trans-Chlorido­tetra­kis­(4-methyl­pyridine-κN)(nitrosyl-κN)ruthenium(II) bis­(hexa­fluorido­phosphate) acetone 0.75-solvate

Shamran Mohammed, H.; Mallet-Ladeira, S.; Cormary, B.; Tassé, M.; Malfant, I.

doi:10.1107/S2414314617017618

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 12| December 2017| x171761

https://doi.org/10.1107/S2414314617017618

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trans-Chloridotetrakis(4-methylpyridine-κN)(nitrosyl-κN)ruthenium(II) bis(hexafluoridophosphate) acetone 0.75-solvate

Hasan Shamran Mohammed,^a Sonia Mallet-Ladeira,^a ^* Benoit Cormary,^a Marine Tassé ^a and Isabelle Malfant ^a

^aLaboratoire de Chimie de Coordination, UPR-CNRS 8241, 205, route de Narbonne, 31077 Toulouse cedex, France
^*Correspondence e-mail: sonia.ladeira@lcc-toulouse.fr

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 25 October 2017; accepted 8 December 2017; online 15 December 2017)

The title compound, [RuCl(NO)(C₆H₇N)₄](PF₆)₂·0.75(CH₃)₂CO, comprises four ligands of 4-picoline in equatorial position around the central atom. Overall, the complex features an octahedral coordination environment around the central Ru^II atom, with the chlorido ligand trans to the nitrosyl. The bond length of the nitrosyl N=O ligand is 1.140 (5) Å, while the angle Ru—N=O is 179.0 (4)°. The asymmetric unit contains four PF₆⁻ counter-anions, two with occupancy of 0.25 and one with occupancy of 0.5. One PF₆⁻ anion is disordered over two sets of sites and one other is disordered with an acetone molecule that occupies the same site.

Keywords: crystal structure; ruthenium nitrosyl; picoline; compressed octahedral coordination environment; nitric oxide.

CCDC reference: 1590068

Structure description

Ruthenium nitrosyl complexes with substituted pyridine ligands possess unique photochromic properties such as Ru(NO) $[\longleftrightarrow]$ Ru(ON) photoisomerization, which could allow for their use as high data storage optics and sensors (Schaniel et al., 2007 ; García et al., 2016 ). In addition, nitric oxide donors such as ruthenium(II) nitrosyl complexes are capable of releasing NO upon irradiation (De Candia et al., 2010 ) and could find use as a means of inducing apoptosis in living beings (Kumar et al., 2015 ), as antimicrobial agents (Schairer et al., 2012 ) and as a way to help wounds heal (Childress et al., 2008 ).

The asymmetric unit of the title salt (Fig. 1) is composed of a trans-[Ru(C₆H₇N)₄Cl(NO)]²⁺ cation and two PF₆⁻ anions (the asymmetric unit contains four sites for PF₆⁻ anions with different occupancies). The Ru^II atom of the trans-[Ru(C₆H₇N)₄Cl(NO)]²⁺ cation features a compressed octahedral coordination sphere with the four N atoms of the 4-picoline ligands in the equatorial positions, and chlorido and nitrosyl ligands located at the trans axial sites. The N1=O1 bond length is 1.140 (5) Å, which is in the range of N=O groups in other examples of octahedral Ru^II–NO⁺ complexes, but shorter than the N=O bond of trans-[Ru(py)₄(Cl)(NO)](PF₆)₂ which is 1.146 (2) Å (Cormary et al., 2009a ,b ), and longer than the N=O bond of trans-[Ru(4-Clpy)₄(Cl)(NO)](PF₆)₂ (Tassé et al., 2016 ), which is 1.125 (5) Å. These differences are due to the substituents (electron donating or withdrawing) on the pyridine ligands. The Ru1—N1=O1 angle is essentially linear [179.0 (4)]°, which implies that the {Ru^IINO⁺}⁶ should be {Ru^IINO⁺}₆ (McCleverty, 2004 ).

Figure 1
The structures of the molecular entities in the title salt with the atom numbering. Displacement ellipsoids are drawn at the 50% probability level. The acetone molecule (open bond) is disordered with one hexafluoridophosphate anion. Hydrogen atoms are omitted for clarity.

The Ru1—Cl1 bond length in the position trans to nitrosyl is 2.3163 (11) Å, which is shorter than that observed in trans-[Ru(py)₄ClNO](PF₆)₂ (2.3206 Å; Cormary et al., 2012 ). The length of the Ru—Cl bond in other complexes without nitrosyl, as trans(Cl,pyz)-[Ru(py)₄Cl(pyz)]PF₆ and trans-(Cl,PhCN)-[Ru(py)₄Cl(PhCN)]PF₆ are 2.415 and 2.3931 Å, respectively (Coe et al., 1995 ), reflecting the ability of nitrosyl as a π acceptor and the ability of chlorido ligand as a good σ donor. The Ru1—N1 distance is 1.757 (4) Å, in agreement with the Ru—N distances found in other ruthenium(II) nitrosyl complexes (Ferlay et al., 2004 ), which is further supported by the stretching vibration of nitrosyl, which is 1895 cm⁻¹ (Becker et al., 2015 ; Sauaia & da Silva, 2003 ; Togano et al., 1992 ).

