Some disorder is seen in the crystal structure of [Rh(CH3)(NH3)5]0.73[RhCl(NH3)5]2.27(S2O6)3. It is, however, clear that the methyl group has a pronounced trans influence on the Rh-N distance, with an elongation of 0.11 Å. No trans influence is observed for the Rh-N distance due to the Cl- ion. Both observations are in agreement with observations in equivalent cobalt complexes.
Supporting information
CCDC reference: 193724
Key indicators
- Single-crystal X-ray study
- T = 122 K
- Mean (S-O) = 0.004 Å
- H-atom completeness 96%
- Disorder in solvent or counterion
- R factor = 0.036
- wR factor = 0.102
- Data-to-parameter ratio = 32.5
checkCIF results
No syntax errors found
Alert Level B:
PLAT_111 Alert B ADDSYM detects (pseudo) centre of symmetry ... 92 Perc Fit
| Author response: Structure solution and refinement has been attempted in several
space groups. In P-1 this leads to disorder, unrealistic thermal
parameters and an R1-factor of 0.1408 (for anisotropic thermal
parameters, but without hydrogen atoms included). In P1 the solution
is identical to the solution in Im and R1=0.0499 (for anisotropic thermal
parameters, but without hydrogen atoms included).
|
PLAT_111 Alert B ADDSYM detects (pseudo) centre of symmetry ... 92 Perc Fit
| Author response: Structure solution and refinement has been attempted in several
space groups. In P-1 this leads to disorder, unrealistic thermal
parameters and an R1-factor of 0.1408 (for anisotropic thermal
parameters, but without hydrogen atoms included). In P1 the solution
is identical to the solution in Im and R1=0.0499 (for anisotropic thermal
parameters, but without hydrogen atoms included).
|
Alert Level C:
STRVAL_01
From the CIF: _refine_ls_abs_structure_Flack 0.430
From the CIF: _refine_ls_abs_structure_Flack_su 0.030
Alert C Flack test results are ambiguous.
PLAT_202 Alert C Isotropic non-H Atoms in Anion/Solvent = 1
PLAT_302 Alert C Anion/Solvent Disorder ....................... 4.00 Perc.
PLAT_420 Alert C D-H Without Acceptor N(11) - *H(11B) ?
PLAT_420 Alert C D-H Without Acceptor N(12) - H(12C) ?
PLAT_420 Alert C D-H Without Acceptor N(21) - H(21B) ?
PLAT_420 Alert C D-H Without Acceptor N(23) - H(23B) ?
PLAT_420 Alert C D-H Without Acceptor N(23) - H(23C) ?
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C0.73 H47.19 Cl2.27 N15 O18 Rh3
Atom count from the _atom_site data: C0.73 H45 Cl2.27 N15 O18 Rh3 S6
CELLZ_01
From the CIF: _cell_formula_units_Z 2
From the CIF: _chemical_formula_sum C0.73 H47.19 Cl2.27 N15 O18 Rh3 S
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 1.46 1.46 0.00
H 94.38 90.00 4.38
Cl 4.54 4.54 0.00
N 30.00 30.00 0.00
O 36.00 36.00 0.00
Rh 6.00 6.00 0.00
S 12.00 12.00 0.00
Difference between formula and atom_site contents detected.
WARNING: H atoms missing from atom site list. Is this intentional?
REFLT_03
From the CIF: _diffrn_reflns_theta_max 35.02
From the CIF: _reflns_number_total 7322
Count of symmetry unique reflns 3751
Completeness (_total/calc) 195.20%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 3571
Fraction of Friedel pairs measured 0.952
Are heavy atom types Z>Si present yes
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
2 Alert Level B = Potential problem
8 Alert Level C = Please check
Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX (Duisenberg, 1992); data reduction: EVALCCD (Duisenberg, 1998) and DREAD (Blessing, 1987); 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).
