Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615007949/yp3092sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615007949/yp3092Isup2.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615007949/yp3092Isup3.cml |
CCDC reference: 1060938
Dichalcogenidoimidodiphosphinates, [(EPR2)2N]– (E = O, S, Se, Te; R = alkyl, aryl), are versatile ligands that can coordinate to elements from the main group (Silvestru & Drake, 2001), d-block (Ly and Woollins, 1998) and f-block (Glover et al., 2007). These species can be viewed as flexible inorganic analogues to planar β-diketonate ligands, and many derivatives are known owing to the varying identities possible for the chalcogen and organic substituents on phosphorus. In keeping with this versatility, these ligands have demonstrated a wealth of different coordination modes and solid-state structures in combination with metals.
We have been exploring the chemistry of the rarer tellurium-containing ligands since reporting a route to the synthesis of their sodium salts (Briand et al., 2002). In addition to studying their coordination chemistry (Chivers et al., 2010), the one-electron chemical oxidation of these anions with iodine was pursued in the context of forming ditelluride dimers. The isopropyl-substituted ligand forms a symmetric dimer, (I), with an unusually long Te—Te distance (Chivers et al., 2005), while the tert-butyl analogue forms an asymmetric dimer, (II) (Ritch et al., 2007), resembling a contact ion pair between a cation and anion (Fig. 1). In this work, an unexpected product, obtained by the oxidation of the phenyl-substituted ligand [(TePPh2)2N]-, is reported as bis(P,P,P',P'-tetraphenylditelluridoimidodiphosphinato-κ2Te,Te')tellurium(II), (III).
To a solution of Na(tmeda)[(TePPh2)2N] (tmeda is tetramethylethylenediamine; 285 mg, 0.366 mmol) in tetrahydrofuran (THF) at 195 K was added a solution of one-half molar equivalent of I2 (45 mg, 0.177 mmol) in THF at 195 K. The resulting mixture was stirred cold for 30 min and then warmed to room temperature for an additional 30 min. The volatiles were removed under vacuum and the residual material was then extracted with toluene and filtered through a 0.45 µm pore size PTFE filter disk. Removal of the volatiles afforded a red solid (60 mg), which was shown to be a complicated mixture of phosphorus-containing compounds (ten resonances in the 31P NMR spectrum). A few X-ray quality red block-like crystals of Te[(TePPh2)2N]2, (III), were obtained from a THF solution layered with n-hexane and stored at 278 K. All solvents were dried (THF and toluene with sodium/benzophenone, andn-hexane with sodium), distilled and stored over 4 Å molecular sieves prior to use, and all manipulations were conducted under argon using a glove-box or Schlenk line.
Crystal data, data collection and structure refinement details are summarized in Table 1. Three of the four phenyl rings in the asymmetric unit exhibit positional disorder and were modelled as isotropic mixtures over two positions. The occupancy factors for the disordered atoms were determined by free variable refinement, and yielded values of ca 0.5. FLAT restraints were applied to four half-occupancy isotropic rings. [Please avoid program specific commands and describe the restraint instead] H atoms were placed in calculated positions, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C), and treated with a riding-model approximation.
The complex mixture obtained in the oxidation of the phenyl-substituted ditelluridoimidodiphosphinate anion is in contrast to the alkyl-substituted derivatives (R = iPr, t-Bu), for which the corresponding reactions with iodine were quite clean (Chivers et al., 2005; Ritch et al., 2007). The red crystals obtained from this mixture possess a molecular spirocyclic square-planar TeII(Te)4 motif (Fig. 2), of which only a few examples are known.
Some extended structures exhibit square-planar Te5 units, such as the anions in the previously-reported salt [NMe4]2[As2Te5], which contains alternating Te56- and As24+ groups in one-dimensional chains (Warren et al., 1994). A spirocyclic Te82- anion is seen in the structure of [K(18-crown-5)2]2[Te8] (Schreiner et al., 1993). More recently, the Te5 unit was oberved in [Na(tmeda)]2[{(t-Bu)N(Te)P[µ-N(t-Bu)]2P(Te)N(t-Bu)}2-µ4-Te], (IV) (tmeda is tetramethylethylenediamine) (Nordheider et al., 2015), which can be described as a Te2+ cation bound by two Te,Te'-chelating dianionic ligands. In this structure, the Te—Te distances range from 3.014 (2) to 3.027 (2) Å an, while the Te5 unit is planar, the cis-Te—Te—Te bond angles range from 74.47 (4) to 105.61 (5)°.