The overall packing shows the presence of rows of cations with PF₆⁻ anions and acetone molecules inserted in between (Fig. 2). The investigation of the interactions in the crystal shows that C—H⋯F hydrogen bonds (Table 1) are dominant (Mohammed et al., 2017 ; Cormary et al., 2009a,b).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯F8	0.95	2.47	3.194 (12)	133
C1—H1⋯F11	0.95	2.48	3.405 (15)	165
C1—H1⋯F10′	0.95	2.3	3.243 (18)	173
C5—H5⋯F3	0.95	2.49	3.328 (6)	147
C7—H7⋯O2	0.95	2.45	3.320 (7)	153
C7—H7⋯F20	0.95	2.51	3.264 (18)	136
C13—H13⋯F22ⁱ	0.95	2.54	3.16 (2)	123
C13—H13⋯F23ⁱ	0.95	2.26	3.047 (18)	140
C14—H14⋯F19ⁱ	0.95	2.4	2.995 (18)	120
C27—H27A⋯F7	0.98	2.41	3.297 (17)	150
C27—H27B⋯F7ⁱⁱ	0.98	2.55	3.418 (17)	147
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+2, -z.

Figure 2
Crystal packing of trans-[Ru(C₆H₇N)₄Cl(NO)](PF₆)₂·0.75(CH₃)₂CO viewed along the b axis, showing cationic rows. Hydrogen atoms and solvent molecules are omitted for clarity.

Synthesis and crystallization

According to literature reports (Cormary et al., 2009a,b), four steps are required to synthesize trans-[Ru(py)₄(Cl)(NO)](PF₆)₂, where the pyridine acts as both a solvent and a ligand. However, in our case, we used ethanol as a solvent, and 4-picoline instead of pyridine, which afforded an orange solid in good yield (142 mg, 81.5%). ¹H NMR (400 MHz, acetone d₆, 298 K): δ (p.p.m.) 8.58 (8Hα, d, J = 6.4 Hz), 7.67 (8Hβ, d, J = 6.0 Hz), 2.61 (12H, s, CH₃). Crystals of the title complex were grown by slow diffusion of diethyl ether vapour into acetone solution over the course of one week.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The asymmetric unit contains four PF₆⁻ counter-anions, two with occupancy of 0.25 and one with occupancy of 0.5. One PF₆⁻ anion is disordered over two sets of sites and one other is disordered with an acetone molecule that occupies the same site. Similarity restraints on bond lengths and angles as well as on displacement parameters were used to model those disorders.

Table 2
Experimental details

Crystal data
Chemical formula	[RuCl(NO)(C₆H₇N)₄](PF₆)₂·0.75C₃H₆O
M_r	872.53
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	11.9904 (7), 12.0159 (8), 13.4432 (9)
α, β, γ (°)	107.065 (2), 98.270 (2), 90.388 (2)
V (Å³)	1829.8 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.68
Crystal size (mm)	0.20 × 0.16 × 0.02

Data collection
Diffractometer	Bruker Kappa APEXII Quazar
Absorption correction	Multi-scan (SADABS; Bruker, 2005 )
T_min, T_max	0.708, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	56033, 6707, 6081
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.149, 1.05
No. of reflections	6707
No. of parameters	635
No. of restraints	441
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.97, −1.45
Computer programs: APEX2 and SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008 ), SHELXL2016/6 (Sheldrick, 2015 ) and ORTEP-3 for Windows and WinGX publication routines (Farrugia, 2012 ).

Structural data

CCDC reference: 1590068

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617017618/bh4031sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617017618/bh4031Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

trans-Chloridotetrakis(4-methylpyridine-κN)(nitrosyl-κN)ruthenium(II) bis(hexafluoridophosphate) acetone 0.75-solvate top

Crystal data top

[RuCl(NO)(C₆H₇N)₄](PF₆)₂·0.75C₃H₆O	Z = 2
M_r = 872.53	F(000) = 876.0
Triclinic, P1	D_x = 1.584 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.9904 (7) Å	Cell parameters from 9786 reflections
b = 12.0159 (8) Å	θ = 2.4–30.8°
c = 13.4432 (9) Å	µ = 0.68 mm⁻¹
α = 107.065 (2)°	T = 100 K
β = 98.270 (2)°	Plate, orange
γ = 90.388 (2)°	0.20 × 0.16 × 0.02 mm
V = 1829.8 (2) Å³

Data collection top

Bruker Kappa APEXII Quazar diffractometer	6707 independent reflections
Radiation source: microfocus sealed tube	6081 reflections with I > 2σ(I)
Multilayer optics monochromator	R_int = 0.039
phi and ω scans	θ_max = 25.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→14
T_min = 0.708, T_max = 0.747	k = −14→14
56033 measured reflections	l = −16→16

Refinement top

Refinement on F²	441 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0779P)² + 9.4314P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.017
6707 reflections	Δρ_max = 1.97 e Å⁻³
635 parameters	Δρ_min = −1.45 e Å⁻³

Special details top

Refinement. All H atoms were fixed geometrically and treated as riding with C—H = 0.95 Å (aromatic), 0.98 Å (methyl) and U_iso(H) =1.2U_eq (aromatic) or U_iso(H) =1.5U_eq (methyl).

