fac-Tri­carbonyl(4,4′-di­methyl-2,2′-bi­pyridine)­tri­phenyl­tin(II)­rhenium(I)

The title organometallic compound, fac-tri­carbonyl-2κ³C-(4,4′-di­methyl-2,2′-bi­pyridine)-2κ²N,N′-tri­phenyl-1κ³C¹-tin(II)­rhenium(I)(Sn—Re), [ReSn(C₆H₅)₃(C₁₂H₁₂N₂)(CO)₃], con­tains three unique π–π stacking interactions. The result is an infinite chain of uninterrupted alternating intra- and intermolecular offset π–π stacking interactions throughout the crystal lattice. This extended π–π stacking arrangement, and an additional isolated intramolecular π–π interaction between the remaining 4,4′-di­methyl-2,2′-bi­pyridine ring and a second phenyl group, impose geometric constraints on the Re and Sn atoms, yielding distorted octahedral and tetrahedral coordinations, respectively, for the metal centers.

S1. Comment

The title compound, fac-(CO)₃(dmbpy)Re(I)Ph₃Sn(I) (dmbpy is 4,4'-dimethyl-2,2'-bipyridine), (I), was prepared and its structure determined as part of a general effort to characterize rhenium polypyridine complexes, or their derivatives, which might be involved in CO₂ reduction (Gibson et al., 2003). \sch

The molecules of (I) pack in a columnar network via an extended arrangement of parallel displaced π–π stacking interactions (Fig. 1). The atomic labelling scheme shown in Fig. 2 identifies the four aromatic rings involved in the detailed structural analysis. The first slipped stack is formed between the phenyl group containing atoms C16—C21 (Ph1) and the six-membered ring of N2/C9—C13 (dmbpy1). The second intramolecular interaction occurs between the phenyl ring defined by atoms C22—C27 (Ph2) and the ring containing atoms N1/C4—C8 (dmbpy2).

The chelating dmbpy ligand contains a pinched N1—Re—N2 bond angle, which requires the Re atom to adopt a distorted octahedral geometry. The Sn—Re—C3 bond angle is non-linear and the Re—C3 bond is slightly longer than the Re—C1 and Re—C2 bonds. Significant differences are observed in bond angles involving the ipso phenyl C atoms, the Sn atom and the Re atom, with the C28—Sn—Re bond angle being more than 10° greater than the other two. This is the consequence of inter- and intramolecular π–π stacking, involving two phenyl groups and both pyridine rings of the dmbpy ligand in each molecule.

It has been noted previously (Magistrato et al., 2001) that such aromatic π–π stacking interactions are rare within ligands of transition metal compounds, and their role in organometallic compounds is largely unknown. However, systems containing bipyridine ligands coordinated to the metal are well suited for π–π interactions because of their low π-electron density (Janiak, 2000).

Both pyridine rings of the dmbpy ligand which are bound to Re in each molecule of (I) are involved in intramolecular π–π stacking interactions with two of the phenyl ligands bound to Sn. With one, the pyridine centroid to phenyl centroid distance is 3.671 Å. In the second, the phenyl ring is slightly tilted away from the pyridine ring, and the pyridine centroid to phenyl centroid distance is 4.121 Å.

This second pyridine ring also participates in an intermolecular π–π stacking interaction with the phenyl group in a second molecule which is involved in the longer-range π–π interaction within that molecule. The intermolecular centroid to centroid distance is 4.221 Å. The angle formed by the two centroid-centroid vectors is 160.05°. The result is a well defined array that is controlled by the π–π interactions but does not have parallel arrangements of the aromatic groups because of the distorting effect of the third phenyl group bound to each Sn atom.

The bond angles around the Sn atom are also affected by the π–π stacking: the C_ipso—Sn—C_ipso bond angles vary from 101.32 (7)° to 110.33 (7)°. The largest angle is associated with the two phenyl rings involved in π–π stacking.

