N (2 Nitro­phen­yl) 1 oxo 2,6,7 trioxa 1 phosphabi­cyclo­[2 2 2]octa­ne 4 carboxamide

organic papers

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11H11N2O7P doi:10.1107/S1600536805023974 Acta Cryst.(2005). E61, o2772–o2774 Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

N

-(2-Nitrophenyl)-1-oxo-2,6,7-trioxa-1-phospha-bicyclo[2.2.2]octane-4-carboxamide

Hong-Jun Zang* and Ming-Lin Guo

College of Materials and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300160, People’s Republic of China

Correspondence e-mail: zhjchem@eyou.com

Key indicators Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.003 A˚

Rfactor = 0.041

wRfactor = 0.115

Data-to-parameter ratio = 13.3

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

In the title compound, C11H11N2O7P, compression of the P—

O—C angles is observed, suggesting that some strain is probably present. The configuration around phosphorus is distorted tetrahedral. In the crystal structure, N—H O and

C—H O hydrogen-bond contacts and van der Waals forces

stabilize the packing of the compound.

Comment

Cage bicyclic phosphates have attracted much interest and many investigations have been reported (Allenet al., 1995; Li

et al., 2002). It is found that cage bicyclic phosphates and their derivatives can serve as effective flame retardants in some polymers. They can produce less toxic gas and smoke compared with halogen-containing fire retardants. Therefore, they are recognized as environmentally friendly flame retar-dants. We report here the structure of a new cage bicyclic

phosphate, namely N

-(2-nitrophenyl)-1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane-4-carboxamide, (I).

The molecular structure of (I) is illustrated in Fig. 1. The

terminal O P bond distance is 1.447 (2) A˚ and the average

bridging P—O distance is 1.566 (3) A˚ . The O P bond length

is shorter than that of O—P, because of the presence of

-bonding. The bond distances and angles are within experi-mental error of those in the other trialkyl phosphates whose structures are known (Nimrodet al., 1968; Liuet al., 1992). The

O—P—O and P—O—C bond angles (about 104 and 115,

respectively) are different from the unstrained angle (about 104 and 120_{, respectively) in dibenzyl hydrogen phosphate,}

which can be assumed to be representative of strainless angles of this type (Dunitz & Rollett, 1956). Some evidence of strain

is present in (I) in the P—O–C angles of 115_{. The}

config-uration around phosphorus is distorted tetrahedral.

In the crystal structure, the nitro group N2/O6/O7 is almost coplanar with the arene ring. Atom O6 of the nitro group is

involved in an intramolecular N1—H1 O6 hydrogen bond

and an intermolecular C2–H2A O6i hydrogen bond

[symmetry code: (i)x,3 2y,

1

2+z]. The molecules are further

loosely aggregated into a three-dimensional molecular

network via a relatively weak C—H O hydrogen bond

(Table 2). A packing diagram is shown in Fig. 2.

Experimental

A dry three-necked round-bottomed flask was charged with 2-nitrophenylamine (2 mmol), 4-chlorocarbinyl-1-oxa-1-phophatrioxa-bicyclo[2.2.2]octane (2 mmol) and acetone (20 ml). To the stirred mixture, triethylamine (2.2 mmol) dissolved in acetone was added dropwise over a period of 0.5 h. After completion of triethylamine addition, the reaction mixture was stirred for 0.5 h at room temperature. The reaction mixture was then refluxed for another 2 h. The product was filtered off and washed thoroughly with water. The product was crystallized by slow evaporation from an N,N -dimethylformamide–water solution (1:4v/v).

Crystal data

C11H11N2O7P

Mr= 314.19 Monoclinic,P21=c

a= 8.2381 (14) A˚

b= 12.269 (2) A˚

c= 12.937 (2) A˚

= 105.075 (3) V= 1262.6 (4) A˚3

Z= 4

Dx= 1.653 Mg m3 MoKradiation Cell parameters from 2576

reflections

= 2.3–26.4

= 0.26 mm1

T= 293 (2) K Prism, yellow 0.340.280.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer

’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.912,Tmax= 0.945

7022 measured reflections

2597 independent reflections 1865 reflections withI> 2(I)

Rint= 0.028

max= 26.4

h=7!10

k=15!13

l=16!14

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.041

wR(F2_{) = 0.115}

S= 1.05 2597 reflections 195 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2_(F

o2) + (0.0526P)2

+ 0.5183P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.28 e A˚

3

min=0.31 e A˚

3

Extinction correction:SHELXL97

Extinction coefficient: 0.043 (3)

Table 1

Selected geometric parameters (A˚ ,_).

