Δ-Bis[(S)-2-(4-isopropyl-4,5-di­hydro­oxazol-2-yl)phenolato-κ2N,O1](1,10-phenanthroline-κ2N,N′)ruthenium(III) hexa­fluorido­phosphate

Kelani, M.T.; Muller, A.; Lammertsma, K.

doi:10.1107/S2414314624008939

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 9| September 2024| x240893

https://doi.org/10.1107/S2414314624008939

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Δ-Bis[(S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)phenolato-κ²N,O¹](1,10-phenanthroline-κ²N,N′)ruthenium(III) hexafluoridophosphate

Monsuru T. Kelani,^a ^* Alfred Muller ^a and Koop Lammertsma ^a

^aDepartment of Chemical Sciences, University of Johannesburg, Auckland Park, 2006, Johannesburg, South Africa
^*Correspondence e-mail: mansieurkelani@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 5 September 2024; accepted 12 September 2024; online 17 September 2024)

The title compound, [Ru(C₁₂H₁₄NO₂)₂(C₁₂H₈N₂)]PF₆ crystallizes in the tetragonal Sohnke space group P4₁2₁2. The two bidentate chiral salicyloxazoline ligands and the phenanthroline co-ligand coordinate to the central Ru^III atom through N,O and N,N atom pairs to form bite angles of 89.76 (15) and 79.0 (2)°, respectively. The octahedral coordination of the bidentate ligands leads to a propeller-like shape, which induces metal-centered chirality onto the complex, with a right-handed (Δ) absolute configuration [the Flack parameter value is −0.003 (14)]. Both the complex cation and the disordered PF₆⁻ counter-anion are located on twofold rotation axes. Apart from Coulombic forces, the crystal cohesion is ensured by non-classical C—H⋯O and C—H⋯F interactions.

Keywords: crystal structure; absolute configuration; ruthenium; chiral-at-metal complex.

CCDC reference: 2383614

Structure description

The syntheses of optically pure metal complexes are usually costly and sophisticated, especially with the use of traditional methods for the resolution of racemic mixtures. A straightforward alternative strategy, therefore, requires the coordination of pure chiral auxiliary ligands tailored for the selective synthesis of diastereomers, which are easily converted to the corresponding enantiomerically pure complexes (Knof & von Zelewsky, 1999 ). Hayoz and co-workers were the first to report the diastereoselective synthesis of optically pure ruthenium polypyridyl complexes in the quest for generating compounds with metal-centered chirality, so-called chiral-at-metal complexes (Hayoz et al., 1993 ). Such metal-centered chirality refers to the type of chirality induced at a central metal atom as a result of an helical octahedral coordination around a metal in bis-chelate or tris-chelate systems. In this context, optically pure salicyloxazoline is often used as an auxiliary ligand to implement and control the absolute configuration at central metal atoms during ligand exchange. In this case, the absolute configurations at the central metal could either be right-handed or left-handed twist systems, which are symbolized by Δ and Λ stereochemical descriptors, respectively (Gong et al., 2010 ). The salicyloxazoline ligand is often used in this manner because of its reversible coordination upon acid protonation of its phenolate group while leaving the stereochemistry of the metal complex intact (Gong et al., 2009 , 2010, 2013 ).

