N-{Bis[meth­yl(phen­yl)amino]phosphor­yl}-2,2,2-trichloro­acetamide

Znovjyak, K.O.; Ovchynnikov, V.A.; Sliva, T.Y.; Shishkina, S.V.; Amirkhanov, V.M.

doi:10.1107/S1600536809042391

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2812

https://doi.org/10.1107/S1600536809042391

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N-{Bis[methyl(phenyl)amino]phosphoryl}-2,2,2-trichloroacetamide

Kateryna O. Znovjyak,^a ^* Vladimir A. Ovchynnikov,^a Tetyana Yu. Sliva,^a Svitlana V. Shishkina ^b and Vladimir M. Amirkhanov ^a

^aDepartment of Chemistry, Kyiv National Taras Shevchenko University, Volodymyrska str. 64, 01033 Kyiv, Ukraine, and ^bSTC "Institute for Single Crystals", National Academy of Science of Ukraine, Lenina ave. 60, 61001, Khar'kov, Ukraine
^*Correspondence e-mail: znovkat@yahoo.com

(Received 28 September 2009; accepted 15 October 2009; online 23 October 2009)

In the asymmetric unit of the crystal structure of the title compound, C₁₆H₁₇Cl₃N₃O₂P, there are two crystallographically independent molecules, which form dimers via N—H⋯O hydrogen bonding between the N—H group and the P=O group. In the molecular structure, the phosphoryl group is anti to the carbonyl group. The two benzene rings are oriented at dihedral angles of 54.3 (2) and 49.7 (2)° in the two independent molecules.

Related literature

For background to the chemistry of phosphorus-containing systems, see: Helm et al. (1999 ); Katti et al. (1991 ). For the biological and pharmacological properties of carbacylamidophosphate derivatives, see: Jaroslav & Swetdloff (1985 ). For structural and conformational studies of related molecules, see: Gholivand et al. (2008a ,b ); Gubina et al. (1999 ); Rebrova et al. (1982 ). For the coordination properties of carbacylamidophosphates, see: Oczko et al. (2003 ); Amirkhanov et al. (1997 ); Trush et al. (2003 ); Gubina et al. (2002 ). For details of the synthesis, see Kirsanov & Derkach (1956 ).

Experimental

Crystal data

C₁₆H₁₇Cl₃N₃O₂P
M_r = 420.65
Monoclinic, P 2₁ /n
a = 12.8226 (10) Å
b = 19.5161 (15) Å
c = 15.1132 (12) Å
β = 93.345 (6)°
V = 3775.6 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 293 K
0.40 × 0.20 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.800, T_max = 0.971
37663 measured reflections
8168 independent reflections
6768 reflections with I > 2σ(I)
R_int = 0.086

Refinement

R[F² > 2σ(F²)] = 0.094
wR(F²) = 0.174
S = 1.16
8168 reflections
451 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11B⋯O21	0.86	1.91	2.741 (5)	161
N21—H21B⋯O11	0.86	1.93	2.752 (5)	159

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809042391/xu2626sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809042391/xu2626Isup2.hkl

checkCIF report

Comment top

The intensive development of the chemistry of the phosphorus containing systems during the last decades has given rise to synthesis of many compounds bonded by phosphorus and nitrogen atoms (Helm et al., 1999; Katti et al., 1991). Carbacylamidophosphates, which have CONHPO in molecular core unit, have attracted attention because of their using in pharmacology, as insecticides, pesticides and ureas inhibitor (Jaroslav et al., 1985). These types of compounds are used as ligands, particularly for lanthanides (Oczko et al., 2003), actinides (Amirkhanov et al., 1997) and 3d-metals (Trush et al. , 2003; Gubina et al., 2002). Thus to date the syntheses and structures of carbacylamidophosphate compounds have been of increased interest (Gholivand et al., 2008a). This paper is devoted to the crystal structure of N-{bis[methyl(phenyl)amino]phosphoryl}-2,2,2-trichloroacetamide (HL).

The title compound contains two crystallographically independent molecules in the asymmetric unit of the unit cell, which aggregate into the non-centrosymmetric dimers (HL)₂ formed by the hydrogen bonds of N—H···OP (Figs. 1 and 2, Table 1). In the crystal structure of the HL the phosphoryl and carbonyl groups are in an anti-position to each other as in the most of the carbacylamidophosphates (Gubina et al., 1999). The bond distances P(1)O(11) and P(2)O(21) are typical for compounds with amide substituents close to phosphorus atoms (1.465–1.482 Å) (Rebrova et al., 1982). The values of CO and C—N bonds lie in the ranges 1.193 (8) Å, 1.207 (8) Å and 1.365 (9) Å, 1.362 (8) Å, respectively and close to the corresponding values of the carbacylamidophosphates (Gholivand et al., 2008b). The P(1)—N(11) (1.684 (5) Å) and P(2)—N(21) (1.692 (5) Å) distances of HL are longer on average by 0.05 Å than P—N bond distances between amide substituents and phosphorus atoms (P(1)—N(12), P(1)—N(13), P(2)—N(22), P(2)—N(23)) which fall in the range 1.634 (4)–1.649 (4) Å.

