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The rhodium complexes [RhCl3(NH3)3], (I), and [Rh(NO3)3(NH3)3], (II), are built from octa­hedral RhX3(NH3)3 units; in (I) they are isolated units, while in (II) the units are stacked in columns with partially filled sites for the Rh atoms. The octa­hedra of monoclinic crystals of (I) are linked by N—H...Cl hydrogen bonds and the Rh3+ ions are located on the mirror planes. In the trigonal crystals of (II), the discontinuous `columns' along the threefold axis are linked by N—H...O hydrogen bonds. The structure of (I) has been solved using laboratory powder diffraction data, the structure of (II) has been solved by single-crystal methods using data from a merohedrally twinned sample. Both compounds possess low solubility in water.

Supporting information


Crystallographic Information File (CIF)
Contains datablocks global, I, II


Rietveld powder data file (CIF format)
Contains datablock I


Structure factor file (CIF format)
Contains datablock I


Structure factor file (CIF format)
Contains datablock II

CCDC references: 971136; 971137

Introduction top

Since the publication of the first work on the synthesis of triamminetrichloridorhodium(III) (Lebedinskij, 1935) there have been reports of the synthesis of only three related complexes, viz. Rh(NO2)3(NH3)3 (Lebedinskij & Shenderetskaya, 1940), Rh(OH)3(NH3)3 and RhCl3(NH3)3 (Pannetier et al., 1969). The absence of reports on the synthesis and study of the properties of this triammine series of complexes with other acido ligands is surprising because they possess very low solubility and can potentially be used both in processes of refining platinum group metals and in the development of gravimetric methods for the determination of rhodium. The complexes that do not contain any halide ions and possess sufficiently high solubility may prove to be good precursors for the creation of catalytic compositions containing rhodium.

The [RhX3(NH3)3] compounds must exist as two geometric isomers, but the overall lack of structural studies of this class of compounds, except for two fac-[Rh(NO2)3(NH3)3] modifications (Khranenko et al., 2002; Gromilov et al., 2005) does not allow us to judge the isomer composition of the complexes obtained previously. The authors (Khranenko et al., 2002) mistakenly indicated the space group P21/m for the structure of the α-phase, while the true space group is P21. But all calculations and other descriptions were made in the true space group. In addition, the absolute structure was not determinated.

Experimental top

Synthesis and crystallization top

A light-yellow powder of fac-[RhCl3(NH3)3], (I), was prepared by heating fac-[Rh(NH3)3(NO2)3] (0.103 g), synthesized according to the procedure of Khranenko et al. (2002), in HCl (25 ml, 1:1 aqueous solution) for 3 h followed by cooling to room temperature. The compound is poorly soluble in water and is stable when stored at ambient temperatures; the yield of (I) was 91%. The composition of the powder was determined by thermal decomposition of the complex in a stream of H2 with the capture of volatile products by an aqueous solution. The Rh content was determined gravimetrically by the solid residue, the content of Cl- was determined using a titration by the Hg2+ solution with difenilkarbazone as an indicator; the content of NH3 was determined by acidimetric titration using the urotropin.

fac-[Rh(NH3)3(NO2)3] and fac-[RhCl3(NH3)3] were used as starting materials for the synthesis of fac-[Rh(NO3)3(NH3)3], (II). On heating fac-[Rh(NH3)3(NO2)3] (0.594 g) in HNO3 (20 ml, 1:1 aqueous solution), the complex compound dissolved with separation of colorless gas and formation of a green–yellow solution. After a brief boiling and subsequent incubation of the solution at room temperature for 2 d, pale-yellow single crystals of (II) were extracted; the yield was 25–30%. The same complex was obtained by heating of fac-[RhCl3(NH3)3] to boiling point in concentrated nitric acid followed by the solution concentrating at room temperature. The same composition and crystal state were confirmed by X-ray phase analysis, CHN analysis and IR spectroscopy. The crystals are poorly soluble in water and are stable when stored in air.

