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In the title co-crystal, C7H5NO4·C5H4N2O3, the two components are linked by an intermolecular hydrogen bond between the O—H and N—O groups [O...O 2.577 (3) Å]. The interplanar angle between the planes of the rings of the mol­ecules is 5.3 (2)°. The rings are stacked in the crystal with a mean interplanar distance of 3.279 (3) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199013724/na1431sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199013724/na1431Isup2.hkl
Contains datablock I

CCDC reference: 142755

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A ZORTEP (Zsolnai, 1995) plot of the asymmetric unit of (I) showing the atomic numbering scheme. Displacement ellipsoids are plotted at the 50% probability level and H atoms are shown as spheres of arbitrary radii.
1:1 Complex of 4-nitrobenzoic acid and 4-nitropyridine N-oxide top
Crystal data top
C7H5NO4·C5H4N2O3F(000) = 632
Mr = 307.22Dx = 1.578 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.221 (1) ÅCell parameters from 25 reflections
b = 22.263 (1) Åθ = 9.3–18.3°
c = 9.411 (1) ŵ = 0.13 mm1
β = 97.30 (2)°T = 293 K
V = 1292.9 (3) Å3Plate, yellow
Z = 40.18 × 0.15 × 0.12 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.024
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 1.8°
Graphite monochromatorh = 07
ω/2θ scansk = 026
2498 measured reflectionsl = 1111
2280 independent reflections2 standard reflections every 120 min
1372 reflections with I > 2σ(I) intensity decay: 1.5%
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)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.132w = 1/[σ2(Fo2) + (0.0379P)2 + 0.7798P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2278 reflectionsΔρmax = 0.19 e Å3
212 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL93 (Sheldrick, 1993), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.178 (7)
Crystal data top
C7H5NO4·C5H4N2O3V = 1292.9 (3) Å3
Mr = 307.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.221 (1) ŵ = 0.13 mm1
b = 22.263 (1) ÅT = 293 K
c = 9.411 (1) Å0.18 × 0.15 × 0.12 mm
β = 97.30 (2)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.024
2498 measured reflections2 standard reflections every 120 min
2280 independent reflections intensity decay: 1.5%
1372 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.132H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.19 e Å3
2278 reflectionsΔρmin = 0.20 e Å3
212 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.0226 (4)0.60822 (11)0.5734 (2)0.0639 (7)
O20.8064 (4)0.75937 (12)0.6781 (3)0.0783 (8)
O30.8160 (4)0.73729 (12)0.4573 (3)0.0762 (8)
N10.1585 (4)0.63809 (11)0.5686 (3)0.0474 (7)
N20.7328 (4)0.73510 (12)0.5671 (3)0.0547 (7)
C10.2290 (5)0.67455 (13)0.6799 (3)0.0462 (7)
H10.14870.678190.75640.044 (8)*
C20.4170 (5)0.70594 (14)0.6805 (3)0.0466 (8)
H20.46670.730620.75750.053 (9)*
C30.5320 (5)0.70066 (13)0.5663 (3)0.0434 (7)
C40.4594 (5)0.66426 (14)0.4530 (3)0.0520 (8)
H40.53700.660980.37520.047 (8)*
C50.2710 (5)0.6328 (2)0.4560 (3)0.0562 (9)
H50.22050.60760.38010.057 (9)*
O40.0131 (4)0.53401 (10)0.2338 (2)0.0638 (7)
O50.2349 (4)0.53209 (12)0.4034 (3)0.0675 (7)
HO50.137 (7)0.561 (2)0.450 (4)0.099 (14)*
O60.7433 (4)0.34291 (11)0.1587 (3)0.0716 (8)
O70.9224 (4)0.33605 (12)0.0221 (3)0.0790 (8)
N30.7714 (4)0.35524 (12)0.0360 (3)0.0529 (7)
C60.1754 (5)0.51581 (13)0.2789 (3)0.0489 (8)
C70.3310 (5)0.47317 (13)0.1994 (3)0.0441 (7)
C80.2820 (5)0.44881 (13)0.0716 (3)0.0471 (8)
H80.15250.458770.03780.045 (8)*
C90.4250 (5)0.40987 (13)0.0056 (3)0.0487 (8)
H90.39270.393140.09100.049 (8)*
C100.6170 (5)0.39630 (13)0.0465 (3)0.0438 (7)
C110.6704 (5)0.41954 (13)0.1731 (3)0.0466 (8)
H110.79990.409250.20660.046 (8)*
C120.5257 (5)0.45865 (13)0.2489 (3)0.0469 (8)
