Octa­carbonyl-μ-di­cyclo­hexyl­phosphido-μ-N,N-diethyl­di­thio­carbamato-dirhenium

The title compound, [Re₂{μ-S₂NC(Et₂)}(μ-PCy₂)(CO)₈] or [Re₂(C₅H₁₀NS₂)(C₁₂H₂₂P)(CO)₈], is the first structurally characterized rhenium complex with a bridging di­thio­carbamate ligand. The Re...Re distance is non-bonding.

Key indicators

• Single-crystal X-ray study
• T = 203 K
• Mean [sigma](C-C) = 0.018 Å
• R factor = 0.051
• wR factor = 0.149
• Data-to-parameter ratio = 19.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
          Tmin and Tmax reported:      0.121     0.187
          Tmin and Tmax expected:      0.101     0.196
          RR =      1.249
          Please check that your absorption correction is appropriate.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

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S1. Comment

The bromo bridge in Re₂(µ-Br)(µ-PCy₂)(CO)₈ is easily substituted by thiolate ligands giving phosphido-thiolato-bridged dirhenium complexes of the general formula Re₂(µ-PCy₂)(µ-SR)(CO)₈ (Egold et al., 2001). We expected the former complex to react in a completely analogous manner with sodium diethyldithiocarbamate. However, this reaction gave the title compound, (I), in which, surprisingly, the dithiocarbamate ligand coordinates in a µ-η¹-η¹-mode. The molecular structure of (I) shows a Re₂ unit which is doubly bridged by a µ-PCy₂ group and the dithiocarbamate ligand. Each Re atom is additionally attached to four terminal CO ligands and attains thus a slightly distorted octahedral coordination. Carbonyl groups 4 and 7, which are both in trans-position to the Re—P bonds, show ecliptic arrangement along the Re···Re vector with a C—Re···Re—C torsion angle of -1.6 (11)°, but the remaining CO ligands are staggered with torsion angles in the range from 39.0 (5)–51.4 (6)°. The clearly non-bonding Re···Re distance of 4.368 (1) Å is bridged by the S₂C(9)NEt₂ ligand, with an S···S bite distance of 3.048 (4) Å. The accompanying S—C—S angle is 123.1 (7)° and the S—Re···Re—S torsion angle of 57.8 (1)° shows the molecule to be twisted along the C9···P vector. The S₂CN group itself is planar and forms a dihedral angle of 47.3 (2)° with the Re₂P plane. The µ-P bridge is symmetric with equal Re—P bond lengths of 2.562 (3) and 2.561 (3) Å, whereas the two Re—S bonds of 2.531 (3) and 2.485 (3) Å differ significantly. Similar patterns of likewise bridging dithio ligands are known for (Et₄N)[Re₂(µ-S)₂(µ-S₂)(µ-S₂COR)(S₂COR)₂] (McConnachie & Stiefel, 1999) and Re₂(CO)₈(µ-S₂CPCy₃) (Alvarez et al., 1991), both with direct Re—Re bonds. The related Re—S bond lengths for these two compounds of 2.442 (2)/2.462 (1) Å and 2.462 (5)/2.518 (5) Å, respectively, are somewhat shorter than those for (I). The first structure exhibits Re^IV atoms with strongly distorted octahedral S₆ coordination spheres and a completely planar Re₂µ-S₂CO fragment. For the second structure the same twisted M₂µ-S₂C geometry is observed as for (I), for Os₂N[S₂CN(CH₃)₂]₅ (Given & Pignolet, 1977) and for Ru₂(CO)₄(µ-S₂CH)(µ-PBu₂)(µ-dppm) (Böttcher et al., 2000) as well. S···S bite distances of these other structures range from 3.02 to 3.15 Å and the S—C—S angles from 128.7 to 130.7°.

