N,N-Dimethyl-N',N''-bis-(2-methyl-phenyl)phospho-ric triamide mono-hydrate.

In the title compound, C(16)H(22)N(3)OP·H(2)O, the P atom adopts a distorted tetra-hedral 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 [(CH(3))(2)N]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 (CH(3))(2)NP(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 mol-ecules form hydrogen bonds to the O atoms of the P=O bond of two different mol-ecules and act as acceptors for the two amino H atoms of the same mol-ecule. 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 = 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

Δρmax = 0.30 e Å−3

Δρmin = −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 ▶).

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

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

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

C16H22N3OP·H2O	F(000) = 688
Mr = 321.35	Dx = 1.244 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4384 reflections
a = 10.7058 (16) Å	θ = 3.0–28.1°
b = 7.2541 (11) Å	µ = 0.17 mm−1
c = 22.091 (3) Å	T = 100 K
β = 90.971 (2)°	Block, colourless
V = 1715.3 (4) Å3	0.20 × 0.14 × 0.14 mm
Z = 4

Bruker APEXII CCD diffractometer	4036 independent reflections
Radiation source: fine-focus sealed tube	3135 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ and ω scans	θmax = 28.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→13
Tmin = 0.967, Tmax = 0.977	k = −9→9
15201 measured reflections	l = −29→29

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0495P)2 + 0.3428P] where P = (Fo2 + 2Fc2)/3
4036 reflections	(Δ/σ)max < 0.001
215 parameters	Δρmax = 0.30 e Å−3
5 restraints	Δρmin = −0.38 e Å−3

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.

	x	y	z	Uiso*/Ueq
P1	0.30253 (4)	0.63760 (6)	0.045212 (19)	0.02129 (13)
O1W	0.43897 (12)	0.18044 (16)	0.04084 (6)	0.0283 (3)
H1W	0.5043 (15)	0.175 (3)	0.0196 (8)	0.034*
H2W	0.4105 (16)	0.072 (2)	0.0412 (8)	0.034*
N1	0.31522 (13)	0.49375 (19)	−0.01239 (6)	0.0235 (3)
H1N	0.3457 (17)	0.385 (2)	−0.0046 (8)	0.028*
O1	0.35590 (11)	0.82247 (16)	0.03322 (5)	0.0273 (3)
N3	0.15544 (13)	0.6646 (2)	0.06265 (7)	0.0273 (3)
C1	0.39835 (17)	0.6608 (3)	0.28289 (8)	0.0336 (4)
H1	0.4026	0.6910	0.3247	0.040*
C2	0.35064 (16)	0.7858 (3)	0.24143 (8)	0.0314 (4)
H2	0.3230	0.9034	0.2545	0.038*
C3	0.34322 (16)	0.7391 (2)	0.18036 (8)	0.0281 (4)
H3	0.3109	0.8255	0.1518	0.034*
C4	0.38270 (15)	0.5666 (2)	0.16075 (7)	0.0233 (3)
N2	0.37225 (13)	0.5161 (2)	0.09875 (6)	0.0243 (3)
H2N	0.4025 (17)	0.411 (2)	0.0871 (8)	0.029*
C6	0.26974 (15)	0.5277 (2)	−0.07211 (7)	0.0232 (3)
C7	0.27217 (15)	0.3843 (2)	−0.11509 (8)	0.0259 (4)
C8	0.22525 (16)	0.4208 (3)	−0.17281 (8)	0.0312 (4)
H8	0.2260	0.3251	−0.2022	0.037*
C9	0.17722 (16)	0.5919 (3)	−0.18920 (8)	0.0327 (4)
H9	0.1445	0.6125	−0.2289	0.039*
C10	0.08215 (18)	0.5071 (3)	0.08193 (10)	0.0458 (5)
H10A	0.0604	0.5220	0.1246	0.069*
H10B	0.1311	0.3941	0.0771	0.069*
H10C	0.0055	0.4992	0.0572	0.069*
C11	0.09013 (19)	0.8401 (3)	0.06091 (9)	0.0403 (5)
H11A	0.0206	0.8333	0.0316	0.060*
H11B	0.1480	0.9376	0.0488	0.060*
H11C	0.0578	0.8679	0.1011	0.060*
C12	0.22373 (16)	0.7000 (2)	−0.08851 (8)	0.0266 (4)
H12	0.2236	0.7970	−0.0596	0.032*
C13	0.17799 (16)	0.7313 (3)	−0.14671 (8)	0.0309 (4)
H13	0.1469	0.8498	−0.1574	0.037*
C14	0.32410 (18)	0.1973 (3)	−0.09952 (8)	0.0336 (4)
H14A	0.3166	0.1163	−0.1349	0.050*
H14B	0.2773	0.1445	−0.0660	0.050*
H14C	0.4123	0.2091	−0.0876	0.050*
C15	0.43306 (15)	0.4396 (2)	0.20245 (8)	0.0257 (4)
C16	0.47558 (18)	0.2518 (3)	0.18325 (8)	0.0330 (4)
H16A	0.5079	0.1843	0.2186	0.050*
H16B	0.5417	0.2642	0.1534	0.050*
H16C	0.4049	0.1843	0.1652	0.050*
C17	0.43986 (16)	0.4911 (3)	0.26294 (8)	0.0322 (4)
H17	0.4742	0.4069	0.2916	0.039*