The phosphorus atoms of HL have distorted tetrahedral configuration where the values of O—P—N angles have the highest deviation from the 109.28°. Inspection of the O(11)—P(1)—N(11) and O(21)—P(2)—N(21) angles indicates that these angles are less than tetrahedral one (105.9 (2)° and 105.4 (2)°, respectively), while others O—P—N angles indicate higher values (111.2 (2)°-119.0 (2)°), that may be explained by the repulsion of amide substituents and PO group.

Related literature top

For background to the chemistry of the phosphorus-containing systems, see: Helm et al. (1999); Katti et al. (1991). For the biological and pharmacological properties of carbacylamidophosphate derivatives, see: Jaroslav & Swetdloff (1985). For structural and conformational studies of related molecules, see: Gholivand et al. (2008a,b); Gubina et al. (1999); Rebrova et al. (1982). For the coordination properties of carbacylamidophosphates, see: Oczko et al. (2003); Amirkhanov et al. (1997); Trush et al. (2003); Gubina et al. (2002). For details of the synthesis, see Kirsanov & Derkach (1956).

Experimental top

The dichloranhydride of trichloroacetylamidophosphoric acid was prepared according to the method reported by Kirsanov (Kirsanov et al., 1956).

The dioxane solution (100 ml) of methylaniline (21.4 g, 0.2 mol) and triethylamine (20.2 g, 0.2 mol) was placed in a three-neck round-bottomed flask and cooled by ice to 268 K. Then the dioxane solution (400 ml) of dichloranhydride of trichloroacetylamidophosphoric acid (27.9 g, 0.1 mol) was added dropwise under vigorous stirring. The temperature was not allowed to rise above 278 K. The stirring was continued for 1 h. The formed precipitate of N(C₂H₅)₃HCl was filtered off and the filtrate evaporated. The oily precipitate of N-{bis[methyl(phenyl)amino]phosphoryl}-2,2,2-trichloroacetamide was isolated and recrystallized from the 2-propanol as white crystalline powder. The colourless crystals of the HL were obtained by slow evaporation of the mother liquor, washed with cool 2-propanol (10 ml) and finally dried in air (yield 85%).

Structure description top

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of hydrogen bonding between the two independent molecules in the unit cell of the title compound with atom numbering scheme. Displacement ellipsoids are shown at 50% probability level. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.
	Fig. 2. A projection of packing diagram of the title compound along the y-direction.

N-{Bis[methyl(phenyl)amino]phosphoryl}-2,2,2-trichloroacetamide top

Crystal data top

C₁₆H₁₇Cl₃N₃O₂P	F(000) = 1728
M_r = 420.65	D_x = 1.480 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 51957 reflections
a = 12.8226 (10) Å	θ = 2.6–32.2°
b = 19.5161 (15) Å	µ = 0.59 mm⁻¹
c = 15.1132 (12) Å	T = 293 K
β = 93.345 (6)°	Plate, colourless
V = 3775.6 (5) Å³	0.40 × 0.20 × 0.05 mm
Z = 8

Data collection top

Oxford Diffraction Xcalibur3 diffractometer	8168 independent reflections
Radiation source: Enhance (Mo) X-ray Source	6768 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.086
Detector resolution: 16.1827 pixels mm^-1	θ_max = 27.5°, θ_min = 2.6°
ω scans	h = −16→16
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −25→25
T_min = 0.800, T_max = 0.971	l = −19→19
37663 measured reflections

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)] = 0.094	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.174	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.0501P)² + 9.3908P] where P = (F_o² + 2F_c²)/3
8168 reflections	(Δ/σ)_max = 0.002
451 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₁₆H₁₇Cl₃N₃O₂P	V = 3775.6 (5) Å³
M_r = 420.65	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.8226 (10) Å	µ = 0.59 mm⁻¹
b = 19.5161 (15) Å	T = 293 K
c = 15.1132 (12) Å	0.40 × 0.20 × 0.05 mm
β = 93.345 (6)°

Data collection top

Oxford Diffraction Xcalibur3 diffractometer	8168 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	6768 reflections with I > 2σ(I)
T_min = 0.800, T_max = 0.971	R_int = 0.086
37663 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.094	0 restraints
wR(F²) = 0.174	H-atom parameters constrained
S = 1.16	Δρ_max = 0.50 e Å⁻³
8168 reflections	Δρ_min = −0.50 e Å⁻³
451 parameters

Special details top

Experimental. ¹H NMR, 400.13 MHz, (DMSO-d₆): 3.06, 3.08 (d, 6H, CH₃), 7.3 (m, 10H, C₆H₅), 10.28 (s, 1H, NH). ³¹P NMR, 162.1 MHz, (DMSO-d₆): 5.46 (m). IR (KBr pellet, cm¹): 3040 (s, N—H), 2850, 1730(s, CO), 1600 (s, CC), 1470 (s, C—N), 1280, 1245, 1210(s, PO), 1090, 1039, 930, 885, 815, 700, 685 (s, C—Cl).

