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Acta Cryst. (2011). E67, m1337    [ doi:10.1107/S1600536811035811 ]

Dibromidooxido[(Z)-N'-(propan-2-ylidene)benzohydrazidato](triphenylphosphane)rhenium(V)

N. Yumata, T. Gerber and R. Betz

Abstract top

The asymmetric unit of the title neutral rhenium(V) coordination compound, [ReBr2(C10H11N2O)O(C18H15P)], contains two molecules. In each of the two molecules the metal atom is octahedrally coordinated, the bromido ligands being cis-orientated. The chelate ligand is present in its imine-tautomeric form. In the crystal, C-H...Br contacts connect the molecules into chains along [101]. The shortest intercentroid distance between two aromatic rings was found to be 3.906 (2) Å.

Comment top

Next to cardiovascular diseases, cancer has become one of the main fatal diseases in industrialized countries. Apart from classical surgery, chemo- and radiotherapeutic treatments have entered the arsenal of possible cures for certain types of cancer. All methods, however, suffer from their own set of problematic side-effects and, as a consequence, the development of radiopharmaceuticals – combining the advantages of chemotherapy as well as radiation methods while at the same time avoiding their unique respective undesired side-effects – has been a topic of research (Gerber et al., 2011). Tailoring and fine-tuning of the envisioned radiopharmaceuticals' properties such as lipophilicity and, in particular, inertness is of paramount importance with respect to possible future in vivo applications in contemporary medicine and requires sound knowledge about structural parameters of the ligands applied if a more heuristic approach in the synthesis is to triumph over pure trial-and-error as it is encountered in this specific field of coordination chemistry up to the present day. In continuation of our interest in rhenium-based coordination compounds that might serve as radiopharmaceuticals, we determined the molecular and crystal structure of the title compound. Information about the crystal structures of rhenium coordination compounds with the central atom in different oxidation states is apparent in the literature (Potgieter et al., 2010).

The central atom in both molecules of the asymmetric unit is hexacoordinate. The ligand sphere features one chelate ligand which is present in its tautomeric imine form. Both oxygen atoms are in trans-position, the bromido ligands are cis-orientated. While the small puckering amplitude of one of the five-membered chelate rings (τ = 4.3 °) precludes a conformational analysis (Cremer & Pople, 1975) in the first molecule of the asymmetric unite, the corresponding five-membered ring in the second molecule adopts an envelope conformation on the rhenium atom (Re2E, Q2 = 0.076 (3) Å, π2 = 358 (3) °). The central atom is displaced by 0.184 (1) Å and 0.188 (1) Å, respectively, from the plane defined by the bromido ligands as well as the coordinating nitrogen atom and phosphorus atom (Fig. 1).

In the crystal, C–H···Br contacts can be observed whose range falls by more than 0.1 Å below the sum of van-der-Waals radii of the respective atoms. These are supported exclusively by hydrogen atoms of phenyl groups on the triphenylphosphane ligand and involve hydrogen atoms in ortho as well as in meta position as donors and the bromido ligand in trans-position to the coordinating phosphorus atom as acceptors. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for these contacts is DD on the unitary level. In total, the molecules are connected to chains along [1 0 1] (Fig. 2). The shortest intercentroid distance between two centers of gravity was found at 3.906 (2) Å.

Related literature top

For the crystal structures of rhenium(I), rhenium(III) and rhenium(V) metal complexes featuring tridentate ONX (X = O, N, S)-donor Schiff bases, see: Potgieter et al. (2010). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995). For puckering analysis, see: Cremer & Pople (1975). For general information about radiopharmaceuticals, see: Gerber et al. (2011).

Experimental top

Benzhydrazide and trans-[ReOBr3(PPh3)2] were refluxed in acetone for 5 h. After cooling to room temperature and filtration the filtrate was stored at room temperature upon which crystals formed in the course of a couple of days.

