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The title compound, C7H6N2O3, crystallizes as a second P21/c polymorph. Compared to the previously known form [Di Rienzo et al. (1977). Acta Cryst. B33, 3854–3858], the amide group is rotated much further out of the ring plane (ca 20°). The mol­ecules are linked by symmetric three-centre N—H(...Onitro)2, and N—H...Oamide hydrogen bonds to form layers parallel to the bc plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021244/na6185sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021244/na6185Isup2.hkl
Contains datablock I

CCDC reference: 202356

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.049
  • wR factor = 0.120
  • Data-to-parameter ratio = 14.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
DIFF_019 Alert A _diffrn_standards_number is missing Number of standards used in measurement. DIFF_020 Alert A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards. DIFF_022 Alert A _diffrn_standards_decay_% is missing Percentage decrease in standards intensity.
3 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check

Comment top

The structure of the title compound, (I), was first determined by Di Rienzo et al. (1977) [space group P21/c, cell constants a = 7.643 (1), b = 6.766 (1), c = 13.847 (2) Å and β = 91.34 (1)°] and was redetermined more precisely, using a high-angle refinement, by Tonogaki et al. (1993). The packing was shown to consist of centrosymmetric pairs of molecules, hydrogen-bonded through their –CONH2 groups; the pairs were further linked by NH···Onitro hydrogen bonds, giving rise to an undulating layer structure. The apparently limited tendency of amides to form centrosymmetric hydrogen-bonded dimers has been discussed by Allen et al. (1998).

By chance, we have now discovered a new modification of (I) (see Experimental), which also crystallizes in P21/c, but with different cell constants. The molecule is shown in Fig. 1. The bond lengths and angles (Table 1) are similar in both modifications; in particular, the angles C3—C4—C5 and C6—C1—C7 are appreciably wider than 120°. The torsion angles, however, show that the substituents are rotated to different extents out of the ring plane. In the previous modification, the amide group was rotated by only ca 2°, but the nitro group by ca 7°; in the current structure, the corresponding interplanar angles are 2.15 (7)° for the nitro group but 20.17 (4)° for the amide group.

The molecular packing is completely different from that of the first modification (Fig. 2 and Table 2). The molecules are first linked by a symmetric three-centre N1—H1'(···Onitro)2 hydrogen bond to form chains parallel to the y axis; Allen et al. (1997) showed in an analysis of hydrogen bonding to nitro groups that such symmetric systems are far from common. Next, the chains are crosslinked via the c-glide operator by N1—H2'···Oamide hydrogen bonds to form layers parallel to the yz plane. Finally, three `weak' hydrogen bonds of the form C—H···O join adjacent layers (not shown in Fig. 2); this is facilitated by the rotation of the molecules relative to the yz plane and of the amide groups relative to the rings.

Experimental top

Attempts to crystallize the phosphinimide 2,3-diphenyl-2-(nitrobenzoylimido)-3,4-dihydro-2H-2σ42λ5– naphtho[2,3-e][1,3,2]-oxazaphosphorin-4-one by slow evaporation from dichloromethane led to crystals of the title compound, presumably by slow hydrolysis by adventitious water (Thönnessen, 2000).

Refinement top

The H atoms of the NH2 group were refined freely; other H atoms were included using a riding model with fixed C—H bond lengths of 0.95 Å; Uiso(H) values were fixed at 1.2 times the Ueq value of the parent atom.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecule of the title compound in the crystal. Ellipsoids represent 50% probability levels. H-atom radii are arbitrary.
[Figure 2] Fig. 2. Packing diagram of the title compound, viewed perpendicular to the yz plane. Hydrogen bonds are indicated by dashed lines.
4-Nitrobenzamide top
Crystal data top
C7H6N2O3F(000) = 344
Mr = 166.14Dx = 1.543 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.0993 (15) ÅCell parameters from 2576 reflections
b = 10.183 (2) Åθ = 1.6–28°
c = 10.1298 (15) ŵ = 0.12 mm1
β = 102.417 (10)°T = 173 K
V = 715.2 (2) Å3Plate, colourless
Z = 40.5 × 0.4 × 0.2 mm
Data collection top
Siemens SMART
diffractometer
1438 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.042
Graphite monochromatorθmax = 28.2°, θmin = 2.9°
ω scansh = 99
4603 measured reflectionsk = 913
1746 independent reflectionsl = 1213
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0419P)2 + 0.429P]
where P = (Fo2 + 2Fc2)/3
1746 reflections(Δ/σ)max < 0.001
117 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C7H6N2O3V = 715.2 (2) Å3
Mr = 166.14Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.0993 (15) ŵ = 0.12 mm1
b = 10.183 (2) ÅT = 173 K
c = 10.1298 (15) Å0.5 × 0.4 × 0.2 mm
β = 102.417 (10)°
Data collection top
Siemens SMART
diffractometer
1438 reflections with I > 2σ(I)
4603 measured reflectionsRint = 0.042
1746 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.120H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.32 e Å3
1746 reflectionsΔρmin = 0.30 e Å3
117 parameters
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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