H120.55910.475420.33400.050 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0599 (15)0.071 (2)0.0641 (15)0.0233 (13)0.0203 (11)0.0126 (12)
O20.064 (2)0.098 (2)0.072 (2)0.0256 (15)0.0055 (13)0.0150 (15)
O30.070 (2)0.099 (2)0.065 (2)0.0165 (15)0.0286 (13)0.0134 (14)
N10.050 (2)0.0471 (15)0.0465 (15)0.0010 (13)0.0114 (12)0.0003 (12)
N20.050 (2)0.059 (2)0.056 (2)0.0007 (14)0.0095 (14)0.0102 (14)
C10.050 (2)0.051 (2)0.040 (2)0.001 (2)0.0148 (14)0.0035 (14)
C20.051 (2)0.049 (2)0.040 (2)0.0022 (15)0.0077 (14)0.0009 (14)
C30.045 (2)0.046 (2)0.040 (2)0.0024 (14)0.0065 (13)0.0077 (13)
C40.056 (2)0.064 (2)0.040 (2)0.000 (2)0.0189 (15)0.0012 (15)
C50.062 (2)0.066 (2)0.043 (2)0.009 (2)0.017 (2)0.011 (2)
O40.0548 (15)0.0654 (15)0.074 (2)0.0134 (12)0.0200 (12)0.0077 (12)
O50.065 (2)0.077 (2)0.063 (2)0.0202 (14)0.0184 (12)0.0210 (13)
O60.079 (2)0.079 (2)0.0584 (15)0.0083 (14)0.0148 (13)0.0219 (13)
O70.076 (2)0.080 (2)0.086 (2)0.0317 (14)0.0300 (15)0.0215 (14)
N30.052 (2)0.048 (2)0.059 (2)0.0008 (13)0.0093 (14)0.0043 (13)
C60.047 (2)0.046 (2)0.054 (2)0.0028 (15)0.0090 (15)0.0005 (15)
C70.044 (2)0.044 (2)0.045 (2)0.0033 (14)0.0062 (13)0.0065 (14)
C80.042 (2)0.049 (2)0.052 (2)0.0031 (15)0.0154 (14)0.0066 (15)
C90.053 (2)0.053 (2)0.042 (2)0.005 (2)0.0132 (14)0.0013 (15)
C100.048 (2)0.039 (2)0.045 (2)0.0017 (14)0.0081 (14)0.0012 (13)
C110.047 (2)0.045 (2)0.050 (2)0.0017 (15)0.0148 (14)0.0022 (14)
C120.053 (2)0.046 (2)0.043 (2)0.002 (2)0.0128 (14)0.0021 (14)
Geometric parameters (Å, º) top
O1—N11.314 (3)O5—HO50.95 (4)
O2—N21.213 (3)O6—N31.221 (3)
O3—N21.214 (3)O7—N31.222 (3)
N1—C51.348 (4)N3—C101.474 (4)
N1—C11.353 (4)C6—C71.488 (4)
N2—C31.465 (4)C7—C81.388 (4)
C1—C21.362 (4)C7—C121.390 (4)
C1—H10.93C8—C91.381 (4)
C2—C31.370 (4)C8—H80.93
C2—H20.93C9—C101.381 (4)
C3—C41.369 (4)C9—H90.93
C4—C51.369 (4)C10—C111.378 (4)
C4—H40.93C11—C121.384 (4)
C5—H50.93C11—H110.93
O4—C61.213 (4)C12—H120.93
O5—C61.324 (4)
O1—N1—C5121.0 (3)O6—N3—C10118.4 (3)
O1—N1—C1118.2 (2)O7—N3—C10117.9 (3)
C5—N1—C1120.8 (3)O4—C6—O5123.8 (3)
O2—N2—O3124.1 (3)O4—C6—C7123.7 (3)
O2—N2—C3117.8 (3)O5—C6—C7112.5 (3)
O3—N2—C3118.1 (3)C8—C7—C12119.8 (3)
N1—C1—C2120.3 (3)C8—C7—C6119.0 (3)
C1—C2—C3119.1 (3)C12—C7—C6121.3 (3)
C4—C3—C2120.6 (3)C9—C8—C7120.3 (3)
C4—C3—N2120.7 (3)C10—C9—C8118.6 (3)
C2—C3—N2118.7 (3)C11—C10—C9122.7 (3)
C5—C4—C3119.1 (3)C11—C10—N3118.4 (3)
N1—C5—C4120.2 (3)C9—C10—N3118.9 (3)
C6—O5—HO5111 (3)C10—C11—C12118.0 (3)
O6—N3—O7123.7 (3)C11—C12—C7120.7 (3)
O1—N1—C1—C2179.3 (3)O4—C6—C7—C12173.2 (3)
C5—N1—C1—C20.8 (4)O5—C6—C7—C126.2 (4)
N1—C1—C2—C30.8 (4)C12—C7—C8—C90.6 (4)
C1—C2—C3—C40.1 (4)C6—C7—C8—C9179.0 (3)
C1—C2—C3—N2179.3 (3)C7—C8—C9—C100.5 (4)
O2—N2—C3—C4169.2 (3)C8—C9—C10—C110.7 (4)
O3—N2—C3—C410.3 (4)C8—C9—C10—N3179.4 (3)
O2—N2—C3—C211.3 (4)O6—N3—C10—C11167.5 (3)
O3—N2—C3—C2169.1 (3)O7—N3—C10—C1111.6 (4)
C2—C3—C4—C50.5 (5)O6—N3—C10—C912.7 (4)
N2—C3—C4—C5180.0 (3)O7—N3—C10—C9168.3 (3)
O1—N1—C5—C4180.0 (3)C9—C10—C11—C120.9 (4)
C1—N1—C5—C40.2 (5)N3—C10—C11—C12179.2 (3)
C3—C4—C5—N10.5 (5)C10—C11—C12—C71.0 (4)
O4—C6—C7—C85.2 (5)C8—C7—C12—C110.8 (4)
O5—C6—C7—C8175.4 (3)C6—C7—C12—C11179.2 (3)

Experimental details

Crystal data
Chemical formulaC7H5NO4·C5H4N2O3
Mr307.22
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)6.221 (1), 22.263 (1), 9.411 (1)
β (°) 97.30 (2)
V3)1292.9 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.18 × 0.15 × 0.12
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2498, 2280, 1372
Rint0.024
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.132, 1.08
No. of reflections2278
No. of parameters212
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Selected geometric parameters (Å, º) top
O1—N11.314 (3)O5—C61.324 (4)
N1—C51.348 (4)C6—C71.488 (4)
N1—C11.353 (4)
O2—N2—C3—C211.3 (4)O7—N3—C10—C1111.6 (4)
O4—C6—C7—C12173.2 (3)
 

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