Refinement top

Carbon-bound H atoms were placed in calculated positions (C—H 0.95 Å for aromatic C atoms, C—H 0.98 Å for methyl groups) and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C) for aromatic carbon atoms and U(H) set to 1.5Ueq(C) for methyl groups.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level).
[Figure 2] Fig. 2. Intermolecular contacts, viewed along [0 0 - 1]. Symmetry operators: i x - 1, -y + 1/2, z - 1/2; ii x + 1, -y + 1/2, z + 1/2.
Dibromidooxido[(Z)-N'-(propan-2- ylidene)benzohydrazidato](triphenylphosphane)rhenium(V) top
Crystal data top
[ReBr2(C10H11N2O)O(C18H15P)]F(000) = 3072
Mr = 799.50Dx = 1.927 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 9749 reflections
a = 19.1130 (5) Åθ = 2.9–28.3°
b = 18.3910 (4) ŵ = 7.40 mm−1
c = 15.8140 (4) ÅT = 200 K
β = 97.410 (1)°Platelet, green
V = 5512.3 (2) Å30.39 × 0.35 × 0.16 mm
Z = 8
Data collection top
Bruker APEXII CCD
diffractometer		13695 independent reflections
Radiation source: fine-focus sealed tube11062 reflections with I > 2σ(I)
graphiteRint = 0.031
φ and ω scansθmax = 28.3°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −25→25
Tmin = 0.589, Tmax = 1.000k = −24→20
50272 measured reflectionsl = −21→20
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0171P)2 + 13.1603P]
where P = (Fo2 + 2Fc2)/3
13695 reflections(Δ/σ)max = 0.003
649 parametersΔρmax = 1.11 e Å−3
0 restraintsΔρmin = −1.33 e Å−3
Crystal data top
[ReBr2(C10H11N2O)O(C18H15P)]V = 5512.3 (2) Å3
Mr = 799.50Z = 8
Monoclinic, P21/cMo Kα radiation
a = 19.1130 (5) ŵ = 7.40 mm−1
b = 18.3910 (4) ÅT = 200 K
c = 15.8140 (4) Å0.39 × 0.35 × 0.16 mm
β = 97.410 (1)°
Data collection top
Bruker APEXII CCD
diffractometer		13695 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		11062 reflections with I > 2σ(I)
Tmin = 0.589, Tmax = 1.000Rint = 0.031
50272 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.028 w = 1/[σ2(Fo2) + (0.0171P)2 + 13.1603P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.066Δρmax = 1.11 e Å−3
S = 1.11Δρmin = −1.33 e Å−3
13695 reflectionsAbsolute structure: ?
649 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
H-atom parameters constrained
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Re10.735701 (7)0.329200 (8)0.354383 (9)0.01810 (4)
Br10.79252 (2)0.26176 (2)0.24550 (3)0.02955 (9)
Br20.85659 (2)0.37295 (2)0.41703 (3)0.03182 (9)
P10.61621 (5)0.29731 (5)0.28519 (6)0.01951 (19)
O10.72398 (14)0.41638 (13)0.27545 (15)0.0217 (5)
O20.71940 (14)0.26514 (14)0.42482 (16)0.0255 (6)
N10.69989 (17)0.41714 (16)0.42803 (19)0.0214 (6)
N20.68319 (17)0.48183 (17)0.3824 (2)0.0241 (7)
C10.69745 (19)0.47580 (19)0.3050 (2)0.0201 (7)
C20.6947 (2)0.4213 (2)0.5092 (2)0.0289 (9)
C30.6707 (3)0.4897 (3)0.5471 (3)0.0453 (12)
H3110.70910.52540.55220.068*
H3210.65750.47940.60370.068*
H3310.62990.50930.51030.068*
C40.7118 (3)0.3590 (3)0.5684 (3)0.0494 (14)
H4110.67180.32520.56350.074*
H4210.72120.37700.62710.074*
H4310.75370.33380.55340.074*
C110.68113 (19)0.5372 (2)0.2456 (2)0.0218 (8)
C120.6662 (2)0.6056 (2)0.2763 (3)0.0278 (9)
H120.66820.61350.33590.033*
C130.6484 (2)0.6622 (2)0.2198 (3)0.0335 (10)
H130.63790.70890.24070.040*
C140.6458 (2)0.6509 (2)0.1333 (3)0.0356 (10)
H140.63380.68990.09480.043*
C150.6607 (2)0.5832 (2)0.1023 (3)0.0362 (10)