	U11	U22	U33	U12	U13	U23
P1	0.0220 (2)	0.0178 (2)	0.0242 (2)	−0.00113 (16)	0.00295 (16)	−0.00023 (16)
O1W	0.0330 (7)	0.0177 (6)	0.0344 (7)	−0.0005 (5)	0.0081 (5)	−0.0033 (5)
N1	0.0295 (8)	0.0169 (7)	0.0240 (7)	0.0007 (6)	0.0004 (6)	0.0001 (6)
O1	0.0294 (6)	0.0196 (6)	0.0330 (6)	−0.0041 (5)	0.0035 (5)	−0.0014 (5)
N3	0.0232 (7)	0.0259 (8)	0.0331 (8)	0.0014 (6)	0.0046 (6)	0.0030 (6)
C1	0.0321 (10)	0.0433 (11)	0.0252 (9)	−0.0036 (8)	−0.0006 (7)	−0.0073 (8)
C2	0.0260 (9)	0.0334 (10)	0.0347 (10)	−0.0008 (8)	0.0012 (7)	−0.0109 (8)
C3	0.0281 (9)	0.0268 (9)	0.0293 (9)	0.0019 (7)	−0.0020 (7)	−0.0030 (7)
C4	0.0206 (8)	0.0248 (9)	0.0244 (8)	−0.0026 (7)	0.0011 (6)	−0.0020 (7)
N2	0.0283 (7)	0.0203 (7)	0.0244 (7)	0.0022 (6)	0.0012 (6)	−0.0042 (6)
C6	0.0209 (8)	0.0245 (9)	0.0242 (8)	−0.0050 (6)	0.0022 (6)	0.0004 (7)
C7	0.0227 (8)	0.0264 (9)	0.0287 (9)	−0.0049 (7)	0.0037 (7)	−0.0035 (7)
C8	0.0286 (9)	0.0384 (11)	0.0267 (9)	−0.0056 (8)	0.0025 (7)	−0.0057 (8)
C9	0.0270 (9)	0.0453 (12)	0.0258 (9)	−0.0048 (8)	−0.0017 (7)	0.0039 (8)
C10	0.0289 (10)	0.0475 (13)	0.0613 (14)	−0.0055 (9)	0.0109 (9)	0.0170 (11)
C11	0.0372 (11)	0.0417 (12)	0.0422 (11)	0.0157 (9)	0.0084 (9)	0.0062 (9)
C12	0.0268 (9)	0.0239 (9)	0.0293 (9)	−0.0037 (7)	−0.0001 (7)	−0.0001 (7)
C13	0.0278 (9)	0.0299 (10)	0.0350 (10)	−0.0041 (7)	−0.0007 (7)	0.0078 (8)
C14	0.0374 (10)	0.0297 (10)	0.0338 (10)	0.0008 (8)	−0.0007 (8)	−0.0085 (8)
C15	0.0202 (8)	0.0267 (9)	0.0302 (9)	−0.0030 (7)	0.0002 (7)	−0.0004 (7)
C16	0.0391 (10)	0.0288 (10)	0.0310 (9)	0.0033 (8)	−0.0018 (8)	0.0042 (7)
C17	0.0295 (9)	0.0391 (11)	0.0278 (9)	−0.0023 (8)	−0.0035 (7)	0.0006 (8)

