Dichloro­oxo(quinoline-8-thiolato-κ²N,S)(triphenyl­phosphine oxide-κO)rhenium(V) acetone solvate

The complex mol­ecule in the title compound, [Re(C₉H₆NS)Cl₂O(C₁₈H₁₅OP)]·C₃H₆O, has distorted octa­hedral geometry. The Re=O bond occupies the position trans to the triphenyl­phosphine oxide O atom. The Re—Cl bond trans to the thiol­ate S atom is longer than that trans to the quinoline N atom, implying a stronger trans influence of the S atom. Intra- and inter­molecular π–π inter­actions are also observed between the π rings in the complex.

S1. Comment

Oxorhenium(V) complexes are of interest because of their characteristic stereochemistry and reactivity as radiopharmaceuticals and O-atom transfer catalysts. We have synthesized oxorhenium(V) complexes using 8-substituted quinoline ligands as asymmetrical bidentate ligands to investigate stereoselectivity. For the N,N-bidentate ligands, the complex using 8-aminoquinoline (8-H₂Nqn), [ReCl₃(8-Nqn)PPh₃] (PPh₃ is triphenylphosphine), lost the Re═O group and the metal atom formed a double bond with the N atom of the quinoline ligand (Miyashita et al., 2001), whereas the complex using 8-amino-2-methylquinoline (2-Me-8-H₂Nqn), [ReOX₂(2-Me-8-HNqn)PPh₃] (X = Cl and Br), retained the Re═O group (Ohashi et al., 2003). Moreover, the complexes were unstable in solution and substitution by OPPh₃ can occur. On the other hand, the corresponding oxorhenium(V) complexes [ReOCl₂(2-X-5-Y-7-Z-8-Oqn)PPh₃] using the N,O-bidentate ligands 2-, 5- and/or 7-substituted 8-hydroxyquinoline (2-X-5-Y-7-Z-8-HOqn; X = H and Me, Y = H, Cl and Br, and Z = H, Cl, Br and I) display no OPPh₃ substitution (Miyashita et al., 2005). To elucidate the stereochemistry and reactivity depending on the coordinating atom, we attempted to synthesize new oxorhenium(V) complexes using the N,S-bidentate ligand 8-mercaptoquinoline (8-HSqn). We report here the crystal structure of the obtained complex, (I).

The asymmetric unit of (I) contains a mononuclear complex molecule and an (CH₃)₂CO molecule. A perspective view of the complex molecule is shown in Fig. 1, and selected bond distances and angles are listed in Table 1. In the complex, the Re atom is coordinated by two O atoms, one establishing a double bond to the metal atom and the other from the OPPh₃ ligand, two Cl atoms, and a deprotonated S atom and an N atom from the 8-Sqn ligand, forming a distorted octahedral geometry. The O atom of OPPh₃ lies in trans position to the Re═O bond along the axial direction, as observed in previously reported oxorhenium(V) complexes (Battistuzzi et al., 2001; Hansen et al., 1995), whereas the S atom, heterocyclic N atom and two cis Cl atoms occupy the equatorial plane. Similar coordination geometry was observed for the oxorhenium(V) complex [ReOCl₂(2-Me-8-HNqn)OPPh₃] (Ohashi et al., 2003).

The Re1—N1 [2.120 (6) Å] and Re1—O1 [1.649 (6) Å] distances in (I) are within the normal range of Re—N single-bond and Re═O multiple-bond distances for the oxorhenium(V) complexes. The Re1—Cl2 bond trans to the S atom [2.448 (2) Å] is significantly longer than the Re1—Cl1 bond trans to the quinoline N atom [2.353 (2) Å]. This difference appears to be a result of the trans influence of the S atom. Indeed, the Re1—S1 distance [2.298 (2) Å] in (I) is shorter than Re—S distances [2.447 (3) and 2.313 (3) Å] in [MeReO(8-Sqn)₂] (Shan et al., 2002), in which two S atoms occupy trans positions with respect to each other. The Re1—O2 distance, which is trans to the Re═O bond, is 2.117 (4) Å in (I). This is consistent with the trans influence of the Re═O linkage on an O atom from an axially bound ligand (Ohashi et al., 2003). In addition, in (I), the Re atom is located at 0.277 (2) Å above the equatorial plane in the direction of the Re═O bond.