S2. Experimental

In a Schlenk tube, 150 mg (0.172 mmol) Re₂(µ-Br)(µ-PCy₂)(CO)₈ was dissolved in 20 ml THF. 39 mg (0.228 mmol) NaS₂CNEt₂ was added and the reaction mixture was stirred for 24 h. The solvent was removed and the resulting residue subjected to TLC (eluent: dichloromethane/hexane, 1:10). From the major band, a pale yellow substance was isolated, which upon recrystallization from dichloromethane/pentane gave 75 mg (46% yield) of the title compound. Spectroscopic data: ν(CO)—IR: 2090 (vw), 2077 (s), 1998 (versus), 1936 (s). ¹H NMR (CDCl₃): 1.23–2.34 (m, 28H; Cy, Me), 4.18 (q, ³J_HH = 6.8 Hz, 4H, NCH₂). ¹³C NMR (CDCl₃): 13.0 (s, Me), 26.0 [s, C⁴(Cy)], 27.5 [d, ²J_CP = 9 Hz, C²(Cy)], 33.2 [s, C³(Cy)], 41.0 [d, ¹J_CP = 11 Hz, C¹(Cy)], 51.2 (s, NCH₂), 183.5 [d, ²J_CP = 40 Hz, CO (trans µ-P)], 188.6 (d, ²J_CP = 6 Hz, CO); 190.2 (d, ²J_CP = 7 Hz, CO), 208.7 (s, S₂CN). ³¹P NMR (CDCl₃): 22.5 (s, µ-P).

S3. Refinement

H atoms were placed at calculated positions, riding on the attached C atoms, with isotropic displacement parameters U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for methyl groups. Residual electron density of 1.25 e ų is found at (0.058, 0.871, 0.327), 0.96 Šfrom Re1.

Computing details

Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of (I) with H atoms omitted. Displacement ellipsoids are drawn at the 50% probability level.

Octacarbonyl-µ-N,N-diethyldithiocarbamato-µ-dicyclohexylphosphido- dirhenium

Crystal data

[Re2(C5H10NS2)(C12H22P)(CO)8]	Z = 2
Mr = 942.01	F(000) = 900
Triclinic, P1	Dx = 2.050 Mg m^−3
a = 9.218 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.891 (2) Å	Cell parameters from 25 reflections
c = 14.624 (2) Å	θ = 7.3–15.6°
α = 96.40 (1)°	µ = 8.16 mm^−1
β = 99.89 (2)°	T = 203 K
γ = 102.06 (2)°	Block, colorless
V = 1526.1 (5) Å^3	0.30 × 0.26 × 0.20 mm

Data collection

Bruker P4 diffractometer	5125 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.053
Graphite monochromator	θmax = 27.5°, θmin = 2.9°
ω scans	h = −11→1
Absorption correction: ψ scan (North et al., 1968)	k = −15→15
Tmin = 0.121, Tmax = 0.187	l = −18→19
8235 measured reflections	3 standard reflections every 397 reflections
6945 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.149	w = 1/[σ^2(Fo^2) + (0.0703P)^2 + 15.7996P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
6945 reflections	Δρmax = 1.25 e Å^−3
353 parameters	Δρmin = −1.04 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0038 (4)

