research papers
Nonorder–disorder allotwinning of the rhenium pincer complex cisRe[(PNP^{CH2}iPr)(CO)_{2}Cl]
^{a}Institute of Applied Synthethic Chemistry, TU Wien, Getreidemarkt 9, 1060 Vienna, Austria, and ^{b}Xray Centre, TU Wien, Getreidemarkt 9, 1060 Vienna, Austria
^{*}Correspondence email: bstoeger@mail.tuwien.ac.at
Crystals of cisRe[(PNP^{CH2}iPr)(CO)_{2}Cl] (1) are made up of two geometrically nonequivalent with respective symmetries of P2_{1}/c and I2/a. The structures were determined in a concurrent taking into account overlap of diffraction spots. The are composed of layers with p_{x}12_{1}/c1 symmetry and are of the nonorder–disorder (OD) type (the layer interfaces are nonequivalent). Whereas the molecules of (1) differ in both the Re atoms are located at nearly identical positions.
Keywords: polytypism; allotwinning.
1. Introduction
et al., 2008) that are composed of equivalent layers (or more generally rods or blocks) arranged into nonequivalent stackings. which are ubiquitous in all classes of materials, can crystallize with different degrees of order, ranging from perfectly ordered to purely random stackings. When crystallizing with only few stacking faults, often form twins, which are made up of macroscopic equivalent domains with different orientations (Hahn & Klapper, 2006).
are modular structures (FerrarisA cognate phenomenon is allotwinning (Nespolo et al., 1999). These edifices are made up of crystalline domains of different Apparently, in allotwins the crystallization conditions vary in such a way that only one of two or more is formed at a time. An alternative formation mechanism that has been proposed is oriented attachment (Nespolo & Ferraris, 2004), where of different kinds form at different places and attach postnucleation in a systematic manner.
Intuitively, both formation mechanisms appear unlikely and indeed examples of allotwins which have been structurally properly characterized are rare. In contrast, our experience with singlecrystal diffraction of inorganic, organic and coordination compounds suggests an ordersofmagnitude higher frequency of allotwins than would be inferred from their reported number.
One reason for the underreporting is certainly the missing support in the common crystallographic software packages. But the biggest hurdle might actually be a failure of recognizing allotwinning, owing to a lack of awareness of the phenomenon. In this communication both points are addressed by giving a detailed account of the structure ^{I} complex cisRe[(PNP^{CH2}iPr)(CO)_{2}Cl] [(1), Fig. 1]. It is shown that, once the nature of the diffraction pattern is understood and proper intensity data are derived, structure solution and can be surprisingly troublefree. The ^{t}Bu analogue of (1), cisRe[(PNP^{CH2}tBu)(CO)_{2}Cl], has been described previously (Vogt et al., 2013) and does not feature polytypism.
of an allotwinned crystal of the ReData reduction is a crucial step in the characterization of allotwins. In the simplest case, the
share a common (used here in the sense of a common subset of translation vectors) and the set of overlapping reflections is well defined. The reflections of all can then be integrated concurrently using a common in Unfortunately, this is often rather dense, leading to a large number of virtual overlaps of nonexisting diffraction spots, and in consequence to suboptimal intensity evaluation.In the general case, the matrix describing the i.e. considering all the reflections separated by less than a threshold value as overlapped). For classical the concurrent integration of multiple domains with overlap information has become a standard. The advantage is that the integration software is aware of the reflectionmask shape and therefore can precisely determine the amount of overlap. We have recently applied such an approach to a multidomain crystal (Stöger et al., 2015).
relationship is nonrational and reflections are partially overlapping. The common strategy (also previously used for classical twinning) then has been to integrate the data of the individuals separately and determine overlaps by heuristics (Structure refinements of allotwins can likewise follow two major strategies. Either the models of the individual polytype are refined separately against the nonoverlapping reflections or in a concurrent
taking into account reflection overlaps. Since allotwins are by definition oriented systematically, reflection overlap is likewise systematic and therefore the latter approach is preferable, even though only few packages support such refinements.Here, we want to advocate an integration with overlap information followed by a concurrent
against the full data set. Such a scheme represents the most controlled and satisfying approach, avoiding heuristics as much as possible.2. Experimental
2.1. Synthesis and crystal growth
The PNP^{CH2}iPr ligand was synthesized according to literature procedures (Leung et al., 2003). PNP^{CH2}iPr (136 mg, 0.4 mmol) and Re(CO)_{5}Cl (144 mg, 0.4 mmol) were refluxed in dioxane (10 ml) for 72 h. The suspension was evaporated to dryness, taken up in dry acetone and filtered over celite. The solvent was removed under reduced pressure, the pale yellow residue washed with npentane (15 ml) and dried under reduced pressure. Yellow crystals of (1) were grown by vapor diffusion of npentane into a CH_{2}Cl_{2} solution of the crude product. Colorless crystals of Re[(PNP^{CH2}iPr)(CO)_{3}]·Cl were obtained as a side product. Anal.: calc. for C_{21}H_{35}ClNO_{2}P_{2}Re (617.12): C 40.87, H 5.72, N 2.27; found: C 40.90, H 5.77, N 2.27%. ^{1}H NMR (600 MHz, δ, CD_{2}Cl_{2}, 20°C) 7.55 (t, J_{HH} = 7.7 Hz, ^{1}H, py^{4}), 7.25 (d, J_{HH} = 7.7 Hz, 2H, py^{3,5}), 3.88 (m, 2H, CH_{2}), 2.48 (m, 2H, CH_{2}), 2.72 (m, 2H, CH), 2.40 (m, 2H, CH), 1.26–1.20 (m, 18H, CH_{3}), 1.09 (dd, J = 15.1, 7.3 Hz, 6H, CH_{3}). ^{13}C{^{1}H} NMR (151 MHz, δ, CD_{2}Cl_{2}, 20°C) 208.9 (m, CO), 199.2 (vt, J_{CP} = 8.2 Hz, CO), 164.4 (vt, J_{CP} = 4.6 Hz, py^{2,6}), 137.4 (s, py^{4}), 120.5 (vt, J_{CP} = 4.4 Hz, py^{3,5}), 42.9 (vt, J_{CP} = 11.2 Hz, CH_{2}), 26.9 (vt, J_{CP} = 13.5 Hz, CH), 24.3 (vt, J_{CP} = 11.7 Hz, CH), 19.8 (vt, J_{CP} = 1.8 Hz, CH_{3}), 19.7 (vt, J_{CP} = 1.5 Hz, CH_{3}), 19.3 (s, CH_{3}), 17.7 (s, CH_{3}). ^{13}P{^{1}H} NMR (101 MHz, δ, CD_{2}Cl_{2}, 20°C) 52.4 (2P). IR (ATR, cm^{−1}): 1900 (νCO), 1806 (νCO).
2.2. Data collection
The yellow blocks of (1) were optically homogeneous, but cleaved into numerous small platelets on cutting with a razor blade. Generally, diffraction quality was mediocre (arcing, splitting of reflections), being worse for larger crystals. Therefore, intensity data of a tiny block asgrown was collected at 200 K in a dry stream of nitrogen on a Bruker KAPPA APEX II diffractometer system using graphite monochromated Mo radiation and fine sliced ω and φscans. The whole reciprocal sphere up to = 60° was collected. Data collection and details are summarized in Tables 1 and 2.


2.3. Cell determination and integration
Depending on the chosen tolerances, automatic Apex3 (Bruker, 2014) software yielded different (nonequivalent) orientation matrices, none of which was able to explain the majority of the diffraction spots. All the proposed cells were metrically monoclinic and shared a common b^{*} basis vector. Indeed, as observed in the RLATT module (Bruker, 2014), virtually all reflections were located in planes normal to b^{*}. The few remaining reflections between these planes were attributed to negligible admixtures and culled for ease of further processing.
determination with theA view along b^{*} revealed two kinds of rows, which span different lattices as indicated in the reconstructed plane in Fig. 2(a). These rows were intuitively interpreted as a sign of with a > 1 and therefore the reflections were separated and the orientation matrices determined individually. Two satisfying lattices were thus obtained, albeit belonging to different Bravais classes (mP and mC).
