fac-[1,2-Bis(pyridin-4-yl)ethane-κN]tricarbon­yl(1,10-phenanthroline-κ²N,N′)rhenium(I) hexa­fluorido­phosphate aceto­nitrile monosolvate

The asymmetric unit of the title compound, [Re(C₁₂H₈N₂)(C₁₂H₁₂N₂)(CO)₃]PF₆.·CH₃CN, contains one cation, one hexa­fluorido­phosphate anion and one aceto­nitrile solvent mol­ecule. The Re^I ion is coordinated by two N atoms from the 1,10-phenanthroline ligand and one N atom from the 1,2-bis­(pyridin-4-yl)ethane ligand [mean Re—N = 2.191 (15) Å] and by three carbonyl ligands [mean Re—C = 1.926 (3) Å] in a distorted octa­hedral geometry. The electrostatic forces and weak C—H...F(O) hydrogen bonds pack cations and anions into the crystal with voids of 82 ų, which are filled by solvent mol­ecules. The crystal packing exhibits short inter­molecular O...O distance of 2.795 (5) Å between two cations related by inversion.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.041
• wR factor = 0.109
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....         10 Why ?
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4 Why ?
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT934_ALERT_3_C Number of (Iobs-Icalc)/SigmaW > 10 Outliers ....          1 Check
PLAT971_ALERT_2_C Check Calcd Residual Density  0.93A From      C5       1.51 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  0.85A From      Re      -2.46 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  0.79A From      Re      -2.43 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  0.87A From      Re      -1.85 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  0.88A From      Re      -1.83 eA-3
PLAT972_ALERT_2_C Check Calcd Residual Density  0.78A From      Re      -1.71 eA-3

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.       8.74 Why ?
PLAT230_ALERT_2_G Hirshfeld Test Diff for    O3     --  C3      ..        8.7 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Re     --  C3      ..        7.0 su
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         20 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  10 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   9 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

Rhenium(I) polypyridyl complexes exhibit very interesting photophysical and photochemical properties which can be exploited in the development of different photochemical molecular devices. Interesting examples can be found in the literature such as light emitting devices (Li et al., 2012; Mizoguchi et al., 2009), photoswitches (Patrocinio et al., 2010, 2013), DNA sensors (Thorp-Greenwood et al., 2012), among others. In this article, we describe the crystal structure of a Re^I polypyridyl complex having 1,2-bis(pyridin-4-yl)ethane (bpa) as ancillary ligand. This complex can be conveniently used as luminescent material and also as a construction unit for binuclear complex in intramolecular energy transfer studies.

The asymmetric unit in the title compound consists of the complex cation [Re(CO)₃(phen)(bpa)]⁺ (phen = 1,10-phenanthroline), PF₆^- anion and one acetonitrile solvent molecule (Fig. 1). The Re^I center has a distorted octahedral environment. It is coordinated by three carbonyl groups arranged in a facial fashion [mean Re–C distance of 1.926 (6) Å], two nitrogen atoms from phen ligand [mean Re–N distance of 2.183 (4) Å] and one nitrogen atom from bpa ligand [Re–N distance of 2.208 (4) Å]. The Re–C and Re–N distances were comparable to those of related systems (Ranjan et al., 2003; Wenger et al., 2004). The bidentate bite angle N–Re–N is 76.0 (2)°. The Re^I lies -0.055 (4) Å from the least-squares plane of 1,10-phenanthroline. In the bpa ligand, the bond distance C21–C22 is 1.526 (8) Å. The C21 ethane carbon atom is nearly coplanar with N3-pyridyl moiety. The C21–C22–C23–C24 and C21–C22–C23–C27 torsion angles are 102.5 (7)° and -75.2 (8)°, respectively. These angles in the free bpa ligand are 78.0 (3)° and -99.5 (3)°, respectively (Ide et al., 1995). The bond lengths in the structure of the free bpa ligand are shorter than those observed in the ligand coordinated to the metallic center. The PF₆^- anion adopts an octahedral geometry with P–F distances varied from 1.587 (4) to 1.612 (3) Å. The components of the structure are connected into a three-dimensional architecture by electrostatic forces and C—H···F and C—H···O hydrogen bonds (Table 1).

