Crystal structures of bis­[2-(pyridin-2-yl)phenyl-κ2N,C1]rhodium(III) complexes containing an aceto­nitrile or monodentate thyminate(1−) ligand

Sakate, M.; Hosoda, H.; Suzuki, T.

doi:10.1107/S2056989016004837

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ISSN: 2056-9890

Volume 72| Part 4| April 2016| Pages 543-547

https://doi.org/10.1107/S2056989016004837

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Crystal structures of bis[2-(pyridin-2-yl)phenyl-κ²N,C¹]rhodium(III) complexes containing an acetonitrile or monodentate thyminate(1−) ligand

Mika Sakate,^a Haruka Hosoda ^a and Takayoshi Suzuki ^a ^*

^aDepartment of Chemistry, Faculty of Science, Okayama University, Okayama 700-8530, Japan
^*Correspondence e-mail: suzuki@okayama-u.ac.jp

Edited by H. Ishida, Okayama University, Japan (Received 5 March 2016; accepted 22 March 2016; online 24 March 2016)

The crystal structures of bis[2-(pyridin-2-yl)phenyl]rhodium(III) complexes with the metal in an octahedral coordination containing chloride and acetonitrile ligands, namely (OC-6-42)-acetonitrilechloridobis[2-(pyridin-2-yl)phenyl-κ²N,C¹]rhodium(III), [RhCl(C₁₁H₈N)₂(CH₃CN)] (1), thyminate(1−) and methanol, namely (OC-6-42)-methanol(5-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ido-κN¹)bis[2-(pyridin-2-yl)phenyl-κ²N,C¹]rhodium(III), [Rh(C₁₁H₈N)₂(C₅H₅N₂O₂)(CH₃OH)]·CH₃OH·0.5H₂O (2), and thyminate(1−) and ethanol, namely (OC-6-42)-ethanol(5-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ido-κN¹)bis[2-(pyridin-2-yl)phenyl-κ²N,C¹]rhodium(III), [Rh(C₁₁H₈N)₂(C₅H₅N₂O₂)(C₂H₅OH)]·C₂H₅OH (3), are reported. The acetonitrile complex, 1, is isostructural with the Ir^III analog. In complexes 2 and 3, the monodeprotonated thyminate (Hthym⁻) ligand coordinates to the Rh^III atom through the N atom, and the resulting Rh—N(Hthym) bond lengths are relatively long [2.261 (2) and 2.252 (2) Å for 2 and 3, respectively] as compared to the Rh—N bonds in the related thyminate complexes. In each of the crystals of 2 and 3, the complexes are linked via a pair of intermolecular N—H⋯O hydrogen bonds between neighbouring Hthym⁻ ligands, forming an inversion dimer. A strong intramolecular O—H⋯O hydrogen bond between the thyminate(1−) and alcohol ligands in mutually cis positions to each other is also observed.

Keywords: crystal structure; monodentate monoanionic thyminate; intramolecular hydrogen-bonding interaction; intermolecular double hydrogen bonds.

CCDC references: 1469935; 1469934; 1469933

1. Chemical context

Thymine (= H₂thym) is one of the nucleobases, which are biologically important and fundamental organic molecules, and can release one or two protons, giving a thyminate(1−) (= Hthym⁻) or thyminate(2−) (= thym^2–) anion. These anions can act as suitable bridging ligands for the construction of functional polymetallic coordination compounds because they provide multiple donor atoms to metal atoms in a configurationally fixed fashion. For example, some tetra- and pentanuclear Pt^II complexes bridged by thym^2– have been described (Khutia et al., 2011 ; Rauterkus & Krebs, 2004 ). We have also reported some cyclic tetranuclear Cp*Rh^III (Cp* = pentamethylcyclopentadienyl) complexes bridged by thym^2– and incorporating an another metal cation in the central hydrophilic cavity of their metallacalix[4]arene motifs (Kashima et al., 2015 ; Sakate et al., 2016 ). In contrast, monoanionic thyminate (Hthym⁻) often acts as an N¹-coordinating monodentate ligand, for example, in [{Cp*Rh(Hthym)}₂(μ-OH)₂] (Sakate et al., 2016), [Cp*IrCl(Hthym)(dmso)] (dmso = dimethylsulfoxide; Krämer et al., 1991 ), [Pt(NH₃)₂(Hthym)(Mecyto)]ClO₄ (Mecyto = 1-methylcytosine; Faggiani et al., 1981 ) and [(Tp^Cum,Me)Zn(Hthym)]·EtAde {Tp^Cum,Me = hydridotris[2-methyl-4-(cumen-4-yl)-1-pyrazoryl]borate, EtAde = 9-ethyladenine; Badura & Vahrenkamp, 2002 }. The Zn^II complex is an interesting example, because the coordinating thyminato ligand forms multiple hydrogen bonds with the co-crystallized 9-ethyladenine molecule.

Our next targets are cyclic polymetallic compounds built up with intermolecular double hydrogen bonds between the coordinating thyminato(1−) and adeninato ligands. One of the complexes in this strategy is [Rh(ppy)₂(Hthym)(ade)]⁻ [ppy⁻ = 2-(pyridin-2-yl)phenyl, ade⁻ = adeninato]. For this purpose, we have prepared stepwise from [Rh(ppy)₂Cl(CH₃CN)] (1), [Rh(ppy)₂(Hthym)(CH₃OH)]·CH₃OH·0.5H₂O (2) to [Rh(ppy)₂(Hthym)(C₂H₅OH)]·C₂H₅OH (3), and have characterized their crystal structures. Attempts to react 2 or 3 with adenine or other monodentate ligands were also examined.

2. Structural commentary

Complexes 1–3 all have an octahedral coordination geometry with a trans(N,N)cis(C,C) configuration of the Rh^III(ppy)₂ fragment. The acetonitrile complex 1 (Fig. 1) is isostructural with the Ir^III analog, [Ir(ppy)₂Cl(CH₃CN)] (Blasberg et al., 2011 ). The mutually trans Rh—N(ppy) bonds are 2.030 (1) and 2.051 (1) Å, and the cis Rh—C(ppy) bonds are almost the same as each other [1.990 (2) and 1.993 (2) Å]. The Rh—Cl and Rh—N(CH₃CN) bonds in 1 are 2.4862 (4) and 2.162 (1) Å, respectively, which are almost at the longest end in the ranges of these bond lengths for the related Rh^III chlorido and acetonitrile complexes. These elongations are caused by the strong trans influence of the phenyl donor group. The acetonitrile molecule is almost linearly coordinated, as evidenced by the bond angles Rh1—N3—C23 = 175.44 (14)° and N3—C23—C24 = 178.48 (19)°.

Figure 1
An ORTEP drawing of the molecular structure of [Rh(ppy)₂Cl(CH₃CN)] (1), showing the atom-numbering scheme, with ellipsoids drawn at the 50% probability level.

Crystals of 2 and 3 are solvatomorphs crystallizing in the space group Pbca, although the lengths of their a axes differ by more than 0.4 Å. In these complexes, the Hthym⁻ anion coordinates to the Rh^III atom as a monodentate ligand through the N¹ atom (Figs. 2 and 3). There is a coordinating solvent (methanol or ethanol) molecule in the cis position to the Hthym⁻ anion. The mutually trans Rh—N(ppy) bond lengths in 2 and 3 are in the range 2.023 (2)–2.038 (2) Å. On the other hand, the mutually cis Rh—C(ppy) bonds show explicit deviation; the Rh—C bonds trans to Hthym⁻ are 1.994 (2) and 1.989 (2) Å for 2 and 3, respectively, while those trans to MeOH/EtOH in 2 and 3 are slightly shorter at 1.972 (2) and 1.976 (2) Å, respectively. The Rh—N(Hhtym) bonds in 2 and 3 are 2.261 (2) and 2.252 (2) Å, respectively, which are remarkably long as compared to those in the other Rh^III–Hthym⁻ complexes. For example, the Rh—N(Hthym) bond in [{Cp*Rh(Hthym)}₂(μ-OH)₂] is 2.126 (3) Å (Sakate et al., 2016). In the cyclic tetranuclear complexes bridged by thym^2–, the Rh—N(thym^2–) bonds are even shorter at 2.07 (1)–2.13 (1) Å. The Rh—O bonds in 2 and 3 are 2.233 (2) and 2.207 (1) Å, respectively, considerably longer than that [2.103 (3) Å] in [RhCl₃(bpy)(CH₃OH)] (Bieda et al., 2009 ). However, much longer Rh—O(MeOH or EtOH) bonds (2.240 and 2.264 Å) are observed in trans(C,O)-[(PCP)RhCl₂(MeOH or EtOH)] [PCP = 2,6-bis(dicyclohexylphosphinomethyl)phenyl; Cross et al., 1995 ]. These examples also indicate the strong trans influence of the phenyl-C donor in the trans position.

Figure 2
An ORTEP drawing of the molecular structure of [Rh(ppy)(Hthym)(MeOH)]·MeOH·0.5H₂O (2), showing the atom-numbering scheme, with ellipsoids drawn at the 30% probability level.

Figure 3
An ORTEP drawing of the molecular structure of [Rh(ppy)(Hthym)(EtOH)]·EtOH (3), showing the atom-numbering scheme, with ellipsoids drawn at the 30% probability level.

In both 2 and 3, there is an intramolecular hydrogen bond between atom O2 of the Hthym⁻ and O51—H1 of MeOH or EtOH in the mutually cis-position (Tables 2 and 3). These hydrogen bonds may stabilize the coordination of solvent MeOH and EtOH molecules in 2 and 3, even though the Rh—O bonds for these ligands are relatively long. In fact, a reaction of complex 2 or 3 with an equivalent amount of PPh₃, P(OMe)₃, imidazole or a mixture of adenine and triethylamine (L) gave a complicated mixture of products, from which no desirable ligand-substituted complexes of the formula, [Rh(ppy)₂(Hthym)(L)] could be isolated.

3. Supramolecular features

In the crystal of the acetonitrile complex 1, there are no remarkable intermolecular hydrogen bonds. As similar to the Ir^III analog (Blasberg et al., 2011), there are weak C—H⋯Cl hydrogen bonds (Table 1), which link the complexes into a layer parallel to the bc plane. In addition, C—H⋯π(ppy) [C8—H8⋯C16ⁱⁱⁱ: H8⋯C16ⁱⁱⁱ = 2.81, C8⋯C16ⁱⁱⁱ = 3.620 (3) Å, C8—H8⋯C16ⁱⁱⁱ = 144°; symmetry code: (iii) x + $[{1\over 2}]$ , y, −z + $[{1\over 2}]$ ] and C—H⋯π(nitrile) [C14—H14⋯C23^iv: H14⋯C23^iv = 2.69, C14⋯C23^iv = 3.427 (2) Å, C14—H14⋯C23^iv = 135°; symmetry code: (iv) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ] interactions are observed.