After proceeding as described in the following section, no chemically reasonable structure mC domain. In all cases, even with C1 symmetry, a virtual overlap of (1) complexes in two orientations was obtained, suggesting an erroneous Therefore, the diffraction pattern was reevaluated and indeed weak reflections that are potential superstructure reflections of the mC domain were identified [red circles in Fig. 2(a)]. Thus, the of the mC domain was reindexed as shown in Fig. 2(b). The resulting still was of the mC kind, but featured a doubled cell volume. It is thus shown that presumably negligible faint reflections can be crucial.
was possible for theOwing to software limitations (lack of support of concurrent integration with different Bravais lattices) both domains were integrated in the primitive reduced settings without restrictions on the cell parameters and with overlap information (HKLF5 style format) using SAINTPlus (Bruker, 2014). In such an integration, overlapping reflections are reduced to a single intensity datum associated with two hkl indices. The hkl indices were later retransformed into the proper monoclinic settings.
To achieve a smooth integration without an excess of discarded reflections, the integration parameters had to be optimized. Notably, the allowed common volume of nonoverlapping reflections had to be increased from the default 4% to 15%. A correction for absorption effects was then applied using the multiscan approach implemented in TWINABS (Bruker, 2014).
2.4. Structure solution and refinement
In a first step, the nonoverlapping reflections of both domains were separated and the overlapping reflections were discarded. The two independent data sets were used for structure solution using the dualspace approach implemented in SHELXT (Sheldrick, 2015). Both models were refined using Jana2006 (Petříček et al., 2014), resulting in satisfactory reliability factors. The correct space groups could thus unambiguously be identified as P2_{1}/c and I2/a. The reduced Icentered setting was used for a better comparability of both structures (shared layer vectors b and c). The models were then combined to a twophase model and the reflection data were replaced by the HKLF5 file with overlap information. The of both domains was refined to a P2_{1}/c:I2/a ratio of ∼1:4.
In the major I2/a domain, all nonH atoms were refined with anisotropic atomic displacement parameters (ADPs). In the minor P2_{1}/c domain, only the heavy atoms (Re, Cl, P) and the C atoms of the methyl groups were refined with anisotropic ADPs. In both domains, the molecules of (1) were disordered with respect to the CO and Cl ligands cis to N. The CO:Cl occupation ratio was refined independently for both phases to ∼4:3 (P2_{1}/c) and ∼3:2 (I2/a). The ADPs of the related positions were constrained to be identical. H atoms were placed at calculated positions and refined as riding on their parent C atoms.
3. Results and discussion
3.1. Molecular structure
Complex (1) adopts an octahedral coordination (Fig. 3), which is characteristic of this class of compounds (Vogt et al., 2013) and will not be expanded upon. Including the disordered Cl and CO ligands, the complex has twofold rotational pseudosymmetry [Fig. 3(b)] with the rotation axis passing through the pyridine ring, the Re atom and the CO ligand trans to N.
3.2. Polytypism
In both observed p_{x}12_{1}/c1 symmetry (Kopsky & Litvin, 2006), where the x subscript indicates a lack of translation in the [100] direction (Fig. 4). These layers will be designated as A_{n}, where n is a sequential number (A_{n} connects to , etc.). The rectangular layer is spanned by the basis . The layers are virtually equivalent in both (see §3.7). The arrangement of the molecules of (1) in an A_{n} layer is shown in Fig. 5.
the molecules of (1) are arranged in layers withBy definition, the P2_{1}/c domain, layers are related by translation with the vector = , which is perpendicular to . For the I2/a domain, on the other hand, adjacent layers are translationally related by = . The set of operations (modulo translations) relating adjacent layers are compiled in Table 3. The overall symmetries of both are schematized in Figs. 6(a) and 6(b).
differ in the stacking of the layers. In both domains adjacent layers are related by translations, though with different translation vectors. In the

The metric parameter s in the definition of calculates from the cell parameters as s = −0.247 ≃ −1/4. Here, the translations connecting adjacent layers are expressed based on the vector , which was arbitrarily chosen to be a basis vector of the P2_{1}/c polytype. could also have been chosen based on the I2/a polytype or as being perpendicular to the layer plane. The latter would complicate further reasoning, because it introduces two metric parameters, one per polytype. For a discussion on metric parameters in see Fichtner (1979).
As shown in Fig. 7, the two stacking possibilities lead to nonequivalent pairs of adjacent layers. Such are said to be of the nonorder–disorder (OD) type (Ferraris et al., 2008). Since every A_{n} layer can contact in two ways to the adjacent A_{n+1} layer, the (1) complexes can in principle be arranged to an infinity of different which all belong to the same nonOD polytype family. In the crystals of (1), two kinds of these connect via common layers. They can therefore be classified as nonOD allotwins.
3.3. The OD perspective
The OD theory (DornbergerSchiff & GrellNiemann, 1961) was developed to explain and describe the common occurrence of in all classes of materials. Modular structures in which adjacent layers contact in only one geometrically equivalent way are said to fulfill the vicinity condition (VC). If the VC allows for one speaks of OD polytypes. The OD theory makes a strong argument by stating that OD are locally equivalent. From the shortrange interaction of atoms follows the energetic equivalence of these OD Indeed, experience shows that most of the observed are of the OD kind.
As shown by (1), in some cases layers can also contact in nonequivalent ways. In our experience, this nonOD type of et al. (2015); Kader et al. (2017)] owing to the flexibility of the side chains in these molecular compounds. Nevertheless, the symmetry formalism developed by OD theory is general and can often also be fruitfully applied to nonOD polytypes.
is more common in organic and coordination compounds than in classical inorganics [see, for example, LumpiThe symmetry of ; Ehresmann, 1957; Ito & Sadanaga, 1976).
(and other modular structures) is described by partial operations (POs), which are the restrictions of motions to the subsets of Euclidean space occupied by the individual layers. Thus every PO is characterized by a motion, a source and a target layer. The composition of POs is only defined if the target of the first is the source of the second. It therefore does not form a group, but a (Brandt, 1927Inside each of the two (1) c glide planes of adjacent layers overlap in both cases, there is only one way to achieve these particular pairs of layers [for a discussion on stacking possibilities in OD structures see Ďurovič (1997)]. In terms of OD theory, both are fully ordered. In other words, they belong to OD families with only one member.
all pairs of layers are equivalent. Thus, they fulfill VC of OD structures. But, since theOD ; Fichtner, 1977). OD groupoids belonging to the same OD family are built according to the same symmetry principle but may differ in metrics (of layer lattices and translational components of operations relating adjacent layers) and concrete stacking arrangements. Since the linear parts of the POs relating adjacent layers are equivalent in both (Table 3), the groupoids of both belong to the same OD family.
families classify groupoids of OD in analogy to types for space groups (DornbergerSchiff & GrellNiemann, 1961In summary, both
of (1) belong to a nonOD family of Interpreted as OD structures, they belong to different singlemember OD families, which are associated with the same OD family.3.4. MDO polytypes
For any polytype family (OD or nonOD), there is a finite set of particularly simple i.e. into that are made up of only a selection of pairs, triples and generally ntuples). Experience shows that the vast majority of ordered are of the MDO kind. Since the in the family of (1) contain different pairs of layers, the MDO are those that are made up of only one kind of pairs. These are precisely the two observed of (1).
which are said to be of a maximum degree of order (MDO). MDO cannot be decomposed into simpler (3.5. Family structure
The
of a polytype family is the fictitious structure that is obtained if all stacking possibilities are realised to the same degree. Determination of the is often a crucial step in categorizing polytype families and the interpretation of diffraction patterns.The symmetry of the s (see §3.2). Here, we will assume s = −¼. The vector connecting the origins of both possible A_{n+1} layers for a given A_{n} layer is = = = . must be a translation vector of the Multiplication of into the translation of either polytype leads to a monoclinic Ccentered (mC) with the centered basis [Fig. 6(c)].
contains the symmetries of all as subgroups. It depends on the metric parameterIf this A_{n} layers (site symmetry 2/m). This structure is the since it contains the symmetry operations of all possible Its overall symmetry is C2/m [Fig. 6(c)].
is applied to either of the two the (1) complexes are an equal disorder of all four orientations observed in theIt has to be noted that the Re atoms in the A_{n} layer are located practically on the 2/m position of the Thus, the locations of the Re atoms are close to identical in all only the ligands can adopt one out of four orientations.