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
P1	0.33568 (8)	0.18559 (6)	0.59326 (7)	0.0137 (2)
Cl11	0.48523 (10)	0.22113 (6)	0.87366 (7)	0.0261 (3)
Cl12	0.34981 (12)	0.11928 (8)	0.94348 (8)	0.0370 (3)
Cl13	0.51399 (12)	0.07733 (7)	0.83310 (9)	0.0365 (3)
O11	0.4195 (2)	0.20901 (16)	0.53685 (19)	0.0171 (7)
N12	0.2449 (3)	0.24477 (19)	0.6008 (3)	0.0168 (8)
N13	0.2727 (3)	0.1149 (2)	0.5658 (2)	0.0183 (8)
N11	0.3948 (3)	0.1685 (2)	0.6933 (2)	0.0183 (8)
H11B	0.4617	0.1718	0.6983	0.022*
C131	0.2676 (3)	0.3157 (2)	0.5929 (3)	0.0154 (9)
C12	0.4208 (4)	0.1426 (2)	0.8517 (3)	0.0197 (10)
C141	0.1944 (3)	0.1152 (2)	0.4930 (3)	0.0179 (9)
C142	0.2132 (4)	0.1471 (2)	0.4134 (3)	0.0209 (10)
H14A	0.2771	0.1681	0.4056	0.025*
C132	0.3617 (3)	0.3435 (2)	0.6318 (3)	0.0185 (10)
H13A	0.4117	0.3149	0.6595	0.022*
O12	0.2530 (3)	0.1401 (2)	0.7707 (2)	0.0311 (9)
C11	0.3452 (4)	0.1500 (2)	0.7667 (3)	0.0195 (10)
C146	0.0988 (4)	0.0838 (2)	0.5038 (3)	0.0216 (10)
H14B	0.0869	0.0622	0.5571	0.026*
C13	0.1359 (3)	0.2280 (2)	0.6205 (3)	0.0192 (10)
H13B	0.0955	0.2693	0.6215	0.029*
H13C	0.1355	0.2058	0.6771	0.029*
H13D	0.1062	0.1979	0.5755	0.029*
C133	0.3785 (4)	0.4132 (3)	0.6281 (3)	0.0247 (11)
H13E	0.4402	0.4315	0.6535	0.030*
C145	0.0208 (4)	0.0844 (2)	0.4363 (3)	0.0254 (11)
H14C	−0.0435	0.0639	0.4442	0.030*
C144	0.0408 (4)	0.1166 (3)	0.3554 (3)	0.0282 (12)
H14D	−0.0101	0.1169	0.3089	0.034*
C136	0.1951 (4)	0.3596 (3)	0.5512 (3)	0.0247 (11)
H13F	0.1332	0.3418	0.5255	0.030*
C134	0.3039 (4)	0.4568 (3)	0.5869 (3)	0.0280 (11)
H13G	0.3150	0.5039	0.5860	0.034*
C135	0.2133 (4)	0.4290 (3)	0.5474 (3)	0.0258 (11)
H13H	0.1644	0.4574	0.5180	0.031*
C143	0.1355 (4)	0.1473 (3)	0.3458 (3)	0.0254 (11)
H14E	0.1480	0.1689	0.2926	0.030*
C14	0.2943 (6)	0.0485 (3)	0.6085 (4)	0.0474 (18)
H14F	0.2489	0.0143	0.5817	0.071*
H14G	0.2826	0.0518	0.6705	0.071*
H14H	0.3657	0.0359	0.6013	0.071*
P2	0.68252 (8)	0.17932 (6)	0.63323 (7)	0.0135 (2)
Cl21	0.66403 (11)	0.10956 (7)	0.28388 (8)	0.0311 (3)
Cl22	0.48977 (10)	0.08272 (7)	0.39052 (8)	0.0278 (3)
Cl23	0.54923 (11)	0.22269 (6)	0.35201 (8)	0.0294 (3)
O21	0.6002 (2)	0.20639 (17)	0.68822 (19)	0.0179 (7)
N22	0.7759 (3)	0.23606 (19)	0.6228 (2)	0.0149 (8)
N23	0.7424 (3)	0.1085 (2)	0.6634 (2)	0.0163 (8)
N21	0.6213 (3)	0.1617 (2)	0.5331 (2)	0.0160 (8)
H21B	0.5546	0.1665	0.5281	0.019*
O22	0.7598 (2)	0.12398 (19)	0.4579 (2)	0.0246 (8)
C241	0.8228 (3)	0.1087 (2)	0.7325 (3)	0.0174 (9)
C22	0.5976 (4)	0.1391 (2)	0.3743 (3)	0.0218 (10)
C21	0.6696 (3)	0.1405 (2)	0.4607 (3)	0.0157 (9)
C246	0.9151 (3)	0.0725 (2)	0.7220 (3)	0.0197 (10)
H24A	0.9224	0.0466	0.6710	0.024*
C23	0.8826 (3)	0.2165 (2)	0.6004 (3)	0.0186 (9)
H23A	0.9252	0.2569	0.5981	0.028*
H23B	0.8797	0.1941	0.5438	0.028*
H23C	0.9121	0.1859	0.6449	0.028*
C231	0.7582 (3)	0.3072 (2)	0.6305 (3)	0.0158 (9)
C232	0.6668 (4)	0.3381 (3)	0.5922 (3)	0.0202 (10)
H23D	0.6148	0.3111	0.5645	0.024*
C243	0.8935 (4)	0.1479 (3)	0.8756 (3)	0.0286 (12)
H24B	0.8859	0.1729	0.9272	0.034*
C242	0.8124 (4)	0.1458 (2)	0.8104 (3)	0.0186 (9)
H24C	0.7507	0.1694	0.8188	0.022*
C236	0.8343 (4)	0.3489 (2)	0.6720 (3)	0.0200 (10)
H23E	0.8945	0.3293	0.6984	0.024*
C235	0.8212 (4)	0.4195 (3)	0.6744 (3)	0.0292 (12)
H23F	0.8730	0.4466	0.7023	0.035*
C234	0.7323 (4)	0.4501 (3)	0.6359 (3)	0.0282 (12)
H23G	0.7247	0.4975	0.6369	0.034*
C233	0.6546 (4)	0.4089 (3)	0.5958 (3)	0.0256 (11)
H23H	0.5938	0.4289	0.5712	0.031*
C245	0.9958 (4)	0.0747 (3)	0.7867 (4)	0.0292 (12)
H24D	1.0572	0.0508	0.7787	0.035*
C244	0.9856 (4)	0.1127 (3)	0.8639 (3)	0.0283 (12)
H24E	1.0401	0.1143	0.9071	0.034*
C24	0.7110 (5)	0.0406 (3)	0.6298 (4)	0.0377 (15)
H24F	0.7568	0.0065	0.6562	0.057*
H24G	0.7150	0.0396	0.5665	0.057*