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.6304 (4)	0.8881 (4)	0.2326 (4)	0.0309 (11)
H1	0.68539	0.869211	0.186822	0.037*
C2	0.5718 (4)	0.9868 (4)	0.2372 (4)	0.0305 (11)
H2	0.58711	1.035077	0.195609	0.037*
C3	0.4900 (4)	1.0160 (4)	0.3028 (4)	0.0228 (9)
C4	0.4713 (4)	0.9410 (4)	0.3609 (3)	0.0201 (9)
H4	0.41542	0.956975	0.405965	0.024*
C5	0.5332 (4)	0.8437 (4)	0.3534 (3)	0.0197 (9)
H5	0.519163	0.793754	0.393985	0.024*
C6	0.4249 (4)	1.1235 (4)	0.3076 (5)	0.0325 (11)
H6A	0.47542	1.186481	0.304613	0.049*
H6B	0.393169	1.14739	0.373452	0.049*
H6C	0.363563	1.106626	0.247743	0.049*
C7	0.4743 (4)	0.5714 (4)	0.2188 (3)	0.0206 (9)
H7	0.474273	0.614333	0.169697	0.025*
C8	0.3770 (4)	0.5116 (4)	0.2197 (4)	0.0222 (9)
H8	0.31122	0.513874	0.171832	0.027*
C9	0.3740 (4)	0.4475 (4)	0.2903 (4)	0.0211 (9)
C10	0.4744 (4)	0.4457 (4)	0.3566 (4)	0.0224 (9)
H10	0.476949	0.401414	0.404821	0.027*
C11	0.5696 (4)	0.5074 (4)	0.3527 (3)	0.0195 (9)
H11	0.63686	0.504821	0.398712	0.023*
C12	0.2682 (4)	0.3837 (5)	0.2947 (4)	0.0330 (11)
H12A	0.205913	0.43656	0.299461	0.05*
H12B	0.278812	0.355418	0.356539	0.05*
H12C	0.250384	0.317457	0.2308	0.05*
C13	0.7807 (4)	0.4245 (4)	0.2301 (4)	0.0238 (10)
H13	0.711679	0.413394	0.182935	0.029*
C14	0.8425 (4)	0.3295 (4)	0.2337 (4)	0.0256 (10)
H14	0.814992	0.254036	0.190147	0.031*
C15	0.9449 (4)	0.3427 (4)	0.3005 (4)	0.0206 (9)
C16	0.9802 (4)	0.4553 (4)	0.3614 (3)	0.0212 (9)
H16	1.050219	0.468697	0.407369	0.025*
C17	0.9153 (4)	0.5477 (4)	0.3561 (3)	0.0201 (9)
H17	0.941325	0.623879	0.398905	0.024*
C18	1.0115 (4)	0.2393 (4)	0.3056 (4)	0.0312 (11)
H18A	0.95983	0.17214	0.295993	0.047*
H18B	1.059468	0.256666	0.374287	0.047*
H18C	1.058811	0.221271	0.249774	0.047*
C19	0.9380 (4)	0.7351 (4)	0.2357 (4)	0.0267 (10)
H19	0.927469	0.657448	0.190019	0.032*
C20	1.0349 (4)	0.7994 (5)	0.2391 (4)	0.0303 (11)
H20	1.09018	0.765519	0.196932	0.036*
C21	1.0520 (4)	0.9135 (4)	0.3042 (4)	0.0277 (10)
C22	0.9687 (4)	0.9581 (4)	0.3645 (4)	0.0274 (10)
H22	0.976902	1.036021	0.409572	0.033*
C23	0.8739 (4)	0.8894 (4)	0.3589 (4)	0.0247 (10)
H23	0.818241	0.921006	0.401461	0.03*
C24	1.1574 (4)	0.9848 (5)	0.3070 (5)	0.0374 (13)
H24A	1.2224	0.935649	0.304872	0.056*
H24B	1.169387	1.050279	0.371881	0.056*
H24C	1.148621	1.014655	0.246002	0.056*
N1	0.6939 (3)	0.6304 (3)	0.1466 (3)	0.0218 (8)
N2	0.6131 (3)	0.8170 (3)	0.2904 (3)	0.0221 (8)
N3	0.5707 (3)	0.5715 (3)	0.2856 (3)	0.0172 (7)
N4	0.8151 (3)	0.5331 (3)	0.2917 (3)	0.0175 (7)
N5	0.8578 (3)	0.7784 (3)	0.2947 (3)	0.0223 (8)
O1	0.6796 (3)	0.6032 (3)	0.0569 (3)	0.0347 (8)
F1	0.1192 (3)	0.7558 (3)	0.4962 (3)	0.0464 (8)
F2	0.2736 (3)	0.7858 (3)	0.6215 (3)	0.0485 (9)
F3	0.3860 (3)	0.7323 (4)	0.4967 (3)	0.0552 (10)
F4	0.2325 (3)	0.7029 (4)	0.3722 (3)	0.0610 (12)
F5	0.2396 (3)	0.6116 (3)	0.4982 (3)	0.0464 (8)
F6	0.2656 (3)	0.8772 (3)	0.4964 (3)	0.0581 (10)
F7	0.6950 (9)	0.9466 (11)	−0.0035 (9)	0.0340 (9)	0.27
F8	0.8214 (10)	0.9891 (10)	0.1350 (9)	0.0348 (9)	0.27
F9	0.9526 (10)	0.9017 (11)	0.0352 (9)	0.0334 (9)	0.27
F10	0.8320 (10)	0.8690 (10)	−0.1035 (9)	0.0338 (9)	0.27
F11	0.7843 (12)	0.8057 (13)	0.0314 (9)	0.0316 (10)	0.27
F12	0.8570 (10)	1.0561 (10)	0.0154 (10)	0.0338 (9)	0.27
F7'	0.7009 (11)	0.8999 (13)	−0.0515 (11)	0.0340 (9)	0.23
F8'	0.8494 (11)	1.0266 (12)	−0.0347 (11)	0.0334 (10)	0.23
F9'	0.9531 (12)	0.9422 (13)	0.0748 (11)	0.0335 (10)	0.23