S2. Experimental

Compound (I) was synthesized according to the published procedure of Luong et al. (1980). fac-Re(dmbpy)(CO)₃Br (0.52 g, 0.97 mmol) in tetrahydrofuran (THF, 25 ml) was stirred for 2 h with Na/Hg (0.2 g Na, 5 ml H g). The mixture was allowed to settle, and the supernatant was drawn off and then added dropwise to Ph₃SnCl (0.44 g, 1.14 mmol) in THF (15 ml) in a foil-covered flask. The mixture was stirred for 2 h, the solvent was evaporated, and the residue was triturated with toluene. Toluene was removed from the extracts by evaporation, the residue was dissolved in THF, and hexane was added to precipitate the product. The product had spectroscopic properties analogous to those reported previously (Andréa et al., 1988). Single crystals of (I) for X-ray analysis were grown by slow diffusion from a solution in THF layered with hexane at 295 K.

S3. Refinement

Coordinates for all H-atom positions were calculated. Methyl groups were allowed to ride (the torsion angle which defines the orientation was allowed to refine) on their parent C atoms and the positions of the phenyl H atoms were constrained so that C—H = 0.95 Å. The U_iso values for all H atoms were refined, except for those of the methyl groups. The maximum residual electron density was 0.82 Å from Re1 and the deepest hole was 1.15 Å from C5.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A packing diagram for (I), illustrating the intra- and intermolecular offset π–π stacking interactions between neighboring phenyl and dimethylpyridyl rings.
	Fig. 2. A view of the molecule of (I), showing the atom-numbering scheme and with 40% probability displacement ellipsoids. H atoms are not shown.

fac-tricarbonyl-2κ³C-(4,4'-dimethyl-2,2'-bipyridine)-2κ²N,N'-triphenyl- 1κ³C¹-tin(II)rhenium(I)(Sn—Re)

Crystal data

[ReSn(C6H5)3(C12H12N2)(CO)3]	F(000) = 1552
Mr = 804.46	Dx = 1.873 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9678 reflections
a = 10.1077 (5) Å	θ = 2.3–28.1°
b = 20.0087 (11) Å	µ = 5.15 mm^−1
c = 14.3020 (8) Å	T = 100 K
β = 99.483 (1)°	Block, orange
V = 2852.9 (3) Å^3	0.39 × 0.14 × 0.14 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	6622 independent reflections
Radiation source: normal-focus sealed tube	6330 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 28.2°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −13→13
Tmin = 0.420, Tmax = 0.490	k = −26→25
24721 measured reflections	l = −18→18

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)] = 0.015	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.039	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0221P)^2 + 1.1474P] where P = (Fo^2 + 2Fc^2)/3
6622 reflections	(Δ/σ)max = 0.003
384 parameters	Δρmax = 0.87 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

Experimental. Data were collected with a Bruker SMART APEX CCD-based diffractometer using /w-scans of width 0.3 °. and 25 s duration at a crystal-to-detector distance of 4.908 cm. Intensity decay over the course of the data collection was evaluated by recollecting the first 50 frames of data at the end of the experiment. No significant decay was noted.

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.

