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Acta Crystallogr Sect E Struct Rep Online. 2008 March 1; 64(Pt 3): o633.
Published online 2008 February 27. doi:  10.1107/S1600536808004777
PMCID: PMC2960869

N,N′-Dibenzyl-N′′-(4-bromo­benzo­yl)-N,N′-dimethyl­phospho­ric triamide

Abstract

In the title compound, C23H25BrN3O2P, the P atom has a distorted tetra­hedral coordination. In the crystal structure, the mol­ecules form centrosymmetric dimers via pairs of essentially linear N—H(...)O hydrogen bonds.

Related literature

For the use of carbacyl­amido­phosphate, see: Barak et al. (2000 [triangle]); Burla et al. (1989 [triangle]); Gubina et al. (2000 [triangle]); Mallender et al. (2000 [triangle]); Trush et al. (2003 [triangle]). For related structures, see: Trush et al. (1999 [triangle]).

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Object name is e-64-0o633-scheme1.jpg

Experimental

Crystal data

  • C23H25BrN3O2P
  • M r = 486.34
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o633-efi1.jpg
  • a = 9.0140 (4) Å
  • b = 13.2690 (5) Å
  • c = 19.377 (1) Å
  • β = 94.1500 (14)°
  • V = 2311.54 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.87 mm−1
  • T = 293 (2) K
  • 0.11 × 0.09 × 0.08 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: none
  • 12951 measured reflections
  • 5214 independent reflections
  • 2593 reflections with I > 2σ(I)
  • R int = 0.051

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.135
  • S = 1.00
  • 5214 reflections
  • 271 parameters
  • H-atom parameters constrained
  • Δρmax = 0.27 e Å−3
  • Δρmin = −0.62 e Å−3

Data collection: COLLECT (Nonius, 1998 [triangle]); cell refinement: DENZO (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004777/zl2095sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808004777/zl2095Isup2.hkl

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

Acknowledgments

SD acknowledges the Alzahra University Research Council for partial support of this work.

supplementary crystallographic information

Comment

Carbacylamidophosphate compounds have attracted substantial interest for many years. These compounds have been employed in coordination chemistry as chelating reagents for various metal ions via their =P(O)N(H)C(O)- moiety (Trush et al., 2003; Gubina et al., 2000), as prodrugs in pharmacology and as pesticides in agriculture (Barak et al., 2000; Mallender et al., 2000). A thorough knowledge of the structural properties of these compounds should be beneficial for a detailed understanding of their pharmacological effects. The title compound, (I), was prepared by the reaction of (pBr-C6H5)C(O)NHP(O)(Cl)2 with two molecules of methylmenzyl amine.

The crystal structure of (I) reveals that, in the molecular core unit C(O)NHP(O), the C(O) and P(O) oxygen atoms are in anti-positions to each other. The phosphorus centre has a slightly distorted tetrahedral coordination, mainly due to the presence of the different substituents. The N3–P1–N1 angle (105.20 (12)°) is narrower than the ideal tetrahedral angle of 109.5, whereas the opposite O2–P1–N3 angle (119.05 (13)°) is wider than the ideal tetrahedral angle. The P1–O2 bond length (1.474 (2) Å) is in good agreement with P–O distances in other carbacylamidophosphates (Trush et al., 1999).

Examination of intermolecular distances indicates that the crystal structure of compound (I) consists of C9H13N2O2P units linked together via N—H···O hydrogen bonds into centrosymmetric dimers featuring eight-membered (OPNH)2 rings (Fig.2, Table 1).

Experimental

Compound (I) was synthesized via the reaction of BrC6H4C(O)NHP(O)Cl2 with two molecules of methylbenzylamine in a 1:4 molar ratio. Methylbenzylamine was added dropwise to a mixture of BrC6H4C(O)NHP(O)Cl2 in chloroform while stirring at room temperature for 4 h. The product was filtered off and then washed with cold water. The compound was recrystallized from ethanol (yield 88%). Analysis, calculated for C23 H25 Br N3 O2 P: C 56.80, H 5.18, N 8.64%; found: C 56.81, H 5.19, N 8.64%.