The Re═O linkage significantly expands the angles to the equatorial Cl and P atoms [Cl1—Re1—O1 = 99.7 (2)° and S1—Re1—O1 = 100.7 (3)°], but not those to the equatorial N atom and the other Cl atom [O1—Re1—N1 = 92.6 (3)° and Cl2—Re1—O1 = 93.1 (3)°]. The O1—Re1—O2 angle is 170.9 (3)° in (I), which deviates from 180° for an ideal octahedral structure. The Re1—O2—P1 angle [159.9 (3)°] is slightly smaller than that in [ReOCl₃(PPh₃)(OPPh₃)] [165.1 (3)°], which has a crowded structure (Bryan et al., 1998). These configurations may arise from the relatively less hindered structure or an intramolecular interaction. The dihedral angle between the N1/C1–C4/C9 ring of the quinoline system and the C10–C15 phenyl ring is 11.8 (3)°. The distance between the two planes is 3.43 (2) Å.

In the crystal packing of (I), the C4–C9 rings of the quinoline systems of adjacent molecules overlap in the axial direction, and the complex molecules form a dimeric structure. The interplanar distances [3.53 (1) Å] between two planes at (x, y, z) and (−x, 1 − y, −z) are within the range of intermolecular π–π stacking. Although the (CH₃)₂CO molecule is also incorporated into the crystal packing, it does not participate in significant intermolecular interactions. The O3—C17ⁱ contact distance is 3.33 (1) Å [symmetry code (i): 1 − x, y − 1/2, 1/2 − z].

The reactions of the starting materials [ReOCl₃(PPh₃)₂] with 8-HSqn produced a brown powder. When the powder was recrystallized from (CH₃)₂CO, compound (I), containing OPPh₃ instead of PPh₃, was obtained. It appears hat PPh₃ was oxidized during the recrystallization process. The strong IR bands of the Re═O and P═O bonds in (I) were observed at 989 and 1143 cm⁻¹, respectively. In the far-IR spectra, the Re—Cl stretching bands were observed as two strong bands (325 and 280 cm⁻¹). These values for the Re═ O and Re—Cl bonds reflect well the corresponding bond distances (Miyashita et al., 2005).

S2. Experimental

To a suspension containing [ReOCl₃(PPh₃)₂] (200 mg, 0.24 mmol) (Johnson et al., 1967) in CH₂Cl₂ (60 ml) was added a solution containing 8-HSqn·HCl (47 mg, 0.24 mmol) in C₆H₅CH₃ (10 ml). The mixture was stirred overnight at room temperature, whereupon the color of the mixture turned from light green to dark brown. After insoluble materials had been filtered off, the filtrate was dried by vacuum line. The resulted dark-brown powder was washed with Et₂O. Recrystallization in a refrigerator from (CH₃)₂CO gave dark-brown prismatic [block?] crystals (yield 83 mg, 45%). Analysis found: C 46.82, H 3.66, N 1.87%; calculated for C₂₇H₂₁Cl₂NO₂PReS·C₃H₆O: C 46.81, H 3.54, N 1.82%.

S3. Refinement

After their presence had been checking in a difference map, all H atoms bonded to the C atoms were fixed geometrically and allowed to ride on their attached atoms [C—H = 0.95 or 0.97 Å; U_iso = 1.2U_eq(C)]. The H atoms were included in the calculations but not refined. [Constrained?]

Computing details

Data collection: WinAFC Difftactometer Control Software (Rigaku Corporation, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.

Figures

Fig. 1. A perspective drawing of the complex molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are shown at the 20% probability level and H atoms have been omitted for clarity.