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

	x	y	z	Uiso*/Ueq
Re1	0.722942 (7)	0.157502 (3)	0.076553 (5)	0.01307 (3)
Sn1	0.795488 (12)	0.143284 (6)	0.271024 (9)	0.01405 (3)
O1	0.96326 (14)	0.25323 (8)	0.08702 (11)	0.0291 (3)
O2	0.89845 (15)	0.03464 (8)	0.05741 (11)	0.0301 (3)
O3	0.66904 (15)	0.16547 (7)	−0.14185 (10)	0.0218 (3)
N1	0.54700 (15)	0.10163 (7)	0.09963 (10)	0.0141 (3)
N2	0.57439 (15)	0.23190 (8)	0.09872 (11)	0.0153 (3)
C1	0.87369 (19)	0.21657 (10)	0.08132 (14)	0.0200 (4)
C2	0.83529 (18)	0.08185 (10)	0.06493 (13)	0.0191 (4)
C3	0.68147 (19)	0.16410 (9)	−0.06046 (14)	0.0171 (4)
C4	0.54037 (18)	0.03430 (9)	0.10454 (13)	0.0158 (4)
H4	0.6136	0.0089	0.0896	0.020 (5)*
C5	0.43323 (18)	0.00055 (9)	0.13001 (13)	0.0174 (4)
H5	0.4333	−0.0469	0.1320	0.013 (5)*
C6	0.32460 (18)	0.03624 (9)	0.15285 (13)	0.0172 (4)
C7	0.32935 (18)	0.10534 (9)	0.14680 (13)	0.0170 (4)
H7	0.2565	0.1313	0.1609	0.017 (5)*
C8	0.44007 (18)	0.13685 (9)	0.12030 (13)	0.0153 (3)
C9	0.45216 (18)	0.20978 (9)	0.11310 (12)	0.0154 (3)
C10	0.34686 (19)	0.25343 (10)	0.11822 (14)	0.0192 (4)
H10	0.2620	0.2363	0.1268	0.024 (6)*
C11	0.36471 (19)	0.32188 (10)	0.11084 (13)	0.0194 (4)
C12	0.4914 (2)	0.34387 (9)	0.09963 (15)	0.0213 (4)
H12	0.5089	0.3904	0.0965	0.034 (7)*
C13	0.59180 (19)	0.29855 (9)	0.09298 (13)	0.0192 (4)
H13	0.6771	0.3149	0.0840	0.019 (5)*
C14	0.20699 (19)	0.00149 (10)	0.18425 (15)	0.0230 (4)
H14A	0.1857	0.0234	0.2413	0.034*
H14B	0.2297	−0.0455	0.1983	0.034*
H14C	0.1291	0.0040	0.1336	0.034*
C15	0.2492 (2)	0.36919 (11)	0.11221 (18)	0.0290 (5)
H15A	0.1809	0.3614	0.0562	0.044*
H15B	0.2814	0.4154	0.1117	0.044*
H15C	0.2101	0.3615	0.1696	0.044*
C16	0.72905 (18)	0.22929 (9)	0.34345 (13)	0.0170 (4)
C17	0.8193 (2)	0.28124 (10)	0.37282 (13)	0.0205 (4)
H17	0.9120	0.2748	0.3712	0.025 (6)*
C18	0.7764 (2)	0.34189 (10)	0.40423 (15)	0.0253 (5)
H18	0.8398	0.3764	0.4233	0.031 (6)*
C19	0.6422 (2)	0.35249 (10)	0.40792 (16)	0.0281 (5)
H19	0.6130	0.3939	0.4297	0.019 (5)*
C20	0.5507 (2)	0.30182 (11)	0.37939 (16)	0.0293 (5)