The title compound, (III), features slightly shorter bond lengths, with Te1—Te3 and Te2—Te3 distances of 2.9806 (6) and 2.9978 (9) Å, respectively, which are still significantly longer than the distances observed in organic ditellurides [e.g. 2.712 (2) Å in Ph2Te2; Llabres et al., 1972]. The geometry is also much closer to ideal square planar; the two unique cis-Te—Te—Te bond angles are 93.51 (3) and 86.49 (3)°. Compared to the dianionic ligands in (IV), which feature rigid P2N2 rings, the [(TePPh2)2N]- ligands in (III) are considerably more flexible, as seen from the Te—P—N—P torsion angles [-9.3 (5) and 67.9 (4)°]. This flexibility may be the reason the geometry of the Te(Te)4 core is closer to ideal square planar than that in (IV).
The bonding parameters of the [(TePPh2)2N]- ligands are indicative of delocalization of π-electron density within the TePNPTe fragment. The P—Te distances of 2.4278 (16) and 2.4331 (15) Å are equal within experimental error, and are significantly longer than a formal double P═Te bond, e.g. the distance of 2.3798 (8) Å in the monotelluridoimidodiphosphinate, TePiPr2NP(H)iPr2 (Chivers et al., 2005). The P—N interatomic distances of 1.593 (5) and 1.594 (5) Å are shorter the formally single P—N bonds observed in the diselenoimidodiphosphinate (SePPh2)2NH [1.678 (4) and 1.686 (3) Å; Bhattacharyya et al., 1995], and the P—N—P bond angle is 134.1 (3)°. Together, these data suggest partial multiple bond character throughout the ligand backbone, which is consistent with other structures containing [(EPR2)2N]- anions (E = O, S, Se, Te; R = alkyl, aryl).
Square-planar Te(E)4 (E = S, Se) complexes involving dichalcogenidoimidodiphosphinates have been observed previously [e.g. TeS4 (Bjørnvåg et al., 1982; Birdsall et al., 2000; Necas et al., 2001), TeSe4 (Novosad et al., 1998; Birdsall et al., 2000), TeS2Se2 (Sekar & Ibers, 2003)], however, compound (III) is the first example of a TeII(Te)4 imidodiphosphinate complex. Similar to the previously reported complexes, the two ligands in (III) are in an anti conformation with respect to each other.
Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO (Nonius, 2001); data reduction: DENZO (Nonius, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
C48H40N2P4Te5 | F(000) = 1324 |
Mr = 1406.70 | Dx = 1.945 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.021 (2) Å | Cell parameters from 41094 reflections |
b = 14.950 (3) Å | θ = 2.7–25.0° |
c = 15.893 (3) Å | µ = 3.17 mm−1 |
β = 113.47 (3)° | T = 173 K |
V = 2402.2 (10) Å3 | Block, red |
Z = 2 | 0.02 × 0.02 × 0.02 mm |
Nonius KappaCCD diffractometer | 3159 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.7° |
Absorption correction: integration (SCALEPACK; Otwinowski & Minor, 1997) | h = −13→13 |