3.6. and stacking faults
Classical different orientations. In contrast, both observed of (1) possess the same oriented 2/m. The operation (Nespolo et al., 1999) is the identity, which is not a valid in classical twins.
is the oriented association of geometrically equivalent domains withMoreover, the 2/m of both observed is precisely the of the polytype family (the group generated by the linear parts of all POs). Thus, in any stacking arrangement following the rules described above, both can appear in only [2/m:2/m] = 1 orientation.
A stacking fault in one polytype can only lead to domains with the same orientation, but related by a nonlattice translation. These kinds of edifices are not twins but have been designated as antiphase domains (Wondratschek & Jeitschko, 1976). In contrast to twins, such domains are hard to show and even harder to evaluate in a quantitative manner. Here, the existence of such stacking faults inside the can only be presumed owing to the generally mediocre diffraction quality.
3.7. Desymmetrization
A characteristic phenomenon in ). The most notable expression of in OD structures is a lowering of the actual layer symmetry compared with the idealized layer symmetry. In fully ordered structures, on the other hand, the layers typically retain their full symmetry. Indeed, in both observed of (1), the actual A_{n} layers retain their p_{x}12_{1}/c1 symmetry from the idealized description.
is (Ďurovič, 1979Besides a reduction in symmetry, a deviation of the geometries of the layers across b parameter of the P2_{1}/c polytype is slightly smaller than that of the I2/a polytype [10.7392 (8) versus 10.7708 (8) Å]. The c parameter shows the opposite behavior [25.629 (2) versus 25.599 (3) Å], resulting in essentially identical fundamental surfaces of the layer lattices (275.23 versus 275.72 Å^{2}). The layers in the P2_{1}/c polytype are marginally thicker ( = 8.988 versus = 8.911 Å).
can also be regarded as Indeed, the determined metric parameters of the (1) differ slightly. TheA finer evaluation of and the deviations are compiled in Table 4. The is substantial (up to ∼0.5 Å), which is expected since the layers are located in different environments. Nevertheless, it is clearly within the range expected for The major contributing factor to the is a distinct shift of the complexes along the [010] direction. The variations of the occupancies of the disordered CO and Cl groups [72.6:27.4 (11) (∼4:3, P2_{1}/c) versus 65.3:34.7 (∼3:2, I2/a)] can likewise be regarded as an effect of desymmetrization.
was obtained by transforming the coordinates of both into a Cartesian coordinate system (retaining the origin) and calculating the distances of the corresponding atoms. Neither the position nor the orientation of the complexes were optimized. An overlay of both is shown in Fig. 8

3.8. The layer interface
As noted above, pairs of adjacent A_{n} layers are nonequivalent and therefore the of (1) are of the nonOD type. Nevertheless, one has to realise that the choice of OD layers is always a matter of interpretation. By choosing noncrystallochemical layers, one might very well turn a nonOD into an OD interpretation, where all are locally equivalent. Therefore it is necessary to scrutinize the layer contact for common features and pseudosymmetry.
In Fig. 9 the layer contacts in both cases of A_{n}A_{n+1} pairs are shown. Whereas at some points the contacts are similar (green ellipses), at others there are interatomic contacts not observed in the other pair (red ellipses). The can therefore be indeed considered of the nonOD type.
Abstracting from the orientations of the molecules, a common feature of both stacking arrangements is that the isopropyl groups protrude into voids in the adjacent layer. One can say that the iPr_{2} groups fit into the same void (Fig. 9). In this light, the interface possesses pseudosymmetry relating the P1 and P2 PiPr_{2} groups. Nevertheless, the deviation from idealized symmetry is too pronounced for the to be considered of the OD type. A direct consequence of this structural feature is the value of the metric parameter s ∼ −¼ and the nearly identical positions of the Re atoms in all polytypes.
is enabled by the fact that both the P1 and the P2 POwing to this arrangement, the CO and Cl ligands are located above either a CO or Cl ligand of the adjacent layer. In the P2_{1}/c polytype the major position CO ligand in one layer is located above the major position of another CO ligand. In the I2/a polytype, on the other hand, CO mostly contacts to Cl. Thus, the CO and Cl ligands may contact to the same or different types, enabling the observed CO/Cl disorder.
3.9. Diffraction pattern
In the following discussion, hkl indexes will be given with respect to the reciprocal (dual) basis of the basis . The (centered) bases of the P2_{1}/c and I2/a are and , respectively (for and s see §3.2). These correspond to the reciprocal lattices and . Supposing s = −¼ and neglecting the minor the reciprocal bases of both are related by = with
It has to be noted that the lattices of both I2/a polytype, reflections of both overlap perfectly only on rods k+l/2 = 2n, (Fig. 10a). These overlapping reflections are located on a Ccentered and correspond to the They are therefore called family reflections. It is easily shown that however long the repetition period or how disordered the stacking, intensity on rods k+l/2 = 2n, , stems only from the and all contribute equally (proportional to their volume fraction) to these reflections. Note that this is only the case here because adjacent layers are translationally equivalent. Since the Re position in all is virtually identical to the (§3.5), the family reflections are significantly stronger.
are related by a shear mapping and therefore does not represent a classical Owing to the centering of theThe reflections on the remaining rods () are called characteristic reflections, because they differ among distinct
The lack of diffuse scattering of these rods indicates that the domains are rather ordered in the crystal under investigation.4. Conclusion
Crystals of (1) are a further addition to the growing body of structurally characterized allotwins. Clearly, the phenomenon is general and deserves attention. As we have shown here, in principle these problems can be handled with the software packages that are available today. Nevertheless, the lack of seamless integration makes such data manipulations and refinements unnecessarily nonroutine. For example, data reduction in the case of the title crystal had to be performed in the triclinic
Besides being additional work, it is preferred to avoid the thus necessary cell transformations owing to imprecise estimation of standard uncertainties on cell parameters.Moreover, the files for the deposition of structural data have to be significantly manually edited. Great care is needed to avoid introduction of errors, which will not be caught by the usual automated checks. In particular, some of the statistical concepts seem to be illdefined. It is, for example, not immediately obvious what an independent observation is in the case of a pair of reflections that was determined as overlapping in one but nonoverlapping in a different scan.
We conclude that more work, from theoreticians as well as software vendors, is needed to bring the softwareassisted characterization of such crystals to the level it deserves.
