N-Benzyl-2-propanaminium O-methyl trichloro­acetamido­phosphate

The title compound, C₁₃H₂₀Cl₃N₂O₄P, was prepared by the reaction of N-isopropyl­benzyl­amine and CCl₃C(O)N(H)P(O)Cl₂, followed by crystallization from CH₃OH and CH₃CN. Centrosymmetric dimers of anions are hydrogen-bonded to neighbouring cations (via –P—O...H—N– and –C=O...H—N– hydrogen bonds) in a one-dimensional polymeric chain. Furthermore, a Cl...Cl inter­action (3.242 Å) and a C—H...π short contact are present in the crystal structure, the former between two adjacent anions and the latter between two neighbouring cations.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.032
• wR factor = 0.076
• Data-to-parameter ratio = 18.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)         70 Ang.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.05 Ratio
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Phosphate derivatives (XYP(O)O^-, where X, Y = O^-, OH, OR, OAr, NRR', halide ion,···) have attracted significant attention due to their utility in supramolecular chemistry and crystal engineering and their ability as the metal complexing agents (Wisser & Janiak, 2007; Ślepokura & Lis, 2006). There is a little reports on N-acylated phosphate derivatives, RC(O)N(H)P(O)R¹O^- (Gholivand et al., 2005) but the investigation about this area are of special interest in this context: 1) having an ionic structure and possibility the exchange of cation to obtain desirable solubility and hydrophobicity which is required to bio-study 2) bearing a close structural resemblance to the β-diketone frame, 3) usually acting as effective chelating groups (Amirkhanov et al., 1997). In previous works, we report on the structure of phosphate compounds containing PO₂Cl₂^- (Gholivand & Pourayoubi, 2004) and CF₃C(O)N(H)P(O)(O)[NH(tert,-C₄H₉]^- anions (Gholivand et al., 2005).

Here, we report the crystal structure of the title compound, N-Benzyl-2-propanaminium O-methyl trichloroacetamidophosphate (Fig. 1). Phosphorus atom in the anion of title compound has a distorted tetrahedral geometry. Centrosymmetric dimmers of anions which is produced via two equal N1—H1N···O2ⁱⁱ hydrogen bonds (Table 1 and Fig. 2) are hydrogen bonded to neighboring cations in a one-dimensional polymeric chain. Furthermore, the crystal packing is stabilized by Cl···Cl (distance 3.242 Å) electrostatic interaction and C—H···π short contact between a hydrogen of the C4 and the phenyl group (Table 1 and Fig. 2, the centroid of the C5–C10 phenyl ring and the symmetry codes are as in Fig. 2).

Related literature

For related literature, see: Amirkhanov et al. (1997); Gholivand & Pourayoubi (2004); Gholivand et al. (2005); Kirsanov & Makitra (1956); Sheldrick (1997); Wisser & Janiak (2007); Ślepokura & Lis (2006).

S2. Experimental

N-isopropylbenzylamine (1.133 g, 7.594 mmol) was added to a solution of CCl₃C(O)N(H)P(O)Cl₂ (0.530 g, 1.899 mmol) (Kirsanov & Makitra, 1956) in CCl₄ (20 ml) and stirred at 273 K. After 12 h, the solvent removed and the residue that formed was stirred with H₂O. After drying, the solid was recrystallized from CH₃OH and CH₃CN.

S3. Refinement

The hydrogen atoms of NH and NH₂ groups were located in difference Fourier maps and the all parameters were freely refined. All H atoms of C were geometrically located in ideal positions and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms, 0.98 Å for methyl H atoms, and 0.99 Å for methylene H atoms, and with U_iso(H) = 1.2U_eq(C) for aromatic and methylene H atoms and 1.5Ueq(C) for methyl H atoms.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL (Bruker, 2005).