Special details

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
Re1	0.14111 (5)	0.83672 (4)	0.34918 (3)	0.02840 (15)
Re2	0.40585 (5)	0.67779 (4)	0.17406 (3)	0.03113 (16)
S1	0.3144 (4)	0.7198 (3)	0.4261 (2)	0.0382 (7)
S2	0.2363 (4)	0.5410 (3)	0.2482 (2)	0.0389 (7)
P1	0.2676 (3)	0.8393 (2)	0.20640 (19)	0.0258 (5)
N1	0.2285 (11)	0.4928 (8)	0.4170 (7)	0.034 (2)
O1	0.3588 (13)	1.0643 (9)	0.4676 (8)	0.062 (3)
C1	0.2847 (14)	0.9797 (11)	0.4202 (9)	0.038 (3)
O2	−0.0675 (12)	0.9805 (10)	0.2577 (7)	0.057 (3)
C2	0.0129 (15)	0.9280 (11)	0.2926 (9)	0.041 (3)
O3	−0.1033 (11)	0.6059 (9)	0.2734 (7)	0.054 (3)
C3	−0.0115 (14)	0.6878 (11)	0.2940 (9)	0.038 (3)
O4	−0.0247 (13)	0.8515 (11)	0.5146 (7)	0.063 (3)
C4	0.0393 (14)	0.8405 (12)	0.4551 (9)	0.039 (3)
O5	0.6601 (11)	0.7622 (9)	0.3552 (8)	0.056 (3)
C5	0.5615 (14)	0.7350 (10)	0.2921 (10)	0.039 (3)
O6	0.1860 (12)	0.5530 (9)	−0.0144 (7)	0.056 (3)
C6	0.2604 (14)	0.6030 (11)	0.0544 (9)	0.037 (3)
O7	0.5701 (13)	0.4818 (10)	0.1339 (9)	0.072 (3)
C7	0.5116 (16)	0.5547 (14)	0.1499 (10)	0.050 (3)
O8	0.5947 (13)	0.8419 (10)	0.0689 (9)	0.066 (3)
C8	0.5255 (14)	0.7805 (11)	0.1070 (10)	0.042 (3)
C9	0.2573 (12)	0.5771 (10)	0.3682 (8)	0.031 (2)
C11	0.4029 (13)	0.9831 (10)	0.2102 (8)	0.032 (2)
H11	0.4349	0.9792	0.1489	0.038*
C12	0.5489 (12)	1.0045 (10)	0.2849 (9)	0.035 (3)
H12A	0.5233	1.0075	0.3473	0.042*
H12B	0.5971	0.9392	0.2756	0.042*
C13	0.6600 (14)	1.1167 (11)	0.2809 (10)	0.045 (3)
H13A	0.6995	1.1085	0.2230	0.054*
H13B	0.7456	1.1310	0.3341	0.054*
C14	0.5869 (15)	1.2209 (10)	0.2837 (11)	0.047 (3)
H14A	0.5618	1.2367	0.3456	0.056*
H14B	0.6596	1.2898	0.2748	0.056*
C15	0.4455 (15)	1.1999 (11)	0.2091 (10)	0.043 (3)
H15A	0.4718	1.1922	0.1469	0.051*
H15B	0.3992	1.2667	0.2154	0.051*
C16	0.3320 (12)	1.0893 (10)	0.2177 (9)	0.034 (2)
H16A	0.2419	1.0763	0.1677	0.041*
H16B	0.3005	1.0991	0.2782	0.041*
C21	0.1244 (13)	0.8439 (11)	0.1002 (7)	0.032 (2)
H21	0.0868	0.9145	0.1152	0.039*
C22	0.1907 (13)	0.8603 (11)	0.0126 (8)	0.035 (2)
H22A	0.2425	0.7979	0.0000	0.042*
H22B	0.2665	0.9343	0.0250	0.042*
C23	0.0721 (16)	0.8598 (12)	−0.0753 (9)	0.045 (3)
H23A	0.0300	0.9285	−0.0670	0.053*
H23B	0.1204	0.8633	−0.1299	0.053*
C24	−0.0550 (14)	0.7499 (12)	−0.0923 (8)	0.040 (3)
H24A	−0.1295	0.7501	−0.1488	0.048*
H24B	−0.0135	0.6811	−0.1024	0.048*
C25	−0.1294 (14)	0.7449 (12)	−0.0100 (9)	0.042 (3)
H25A	−0.2133	0.6757	−0.0225	0.050*
H25B	−0.1715	0.8135	−0.0008	0.050*
C26	−0.0166 (12)	0.7405 (10)	0.0813 (8)	0.033 (2)
H26A	−0.0678	0.7431	0.1347	0.039*
H26B	0.0158	0.6670	0.0752	0.039*
C31	0.2241 (15)	0.5097 (12)	0.5180 (9)	0.042 (3)
H31A	0.1434	0.4484	0.5298	0.051*
H31B	0.1994	0.5846	0.5346	0.051*
C32	0.3720 (18)	0.5071 (13)	0.5800 (10)	0.052 (4)
H32A	0.3628	0.5180	0.6453	0.077*
H32B	0.4519	0.5690	0.5699	0.077*
H32C	0.3963	0.4326	0.5646	0.077*
C33	0.1940 (14)	0.3673 (10)	0.3739 (8)	0.036 (3)