F10'	0.7997 (14)	0.8134 (15)	0.0592 (10)	0.0303 (11)	0.23
F11'	0.7765 (12)	1.0179 (12)	0.1058 (10)	0.0341 (9)	0.23
F12'	0.8823 (12)	0.8345 (12)	−0.0761 (10)	0.0332 (10)	0.23
P1	0.25256 (11)	0.74423 (12)	0.49665 (11)	0.0304 (3)
P2	0.8262 (2)	0.9222 (2)	0.0147 (2)	0.0315 (5)	0.5
P3	0.0096 (7)	0.4947 (8)	1.0065 (7)	0.0235 (11)	0.25
F13	−0.0554 (15)	0.5012 (18)	0.8912 (15)	0.055 (3)	0.25
F14	0.0159 (14)	0.6360 (14)	1.0186 (13)	0.043 (3)	0.25
F15	0.0819 (13)	0.5449 (11)	1.1104 (12)	0.037 (3)	0.25
F16	0.0327 (13)	0.3706 (15)	0.9944 (14)	0.044 (3)	0.25
F17	−0.1002 (13)	0.4859 (13)	1.0649 (11)	0.035 (3)	0.25
F18	0.1247 (11)	0.4940 (14)	0.9658 (13)	0.044 (3)	0.25
O2	0.4360 (6)	0.6354 (5)	−0.0073 (5)	0.0506 (13)	0.75
C25	0.3205 (8)	0.7753 (7)	0.0657 (7)	0.0543 (17)	0.75
H25A	0.246098	0.753724	0.022434	0.081*	0.75
H25B	0.330631	0.860441	0.092797	0.081*	0.75
H25C	0.326049	0.74244	0.124747	0.081*	0.75
C26	0.4079 (9)	0.7297 (10)	0.0018 (8)	0.0626 (17)	0.75
C27	0.4482 (11)	0.8030 (10)	−0.0534 (10)	0.072 (2)	0.75
H27A	0.516295	0.848073	−0.011498	0.107*	0.75
H27B	0.389859	0.856427	−0.065322	0.107*	0.75
H27C	0.46595	0.754874	−0.121279	0.107*	0.75
P4	0.3853 (8)	0.7754 (8)	0.0142 (8)	0.0695 (16)	0.25
F19	0.2485 (12)	0.7786 (15)	−0.0055 (14)	0.073 (3)	0.25
F20	0.3720 (17)	0.7832 (16)	0.1335 (11)	0.078 (3)	0.25
F21	0.5042 (14)	0.7665 (17)	0.0707 (15)	0.081 (3)	0.25
F22	0.3936 (17)	0.7839 (17)	−0.0996 (13)	0.075 (3)	0.25
F23	0.3516 (18)	0.6382 (13)	−0.0083 (15)	0.073 (3)	0.25
F24	0.3869 (17)	0.9163 (12)	0.0572 (15)	0.079 (3)	0.25
Ru1	0.71356 (3)	0.67328 (3)	0.28492 (3)	0.01662 (13)
Cl1	0.73954 (9)	0.73137 (9)	0.46724 (8)	0.0205 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.029 (3)	0.031 (3)	0.046 (3)	0.011 (2)	0.022 (2)	0.025 (2)
C2	0.029 (3)	0.028 (3)	0.047 (3)	0.008 (2)	0.018 (2)	0.025 (2)
C3	0.018 (2)	0.019 (2)	0.032 (2)	0.0013 (17)	0.0030 (18)	0.0085 (19)
C4	0.016 (2)	0.024 (2)	0.019 (2)	0.0009 (17)	0.0035 (16)	0.0033 (17)
C5	0.017 (2)	0.022 (2)	0.021 (2)	−0.0001 (17)	0.0038 (17)	0.0080 (17)
C6	0.027 (3)	0.023 (2)	0.050 (3)	0.009 (2)	0.008 (2)	0.014 (2)
C7	0.021 (2)	0.023 (2)	0.022 (2)	0.0048 (17)	0.0031 (17)	0.0119 (18)
C8	0.021 (2)	0.023 (2)	0.023 (2)	0.0028 (18)	0.0007 (18)	0.0078 (18)
C9	0.024 (2)	0.014 (2)	0.024 (2)	−0.0010 (17)	0.0038 (18)	0.0034 (17)
C10	0.032 (2)	0.015 (2)	0.020 (2)	−0.0028 (18)	0.0015 (18)	0.0067 (17)
C11	0.025 (2)	0.015 (2)	0.018 (2)	0.0014 (17)	−0.0010 (17)	0.0053 (16)
C12	0.028 (3)	0.031 (3)	0.043 (3)	−0.008 (2)	0.003 (2)	0.015 (2)
C13	0.016 (2)	0.021 (2)	0.029 (2)	−0.0004 (17)	−0.0018 (18)	0.0022 (19)
C14	0.021 (2)	0.015 (2)	0.037 (3)	−0.0017 (17)	0.0027 (19)	0.0030 (19)
C15	0.017 (2)	0.024 (2)	0.026 (2)	0.0038 (17)	0.0099 (17)	0.0128 (18)
C16	0.014 (2)	0.030 (2)	0.021 (2)	0.0014 (18)	0.0020 (16)	0.0093 (19)
C17	0.017 (2)	0.021 (2)	0.021 (2)	−0.0024 (17)	0.0028 (17)	0.0042 (17)
C18	0.029 (3)	0.028 (3)	0.044 (3)	0.009 (2)	0.009 (2)	0.019 (2)
C19	0.025 (2)	0.024 (2)	0.034 (3)	0.0040 (19)	0.012 (2)	0.010 (2)
C20	0.023 (2)	0.036 (3)	0.041 (3)	0.008 (2)	0.013 (2)	0.021 (2)
C21	0.024 (2)	0.027 (2)	0.041 (3)	0.0039 (19)	0.005 (2)	0.024 (2)
C22	0.028 (2)	0.022 (2)	0.039 (3)	0.0017 (19)	0.005 (2)	0.019 (2)
C23	0.027 (2)	0.019 (2)	0.033 (3)	0.0049 (18)	0.010 (2)	0.0129 (19)