H150.65870.57570.04260.043*
C160.6784 (2)0.5264 (2)0.1581 (3)0.0289 (9)
H160.68880.47990.13680.035*
C210.5865 (2)0.3391 (2)0.1828 (2)0.0237 (8)
C220.5194 (2)0.3683 (3)0.1637 (3)0.0364 (10)
H220.48770.36770.20530.044*
C230.4984 (3)0.3984 (3)0.0841 (3)0.0475 (13)
H230.45250.41870.07140.057*
C240.5439 (3)0.3990 (3)0.0233 (3)0.0439 (12)
H240.52960.4203−0.03090.053*
C250.6101 (3)0.3688 (3)0.0409 (3)0.0394 (11)
H250.64110.3686−0.00150.047*
C260.6317 (2)0.3389 (2)0.1204 (3)0.0295 (9)
H260.67750.31820.13240.035*
C310.5533 (2)0.3228 (2)0.3572 (2)0.0235 (8)
C320.5277 (2)0.2710 (2)0.4097 (3)0.0333 (10)
H320.53900.22110.40360.040*
C330.4857 (3)0.2918 (3)0.4709 (3)0.0430 (12)
H330.46890.25640.50710.052*
C340.4686 (3)0.3640 (3)0.4792 (3)0.0429 (12)
H340.43940.37820.52050.051*
C350.4938 (2)0.4158 (3)0.4274 (3)0.0376 (10)
H350.48190.46550.43340.045*
C360.5362 (2)0.3956 (2)0.3673 (3)0.0288 (9)
H360.55380.43160.33240.035*
C410.6015 (2)0.2002 (2)0.2683 (2)0.0224 (8)
C420.5376 (2)0.1775 (2)0.2246 (3)0.0363 (10)
H420.50430.21260.20070.044*
C430.5220 (2)0.1044 (2)0.2156 (3)0.0425 (12)
H430.47810.08950.18540.051*
C440.5698 (2)0.0531 (2)0.2502 (3)0.0371 (10)
H440.55870.00280.24450.045*
C450.6337 (2)0.0747 (2)0.2931 (3)0.0348 (10)
H450.66680.03920.31640.042*
C460.6499 (2)0.1481 (2)0.3026 (3)0.0281 (9)
H460.69400.16280.33230.034*
Re20.234120 (8)0.330538 (8)0.174643 (9)0.01962 (4)
Br30.34651 (2)0.37327 (2)0.26052 (3)0.03643 (10)
Br40.30700 (2)0.27118 (2)0.07404 (3)0.03180 (9)
P20.12037 (5)0.30358 (5)0.08588 (6)0.01950 (19)
O30.22884 (14)0.42150 (13)0.10244 (16)0.0233 (6)
O40.21229 (15)0.26075 (15)0.23405 (16)0.0263 (6)
N30.18502 (17)0.41223 (17)0.24467 (19)0.0233 (7)
N40.17059 (18)0.47831 (17)0.20169 (19)0.0246 (7)
C50.19517 (19)0.4780 (2)0.1291 (2)0.0208 (7)
C60.1668 (2)0.4106 (2)0.3211 (3)0.0335 (10)
C70.1285 (3)0.4726 (3)0.3551 (3)0.0473 (13)
H7110.07970.45820.35920.071*
H7210.12880.51430.31660.071*
H7310.15200.48600.41170.071*
C80.1822 (3)0.3458 (3)0.3778 (3)0.0515 (14)
H8110.22860.32600.37010.077*
H8210.14590.30870.36290.077*
H8310.18220.36040.43740.077*
C510.1850 (2)0.5422 (2)0.0732 (2)0.0227 (8)
C520.1554 (2)0.6056 (2)0.1016 (3)0.0281 (9)
H520.14200.60760.15730.034*
C530.1455 (2)0.6653 (2)0.0489 (3)0.0318 (9)
H530.12590.70860.06870.038*
C540.1640 (2)0.6627 (2)−0.0328 (3)0.0337 (10)
H540.15650.7039−0.06920.040*
C550.1935 (2)0.6000 (2)−0.0616 (3)0.0357 (10)
H550.20640.5981−0.11760.043*
C560.2042 (2)0.5402 (2)−0.0087 (3)0.0284 (9)
H560.22480.4974−0.02830.034*
C610.1077 (2)0.3279 (2)−0.0267 (2)0.0229 (8)
C620.1628 (2)0.3508 (2)−0.0694 (2)0.0258 (8)
H620.20910.3548−0.03970.031*
C630.1504 (2)0.3678 (2)−0.1550 (2)0.0308 (9)
H630.18830.3834−0.18400.037*
C640.0835 (2)0.3623 (2)−0.1987 (2)0.0334 (10)
H640.07510.3746−0.25740.040*
C650.0284 (2)0.3389 (3)−0.1569 (3)0.0367 (10)
H65−0.01770.3345−0.18710.044*
C660.0404 (2)0.3218 (2)−0.0714 (3)0.0330 (9)
H660.00240.3058−0.04280.040*
C710.0498 (2)0.3505 (2)0.1299 (2)0.0241 (8)
C720.0273 (2)0.3236 (2)0.2048 (3)0.0346 (10)
H720.04580.27890.22810.042*
C73−0.0212 (3)0.3611 (3)0.2450 (3)0.0460 (12)
H73−0.03680.34210.29520.055*
C74−0.0471 (3)0.4268 (3)0.2117 (3)0.0491 (13)
H74−0.08060.45300.23920.059*
C75−0.0246 (3)0.4544 (3)0.1392 (3)0.0445 (12)
