Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021244/na6185sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021244/na6185Isup2.hkl |
CCDC reference: 202356
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (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
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
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).
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.
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.
C7H6N2O3 | F(000) = 344 |
Mr = 166.14 | Dx = 1.543 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0993 (15) Å | Cell parameters from 2576 reflections |
b = 10.183 (2) Å | θ = 1.6–28° |
c = 10.1298 (15) Å | µ = 0.12 mm−1 |
β = 102.417 (10)° | T = 173 K |
V = 715.2 (2) Å3 | Plate, colourless |
Z = 4 | 0.5 × 0.4 × 0.2 mm |
Siemens SMART diffractometer | 1438 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
Graphite monochromator | θmax = 28.2°, θmin = 2.9° |
ω scans | h = −9→9 |
4603 measured reflections | k = −9→13 |
1746 independent reflections | l = −12→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H 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 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C7H6N2O3 | V = 715.2 (2) Å3 |
Mr = 166.14 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.0993 (15) Å | µ = 0.12 mm−1 |
b = 10.183 (2) Å | T = 173 K |
c = 10.1298 (15) Å | 0.5 × 0.4 × 0.2 mm |
β = 102.417 (10)° |
Siemens SMART diffractometer | 1438 reflections with I > 2σ(I) |
4603 measured reflections | Rint = 0.042 |
1746 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.32 e Å−3 |
1746 reflections | Δρmin = −0.30 e Å−3 |
117 parameters |
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 |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2595 (2) | 0.57451 (14) | 0.51804 (14) | 0.0193 (3) | |
C2 | 0.3409 (2) | 0.49565 (15) | 0.62834 (15) | 0.0218 (3) | |
H2 | 0.3980 | 0.5352 | 0.7123 | 0.026* | |
C3 | 0.3390 (2) | 0.35940 (15) | 0.61615 (15) | 0.0230 (3) | |
H3 | 0.3953 | 0.3050 | 0.6904 | 0.028* | |
C4 | 0.2523 (2) | 0.30567 (15) | 0.49214 (15) | 0.0211 (3) | |
C5 | 0.1726 (2) | 0.38100 (15) | 0.37974 (15) | 0.0225 (3) | |
H5 | 0.1159 | 0.3408 | 0.2960 | 0.027* | |
C6 | 0.1782 (2) | 0.51691 (15) | 0.39312 (15) | 0.0219 (3) | |
H6 | 0.1268 | 0.5708 | 0.3174 | 0.026* | |
C7 | 0.2575 (2) | 0.72082 (15) | 0.54168 (15) | 0.0215 (3) | |
N1 | 0.2306 (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)* | |
N2 | 0.2443 (2) | 0.16094 (14) | 0.48053 (14) | 0.0266 (3) | |
O1 | 0.27697 (19) | 0.76407 (12) | 0.65812 (11) | 0.0316 (3) | |
O2 | 0.3159 (2) | 0.09500 (13) | 0.57957 (15) | 0.0498 (4) | |
O3 | 0.1651 (2) | 0.11223 (13) | 0.37189 (14) | 0.0407 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0202 (7) | 0.0176 (7) | 0.0210 (7) | −0.0004 (5) | 0.0067 (5) | −0.0008 (6) |
C2 | 0.0248 (7) | 0.0219 (8) | 0.0179 (7) | −0.0011 (6) | 0.0030 (5) | −0.0020 (6) |
C3 | 0.0259 (7) | 0.0218 (8) | 0.0201 (7) | 0.0016 (6) | 0.0022 (6) | 0.0027 (6) |
C4 | 0.0231 (7) | 0.0158 (7) | 0.0253 (8) | −0.0002 (5) | 0.0074 (6) | −0.0006 (6) |
C5 | 0.0252 (7) | 0.0226 (7) | 0.0189 (7) | −0.0035 (6) | 0.0029 (5) | −0.0035 (6) |
C6 | 0.0251 (7) | 0.0212 (7) | 0.0189 (7) | −0.0003 (6) | 0.0034 (5) | 0.0021 (6) |
C7 | 0.0228 (7) | 0.0199 (7) | 0.0224 (7) | −0.0011 (5) | 0.0063 (5) | −0.0014 (6) |
N1 | 0.0482 (9) | 0.0160 (7) | 0.0257 (7) | 0.0002 (6) | 0.0111 (6) | 0.0001 (6) |
N2 | 0.0321 (7) | 0.0181 (6) | 0.0304 (7) | −0.0009 (5) | 0.0083 (6) | −0.0009 (5) |
O1 | 0.0492 (8) | 0.0231 (6) | 0.0232 (6) | −0.0022 (5) | 0.0093 (5) | −0.0052 (5) |