Supporting information
https://doi.org//10.1107/S205252061701006X/ps5063sup1.cif
contains datablocks RePNP1, RePNP2. DOI:Structure factors: contains datablock I. DOI: https://doi.org//10.1107/S205252061701006X/ps5063RePNP1sup2.hkl
Structure factors: contains datablock I. DOI: https://doi.org//10.1107/S205252061701006X/ps5063RePNP2sup3.hkl
For both structures, data collection: Apex 3 (Bruker, 2016); cell
SAINTPlus (Bruker, 2016); data reduction: SAINTPlus (Bruker, 2016); program(s) used to solve structure: SHELXT (G. Sheldrick, 2015); program(s) used to refine structure: Jana 2006 (V. Petříček et al., 2014); molecular graphics: Mercury (C. F. Macrae et al., 2008).C_{21}H_{35}ClNO_{2}P_{2}Re  F(000) = 2448 
M_{r} = 617.1  D_{x} = 1.657 Mg m^{−}^{3} 
Monoclinic, P2_{1}/c  Mo Kα radiation, λ = 0.71075 Å 
Hall symbol: P 2ycb  Cell parameters from 39 reflections 
a = 9.6475 (7) Å  θ = 2.0–15.2° 
b = 10.7392 (8) Å  µ = 5.17 mm^{−}^{1} 
c = 25.629 (2) Å  T = 200 K 
β = 68.684 (3)°  Block, yellow 
V = 2473.7 (3) Å^{3}  0.45 × 0.35 × 0.25 mm 
Z = 4 
Bruker KAPPA APEX II CCD diffractometer  7417 reflections with I > 3σ(I) 
Radiation source: Xray tube  R_{int} = 0.039 
ω– and φ–scans  θ_{max} = 30.2°, θ_{min} = 1.7° 
Absorption correction: multiscan SADABS  h = −26→13 
T_{min} = 0.10, T_{max} = 0.27  k = −15→15 
33905 measured reflections  l = −33→36 
12472 independent reflections 
Refinement on F  310 constraints 
R[F^{2} > 2σ(F^{2})] = 0.048  Hatom parameters constrained 
wR(F^{2}) = 0.053  Weighting scheme based on measured s.u.'s w = 1/(σ^{2}(F) + 0.0001F^{2}) 
S = 1.71  (Δ/σ)_{max} = 0.028 
12472 reflections  Δρ_{max} = 3.48 e Å^{−}^{3} 
452 parameters  Δρ_{min} = −2.28 e Å^{−}^{3} 
0 restraints 
x  y  z  U_{iso}*/U_{eq}  Occ. (<1)  
Re1  −0.00319 (5)  0.22461 (6)  0.14034 (3)  0.02243 (19)  
Cl1  −0.1601 (6)  0.2362 (6)  0.0813 (2)  0.0307 (19)  0.726 (11) 
Cl1'  0.1562 (17)  0.1975 (15)  0.1950 (6)  0.0307 (19)  0.274 (11) 
P1  −0.1989 (3)  0.1497 (3)  0.22106 (13)  0.0282 (14)  
P2  0.1973 (3)  0.2235 (4)  0.05157 (12)  0.0291 (12)  
O1  0.1893 (14)  0.2044 (13)  0.2098 (5)  0.029 (4)*  0.726 (11) 
O2  −0.0400 (11)  0.4986 (10)  0.1662 (4)  0.063 (3)*  
O1'  −0.204 (4)  0.271 (4)  0.0738 (15)  0.029 (4)*  0.274 (11) 
N1  0.0105 (8)  0.0195 (11)  0.1226 (3)  0.021 (3)*  
C1  −0.0633 (13)  −0.0637 (12)  0.1631 (5)  0.027 (3)*  
C2  −0.0600 (14)  −0.1891 (13)  0.1517 (5)  0.038 (4)*  
C3  0.0276 (15)  −0.2350 (13)  0.0976 (6)  0.050 (4)*  
C4  0.0994 (13)  −0.1477 (11)  0.0575 (5)  0.038 (3)*  
C5  0.0915 (14)  −0.0222 (12)  0.0686 (5)  0.035 (4)*  
C6  −0.1368 (13)  −0.0140 (12)  0.2206 (5)  0.043 (4)*  
C7  0.1605 (11)  0.0748 (10)  0.0242 (4)  0.022 (3)*  
C8  −0.2075 (13)  0.2010 (11)  0.2911 (5)  0.031 (3)*  
C9  −0.3008 (16)  0.1141 (14)  0.3404 (5)  0.058 (7)  
C10  −0.2551 (18)  0.3338 (15)  0.3033 (6)  0.066 (9)  
C11  −0.3937 (15)  0.1394 (14)  0.2238 (6)  0.051 (4)*  
C12  −0.404 (2)  0.0448 (16)  0.1802 (8)  0.097 (12)  
C13  −0.446 (2)  0.2712 (18)  0.2128 (8)  0.080 (10)  
C14  0.3923 (15)  0.2077 (15)  0.0467 (6)  0.035 (3)*  
C15  0.4237 (16)  0.0896 (14)  0.0713 (6)  0.052 (7)  
C16  0.4397 (16)  0.3244 (15)  0.0687 (6)  0.060 (8)  
C17  0.1934 (16)  0.3307 (13)  −0.0036 (6)  0.049 (4)*  
C18  0.3119 (19)  0.3121 (16)  −0.0591 (6)  0.079 (8)  
C19  0.1900 (15)  0.4669 (14)  0.0133 (7)  0.077 (9)  
C20  0.1177 (19)  0.216 (2)  0.1817 (7)  0.011 (4)*  0.726 (11) 
C21  −0.0212 (15)  0.3842 (14)  0.1563 (6)  0.051 (4)*  
C20'  −0.129 (4)  0.264 (4)  0.0995 (17)  0.011 (4)*  0.274 (11) 
H1c2  −0.1171  −0.245948  0.180352  0.0452*  
H1c3  0.0361  −0.322519  0.089396  0.0595*  
H1c4  0.157457  −0.175661  0.020411  0.046*  
H1c6  −0.069612  −0.019443  0.240466  0.052*  
H2c6  −0.220652  −0.065312  0.240807  0.052*  
H1c7  0.097472  0.088347  0.003156  0.0266*  
H2c7  0.251289  0.04286  −0.002692  0.0266*  
H1c8  −0.106362  0.194517  0.288934  0.0372*  
H1c9  −0.273575  0.12923  0.372345  0.0702*  
H2c9  −0.404772  0.131213  0.349997  0.0702*  
H3c9  −0.281107  0.028704  0.329101  0.0702*  
H1c10  −0.191049  0.38612  0.274065  0.0789*  
H2c10  −0.355801  0.342705  0.30513  0.0789*  
H3c10  −0.248978  0.357792  0.338453  0.0789*  
H1c11  −0.457594  0.111295  0.260194  0.0611*  
H1c12  −0.34323  −0.026338  0.179804  0.1162*  
H2c12  −0.505342  0.018967  0.189767  0.1162*  
H3c12  −0.36925  0.082869  0.143815  0.1162*  
H1c13  −0.469047  0.321268  0.245934  0.0957*  
H2c13  −0.368026  0.310326  0.182456  0.0957*  
H3c13  −0.533004  0.26312  0.203258  0.0957*  
H1c14  0.453876  0.199941  0.007818  0.0417*  
H1c15  0.404164  0.01972  0.051575  0.0627*  
H2c15  0.52611  0.088265  0.067871  0.0627*  
H3c15  0.360947  0.084863  0.110089  0.0627*  
H1c16  0.446597  0.392143  0.043455  0.0717*  