Tmin = 0.939, Tmax = 0.939 | k = −17→17 |
8246 measured reflections | l = −18→18 |
4216 independent reflections |
Refinement on F2 | 12 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0334P)2 + 3.8459P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.002 |
4216 reflections | Δρmax = 0.60 e Å−3 |
253 parameters | Δρmin = −0.71 e Å−3 |
C48H40N2P4Te5 | V = 2402.2 (10) Å3 |
Mr = 1406.70 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.021 (2) Å | µ = 3.17 mm−1 |
b = 14.950 (3) Å | T = 173 K |
c = 15.893 (3) Å | 0.02 × 0.02 × 0.02 mm |
β = 113.47 (3)° |
Nonius KappaCCD diffractometer | 4216 independent reflections |
Absorption correction: integration (SCALEPACK; Otwinowski & Minor, 1997) | 3159 reflections with I > 2σ(I) |
Tmin = 0.939, Tmax = 0.939 | Rint = 0.033 |
8246 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 12 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.60 e Å−3 |
4216 reflections | Δρmin = −0.71 e Å−3 |
253 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Te1 | 1.04321 (4) | 0.36828 (3) | 0.15000 (3) | 0.04004 (13) | |
Te2 | 1.26616 (4) | 0.58511 (3) | 0.09597 (3) | 0.04165 (13) | |
Te3 | 1.0000 | 0.5000 | 0.0000 | 0.03290 (14) | |
P1 | 1.05091 (14) | 0.48895 (9) | 0.25423 (10) | 0.0310 (3) | |
P2 | 1.29607 (13) | 0.56634 (9) | 0.25510 (9) | 0.0302 (3) | |
N1 | 1.1666 (4) | 0.5605 (3) | 0.2763 (3) | 0.0344 (11) | |
C1 | 1.0619 (5) | 0.4377 (4) | 0.3609 (4) | 0.0324 (13) | |
C2 | 1.1378 (6) | 0.4791 (4) | 0.4437 (4) | 0.0431 (15) | |
H2 | 1.1827 | 0.5334 | 0.4439 | 0.052* | |
C3 | 1.1476 (7) | 0.4415 (5) | 0.5252 (5) | 0.0582 (19) | |
H3 | 1.2020 | 0.4691 | 0.5814 | 0.070* | |
C4 | 1.0799 (8) | 0.3644 (5) | 0.5263 (5) | 0.062 (2) | |
H4 | 1.0859 | 0.3397 | 0.5829 | 0.074* | |
C5 | 1.0031 (8) | 0.3234 (4) | 0.4444 (5) | 0.060 (2) | |
H5 | 0.9566 | 0.2699 | 0.4447 | 0.072* | |
C6 | 0.9936 (7) | 0.3599 (4) | 0.3621 (5) | 0.0515 (17) | |
H6 | 0.9401 | 0.3316 | 0.3060 | 0.062* | |
C7 | 0.898 (2) | 0.5566 (13) | 0.2135 (9) | 0.028 (7)* | 0.507 (13) |
C8 | 0.9012 (13) | 0.6397 (8) | 0.1819 (8) | 0.036 (3)* | 0.507 (13) |
H8 | 0.9815 | 0.6634 | 0.1823 | 0.044* | 0.507 (13) |
C9 | 0.7878 (12) | 0.6901 (9) | 0.1490 (8) | 0.042 (3)* | 0.507 (13) |
H9 | 0.7900 | 0.7486 | 0.1263 | 0.050* | 0.507 (13) |
C10 | 0.6738 (18) | 0.6578 (12) | 0.1483 (9) | 0.050 (5)* | 0.507 (13) |
H10 | 0.5960 | 0.6934 | 0.1259 | 0.059* | 0.507 (13) |
C11 | 0.6700 (13) | 0.5693 (9) | 0.1816 (9) | 0.047 (4)* | 0.507 (13) |
H11 | 0.5898 | 0.5457 | 0.1813 | 0.056* | 0.507 (13) |
C12 | 0.7852 (11) | 0.5183 (8) | 0.2144 (8) | 0.039 (3)* | 0.507 (13) |
H12 | 0.7858 | 0.4592 | 0.2366 | 0.046* | 0.507 (13) |
C7A | 0.897 (2) | 0.5446 (15) | 0.2063 (10) | 0.026 (7)* | 0.493 (13) |
C8A | 0.8894 (14) | 0.6383 (9) | 0.2152 (9) | 0.044 (4)* | 0.493 (13) |
