The title compound, [Rh(η5-C5Me5)Cl(C13H12ClN3)]Cl, is chiral at the metal and crystallizes as a racemate. Upon coordination, the hydrazinylidenepyridine ligand is non-planar, an angle of 54.42 (7)° being observed between the pyridine ring and the aromatic ring of the [2-(4-chlorophenyl)hydrazin-1-ylidene]ethyl group.
Keywords: crystal structure, rhodium(III) complex, pentamethylcyclopentadienyl, piano-stool geometry, N—H⋯Cl hydrogen bond
Abstract
The cation of the title compound, [Rh(η5-C5Me5)Cl(C13H12ClN3)]Cl, adopts a typical piano-stool geometry. The complex is chiral at the metal and crystallizes as a racemate. Upon coordination, the hydrazinylidenepyridine ligand is non-planar, an angle of 54.42 (7)° being observed between the pyridine ring and the aromatic ring of the [2-(4-chlorophenyl)hydrazin-1-ylidene]ethyl group. In the crystal, a weak interionic N—H⋯Cl hydrogen bond is observed.
Chemical context
Chiral-at-metal pentamethylcyclopentadienyl rhodium complexes are popular catalysts in enantioselective reactions (Carmona et al., 1999 ▸; Davies et al., 2004 ▸). To obtain such chiral-at-metal complexes, a non-symmetrical bidentate ligand can be used. Among bidentate ligands, hydrazinylidenepyridine derivatives are easy to synthesise (Liu et al., 2002 ▸; Ghedini et al., 2004 ▸; Marandi et al., 2015 ▸), and when coupled to metal centers not only can they introduce chirality, but also they can generate biologically relevant complexes (Ghosh et al., 2011 ▸, 2012 ▸). Herein, we present the synthesis and characterization of a chiral-at-metal pentamethylcyclopentadienyl rhodium(III) hydrazinylidenepyridine complex, [Rh(η5-C5Me5)Cl(C13H12ClN3)]Cl.
Structural commentary
The molecular structure of the title compound is presented in Fig. 1 ▸. The cationic complex adopts a typical piano-stool geometry and it is chiral at the metal centre. The salt crystallizes as a racemate in the orthorhombic space group Pbca. In the complex, the hydrazinylidenepyridine ligand is N,N-coordinating, the N-hydrazono and the N-pyridine groups forming with the rhodium(III) atom a five-membered metallacycle. Upon coordination, the hydrazinylidenepyridine ligand is non-planar, an angle of 54.42 (7)° being observed between the planes of pyridine and the benzene ring of the [(4-chlorophenyl)hydrazono]ethyl group. Otherwise, all geometrical data around the rhodium(III) atom are similar to those found in analogous N,N-chelated pentamethylcyclopentadienyl rhodium complexes (Gupta et al., 2011 ▸; Payne et al., 2013 ▸).
Figure 1.
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
Supramolecular features
The N—H group of the hydrazinylidenepyridine ligand interacts weakly with the counter-anion giving rise to a nearly linear hydrogen bond (Table 1 ▸). No significant C—H⋯π or π–π stacking interactions are observed.
Table 1. Hydrogen-bond geometry (, ).
| DHA | DH | HA | D A | DHA |
|---|---|---|---|---|
| N3H3NCl3 | 0.83(3) | 2.27(3) | 3.087(2) | 171(3) |
Synthesis and crystallization
The title compound was synthesized by reacting one equivalent of [(η5-C5Me5)2Rh2(μ-Cl)2Cl2] (100 mg, 0.16 mmol) with two equivalents of 2-{1-[2-(4-chlorophenyl)hydrazono]ethyl}pyridine (Liu et al., 2002 ▸; 79 mg, 0.32 mmol) in methanol (25 ml), and the mixture was refluxed for 6 h. The solution turned from yellow to dark red. Then, the volume was reduced to 2 ml and diethyl ether was added to induce precipitation of a red–brown solid. After filtration, the solid was purified by column chromatography (silica gel, chloroform/methanol 9.8:0.2 v/v). Crystals suitable for X-ray structure analysis were obtained by slow evaporation of a dichloromethane/n-pentane solution (1:1 v/v) containing the title compound. Yield: 80%. IR (KBr, ν, cm−1): 1592 (s, C=N). 1H NMR (400 MHz, CD3CN, 298 K): δ (p.p.m.) = 9.21 (br s, 1H, NH), 8.76 (d, 3 J H-H = 5.6 Hz, 1H, Har), 8.16 (dd, 3 J H-H = 8.0 Hz, 1H, Har), 8.01 (d, 3 J H-H = 8.0 Hz, 1H, Har), 7.77 (dd, 3 J H-H = 6.8 Hz, 1H, Har), 7.45 (d, 3 J H-H = 8.8 Hz, 2H, Har), 7.36 (d, 3 J H-H = 8.8 Hz, 2H, Har), 2.58 (s, 3H, CH3), 1.43 (s, 15H, C5Me5). MS (ESI positive mode): m/z 518.0 [M − Cl]+.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Except for the N-bound H atom, which was refined freely, all hydrogen atoms were included in calculated positions and treated as riding atoms using SHELXL97 default parameters, with C—H = 0.93 Å for Carom and 0.96 Å for CH3, and with U iso(H) = 1.2 U eq(C) or 1.5 U eq(C) for methyl H atoms.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | [Rh(C10H15)Cl(C13H12ClN3)]Cl |
| M r | 554.74 |
| Crystal system, space group | Orthorhombic, P b c a |
| Temperature (K) | 173 |
| a, b, c () | 13.0774(5), 13.4537(5), 26.5153(9) |
| V (3) | 4665.1(3) |
| Z | 8 |
| Radiation type | Mo K |
| (mm1) | 1.09 |
| Crystal size (mm) | 0.21 0.20 0.13 |
| Data collection | |
| Diffractometer | STOE IPDS diffractometer |
| Absorption correction | Empirical (using intensity measurements) (DIFABS; Walker Stuart, 1983 ▸) |
| T min, T max | 0.629, 0.890 |
| No. of measured, independent and observed [I > 2(I)] reflections | 82717, 6320, 4619 |
| R int | 0.074 |
| (sin /)max (1) | 0.687 |
| Refinement | |
| R[F 2 > 2(F 2)], wR(F 2), S | 0.032, 0.054, 0.96 |
| No. of reflections | 6320 |
| No. of parameters | 281 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| max, min (e 3) | 0.48, 0.62 |
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901500184X/rz5146sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500184X/rz5146Isup2.hkl
CCDC reference: 1045840
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
RN thanks the Swiss Confederation for a Swiss Government Scholarship.