H24H	0.6405	0.0313	0.6445	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0101 (5)	0.0170 (6)	0.0141 (5)	0.0013 (4)	0.0009 (4)	−0.0008 (4)
Cl11	0.0343 (6)	0.0281 (6)	0.0160 (6)	−0.0131 (5)	0.0028 (5)	−0.0025 (5)
Cl12	0.0538 (9)	0.0416 (8)	0.0167 (6)	−0.0202 (7)	0.0116 (6)	0.0007 (6)
Cl13	0.0501 (8)	0.0352 (7)	0.0235 (6)	0.0177 (7)	−0.0046 (6)	0.0018 (6)
O11	0.0131 (14)	0.0230 (17)	0.0154 (15)	0.0037 (13)	0.0022 (12)	0.0021 (13)
N12	0.0096 (17)	0.0166 (19)	0.024 (2)	−0.0009 (15)	0.0042 (15)	−0.0009 (16)
N13	0.0184 (19)	0.018 (2)	0.0180 (19)	0.0055 (16)	0.0004 (15)	−0.0008 (16)
N11	0.0138 (18)	0.027 (2)	0.0139 (18)	−0.0017 (16)	0.0012 (15)	0.0016 (16)
C131	0.022 (2)	0.013 (2)	0.012 (2)	−0.0011 (18)	0.0037 (17)	−0.0048 (17)
C12	0.028 (2)	0.020 (2)	0.011 (2)	−0.006 (2)	0.0058 (18)	−0.0021 (18)
C141	0.017 (2)	0.021 (2)	0.015 (2)	0.0052 (18)	−0.0025 (17)	−0.0057 (18)
C142	0.022 (2)	0.020 (2)	0.020 (2)	0.0019 (19)	−0.0003 (19)	−0.0003 (19)
C132	0.016 (2)	0.019 (2)	0.020 (2)	0.0038 (18)	−0.0027 (18)	−0.0049 (19)
O12	0.0237 (18)	0.045 (2)	0.0250 (19)	−0.0120 (17)	0.0089 (15)	0.0000 (17)
C11	0.018 (2)	0.023 (2)	0.018 (2)	−0.0042 (19)	0.0045 (18)	−0.0016 (19)
C146	0.022 (2)	0.020 (2)	0.023 (2)	−0.0019 (19)	0.0037 (19)	−0.001 (2)
C13	0.011 (2)	0.020 (2)	0.028 (2)	0.0007 (18)	0.0060 (18)	−0.004 (2)
C133	0.022 (2)	0.023 (3)	0.028 (3)	−0.003 (2)	−0.003 (2)	−0.004 (2)
C145	0.025 (3)	0.016 (2)	0.035 (3)	−0.001 (2)	−0.006 (2)	−0.005 (2)
C144	0.029 (3)	0.026 (3)	0.029 (3)	0.009 (2)	−0.010 (2)	−0.010 (2)
C136	0.020 (2)	0.030 (3)	0.023 (3)	0.002 (2)	−0.004 (2)	0.000 (2)
C134	0.035 (3)	0.023 (3)	0.026 (3)	−0.004 (2)	0.002 (2)	0.001 (2)
C135	0.029 (3)	0.018 (2)	0.030 (3)	0.005 (2)	−0.004 (2)	0.004 (2)
C143	0.029 (3)	0.031 (3)	0.016 (2)	0.007 (2)	0.001 (2)	0.001 (2)
C14	0.070 (4)	0.018 (3)	0.050 (4)	0.008 (3)	−0.036 (3)	−0.003 (3)
P2	0.0119 (5)	0.0167 (6)	0.0121 (5)	−0.0011 (4)	0.0019 (4)	−0.0004 (4)
Cl21	0.0445 (8)	0.0346 (7)	0.0148 (6)	0.0109 (6)	0.0077 (5)	−0.0020 (5)
Cl22	0.0254 (6)	0.0321 (6)	0.0255 (6)	−0.0047 (5)	−0.0026 (5)	−0.0060 (6)
Cl23	0.0440 (8)	0.0250 (6)	0.0190 (6)	0.0131 (6)	−0.0002 (5)	0.0036 (5)
O21	0.0132 (15)	0.0270 (18)	0.0137 (15)	−0.0029 (13)	0.0026 (12)	−0.0028 (13)
N22	0.0092 (16)	0.0137 (18)	0.022 (2)	0.0001 (14)	0.0035 (14)	0.0001 (15)
N23	0.0163 (18)	0.0181 (19)	0.0143 (18)	0.0005 (15)	−0.0014 (15)	−0.0018 (15)
N21	0.0102 (17)	0.027 (2)	0.0108 (18)	−0.0024 (15)	0.0007 (14)	−0.0025 (15)
O22	0.0184 (17)	0.040 (2)	0.0163 (16)	0.0067 (15)	0.0070 (13)	−0.0031 (15)
C241	0.018 (2)	0.012 (2)	0.022 (2)	−0.0018 (18)	0.0010 (18)	0.0049 (18)
C22	0.024 (2)	0.021 (2)	0.019 (2)	0.002 (2)	0.0006 (19)	−0.0039 (19)
C21	0.015 (2)	0.019 (2)	0.013 (2)	−0.0021 (18)	0.0012 (17)	0.0024 (17)
C246	0.021 (2)	0.016 (2)	0.022 (2)	0.0041 (19)	−0.0019 (19)	−0.0015 (19)
C23	0.012 (2)	0.019 (2)	0.025 (2)	−0.0022 (18)	0.0021 (18)	0.0058 (19)
C231	0.016 (2)	0.020 (2)	0.013 (2)	0.0018 (18)	0.0052 (17)	0.0018 (17)
C232	0.016 (2)	0.027 (3)	0.018 (2)	0.0048 (19)	0.0019 (18)	0.0055 (19)
C243	0.034 (3)	0.030 (3)	0.020 (3)	−0.007 (2)	−0.008 (2)	0.000 (2)
C242	0.021 (2)	0.017 (2)	0.018 (2)	0.0008 (19)	0.0017 (18)	0.0022 (18)
C236	0.026 (2)	0.021 (2)	0.013 (2)	−0.002 (2)	−0.0007 (18)	0.0002 (18)
C235	0.045 (3)	0.019 (3)	0.023 (3)	−0.009 (2)	0.002 (2)	−0.007 (2)
C234	0.050 (3)	0.015 (2)	0.020 (2)	0.004 (2)	0.008 (2)	0.003 (2)
C233	0.035 (3)	0.024 (3)	0.018 (2)	0.010 (2)	0.006 (2)	0.004 (2)
C245	0.025 (3)	0.027 (3)	0.035 (3)	0.008 (2)	−0.002 (2)	0.009 (2)
C244	0.030 (3)	0.028 (3)	0.026 (3)	−0.004 (2)	−0.011 (2)	0.003 (2)
C24	0.058 (4)	0.019 (3)	0.033 (3)	−0.006 (3)	−0.023 (3)	0.000 (2)

