Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199013724/na1431sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199013724/na1431Isup2.hkl |
CCDC reference: 142755
Crystals of (I) used in the present work were obtained by slow evaporation from an equimolecular solution of NPNO and PNBA in absolute ethanol. Initial reagents were ex Aldrich and they were used without additional purification. The sublimation point is 414 (1) K.
The ring H atoms were added at calculated positions. Those H atoms treated with a riding model with SHELXL93 (Sheldrick, 1993) defaults (C—H 0.93 Å) were not refined. The HO5 atom was located from a difference Fourier map and its coordinates were refined.
Data collection: CAD-4 Software (Enraf-Nonius 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 SDP (Frenz, 1978); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93; molecular graphics: ZORTEP (Zsolnai, 1995); software used to prepare material for publication: SHELXL93.
C7H5NO4·C5H4N2O3 | F(000) = 632 |
Mr = 307.22 | Dx = 1.578 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 6.221 (1) Å | Cell parameters from 25 reflections |
b = 22.263 (1) Å | θ = 9.3–18.3° |
c = 9.411 (1) Å | µ = 0.13 mm−1 |
β = 97.30 (2)° | T = 293 K |
V = 1292.9 (3) Å3 | Plate, yellow |
Z = 4 | 0.18 × 0.15 × 0.12 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.024 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.8° |
Graphite monochromator | h = 0→7 |
ω/2θ scans | k = 0→26 |
2498 measured reflections | l = −11→11 |
2280 independent reflections | 2 standard reflections every 120 min |
1372 reflections with I > 2σ(I) | intensity decay: 1.5% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0379P)2 + 0.7798P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2278 reflections | Δρmax = 0.19 e Å−3 |
212 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL93 (Sheldrick, 1993), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.178 (7) |
C7H5NO4·C5H4N2O3 | V = 1292.9 (3) Å3 |
Mr = 307.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.221 (1) Å | µ = 0.13 mm−1 |
b = 22.263 (1) Å | T = 293 K |
c = 9.411 (1) Å | 0.18 × 0.15 × 0.12 mm |
β = 97.30 (2)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.024 |
2498 measured reflections | 2 standard reflections every 120 min |
2280 independent reflections | intensity decay: 1.5% |
1372 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.19 e Å−3 |
2278 reflections | Δρmin = −0.20 e Å−3 |
212 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. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.0226 (4) | 0.60822 (11) | 0.5734 (2) | 0.0639 (7) | |
O2 | 0.8064 (4) | 0.75937 (12) | 0.6781 (3) | 0.0783 (8) | |
O3 | 0.8160 (4) | 0.73729 (12) | 0.4573 (3) | 0.0762 (8) | |
N1 | 0.1585 (4) | 0.63809 (11) | 0.5686 (3) | 0.0474 (7) | |
N2 | 0.7328 (4) | 0.73510 (12) | 0.5671 (3) | 0.0547 (7) | |