Refinement

H atoms were placed in idealized positions with C—H distances at 0.97, 0.96 and 0.93 Å for CH2, CH3 and aromatic CH groups, respectively using a riding model. Uiso(H) for H was assigned as 1.2 Ueq(Ci) of the attached C atoms (1.5 for methyl). No absorption correction was applied due to the small cystal size and the sufficiently low µ value.

Figures

Fig. 1.
Molecular structure of I showing the atom-labelling scheme with thermal ellipsoids drawn at the 50% probability level.
Fig. 2.
Representation of the hydrogen bonds in the structure of (I). For clarity, only the O2 atom in the second molecule is labeled (O2i), Symmetry code i: 2 - x, 1 - y, -z.

Crystal data

C23H25BrN3O2PF000 = 1000
Mr = 486.34Dx = 1.397 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 10293 reflections
a = 9.0140 (4) Åθ = 1.0–27.5º
b = 13.2690 (5) ŵ = 1.87 mm1
c = 19.3770 (10) ÅT = 293 (2) K
β = 94.1500 (14)ºPrism, colorless
V = 2311.54 (18) Å30.11 × 0.09 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer2593 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.051
Monochromator: graphiteθmax = 27.5º
T = 293(2) Kθmin = 1.9º
π scansh = −11→10
Absorption correction: nonek = −17→14
12951 measured reflectionsl = −17→25
5214 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.135  w = 1/[σ2(Fo2) + (0.052P)2 + 0.3719P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
5214 reflectionsΔρmax = 0.27 e Å3
271 parametersΔρmin = −0.62 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
Br10.97528 (7)0.99976 (3)0.19720 (3)0.1095 (3)
P10.97988 (9)0.37741 (5)0.08475 (4)0.0427 (2)
O10.8889 (3)0.48944 (15)0.21515 (13)0.0676 (7)
O21.0335 (2)0.37714 (14)0.01466 (10)0.0493 (5)
N10.9570 (3)0.49921 (14)0.10487 (13)0.0453 (6)
H10.96610.54140.07170.054*
N21.0988 (3)0.32013 (17)0.13878 (12)0.0478 (7)
N30.8203 (3)0.32336 (16)0.09738 (13)0.0474 (6)
C10.9380 (3)0.6529 (2)0.17215 (15)0.0440 (7)
C20.8517 (3)0.7031 (2)0.21718 (16)0.0505 (8)
H20.78720.66650.24290.061*
C30.8593 (4)0.8061 (2)0.22469 (17)0.0588 (9)
H30.79860.83950.25410.071*
C40.9584 (4)0.8585 (2)0.18784 (18)0.0615 (10)
C51.0478 (4)0.8100 (2)0.14387 (19)0.0682 (10)
H51.11520.84650.11960.082*
C61.0366 (4)0.7066 (2)0.13596 (17)0.0564 (9)
H61.09610.67330.10600.068*
C70.9257 (3)0.5404 (2)0.16691 (17)0.0486 (8)
C81.0706 (4)0.2882 (3)0.20873 (17)0.0669 (10)
H8A0.96970.30390.21760.100*
H8B1.13730.32280.24160.100*
H8C1.08610.21680.21310.100*
C91.2491 (4)0.2979 (2)0.11888 (18)0.0566 (9)
H9A1.32000.31710.15660.068*
H9B1.26860.33900.07920.068*
C101.2746 (3)0.1886 (2)0.10116 (17)0.0506 (8)
C111.3680 (4)0.1286 (3)0.14281 (19)0.0680 (10)
H111.41110.15430.18420.082*
C121.3988 (5)0.0301 (3)0.1237 (3)0.0867 (13)
H121.4631−0.00950.15200.104*
C131.3348 (5)−0.0078 (3)0.0640 (3)0.0903 (14)
H131.3546−0.07380.05130.108*