7.0672 (0.0020) x + 0.5190 (0.0295) y − 1.3754 (0.0100) z = 1.4488 (0.0246)

* 0.0000 (0.0000) C7 * 0.0000 (0.0000) N1 * 0.0000 (0.0000) O1

Rms deviation of fitted atoms = 0.0000

− 6.8377 (0.0019) x − 0.2696 (0.0062) y + 4.7458 (0.0058) z = 0.5185 (0.0042)

Angle to previous plane (with approximate e.s.d.) = 20.17 (0.04)

* 0.0110 (0.0010) C1 * −0.0011 (0.0011) C2 * −0.0093 (0.0011) C3 * 0.0097 (0.0010) C4 * 0.0005 (0.0011) C5 * −0.0108 (0.0011) C6

Rms deviation of fitted atoms = 0.0084

− 6.7974 (0.0027) x + 0.0439 (0.0309) y + 4.9393 (0.0100) z = 0.7197 (0.0068)

Angle to previous plane (with approximate e.s.d.) = 2.15 (0.07)

* 0.0000 (0.0000) N2 * 0.0000 (0.0000) O2 * 0.0000 (0.0000) O3

Rms deviation of fitted atoms = 0.0000

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2595 (2)0.57451 (14)0.51804 (14)0.0193 (3)
C20.3409 (2)0.49565 (15)0.62834 (15)0.0218 (3)
H20.39800.53520.71230.026*
C30.3390 (2)0.35940 (15)0.61615 (15)0.0230 (3)
H30.39530.30500.69040.028*
C40.2523 (2)0.30567 (15)0.49214 (15)0.0211 (3)
C50.1726 (2)0.38100 (15)0.37974 (15)0.0225 (3)
H50.11590.34080.29600.027*
C60.1782 (2)0.51691 (15)0.39312 (15)0.0219 (3)
H60.12680.57080.31740.026*
C70.2575 (2)0.72082 (15)0.54168 (15)0.0215 (3)
N10.2306 (2)0.79970 (15)0.43350 (15)0.0295 (3)
H1'0.233 (3)0.883 (3)0.447 (2)0.042 (6)*
H2'0.243 (3)0.772 (2)0.351 (2)0.043 (6)*
N20.2443 (2)0.16094 (14)0.48053 (14)0.0266 (3)
O10.27697 (19)0.76407 (12)0.65812 (11)0.0316 (3)
O20.3159 (2)0.09500 (13)0.57957 (15)0.0498 (4)
O30.1651 (2)0.11223 (13)0.37189 (14)0.0407 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0202 (7)0.0176 (7)0.0210 (7)0.0004 (5)0.0067 (5)0.0008 (6)
C20.0248 (7)0.0219 (8)0.0179 (7)0.0011 (6)0.0030 (5)0.0020 (6)
C30.0259 (7)0.0218 (8)0.0201 (7)0.0016 (6)0.0022 (6)0.0027 (6)
C40.0231 (7)0.0158 (7)0.0253 (8)0.0002 (5)0.0074 (6)0.0006 (6)
C50.0252 (7)0.0226 (7)0.0189 (7)0.0035 (6)0.0029 (5)0.0035 (6)
C60.0251 (7)0.0212 (7)0.0189 (7)0.0003 (6)0.0034 (5)0.0021 (6)
C70.0228 (7)0.0199 (7)0.0224 (7)0.0011 (5)0.0063 (5)0.0014 (6)
N10.0482 (9)0.0160 (7)0.0257 (7)0.0002 (6)0.0111 (6)0.0001 (6)
N20.0321 (7)0.0181 (6)0.0304 (7)0.0009 (5)0.0083 (6)0.0009 (5)
O10.0492 (8)0.0231 (6)0.0232 (6)0.0022 (5)0.0093 (5)0.0052 (5)
O20.0791 (11)0.0202 (7)0.0425 (8)0.0019 (7)0.0036 (7)0.0082 (6)
O30.0588 (9)0.0236 (6)0.0371 (7)0.0039 (6)0.0046 (6)0.0099 (6)
Geometric parameters (Å, º) top
C1—C21.396 (2)C5—C61.390 (2)
C1—C61.401 (2)C5—H50.9500
C1—C71.510 (2)C6—H60.9500
C2—C31.393 (2)C7—O11.239 (2)
C2—H20.9500C7—N11.339 (2)
C3—C41.387 (2)N1—H1'0.86 (3)
C3—H30.9500N1—H2'0.90 (2)
