.31 (3) | C15—C14—H31 | 109.5 |
N4—Rh2—Rh2ii | 85.79 (3) | H30—C14—H31 | 108.1 |
O3ii—Rh2—Rh2ii | 89.69 (3) | C16A—C15—C14 | 114.33 (16) |
O4ii—Rh2—Rh2ii | 90.17 (3) | C14—C15—C16B | 103.7 (3) |
O6—Rh2—Rh2ii | 176.44 (3) | C16A—C15—H32A | 108.7 |
C9—N3—Rh2 | 123.36 (10) | C14—C15—H32A | 108.7 |
C9—N3—H3 | 118.3 | C16A—C15—H33A | 108.7 |
Rh2—N3—H3 | 118.3 | C14—C15—H33A | 108.7 |
C9—O3—Rh2ii | 119.12 (9) | H32A—C15—H33A | 107.6 |
C13—N4—Rh2 | 124.55 (8) | C14—C15—H32B | 111.0 |
C13—N4—H4 | 117.7 | C16B—C15—H32B | 111.0 |
Rh2—N4—H4 | 117.7 | C14—C15—H33B | 111.0 |
C13—O4—Rh2ii | 117.55 (8) | C16B—C15—H33B | 111.0 |
Rh1—O5—H5 | 132.3 (12) | H32B—C15—H33B | 109.0 |
Rh1—O5—H6 | 114.5 (14) | C15—C16A—H36A | 109.5 |
H5—O5—H6 | 109.9 (18) | C15—C16A—H34A | 109.5 |
Rh2—O6—H7 | 128.3 (12) | H36A—C16A—H34A | 109.5 |
Rh2—O6—H8 | 111.3 (15) | C15—C16A—H35A | 109.5 |
H7—O6—H8 | 107.8 (19) | H36A—C16A—H35A | 109.5 |
O1—C1—N1 | 121.56 (12) | H34A—C16A—H35A | 109.5 |
O1—C1—C2 | 117.49 (12) | C15—C16B—H36B | 109.5 |
N1—C1—C2 | 120.94 (11) | C15—C16B—H34B | 109.5 |
C1—C2—C3 | 111.95 (14) | H36B—C16B—H34B | 109.5 |
C1—C2—H9 | 109.2 | C15—C16B—H35B | 109.5 |
C3—C2—H9 | 109.2 | H36B—C16B—H35B | 109.5 |
C1—C2—H10 | 109.2 | H34B—C16B—H35B | 109.5 |
C3—C2—H10 | 109.2 | F4B—P1—F5B | 97.0 (3) |
H9—C2—H10 | 107.9 | F3A—P1—F6A | 94.93 (12) |
C4—C3—C2 | 113.47 (16) | F3A—P1—F4A | 88.81 (13) |
C4—C3—H11 | 108.9 | F6A—P1—F4A | 175.25 (16) |
C2—C3—H11 | 108.9 | F4B—P1—F2 | 86.2 (2) |
C4—C3—H12 | 108.9 | F5B—P1—F2 | 90.3 (2) |
C2—C3—H12 | 108.9 | F3A—P1—F2 | 90.33 (11) |
H11—C3—H12 | 107.7 | F6A—P1—F2 | 84.65 (11) |
C3—C4—H13 | 109.5 | F4A—P1—F2 | 98.28 (14) |
C3—C4—H14 | 109.5 | F4B—P1—F1 | 97.5 (2) |
H13—C4—H14 | 109.5 | F5B—P1—F1 | 89.9 (2) |
C3—C4—H15 | 109.5 | F3A—P1—F1 | 87.96 (11) |
H13—C4—H15 | 109.5 | F6A—P1—F1 | 92.16 (11) |
H14—C4—H15 | 109.5 | F4A—P1—F1 | 85.03 (13) |
O2—C5—N2 | 121.26 (13) | F2—P1—F1 | 176.24 (8) |
O2—C5—C6 | 116.27 (13) | F4B—P1—F3B | 92.0 (2) |
N2—C5—C6 | 122.47 (11) | F5B—P1—F3B | 170.3 (2) |
C5—C6—C7 | 115.29 (14) | F2—P1—F3B | 86.38 (17) |
C5—C6—H16 | 108.5 | F1—P1—F3B | 92.79 (18) |
C7—C6—H16 | 108.5 | F3A—P1—F5A | 175.56 (11) |
C5—C6—H17 | 108.5 | F6A—P1—F5A | 88.61 (12) |
C7—C6—H17 | 108.5 | F4A—P1—F5A | 87.53 (13) |
H16—C6—H17 | 107.5 | F2—P1—F5A | 92.68 (11) |