H20	0.4583	0.3085	0.3818	0.041 (7)*
C21	0.5942 (2)	0.24113 (10)	0.34718 (14)	0.0232 (4)
H21	0.5303	0.2071	0.3273	0.021 (6)*
C22	0.70719 (18)	0.05239 (9)	0.31618 (13)	0.0171 (4)
C23	0.75462 (19)	−0.00877 (10)	0.28693 (13)	0.0195 (4)
H23	0.8311	−0.0090	0.2562	0.017 (5)*
C24	0.6928 (2)	−0.06912 (10)	0.30156 (14)	0.0214 (4)
H24	0.7275	−0.1098	0.2813	0.019 (5)*
C25	0.5809 (2)	−0.06981 (10)	0.34558 (14)	0.0228 (4)
H25	0.5378	−0.1109	0.3551	0.024 (6)*
C26	0.53156 (19)	−0.01010 (10)	0.37579 (14)	0.0219 (4)
H26	0.4548	−0.0103	0.4063	0.024 (6)*
C27	0.59463 (19)	0.05014 (10)	0.36141 (13)	0.0193 (4)
H27	0.5604	0.0906	0.3828	0.014 (5)*
C28	1.00401 (18)	0.13035 (10)	0.33379 (13)	0.0176 (4)
C29	1.10119 (19)	0.17656 (10)	0.31667 (14)	0.0202 (4)
H29	1.0762	0.2124	0.2739	0.015 (5)*
C30	1.2344 (2)	0.17082 (11)	0.36152 (15)	0.0232 (4)
H30	1.2987	0.2032	0.3502	0.033 (7)*
C31	1.27284 (18)	0.11795 (11)	0.42250 (14)	0.0238 (4)
H31	1.3636	0.1139	0.4526	0.033 (6)*
C32	1.1791 (2)	0.07104 (10)	0.43963 (14)	0.0229 (4)
H32	1.2053	0.0347	0.4812	0.028 (6)*
C33	1.04596 (19)	0.07734 (10)	0.39565 (13)	0.0204 (4)
H33	0.9822	0.0450	0.4079	0.022 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Re1	0.01193 (4)	0.01401 (4)	0.01353 (4)	−0.00048 (2)	0.00281 (3)	−0.00083 (2)
Sn1	0.01178 (6)	0.01612 (6)	0.01415 (7)	−0.00086 (4)	0.00184 (5)	−0.00105 (5)
O1	0.0238 (7)	0.0309 (8)	0.0334 (9)	−0.0113 (6)	0.0073 (6)	−0.0032 (7)
O2	0.0279 (8)	0.0290 (8)	0.0337 (9)	0.0113 (6)	0.0063 (7)	−0.0027 (7)
O3	0.0280 (8)	0.0211 (7)	0.0154 (7)	0.0005 (5)	0.0012 (6)	−0.0006 (5)
N1	0.0140 (7)	0.0145 (7)	0.0131 (7)	−0.0002 (6)	0.0005 (6)	−0.0013 (6)
N2	0.0165 (7)	0.0152 (7)	0.0146 (8)	0.0002 (6)	0.0036 (6)	−0.0009 (6)
C1	0.0199 (9)	0.0236 (10)	0.0168 (9)	0.0007 (8)	0.0042 (7)	−0.0011 (8)
C2	0.0153 (9)	0.0236 (10)	0.0181 (9)	−0.0010 (7)	0.0023 (7)	−0.0017 (8)
C3	0.0149 (9)	0.0127 (8)	0.0239 (11)	0.0001 (6)	0.0039 (7)	0.0004 (7)
C4	0.0168 (9)	0.0161 (9)	0.0137 (9)	0.0007 (7)	−0.0003 (7)	−0.0026 (7)
C5	0.0214 (9)	0.0142 (9)	0.0151 (9)	−0.0017 (7)	−0.0016 (7)	−0.0017 (7)