Composition of the synthesized complex compounds was set based on the CHN analyses. The analysis data for the (I) are in good agreement with the formula: Rh 39.8, Cl 40.6, NH3 19.7%; calculated: Rh 39.5, Cl 40.9, NH3 19.6%. IR (cm-1): 491 (ν Rh—N), 775, 821, 855 (ρ NH3), 1279, 1302 (δ N—H), 1546, 1572, 1616 (δ N—H), 3181 and 3276 (ν N—H).

The results for (II) (N 23.51, H 2.84%) can be inter­preted in two ways: (i) the values of N 24.71% and H 2.65% correspond to the formula of (II) but the values of N 23.47% and H 3.07% correspond to (II).H2O. Despite the fact that the formula (II).H2O best describes the analysis results, IR spectroscopy and the XRD data did not confirm the existence of a hydrate or absorbed water in the compound. IR (cm-1): 530 (ν Rh—N), 792, 835, 1009 (ρ NH3), 1279 and 1508 (bands cleavage ν N—O), 1356 and 1723 (δ N—H), 3229 and 3301 (ν N—H). We believe that the difference between the results of nitro­gen analysis and the theoretical calculation for (II) is the systematic error dependent standard analysis procedure.

The assignment of the solid phases to faced isomers of the complexes was made under the assumption that the isomerization of (I) and (II) is absent in the synthesis process.

The nitro­gen and hydrogen content in the crystal phase were determined by elemental CHN analysis with Euro EA 3000 equipment. The IR spectra were recorded with an IR SCIMITAR FTS 2000 spectrometer using tablets of KBr in wavenumber range of 400–4000 cm-1 in increments of 1 cm-1.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. To determine the structure of (I), the powder X-ray data were collected with the X-ray D8ADVANCE (Bruker AXS) diffractometer at 300 K. The experiment used the variable scan speed technique (VCT) and variable step (VSS) (Madsen & Hill, 1992; Madsen & Hill, 1994; David, 1992). The exposure time increased with increasing of 2θ-angle resulting in a significant improvement in the quality of the collected X-ray data. Typically, the peak half width (FWHM) must contain 5–8 experimental points but increasing of 2θ-angle significantly broadens the peaks, so the step can be increased in areas with high angles to reduce the duration of the experiment.

The experimental diffractogram was divided into four parts: (i) 5° 2θ 39.9°, with a step of 0.016θ and an exposure of 3 s; (ii) 39.9° 2θ 61.5°, with a step of 0.024θ and an exposure of 9 s; (iii) 61.5° 2θ 97.3°, with a step of 0.032θ and an exposure of 15 s; (iv) 97.3° 2θ 140°, with a step of 0.040θ and an exposure of 30 s. The total time of its registration was approximately 19 h. Due to the detector VANTEC the real time of registration at a point reached ~700 s. The partition of the experiment for VCT/VSS was executed with XRD Wizard program (Bruker, 2007). Then the experimental data have been converted to a conventional in the X-ray analysis XYE-file containing the 2θi coordinate, the intensity Ii and the standard deviation σ(Ii) for each experimental point. The refinement with the Rietveld method, implemented in the program TOPAS4.2 (Bruker, 2008b) takes into account the standard deviation of intensity at each point by the introduction into the least-squares treatment the weight wi = σ(Ii)-2 for each point.