C8—C7—C6 | 113.35 (13) | F1—P1—F5A | 89.23 (11) |
C8—C7—H18 | 108.9 | F4B—P1—F6B | 174.3 (3) |
C6—C7—H18 | 108.9 | F5B—P1—F6B | 86.8 (3) |
C8—C7—H19 | 108.9 | F2—P1—F6B | 89.52 (17) |
C6—C7—H19 | 108.9 | F1—P1—F6B | 86.75 (17) |
H18—C7—H19 | 107.7 | F3B—P1—F6B | 84.0 (2) |
C7—C8—H20 | 109.5 | F5A—P1—F6B | 113.68 (19) |
| | | |
N2—Rh1—N1—C1 | 83.16 (12) | Rh1i—O2—C5—N2 | −1.96 (17) |
O2i—Rh1—N1—C1 | −92.61 (12) | Rh1i—O2—C5—C6 | 178.18 (9) |
O5—Rh1—N1—C1 | 174.42 (12) | Rh1—N2—C5—O2 | −0.36 (18) |
Rh1i—Rh1—N1—C1 | −3.02 (12) | Rh1—N2—C5—C6 | 179.49 (10) |
N1—Rh1—N2—C5 | −84.33 (11) | O2—C5—C6—C7 | −150.55 (12) |
O1i—Rh1—N2—C5 | 91.74 (11) | N2—C5—C6—C7 | 29.60 (19) |
O5—Rh1—N2—C5 | −175.07 (11) | C5—C6—C7—C8 | 64.03 (19) |
Rh1i—Rh1—N2—C5 | 1.89 (11) | Rh2ii—O3—C9—N3 | −3.89 (16) |
N4—Rh2—N3—C9 | −85.00 (10) | Rh2ii—O3—C9—C10 | 173.86 (9) |
O4ii—Rh2—N3—C9 | 90.90 (10) | Rh2—N3—C9—O3 | 1.86 (17) |
O6—Rh2—N3—C9 | 179.37 (10) | Rh2—N3—C9—C10 | −175.78 (9) |
Rh2ii—Rh2—N3—C9 | 0.63 (10) | O3—C9—C10—C11 | −62.58 (17) |
N3—Rh2—N4—C13 | 85.41 (13) | N3—C9—C10—C11 | 115.16 (14) |
O3ii—Rh2—N4—C13 | −90.46 (13) | C9—C10—C11—C12 | −61.13 (19) |
O6—Rh2—N4—C13 | −177.31 (13) | Rh2—N4—C13—O4 | −0.4 (2) |
Rh2ii—Rh2—N4—C13 | −0.71 (12) | Rh2—N4—C13—C14 | −177.15 (11) |
Rh1i—O1—C1—N1 | −2.66 (19) | Rh2ii—O4—C13—N4 | 1.55 (19) |
Rh1i—O1—C1—C2 | 176.47 (10) | Rh2ii—O4—C13—C14 | 178.53 (10) |
Rh1—N1—C1—O1 | 4.2 (2) | N4—C13—C14—C15 | 112.56 (16) |
Rh1—N1—C1—C2 | −174.88 (11) | O4—C13—C14—C15 | −64.40 (17) |
O1—C1—C2—C3 | −67.42 (16) | C13—C14—C15—C16A | −57.52 (18) |
N1—C1—C2—C3 | 111.72 (16) | C13—C14—C15—C16B | −72.9 (3) |
C1—C2—C3—C4 | −61.37 (17) | | |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O4ii | 0.75 (2) | 2.02 (2) | 2.7651 (15) | 171.5 (16) |
O5—H6···F6Aiii | 0.766 (16) | 2.277 (19) | 2.970 (2) | 151.2 (19) |
O5—H6···F6Biii | 0.766 (16) | 2.215 (19) | 2.902 (4) | 149.8 (19) |
O5—H6···F2iii | 0.766 (16) | 2.540 (16) | 3.2410 (17) | 153.1 (19) |
O6—H7···O2i | 0.801 (19) | 2.044 (19) | 2.8420 (15) | 174.5 (15) |
O6—H8···F1 | 0.664 (17) | 2.273 (15) | 2.8931 (13) | 156 (2) |
N1—H1···F6Aiii | 0.88 | 2.47 | 3.071 (2) | 126 |
N3—H3···O1i | 0.88 | 2.20 | 3.0706 (15) | 170 |
N4—H4···F3A | 0.88 | 2.30 | 3.077 (2) | 148 |