C24	0.024 (3)	0.036 (3)	0.060 (4)	−0.001 (2)	0.006 (2)	0.027 (3)
N1	0.0195 (19)	0.025 (2)	0.026 (2)	0.0052 (15)	0.0081 (15)	0.0129 (16)
N2	0.0233 (19)	0.0204 (19)	0.028 (2)	0.0043 (15)	0.0112 (16)	0.0126 (16)
N3	0.0185 (18)	0.0170 (17)	0.0171 (17)	0.0026 (14)	0.0031 (14)	0.0062 (14)
N4	0.0172 (17)	0.0154 (17)	0.0184 (18)	0.0016 (14)	0.0013 (14)	0.0031 (14)
N5	0.0224 (19)	0.0203 (19)	0.029 (2)	0.0023 (15)	0.0092 (16)	0.0120 (16)
O1	0.041 (2)	0.044 (2)	0.0202 (19)	0.0019 (17)	0.0056 (15)	0.0116 (16)
F1	0.0316 (17)	0.053 (2)	0.054 (2)	0.0105 (15)	0.0143 (15)	0.0123 (17)
F2	0.060 (2)	0.051 (2)	0.0327 (18)	−0.0212 (17)	0.0054 (16)	0.0112 (15)
F3	0.0299 (18)	0.082 (3)	0.073 (3)	0.0146 (17)	0.0175 (17)	0.048 (2)
F4	0.068 (3)	0.089 (3)	0.0325 (18)	0.048 (2)	0.0165 (17)	0.0241 (19)
F5	0.049 (2)	0.0329 (17)	0.055 (2)	0.0018 (15)	−0.0028 (16)	0.0152 (15)
F6	0.071 (3)	0.045 (2)	0.080 (3)	0.0111 (18)	0.037 (2)	0.039 (2)
F7	0.0338 (17)	0.0376 (18)	0.0283 (17)	−0.0025 (15)	0.0035 (16)	0.0068 (15)
F8	0.0351 (17)	0.0380 (18)	0.0277 (18)	−0.0029 (16)	0.0015 (16)	0.0059 (16)
F9	0.0347 (17)	0.0374 (18)	0.0272 (18)	−0.0027 (16)	0.0038 (16)	0.0090 (16)
F10	0.0348 (16)	0.0385 (17)	0.0269 (16)	−0.0036 (14)	0.0046 (15)	0.0078 (15)
F11	0.0341 (17)	0.0341 (17)	0.0267 (18)	−0.0038 (15)	0.0025 (16)	0.0104 (16)
F12	0.0345 (17)	0.0371 (18)	0.0277 (18)	−0.0026 (15)	0.0032 (16)	0.0073 (16)
F7'	0.0343 (16)	0.0379 (17)	0.0278 (17)	−0.0031 (14)	0.0026 (15)	0.0077 (15)
F8'	0.0345 (17)	0.0377 (18)	0.0270 (18)	−0.0025 (16)	0.0037 (16)	0.0089 (16)
F9'	0.0348 (17)	0.0372 (18)	0.0268 (18)	−0.0027 (16)	0.0023 (16)	0.0081 (16)
F10'	0.0338 (19)	0.0328 (19)	0.025 (2)	−0.0036 (17)	0.0028 (18)	0.0111 (18)
F11'	0.0343 (16)	0.0375 (17)	0.0279 (17)	−0.0030 (15)	0.0034 (15)	0.0066 (15)
F12'	0.0342 (17)	0.0377 (18)	0.0269 (17)	−0.0034 (16)	0.0054 (16)	0.0083 (16)
P1	0.0291 (7)	0.0357 (7)	0.0323 (7)	0.0069 (5)	0.0102 (5)	0.0167 (6)
P2	0.0325 (12)	0.0361 (12)	0.0257 (12)	−0.0032 (9)	0.0039 (10)	0.0092 (10)
P3	0.0237 (14)	0.0231 (13)	0.0212 (13)	0.0048 (9)	0.0046 (10)	0.0021 (9)
F13	0.044 (7)	0.072 (8)	0.045 (5)	0.002 (6)	−0.003 (5)	0.017 (6)
F14	0.048 (6)	0.030 (4)	0.042 (5)	−0.001 (5)	0.007 (5)	−0.006 (4)
F15	0.043 (5)	0.017 (5)	0.033 (4)	0.000 (4)	0.000 (4)	−0.017 (4)
F16	0.037 (6)	0.036 (4)	0.049 (6)	0.011 (5)	0.004 (5)	0.000 (4)
F17	0.034 (3)	0.036 (3)	0.034 (3)	0.0025 (19)	0.008 (2)	0.0086 (19)
F18	0.023 (5)	0.062 (6)	0.047 (5)	0.017 (4)	0.012 (4)	0.014 (5)
O2	0.056 (3)	0.046 (3)	0.054 (3)	0.015 (2)	0.013 (3)	0.019 (2)
C25	0.058 (3)	0.041 (3)	0.050 (3)	0.016 (3)	−0.030 (3)	0.011 (3)
C26	0.066 (3)	0.059 (3)	0.054 (3)	0.018 (3)	−0.015 (3)	0.015 (3)
C27	0.083 (4)	0.056 (4)	0.068 (4)	0.003 (4)	−0.017 (4)	0.019 (3)
P4	0.0704 (18)	0.0676 (18)	0.0678 (17)	0.0055 (10)	0.0040 (10)	0.0192 (10)
F19	0.084 (5)	0.058 (6)	0.064 (6)	0.004 (5)	−0.023 (5)	0.014 (5)
F20	0.093 (5)	0.063 (5)	0.064 (4)	0.014 (5)	−0.019 (4)	0.011 (4)
F21	0.087 (4)	0.067 (4)	0.073 (4)	0.014 (4)	−0.019 (4)	0.009 (4)
F22	0.080 (6)	0.063 (5)	0.070 (5)	0.003 (5)	−0.018 (5)	0.014 (4)
F23	0.082 (5)	0.059 (4)	0.065 (5)	0.010 (4)	−0.012 (5)	0.011 (4)
F24	0.084 (6)	0.057 (4)	0.077 (5)	0.008 (4)	−0.029 (5)	0.009 (4)
Ru1	0.0176 (2)	0.0165 (2)	0.0185 (2)	0.00384 (13)	0.00650 (13)	0.00763 (14)
Cl1	0.0243 (5)	0.0185 (5)	0.0186 (5)	−0.0003 (4)	0.0055 (4)	0.0041 (4)