C141.2410 (5)0.0505 (3)0.0221 (2)0.0830 (12)
H141.19800.0241−0.01910.100*
C151.2100 (4)0.1478 (3)0.04062 (19)0.0646 (10)
H151.14500.18650.01220.078*
C160.8132 (4)0.2134 (2)0.0867 (2)0.0710 (11)
H16A0.90950.18460.09810.107*
H16B0.78290.19940.03910.107*
H16C0.74250.18480.11580.107*
C170.6770 (3)0.3738 (2)0.08216 (17)0.0545 (8)
H17A0.68720.44390.09590.065*
H17B0.60430.34330.11020.065*
C180.6182 (3)0.3696 (2)0.00736 (16)0.0463 (8)
C190.5215 (4)0.2942 (3)−0.01586 (19)0.0655 (10)
H190.49080.24630.01520.079*
C200.4698 (4)0.2890 (3)−0.0847 (2)0.0781 (11)
H200.40560.2374−0.09980.094*
C210.5125 (4)0.3591 (3)−0.13033 (19)0.0726 (11)
H210.47610.3562−0.17640.087*
C220.6101 (4)0.4348 (3)−0.10826 (19)0.0665 (10)
H220.64100.4823−0.13950.080*
C230.6611 (4)0.4394 (2)−0.03991 (19)0.0574 (9)
H230.72610.4907−0.02510.069*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.1798 (6)0.0408 (2)0.1100 (5)−0.0035 (2)0.0253 (4)−0.0180 (2)
P10.0553 (5)0.0330 (4)0.0398 (5)0.0004 (4)0.0042 (4)0.0012 (3)
O10.108 (2)0.0516 (14)0.0455 (14)−0.0064 (12)0.0206 (14)0.0020 (11)
O20.0716 (14)0.0369 (11)0.0401 (13)0.0037 (9)0.0092 (11)0.0006 (9)
N10.0654 (17)0.0327 (13)0.0383 (15)−0.0008 (11)0.0068 (13)0.0019 (10)
N20.0522 (17)0.0476 (14)0.0432 (16)0.0058 (12)0.0009 (13)0.0108 (12)
N30.0476 (16)0.0404 (14)0.0542 (17)−0.0004 (11)0.0035 (13)0.0044 (12)
C10.0524 (19)0.0436 (17)0.0356 (18)0.0029 (14)−0.0001 (15)−0.0034 (14)
C20.052 (2)0.0533 (19)0.0466 (19)−0.0017 (15)0.0035 (16)−0.0025 (16)
C30.071 (3)0.053 (2)0.051 (2)0.0103 (17)0.0030 (18)−0.0144 (17)
C40.087 (3)0.0387 (18)0.058 (2)0.0037 (17)0.001 (2)−0.0077 (16)
C50.091 (3)0.053 (2)0.063 (2)−0.0175 (18)0.016 (2)−0.0092 (18)
C60.073 (2)0.0428 (18)0.056 (2)−0.0014 (16)0.0195 (18)−0.0081 (16)
C70.060 (2)0.0449 (17)0.042 (2)0.0006 (15)0.0078 (16)−0.0022 (16)
C80.090 (3)0.063 (2)0.047 (2)0.0128 (19)0.0006 (19)0.0097 (17)
C90.051 (2)0.0508 (19)0.067 (2)−0.0036 (15)−0.0023 (17)0.0058 (17)
C100.0425 (19)0.0478 (18)0.062 (2)−0.0007 (14)0.0061 (17)0.0063 (17)
C110.064 (2)0.063 (2)0.075 (3)0.0067 (18)−0.006 (2)0.005 (2)
C120.092 (3)0.068 (3)0.099 (4)0.028 (2)−0.006 (3)0.016 (3)
C130.096 (3)0.063 (3)0.113 (4)0.017 (2)0.012 (3)−0.011 (2)
C140.083 (3)0.078 (3)0.087 (3)0.005 (2)0.004 (2)−0.021 (2)
C150.062 (2)0.062 (2)0.068 (3)0.0057 (18)−0.004 (2)0.0013 (19)
C160.074 (3)0.0398 (18)0.098 (3)−0.0097 (16)−0.003 (2)0.0053 (19)
C170.052 (2)0.058 (2)0.054 (2)0.0010 (16)0.0072 (17)−0.0010 (16)
C180.0409 (18)0.0485 (18)0.050 (2)0.0054 (14)0.0055 (15)−0.0038 (15)
C190.061 (2)0.070 (2)0.064 (3)−0.0133 (18)0.0004 (19)0.005 (2)
C200.081 (3)0.073 (2)0.077 (3)−0.020 (2)−0.015 (2)0.001 (2)
C210.083 (3)0.077 (3)0.055 (2)0.007 (2)−0.011 (2)−0.004 (2)
C220.071 (3)0.068 (2)0.059 (3)0.0012 (19)−0.002 (2)0.0139 (19)
C230.059 (2)0.050 (2)0.062 (2)−0.0029 (15)−0.0046 (18)0.0030 (17)