The powder diffraction patter of RhCl3(NH3)3 indicated monoclinic symmetry, space group P21/m or P21. The unit-cell volume corresponds to 5–6 non-H atoms in the asymmetric part of the centrosymmetric space group P21/m and hence it was selected. The structure was solved by its modelling in the direct space followed by phase annealing by TOPAS4.2 (Bruker, 2008b). One ion of Rh3+, two ions of Cl- and two atoms of N were generated and dynamic population of positions was used for all atoms (Favre-Nicolin & Černý, 2002, 2004). The phase annealing gave a model of the structure which has been refined using the Rietveld refinement by TOPAS4.2. The VCT technique allowed to refine anisotropic atomic displacement parameters of rhodium. Isotropic diplacement parameters of all rest of non-H atoms obtained reasonable values. At this stage, the difference synthesis showed several maxima corresponding to the hydrogen atoms of NH3 groups. This information allowed unambiguously assign all hydrogen atoms and refine their positions with a soft constraint on the bond lengths N—H = 0.9 Å, as well as the tetra­hedral angles Rh—N—H and H—N—H (109.4°). Isotropic displacement parameters of the hydrogen atoms were fixed at 0.038 Å2. Agreement between observed and calculated patterns is shown in Fig. 1. Checking the structure using the program PLATON (Spek, 2009) did not reveal any unreported features. .

Crystals of (II) possess a perfect cleavage, as a result the powder samples showed strong texturing, making it difficult for the structural study. Therefore, due to the presence of single crystals in the sequel, the single-crystal diffraction techniques were used at 296 K with the Bruker SMART APEXII diffractometer. Initial characteristics of the experiment and the results of automatic detection of symmetry indicated possible merohedral twinning of the crystal. Thus, the |E2-1| value was extremely low (0.316), Rsym for 15 space groups had values of 0.016 to 0.019, while the best value of the combined quality criteria (CFOM) was very high (32.5). The simplest possible space group, P3, was chosen and was confirmed in the process of a refinement. Direct methods allowed determine the rhodium coordinates but the difference electron density maps did not help to solve the structure completely, although the o­cta­hedral environment of Rh atom was recognizable. At this stage, twinning law (010, 100, 001) was introduced and the absolute structure was determined. All non-H atoms were clearly located at the same time and refined in the anisotropic approximation. The Rh atom is disordered in two positions on the threefold axis and due to this fact the H atoms were not located.

Further details of the crystal structure investigations may be obtained from the Fachinformationszentrum Karlsruhe, FRG, 76344 Eggenstein-Leopoldshafen. (Fax: +49–7247–808–666; e-mail:, on quoting the deposition number CSD-426435 for (I) and CSD-426436 for (II).

Results and discussion top

Both crystal structures are constructed from the neutral complexes [RhX3(NH3)3] (X = NO3 and Cl), which are faced isomers. The structure of the complexes with the atom-numbering scheme are shown in Fig. 2.

In (I), the [RhCl3(NH3)3] complex has an o­cta­hedral structure and the Rh1, Cl1, N1 and H1 atoms are arranged on a mirror plane. Rh—Cl and Rh—N bond lengths (Table 2), lying on the mirror plane, are 0.016 and 0.074 Å longer than the others. Deviations of valence cis angles on the RhIII atom from the ideal value of 90° do not exceed 6.8°. The o­cta­hedral complexes are connencted by N—H···Cl hydrogen bonds in the crystal (Table 3); the packing of the o­cta­hedra is shown in Fig. 3. It should be noted that, as in the crystals of the α- and β-phase of [Rh(NH3)3(NO2)3] (Khranenko et al., 2002; Gromilov et al., 2005), in this case the RhIII atoms (and with them the o­cta­hedra) are arranged in a substanti­ally flat hexagonal grids. The grids are oriented perpendicularly to the c axis and repeated by its value (Fig. 3). Deviations of RhIII atoms out of the grid do not exceed 0.114 Å, the distances between atoms in a grid fall within the range from 5.7284 (12) to 6.7279 (13) Å (= a axis).