C1 | 0.2290 (5) | 0.67455 (13) | 0.6799 (3) | 0.0462 (7) | |
H1 | 0.1487 | 0.67819 | 0.7564 | 0.044 (8)* | |
C2 | 0.4170 (5) | 0.70594 (14) | 0.6805 (3) | 0.0466 (8) | |
H2 | 0.4667 | 0.73062 | 0.7575 | 0.053 (9)* | |
C3 | 0.5320 (5) | 0.70066 (13) | 0.5663 (3) | 0.0434 (7) | |
C4 | 0.4594 (5) | 0.66426 (14) | 0.4530 (3) | 0.0520 (8) | |
H4 | 0.5370 | 0.66098 | 0.3752 | 0.047 (8)* | |
C5 | 0.2710 (5) | 0.6328 (2) | 0.4560 (3) | 0.0562 (9) | |
H5 | 0.2205 | 0.6076 | 0.3801 | 0.057 (9)* | |
O4 | −0.0131 (4) | 0.53401 (10) | 0.2338 (2) | 0.0638 (7) | |
O5 | −0.2349 (4) | 0.53209 (12) | 0.4034 (3) | 0.0675 (7) | |
HO5 | −0.137 (7) | 0.561 (2) | 0.450 (4) | 0.099 (14)* | |
O6 | −0.7433 (4) | 0.34291 (11) | −0.1587 (3) | 0.0716 (8) | |
O7 | −0.9224 (4) | 0.33605 (12) | 0.0221 (3) | 0.0790 (8) | |
N3 | −0.7714 (4) | 0.35524 (12) | −0.0360 (3) | 0.0529 (7) | |
C6 | −0.1754 (5) | 0.51581 (13) | 0.2789 (3) | 0.0489 (8) | |
C7 | −0.3310 (5) | 0.47317 (13) | 0.1994 (3) | 0.0441 (7) | |
C8 | −0.2820 (5) | 0.44881 (13) | 0.0716 (3) | 0.0471 (8) | |
H8 | −0.1525 | 0.45877 | 0.0378 | 0.045 (8)* | |
C9 | −0.4250 (5) | 0.40987 (13) | −0.0056 (3) | 0.0487 (8) | |
H9 | −0.3927 | 0.39314 | −0.0910 | 0.049 (8)* | |
C10 | −0.6170 (5) | 0.39630 (13) | 0.0465 (3) | 0.0438 (7) | |
C11 | −0.6704 (5) | 0.41954 (13) | 0.1731 (3) | 0.0466 (8) | |
H11 | −0.7999 | 0.40925 | 0.2066 | 0.046 (8)* | |
C12 | −0.5257 (5) | 0.45865 (13) | 0.2489 (3) | 0.0469 (8) | |
H12 | −0.5591 | 0.47542 | 0.3340 | 0.050 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0599 (15) | 0.071 (2) | 0.0641 (15) | −0.0233 (13) | 0.0203 (11) | −0.0126 (12) |
O2 | 0.064 (2) | 0.098 (2) | 0.072 (2) | −0.0256 (15) | 0.0055 (13) | −0.0150 (15) |
O3 | 0.070 (2) | 0.099 (2) | 0.065 (2) | −0.0165 (15) | 0.0286 (13) | 0.0134 (14) |
N1 | 0.050 (2) | 0.0471 (15) | 0.0465 (15) | −0.0010 (13) | 0.0114 (12) | −0.0003 (12) |
N2 | 0.050 (2) | 0.059 (2) | 0.056 (2) | 0.0007 (14) | 0.0095 (14) | 0.0102 (14) |
C1 | 0.050 (2) | 0.051 (2) | 0.040 (2) | 0.001 (2) | 0.0148 (14) | −0.0035 (14) |
C2 | 0.051 (2) | 0.049 (2) | 0.040 (2) | 0.0022 (15) | 0.0077 (14) | −0.0009 (14) |
C3 | 0.045 (2) | 0.046 (2) | 0.040 (2) | 0.0024 (14) | 0.0065 (13) | 0.0077 (13) |
C4 | 0.056 (2) | 0.064 (2) | 0.040 (2) | 0.000 (2) | 0.0189 (15) | 0.0012 (15) |
C5 | 0.062 (2) | 0.066 (2) | 0.043 (2) | −0.009 (2) | 0.017 (2) | −0.011 (2) |
O4 | 0.0548 (15) | 0.0654 (15) | 0.074 (2) | −0.0134 (12) | 0.0200 (12) | −0.0077 (12) |
O5 | 0.065 (2) | 0.077 (2) | 0.063 (2) | −0.0202 (14) | 0.0184 (12) | −0.0210 (13) |
O6 | 0.079 (2) | 0.079 (2) | 0.0584 (15) | −0.0083 (14) | 0.0148 (13) | −0.0219 (13) |
O7 | 0.076 (2) | 0.080 (2) | 0.086 (2) | −0.0317 (14) | 0.0300 (15) | −0.0215 (14) |
N3 | 0.052 (2) | 0.048 (2) | 0.059 (2) | 0.0008 (13) | 0.0093 (14) | −0.0043 (13) |
C6 | 0.047 (2) | 0.046 (2) | 0.054 (2) | 0.0028 (15) | 0.0090 (15) | −0.0005 (15) |