Related literature

For photophysical and photochemical properties of rhenium(I)–polypyridyl complexes, see: Li et al. (2012); Mizoguchi et al. (2009); Patrocinio et al. (2010, 2013); Thorp-Greenwood et al. (2012). For similar compounds and their crystal structures, see: Ranjan et al. (2003); Wenger et al. (2004); Ide et al. (1995). For details of the synthetic procedure, see: Patrocinio et al. (2010); Patrocinio & Murakami Iha (2008); Argazzi et al. (2001).

S2. Experimental

The fac-[Re(CO)₃(phen)(bpa)]PF₆ compound (phen = 1,10-phenanthroline, bpa = 1,2-bis(4-pyridyl)ethane) was prepared following the procedures described earlier (Patrocinio et al., 2010; Patrocinio & Murakami Iha, 2008; Argazzi et al., 2001). Briefly, [ClRe(CO)₅] and an excess of the polipyridyl ligand were refluxed in toluene for 5–7 h to yield a yellow solid, fac-[ClRe(CO)₃(NN)]. The product was collected by filtration and recrystallized from CH₂Cl₂ by slow addition of n-pentane. Then, the fac-[ClRe(CO)₃(NN)] complexes were suspended in argon-saturated CH₂Cl₂ and trifluoromethanesulfonic acid was added to reaction mixture to yield the respective intermediates fac-[Re(CO)₃(NN)(CF₃SO₃)], which were precipitated by slow addition of ethyl ether. Finally, an excess of the bpa ligand were added to fac-[Re(CO)₃(NN)(CF₃SO₃)] in methanol and the mixture were kept in reflux under argon atmosphere during 8–9 h. After cooling, the final products were obtained by addition of solid NH₄PF₆. The solids were separated by filtration, washed with water to remove the NH₄PF₆ excess and ethyl ether to dry fac-[Re(CO)₃(phen)(bpa)]PF₆ were crystallized by slow diffusion of diethyl ether into an acetonitrile solution at room temperature.

S3. Refinement

H atoms were included in calculated positions (C–H = 0.93 Å for aromatic H, C–H = 0.97 Å for methylene H and C–H = 0.96 Å for methyl H), and refined using a riding model with U_iso(H) = 1.2 or 1.5 U_eq of the carrier atom.

Computing details

Data collection: COLLECT (Hooft, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures

Fig. 1. A view of the asymmetric unit of the title compound, showing the atom labeling and 30% probability displacement ellipsoids.

fac-[1,2-Bis(pyridin-4-yl)ethane-κN]tricarbonyl(1,10-phenanthroline-κ²N,N')rhenium(I) hexafluoridophosphate acetonitrile monosolvate

Crystal data

[Re(C12H8N2)(C12H12N2)(CO)3]PF6·C2H3N	F(000) = 1600
Mr = 820.69	Dx = 1.873 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.5992 (2) Å	Cell parameters from 20552 reflections
b = 16.1201 (3) Å	θ = 2.9–26.7°
c = 17.3449 (2) Å	µ = 4.31 mm^−1
β = 100.879 (1)°	T = 100 K
V = 2910.29 (8) Å^3	Prism, colourless
Z = 4	0.29 × 0.20 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer	6066 independent reflections
Radiation source: Enraf–Nonius FR590	5415 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.106
Detector resolution: 9 pixels mm^-1	θmax = 26.6°, θmin = 3.1°
CCD rotation images, thick slices scans	h = −13→13
Absorption correction: gaussian (Coppens et al., 1965)	k = −18→20
Tmin = 0.386, Tmax = 0.613	l = −21→21
35034 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0541P)^2 + 8.7438P] where P = (Fo^2 + 2Fc^2)/3
6066 reflections	(Δ/σ)max = 0.002
406 parameters	Δρmax = 1.39 e Å^−3
0 restraints	Δρmin = −2.50 e Å^−3

