N,N-Dimethyl-N′,N′′-diphenyl­phospho­ric triamide

Pourayoubi, M.; Yousefi, M.; Eslami, F.; Rheingold, A.L.; Chen, C.

doi:10.1107/S1600536811046058

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3220

https://doi.org/10.1107/S1600536811046058

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N,N-Dimethyl-N′,N′′-diphenylphosphoric triamide

Mehrdad Pourayoubi,^a ^* Mohammad Yousefi,^b Farnaz Eslami,^b Arnold L. Rheingold ^c and Chao Chen ^c

^aDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad, 91779, Iran, ^bDepartment of Chemistry, Shahr-e Rey Branch, Islamic Azad University, Tehran, Iran, and ^cDepartment of Chemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093, USA
^*Correspondence e-mail: mehrdad_pourayoubi@yahoo.com

(Received 27 October 2011; accepted 1 November 2011; online 9 November 2011)

In the title compound, C₁₄H₁₈N₃OP, a crystallographic mirror plane bisects the molecule (the C,N,C atoms of the dimethylamido moiety and the P=O unit lie on the mirror plane). The P atom has a distorted tetrahedral geometry; the bond angles at P are in the range 98.98 (11)–115.28 (7)°. In the crystal, the O atom of the P=O group acts as a double hydrogen-bond acceptor for two symmetry-equivalent N—H⋯O hydrogen bonds, building [001] chains containing R₂¹(6) loops.

Related literature

For bond lengths and angles in compounds having a [(N)P(O)(N)₂] skeleton, see: Sabbaghi et al. (2011 ). For the double hydrogen-bond acceptor capability of the phosphoryl group, see: Pourayoubi et al. (2011 ).

Experimental

Crystal data

C₁₄H₁₈N₃OP
M_r = 275.28
Orthorhombic, C m c 2₁
a = 15.501 (3) Å
b = 10.8569 (17) Å
c = 8.1579 (13) Å
V = 1372.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 100 K
0.60 × 0.15 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.891, T_max = 0.975
5356 measured reflections
1317 independent reflections
1272 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.084
S = 1.04
1317 reflections
108 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ), 604 Friedel pairs
Flack parameter: −0.11 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.88	2.22	2.982 (2)	145
Symmetry code: (i) $[-x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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: SHELXTL and enCIFer (Allen et al., 2004 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811046058/hb6483sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046058/hb6483Isup2.hkl

checkCIF report

Comment top

The title molecule, Fig. 1, has crystallographically imposed mirror symmetry. In the (CH₃)₂NP(O) unit, the O—P—N—C torsion angles, showing the orientations of the methyl groups with respect to the phosphoryl group, are 0.0 and 180.0°.

The P═O and P—N bond lengths and the C—N—P bond angles match those found for the other compounds having a [(N)P(O)(N)₂] skeleton (Sabbaghi et al., 2011).

The tetrahedral geometry of the phosphorus atom is significantly distorted as it has been noted for the other phosphoric triamides: the bond angles at the P atom vary in the range from 98.98 (11) [N1ⁱ—P1—N1; symmetry code (i): -x, y, z] to 115.28 (7)° [O1—P1—N1].

The O atom of the P═O group acts as a double hydrogen-bond acceptor (Pourayoubi et al., 2011) to form the [N—H]₂···O(P) grouping within a 1-D hydrogen-bonded arrangement along the c axis (Fig. 2, Table 1).

Related literature top

For bond lengths and angles in compounds having a [(N)P(O)(N)₂] skeleton, see: Sabbaghi et al. (2011). For the double hydrogen-bond acceptor capability of the phosphoryl group, see: Pourayoubi et al. (2011).

Experimental top

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 vacuum.

Synthesis of title compound: to a solution of ((CH₃)₂N)P(O)Cl₂ (3.7 mmol) in CH₃CN (15 ml), a solution of aniline (14.8 mmol) in CH₃CN (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 CH₃CN at room temperature to yield colourless rods.

Structure description top

The P═O and P—N bond lengths and the C—N—P bond angles match those found for the other compounds having a [(N)P(O)(N)₂] skeleton (Sabbaghi et al., 2011).

For bond lengths and angles in compounds having a [(N)P(O)(N)₂] skeleton, see: Sabbaghi et al. (2011). For the double hydrogen-bond acceptor capability of the phosphoryl group, see: Pourayoubi et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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: SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004).

Figures top

	Fig. 1. The molecular structure of the title compound with ellipsoids shown at the 50% probability level.
	Fig. 2. A view of the crystal packing showing the formation of 1-D arrangement through N—H···O hydrogen bonds (shown as dotted lines), carbon bound H atoms have been omitted for clarity.