Crystal data top
[Rh(CH3)(NH3)5]0.73[RhCl(NH3)5]2.27(S2O6)3 | F(000) = 960 |
Mr = 1135.58 | Dx = 2.258 Mg m−3 |
Monoclinic, Im | Mo Kα radiation, λ = 0.71073 Å |
a = 6.271 (2) Å | Cell parameters from 474 reflections |
b = 27.205 (3) Å | θ = 4.4–31.0° |
c = 9.871 (2) Å | µ = 2.11 mm−1 |
β = 97.29 (1)° | T = 122 K |
V = 1670.4 Å3 | Rod, colourless |
Z = 2 | 0.37 × 0.17 × 0.08 mm |
Data collection top
Nonius KappaCCD diffractometer | 7322 independent reflections |
Radiation source: fine-focus sealed tube | 7148 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 9 pixels mm-1 | θmax = 35.0°, θmin = 2.2° |
θ and φ scans | h = −10→10 |
Absorption correction: integration Gaussian integration (Coppens, 1970) | k = −43→43 |
Tmin = 0.542, Tmax = 0.898 | l = −15→15 |
34422 measured reflections | |
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)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0598P)2 + 6.9449P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.023 |
7322 reflections | Δρmax = 3.30 e Å−3 |
225 parameters | Δρmin = −1.68 e Å−3 |
4 restraints | Absolute structure: Flack (1983), 0000 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.43 (3) |
Special details top
Experimental. Gaussian integration (Coppens, 1970) |
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) |
Rh2 | 0.96197 (3) | 0.166778 (9) | 0.62172 (2) | 0.01111 (5) | |
N21 | 0.8546 (6) | 0.11675 (12) | 0.7539 (3) | 0.0144 (6) | |
H21A | 0.9600 | 0.0959 | 0.7826 | 0.022* | |
H21B | 0.7435 | 0.1002 | 0.7111 | 0.022* | |
H21C | 0.8137 | 0.1325 | 0.8253 | 0.022* | |
N22 | 1.2650 (7) | 0.15910 (15) | 0.7268 (4) | 0.0214 (7) | |
H22A | 1.2813 | 0.1801 | 0.7966 | 0.032* | |
H22B | 1.3627 | 0.1654 | 0.6712 | 0.032* | |
H22C | 1.2821 | 0.1285 | 0.7582 | 0.032* | |
N23 | 0.8991 (6) | 0.22508 (13) | 0.7440 (3) | 0.0167 (6) | |
H23A | 0.8660 | 0.2138 | 0.8233 | 0.025* | |
H23B | 0.7893 | 0.2424 | 0.7026 | 0.025* | |
H23C | 1.0149 | 0.2442 | 0.7588 | 0.025* | |
N24 | 1.0663 (6) | 0.21550 (15) | 0.4822 (4) | 0.0188 (6) | |
H24A | 1.1241 | 0.2418 | 0.5261 | 0.028* | |
H24B | 0.9552 | 0.2247 | 0.4224 | 0.028* | |
H24C | 1.1643 | 0.2009 | 0.4382 | 0.028* | |
N25 | 1.0187 (7) | 0.10934 (15) | 0.4902 (4) | 0.0203 (7) | |
H25A | 1.1585 | 0.1078 | 0.4828 | 0.030* | |
H25B | 0.9455 | 0.1147 | 0.4083 | 0.030* | |
H25C | 0.9762 | 0.0811 | 0.5235 | 0.030* | |
Cl | 0.61140 (19) | 0.17248 (4) | 0.50636 (11) | 0.02194 (19) | |
Rh1 | 0.48747 (5) | 0.0000 | 0.15369 (3) | 0.01348 (8) | |
N13 | 0.5745 (7) | 0.05419 (14) | 0.0245 (4) | 0.0195 (7) | |