Figures

	Fig. 1. Structure of title compound showing the atom-labeling scheme with thermal ellipsoid at 50% probability.
	Fig. 2. The N—H···O hydrogen bonds, Cl···Cl and C—H···π interations (dotted lines) in the title compound. [Symmetry code: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 2, -y + 2, -z + 1; (iii) -x + 2, -y + 2, -z; (iv) -x + 2, -y + 1, -z.]

N-Benzyl-2-propanaminium O-methyl trichloroacetamidophosphate

Crystal data

C13H20Cl3N2O4P	Z = 2
Mr = 405.63	F(000) = 420
Triclinic, P1	Dx = 1.461 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5690 (7) Å	Cell parameters from 511 reflections
b = 9.7554 (7) Å	θ = 3–27°
c = 10.5083 (7) Å	µ = 0.60 mm^−1
α = 78.757 (1)°	T = 120 K
β = 73.902 (1)°	Prism, colourless
γ = 83.115 (2)°	0.35 × 0.20 × 0.20 mm
V = 922.14 (11) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	4012 independent reflections
Radiation source: fine-focus sealed tube	3317 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 10.0 pixels mm^-1	θmax = 27.0°, θmin = 2.1°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 1999)	k = −12→12
Tmin = 0.817, Tmax = 0.889	l = −13→13
7569 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0303P)^2 + 0.4098P] where P = (Fo^2 + 2Fc^2)/3
4012 reflections	(Δ/σ)max < 0.001
223 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

Experimental. Spectroscopic analysis: IR (KBr, cm^-1) 3417, 3039, 2983, 2940, 2841, 2705, 2434, 1712, 1601, 1469, 1394, 1257, 1233, 1185, 1094, 1057, 865, 810, 749, 676; ³¹P & ¹H-NMR {(D₆)DMSO}: 2.74 (1P). ¹H-NMR ((D₆)DMSO) 1.27 (6H, CH₃), 3.86 (1H, CH), 4.09 (2H, CH₂), 4.31 (3H, OCH₃), 7.10–7.53 (7H, 5 Ar—H & 2 NH), 8.82 (1H, NH); Anal. Calc.: C 38.49, H 4.97, N 6.91. found: C 38.40, H 4.91, N 6.87.

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 (Ų)