The main and unique feature of crystalline complex (II) is its columnar structure. The columns are constructed from the distorted [Rh(NO3)3(NH3)3] o­cta­hedra lying on a threefold axis (Fig. 4). The rhodium atom occupies two positions on the axis with different degrees of occupation: the position with coordinates (0, 1/2, 0), Rh1, has a site-occupation factor (sof) of 0.8039 (18), while for the second, Rh2, sof is 0.1961 (18). So, these `columns' are not continuous but consist of the isolated Rh1 and Rh2 o­cta­hedra and of the Rh1+Rh2 o­cta­hedral pairs connected via common face of O-type, (Fig. 2b); the Rh1···Rh2 distance is 2.8129 (18) Å. The position of Rh2 is not at the bottom of the cell so that the second distance between the positions is 2.4431 (18) Å; hereupon the o­cta­hedral parameters for Rh1 and Rh2 are different (Table 4). If the Rh1 atom is closer to the o­cta­hedral O-face, the Rh2 is closer to the N-face. The maximal deviation of the bond angles from 90° in the o­cta­hedra is 12.9° (Table 4). The anisotropic atomic dispacement parameters show on librational vibrations of the o­cta­hedra around the threefold axis parallel with cell axis c. The columns form channels along the threefold axes which could accomodate water molecules in channels' cavities (Fig. 5). Then distances between the water molecule and nearest environment would be Ow—O = 2.83 Å and Ow—N = 2.99 Å. If we will take into account the gaps between the o­cta­hedra in the columns, then the crystallization at different conditions might allow water molecules to occupy the denoted positions. In (II), the RhIII atoms are arranged strictly in hexagonal grids. The grids lie in the ab cell plane with the Rh···Rh distances equal to the a cell parameter.

An important feature of the structure is that the o­cta­hedra with empty metal positions can not be located side by side; the monoatomic face can not be placed separately. But if the metal is present in one polyhedron, say Rh1, and not in the other with common N-face, Rh2, then H atoms of NH3 groups are creating specific N—H···O hydrogen bonds between the columns. The arrangement of H atoms in the presence of Rh2 and absence of Rh1 is different as well as arrangement of hydrogen bonds. In connection with the mentioned disorder of H atoms they were not located, but N···O distances (2.92–3.09 Å) between columns indicate a presence of hydrogen bonds.

Related literature top

For related literature, see: David (1992); Favre-Nicolin & Cerny (2002, 2004); Gromilov et al. (2005); Khranenko et al. (2002); Lebedinskij (1935); Lebedinskij & Shenderetskaya (1940); Madsen & Hill (1992, 1994); Sheldrick (2008); Spek (2009); Wizard (2002–2007).

Computing details top

Data collection: XRD Wizard (Bruker, 2007) for (I); APEX2 (Bruker, 2008a) for (II). Cell refinement: TOPAS Rietveld (Bruker, 2008b) for (I); APEX2 (Bruker, 2008a) for (II). Data reduction: XRD Wizard (Bruker, 2007) for (I); SAINT (Bruker, 2008a) for (II). Program(s) used to solve structure: TOPAS Phase annealing (Bruker, 2008b) for (I); SHELXS97 (Sheldrick, 2008) for (II). Program(s) used to refine structure: TOPAS Rietveld (Bruker, 2008b) for (I); SHELXL97 (Sheldrick, 2008) for (II). Molecular graphics: SHELXTL (Sheldrick, 2008) for (II). Software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) for (II).