H75−0.04240.49980.11720.053*
C760.0236 (2)0.4168 (2)0.0980 (3)0.0323 (9)
H760.03890.43630.04780.039*
C810.0972 (2)0.2071 (2)0.0871 (2)0.0224 (8)
C820.1500 (2)0.1548 (2)0.0970 (2)0.0261 (8)
H820.19810.16930.10580.031*
C830.1329 (2)0.0814 (2)0.0944 (3)0.0309 (9)
H830.16940.04600.10100.037*
C840.0632 (2)0.0598 (2)0.0822 (3)0.0329 (10)
H840.05160.00960.08060.039*
C850.0101 (2)0.1115 (2)0.0723 (3)0.0354 (10)
H85−0.03790.09670.06370.043*
C860.0270 (2)0.1849 (2)0.0749 (3)0.0311 (9)
H86−0.00960.22020.06840.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Re10.01965 (7)0.01528 (7)0.01927 (7)0.00080 (6)0.00211 (5)0.00075 (5)
Br10.0336 (2)0.0283 (2)0.02781 (19)0.00461 (17)0.00804 (16)−0.00207 (16)
Br20.0251 (2)0.0300 (2)0.0393 (2)−0.00504 (17)0.00004 (17)−0.00410 (18)
P10.0186 (5)0.0168 (4)0.0226 (4)0.0018 (4)0.0007 (4)0.0004 (4)
O10.0285 (14)0.0158 (12)0.0210 (12)0.0032 (11)0.0046 (11)0.0015 (10)
O20.0267 (14)0.0231 (14)0.0263 (14)0.0032 (11)0.0024 (11)0.0039 (11)
N10.0257 (17)0.0173 (15)0.0213 (15)0.0032 (13)0.0032 (13)−0.0004 (12)
N20.0287 (17)0.0183 (16)0.0248 (16)0.0028 (14)0.0014 (13)0.0013 (13)
C10.0172 (17)0.0178 (18)0.0246 (18)−0.0031 (14)−0.0002 (14)−0.0013 (14)
C20.033 (2)0.029 (2)0.0251 (19)0.0011 (18)0.0053 (17)−0.0027 (16)
C30.062 (3)0.045 (3)0.030 (2)0.016 (3)0.011 (2)−0.010 (2)
C40.083 (4)0.041 (3)0.026 (2)0.014 (3)0.012 (2)0.008 (2)
C110.0202 (18)0.0181 (18)0.0271 (19)0.0004 (15)0.0032 (15)0.0023 (15)
C120.031 (2)0.0198 (19)0.033 (2)−0.0027 (17)0.0050 (17)0.0001 (16)
C130.033 (2)0.019 (2)0.049 (3)0.0045 (17)0.009 (2)0.0052 (18)
C140.032 (2)0.032 (2)0.043 (2)0.0039 (19)0.0039 (19)0.018 (2)
C150.041 (3)0.035 (2)0.032 (2)0.002 (2)0.0011 (19)0.0102 (19)
C160.035 (2)0.024 (2)0.028 (2)0.0020 (17)0.0047 (17)0.0019 (16)
C210.029 (2)0.0169 (18)0.0239 (18)0.0008 (15)−0.0010 (15)0.0008 (14)
C220.034 (2)0.040 (3)0.034 (2)0.009 (2)−0.0013 (19)0.000 (2)
C230.050 (3)0.048 (3)0.039 (3)0.019 (3)−0.013 (2)0.003 (2)
C240.066 (4)0.033 (2)0.028 (2)0.000 (2)−0.011 (2)0.0034 (19)
C250.055 (3)0.040 (3)0.022 (2)−0.013 (2)0.001 (2)−0.0006 (18)
C260.031 (2)0.030 (2)0.027 (2)−0.0029 (18)0.0010 (16)−0.0032 (17)
C310.0187 (18)0.025 (2)0.0259 (19)0.0029 (16)0.0003 (15)−0.0008 (15)
C320.037 (2)0.030 (2)0.034 (2)0.0067 (19)0.0094 (19)0.0039 (18)
C330.044 (3)0.052 (3)0.035 (2)0.006 (2)0.015 (2)0.006 (2)
C340.038 (3)0.062 (3)0.030 (2)0.015 (2)0.010 (2)−0.007 (2)
C350.032 (2)0.037 (3)0.044 (3)0.010 (2)0.003 (2)−0.011 (2)
C360.024 (2)0.025 (2)0.037 (2)0.0036 (17)0.0036 (17)−0.0046 (17)
C410.0214 (19)0.0181 (18)0.0279 (19)0.0010 (15)0.0042 (15)−0.0020 (15)
C420.032 (2)0.025 (2)0.048 (3)0.0042 (19)−0.009 (2)−0.0017 (19)
C430.031 (2)0.030 (2)0.063 (3)−0.004 (2)−0.008 (2)−0.009 (2)
C440.039 (3)0.020 (2)0.052 (3)−0.0037 (19)0.002 (2)−0.0067 (19)
C450.032 (2)0.021 (2)0.050 (3)0.0038 (18)−0.003 (2)−0.0011 (19)
C460.026 (2)0.0202 (19)0.037 (2)−0.0003 (16)0.0000 (17)−0.0027 (17)
Re20.02176 (8)0.01789 (7)0.01966 (7)−0.00075 (6)0.00433 (5)0.00207 (5)
Br30.0303 (2)0.0309 (2)0.0458 (2)−0.00655 (18)−0.00375 (18)−0.00186 (19)
Br40.0334 (2)0.0324 (2)0.0322 (2)0.00594 (18)0.01408 (17)0.00429 (17)
P20.0210 (5)0.0188 (4)0.0194 (4)0.0006 (4)0.0053 (4)0.0011 (4)
O30.0292 (14)0.0176 (13)0.0243 (13)0.0014 (11)0.0077 (11)0.0033 (10)