Dichlorooxo(quinoline-8-thiolato-κ²N,S)(triphenylphosphine oxide-κO)rhenium(V) acetone solvate

Crystal data

[Re(C9H6NS)Cl2O(C18H15O)]·C3H6O	F(000) = 1512
Mr = 769.70	Dx = 1.701 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.7107 Å
a = 11.569 (3) Å	Cell parameters from 25 reflections
b = 15.152 (7) Å	θ = 14.5–14.9°
c = 17.660 (8) Å	µ = 4.38 mm^−1
β = 103.90 (3)°	T = 296 K
V = 3005 (2) Å^3	Block, black
Z = 4	0.63 × 0.53 × 0.40 mm

Data collection

Rigaku AFC-7S diffractometer	Rint = 0.025
ω–2θ scans	θmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = −15→4
Tmin = 0.148, Tmax = 0.174	k = −19→0
7600 measured reflections	l = −22→22
6887 independent reflections	3 standard reflections every 150 reflections
4608 reflections with F^2 > 2σ(F^2)	intensity decay: 0.2%

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + {0.08[Max(Fo^2,0) + 2Fc^2]/3}^2]
wR(F^2) = 0.149	(Δ/σ)max = 0.0001
S = 1.12	Δρmax = 1.07 e Å^−3
6887 reflections	Δρmin = −1.86 e Å^−3
352 parameters