Figures top
[Figure 1] Fig. 1. The results of Rietveld refinement of the RhCl3(NH3)3 structure, showing experimental (red points), calculated (line) and difference (line below) powder patterns.
[Figure 2] Fig. 2. The building blocks of (I) and (II), showing the atom-numbering schemes (50% probability ellipsoids). (a) The octahedral RhCl3(NH3)3 complex and (b) the paired Rh(NO3)3(NH3)3 octahedra.
[Figure 3] Fig. 3. The packing of building blocks in the RhCl3(NH3)3 crystal.
[Figure 4] Fig. 4. The columnar packing in the Rh(NO3)3(NH3)3 structure, with darker octahedra shown around Rh1.
[Figure 5] Fig. 5. A cavity between Rh(NO3)3(NH3)3 columns, with the water O atom (Ow) shown as a hatched circle. The atomic radii correspond to van der Waals radii.
(I) fac-Triamminetrichloridorhodium(III) top
Crystal data top
[RhCl3(NH3)3]V = 358.21 (2) Å3
Mr = 260.36Z = 2
Monoclinic, P21/mDx = 2.414 Mg m3
Hall symbol: -P 2ybCu Kα1 radiation, λ = 1.5406, 1.5444 Å
a = 6.7279 (3) ÅT = 300 K
b = 9.7888 (4) Åyellow
c = 5.4611 (2) Å?, ? × ? × ? mm
β = 95.149 (2)°
Data collection top
VANTEC linear detector
Scan method: step
None monochromator2θmin = 5°, 2θmax = 139.987°, 2θstep = 0.016°
Data collection mode: reflection
Refinement top
Rp = 4.215Profile function: PearsonVII
Rwp = 4.55578 parameters
Rexp = 1.53816 restraints
RBragg = 1.790Only H-atom coordinates refined
χ2 = 8.768(Δ/σ)max = 0.010
8436.68125 data pointsPreferred orientation correction: PO-March Dollase - 1 Dir (0 0 1)
Crystal data top
[RhCl3(NH3)3]β = 95.149 (2)°
Mr = 260.36V = 358.21 (2) Å3
Monoclinic, P21/mZ = 2
a = 6.7279 (3) ÅCu Kα1 radiation, λ = 1.5406, 1.5444 Å
b = 9.7888 (4) ÅT = 300 K
c = 5.4611 (2) Å?, ? × ? × ? mm
Data collection top
VANTEC linear detector
Scan method: step
Data collection mode: reflection2θmin = 5°, 2θmax = 139.987°, 2θstep = 0.016°
Refinement top
Rp = 4.2158436.68125 data points
Rwp = 4.55578 parameters
Rexp = 1.53816 restraints
RBragg = 1.790Only H-atom coordinates refined
χ2 = 8.768
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
Rh0.2195 (2)0.250.4826 (2)0.0318 (7)
N10.4960 (9)0.250.327 (1)0.040 (4)*
N20.1122 (6)0.0942 (3)0.2608 (7)0.033 (3)*
Cl10.0810 (5)0.250.6825 (6)0.038 (2)*
Cl20.3532 (4)0.0777 (2)0.7530 (4)0.035 (1)*
H10.606 (8)0.250.454 (9)0.06*
H20.498 (5)0.176 (3)0.232 (6)0.06*
H30.141 (5)0.110 (3)0.104 (6)0.05*
H40.161 (6)0.006 (4)0.323 (5)0.05*
H50.035 (6)0.106 (3)0.253 (6)0.05*
Atomic displacement parameters (Å2) top
Rh0.0490 (15)0.0229 (12)0.0229 (11)00.0003 (6)0
Geometric parameters (Å, º) top
Rh—N12.113 (5)N1—H20.89 (3)