supplementary crystallographic information
Crystal data
| [Rh(C10H15)Cl(C13H12ClN3)]Cl | F(000) = 2256 |
| Mr = 554.74 | Dx = 1.580 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 8000 reflections |
| a = 13.0774 (5) Å | θ = 2.4–28.9° |
| b = 13.4537 (5) Å | µ = 1.09 mm−1 |
| c = 26.5153 (9) Å | T = 173 K |
| V = 4665.1 (3) Å3 | Rod, yellow |
| Z = 8 | 0.21 × 0.20 × 0.13 mm |
Data collection
| STOE IPDS diffractometer | 6320 independent reflections |
| Radiation source: fine-focus sealed tube | 4619 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.074 |
| Detector resolution: 0.81 pixels mm-1 | θmax = 29.3°, θmin = 2.2° |
| phi oscillation scans | h = −17→17 |
| Absorption correction: empirical (using intensity measurements) (DIFABS; Walker & Stuart, 1983) | k = −18→18 |
| Tmin = 0.629, Tmax = 0.890 | l = −36→36 |
| 82717 measured reflections |
Refinement
| 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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.96 | w = 1/[σ2(Fo2) + (0.0236P)2] where P = (Fo2 + 2Fc2)/3 |
| 6320 reflections | (Δ/σ)max = 0.005 |
| 281 parameters | Δρmax = 0.48 e Å−3 |
| 0 restraints | Δρmin = −0.62 e Å−3 |
Special details
| Experimental. A crystal was mounted at 173 K on a Stoe Image Plate Diffraction System (Stoe & Cie, 2000) using Mo Kα graphite monochromated radiation. Image plate distance 100 mm, φ oscillation scans 0 - 180°, step Δφ = 0.8°, 5 minutes per frame. |
| 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)
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.57249 (18) | −0.00756 (18) | 0.60832 (10) | 0.0279 (5) | |
| H1 | 0.5871 | 0.0234 | 0.5778 | 0.034* | |
| C2 | 0.6422 (2) | −0.07526 (19) | 0.62774 (11) | 0.0355 (6) | |
| H2 | 0.7029 | −0.0886 | 0.6107 | 0.043* | |
| C3 | 0.6205 (2) | −0.12238 (18) | 0.67247 (10) | 0.0350 (6) | |
| H3 | 0.6658 | −0.1687 | 0.6859 | 0.042* | |
| C4 | 0.5302 (2) | −0.09975 (19) | 0.69720 (9) | 0.0312 (5) | |
| H4 | 0.5145 | −0.1304 | 0.7277 | 0.037* | |
| C5 | 0.46296 (18) | −0.03094 (16) | 0.67623 (8) | 0.0218 (5) | |
| C6 | 0.36119 (19) | −0.01036 (16) | 0.69694 (8) | 0.0217 (5) | |
| C7 | 0.3320 (2) | −0.04681 (19) | 0.74812 (9) | 0.0315 (6) | |
| H7A | 0.2787 | −0.0055 | 0.7616 | 0.047* | |
| H7B | 0.3905 | −0.0443 | 0.7700 | 0.047* | |
| H7C | 0.3080 | −0.1141 | 0.7457 | 0.047* | |
| C8 | 0.11641 (18) | 0.05175 (16) | 0.65302 (8) | 0.0214 (5) | |
| C9 | 0.11770 (18) | 0.00803 (16) | 0.60562 (9) | 0.0228 (4) | |
| H9 | 0.1771 | −0.0224 | 0.5940 | 0.027* | |
| C10 | 0.03097 (19) | 0.00944 (18) | 0.57538 (9) | 0.0263 (5) | |
| H10 | 0.0324 | −0.0192 | 0.5435 | 0.032* | |
| C11 | −0.05724 (18) | 0.05360 (19) | 0.59299 (9) | 0.0282 (6) | |