P1—O1 1.4472 (18) P1—O4 1.5637 (17) P1—O3 1.5643 (18)

P1—O2 1.5710 (19) O6—N2 1.231 (3) O7—N2 1.221 (2)

O1—P1—O4 114.72 (10) O1—P1—O3 114.18 (10) O4—P1—O3 104.62 (10) O1—P1—O2 114.69 (11) O4—P1—O2 103.41 (10) O3—P1—O2 103.90 (11)

C1—O2—P1 114.59 (14) C3—O3—P1 115.97 (13) C2—O4—P1 114.39 (13) O7—N2—O6 122.0 (2) O7—N2—C11 118.1 (2) O6—N2—C11 119.86 (18)

O7—N2—C11—C10 10.7 (3) O6—N2—C11—C10 169.7 (2)

O7—N2—C11—C6 168.6 (2) O6—N2—C11—C6 11.0 (3)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N1—H1 O6 0.82 (3) 1.97 (3) 2.632 (3) 138 (2) N1—H1 N2 0.82 (3) 2.54 (2) 2.928 (3) 111 (2) C2—H2A O6i

0.97 2.59 3.511 (3) 159 C3—H3B O1ii

0.97 2.50 3.351 (3) 147 C7—H7 O5 0.93 2.19 2.824 (3) 124 C7—H7 O3i

0.93 2.42 3.216 (3) 144 C10—H10 O7 0.93 2.36 2.675 (3) 100

Symmetry codes: (i)x;yþ3 2;zþ

1

2; (ii)x;y 1 2;zþ

3 2.

The H atom bonded to atom N1 was located in a difference Fourier map and refined isotropically. C-bound H atoms were included in the refinement in the riding-model approximation, with C—H = 0.93– 0.97 A˚ andUiso(H) = 1.2Ueq(C).

organic papers

Acta Cryst.(2005). E61, o2772–o2774 Zang and Guo _C

11H11N2O7P

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A view of the molecular structure of (I), showing the atom-numbering scheme. Dispacement ellipsoids are drawn at the 30% probability level. The intramolecular N1—H1 O6 hydrogen bond is indicated by a dashed line.

Figure 2

Data collection:SMART(Bruker, 1997); cell refinement:SAINT

(Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.

References

Allen, D.W., Anderton, E. C., Bradley C. & Shiel, L. E. (1995).Polym. Degrad. Stabil.47, 67–72.

Bruker (1997).SMART(Version 5.051) andSAINT(Version 5.06). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2000). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.

Dunitz, J. D. & Rollett, J. S. (1956).Acta Cryst.9, 327–332.

Li, X., Ou, Y.-X. & Shi, Y.-S. (2002).Polym. Degrad. Stabil.77, 383–390. Liu, X.-L., Sun, M., Miao, F.-M., Li, Y.-G. & Wang, J.-J. (1992).Acta Phys.

Chim. Sin.8, 100–108.

Nimrod, D. M., Fitzwater, D. R. & Verkade, J. G. (1968).J. Am. Chem. Soc.90, 2780–2784.

Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany.

organic papers

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supporting information

sup-1 Acta Cryst. (2005). E61, o2772–o2774

supporting information

Acta Cryst. (2005). E61, o2772–o2774 [https://doi.org/10.1107/S1600536805023974]

N

-(2-Nitrophenyl)-1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane-4-carboxamide

Hong-Jun Zang and Ming-Lin Guo

N-(2-Nitrophenyl)-1-oxo-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane- 4-carboxamide

Crystal data

C11H11N2O7P Mr = 314.19

Monoclinic, P21/c

Hall symbol: -P 2ybc

a = 8.2381 (14) Å

b = 12.269 (2) Å

c = 12.937 (2) Å

β = 105.075 (3)°

V = 1262.6 (4) Å3 Z = 4

F(000) = 648

Dx = 1.653 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2576 reflections

θ = 2.3–26.4°

µ = 0.26 mm−1 T = 293 K Prism, yellow

0.34 × 0.28 × 0.24 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.912, Tmax = 0.945

7022 measured reflections 2597 independent reflections 1865 reflections with I > 2σ(I)

Rint = 0.028

θmax = 26.4°, θmin = 2.3°

h = −7→10

k = −15→13

l = −16→14

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.041} wR(F2_{) = 0.115} S = 1.05 2597 reflections 195 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(Fo2_{) + (0.0526P)}2 _{+ 0.5183P]}

where P = (Fo2 _{+ 2Fc}2_)/3

(Δ/σ)max = 0.001

Δρmax = 0.28 e Å−3

Δρmin = −0.31 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

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sup-2 Acta Cryst. (2005). E61, o2772–o2774

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

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sup-3 Acta Cryst. (2005). E61, o2772–o2774

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

P1 0.0488 (4) 0.0333 (3) 0.0421 (3) 0.0002 (2) 0.0053 (3) −0.0009 (2) O1 0.0764 (13) 0.0372 (9) 0.0632 (11) 0.0039 (8) 0.0053 (9) 0.0052 (8) O2 0.0425 (9) 0.0481 (10) 0.0866 (13) 0.0067 (7) 0.0158 (9) 0.0085 (9) O3 0.1146 (15) 0.0368 (9) 0.0410 (9) 0.0030 (9) 0.0298 (10) 0.0050 (7) O4 0.0541 (10) 0.0338 (9) 0.0581 (10) −0.0061 (7) −0.0069 (8) 0.0004 (7) O5 0.174 (2) 0.0438 (11) 0.0627 (12) 0.0184 (12) 0.0733 (14) 0.0100 (9) O6 0.0870 (14) 0.0595 (12) 0.0530 (11) 0.0042 (10) 0.0350 (10) 0.0003 (9) O7 0.0778 (13) 0.0747 (14) 0.0703 (13) 0.0112 (10) 0.0372 (11) −0.0223 (10) N1 0.0528 (12) 0.0359 (10) 0.0322 (10) 0.0020 (8) 0.0172 (9) 0.0014 (8) N2 0.0407 (11) 0.0589 (13) 0.0460 (11) 0.0065 (9) 0.0127 (9) −0.0096 (10) C1 0.0476 (14) 0.0468 (14) 0.0693 (17) 0.0011 (11) 0.0253 (12) 0.0064 (12) C2 0.0541 (14) 0.0361 (12) 0.0466 (13) −0.0024 (10) −0.0023 (11) 0.0006 (10) C3 0.0785 (17) 0.0305 (12) 0.0397 (12) −0.0011 (11) 0.0245 (12) 0.0005 (9) C4 0.0426 (12) 0.0326 (11) 0.0326 (10) −0.0017 (9) 0.0136 (9) −0.0021 (8) C5 0.0564 (14) 0.0357 (12) 0.0355 (11) −0.0016 (10) 0.0194 (10) 0.0000 (9) C6 0.0367 (11) 0.0363 (12) 0.0333 (11) −0.0003 (9) 0.0036 (9) −0.0018 (9) C7 0.0549 (14) 0.0382 (13) 0.0436 (13) −0.0044 (10) 0.0140 (11) 0.0003 (10) C8 0.0635 (16) 0.0418 (14) 0.0497 (14) −0.0070 (11) 0.0111 (12) 0.0055 (11) C9 0.0629 (16) 0.0361 (13) 0.0676 (17) 0.0014 (11) 0.0082 (13) 0.0035 (12) C10 0.0507 (14) 0.0449 (14) 0.0601 (16) 0.0048 (11) 0.0078 (12) −0.0119 (12) C11 0.0375 (12) 0.0423 (13) 0.0402 (12) 0.0018 (9) 0.0044 (9) −0.0047 (9)

