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Acta Cryst. (2007). E63, m2473    [ doi:10.1107/S1600536807042444 ]

fac-Trichloridotrispyrazolerhodium(III)

R. Bieda, M. C. Winter and W. S. Sheldrick

Abstract top

The title compound, fac-[RhCl3(pzH)3] (pzH = pyrazole) or fac-[RhCl3(C3H4N2)3], was prepared by treating RhCl3·3H2O with three equivalents of pyrazole. It contains a central RhIII atom coordinated in a facial manner by three pyrazole N atoms and three chloride ligands. As a result of their participation in weak intramolecular N-H...Cl hydrogen bonds, the pyrazole rings adopt a propeller-like arrangement. The mean planes of the pyrazole ligands exhibit dihedral angles of 26.83 (17), 2.03 (10) and 18.83 (14)° with the planes containing their coordinating N atoms, the RhIII atom and the acceptor Cl atoms of their individual N-H...Cl interactions.

Comment top

The complexes mer-[MCl3(Me2pzH)3] .CH3OH (M = Rh, Ir; Me2pzH = 3,5-dimethylpyrazole) have been prepared by treating MCl3 .xH2O with three equivalents of 3,5-dimethylpyrazole in methanol at 85°C (Cushing et al., 2006). Only the mer-isomers were obtained on subsequent recrystallization from methanol solution. mer-[RhCl3(Me2pzH)3] has also been characterized as a decomposition product of the reaction of [RhCl3(CH3CN)3] with Tl[HB(Me2pz)]3 (Albinati et al., 1999). A facial tris(dimethylpyrazole) ReI complex fac-[Re(CO)3(Me2pzH)3][B(Ar)4] (Ar = 3,5-bis(trifluoromethylphenyl)) is also known (Nicto et al., 2005).

We now report the crystal structure of fac-[RhCl3(pzH)3] (I), which was obtained by treating RhCl3 .3H2O in a 2-propanol/water mixture with three equivalents of pyrazole. (I) was recrystallized as the fac-isomer from methanol solution and exhibits the expected 1H NMR resonances at 6.57 (t), 6.88 (d) and 7.89 (d) for the C—H protons and 12.48 (d) for the N—H protons of the pure isomer in CDCl3 solution. A 2:1 mixture of the fac and mer isomers is observed after 5 h in methanol solution. As depicted in Fig. 1, the pyrazole ligands adopt a propellor-like arrangement in (I) and participate in intramolecular N—H···Cl hydrogen bonds (Table 1) to the nearest chloride ligand. Their best planes exhibit respective dihedral angles of 26.83 (17), 2.03 (10) and 18.83 (14)° to the planes containing their coordinating nitrogen atoms, Rh1 and the acceptor Cl atoms of their N—H···Cl interactions. The molecules are linked into a network by intermolecular N—H···Cl and C—H···Cl hydrogen bonds (Fig. 2).

Related literature top

For related literature, see: Albinati et al. (1999); Cushing et al. (2006); Nicto et al. (2005).

Experimental top

fac-[RhCl3(pzH)3] (I) was prepared by treating 50.5 mg RhCl3 .3H2O (0.19 mmol) in 0.9 ml 2-propanol/water (5:1) with 3 equivalents of pyrazole (40.2 mg, 0.59 mmol). After stirring for 1.5 h, the resulting yellow precipitate was removed by centrifugation and washed with 2 ml of 2-propanol to afford fac-[RhCl3(pzH)3] in 17% yield (13.7 mg). Elemental anlysis (Vario EL) for C9H12Cl3N6Rh .H2O (M = 431.5): C 25.4 (calc. 25.7), H 3.2 (calc. 3.4), N 19.4 (calc. 19.3). FAB MS on a VG Autospec: m/z 435(3%) [M+Na]+, 377(15%) [M—Cl]+. 1H NMR (CDCl3) on a Bruker DRX 400: δ 6.57 (t, 3H, pzH-b), 6.88 (d, 3H, pzH-c), 7.89 (d, 3H, pyH-a), 12.48 (d, 3H, NH). Suitable crystals for X-ray analysis were obtained by slow evaporation of a methanol solution of (I).