H13A | 0.6521 | 0.0410 | −0.0357 | 0.029* | |
H13B | 0.6522 | 0.0770 | 0.0731 | 0.029* | |
H13C | 0.4568 | 0.0679 | −0.0196 | 0.029* | |
N12 | 0.4006 (8) | 0.05356 (17) | 0.2846 (4) | 0.0249 (8) | |
H12A | 0.3951 | 0.0826 | 0.2427 | 0.037* | |
H12B | 0.4972 | 0.0547 | 0.3588 | 0.037* | |
H12C | 0.2720 | 0.0465 | 0.3086 | 0.037* | |
Cl1 | 0.8391 (8) | 0.0000 | 0.2738 (5) | 0.0126 (12)* | 0.27 (1) |
C11 | 0.782 (3) | 0.0000 | 0.2567 (17) | 0.041 (3)* | 0.73 (2) |
N11 | 0.1657 (10) | 0.0000 | 0.0412 (6) | 0.0221 (10) | |
H11A | 0.1179 | 0.0308 | 0.0312 | 0.033* | 0.50 |
H11B | 0.0780 | −0.0173 | 0.0869 | 0.033* | 0.50 |
H11C | 0.1695 | −0.0134 | −0.0407 | 0.033* | 0.50 |
S3 | 0.5967 (3) | 0.0000 | 0.64904 (13) | 0.0166 (2) | |
S4 | 0.2697 (3) | 0.0000 | 0.68079 (18) | 0.0222 (3) | |
O32 | 0.6211 (6) | −0.04480 (10) | 0.5726 (3) | 0.0252 (7) | |
O31 | 0.7225 (8) | 0.0000 | 0.7845 (4) | 0.0180 (8) | |
O42 | 0.2457 (6) | 0.04457 (11) | 0.7579 (4) | 0.0270 (7) | |
O41 | 0.1538 (10) | 0.0000 | 0.5435 (6) | 0.0352 (14) | |
S1 | 0.82960 (19) | 0.17203 (3) | 0.12449 (10) | 0.01545 (17) | |
S2 | 1.15676 (19) | 0.16083 (3) | 0.09385 (12) | 0.01922 (19) | |
O11 | 0.7843 (6) | 0.13023 (11) | 0.2063 (3) | 0.0240 (6) | |
O12 | 0.8273 (5) | 0.21944 (10) | 0.1934 (3) | 0.0216 (5) | |
O13 | 0.7098 (6) | 0.17221 (11) | −0.0127 (3) | 0.0173 (6) | |
O21 | 1.2712 (8) | 0.16123 (12) | 0.2308 (4) | 0.0313 (9) | |
O22 | 1.2068 (5) | 0.20179 (11) | 0.0079 (4) | 0.0266 (6) | |
O23 | 1.1573 (5) | 0.11329 (11) | 0.0254 (4) | 0.0251 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rh2 | 0.01615 (10) | 0.00997 (9) | 0.00688 (8) | 0.00083 (7) | 0.00018 (6) | 0.00031 (7) |
N21 | 0.0199 (13) | 0.0112 (11) | 0.0112 (12) | 0.0006 (10) | −0.0023 (10) | 0.0003 (9) |
N22 | 0.0223 (17) | 0.0257 (13) | 0.0162 (15) | −0.0033 (13) | 0.0020 (12) | −0.0041 (12) |
N23 | 0.0243 (15) | 0.0134 (12) | 0.0120 (13) | 0.0025 (10) | 0.0012 (10) | −0.0011 (10) |
N24 | 0.0219 (14) | 0.0225 (15) | 0.0122 (13) | −0.0033 (11) | 0.0024 (11) | 0.0009 (11) |
N25 | 0.0288 (17) | 0.0186 (14) | 0.0124 (13) | 0.0050 (12) | −0.0015 (11) | −0.0038 (10) |
Cl | 0.0217 (4) | 0.0251 (4) | 0.0188 (4) | 0.0006 (3) | 0.0016 (3) | 0.0014 (3) |
Rh1 | 0.02122 (18) | 0.01070 (14) | 0.00788 (13) | 0.000 | −0.00064 (12) | 0.000 |
N13 | 0.0298 (17) | 0.0141 (12) | 0.0137 (14) | −0.0009 (11) | −0.0004 (12) | 0.0003 (10) |
N12 | 0.036 (2) | 0.0239 (17) | 0.0136 (15) | 0.0077 (14) | 0.0006 (13) | −0.0024 (12) |
