N,N′-Dimethyl-N′′-(trichloroacet­yl)phospho­ramide

Ovchynnikov, V.

doi:10.1107/S1600536813030389

organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page o1759

doi:10.1107/S1600536813030389

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N,N′-Dimethyl-N′′-(trichloroacetyl)phosphoramide

Vladimir Ovchynnikov ^a ^*

^aDepartment of Inorganic Chemistry, Kiev National Taras Shevchenko University, Vladimirskaya St. 64/13, Kiev 01601, Ukraine
^*Correspondence e-mail: ovchynnikov@univ.kiev.ua

(Received 22 October 2013; accepted 6 November 2013; online 9 November 2013)

In the title compound, C₄H₉Cl₃N₃O₂P or CCl₃C(O)NHP(O)(NHCH₃)₂, the P atom has a strongly distorted tetrahedral geometry due to the formation of intermolecular strong hydrogen bonds involving the N atoms. In the crystal, N—H⋯O=P and N—H⋯O=C hydrogen bonds connect the molecules into a two-dimensional array parallel to (100). An intramolecular P⋯O contact [P⋯O = 2.975 (3) Å] is observed. The CCl₃ group is rotationally disordered, with occupancies of 0.60 (3) and 0.40 (3)

CCDC reference: 970429

Related literature

For the use of carbacylamidophosphates as potential new ligands for metal ions, see: Skopenko et al. (2004 ); Znovjyak et al. (2009 ); Yizhak et al. (2013 ); Gubina et al. (2009 ). For their biological activity, see: Amirkhanov et al. (1996 ); Rebrova et al. (1984 ). For P=O and C=O bond lengths, see: Mizrahi & Modro (1982 ); Amirkhanov et al. (1997 ); Gubina & Amirkhanov (2000 ). For the preparation of trichloroacetylamidophosphoric acid dichloranhydride, see: Kirsanov & Derkach (1956 ).

Experimental

Crystal data

C₄H₉Cl₃N₃O₂P
M_r = 268.46
Monoclinic, P 2₁ /c
a = 10.231 (2) Å
b = 8.754 (2) Å
c = 12.826 (3) Å
β = 101.27 (3)°
V = 1126.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 K
0.4 × 0.3 × 0.3 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
3806 measured reflections
1908 independent reflections
1419 reflections with I > 2σ(I)
R_int = 0.060
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.077
wR(F²) = 0.195
S = 1.08
1908 reflections
157 parameters
33 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.81 (3)	2.00 (4)	2.782 (5)	164 (5)
N3—H3⋯O1ⁱ	0.81 (3)	2.21 (4)	2.953 (4)	153 (4)
N2—H2⋯O2ⁱⁱ	0.81 (3)	2.38 (4)	3.077 (5)	146 (6)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1995 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 970429

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813030389/bg2520sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813030389/bg2520Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813030389/bg2520Isup3.cml

checkCIF report

Introduction top

Carbacylamidophosphates of the general formula RC(O)NHP(O)R'₂ are potential new ligands for metal ions (Skopenko et al., 2004; Znovjyak et al., 2009; Gubina et al., 2009). Many of these compounds also show biological activity (Amirkhanov et al., 1996, Rebrova et al., 1984). This work reports the structure of N,N'-Dimethyl-N''-trichloracetylphosphoramide (C₄H₉N₃O₂PCl₃) (I).

Experimental top

Synthesis and crystallization top

The dichloranhydride of trichloroacetylamidophosphoric acid was prepared according to the method reported by Kirsanov (Kirsanov & Derkach, 1956). The dioxane solution (200 ml) of dichloranhydride of trichloroacetylamidophosphoric acid (27.9 g, 0.1 mol) was placed in a three-neck round-bottomed flask and cooled by ice to 268 K. Then the dry methylamine was bubbled through the dioxane solution of CCl₃C(O)NHP(O)Cl₂ under stirring until the solution became alkaline. The temperature was not allowed to rise above 278 K. The stirring was continued for 1 h and the solution was left under ambient conditions. H₂NCH₃·HCl was filtered off after 12 h and the filtrate was evaporated. The oily precipitate of I was added to acetone which led to the formation of a white crystalline powder (yield 80%). White crystals suitable for X-ray analysis were obtained from slow evaporation of a 2-propanol solution.