	x	y	z	Uiso*/Ueq
P	1.08073 (5)	0.93186 (5)	0.29290 (4)	0.01267 (11)
Cl1	0.80897 (6)	0.61153 (6)	0.65929 (5)	0.02861 (13)
Cl2	0.62282 (5)	0.84713 (5)	0.56791 (5)	0.02585 (12)
Cl3	0.64223 (5)	0.58645 (5)	0.47578 (5)	0.02247 (12)
O1	1.04164 (14)	0.95140 (13)	0.16261 (12)	0.0156 (3)
O2	1.10748 (15)	1.05510 (14)	0.34305 (12)	0.0203 (3)
O3	1.21581 (14)	0.81854 (14)	0.28100 (13)	0.0216 (3)
O4	0.90319 (14)	0.68874 (13)	0.30462 (12)	0.0179 (3)
N1	0.94452 (17)	0.85137 (16)	0.41709 (15)	0.0156 (3)
H1N	0.923 (2)	0.882 (2)	0.492 (2)	0.028 (6)*
N2	0.87102 (16)	0.83093 (15)	0.04059 (15)	0.0120 (3)
H2NB	0.923 (2)	0.844 (2)	0.100 (2)	0.019 (5)*
H2NA	0.896 (2)	0.899 (2)	−0.030 (2)	0.024 (6)*
C1	0.87439 (19)	0.74740 (18)	0.40134 (16)	0.0133 (4)
C2	0.7413 (2)	0.70091 (19)	0.52235 (17)	0.0165 (4)
C3	1.2809 (3)	0.7801 (3)	0.3920 (3)	0.0404 (6)
H3A	1.3707	0.7208	0.3658	0.061*
H3B	1.2126	0.7284	0.4688	0.061*
H3C	1.3038	0.8648	0.4170	0.061*
C4	0.9180 (2)	0.69270 (18)	−0.00419 (18)	0.0166 (4)
H4A	0.8734	0.6864	−0.0772	0.020*
H4B	0.8822	0.6169	0.0718	0.020*
C5	1.0810 (2)	0.67174 (18)	−0.05357 (17)	0.0147 (4)
C6	1.1466 (2)	0.68353 (19)	−0.19101 (18)	0.0181 (4)
H6A	1.0887	0.7080	−0.2534	0.022*
C7	1.2966 (2)	0.6595 (2)	−0.23676 (19)	0.0222 (4)
H7A	1.3409	0.6668	−0.3305	0.027*
C8	1.3821 (2)	0.6250 (2)	−0.14661 (19)	0.0217 (4)
H8A	1.4847	0.6082	−0.1783	0.026*
C9	1.3171 (2)	0.6150 (2)	−0.00961 (19)	0.0205 (4)
H9A	1.3754	0.5918	0.0525	0.025*
C10	1.1677 (2)	0.63857 (18)	0.03649 (18)	0.0164 (4)
H10A	1.1238	0.6321	0.1302	0.020*
C11	0.71066 (19)	0.84825 (19)	0.10844 (18)	0.0164 (4)
H11A	0.6871	0.7726	0.1888	0.020*
C12	0.6802 (2)	0.9887 (2)	0.1561 (2)	0.0227 (4)
H12A	0.7401	0.9921	0.2173	0.034*
H12B	0.5768	1.0006	0.2033	0.034*
H12C	0.7039	1.0641	0.0785	0.034*
C13	0.6198 (2)	0.8340 (2)	0.0142 (2)	0.0236 (4)