The complex cation of the title salt constitutes of two optically pure bidentate salicyloxazoline ligands and a phenanthroline co-ligand arranged within an octahedral coordination sphere around the central Ru^III atom, which is located about a twofold rotation axis bisecting the phenantroline ligand (Fig. 1). This right-handed twist of the ligands leads to a Δ stereochemical configuration of the complex; the correctness of the absolute configuration is indicated by a Flack parameter (Parsons et al., 2013 ) value of −0.003 (14). The bite angles, 89.76 (15)°, for the salicyloxazoline ligands are comparable with reported values, e.g. 86.68° (Brunner et al., 1998 ), 88.29° (Davenport et al., 2004 ), 86.88° (Kelani et al., 2024 ), or 90.00 (Gong et al., 2010) while that for the phenanthroline ligand, 79.0 (2)°, is almost similar to that of 80.12° (Gong et al., 2010). The bond lengths of the Ru^III atom with the ligating atoms of 1.974 (3), 2.079 (4) and 2.072 (4) Å to O1, N1(phenanthroline) and N2(salicyloxazoline) atoms, respectively, also agree well with reported values. The crystal packing (Fig. 2) includes the disordered PF₆⁻ counter-anion (located about a twofold rotation axis). Non-classical intermolecular interactions featuring C—H⋯O and C—H⋯F contacts (Table 1) are present.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.95	2.59	3.102 (6)	114
C16—H16⋯O1ⁱ	1.00	2.53	3.224 (6)	126
C17—H17A⋯F3ⁱⁱ	0.98	2.52	3.464 (11)	162
C18—H18A⋯F2	0.98	2.48	3.357 (12)	149
Symmetry codes: (i) ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{7\over 4}}]$ .

Figure 1
The molecular structure of the title compound drawn with displacement ellipsoids at the 50% probability level; hydrogen atoms and the PF₆⁻ counter-anion were removed for clarity. Non-labelled atoms are generated by a twofold rotation axis (symmetry operation: y, x, –z).

Figure 2
Crystal packing arrangement of the title compound in a view along the c axis. Non-classical hydrogen-bonding interactions are indicated by dotted lines.

Synthesis and crystallization

Dichlorido-bis(1,10-phenanthroline)ruthenium(II) (50.0 mg, 0.09 mmol, 1 eq) was added to (S)-isopropyl-2-(2-hydroxyphenyl)oxazoline (38.5 mg, 0.2 mmol, 2 eq) in ethanol in the presence of K₂CO₃ (26.0 mg, 0.2 mmol, 2 eq). The reaction mixture was refluxed for 6 h under continuous stirring after which it was cooled to room temperature and then concentrated in vacuo under reduced pressure. The crude product was purified by column chromatography with silica gel using a solvent system of CH₂Cl₂:CH₃OH:CH₃CN = 9.7:0.2:0.1 v:v:v) to obtain a purple crystalline compound. Yield, 31 mg (46%, 0.04 mmol).

Refinement

Details of the data collection, solution and refinement are given in Table 2. The disordered PF₆⁻ anion was treated as equally disordered around the twofold rotation axis and was kept stable with SADI, SIMU and DELU restraints in SHELXL (Sheldrick, 2015b ). The highest remaining maximum and minimum electron density are 1.32 and 0.76 Å away from F1A and Ru1, respectively.

Table 2
Experimental details

Crystal data
Chemical formula	[Ru(C₁₂H₁₄NO₂)₂(C₁₂H₈N₂)]PF₆
M_r	834.73
Crystal system, space group	Tetragonal, P4₁2₁2
Temperature (K)	173
a, c (Å)	15.3094 (13), 15.315 (2)
V (Å³)	3589.5 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.56
Crystal size (mm)	0.46 × 0.43 × 0.42

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.638, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	53896, 4516, 3564
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.107, 1.04
No. of reflections	4516
No. of parameters	245
No. of restraints	26
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.41
Absolute structure	Flack x determined using 1296 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	−0.003 (14)
Computer programs: APEX2 and SAINT (Bruker, 2010 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b), Mercury (Macrae et al.., 2020 ), publCIF (Westrip, 2010 ) and WinGX (Farrugia, 2012 ).