Refinement top

H atoms of methyl groups were placed at calculated positions and treated as riding on the parent atoms, with U_iso(H) = 1.5 U_eq(C). H atoms of the amide group were located in a difference Fourier map and and further refined with similarity restraints for d(N—H) and U_iso(H) = 1.2U_eq(N). The CCl₃ group apperas rotationally disordered around the C1—C2 bond, with occupations of 0.60/0.40 (3)

Results and discussion top

In the title compound (I), the phosphorus environment has a strong distorted tetrahedral conformation due to the formation of strong N1—H1···O1 and N3—H3···O1 hydrogen bonds (Table 2, Fig.1). The N1—P—N3 angle has a value 98.72° and as a consequence there is an increase in the O1—P1—N3 and O1—P1—N1 angles (119.2° and 111.29°, respectively). The orientation of the C(O) and P(O) groups differs from the conformation of most CAF-ligands (Gubina & Amirkhanov, 2000), the angle between the O2C1N1 and N1PO1 planes having a value 57.3° (the pseudo-torsion angle O=C···P=O is -53.39°).

In the crystal, two intermolecular N–H···O=P hydrogen bonds connect molecules into a chain and a third N—H···O=C hydrogen bond connects the chains into a 2D array parallel to (100) (Fig.2). An intramolecular P···O contact is also present in the crystal [d(P···O) = 2.975 (3) Å], sorter than the sum of commonly accepted Van der Waals Radii (3.3 Å).

Related literature top

For the use of carbacylamidophosphates as potential new ligands for metal ions, see: Skopenko et al. (2004); Znovjyak et al. (2009); Yizhak et al. (2013); Gubina et al. (2009). For their biological activity, see: Amirkhanov et al. (1996); Rebrova et al. (1984). For P=O and C=O bond lengths, see: Mizrahi & Modro (1982); Amirkhanov et al. (1997); Gubina & Amirkhanov (2000). For the preparation of trichloroacetylamidophosphoric acid dichloranhydride, see: Kirsanov & Derkach (1956).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1995); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1995); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. A view of the title compound (I) showing the atom-numbering scheme and the formation of three type of hydrogen bonds (dashed lines). Displacement ellipsoids drawn at a 30% probability level.
	Fig. 2. Packing view of (I) along the b axis. Only the major fraction of the CCl₃ group has been represented.

N,N'-Dimethyl-N''-(trichloroacetyl)phosphoramide top

Crystal data top

C₄H₉Cl₃N₃O₂P	F(000) = 544
M_r = 268.46	D_x = 1.583 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2348 reflections
a = 10.231 (2) Å	θ = 2.0–27.1°
b = 8.754 (2) Å	µ = 0.93 mm⁻¹
c = 12.826 (3) Å	T = 293 K
β = 101.27 (3)°	Block, colorless
V = 1126.6 (4) Å³	0.4 × 0.3 × 0.3 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.060
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.0°
Graphite monochromator	h = −12→12
ω/Θ scans	k = 0→10
3806 measured reflections	l = −15→15
1908 independent reflections	3 standard reflections every 200 reflections
1419 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.195	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.1369P)²] where P = (F_o² + 2F_c²)/3
1908 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.82 e Å⁻³
33 restraints	Δρ_min = −0.77 e Å⁻³