Special details

Experimental. a grid of 8 x 8 x 8 = 512 sampling points was used in the absorption correction

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Re	0.804584 (18)	0.150099 (11)	0.635436 (10)	0.01716 (9)
O1	0.5921 (4)	0.0300 (3)	0.5622 (2)	0.0328 (9)
O2	0.9983 (4)	0.0058 (2)	0.6471 (2)	0.0302 (9)
O3	0.8369 (4)	0.1791 (3)	0.46486 (19)	0.0268 (8)
N1	0.7658 (4)	0.1315 (3)	0.7536 (2)	0.0199 (9)
N2	0.6642 (4)	0.2458 (3)	0.6470 (2)	0.0193 (8)
N3	0.9448 (4)	0.2463 (3)	0.6853 (2)	0.0196 (8)
N4	1.3479 (5)	0.6998 (3)	0.9550 (3)	0.0292 (10)
N5	0.7950 (6)	0.3895 (4)	0.8097 (4)	0.0460 (14)
C1	0.6701 (5)	0.0737 (3)	0.5915 (3)	0.0225 (11)
C2	0.9281 (5)	0.0614 (3)	0.6420 (3)	0.0234 (11)
C3	0.8273 (5)	0.1710 (3)	0.5297 (3)	0.0244 (11)
C4	0.8152 (5)	0.0726 (3)	0.8044 (3)	0.0237 (11)
H4	0.8778	0.0375	0.7916	0.028*
C5	0.7759 (6)	0.0619 (4)	0.8764 (3)	0.0304 (12)
H5	0.8109	0.0193	0.9099	0.036*
C6	0.6858 (6)	0.1141 (4)	0.8979 (3)	0.0278 (12)
H6	0.6604	0.108	0.946	0.033*
C7	0.6330 (5)	0.1772 (3)	0.8453 (3)	0.0221 (10)
C8	0.5392 (5)	0.2344 (3)	0.8619 (3)	0.0228 (10)
H8	0.5104	0.2306	0.9092	0.027*
C9	0.4913 (5)	0.2947 (3)	0.8094 (3)	0.0228 (10)
H9	0.4314	0.3322	0.8219	0.027*
C10	0.5316 (5)	0.3013 (3)	0.7355 (3)	0.0206 (10)
C11	0.4825 (6)	0.3620 (3)	0.6783 (3)	0.0255 (12)
H11	0.4231	0.4012	0.6881	0.031*
C12	0.5247 (6)	0.3614 (3)	0.6080 (3)	0.0260 (12)
H12	0.4927	0.4001	0.5695	0.031*
C13	0.6158 (5)	0.3028 (3)	0.5941 (3)	0.0215 (10)
H13	0.6433	0.3039	0.5463	0.026*
C14	0.6757 (5)	0.1834 (3)	0.7736 (3)	0.0182 (9)
C15	0.6230 (5)	0.2453 (3)	0.7174 (3)	0.0189 (10)
C16	0.9463 (5)	0.3204 (3)	0.6488 (3)	0.0225 (10)
H16	0.8911	0.3283	0.6009	0.027*
C17	1.0259 (5)	0.3845 (3)	0.6794 (3)	0.0241 (11)
H17	1.0224	0.4346	0.6526	0.029*
C18	1.1111 (5)	0.3747 (3)	0.7497 (3)	0.0222 (10)
C19	1.1136 (5)	0.2970 (3)	0.7860 (3)	0.0229 (11)
H19	1.1716	0.2868	0.8324	0.027*
C20	1.0294 (5)	0.2353 (3)	0.7528 (3)	0.0212 (10)
H20	1.0316	0.1844	0.7781	0.025*
C21	1.1946 (5)	0.4445 (3)	0.7878 (3)	0.0237 (10)
H21A	1.2319	0.4734	0.7484	0.028*
H21B	1.2641	0.4223	0.8268	0.028*