Rh1—N22.039 (4)N2—H30.91 (3)
Rh1—Cl12.382 (4)N2—H40.98 (4)
Rh1—Cl22.366 (2)N2—H50.99 (4)
N1—H10.96 (5)
N2—Rh1—N2i96.81 (15)N1—Rh1—Cl287.21 (12)
N2—Rh1—N192.22 (15)Cl1—Rh1—Cl290.28 (8)
N2—Rh1—Cl190.15 (12)Cl2—Rh1—Cl2i90.96 (8)
N2—Rh1—Cl286.11 (11)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
N1—H1···Cl1ii0.97 (5)2.35 (5)3.297 (7)166 (4)
N1—H2···Cl2iii0.89 (3)2.68 (3)3.405 (4)140 (3)
N2—H3···Cl2iv0.91 (3)2.51 (3)3.340 (5)152 (3)
N2—H4···Cl1v0.98 (4)2.56 (4)3.392 (3)143 (3)
N2—H5···Cl2vi0.99 (4)2.79 (4)3.550 (5)134 (3)
Symmetry codes: (ii) x+1, y, z; (iii) x+1, y, z+1; (iv) x, y, z1; (v) x, y1/2, z+1; (vi) x, y, z+1.
(II) fac-Triamminetrinitratorhodium(III) top
Crystal data top
[Rh(NO3)3(NH3)3]Dx = 2.208 Mg m3
Mr = 340.04Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3Cell parameters from 3627 reflections
Hall symbol: P 3θ = 3.1–32.9°
a = 7.496 (1) ŵ = 1.72 mm1
c = 5.2560 (8) ÅT = 296 K
V = 255.77 (7) Å3Needle, yellow
Z = 10.40 × 0.15 × 0.15 mm
F(000) = 168
Data collection top
Bruker APEXII CCD area-detector
879 independent reflections
Radiation source: fine-focus sealed tube879 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
phi and ω scansθmax = 33.0°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = 1111
Tmin = 0.546, Tmax = 0.782k = 1111
3780 measured reflectionsl = 83
Refinement top
Refinement on F2H-atom parameters not defined
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0355P)2]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.019(Δ/σ)max < 0.001
wR(F2) = 0.048Δρmax = 1.11 e Å3
S = 1.12Δρmin = 0.32 e Å3
879 reflectionsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
54 parametersExtinction coefficient: 0.035 (8)
0 restraintsAbsolute structure: Flack (1983), 230 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.03 (9)
Secondary atom site location: difference Fourier map
Crystal data top
[Rh(NO3)3(NH3)3]Z = 1
Mr = 340.04Mo Kα radiation
Trigonal, P3µ = 1.72 mm1
a = 7.496 (1) ÅT = 296 K
c = 5.2560 (8) Å0.40 × 0.15 × 0.15 mm
V = 255.77 (7) Å3
Data collection top
Bruker APEXII CCD area-detector
879 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
879 reflections with I > 2σ(I)
Tmin = 0.546, Tmax = 0.782Rint = 0.030
3780 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.019H-atom parameters not defined
wR(F2) = 0.048Δρmax = 1.11 e Å3
S = 1.12Δρmin = 0.32 e Å3
879 reflectionsAbsolute structure: Flack (1983), 230 Friedel pairs
54 parametersAbsolute structure parameter: 0.03 (9)
0 restraints
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