N4—H4···F3B | 0.88 | 2.37 | 3.095 (4) | 140 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z. |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | [Rh2(C2H4NO)4(H2O)2]PF6 | [Rh2(C2H4NO)4(H2O)2]PF6·2H2O | [Rh2(C3H6NO)4(H2O)2]PF6·2H2O | [Rh2(C4H8NO)4(H2O)2]PF6 |
Mr | 619.07 | 655.10 | 711.21 | 731.28 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 118 | 118 | 118 | 173 |
a, b, c (Å) | 6.631 (3), 7.719 (4), 9.645 (4) | 11.6900 (17), 11.5700 (13), 7.9800 (13) | 8.980 (2), 11.866 (3), 12.682 (4) | 9.1037 (4), 11.0653 (1), 14.0104 (5) |
α, β, γ (°) | 92.014 (5), 92.205 (5), 110.471 (7) | 90, 110.510 (6), 90 | 87.696 (10), 85.095 (8), 69.032 (6) | 73.667 (10), 82.14 (1), 79.49 (1) |
V (Å3) | 461.6 (4) | 1010.9 (3) | 1257.2 (6) | 1326.18 (11) |
Z | 1 | 2 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.97 | 1.81 | 1.46 | 1.38 |
Crystal size (mm) | 0.10 × 0.10 × 0.03 | 0.30 × 0.30 × 0.15 | 0.30 × 0.10 × 0.10 | 0.35 × 0.10 × 0.03 |
|
Data collection |
Diffractometer | Rigaku/MSC Mercury CCD diffractometer | Rigaku/MSC Mercury CCD diffractometer | Rigaku/MSC Mercury CCD diffractometer | Rigaku/MSC Mercury CCD diffractometer |
Absorption correction | Integration (NUMABS; Higashi, 1999) | Integration (NUMABS; Higashi, 1999) | Integration (NUMABS; Higashi, 1999) | Integration (NUMABS; Higashi, 1999) |
Tmin, Tmax | 0.751, 0.940 | 0.712, 0.828 | 0.619, 0.773 | 0.643, 0.960 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3818, 2096, 1903 | 7888, 2308, 2208 | 10284, 5685, 5122 | 10813, 6014, 5456 |
Rint | 0.026 | 0.026 | 0.023 | 0.028 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 | 0.649 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.058, 1.04 | 0.027, 0.056, 1.17 | 0.026, 0.065, 1.06 | 0.041, 0.069, 1.17 |
No. of reflections | 2096 | 2308 | 5685 | 6014 |
No. of parameters | 133 | 151 | 327 | 373 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.64 | 0.48, −0.60 | 0.66, −0.76 | 0.75, −0.71 |
Selected bond lengths (Å) for (I) topRh1—Rh1i | 2.4085 (10) | Rh1—O3 | 2.284 (2) |
Rh1—O1i | 2.029 (2) | Rh1—N1 | 1.983 (3) |
Rh1—O2i | 2.040 (2) | Rh1—N2 | 1.969 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H4···O2ii | 0.80 (4) | 1.97 (4) | 2.760 (3) | 170 (4) |
O3—H3···F1 | 0.75 (4) | 2.20 (4) | 2.924 (3) | 162 (4) |
N1—H1···F1 | 0.88 | 2.35 | 3.064 (3) | 138.3 |