C22	1.1154 (6)	0.5050 (4)	0.8268 (4)	0.0398 (15)
H22A	1.0503	0.5301	0.7868	0.048*
H22B	1.072	0.4747	0.8624	0.048*
C23	1.1966 (5)	0.5727 (4)	0.8718 (3)	0.0286 (13)
C24	1.1984 (6)	0.6522 (3)	0.8408 (4)	0.0302 (13)
H24	1.1498	0.6645	0.7917	0.036*
C25	1.2736 (6)	0.7129 (3)	0.8839 (3)	0.0276 (12)
H25	1.2727	0.7658	0.8624	0.033*
C26	1.3481 (6)	0.6218 (4)	0.9832 (3)	0.0323 (13)
H26	1.3998	0.6103	1.0315	0.039*
C27	1.2757 (6)	0.5582 (4)	0.9441 (3)	0.0339 (13)
H27	1.2798	0.5055	0.9662	0.041*
C28	0.8459 (7)	0.3541 (4)	0.8642 (4)	0.0392 (16)
C29	0.9137 (7)	0.3104 (5)	0.9339 (4)	0.0464 (16)
H29A	0.9862	0.2814	0.9212	0.07*
H29B	0.8565	0.2714	0.9513	0.07*
H29C	0.9427	0.3498	0.975	0.07*
P	0.72529 (14)	0.43615 (8)	0.41578 (7)	0.0227 (3)
F1	0.6050 (3)	0.4560 (2)	0.45748 (19)	0.0332 (7)
F2	0.7573 (3)	0.53361 (19)	0.41536 (18)	0.0299 (7)
F3	0.8432 (4)	0.4168 (2)	0.3742 (2)	0.0422 (9)
F4	0.6912 (4)	0.33928 (19)	0.4165 (2)	0.0399 (9)
F5	0.6330 (3)	0.44566 (19)	0.33112 (17)	0.0294 (7)
F6	0.8144 (4)	0.4265 (2)	0.50075 (19)	0.0373 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Re	0.01953 (14)	0.01844 (14)	0.01390 (12)	0.00022 (7)	0.00417 (8)	0.00007 (6)
O1	0.033 (2)	0.034 (2)	0.031 (2)	−0.0109 (18)	0.0033 (17)	−0.0095 (17)
O2	0.031 (2)	0.027 (2)	0.033 (2)	0.0107 (17)	0.0089 (17)	0.0046 (16)
O3	0.033 (2)	0.037 (2)	0.0114 (17)	−0.0021 (18)	0.0074 (14)	0.0034 (15)
N1	0.028 (2)	0.023 (2)	0.0108 (18)	0.0000 (18)	0.0081 (16)	0.0028 (16)
N2	0.024 (2)	0.017 (2)	0.0179 (19)	0.0026 (16)	0.0055 (16)	0.0011 (16)
N3	0.019 (2)	0.021 (2)	0.0177 (19)	−0.0012 (17)	0.0015 (16)	0.0001 (16)
N4	0.036 (3)	0.024 (2)	0.026 (2)	−0.003 (2)	0.0039 (19)	−0.0001 (19)
N5	0.043 (3)	0.043 (3)	0.049 (3)	−0.006 (3)	0.001 (3)	−0.008 (3)
C1	0.021 (3)	0.030 (3)	0.018 (2)	0.002 (2)	0.0066 (19)	−0.001 (2)
C2	0.027 (3)	0.027 (3)	0.017 (2)	−0.005 (2)	0.007 (2)	0.002 (2)
C3	0.018 (3)	0.019 (2)	0.034 (3)	−0.001 (2)	0.002 (2)	−0.001 (2)
C4	0.025 (3)	0.025 (3)	0.023 (2)	0.004 (2)	0.011 (2)	0.010 (2)
C5	0.046 (4)	0.027 (3)	0.020 (2)	0.009 (2)	0.009 (2)	0.007 (2)
C6	0.030 (3)	0.036 (3)	0.018 (2)	0.003 (2)	0.008 (2)	0.002 (2)