C4—C51.388 (2)N2—O21.223 (2)
C4—N21.479 (2)N2—O31.228 (2)
C2—C1—C6120.06 (14)C6—C5—H5120.9
C2—C1—C7117.20 (13)C5—C6—C1120.15 (14)
C6—C1—C7122.70 (14)C5—C6—H6119.9
C3—C2—C1120.50 (14)C1—C6—H6119.9
C3—C2—H2119.7O1—C7—N1122.22 (15)
C1—C2—H2119.7O1—C7—C1119.94 (14)
C4—C3—C2117.85 (14)N1—C7—C1117.83 (14)
C4—C3—H3121.1C7—N1—H1'117.9 (15)
C2—C3—H3121.1C7—N1—H2'123.1 (15)
C3—C4—C5123.23 (14)H1'—N1—H2'117 (2)
C3—C4—N2117.85 (14)O2—N2—O3122.88 (15)
C5—C4—N2118.92 (14)O2—N2—C4118.68 (14)
C4—C5—C6118.16 (14)O3—N2—C4118.44 (14)
C4—C5—H5120.9
C6—C1—C2—C31.2 (2)C7—C1—C6—C5175.62 (14)
C7—C1—C2—C3176.67 (14)C2—C1—C7—O119.2 (2)
C1—C2—C3—C40.7 (2)C6—C1—C7—O1158.62 (15)
C2—C3—C4—C51.8 (2)C2—C1—C7—N1162.03 (14)
C2—C3—C4—N2177.95 (13)C6—C1—C7—N120.1 (2)
C3—C4—C5—C60.9 (2)C3—C4—N2—O20.8 (2)
N2—C4—C5—C6178.85 (14)C5—C4—N2—O2179.50 (15)
C4—C5—C6—C11.1 (2)C3—C4—N2—O3178.81 (14)
C2—C1—C6—C52.1 (2)C5—C4—N2—O30.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.86 (3)2.47 (3)3.257 (2)153 (2)
N1—H1···O2i0.86 (3)2.55 (3)3.349 (2)156 (2)
N1—H2···O1ii0.90 (2)2.06 (2)2.951 (2)172 (2)
C3—H3···O1iii0.952.533.305 (2)139
C2—H2···O2iv0.952.663.552 (2)156
C6—H6···O3v0.952.543.358 (2)145
Symmetry codes: (i) x, y+1, z; (ii) x, y+3/2, z1/2; (iii) x+1, y1/2, z+3/2; (iv) x+1, y+1/2, z+3/2; (v) x, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC7H6N2O3
Mr166.14
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)7.0993 (15), 10.183 (2), 10.1298 (15)
β (°) 102.417 (10)
V3)715.2 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.5 × 0.4 × 0.2
Data collection
DiffractometerSiemens SMART
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4603, 1746, 1438
Rint0.042
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.120, 1.09
No. of reflections1746
No. of parameters117
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.30

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.

Selected bond and torsion angles (º) top
C6—C1—C7122.70 (14)C3—C4—C5123.23 (14)
C2—C1—C7—O119.2 (2)C3—C4—N2—O20.8 (2)
C6—C1—C7—O1158.62 (15)C5—C4—N2—O2179.50 (15)
C2—C1—C7—N1162.03 (14)C3—C4—N2—O3178.81 (14)
C6—C1—C7—N120.1 (2)C5—C4—N2—O30.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1'···O3i0.86 (3)2.47 (3)3.257 (2)153 (2)
N1—H1'···O2i0.86 (3)2.55 (3)3.349 (2)156 (2)
N1—H2'···O1ii0.90 (2)2.06 (2)2.951 (2)172 (2)
C3—H3···O1iii0.952.533.305 (2)139
C2—H2···O2iv0.952.663.552 (2)156
C6—H6···O3v0.952.543.358 (2)145
Symmetry codes: (i) x, y+1, z; (ii) x, y+3/2, z1/2; (iii) x+1, y1/2, z+3/2; (iv) x+1, y+1/2, z+3/2; (v) x, y+1/2, z+1/2.
 

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