C6	0.0170 (9)	0.0194 (9)	0.0140 (9)	−0.0034 (7)	−0.0004 (7)	0.0008 (7)
C7	0.0144 (8)	0.0210 (9)	0.0154 (9)	0.0007 (7)	0.0017 (7)	−0.0005 (7)
C8	0.0147 (8)	0.0161 (9)	0.0143 (9)	0.0002 (7)	0.0001 (7)	−0.0006 (7)
C9	0.0174 (9)	0.0165 (9)	0.0124 (8)	−0.0010 (7)	0.0025 (7)	−0.0005 (7)
C10	0.0173 (9)	0.0204 (9)	0.0201 (9)	0.0007 (7)	0.0035 (7)	−0.0013 (7)
C11	0.0210 (9)	0.0198 (9)	0.0172 (9)	0.0051 (7)	0.0023 (7)	0.0009 (7)
C12	0.0282 (11)	0.0148 (9)	0.0215 (10)	0.0003 (7)	0.0059 (8)	0.0001 (7)
C13	0.0212 (9)	0.0165 (9)	0.0209 (10)	−0.0020 (7)	0.0060 (7)	0.0010 (7)
C14	0.0208 (10)	0.0226 (10)	0.0268 (11)	−0.0042 (8)	0.0074 (8)	0.0026 (8)
C15	0.0260 (11)	0.0207 (10)	0.0406 (13)	0.0093 (8)	0.0060 (10)	0.0023 (9)
C16	0.0206 (9)	0.0182 (9)	0.0117 (8)	0.0006 (7)	0.0013 (7)	0.0002 (7)
C17	0.0211 (9)	0.0222 (10)	0.0175 (9)	−0.0021 (7)	0.0007 (7)	0.0005 (8)
C18	0.0365 (13)	0.0207 (11)	0.0172 (10)	−0.0053 (8)	0.0005 (9)	−0.0010 (7)
C19	0.0423 (13)	0.0205 (10)	0.0221 (11)	0.0056 (9)	0.0072 (10)	−0.0018 (8)
C20	0.0271 (11)	0.0306 (11)	0.0321 (12)	0.0069 (9)	0.0111 (9)	−0.0014 (9)
C21	0.0217 (10)	0.0229 (10)	0.0254 (11)	−0.0024 (8)	0.0057 (8)	−0.0029 (8)
C22	0.0159 (8)	0.0207 (9)	0.0136 (9)	−0.0018 (7)	−0.0004 (7)	0.0006 (7)
C23	0.0189 (9)	0.0231 (10)	0.0160 (9)	0.0002 (7)	0.0011 (7)	0.0017 (7)
C24	0.0259 (10)	0.0174 (9)	0.0187 (9)	0.0017 (8)	−0.0027 (8)	0.0011 (7)
C25	0.0244 (10)	0.0207 (10)	0.0212 (10)	−0.0066 (8)	−0.0024 (8)	0.0051 (8)
C26	0.0174 (9)	0.0285 (10)	0.0195 (10)	−0.0031 (8)	0.0025 (7)	0.0030 (8)
C27	0.0189 (9)	0.0215 (10)	0.0171 (9)	−0.0001 (7)	0.0017 (7)	−0.0017 (7)
C28	0.0146 (8)	0.0209 (9)	0.0169 (9)	0.0014 (7)	0.0020 (7)	−0.0051 (7)
C29	0.0185 (9)	0.0210 (9)	0.0213 (10)	0.0005 (7)	0.0040 (7)	−0.0020 (8)
C30	0.0157 (9)	0.0280 (10)	0.0265 (11)	−0.0026 (8)	0.0054 (8)	−0.0065 (9)
C31	0.0154 (9)	0.0327 (12)	0.0225 (11)	0.0042 (8)	0.0006 (8)	−0.0072 (8)
C32	0.0231 (10)	0.0248 (10)	0.0197 (10)	0.0061 (8)	0.0004 (8)	−0.0031 (8)
C33	0.0202 (9)	0.0225 (10)	0.0185 (9)	0.0003 (7)	0.0029 (7)	−0.0039 (8)

