N,N-Dimethyl-N′,N′′-bis­(2-methyl­phenyl)phospho­ric triamide mono­hydrate

Farnaz Eslami; Mehrdad Pourayoubi; Mohammad Yousefi; Arnold L Rheingold; James A Golen

doi:10.1107/S1600536812033995

. 2012 Aug 4;68(Pt 9):o2650. doi: 10.1107/S1600536812033995

N,N-Dimethyl-N′,N′′-bis(2-methylphenyl)phosphoric triamide monohydrate

Farnaz Eslami ^a, Mehrdad Pourayoubi ^b,^*, Mohammad Yousefi ^a, Arnold L Rheingold ^c, James A Golen ^c

PMCID: PMC3435677 PMID: 22969548

Abstract

In the title compound, C₁₆H₂₂N₃OP·H₂O, the P atom adopts a distorted tetrahedral environment with the bond angles around the P atom in the range 99.98 (7)–116.20 (7)°. The P—N bond length in the [(CH₃)₂N]P(O) fragment [1.6392 (14) Å] is slightly shorter than two other P—N bonds [1.6439 (15) and 1.6530 (14) Å]. In the (CH₃)₂NP(O) fragment, one of the methyl groups is syn to the P=O bond, whereas the other one is anti to the P=O bond [C—N—P=O torsion angles = 4.80 (17) and −174.57 (15)°]. In the crystal, the water molecules form hydrogen bonds to the O atoms of the P=O bond of two different molecules and act as acceptors for the two amino H atoms of the same molecule. As a result, chains parallel to [010] are formed.

Related literature

For phosphoramidates having a [(CH₃)₂N]P(O) fragment and for P=O and P—N bond lengths, see: Pourayoubi, Tarahhomi et al. (2012 ▶); Pourayoubi et al. (2011 ▶). For the double H-atom acceptor capability of the P=O group, see: Pourayoubi, Nečas & Negari (2012 ▶).

Experimental

Crystal data

C₁₆H₂₂N₃OP·H₂O
M _r = 321.35
Monoclinic,
a = 10.7058 (16) Å
b = 7.2541 (11) Å
c = 22.091 (3) Å
β = 90.971 (2)°
V = 1715.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 100 K
0.20 × 0.14 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.967, T _max = 0.977
15201 measured reflections
4036 independent reflections
3135 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.115
S = 1.04
4036 reflections
215 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812033995/bt5974sup1.cif

e-68-o2650-sup1.cif^{(24.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033995/bt5974Isup2.hkl

e-68-o2650-Isup2.hkl^{(197.8KB, 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
O1W—H2W⋯O1ⁱ	0.84 (1)	1.91 (2)	2.7491 (17)	173 (2)
O1W—H1W⋯O1ⁱⁱ	0.85 (1)	1.91 (1)	2.7607 (17)	175 (2)
N1—H1N⋯O1W	0.87 (1)	2.04 (2)	2.8724 (19)	159 (2)
N2—H2N⋯O1W	0.87 (1)	2.00 (2)	2.8473 (18)	164 (2)

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

Acknowledgments

Support of this investigation by Shahr-e Rey Branch, Islamic Azad University, is gratefully acknowledged.

supplementary crystallographic information

Comment

The crystal structure determination of the title hydrate phosphoric triamide (Fig. 1) was performed as a part of work on synthesis and X-ray crystallography of compounds with a [(CH₃)₂N]P(O) fragment (Pourayoubi, Tarahhomi et al., 2012; Pourayoubi et al., 2011).

In the phosphoric triamide molecule, the P atom adopts a distorted (N)P(O)(N)₂ tetrahedral environment. The P═O and P—N bond lengths are within the expected values (Pourayoubi, Tarahhomi et al., 2012; Pourayoubi et al., 2011). The sum of three bond angles at the nitrogen atom of the dimethylamido fragment, C11—N3—C10 + C11—N3—P1 + C10—N3—P1, of 360° suggests sp² hybridization for this N atom. Moreover, the C6—N1—P1 and C4—N2—P1 bond angles are 125.07 (12)° and 125.66 (12)°, respectively. The P—N bond length of the [(CH₃)₂N]P(O) fragment is shorter than two other P—N bonds.

In the crystal, the oxygen atoms of phosphoryl group and water molecule act as double-hydrogen bond acceptors (for a definition of double-hydrogen bond acceptor, see: Pourayoubi, Nečas & Negari, 2012) to form O—H···O···H—O and N—H···O···H—N groups. The phosphoric triamide and water molecules are aggregated through these hydrogen bonds in a linear arrangement parallel to the b axis, Fig. 2.

Experimental

Synthesis of ((CH₃)₂N)P(O)Cl₂: [(CH₃)₂NH₂]Cl (0.184 mol) and P(O)Cl₃ (0.552 mol) were refluxed for 8 h and afterwards the excess of P(O)Cl₃ was removed in vacuo.

Synthesis of title compound: To a solution of ((CH₃)₂N)P(O)Cl₂ (3.7 mmol) in CHCl₃ (15 ml), a solution of ortho-toluidine (14.8 mmol) in the same solvent (25 ml) was added at 273 K. After 4 h stirring, the solvent was removed and product was washed with deionized water and recrystallized from chloroform/n-hexene at room temperature to yield colourless crystals.