O40.0303 (15)0.0265 (14)0.0219 (13)−0.0014 (12)0.0025 (11)0.0034 (11)
N30.0295 (17)0.0184 (16)0.0220 (15)−0.0019 (13)0.0039 (13)−0.0001 (12)
N40.0323 (18)0.0196 (16)0.0221 (15)0.0000 (14)0.0041 (13)0.0003 (13)
C50.0195 (18)0.0201 (18)0.0218 (17)−0.0039 (15)−0.0011 (14)−0.0022 (14)
C60.047 (3)0.033 (2)0.0221 (19)−0.002 (2)0.0112 (18)−0.0043 (17)
C70.067 (4)0.047 (3)0.033 (2)0.004 (3)0.025 (2)−0.007 (2)
C80.092 (4)0.044 (3)0.022 (2)0.006 (3)0.020 (2)0.006 (2)
C510.0203 (18)0.0203 (19)0.0267 (19)−0.0035 (15)0.0005 (15)0.0024 (15)
C520.027 (2)0.023 (2)0.034 (2)−0.0011 (17)0.0030 (17)−0.0008 (17)
C530.026 (2)0.020 (2)0.047 (3)0.0011 (17)−0.0019 (18)−0.0033 (18)
C540.032 (2)0.023 (2)0.043 (2)−0.0047 (18)−0.0029 (19)0.0092 (18)
C550.043 (3)0.033 (2)0.032 (2)−0.002 (2)0.009 (2)0.0068 (18)
C560.034 (2)0.022 (2)0.031 (2)−0.0009 (17)0.0071 (17)0.0054 (16)
C610.030 (2)0.0203 (18)0.0189 (17)0.0047 (16)0.0056 (15)0.0025 (14)
C620.031 (2)0.0233 (19)0.0238 (19)−0.0021 (17)0.0065 (16)−0.0019 (15)
C630.042 (2)0.029 (2)0.0227 (19)−0.0019 (19)0.0104 (18)−0.0005 (16)
C640.051 (3)0.033 (2)0.0165 (18)0.008 (2)0.0038 (18)−0.0013 (16)
C650.032 (2)0.050 (3)0.026 (2)0.006 (2)−0.0031 (17)−0.0018 (19)
C660.027 (2)0.044 (3)0.027 (2)0.0034 (19)0.0041 (17)0.0043 (18)
C710.0231 (19)0.0240 (19)0.0263 (19)−0.0009 (16)0.0074 (15)−0.0044 (15)
C720.035 (2)0.036 (2)0.035 (2)0.000 (2)0.0121 (19)0.0014 (19)
C730.037 (3)0.065 (4)0.039 (3)−0.002 (2)0.017 (2)−0.009 (2)
C740.035 (3)0.062 (4)0.052 (3)0.008 (2)0.014 (2)−0.025 (3)
C750.039 (3)0.034 (3)0.060 (3)0.014 (2)0.004 (2)−0.014 (2)
C760.033 (2)0.027 (2)0.037 (2)0.0004 (18)0.0050 (18)−0.0038 (18)
C810.029 (2)0.0206 (19)0.0178 (17)−0.0019 (16)0.0034 (15)−0.0007 (14)
C820.030 (2)0.024 (2)0.0255 (19)0.0008 (16)0.0079 (16)−0.0010 (15)
C830.041 (2)0.024 (2)0.029 (2)0.0032 (18)0.0068 (18)−0.0031 (16)
C840.049 (3)0.022 (2)0.026 (2)−0.0059 (19)−0.0021 (19)−0.0004 (16)
C850.032 (2)0.034 (2)0.037 (2)−0.0116 (19)−0.0091 (18)0.0049 (19)
C860.031 (2)0.026 (2)0.034 (2)−0.0006 (18)−0.0034 (18)0.0038 (17)
Geometric parameters (Å, °) top
Re1—O21.678 (3)Re2—O41.675 (3)
Re1—O12.027 (2)Re2—O32.021 (2)
Re1—N12.155 (3)Re2—N32.152 (3)
Re1—P12.4724 (10)Re2—P22.4810 (10)
Re1—Br12.4829 (4)Re2—Br42.4970 (4)
Re1—Br22.5252 (4)Re2—Br32.5147 (5)
P1—C211.816 (4)P2—C711.814 (4)
P1—C311.821 (4)P2—C611.821 (4)
P1—C411.821 (4)P2—C811.830 (4)
O1—C11.315 (4)O3—C51.320 (4)
N1—C21.303 (5)N3—C61.301 (5)
N1—N21.406 (4)N3—N41.402 (4)
N2—C11.294 (5)N4—C51.295 (5)
C1—C111.476 (5)C5—C511.473 (5)
C2—C41.489 (6)C6—C71.491 (6)
C2—C31.491 (6)C6—C81.496 (6)
C3—H3110.9800C7—H7110.9800
C3—H3210.9800C7—H7210.9800
C3—H3310.9800C7—H7310.9800
C4—H4110.9800C8—H8110.9800
C4—H4210.9800C8—H8210.9800
C4—H4310.9800C8—H8310.9800
C11—C121.391 (5)C51—C561.392 (5)
C11—C161.393 (5)C51—C521.395 (5)
C12—C131.385 (6)C52—C531.377 (6)
C12—H120.9500C52—H520.9500
C13—C141.378 (6)C53—C541.384 (6)
C13—H130.9500C53—H530.9500
C14—C151.381 (6)C54—C551.387 (6)
C14—H140.9500C54—H540.9500
C15—C161.382 (6)C55—C561.380 (6)
C15—H150.9500C55—H550.9500
C16—H160.9500C56—H560.9500
C21—C221.387 (6)C61—C621.387 (5)
C21—C261.393 (6)C61—C661.391 (6)
C22—C231.386 (6)C62—C631.380 (5)
C22—H220.9500C62—H620.9500
C23—C241.378 (7)C63—C641.377 (6)
C23—H230.9500C63—H630.9500