H2c16  0.367633  0.344069  0.104944  0.0717*  
H3c16  0.534916  0.310948  0.071678  0.0717*  
H1c17  0.101397  0.3094  −0.007769  0.0585*  
H1c18  0.323302  0.224749  −0.067492  0.0949*  
H2c18  0.285512  0.354398  −0.087111  0.0949*  
H3c18  0.403961  0.345113  −0.058586  0.0949*  
H1c19  0.277549  0.485785  0.021249  0.0928*  
H2c19  0.186992  0.518749  −0.016781  0.0928*  
H3c19  0.103201  0.482017  0.046078  0.0928* 
U^{11}  U^{22}  U^{33}  U^{12}  U^{13}  U^{23}  
Re1  0.0195 (3)  0.0215 (3)  0.0251 (3)  0.0004 (3)  −0.00655 (16)  −0.0028 (3) 
Cl1  0.026 (3)  0.044 (4)  0.023 (2)  0.008 (2)  −0.0103 (19)  −0.001 (2) 
Cl1'  0.026 (3)  0.044 (4)  0.023 (2)  0.008 (2)  −0.0103 (19)  −0.001 (2) 
P1  0.0234 (19)  0.041 (3)  0.0181 (17)  −0.0024 (17)  −0.0045 (14)  −0.0022 (16) 
P2  0.0200 (16)  0.046 (2)  0.0185 (15)  0.0002 (18)  −0.0035 (12)  0.0002 (17) 
C9  0.052 (10)  0.090 (13)  0.030 (9)  0.004 (10)  −0.010 (7)  0.002 (8) 
C10  0.059 (12)  0.091 (14)  0.054 (12)  0.003 (11)  −0.030 (9)  −0.023 (10) 
C12  0.054 (14)  0.108 (18)  0.138 (19)  −0.029 (13)  −0.046 (14)  0.032 (15) 
C13  0.035 (11)  0.14 (2)  0.073 (13)  0.015 (12)  −0.027 (10)  −0.039 (12) 
C15  0.025 (9)  0.083 (13)  0.047 (10)  0.020 (9)  −0.011 (7)  −0.021 (9) 
C16  0.019 (8)  0.083 (14)  0.069 (12)  −0.020 (9)  −0.006 (8)  0.025 (10) 
C18  0.071 (13)  0.112 (15)  0.031 (9)  0.020 (13)  0.009 (9)  0.021 (10) 
C19  0.069 (13)  0.080 (14)  0.064 (13)  0.001 (11)  −0.002 (10)  0.030 (10) 
Re1—P1  2.378 (3)  C8—C10  1.50 (2) 
Re1—P2  2.391 (3)  C8—H1c8  0.96 
Re1—C20  1.84 (2)  C9—H1c9  0.96 
Re1—C21  1.756 (15)  C9—H2c9  0.96 
Re1—C20'  1.92 (5)  C9—H3c9  0.96 
Cl1—O1'  0.65 (4)  C10—H1c10  0.96 
Cl1—N1  3.243 (12)  C10—H2c10  0.96 
Cl1—C20'  0.70 (5)  C10—H3c10  0.96 
Cl1'—O1  0.58 (2)  C11—C12  1.54 (3) 
Cl1'—N1  3.31 (2)  C11—C13  1.56 (3) 
Cl1'—C20  0.62 (3)  C11—H1c11  0.96 
P1—C6  1.856 (13)  C12—H1c12  0.96 
P1—C8  1.850 (13)  C12—H2c12  0.96 
P1—C11  1.858 (16)  C12—H3c12  0.96 
P2—C7  1.831 (12)  C13—H1c13  0.96 
P2—C14  1.848 (15)  C13—H2c13  0.96 
P2—C17  1.833 (15)  C13—H3c13  0.96 
O1—C20  1.17 (3)  C14—C15  1.50 (2) 
O2—C21  1.254 (18)  C14—C16  1.51 (2) 
O1'—C20'  1.15 (7)  C14—H1c14  0.96 
N1—C1  1.358 (14)  C15—H1c15  0.96 
N1—C5  1.393 (14)  C15—H2c15  0.96 
C1—C2  1.376 (19)  C15—H3c15  0.96 
C1—C6  1.483 (17)  C16—H1c16  0.96 
C2—C3  1.425 (18)  C16—H2c16  0.96 
C2—H1c2  0.96  C16—H3c16  0.96 
C3—C4  1.376 (18)  C17—C18  1.479 (18) 
C3—H1c3  0.96  C17—C19  1.52 (2) 
C4—C5  1.373 (18)  C17—H1c17  0.96 
C4—H1c4  0.96  C18—H1c18  0.96 
C5—C7  1.507 (16)  C18—H2c18  0.96 
C6—H1c6  0.96  C18—H3c18  0.96 
C6—H2c6  0.96  C19—H1c19  0.96 
C7—H1c7  0.96  C19—H2c19  0.96 
C7—H2c7  0.96  C19—H3c19  0.96 
C8—C9  1.565 (17)  
P1—Re1—P2  159.74 (13)  C8—C9—H3c9  109.47 
P1—Re1—C20  87.2 (5)  H1c9—C9—H2c9  109.47 
P1—Re1—C21  98.5 (4)  H1c9—C9—H3c9  109.47 
P1—Re1—C20'  95.1 (11)  H2c9—C9—H3c9  109.47 
P2—Re1—C20  94.9 (4)  C8—C10—H1c10  109.47 
P2—Re1—C21  101.8 (4)  C8—C10—H2c10  109.47 
P2—Re1—C20'  86.3 (10)  C8—C10—H3c10  109.47 
C20—Re1—C21  86.7 (9)  H1c10—C10—H2c10  109.47 
C20—Re1—C20'  170.0 (16)  H1c10—C10—H3c10  109.47 
C21—Re1—C20'  83.4 (15)  H2c10—C10—H3c10  109.47 
O1'—Cl1—N1  168 (4)  P1—C11—C12  110.0 (10) 
O1'—Cl1—C20'  116 (5)  P1—C11—C13  109.1 (11) 
N1—Cl1—C20'  72 (4)  P1—C11—H1c11  109.84 
O1—Cl1'—N1  152 (2)  C12—C11—C13  110.9 (15) 
O1—Cl1'—C20  153 (4)  C12—C11—H1c11  108.06 
N1—Cl1'—C20  55 (3)  C13—C11—H1c11  108.94 
Re1—P1—C6  99.4 (4)  C11—C12—H1c12  109.47 
Re1—P1—C8  119.0 (4)  C11—C12—H2c12  109.47 
Re1—P1—C11  121.7 (5)  C11—C12—H3c12  109.47 
C6—P1—C8  100.9 (6)  H1c12—C12—H2c12  109.47 
C6—P1—C11  105.3 (6)  H1c12—C12—H3c12  109.47 
C8—P1—C11  107.0 (6)  H2c12—C12—H3c12  109.47 
Re1—P2—C7  99.5 (3)  C11—C13—H1c13  109.47 
Re1—P2—C14  121.1 (5)  C11—C13—H2c13  109.47 
Re1—P2—C17  119.6 (4)  C11—C13—H3c13  109.47 
C7—P2—C14  103.2 (6)  H1c13—C13—H2c13  109.47 
C7—P2—C17  101.0 (6)  H1c13—C13—H3c13  109.47 
C14—P2—C17  108.1 (7)  H2c13—C13—H3c13  109.47 
Cl1'—O1—C20  14 (2)  P2—C14—C15  114.0 (10) 
Cl1—O1'—C20'  34 (3)  P2—C14—C16  109.7 (10) 
Cl1—N1—Cl1'  97.9 (4)  P2—C14—H1c14  107.98 
Cl1—N1—C1  122.3 (7)  C15—C14—C16  114.3 (14) 
Cl1—N1—C5  94.2 (8)  C15—C14—H1c14  102.68 
Cl1'—N1—C1  99.4 (8)  C16—C14—H1c14  107.63 
Cl1'—N1—C5  122.9 (8)  C14—C15—H1c15  109.47 
C1—N1—C5  119.8 (11)  C14—C15—H2c15  109.47 
N1—C1—C2  121.0 (10)  C14—C15—H3c15  109.47 
N1—C1—C6  116.8 (11)  H1c15—C15—H2c15  109.47 
C2—C1—C6  122.0 (11)  H1c15—C15—H3c15  109.47 
C1—C2—C3  120.4 (11)  H2c15—C15—H3c15  109.47 
C1—C2—H1c2  119.81  C14—C16—H1c16  109.47 
C3—C2—H1c2  119.81  C14—C16—H2c16  109.47 
C2—C3—C4  116.7 (12)  C14—C16—H3c16  109.47 
C2—C3—H1c3  121.63  H1c16—C16—H2c16  109.47 
