N,N′,N′′,N′′′-Tetrakis(2-methylphenyl)­oxybis(phospho­nic diamide): a redetermination at 150 K with Mo Kα radiation

Mehrdad Pourayoubi; Zdeňka Padělková; Mahnaz Rostami Chaijan; Aleš Růžička

doi:10.1107/S1600536811002091

. 2011 Jan 22;67(Pt 2):o450–o451. doi: 10.1107/S1600536811002091

N,N′,N′′,N′′′-Tetrakis(2-methylphenyl)oxybis(phosphonic diamide): a redetermination at 150 K with Mo Kα radiation

Mehrdad Pourayoubi ^a,^*, Zdeňka Padělková ^b, Mahnaz Rostami Chaijan ^a, Aleš Růžička ^b

PMCID: PMC3051449 PMID: 21523113

Abstract

The structure of the title compound, C₂₈H₃₂N₄O₃P₂, has been redetermined at 150 K, with much improved precision. The structure and molecular packing of the title compound was previously determined using Cu Kα radiation, with an R value of 0.0933 [Cameron et al. (1978 ▶). Z. Naturforsch. Teil B, 33, 728–730]. The c-axis length in this structure [13.8401 (8) Å] is almost half that reported in the original study. In the title compound, two (C₆H₄(2-CH₃)NH)₂P(O) units are bridged via an O atom [P—O—P = 133.31 (11)°]. The P atoms adopt a slightly distorted tetrahedral coordination geometry. In the crystal, molecules are linked via N—H⋯OP hydrogen bonds into extended chains parallel to the c axis. An intramolecular N—H⋯O=P hydrogen bond is also found in the molecule.

Related literature

For the previous determination of this structure, see: Cameron et al. (1978 ▶). For bond lengths and angles in related structures, see: Pourayoubi et al. (2010 ▶); Sabbaghi et al. (2010 ▶).

Experimental

Crystal data

C₂₈H₃₂N₄O₃P₂
M _r = 534.52
Monoclinic,
a = 14.2621 (6) Å
b = 15.7029 (11) Å
c = 13.8401 (8) Å
β = 118.915 (4)°
V = 2713.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 150 K
0.45 × 0.33 × 0.21 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer
Absorption correction: Gaussian integration (Coppens & Hamilton, 1970 ▶) T _min = 0.942, T _max = 0.969
19090 measured reflections
6133 independent reflections
4719 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.121
S = 1.18
6133 reflections
334 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶) and DENZO (Otwinowski & Minor, 1997 ▶); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002091/sj5092sup1.cif

e-67-0o450-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002091/sj5092Isup2.hkl

e-67-0o450-Isup2.hkl^{(300.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N111—H111⋯O3ⁱ	0.86	2.16	2.926 (2)	149
N112—H112⋯O3	0.86	2.16	2.906 (2)	144
N113—H113⋯O2ⁱⁱ	0.86	1.97	2.814 (2)	167

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors wish to thank the Ministry of Education of the Czech Republic for the Research University Grant (project No. VZ0021627501). Partial support of this work by Ferdowsi University of Mashhad is gratefully acknowledged.

supplementary crystallographic information

Comment

The structure and molecular packing of µ-oxo-bis(phosphenyl-o-toluidide) was previously reported at ambient temperature by Cameron et al. (1978) using 2595 independent reflections significantly above the background with Cu Kα radiation; R = 0.0933. The unit-cell length c and density were respectively reported as 25.26 (3) Å and 1.255 g cm^-3.

Here, we report on the low temperature X-ray determination of the title compound (Fig. 1) at 150 K using Mo Kα radiation, with some improved precision. The unit-cell length c (of 13.8401 (8) Å) and density (of 1.309 g cm^-3) in this structure are very different from the previously reported values.

In the title compound, two (C₆H₄(2-CH₃)NH)₂P(O) moieties are bridged via an oxygen atom (P1—O1—P2 angle = 133.31 (11)°); the P1—O1 and P2—O1 bond lengths of 1.6014 (16) and 1.6017 (16) Å are standard for the P—O—P moiety (Pourayoubi et al., 2010). The P atoms adopt a slightly distorted tetrahedral environment. The bond angles around the P atoms are in the range of 101.05 (9)° to 116.62 (11)° for P1 and 100.12 (10)° to 117.97 (11)° for P2.

The P1—O2 and P2—O3 bond lengths (1.4681 (17) and 1.4736 (17) Å) and the P—N bond lengths (1.630 (2), 1.6376 (19), 1.612 (2) and 1.634 (2) Å) are standard for this type of compound; for example in [4-H₃C—C₆H₄O]P(O)[NHC₆H₄-2-CH₃]₂ (Sabbaghi et al., 2010), P═O = 1.4692 (12) Å and P—N = 1.6268 (15) and 1.6279 (15) Å).

An intramolecular N–H···OP hydrogen bond (N···O = 2.906 (2) Å) is found between the oxygen atom of the P2 phosphoryl group and the N–H hydrogen atom of one of the amide moieties linked to the P1 atom. In the crystal structure, molecules are linked via N–H···OP hydrogen bonds (Fig. 2) into extended chains parallel to the c axis (N···O = 2.814 (2) & 2.926 (2) Å).

Experimental

To a solution of (11.42 mmol) phosphoryl chloride in chloroform (10 ml), a solution of o-toluidine (68.52 mmol) in chloroform (10 ml) was added dropwise at 268 K. After 4 h, the solvent was removed in vacuum. Single crystals were obtained from a mixture of chloroform/n-heptane after slow evaporation at room temperature. ³¹P{¹H} NMR (202.45 MHz, DMSO-d6, 300.0 K, H₃PO₄ external): -5.01 p.p.m. (s). ¹H NMR (500.13 MHz, DMSO-d6, 300.0 K, TMS): 2.03 (s, 12H, 4CH₃), 6.87–7.06 (m, 12H, Ar—H), 7.29 (m, 4H, Ar—H), 7.35 p.p.m. (d, ²J(P,H) = 7.9 Hz, 4H, NH). IR (KBr, cm^-1): 3746.3, 3413.2, 3300.4, 3188.5, 2927.3, 2854.8, 2358.8, 1675.8, 1599.4, 1496.1, 1402.5, 1226.5, 1111.8, 980.2, 844.9, 750.9.