Geometric parameters (Å, °)

Br1—C41.889 (3)C10—C111.377 (4)
P1—O21.474 (2)C10—C151.382 (4)
P1—N21.631 (2)C11—C121.392 (5)
P1—N31.642 (2)C11—H110.9300
P1—N11.679 (2)C12—C131.353 (6)
O1—C71.218 (4)C12—H120.9300
N1—C71.368 (4)C13—C141.369 (6)
N1—H10.8600C13—H130.9300
N2—C81.460 (4)C14—C151.375 (5)
N2—C91.465 (4)C14—H140.9300
N3—C171.465 (4)C15—H150.9300
N3—C161.474 (4)C16—H16A0.9600
C1—C61.370 (4)C16—H16B0.9600
C1—C21.381 (4)C16—H16C0.9600
C1—C71.501 (4)C17—C181.508 (4)
C2—C31.376 (4)C17—H17A0.9700
C2—H20.9300C17—H17B0.9700
C3—C41.372 (5)C18—C231.377 (4)
C3—H30.9300C18—C191.381 (4)
C4—C51.374 (5)C19—C201.382 (5)
C5—C61.385 (4)C19—H190.9300
C5—H50.9300C20—C211.359 (5)
C6—H60.9300C20—H200.9300
C8—H8A0.9600C21—C221.382 (5)
C8—H8B0.9600C21—H210.9300
C8—H8C0.9600C22—C231.371 (5)
C9—C101.512 (4)C22—H220.9300
C9—H9A0.9700C23—H230.9300
C9—H9B0.9700
O2—P1—N2110.25 (13)C11—C10—C15118.3 (3)
O2—P1—N3119.05 (13)C11—C10—C9121.2 (3)
N2—P1—N3104.06 (12)C15—C10—C9120.4 (3)
O2—P1—N1105.69 (12)C10—C11—C12120.8 (3)
N2—P1—N1112.69 (13)C10—C11—H11119.6
N3—P1—N1105.20 (12)C12—C11—H11119.6
C7—N1—P1128.7 (2)C13—C12—C11119.7 (4)
C7—N1—H1115.7C13—C12—H12120.1
P1—N1—H1115.7C11—C12—H12120.1
C8—N2—C9114.4 (2)C12—C13—C14120.3 (4)
C8—N2—P1125.5 (2)C12—C13—H13119.9
C9—N2—P1120.1 (2)C14—C13—H13119.9
C17—N3—C16113.3 (2)C13—C14—C15120.3 (4)
C17—N3—P1122.65 (19)C13—C14—H14119.8
C16—N3—P1116.2 (2)C15—C14—H14119.8
C6—C1—C2119.3 (3)C14—C15—C10120.6 (3)
C6—C1—C7122.0 (3)C14—C15—H15119.7
C2—C1—C7118.7 (3)C10—C15—H15119.7
C3—C2—C1121.3 (3)N3—C16—H16A109.5
C3—C2—H2119.3N3—C16—H16B109.5
C1—C2—H2119.3H16A—C16—H16B109.5
C4—C3—C2118.5 (3)N3—C16—H16C109.5
C4—C3—H3120.7H16A—C16—H16C109.5
C2—C3—H3120.7H16B—C16—H16C109.5
C3—C4—C5121.3 (3)N3—C17—C18114.8 (3)
C3—C4—Br1120.2 (3)N3—C17—H17A108.6
C5—C4—Br1118.5 (3)C18—C17—H17A108.6
C4—C5—C6119.4 (3)N3—C17—H17B108.6
C4—C5—H5120.3C18—C17—H17B108.6
C6—C5—H5120.3H17A—C17—H17B107.5
C1—C6—C5120.2 (3)C23—C18—C19118.1 (3)
C1—C6—H6119.9C23—C18—C17121.2 (3)