H33A	0.2267	0.3212	0.4216	0.043*
H33B	0.2506	0.3590	0.3236	0.043*
C34	0.0256 (15)	0.3215 (12)	0.3341 (9)	0.044 (3)
H34A	0.0062	0.2404	0.3066	0.067*
H34B	−0.0065	0.3664	0.2863	0.067*
H34C	−0.0304	0.3285	0.3841	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Re1	0.0244 (3)	0.0336 (3)	0.0273 (2)	0.00840 (18)	0.00453 (18)	0.00319 (17)
Re2	0.0264 (3)	0.0340 (3)	0.0344 (3)	0.01141 (19)	0.0060 (2)	0.00311 (19)
S1	0.0436 (17)	0.0318 (14)	0.0336 (15)	0.0109 (13)	−0.0072 (13)	−0.0004 (11)
S2	0.0428 (17)	0.0366 (15)	0.0318 (14)	0.0010 (13)	0.0061 (13)	0.0002 (12)
P1	0.0210 (13)	0.0281 (13)	0.0272 (13)	0.0058 (10)	0.0034 (11)	0.0017 (10)
N1	0.033 (5)	0.036 (5)	0.034 (5)	0.011 (4)	0.008 (4)	0.005 (4)
O1	0.059 (7)	0.059 (6)	0.056 (6)	−0.004 (5)	0.014 (5)	−0.013 (5)
C1	0.032 (6)	0.041 (6)	0.041 (7)	0.011 (5)	0.012 (5)	0.000 (5)
O2	0.055 (6)	0.087 (8)	0.043 (5)	0.045 (6)	0.009 (5)	0.017 (5)
C2	0.037 (7)	0.044 (7)	0.041 (7)	0.019 (6)	0.002 (6)	−0.002 (5)
O3	0.033 (5)	0.054 (6)	0.065 (7)	−0.006 (4)	0.009 (5)	0.005 (5)
C3	0.031 (6)	0.045 (7)	0.041 (7)	0.008 (5)	0.010 (5)	0.012 (5)
O4	0.063 (7)	0.088 (8)	0.045 (6)	0.016 (6)	0.031 (5)	0.010 (5)
C4	0.032 (6)	0.053 (7)	0.035 (6)	0.012 (6)	0.010 (5)	0.010 (5)
O5	0.042 (6)	0.051 (6)	0.066 (7)	0.008 (5)	−0.007 (5)	0.004 (5)
C5	0.032 (6)	0.031 (6)	0.049 (7)	0.005 (5)	0.006 (6)	−0.002 (5)
O6	0.059 (6)	0.060 (6)	0.041 (5)	0.019 (5)	−0.005 (5)	−0.015 (5)
C6	0.033 (6)	0.041 (6)	0.039 (7)	0.017 (5)	0.006 (5)	0.006 (5)
O7	0.065 (7)	0.063 (7)	0.094 (9)	0.043 (6)	0.012 (7)	−0.005 (6)
C7	0.039 (7)	0.067 (9)	0.044 (7)	0.023 (7)	−0.001 (6)	−0.001 (7)
O8	0.058 (7)	0.071 (7)	0.087 (8)	0.020 (6)	0.048 (7)	0.021 (6)
C8	0.030 (6)	0.044 (7)	0.061 (8)	0.015 (5)	0.024 (6)	0.008 (6)
C9	0.024 (5)	0.038 (6)	0.032 (6)	0.013 (5)	0.000 (5)	0.001 (5)
C11	0.027 (6)	0.037 (6)	0.030 (5)	0.007 (5)	0.005 (5)	0.003 (4)
C12	0.022 (5)	0.037 (6)	0.045 (7)	0.006 (5)	0.005 (5)	0.007 (5)
C13	0.028 (6)	0.043 (7)	0.057 (8)	0.003 (5)	0.002 (6)	0.003 (6)
C14	0.035 (7)	0.029 (6)	0.064 (9)	−0.004 (5)	−0.002 (6)	−0.005 (6)
C15	0.038 (7)	0.034 (6)	0.055 (8)	0.005 (5)	0.009 (6)	0.003 (6)
C16	0.021 (5)	0.036 (6)	0.043 (6)	0.009 (4)	0.000 (5)	0.000 (5)
C21	0.028 (6)	0.050 (7)	0.021 (5)	0.016 (5)	0.002 (4)	0.004 (5)
C22	0.031 (6)	0.045 (7)	0.029 (6)	0.012 (5)	0.003 (5)	0.007 (5)
C23	0.049 (8)	0.051 (8)	0.039 (7)	0.022 (6)	0.009 (6)	0.010 (6)
C24	0.030 (6)	0.055 (8)	0.028 (6)	0.015 (6)	−0.008 (5)	−0.004 (5)
C25	0.034 (7)	0.049 (7)	0.037 (6)	0.010 (6)	0.000 (5)	−0.004 (5)
C26	0.016 (5)	0.041 (6)	0.034 (6)	0.003 (4)	−0.002 (4)	−0.006 (5)
C31	0.046 (8)	0.047 (7)	0.037 (7)	0.014 (6)	0.013 (6)	0.002 (5)
C32	0.068 (10)	0.052 (8)	0.043 (7)	0.033 (7)	0.007 (7)	0.009 (6)
C33	0.041 (7)	0.032 (6)	0.034 (6)	0.005 (5)	0.011 (5)	0.008 (5)
C34	0.039 (7)	0.050 (7)	0.043 (7)	0.001 (6)	0.018 (6)	0.004 (6)