N11 | 0.026 (2) | 0.022 (2) | 0.018 (2) | 0.000 | 0.0019 (17) | 0.000 |
S3 | 0.0307 (6) | 0.0090 (4) | 0.0081 (4) | 0.000 | −0.0050 (4) | 0.000 |
S4 | 0.0227 (6) | 0.0124 (5) | 0.0282 (7) | 0.000 | −0.0102 (5) | 0.000 |
O32 | 0.0491 (19) | 0.0120 (11) | 0.0131 (11) | 0.0067 (11) | −0.0011 (11) | −0.0030 (8) |
O31 | 0.0231 (19) | 0.0192 (16) | 0.0101 (15) | 0.000 | −0.0048 (13) | 0.000 |
O42 | 0.0258 (14) | 0.0196 (13) | 0.0342 (17) | 0.0064 (10) | −0.0019 (12) | −0.0045 (11) |
O41 | 0.038 (3) | 0.0211 (19) | 0.039 (3) | 0.000 | −0.026 (2) | 0.000 |
S1 | 0.0246 (4) | 0.0104 (3) | 0.0101 (3) | 0.0018 (3) | −0.0026 (3) | −0.0004 (3) |
S2 | 0.0227 (4) | 0.0132 (3) | 0.0191 (4) | 0.0037 (3) | −0.0079 (3) | −0.0040 (3) |
O11 | 0.0409 (17) | 0.0160 (11) | 0.0141 (11) | −0.0033 (11) | −0.0001 (10) | −0.0007 (9) |
O12 | 0.0354 (15) | 0.0123 (10) | 0.0155 (11) | 0.0035 (9) | −0.0028 (10) | −0.0047 (8) |
O13 | 0.0215 (14) | 0.0201 (11) | 0.0085 (11) | 0.0034 (9) | −0.0051 (9) | −0.0011 (9) |
O21 | 0.038 (2) | 0.0246 (14) | 0.0260 (18) | 0.0045 (13) | −0.0175 (15) | −0.0053 (12) |
O22 | 0.0271 (14) | 0.0191 (12) | 0.0326 (16) | −0.0005 (10) | 0.0001 (12) | −0.0021 (11) |
O23 | 0.0262 (14) | 0.0160 (11) | 0.0302 (16) | 0.0074 (10) | −0.0074 (11) | −0.0073 (11) |
Geometric parameters (Å, º) top
Rh2—N22 | 2.057 (4) | Rh1—N11 | 2.177 (6) |
Rh2—N21 | 2.057 (4) | Rh1—Cl1 | 2.368 (5) |
Rh2—N23 | 2.061 (4) | N13—H13A | 0.8900 |
Rh2—N24 | 2.076 (4) | N13—H13B | 0.8900 |
Rh2—N25 | 2.091 (4) | N13—H13C | 0.8900 |
Rh2—Cl | 2.3492 (12) | N12—H12A | 0.8900 |
N21—H21A | 0.8900 | N12—H12B | 0.8900 |
N21—H21B | 0.8900 | N12—H12C | 0.8900 |
N21—H21C | 0.8900 | N11—H11A | 0.8900 |
N22—H22A | 0.8900 | N11—H11B | 0.8900 |
N22—H22B | 0.8900 | N11—H11C | 0.8900 |
N22—H22C | 0.8900 | S3—O32 | 1.451 (3) |
N23—H23A | 0.8900 | S3—O31 | 1.463 (5) |
N23—H23B | 0.8900 | S3—S4 | 2.113 (3) |
N23—H23C | 0.8900 | S4—O42 | 1.450 (3) |
N24—H24A | 0.8900 | S4—O41 | 1.454 (5) |
N24—H24B | 0.8900 | S1—O11 | 1.444 (3) |
N24—H24C | 0.8900 | S1—O12 | 1.459 (3) |
N25—H25A | 0.8900 | S1—O13 | 1.463 (3) |
N25—H25B | 0.8900 | S1—S2 | 2.133 (2) |
N25—H25C | 0.8900 | S2—O21 | 1.448 (4) |
Rh1—C11 | 1.99 (2) | S2—O22 | 1.458 (4) |
Rh1—N12 | 2.066 (4) | S2—O23 | 1.460 (3) |
Rh1—N13 | 2.068 (4) | | |
| | | |
N22—Rh2—N21 | 88.21 (15) | N12—Rh1—N13i | 179.34 (18) |
N22—Rh2—N23 | 90.91 (15) | N12—Rh1—N13 | 89.67 (16) |
N21—Rh2—N23 | 92.04 (14) | N13i—Rh1—N13 | 91.0 (2) |
N22—Rh2—N24 | 92.90 (16) | C11—Rh1—N11 | 180.0 (5) |
N21—Rh2—N24 | 177.83 (15) | N12—Rh1—N11 | 91.04 (17) |