Table 1
Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl1ⁱ	0.95	2.79	3.613 (2)	145
C14—H14⋯Cl1ⁱⁱ	0.95	2.78	3.452 (2)	128
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

In each crystal of the thyminato(1−) complexes of 2 and 3, together with an intramolecular hydrogen bond mentioned above, there is a pair of intermolecular N—H⋯O hydrogen bonds (Tables 2 and 3) with an R₂²(8) ring motif between the neighboring Hthym⁻ ligands, forming an inversion dimer (Figs. 4 and 5). The methanol and ethanol molecules of crystallization in 2 and 3 are each linked to the Hthym⁻ ligand via an intermolecular O—H⋯O hydrogen bond.

Table 2
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O51—H1⋯O2	0.84 (2)	1.69 (2)	2.527 (3)	170 (3)
N3—H3⋯O2ⁱ	0.88	1.97	2.844 (3)	173
O61—H2⋯O4ⁱⁱ	0.84	2.01	2.802 (5)	157
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Table 3
Hydrogen-bond geometry (Å, °) for 3

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O51—H1⋯O2	0.83 (1)	1.72 (2)	2.527 (2)	164 (2)
N3—H3⋯O2ⁱ	0.88	1.99	2.854 (2)	165
O61—H2⋯O4ⁱⁱ	0.84 (1)	2.01 (4)	2.792 (3)	156 (4)
Symmetry codes: (i) -x, -y, -z+1; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Figure 4
A perspective view of 2, showing the intra- and intermolecular O—H⋯O hydrogen bonds (dotted lines) between the Hthym⁻ and MeOH ligands.

Figure 5
A perspective view of 3, showing the intra- and intermolecular O—H⋯O hydrogen-bonds (dotted lines) between the Hthym⁻ and EtOH ligands.

4. Synthesis and crystallization

The starting rhodium(III) complex, [Rh(ppy)₂Cl]₂, was prepared by a literature method (Sprouse et al., 1984 ). [Rh(ppy)₂Cl]₂ (0.050 g, 0.060 mmol) was dissolved in dichloromethane (5 mL) and acetonitrile (5 mL) was added to the solution. The mixture was allowed to stand in an open air to evaporate the solvent slowly, giving yellow crystals of 1. Yield: 0.047 g (80%). Analysis found: C 58.64, H 3.65, N 8.49%. Calculated for C₂₄H₁₉ClN₃Rh: C 59.09, H 3.93, N 8.61%.

To a methanol suspension (10 mL) of [Rh(ppy)₂Cl]₂ (0.090 g, 0.10 mmol) was added Ag(CF₃SO₃) (0.051 g, 0.20 mmol). The mixture was stirred at room temperature in the dark overnight, and the resulting white precipitate of AgCl was filtered off. A methanol solution (10 mL) containing thymine (0.025 g, 0.20 mmol) and triethylamine (28 µL, 0.20 mmol) was carefully layered on the filtrate, and the mixture was allowed to stand overnight to give yellow crystals of 2. Yield: 0.082 g (68%). Analysis found: C 58.05, H 4.62, N 9.30%. Calculated for C₂₉H₃₀N₄O_4.5Rh {= [Rh(ppy)₂(Hthym)(CH₃OH)]·CH₃OH·0.5H₂O}: C 57.15, H 4.96, N 9.19%. Complex 3 was prepared by a similar method to the above using ethanol as a solvent, instead of methanol. Yield: 64%. Analysis found: C 59.03, H 4.82, N 8.82%. Calculated for C₃₁H₃₃N₄O₄Rh: C 59.24, H 5.29, N 8.91%.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All H atoms bonded to C and N atoms in 1–3 were refined using a riding model, with C—H = 0.95 or 0.98 Å and N—H = 0.88 Å, and with U_iso(H) = 1.2U_eq(C, N). The positions of the O-bound H atoms of the coordinating methanol molecule in 2 and the coordinating and solvated ethanol molecules in 3 were refined with the restraints O—H = 0.84 (1) Å, and with U_iso(H) = 1.2U_eq(O), while the H atom of the solvated methanol in 2 was refined using a riding model with O—H = 0.84 Å and U_iso(H) = 1.2U_eq(O). In the crystal of 2, other than the complex and methanol molecules, there is a small electron density remaining in the void, and this was assumed to be a water molecule of crystallization. The H atoms of this water molecule were not introduced in the calculation because of the highly disordered state of the water molecule, which resulted in large thermal displacement parameters for the O atom.

Table 4
Experimental details

	1	2	3
Crystal data
Chemical formula	[RhCl(C₁₁H₈N)₂(C₂H₃N)]	[Rh(C₁₁H₈N)₂(C₅H₅N₂O₂)(CH₄O)]·CH₄O·0.5H₂O	[Rh(C₁₁H₈N)₂(C₅H₅N₂O₂)(C₂H₆O)]·C₂H₆O
M_r	487.78	609.48	628.52
Crystal system, space group	Orthorhombic, Pbca	Orthorhombic, Pbca	Orthorhombic, Pbca
Temperature (K)	193	192	192
a, b, c (Å)	16.5415 (9), 14.6600 (11), 17.0026 (12)	10.6964 (7), 15.5329 (9), 32.6325 (15)	11.1082 (5), 15.5556 (6), 32.6747 (15)
V (Å³)	4123.1 (5)	5421.8 (5)	5646.0 (4)
Z	8	8	8
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.97	0.67	0.65
Crystal size (mm)	0.40 × 0.30 × 0.20	0.30 × 0.20 × 0.10	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID	Rigaku R-AXIS RAPID	Rigaku R-AXIS RAPID
Absorption correction	Numerical (NUMABS; Rigaku, 1999 )	Numerical (NUMABS; Rigaku, 1999)	Numerical (NUMABS; Rigaku, 1999)
T_min, T_max	0.697, 0.829	0.824, 0.936	0.829, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	38163, 4709, 4327	47794, 6196, 5307	52659, 6470, 5886
R_int	0.042	0.046	0.030
(sin θ/λ)_max (Å⁻¹)	0.649	0.649	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.060, 1.07	0.034, 0.096, 1.04	0.029, 0.076, 1.07
No. of reflections	4709	6196	6470
No. of parameters	263	356	370
No. of restraints	0	1	2
H-atom treatment	H-atom parameters constrained	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.35	1.29, −0.61	1.08, −0.40
Computer programs: RAPID AUTO (Rigaku, 2006 ), CrystalStructure (Rigaku, 2010 ), Il Milione (Burla et al., 2007 ), SHELXS2013 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ) and ORTEP-3 for Windows (Farrugia, 2012 ).

Supporting information

CCDC references: 1469935; 1469934; 1469933

Crystal structure: contains datablocks 1, 2, 3, global. DOI: https://doi.org/10.1107/S2056989016004837/is5448sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989016004837/is54481sup5.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989016004837/is54482sup6.hkl

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S2056989016004837/is54483sup7.hkl

checkCIF report

Computing details top

For all compounds, data collection: RAPID AUTO (Rigaku, 2006); cell refinement: RAPID AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku, 2010). Program(s) used to solve structure: Il Milione (Burla et al., 2007) for (1); SHELXS2013 (Sheldrick, 2008) for (2), (3). Program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015) for (1), (3); SHELXL2013 (Sheldrick, 2008) for (2). For all compounds, molecular graphics: ORTEP-3 for Windows (Farrugia, 2012). Software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015) for (1), (3); SHELXS2013 (Sheldrick, 2008) for (2).

(1) (OC-6-42)-Acetonitrilechloridobis[2-(pyridin-2-yl)phenyl-κ²N,C¹]rhodium(III) top

Crystal data top

[RhCl(C₁₁H₈N)₂(C₂H₃N)]	D_x = 1.572 Mg m⁻³
M_r = 487.78	Mo Kα radiation, λ = 0.71075 Å
Orthorhombic, Pbca	Cell parameters from 31949 reflections
a = 16.5415 (9) Å	θ = 3.0–27.6°
b = 14.6600 (11) Å	µ = 0.97 mm⁻¹
c = 17.0026 (12) Å	T = 193 K
V = 4123.1 (5) Å³	Block, yellow
Z = 8	0.40 × 0.30 × 0.20 mm
F(000) = 1968

Data collection top

Rigaku R-AXIS RAPID diffractometer	4709 independent reflections
Radiation source: fine-focus sealed tube	4327 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −20→21
Absorption correction: numerical (NUMABS; Rigaku, 1999)	k = −18→18
T_min = 0.697, T_max = 0.829	l = −22→22
38163 measured reflections

Refinement top

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0309P)² + 1.6125P] where P = (F_o² + 2F_c²)/3
4709 reflections	(Δ/σ)_max = 0.001
263 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Special details top

Experimental. The ¹H NMR spectrum of 1 in CD₂Cl₂ at 22 °C: δ 1.97 (s, 3H, MeCN), 5.90 (d, J = 7.8 Hz, 2H, ppy), 6.70 (td, J = 7.6 and 1.4 Hz, 2H, ppy), 6.77–6.96 (m, 4H, ppy), 7.62 (dd, J = 7.7 and 1.4 Hz, 2H, ppy), 7.81–7.98 (m, 4H, ppy) and 9.22 (d, J = 5.7 Hz, 2H, ppy).