C24—C251.377 (7)C64—C651.382 (6)
C24—H240.9500C64—H640.9500
C25—C261.386 (6)C65—C661.378 (6)
C25—H250.9500C65—H650.9500
C26—H260.9500C66—H660.9500
C31—C361.393 (5)C71—C761.388 (6)
C31—C321.395 (6)C71—C721.401 (5)
C32—C331.388 (6)C72—C731.376 (6)
C32—H320.9500C72—H720.9500
C33—C341.376 (7)C73—C741.383 (8)
C33—H330.9500C73—H730.9500
C34—C351.383 (7)C74—C751.373 (7)
C34—H340.9500C74—H740.9500
C35—C361.378 (6)C75—C761.382 (6)
C35—H350.9500C75—H750.9500
C36—H360.9500C76—H760.9500
C41—C421.388 (6)C81—C821.389 (5)
C41—C461.392 (5)C81—C861.391 (6)
C42—C431.381 (6)C82—C831.387 (6)
C42—H420.9500C82—H820.9500
C43—C441.377 (6)C83—C841.381 (6)
C43—H430.9500C83—H830.9500
C44—C451.376 (6)C84—C851.384 (6)
C44—H440.9500C84—H840.9500
C45—C461.389 (6)C85—C861.388 (6)
C45—H450.9500C85—H850.9500
C46—H460.9500C86—H860.9500
O2—Re1—O1161.65 (12)O4—Re2—O3162.46 (12)
O2—Re1—N193.96 (12)O4—Re2—N395.14 (12)
O1—Re1—N173.84 (10)O3—Re2—N373.71 (11)
O2—Re1—P183.53 (10)O4—Re2—P284.30 (10)
O1—Re1—P183.83 (8)O3—Re2—P282.50 (8)
N1—Re1—P194.44 (9)N3—Re2—P291.27 (9)
O2—Re1—Br1104.18 (9)O4—Re2—Br4102.84 (9)
O1—Re1—Br189.52 (7)O3—Re2—Br489.61 (7)
N1—Re1—Br1161.31 (8)N3—Re2—Br4161.64 (8)
P1—Re1—Br192.08 (2)P2—Re2—Br494.15 (2)
O2—Re1—Br2101.66 (9)O4—Re2—Br3101.18 (9)
O1—Re1—Br290.71 (8)O3—Re2—Br391.34 (8)
N1—Re1—Br283.52 (9)N3—Re2—Br384.42 (9)
P1—Re1—Br2174.53 (2)P2—Re2—Br3173.29 (3)
Br1—Re1—Br288.359 (15)Br4—Re2—Br388.444 (16)
C21—P1—C31107.05 (18)C71—P2—C61104.28 (18)
C21—P1—C41105.04 (17)C71—P2—C81105.30 (18)
C31—P1—C41104.00 (17)C61—P2—C81104.29 (17)
C21—P1—Re1117.33 (13)C71—P2—Re2109.17 (13)
C31—P1—Re1107.98 (13)C61—P2—Re2120.00 (13)
C41—P1—Re1114.44 (13)C81—P2—Re2112.58 (13)
C1—O1—Re1117.1 (2)C5—O3—Re2117.5 (2)
C2—N1—N2114.5 (3)C6—N3—N4114.3 (3)
C2—N1—Re1130.3 (3)C6—N3—Re2130.4 (3)
N2—N1—Re1115.1 (2)N4—N3—Re2115.3 (2)
C1—N2—N1110.6 (3)C5—N4—N3110.8 (3)
N2—C1—O1123.0 (3)N4—C5—O3122.3 (3)
N2—C1—C11118.9 (3)N4—C5—C51119.6 (3)
O1—C1—C11118.0 (3)O3—C5—C51118.2 (3)
N1—C2—C4122.4 (4)N3—C6—C7121.3 (4)
N1—C2—C3120.8 (4)N3—C6—C8121.3 (4)
C4—C2—C3116.8 (4)C7—C6—C8117.5 (4)
C2—C3—H311109.5C6—C7—H711109.5
C2—C3—H321109.5C6—C7—H721109.5
H311—C3—H321109.5H711—C7—H721109.5
C2—C3—H331109.5C6—C7—H731109.5
H311—C3—H331109.5H711—C7—H731109.5
H321—C3—H331109.5H721—C7—H731109.5
C2—C4—H411109.5C6—C8—H811109.5
C2—C4—H421109.5C6—C8—H821109.5
H411—C4—H421109.5H811—C8—H821109.5
C2—C4—H431109.5C6—C8—H831109.5
H411—C4—H431109.5H811—C8—H831109.5
H421—C4—H431109.5H821—C8—H831109.5
C12—C11—C16119.5 (4)C56—C51—C52119.2 (4)
C12—C11—C1120.4 (3)C56—C51—C5120.4 (3)
C16—C11—C1120.0 (3)C52—C51—C5120.3 (3)
C13—C12—C11119.9 (4)C53—C52—C51120.1 (4)
C13—C12—H12120.0C53—C52—H52119.9
C11—C12—H12120.0C51—C52—H52119.9
C14—C13—C12120.1 (4)C52—C53—C54120.4 (4)
C14—C13—H13120.0C52—C53—H53119.8
C12—C13—H13120.0C54—C53—H53119.8
C13—C14—C15120.4 (4)C53—C54—C55119.9 (4)
C13—C14—H14119.8C53—C54—H54120.1
C15—C14—H14119.8C55—C54—H54120.1
C14—C15—C16120.0 (4)C56—C55—C54119.9 (4)
C14—C15—H15120.0C56—C55—H55120.0
C16—C15—H15120.0C54—C55—H55120.0
C15—C16—C11120.1 (4)C55—C56—C51120.4 (4)
C15—C16—H16120.0C55—C56—H56119.8
C11—C16—H16120.0C51—C56—H56119.8
C22—C21—C26119.1 (4)C62—C61—C66119.2 (4)
C22—C21—P1122.2 (3)C62—C61—P2122.5 (3)
C26—C21—P1118.6 (3)C66—C61—P2118.3 (3)