H8A | 0.9684 | 0.6718 | 0.2447 | 0.052* | 0.493 (13) |
C9A | 0.7678 (15) | 0.6824 (10) | 0.1812 (9) | 0.050 (4)* | 0.493 (13) |
H9A | 0.7643 | 0.7454 | 0.1872 | 0.060* | 0.493 (13) |
C10A | 0.6512 (16) | 0.6335 (11) | 0.1383 (9) | 0.037 (4)* | 0.493 (13) |
H10A | 0.5681 | 0.6631 | 0.1165 | 0.044* | 0.493 (13) |
C11A | 0.6563 (12) | 0.5465 (8) | 0.1282 (8) | 0.040 (3)* | 0.493 (13) |
H11A | 0.5770 | 0.5138 | 0.0972 | 0.048* | 0.493 (13) |
C12A | 0.7759 (11) | 0.5025 (8) | 0.1621 (8) | 0.035 (3)* | 0.493 (13) |
H12A | 0.7754 | 0.4394 | 0.1549 | 0.042* | 0.493 (13) |
C13 | 1.3903 (19) | 0.6627 (12) | 0.3096 (12) | 0.025 (6)* | 0.47 (4) |
C14 | 1.5141 (16) | 0.6797 (11) | 0.3150 (16) | 0.043 (5)* | 0.47 (4) |
H14 | 1.5523 | 0.6401 | 0.2857 | 0.051* | 0.47 (4) |
C15 | 1.5863 (16) | 0.7525 (10) | 0.3617 (15) | 0.042 (5)* | 0.47 (4) |
H15 | 1.6723 | 0.7626 | 0.3632 | 0.051* | 0.47 (4) |
C16 | 1.5365 (19) | 0.8087 (11) | 0.4047 (10) | 0.033 (5)* | 0.47 (4) |
H16 | 1.5892 | 0.8571 | 0.4386 | 0.040* | 0.47 (4) |
C17 | 1.412 (2) | 0.7985 (10) | 0.4014 (10) | 0.035 (4)* | 0.47 (4) |
H17 | 1.3763 | 0.8393 | 0.4314 | 0.042* | 0.47 (4) |
C18 | 1.336 (2) | 0.7235 (16) | 0.3506 (15) | 0.042 (7)* | 0.47 (4) |
H18 | 1.2477 | 0.7155 | 0.3452 | 0.050* | 0.47 (4) |
C13A | 1.3736 (17) | 0.6690 (12) | 0.3191 (12) | 0.027 (5)* | 0.53 (4) |
C14A | 1.5115 (14) | 0.6797 (10) | 0.3414 (13) | 0.038 (4)* | 0.53 (4) |
H14A | 1.5595 | 0.6363 | 0.3234 | 0.046* | 0.53 (4) |
C15A | 1.5741 (15) | 0.7563 (10) | 0.3906 (13) | 0.042 (4)* | 0.53 (4) |
H15A | 1.6660 | 0.7654 | 0.4072 | 0.051* | 0.53 (4) |
C16A | 1.499 (2) | 0.8196 (10) | 0.4153 (10) | 0.037 (4)* | 0.53 (4) |
H16A | 1.5396 | 0.8723 | 0.4475 | 0.045* | 0.53 (4) |
C17A | 1.365 (2) | 0.8045 (9) | 0.3923 (9) | 0.038 (4)* | 0.53 (4) |
H17A | 1.3135 | 0.8470 | 0.4085 | 0.046* | 0.53 (4) |
C18A | 1.308 (2) | 0.7299 (11) | 0.3472 (12) | 0.031 (5)* | 0.53 (4) |
H18A | 1.2173 | 0.7194 | 0.3344 | 0.037* | 0.53 (4) |
C19 | 1.4013 (15) | 0.4821 (11) | 0.3088 (12) | 0.028 (6)* | 0.478 (19) |
C20 | 1.4711 (12) | 0.4284 (8) | 0.2699 (8) | 0.026 (3)* | 0.478 (19) |
H20 | 1.4557 | 0.4380 | 0.2073 | 0.031* | 0.478 (19) |
C21 | 1.5617 (14) | 0.3617 (9) | 0.3181 (9) | 0.037 (4)* | 0.478 (19) |
H21 | 1.6077 | 0.3277 | 0.2897 | 0.044* | 0.478 (19) |
C22 | 1.5817 (15) | 0.3474 (10) | 0.4103 (11) | 0.037 (5)* | 0.478 (19) |
H22 | 1.6396 | 0.3009 | 0.4440 | 0.044* | 0.478 (19) |
C23 | 1.5227 (14) | 0.3964 (11) | 0.4504 (13) | 0.054 (4)* | 0.478 (19) |
H23 | 1.5422 | 0.3870 | 0.5136 | 0.065* | 0.478 (19) |
C24 | 1.4321 (12) | 0.4618 (10) | 0.4031 (10) | 0.038 (4)* | 0.478 (19) |
H24 | 1.3887 | 0.4943 | 0.4344 | 0.046* | 0.478 (19) |
C19A | 1.4201 (15) | 0.4712 (9) | 0.3069 (10) | 0.026 (5)* | 0.522 (19) |
C20A | 1.5171 (14) | 0.4543 (9) | 0.2756 (8) | 0.042 (3)* | 0.522 (19) |