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Rh1	0.12078 (2)	0.55701 (2)	0.36161 (2)	0.01986 (5)
Cl1	0.10904 (2)	0.64708 (3)	0.48498 (2)	0.02906 (9)
N1	0.15175 (8)	0.44472 (8)	0.42460 (8)	0.0238 (3)
N2	0.09842 (8)	0.66466 (9)	0.28773 (8)	0.0235 (3)
N3	−0.00853 (9)	0.53554 (10)	0.36314 (8)	0.0265 (3)
C1	0.09933 (10)	0.38632 (11)	0.45823 (9)	0.0272 (3)
H1	0.0433	0.4006	0.4579	0.033*
C2	0.12459 (10)	0.30643 (13)	0.49304 (11)	0.0339 (4)
H2	0.0865	0.2662	0.5165	0.041*
C3	0.20657 (11)	0.28542 (12)	0.49338 (11)	0.0358 (4)
H3	0.2251	0.2298	0.5157	0.043*
C4	0.26051 (10)	0.34604 (12)	0.46102 (10)	0.0309 (3)
H4	0.3167	0.3329	0.4617	0.037*
C5	0.23289 (9)	0.42661 (11)	0.42724 (9)	0.0247 (3)
C6	0.28290 (9)	0.49821 (11)	0.39221 (9)	0.0252 (3)
C7	0.36733 (10)	0.49704 (13)	0.39354 (10)	0.0326 (4)
H7	0.3954	0.4472	0.4166	0.039*
C8	0.40989 (12)	0.56954 (14)	0.36084 (11)	0.0381 (4)
H8	0.4673	0.5693	0.3614	0.046*
C9	0.36859 (10)	0.64198 (13)	0.32751 (12)	0.0370 (4)
H9	0.3979	0.6915	0.3054	0.044*
C10	0.28439 (10)	0.64280 (12)	0.32621 (10)	0.0305 (3)
H10	0.2568	0.6929	0.3031	0.037*
C11	0.24040 (10)	0.57124 (11)	0.35831 (8)	0.0234 (3)
C12	0.07628 (10)	0.74823 (11)	0.31092 (10)	0.0302 (3)
H12	0.0715	0.7604	0.3656	0.036*
C13	0.06014 (12)	0.81726 (12)	0.25807 (11)	0.0373 (4)
H13	0.0435	0.8758	0.2758	0.045*
C14	0.06879 (12)	0.79919 (12)	0.17872 (11)	0.0381 (4)
H14	0.0591	0.8459	0.1411	0.046*
C15	0.09143 (11)	0.71342 (12)	0.15440 (10)	0.0322 (4)
H15	0.0978	0.7007	0.1000	0.039*
C16	0.10502 (9)	0.64548 (11)	0.20997 (9)	0.0243 (3)
C17	0.12356 (8)	0.54991 (11)	0.19292 (10)	0.0238 (3)
C18	0.12867 (10)	0.51469 (13)	0.11672 (10)	0.0301 (4)
H18	0.1222	0.5540	0.0728	0.036*
C19	0.14314 (12)	0.42299 (13)	0.10501 (11)	0.0363 (4)
H19	0.1462	0.3990	0.0532	0.044*
C20	0.15317 (12)	0.36630 (13)	0.16931 (11)	0.0383 (4)
H20	0.1636	0.3033	0.1614	0.046*
C21	0.14813 (11)	0.40060 (12)	0.24553 (10)	0.0315 (3)
H21	0.1555	0.3607	0.2890	0.038*
C22	0.13243 (8)	0.49280 (11)	0.25894 (9)	0.0233 (3)
C23	−0.07658 (11)	0.52843 (12)	0.36004 (9)	0.0285 (3)
C24	−0.16431 (11)	0.51736 (16)	0.35764 (12)	0.0425 (5)
H24A	−0.1903	0.5768	0.3653	0.051*
H24B	−0.1813	0.4756	0.3995	0.051*
H24C	−0.1802	0.4923	0.3065	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.01770 (8)	0.02111 (8)	0.02077 (8)	−0.00061 (4)	0.00062 (4)	0.00068 (4)
Cl1	0.03143 (19)	0.0321 (2)	0.02369 (18)	−0.00410 (15)	0.00318 (15)	−0.00310 (15)
N1	0.0238 (7)	0.0248 (7)	0.0228 (6)	−0.0004 (5)	0.0003 (5)	0.0010 (5)
N2	0.0213 (6)	0.0243 (7)	0.0249 (6)	−0.0005 (5)	−0.0002 (5)	0.0017 (5)
N3	0.0238 (7)	0.0272 (7)	0.0286 (7)	−0.0010 (5)	0.0007 (5)	0.0000 (5)
C1	0.0245 (7)	0.0302 (8)	0.0268 (8)	−0.0028 (6)	0.0017 (6)	0.0020 (6)
C2	0.0350 (9)	0.0313 (9)	0.0355 (9)	−0.0043 (7)	0.0047 (7)	0.0069 (7)
C3	0.0401 (10)	0.0285 (9)	0.0386 (9)	0.0051 (7)	0.0012 (8)	0.0085 (7)
C4	0.0276 (8)	0.0321 (9)	0.0329 (8)	0.0057 (6)	0.0000 (7)	0.0029 (7)
C5	0.0231 (8)	0.0277 (8)	0.0233 (7)	0.0014 (6)	0.0011 (6)	−0.0003 (6)
C6	0.0220 (7)	0.0296 (8)	0.0241 (7)	0.0004 (6)	0.0009 (6)	−0.0008 (6)
C7	0.0225 (8)	0.0409 (10)	0.0345 (9)	0.0027 (7)	0.0017 (7)	0.0017 (8)
C8	0.0189 (9)	0.0473 (12)	0.0480 (12)	−0.0035 (7)	0.0055 (7)	0.0016 (8)
C9	0.0274 (8)	0.0365 (10)	0.0470 (11)	−0.0098 (7)	0.0076 (8)	0.0027 (8)
C10	0.0266 (8)	0.0292 (8)	0.0356 (9)	−0.0032 (6)	0.0024 (7)	0.0010 (7)
C11	0.0195 (7)	0.0275 (8)	0.0232 (7)	−0.0026 (6)	0.0028 (6)	−0.0028 (6)
C12	0.0353 (8)	0.0276 (8)	0.0275 (8)	0.0017 (7)	−0.0012 (7)	−0.0011 (6)
C13	0.0496 (11)	0.0245 (8)	0.0377 (9)	0.0061 (7)	−0.0038 (8)	0.0000 (7)
C14	0.0524 (11)	0.0283 (9)	0.0336 (9)	0.0017 (8)	−0.0068 (8)	0.0070 (7)
C15	0.0389 (10)	0.0328 (9)	0.0248 (8)	−0.0019 (7)	−0.0012 (7)	0.0041 (7)
C16	0.0200 (7)	0.0274 (8)	0.0254 (7)	−0.0016 (6)	−0.0008 (6)	0.0011 (6)
C17	0.0184 (7)	0.0268 (8)	0.0261 (8)	−0.0007 (5)	−0.0003 (6)	−0.0006 (6)
C18	0.0299 (8)	0.0361 (10)	0.0243 (8)	0.0018 (7)	0.0008 (6)	−0.0006 (7)
C19	0.0409 (10)	0.0388 (10)	0.0291 (9)	0.0022 (8)	0.0017 (8)	−0.0089 (7)
C20	0.0463 (11)	0.0282 (9)	0.0403 (10)	0.0030 (8)	0.0018 (9)	−0.0077 (7)
C21	0.0360 (9)	0.0275 (9)	0.0308 (8)	0.0009 (7)	0.0012 (7)	−0.0005 (7)
C22	0.0194 (7)	0.0260 (8)	0.0244 (7)	−0.0020 (5)	0.0010 (6)	−0.0015 (6)
C23	0.0276 (9)	0.0283 (9)	0.0296 (8)	−0.0005 (7)	0.0000 (6)	0.0006 (6)
C24	0.0220 (9)	0.0547 (13)	0.0507 (12)	−0.0032 (8)	−0.0031 (8)	0.0034 (9)

Geometric parameters (Å, º) top

Rh1—C11	1.9904 (16)	C9—H9	0.9500
Rh1—C22	1.9926 (15)	C10—C11	1.388 (2)
Rh1—N1	2.0296 (13)	C10—H10	0.9500
Rh1—N2	2.0507 (13)	C12—C13	1.379 (2)
Rh1—N3	2.1621 (14)	C12—H12	0.9500
Rh1—Cl1	2.4862 (4)	C13—C14	1.382 (3)
N1—C1	1.346 (2)	C13—H13	0.9500
N1—C5	1.369 (2)	C14—C15	1.376 (3)
N2—C12	1.338 (2)	C14—H14	0.9500
N2—C16	1.356 (2)	C15—C16	1.391 (2)
N3—C23	1.132 (2)	C15—H15	0.9500
C1—C2	1.377 (2)	C16—C17	1.463 (2)
C1—H1	0.9500	C17—C18	1.397 (2)
C2—C3	1.391 (2)	C17—C22	1.408 (2)
C2—H2	0.9500	C18—C19	1.380 (3)
C3—C4	1.374 (2)	C18—H18	0.9500
C3—H3	0.9500	C19—C20	1.383 (3)
C4—C5	1.391 (2)	C19—H19	0.9500
C4—H4	0.9500	C20—C21	1.393 (2)
C5—C6	1.463 (2)	C20—H20	0.9500
C6—C7	1.397 (2)	C21—C22	1.395 (2)
C6—C11	1.405 (2)	C21—H21	0.9500
C7—C8	1.391 (3)	C23—C24	1.461 (3)
C7—H7	0.9500	C24—H24A	0.9800
C8—C9	1.384 (3)	C24—H24B	0.9800
C8—H8	0.9500	C24—H24C	0.9800
C9—C10	1.393 (2)

C11—Rh1—C22	85.91 (6)	C10—C9—H9	119.8
C11—Rh1—N1	81.31 (6)	C11—C10—C9	120.75 (17)
C22—Rh1—N1	93.13 (6)	C11—C10—H10	119.6
C11—Rh1—N2	94.67 (6)	C9—C10—H10	119.6
C22—Rh1—N2	81.05 (6)	C10—C11—C6	118.35 (15)
N1—Rh1—N2	173.19 (5)	C10—C11—Rh1	127.68 (13)
C11—Rh1—N3	177.47 (6)	C6—C11—Rh1	113.96 (11)
C22—Rh1—N3	92.15 (5)	N2—C12—C13	122.19 (16)
N1—Rh1—N3	97.20 (5)	N2—C12—H12	118.9
N2—Rh1—N3	86.62 (5)	C13—C12—H12	118.9
C11—Rh1—Cl1	92.62 (4)	C12—C13—C14	118.37 (16)
C22—Rh1—Cl1	176.01 (5)	C12—C13—H13	120.8
N1—Rh1—Cl1	90.30 (4)	C14—C13—H13	120.8
N2—Rh1—Cl1	95.40 (4)	C15—C14—C13	119.78 (16)
N3—Rh1—Cl1	89.42 (4)	C15—C14—H14	120.1
C1—N1—C5	119.62 (14)	C13—C14—H14	120.1
C1—N1—Rh1	125.26 (11)	C14—C15—C16	119.62 (16)
C5—N1—Rh1	114.97 (10)	C14—C15—H15	120.2
C12—N2—C16	119.94 (14)	C16—C15—H15	120.2
C12—N2—Rh1	124.99 (11)	N2—C16—C15	120.05 (15)
C16—N2—Rh1	115.03 (11)	N2—C16—C17	114.12 (14)
C23—N3—Rh1	175.44 (14)	C15—C16—C17	125.79 (15)
N1—C1—C2	121.87 (15)	C18—C17—C22	120.88 (15)
N1—C1—H1	119.1	C18—C17—C16	123.39 (15)
C2—C1—H1	119.1	C22—C17—C16	115.67 (15)
C1—C2—C3	119.09 (16)	C19—C18—C17	120.29 (17)
C1—C2—H2	120.5	C19—C18—H18	119.9
C3—C2—H2	120.5	C17—C18—H18	119.9
C4—C3—C2	119.22 (16)	C18—C19—C20	119.47 (17)
C4—C3—H3	120.4	C18—C19—H19	120.3
C2—C3—H3	120.4	C20—C19—H19	120.3
C3—C4—C5	120.08 (15)	C19—C20—C21	120.76 (17)
C3—C4—H4	120.0	C19—C20—H20	119.6
C5—C4—H4	120.0	C21—C20—H20	119.6
N1—C5—C4	120.04 (15)	C20—C21—C22	120.86 (16)
N1—C5—C6	113.69 (14)	C20—C21—H21	119.6
C4—C5—C6	126.28 (15)	C22—C21—H21	119.6
C7—C6—C11	121.09 (15)	C21—C22—C17	117.72 (14)
C7—C6—C5	123.36 (15)	C21—C22—Rh1	128.23 (12)
C11—C6—C5	115.52 (14)	C17—C22—Rh1	114.05 (12)
C8—C7—C6	119.36 (17)	N3—C23—C24	178.48 (19)
C8—C7—H7	120.3	C23—C24—H24A	109.5
C6—C7—H7	120.3	C23—C24—H24B	109.5
C9—C8—C7	120.01 (17)	H24A—C24—H24B	109.5
C9—C8—H8	120.0	C23—C24—H24C	109.5
C7—C8—H8	120.0	H24A—C24—H24C	109.5
C8—C9—C10	120.43 (17)	H24B—C24—H24C	109.5
C8—C9—H9	119.8