Geometric parameters (Å, º)

Re1—C2	1.913 (12)	C14—H14A	0.980
Re1—C4	1.946 (12)	C14—H14B	0.980
Re1—C1	1.979 (13)	C15—C16	1.532 (16)
Re1—C3	2.005 (13)	C15—H15A	0.980
Re1—S1	2.531 (3)	C15—H15B	0.980
Re1—P1	2.561 (3)	C16—H16A	0.980
Re2—C8	1.935 (13)	C16—H16B	0.980
Re2—C7	1.954 (14)	C21—C22	1.525 (15)
Re2—C5	1.995 (13)	C21—C26	1.553 (16)
Re2—C6	2.000 (13)	C21—H21	0.990
Re2—S2	2.485 (3)	C22—C23	1.536 (17)
Re2—P1	2.562 (3)	C22—H22A	0.980
S1—C9	1.740 (12)	C22—H22B	0.980
S2—C9	1.727 (12)	C23—C24	1.527 (19)
P1—C21	1.871 (11)	C23—H23A	0.980
P1—C11	1.883 (12)	C23—H23B	0.980
N1—C9	1.303 (15)	C24—C25	1.485 (17)
N1—C31	1.476 (15)	C24—H24A	0.980
N1—C33	1.500 (15)	C24—H24B	0.980
O1—C1	1.163 (15)	C25—C26	1.559 (16)
O2—C2	1.155 (15)	C25—H25A	0.980
O3—C3	1.121 (15)	C25—H25B	0.980
O4—C4	1.142 (15)	C26—H26A	0.980
O5—C5	1.142 (15)	C26—H26B	0.980
O6—C6	1.138 (15)	C31—C32	1.510 (19)
O7—C7	1.136 (16)	C31—H31A	0.980
O8—C8	1.127 (15)	C31—H31B	0.980
C11—C12	1.536 (16)	C32—H32A	0.970
C11—C16	1.540 (15)	C32—H32B	0.970
C11—H11	0.990	C32—H32C	0.970
C12—C13	1.517 (16)	C33—C34	1.520 (18)
C12—H12A	0.980	C33—H33A	0.980
C12—H12B	0.980	C33—H33B	0.980
C13—C14	1.529 (18)	C34—H34A	0.970
C13—H13A	0.980	C34—H34B	0.970
C13—H13B	0.980	C34—H34C	0.970
C14—C15	1.505 (19)
C2—Re1—C4	88.5 (6)	C13—C14—H14B	109.2
C2—Re1—C1	90.4 (5)	H14A—C14—H14B	107.9
C4—Re1—C1	85.8 (5)	C14—C15—C16	110.8 (11)
C2—Re1—C3	92.1 (5)	C14—C15—H15A	109.5
C4—Re1—C3	86.9 (5)	C16—C15—H15A	109.5
C1—Re1—C3	172.3 (5)	C14—C15—H15B	109.5
C2—Re1—S1	178.8 (4)	C16—C15—H15B	109.5
C4—Re1—S1	91.4 (4)	H15A—C15—H15B	108.1
C1—Re1—S1	88.4 (4)	C15—C16—C11	110.7 (9)
C3—Re1—S1	89.1 (4)	C15—C16—H16A	109.5
C2—Re1—P1	88.6 (4)	C11—C16—H16A	109.5
C4—Re1—P1	177.0 (4)	C15—C16—H16B	109.5
C1—Re1—P1	93.8 (4)	C11—C16—H16B	109.5
C3—Re1—P1	93.6 (4)	H16A—C16—H16B	108.1
S1—Re1—P1	91.58 (10)	C22—C21—C26	112.2 (9)
C8—Re2—C7	92.4 (6)	C22—C21—P1	113.9 (8)
C8—Re2—C5	90.7 (6)	C26—C21—P1	112.9 (8)
C7—Re2—C5	87.1 (5)	C22—C21—H21	105.7
C8—Re2—C6	90.8 (6)	C26—C21—H21	105.7