Refinement top

H atoms were constrained to idealized positions and refined using a riding model, with C—H distances of 0.93 Å and N—H distances of 0.86 Å; Uiso(H) = 1.2 Uiso(C) for the former and Uiso(H) = 1.2 Uiso(N) for the latter protons.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1995); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Hydrogen bonds between the anions and cations of (I). The colour code is the same as in Fig. 1.
fac-Trichloridotrispyrazolerhodium(III) top
Crystal data top
[RhCl3(C3H4N2)3]F(000) = 816
Mr = 413.51Dx = 1.959 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 14706 reflections
a = 8.2041 (3) Åθ = 2.5–27.5°
b = 11.9243 (4) ŵ = 1.78 mm−1
c = 14.5839 (5) ÅT = 108 K
β = 100.624 (3)°Prismatic, orange
V = 1402.26 (8) Å30.52 × 0.18 × 0.13 mm
Z = 4
Data collection top
Oxford Diffraction Sapphire2 CCD
diffractometer		3236 independent reflections
Radiation source: fine-focus sealed tube2701 reflections with I > 2σ(I)
graphiteRint = 0.041
1109 images at 1.0 deg in ω and 20 s scansθmax = 27.6°, θmin = 2.8°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		h = −10→10
Tmin = 0.692, Tmax = 0.802k = −15→14
25826 measured reflectionsl = −19→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0483P)2]
where P = (Fo2 + 2Fc2)/3
3236 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.88 e Å−3
0 restraintsΔρmin = −0.78 e Å−3
Crystal data top
[RhCl3(C3H4N2)3]V = 1402.26 (8) Å3
Mr = 413.51Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.2041 (3) ŵ = 1.78 mm−1
b = 11.9243 (4) ÅT = 108 K
c = 14.5839 (5) Å0.52 × 0.18 × 0.13 mm
β = 100.624 (3)°
Data collection top
Oxford Diffraction Sapphire2 CCD
diffractometer		3236 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		2701 reflections with I > 2σ(I)
Tmin = 0.692, Tmax = 0.802Rint = 0.041
25826 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.081Δρmax = 0.88 e Å−3
S = 1.05Δρmin = −0.78 e Å−3
3236 reflectionsAbsolute structure: ?
172 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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*/Ueq
Rh1−0.00400 (3)0.990704 (18)0.245999 (14)0.01730 (9)
Cl10.19460 (10)0.92389 (8)0.16155 (5)0.03188 (19)
Cl20.01555 (10)0.82640 (6)0.33384 (5)0.02876 (18)
Cl30.19940 (9)1.07268 (7)0.35894 (5)0.02689 (17)
N11−0.1773 (3)1.0492 (2)0.31679 (17)0.0195 (5)
N12−0.1894 (4)1.0192 (2)0.40354 (19)0.0319 (6)
H12−0.12450.97290.43770.038*
C13−0.3195 (5)1.0729 (3)0.4296 (2)0.0358 (8)
H13−0.35411.06600.48660.043*
C14−0.3900 (4)1.1389 (3)0.3568 (2)0.0290 (7)
H14−0.48171.18550.35400.035*
C15−0.2986 (4)1.1227 (2)0.2887 (2)0.0201 (6)