C5—N1—C1—C2	−2.5 (2)	C16—N2—C12—C13	−0.5 (2)
Rh1—N1—C1—C2	173.05 (13)	Rh1—N2—C12—C13	−178.34 (13)
N1—C1—C2—C3	−0.1 (3)	N2—C12—C13—C14	−1.2 (3)
C1—C2—C3—C4	1.9 (3)	C12—C13—C14—C15	1.3 (3)
C2—C3—C4—C5	−1.1 (3)	C13—C14—C15—C16	0.3 (3)
C1—N1—C5—C4	3.2 (2)	C12—N2—C16—C15	2.2 (2)
Rh1—N1—C5—C4	−172.74 (12)	Rh1—N2—C16—C15	−179.80 (12)
C1—N1—C5—C6	−176.83 (14)	C12—N2—C16—C17	−175.52 (14)
Rh1—N1—C5—C6	7.22 (17)	Rh1—N2—C16—C17	2.54 (16)
C3—C4—C5—N1	−1.5 (2)	C14—C15—C16—N2	−2.1 (3)
C3—C4—C5—C6	178.60 (16)	C14—C15—C16—C17	175.30 (16)
N1—C5—C6—C7	175.24 (15)	N2—C16—C17—C18	176.48 (14)
C4—C5—C6—C7	−4.8 (3)	C15—C16—C17—C18	−1.0 (2)
N1—C5—C6—C11	−3.0 (2)	N2—C16—C17—C22	−0.54 (19)
C4—C5—C6—C11	176.96 (16)	C15—C16—C17—C22	−178.06 (15)
C11—C6—C7—C8	0.1 (3)	C22—C17—C18—C19	−0.5 (2)
C5—C6—C7—C8	−178.03 (16)	C16—C17—C18—C19	−177.33 (15)
C6—C7—C8—C9	0.1 (3)	C17—C18—C19—C20	−0.5 (3)
C7—C8—C9—C10	−0.2 (3)	C18—C19—C20—C21	0.6 (3)
C8—C9—C10—C11	0.1 (3)	C19—C20—C21—C22	0.3 (3)
C9—C10—C11—C6	0.1 (2)	C20—C21—C22—C17	−1.3 (2)
C9—C10—C11—Rh1	−178.98 (14)	C20—C21—C22—Rh1	178.95 (14)
C7—C6—C11—C10	−0.2 (2)	C18—C17—C22—C21	1.3 (2)
C5—C6—C11—C10	178.05 (14)	C16—C17—C22—C21	178.43 (14)
C7—C6—C11—Rh1	179.01 (13)	C18—C17—C22—Rh1	−178.86 (11)
C5—C6—C11—Rh1	−2.72 (17)	C16—C17—C22—Rh1	−1.75 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl1ⁱ	0.95	2.79	3.613 (2)	145
C14—H14···Cl1ⁱⁱ	0.95	2.78	3.452 (2)	128

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+3/2, z−1/2.

(2) (OC-6-42)-Methanol(5-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ido-κN¹)bis[2-(pyridin-2-yl)phenyl-κ²N,C¹]rhodium(III) top

Crystal data top

[Rh(C₁₁H₈N)₂(C₅H₅N₂O₂)(CH₄O)]·CH₄O·0.5H₂O	D_x = 1.493 Mg m⁻³
M_r = 609.48	Mo Kα radiation, λ = 0.71075 Å
Orthorhombic, Pbca	Cell parameters from 34894 reflections
a = 10.6964 (7) Å	θ = 3.1–27.5°
b = 15.5329 (9) Å	µ = 0.67 mm⁻¹
c = 32.6325 (15) Å	T = 192 K
V = 5421.8 (5) Å³	Block, yellow
Z = 8	0.30 × 0.20 × 0.10 mm
F(000) = 2504

Data collection top

Rigaku R-AXIS RAPID diffractometer	6196 independent reflections
Radiation source: fine-focus sealed tube	5307 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −13→13
Absorption correction: numerical (NUMABS; Rigaku, 1999)	k = −20→20
T_min = 0.824, T_max = 0.936	l = −42→40
47794 measured reflections

Refinement top

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0469P)² + 5.8148P] where P = (F_o² + 2F_c²)/3
6196 reflections	(Δ/σ)_max = 0.001
356 parameters	Δρ_max = 1.29 e Å⁻³
1 restraint	Δρ_min = −0.61 e Å⁻³