C7	0.021 (3)	0.028 (3)	0.017 (2)	−0.004 (2)	0.0031 (19)	−0.004 (2)
C8	0.026 (3)	0.026 (3)	0.018 (2)	−0.002 (2)	0.0067 (19)	−0.003 (2)
C9	0.022 (3)	0.026 (3)	0.022 (2)	0.000 (2)	0.008 (2)	−0.005 (2)
C10	0.022 (3)	0.016 (2)	0.024 (2)	−0.0013 (19)	0.0051 (19)	−0.0038 (19)
C11	0.028 (3)	0.027 (3)	0.021 (3)	0.007 (2)	0.002 (2)	−0.002 (2)
C12	0.024 (3)	0.025 (3)	0.028 (3)	0.002 (2)	0.003 (2)	0.007 (2)
C13	0.022 (3)	0.024 (3)	0.019 (2)	0.000 (2)	0.0039 (19)	0.005 (2)
C14	0.018 (2)	0.020 (2)	0.016 (2)	−0.0026 (19)	0.0016 (18)	−0.0006 (18)
C15	0.019 (2)	0.020 (2)	0.018 (2)	−0.0019 (19)	0.0054 (18)	−0.0004 (19)
C16	0.026 (3)	0.024 (3)	0.017 (2)	0.000 (2)	0.0020 (19)	0.003 (2)
C17	0.028 (3)	0.020 (3)	0.024 (3)	0.000 (2)	0.006 (2)	0.005 (2)
C18	0.021 (3)	0.021 (3)	0.026 (3)	0.001 (2)	0.009 (2)	−0.001 (2)
C19	0.023 (3)	0.027 (3)	0.017 (2)	−0.001 (2)	0.0006 (19)	0.002 (2)
C20	0.027 (3)	0.020 (2)	0.017 (2)	−0.001 (2)	0.0037 (19)	0.0004 (19)
C21	0.028 (3)	0.024 (3)	0.020 (2)	−0.003 (2)	0.006 (2)	−0.001 (2)
C22	0.025 (3)	0.034 (3)	0.061 (4)	−0.003 (3)	0.010 (3)	−0.019 (3)
C23	0.022 (3)	0.027 (3)	0.039 (3)	−0.004 (2)	0.012 (2)	−0.012 (2)
C24	0.031 (3)	0.032 (3)	0.026 (3)	0.007 (2)	0.000 (2)	−0.004 (2)
C25	0.031 (3)	0.023 (3)	0.029 (3)	0.000 (2)	0.005 (2)	0.000 (2)
C26	0.042 (4)	0.031 (3)	0.024 (3)	−0.001 (3)	0.007 (2)	0.002 (2)
C27	0.049 (4)	0.023 (3)	0.033 (3)	−0.002 (3)	0.018 (3)	0.006 (2)
C28	0.036 (4)	0.036 (4)	0.045 (4)	−0.009 (3)	0.007 (3)	−0.013 (3)
C29	0.045 (4)	0.048 (4)	0.045 (4)	−0.005 (3)	0.006 (3)	−0.005 (3)
P	0.0310 (8)	0.0219 (7)	0.0153 (6)	0.0034 (5)	0.0046 (5)	0.0005 (5)
F1	0.0371 (19)	0.0351 (18)	0.0312 (16)	0.0021 (15)	0.0162 (14)	−0.0018 (14)
F2	0.0366 (19)	0.0246 (17)	0.0267 (15)	−0.0045 (13)	0.0013 (13)	0.0017 (13)
F3	0.048 (2)	0.048 (2)	0.0354 (18)	0.0192 (18)	0.0200 (16)	0.0068 (16)
F4	0.075 (3)	0.0202 (17)	0.0249 (17)	0.0009 (16)	0.0113 (18)	−0.0003 (13)
F5	0.0396 (19)	0.0265 (16)	0.0184 (14)	−0.0059 (14)	−0.0035 (13)	0.0014 (12)
F6	0.045 (2)	0.040 (2)	0.0226 (16)	0.0098 (16)	−0.0042 (14)	0.0071 (14)