H20A | 1.5204 | 0.4853 | 0.2244 | 0.051* | 0.522 (19) |
C21A | 1.6107 (15) | 0.3895 (9) | 0.3224 (8) | 0.046 (4)* | 0.522 (19) |
H21A | 1.6786 | 0.3754 | 0.3020 | 0.055* | 0.522 (19) |
C22A | 1.6070 (15) | 0.3472 (9) | 0.3946 (9) | 0.036 (4)* | 0.522 (19) |
H22A | 1.6743 | 0.3052 | 0.4263 | 0.044* | 0.522 (19) |
C23A | 1.5020 (14) | 0.3639 (10) | 0.4264 (10) | 0.046 (4)* | 0.522 (19) |
H23A | 1.4973 | 0.3316 | 0.4765 | 0.055* | 0.522 (19) |
C24A | 1.4088 (13) | 0.4290 (9) | 0.3805 (9) | 0.041 (3)* | 0.522 (19) |
H24A | 1.3396 | 0.4439 | 0.3994 | 0.049* | 0.522 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Te1 | 0.0506 (3) | 0.0344 (2) | 0.0348 (2) | 0.00087 (18) | 0.01672 (19) | −0.00028 (17) |
Te2 | 0.0320 (2) | 0.0580 (3) | 0.0303 (2) | −0.00880 (18) | 0.00750 (17) | 0.00862 (18) |
Te3 | 0.0310 (3) | 0.0380 (3) | 0.0280 (3) | 0.0006 (2) | 0.0099 (2) | −0.0024 (2) |
P1 | 0.0284 (8) | 0.0322 (8) | 0.0328 (8) | −0.0008 (6) | 0.0126 (6) | 0.0018 (6) |
P2 | 0.0248 (7) | 0.0330 (8) | 0.0279 (7) | −0.0034 (6) | 0.0053 (6) | 0.0040 (6) |
N1 | 0.030 (2) | 0.036 (3) | 0.037 (3) | −0.005 (2) | 0.013 (2) | −0.001 (2) |
C1 | 0.028 (3) | 0.035 (3) | 0.033 (3) | 0.004 (2) | 0.012 (2) | 0.007 (3) |
C2 | 0.038 (3) | 0.058 (4) | 0.034 (3) | 0.004 (3) | 0.015 (3) | 0.004 (3) |
C3 | 0.055 (4) | 0.082 (5) | 0.036 (4) | 0.013 (4) | 0.017 (3) | 0.011 (4) |
C4 | 0.077 (5) | 0.069 (5) | 0.052 (5) | 0.027 (4) | 0.038 (4) | 0.025 (4) |
C5 | 0.094 (6) | 0.037 (4) | 0.070 (5) | 0.005 (4) | 0.054 (5) | 0.018 (4) |
C6 | 0.065 (4) | 0.038 (4) | 0.054 (4) | −0.005 (3) | 0.026 (4) | 0.004 (3) |
Te1—Te3 | 2.9806 (6) | C11A—C12A | 1.376 (16) |
Te1—P1 | 2.4278 (16) | C12A—H12A | 0.9500 |
Te2—Te3 | 2.9978 (9) | C13—C14 | 1.36 (2) |
Te2—P2 | 2.4331 (15) | C13—C18 | 1.39 (3) |
Te3—Te1i | 2.9806 (6) | C14—H14 | 0.9500 |
Te3—Te2i | 2.9979 (9) | C14—C15 | 1.38 (2) |
P1—N1 | 1.593 (5) | C15—H15 | 0.9500 |
P1—C1 | 1.820 (6) | C15—C16 | 1.33 (2) |
P1—C7 | 1.85 (2) | C16—H16 | 0.9500 |
P1—C7A | 1.77 (2) | C16—C17 | 1.36 (2) |
P2—N1 | 1.594 (5) | C17—H17 | 0.9500 |
P2—C13 | 1.786 (18) | C17—C18 | 1.44 (3) |
P2—C13A | 1.851 (17) | C18—H18 | 0.9500 |
P2—C19 | 1.695 (19) | C13A—C14A | 1.43 (2) |
P2—C19A | 1.917 (17) | C13A—C18A | 1.34 (3) |
C1—C2 | 1.392 (8) | C14A—H14A | 0.9500 |
C1—C6 | 1.390 (8) | C14A—C15A | 1.40 (2) |
C2—H2 | 0.9500 | C15A—H15A | 0.9500 |
C2—C3 | 1.376 (9) | C15A—C16A | 1.41 (2) |
C3—H3 | 0.9500 | C16A—H16A | 0.9500 |
C3—C4 | 1.377 (10) | C16A—C17A | 1.39 (2) |
C4—H4 | 0.9500 | C17A—H17A | 0.9500 |
C4—C5 | 1.382 (10) | C17A—C18A | 1.34 (2) |
C5—H5 | 0.9500 | C18A—H18A | 0.9500 |
C5—C6 | 1.383 (9) | C19—C20 | 1.41 (2) |
C6—H6 | 0.9500 | C19—C24 | 1.43 (2) |
C7—C8 | 1.35 (2) | C20—H20 | 0.9500 |
C7—C12 | 1.38 (2) | C20—C21 | 1.402 (16) |