Special details top

Experimental. The ¹H NMR spectrum of 2 in CDCl₃ at 22 °C: δ 1.50 (s, 3H, Hthym CH₃), 6.17 (d, J = 7.7 Hz, 2H, ppy), 6.40 (s, 1H, Hthym C⁶-H), 6.81 (t, J = 7.3 Hz, 2H ppy), 6.94 (t, J = 7.6 Hz, 2H, ppy), 7.28–7.31 (m, 2H, ppy), 7.58–7.60 (m, 2H, ppy), 7.87–7.91 (m, 4H, ppy), 8.35 (s, 1H, Hthym N³-H), 8.59 (d, J = 5.3 Hz, 1H ppy) and 8.99 (d, J = 5.3 Hz, 1H, ppy).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Rh1	0.21119 (2)	0.49429 (2)	0.36187 (2)	0.02250 (7)
O2	0.0485 (2)	0.47720 (13)	0.45127 (6)	0.0465 (5)
O4	0.18704 (18)	0.69252 (12)	0.53187 (5)	0.0375 (4)
O61	0.2102 (6)	0.3378 (3)	0.57003 (13)	0.1420 (19)
H2	0.2587	0.2984	0.5624	0.170*
O71	0.5000	0.5000	0.5000	0.523 (18)
O51	0.07868 (16)	0.39468 (11)	0.38528 (5)	0.0320 (4)
H1	0.067 (3)	0.4167 (17)	0.4086 (5)	0.038*
N1	0.19674 (18)	0.56450 (13)	0.42240 (6)	0.0267 (4)
N3	0.12027 (19)	0.58796 (14)	0.48895 (6)	0.0321 (4)
H3	0.0659	0.5725	0.5078	0.039*
N11	0.36388 (18)	0.43094 (12)	0.38330 (6)	0.0272 (4)
N22	0.06810 (18)	0.55596 (13)	0.33315 (6)	0.0275 (4)
C1	0.3749 (3)	0.74950 (19)	0.47238 (8)	0.0464 (7)
H1A	0.4254	0.7569	0.4476	0.056*
H1B	0.4295	0.7349	0.4955	0.056*
H1C	0.3303	0.8032	0.4784	0.056*
C2	0.1210 (2)	0.54094 (16)	0.45317 (7)	0.0301 (5)
C4	0.1962 (2)	0.65651 (15)	0.49803 (7)	0.0286 (5)
C5	0.2822 (2)	0.67846 (16)	0.46584 (7)	0.0301 (5)
C6	0.2756 (2)	0.63197 (16)	0.43056 (7)	0.0306 (5)
H6	0.3316	0.6480	0.4093	0.037*
C12	0.3605 (3)	0.35579 (16)	0.40370 (8)	0.0339 (5)
H12	0.2819	0.3308	0.4102	0.041*
C13	0.4688 (3)	0.31390 (18)	0.41551 (9)	0.0432 (6)
H13	0.4647	0.2609	0.4300	0.052*
C14	0.5827 (3)	0.3501 (2)	0.40600 (10)	0.0485 (7)
H14	0.6581	0.3224	0.4139	0.058*
C15	0.5860 (3)	0.42733 (18)	0.38490 (9)	0.0417 (6)
H15	0.6640	0.4526	0.3779	0.050*
C16	0.4754 (2)	0.46771 (16)	0.37397 (7)	0.0292 (5)
C17	0.4635 (2)	0.54941 (15)	0.35162 (7)	0.0275 (5)
C18	0.5653 (2)	0.60157 (17)	0.34154 (8)	0.0367 (6)
H18	0.6478	0.5839	0.3483	0.044*
C19	0.5459 (3)	0.67878 (18)	0.32166 (9)	0.0410 (6)
H19	0.6150	0.7144	0.3148	0.049*
C20	0.4252 (2)	0.70452 (17)	0.31173 (8)	0.0368 (6)
H20	0.4119	0.7578	0.2981	0.044*
C21	0.3236 (2)	0.65245 (16)	0.32164 (7)	0.0299 (5)
H21	0.2416	0.6705	0.3145	0.036*
C22	0.3404 (2)	0.57451 (15)	0.34184 (6)	0.0254 (4)
C23	−0.0065 (2)	0.61523 (17)	0.35045 (8)	0.0354 (5)
H23	0.0084	0.6314	0.3781	0.042*
C24	−0.1031 (3)	0.65325 (19)	0.32980 (9)	0.0440 (7)
H24	−0.1535	0.6956	0.3428	0.053*
C25	−0.1262 (3)	0.6288 (2)	0.28947 (9)	0.0465 (7)
H25	−0.1927	0.6542	0.2745	0.056*
C26	−0.0512 (2)	0.56704 (18)	0.27151 (8)	0.0383 (6)
H26	−0.0667	0.5491	0.2442	0.046*
C27	0.0469 (2)	0.53132 (16)	0.29358 (7)	0.0288 (5)
C28	0.1342 (2)	0.46567 (16)	0.27854 (7)	0.0282 (5)
C29	0.1326 (3)	0.43303 (17)	0.23851 (7)	0.0359 (5)
H29	0.0719	0.4527	0.2195	0.043*
C30	0.2196 (3)	0.37214 (19)	0.22686 (8)	0.0401 (6)
H30	0.2188	0.3498	0.1998	0.048*
C31	0.3081 (3)	0.34358 (17)	0.25468 (8)	0.0381 (6)
H31	0.3680	0.3018	0.2465	0.046*
C32	0.3101 (2)	0.37542 (16)	0.29443 (8)	0.0321 (5)
H32	0.3710	0.3548	0.3132	0.039*
C33	0.2237 (2)	0.43744 (15)	0.30723 (7)	0.0263 (5)
C51	−0.0423 (3)	0.3826 (2)	0.36788 (9)	0.0435 (7)
H51A	−0.0836	0.3338	0.3813	0.052*
H51B	−0.0341	0.3709	0.3385	0.052*
H51C	−0.0923	0.4348	0.3719	0.052*
C61	0.2442 (8)	0.4080 (4)	0.55466 (19)	0.136 (3)
H61A	0.3340	0.4059	0.5488	0.164*
H61B	0.2271	0.4548	0.5740	0.164*
H61C	0.1981	0.4181	0.5292	0.164*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.02134 (11)	0.02767 (11)	0.01849 (11)	0.00008 (6)	0.00094 (6)	−0.00116 (6)
O2	0.0542 (13)	0.0539 (11)	0.0314 (10)	−0.0286 (10)	0.0183 (9)	−0.0145 (9)
O4	0.0430 (10)	0.0444 (10)	0.0252 (8)	−0.0030 (8)	0.0005 (7)	−0.0095 (7)
O61	0.255 (6)	0.082 (2)	0.089 (3)	0.020 (3)	0.047 (3)	−0.015 (2)
O71	0.76 (5)	0.48 (3)	0.33 (2)	0.23 (3)	0.14 (3)	0.003 (18)
O51	0.0315 (9)	0.0361 (9)	0.0283 (8)	−0.0060 (7)	0.0054 (7)	−0.0050 (7)
N1	0.0281 (10)	0.0318 (10)	0.0200 (9)	−0.0024 (8)	0.0025 (7)	−0.0021 (8)
N3	0.0340 (11)	0.0420 (11)	0.0203 (9)	−0.0089 (9)	0.0083 (8)	−0.0063 (8)
N11	0.0283 (10)	0.0317 (10)	0.0215 (9)	0.0022 (8)	−0.0007 (7)	−0.0006 (8)
N22	0.0238 (10)	0.0340 (10)	0.0247 (9)	0.0013 (8)	−0.0003 (7)	−0.0008 (8)
C1	0.0575 (18)	0.0505 (16)	0.0314 (13)	−0.0242 (15)	0.0039 (12)	−0.0054 (12)
C2	0.0311 (12)	0.0364 (12)	0.0227 (11)	−0.0044 (10)	0.0033 (9)	−0.0043 (9)
C4	0.0305 (12)	0.0333 (12)	0.0219 (11)	0.0024 (9)	−0.0027 (9)	−0.0008 (9)
C5	0.0341 (13)	0.0331 (12)	0.0231 (11)	−0.0045 (10)	−0.0006 (9)	−0.0001 (9)
C6	0.0343 (13)	0.0352 (12)	0.0222 (11)	−0.0048 (10)	0.0027 (9)	−0.0004 (9)
C12	0.0377 (14)	0.0323 (12)	0.0318 (12)	−0.0002 (10)	−0.0025 (10)	0.0038 (10)
C13	0.0503 (17)	0.0382 (14)	0.0412 (15)	0.0050 (12)	−0.0116 (12)	0.0081 (12)
C14	0.0406 (16)	0.0465 (16)	0.0583 (18)	0.0106 (13)	−0.0144 (13)	0.0058 (14)
C15	0.0286 (13)	0.0460 (15)	0.0503 (16)	0.0023 (11)	−0.0068 (11)	0.0039 (13)
C16	0.0275 (12)	0.0352 (12)	0.0250 (11)	0.0010 (10)	−0.0013 (9)	−0.0008 (10)
C17	0.0256 (11)	0.0324 (12)	0.0244 (11)	0.0005 (9)	0.0014 (9)	−0.0004 (9)
C18	0.0255 (12)	0.0438 (14)	0.0408 (14)	−0.0017 (10)	0.0021 (10)	0.0027 (11)
C19	0.0325 (14)	0.0440 (15)	0.0464 (15)	−0.0086 (11)	0.0056 (11)	0.0062 (12)
C20	0.0405 (15)	0.0347 (13)	0.0354 (13)	−0.0019 (11)	0.0028 (11)	0.0070 (10)
C21	0.0286 (12)	0.0344 (12)	0.0265 (11)	0.0027 (9)	0.0013 (9)	0.0002 (9)
C22	0.0248 (11)	0.0315 (11)	0.0200 (10)	−0.0009 (9)	0.0034 (8)	−0.0039 (9)
C23	0.0319 (13)	0.0420 (14)	0.0323 (12)	0.0057 (11)	0.0005 (10)	−0.0068 (11)
C24	0.0374 (15)	0.0517 (16)	0.0429 (15)	0.0159 (12)	−0.0012 (12)	−0.0071 (13)
C25	0.0372 (15)	0.0627 (18)	0.0395 (15)	0.0171 (13)	−0.0062 (12)	0.0025 (13)
C26	0.0359 (14)	0.0506 (15)	0.0284 (12)	0.0075 (12)	−0.0061 (10)	−0.0017 (11)
C27	0.0263 (12)	0.0368 (12)	0.0233 (11)	−0.0005 (10)	−0.0002 (9)	0.0014 (9)
C28	0.0280 (12)	0.0346 (12)	0.0219 (10)	−0.0010 (9)	0.0002 (9)	−0.0015 (9)
C29	0.0371 (14)	0.0451 (14)	0.0255 (12)	−0.0014 (11)	−0.0029 (10)	−0.0048 (10)
C30	0.0437 (16)	0.0508 (16)	0.0257 (12)	−0.0038 (12)	0.0023 (10)	−0.0116 (11)
C31	0.0372 (14)	0.0406 (13)	0.0366 (14)	0.0035 (11)	0.0067 (11)	−0.0123 (11)
C32	0.0289 (12)	0.0368 (13)	0.0306 (12)	0.0020 (10)	0.0005 (9)	−0.0048 (10)
C33	0.0258 (12)	0.0307 (11)	0.0223 (10)	−0.0036 (9)	0.0019 (8)	−0.0020 (9)
C51	0.0346 (15)	0.0534 (17)	0.0424 (15)	−0.0136 (13)	0.0015 (11)	−0.0088 (13)
C61	0.243 (8)	0.070 (3)	0.095 (4)	−0.039 (4)	−0.041 (5)	−0.015 (3)

Geometric parameters (Å, º) top

Rh1—C22	1.972 (2)	C16—C17	1.469 (3)
Rh1—C33	1.994 (2)	C17—C18	1.397 (3)
Rh1—N11	2.0309 (19)	C17—C22	1.410 (3)
Rh1—N22	2.0344 (19)	C18—C19	1.379 (4)
Rh1—O51	2.2331 (17)	C18—H18	0.9500
Rh1—N1	2.2614 (19)	C19—C20	1.390 (4)
O2—C2	1.259 (3)	C19—H19	0.9500
O4—C4	1.242 (3)	C20—C21	1.393 (3)
O61—C61	1.255 (6)	C20—H20	0.9500
O61—H2	0.8400	C21—C22	1.390 (3)
O51—C51	1.425 (3)	C21—H21	0.9500
O51—H1	0.844 (10)	C23—C24	1.368 (4)
N1—C2	1.341 (3)	C23—H23	0.9500
N1—C6	1.371 (3)	C24—C25	1.392 (4)
N3—C4	1.372 (3)	C24—H24	0.9500
N3—C2	1.377 (3)	C25—C26	1.380 (4)
N3—H3	0.8800	C25—H25	0.9500
N11—C12	1.344 (3)	C26—C27	1.388 (3)
N11—C16	1.357 (3)	C26—H26	0.9500
N22—C23	1.343 (3)	C27—C28	1.467 (3)
N22—C27	1.366 (3)	C28—C29	1.401 (3)
C1—C5	1.499 (3)	C28—C33	1.409 (3)
C1—H1A	0.9800	C29—C30	1.380 (4)
C1—H1B	0.9800	C29—H29	0.9500
C1—H1C	0.9800	C30—C31	1.384 (4)
C4—C5	1.437 (3)	C30—H30	0.9500
C5—C6	1.361 (3)	C31—C32	1.389 (4)
C6—H6	0.9500	C31—H31	0.9500
C12—C13	1.383 (4)	C32—C33	1.398 (3)
C12—H12	0.9500	C32—H32	0.9500
C13—C14	1.377 (4)	C51—H51A	0.9800
C13—H13	0.9500	C51—H51B	0.9800
C14—C15	1.383 (4)	C51—H51C	0.9800
C14—H14	0.9500	C61—H61A	0.9800
C15—C16	1.386 (4)	C61—H61B	0.9800
C15—H15	0.9500	C61—H61C	0.9800