Geometric parameters (Å, º)

P1—O1 1.4472 (18) C2—C4 1.529 (3) P1—O4 1.5637 (17) C2—H2A 0.9700 P1—O3 1.5643 (18) C2—H2B 0.9700 P1—O2 1.5710 (19) C3—C4 1.532 (3) O2—C1 1.464 (3) C3—H3A 0.9700 O3—C3 1.457 (3) C3—H3B 0.9700 O4—C2 1.460 (3) C4—C5 1.536 (3) O5—C5 1.206 (3) C6—C7 1.393 (3) O6—N2 1.231 (3) C6—C11 1.412 (3) O7—N2 1.221 (2) C7—C8 1.379 (3) N1—C5 1.347 (3) C7—H7 0.9300 N1—C6 1.401 (3) C8—C9 1.382 (4) N1—H1 0.82 (3) C8—H8 0.9300 N2—C11 1.466 (3) C9—C10 1.366 (4) C1—C4 1.534 (3) C9—H9 0.9300 C1—H1A 0.9700 C10—C11 1.385 (3) C1—H1B 0.9700 C10—H10 0.9300

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O1—P1—O2 114.69 (11) C2—C4—C3 109.06 (19) O4—P1—O2 103.41 (10) C2—C4—C1 108.74 (19) O3—P1—O2 103.90 (11) C3—C4—C1 108.22 (19) C1—O2—P1 114.59 (14) C2—C4—C5 107.84 (17) C3—O3—P1 115.97 (13) C3—C4—C5 115.55 (17) C2—O4—P1 114.39 (13) C1—C4—C5 107.26 (17) C5—N1—C6 128.45 (19) O5—C5—N1 124.8 (2) C5—N1—H1 118.0 (18) O5—C5—C4 118.71 (19) C6—N1—H1 113.5 (18) N1—C5—C4 116.47 (18) O7—N2—O6 122.0 (2) C7—C6—N1 121.63 (19) O7—N2—C11 118.1 (2) C7—C6—C11 116.8 (2) O6—N2—C11 119.86 (18) N1—C6—C11 121.6 (2) O2—C1—C4 109.92 (18) C8—C7—C6 121.3 (2) O2—C1—H1A 109.7 C8—C7—H7 119.4 C4—C1—H1A 109.7 C6—C7—H7 119.4 O2—C1—H1B 109.7 C7—C8—C9 120.9 (2) C4—C1—H1B 109.7 C7—C8—H8 119.6 H1A—C1—H1B 108.2 C9—C8—H8 119.6 O4—C2—C4 110.44 (17) C10—C9—C8 119.3 (2) O4—C2—H2A 109.6 C10—C9—H9 120.4 C4—C2—H2A 109.6 C8—C9—H9 120.4 O4—C2—H2B 109.6 C9—C10—C11 120.6 (2) C4—C2—H2B 109.6 C9—C10—H10 119.7 H2A—C2—H2B 108.1 C11—C10—H10 119.7 O3—C3—C4 108.98 (17) C10—C11—C6 121.2 (2) O3—C3—H3A 109.9 C10—C11—N2 116.6 (2) C4—C3—H3A 109.9 C6—C11—N2 122.2 (2)

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sup-5 Acta Cryst. (2005). E61, o2772–o2774

O2—C1—C4—C5 174.83 (18) O6—N2—C11—C10 −169.7 (2) C6—N1—C5—O5 7.2 (4) O7—N2—C11—C6 −168.6 (2) C6—N1—C5—C4 −174.01 (19) O6—N2—C11—C6 11.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1—H1···O6 0.82 (3) 1.97 (3) 2.632 (3) 138 (2) N1—H1···N2 0.82 (3) 2.54 (2) 2.928 (3) 111 (2) C2—H2A···O6i _{0.97 2.59 3.511 (3) 159}

C3—H3B···O1ii _{0.97 2.50 3.351 (3) 147}

C7—H7···O5 0.93 2.19 2.824 (3) 124 C7—H7···O3i _{0.93 2.42 3.216 (3) 144}

C10—H10···O7 0.93 2.36 2.675 (3) 100