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Acta Cryst. (2007). E63, o3016    [ doi:10.1107/S1600536807023379 ]

2-Nitrobenzyl diphenyl phosphate

W.-W. Jin, C.-B. Chen and X.-Y. Li

Abstract top

In the title compound, C19H16NO6P, the dihedral angles between the nitrobenzyl ring and the phenyl rings are 53.74 (3) and 63.30 (2)°, and that between the two phenyl rings is 88.86 (3)°. Intermolecular C-H...O hydrogen bonds result in the stabilization of the crystal structure.

Comment top

Phosphates are extremely useful compounds which have received much attention as genetic materials, co-enzymes and in biochemistry in general. Phosphates have well known roles as intermediates in biochemical transformations (Schick et al., 1995). The title compound (I) is formed by the reaction of diphenylphosphite with an aromatic aldehyde in presence of triethylamine. We also find that the title compound may be obtained from a hydroxyphosphonate rearrangement. In this paper, we present an X-ray crystallographic analysis of (I), shown in Fig. 1. The dihedral angles between the benzene rings A (C1—C6), B (C8—C13) and C (C14—C19) are A/B = 53.74 (3)°, A/C = 63.30 (2)° and B/C = 88.86 (3)°. In the crystal structure, intermolecular C—H···O hydrogen bonds are effective in stabilizing the structure (Fig. 2, Table 2).

Related literature top

For related literature, see: Schick et al. (1995).

Experimental top

To a solution of 2-nitrobenzylaldehyde (1 mmol) in tetrahydrofuran (0.60 ml) was added diphenyl phosphite (1 mmol) at ice-bath temperature. After 15 minutes, triethylamine (0.14 ml) was added, and the reaction mixture was stirred for a further 2 h at ice-bath temperature. The resulting solution was washed with saturated NaHCO3 solution, extracted with dichloromethane and dried over MgSO4. The solution was then filtered and purified by column chromatography on silica gel, using ethyl acetate and petroleum as eluant, to afford compound (I).

1H NMR (CDCl3, 400 MHz): 8.17 (d, J = 8.0 Hz, 1H), 7.73 (d, J = 8.0 Hz, 1H), 7.65 (t, J = 7.6 Hz, 1H), 7.51 (d, J = 8.0 Hz, 1H), 7.35 (t, J = 8.0 Hz, 4H), 7.19–7.26 (m, 6H), 5.74 (d, J = 8.0 Hz, 2H). Crystals suitable for X-ray diffraction were grown from a dichloromethane-ether solution at 298 K.

Refinement top

All H atoms were initially located in a difference Fourier map. The phenyl H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.93 Å. Methylene groups were treated similarly, with C—H distances of 0.97 Å.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. View of compound (I), showing the atomic labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are represented by circles of arbitrary size.
[Figure 2] Fig. 2. Hydrogen bonding in the crystal structure of (I). Hydrogen bonds are shown as dashed lines.
2-Nitrobenzyl diphenyl phosphate top
Crystal data top
C19H16NO6PF(000) = 400
Mr = 385.30Dx = 1.41 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 4390 reflections
a = 6.0641 (5) Åθ = 2.3–27.1°
b = 8.9176 (8) ŵ = 0.19 mm−1
c = 16.7851 (14) ÅT = 295 K
β = 90.727 (1)°Block, colorless
V = 907.62 (13) Å30.20 × 0.10 × 0.10 mm
Z = 2
Data collection top
Bruker SMART 4K CCD area-detector
diffractometer		3883 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.022
graphiteθmax = 28.0°, θmin = 2.4°
phi and ω scansh = −7→7
9691 measured reflectionsk = −11→11
4190 independent reflectionsl = −21→21
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.097 w = 1/[σ2(Fo2) + (0.0618P)2 + 0.0077P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
4190 reflectionsΔρmax = 0.21 e Å−3
244 parametersΔρmin = −0.27 e Å−3
1 restraintAbsolute structure: Flack (1983), 1868 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.08 (7)
Crystal data top
C19H16NO6PV = 907.62 (13) Å3
Mr = 385.30Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.0641 (5) ŵ = 0.19 mm−1
b = 8.9176 (8) ÅT = 295 K
c = 16.7851 (14) Å0.20 × 0.10 × 0.10 mm
β = 90.727 (1)°
Data collection top
Bruker SMART 4K CCD area-detector
diffractometer		3883 reflections with I > 2σ(I)
9691 measured reflectionsRint = 0.022
4190 independent reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.097Δρmax = 0.21 e Å−3
S = 1.05Δρmin = −0.27 e Å−3
4190 reflectionsAbsolute structure: Flack (1983), 1868 Friedel pairs
244 parametersFlack parameter: 0.08 (7)
1 restraint
Special details top