C22—Rh1—C33	86.35 (9)	C18—C17—C22	121.0 (2)
C22—Rh1—N11	81.77 (9)	C18—C17—C16	123.4 (2)
C33—Rh1—N11	92.25 (8)	C22—C17—C16	115.6 (2)
C22—Rh1—N22	94.40 (9)	C19—C18—C17	119.8 (2)
C33—Rh1—N22	81.20 (9)	C19—C18—H18	120.1
N11—Rh1—N22	172.65 (7)	C17—C18—H18	120.1
C22—Rh1—O51	174.82 (8)	C18—C19—C20	120.0 (2)
C33—Rh1—O51	92.39 (8)	C18—C19—H19	120.0
N11—Rh1—O51	93.27 (7)	C20—C19—H19	120.0
N22—Rh1—O51	90.36 (7)	C19—C20—C21	120.2 (2)
C22—Rh1—N1	91.88 (8)	C19—C20—H20	119.9
C33—Rh1—N1	177.45 (8)	C21—C20—H20	119.9
N11—Rh1—N1	89.31 (7)	C22—C21—C20	121.0 (2)
N22—Rh1—N1	97.12 (7)	C22—C21—H21	119.5
O51—Rh1—N1	89.54 (6)	C20—C21—H21	119.5
C61—O61—H2	109.5	C21—C22—C17	117.9 (2)
C51—O51—Rh1	122.08 (16)	C21—C22—Rh1	128.13 (18)
C51—O51—H1	106 (2)	C17—C22—Rh1	113.87 (17)
Rh1—O51—H1	97 (2)	N22—C23—C24	122.5 (2)
C2—N1—C6	115.77 (19)	N22—C23—H23	118.7
C2—N1—Rh1	124.30 (15)	C24—C23—H23	118.7
C6—N1—Rh1	119.75 (15)	C23—C24—C25	118.8 (3)
C4—N3—C2	126.3 (2)	C23—C24—H24	120.6
C4—N3—H3	116.9	C25—C24—H24	120.6
C2—N3—H3	116.9	C26—C25—C24	119.2 (2)
C12—N11—C16	120.0 (2)	C26—C25—H25	120.4
C12—N11—Rh1	124.73 (17)	C24—C25—H25	120.4
C16—N11—Rh1	115.20 (15)	C25—C26—C27	119.8 (2)
C23—N22—C27	119.4 (2)	C25—C26—H26	120.1
C23—N22—Rh1	125.19 (16)	C27—C26—H26	120.1
C27—N22—Rh1	115.39 (15)	N22—C27—C26	120.3 (2)
C5—C1—H1A	109.5	N22—C27—C28	113.9 (2)
C5—C1—H1B	109.5	C26—C27—C28	125.8 (2)
H1A—C1—H1B	109.5	C29—C28—C33	121.0 (2)
C5—C1—H1C	109.5	C29—C28—C27	123.8 (2)
H1A—C1—H1C	109.5	C33—C28—C27	115.3 (2)
H1B—C1—H1C	109.5	C30—C29—C28	119.8 (2)
O2—C2—N1	123.4 (2)	C30—C29—H29	120.1
O2—C2—N3	117.1 (2)	C28—C29—H29	120.1
N1—C2—N3	119.6 (2)	C29—C30—C31	120.0 (2)
O4—C4—N3	119.6 (2)	C29—C30—H30	120.0
O4—C4—C5	126.4 (2)	C31—C30—H30	120.0
N3—C4—C5	113.9 (2)	C30—C31—C32	120.6 (2)
C6—C5—C4	117.4 (2)	C30—C31—H31	119.7
C6—C5—C1	123.0 (2)	C32—C31—H31	119.7
C4—C5—C1	119.6 (2)	C31—C32—C33	120.9 (2)
C5—C6—N1	127.0 (2)	C31—C32—H32	119.5
C5—C6—H6	116.5	C33—C32—H32	119.5
N1—C6—H6	116.5	C32—C33—C28	117.7 (2)
N11—C12—C13	121.6 (2)	C32—C33—Rh1	128.05 (18)
N11—C12—H12	119.2	C28—C33—Rh1	114.24 (16)
C13—C12—H12	119.2	O51—C51—H51A	109.5
C14—C13—C12	119.0 (3)	O51—C51—H51B	109.5
C14—C13—H13	120.5	H51A—C51—H51B	109.5
C12—C13—H13	120.5	O51—C51—H51C	109.5
C13—C14—C15	119.3 (3)	H51A—C51—H51C	109.5
C13—C14—H14	120.4	H51B—C51—H51C	109.5
C15—C14—H14	120.4	O61—C61—H61A	109.5
C14—C15—C16	119.9 (3)	O61—C61—H61B	109.5
C14—C15—H15	120.0	H61A—C61—H61B	109.5
C16—C15—H15	120.0	O61—C61—H61C	109.5
N11—C16—C15	120.1 (2)	H61A—C61—H61C	109.5
N11—C16—C17	113.5 (2)	H61B—C61—H61C	109.5
C15—C16—C17	126.4 (2)

C6—N1—C2—O2	−175.8 (3)	C18—C19—C20—C21	−0.2 (4)
Rh1—N1—C2—O2	−0.7 (4)	C19—C20—C21—C22	0.5 (4)
C6—N1—C2—N3	4.4 (3)	C20—C21—C22—C17	−0.6 (3)
Rh1—N1—C2—N3	179.45 (17)	C20—C21—C22—Rh1	175.86 (18)
C4—N3—C2—O2	176.3 (2)	C18—C17—C22—C21	0.4 (3)
C4—N3—C2—N1	−3.8 (4)	C16—C17—C22—C21	178.3 (2)
C2—N3—C4—O4	−178.9 (2)	C18—C17—C22—Rh1	−176.57 (19)
C2—N3—C4—C5	0.3 (4)	C16—C17—C22—Rh1	1.4 (3)
O4—C4—C5—C6	−178.7 (2)	C27—N22—C23—C24	−0.8 (4)
N3—C4—C5—C6	2.1 (3)	Rh1—N22—C23—C24	−178.6 (2)
O4—C4—C5—C1	2.1 (4)	N22—C23—C24—C25	0.9 (5)
N3—C4—C5—C1	−177.2 (2)	C23—C24—C25—C26	0.0 (5)
C4—C5—C6—N1	−1.4 (4)	C24—C25—C26—C27	−1.0 (5)
C1—C5—C6—N1	177.9 (3)	C23—N22—C27—C26	−0.2 (4)
C2—N1—C6—C5	−2.0 (4)	Rh1—N22—C27—C26	177.76 (19)
Rh1—N1—C6—C5	−177.3 (2)	C23—N22—C27—C28	−179.4 (2)
C16—N11—C12—C13	−0.3 (4)	Rh1—N22—C27—C28	−1.5 (3)
Rh1—N11—C12—C13	176.5 (2)	C25—C26—C27—N22	1.1 (4)
N11—C12—C13—C14	−0.2 (4)	C25—C26—C27—C28	−179.8 (3)
C12—C13—C14—C15	0.0 (4)	N22—C27—C28—C29	−177.8 (2)
C13—C14—C15—C16	0.7 (5)	C26—C27—C28—C29	3.0 (4)
C12—N11—C16—C15	1.0 (3)	N22—C27—C28—C33	1.2 (3)
Rh1—N11—C16—C15	−176.1 (2)	C26—C27—C28—C33	−178.0 (2)
C12—N11—C16—C17	179.9 (2)	C33—C28—C29—C30	0.2 (4)
Rh1—N11—C16—C17	2.8 (3)	C27—C28—C29—C30	179.1 (2)
C14—C15—C16—N11	−1.2 (4)	C28—C29—C30—C31	−0.1 (4)
C14—C15—C16—C17	−180.0 (3)	C29—C30—C31—C32	0.2 (4)
N11—C16—C17—C18	175.1 (2)	C30—C31—C32—C33	−0.5 (4)
C15—C16—C17—C18	−6.0 (4)	C31—C32—C33—C28	0.6 (4)
N11—C16—C17—C22	−2.8 (3)	C31—C32—C33—Rh1	−178.35 (19)
C15—C16—C17—C22	176.1 (2)	C29—C28—C33—C32	−0.5 (3)
C22—C17—C18—C19	−0.1 (4)	C27—C28—C33—C32	−179.4 (2)
C16—C17—C18—C19	−177.9 (2)	C29—C28—C33—Rh1	178.66 (19)
C17—C18—C19—C20	0.0 (4)	C27—C28—C33—Rh1	−0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O51—H1···O2	0.84 (2)	1.69 (2)	2.527 (3)	170 (3)
N3—H3···O2ⁱ	0.88	1.97	2.844 (3)	173
O61—H2···O4ⁱⁱ	0.84	2.01	2.802 (5)	157

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, z.

(3) (OC-6-42)-Ethanol(5-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ido-κN¹)bis[2-(pyridin-2-yl)phenyl-κ²N,C¹]rhodium(III) top

Crystal data top

[Rh(C₁₁H₈N)₂(C₅H₅N₂O₂)(C₂H₆O)]·C₂H₆O	D_x = 1.479 Mg m⁻³
M_r = 628.52	Mo Kα radiation, λ = 0.71075 Å
Orthorhombic, Pbca	Cell parameters from 41739 reflections
a = 11.1082 (5) Å	θ = 3.1–27.6°
b = 15.5556 (6) Å	µ = 0.65 mm⁻¹
c = 32.6747 (15) Å	T = 192 K
V = 5646.0 (4) Å³	Block, yellow
Z = 8	0.30 × 0.20 × 0.20 mm
F(000) = 2592

Data collection top

Rigaku R-AXIS RAPID diffractometer	6470 independent reflections
Radiation source: fine-focus sealed tube	5886 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −14→14
Absorption correction: numerical (NUMABS; Rigaku, 1999)	k = −20→20
T_min = 0.829, T_max = 0.881	l = −42→40
52659 measured reflections

Refinement top

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0365P)² + 4.0646P] where P = (F_o² + 2F_c²)/3
6470 reflections	(Δ/σ)_max = 0.002
370 parameters	Δρ_max = 1.08 e Å⁻³
2 restraints	Δρ_min = −0.40 e Å⁻³