N,N-Dimethyl-N',N''-diphenylphosphoric triamide top

Crystal data top

C₁₄H₁₈N₃OP	D_x = 1.332 Mg m⁻³
M_r = 275.28	Melting point: NOT MEASURED K
Orthorhombic, Cmc2₁	Mo Kα radiation, λ = 0.71073 Å
a = 15.501 (3) Å	Cell parameters from 3006 reflections
b = 10.8569 (17) Å	θ = 3.4–25.5°
c = 8.1579 (13) Å	µ = 0.20 mm⁻¹
V = 1372.9 (4) Å³	T = 100 K
Z = 4	Rod, colourless
F(000) = 584	0.60 × 0.15 × 0.13 mm

Data collection top

Bruker APEXII CCD diffractometer	1317 independent reflections
Radiation source: fine-focus sealed tube	1272 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
φ and ω scans	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −18→14
T_min = 0.891, T_max = 0.975	k = −13→11
5356 measured reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0623P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
1317 reflections	Δρ_max = 0.22 e Å⁻³
108 parameters	Δρ_min = −0.22 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 604 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.11 (10)

Crystal data top

C₁₄H₁₈N₃OP	V = 1372.9 (4) Å³
M_r = 275.28	Z = 4
Orthorhombic, Cmc2₁	Mo Kα radiation
a = 15.501 (3) Å	µ = 0.20 mm⁻¹
b = 10.8569 (17) Å	T = 100 K
c = 8.1579 (13) Å	0.60 × 0.15 × 0.13 mm

Data collection top

Bruker APEXII CCD diffractometer	1317 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1272 reflections with I > 2σ(I)
T_min = 0.891, T_max = 0.975	R_int = 0.031
5356 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.084	Δρ_max = 0.22 e Å⁻³
S = 1.04	Δρ_min = −0.22 e Å⁻³
1317 reflections	Absolute structure: Flack (1983), 604 Friedel pairs
108 parameters	Absolute structure parameter: −0.11 (10)
1 restraint

Special details top

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
H13	−0.0531 (17)	0.819 (2)	−0.158 (3)	0.043 (6)*
H11	0.0000	0.708 (4)	−0.186 (5)	0.052 (11)*
H12	0.0000	0.849 (4)	0.262 (6)	0.053 (11)*
H4	−0.0525 (13)	0.9247 (19)	0.112 (3)	0.028 (5)*
P1	0.0000	0.62183 (5)	0.12667 (6)	0.02090 (19)
O1	0.0000	0.63022 (15)	0.3089 (2)	0.0251 (4)
N1	0.08103 (10)	0.54350 (14)	0.0464 (2)	0.0254 (4)
H1A	0.0696	0.4706	0.0047	0.031*
N2	0.0000	0.76094 (19)	0.0485 (3)	0.0243 (5)
C1	0.34009 (13)	0.66067 (19)	0.0212 (2)	0.0271 (4)
H1	0.3986	0.6864	0.0142	0.033*
C2	0.31200 (13)	0.55744 (18)	−0.0645 (2)	0.0283 (4)
H2	0.3515	0.5125	−0.1303	0.034*
C3	0.22643 (11)	0.51958 (17)	−0.0546 (2)	0.0243 (4)
H3	0.2080	0.4485	−0.1128	0.029*
C4	0.16777 (13)	0.58505 (18)	0.0398 (2)	0.0232 (4)
C5	0.28212 (11)	0.72536 (16)	0.1165 (3)	0.0252 (4)
H5	0.3011	0.7954	0.1762	0.030*
C6	0.19609 (10)	0.68909 (16)	0.1260 (3)	0.0241 (4)
H6	0.1566	0.7349	0.1910	0.029*
C7	0.0000	0.8737 (2)	0.1449 (4)	0.0269 (6)
C8	0.0000	0.7773 (3)	−0.1284 (4)	0.0329 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0224 (3)	0.0191 (3)	0.0212 (3)	0.000	0.000	0.0002 (3)
O1	0.0304 (10)	0.0227 (9)	0.0221 (10)	0.000	0.000	0.0036 (7)
N1	0.0246 (8)	0.0218 (8)	0.0300 (8)	−0.0009 (6)	0.0010 (6)	−0.0034 (6)
N2	0.0304 (11)	0.0218 (11)	0.0208 (12)	0.000	0.000	−0.0001 (8)
C1	0.0239 (9)	0.0308 (10)	0.0265 (9)	0.0005 (8)	−0.0006 (8)	0.0058 (8)
C2	0.0286 (9)	0.0314 (10)	0.0248 (9)	0.0073 (8)	0.0025 (8)	0.0006 (8)
C3	0.0289 (9)	0.0215 (9)	0.0225 (9)	0.0025 (7)	−0.0021 (8)	0.0006 (7)
C4	0.0264 (9)	0.0208 (10)	0.0224 (10)	0.0021 (8)	−0.0024 (7)	0.0032 (7)
C5	0.0296 (8)	0.0230 (8)	0.0230 (9)	0.0005 (7)	−0.0033 (9)	0.0038 (8)
C6	0.0269 (8)	0.0226 (8)	0.0227 (7)	0.0043 (7)	0.0013 (8)	−0.0007 (8)
C7	0.0342 (13)	0.0224 (13)	0.0241 (14)	0.000	0.000	0.0001 (10)
C8	0.0446 (17)	0.0310 (16)	0.0232 (14)	0.000	0.000	0.0029 (12)