C8—H8 | 0.9500 | C21—H21 | 0.9500 |
C8—C9 | 1.372 (17) | C21—C22 | 1.41 (2) |
C9—H9 | 0.9500 | C22—H22 | 0.9500 |
C9—C10 | 1.34 (2) | C22—C23 | 1.30 (2) |
C10—H10 | 0.9500 | C23—H23 | 0.9500 |
C10—C11 | 1.43 (2) | C23—C24 | 1.39 (2) |
C11—H11 | 0.9500 | C24—H24 | 0.9500 |
C11—C12 | 1.393 (17) | C19A—C20A | 1.37 (2) |
C12—H12 | 0.9500 | C19A—C24A | 1.38 (2) |
C7A—C8A | 1.41 (3) | C20A—H20A | 0.9500 |
C7A—C12A | 1.39 (2) | C20A—C21A | 1.394 (17) |
C8A—H8A | 0.9500 | C21A—H21A | 0.9500 |
C8A—C9A | 1.40 (2) | C21A—C22A | 1.33 (2) |
C9A—H9A | 0.9500 | C22A—H22A | 0.9500 |
C9A—C10A | 1.40 (2) | C22A—C23A | 1.46 (2) |
C10A—H10A | 0.9500 | C23A—H23A | 0.9500 |
C10A—C11A | 1.31 (2) | C23A—C24A | 1.392 (18) |
C11A—H11A | 0.9500 | C24A—H24A | 0.9500 |
P1—Te1—Te3 | 90.34 (4) | C10A—C11A—C12A | 120.4 (13) |
P2—Te2—Te3 | 100.37 (4) | C12A—C11A—H11A | 119.8 |
Te1—Te3—Te1i | 180.0 | C7A—C12A—H12A | 118.0 |
Te1—Te3—Te2 | 93.51 (3) | C11A—C12A—C7A | 124.0 (13) |
Te1—Te3—Te2i | 86.49 (3) | C11A—C12A—H12A | 118.0 |
Te1i—Te3—Te2 | 86.49 (3) | C14—C13—P2 | 123.9 (14) |
Te1i—Te3—Te2i | 93.51 (3) | C14—C13—C18 | 117.3 (17) |
Te2—Te3—Te2i | 180.0 | C18—C13—P2 | 118.7 (15) |
N1—P1—Te1 | 117.19 (18) | C13—C14—H14 | 118.9 |
N1—P1—C1 | 109.1 (3) | C13—C14—C15 | 122.3 (17) |
N1—P1—C7 | 104.3 (6) | C15—C14—H14 | 118.9 |
N1—P1—C7A | 109.0 (7) | C14—C15—H15 | 119.8 |
C1—P1—Te1 | 107.11 (19) | C16—C15—C14 | 120.4 (15) |
C1—P1—C7 | 105.7 (5) | C16—C15—H15 | 119.8 |
C7—P1—Te1 | 112.9 (4) | C15—C16—H16 | 119.2 |
C7A—P1—Te1 | 106.8 (6) | C15—C16—C17 | 121.7 (15) |
C7A—P1—C1 | 107.3 (5) | C17—C16—H16 | 119.2 |
N1—P2—Te2 | 117.66 (18) | C16—C17—H17 | 121.3 |
N1—P2—C13 | 109.8 (7) | C16—C17—C18 | 117.4 (16) |
N1—P2—C13A | 100.7 (7) | C18—C17—H17 | 121.3 |
N1—P2—C19 | 110.1 (6) | C13—C18—C17 | 120.8 (18) |
N1—P2—C19A | 114.4 (5) | C13—C18—H18 | 119.6 |
C13—P2—Te2 | 102.9 (6) | C17—C18—H18 | 119.6 |
C13A—P2—Te2 | 108.5 (5) | C14A—C13A—P2 | 116.3 (13) |
C13A—P2—C19A | 106.6 (6) | C18A—C13A—P2 | 123.5 (13) |
C19—P2—Te2 | 113.1 (7) | C18A—C13A—C14A | 120.2 (17) |
C19—P2—C13 | 101.9 (7) | C13A—C14A—H14A | 121.0 |
C19A—P2—Te2 | 108.1 (5) | C15A—C14A—C13A | 118.0 (14) |
P1—N1—P2 | 134.1 (3) | C15A—C14A—H14A | 121.0 |
C2—C1—P1 | 119.0 (4) | C14A—C15A—H15A | 120.4 |
C6—C1—P1 | 122.0 (5) | C14A—C15A—C16A | 119.3 (13) |
C6—C1—C2 | 118.9 (5) | C16A—C15A—H15A | 120.4 |
C1—C2—H2 | 120.0 | C15A—C16A—H16A | 120.1 |
C3—C2—C1 | 120.0 (6) | C17A—C16A—C15A | 119.9 (13) |
C3—C2—H2 | 120.0 | C17A—C16A—H16A | 120.1 |
C2—C3—H3 | 119.5 | C16A—C17A—H17A | 120.2 |
C2—C3—C4 | 120.9 (7) | C18A—C17A—C16A | 119.6 (15) |
C4—C3—H3 | 119.5 | C18A—C17A—H17A | 120.2 |
C3—C4—H4 | 120.3 | C13A—C18A—H18A | 118.5 |
C3—C4—C5 | 119.5 (6) | C17A—C18A—C13A | 123.0 (17) |
C5—C4—H4 | 120.3 | C17A—C18A—H18A | 118.5 |