xyzUiso*/UeqOcc. (<1)
Rh10.00000.00000.50000.01434 (9)0.8039 (18)
Rh20.00000.00000.0352 (3)0.0161 (7)0.1961 (18)
O10.2025 (13)0.001 (2)0.2430 (16)0.0300 (10)
N10.2245 (15)0.2239 (16)0.741 (2)0.0311 (12)
N20.3732 (7)0.0006 (9)0.2773 (9)0.0574 (15)
O20.4248 (16)0.001 (3)0.4969 (19)0.101 (2)
O30.4708 (14)0.0001 (19)0.0867 (13)0.125 (3)
Atomic displacement parameters (Å2) top
Rh10.01485 (9)0.01485 (9)0.01332 (17)0.00742 (5)0.0000.000
Rh20.0208 (5)0.0208 (5)0.0068 (16)0.0104 (2)0.0000.000
O10.0222 (19)0.050 (2)0.0254 (15)0.0237 (18)0.0049 (17)0.0002 (14)
N10.021 (2)0.027 (3)0.0293 (18)0.0006 (17)0.0005 (18)0.001 (2)
N20.041 (2)0.101 (4)0.050 (3)0.050 (3)0.0028 (19)0.000 (3)
O20.081 (6)0.212 (7)0.055 (3)0.106 (6)0.023 (3)0.000 (3)
O30.110 (7)0.215 (9)0.082 (5)0.105 (7)0.048 (5)0.000 (6)
Geometric parameters (Å, º) top
Rh1—N12.106 (9)Rh2—O1ii2.106 (7)
Rh1—N1i2.106 (9)Rh2—N1iv2.051 (9)
Rh1—N1ii2.106 (9)Rh2—N1v2.051 (9)
Rh1—O1ii2.030 (8)Rh2—N1vi2.051 (9)
Rh1—O12.030 (7)Rh2—Rh1vi2.4431 (18)
Rh1—O1i2.030 (7)O1—N21.292 (8)
Rh1—Rh2iii2.4431 (18)N1—Rh2iii2.051 (9)
Rh1—Rh22.8129 (18)N2—O31.242 (7)
Rh2—O1i2.106 (7)N2—O21.220 (10)
Rh2—O12.106 (7)
N1—Rh1—N1i87.5 (4)O1—Rh2—N1iv171.0 (5)
N1—Rh1—N1ii87.5 (4)O1ii—Rh2—N1iv96.0 (6)
N1i—Rh1—N1ii87.5 (4)O1i—Rh2—N1v171.0 (5)
N1—Rh1—O1ii175.3 (5)O1—Rh2—N1v96.0 (6)
N1i—Rh1—O1ii96.0 (6)O1ii—Rh2—N1v95.8 (5)
N1ii—Rh1—O1ii95.8 (6)N1iv—Rh2—N1v90.4 (4)
N1—Rh1—O195.8 (6)O1i—Rh2—N1vi96.0 (6)
N1i—Rh1—O1175.3 (4)O1—Rh2—N1vi95.8 (5)
N1ii—Rh1—O196.0 (6)O1ii—Rh2—N1vi171.0 (5)
O1ii—Rh1—O180.6 (3)N1iv—Rh2—N1vi90.4 (4)
N1—Rh1—O1i96.0 (6)N1v—Rh2—N1vi90.4 (4)
N1i—Rh1—O1i95.8 (6)O1i—Rh2—Rh1vi134.0 (2)
N1ii—Rh1—O1i175.3 (4)O1—Rh2—Rh1vi134.0 (2)
O1ii—Rh1—O1i80.6 (3)O1ii—Rh2—Rh1vi134.0 (2)
O1—Rh1—O1i80.6 (3)N1iv—Rh2—Rh1vi55.0 (3)
N1—Rh1—Rh2iii53.0 (3)N1v—Rh2—Rh1vi55.0 (3)
N1i—Rh1—Rh2iii53.0 (3)N1vi—Rh2—Rh1vi55.0 (3)
N1ii—Rh1—Rh2iii53.0 (3)O1i—Rh2—Rh146.0 (2)
O1ii—Rh1—Rh2iii131.7 (2)O1—Rh2—Rh146.0 (2)
O1—Rh1—Rh2iii131.7 (2)O1ii—Rh2—Rh146.0 (2)
O1i—Rh1—Rh2iii131.7 (2)N1iv—Rh2—Rh1125.0 (3)
N1—Rh1—Rh2127.0 (3)N1v—Rh2—Rh1125.0 (3)
N1i—Rh1—Rh2127.0 (3)N1vi—Rh2—Rh1125.0 (3)
N1ii—Rh1—Rh2127.0 (3)Rh1vi—Rh2—Rh1180.0
O1ii—Rh1—Rh248.3 (2)N2—O1—Rh1130.3 (6)
O1—Rh1—Rh248.3 (2)N2—O1—Rh2144.0 (6)
O1i—Rh1—Rh248.3 (2)Rh1—O1—Rh285.7 (2)
Rh2iii—Rh1—Rh2180.000 (1)Rh1—N1—Rh2iii72.0 (2)
O1i—Rh2—O177.1 (3)O3—N2—O2124.9 (6)
O1i—Rh2—O1ii77.1 (3)O3—N2—O1118.2 (6)
O1—Rh2—O1ii77.1 (3)O2—N2—O1116.9 (6)
O1i—Rh2—N1iv95.8 (5)
Symmetry codes: (i) y, xy, z; (ii) x+y, x, z; (iii) x, y, z+1; (iv) y, xy, z1; (v) x+y, x, z1; (vi) x, y, z1.