H15−0.31821.15800.23090.024*
N21−0.0229 (3)1.1355 (2)0.16938 (17)0.0211 (5)
N220.0733 (3)1.2255 (2)0.19646 (18)0.0258 (6)
H220.14801.22840.24630.031*
C230.0374 (4)1.3100 (3)0.1356 (2)0.0278 (7)
H230.08731.38030.13980.033*
C24−0.0870 (4)1.2733 (3)0.0658 (2)0.0271 (7)
H24−0.13811.31300.01350.033*
C25−0.1203 (4)1.1638 (3)0.0903 (2)0.0267 (7)
H25−0.19971.11730.05580.032*
N31−0.1879 (3)0.9203 (2)0.14972 (17)0.0208 (5)
N32−0.1648 (4)0.8932 (2)0.06342 (18)0.0292 (6)
H32−0.07310.90160.04360.035*
C33−0.3044 (5)0.8512 (3)0.0127 (2)0.0390 (9)
H33−0.31840.8265−0.04880.047*
C34−0.4233 (4)0.8513 (3)0.0680 (3)0.0379 (8)
H34−0.53250.82680.05200.045*
C35−0.3450 (4)0.8960 (3)0.1528 (2)0.0297 (7)
H35−0.39520.90730.20430.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Rh10.01787 (13)0.02047 (13)0.01265 (12)0.00115 (8)0.00043 (8)0.00065 (8)
Cl10.0259 (4)0.0454 (5)0.0252 (4)0.0060 (3)0.0069 (3)−0.0037 (3)
Cl20.0346 (4)0.0227 (4)0.0259 (4)0.0059 (3)−0.0025 (3)0.0035 (3)
Cl30.0261 (4)0.0300 (4)0.0206 (3)−0.0029 (3)−0.0061 (3)0.0014 (3)
N110.0220 (12)0.0179 (12)0.0172 (11)−0.0001 (9)0.0001 (9)0.0013 (9)
N120.0423 (17)0.0324 (15)0.0203 (13)0.0064 (13)0.0040 (12)0.0056 (11)
C130.053 (2)0.0321 (18)0.0272 (17)0.0060 (16)0.0211 (16)0.0030 (14)
C140.0290 (17)0.0246 (16)0.0361 (18)0.0027 (13)0.0126 (14)−0.0006 (13)
C150.0221 (14)0.0204 (14)0.0174 (13)0.0029 (11)0.0021 (11)0.0038 (11)
N210.0177 (12)0.0254 (13)0.0198 (12)−0.0026 (10)0.0025 (9)0.0007 (10)
N220.0267 (13)0.0303 (14)0.0189 (12)−0.0040 (11)0.0003 (10)0.0018 (10)
C230.0324 (17)0.0286 (17)0.0237 (15)−0.0048 (13)0.0084 (13)0.0039 (12)
C240.0305 (16)0.0307 (17)0.0199 (14)0.0027 (13)0.0040 (12)0.0066 (12)
C250.0267 (16)0.0323 (17)0.0197 (14)−0.0022 (13)0.0010 (12)0.0024 (12)
N310.0238 (12)0.0207 (12)0.0167 (11)−0.0001 (10)0.0006 (9)0.0000 (9)
N320.0337 (15)0.0347 (15)0.0187 (12)−0.0005 (12)0.0036 (11)−0.0052 (11)
C330.044 (2)0.040 (2)0.0280 (18)0.0013 (16)−0.0076 (15)−0.0123 (15)
C340.0285 (18)0.038 (2)0.042 (2)−0.0012 (15)−0.0078 (15)−0.0092 (16)
C350.0249 (16)0.0360 (18)0.0275 (16)−0.0022 (13)0.0026 (13)−0.0042 (14)
Geometric parameters (Å, °) top
Rh1—N112.029 (3)N22—C231.339 (4)
Rh1—N312.043 (2)N22—H220.8600
Rh1—N212.047 (3)C23—C241.373 (5)
Rh1—Cl22.3302 (8)C23—H230.9300
Rh1—Cl32.3323 (7)C24—C251.394 (5)
Rh1—Cl12.3550 (8)C24—H240.9300
N11—C151.333 (4)C25—H250.9300
N11—N121.336 (4)N31—C351.330 (4)
N12—C131.358 (5)N31—N321.346 (3)
N12—H120.8600N32—C331.341 (4)
C13—C141.363 (5)N32—H320.8600
C13—H130.9300C33—C341.375 (6)
C14—C151.363 (4)C33—H330.9300
C14—H140.9300C34—C351.392 (5)
C15—H150.9300C34—H340.9300