C4—C3—H1c3  121.63  H1c16—C16—H3c16  109.47 
C3—C4—C5  122.6 (11)  H2c16—C16—H3c16  109.47 
C3—C4—H1c4  118.7  P2—C17—C18  115.6 (11) 
C5—C4—H1c4  118.7  P2—C17—C19  112.9 (11) 
N1—C5—C4  119.3 (11)  P2—C17—H1c17  102.47 
N1—C5—C7  117.5 (11)  C18—C17—C19  109.4 (12) 
C4—C5—C7  123.1 (11)  C18—C17—H1c17  106.47 
P1—C6—C1  112.6 (9)  C19—C17—H1c17  109.56 
P1—C6—H1c6  109.47  C17—C18—H1c18  109.47 
P1—C6—H2c6  109.47  C17—C18—H2c18  109.47 
C1—C6—H1c6  109.47  C17—C18—H3c18  109.47 
C1—C6—H2c6  109.47  H1c18—C18—H2c18  109.47 
H1c6—C6—H2c6  106.18  H1c18—C18—H3c18  109.47 
P2—C7—C5  114.1 (9)  H2c18—C18—H3c18  109.47 
P2—C7—H1c7  109.47  C17—C19—H1c19  109.47 
P2—C7—H2c7  109.47  C17—C19—H2c19  109.47 
C5—C7—H1c7  109.47  C17—C19—H3c19  109.47 
C5—C7—H2c7  109.47  H1c19—C19—H2c19  109.47 
H1c7—C7—H2c7  104.4  H1c19—C19—H3c19  109.47 
P1—C8—C9  114.6 (9)  H2c19—C19—H3c19  109.47 
P1—C8—C10  112.9 (10)  Re1—C20—Cl1'  164 (3) 
P1—C8—H1c8  103.71  Re1—C20—O1  175.5 (17) 
C9—C8—C10  110.9 (10)  Cl1'—C20—O1  13.0 (19) 
C9—C8—H1c8  106.06  Re1—C21—O2  176.3 (15) 
C10—C8—H1c8  108.01  Re1—C20'—Cl1  141 (5) 
C8—C9—H1c9  109.47  Re1—C20'—O1'  171 (4) 
C8—C9—H2c9  109.47  Cl1—C20'—O1'  30 (3) 
C_{21}H_{35}ClNO_{2}P_{2}Re  F(000) = 2448 
M_{r} = 617.1  D_{x} = 1.668 Mg m^{−}^{3} 
Monoclinic, I2/a  Mo Kα radiation, λ = 0.71075 Å 
Hall symbol: I 2ya  Cell parameters from 39 reflections 
a = 18.6854 (13) Å  θ = 2.0–18.1° 
b = 10.7708 (8) Å  µ = 5.20 mm^{−}^{1} 
c = 25.599 (3) Å  T = 200 K 
β = 107.480 (4)°  Block, yellow 
V = 4914.1 (7) Å^{3}  0.45 × 0.35 × 0.25 mm 
Z = 8 
Bruker KAPPA APEX II CCD diffractometer  7417 reflections with I > 3σ(I) 
Radiation source: Xray tube  R_{int} = 0.039 
ω– and φ–scans  θ_{max} = 30.2°, θ_{min} = 1.7° 
Absorption correction: multiscan SADABS  h = −26→13 
T_{min} = 0.10, T_{max} = 0.27  k = −15→15 
33905 measured reflections  l = −33→36 
12472 independent reflections 
Refinement on F  310 constraints 
R[F^{2} > 2σ(F^{2})] = 0.048  Hatom parameters constrained 
wR(F^{2}) = 0.053  Weighting scheme based on measured s.u.'s w = 1/(σ^{2}(F) + 0.0001F^{2}) 
S = 1.71  (Δ/σ)_{max} = 0.028 
12472 reflections  Δρ_{max} = 2.22 e Å^{−}^{3} 
452 parameters  Δρ_{min} = −1.61 e Å^{−}^{3} 
0 restraints 
x  y  z  U_{iso}*/U_{eq}  Occ. (<1)  
Re1_2  −0.004119 (11)  0.24737 (3)  0.135038 (9)  0.02316 (7)  
Cl1_2  −0.08322 (15)  0.2437 (6)  0.03796 (12)  0.0336 (13)  0.653 (15) 
Cl1'_2  0.0762 (3)  0.2314 (8)  0.2309 (3)  0.029 (3)  0.347 (15) 
P1_2  −0.10247 (9)  0.17697 (17)  0.16889 (7)  0.0273 (6)  
P2_2  0.09694 (7)  0.24383 (18)  0.09564 (6)  0.0262 (4)  
O1_2  0.0960 (6)  0.2513 (11)  0.2545 (5)  0.044 (3)  0.653 (15) 
O2_2  −0.0268 (3)  0.5242 (5)  0.1481 (2)  0.069 (3)  
O1'_2  −0.1042 (11)  0.251 (3)  0.0184 (8)  0.044 (3)  0.347 (15) 
N1_2  0.0063 (2)  0.0468 (5)  0.12489 (17)  0.0224 (19)  
C1_2  −0.0300 (3)  −0.0366 (6)  0.1491 (2)  0.028 (2)  
C2_2  −0.0275 (4)  −0.1640 (7)  0.1405 (2)  0.040 (3)  
C3_2  0.0130 (4)  −0.2098 (6)  0.1094 (3)  0.039 (3)  
C4_2  0.0510 (3)  −0.1290 (6)  0.0849 (2)  0.034 (2)  
C5_2  0.0460 (3)  −0.0015 (6)  0.0926 (2)  0.028 (2)  
C6_2  −0.0698 (3)  0.0189 (5)  0.1867 (2)  0.034 (2)  
C7_2  0.0806 (3)  0.0900 (6)  0.0625 (2)  0.038 (3)  
C8_2  −0.1065 (3)  0.2341 (5)  0.2361 (2)  0.030 (2)  
C9_2  −0.1536 (4)  0.1532 (7)  0.2623 (3)  0.049 (3)  
C10_2  −0.1315 (4)  0.3695 (7)  0.2336 (3)  0.056 (3)  
C11_2  −0.2010 (3)  0.1609 (6)  0.1248 (2)  0.038 (3)  
C12_2  −0.2088 (4)  0.0621 (6)  0.0809 (3)  0.053 (3)  
C13_2  −0.2313 (4)  0.2863 (6)  0.0978 (3)  0.059 (3)  
C14_2  0.1961 (3)  0.2361 (6)  0.1363 (2)  0.033 (2)  
C15_2  0.2113 (4)  0.1264 (6)  0.1754 (2)  0.041 (3)  
C16_2  0.2212 (4)  0.3563 (7)  0.1683 (3)  0.060 (4)  
C17_2  0.0931 (3)  0.3451 (6)  0.0360 (3)  0.041 (3)  
C18_2  0.1536 (5)  0.3213 (8)  0.0098 (3)  0.082 (4)  
C19_2  0.0915 (5)  0.4837 (7)  0.0521 (3)  0.073 (4)  
C20_2  0.0551 (7)  0.2501 (16)  0.2062 (5)  0.032 (3)  0.653 (15) 
C21_2  −0.0180 (4)  0.4187 (8)  0.1424 (3)  0.043 (3)  
C20'_2  −0.0644 (11)  0.256 (3)  0.0633 (11)  0.032 (3)  0.347 (15) 
H1c2_2  −0.054814  −0.219512  0.156832  0.0477*  
H1c3_2  0.015605  −0.297733  0.104212  0.0465*  
H1c4_2  0.08036  −0.160482  0.062814  0.0412*  
H1c6_2  −0.037243  0.016896  0.223673  0.0408*  
H2c6_2  −0.111503  −0.032844  0.187012  0.0408*  
H1c7_2  0.048623  0.098811  0.025497  0.0451*  
H2c7_2  0.127121  0.057383  0.059765  0.0451*  
H1c8_2  −0.055795  0.228527  0.259525  0.0355*  
H1c9_2  −0.129294  0.074437  0.272382  0.0585*  
H2c9_2  −0.158686  0.193822  0.29437  0.0585*  
H3c9_2  −0.202381  0.140448  0.236618  0.0585*  
H1c10_2  −0.118868  0.411065  0.204384  0.067*  
H2c10_2  −0.184801  0.373099  0.227184  0.067*  
H3c10_2  −0.106558  0.409627  0.267717  0.067*  