C7—Re2—C6	86.0 (5)	P1—C21—H21	105.7
C5—Re2—C6	172.9 (5)	C21—C22—C23	113.8 (10)
C8—Re2—S2	175.3 (4)	C21—C22—H22A	108.8
C7—Re2—S2	88.1 (5)	C23—C22—H22A	108.8
C5—Re2—S2	93.9 (4)	C21—C22—H22B	108.8
C6—Re2—S2	84.6 (4)	C23—C22—H22B	108.8
C8—Re2—P1	87.7 (4)	H22A—C22—H22B	107.7
C7—Re2—P1	179.8 (4)	C24—C23—C22	110.4 (10)
C5—Re2—P1	92.7 (4)	C24—C23—H23A	109.6
C6—Re2—P1	94.2 (3)	C22—C23—H23A	109.6
S2—Re2—P1	91.86 (10)	C24—C23—H23B	109.6
C9—S1—Re1	108.5 (4)	C22—C23—H23B	109.6
C9—S2—Re2	114.9 (4)	H23A—C23—H23B	108.1
C21—P1—C11	98.8 (5)	C25—C24—C23	109.7 (10)
C21—P1—Re1	109.0 (4)	C25—C24—H24A	109.7
C11—P1—Re1	111.9 (4)	C23—C24—H24A	109.7
C21—P1—Re2	110.7 (4)	C25—C24—H24B	109.7
C11—P1—Re2	107.9 (4)	C23—C24—H24B	109.7
Re1—P1—Re2	117.03 (11)	H24A—C24—H24B	108.2
C9—N1—C31	124.5 (10)	C24—C25—C26	111.8 (10)
C9—N1—C33	122.1 (10)	C24—C25—H25A	109.3
C31—N1—C33	113.4 (9)	C26—C25—H25A	109.3
O1—C1—Re1	173.2 (11)	C24—C25—H25B	109.3
O2—C2—Re1	178.2 (13)	C26—C25—H25B	109.3
O3—C3—Re1	171.2 (11)	H25A—C25—H25B	107.9
O4—C4—Re1	173.7 (12)	C21—C26—C25	111.2 (10)
O5—C5—Re2	172.9 (11)	C21—C26—H26A	109.4
O6—C6—Re2	173.5 (11)	C25—C26—H26A	109.4
O7—C7—Re2	178.2 (13)	C21—C26—H26B	109.4
O8—C8—Re2	178.8 (12)	C25—C26—H26B	109.4
N1—C9—S2	118.0 (9)	H26A—C26—H26B	108.0
N1—C9—S1	118.9 (9)	N1—C31—C32	112.8 (11)
S2—C9—S1	123.1 (7)	N1—C31—H31A	109.0
C12—C11—C16	110.3 (9)	C32—C31—H31A	109.0
C12—C11—P1	113.9 (8)	N1—C31—H31B	109.0
C16—C11—P1	114.7 (8)	C32—C31—H31B	109.0
C12—C11—H11	105.7	H31A—C31—H31B	107.8
C16—C11—H11	105.7	C31—C32—H32A	109.5
P1—C11—H11	105.7	C31—C32—H32B	109.5
C13—C12—C11	112.3 (10)	H32A—C32—H32B	109.5
C13—C12—H12A	109.1	C31—C32—H32C	109.5
C11—C12—H12A	109.1	H32A—C32—H32C	109.5
C13—C12—H12B	109.1	H32B—C32—H32C	109.5
C11—C12—H12B	109.1	N1—C33—C34	111.0 (10)
H12A—C12—H12B	107.9	N1—C33—H33A	109.4
C12—C13—C14	112.1 (10)	C34—C33—H33A	109.4
C12—C13—H13A	109.2	N1—C33—H33B	109.4
C14—C13—H13A	109.2	C34—C33—H33B	109.4
C12—C13—H13B	109.2	H33A—C33—H33B	108.0
C14—C13—H13B	109.2	C33—C34—H34A	109.5