Geometric parameters (Å, º) top

P1—O1	1.489 (2)	C2—H2	0.9500
P1—N2	1.639 (2)	C3—C4	1.388 (3)
P1—N1ⁱ	1.6521 (16)	C3—H3	0.9500
P1—N1	1.6522 (16)	C4—C6	1.401 (3)
N1—C4	1.419 (2)	C5—C6	1.393 (2)
N1—H1A	0.8800	C5—H5	0.9500
N2—C8	1.454 (3)	C6—H6	0.9500
N2—C7	1.455 (3)	C7—H12	0.99 (5)
C1—C5	1.380 (3)	C7—H4	1.02 (2)
C1—C2	1.391 (3)	C8—H13	0.97 (3)
C1—H1	0.9500	C8—H11	0.89 (4)
C2—C3	1.391 (3)

O1—P1—N2	109.39 (11)	C4—C3—C2	120.39 (18)
O1—P1—N1ⁱ	115.28 (7)	C4—C3—H3	119.8
N2—P1—N1ⁱ	108.66 (8)	C2—C3—H3	119.8
O1—P1—N1	115.28 (7)	C3—C4—C6	119.10 (17)
N2—P1—N1	108.66 (8)	C3—C4—N1	118.62 (16)
N1ⁱ—P1—N1	98.98 (11)	C6—C4—N1	122.28 (16)
C4—N1—P1	124.87 (13)	C1—C5—C6	120.74 (18)
C4—N1—H1A	117.6	C1—C5—H5	119.6
P1—N1—H1A	117.6	C6—C5—H5	119.6
C8—N2—C7	115.7 (2)	C5—C6—C4	119.99 (17)
C8—N2—P1	119.9 (2)	C5—C6—H6	120.0
C7—N2—P1	124.38 (19)	C4—C6—H6	120.0
C5—C1—C2	119.30 (18)	N2—C7—H12	107 (2)
C5—C1—H1	120.4	N2—C7—H4	108.2 (13)
C2—C1—H1	120.4	H12—C7—H4	113.7 (18)
C1—C2—C3	120.49 (18)	N2—C8—H13	107.6 (15)
C1—C2—H2	119.8	N2—C8—H11	115 (3)
C3—C2—H2	119.8	H13—C8—H11	105.1 (19)

O1—P1—N1—C4	−72.29 (16)	C1—C2—C3—C4	0.6 (3)
N2—P1—N1—C4	50.87 (18)	C2—C3—C4—C6	−0.5 (3)
N1ⁱ—P1—N1—C4	164.16 (11)	C2—C3—C4—N1	179.88 (17)
O1—P1—N2—C8	180.0	P1—N1—C4—C3	−169.43 (13)
N1ⁱ—P1—N2—C8	−53.37 (7)	P1—N1—C4—C6	11.0 (2)
N1—P1—N2—C8	53.37 (7)	C2—C1—C5—C6	−0.7 (3)
O1—P1—N2—C7	0.0	C1—C5—C6—C4	0.7 (3)
N1ⁱ—P1—N2—C7	126.63 (7)	C3—C4—C6—C5	−0.1 (3)
N1—P1—N2—C7	−126.63 (7)	N1—C4—C6—C5	179.45 (18)
C5—C1—C2—C3	0.0 (3)

Symmetry code: (i) −x, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱⁱ	0.88	2.22	2.982 (2)	145

Symmetry code: (ii) −x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈N₃OP
M_r	275.28
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	100
a, b, c (Å)	15.501 (3), 10.8569 (17), 8.1579 (13)
V (Å³)	1372.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.60 × 0.15 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.891, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	5356, 1317, 1272
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.084, 1.04
No. of reflections	1317
No. of parameters	108
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22
Absolute structure	Flack (1983), 604 Friedel pairs
Absolute structure parameter	−0.11 (10)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88	2.22	2.982 (2)	145

Symmetry code: (i) −x, −y+1, z−1/2.

Acknowledgements

Support of this investigation by the Ferdowsi University of Mashhad is gratefully acknowledged.

References

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