N1—H1···F3 | 0.88 | 2.44 | 3.285 (3) | 161.5 |
N2—H2···O1iii | 0.88 | 2.21 | 3.022 (3) | 153.9 |
Symmetry codes: (ii) x, y−1, z; (iii) x+1, y, z. |
Selected bond lengths (Å) for (II) topRh1—Rh1i | 2.4010 (4) | Rh1—O3 | 2.2402 (19) |
Rh1—O1i | 2.0299 (17) | Rh1—N1 | 1.980 (2) |
Rh1—O2i | 2.0425 (18) | Rh1—N2 | 1.973 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2ii | 0.93 (4) | 1.86 (4) | 2.778 (3) | 168 (3) |
O3—H4···O4 | 0.78 (4) | 2.00 (4) | 2.774 (3) | 173 (4) |
O4—H11···F1 | 0.72 (5) | 2.22 (6) | 2.937 (4) | 170 (5) |
O4—H12···F1iii | 0.80 (6) | 2.18 (6) | 2.923 (3) | 156 (5) |
N1—H1···O4iii | 0.88 | 2.44 | 3.213 (3) | 146.3 |
N2—H2···O1ii | 0.88 | 2.27 | 3.073 (3) | 152.2 |
N2—H2···O3iii | 0.88 | 2.59 | 3.192 (3) | 126.0 |
Symmetry codes: (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y+3/2, z+1/2. |
Selected bond lengths (Å) for (III) topRh1—Rh1i | 2.4105 (6) | Rh2—Rh2ii | 2.4095 (7) |
Rh1—O1i | 2.0356 (17) | Rh2—O3ii | 2.0289 (18) |
Rh1—O2i | 2.0469 (18) | Rh2—O4ii | 2.0318 (17) |
Rh1—O5 | 2.2388 (19) | Rh2—O6 | 2.237 (2) |
Rh1—N1 | 1.983 (2) | Rh2—N3 | 1.985 (2) |
Rh1—N2 | 1.979 (2) | Rh2—N4 | 1.977 (2) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H6···O7iii | 0.82 (4) | 1.91 (4) | 2.706 (3) | 164 (3) |
O5—H5···O8 | 0.86 (4) | 1.89 (4) | 2.755 (3) | 176 (3) |
O6—H7···O2i | 0.76 (4) | 2.04 (4) | 2.789 (3) | 168 (4) |
O6—H8···O8 | 0.81 (4) | 1.90 (4) | 2.711 (3) | 173 (4) |
O7—H10···O4ii | 0.72 (4) | 2.07 (4) | 2.775 (3) | 163 (4) |
O7—H9···F6iv | 0.84 (4) | 2.07 (4) | 2.879 (3) | 164 (3) |
O8—H11···O1v | 0.77 (4) | 1.97 (4) | 2.729 (3) | 168 (4) |
O8—H12···F1 | 0.80 (4) | 2.05 (4) | 2.845 (3) | 173 (3) |
N1—H1···F3 | 0.88 | 2.28 | 3.123 (3) | 160.7 |
N2—H2···O7iii | 0.88 | 2.14 | 2.963 (3) | 155.3 |
N4—H4···F4 | 0.88 | 2.26 | 3.120 (3) | 167.5 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x+1, y−1, z; (v) x+1, y, z. |
Selected bond lengths (Å) for (IV) topRh1—Rh1i | 2.4026 (3) | Rh2—Rh2ii | 2.4064 (3) |
Rh1—O1i | 2.0389 (10) | Rh2—O3ii | 2.0118 (11) |
Rh1—O2i | 2.0314 (10) | Rh2—O4ii | 2.0268 (9) |
Rh1—O5 | 2.2608 (10) | Rh2—O6 | 2.2844 (10) |
Rh1—N1 | 1.9706 (12) | Rh2—N3 | 1.9843 (13) |
Rh1—N2 | 1.9735 (13) | Rh2—N4 | 1.9845 (11) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O4ii | 0.75 (2) | 2.02 (2) | 2.7651 (15) | 171.5 (16) |