Special details

Refinement. Refinement using reflections with F² > −10.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Re1	0.04250 (2)	0.24780 (2)	0.11629 (2)	0.04774 (8)
Cl1	0.0391 (2)	0.0952 (1)	0.0909 (2)	0.0855 (8)
Cl2	0.0364 (2)	0.2135 (2)	0.2507 (1)	0.0754 (7)
S1	0.0971 (2)	0.2770 (1)	0.0020 (1)	0.0585 (5)
P1	0.3452 (1)	0.23789 (9)	0.22467 (9)	0.0355 (4)
O1	−0.1014 (5)	0.2690 (4)	0.0898 (5)	0.086 (2)
O2	0.2268 (4)	0.2321 (3)	0.1664 (3)	0.042 (1)
O3	0.2946 (9)	−0.2152 (6)	0.1041 (5)	0.120 (3)
N1	0.0860 (5)	0.3822 (4)	0.1420 (4)	0.053 (2)
C1	0.0728 (8)	0.4197 (6)	0.2060 (5)	0.072 (3)
C2	0.0931 (10)	0.5115 (6)	0.2175 (6)	0.088 (3)
C3	0.1274 (8)	0.5613 (5)	0.1653 (6)	0.074 (3)
C4	0.1463 (6)	0.5235 (5)	0.0962 (5)	0.062 (2)
C5	0.1806 (7)	0.5724 (5)	0.0400 (6)	0.073 (3)
C6	0.1910 (7)	0.5287 (6)	−0.0275 (6)	0.076 (3)
C7	0.1690 (7)	0.4392 (6)	−0.0402 (5)	0.063 (2)
C8	0.1346 (6)	0.3899 (5)	0.0149 (5)	0.057 (2)
C9	0.1224 (5)	0.4317 (4)	0.0856 (4)	0.042 (2)
C10	0.3576 (6)	0.3327 (4)	0.2869 (4)	0.046 (2)
C11	0.3065 (7)	0.3319 (5)	0.3497 (4)	0.057 (2)
C12	0.308 (1)	0.4080 (6)	0.3940 (5)	0.084 (3)
C13	0.361 (1)	0.4824 (6)	0.3754 (6)	0.095 (4)
C14	0.4144 (10)	0.4839 (6)	0.3120 (7)	0.088 (4)
C15	0.4078 (8)	0.4096 (5)	0.2665 (5)	0.063 (2)
C16	0.4592 (6)	0.2410 (4)	0.1713 (4)	0.039 (2)
C17	0.5797 (6)	0.2441 (4)	0.2088 (4)	0.048 (2)
C18	0.6631 (6)	0.2427 (4)	0.1635 (5)	0.052 (2)
C19	0.6274 (8)	0.2392 (5)	0.0833 (5)	0.064 (3)
C20	0.5093 (8)	0.2353 (6)	0.0474 (5)	0.069 (3)
C21	0.4243 (7)	0.2365 (5)	0.0913 (5)	0.061 (2)
C22	0.3722 (6)	0.1423 (4)	0.2861 (4)	0.039 (2)
C23	0.4662 (6)	0.1373 (5)	0.3505 (4)	0.052 (2)
C24	0.4917 (7)	0.0605 (6)	0.3938 (4)	0.061 (2)
C25	0.4204 (8)	−0.0129 (5)	0.3715 (5)	0.060 (2)
C26	0.3246 (7)	−0.0084 (4)	0.3075 (5)	0.058 (2)
C27	0.3010 (6)	0.0685 (4)	0.2648 (4)	0.047 (2)
C28	0.2370 (9)	−0.1473 (6)	0.0974 (5)	0.074 (3)
C29	0.2668 (10)	−0.0719 (8)	0.0555 (7)	0.097 (4)
C30	0.131 (1)	−0.1387 (7)	0.1274 (6)	0.091 (4)
H1	0.0495	0.3849	0.2446	0.0858*
H2	0.0813	0.5375	0.2643	0.1047*
H3	0.1411	0.6218	0.1757	0.0900*
H4	0.1960	0.6338	0.0463	0.0902*
H5	0.2134	0.5604	−0.0682	0.0906*
H6	0.1775	0.4122	−0.0869	0.0746*
H7	0.2701	0.2796	0.3629	0.0685*
H8	0.2751	0.4079	0.4382	0.1000*
H9	0.3616	0.5343	0.4063	0.1139*
H10	0.4554	0.5352	0.3020	0.1067*
H11	0.4372	0.4112	0.2205	0.0750*
H12	0.6046	0.2471	0.2642	0.0581*
H13	0.7457	0.2441	0.1880	0.0630*
H14	0.6845	0.2394	0.0527	0.0764*
H15	0.4848	0.2312	−0.0080	0.0826*
H16	0.3418	0.2346	0.0658	0.0729*
H17	0.5154	0.1877	0.3658	0.0617*
H18	0.5568	0.0580	0.4381	0.0729*
H19	0.4379	−0.0658	0.4008	0.0717*
H20	0.2755	−0.0588	0.2930	0.0703*
H21	0.2353	0.0711	0.2204	0.0573*
H22	0.2311	−0.0181	0.0689	0.1113*
H23	0.2406	−0.0795	0.0004	0.1113*