Structural data

CCDC reference: 2383614

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624008939/wm4221sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624008939/wm4221Isup3.hkl

checkCIF report

Computing details top

Δ-Bis[(S)-2-(4-isopropyl-4,5-dihydrooxazol-2-yl)phenolato-κ²N,O¹](1,10-phenanthroline-κ²N,N')ruthenium(III) hexafluoridophosphate top

Crystal data top

[Ru(C₁₂H₁₄NO₂)₂(C₁₂H₈N₂)]PF₆	D_x = 1.545 Mg m⁻³
M_r = 834.73	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₁2₁2	Cell parameters from 8341 reflections
a = 15.3094 (13) Å	θ = 2.3–20.4°
c = 15.315 (2) Å	µ = 0.56 mm⁻¹
V = 3589.5 (8) Å³	T = 173 K
Z = 4	Cuboid, purple
F(000) = 1700	0.46 × 0.43 × 0.42 mm

Data collection top

Bruker APEXII CCD diffractometer	4516 independent reflections
Radiation source: sealed-tube	3564 reflections with I > 2σ(I)
Triumph monochromator	R_int = 0.067
φ and ω scans	θ_max = 28.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −20→20
T_min = 0.638, T_max = 0.746	k = −20→20
53896 measured reflections	l = −20→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0587P)² + 0.7144P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
4516 reflections	Δρ_max = 0.38 e Å⁻³
245 parameters	Δρ_min = −0.41 e Å⁻³
26 restraints	Absolute structure: Flack x determined using 1296 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.003 (14)