| C12 | −0.06171 (19) | 0.09489 (19) | 0.64099 (10) | 0.0310 (6) | |
| H12 | −0.1222 | 0.1227 | 0.6529 | 0.037* | |
| C13 | 0.02538 (18) | 0.09408 (18) | 0.67088 (9) | 0.0277 (5) | |
| H13 | 0.0234 | 0.1218 | 0.7030 | 0.033* | |
| C14 | 0.41151 (18) | 0.21684 (16) | 0.54714 (8) | 0.0185 (4) | |
| C15 | 0.46438 (17) | 0.23872 (16) | 0.59274 (8) | 0.0197 (5) | |
| C16 | 0.39032 (18) | 0.25436 (15) | 0.63199 (8) | 0.0203 (5) | |
| C17 | 0.29044 (17) | 0.24955 (15) | 0.60875 (9) | 0.0206 (5) | |
| C18 | 0.30297 (17) | 0.22316 (15) | 0.55724 (8) | 0.0186 (4) | |
| C19 | 0.4574 (2) | 0.19802 (19) | 0.49645 (8) | 0.0277 (5) | |
| H19A | 0.4671 | 0.2601 | 0.4792 | 0.042* | |
| H19B | 0.4124 | 0.1565 | 0.4771 | 0.042* | |
| H19C | 0.5221 | 0.1654 | 0.5004 | 0.042* | |
| C20 | 0.57832 (18) | 0.2459 (2) | 0.59914 (11) | 0.0314 (6) | |
| H20A | 0.6115 | 0.2052 | 0.5743 | 0.047* | |
| H20B | 0.5969 | 0.2235 | 0.6323 | 0.047* | |
| H20C | 0.5994 | 0.3138 | 0.5949 | 0.047* | |
| C21 | 0.4125 (2) | 0.28192 (18) | 0.68547 (9) | 0.0310 (6) | |
| H21A | 0.4770 | 0.2540 | 0.6954 | 0.046* | |
| H21B | 0.3594 | 0.2565 | 0.7069 | 0.046* | |
| H21C | 0.4153 | 0.3530 | 0.6885 | 0.046* | |
| C22 | 0.1914 (2) | 0.27337 (17) | 0.63382 (10) | 0.0288 (5) | |
| H22A | 0.1771 | 0.3430 | 0.6302 | 0.043* | |
| H22B | 0.1957 | 0.2570 | 0.6690 | 0.043* | |
| H22C | 0.1376 | 0.2354 | 0.6185 | 0.043* | |
| C23 | 0.22078 (19) | 0.20957 (18) | 0.51908 (9) | 0.0272 (5) | |
| H23A | 0.1577 | 0.1938 | 0.5358 | 0.041* | |
| H23B | 0.2389 | 0.1563 | 0.4967 | 0.041* | |
| H23C | 0.2126 | 0.2698 | 0.5001 | 0.041* | |
| Cl1 | 0.34471 (4) | −0.02319 (4) | 0.54150 (2) | 0.02355 (12) | |
| Cl2 | −0.16517 (5) | 0.05548 (6) | 0.55360 (3) | 0.04123 (17) | |
| Cl3 | 0.19592 (5) | 0.18619 (5) | 0.77896 (2) | 0.03405 (14) | |
| N1 | 0.48505 (14) | 0.01482 (14) | 0.63192 (7) | 0.0207 (4) | |
| N2 | 0.29842 (14) | 0.03410 (13) | 0.66601 (7) | 0.0184 (4) | |
| N3 | 0.20095 (15) | 0.05148 (15) | 0.68473 (7) | 0.0229 (4) | |
| H3N | 0.199 (2) | 0.082 (2) | 0.7119 (11) | 0.036 (8)* | |
| Rh1 | 0.371080 (13) | 0.107403 (11) | 0.602805 (6) | 0.01552 (4) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0221 (12) | 0.0290 (12) | 0.0328 (13) | 0.0055 (10) | 0.0013 (11) | 0.0033 (11) |
| C2 | 0.0236 (14) | 0.0349 (13) | 0.0481 (15) | 0.0099 (11) | −0.0049 (12) | −0.0034 (12) |
| C3 | 0.0299 (14) | 0.0300 (13) | 0.0453 (14) | 0.0086 (12) | −0.0162 (13) | 0.0007 (11) |
| C4 | 0.0368 (14) | 0.0278 (12) | 0.0289 (12) | 0.0045 (12) | −0.0134 (11) | 0.0037 (11) |
| C5 | 0.0260 (13) | 0.0187 (11) | 0.0207 (11) | −0.0015 (9) | −0.0078 (9) | −0.0006 (9) |
| C6 | 0.0296 (13) | 0.0185 (10) | 0.0169 (10) | −0.0028 (10) | −0.0025 (10) | −0.0004 (8) |