Geometric parameters (Å, º) top

P1—O11	1.483 (3)	P2—O21	1.478 (3)
P1—N13	1.639 (4)	P2—N23	1.634 (4)
P1—N12	1.649 (4)	P2—N22	1.645 (4)
P1—N11	1.684 (4)	P2—N21	1.698 (4)
Cl11—C12	1.763 (5)	Cl21—C22	1.749 (5)
Cl12—C12	1.763 (5)	Cl22—C22	1.795 (5)
Cl13—C12	1.780 (5)	Cl23—C22	1.771 (5)
N12—C131	1.421 (6)	N22—C231	1.413 (6)
N12—C13	1.482 (5)	N22—C23	1.478 (5)
N13—C141	1.444 (6)	N23—C241	1.424 (6)
N13—C14	1.469 (6)	N23—C24	1.466 (6)
N11—C11	1.359 (6)	N21—C21	1.353 (5)
N11—H11B	0.8600	N21—H21B	0.8600
C131—C136	1.388 (6)	O22—C21	1.203 (5)
C131—C132	1.419 (6)	C241—C242	1.396 (6)
C12—C11	1.570 (7)	C241—C246	1.396 (6)
C141—C142	1.388 (6)	C22—C21	1.555 (6)
C141—C146	1.388 (6)	C246—C245	1.382 (7)
C142—C143	1.385 (7)	C246—H24A	0.9300
C142—H14A	0.9300	C23—H23A	0.9600
C132—C133	1.379 (7)	C23—H23B	0.9600
C132—H13A	0.9300	C23—H23C	0.9600
O12—C11	1.203 (6)	C231—C236	1.391 (6)
C146—C145	1.386 (7)	C231—C232	1.412 (6)
C146—H14B	0.9300	C232—C233	1.393 (7)
C13—H13B	0.9600	C232—H23D	0.9300
C13—H13C	0.9600	C243—C244	1.387 (8)
C13—H13D	0.9600	C243—C242	1.391 (6)
C133—C134	1.399 (7)	C243—H24B	0.9300
C133—H13E	0.9300	C242—H24C	0.9300
C145—C144	1.412 (8)	C236—C235	1.389 (7)
C145—H14C	0.9300	C236—H23E	0.9300
C144—C143	1.371 (7)	C235—C234	1.385 (8)
C144—H14D	0.9300	C235—H23F	0.9300
C136—C135	1.376 (7)	C234—C233	1.392 (7)
C136—H13F	0.9300	C234—H23G	0.9300
C134—C135	1.386 (7)	C233—H23H	0.9300
C134—H13G	0.9300	C245—C244	1.395 (7)
C135—H13H	0.9300	C245—H24D	0.9300
C143—H14E	0.9300	C244—H24E	0.9300
C14—H14F	0.9600	C24—H24F	0.9600
C14—H14G	0.9600	C24—H24G	0.9600
C14—H14H	0.9600	C24—H24H	0.9600