Special details top

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	Occ. (<1)
C1	0.2882 (4)	0.4278 (4)	0.6429 (3)	0.0615 (13)
H1	0.237967	0.400278	0.666771	0.074*
C2	0.3215 (4)	0.5005 (4)	0.6832 (4)	0.0760 (18)
H2	0.294934	0.521584	0.735125	0.091*
C3	0.3917 (5)	0.5426 (4)	0.6499 (4)	0.0828 (19)
H3	0.412522	0.594417	0.676826	0.099*
C4	0.4345 (4)	0.5090 (4)	0.5742 (4)	0.0615 (13)
C5	0.3979 (3)	0.4353 (3)	0.5381 (3)	0.0463 (10)
C6	0.5100 (4)	0.5455 (4)	0.5356 (4)	0.0723 (16)
H6	0.535851	0.595990	0.560765	0.087*
C7	0.3015 (3)	0.1129 (3)	0.4108 (3)	0.0539 (12)
C8	0.2786 (4)	0.0607 (4)	0.3381 (3)	0.0678 (14)
H8	0.238849	0.082913	0.295931	0.081*
C9	0.3130 (5)	−0.0217 (4)	0.3273 (4)	0.0815 (19)
H9	0.295857	−0.055716	0.278301	0.098*
C10	0.3710 (5)	−0.0552 (4)	0.3853 (5)	0.0852 (19)
H10	0.393287	−0.112595	0.377536	0.102*
C11	0.3975 (4)	−0.0054 (4)	0.4556 (5)	0.0759 (17)
H11	0.439237	−0.028411	0.495301	0.091*
C12	0.3633 (4)	0.0795 (3)	0.4695 (3)	0.0592 (12)
C13	0.3904 (3)	0.1261 (4)	0.5476 (3)	0.0553 (12)
C14	0.4704 (4)	0.1478 (5)	0.6678 (4)	0.0838 (19)
H14A	0.529714	0.171713	0.658200	0.101*
H14B	0.468526	0.119533	0.725909	0.101*
C15	0.4011 (3)	0.2208 (4)	0.6615 (3)	0.0618 (13)
H15	0.430056	0.279348	0.662139	0.074*
C16	0.3308 (4)	0.2163 (4)	0.7321 (3)	0.0730 (15)
H16	0.285475	0.260943	0.717068	0.088*
C17	0.2847 (5)	0.1280 (5)	0.7371 (4)	0.102 (2)
H17A	0.240548	0.129560	0.783417	0.152*
H17B	0.256291	0.115575	0.681064	0.152*
H17C	0.327529	0.082258	0.749904	0.152*
C18	0.3698 (6)	0.2424 (7)	0.8209 (4)	0.122 (3)
H18A	0.398851	0.299210	0.815570	0.183*
H18B	0.323026	0.246367	0.864392	0.183*
H18C	0.412379	0.198299	0.839249	0.183*
N1	0.3248 (2)	0.3946 (3)	0.5709 (2)	0.0483 (9)
N2	0.3638 (3)	0.2026 (3)	0.5728 (2)	0.0523 (9)
O1	0.2614 (2)	0.1896 (2)	0.4175 (2)	0.0570 (9)
O2	0.4479 (3)	0.0854 (3)	0.5994 (3)	0.0767 (11)
F1A	0.6349 (16)	0.2780 (8)	0.7374 (14)	0.203 (8)	0.5
F1B	0.6026 (17)	0.3041 (13)	0.8114 (17)	0.250 (11)	0.5
F2	0.5257 (5)	0.3866 (6)	0.7660 (8)	0.247 (5)
F3	0.6459 (7)	0.4151 (7)	0.8395 (6)	0.241 (4)
P1	0.6246 (2)	0.3754 (2)	0.750000	0.1405 (16)
Ru1	0.28566 (2)	0.28566 (2)	0.500000	0.04461 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.049 (3)	0.084 (4)	0.051 (2)	0.001 (3)	0.006 (2)	−0.025 (2)
C2	0.064 (3)	0.093 (4)	0.072 (3)	0.001 (3)	0.007 (3)	−0.046 (3)
C3	0.096 (5)	0.072 (4)	0.080 (4)	0.000 (3)	−0.015 (4)	−0.036 (3)
C4	0.060 (3)	0.062 (3)	0.063 (3)	−0.004 (2)	−0.009 (3)	−0.013 (3)
C5	0.046 (2)	0.048 (2)	0.046 (2)	0.0082 (19)	−0.0020 (19)	−0.0070 (19)
C6	0.067 (4)	0.060 (3)	0.090 (4)	−0.017 (3)	−0.005 (3)	−0.006 (3)
C7	0.063 (3)	0.050 (3)	0.049 (2)	−0.013 (2)	0.009 (2)	−0.0008 (19)
C8	0.076 (4)	0.068 (3)	0.060 (3)	−0.015 (3)	0.009 (3)	−0.015 (3)
C9	0.098 (5)	0.065 (4)	0.081 (4)	−0.015 (3)	0.020 (4)	−0.025 (3)
C10	0.091 (5)	0.059 (4)	0.106 (5)	−0.001 (3)	0.021 (4)	−0.018 (4)
C11	0.069 (4)	0.060 (3)	0.099 (4)	0.001 (3)	0.020 (3)	−0.003 (3)
C12	0.063 (3)	0.056 (3)	0.060 (3)	−0.006 (2)	0.013 (2)	0.005 (2)
C13	0.055 (3)	0.057 (3)	0.054 (3)	−0.001 (2)	0.004 (2)	0.004 (2)
C14	0.078 (4)	0.108 (5)	0.066 (3)	0.011 (4)	−0.018 (3)	0.017 (4)
C15	0.063 (3)	0.073 (3)	0.049 (2)	−0.003 (3)	−0.012 (2)	0.005 (3)
C16	0.076 (3)	0.098 (4)	0.044 (3)	−0.001 (4)	−0.003 (2)	0.001 (3)
C17	0.110 (5)	0.124 (6)	0.071 (4)	−0.029 (5)	0.013 (4)	0.019 (4)
C18	0.125 (6)	0.195 (10)	0.047 (3)	−0.025 (6)	−0.005 (4)	−0.020 (4)
N1	0.042 (2)	0.061 (2)	0.0424 (18)	0.0039 (17)	−0.0001 (16)	−0.0117 (17)
N2	0.054 (2)	0.064 (3)	0.0390 (16)	−0.0075 (19)	−0.0008 (16)	0.0044 (19)
O1	0.071 (2)	0.0503 (19)	0.0500 (17)	−0.0074 (16)	−0.0063 (16)	−0.0046 (14)
O2	0.082 (3)	0.072 (3)	0.075 (3)	0.009 (2)	−0.015 (2)	0.012 (2)
F1A	0.29 (2)	0.091 (7)	0.225 (17)	0.020 (10)	−0.067 (18)	−0.003 (11)
F1B	0.24 (2)	0.145 (16)	0.36 (3)	−0.025 (16)	0.01 (2)	0.080 (16)
F2	0.149 (6)	0.235 (9)	0.357 (14)	−0.025 (6)	−0.022 (8)	−0.047 (11)
F3	0.268 (10)	0.262 (11)	0.194 (8)	−0.019 (9)	−0.078 (8)	−0.046 (8)
P1	0.1223 (17)	0.1223 (17)	0.177 (4)	−0.025 (2)	−0.051 (2)	−0.051 (2)
Ru1	0.04954 (19)	0.04954 (19)	0.0347 (2)	−0.0046 (2)	0.00213 (16)	−0.00213 (16)