Geometric parameters (Å, º)

Re—C1	1.929 (5)	C13—H13	0.93
Re—C2	1.927 (6)	C14—C15	1.432 (7)
Re—C3	1.923 (6)	C16—C17	1.375 (8)
Re—N1	2.186 (4)	C16—H16	0.93
Re—N2	2.179 (4)	C17—C18	1.384 (7)
Re—N3	2.208 (4)	C17—H17	0.93
O1—C1	1.131 (7)	C18—C19	1.399 (7)
O2—C2	1.158 (7)	C18—C21	1.504 (7)
O3—C3	1.156 (7)	C19—C20	1.387 (7)
N1—C4	1.334 (6)	C19—H19	0.93
N1—C14	1.363 (7)	C20—H20	0.93
N2—C13	1.330 (6)	C21—C22	1.526 (8)
N2—C15	1.372 (6)	C21—H21A	0.97
N3—C20	1.346 (6)	C21—H21B	0.97
N3—C16	1.353 (7)	C22—C23	1.513 (8)
N4—C25	1.348 (7)	C22—H22A	0.97
N4—C26	1.349 (8)	C22—H22B	0.97
N5—C28	1.148 (9)	C23—C27	1.390 (8)
C4—C5	1.400 (7)	C23—C24	1.391 (8)
C4—H4	0.93	C24—C25	1.388 (8)
C5—C6	1.376 (8)	C24—H24	0.93
C5—H5	0.93	C25—H25	0.93
C6—C7	1.410 (8)	C26—C27	1.379 (9)
C6—H6	0.93	C26—H26	0.93
C7—C14	1.405 (7)	C27—H27	0.93
C7—C8	1.425 (7)	C28—C29	1.466 (10)
C8—C9	1.363 (7)	C29—H29A	0.96
C8—H8	0.93	C29—H29B	0.96
C9—C10	1.431 (7)	C29—H29C	0.96
C9—H9	0.93	P—F3	1.587 (4)
C10—C15	1.403 (7)	P—F6	1.601 (3)
C10—C11	1.420 (7)	P—F4	1.603 (3)
C11—C12	1.375 (8)	P—F2	1.608 (3)
C11—H11	0.93	P—F5	1.611 (3)
C12—C13	1.404 (8)	P—F1	1.612 (3)
C12—H12	0.93
C3—Re—C2	88.9 (2)	N3—C16—C17	122.9 (5)
C3—Re—C1	87.2 (2)	N3—C16—H16	118.6
C2—Re—C1	89.6 (2)	C17—C16—H16	118.6
C3—Re—N2	100.01 (19)	C16—C17—C18	120.4 (5)
C2—Re—N2	171.09 (18)	C16—C17—H17	119.8
C1—Re—N2	91.25 (19)	C18—C17—H17	119.8
C3—Re—N1	175.83 (19)	C17—C18—C19	116.9 (5)
C2—Re—N1	95.09 (19)	C17—C18—C21	122.2 (5)
C1—Re—N1	91.52 (19)	C19—C18—C21	120.9 (5)
N2—Re—N1	76.02 (16)	C20—C19—C18	119.9 (5)
C3—Re—N3	93.08 (19)	C20—C19—H19	120
C2—Re—N3	95.64 (19)	C18—C19—H19	120
C1—Re—N3	174.74 (19)	N3—C20—C19	122.6 (5)
N2—Re—N3	83.52 (16)	N3—C20—H20	118.7
N1—Re—N3	87.78 (16)	C19—C20—H20	118.7
C4—N1—C14	118.4 (4)	C18—C21—C22	110.2 (5)
C4—N1—Re	126.7 (4)	C18—C21—H21A	109.6
C14—N1—Re	114.8 (3)	C22—C21—H21A	109.6
C13—N2—C15	118.2 (4)	C18—C21—H21B	109.6
C13—N2—Re	127.4 (3)	C22—C21—H21B	109.6
C15—N2—Re	114.5 (3)	H21A—C21—H21B	108.1
C20—N3—C16	117.3 (4)	C23—C22—C21	112.6 (5)