H13A—C13—H13B	107.9	C33—C34—H34B	109.5
C15—C14—C13	112.0 (11)	H34A—C34—H34B	109.5
C15—C14—H14A	109.2	C33—C34—H34C	109.5
C13—C14—H14A	109.2	H34A—C34—H34C	109.5
C15—C14—H14B	109.2	H34B—C34—H34C	109.5
C4—Re1—S1—C9	106.2 (6)	Re2—S2—C9—N1	−150.3 (8)
C1—Re1—S1—C9	−168.0 (6)	Re2—S2—C9—S1	29.9 (8)
C3—Re1—S1—C9	19.3 (6)	Re1—S1—C9—N1	−126.1 (8)
P1—Re1—S1—C9	−74.3 (4)	Re1—S1—C9—S2	53.7 (8)
C7—Re2—S2—C9	111.3 (6)	C21—P1—C11—C12	−173.7 (8)
C5—Re2—S2—C9	24.4 (5)	Re1—P1—C11—C12	71.7 (9)
C6—Re2—S2—C9	−162.5 (5)	Re2—P1—C11—C12	−58.4 (9)
P1—Re2—S2—C9	−68.5 (4)	C21—P1—C11—C16	58.0 (9)
C2—Re1—P1—C21	−31.7 (6)	Re1—P1—C11—C16	−56.6 (9)
C1—Re1—P1—C21	−122.1 (6)	Re2—P1—C11—C16	173.2 (7)
C3—Re1—P1—C21	60.3 (6)	C16—C11—C12—C13	−53.9 (13)
S1—Re1—P1—C21	149.5 (4)	P1—C11—C12—C13	175.6 (9)
C2—Re1—P1—C11	76.5 (6)	C11—C12—C13—C14	52.3 (15)
C1—Re1—P1—C11	−13.9 (5)	C12—C13—C14—C15	−53.4 (16)
C3—Re1—P1—C11	168.5 (5)	C13—C14—C15—C16	56.1 (15)
S1—Re1—P1—C11	−102.3 (4)	C14—C15—C16—C11	−57.9 (14)
C2—Re1—P1—Re2	−158.2 (4)	C12—C11—C16—C15	56.3 (13)
C1—Re1—P1—Re2	111.4 (4)	P1—C11—C16—C15	−173.6 (8)
C3—Re1—P1—Re2	−66.2 (4)	C11—P1—C21—C22	56.2 (10)
S1—Re1—P1—Re2	22.96 (12)	Re1—P1—C21—C22	173.1 (8)
C8—Re2—P1—C21	78.1 (6)	Re2—P1—C21—C22	−56.8 (9)
C5—Re2—P1—C21	168.7 (5)	C11—P1—C21—C26	−174.3 (8)
C6—Re2—P1—C21	−12.5 (5)	Re1—P1—C21—C26	−57.4 (8)
S2—Re2—P1—C21	−97.2 (4)	Re2—P1—C21—C26	72.7 (8)
C8—Re2—P1—C11	−29.0 (6)	C26—C21—C22—C23	48.1 (14)
C5—Re2—P1—C11	61.6 (5)	P1—C21—C22—C23	178.0 (9)
C6—Re2—P1—C11	−119.6 (5)	C21—C22—C23—C24	−54.0 (14)
S2—Re2—P1—C11	155.7 (4)	C22—C23—C24—C25	59.8 (14)
C8—Re2—P1—Re1	−156.3 (4)	C23—C24—C25—C26	−61.1 (14)
C5—Re2—P1—Re1	−65.6 (4)	C22—C21—C26—C25	−47.2 (13)
C6—Re2—P1—Re1	113.1 (4)	P1—C21—C26—C25	−177.5 (8)
S2—Re2—P1—Re1	28.42 (12)	C24—C25—C26—C21	54.9 (14)
C31—N1—C9—S2	−172.7 (9)	C9—N1—C31—C32	−95.6 (14)
C33—N1—C9—S2	6.5 (15)	C33—N1—C31—C32	85.2 (13)
C31—N1—C9—S1	7.2 (16)	C9—N1—C33—C34	−88.2 (13)
C33—N1—C9—S1	−173.7 (8)	C31—N1—C33—C34	91.0 (12)