Geometric parameters (Å, º) top

C1—N2	1.344 (6)	C23—N5	1.354 (6)
C1—C2	1.373 (7)	C23—H23	0.95
C1—H1	0.95	C24—H24A	0.98
C2—C3	1.391 (7)	C24—H24B	0.98
C2—H2	0.95	C24—H24C	0.98
C3—C4	1.391 (6)	N1—O1	1.140 (5)
C3—C6	1.504 (6)	N1—Ru1	1.757 (4)
C4—C5	1.375 (6)	N2—Ru1	2.102 (4)
C4—H4	0.95	N3—Ru1	2.101 (4)
C5—N2	1.348 (6)	N4—Ru1	2.101 (4)
C5—H5	0.95	N5—Ru1	2.101 (4)
C6—H6A	0.98	F1—P1	1.605 (3)
C6—H6B	0.98	F2—P1	1.585 (3)
C6—H6C	0.98	F3—P1	1.607 (3)
C7—N3	1.358 (6)	F4—P1	1.580 (4)
C7—C8	1.369 (6)	F5—P1	1.606 (3)
C7—H7	0.95	F6—P1	1.605 (4)
C8—C9	1.391 (6)	F7—P2	1.600 (12)
C8—H8	0.95	F8—P2	1.590 (11)
C9—C10	1.395 (6)	F9—P2	1.535 (12)
C9—C12	1.495 (6)	F10—P2	1.541 (11)
C10—C11	1.372 (6)	F11—P2	1.572 (16)
C10—H10	0.95	F12—P2	1.645 (12)
C11—N3	1.348 (6)	F7'—P2	1.610 (13)
C11—H11	0.95	F8'—P2	1.621 (14)
C12—H12A	0.98	F9'—P2	1.597 (14)
C12—H12B	0.98	F10'—P2	1.635 (17)
C12—H12C	0.98	F11'—P2	1.603 (13)
C13—N4	1.349 (6)	F12'—P2	1.595 (13)
C13—C14	1.374 (7)	P3—F16	1.484 (19)
C13—H13	0.95	P3—F15	1.489 (16)
C14—C15	1.391 (7)	P3—F18	1.555 (17)
C14—H14	0.95	P3—F17	1.644 (18)
C15—C16	1.387 (7)	P3—F13	1.655 (19)
C15—C18	1.495 (6)	P3—F14	1.658 (19)
C16—C17	1.373 (6)	O2—C26	1.161 (12)
C16—H16	0.95	C25—C26	1.459 (16)
C17—N4	1.353 (6)	C25—H25A	0.98
C17—H17	0.95	C25—H25B	0.98
C18—H18A	0.98	C25—H25C	0.98
C18—H18B	0.98	C26—C27	1.428 (17)
C18—H18C	0.98	C27—H27A	0.98
C19—N5	1.345 (6)	C27—H27B	0.98
C19—C20	1.379 (7)	C27—H27C	0.98
C19—H19	0.95	P4—F21	1.535 (13)
C20—C21	1.389 (7)	P4—F22	1.580 (14)
C20—H20	0.95	P4—F20	1.610 (14)
C21—C22	1.388 (7)	P4—F24	1.620 (13)
C21—C24	1.511 (7)	P4—F23	1.624 (14)
C22—C23	1.380 (7)	P4—F19	1.626 (14)
C22—H22	0.95	Ru1—Cl1	2.3163 (11)