Experimental details

Crystal data
Chemical formula[RhCl3(NH3)3][Rh(NO3)3(NH3)3]
Crystal system, space groupMonoclinic, P21/mTrigonal, P3
Temperature (K)300296
a, b, c (Å)6.7279 (3), 9.7888 (4), 5.4611 (2)7.496 (1), 7.496 (1), 5.2560 (8)
α, β, γ (°)90, 95.149 (2), 9090, 90, 120
V3)358.21 (2)255.77 (7)
Radiation typeCu Kα1, λ = 1.5406, 1.5444 ÅMo Kα
µ (mm1)1.72
Specimen shape, size (mm)?, ? × ? × ?0.40 × 0.15 × 0.15
Data collection
DiffractometerVANTEC linear detector
Bruker APEXII CCD area-detector
Specimen mounting?
Data collection modeReflection
Data collection methodStepphi and ω scans
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.546, 0.782
No. of measured, independent and
observed reflections
3780, 879, 879
θ values (°)2θmin = 5 2θmax = 139.987 2θstep = 0.016θmax = 33.0, θmin = 3.1
Distance from source to specimen (mm)0.767
R factors and goodness of fitRp = 4.215, Rwp = 4.555, Rexp = 1.538, RBragg = 1.790, χ2 = 8.768R[F2 > 2σ(F2)] = 0.019, wR(F2) = 0.048, S = 1.12
No. of reflections/data points8436.68125879
No. of parameters7854
No. of restraints160
H-atom treatmentOnly H-atom coordinates refinedH-atom parameters not defined
Δρmax, Δρmin (e Å3)1.11, 0.32
Absolute structureFlack (1983), 230 Friedel pairs
Absolute structure parameter0.03 (9)

Computer programs: XRD Wizard (Bruker, 2007), APEX2 (Bruker, 2008a), TOPAS Rietveld (Bruker, 2008b), SAINT (Bruker, 2008a), TOPAS Phase annealing (Bruker, 2008b), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) for (I) top
Rh—N12.113 (5)Rh1—Cl12.382 (4)
Rh1—N22.039 (4)Rh1—Cl22.366 (2)
N2—Rh1—N2i96.81 (15)N1—Rh1—Cl287.21 (12)
N2—Rh1—N192.22 (15)Cl1—Rh1—Cl290.28 (8)
N2—Rh1—Cl190.15 (12)Cl2—Rh1—Cl2i90.96 (8)
N2—Rh1—Cl286.11 (11)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) for (I) top
N1—H1···Cl1ii0.97 (5)2.35 (5)3.297 (7)166 (4)
N1—H2···Cl2iii0.89 (3)2.68 (3)3.405 (4)140 (3)
N2—H3···Cl2iv0.91 (3)2.51 (3)3.340 (5)152 (3)
N2—H4···Cl1v0.98 (4)2.56 (4)3.392 (3)143 (3)
N2—H5···Cl2vi0.99 (4)2.79 (4)3.550 (5)134 (3)
Symmetry codes: (ii) x+1, y, z; (iii) x+1, y, z+1; (iv) x, y, z1; (v) x, y1/2, z+1; (vi) x, y, z+1.
Selected geometric parameters (Å, º) for (II) top
Rh1—N12.106 (9)N2—O31.242 (7)
Rh1—O1i2.030 (8)N2—O21.220 (10)
O1—N21.292 (8)
N1—Rh1—N1ii87.5 (4)O1ii—Rh2—O177.1 (3)
N1—Rh1—O1i175.3 (5)O1ii—Rh2—N1iii95.8 (5)
N1ii—Rh1—O1i96.0 (6)O1—Rh2—N1iii171.0 (5)
N1i—Rh1—O1i95.8 (6)O1i—Rh2—N1iii96.0 (6)
O1i—Rh1—O180.6 (3)N1iii—Rh2—N1iv90.4 (4)
Symmetry codes: (i) x+y, x, z; (ii) y, xy, z; (iii) y, xy, z1; (iv) x+y, x, z1.

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