Geometric parameters (Å, º) top

C1—N1	1.337 (5)	C13—N2	1.299 (7)
C1—C2	1.370 (8)	C13—O2	1.338 (6)
C1—H1	0.9500	C14—O2	1.458 (7)
C2—C3	1.353 (9)	C14—C15	1.544 (8)
C2—H2	0.9500	C14—H14A	0.9900
C3—C4	1.426 (8)	C14—H14B	0.9900
C3—H3	0.9500	C15—N2	1.499 (6)
C4—C5	1.375 (7)	C15—C16	1.528 (7)
C4—C6	1.414 (8)	C15—H15	1.0000
C5—N1	1.376 (6)	C16—C17	1.527 (10)
C5—C5ⁱ	1.421 (8)	C16—C18	1.538 (8)
C6—C6ⁱ	1.335 (12)	C16—H16	1.0000
C6—H6	0.9500	C17—H17A	0.9800
C7—O1	1.329 (6)	C17—H17B	0.9800
C7—C12	1.402 (7)	C17—H17C	0.9800
C7—C8	1.414 (7)	C18—H18A	0.9800
C8—C9	1.377 (9)	C18—H18B	0.9800
C8—H8	0.9500	C18—H18C	0.9800
C9—C10	1.356 (10)	N1—Ru1	2.079 (4)
C9—H9	0.9500	N2—Ru1	2.072 (4)
C10—C11	1.380 (9)	O1—Ru1	1.974 (3)
C10—H10	0.9500	F1A—P1	1.512 (12)
C11—C12	1.418 (8)	F1B—P1	1.479 (14)
C11—H11	0.9500	F2—P1	1.544 (8)
C12—C13	1.453 (7)	F3—P1	1.535 (8)