C7 | 0.044 (2) | 0.044 (2) | 0.045 (2) | 0.0033 (14) | 0.0062 (13) | 0.0065 (14) |
C8 | 0.042 (2) | 0.049 (2) | 0.052 (2) | 0.0031 (15) | 0.0154 (14) | 0.0066 (15) |
C9 | 0.053 (2) | 0.053 (2) | 0.042 (2) | 0.005 (2) | 0.0132 (14) | −0.0013 (15) |
C10 | 0.048 (2) | 0.039 (2) | 0.045 (2) | 0.0017 (14) | 0.0081 (14) | 0.0012 (13) |
C11 | 0.047 (2) | 0.045 (2) | 0.050 (2) | −0.0017 (15) | 0.0148 (14) | 0.0022 (14) |
C12 | 0.053 (2) | 0.046 (2) | 0.043 (2) | 0.002 (2) | 0.0128 (14) | −0.0021 (14) |
O1—N1 | 1.314 (3) | O5—HO5 | 0.95 (4) |
O2—N2 | 1.213 (3) | O6—N3 | 1.221 (3) |
O3—N2 | 1.214 (3) | O7—N3 | 1.222 (3) |
N1—C5 | 1.348 (4) | N3—C10 | 1.474 (4) |
N1—C1 | 1.353 (4) | C6—C7 | 1.488 (4) |
N2—C3 | 1.465 (4) | C7—C8 | 1.388 (4) |
C1—C2 | 1.362 (4) | C7—C12 | 1.390 (4) |
C1—H1 | 0.93 | C8—C9 | 1.381 (4) |
C2—C3 | 1.370 (4) | C8—H8 | 0.93 |
C2—H2 | 0.93 | C9—C10 | 1.381 (4) |
C3—C4 | 1.369 (4) | C9—H9 | 0.93 |
C4—C5 | 1.369 (4) | C10—C11 | 1.378 (4) |
C4—H4 | 0.93 | C11—C12 | 1.384 (4) |
C5—H5 | 0.93 | C11—H11 | 0.93 |
O4—C6 | 1.213 (4) | C12—H12 | 0.93 |
O5—C6 | 1.324 (4) | ||
O1—N1—C5 | 121.0 (3) | O6—N3—C10 | 118.4 (3) |
O1—N1—C1 | 118.2 (2) | O7—N3—C10 | 117.9 (3) |
C5—N1—C1 | 120.8 (3) | O4—C6—O5 | 123.8 (3) |
O2—N2—O3 | 124.1 (3) | O4—C6—C7 | 123.7 (3) |
O2—N2—C3 | 117.8 (3) | O5—C6—C7 | 112.5 (3) |
O3—N2—C3 | 118.1 (3) | C8—C7—C12 | 119.8 (3) |
N1—C1—C2 | 120.3 (3) | C8—C7—C6 | 119.0 (3) |
C1—C2—C3 | 119.1 (3) | C12—C7—C6 | 121.3 (3) |
C4—C3—C2 | 120.6 (3) | C9—C8—C7 | 120.3 (3) |
C4—C3—N2 | 120.7 (3) | C10—C9—C8 | 118.6 (3) |
C2—C3—N2 | 118.7 (3) | C11—C10—C9 | 122.7 (3) |
C5—C4—C3 | 119.1 (3) | C11—C10—N3 | 118.4 (3) |
N1—C5—C4 | 120.2 (3) | C9—C10—N3 | 118.9 (3) |
C6—O5—HO5 | 111 (3) | C10—C11—C12 | 118.0 (3) |
O6—N3—O7 | 123.7 (3) | C11—C12—C7 | 120.7 (3) |
O1—N1—C1—C2 | 179.3 (3) | O4—C6—C7—C12 | −173.2 (3) |
C5—N1—C1—C2 | −0.8 (4) | O5—C6—C7—C12 | 6.2 (4) |
N1—C1—C2—C3 | 0.8 (4) | C12—C7—C8—C9 | −0.6 (4) |
C1—C2—C3—C4 | −0.1 (4) | C6—C7—C8—C9 | −179.0 (3) |
C1—C2—C3—N2 | 179.3 (3) | C7—C8—C9—C10 | 0.5 (4) |
O2—N2—C3—C4 | −169.2 (3) | C8—C9—C10—C11 | −0.7 (4) |
O3—N2—C3—C4 | 10.3 (4) | C8—C9—C10—N3 | 179.4 (3) |
O2—N2—C3—C2 | 11.3 (4) | O6—N3—C10—C11 | 167.5 (3) |
O3—N2—C3—C2 | −169.1 (3) | O7—N3—C10—C11 | −11.6 (4) |
C2—C3—C4—C5 | −0.5 (5) | O6—N3—C10—C9 | −12.7 (4) |
N2—C3—C4—C5 | −180.0 (3) | O7—N3—C10—C9 | 168.3 (3) |
O1—N1—C5—C4 | 180.0 (3) | C9—C10—C11—C12 | 0.9 (4) |
C1—N1—C5—C4 | 0.2 (5) | N3—C10—C11—C12 | −179.2 (3) |
C3—C4—C5—N1 | 0.5 (5) | C10—C11—C12—C7 | −1.0 (4) |
O4—C6—C7—C8 | 5.2 (5) | C8—C7—C12—C11 | 0.8 (4) |
O5—C6—C7—C8 | −175.4 (3) | C6—C7—C12—C11 | 179.2 (3) |
Experimental details
Crystal data | |
Chemical formula | C7H5NO4·C5H4N2O3 |
Mr | 307.22 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 6.221 (1), 22.263 (1), 9.411 (1) |
β (°) | 97.30 (2) |