C4—C5—H5 | 119.9 | C20—C19—P2 | 125.7 (13) |
C4—C5—C6 | 120.1 (7) | C20—C19—C24 | 113.2 (15) |
C6—C5—H5 | 119.9 | C24—C19—P2 | 121.0 (14) |
C1—C6—H6 | 119.8 | C19—C20—H20 | 118.1 |
C5—C6—C1 | 120.5 (6) | C21—C20—C19 | 123.9 (12) |
C5—C6—H6 | 119.8 | C21—C20—H20 | 118.1 |
C8—C7—P1 | 118.9 (15) | C20—C21—H21 | 121.3 |
C8—C7—C12 | 123.1 (18) | C20—C21—C22 | 117.4 (12) |
C12—C7—P1 | 118.1 (13) | C22—C21—H21 | 121.3 |
C7—C8—H8 | 120.2 | C21—C22—H22 | 119.3 |
C7—C8—C9 | 119.7 (15) | C23—C22—C21 | 121.4 (15) |
C9—C8—H8 | 120.2 | C23—C22—H22 | 119.3 |
C8—C9—H9 | 119.5 | C22—C23—H23 | 119.2 |
C10—C9—C8 | 120.9 (14) | C22—C23—C24 | 121.6 (16) |
C10—C9—H9 | 119.5 | C24—C23—H23 | 119.2 |
C9—C10—H10 | 120.2 | C19—C24—H24 | 118.8 |
C9—C10—C11 | 119.6 (15) | C23—C24—C19 | 122.5 (15) |
C11—C10—H10 | 120.2 | C23—C24—H24 | 118.8 |
C10—C11—H11 | 120.4 | C20A—C19A—P2 | 120.4 (12) |
C12—C11—C10 | 119.3 (13) | C20A—C19A—C24A | 124.9 (15) |
C12—C11—H11 | 120.4 | C24A—C19A—P2 | 114.5 (12) |
C7—C12—C11 | 117.5 (13) | C19A—C20A—H20A | 121.6 |
C7—C12—H12 | 121.3 | C19A—C20A—C21A | 116.9 (13) |
C11—C12—H12 | 121.3 | C21A—C20A—H20A | 121.6 |
C8A—C7A—P1 | 120.6 (15) | C20A—C21A—H21A | 119.3 |
C12A—C7A—P1 | 124.7 (15) | C22A—C21A—C20A | 121.5 (14) |
C12A—C7A—C8A | 114.6 (17) | C22A—C21A—H21A | 119.3 |
C7A—C8A—H8A | 119.5 | C21A—C22A—H22A | 119.3 |
C9A—C8A—C7A | 121.1 (15) | C21A—C22A—C23A | 121.5 (13) |
C9A—C8A—H8A | 119.5 | C23A—C22A—H22A | 119.3 |
C8A—C9A—H9A | 120.1 | C22A—C23A—H23A | 121.3 |
C8A—C9A—C10A | 119.8 (13) | C24A—C23A—C22A | 117.3 (12) |
C10A—C9A—H9A | 120.1 | C24A—C23A—H23A | 121.3 |
C9A—C10A—H10A | 120.0 | C19A—C24A—C23A | 117.9 (13) |
C11A—C10A—C9A | 120.1 (14) | C19A—C24A—H24A | 121.1 |
C11A—C10A—H10A | 120.0 | C23A—C24A—H24A | 121.1 |
C10A—C11A—H11A | 119.8 | ||
Te1—P1—N1—P2 | −9.3 (5) | C7—P1—C1—C2 | −95.2 (7) |
Te1—P1—C1—C2 | 144.2 (4) | C7—P1—C1—C6 | 82.8 (8) |
Te1—P1—C1—C6 | −37.9 (5) | C7—C8—C9—C10 | 0.4 (6) |
Te1—P1—C7—C8 | −107.5 (7) | C8—C7—C12—C11 | −0.7 (11) |
Te1—P1—C7—C12 | 70.5 (8) | C8—C9—C10—C11 | −0.6 (11) |
Te1—P1—C7A—C8A | −144.4 (7) | C9—C10—C11—C12 | 0.2 (14) |
Te1—P1—C7A—C12A | 38.9 (10) | C10—C11—C12—C7 | 0.4 (13) |
Te2—P2—N1—P1 | 67.9 (4) | C12—C7—C8—C9 | 0.3 (6) |
Te2—P2—C13—C14 | −63.3 (17) | C7A—P1—N1—P2 | −130.7 (6) |
Te2—P2—C13—C18 | 118.0 (15) | C7A—P1—C1—C2 | −101.4 (9) |
Te2—P2—C13A—C14A | −76.0 (12) | C7A—P1—C1—C6 | 76.5 (9) |
Te2—P2—C13A—C18A | 106.4 (15) | C7A—C8A—C9A—C10A | 0.5 (5) |
Te2—P2—C19—C20 | 2.3 (9) | C8A—C7A—C12A—C11A | 0.5 (11) |
Te2—P2—C19—C24 | 179.3 (7) | C8A—C9A—C10A—C11A | −1.5 (11) |
P1—C1—C2—C3 | −179.9 (5) | C9A—C10A—C11A—C12A | 2.0 (14) |
P1—C1—C6—C5 | −179.2 (5) | C10A—C11A—C12A—C7A | −1.6 (14) |
P1—C7—C8—C9 | 178.2 (8) | C12A—C7A—C8A—C9A | 0.0 (5) |
P1—C7—C12—C11 | −178.6 (8) | C13—P2—N1—P1 | −175.0 (7) |