H13A	0.6363	0.7388	−0.0066	0.035*
H13B	0.6483	0.9016	−0.0690	0.035*
H13C	0.5163	0.8525	0.0576	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P	0.0146 (2)	0.0143 (2)	0.0096 (2)	−0.00439 (18)	−0.00358 (17)	−0.00053 (17)
Cl1	0.0312 (3)	0.0351 (3)	0.0186 (2)	−0.0134 (2)	−0.0111 (2)	0.0109 (2)
Cl2	0.0193 (3)	0.0232 (3)	0.0332 (3)	−0.00429 (19)	0.0020 (2)	−0.0118 (2)
Cl3	0.0223 (3)	0.0209 (2)	0.0264 (2)	−0.01088 (19)	−0.00513 (19)	−0.00544 (19)
O1	0.0198 (7)	0.0157 (6)	0.0122 (6)	−0.0049 (5)	−0.0055 (5)	−0.0007 (5)
O2	0.0270 (8)	0.0215 (7)	0.0140 (6)	−0.0128 (6)	−0.0035 (5)	−0.0027 (5)
O3	0.0174 (7)	0.0226 (7)	0.0234 (7)	0.0012 (6)	−0.0071 (6)	0.0003 (6)
O4	0.0233 (7)	0.0167 (7)	0.0145 (6)	−0.0043 (5)	−0.0043 (5)	−0.0039 (5)
N1	0.0201 (8)	0.0174 (8)	0.0102 (7)	−0.0073 (6)	−0.0026 (6)	−0.0027 (6)
N2	0.0141 (8)	0.0103 (7)	0.0118 (7)	−0.0013 (6)	−0.0044 (6)	−0.0008 (6)
C1	0.0147 (9)	0.0129 (8)	0.0126 (8)	−0.0019 (7)	−0.0060 (7)	0.0013 (7)
C2	0.0187 (10)	0.0160 (9)	0.0155 (8)	−0.0053 (7)	−0.0045 (7)	−0.0018 (7)
C3	0.0419 (15)	0.0336 (13)	0.0541 (15)	0.0008 (11)	−0.0358 (13)	0.0048 (11)
C4	0.0175 (9)	0.0127 (9)	0.0211 (9)	−0.0002 (7)	−0.0059 (7)	−0.0059 (7)
C5	0.0157 (9)	0.0095 (8)	0.0192 (9)	−0.0006 (7)	−0.0033 (7)	−0.0055 (7)
C6	0.0218 (10)	0.0168 (9)	0.0173 (9)	0.0001 (8)	−0.0066 (8)	−0.0051 (7)
C7	0.0250 (11)	0.0225 (10)	0.0167 (9)	−0.0021 (8)	0.0005 (8)	−0.0057 (8)
C8	0.0165 (10)	0.0189 (10)	0.0265 (10)	0.0023 (8)	−0.0019 (8)	−0.0036 (8)
C9	0.0196 (10)	0.0188 (10)	0.0237 (10)	0.0020 (8)	−0.0097 (8)	−0.0016 (8)
C10	0.0197 (10)	0.0136 (9)	0.0147 (8)	−0.0007 (7)	−0.0027 (7)	−0.0026 (7)
C11	0.0130 (9)	0.0166 (9)	0.0183 (9)	0.0008 (7)	−0.0029 (7)	−0.0025 (7)
C12	0.0182 (10)	0.0223 (10)	0.0286 (10)	0.0054 (8)	−0.0055 (8)	−0.0117 (8)
C13	0.0172 (10)	0.0255 (11)	0.0318 (11)	0.0014 (8)	−0.0108 (8)	−0.0088 (9)