| C7 | 0.0438 (16) | 0.0298 (13) | 0.0207 (12) | 0.0022 (12) | −0.0004 (11) | 0.0060 (10) |
| C8 | 0.0220 (12) | 0.0184 (10) | 0.0239 (10) | −0.0042 (9) | 0.0025 (10) | 0.0013 (8) |
| C9 | 0.0213 (12) | 0.0232 (10) | 0.0240 (10) | −0.0001 (9) | 0.0025 (10) | 0.0005 (10) |
| C10 | 0.0263 (13) | 0.0288 (12) | 0.0238 (12) | −0.0033 (10) | 0.0001 (10) | −0.0005 (10) |
| C11 | 0.0194 (12) | 0.0308 (13) | 0.0345 (15) | −0.0045 (10) | −0.0032 (10) | 0.0075 (10) |
| C12 | 0.0220 (12) | 0.0282 (13) | 0.0427 (14) | 0.0001 (11) | 0.0081 (11) | 0.0021 (11) |
| C13 | 0.0257 (12) | 0.0289 (13) | 0.0286 (12) | −0.0009 (10) | 0.0075 (10) | −0.0023 (10) |
| C14 | 0.0233 (11) | 0.0158 (10) | 0.0163 (10) | 0.0010 (9) | −0.0006 (9) | 0.0015 (8) |
| C15 | 0.0224 (11) | 0.0159 (10) | 0.0209 (12) | −0.0034 (9) | −0.0014 (9) | 0.0041 (8) |
| C16 | 0.0271 (14) | 0.0159 (9) | 0.0178 (10) | −0.0011 (9) | −0.0007 (9) | −0.0006 (8) |
| C17 | 0.0239 (11) | 0.0134 (9) | 0.0245 (12) | 0.0018 (8) | 0.0017 (10) | 0.0020 (9) |
| C18 | 0.0200 (11) | 0.0146 (10) | 0.0212 (11) | 0.0015 (9) | −0.0015 (9) | 0.0030 (8) |
| C19 | 0.0317 (14) | 0.0321 (13) | 0.0192 (11) | 0.0044 (11) | 0.0045 (10) | 0.0011 (10) |
| C20 | 0.0235 (12) | 0.0361 (13) | 0.0345 (13) | −0.0079 (11) | −0.0043 (12) | 0.0089 (12) |
| C21 | 0.0482 (16) | 0.0258 (12) | 0.0190 (11) | 0.0002 (11) | −0.0051 (11) | −0.0021 (10) |
| C22 | 0.0316 (14) | 0.0191 (11) | 0.0358 (14) | 0.0067 (10) | 0.0113 (11) | 0.0010 (10) |
| C23 | 0.0270 (14) | 0.0261 (12) | 0.0285 (12) | 0.0010 (10) | −0.0083 (10) | 0.0028 (10) |
| Cl1 | 0.0249 (3) | 0.0202 (2) | 0.0255 (3) | 0.0013 (2) | 0.0007 (2) | −0.0065 (2) |
| Cl2 | 0.0240 (3) | 0.0549 (4) | 0.0448 (4) | −0.0029 (3) | −0.0080 (3) | 0.0091 (3) |
| Cl3 | 0.0422 (4) | 0.0344 (3) | 0.0256 (3) | −0.0010 (3) | 0.0048 (3) | −0.0084 (2) |
| N1 | 0.0191 (10) | 0.0193 (9) | 0.0236 (10) | 0.0007 (8) | −0.0038 (8) | 0.0007 (8) |
| N2 | 0.0208 (10) | 0.0158 (9) | 0.0186 (9) | −0.0012 (7) | 0.0004 (8) | −0.0013 (7) |
| N3 | 0.0221 (10) | 0.0279 (11) | 0.0188 (9) | −0.0007 (9) | 0.0027 (8) | −0.0045 (8) |
| Rh1 | 0.01625 (7) | 0.01479 (6) | 0.01552 (6) | 0.00163 (7) | −0.00072 (8) | 0.00038 (7) |
Geometric parameters (Å, º)
| C1—N1 | 1.338 (3) | C15—C16 | 1.437 (3) |
| C1—C2 | 1.388 (3) | C15—C20 | 1.503 (3) |
| C1—H1 | 0.9300 | C15—Rh1 | 2.164 (2) |
| C2—C3 | 1.375 (4) | C16—C17 | 1.446 (3) |
| C2—H2 | 0.9300 | C16—C21 | 1.494 (3) |
| C3—C4 | 1.385 (4) | C16—Rh1 | 2.138 (2) |
| C3—H3 | 0.9300 | C17—C18 | 1.421 (3) |
| C4—C5 | 1.392 (3) | C17—C22 | 1.491 (3) |
| C4—H4 | 0.9300 | C17—Rh1 | 2.190 (2) |
| C5—N1 | 1.357 (3) | C18—C23 | 1.487 (3) |
| C5—C6 | 1.466 (3) | C18—Rh1 | 2.163 (2) |