C20—N3—Re	122.5 (3)	C23—C22—H22A	109.1
C16—N3—Re	120.2 (3)	C21—C22—H22A	109.1
C25—N4—C26	116.0 (5)	C23—C22—H22B	109.1
O1—C1—Re	176.6 (5)	C21—C22—H22B	109.1
O2—C2—Re	176.9 (5)	H22A—C22—H22B	107.8
O3—C3—Re	175.7 (5)	C27—C23—C24	117.0 (5)
N1—C4—C5	122.1 (5)	C27—C23—C22	122.1 (6)
N1—C4—H4	119	C24—C23—C22	120.8 (6)
C5—C4—H4	119	C25—C24—C23	119.3 (5)
C6—C5—C4	120.3 (5)	C25—C24—H24	120.4
C6—C5—H5	119.8	C23—C24—H24	120.4
C4—C5—H5	119.8	N4—C25—C24	124.0 (5)
C5—C6—C7	118.6 (5)	N4—C25—H25	118
C5—C6—H6	120.7	C24—C25—H25	118
C7—C6—H6	120.7	N4—C26—C27	123.5 (5)
C14—C7—C6	117.9 (5)	N4—C26—H26	118.3
C14—C7—C8	119.2 (5)	C27—C26—H26	118.3
C6—C7—C8	122.9 (5)	C26—C27—C23	120.2 (5)
C9—C8—C7	120.8 (5)	C26—C27—H27	119.9
C9—C8—H8	119.6	C23—C27—H27	119.9
C7—C8—H8	119.6	N5—C28—C29	178.5 (8)
C8—C9—C10	121.0 (5)	C28—C29—H29A	109.5
C8—C9—H9	119.5	C28—C29—H29B	109.5
C10—C9—H9	119.5	H29A—C29—H29B	109.5
C15—C10—C11	117.7 (5)	C28—C29—H29C	109.5
C15—C10—C9	119.2 (5)	H29A—C29—H29C	109.5
C11—C10—C9	123.0 (5)	H29B—C29—H29C	109.5
C12—C11—C10	118.5 (5)	F3—P—F6	91.2 (2)
C12—C11—H11	120.7	F3—P—F4	90.6 (2)
C10—C11—H11	120.7	F6—P—F4	89.6 (2)
C11—C12—C13	120.4 (5)	F3—P—F2	90.3 (2)
C11—C12—H12	119.8	F6—P—F2	90.64 (18)
C13—C12—H12	119.8	F4—P—F2	179.1 (2)
N2—C13—C12	122.3 (5)	F3—P—F5	89.95 (19)
N2—C13—H13	118.8	F6—P—F5	178.8 (2)
C12—C13—H13	118.8	F4—P—F5	90.05 (19)
N1—C14—C7	122.7 (5)	F2—P—F5	89.73 (17)
N1—C14—C15	117.1 (4)	F3—P—F1	179.6 (2)
C7—C14—C15	120.1 (5)	F6—P—F1	89.17 (19)
N2—C15—C10	122.9 (4)	F4—P—F1	89.5 (2)
N2—C15—C14	117.5 (4)	F2—P—F1	89.67 (18)
C10—C15—C14	119.5 (4)	F5—P—F1	89.68 (19)
C2—Re—N1—C4	−2.6 (5)	Re—N1—C14—C7	176.1 (4)
C1—Re—N1—C4	87.1 (5)	C4—N1—C14—C15	−179.1 (5)
N2—Re—N1—C4	178.0 (5)	Re—N1—C14—C15	−2.9 (6)
N3—Re—N1—C4	−98.1 (5)	C6—C7—C14—N1	−0.3 (8)
C2—Re—N1—C14	−178.5 (4)	C8—C7—C14—N1	179.5 (5)
C1—Re—N1—C14	−88.8 (4)	C6—C7—C14—C15	178.6 (5)
N2—Re—N1—C14	2.1 (3)	C8—C7—C14—C15	−1.6 (7)
N3—Re—N1—C14	86.0 (4)	C13—N2—C15—C10	0.7 (7)
C3—Re—N2—C13	−2.3 (5)	Re—N2—C15—C10	−179.1 (4)