P1—C7A—C8A—C9A | −177.1 (9) | C13—P2—C19—C20 | −107.4 (11) |
P1—C7A—C12A—C11A | 177.4 (9) | C13—P2—C19—C24 | 69.6 (11) |
P2—C13—C14—C15 | −176.6 (13) | C13—C14—C15—C16 | 1 (3) |
P2—C13—C18—C17 | 175.2 (14) | C14—C13—C18—C17 | −4 (3) |
P2—C13A—C14A—C15A | −179.4 (11) | C14—C15—C16—C17 | −3 (2) |
P2—C13A—C18A—C17A | −179.0 (13) | C15—C16—C17—C18 | 1 (2) |
P2—C19—C20—C21 | 177.1 (9) | C16—C17—C18—C13 | 2 (3) |
P2—C19—C24—C23 | −176.7 (9) | C18—C13—C14—C15 | 2 (3) |
P2—C19A—C20A—C21A | 174.3 (7) | C13A—P2—N1—P1 | −174.5 (6) |
P2—C19A—C24A—C23A | −175.1 (8) | C13A—C14A—C15A—C16A | −1 (2) |
N1—P1—C1—C2 | 16.4 (5) | C14A—C13A—C18A—C17A | 4 (2) |
N1—P1—C1—C6 | −165.6 (5) | C14A—C15A—C16A—C17A | 1 (2) |
N1—P1—C7—C8 | 20.8 (7) | C15A—C16A—C17A—C18A | 0 (2) |
N1—P1—C7—C12 | −161.2 (7) | C16A—C17A—C18A—C13A | −3 (2) |
N1—P1—C7A—C8A | −16.9 (8) | C18A—C13A—C14A—C15A | −2 (2) |
N1—P1—C7A—C12A | 166.4 (8) | C19—P2—N1—P1 | −63.6 (7) |
N1—P2—C13—C14 | 170.6 (15) | C19—P2—C13—C14 | 54.0 (18) |
N1—P2—C13—C18 | −8.0 (17) | C19—P2—C13—C18 | −124.7 (16) |
N1—P2—C13A—C14A | 159.8 (11) | C19—C20—C21—C22 | 1.0 (5) |
N1—P2—C13A—C18A | −17.7 (15) | C20—C19—C24—C23 | 0.7 (11) |
N1—P2—C19—C20 | 136.2 (8) | C20—C21—C22—C23 | −2.7 (12) |
N1—P2—C19—C24 | −46.8 (9) | C21—C22—C23—C24 | 3.5 (16) |
C1—P1—N1—P2 | 112.5 (4) | C22—C23—C24—C19 | −2.4 (15) |
C1—P1—C7—C8 | 135.7 (6) | C24—C19—C20—C21 | −0.1 (5) |
C1—P1—C7—C12 | −46.3 (8) | C19A—P2—N1—P1 | −60.7 (6) |
C1—P1—C7A—C8A | 101.1 (8) | C19A—P2—C13A—C14A | 40.1 (14) |
C1—P1—C7A—C12A | −75.7 (10) | C19A—P2—C13A—C18A | −137.4 (14) |
C1—C2—C3—C4 | −2.1 (10) | C19A—C20A—C21A—C22A | −1.0 (5) |
C2—C1—C6—C5 | −1.3 (9) | C20A—C19A—C24A—C23A | −0.5 (11) |
C2—C3—C4—C5 | 1.3 (11) | C20A—C21A—C22A—C23A | 2.5 (11) |
C3—C4—C5—C6 | −0.5 (11) | C21A—C22A—C23A—C24A | −2.9 (13) |
C4—C5—C6—C1 | 0.5 (11) | C22A—C23A—C24A—C19A | 1.8 (12) |
C6—C1—C2—C3 | 2.1 (9) | C24A—C19A—C20A—C21A | 0.0 (5) |
C7—P1—N1—P2 | −134.9 (5) |
Symmetry code: (i) −x+2, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C48H40N2P4Te5 |
Mr | 1406.70 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 11.021 (2), 14.950 (3), 15.893 (3) |
β (°) | 113.47 (3) |
V (Å3) | 2402.2 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.17 |
Crystal size (mm) | 0.02 × 0.02 × 0.02 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Integration (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.939, 0.939 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8246, 4216, 3159 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.083, 1.08 |
No. of reflections | 4216 |
No. of parameters | 253 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.71 |
Computer programs: COLLECT (Nonius, 2001), DENZO (Nonius, 2001), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).