Geometric parameters (Å, º)

Re1—C1	1.9207 (19)	C15—H15A	0.98
Re1—C2	1.9160 (19)	C15—H15B	0.98
Re1—C3	1.940 (2)	C15—H15C	0.98
Re1—N1	2.1713 (15)	C16—C21	1.393 (3)
Re1—N2	2.1743 (15)	C16—C17	1.401 (3)
Re1—Sn1	2.7717 (2)	C17—C18	1.388 (3)
Sn1—C16	2.1712 (19)	C17—H17	0.95
Sn1—C22	2.1706 (19)	C18—C19	1.383 (3)
Sn1—C28	2.1661 (18)	C18—H18	0.95
O1—C1	1.158 (2)	C19—C20	1.388 (3)
O2—C2	1.155 (2)	C19—H19	0.95
O3—C3	1.150 (2)	C20—C21	1.395 (3)
N1—C4	1.351 (2)	C20—H20	0.95
N1—C8	1.363 (2)	C21—H21	0.95
N2—C13	1.349 (2)	C22—C27	1.399 (3)
N2—C9	1.360 (2)	C22—C23	1.403 (3)
C4—C5	1.375 (3)	C23—C24	1.391 (3)
C4—H4	0.95	C23—H23	0.95
C5—C6	1.393 (3)	C24—C25	1.383 (3)
C5—H5	0.95	C24—H24	0.95
C6—C7	1.387 (3)	C25—C26	1.391 (3)
C6—C14	1.508 (3)	C25—H25	0.95
C7—C8	1.390 (3)	C26—C27	1.394 (3)
C7—H7	0.95	C26—H26	0.95
C8—C9	1.469 (2)	C27—H27	0.95
C9—C10	1.388 (3)	C28—C29	1.400 (3)
C10—C11	1.388 (3)	C28—C33	1.401 (3)
C10—H10	0.95	C29—C30	1.398 (3)
C11—C12	1.389 (3)	C29—H29	0.95
C11—C15	1.506 (3)	C30—C31	1.385 (3)
C12—C13	1.376 (3)	C30—H30	0.95
C12—H12	0.95	C31—C32	1.384 (3)
C13—H13	0.95	C31—H31	0.95
C14—H14A	0.98	C32—C33	1.394 (3)
C14—H14B	0.98	C32—H32	0.95
C14—H14C	0.98	C33—H33	0.95
C1—Re1—C2	90.64 (8)	C6—C14—H14C	109.5
C1—Re1—C3	91.84 (8)	H14A—C14—H14C	109.5
C2—Re1—C3	89.92 (8)	H14B—C14—H14C	109.5
C1—Re1—N1	167.49 (7)	C11—C15—H15A	109.5
C2—Re1—N1	96.80 (7)	C11—C15—H15B	109.5
C3—Re1—N1	98.19 (7)	H15A—C15—H15B	109.5
C1—Re1—N2	97.84 (7)	C11—C15—H15C	109.5
C2—Re1—N2	170.74 (7)	H15A—C15—H15C	109.5
C3—Re1—N2	93.51 (7)	H15B—C15—H15C	109.5
N1—Re1—N2	74.20 (6)	C21—C16—C17	117.07 (18)
Sn1—Re1—C1	87.16 (6)	C21—C16—Sn1	122.31 (14)
Sn1—Re1—C2	86.75 (6)	C17—C16—Sn1	119.59 (14)
Sn1—Re1—C3	176.52 (5)	C18—C17—C16	121.55 (19)
Sn1—Re1—N1	83.25 (4)	C18—C17—H17	119.2
Sn1—Re1—N2	89.94 (4)	C16—C17—H17	119.2
C28—Sn1—C22	101.32 (7)	C19—C18—C17	120.47 (19)
C28—Sn1—C16	104.67 (7)	C19—C18—H18	119.8
C22—Sn1—C16	110.33 (7)	C17—C18—H18	119.8
C28—Sn1—Re1	120.44 (5)	C18—C19—C20	119.15 (19)
C22—Sn1—Re1	109.32 (5)	C18—C19—H19	120.4
C16—Sn1—Re1	110.24 (5)	C20—C19—H19	120.4
C4—N1—C8	117.15 (15)	C19—C20—C21	120.2 (2)