C1—Re—N2—C13	−89.7 (5)	C13—N2—C15—C14	179.9 (4)
N1—Re—N2—C13	179.1 (5)	Re—N2—C15—C14	0.0 (6)
N3—Re—N2—C13	89.7 (4)	C11—C10—C15—N2	−1.3 (7)
C3—Re—N2—C15	177.6 (4)	C9—C10—C15—N2	178.2 (5)
C1—Re—N2—C15	90.1 (4)	C11—C10—C15—C14	179.6 (5)
N1—Re—N2—C15	−1.1 (3)	C9—C10—C15—C14	−1.0 (7)
N3—Re—N2—C15	−90.4 (3)	N1—C14—C15—N2	1.9 (7)
C3—Re—N3—C20	−139.5 (4)	C7—C14—C15—N2	−177.1 (5)
C2—Re—N3—C20	−50.3 (4)	N1—C14—C15—C10	−178.9 (5)
N2—Re—N3—C20	120.7 (4)	C7—C14—C15—C10	2.1 (7)
N1—Re—N3—C20	44.6 (4)	C20—N3—C16—C17	−2.7 (8)
C3—Re—N3—C16	41.9 (4)	Re—N3—C16—C17	176.0 (4)
C2—Re—N3—C16	131.1 (4)	N3—C16—C17—C18	1.2 (8)
N2—Re—N3—C16	−57.9 (4)	C16—C17—C18—C19	1.5 (8)
N1—Re—N3—C16	−134.0 (4)	C16—C17—C18—C21	−176.4 (5)
C14—N1—C4—C5	1.1 (8)	C17—C18—C19—C20	−2.5 (8)
Re—N1—C4—C5	−174.7 (4)	C21—C18—C19—C20	175.4 (5)
N1—C4—C5—C6	−1.6 (9)	C16—N3—C20—C19	1.6 (8)
C4—C5—C6—C7	1.1 (9)	Re—N3—C20—C19	−177.0 (4)
C5—C6—C7—C14	−0.2 (8)	C18—C19—C20—N3	1.0 (8)
C5—C6—C7—C8	−180.0 (5)	C17—C18—C21—C22	76.3 (7)
C14—C7—C8—C9	−0.1 (8)	C19—C18—C21—C22	−101.5 (6)
C6—C7—C8—C9	179.6 (5)	C18—C21—C22—C23	175.2 (5)
C7—C8—C9—C10	1.3 (8)	C21—C22—C23—C27	−75.2 (8)
C8—C9—C10—C15	−0.7 (8)	C21—C22—C23—C24	102.5 (7)
C8—C9—C10—C11	178.7 (5)	C27—C23—C24—C25	−2.5 (9)
C15—C10—C11—C12	1.4 (8)	C22—C23—C24—C25	179.7 (6)
C9—C10—C11—C12	−178.0 (5)	C26—N4—C25—C24	1.1 (9)
C10—C11—C12—C13	−1.0 (8)	C23—C24—C25—N4	0.8 (10)
C15—N2—C13—C12	−0.2 (8)	C25—N4—C26—C27	−1.4 (9)
Re—N2—C13—C12	179.6 (4)	N4—C26—C27—C23	−0.3 (10)
C11—C12—C13—N2	0.4 (8)	C24—C23—C27—C26	2.2 (9)
C4—N1—C14—C7	−0.1 (7)	C22—C23—C27—C26	−180.0 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···F4	0.93	2.47	3.377 (6)	166
C16—H16···F6	0.93	2.38	3.180 (6)	145
C11—H11···F5^i	0.93	2.55	3.327 (6)	142
C12—H12···F1^i	0.93	2.55	3.355 (6)	145
C5—H5···F1^ii	0.93	2.52	3.382 (6)	154
C19—H19···F4^iii	0.93	2.49	3.150 (6)	128
C20—H20···F5^iii	0.93	2.45	3.317 (6)	154
C21—H21A···F5^iv	0.97	2.53	3.486 (6)	168
C22—H22B···O1^v	0.97	2.53	3.211 (8)	127

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