O11—P1—N13	118.48 (19)	O21—P2—N23	119.01 (19)
O11—P1—N12	111.25 (19)	O21—P2—N22	111.15 (19)
N13—P1—N12	105.49 (19)	N23—P2—N22	105.29 (19)
O11—P1—N11	105.88 (18)	O21—P2—N21	105.39 (18)
N13—P1—N11	104.5 (2)	N23—P2—N21	105.18 (19)
N12—P1—N11	111.0 (2)	N22—P2—N21	110.60 (19)
C131—N12—C13	115.6 (4)	C231—N22—C23	115.3 (3)
C131—N12—P1	121.8 (3)	C231—N22—P2	122.2 (3)
C13—N12—P1	122.5 (3)	C23—N22—P2	122.5 (3)
C141—N13—C14	116.3 (4)	C241—N23—C24	115.4 (4)
C141—N13—P1	120.0 (3)	C241—N23—P2	120.7 (3)
C14—N13—P1	123.6 (3)	C24—N23—P2	123.5 (3)
C11—N11—P1	125.3 (3)	C21—N21—P2	124.9 (3)
C11—N11—H11B	117.3	C21—N21—H21B	117.5
P1—N11—H11B	117.3	P2—N21—H21B	117.5
C136—C131—C132	118.8 (4)	C242—C241—C246	118.9 (4)
C136—C131—N12	120.3 (4)	C242—C241—N23	121.3 (4)
C132—C131—N12	120.8 (4)	C246—C241—N23	119.8 (4)
C11—C12—Cl11	109.5 (3)	C21—C22—Cl21	111.7 (3)
C11—C12—Cl12	110.2 (3)	C21—C22—Cl23	109.1 (3)
Cl11—C12—Cl12	109.5 (2)	Cl21—C22—Cl23	109.6 (3)
C11—C12—Cl13	109.0 (3)	C21—C22—Cl22	108.7 (3)
Cl11—C12—Cl13	109.9 (3)	Cl21—C22—Cl22	108.6 (3)
Cl12—C12—Cl13	108.7 (3)	Cl23—C22—Cl22	109.0 (3)
C142—C141—C146	119.8 (4)	O22—C21—N21	126.7 (4)
C142—C141—N13	120.9 (4)	O22—C21—C22	119.3 (4)
C146—C141—N13	119.2 (4)	N21—C21—C22	114.0 (4)
C143—C142—C141	119.2 (5)	C245—C246—C241	120.5 (5)
C143—C142—H14A	120.4	C245—C246—H24A	119.8
C141—C142—H14A	120.4	C241—C246—H24A	119.8
C133—C132—C131	119.5 (4)	N22—C23—H23A	109.5
C133—C132—H13A	120.3	N22—C23—H23B	109.5
C131—C132—H13A	120.3	H23A—C23—H23B	109.5
O12—C11—N11	126.2 (4)	N22—C23—H23C	109.5
O12—C11—C12	120.4 (4)	H23A—C23—H23C	109.5
N11—C11—C12	113.4 (4)	H23B—C23—H23C	109.5
C145—C146—C141	121.0 (5)	C236—C231—N22	120.0 (4)
C145—C146—H14B	119.5	C236—C231—C232	118.6 (4)
C141—C146—H14B	119.5	N22—C231—C232	121.2 (4)
N12—C13—H13B	109.5	C233—C232—C231	120.0 (5)
N12—C13—H13C	109.5	C233—C232—H23D	120.0
H13B—C13—H13C	109.5	C231—C232—H23D	120.0
N12—C13—H13D	109.5	C244—C243—C242	120.1 (5)
H13B—C13—H13D	109.5	C244—C243—H24B	119.9
H13C—C13—H13D	109.5	C242—C243—H24B	119.9
C132—C133—C134	120.9 (5)	C243—C242—C241	120.5 (5)
C132—C133—H13E	119.5	C243—C242—H24C	119.7
C134—C133—H13E	119.5	C241—C242—H24C	119.7
C146—C145—C144	118.8 (5)	C235—C236—C231	120.6 (5)
C146—C145—H14C	120.6	C235—C236—H23E	119.7
C144—C145—H14C	120.6	C231—C236—H23E	119.7
C143—C144—C145	119.6 (5)	C234—C235—C236	121.0 (5)
C143—C144—H14D	120.2	C234—C235—H23F	119.5
C145—C144—H14D	120.2	C236—C235—H23F	119.5
C135—C136—C131	121.1 (5)	C235—C234—C233	118.9 (5)
C135—C136—H13F	119.5	C235—C234—H23G	120.5
C131—C136—H13F	119.5	C233—C234—H23G	120.5
C135—C134—C133	119.2 (5)	C232—C233—C234	120.8 (5)
C135—C134—H13G	120.4	C232—C233—H23H	119.6
C133—C134—H13G	120.4	C234—C233—H23H	119.6
C136—C135—C134	120.5 (5)	C246—C245—C244	120.4 (5)
C136—C135—H13H	119.8	C246—C245—H24D	119.8
C134—C135—H13H	119.8	C244—C245—H24D	119.8
C144—C143—C142	121.6 (5)	C243—C244—C245	119.5 (5)
C144—C143—H14E	119.2	C243—C244—H24E	120.2
C142—C143—H14E	119.2	C245—C244—H24E	120.2
N13—C14—H14F	109.5	N23—C24—H24F	109.5
N13—C14—H14G	109.5	N23—C24—H24G	109.5
H14F—C14—H14G	109.5	H24F—C24—H24G	109.5
N13—C14—H14H	109.5	N23—C24—H24H	109.5
H14F—C14—H14H	109.5	H24F—C24—H24H	109.5
H14G—C14—H14H	109.5	H24G—C24—H24H	109.5