H24	0.3516	−0.0624	0.0680	0.1113*
H25	0.1467	−0.1530	0.1822	0.1026*
H26	0.0984	−0.0795	0.1217	0.1026*
H27	0.0681	−0.1775	0.1007	0.1026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Re1	0.0317 (2)	0.0409 (2)	0.0690 (2)	−0.0017 (1)	0.0091 (1)	0.0124 (1)
Cl1	0.089 (2)	0.045 (1)	0.104 (2)	−0.013 (1)	−0.013 (1)	0.001 (1)
Cl2	0.077 (1)	0.069 (1)	0.094 (2)	0.000 (1)	0.048 (1)	0.022 (1)
S1	0.056 (1)	0.0544 (10)	0.060 (1)	−0.0015 (9)	0.0036 (9)	−0.0006 (8)
P1	0.0337 (7)	0.0341 (8)	0.0396 (7)	−0.0008 (6)	0.0107 (6)	0.0006 (6)
O1	0.038 (3)	0.078 (4)	0.136 (6)	−0.006 (3)	0.010 (3)	0.041 (4)
O2	0.033 (2)	0.041 (2)	0.050 (2)	0.004 (2)	0.006 (2)	0.004 (2)
O3	0.161 (8)	0.093 (5)	0.090 (5)	0.062 (6)	−0.002 (5)	0.006 (4)
N1	0.046 (3)	0.045 (3)	0.070 (4)	0.007 (3)	0.019 (3)	0.007 (3)
C1	0.080 (6)	0.069 (5)	0.075 (6)	0.027 (4)	0.037 (5)	0.008 (4)
C2	0.115 (8)	0.055 (5)	0.098 (7)	0.033 (5)	0.032 (6)	0.003 (5)
C3	0.085 (6)	0.049 (4)	0.089 (7)	0.017 (4)	0.025 (5)	−0.011 (4)
C4	0.048 (4)	0.041 (4)	0.095 (6)	0.007 (3)	0.014 (4)	0.017 (4)
C5	0.051 (5)	0.042 (4)	0.127 (8)	0.012 (3)	0.025 (5)	0.034 (5)
C6	0.049 (5)	0.083 (6)	0.101 (7)	0.008 (4)	0.031 (5)	0.034 (5)
C7	0.047 (4)	0.073 (5)	0.073 (5)	0.010 (4)	0.023 (4)	0.024 (4)
C8	0.036 (4)	0.053 (4)	0.077 (5)	0.004 (3)	0.006 (3)	0.011 (4)
C9	0.033 (3)	0.028 (3)	0.063 (4)	0.003 (2)	0.010 (3)	0.007 (3)
C10	0.048 (4)	0.038 (3)	0.049 (4)	−0.001 (3)	0.009 (3)	−0.004 (3)
C11	0.080 (5)	0.041 (3)	0.058 (4)	0.002 (3)	0.035 (4)	−0.001 (3)
C12	0.135 (9)	0.059 (5)	0.070 (6)	0.002 (5)	0.049 (6)	−0.014 (4)
C13	0.15 (1)	0.049 (5)	0.094 (8)	0.000 (6)	0.042 (7)	−0.026 (5)
C14	0.109 (8)	0.048 (5)	0.116 (9)	−0.025 (5)	0.044 (7)	−0.019 (5)
C15	0.077 (6)	0.043 (4)	0.080 (5)	−0.012 (4)	0.042 (4)	−0.005 (4)
C16	0.038 (3)	0.039 (3)	0.043 (3)	−0.003 (2)	0.012 (2)	0.001 (3)
C17	0.034 (3)	0.059 (4)	0.049 (3)	−0.006 (3)	0.006 (3)	−0.005 (3)
C18	0.034 (3)	0.052 (4)	0.073 (5)	−0.005 (3)	0.017 (3)	−0.002 (3)
C19	0.059 (5)	0.078 (6)	0.063 (5)	−0.016 (4)	0.031 (4)	−0.009 (4)
C20	0.051 (4)	0.111 (7)	0.050 (4)	−0.011 (4)	0.022 (3)	−0.005 (4)
C21	0.042 (4)	0.086 (6)	0.054 (4)	−0.013 (4)	0.012 (3)	0.006 (4)
C22	0.042 (3)	0.041 (3)	0.038 (3)	0.001 (3)	0.016 (3)	0.001 (2)
C23	0.043 (4)	0.055 (4)	0.052 (4)	−0.003 (3)	0.002 (3)	0.005 (3)
C24	0.054 (4)	0.074 (5)	0.053 (4)	0.009 (4)	0.009 (3)	0.017 (4)
C25	0.066 (5)	0.056 (4)	0.063 (5)	0.023 (4)	0.023 (4)	0.019 (4)
C26	0.073 (5)	0.034 (3)	0.067 (5)	−0.001 (3)	0.018 (4)	0.004 (3)
C27	0.045 (4)	0.044 (3)	0.050 (4)	0.000 (3)	0.006 (3)	0.002 (3)
C28	0.089 (7)	0.074 (6)	0.051 (5)	0.011 (5)	0.002 (4)	0.005 (4)
C29	0.090 (8)	0.101 (8)	0.110 (9)	0.012 (6)	0.042 (7)	0.016 (7)
C30	0.117 (9)	0.074 (6)	0.077 (6)	−0.022 (6)	0.014 (6)	0.001 (5)