| C6—N2 | 1.306 (3) | C19—H19A | 0.9600 |
| C6—C7 | 1.493 (3) | C19—H19B | 0.9600 |
| C7—H7A | 0.9600 | C19—H19C | 0.9600 |
| C7—H7B | 0.9600 | C20—H20A | 0.9600 |
| C7—H7C | 0.9600 | C20—H20B | 0.9600 |
| C8—C9 | 1.388 (3) | C20—H20C | 0.9600 |
| C8—N3 | 1.389 (3) | C21—H21A | 0.9600 |
| C8—C13 | 1.402 (3) | C21—H21B | 0.9600 |
| C9—C10 | 1.389 (3) | C21—H21C | 0.9600 |
| C9—H9 | 0.9300 | C22—H22A | 0.9600 |
| C10—C11 | 1.379 (3) | C22—H22B | 0.9600 |
| C10—H10 | 0.9300 | C22—H22C | 0.9600 |
| C11—C12 | 1.390 (4) | C23—H23A | 0.9600 |
| C11—Cl2 | 1.756 (2) | C23—H23B | 0.9600 |
| C12—C13 | 1.388 (4) | C23—H23C | 0.9600 |
| C12—H12 | 0.9300 | Cl1—Rh1 | 2.4183 (6) |
| C13—H13 | 0.9300 | N1—Rh1 | 2.0902 (18) |
| C14—C15 | 1.424 (3) | N2—N3 | 1.388 (3) |
| C14—C18 | 1.447 (3) | N2—Rh1 | 2.1643 (18) |
| C14—C19 | 1.493 (3) | N3—H3N | 0.83 (3) |
| C14—Rh1 | 2.151 (2) | ||
| N1—C1—C2 | 122.4 (2) | C14—C18—Rh1 | 69.95 (12) |
| N1—C1—H1 | 118.8 | C23—C18—Rh1 | 126.08 (15) |
| C2—C1—H1 | 118.8 | C14—C19—H19A | 109.5 |
| C3—C2—C1 | 119.1 (3) | C14—C19—H19B | 109.5 |
| C3—C2—H2 | 120.4 | H19A—C19—H19B | 109.5 |
| C1—C2—H2 | 120.4 | C14—C19—H19C | 109.5 |
| C2—C3—C4 | 118.9 (2) | H19A—C19—H19C | 109.5 |
| C2—C3—H3 | 120.6 | H19B—C19—H19C | 109.5 |
| C4—C3—H3 | 120.6 | C15—C20—H20A | 109.5 |
| C3—C4—C5 | 119.7 (2) | C15—C20—H20B | 109.5 |
| C3—C4—H4 | 120.2 | H20A—C20—H20B | 109.5 |
| C5—C4—H4 | 120.2 | C15—C20—H20C | 109.5 |
| N1—C5—C4 | 120.9 (2) | H20A—C20—H20C | 109.5 |
| N1—C5—C6 | 115.58 (19) | H20B—C20—H20C | 109.5 |
| C4—C5—C6 | 123.3 (2) | C16—C21—H21A | 109.5 |
| N2—C6—C5 | 114.96 (19) | C16—C21—H21B | 109.5 |
| N2—C6—C7 | 124.1 (2) | H21A—C21—H21B | 109.5 |
| C5—C6—C7 | 120.7 (2) | C16—C21—H21C | 109.5 |
| C6—C7—H7A | 109.5 | H21A—C21—H21C | 109.5 |
| C6—C7—H7B | 109.5 | H21B—C21—H21C | 109.5 |
| H7A—C7—H7B | 109.5 | C17—C22—H22A | 109.5 |
| C6—C7—H7C | 109.5 | C17—C22—H22B | 109.5 |
| H7A—C7—H7C | 109.5 | H22A—C22—H22B | 109.5 |
| H7B—C7—H7C | 109.5 | C17—C22—H22C | 109.5 |
| C9—C8—N3 | 122.5 (2) | H22A—C22—H22C | 109.5 |
| C9—C8—C13 | 119.2 (2) | H22B—C22—H22C | 109.5 |
| N3—C8—C13 | 118.2 (2) | C18—C23—H23A | 109.5 |
| C8—C9—C10 | 120.5 (2) | C18—C23—H23B | 109.5 |
| C8—C9—H9 | 119.8 | H23A—C23—H23B | 109.5 |
| C10—C9—H9 | 119.8 | C18—C23—H23C | 109.5 |
| C11—C10—C9 | 119.6 (2) | H23A—C23—H23C | 109.5 |
| C11—C10—H10 | 120.2 | H23B—C23—H23C | 109.5 |
| C9—C10—H10 | 120.2 | C1—N1—C5 | 119.0 (2) |
| C10—C11—C12 | 121.2 (2) | C1—N1—Rh1 | 124.81 (16) |
| C10—C11—Cl2 | 118.5 (2) | C5—N1—Rh1 | 115.99 (15) |
| C12—C11—Cl2 | 120.3 (2) | C6—N2—N3 | 115.47 (18) |
| C13—C12—C11 | 119.0 (2) | C6—N2—Rh1 | 114.78 (15) |
| C13—C12—H12 | 120.5 | N3—N2—Rh1 | 127.12 (14) |