O11—P1—N12—C131	−28.0 (4)	O21—P2—N22—C231	−25.4 (4)
N13—P1—N12—C131	−157.7 (3)	N23—P2—N22—C231	−155.6 (3)
N11—P1—N12—C131	89.6 (4)	N21—P2—N22—C231	91.3 (4)
O11—P1—N12—C13	155.0 (3)	O21—P2—N22—C23	157.6 (3)
N13—P1—N12—C13	25.3 (4)	N23—P2—N22—C23	27.4 (4)
N11—P1—N12—C13	−87.4 (4)	N21—P2—N22—C23	−85.7 (4)
O11—P1—N13—C141	−76.1 (4)	O21—P2—N23—C241	−78.4 (4)
N12—P1—N13—C141	49.2 (4)	N22—P2—N23—C241	47.0 (4)
N11—P1—N13—C141	166.4 (3)	N21—P2—N23—C241	163.9 (3)
O11—P1—N13—C14	100.7 (5)	O21—P2—N23—C24	94.6 (4)
N12—P1—N13—C14	−134.0 (5)	N22—P2—N23—C24	−140.0 (4)
N11—P1—N13—C14	−16.8 (5)	N21—P2—N23—C24	−23.1 (5)
O11—P1—N11—C11	175.3 (4)	O21—P2—N21—C21	174.9 (4)
N13—P1—N11—C11	−58.8 (4)	N23—P2—N21—C21	−58.6 (4)
N12—P1—N11—C11	54.4 (4)	N22—P2—N21—C21	54.6 (4)
C13—N12—C131—C136	−39.0 (6)	C24—N23—C241—C242	−130.4 (5)
P1—N12—C131—C136	143.8 (4)	P2—N23—C241—C242	43.1 (6)
C13—N12—C131—C132	137.3 (4)	C24—N23—C241—C246	51.1 (6)
P1—N12—C131—C132	−39.9 (6)	P2—N23—C241—C246	−135.4 (4)
C14—N13—C141—C142	−131.8 (5)	P2—N21—C21—O22	8.5 (7)
P1—N13—C141—C142	45.3 (5)	P2—N21—C21—C22	−170.9 (3)
C14—N13—C141—C146	49.2 (6)	Cl21—C22—C21—O22	1.8 (6)
P1—N13—C141—C146	−133.7 (4)	Cl23—C22—C21—O22	−119.6 (4)
C146—C141—C142—C143	0.2 (7)	Cl22—C22—C21—O22	121.6 (4)
N13—C141—C142—C143	−178.8 (4)	Cl21—C22—C21—N21	−178.7 (3)
C136—C131—C132—C133	0.6 (7)	Cl23—C22—C21—N21	59.9 (5)
N12—C131—C132—C133	−175.7 (4)	Cl22—C22—C21—N21	−58.9 (5)
P1—N11—C11—O12	3.4 (8)	C242—C241—C246—C245	−1.5 (7)
P1—N11—C11—C12	−175.9 (3)	N23—C241—C246—C245	177.0 (4)
Cl11—C12—C11—O12	−120.4 (5)	C23—N22—C231—C236	−40.6 (6)
Cl12—C12—C11—O12	0.1 (6)	P2—N22—C231—C236	142.1 (4)
Cl13—C12—C11—O12	119.3 (5)	C23—N22—C231—C232	135.6 (4)
Cl11—C12—C11—N11	59.0 (5)	P2—N22—C231—C232	−41.6 (6)
Cl12—C12—C11—N11	179.5 (3)	C236—C231—C232—C233	0.5 (7)
Cl13—C12—C11—N11	−61.3 (5)	N22—C231—C232—C233	−175.8 (4)
C142—C141—C146—C145	−0.6 (7)	C244—C243—C242—C241	−0.2 (7)
N13—C141—C146—C145	178.5 (4)	C246—C241—C242—C243	1.3 (7)
C131—C132—C133—C134	0.2 (7)	N23—C241—C242—C243	−177.2 (4)
C141—C146—C145—C144	0.9 (7)	N22—C231—C236—C235	175.3 (4)
C146—C145—C144—C143	−1.0 (7)	C232—C231—C236—C235	−1.0 (7)
C132—C131—C136—C135	0.0 (7)	C231—C236—C235—C234	0.2 (8)
N12—C131—C136—C135	176.3 (4)	C236—C235—C234—C233	1.2 (8)
C132—C133—C134—C135	−1.6 (8)	C231—C232—C233—C234	0.9 (7)
C131—C136—C135—C134	−1.4 (8)	C235—C234—C233—C232	−1.7 (7)
C133—C134—C135—C136	2.2 (8)	C241—C246—C245—C244	0.7 (8)
C145—C144—C143—C142	0.7 (8)	C242—C243—C244—C245	−0.6 (8)
C141—C142—C143—C144	−0.3 (7)	C246—C245—C244—C243	0.4 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11B···O21	0.86	1.91	2.741 (5)	161
N21—H21B···O11	0.86	1.93	2.752 (5)	159