O5—H6···F6Aiii | 0.766 (16) | 2.277 (19) | 2.970 (2) | 151.2 (19) |
O5—H6···F6Biii | 0.766 (16) | 2.215 (19) | 2.902 (4) | 149.8 (19) |
O5—H6···F2iii | 0.766 (16) | 2.540 (16) | 3.2410 (17) | 153.1 (19) |
O6—H7···O2i | 0.801 (19) | 2.044 (19) | 2.8420 (15) | 174.5 (15) |
O6—H8···F1 | 0.664 (17) | 2.273 (15) | 2.8931 (13) | 156 (2) |
N1—H1···F6Aiii | 0.88 | 2.47 | 3.071 (2) | 126.0 |
N3—H3···O1i | 0.88 | 2.20 | 3.0706 (15) | 169.7 |
N4—H4···F3A | 0.88 | 2.30 | 3.077 (2) | 147.5 |
N4—H4···F3B | 0.88 | 2.37 | 3.095 (4) | 140.0 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z. |
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Amidate-bridged paddlewheel complexes are useful modules in making assembled structures, because they have hydrogen-donating NH and hydrogen-accepting O sites in addition to the axial coordination sites. We have studied assembled complexes of acetamidate-bridged paddlewheel dirhodium complexes with halide linkers, namely one-dimensional chain structures of [Rh2(acam)4(µ-X)].nH2O (Hacam is acetamide; X = Cl, Br and I; n = 0, 2, 3 and 7; Yang et al., 2000, 2001), a two-dimensional honeycomb structure of [{Rh2(acam)4}3(µ3-Cl)2]·4H2O (Takazaki et al., 2003) and a three-dimensional diamondoid structure of [{Rh2(acam)4}2(µ4-I)]·6H2O (Fuma et al., 2004). In all these structures, direct hydrogen bonds between the NH groups and O atoms of the amidate ligands play an important role in constructing the structures. In the crystals with water of crystallization, hydrogen bonds between the amidate ligands and water molecules affect the physical properties (Fuma et al., 2004). We have also reported anionic chain structures of the dirhodium complexes with tetrachloroplatinate and tetrachloropalladate linkers, [Rh2(acam)4(H2O)2][Rh2(acam)4(µ-MCl4)]·2H2O (M = Pd and Pt; Yang et al., 2006). In these structures, the cationic complex [Rh2(acam)4(H2O)2]+ participates in hydrogen-bonding networks using the bridging amidate and axial aqua ligands. In this paper, we report a variation of hydrogen-bonding networks in the hexafluorophosphate salts of amidate-bridged dirhodium complexes, [Rh2(acam)4(H2O)2]PF6, (I), [Rh2(acam)4(H2O)2]PF6·2H2O, (II), [Rh2(pram)4(H2O)2]PF6·2H2O (Hpram is propionamide), (III), and [Rh2(buam)4(H2O)2]PF6 (Hbuam is butyramide), (IV).