P1—O1	1.4833 (12)	C7—C14	1.504 (2)
P1—N3	1.6392 (14)	C8—C9	1.389 (3)
P1—N2	1.6439 (15)	C8—H8	0.9500
P1—N1	1.6530 (14)	C9—C13	1.380 (3)
O1W—H1W	0.850 (14)	C9—H9	0.9500
O1W—H2W	0.841 (14)	C10—H10A	0.9800
N1—C6	1.420 (2)	C10—H10B	0.9800
N1—H1N	0.871 (14)	C10—H10C	0.9800
N3—C11	1.453 (2)	C11—H11A	0.9800
N3—C10	1.454 (2)	C11—H11B	0.9800
C1—C2	1.381 (3)	C11—H11C	0.9800
C1—C17	1.383 (3)	C12—C13	1.387 (2)
C1—H1	0.9500	C12—H12	0.9500
C2—C3	1.392 (2)	C13—H13	0.9500
C2—H2	0.9500	C14—H14A	0.9800
C3—C4	1.392 (2)	C14—H14B	0.9800
C3—H3	0.9500	C14—H14C	0.9800
C4—C15	1.404 (2)	C15—C17	1.388 (2)
C4—N2	1.420 (2)	C15—C16	1.500 (2)
N2—H2N	0.869 (14)	C16—H16A	0.9800
C6—C12	1.389 (2)	C16—H16B	0.9800
C6—C7	1.409 (2)	C16—H16C	0.9800
C7—C8	1.388 (2)	C17—H17	0.9500
O1—P1—N3	107.97 (7)	C13—C9—H9	120.7
O1—P1—N2	116.20 (7)	C8—C9—H9	120.7
N3—P1—N2	108.73 (7)	N3—C10—H10A	109.5
O1—P1—N1	113.35 (7)	N3—C10—H10B	109.5
N3—P1—N1	110.37 (7)	H10A—C10—H10B	109.5
N2—P1—N1	99.98 (7)	N3—C10—H10C	109.5
H1W—O1W—H2W	105.3 (15)	H10A—C10—H10C	109.5
C6—N1—P1	125.07 (12)	H10B—C10—H10C	109.5
C6—N1—H1N	117.5 (12)	N3—C11—H11A	109.5
P1—N1—H1N	117.1 (12)	N3—C11—H11B	109.5
C11—N3—C10	115.75 (15)	H11A—C11—H11B	109.5
C11—N3—P1	124.21 (12)	N3—C11—H11C	109.5
C10—N3—P1	120.03 (12)	H11A—C11—H11C	109.5
C2—C1—C17	119.38 (17)	H11B—C11—H11C	109.5
C2—C1—H1	120.3	C13—C12—C6	120.50 (17)
C17—C1—H1	120.3	C13—C12—H12	119.8
C1—C2—C3	119.80 (17)	C6—C12—H12	119.8
C1—C2—H2	120.1	C9—C13—C12	120.55 (18)
C3—C2—H2	120.1	C9—C13—H13	119.7
C4—C3—C2	120.53 (17)	C12—C13—H13	119.7
C4—C3—H3	119.7	C7—C14—H14A	109.5
C2—C3—H3	119.7	C7—C14—H14B	109.5
C3—C4—C15	120.06 (15)	H14A—C14—H14B	109.5
C3—C4—N2	120.83 (15)	C7—C14—H14C	109.5
C15—C4—N2	119.11 (15)	H14A—C14—H14C	109.5
C4—N2—P1	125.66 (12)	H14B—C14—H14C	109.5
C4—N2—H2N	119.2 (12)	C17—C15—C4	117.90 (16)
P1—N2—H2N	115.1 (12)	C17—C15—C16	120.38 (16)
C12—C6—C7	119.93 (15)	C4—C15—C16	121.70 (15)
C12—C6—N1	120.84 (15)	C15—C16—H16A	109.5
C7—C6—N1	119.23 (15)	C15—C16—H16B	109.5
C8—C7—C6	117.91 (17)	H16A—C16—H16B	109.5
C8—C7—C14	120.57 (16)	C15—C16—H16C	109.5
C6—C7—C14	121.52 (15)	H16A—C16—H16C	109.5
C7—C8—C9	122.43 (17)	H16B—C16—H16C	109.5
C7—C8—H8	118.8	C1—C17—C15	122.30 (18)
C9—C8—H8	118.8	C1—C17—H17	118.8
C13—C9—C8	118.67 (17)	C15—C17—H17	118.8
O1—P1—N1—C6	−55.73 (15)	P1—N1—C6—C7	−171.82 (12)
N3—P1—N1—C6	65.52 (15)	C12—C6—C7—C8	−1.3 (2)
N2—P1—N1—C6	179.92 (13)	N1—C6—C7—C8	178.99 (14)
O1—P1—N3—C11	4.80 (17)	C12—C6—C7—C14	178.50 (16)
N2—P1—N3—C11	131.68 (15)	N1—C6—C7—C14	−1.2 (2)
N1—P1—N3—C11	−119.60 (15)	C6—C7—C8—C9	0.3 (2)
O1—P1—N3—C10	−174.57 (15)	C14—C7—C8—C9	−179.55 (16)
N2—P1—N3—C10	−47.69 (17)	C7—C8—C9—C13	1.0 (3)
N1—P1—N3—C10	61.04 (16)	C7—C6—C12—C13	1.1 (2)
C17—C1—C2—C3	0.9 (3)	N1—C6—C12—C13	−179.17 (15)
C1—C2—C3—C4	0.5 (3)	C8—C9—C13—C12	−1.2 (3)
C2—C3—C4—C15	−1.4 (2)	C6—C12—C13—C9	0.1 (3)
C2—C3—C4—N2	178.28 (15)	C3—C4—C15—C17	1.0 (2)
C3—C4—N2—P1	−6.6 (2)	N2—C4—C15—C17	−178.72 (14)
C15—C4—N2—P1	173.12 (12)	C3—C4—C15—C16	179.43 (16)
O1—P1—N2—C4	61.98 (15)	N2—C4—C15—C16	−0.2 (2)
N3—P1—N2—C4	−60.03 (15)	C2—C1—C17—C15	−1.3 (3)
N1—P1—N2—C4	−175.68 (13)	C4—C15—C17—C1	0.4 (3)
P1—N1—C6—C12	8.5 (2)	C16—C15—C17—C1	−178.08 (17)

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)

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)

Symmetry codes: (i) ; (ii) .