Experimental details

Crystal data
Chemical formula	C₁₆H₁₇Cl₃N₃O₂P
M_r	420.65
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	12.8226 (10), 19.5161 (15), 15.1132 (12)
β (°)	93.345 (6)
V (Å³)	3775.6 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.59
Crystal size (mm)	0.40 × 0.20 × 0.05

Data collection
Diffractometer	Oxford Diffraction Xcalibur3
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.800, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	37663, 8168, 6768
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.094, 0.174, 1.16
No. of reflections	8168
No. of parameters	451
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.50

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11B···O21	0.86	1.91	2.741 (5)	161.0
N21—H21B···O11	0.86	1.93	2.752 (5)	158.9

Acknowledgements

The authors thank the Fundamental Researchers State Fund of Ukraine for partial support of this research.

References

Amirkhanov, V., Sieler, J., Trush, V., Ovchynnikov, V. & Domasevitch, K. (1997). Z. Naturforsch. Teil B, 52, 1194–1198. CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Gholivand, K., Alizadehgan, A., Mojahed, F. & Soleimani, P. (2008a). Polyhedron, 27, 1639–1649. Web of Science CSD CrossRef CAS Google Scholar
Gholivand, K., Vedova, C., Erben, M., Mahzouni, H., Shariatinia, Z. & Amiri, S. (2008b). J. Mol. Struct. 874, 178–186. Web of Science CSD CrossRef CAS Google Scholar
Gubina, K., Ovchynnikov, V., Amirkhanov, V., Sliva, T., Skopenko, V., Głowiak, T. & Kozłowski, H. (1999). Z. Naturforsch. Teil B, 54, 1357–1359. CAS Google Scholar
Gubina, K., Ovchynnikov, V., Świątek-Kozłowska, J., Amirkhanov, V., Sliva, T. & Domasevitch, K. (2002). Polyhedron, 21, 963–967. Web of Science CSD CrossRef CAS Google Scholar
Helm, M., Katz, T., Imioczyk, R., Hands, R. & Norman, A. (1999). Inorg. Chem. 38, 3167–3172. Web of Science CrossRef CAS Google Scholar
Jaroslav, K. & Swetdloff, F. (1985). US Patent 4 517 003. Google Scholar
Katti, K., Pinkerton, A. & Cavell, R. (1991). Inorg. Chem. 30, 2631–2633. CSD CrossRef CAS Web of Science Google Scholar
Kirsanov, A. & Derkach, G. (1956). Zh. Obshch. Khim. 26, 2009–2014. CAS Google Scholar
Oczko, G., Legendziewicz, J., Trush, V. & Amirkhanov, V. (2003). New J. Chem. 27, 948–956. Web of Science CSD CrossRef CAS Google Scholar
Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Rebrova, O., Biyushkin, V., Malinovski, T., Ovrucki, V., Procenko, L., Dneprova, T. & Mazus, M. (1982). Dokl. Akad. Nauk USSR, 324, 103–108. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Trush, E., Amirkhanov, V., Ovchynnikov, V., Świątek-Kozłowska, J., Lanikina, K. & Domasevitch, K. (2003). Polyhedron, 22, 1221–1229. Web of Science CSD CrossRef CAS Google Scholar