C4—N1—Re1	124.76 (12)	C19—C20—H20	119.9
C8—N1—Re1	117.74 (12)	C21—C20—H20	119.9
C13—N2—C9	117.51 (16)	C16—C21—C20	121.59 (19)
C13—N2—Re1	124.59 (12)	C16—C21—H21	119.2
C9—N2—Re1	117.75 (12)	C20—C21—H21	119.2
O1—C1—Re1	177.56 (17)	C27—C22—C23	116.98 (17)
O2—C2—Re1	177.24 (17)	C27—C22—Sn1	124.75 (14)
O3—C3—Re1	173.35 (16)	C23—C22—Sn1	117.69 (13)
N1—C4—C5	123.46 (17)	C24—C23—C22	121.90 (18)
N1—C4—H4	118.3	C24—C23—H23	119.1
C5—C4—H4	118.3	C22—C23—H23	119.1
C4—C5—C6	119.72 (17)	C25—C24—C23	119.91 (19)
C4—C5—H5	120.1	C25—C24—H24	120.0
C6—C5—H5	120.1	C23—C24—H24	120.0
C7—C6—C5	117.37 (17)	C24—C25—C26	119.66 (18)
C7—C6—C14	121.03 (17)	C24—C25—H25	120.2
C5—C6—C14	121.60 (17)	C26—C25—H25	120.2
C6—C7—C8	120.45 (17)	C25—C26—C27	120.06 (18)
C6—C7—H7	119.8	C25—C26—H26	120.0
C8—C7—H7	119.8	C27—C26—H26	120.0
N1—C8—C7	121.83 (17)	C26—C27—C22	121.49 (18)
N1—C8—C9	114.85 (15)	C26—C27—H27	119.3
C7—C8—C9	123.32 (17)	C22—C27—H27	119.3
N2—C9—C10	121.79 (17)	C29—C28—C33	117.55 (17)
N2—C9—C8	114.97 (15)	C29—C28—Sn1	120.76 (14)
C10—C9—C8	123.22 (16)	C33—C28—Sn1	121.64 (14)
C9—C10—C11	120.44 (18)	C30—C29—C28	121.08 (19)
C9—C10—H10	119.8	C30—C29—H29	119.5
C11—C10—H10	119.8	C28—C29—H29	119.5
C12—C11—C10	117.10 (17)	C31—C30—C29	120.05 (19)
C12—C11—C15	122.31 (18)	C31—C30—H30	120.0
C10—C11—C15	120.57 (18)	C29—C30—H30	120.0
C13—C12—C11	120.26 (18)	C32—C31—C30	120.02 (18)
C13—C12—H12	119.9	C32—C31—H31	120.0
C11—C12—H12	119.9	C30—C31—H31	120.0
N2—C13—C12	122.84 (18)	C31—C32—C33	119.80 (19)
N2—C13—H13	118.6	C31—C32—H32	120.1
C12—C13—H13	118.6	C33—C32—H32	120.1
C6—C14—H14A	109.5	C32—C33—C28	121.50 (19)
C6—C14—H14B	109.5	C32—C33—H33	119.2
H14A—C14—H14B	109.5	C28—C33—H33	119.2
C2—Re1—Sn1—C28	47.64 (8)	C8—C9—C10—C11	−179.95 (17)
C1—Re1—Sn1—C28	−43.16 (8)	C9—C10—C11—C12	−0.8 (3)
N1—Re1—Sn1—C28	144.89 (7)	C9—C10—C11—C15	177.39 (19)
N2—Re1—Sn1—C28	−141.01 (7)	C10—C11—C12—C13	2.2 (3)
C2—Re1—Sn1—C22	−68.92 (8)	C15—C11—C12—C13	−176.0 (2)
C1—Re1—Sn1—C22	−159.73 (8)	C9—N2—C13—C12	−1.0 (3)
N1—Re1—Sn1—C22	28.32 (7)	Re1—N2—C13—C12	174.40 (15)
N2—Re1—Sn1—C22	102.42 (7)	C11—C12—C13—N2	−1.3 (3)
C2—Re1—Sn1—C16	169.63 (8)	C28—Sn1—C16—C21	−158.45 (16)