Crystal data top

C₄H₉Cl₃N₃O₂P	V = 1126.6 (4) Å³
M_r = 268.46	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.231 (2) Å	µ = 0.93 mm⁻¹
b = 8.754 (2) Å	T = 293 K
c = 12.826 (3) Å	0.4 × 0.3 × 0.3 mm
β = 101.27 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.060
3806 measured reflections	3 standard reflections every 200 reflections
1908 independent reflections	intensity decay: 1%
1419 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.077	33 restraints
wR(F²) = 0.195	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.82 e Å⁻³
1908 reflections	Δρ_min = −0.77 e Å⁻³
157 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
P1	0.55195 (8)	0.17846 (12)	0.16971 (7)	0.0379 (4)
Cl1	0.0184 (6)	0.1759 (10)	0.0571 (8)	0.098 (2)	0.60 (3)
Cl2	0.1528 (7)	0.2717 (16)	0.2675 (4)	0.108 (2)	0.60 (3)
Cl3	0.1588 (6)	0.4570 (7)	0.0816 (9)	0.114 (3)	0.60 (3)
Cl1A	0.0175 (8)	0.1557 (17)	0.0770 (15)	0.108 (5)	0.40 (3)
Cl2A	0.1466 (9)	0.321 (3)	0.2554 (10)	0.134 (5)	0.40 (3)
Cl3A	0.1524 (15)	0.434 (2)	0.050 (2)	0.185 (9)	0.40 (3)
O1	0.5607 (3)	0.0273 (4)	0.2191 (3)	0.0597 (8)
O2	0.2813 (3)	0.0649 (4)	0.0732 (3)	0.0683 (10)
N1	0.3994 (3)	0.2573 (4)	0.1646 (3)	0.0461 (8)
H1	0.396 (5)	0.335 (5)	0.197 (4)	0.055*
N2	0.5807 (5)	0.1646 (5)	0.0515 (3)	0.0668 (12)
H2	0.602 (6)	0.080 (5)	0.036 (5)	0.080*
N3	0.6418 (3)	0.3153 (4)	0.2290 (3)	0.0495 (9)
H3	0.605 (4)	0.373 (6)	0.263 (3)	0.059*
C1	0.2872 (4)	0.1851 (5)	0.1188 (3)	0.0508 (10)
C2	0.1579 (4)	0.2697 (6)	0.1287 (4)	0.0724 (15)
C3	0.5757 (12)	0.2923 (9)	−0.0197 (5)	0.130 (4)
H3A	0.6401	0.2781	−0.0641	0.195*
H3B	0.5954	0.3845	0.0208	0.195*
H3C	0.4882	0.2994	−0.0632	0.195*
C4	0.7862 (4)	0.3127 (8)	0.2458 (5)	0.0814 (17)
H4A	0.8171	0.4026	0.2152	0.122*
H4B	0.8145	0.2236	0.2126	0.122*
H4C	0.8226	0.3102	0.3207	0.122*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0356 (5)	0.0399 (6)	0.0419 (6)	0.0050 (3)	0.0166 (4)	0.0026 (4)
Cl1	0.049 (3)	0.089 (3)	0.137 (4)	−0.0087 (18)	−0.028 (3)	−0.040 (3)
Cl2	0.069 (3)	0.172 (6)	0.090 (3)	0.021 (3)	0.0296 (16)	−0.044 (4)
Cl3	0.059 (2)	0.058 (2)	0.198 (5)	0.0179 (14)	−0.041 (3)	−0.004 (3)
Cl1A	0.037 (3)	0.109 (7)	0.176 (9)	0.002 (3)	0.017 (4)	−0.075 (6)
Cl2A	0.040 (3)	0.161 (9)	0.208 (11)	−0.018 (4)	0.043 (4)	−0.130 (8)
Cl3A	0.116 (7)	0.096 (8)	0.292 (17)	0.032 (5)	−0.084 (9)	0.022 (9)
O1	0.0463 (14)	0.0482 (19)	0.086 (2)	0.0032 (12)	0.0153 (13)	0.0251 (16)
O2	0.0524 (17)	0.062 (2)	0.087 (2)	0.0047 (14)	0.0037 (15)	−0.0299 (18)
N1	0.0347 (15)	0.053 (2)	0.0496 (17)	0.0054 (14)	0.0070 (12)	−0.0148 (16)
N2	0.103 (3)	0.050 (3)	0.060 (2)	0.004 (2)	0.049 (2)	−0.0094 (19)
N3	0.0321 (16)	0.061 (2)	0.059 (2)	−0.0007 (13)	0.0171 (13)	−0.0123 (17)
C1	0.045 (2)	0.051 (3)	0.055 (2)	0.0054 (16)	0.0051 (17)	−0.0146 (19)
C2	0.039 (2)	0.072 (4)	0.099 (4)	0.006 (2)	−0.005 (2)	−0.034 (3)
C3	0.263 (11)	0.083 (5)	0.062 (3)	0.001 (6)	0.076 (5)	0.006 (3)
C4	0.038 (2)	0.090 (4)	0.119 (5)	−0.008 (2)	0.023 (2)	−0.016 (3)