| C11—C12—H12 | 120.5 | N2—N3—C8 | 121.01 (19) |
| C12—C13—C8 | 120.5 (2) | N2—N3—H3N | 115 (2) |
| C12—C13—H13 | 119.8 | C8—N3—H3N | 120 (2) |
| C8—C13—H13 | 119.8 | N1—Rh1—C16 | 109.48 (8) |
| C15—C14—C18 | 107.88 (19) | N1—Rh1—C14 | 119.08 (8) |
| C15—C14—C19 | 127.2 (2) | C16—Rh1—C14 | 65.57 (8) |
| C18—C14—C19 | 124.8 (2) | N1—Rh1—C18 | 158.28 (8) |
| C15—C14—Rh1 | 71.22 (12) | C16—Rh1—C18 | 65.47 (8) |
| C18—C14—Rh1 | 70.85 (12) | C14—Rh1—C18 | 39.20 (9) |
| C19—C14—Rh1 | 126.89 (16) | N1—Rh1—C15 | 97.47 (8) |
| C14—C15—C16 | 108.55 (19) | C16—Rh1—C15 | 39.03 (8) |
| C14—C15—C20 | 126.2 (2) | C14—Rh1—C15 | 38.53 (8) |
| C16—C15—C20 | 125.2 (2) | C18—Rh1—C15 | 64.87 (8) |
| C14—C15—Rh1 | 70.25 (12) | N1—Rh1—N2 | 75.85 (7) |
| C16—C15—Rh1 | 69.52 (12) | C16—Rh1—N2 | 101.11 (7) |
| C20—C15—Rh1 | 126.73 (16) | C14—Rh1—N2 | 162.04 (8) |
| C15—C16—C17 | 107.07 (18) | C18—Rh1—N2 | 125.44 (8) |
| C15—C16—C21 | 126.4 (2) | C15—Rh1—N2 | 135.66 (7) |
| C17—C16—C21 | 126.2 (2) | N1—Rh1—C17 | 146.86 (8) |
| C15—C16—Rh1 | 71.45 (12) | C16—Rh1—C17 | 39.01 (8) |
| C17—C16—Rh1 | 72.42 (12) | C14—Rh1—C17 | 64.52 (8) |
| C21—C16—Rh1 | 126.57 (16) | C18—Rh1—C17 | 38.09 (8) |
| C18—C17—C16 | 108.47 (19) | C15—Rh1—C17 | 64.36 (8) |
| C18—C17—C22 | 125.6 (2) | N2—Rh1—C17 | 97.52 (8) |
| C16—C17—C22 | 125.8 (2) | N1—Rh1—Cl1 | 85.24 (5) |
| C18—C17—Rh1 | 69.94 (12) | C16—Rh1—Cl1 | 158.74 (6) |
| C16—C17—Rh1 | 68.57 (12) | C14—Rh1—Cl1 | 94.08 (6) |
| C22—C17—Rh1 | 129.66 (16) | C18—Rh1—Cl1 | 95.10 (6) |
| C17—C18—C14 | 107.81 (19) | C15—Rh1—Cl1 | 126.21 (6) |
| C17—C18—C23 | 127.0 (2) | N2—Rh1—Cl1 | 97.29 (5) |
| C14—C18—C23 | 125.2 (2) | C17—Rh1—Cl1 | 127.90 (6) |
| C17—C18—Rh1 | 71.97 (12) | ||
| N1—C1—C2—C3 | 1.0 (4) | C15—C16—Rh1—N2 | 156.22 (12) |
| C1—C2—C3—C4 | −0.9 (4) | C17—C16—Rh1—N2 | −88.24 (13) |
| C2—C3—C4—C5 | 0.6 (4) | C21—C16—Rh1—N2 | 34.2 (2) |
| C3—C4—C5—N1 | −0.4 (4) | C15—C16—Rh1—C17 | −115.54 (17) |
| C3—C4—C5—C6 | 173.4 (2) | C21—C16—Rh1—C17 | 122.5 (3) |
| N1—C5—C6—N2 | 12.0 (3) | C15—C16—Rh1—Cl1 | −54.3 (2) |
| C4—C5—C6—N2 | −162.0 (2) | C17—C16—Rh1—Cl1 | 61.2 (2) |
| N1—C5—C6—C7 | −173.1 (2) | C21—C16—Rh1—Cl1 | −176.30 (14) |
| C4—C5—C6—C7 | 12.9 (3) | C15—C14—Rh1—N1 | −62.63 (15) |
| N3—C8—C9—C10 | 179.5 (2) | C18—C14—Rh1—N1 | 179.89 (11) |
| C13—C8—C9—C10 | 2.4 (3) | C19—C14—Rh1—N1 | 60.3 (2) |
| C8—C9—C10—C11 | −0.8 (3) | C15—C14—Rh1—C16 | 36.94 (13) |
| C9—C10—C11—C12 | −1.5 (4) | C18—C14—Rh1—C16 | −80.53 (14) |
| C9—C10—C11—Cl2 | 179.27 (18) | C19—C14—Rh1—C16 | 159.8 (2) |
| C10—C11—C12—C13 | 2.0 (4) | C15—C14—Rh1—C18 | 117.47 (18) |
| Cl2—C11—C12—C13 | −178.73 (19) | C19—C14—Rh1—C18 | −119.6 (3) |
| C11—C12—C13—C8 | −0.3 (4) | C18—C14—Rh1—C15 | −117.47 (18) |