N23—Rh2—N24 | 89.81 (15) | N13—Rh1—N11 | 89.17 (15) |
N22—Rh2—N25 | 91.04 (15) | N12—Rh1—Cl1 | 89.40 (15) |
N21—Rh2—N25 | 89.69 (14) | N13—Rh1—Cl1 | 90.40 (14) |
N23—Rh2—N25 | 177.43 (15) | N11—Rh1—Cl1 | 179.4 (2) |
N24—Rh2—N25 | 88.42 (16) | Rh1—N13—H13A | 109.5 |
N22—Rh2—Cl | 177.54 (13) | Rh1—N13—H13B | 109.5 |
N21—Rh2—Cl | 89.40 (10) | H13A—N13—H13B | 109.5 |
N23—Rh2—Cl | 89.79 (11) | Rh1—N13—H13C | 109.5 |
N24—Rh2—Cl | 89.46 (11) | H13A—N13—H13C | 109.5 |
N25—Rh2—Cl | 88.33 (11) | H13B—N13—H13C | 109.5 |
Rh2—N21—H21A | 109.5 | Rh1—N12—H12A | 109.5 |
Rh2—N21—H21B | 109.5 | Rh1—N12—H12B | 109.5 |
H21A—N21—H21B | 109.5 | H12A—N12—H12B | 109.5 |
Rh2—N21—H21C | 109.5 | Rh1—N12—H12C | 109.5 |
H21A—N21—H21C | 109.5 | H12A—N12—H12C | 109.5 |
H21B—N21—H21C | 109.5 | H12B—N12—H12C | 109.5 |
Rh2—N22—H22A | 109.5 | Rh1—N11—H11A | 109.5 |
Rh2—N22—H22B | 109.5 | Rh1—N11—H11B | 109.5 |
H22A—N22—H22B | 109.5 | H11A—N11—H11B | 109.5 |
Rh2—N22—H22C | 109.5 | Rh1—N11—H11C | 109.5 |
H22A—N22—H22C | 109.5 | H11A—N11—H11C | 109.5 |
H22B—N22—H22C | 109.5 | H11B—N11—H11C | 109.5 |
Rh2—N23—H23A | 109.5 | O32—S3—O32i | 114.2 (3) |
Rh2—N23—H23B | 109.5 | O32—S3—O31 | 113.23 (16) |
H23A—N23—H23B | 109.5 | O32—S3—S4 | 104.19 (18) |
Rh2—N23—H23C | 109.5 | O31—S3—S4 | 106.6 (2) |
H23A—N23—H23C | 109.5 | O42—S4—O42i | 113.5 (3) |
H23B—N23—H23C | 109.5 | O42—S4—O41 | 114.60 (19) |
Rh2—N24—H24A | 109.5 | O42—S4—S3 | 104.20 (15) |
Rh2—N24—H24B | 109.5 | O41—S4—S3 | 104.0 (3) |
H24A—N24—H24B | 109.5 | O11—S1—O12 | 114.93 (18) |
Rh2—N24—H24C | 109.5 | O11—S1—O13 | 113.95 (19) |
H24A—N24—H24C | 109.5 | O12—S1—O13 | 113.22 (17) |
H24B—N24—H24C | 109.5 | O11—S1—S2 | 103.18 (16) |
Rh2—N25—H25A | 109.5 | O12—S1—S2 | 105.00 (15) |
Rh2—N25—H25B | 109.5 | O13—S1—S2 | 105.03 (16) |
H25A—N25—H25B | 109.5 | O21—S2—O22 | 114.8 (2) |
Rh2—N25—H25C | 109.5 | O21—S2—O23 | 114.1 (2) |
H25A—N25—H25C | 109.5 | O22—S2—O23 | 113.2 (2) |
H25B—N25—H25C | 109.5 | O21—S2—S1 | 103.8 (2) |
C11—Rh1—N12 | 89.0 (3) | O22—S2—S1 | 104.77 (14) |
N12—Rh1—N12i | 89.7 (3) | O23—S2—S1 | 104.55 (15) |
C11—Rh1—N13i | 90.8 (3) | | |
| | | |
O32—S3—S4—O42 | 179.6 (2) | O13—S1—S2—O21 | 179.5 (2) |
O31—S3—S4—O42 | 59.64 (17) | O11—S1—S2—O22 | 178.43 (19) |
O32—S3—S4—O42i | 60.3 (2) | O12—S1—S2—O22 | −60.8 (2) |
O32i—S3—S4—O41 | 60.01 (14) | O13—S1—S2—O22 | 58.8 (2) |
O31—S3—S4—O41 | 180.0 | O11—S1—S2—O23 | 59.1 (2) |
O11—S1—S2—O21 | −60.8 (2) | O12—S1—S2—O23 | 179.8 (2) |
O12—S1—S2—O21 | 59.9 (2) | O13—S1—S2—O23 | −60.5 (2) |
Symmetry code: (i) x, −y, z. |