The structure of (I) is shown in Fig. 1. Compound (I) is isostructural with [Rh2(acam)4(H2O)2]ClO4 (Baranovskii et al., 1986). The dirhodium complex lies around an inversion center, (1/2, 1/2, 1/2). The hexafluorophosphate ion lies on another inversion center, (1/2, 0, 0). The complex is the so-called (2,2)-cis isomer, in which each Rh atom is coordinated by two cis N and two cis O atoms. The complexes form a hydrogen-bonded chain along the b axis, with the axial aqua ligand (O3) donating an H atom to one of the amidate O atoms (O2ii) [symmetry code: (ii) x, y − 1, z] (Table 2 and Fig. 2). The complexes also form hydrogen bonds between amidate atom N2 and amidate atom O1iii [symmetry code: (iii) x + 1, y, z]. These hydrogen bonds connect the complexes two-dimensionally in the ab plane. The hexafluorophosphate ion is also hydrogen bonded from the amidate (N1) and axial aqua ligand, and these connect the hydrogen-bonding sheets three-dimensionally. In this structure, all the N and O atoms are included in the hydrogen-bonding network.
The structure of (II) is shown in Fig. 3. In this structure, there is one independent complex on an inversion center, (1/2, 1/2, 1/2), that has an equivalent site (1/2, 0, 0). The hexafluorophosphate ion lies on another inversion center, (0, 1/2, 0), that has an equivalent site (0, 0, 1/2) and one water molecule at the general position. The crystal structure is shown in Fig. 4. In compound (II), two aqua ligands, two amidate N atoms and four amidate O atoms are used for direct hydrogen bonding between the complexes, the same as in (I), but the network structure is different from that in (I). The complex donates an H atom of the axial aqua ligand (O3) to the amidate atom O2ii [symmetry code: (ii) −x + 1, y + 1/2, −z + 3/2]. The complex also donates the amin H atom of N2 to the amidate oxygen atom (O1ii). The resulting two-dimensional sheet structure is extended in the bc plane. The aqua ligand (O3) and amide atom N1 also hydrogen bond to water molecules (O4 and O4iii) [symmetry code: (iii) x, −y + 3/2, z + 1/2]. The water molecule (O4) donates H atoms to F atoms of the hexafluorophosphate ions F1 and F1iii. The water molecule and the hexafluorophosphate ion then connect the hydrogen-bonding sheets.
The structure of (III) is shown in Fig. 5. In the unit cell there are two independent dirhodium complexes that lie around inversion centers, (1/2, 1/2, 1/2) and (0, 1/2, 0). Two independent water molecules are also included. The hydrogen-bonding network in (III) is shown in Fig. 6. There is only one hydrogen bond that directly connects the complexes in (III); the aqua ligand O6 hydrogen bonds to the amidate atom O2i [symmetry code: (i) −x, 1 − y, −z]. The resulting one-dimensional hydrogen-bonding chain extends in the [111] direction. The water molecules connect the chains two-dimensionally. One water molecule (O7) acts as a hydrogen-bond donor to atom O4ii [symmetry code: (ii) −x + 1, −y + 1, −z + 1] and accepts hydrogen bonds from N2iii and O5iii [symmetry code: (iii) −x + 1, −y + 1, −z]. The other water molecule (O8) acts as a donor to atom O1v [symmetry code: (v) x + 1, y, z] and an acceptor from atoms O5 and O6. Hydrogen bonds to the F atoms of the hexafluorophosphate ion also exist.
The structure of (IV) is shown in Fig. 7. Compound (IV) also has two independent dirhodium complexes in the unit cell. One complex lies on an inversion center at (1/2, 1/2, 1/2) and the other on another inversion center at (1/2, 1/2, 0). The two independent complexes are hydrogen bonded to each other (Table 8 and Fig. 8). Axial aqua ligands of both complexes act as donors to the O atoms of the neighboring complexes [O5 to O4ii and O6 to O2i; symmetry codes: (i) −x + 1, −y + 1, −z; (ii) −x + 1, −y + 1, −z + 1]. Amidate atom N3 acts as a donor to amidate atom O1i. These hydrogen bonds connect the complexes into a one-dimensional chain in the c direction. The hexafluorophosphate ion accepts hydrogen bonds from atoms N4 and O6 and from N1iv and O5iv [symmetry code: (iv) x, y + 1, z]. The anion thus connects the chains two-dimensionally.