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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042444/bv2069sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042444/bv2069Isup2.hkl
Contains datablock I

CCDC reference: 663560

Key indicators

  • Single-crystal X-ray study
  • T = 108 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.032
  • wR factor = 0.081
  • Data-to-parameter ratio = 18.8

checkCIF/PLATON results

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Alert level C PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Rh1 - Cl2 .. 8.26 su PLAT480_ALERT_4_C Long H...A H-Bond Reported H22 .. CL1 .. 2.88 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Rh1 (3) 3.09
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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.

Structure description 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).

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

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 m3
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 mm1
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)
Graphite monochromatorRint = 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 = 1010
Tmin = 0.692, Tmax = 0.802k = 1514
25826 measured reflectionsl = 1918
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 Å3
0 restraintsΔρmin = 0.78 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.05Δρmax = 0.88 e Å3
3236 reflectionsΔρmin = 0.78 e Å3
172 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
xyzUiso*/Ueq
Rh10.00400 (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)
N110.1773 (3)1.0492 (2)0.31679 (17)0.0195 (5)
N120.1894 (4)1.0192 (2)0.40354 (19)0.0319 (6)
H120.12450.97290.43770.038*
C130.3195 (5)1.0729 (3)0.4296 (2)0.0358 (8)
H130.35411.06600.48660.043*
C140.3900 (4)1.1389 (3)0.3568 (2)0.0290 (7)
H140.48171.18550.35400.035*
C150.2986 (4)1.1227 (2)0.2887 (2)0.0201 (6)
H150.31821.15800.23090.024*
N210.0229 (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*
C240.0870 (4)1.2733 (3)0.0658 (2)0.0271 (7)
H240.13811.31300.01350.033*
C250.1203 (4)1.1638 (3)0.0903 (2)0.0267 (7)
H250.19971.11730.05580.032*
N310.1879 (3)0.9203 (2)0.14972 (17)0.0208 (5)
N320.1648 (4)0.8932 (2)0.06342 (18)0.0292 (6)
H320.07310.90160.04360.035*
C330.3044 (5)0.8512 (3)0.0127 (2)0.0390 (9)
H330.31840.82650.04880.047*
C340.4233 (4)0.8513 (3)0.0680 (3)0.0379 (8)
H340.53250.82680.05200.045*
C350.3450 (4)0.8960 (3)0.1528 (2)0.0297 (7)
H350.39520.90730.20430.036*
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, º) 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, º) 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) x1/2, y+1/2, z+1/2; (ii) x1/2, y+3/2, z1/2; (iii) x1/2, y+5/2, z1/2; (iv) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[RhCl3(C3H4N2)3]
Mr413.51
Crystal system, space groupMonoclinic, P21/n
Temperature (K)108
a, b, c (Å)8.2041 (3), 11.9243 (4), 14.5839 (5)
β (°) 100.624 (3)
V3)1402.26 (8)
Z4
Radiation typeMo Kα
µ (mm1)1.78
Crystal size (mm)0.52 × 0.18 × 0.13
Data collection
DiffractometerOxford Diffraction Sapphire2 CCD
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2006)
Tmin, Tmax0.692, 0.802
No. of measured, independent and
observed [I > 2σ(I)] reflections
25826, 3236, 2701
Rint0.041
(sin θ/λ)max1)0.652
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.081, 1.05
No. of reflections3236
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.88, 0.78

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1995), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N32—H32···Cl10.862.543.053 (3)119.0
N12—H12···Cl20.862.703.127 (3)111.8
N22—H22···Cl30.862.463.017 (3)122.8
C15—H15···Cl2i0.932.643.330 (3)131.3
C33—H33···Cl2ii0.932.693.471 (3)141.7
C24—H24···Cl3iii0.932.763.688 (3)177.9
N22—H22···Cl1iv0.862.883.472 (3)128.0
Symmetry codes: (i) x1/2, y+1/2, z+1/2; (ii) x1/2, y+3/2, z1/2; (iii) x1/2, y+5/2, z1/2; (iv) x+1/2, y+1/2, z+1/2.
 

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