V (Å3) | 1292.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.18 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2498, 2280, 1372 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.132, 1.08 |
No. of reflections | 2278 |
No. of parameters | 212 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.20 |
Computer programs: CAD-4 Software (Enraf-Nonius 1989), CAD-4 Software, CAD-4 SDP (Frenz, 1978), SHELXS86 (Sheldrick, 1990), SHELXL93, ZORTEP (Zsolnai, 1995).
O1—N1 | 1.314 (3) | O5—C6 | 1.324 (4) |
N1—C5 | 1.348 (4) | C6—C7 | 1.488 (4) |
N1—C1 | 1.353 (4) | ||
O2—N2—C3—C2 | 11.3 (4) | O7—N3—C10—C11 | −11.6 (4) |
O4—C6—C7—C12 | −173.2 (3) |
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Over several years, a systematic study of molecular complexes of 4-nitropyridine N-oxide (NPNO) with diverse hydrogen-bond donors (Moreno-Fuquen et al., 1996) has been carried out. Some molecular complexes associated with NPNO show potential for application in non-linear optics: the NPNO and 3-nitrophenol molecular complex has a satisfactory second harmonic generation (SHG) response (Moreno-Fuquen et al., 1995). The synthesis and characterization of the title NPNO and 4-nitrobenzoic acid (PNBA) complex, (I), have a threefold purpose: a) to add to the crystallographic information available on compounds based on NPNO, b) to analyze the type of hydrogen bond in the title complex and c) to explore its possible application in non-linear optics.
Fig. 1 shows the NPNO + PNBA adduct, (I), with the adopted atom-numbering scheme. The molecular complex is held together by an intermolecular hydrogen bond between O1 of the N-oxide group of NPNO and O—H of the carboxyl group of PNBA, with an O1···O5 distance of 2.577 (3) Å and an O1···HO5—O5 angle of 161 (3)°. The O5—HO5 and O1···HO5 distances are 0.95 (4) and 1.67 (4) Å, respectively. From the O···O bond length value, the strength of the hydrogen bond can be classified as strong (Emsley, 1984).
The dihedral angle formed by the planes which essentially contain the rings of the molecules is 5.3 (2)°. If one compares the values of bond lengths and angles in the title complex with the values in the free molecules (Tonogaki et al., 1993; Wang et al., 1976), CCDC references NBZOAC06 and NTPYRO12 (Allen et al., 1991), the C6—C7 and C6—O5 bond lengths change from 1.488 (4) and 1.324 (4) Å in (I) to 1.500 (9) and 1.289 (9) Å in the free molecule, while the C1—N1, N1—C5 and O1—N1 bond lengths change from 1.353 (4), 1.348 (4) and 1.314 (3) Å in (I) to 1.369, 1.370 and 1.291 Å in the free molecule. There are no significant differences for the other parameters.
The molecules of the (I) are stacked in the crystal with the NPNO ring at a mean interplanar distance of 3.279 (3) Å from the PNBA ring at −x, 1 − y, 1 − z. The presence of a centre of symmetry in the crystal inhibits an SHG response.