Geometric parameters (Å, º)

P—O2	1.478 (1)	C4—H4B	0.9900
P—O1	1.489 (1)	C5—C10	1.393 (2)
P—O3	1.591 (1)	C5—C6	1.394 (2)
P—N1	1.709 (2)	C6—C7	1.388 (3)
Cl1—C2	1.772 (2)	C6—H6A	0.9500
Cl2—C2	1.768 (2)	C7—C8	1.386 (3)
Cl3—C2	1.764 (2)	C7—H7A	0.9500
O3—C3	1.437 (2)	C8—C9	1.390 (3)
O4—C1	1.212 (2)	C8—H8A	0.9500
N1—C1	1.340 (2)	C9—C10	1.383 (3)
N1—H1N	0.86 (2)	C9—H9A	0.9500
N2—C4	1.492 (2)	C10—H10A	0.9500
N2—C11	1.507 (2)	C11—C12	1.518 (3)
N2—H2NB	0.93 (2)	C11—C13	1.522 (2)
N2—H2NA	0.89 (2)	C11—H11A	1.0000
C1—C2	1.568 (2)	C12—H12A	0.9800
C3—H3A	0.9800	C12—H12B	0.9800
C3—H3B	0.9800	C12—H12C	0.9800
C3—H3C	0.9800	C13—H13A	0.9800
C4—C5	1.503 (3)	C13—H13B	0.9800
C4—H4A	0.9900	C13—H13C	0.9800
O2—P—O1	119.68 (7)	C10—C5—C6	119.34 (17)
O2—P—O3	111.84 (8)	C10—C5—C4	120.82 (16)
O1—P—O3	105.46 (7)	C6—C5—C4	119.83 (16)
O2—P—N1	105.49 (8)	C7—C6—C5	120.01 (17)
O1—P—N1	108.94 (7)	C7—C6—H6A	120.0
O3—P—N1	104.44 (8)	C5—C6—H6A	120.0
C3—O3—P	118.41 (14)	C8—C7—C6	120.40 (18)
C1—N1—P	123.40 (13)	C8—C7—H7A	119.8
C1—N1—H1N	121.3 (15)	C6—C7—H7A	119.8
P—N1—H1N	115.3 (15)	C7—C8—C9	119.67 (18)
C4—N2—C11	113.87 (13)	C7—C8—H8A	120.2
C4—N2—H2NB	110.0 (13)	C9—C8—H8A	120.2
C11—N2—H2NB	108.1 (13)	C10—C9—C8	120.13 (17)
C4—N2—H2NA	109.0 (14)	C10—C9—H9A	119.9
C11—N2—H2NA	110.7 (14)	C8—C9—H9A	119.9
H2NB—N2—H2NA	104.8 (18)	C9—C10—C5	120.43 (17)
O4—C1—N1	126.73 (16)	C9—C10—H10A	119.8
O4—C1—C2	118.51 (15)	C5—C10—H10A	119.8
N1—C1—C2	114.75 (15)	N2—C11—C12	108.21 (14)
C1—C2—Cl3	109.39 (12)	N2—C11—C13	110.70 (15)
C1—C2—Cl2	110.96 (12)	C12—C11—C13	112.64 (16)
Cl3—C2—Cl2	108.20 (10)	N2—C11—H11A	108.4
C1—C2—Cl1	108.37 (12)	C12—C11—H11A	108.4
Cl3—C2—Cl1	109.21 (10)	C13—C11—H11A	108.4
Cl2—C2—Cl1	110.69 (10)	C11—C12—H12A	109.5
O3—C3—H3A	109.5	C11—C12—H12B	109.5
O3—C3—H3B	109.5	H12A—C12—H12B	109.5
H3A—C3—H3B	109.5	C11—C12—H12C	109.5
O3—C3—H3C	109.5	H12A—C12—H12C	109.5
H3A—C3—H3C	109.5	H12B—C12—H12C	109.5
H3B—C3—H3C	109.5	C11—C13—H13A	109.5
N2—C4—C5	112.12 (14)	C11—C13—H13B	109.5
N2—C4—H4A	109.2	H13A—C13—H13B	109.5
C5—C4—H4A	109.2	C11—C13—H13C	109.5
N2—C4—H4B	109.2	H13A—C13—H13C	109.5
C5—C4—H4B	109.2	H13B—C13—H13C	109.5
H4A—C4—H4B	107.9
O2—P—O3—C3	46.85 (16)	C11—N2—C4—C5	−172.01 (14)
O1—P—O3—C3	178.48 (14)	N2—C4—C5—C10	76.1 (2)
N1—P—O3—C3	−66.75 (16)	N2—C4—C5—C6	−104.87 (18)
O2—P—N1—C1	169.64 (15)	C10—C5—C6—C7	1.3 (3)
O1—P—N1—C1	39.97 (17)	C4—C5—C6—C7	−177.78 (17)
O3—P—N1—C1	−72.32 (16)	C5—C6—C7—C8	−0.6 (3)
P—N1—C1—O4	6.3 (3)	C6—C7—C8—C9	−0.3 (3)
P—N1—C1—C2	−173.17 (12)	C7—C8—C9—C10	0.4 (3)
O4—C1—C2—Cl3	−9.6 (2)	C8—C9—C10—C5	0.4 (3)
N1—C1—C2—Cl3	169.95 (13)	C6—C5—C10—C9	−1.2 (3)
O4—C1—C2—Cl2	−128.87 (15)	C4—C5—C10—C9	177.87 (16)
N1—C1—C2—Cl2	50.65 (18)	C4—N2—C11—C12	176.53 (14)
O4—C1—C2—Cl1	109.40 (16)	C4—N2—C11—C13	−59.6 (2)
N1—C1—C2—Cl1	−71.08 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···Cg^i	0.99	2.86 (2)	3.635 (2)	135
N1—H1N···O2^ii	0.86 (2)	1.88 (2)	2.743 (2)	175 (2)
N2—H2NB···O1	0.93 (2)	1.95 (2)	2.811 (2)	153 (2)
N2—H2NA···O1^iii	0.89 (2)	1.84 (2)	2.727 (2)	173 (2)
N2—H2NB···O4	0.93 (2)	2.35 (2)	2.930 (2)	120 (2)

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