C23—C22—C21120.3 (4)C63—C62—C61120.1 (4)
C23—C22—H22119.8C63—C62—H62119.9
C21—C22—H22119.8C61—C62—H62119.9
C24—C23—C22120.1 (5)C64—C63—C62120.4 (4)
C24—C23—H23120.0C64—C63—H63119.8
C22—C23—H23120.0C62—C63—H63119.8
C25—C24—C23120.1 (4)C63—C64—C65120.0 (4)
C25—C24—H24119.9C63—C64—H64120.0
C23—C24—H24119.9C65—C64—H64120.0
C24—C25—C26120.2 (4)C66—C65—C64120.0 (4)
C24—C25—H25119.9C66—C65—H65120.0
C26—C25—H25119.9C64—C65—H65120.0
C25—C26—C21120.1 (4)C65—C66—C61120.4 (4)
C25—C26—H26119.9C65—C66—H66119.8
C21—C26—H26119.9C61—C66—H66119.8
C36—C31—C32119.0 (4)C76—C71—C72118.8 (4)
C36—C31—P1120.2 (3)C76—C71—P2121.9 (3)
C32—C31—P1120.5 (3)C72—C71—P2118.8 (3)
C33—C32—C31120.3 (4)C73—C72—C71120.8 (4)
C33—C32—H32119.8C73—C72—H72119.6
C31—C32—H32119.8C71—C72—H72119.6
C34—C33—C32119.9 (4)C72—C73—C74119.4 (5)
C34—C33—H33120.1C72—C73—H73120.3
C32—C33—H33120.1C74—C73—H73120.3
C33—C34—C35120.2 (4)C75—C74—C73120.4 (4)
C33—C34—H34119.9C75—C74—H74119.8
C35—C34—H34119.9C73—C74—H74119.8
C36—C35—C34120.2 (4)C74—C75—C76120.5 (5)
C36—C35—H35119.9C74—C75—H75119.7
C34—C35—H35119.9C76—C75—H75119.7
C35—C36—C31120.4 (4)C75—C76—C71120.0 (4)
C35—C36—H36119.8C75—C76—H76120.0
C31—C36—H36119.8C71—C76—H76120.0
C42—C41—C46119.0 (4)C82—C81—C86119.1 (4)
C42—C41—P1118.5 (3)C82—C81—P2119.9 (3)
C46—C41—P1122.4 (3)C86—C81—P2120.9 (3)
C43—C42—C41120.6 (4)C83—C82—C81120.4 (4)
C43—C42—H42119.7C83—C82—H82119.8
C41—C42—H42119.7C81—C82—H82119.8
C44—C43—C42120.2 (4)C84—C83—C82120.2 (4)
C44—C43—H43119.9C84—C83—H83119.9
C42—C43—H43119.9C82—C83—H83119.9
C45—C44—C43119.9 (4)C83—C84—C85119.9 (4)
C45—C44—H44120.0C83—C84—H84120.1
C43—C44—H44120.0C85—C84—H84120.1
C44—C45—C46120.3 (4)C84—C85—C86120.1 (4)
C44—C45—H45119.8C84—C85—H85120.0
C46—C45—H45119.8C86—C85—H85120.0
C45—C46—C41119.9 (4)C85—C86—C81120.4 (4)
C45—C46—H46120.0C85—C86—H86119.8
C41—C46—H46120.0C81—C86—H86119.8
O2—Re1—P1—C21−173.65 (17)O4—Re2—P2—C7185.74 (17)
O1—Re1—P1—C2119.68 (15)O3—Re2—P2—C71−82.68 (15)
N1—Re1—P1—C2192.87 (16)N3—Re2—P2—C71−9.29 (16)
Br1—Re1—P1—C21−69.61 (14)Br4—Re2—P2—C71−171.74 (14)
O2—Re1—P1—C3165.38 (16)O4—Re2—P2—C61−154.11 (17)
O1—Re1—P1—C31−101.29 (15)O3—Re2—P2—C6137.47 (16)
N1—Re1—P1—C31−28.11 (15)N3—Re2—P2—C61110.86 (16)
Br1—Re1—P1—C31169.42 (13)Br4—Re2—P2—C61−51.59 (14)
O2—Re1—P1—C41−49.88 (16)O4—Re2—P2—C81−30.82 (16)
O1—Re1—P1—C41143.44 (15)O3—Re2—P2—C81160.76 (14)
N1—Re1—P1—C41−143.37 (16)N3—Re2—P2—C81−125.85 (15)
Br1—Re1—P1—C4154.15 (13)Br4—Re2—P2—C8171.70 (13)
O2—Re1—O1—C145.1 (5)O4—Re2—O3—C546.6 (5)
N1—Re1—O1—C1−4.7 (2)N3—Re2—O3—C5−5.5 (3)
P1—Re1—O1—C191.7 (2)P2—Re2—O3—C588.1 (2)
Br1—Re1—O1—C1−176.1 (2)Br4—Re2—O3—C5−177.7 (2)
Br2—Re1—O1—C1−87.8 (2)Br3—Re2—O3—C5−89.3 (2)
O2—Re1—N1—C222.8 (4)O4—Re2—N3—C619.8 (4)
O1—Re1—N1—C2−171.2 (4)O3—Re2—N3—C6−174.0 (4)
P1—Re1—N1—C2106.6 (4)P2—Re2—N3—C6104.2 (4)
Br1—Re1—N1—C2−143.4 (3)Br4—Re2—N3—C6−148.5 (3)
Br2—Re1—N1—C2−78.5 (4)Br3—Re2—N3—C6−80.9 (4)
O2—Re1—N1—N2−161.3 (3)O4—Re2—N3—N4−160.7 (3)
O1—Re1—N1—N24.7 (2)O3—Re2—N3—N45.5 (2)
P1—Re1—N1—N2−77.5 (2)P2—Re2—N3—N4−76.3 (2)
Br1—Re1—N1—N232.5 (4)Br4—Re2—N3—N430.9 (5)
Br2—Re1—N1—N297.3 (2)Br3—Re2—N3—N498.5 (2)
C2—N1—N2—C1172.6 (3)C6—N3—N4—C5174.9 (4)
Re1—N1—N2—C1−4.0 (4)Re2—N3—N4—C5−4.7 (4)
N1—N2—C1—O1−0.1 (5)N3—N4—C5—O30.0 (5)
N1—N2—C1—C11177.7 (3)N3—N4—C5—C51179.4 (3)