Geometric parameters (Å, º) top

P1—O1	1.462 (3)	N1—H1	0.81 (3)
P1—N2	1.605 (4)	N2—C3	1.437 (8)
P1—N3	1.608 (4)	N2—H2	0.81 (3)
P1—N1	1.696 (3)	N3—C4	1.451 (5)
Cl1—C2	1.744 (6)	N3—H3	0.81 (3)
Cl2—C2	1.791 (7)	C1—C2	1.544 (6)
Cl3—C2	1.748 (7)	C3—H3A	0.9600
Cl1A—C2	1.768 (8)	C3—H3B	0.9600
Cl2A—C2	1.710 (9)	C3—H3C	0.9600
Cl3A—C2	1.753 (9)	C4—H4A	0.9600
O2—C1	1.199 (5)	C4—H4B	0.9600
N1—C1	1.342 (5)	C4—H4C	0.9600

O1—P1—N2	109.5 (2)	C1—C2—Cl3A	106.1 (7)
O1—P1—N3	119.3 (2)	Cl2A—C2—Cl3A	109.4 (7)
N2—P1—N3	108.0 (2)	Cl1—C2—Cl3A	98.8 (8)
O1—P1—N1	111.30 (18)	C1—C2—Cl1A	110.2 (4)
N2—P1—N1	109.4 (2)	Cl2A—C2—Cl1A	107.6 (5)
N3—P1—N1	98.72 (18)	Cl3—C2—Cl1A	117.3 (7)
C1—N1—P1	121.8 (3)	Cl3A—C2—Cl1A	108.4 (6)
C1—N1—H1	120 (3)	C1—C2—Cl2	106.2 (4)
P1—N1—H1	118 (3)	Cl1—C2—Cl2	110.4 (5)
C3—N2—P1	123.4 (4)	Cl3—C2—Cl2	109.7 (5)
C3—N2—H2	122 (4)	Cl3A—C2—Cl2	124.1 (9)
P1—N2—H2	114 (4)	Cl1A—C2—Cl2	101.5 (6)
C4—N3—P1	122.0 (4)	N2—C3—H3A	109.5
C4—N3—H3	120 (3)	N2—C3—H3B	109.5
P1—N3—H3	116 (4)	H3A—C3—H3B	109.5
O2—C1—N1	125.7 (4)	N2—C3—H3C	109.5
O2—C1—C2	119.9 (4)	H3A—C3—H3C	109.5
N1—C1—C2	114.3 (4)	H3B—C3—H3C	109.5
C1—C2—Cl2A	115.0 (6)	N3—C4—H4A	109.5
C1—C2—Cl1	110.9 (4)	N3—C4—H4B	109.5
Cl2A—C2—Cl1	115.0 (5)	H4A—C4—H4B	109.5
C1—C2—Cl3	111.0 (4)	N3—C4—H4C	109.5
Cl2A—C2—Cl3	95.1 (8)	H4A—C4—H4C	109.5
Cl1—C2—Cl3	108.6 (5)	H4B—C4—H4C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.81 (3)	2.00 (4)	2.782 (5)	164 (5)
N3—H3···O1ⁱ	0.81 (3)	2.21 (4)	2.953 (4)	153 (4)
N2—H2···O2ⁱⁱ	0.81 (3)	2.38 (4)	3.077 (5)	146 (6)

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.81 (3)	2.00 (4)	2.782 (5)	164 (5)
N3—H3···O1ⁱ	0.81 (3)	2.21 (4)	2.953 (4)	153 (4)
N2—H2···O2ⁱⁱ	0.81 (3)	2.38 (4)	3.077 (5)	146 (6)

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y, −z.

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