O2 | 0.0791 (11) | 0.0202 (7) | 0.0425 (8) | 0.0019 (7) | −0.0036 (7) | 0.0082 (6) |
O3 | 0.0588 (9) | 0.0236 (6) | 0.0371 (7) | −0.0039 (6) | 0.0046 (6) | −0.0099 (6) |
C1—C2 | 1.396 (2) | C5—C6 | 1.390 (2) |
C1—C6 | 1.401 (2) | C5—H5 | 0.9500 |
C1—C7 | 1.510 (2) | C6—H6 | 0.9500 |
C2—C3 | 1.393 (2) | C7—O1 | 1.239 (2) |
C2—H2 | 0.9500 | C7—N1 | 1.339 (2) |
C3—C4 | 1.387 (2) | N1—H1' | 0.86 (3) |
C3—H3 | 0.9500 | N1—H2' | 0.90 (2) |
C4—C5 | 1.388 (2) | N2—O2 | 1.223 (2) |
C4—N2 | 1.479 (2) | N2—O3 | 1.228 (2) |
C2—C1—C6 | 120.06 (14) | C6—C5—H5 | 120.9 |
C2—C1—C7 | 117.20 (13) | C5—C6—C1 | 120.15 (14) |
C6—C1—C7 | 122.70 (14) | C5—C6—H6 | 119.9 |
C3—C2—C1 | 120.50 (14) | C1—C6—H6 | 119.9 |
C3—C2—H2 | 119.7 | O1—C7—N1 | 122.22 (15) |
C1—C2—H2 | 119.7 | O1—C7—C1 | 119.94 (14) |
C4—C3—C2 | 117.85 (14) | N1—C7—C1 | 117.83 (14) |
C4—C3—H3 | 121.1 | C7—N1—H1' | 117.9 (15) |
C2—C3—H3 | 121.1 | C7—N1—H2' | 123.1 (15) |
C3—C4—C5 | 123.23 (14) | H1'—N1—H2' | 117 (2) |
C3—C4—N2 | 117.85 (14) | O2—N2—O3 | 122.88 (15) |
C5—C4—N2 | 118.92 (14) | O2—N2—C4 | 118.68 (14) |
C4—C5—C6 | 118.16 (14) | O3—N2—C4 | 118.44 (14) |
C4—C5—H5 | 120.9 | ||
C6—C1—C2—C3 | −1.2 (2) | C7—C1—C6—C5 | −175.62 (14) |
C7—C1—C2—C3 | 176.67 (14) | C2—C1—C7—O1 | −19.2 (2) |
C1—C2—C3—C4 | −0.7 (2) | C6—C1—C7—O1 | 158.62 (15) |
C2—C3—C4—C5 | 1.8 (2) | C2—C1—C7—N1 | 162.03 (14) |
C2—C3—C4—N2 | −177.95 (13) | C6—C1—C7—N1 | −20.1 (2) |
C3—C4—C5—C6 | −0.9 (2) | C3—C4—N2—O2 | −0.8 (2) |
N2—C4—C5—C6 | 178.85 (14) | C5—C4—N2—O2 | 179.50 (15) |
C4—C5—C6—C1 | −1.1 (2) | C3—C4—N2—O3 | 178.81 (14) |
C2—C1—C6—C5 | 2.1 (2) | C5—C4—N2—O3 | −0.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1′···O3i | 0.86 (3) | 2.47 (3) | 3.257 (2) | 153 (2) |
N1—H1′···O2i | 0.86 (3) | 2.55 (3) | 3.349 (2) | 156 (2) |
N1—H2′···O1ii | 0.90 (2) | 2.06 (2) | 2.951 (2) | 172 (2) |
C3—H3···O1iii | 0.95 | 2.53 | 3.305 (2) | 139 |
C2—H2···O2iv | 0.95 | 2.66 | 3.552 (2) | 156 |
C6—H6···O3v | 0.95 | 2.54 | 3.358 (2) | 145 |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −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 formula | C7H6N2O3 |
Mr | 166.14 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 7.0993 (15), 10.183 (2), 10.1298 (15) |
β (°) | 102.417 (10) |
V (Å3) | 715.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.5 × 0.4 × 0.2 |
Data collection | |
Diffractometer | Siemens SMART diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4603, 1746, 1438 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.120, 1.09 |
No. of reflections | 1746 |
No. of parameters | 117 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.30 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
C6—C1—C7 | 122.70 (14) | C3—C4—C5 | 123.23 (14) |
C2—C1—C7—O1 | −19.2 (2) | C3—C4—N2—O2 | −0.8 (2) |
C6—C1—C7—O1 | 158.62 (15) | C5—C4—N2—O2 | 179.50 (15) |
C2—C1—C7—N1 | 162.03 (14) | C3—C4—N2—O3 | 178.81 (14) |
C6—C1—C7—N1 | −20.1 (2) | C5—C4—N2—O3 | −0.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1'···O3i | 0.86 (3) | 2.47 (3) | 3.257 (2) | 153 (2) |
N1—H1'···O2i | 0.86 (3) | 2.55 (3) | 3.349 (2) | 156 (2) |
N1—H2'···O1ii | 0.90 (2) | 2.06 (2) | 2.951 (2) | 172 (2) |
C3—H3···O1iii | 0.95 | 2.53 | 3.305 (2) | 139 |
C2—H2···O2iv | 0.95 | 2.66 | 3.552 (2) | 156 |
C6—H6···O3v | 0.95 | 2.54 | 3.358 (2) | 145 |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, y+1/2, −z+3/2; (v) −x, y+1/2, −z+1/2. |
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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 N—H···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.