Geometric parameters (Å, º)

Re1—Cl1	2.353 (2)	C13—C14	1.41 (1)
Re1—Cl2	2.448 (2)	C13—H9	0.956
Re1—S1	2.298 (2)	C14—C15	1.37 (1)
Re1—O1	1.649 (6)	C14—H10	0.950
Re1—O2	2.117 (4)	C15—H11	0.954
Re1—N1	2.120 (6)	C16—C17	1.393 (9)
S1—C8	1.765 (8)	C16—C21	1.37 (1)
P1—O2	1.506 (4)	C17—C18	1.395 (10)
P1—C10	1.794 (7)	C17—H12	0.951
P1—C16	1.796 (7)	C18—C19	1.38 (1)
P1—C22	1.792 (6)	C18—H13	0.949
O3—C28	1.22 (1)	C19—C20	1.36 (1)
N1—C1	1.306 (10)	C19—H14	0.949
N1—C9	1.391 (8)	C20—C21	1.39 (1)
C1—C2	1.42 (1)	C20—H15	0.953
C1—H1	0.950	C21—H16	0.953
C2—C3	1.32 (1)	C22—C23	1.373 (9)
C2—H2	0.955	C22—C27	1.387 (9)
C3—C4	1.41 (1)	C23—C24	1.385 (10)
C3—H3	0.941	C23—H17	0.951
C4—C5	1.37 (1)	C24—C25	1.38 (1)
C4—C9	1.421 (9)	C24—H18	0.948
C5—C6	1.39 (1)	C25—C26	1.38 (1)
C5—H4	0.947	C25—H19	0.948
C6—C7	1.39 (1)	C26—C27	1.380 (9)
C6—H5	0.951	C26—H20	0.949
C7—C8	1.36 (1)	C27—H21	0.953
C7—H6	0.948	C28—C29	1.45 (1)
C8—C9	1.44 (1)	C28—C30	1.45 (1)
C10—C11	1.377 (9)	C29—H22	0.969
C10—C15	1.388 (9)	C29—H23	0.954
C11—C12	1.39 (1)	C29—H24	0.964
C11—H7	0.951	C30—H25	0.965
C12—C13	1.36 (1)	C30—H26	0.970
C12—H8	0.948	C30—H27	0.967
Cl2···C2^i	3.511 (9)	O3···C23^iv	3.50 (1)
Cl2···C3^i	3.530 (8)	O3···C5^v	3.56 (1)
O1···C19^ii	3.14 (1)	C4···C7^iii	3.59 (1)
O1···C5^iii	3.295 (10)	C5···C8^iii	3.59 (1)
O1···C18^ii	3.312 (10)	C6···C25^vi	3.54 (1)
O1···C6^iii	3.34 (1)	C6···C9^iii	3.57 (1)
O3···C17^iv	3.33 (1)
Cl1—Re1—Cl2	88.46 (9)	C13—C12—H8	119.5
Cl1—Re1—S1	91.00 (9)	C12—C13—C14	121.0 (8)
Cl1—Re1—O1	99.7 (2)	C12—C13—H9	119.2
Cl1—Re1—O2	86.5 (1)	C14—C13—H9	119.7
Cl1—Re1—N1	167.5 (2)	C13—C14—C15	118.7 (8)
Cl2—Re1—S1	166.11 (8)	C13—C14—H10	119.9
Cl2—Re1—O1	93.1 (3)	C15—C14—H10	121.5
Cl2—Re1—O2	80.3 (1)	C10—C15—C14	120.2 (7)
Cl2—Re1—N1	93.3 (2)	C10—C15—H11	119.9
S1—Re1—O1	100.7 (3)	C14—C15—H11	119.8
S1—Re1—O2	85.8 (1)	P1—C16—C17	121.9 (5)
S1—Re1—N1	84.4 (2)	P1—C16—C21	117.8 (5)
O1—Re1—O2	170.9 (3)	C17—C16—C21	120.3 (6)
O1—Re1—N1	92.6 (3)	C16—C17—C18	118.5 (7)