H1c11_2  −0.230263  0.135251  0.147993  0.0451*  
H1c12_2  −0.201972  −0.01861  0.097629  0.0634*  
H2c12_2  −0.257805  0.067166  0.054781  0.0634*  
H3c12_2  −0.171432  0.075327  0.062658  0.0634*  
H1c13_2  −0.240316  0.340892  0.124821  0.0708*  
H2c13_2  −0.195111  0.323138  0.082733  0.0708*  
H3c13_2  −0.277393  0.272781  0.069125  0.0708*  
H1c14_2  0.224492  0.225041  0.111071  0.0392*  
H1c15_2  0.189321  0.052816  0.155984  0.0497*  
H2c15_2  0.2645  0.114864  0.190609  0.0497*  
H3c15_2  0.189794  0.142055  0.204465  0.0497*  
H1c16_2  0.224778  0.421134  0.143448  0.0716*  
H2c16_2  0.185384  0.379363  0.186668  0.0716*  
H3c16_2  0.269407  0.343904  0.194813  0.0716*  
H1c17_2  0.047321  0.324137  0.008274  0.0494*  
H1c18_2  0.158223  0.233513  0.005167  0.0987*  
H2c18_2  0.14087  0.361401  −0.025263  0.0987*  
H3c18_2  0.200298  0.353612  0.032795  0.0987*  
H1c19_2  0.066381  0.491639  0.079563  0.0876*  
H2c19_2  0.141921  0.514151  0.066215  0.0876*  
H3c19_2  0.065151  0.53114  0.020359  0.0876* 
U^{11}  U^{22}  U^{33}  U^{12}  U^{13}  U^{23}  
Re1_2  0.01986 (11)  0.02218 (13)  0.02893 (11)  0.0011 (2)  0.00960 (8)  0.0002 (2) 
Cl1_2  0.0228 (17)  0.0518 (18)  0.024 (2)  −0.002 (2)  0.0042 (14)  0.009 (3) 
Cl1'_2  0.021 (4)  0.033 (6)  0.035 (6)  0.005 (3)  0.012 (4)  −0.006 (3) 
P1_2  0.0216 (8)  0.0324 (10)  0.0305 (8)  −0.0013 (8)  0.0116 (7)  0.0021 (8) 
P2_2  0.0219 (6)  0.0323 (8)  0.0260 (6)  −0.0037 (11)  0.0096 (5)  0.0016 (11) 
O1_2  0.030 (4)  0.071 (6)  0.029 (4)  −0.010 (5)  0.005 (3)  −0.024 (6) 
O2_2  0.090 (5)  0.027 (4)  0.109 (5)  0.015 (3)  0.060 (4)  0.005 (4) 
O1'_2  0.030 (4)  0.071 (6)  0.029 (4)  −0.010 (5)  0.005 (3)  −0.024 (6) 
N1_2  0.032 (3)  0.014 (3)  0.022 (3)  −0.002 (2)  0.009 (2)  0.0017 (18) 
C1_2  0.037 (4)  0.016 (4)  0.032 (3)  0.009 (3)  0.013 (3)  0.003 (3) 
C2_2  0.054 (4)  0.036 (5)  0.034 (4)  −0.005 (4)  0.019 (3)  0.002 (3) 
C3_2  0.066 (5)  0.009 (3)  0.041 (4)  0.006 (3)  0.016 (4)  −0.004 (3) 
C4_2  0.043 (4)  0.029 (4)  0.033 (3)  0.005 (3)  0.014 (3)  −0.001 (3) 
C5_2  0.027 (3)  0.035 (4)  0.024 (3)  0.000 (3)  0.009 (3)  −0.001 (3) 
C6_2  0.046 (4)  0.031 (4)  0.036 (4)  0.003 (3)  0.029 (3)  0.008 (3) 
C7_2  0.036 (4)  0.057 (5)  0.022 (3)  −0.002 (4)  0.012 (3)  0.000 (3) 
C8_2  0.034 (3)  0.027 (4)  0.036 (3)  −0.009 (3)  0.023 (3)  −0.009 (3) 
C9_2  0.049 (5)  0.066 (6)  0.039 (4)  −0.012 (4)  0.026 (4)  −0.001 (4) 
C10_2  0.051 (5)  0.064 (6)  0.068 (6)  −0.007 (4)  0.041 (4)  −0.021 (4) 
C11_2  0.024 (3)  0.046 (5)  0.043 (4)  −0.008 (3)  0.010 (3)  0.001 (4) 
C12_2  0.045 (5)  0.067 (5)  0.045 (4)  −0.023 (5)  0.011 (4)  −0.002 (4) 
C13_2  0.031 (4)  0.079 (7)  0.065 (5)  0.017 (4)  0.012 (4)  −0.001 (4) 
C14_2  0.020 (3)  0.043 (5)  0.035 (3)  −0.002 (4)  0.007 (2)  −0.001 (4) 
C15_2  0.033 (4)  0.061 (5)  0.028 (4)  0.017 (4)  0.007 (3)  0.003 (4) 
C16_2  0.046 (5)  0.060 (6)  0.064 (6)  −0.012 (5)  0.001 (5)  0.007 (5) 
C17_2  0.025 (3)  0.048 (5)  0.054 (5)  0.005 (3)  0.018 (3)  0.027 (4) 
C18_2  0.058 (6)  0.129 (8)  0.078 (6)  0.004 (7)  0.048 (5)  0.054 (7) 
C19_2  0.070 (7)  0.054 (6)  0.084 (7)  −0.010 (5)  0.007 (5)  0.038 (5) 
C20_2  0.022 (5)  0.045 (6)  0.025 (5)  0.011 (8)  0.000 (4)  0.005 (9) 
C21_2  0.029 (4)  0.061 (6)  0.047 (5)  −0.002 (4)  0.021 (3)  −0.003 (4) 
C20'_2  0.022 (5)  0.045 (6)  0.025 (5)  0.011 (8)  0.000 (4)  0.005 (9) 
Re1_2—P1_2  2.3790 (19)  C8_2—C9_2  1.529 (10) 
Re1_2—P2_2  2.3935 (16)  C8_2—C10_2  1.527 (9) 
Re1_2—N1_2  2.191 (5)  C8_2—H1c8_2  0.96 
Re1_2—C20_2  1.825 (12)  C9_2—H1c9_2  0.96 
Re1_2—C21_2  1.881 (8)  C9_2—H2c9_2  0.96 
Re1_2—C20'_2  1.85 (2)  C9_2—H3c9_2  0.96 
Cl1_2—O1'_2  0.541 (17)  C10_2—H1c10_2  0.96 
Cl1_2—N1_2  3.164 (6)  C10_2—H2c10_2  0.96 
Cl1_2—C20'_2  0.65 (2)  C10_2—H3c10_2  0.96 
Cl1'_2—O1_2  0.642 (12)  C11_2—C12_2  1.523 (9) 
Cl1'_2—N1_2  3.301 (9)  C11_2—C13_2  1.545 (9) 
Cl1'_2—C20_2  0.670 (14)  C11_2—H1c11_2  0.96 
P1_2—C6_2  1.820 (6)  C12_2—H1c12_2  0.96 
P1_2—C8_2  1.849 (6)  C12_2—H2c12_2  0.96 
P1_2—C11_2  1.857 (5)  C12_2—H3c12_2  0.96 
P2_2—C7_2  1.845 (6)  C13_2—H1c13_2  0.96 
P2_2—C14_2  1.834 (5)  C13_2—H2c13_2  0.96 
P2_2—C17_2  1.861 (7)  C13_2—H3c13_2  0.96 
O1_2—C20_2  1.244 (15)  C14_2—C15_2  1.519 (9) 
O2_2—C21_2  1.163 (10)  C14_2—C16_2  1.528 (9) 
O1'_2—C20'_2  1.17 (3)  C14_2—H1c14_2  0.96 
N1_2—C1_2  1.379 (8)  C15_2—H1c15_2  0.96 
N1_2—C5_2  1.369 (8)  C15_2—H2c15_2  0.96 
C1_2—C2_2  1.393 (9)  C15_2—H3c15_2  0.96 
C1_2—C6_2  1.506 (10)  C16_2—H1c16_2  0.96 
C2_2—C3_2  1.346 (11)  C16_2—H2c16_2  0.96 
C2_2—H1c2_2  0.96  C16_2—H3c16_2  0.96 
C3_2—C4_2  1.386 (10)  C17_2—C18_2  1.497 (12) 
C3_2—H1c3_2  0.96  C17_2—C19_2  1.551 (10) 
C4_2—C5_2  1.394 (9)  C17_2—H1c17_2  0.96 
C4_2—H1c4_2  0.96  C18_2—H1c18_2  0.96 