N1—C1—C2	121.6 (5)	H17A—C17—H17B	109.5
N1—C1—H1	119.2	C16—C17—H17C	109.5
C2—C1—H1	119.2	H17A—C17—H17C	109.5
C3—C2—C1	120.8 (5)	H17B—C17—H17C	109.5
C3—C2—H2	119.6	C16—C18—H18A	109.5
C1—C2—H2	119.6	C16—C18—H18B	109.5
C2—C3—C4	120.0 (5)	H18A—C18—H18B	109.5
C2—C3—H3	120.0	C16—C18—H18C	109.5
C4—C3—H3	120.0	H18A—C18—H18C	109.5
C5—C4—C6	119.3 (5)	H18B—C18—H18C	109.5
C5—C4—C3	115.8 (5)	C1—N1—C5	118.0 (4)
C6—C4—C3	124.9 (5)	C1—N1—Ru1	127.9 (4)
C4—C5—N1	123.8 (4)	C5—N1—Ru1	114.1 (3)
C4—C5—C5ⁱ	119.8 (3)	C13—N2—C15	108.5 (4)
N1—C5—C5ⁱ	116.4 (2)	C13—N2—Ru1	125.1 (3)
C6ⁱ—C6—C4	120.9 (3)	C15—N2—Ru1	126.4 (4)
C6ⁱ—C6—H6	119.5	C7—O1—Ru1	128.4 (3)
C4—C6—H6	119.5	C13—O2—C14	106.1 (4)
O1—C7—C12	125.7 (4)	F1B—P1—F1Bⁱⁱ	138 (2)
O1—C7—C8	116.5 (5)	F1B—P1—F1Aⁱⁱ	93.8 (14)
C12—C7—C8	117.8 (5)	F1Bⁱⁱ—P1—F1Aⁱⁱ	51.5 (10)
C9—C8—C7	121.1 (6)	F1A—P1—F1Aⁱⁱ	79.1 (18)
C9—C8—H8	119.4	F1B—P1—F3	76.9 (11)
C7—C8—H8	119.4	F1Bⁱⁱ—P1—F3	108.7 (11)
C10—C9—C8	121.2 (6)	F1A—P1—F3	118.9 (9)
C10—C9—H9	119.4	F1Aⁱⁱ—P1—F3	73.6 (8)
C8—C9—H9	119.4	F1B—P1—F3ⁱⁱ	108.7 (11)
C9—C10—C11	119.6 (6)	F1Bⁱⁱ—P1—F3ⁱⁱ	76.9 (11)
C9—C10—H10	120.2	F1A—P1—F3ⁱⁱ	73.6 (8)
C11—C10—H10	120.2	F1Aⁱⁱ—P1—F3ⁱⁱ	118.9 (9)
C10—C11—C12	121.0 (7)	F3—P1—F3ⁱⁱ	165.1 (9)
C10—C11—H11	119.5	F1B—P1—F2	75.9 (10)
C12—C11—H11	119.5	F1Bⁱⁱ—P1—F2	143.1 (12)
C7—C12—C11	119.1 (5)	F1A—P1—F2	103.4 (10)
C7—C12—C13	122.9 (5)	F1Aⁱⁱ—P1—F2	163.5 (9)
C11—C12—C13	117.9 (5)	F3—P1—F2	91.3 (7)
N2—C13—O2	116.7 (4)	F3ⁱⁱ—P1—F2	77.1 (5)
N2—C13—C12	126.7 (5)	F1B—P1—F2ⁱⁱ	143.1 (12)
O2—C13—C12	116.6 (5)	F1Bⁱⁱ—P1—F2ⁱⁱ	75.9 (10)
O2—C14—C15	105.4 (4)	F1A—P1—F2ⁱⁱ	163.5 (9)
O2—C14—H14A	110.7	F1Aⁱⁱ—P1—F2ⁱⁱ	103.4 (10)
C15—C14—H14A	110.7	F3—P1—F2ⁱⁱ	77.1 (5)
O2—C14—H14B	110.7	F3ⁱⁱ—P1—F2ⁱⁱ	91.3 (7)
C15—C14—H14B	110.7	F2—P1—F2ⁱⁱ	78.9 (8)
H14A—C14—H14B	108.8	O1—Ru1—O1ⁱ	97.4 (2)
N2—C15—C16	111.3 (4)	O1—Ru1—N2	89.76 (15)
N2—C15—C14	100.6 (4)	O1ⁱ—Ru1—N2	88.30 (15)
C16—C15—C14	114.1 (5)	O1—Ru1—N2ⁱ	88.30 (15)
N2—C15—H15	110.2	O1ⁱ—Ru1—N2ⁱ	89.77 (15)
C16—C15—H15	110.2	N2—Ru1—N2ⁱ	177.1 (2)
C14—C15—H15	110.2	O1—Ru1—N1	170.53 (15)
C17—C16—C15	113.6 (5)	O1ⁱ—Ru1—N1	91.80 (15)
C17—C16—C18	111.4 (5)	N2—Ru1—N1	92.57 (16)
C15—C16—C18	109.9 (5)	N2ⁱ—Ru1—N1	89.70 (15)
C17—C16—H16	107.2	O1—Ru1—N1ⁱ	91.80 (15)
C15—C16—H16	107.2	O1ⁱ—Ru1—N1ⁱ	170.53 (15)
C18—C16—H16	107.2	N2—Ru1—N1ⁱ	89.70 (15)
C16—C17—H17A	109.5	N2ⁱ—Ru1—N1ⁱ	92.56 (16)
C16—C17—H17B	109.5	N1—Ru1—N1ⁱ	79.0 (2)