C1—Re1—Sn1—C16	78.83 (8)	C22—Sn1—C16—C21	−50.19 (17)
N1—Re1—Sn1—C16	−93.12 (7)	Re1—Sn1—C16—C21	70.65 (16)
N2—Re1—Sn1—C16	−19.02 (7)	C28—Sn1—C16—C17	33.47 (16)
C2—Re1—N1—C4	1.55 (15)	C22—Sn1—C16—C17	141.74 (14)
C3—Re1—N1—C4	92.45 (15)	Re1—Sn1—C16—C17	−97.42 (14)
N2—Re1—N1—C4	−176.20 (15)	C21—C16—C17—C18	0.0 (3)
Sn1—Re1—N1—C4	−84.35 (14)	Sn1—C16—C17—C18	168.66 (15)
C2—Re1—N1—C8	174.48 (13)	C16—C17—C18—C19	0.4 (3)
C3—Re1—N1—C8	−94.62 (14)	C17—C18—C19—C20	−0.3 (3)
N2—Re1—N1—C8	−3.27 (13)	C18—C19—C20—C21	−0.2 (3)
Sn1—Re1—N1—C8	88.58 (12)	C17—C16—C21—C20	−0.5 (3)
C1—Re1—N2—C13	13.20 (16)	Sn1—C16—C21—C20	−168.84 (16)
C3—Re1—N2—C13	−79.15 (16)	C19—C20—C21—C16	0.6 (3)
N1—Re1—N2—C13	−176.68 (16)	C28—Sn1—C22—C27	128.60 (16)
Sn1—Re1—N2—C13	100.32 (15)	C16—Sn1—C22—C27	18.13 (17)
C1—Re1—N2—C9	−171.41 (13)	Re1—Sn1—C22—C27	−103.26 (15)
C3—Re1—N2—C9	96.24 (14)	C28—Sn1—C22—C23	−60.41 (15)
N1—Re1—N2—C9	−1.29 (12)	C16—Sn1—C22—C23	−170.87 (13)
Sn1—Re1—N2—C9	−84.29 (13)	Re1—Sn1—C22—C23	67.74 (14)
C8—N1—C4—C5	−0.7 (3)	C27—C22—C23—C24	0.3 (3)
Re1—N1—C4—C5	172.22 (13)	Sn1—C22—C23—C24	−171.44 (14)
N1—C4—C5—C6	−0.4 (3)	C22—C23—C24—C25	0.4 (3)
C4—C5—C6—C7	1.2 (3)	C23—C24—C25—C26	−0.6 (3)
C4—C5—C6—C14	−177.98 (17)	C24—C25—C26—C27	0.2 (3)
C5—C6—C7—C8	−1.0 (3)	C25—C26—C27—C22	0.5 (3)
C14—C6—C7—C8	178.20 (17)	C23—C22—C27—C26	−0.7 (3)
C4—N1—C8—C7	1.0 (3)	Sn1—C22—C27—C26	170.36 (14)
Re1—N1—C8—C7	−172.50 (13)	C22—Sn1—C28—C29	175.56 (15)
C4—N1—C8—C9	−179.53 (15)	C16—Sn1—C28—C29	−69.69 (16)
Re1—N1—C8—C9	7.0 (2)	Re1—Sn1—C28—C29	54.97 (16)
C6—C7—C8—N1	−0.1 (3)	C22—Sn1—C28—C33	−7.01 (16)
C6—C7—C8—C9	−179.56 (17)	C16—Sn1—C28—C33	107.74 (16)
C13—N2—C9—C10	2.4 (3)	Re1—Sn1—C28—C33	−127.61 (14)
Re1—N2—C9—C10	−173.31 (14)	C33—C28—C29—C30	−1.5 (3)
C13—N2—C9—C8	−179.02 (16)	Sn1—C28—C29—C30	176.00 (14)
Re1—N2—C9—C8	5.3 (2)	C28—C29—C30—C31	1.4 (3)
N1—C8—C9—N2	−7.9 (2)	C29—C30—C31—C32	−0.5 (3)
C7—C8—C9—N2	171.55 (17)	C30—C31—C32—C33	−0.2 (3)
N1—C8—C9—C10	170.61 (17)	C31—C32—C33—C28	0.1 (3)
C7—C8—C9—C10	−9.9 (3)	C29—C28—C33—C32	0.8 (3)
N2—C9—C10—C11	−1.5 (3)	Sn1—C28—C33—C32	−176.74 (14)