C5—C6—H6119.9C19—C18—C17120.7 (3)
O1—C7—N1122.5 (3)C18—C19—C20120.7 (3)
O1—C7—C1121.5 (3)C18—C19—H19119.6
N1—C7—C1116.0 (3)C20—C19—H19119.6
N2—C8—H8A109.5C21—C20—C19120.2 (3)
N2—C8—H8B109.5C21—C20—H20119.9
H8A—C8—H8B109.5C19—C20—H20119.9
N2—C8—H8C109.5C20—C21—C22120.0 (3)
H8A—C8—H8C109.5C20—C21—H21120.0
H8B—C8—H8C109.5C22—C21—H21120.0
N2—C9—C10114.3 (2)C23—C22—C21119.5 (3)
N2—C9—H9A108.7C23—C22—H22120.3
C10—C9—H9A108.7C21—C22—H22120.3
N2—C9—H9B108.7C22—C23—C18121.5 (3)
C10—C9—H9B108.7C22—C23—H23119.3
H9A—C9—H9B107.6C18—C23—H23119.3
O2—P1—N1—C7−171.6 (3)C2—C1—C7—O1−27.1 (4)
N2—P1—N1—C7−51.2 (3)C6—C1—C7—N1−30.6 (4)
N3—P1—N1—C761.6 (3)C2—C1—C7—N1152.3 (3)
O2—P1—N2—C8−167.1 (2)C8—N2—C9—C1076.2 (3)
N3—P1—N2—C8−38.3 (3)P1—N2—C9—C10−104.6 (3)
N1—P1—N2—C875.1 (3)N2—C9—C10—C11−111.6 (3)
O2—P1—N2—C913.8 (2)N2—C9—C10—C1571.6 (4)
N3—P1—N2—C9142.6 (2)C15—C10—C11—C121.2 (5)
N1—P1—N2—C9−104.0 (2)C9—C10—C11—C12−175.6 (3)
O2—P1—N3—C17−81.9 (3)C10—C11—C12—C13−0.8 (6)
N2—P1—N3—C17154.9 (2)C11—C12—C13—C140.5 (7)
N1—P1—N3—C1736.2 (3)C12—C13—C14—C15−0.5 (7)
O2—P1—N3—C1664.9 (3)C13—C14—C15—C101.0 (6)
N2—P1—N3—C16−58.3 (3)C11—C10—C15—C14−1.3 (5)
N1—P1—N3—C16−177.0 (2)C9—C10—C15—C14175.6 (3)
C6—C1—C2—C32.2 (5)C16—N3—C17—C18−65.4 (3)
C7—C1—C2—C3179.4 (3)P1—N3—C17—C1882.3 (3)
C1—C2—C3—C4−2.0 (5)N3—C17—C18—C23−85.4 (4)
C2—C3—C4—C50.5 (5)N3—C17—C18—C1993.4 (3)
C2—C3—C4—Br1−179.1 (2)C23—C18—C19—C200.2 (5)
C3—C4—C5—C60.7 (6)C17—C18—C19—C20−178.7 (3)
Br1—C4—C5—C6−179.6 (3)C18—C19—C20—C21−0.7 (6)
C2—C1—C6—C5−0.9 (5)C19—C20—C21—C221.2 (6)
C7—C1—C6—C5−178.0 (3)C20—C21—C22—C23−1.1 (6)
C4—C5—C6—C1−0.5 (5)C21—C22—C23—C180.5 (5)
P1—N1—C7—O1−10.8 (5)C19—C18—C23—C22−0.1 (5)
P1—N1—C7—C1169.7 (2)C17—C18—C23—C22178.8 (3)
C6—C1—C7—O1150.0 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.861.992.845 (3)170.4

Symmetry codes: (i) −x+2, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2095).

References

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