N1—C1—C2—C3	1.6 (10)	O2—C14—C15—N2	−15.9 (6)
C1—C2—C3—C4	−2.9 (11)	O2—C14—C15—C16	103.4 (5)
C2—C3—C4—C5	2.0 (9)	N2—C15—C16—C17	58.9 (7)
C2—C3—C4—C6	−177.6 (7)	C14—C15—C16—C17	−54.2 (7)
C6—C4—C5—N1	179.7 (5)	N2—C15—C16—C18	−175.5 (6)
C3—C4—C5—N1	0.1 (8)	C14—C15—C16—C18	71.4 (8)
C6—C4—C5—C5ⁱ	−1.3 (9)	C2—C1—N1—C5	0.5 (8)
C3—C4—C5—C5ⁱ	179.1 (6)	C2—C1—N1—Ru1	179.8 (5)
C5—C4—C6—C6ⁱ	0.8 (11)	C4—C5—N1—C1	−1.3 (7)
C3—C4—C6—C6ⁱ	−179.6 (7)	C5ⁱ—C5—N1—C1	179.6 (5)
O1—C7—C8—C9	−176.8 (5)	C4—C5—N1—Ru1	179.2 (4)
C12—C7—C8—C9	2.8 (8)	C5ⁱ—C5—N1—Ru1	0.2 (6)
C7—C8—C9—C10	−1.0 (10)	O2—C13—N2—C15	−5.2 (6)
C8—C9—C10—C11	−1.2 (10)	C12—C13—N2—C15	173.8 (5)
C9—C10—C11—C12	1.6 (10)	O2—C13—N2—Ru1	173.3 (3)
O1—C7—C12—C11	177.1 (5)	C12—C13—N2—Ru1	−7.7 (7)
C8—C7—C12—C11	−2.4 (7)	C16—C15—N2—C13	−108.2 (5)
O1—C7—C12—C13	1.0 (8)	C14—C15—N2—C13	13.0 (6)
C8—C7—C12—C13	−178.5 (5)	C16—C15—N2—Ru1	73.3 (6)
C10—C11—C12—C7	0.3 (8)	C14—C15—N2—Ru1	−165.4 (4)
C10—C11—C12—C13	176.5 (5)	C12—C7—O1—Ru1	8.7 (7)
C7—C12—C13—N2	−1.2 (8)	C8—C7—O1—Ru1	−171.7 (3)
C11—C12—C13—N2	−177.3 (5)	N2—C13—O2—C14	−5.9 (6)
C7—C12—C13—O2	177.9 (5)	C12—C13—O2—C14	175.0 (5)
C11—C12—C13—O2	1.7 (7)	C15—C14—O2—C13	13.9 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.95	2.59	3.102 (6)	114
C16—H16···O1ⁱ	1.00	2.53	3.224 (6)	126
C17—H17A···F3ⁱⁱⁱ	0.98	2.52	3.464 (11)	162
C18—H18A···F2	0.98	2.48	3.357 (12)	149

Symmetry codes: (i) y, x, −z+1; (iii) x−1/2, −y+1/2, −z+7/4.

Acknowledgements

We thank Dr B. Vatsha at the Department of Chemical Sciences, University of Johannesburg, for the opportunity provided towards the collection of the data.

Funding information

Funding for this research was provided by: National Research Foundation (grant No. 120842).

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