| C9—C8—C13—C12 | −1.9 (3) | C19—C14—Rh1—C15 | 122.9 (3) |
| N3—C8—C13—C12 | −179.0 (2) | C15—C14—Rh1—N2 | 81.3 (3) |
| C18—C14—C15—C16 | 2.6 (2) | C18—C14—Rh1—N2 | −36.1 (3) |
| C19—C14—C15—C16 | 178.3 (2) | C19—C14—Rh1—N2 | −155.8 (2) |
| Rh1—C14—C15—C16 | −59.16 (15) | C15—C14—Rh1—C17 | 80.15 (14) |
| C18—C14—C15—C20 | −176.6 (2) | C18—C14—Rh1—C17 | −37.33 (12) |
| C19—C14—C15—C20 | −0.9 (4) | C19—C14—Rh1—C17 | −157.0 (2) |
| Rh1—C14—C15—C20 | 121.6 (2) | C15—C14—Rh1—Cl1 | −149.45 (12) |
| C18—C14—C15—Rh1 | 61.73 (15) | C18—C14—Rh1—Cl1 | 93.08 (12) |
| C19—C14—C15—Rh1 | −122.5 (2) | C19—C14—Rh1—Cl1 | −26.6 (2) |
| C14—C15—C16—C17 | −4.5 (2) | C17—C18—Rh1—N1 | −117.7 (2) |
| C20—C15—C16—C17 | 174.7 (2) | C14—C18—Rh1—N1 | −0.3 (3) |
| Rh1—C15—C16—C17 | −64.13 (14) | C23—C18—Rh1—N1 | 119.2 (2) |
| C14—C15—C16—C21 | −178.1 (2) | C17—C18—Rh1—C16 | −36.65 (13) |
| C20—C15—C16—C21 | 1.1 (4) | C14—C18—Rh1—C16 | 80.81 (14) |
| Rh1—C15—C16—C21 | 122.2 (2) | C23—C18—Rh1—C16 | −159.7 (2) |
| C14—C15—C16—Rh1 | 59.61 (15) | C17—C18—Rh1—C14 | −117.46 (18) |
| C20—C15—C16—Rh1 | −121.2 (2) | C23—C18—Rh1—C14 | 119.5 (2) |
| C15—C16—C17—C18 | 4.8 (2) | C17—C18—Rh1—C15 | −79.84 (14) |
| C21—C16—C17—C18 | 178.4 (2) | C14—C18—Rh1—C15 | 37.62 (12) |
| Rh1—C16—C17—C18 | −58.69 (14) | C23—C18—Rh1—C15 | 157.1 (2) |
| C15—C16—C17—C22 | −172.3 (2) | C17—C18—Rh1—N2 | 49.64 (15) |
| C21—C16—C17—C22 | 1.3 (4) | C14—C18—Rh1—N2 | 167.10 (11) |
| Rh1—C16—C17—C22 | 124.2 (2) | C23—C18—Rh1—N2 | −73.4 (2) |
| C15—C16—C17—Rh1 | 63.49 (14) | C14—C18—Rh1—C17 | 117.46 (18) |
| C21—C16—C17—Rh1 | −122.9 (2) | C23—C18—Rh1—C17 | −123.0 (3) |
| C16—C17—C18—C14 | −3.3 (2) | C17—C18—Rh1—Cl1 | 152.34 (12) |
| C22—C17—C18—C14 | 173.9 (2) | C14—C18—Rh1—Cl1 | −90.20 (12) |
| Rh1—C17—C18—C14 | −61.10 (15) | C23—C18—Rh1—Cl1 | 29.3 (2) |
| C16—C17—C18—C23 | 179.9 (2) | C14—C15—Rh1—N1 | 128.49 (13) |
| C22—C17—C18—C23 | −3.0 (4) | C16—C15—Rh1—N1 | −111.85 (13) |
| Rh1—C17—C18—C23 | 122.0 (2) | C20—C15—Rh1—N1 | 7.5 (2) |
| C16—C17—C18—Rh1 | 57.85 (14) | C14—C15—Rh1—C16 | −119.66 (18) |
| C22—C17—C18—Rh1 | −125.0 (2) | C20—C15—Rh1—C16 | 119.3 (3) |
| C15—C14—C18—C17 | 0.4 (2) | C16—C15—Rh1—C14 | 119.66 (18) |
| C19—C14—C18—C17 | −175.4 (2) | C20—C15—Rh1—C14 | −121.0 (3) |
| Rh1—C14—C18—C17 | 62.40 (15) | C14—C15—Rh1—C18 | −38.27 (13) |
| C15—C14—C18—C23 | 177.4 (2) | C16—C15—Rh1—C18 | 81.39 (14) |
| C19—C14—C18—C23 | 1.5 (4) | C20—C15—Rh1—C18 | −159.3 (2) |
| Rh1—C14—C18—C23 | −120.7 (2) | C14—C15—Rh1—N2 | −154.14 (12) |
| C15—C14—C18—Rh1 | −61.96 (15) | C16—C15—Rh1—N2 | −34.48 (17) |
| C19—C14—C18—Rh1 | 122.2 (2) | C20—C15—Rh1—N2 | 84.8 (2) |
| C2—C1—N1—C5 | −0.7 (4) | C14—C15—Rh1—C17 | −80.61 (14) |