C5_2—C7_2  1.511 (9)  C18_2—H2c18_2  0.96 
C6_2—H1c6_2  0.96  C18_2—H3c18_2  0.96 
C6_2—H2c6_2  0.96  C19_2—H1c19_2  0.96 
C7_2—H1c7_2  0.96  C19_2—H2c19_2  0.96 
C7_2—H2c7_2  0.96  C19_2—H3c19_2  0.96 
P1_2—Re1_2—P2_2  160.38 (7)  C9_2—C8_2—H1c8_2  106.25 
P1_2—Re1_2—N1_2  80.49 (14)  C10_2—C8_2—H1c8_2  108.49 
P1_2—Re1_2—C20_2  86.8 (5)  C8_2—C9_2—H1c9_2  109.47 
P1_2—Re1_2—C21_2  97.5 (2)  C8_2—C9_2—H2c9_2  109.47 
P1_2—Re1_2—C20'_2  94.1 (8)  C8_2—C9_2—H3c9_2  109.47 
P2_2—Re1_2—N1_2  79.92 (14)  H1c9_2—C9_2—H2c9_2  109.47 
P2_2—Re1_2—C20_2  95.9 (5)  H1c9_2—C9_2—H3c9_2  109.47 
P2_2—Re1_2—C21_2  102.0 (2)  H2c9_2—C9_2—H3c9_2  109.47 
P2_2—Re1_2—C20'_2  84.5 (8)  C8_2—C10_2—H1c10_2  109.47 
N1_2—Re1_2—C20_2  94.9 (6)  C8_2—C10_2—H2c10_2  109.47 
N1_2—Re1_2—C21_2  177.3 (2)  C8_2—C10_2—H3c10_2  109.47 
N1_2—Re1_2—C20'_2  89.0 (10)  H1c10_2—C10_2—H2c10_2  109.47 
C20_2—Re1_2—C21_2  86.8 (6)  H1c10_2—C10_2—H3c10_2  109.47 
C20_2—Re1_2—C20'_2  176.1 (11)  H2c10_2—C10_2—H3c10_2  109.47 
C21_2—Re1_2—C20'_2  89.3 (10)  P1_2—C11_2—C12_2  111.8 (5) 
O1'_2—Cl1_2—N1_2  146 (3)  P1_2—C11_2—C13_2  110.7 (4) 
O1'_2—Cl1_2—C20'_2  156 (4)  P1_2—C11_2—H1c11_2  107.19 
N1_2—Cl1_2—C20'_2  55 (3)  C12_2—C11_2—C13_2  109.9 (5) 
O1_2—Cl1'_2—N1_2  161.2 (13)  C12_2—C11_2—H1c11_2  108.04 
O1_2—Cl1'_2—C20_2  143 (2)  C13_2—C11_2—H1c11_2  109.15 
N1_2—Cl1'_2—C20_2  55.1 (16)  C11_2—C12_2—H1c12_2  109.47 
Re1_2—P1_2—C6_2  98.7 (2)  C11_2—C12_2—H2c12_2  109.47 
Re1_2—P1_2—C8_2  119.0 (2)  C11_2—C12_2—H3c12_2  109.47 
Re1_2—P1_2—C11_2  122.8 (2)  H1c12_2—C12_2—H2c12_2  109.47 
C6_2—P1_2—C8_2  100.5 (3)  H1c12_2—C12_2—H3c12_2  109.47 
C6_2—P1_2—C11_2  105.2 (3)  H2c12_2—C12_2—H3c12_2  109.47 
C8_2—P1_2—C11_2  106.6 (3)  C11_2—C13_2—H1c13_2  109.47 
Re1_2—P2_2—C7_2  99.5 (2)  C11_2—C13_2—H2c13_2  109.47 
Re1_2—P2_2—C14_2  123.4 (2)  C11_2—C13_2—H3c13_2  109.47 
Re1_2—P2_2—C17_2  119.7 (2)  H1c13_2—C13_2—H2c13_2  109.47 
C7_2—P2_2—C14_2  102.7 (3)  H1c13_2—C13_2—H3c13_2  109.47 
C7_2—P2_2—C17_2  100.9 (3)  H2c13_2—C13_2—H3c13_2  109.47 
C14_2—P2_2—C17_2  106.0 (3)  P2_2—C14_2—C15_2  111.6 (4) 
Cl1'_2—O1_2—C20_2  18.9 (12)  P2_2—C14_2—C16_2  111.2 (5) 
Cl1_2—O1'_2—C20'_2  13 (2)  P2_2—C14_2—H1c14_2  106.96 
Re1_2—N1_2—Cl1_2  51.36 (13)  C15_2—C14_2—C16_2  109.9 (5) 
Re1_2—N1_2—Cl1'_2  48.40 (16)  C15_2—C14_2—H1c14_2  108.38 
Re1_2—N1_2—C1_2  121.1 (4)  C16_2—C14_2—H1c14_2  108.76 
Re1_2—N1_2—C5_2  122.0 (4)  C14_2—C15_2—H1c15_2  109.47 
Cl1_2—N1_2—Cl1'_2  99.8 (2)  C14_2—C15_2—H2c15_2  109.47 
Cl1_2—N1_2—C1_2  121.7 (3)  C14_2—C15_2—H3c15_2  109.47 
Cl1_2—N1_2—C5_2  95.6 (3)  H1c15_2—C15_2—H2c15_2  109.47 
Cl1'_2—N1_2—C1_2  98.6 (4)  H1c15_2—C15_2—H3c15_2  109.47 
Cl1'_2—N1_2—C5_2  125.0 (3)  H2c15_2—C15_2—H3c15_2  109.47 
C1_2—N1_2—C5_2  116.9 (5)  C14_2—C16_2—H1c16_2  109.47 
N1_2—C1_2—C2_2  121.8 (6)  C14_2—C16_2—H2c16_2  109.47 
N1_2—C1_2—C6_2  115.6 (5)  C14_2—C16_2—H3c16_2  109.47 
C2_2—C1_2—C6_2  122.6 (6)  H1c16_2—C16_2—H2c16_2  109.47 
C1_2—C2_2—C3_2  120.4 (7)  H1c16_2—C16_2—H3c16_2  109.47 
C1_2—C2_2—H1c2_2  119.82  H2c16_2—C16_2—H3c16_2  109.47 
C3_2—C2_2—H1c2_2  119.82  P2_2—C17_2—C18_2  114.7 (5) 
C2_2—C3_2—C4_2  119.6 (6)  P2_2—C17_2—C19_2  110.2 (5) 
C2_2—C3_2—H1c3_2  120.22  P2_2—C17_2—H1c17_2  105.88 
C4_2—C3_2—H1c3_2  120.22  C18_2—C17_2—C19_2  111.2 (6) 
C3_2—C4_2—C5_2  119.3 (6)  C18_2—C17_2—H1c17_2  104.74 
C3_2—C4_2—H1c4_2  120.37  C19_2—C17_2—H1c17_2  109.79 
C5_2—C4_2—H1c4_2  120.37  C17_2—C18_2—H1c18_2  109.47 
N1_2—C5_2—C4_2  122.1 (6)  C17_2—C18_2—H2c18_2  109.47 
N1_2—C5_2—C7_2  116.9 (5)  C17_2—C18_2—H3c18_2  109.47 
C4_2—C5_2—C7_2  120.9 (6)  H1c18_2—C18_2—H2c18_2  109.47 
P1_2—C6_2—C1_2  113.9 (4)  H1c18_2—C18_2—H3c18_2  109.47 
P1_2—C6_2—H1c6_2  109.47  H2c18_2—C18_2—H3c18_2  109.47 
P1_2—C6_2—H2c6_2  109.47  C17_2—C19_2—H1c19_2  109.47 
C1_2—C6_2—H1c6_2  109.47  C17_2—C19_2—H2c19_2  109.47 
C1_2—C6_2—H2c6_2  109.47  C17_2—C19_2—H3c19_2  109.47 
H1c6_2—C6_2—H2c6_2  104.7  H1c19_2—C19_2—H2c19_2  109.47 
P2_2—C7_2—C5_2  112.9 (5)  H1c19_2—C19_2—H3c19_2  109.47 
P2_2—C7_2—H1c7_2  109.47  H2c19_2—C19_2—H3c19_2  109.47 
P2_2—C7_2—H2c7_2  109.47  Re1_2—C20_2—Cl1'_2  162 (2) 
C5_2—C7_2—H1c7_2  109.47  Re1_2—C20_2—O1_2  179.3 (13) 
C5_2—C7_2—H2c7_2  109.47  Cl1'_2—C20_2—O1_2  18.1 (11) 
H1c7_2—C7_2—H2c7_2  105.86  Re1_2—C21_2—O2_2  178.4 (7) 
P1_2—C8_2—C9_2  114.1 (4)  Re1_2—C20'_2—Cl1_2  164 (4) 
P1_2—C8_2—C10_2  112.1 (4)  Re1_2—C20'_2—O1'_2  174 (3) 
P1_2—C8_2—H1c8_2  104.62  Cl1_2—C20'_2—O1'_2  10.9 (18) 
C9_2—C8_2—C10_2  110.7 (6) 
D—H···A  D—H  H···A  D···A  D—H···A 
C3_2—H1c3_2···O2_2^{i}  0.96  2.47  3.193 (9)  131.84 
C4_2—H1c4_2···O1′_2^{ii}  0.96  2.46  3.36 (2)  156.88 
Symmetry codes: (i) x, y−1, z; (ii) −x, −y, −z. 
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