O2—Re1—N1	81.7 (2)	C16—C17—H12	120.8
Re1—S1—C8	100.6 (3)	C18—C17—H12	120.7
O2—P1—C10	113.0 (3)	C17—C18—C19	120.9 (7)
O2—P1—C16	107.7 (3)	C17—C18—H13	119.8
O2—P1—C22	111.4 (3)	C19—C18—H13	119.4
C10—P1—C16	109.9 (3)	C18—C19—C20	119.9 (7)
C10—P1—C22	107.4 (3)	C18—C19—H14	120.5
C16—P1—C22	107.2 (3)	C20—C19—H14	119.6
Re1—O2—P1	159.9 (3)	C19—C20—C21	120.3 (8)
Re1—N1—C1	122.2 (5)	C19—C20—H15	119.9
Re1—N1—C9	117.5 (5)	C21—C20—H15	119.8
C1—N1—C9	120.2 (7)	C16—C21—C20	120.1 (7)
N1—C1—C2	120.1 (8)	C16—C21—H16	120.1
N1—C1—H1	119.5	C20—C21—H16	119.8
C2—C1—H1	120.4	P1—C22—C23	122.3 (5)
C1—C2—C3	121.7 (9)	P1—C22—C27	118.8 (5)
C1—C2—H2	118.4	C23—C22—C27	118.8 (6)
C3—C2—H2	119.9	C22—C23—C24	121.6 (7)
C2—C3—C4	120.3 (8)	C22—C23—H17	119.5
C2—C3—H3	118.8	C24—C23—H17	119.0
C4—C3—H3	120.8	C23—C24—C25	119.1 (7)
C3—C4—C5	122.5 (8)	C23—C24—H18	120.7
C3—C4—C9	116.5 (7)	C25—C24—H18	120.2
C5—C4—C9	120.9 (8)	C24—C25—C26	119.9 (7)
C4—C5—C6	117.4 (8)	C24—C25—H19	119.3
C4—C5—H4	121.5	C26—C25—H19	120.8
C6—C5—H4	121.1	C25—C26—C27	120.2 (7)
C5—C6—C7	123.6 (8)	C25—C26—H20	119.5
C5—C6—H5	120.1	C27—C26—H20	120.3
C7—C6—H5	116.3	C22—C27—C26	120.4 (6)
C6—C7—C8	119.7 (8)	C22—C27—H21	119.7
C6—C7—H6	120.7	C26—C27—H21	119.9
C8—C7—H6	119.6	O3—C28—C29	121 (1)
S1—C8—C7	123.1 (7)	O3—C28—C30	121 (1)
S1—C8—C9	117.9 (5)	C29—C28—C30	116.2 (9)
C7—C8—C9	119.0 (7)	C28—C29—H22	111.8
N1—C9—C4	121.1 (7)	C28—C29—H23	111.7
N1—C9—C8	119.5 (6)	C28—C29—H24	110.8
C4—C9—C8	119.4 (6)	H22—C29—H23	107.6
P1—C10—C11	120.0 (5)	H22—C29—H24	106.7
P1—C10—C15	119.4 (5)	H23—C29—H24	108.0
C11—C10—C15	120.3 (6)	C28—C30—H25	112.0
C10—C11—C12	119.6 (7)	C28—C30—H26	112.8
C10—C11—H7	120.3	C28—C30—H27	111.8
C12—C11—H7	120.0	H25—C30—H26	106.6
C11—C12—C13	119.9 (8)	H25—C30—H27	106.9
C11—C12—H8	120.5	H26—C30—H27	106.4
Re1—S1—C8—C7	−177.4 (6)	N1—C9—C8—C7	179.2 (6)
Re1—S1—C8—C9	−0.4 (5)	C1—N1—C9—C4	0 (1)
Re1—O2—P1—C10	−28.8 (9)	C1—N1—C9—C8	−179.0 (7)
Re1—O2—P1—C16	−150.3 (8)	C1—C2—C3—C4	0 (1)