| C2—C1—N1—Rh1 | −175.13 (19) | C16—C15—Rh1—C17 | 39.05 (13) |
| C4—C5—N1—C1 | 0.4 (3) | C20—C15—Rh1—C17 | 158.4 (2) |
| C6—C5—N1—C1 | −173.8 (2) | C14—C15—Rh1—Cl1 | 38.93 (15) |
| C4—C5—N1—Rh1 | 175.32 (17) | C16—C15—Rh1—Cl1 | 158.59 (10) |
| C6—C5—N1—Rh1 | 1.1 (2) | C20—C15—Rh1—Cl1 | −82.1 (2) |
| C5—C6—N2—N3 | 178.27 (18) | C6—N2—Rh1—N1 | 14.84 (15) |
| C7—C6—N2—N3 | 3.5 (3) | N3—N2—Rh1—N1 | 175.49 (18) |
| C5—C6—N2—Rh1 | −18.7 (2) | C6—N2—Rh1—C16 | −92.67 (16) |
| C7—C6—N2—Rh1 | 166.52 (18) | N3—N2—Rh1—C16 | 67.98 (18) |
| C6—N2—N3—C8 | −148.6 (2) | C6—N2—Rh1—C14 | −133.1 (2) |
| Rh1—N2—N3—C8 | 50.9 (3) | N3—N2—Rh1—C14 | 27.5 (3) |
| C9—C8—N3—N2 | 19.0 (3) | C6—N2—Rh1—C18 | −160.37 (15) |
| C13—C8—N3—N2 | −163.9 (2) | N3—N2—Rh1—C18 | 0.3 (2) |
| C1—N1—Rh1—C16 | −96.4 (2) | C6—N2—Rh1—C15 | −71.37 (19) |
| C5—N1—Rh1—C16 | 89.00 (16) | N3—N2—Rh1—C15 | 89.28 (19) |
| C1—N1—Rh1—C14 | −24.2 (2) | C6—N2—Rh1—C17 | −132.06 (16) |
| C5—N1—Rh1—C14 | 161.22 (15) | N3—N2—Rh1—C17 | 28.58 (18) |
| C1—N1—Rh1—C18 | −24.0 (3) | C6—N2—Rh1—Cl1 | 98.03 (15) |
| C5—N1—Rh1—C18 | 161.41 (19) | N3—N2—Rh1—Cl1 | −101.32 (16) |
| C1—N1—Rh1—C15 | −58.1 (2) | C18—C17—Rh1—N1 | 143.18 (15) |
| C5—N1—Rh1—C15 | 127.31 (16) | C16—C17—Rh1—N1 | 22.8 (2) |
| C1—N1—Rh1—N2 | 166.6 (2) | C22—C17—Rh1—N1 | −96.6 (2) |
| C5—N1—Rh1—N2 | −7.99 (15) | C18—C17—Rh1—C16 | 120.37 (18) |
| C1—N1—Rh1—C17 | −111.4 (2) | C22—C17—Rh1—C16 | −119.4 (3) |
| C5—N1—Rh1—C17 | 74.0 (2) | C18—C17—Rh1—C14 | 38.40 (13) |
| C1—N1—Rh1—Cl1 | 67.84 (19) | C16—C17—Rh1—C14 | −81.97 (13) |
| C5—N1—Rh1—Cl1 | −106.75 (15) | C22—C17—Rh1—C14 | 158.6 (2) |
| C15—C16—Rh1—N1 | 77.45 (13) | C16—C17—Rh1—C18 | −120.37 (18) |
| C17—C16—Rh1—N1 | −167.01 (12) | C22—C17—Rh1—C18 | 120.2 (3) |
| C21—C16—Rh1—N1 | −44.5 (2) | C18—C17—Rh1—C15 | 81.31 (14) |
| C15—C16—Rh1—C14 | −36.48 (12) | C16—C17—Rh1—C15 | −39.07 (12) |
| C17—C16—Rh1—C14 | 79.06 (13) | C22—C17—Rh1—C15 | −158.5 (2) |
| C21—C16—Rh1—C14 | −158.5 (2) | C18—C17—Rh1—N2 | −141.23 (13) |
| C15—C16—Rh1—C18 | −79.73 (13) | C16—C17—Rh1—N2 | 98.39 (12) |
| C17—C16—Rh1—C18 | 35.81 (12) | C22—C17—Rh1—N2 | −21.0 (2) |
| C21—C16—Rh1—C18 | 158.3 (2) | C18—C17—Rh1—Cl1 | −35.87 (15) |
| C17—C16—Rh1—C15 | 115.54 (17) | C16—C17—Rh1—Cl1 | −156.25 (10) |
| C21—C16—Rh1—C15 | −122.0 (3) | C22—C17—Rh1—Cl1 | 84.3 (2) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3N···Cl3 | 0.83 (3) | 2.27 (3) | 3.087 (2) | 171 (3) |
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901500184X/rz5146sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500184X/rz5146Isup2.hkl
CCDC reference: 1045840
Additional supporting information: crystallographic information; 3D view; checkCIF report