N2—C1—C2	122.7 (4)	F2—P1—F6	89.9 (2)
N2—C1—H1	118.7	F1—P1—F6	90.2 (2)
C2—C1—H1	118.7	F4—P1—F5	90.6 (2)
C1—C2—C3	120.0 (4)	F2—P1—F5	89.52 (19)
C1—C2—H2	120	F1—P1—F5	89.8 (2)
C3—C2—H2	120	F6—P1—F5	179.4 (2)
C2—C3—C4	117.0 (4)	F4—P1—F3	89.9 (2)
C2—C3—C6	120.3 (4)	F2—P1—F3	89.7 (2)
C4—C3—C6	122.7 (4)	F1—P1—F3	179.8 (3)
C5—C4—C3	120.3 (4)	F6—P1—F3	89.9 (2)
C5—C4—H4	119.8	F5—P1—F3	90.1 (2)
C3—C4—H4	119.8	F9—P2—F10	87.3 (6)
N2—C5—C4	122.1 (4)	F9—P2—F11	95.7 (7)
N2—C5—H5	119	F10—P2—F11	95.3 (6)
C4—C5—H5	119	F9—P2—F8	93.5 (6)
C3—C6—H6A	109.5	F10—P2—F8	174.5 (7)
C3—C6—H6B	109.5	F11—P2—F8	90.0 (6)
H6A—C6—H6B	109.5	F12'—P2—F9'	82.8 (7)
C3—C6—H6C	109.5	F9—P2—F7	178.3 (7)
H6A—C6—H6C	109.5	F10—P2—F7	94.2 (6)
H6B—C6—H6C	109.5	F11—P2—F7	84.9 (7)
N3—C7—C8	122.4 (4)	F8—P2—F7	85.0 (6)
N3—C7—H7	118.8	F12'—P2—F11'	175.7 (7)
C8—C7—H7	118.8	F9'—P2—F11'	94.7 (7)
C7—C8—C9	120.4 (4)	F12'—P2—F7'	94.5 (7)
C7—C8—H8	119.8	F9'—P2—F7'	177.0 (8)
C9—C8—H8	119.8	F11'—P2—F7'	87.9 (7)
C8—C9—C10	116.7 (4)	F12'—P2—F8'	89.3 (7)
C8—C9—C12	121.4 (4)	F9'—P2—F8'	89.2 (7)
C10—C9—C12	121.9 (4)	F11'—P2—F8'	87.0 (7)
C11—C10—C9	120.6 (4)	F7'—P2—F8'	89.6 (7)
C11—C10—H10	119.7	F12'—P2—F10'	89.1 (8)
C9—C10—H10	119.7	F9'—P2—F10'	92.8 (7)
N3—C11—C10	122.1 (4)	F11'—P2—F10'	94.6 (8)
N3—C11—H11	118.9	F7'—P2—F10'	88.3 (7)
C10—C11—H11	118.9	F8'—P2—F10'	177.3 (7)
C9—C12—H12A	109.5	F9—P2—F12	89.9 (6)
C9—C12—H12B	109.5	F10—P2—F12	94.1 (6)
H12A—C12—H12B	109.5	F11—P2—F12	169.2 (7)
C9—C12—H12C	109.5	F8—P2—F12	80.4 (6)
H12A—C12—H12C	109.5	F7—P2—F12	89.2 (6)
H12B—C12—H12C	109.5	F16—P3—F15	97.2 (10)
N4—C13—C14	121.9 (4)	F16—P3—F18	82.2 (10)
N4—C13—H13	119	F15—P3—F18	82.2 (10)
C14—C13—H13	119	F16—P3—F17	91.7 (10)
C13—C14—C15	120.7 (4)	F15—P3—F17	90.8 (10)
C13—C14—H14	119.7	F18—P3—F17	170.0 (8)
C15—C14—H14	119.7	F16—P3—F13	107.0 (11)
C16—C15—C14	116.6 (4)	F15—P3—F13	153.1 (10)
C16—C15—C18	122.6 (4)	F18—P3—F13	89.5 (10)
C14—C15—C18	120.8 (4)	F17—P3—F13	99.9 (9)
C17—C16—C15	120.8 (4)	F16—P3—F14	166.5 (10)
C17—C16—H16	119.6	F15—P3—F14	77.2 (9)
C15—C16—H16	119.6	F18—P3—F14	84.9 (10)
N4—C17—C16	121.8 (4)	F17—P3—F14	100.5 (9)
N4—C17—H17	119.1	F13—P3—F14	76.6 (10)
C16—C17—H17	119.1	C26—C25—H25A	109.5
C15—C18—H18A	109.5	C26—C25—H25B	109.5
C15—C18—H18B	109.5	H25A—C25—H25B	109.5
H18A—C18—H18B	109.5	C26—C25—H25C	109.5
C15—C18—H18C	109.5	H25A—C25—H25C	109.5