Re1—O2—P1—C22	92.3 (8)	C2—C1—N1—C9	1 (1)
Re1—N1—C1—C2	−174.4 (7)	C2—C3—C4—C5	179.2 (9)
Re1—N1—C9—C4	176.2 (5)	C2—C3—C4—C9	2 (1)
Re1—N1—C9—C8	−2.9 (8)	C3—C4—C5—C6	−177.0 (8)
Cl1—Re1—S1—C8	−169.2 (2)	C3—C4—C9—C8	177.2 (7)
Cl1—Re1—O2—P1	−129.1 (8)	C4—C5—C6—C7	0 (1)
Cl1—Re1—N1—C1	−113.4 (9)	C4—C9—C8—C7	0.1 (10)
Cl1—Re1—N1—C9	70 (1)	C5—C4—C9—C8	0 (1)
Cl2—Re1—S1—C8	−81.5 (4)	C5—C6—C7—C8	0 (1)
Cl2—Re1—O2—P1	−40.1 (8)	C6—C5—C4—C9	0 (1)
Cl2—Re1—N1—C1	−15.8 (6)	C6—C7—C8—C9	0 (1)
Cl2—Re1—N1—C9	168.3 (5)	C10—P1—C16—C17	58.1 (6)
S1—Re1—O2—P1	139.6 (8)	C10—P1—C16—C21	−124.5 (6)
S1—Re1—N1—C1	178.0 (6)	C10—P1—C22—C23	−46.6 (7)
S1—Re1—N1—C9	2.0 (5)	C10—P1—C22—C27	138.2 (5)
S1—C8—C7—C6	176.6 (6)	C10—C11—C12—C13	0 (1)
S1—C8—C9—N1	2.2 (8)	C10—C15—C14—C13	−5 (1)
S1—C8—C9—C4	−177.0 (5)	C11—C10—P1—C16	−159.8 (6)
P1—O2—Re1—N1	54.7 (8)	C11—C10—P1—C22	−43.5 (7)
P1—C10—C11—C12	−174.8 (7)	C11—C10—C15—C14	4 (1)
P1—C10—C15—C14	177.8 (8)	C11—C12—C13—C14	0 (1)
P1—C16—C17—C18	177.3 (5)	C12—C11—C10—C15	−1 (1)
P1—C16—C21—C20	−177.5 (7)	C12—C13—C14—C15	3 (1)
P1—C22—C23—C24	−174.6 (6)	C15—C10—P1—C16	26.9 (7)
P1—C22—C27—C26	175.2 (6)	C15—C10—P1—C22	143.2 (6)
O1—Re1—S1—C8	90.8 (3)	C16—P1—C22—C23	71.5 (6)
O1—Re1—N1—C1	77.5 (7)	C16—P1—C22—C27	−103.8 (6)
O1—Re1—N1—C9	−98.4 (5)	C16—C17—C18—C19	0 (1)
O2—Re1—S1—C8	−82.8 (3)	C16—C21—C20—C19	0 (1)
O2—Re1—N1—C1	−95.5 (6)	C17—C16—P1—C22	−58.3 (6)
O2—Re1—N1—C9	88.6 (5)	C17—C16—C21—C20	0 (1)
O2—P1—C10—C11	79.8 (7)	C17—C18—C19—C20	−1 (1)
O2—P1—C10—C15	−93.5 (6)	C18—C17—C16—C21	0.1 (10)
O2—P1—C16—C17	−178.3 (5)	C18—C19—C20—C21	1 (1)
O2—P1—C16—C21	−1.0 (6)	C21—C16—P1—C22	119.0 (6)
O2—P1—C22—C23	−170.9 (5)	C22—C23—C24—C25	0 (1)
O2—P1—C22—C27	13.8 (6)	C22—C27—C26—C25	0 (1)
N1—Re1—S1—C8	−0.8 (3)	C23—C22—C27—C26	0 (1)
N1—C1—C2—C3	−1 (1)	C23—C24—C25—C26	0 (1)
N1—C9—C4—C3	−1 (1)	C24—C23—C22—C27	0 (1)
N1—C9—C4—C5	−179.1 (7)	C24—C25—C26—C27	1 (1)

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