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
xyzUiso*/Ueq
C11.1681 (3)0.2682 (3)0.08864 (11)0.0471 (4)
C21.2298 (4)0.1344 (3)0.05385 (12)0.0595 (6)
H21.35920.12860.02480.071*
C31.0996 (4)0.0109 (3)0.06240 (12)0.0631 (5)
H31.1400−0.08000.03960.076*
C40.9084 (4)0.0217 (3)0.10492 (12)0.0577 (5)
H40.8189−0.06230.11030.069*
C50.8472 (3)0.1545 (2)0.13962 (11)0.0480 (4)
H50.71680.15860.16810.058*
C60.9758 (3)0.2833 (2)0.13314 (10)0.0416 (4)
C70.9080 (3)0.4270 (2)0.17274 (11)0.0455 (4)
H7A1.02110.45890.21040.055*
H7B0.88810.50530.13320.055*
C80.5830 (3)0.8082 (2)0.26077 (10)0.0407 (4)
C90.3789 (4)0.8659 (2)0.24225 (14)0.0581 (5)
H90.27990.81220.21050.070*
C100.3237 (4)1.0049 (3)0.27156 (16)0.0709 (6)
H100.18631.04570.25930.085*
C110.4677 (5)1.0833 (3)0.31827 (16)0.0687 (7)
H110.42871.17740.33740.082*
C120.6692 (4)1.0244 (3)0.33722 (14)0.0680 (6)
H120.76611.07800.36980.082*
C130.7307 (3)0.8847 (2)0.30818 (12)0.0536 (5)
H130.86820.84420.32060.064*
C140.7906 (3)0.42840 (18)0.40687 (9)0.0369 (3)
C150.9879 (3)0.3524 (2)0.41512 (12)0.0465 (4)
H151.10010.36580.37850.056*
C161.0152 (4)0.2558 (3)0.47902 (13)0.0575 (5)
H161.14690.20350.48530.069*
C170.8504 (4)0.2363 (2)0.53315 (13)0.0554 (5)
H170.87080.17160.57610.066*
C180.6538 (3)0.3128 (2)0.52381 (11)0.0525 (5)
H180.54150.29870.56030.063*
C190.6229 (3)0.4103 (2)0.46058 (10)0.0446 (4)
H190.49120.46270.45440.054*
N11.3160 (3)0.3970 (2)0.07554 (10)0.0561 (4)
O11.4834 (3)0.3768 (3)0.03849 (12)0.0898 (6)
O21.2634 (3)0.5195 (2)0.10143 (10)0.0750 (4)
O30.7011 (2)0.39994 (15)0.21402 (8)0.0467 (3)
O40.3803 (2)0.48193 (15)0.29503 (8)0.0497 (3)
O50.6448 (2)0.66933 (14)0.22804 (7)0.0467 (3)
O60.7736 (2)0.53291 (14)0.34462 (7)0.0445 (3)
P10.60419 (7)0.51722 (5)0.27268 (2)0.03749 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0406 (9)0.0635 (12)0.0372 (9)0.0015 (8)0.0018 (7)0.0020 (8)
C20.0499 (12)0.0801 (16)0.0487 (10)0.0117 (11)0.0109 (9)−0.0105 (11)
C30.0671 (13)0.0659 (13)0.0565 (11)0.0134 (13)0.0070 (9)−0.0201 (11)
C40.0644 (12)0.0523 (10)0.0566 (10)−0.0039 (11)0.0058 (9)−0.0096 (11)
C50.0475 (10)0.0521 (10)0.0446 (9)0.0000 (9)0.0082 (7)−0.0051 (8)
C60.0389 (9)0.0503 (10)0.0357 (8)0.0020 (7)0.0016 (6)−0.0002 (7)
C70.0444 (10)0.0475 (10)0.0450 (9)−0.0043 (8)0.0106 (8)−0.0042 (8)
C80.0481 (10)0.0353 (8)0.0387 (8)0.0004 (7)0.0039 (7)0.0063 (7)
C90.0539 (12)0.0493 (11)0.0709 (13)0.0040 (9)−0.0128 (10)0.0028 (10)
C100.0636 (13)0.0541 (13)0.0950 (17)0.0157 (12)0.0072 (12)0.0089 (13)