N21—C251.320 (4)C35—H350.9300
N21—N221.348 (4)
N11—Rh1—N3189.60 (10)C25—N21—N22106.3 (3)
N11—Rh1—N2189.87 (10)C25—N21—Rh1131.7 (2)
N31—Rh1—N2189.96 (10)N22—N21—Rh1122.04 (18)
N11—Rh1—Cl289.61 (7)C23—N22—N21111.0 (3)
N31—Rh1—Cl289.98 (7)C23—N22—H22124.5
N21—Rh1—Cl2179.48 (7)N21—N22—H22124.5
N11—Rh1—Cl388.49 (7)N22—C23—C24107.1 (3)
N31—Rh1—Cl3178.08 (7)N22—C23—H23126.4
N21—Rh1—Cl390.25 (7)C24—C23—H23126.4
Cl2—Rh1—Cl389.79 (3)C23—C24—C25105.2 (3)
N11—Rh1—Cl1179.07 (7)C23—C24—H24127.4
N31—Rh1—Cl189.77 (7)C25—C24—H24127.4
N21—Rh1—Cl189.43 (7)N21—C25—C24110.3 (3)
Cl2—Rh1—Cl191.08 (3)N21—C25—H25124.8
Cl3—Rh1—Cl192.14 (3)C24—C25—H25124.8
C15—N11—N12106.6 (3)C35—N31—N32106.5 (3)
C15—N11—Rh1128.6 (2)C35—N31—Rh1131.6 (2)
N12—N11—Rh1124.8 (2)N32—N31—Rh1121.9 (2)
N11—N12—C13109.8 (3)C33—N32—N31110.6 (3)
N11—N12—H12125.1C33—N32—H32124.7
C13—N12—H12125.1N31—N32—H32124.7
N12—C13—C14107.2 (3)N32—C33—C34107.6 (3)
N12—C13—H13126.4N32—C33—H33126.2
C14—C13—H13126.4C34—C33—H33126.2
C13—C14—C15105.9 (3)C33—C34—C35105.1 (3)
C13—C14—H14127.0C33—C34—H34127.4
C15—C14—H14127.0C35—C34—H34127.4
N11—C15—C14110.5 (3)N31—C35—C34110.2 (3)
N11—C15—H15124.8N31—C35—H35124.9
C14—C15—H15124.8C34—C35—H35124.9
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N32—H32···Cl10.862.543.053 (3)119
N12—H12···Cl20.862.703.127 (3)112
N22—H22···Cl30.862.463.017 (3)123
C15—H15···Cl2i0.932.643.330 (3)131
C33—H33···Cl2ii0.932.693.471 (3)142
C24—H24···Cl3iii0.932.763.688 (3)178
N22—H22···Cl1iv0.862.883.472 (3)128
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) x−1/2, −y+3/2, z−1/2; (iii) x−1/2, −y+5/2, z−1/2; (iv) −x+1/2, y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N32—H32···Cl10.862.543.053 (3)119
N12—H12···Cl20.862.703.127 (3)112
N22—H22···Cl30.862.463.017 (3)123
C15—H15···Cl2i0.932.643.330 (3)131
C33—H33···Cl2ii0.932.693.471 (3)142
C24—H24···Cl3iii0.932.763.688 (3)178
N22—H22···Cl1iv0.862.883.472 (3)128
Symmetry codes: (i) −x−1/2, y+1/2, −z+1/2; (ii) x−1/2, −y+3/2, z−1/2; (iii) x−1/2, −y+5/2, z−1/2; (iv) −x+1/2, y+1/2, −z+1/2.
references
References top

Albinati, A., Bucher, U. E., Gramlich, V., Renn, O., Rügger, H. & Venanzi, L. M. (1999). Inorg. Chim. Acta, 284, 191–204.

Cushing, G. W., Howard, W. A. & Pang, K. (2006). J. Mol. Struct. 797, 165–173.

Nicto, S., Pérez, J., Riera, V., Miguel, D. & Alvarez, C. (2005). Chem. Commun. pp. 546–548.

Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171.29.2. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Sheldrick, G. M. (1995). SHELXTL-Plus. VersionRelease 5.03. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.