Special details top

Experimental. The ¹H NMR spectrum of 3 in CDCl₃ at 22 °C: δ 1.53 (s, 3H, Hthym CH₃), 6.17 (d, J = 7.7 Hz, 2H, ppy), 6.42 (s, 1H, Hthym C⁶-H), 6.81 (t, J = 7.4 Hz, 2H, ppy), 6.95 (t, J = 7.40 Hz, 2H, ppy), 7.28–7.30 (m, 2H, ppy), 7.58–7.61 (m, 2H, ppy), 7.88–7.92 (m, 4H, ppy), 8.10 (s, 1H, Hthym N³-H), 8.59 (d, J = 5.5 Hz, 1H, ppy) and 9.01 (d, J = 5.8 Hz, 1H, ppy).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Rh1	0.21339 (2)	0.02045 (2)	0.63615 (2)	0.02373 (6)
O2	0.04210 (14)	0.02427 (10)	0.54944 (5)	0.0446 (4)
O4	0.18318 (15)	−0.19254 (10)	0.47134 (4)	0.0420 (3)
O51	0.09395 (13)	0.11923 (9)	0.60966 (4)	0.0350 (3)
H1	0.065 (2)	0.0932 (14)	0.5896 (5)	0.042*
O61	0.2437 (4)	0.16196 (16)	0.42791 (10)	0.1286 (13)
H2	0.286 (4)	0.200 (3)	0.4388 (16)	0.154*
N1	0.20026 (14)	−0.05157 (11)	0.57654 (5)	0.0281 (3)
N3	0.11666 (15)	−0.08594 (11)	0.51266 (5)	0.0332 (4)
H3	0.0599	−0.0752	0.4946	0.040*
N11	0.36121 (14)	0.08209 (10)	0.61499 (5)	0.0284 (3)
N22	0.06964 (15)	−0.03762 (10)	0.66331 (5)	0.0303 (3)
C1	0.3788 (2)	−0.23404 (14)	0.52698 (7)	0.0427 (5)
H1A	0.4369	−0.2336	0.5496	0.051*
H1B	0.4207	−0.2223	0.5012	0.051*
H1C	0.3400	−0.2905	0.5255	0.051*
C2	0.11859 (17)	−0.03524 (13)	0.54715 (6)	0.0308 (4)
C4	0.19492 (17)	−0.15193 (13)	0.50373 (6)	0.0313 (4)
C5	0.28503 (17)	−0.16615 (12)	0.53424 (6)	0.0305 (4)
C6	0.28117 (16)	−0.11607 (13)	0.56826 (6)	0.0300 (4)
H6	0.3407	−0.1268	0.5885	0.036*
C12	0.35950 (19)	0.15538 (13)	0.59301 (6)	0.0368 (4)
H12	0.2841	0.1797	0.5856	0.044*
C13	0.4633 (2)	0.19605 (15)	0.58094 (7)	0.0445 (5)
H13	0.4598	0.2478	0.5655	0.053*
C14	0.5724 (2)	0.16073 (16)	0.59152 (8)	0.0490 (6)
H14	0.6454	0.1877	0.5834	0.059*
C15	0.57473 (19)	0.08549 (15)	0.61410 (7)	0.0430 (5)
H15	0.6496	0.0605	0.6216	0.052*
C16	0.46783 (17)	0.04653 (13)	0.62583 (6)	0.0310 (4)
C17	0.45550 (17)	−0.03176 (12)	0.65058 (6)	0.0298 (4)
C18	0.55323 (19)	−0.07910 (14)	0.66478 (7)	0.0390 (5)
H18	0.6329	−0.0618	0.6582	0.047*
C19	0.5340 (2)	−0.15135 (14)	0.68842 (7)	0.0421 (5)
H19	0.6006	−0.1835	0.6984	0.050*
C20	0.4182 (2)	−0.17709 (13)	0.69765 (6)	0.0376 (4)
H20	0.4055	−0.2267	0.7140	0.045*
C21	0.32003 (18)	−0.13088 (12)	0.68316 (6)	0.0317 (4)
H21	0.2408	−0.1495	0.6895	0.038*
C22	0.33663 (16)	−0.05717 (12)	0.65930 (5)	0.0263 (3)
C23	−0.00383 (19)	−0.09457 (14)	0.64515 (6)	0.0373 (4)
H23	0.0148	−0.1136	0.6183	0.045*
C24	−0.1053 (2)	−0.12629 (16)	0.66412 (7)	0.0475 (5)
H24	−0.1558	−0.1666	0.6507	0.057*
C25	−0.1317 (2)	−0.09808 (18)	0.70328 (7)	0.0500 (6)
H25	−0.2011	−0.1190	0.7171	0.060*
C26	−0.0573 (2)	−0.03967 (16)	0.72216 (7)	0.0428 (5)
H26	−0.0752	−0.0199	0.7490	0.051*
C27	0.04446 (18)	−0.00956 (13)	0.70185 (6)	0.0319 (4)
C28	0.13082 (18)	0.05356 (13)	0.71778 (6)	0.0315 (4)
C29	0.1252 (2)	0.08784 (14)	0.75730 (6)	0.0410 (5)
H29	0.0629	0.0706	0.7755	0.049*
C30	0.2101 (2)	0.14662 (17)	0.76979 (7)	0.0471 (6)
H30	0.2067	0.1698	0.7967	0.057*
C31	0.3000 (2)	0.17192 (15)	0.74343 (7)	0.0455 (5)
H31	0.3587	0.2123	0.7523	0.055*
C32	0.30553 (18)	0.13867 (13)	0.70386 (6)	0.0357 (4)
H32	0.3674	0.1573	0.6859	0.043*
C33	0.22157 (16)	0.07850 (12)	0.69031 (6)	0.0284 (4)
C51	0.0044 (2)	0.16798 (18)	0.62979 (8)	0.0531 (6)
H51A	0.0037	0.2267	0.6181	0.064*
H51B	0.0261	0.1730	0.6591	0.064*
C52	−0.1159 (2)	0.1322 (2)	0.62678 (9)	0.0660 (8)
H52A	−0.1196	0.0782	0.6422	0.079*
H52B	−0.1351	0.1212	0.5980	0.079*
H52C	−0.1741	0.1731	0.6381	0.079*
C61	0.2473 (4)	0.0866 (2)	0.44860 (13)	0.0826 (10)
H61A	0.2355	0.0396	0.4286	0.099*
H61B	0.1776	0.0854	0.4675	0.099*
C62	0.3536 (3)	0.0669 (2)	0.47211 (13)	0.0849 (10)
H62A	0.3677	0.1127	0.4922	0.102*
H62B	0.4231	0.0626	0.4537	0.102*
H62C	0.3423	0.0121	0.4864	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.02103 (8)	0.02848 (9)	0.02167 (8)	−0.00084 (5)	−0.00246 (5)	−0.00128 (5)
O2	0.0414 (8)	0.0577 (10)	0.0347 (8)	0.0210 (7)	−0.0152 (7)	−0.0141 (7)
O4	0.0502 (9)	0.0446 (8)	0.0313 (7)	0.0013 (7)	−0.0040 (6)	−0.0118 (6)
O51	0.0326 (7)	0.0364 (7)	0.0359 (7)	0.0067 (6)	−0.0090 (6)	−0.0056 (6)
O61	0.227 (4)	0.0573 (14)	0.101 (2)	0.0135 (19)	−0.095 (2)	−0.0207 (14)
N1	0.0277 (8)	0.0331 (8)	0.0236 (7)	0.0015 (6)	−0.0042 (6)	−0.0021 (6)
N3	0.0317 (8)	0.0428 (9)	0.0251 (7)	0.0027 (7)	−0.0081 (6)	−0.0056 (7)
N11	0.0260 (7)	0.0333 (8)	0.0260 (7)	−0.0025 (6)	−0.0026 (6)	0.0011 (6)
N22	0.0264 (8)	0.0360 (8)	0.0285 (8)	−0.0027 (7)	−0.0026 (6)	0.0006 (6)
C1	0.0490 (13)	0.0445 (12)	0.0346 (10)	0.0128 (10)	0.0014 (9)	−0.0023 (9)
C2	0.0287 (9)	0.0379 (10)	0.0258 (9)	0.0011 (8)	−0.0031 (7)	−0.0039 (7)
C4	0.0338 (10)	0.0332 (9)	0.0269 (9)	−0.0039 (8)	0.0016 (7)	−0.0011 (7)
C5	0.0338 (10)	0.0308 (9)	0.0269 (9)	0.0012 (8)	0.0018 (7)	0.0015 (7)
C6	0.0302 (10)	0.0352 (9)	0.0247 (8)	0.0015 (8)	−0.0028 (7)	0.0006 (7)
C12	0.0361 (10)	0.0391 (10)	0.0351 (10)	−0.0013 (9)	−0.0034 (8)	0.0078 (8)
C13	0.0453 (13)	0.0424 (11)	0.0458 (12)	−0.0057 (10)	0.0020 (10)	0.0147 (10)
C14	0.0367 (12)	0.0525 (13)	0.0579 (14)	−0.0114 (10)	0.0062 (10)	0.0125 (11)
C15	0.0275 (10)	0.0492 (12)	0.0521 (13)	−0.0019 (9)	0.0012 (9)	0.0080 (10)
C16	0.0269 (9)	0.0353 (9)	0.0308 (9)	−0.0014 (8)	−0.0013 (7)	−0.0008 (8)
C17	0.0266 (9)	0.0325 (9)	0.0304 (9)	−0.0005 (7)	−0.0041 (7)	−0.0015 (7)
C18	0.0274 (10)	0.0408 (11)	0.0487 (12)	0.0020 (9)	−0.0060 (9)	0.0024 (9)
C19	0.0381 (11)	0.0394 (11)	0.0487 (12)	0.0062 (9)	−0.0111 (9)	0.0050 (9)
C20	0.0487 (12)	0.0306 (9)	0.0335 (10)	0.0024 (9)	−0.0035 (9)	0.0030 (8)
C21	0.0348 (10)	0.0331 (9)	0.0271 (9)	−0.0017 (8)	−0.0004 (8)	−0.0006 (7)
C22	0.0275 (9)	0.0298 (8)	0.0217 (8)	0.0003 (7)	−0.0044 (7)	−0.0033 (7)
C23	0.0329 (10)	0.0448 (11)	0.0343 (10)	−0.0078 (9)	−0.0016 (8)	−0.0031 (9)
C24	0.0382 (12)	0.0567 (14)	0.0475 (12)	−0.0181 (11)	−0.0037 (10)	0.0005 (11)
C25	0.0351 (11)	0.0698 (16)	0.0450 (12)	−0.0142 (11)	0.0028 (10)	0.0105 (11)
C26	0.0367 (11)	0.0573 (13)	0.0344 (10)	−0.0038 (10)	0.0049 (9)	0.0038 (9)
C27	0.0290 (9)	0.0395 (10)	0.0272 (9)	0.0011 (8)	−0.0001 (7)	0.0024 (8)
C28	0.0319 (10)	0.0365 (9)	0.0262 (9)	0.0039 (8)	−0.0026 (7)	−0.0002 (8)
C29	0.0464 (12)	0.0499 (12)	0.0266 (9)	0.0052 (10)	0.0011 (9)	−0.0032 (8)
C30	0.0555 (14)	0.0558 (14)	0.0300 (10)	0.0076 (11)	−0.0072 (9)	−0.0123 (10)
C31	0.0458 (13)	0.0454 (12)	0.0455 (13)	−0.0004 (10)	−0.0135 (10)	−0.0160 (10)
C32	0.0325 (10)	0.0374 (10)	0.0373 (11)	−0.0006 (8)	−0.0039 (8)	−0.0061 (8)
C33	0.0271 (9)	0.0311 (9)	0.0269 (8)	0.0035 (7)	−0.0050 (7)	−0.0034 (7)
C51	0.0538 (15)	0.0620 (15)	0.0435 (12)	0.0242 (13)	−0.0116 (11)	−0.0180 (11)
C52	0.0464 (15)	0.099 (2)	0.0528 (15)	0.0173 (15)	0.0058 (12)	0.0035 (15)
C61	0.086 (2)	0.0521 (17)	0.110 (3)	−0.0008 (17)	−0.019 (2)	−0.0211 (18)
C62	0.090 (3)	0.0581 (18)	0.106 (3)	−0.0073 (18)	−0.012 (2)	0.0058 (18)