C110.0900 (18)0.0394 (10)0.0775 (15)−0.0010 (11)0.0233 (13)−0.0038 (10)
C120.0841 (16)0.0547 (12)0.0652 (12)−0.0249 (14)−0.0009 (11)−0.0077 (13)
C130.0475 (11)0.0555 (12)0.0577 (11)−0.0097 (9)−0.0047 (9)0.0046 (9)
C140.0406 (9)0.0314 (8)0.0386 (7)−0.0039 (6)−0.0019 (6)−0.0029 (6)
C150.0350 (9)0.0470 (10)0.0576 (10)−0.0027 (8)0.0038 (8)0.0022 (8)
C160.0446 (11)0.0514 (11)0.0761 (15)0.0056 (9)−0.0096 (10)0.0092 (11)
C170.0690 (14)0.0455 (10)0.0513 (11)0.0000 (9)−0.0125 (10)0.0092 (9)
C180.0586 (12)0.0555 (11)0.0435 (9)−0.0019 (9)0.0080 (8)0.0018 (9)
C190.0430 (10)0.0440 (9)0.0470 (9)0.0055 (7)0.0054 (7)−0.0015 (8)
N10.0447 (9)0.0784 (13)0.0453 (8)−0.0064 (9)0.0064 (7)0.0105 (9)
O10.0597 (10)0.1117 (16)0.0989 (13)−0.0036 (10)0.0374 (10)0.0141 (12)
O20.0738 (10)0.0738 (10)0.0778 (10)−0.0244 (10)0.0200 (8)−0.0061 (10)
O30.0446 (7)0.0426 (7)0.0532 (7)−0.0040 (5)0.0128 (6)−0.0068 (6)
O40.0392 (7)0.0580 (9)0.0520 (7)0.0011 (5)0.0053 (5)0.0027 (6)
O50.0587 (8)0.0401 (6)0.0414 (6)0.0050 (6)0.0087 (5)0.0037 (5)
O60.0471 (6)0.0403 (6)0.0460 (6)−0.0067 (6)−0.0018 (5)0.0079 (6)
P10.0378 (2)0.0362 (2)0.0386 (2)0.00156 (19)0.00463 (15)0.00116 (18)
Geometric parameters (Å, °) top
C1—C21.382 (3)C11—H110.9300
C1—C61.399 (2)C12—C131.390 (4)
C1—N11.476 (3)C12—H120.9300
C2—C31.364 (4)C13—H130.9300
C2—H20.9300C14—C191.377 (2)
C3—C41.372 (3)C14—C151.381 (3)
C3—H30.9300C14—O61.403 (2)
C4—C51.373 (3)C15—C161.384 (3)
C4—H40.9300C15—H150.9300
C5—C61.394 (3)C16—C171.370 (3)
C5—H50.9300C16—H160.9300
C6—C71.503 (3)C17—C181.381 (3)
C7—O31.461 (2)C17—H170.9300
C7—H7A0.9700C18—C191.383 (3)
C7—H7B0.9700C18—H180.9300
C8—C131.372 (3)C19—H190.9300
C8—C91.373 (3)N1—O11.211 (2)
C8—O51.408 (2)N1—O21.219 (3)
C9—C101.376 (3)O3—P11.5568 (13)
C9—H90.9300O4—P11.4475 (14)
C10—C111.360 (4)O5—P11.5706 (13)
C10—H100.9300O6—P11.5815 (13)
C11—C121.363 (4)
C2—C1—C6122.76 (19)C11—C12—C13120.4 (2)
C2—C1—N1116.14 (17)C11—C12—H12119.8
C6—C1—N1121.10 (19)C13—C12—H12119.8
C3—C2—C1119.48 (18)C8—C13—C12118.2 (2)
C3—C2—H2120.3C8—C13—H13120.9
C1—C2—H2120.3C12—C13—H13120.9
C2—C3—C4119.5 (2)C19—C14—C15121.53 (17)
C2—C3—H3120.3C19—C14—O6121.17 (16)
C4—C3—H3120.3C15—C14—O6117.15 (15)
C3—C4—C5121.1 (2)C14—C15—C16118.56 (17)
C3—C4—H4119.5C14—C15—H15120.7
C5—C4—H4119.5C16—C15—H15120.7
C4—C5—C6121.55 (18)C17—C16—C15120.8 (2)
C4—C5—H5119.2C17—C16—H16119.6
C6—C5—H5119.2C15—C16—H16119.6
C5—C6—C1115.66 (17)C16—C17—C18119.84 (19)
C5—C6—C7120.78 (15)C16—C17—H17120.1
C1—C6—C7123.56 (17)C18—C17—H17120.1
O3—C7—C6108.07 (14)C17—C18—C19120.42 (18)