H18A—C18—H18C	109.5	H25B—C25—H25C	109.5
H18B—C18—H18C	109.5	O2—C26—C27	123.4 (12)
N5—C19—C20	122.3 (5)	O2—C26—C25	119.9 (11)
N5—C19—H19	118.9	C27—C26—C25	116.5 (10)
C20—C19—H19	118.9	C26—C27—H27A	109.5
C19—C20—C21	120.1 (5)	C26—C27—H27B	109.5
C19—C20—H20	119.9	H27A—C27—H27B	109.5
C21—C20—H20	119.9	C26—C27—H27C	109.5
C22—C21—C20	117.4 (4)	H27A—C27—H27C	109.5
C22—C21—C24	122.4 (5)	H27B—C27—H27C	109.5
C20—C21—C24	120.3 (5)	F21—P4—F22	109.3 (13)
C23—C22—C21	120.1 (5)	F21—P4—F20	73.6 (12)
C23—C22—H22	119.9	F22—P4—F20	172.8 (12)
C21—C22—H22	119.9	F21—P4—F24	94.8 (11)
N5—C23—C22	122.0 (4)	F22—P4—F24	89.3 (11)
N5—C23—H23	119	F20—P4—F24	83.8 (11)
C22—C23—H23	119	F21—P4—F23	93.5 (11)
C21—C24—H24A	109.5	F22—P4—F23	102.7 (11)
C21—C24—H24B	109.5	F20—P4—F23	83.6 (11)
H24A—C24—H24B	109.5	F24—P4—F23	162.2 (14)
C21—C24—H24C	109.5	F21—P4—F19	158.8 (13)
H24A—C24—H24C	109.5	F22—P4—F19	91.9 (11)
H24B—C24—H24C	109.5	F20—P4—F19	85.5 (11)
O1—N1—Ru1	179.0 (4)	F24—P4—F19	86.5 (10)
C1—N2—C5	117.9 (4)	F23—P4—F19	80.2 (10)
C1—N2—Ru1	119.9 (3)	N1—Ru1—N3	91.79 (16)
C5—N2—Ru1	122.1 (3)	N1—Ru1—N4	92.55 (15)
C11—N3—C7	117.8 (4)	N3—Ru1—N4	89.70 (14)
C11—N3—Ru1	122.3 (3)	N1—Ru1—N5	91.84 (16)
C7—N3—Ru1	119.9 (3)	N3—Ru1—N5	176.37 (14)
C13—N4—C17	118.1 (4)	N4—Ru1—N5	90.17 (14)
C13—N4—Ru1	119.6 (3)	N1—Ru1—N2	91.71 (16)
C17—N4—Ru1	122.2 (3)	N3—Ru1—N2	89.97 (14)
C19—N5—C23	118.1 (4)	N4—Ru1—N2	175.74 (14)
C19—N5—Ru1	119.5 (3)	N5—Ru1—N2	89.90 (15)
C23—N5—Ru1	122.4 (3)	N1—Ru1—Cl1	179.52 (13)
F4—P1—F2	179.6 (2)	N3—Ru1—Cl1	88.51 (10)
F4—P1—F1	89.9 (2)	N4—Ru1—Cl1	87.83 (10)
F2—P1—F1	90.4 (2)	N5—Ru1—Cl1	87.86 (11)
F4—P1—F6	90.0 (2)	N2—Ru1—Cl1	87.92 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···F8	0.95	2.47	3.194 (12)	133
C1—H1···F11	0.95	2.48	3.405 (15)	165
C1—H1···F10′	0.95	2.3	3.243 (18)	173
C5—H5···F3	0.95	2.49	3.328 (6)	147
C7—H7···O2	0.95	2.45	3.320 (7)	153
C7—H7···F20	0.95	2.51	3.264 (18)	136
C13—H13···F22ⁱ	0.95	2.54	3.16 (2)	123
C13—H13···F23ⁱ	0.95	2.26	3.047 (18)	140
C14—H14···F19ⁱ	0.95	2.4	2.995 (18)	120
C27—H27A···F7	0.98	2.41	3.297 (17)	150
C27—H27B···F7ⁱⁱ	0.98	2.55	3.418 (17)	147

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

Funding information

HSM thanks the Iraqi/French institution for a grant, and Campus France (Moyen-Orient, 776290 J) for financial support.

References

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