Re1—O1—C1—N24.5 (5)Re2—O3—C5—N45.1 (5)
Re1—O1—C1—C11−173.4 (2)Re2—O3—C5—C51−174.3 (2)
N2—N1—C2—C4−178.6 (4)N4—N3—C6—C74.8 (6)
Re1—N1—C2—C4−2.6 (6)Re2—N3—C6—C7−175.8 (3)
N2—N1—C2—C31.7 (6)N4—N3—C6—C8−176.4 (4)
Re1—N1—C2—C3177.6 (3)Re2—N3—C6—C83.0 (7)
N2—C1—C11—C1214.6 (5)N4—C5—C51—C56−173.1 (4)
O1—C1—C11—C12−167.5 (3)O3—C5—C51—C566.3 (5)
N2—C1—C11—C16−163.4 (4)N4—C5—C51—C526.3 (6)
O1—C1—C11—C1614.6 (5)O3—C5—C51—C52−174.3 (3)
C16—C11—C12—C130.4 (6)C56—C51—C52—C53−0.1 (6)
C1—C11—C12—C13−177.6 (4)C5—C51—C52—C53−179.5 (4)
C11—C12—C13—C14−0.4 (6)C51—C52—C53—C540.8 (6)
C12—C13—C14—C150.3 (7)C52—C53—C54—C55−0.8 (7)
C13—C14—C15—C16−0.2 (7)C53—C54—C55—C560.2 (7)
C14—C15—C16—C110.2 (7)C54—C55—C56—C510.5 (7)
C12—C11—C16—C15−0.3 (6)C52—C51—C56—C55−0.5 (6)
C1—C11—C16—C15177.7 (4)C5—C51—C56—C55178.9 (4)
C31—P1—C21—C22−13.9 (4)C71—P2—C61—C62133.1 (3)
C41—P1—C21—C2296.2 (4)C81—P2—C61—C62−116.6 (3)
Re1—P1—C21—C22−135.4 (3)Re2—P2—C61—C6210.6 (4)
C31—P1—C21—C26168.8 (3)C71—P2—C61—C66−48.2 (4)
C41—P1—C21—C26−81.1 (3)C81—P2—C61—C6662.0 (4)
Re1—P1—C21—C2647.3 (3)Re2—P2—C61—C66−170.8 (3)
C26—C21—C22—C23−1.5 (7)C66—C61—C62—C630.6 (6)
P1—C21—C22—C23−178.7 (4)P2—C61—C62—C63179.2 (3)
C21—C22—C23—C240.4 (8)C61—C62—C63—C640.0 (6)
C22—C23—C24—C250.9 (8)C62—C63—C64—C65−0.7 (6)
C23—C24—C25—C26−1.2 (7)C63—C64—C65—C660.7 (7)
C24—C25—C26—C210.1 (7)C64—C65—C66—C610.0 (7)
C22—C21—C26—C251.2 (6)C62—C61—C66—C65−0.6 (6)
P1—C21—C26—C25178.5 (3)P2—C61—C66—C65−179.3 (3)
C21—P1—C31—C36−52.4 (4)C61—P2—C71—C76−31.9 (4)
C41—P1—C31—C36−163.3 (3)C81—P2—C71—C76−141.4 (3)
Re1—P1—C31—C3674.7 (3)Re2—P2—C71—C7697.5 (3)
C21—P1—C31—C32134.6 (3)C61—P2—C71—C72156.3 (3)
C41—P1—C31—C3223.7 (4)C81—P2—C71—C7246.8 (4)
Re1—P1—C31—C32−98.3 (3)Re2—P2—C71—C72−74.3 (3)
C36—C31—C32—C330.0 (6)C76—C71—C72—C731.7 (7)
P1—C31—C32—C33173.1 (4)P2—C71—C72—C73173.7 (4)
C31—C32—C33—C340.8 (7)C71—C72—C73—C74−1.1 (7)
C32—C33—C34—C35−0.9 (8)C72—C73—C74—C750.0 (8)
C33—C34—C35—C360.0 (7)C73—C74—C75—C760.6 (8)
C34—C35—C36—C310.8 (7)C74—C75—C76—C710.0 (7)
C32—C31—C36—C35−0.8 (6)C72—C71—C76—C75−1.1 (6)
P1—C31—C36—C35−173.9 (3)P2—C71—C76—C75−172.9 (4)
C21—P1—C41—C42−45.5 (4)C71—P2—C81—C82−149.4 (3)
C31—P1—C41—C4266.8 (4)C61—P2—C81—C82101.1 (3)
Re1—P1—C41—C42−175.6 (3)Re2—P2—C81—C82−30.6 (3)
C21—P1—C41—C46138.9 (3)C71—P2—C81—C8633.0 (4)
C31—P1—C41—C46−108.8 (3)C61—P2—C81—C86−76.5 (3)
Re1—P1—C41—C468.8 (4)Re2—P2—C81—C86151.8 (3)
C46—C41—C42—C430.4 (7)C86—C81—C82—C830.4 (6)
P1—C41—C42—C43−175.3 (4)P2—C81—C82—C83−177.2 (3)
C41—C42—C43—C440.2 (8)C81—C82—C83—C84−0.3 (6)
C42—C43—C44—C45−0.7 (8)C82—C83—C84—C850.2 (6)
C43—C44—C45—C460.8 (7)C83—C84—C85—C86−0.2 (6)
C44—C45—C46—C41−0.2 (7)C84—C85—C86—C810.3 (6)
C42—C41—C46—C45−0.4 (6)C82—C81—C86—C85−0.4 (6)
P1—C41—C46—C45175.2 (3)P2—C81—C86—C85177.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C22—H22···Br30.952.943.819 (5)154.
C85—H85···Br2i0.952.923.587 (4)128.
Symmetry codes: (i) x−1, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C22—H22···Br30.952.943.819 (5)154.
C85—H85···Br2i0.952.923.587 (4)128.
Symmetry codes: (i) x−1, −y+1/2, z−1/2.
Acknowledgements top

The authors thank Mrs Rose van der Vyver for helpful discussions and a lifetime of joy.

references
References top

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