Geometric parameters (Å, º) top

Rh1—C22	1.9760 (18)	C18—C19	1.380 (3)
Rh1—C33	1.9890 (18)	C18—H18	0.9500
Rh1—N11	2.0232 (15)	C19—C20	1.381 (3)
Rh1—N22	2.0381 (16)	C19—H19	0.9500
Rh1—O51	2.2068 (14)	C20—C21	1.389 (3)
Rh1—N1	2.2516 (15)	C20—H20	0.9500
O2—C2	1.259 (2)	C21—C22	1.399 (3)
O4—C4	1.240 (2)	C21—H21	0.9500
O51—C51	1.414 (3)	C23—C24	1.377 (3)
O51—H1	0.833 (10)	C23—H23	0.9500
O61—C61	1.354 (4)	C24—C25	1.384 (3)
O61—H2	0.836 (10)	C24—H24	0.9500
N1—C2	1.345 (2)	C25—C26	1.375 (3)
N1—C6	1.374 (2)	C25—H25	0.9500
N3—C2	1.376 (2)	C26—C27	1.392 (3)
N3—C4	1.376 (3)	C26—H26	0.9500
N3—H3	0.8800	C27—C28	1.468 (3)
N11—C12	1.347 (2)	C28—C29	1.399 (3)
N11—C16	1.354 (2)	C28—C33	1.404 (3)
N22—C23	1.343 (3)	C29—C30	1.376 (3)
N22—C27	1.362 (3)	C29—H29	0.9500
C1—C5	1.502 (3)	C30—C31	1.377 (4)
C1—H1A	0.9800	C30—H30	0.9500
C1—H1B	0.9800	C31—C32	1.394 (3)
C1—H1C	0.9800	C31—H31	0.9500
C4—C5	1.430 (3)	C32—C33	1.393 (3)
C5—C6	1.358 (3)	C32—H32	0.9500
C6—H6	0.9500	C51—C52	1.450 (4)
C12—C13	1.373 (3)	C51—H51A	0.9900
C12—H12	0.9500	C51—H51B	0.9900
C13—C14	1.375 (3)	C52—H52A	0.9800
C13—H13	0.9500	C52—H52B	0.9800
C14—C15	1.384 (3)	C52—H52C	0.9800
C14—H14	0.9500	C61—C62	1.442 (5)
C15—C16	1.387 (3)	C61—H61A	0.9900
C15—H15	0.9500	C61—H61B	0.9900
C16—C17	1.468 (3)	C62—H62A	0.9800
C17—C18	1.391 (3)	C62—H62B	0.9800
C17—C22	1.407 (3)	C62—H62C	0.9800

C22—Rh1—C33	84.55 (7)	C18—C19—C20	120.18 (19)
C22—Rh1—N11	81.84 (7)	C18—C19—H19	119.9
C33—Rh1—N11	92.97 (7)	C20—C19—H19	119.9
C22—Rh1—N22	96.04 (7)	C19—C20—C21	120.44 (19)
C33—Rh1—N22	81.34 (7)	C19—C20—H20	119.8
N11—Rh1—N22	174.11 (6)	C21—C20—H20	119.8
C22—Rh1—O51	172.81 (7)	C20—C21—C22	120.71 (19)
C33—Rh1—O51	93.46 (6)	C20—C21—H21	119.6
N11—Rh1—O51	91.38 (6)	C22—C21—H21	119.6
N22—Rh1—O51	90.48 (6)	C21—C22—C17	117.82 (17)
C22—Rh1—N1	94.13 (6)	C21—C22—Rh1	128.53 (14)
C33—Rh1—N1	176.92 (7)	C17—C22—Rh1	113.63 (13)
N11—Rh1—N1	89.59 (6)	N22—C23—C24	122.3 (2)
N22—Rh1—N1	96.06 (6)	N22—C23—H23	118.8
O51—Rh1—N1	88.18 (5)	C24—C23—H23	118.8
C51—O51—Rh1	127.90 (14)	C23—C24—C25	118.4 (2)
C51—O51—H1	110.9 (17)	C23—C24—H24	120.8
Rh1—O51—H1	101.5 (17)	C25—C24—H24	120.8
C61—O61—H2	113 (4)	C26—C25—C24	119.8 (2)
C2—N1—C6	116.01 (16)	C26—C25—H25	120.1
C2—N1—Rh1	124.55 (13)	C24—C25—H25	120.1
C6—N1—Rh1	119.42 (12)	C25—C26—C27	119.8 (2)
C2—N3—C4	126.26 (16)	C25—C26—H26	120.1
C2—N3—H3	116.9	C27—C26—H26	120.1
C4—N3—H3	116.9	N22—C27—C26	119.99 (19)
C12—N11—C16	119.82 (17)	N22—C27—C28	114.08 (17)
C12—N11—Rh1	124.86 (13)	C26—C27—C28	125.92 (19)
C16—N11—Rh1	115.27 (12)	C29—C28—C33	121.12 (19)
C23—N22—C27	119.70 (17)	C29—C28—C27	123.58 (19)
C23—N22—Rh1	125.17 (14)	C33—C28—C27	115.30 (16)
C27—N22—Rh1	114.94 (13)	C30—C29—C28	119.8 (2)
C5—C1—H1A	109.5	C30—C29—H29	120.1
C5—C1—H1B	109.5	C28—C29—H29	120.1
H1A—C1—H1B	109.5	C29—C30—C31	120.1 (2)
C5—C1—H1C	109.5	C29—C30—H30	119.9
H1A—C1—H1C	109.5	C31—C30—H30	119.9
H1B—C1—H1C	109.5	C30—C31—C32	120.4 (2)
O2—C2—N1	123.48 (17)	C30—C31—H31	119.8
O2—C2—N3	117.38 (17)	C32—C31—H31	119.8
N1—C2—N3	119.14 (17)	C33—C32—C31	121.0 (2)
O4—C4—N3	119.64 (18)	C33—C32—H32	119.5
O4—C4—C5	126.16 (19)	C31—C32—H32	119.5
N3—C4—C5	114.19 (17)	C32—C33—C28	117.59 (18)
C6—C5—C4	117.37 (17)	C32—C33—Rh1	128.18 (15)
C6—C5—C1	123.66 (18)	C28—C33—Rh1	114.23 (13)
C4—C5—C1	118.96 (18)	O51—C51—C52	114.3 (2)
C5—C6—N1	126.91 (17)	O51—C51—H51A	108.7
C5—C6—H6	116.5	C52—C51—H51A	108.7
N1—C6—H6	116.5	O51—C51—H51B	108.7
N11—C12—C13	122.1 (2)	C52—C51—H51B	108.7
N11—C12—H12	119.0	H51A—C51—H51B	107.6
C13—C12—H12	119.0	C51—C52—H52A	109.5
C12—C13—C14	118.9 (2)	C51—C52—H52B	109.5
C12—C13—H13	120.5	H52A—C52—H52B	109.5
C14—C13—H13	120.5	C51—C52—H52C	109.5
C13—C14—C15	119.3 (2)	H52A—C52—H52C	109.5
C13—C14—H14	120.4	H52B—C52—H52C	109.5
C15—C14—H14	120.4	O61—C61—C62	118.3 (3)
C14—C15—C16	120.0 (2)	O61—C61—H61A	107.7
C14—C15—H15	120.0	C62—C61—H61A	107.7
C16—C15—H15	120.0	O61—C61—H61B	107.7
N11—C16—C15	119.87 (18)	C62—C61—H61B	107.7
N11—C16—C17	113.66 (16)	H61A—C61—H61B	107.1
C15—C16—C17	126.47 (18)	C61—C62—H62A	109.5
C18—C17—C22	121.06 (18)	C61—C62—H62B	109.5
C18—C17—C16	123.36 (18)	H62A—C62—H62B	109.5
C22—C17—C16	115.59 (16)	C61—C62—H62C	109.5
C19—C18—C17	119.8 (2)	H62A—C62—H62C	109.5
C19—C18—H18	120.1	H62B—C62—H62C	109.5
C17—C18—H18	120.1

C6—N1—C2—O2	−176.78 (19)	C19—C20—C21—C22	−0.6 (3)
Rh1—N1—C2—O2	2.0 (3)	C20—C21—C22—C17	0.0 (3)
C6—N1—C2—N3	3.7 (3)	C20—C21—C22—Rh1	−178.63 (14)
Rh1—N1—C2—N3	−177.51 (13)	C18—C17—C22—C21	0.9 (3)
C4—N3—C2—O2	177.57 (19)	C16—C17—C22—C21	−179.34 (16)
C4—N3—C2—N1	−2.9 (3)	C18—C17—C22—Rh1	179.69 (16)
C2—N3—C4—O4	−179.81 (19)	C16—C17—C22—Rh1	−0.5 (2)
C2—N3—C4—C5	−0.1 (3)	C27—N22—C23—C24	0.0 (3)
O4—C4—C5—C6	−178.4 (2)	Rh1—N22—C23—C24	−174.60 (17)
N3—C4—C5—C6	1.9 (3)	N22—C23—C24—C25	0.1 (4)
O4—C4—C5—C1	2.3 (3)	C23—C24—C25—C26	0.1 (4)
N3—C4—C5—C1	−177.40 (18)	C24—C25—C26—C27	−0.2 (4)
C4—C5—C6—N1	−1.0 (3)	C23—N22—C27—C26	−0.2 (3)
C1—C5—C6—N1	178.31 (19)	Rh1—N22—C27—C26	174.94 (16)
C2—N1—C6—C5	−1.9 (3)	C23—N22—C27—C28	−179.02 (18)
Rh1—N1—C6—C5	179.19 (16)	Rh1—N22—C27—C28	−3.9 (2)
C16—N11—C12—C13	0.1 (3)	C25—C26—C27—N22	0.3 (3)
Rh1—N11—C12—C13	177.28 (17)	C25—C26—C27—C28	179.0 (2)
N11—C12—C13—C14	0.2 (4)	N22—C27—C28—C29	−177.02 (19)
C12—C13—C14—C15	−0.2 (4)	C26—C27—C28—C29	4.3 (3)
C13—C14—C15—C16	0.0 (4)	N22—C27—C28—C33	3.2 (3)
C12—N11—C16—C15	−0.3 (3)	C26—C27—C28—C33	−175.5 (2)
Rh1—N11—C16—C15	−177.76 (16)	C33—C28—C29—C30	−0.4 (3)
C12—N11—C16—C17	178.46 (17)	C27—C28—C29—C30	179.8 (2)
Rh1—N11—C16—C17	1.0 (2)	C28—C29—C30—C31	0.3 (3)
C14—C15—C16—N11	0.3 (3)	C29—C30—C31—C32	0.3 (4)
C14—C15—C16—C17	−178.3 (2)	C30—C31—C32—C33	−0.9 (3)
N11—C16—C17—C18	179.47 (18)	C31—C32—C33—C28	0.7 (3)
C15—C16—C17—C18	−1.9 (3)	C31—C32—C33—Rh1	−178.48 (16)
N11—C16—C17—C22	−0.3 (3)	C29—C28—C33—C32	−0.1 (3)
C15—C16—C17—C22	178.3 (2)	C27—C28—C33—C32	179.67 (18)
C22—C17—C18—C19	−1.2 (3)	C29—C28—C33—Rh1	179.23 (16)
C16—C17—C18—C19	179.0 (2)	C27—C28—C33—Rh1	−1.0 (2)
C17—C18—C19—C20	0.6 (3)	Rh1—O51—C51—C52	−94.8 (2)
C18—C19—C20—C21	0.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O51—H1···O2	0.83 (1)	1.72 (2)	2.527 (2)	164 (2)
N3—H3···O2ⁱ	0.88	1.99	2.854 (2)	165
O61—H2···O4ⁱⁱ	0.84 (1)	2.01 (4)	2.792 (3)	156 (4)

Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1/2, y+1/2, z.

Acknowledgements

This work was partly supported by a Grant-in-Aid for Scientific Research No. 25410070 from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

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Volume 72| Part 4| April 2016| Pages 543-547

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