O3—C7—H7A110.1C17—C18—H18119.8
C6—C7—H7A110.1C19—C18—H18119.8
O3—C7—H7B110.1C14—C19—C18118.83 (18)
C6—C7—H7B110.1C14—C19—H19120.6
H7A—C7—H7B108.4C18—C19—H19120.6
C13—C8—C9121.7 (2)O1—N1—O2122.8 (2)
C13—C8—O5119.27 (17)O1—N1—C1118.4 (2)
C9—C8—O5119.02 (17)O2—N1—C1118.81 (16)
C8—C9—C10118.6 (2)C7—O3—P1121.49 (11)
C8—C9—H9120.7C8—O5—P1121.98 (10)
C10—C9—H9120.7C14—O6—P1123.41 (11)
C11—C10—C9120.8 (2)O4—P1—O3112.38 (8)
C11—C10—H10119.6O4—P1—O5117.69 (8)
C9—C10—H10119.6O3—P1—O5102.46 (7)
C10—C11—C12120.2 (2)O4—P1—O6115.06 (7)
C10—C11—H11119.9O3—P1—O6107.19 (8)
C12—C11—H11119.9O5—P1—O6100.58 (7)
C6—C1—C2—C30.2 (3)C15—C16—C17—C180.5 (3)
N1—C1—C2—C3−179.07 (19)C16—C17—C18—C19−0.6 (3)
C1—C2—C3—C40.5 (3)C15—C14—C19—C18−0.4 (3)
C2—C3—C4—C5−0.6 (3)O6—C14—C19—C18−175.85 (17)
C3—C4—C5—C60.0 (3)C17—C18—C19—C140.6 (3)
C4—C5—C6—C10.6 (3)C2—C1—N1—O1−2.7 (3)
C4—C5—C6—C7−178.93 (18)C6—C1—N1—O1177.95 (18)
C2—C1—C6—C5−0.8 (3)C2—C1—N1—O2176.26 (19)
N1—C1—C6—C5178.51 (17)C6—C1—N1—O2−3.1 (3)
C2—C1—C6—C7178.76 (19)C6—C7—O3—P1169.83 (12)
N1—C1—C6—C7−2.0 (3)C13—C8—O5—P189.90 (19)
C5—C6—C7—O30.0 (2)C9—C8—O5—P1−92.19 (19)
C1—C6—C7—O3−179.49 (16)C19—C14—O6—P1−67.5 (2)
C13—C8—C9—C100.8 (3)C15—C14—O6—P1116.86 (16)
O5—C8—C9—C10−177.09 (18)C7—O3—P1—O4168.89 (14)
C8—C9—C10—C11−0.3 (4)C7—O3—P1—O541.62 (15)
C9—C10—C11—C12−0.5 (4)C7—O3—P1—O6−63.76 (15)
C10—C11—C12—C130.9 (4)C8—O5—P1—O456.83 (16)
C9—C8—C13—C12−0.4 (3)C8—O5—P1—O3−179.38 (14)
O5—C8—C13—C12177.48 (16)C8—O5—P1—O6−68.94 (14)
C11—C12—C13—C8−0.5 (3)C14—O6—P1—O447.55 (15)
C19—C14—C15—C160.2 (3)C14—O6—P1—O3−78.22 (14)
O6—C14—C15—C16175.83 (17)C14—O6—P1—O5175.07 (13)
C14—C15—C16—C17−0.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15···O4i0.932.453.344 (2)162
C7—H7A···O4i0.972.593.537 (2)164
Symmetry codes: (i) x+1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15···O4i0.932.453.344 (2)162
C7—H7A···O4i0.972.593.537 (2)164
Symmetry codes: (i) x+1, y, z.
Acknowledgements top

The authors are grateful to the Central China Normal University. We thank Professor Wen-Jing Xiao for fruitful discussions.

references
References top

Bruker (2001). SMART (Version 5.628), SAINT-Plus (Version 6.45) and SHELXTL (Version 5.0). Bruker AXS Inc., Madison, Wisconsin, USA. SIANT-Plus or just SAINT as used in CIF?

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Schick, A., Kolter, T., Giannis, A. & Sandhoff, K. (1995). Tetrahedron, 51, 11207–11218.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.