Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680102089X/ya6072sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680102089X/ya6072Isup2.hkl |
CCDC reference: 180543
Crystals of (I) were obtained from a mixture of equimolecular solutions of PPNO and DNBA in acetonitrile, which was left to evaporate slowly. Initial reagents were purchased from Aldrich and were used without additional purification. The melting point of the crystals of (I) is 403 (1) K.
All H atoms, with the exception of the carboxylic group HO3 atom, were placed in geometrically calculated positions and included in the refinement as riding. The displacement parameters of the H atoms were given a value of 1.2Ueq, where Ueq is the equivalent displacement parameter of the carrier atom. The HO3 atom was located in the difference Fourier synthesis and refined isotropically.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Enraf-Nonius 1989); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ZORTEP (Zsolnai, 1995); software used to prepare material for publication: SHELXL97.
C7H4N2O6·C6H7NO | Dx = 1.559 Mg m−3 Dm = 1.547 Mg m−3 Dm measured by floatation in KI solution |
Mr = 321.25 | Melting point: 403(1) K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2223 (2) Å | Cell parameters from 2643 reflections |
b = 6.3266 (1) Å | θ = 1.0–27.5° |
c = 23.4991 (4) Å | µ = 0.13 mm−1 |
β = 93.6067 (7)° | T = 123 K |
V = 1368.36 (4) Å3 | Cut_plate, yellow |
Z = 4 | 0.20 × 0.15 × 0.08 mm |
F(000) = 664 |
Nonius KappaCCD diffractometer | 2759 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.011 |
Graphite monochromator | θmax = 27.5°, θmin = 2.4° |
ϕ and ω scans | h = 0→11 |
4607 measured reflections | k = −7→8 |
2973 independent reflections | l = −30→30 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0423P)2 + 0.05663P], where P = (Fo2 + 2Fc2)/3 |
2973 reflections | (Δ/σ)max < 0.001 |
212 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C7H4N2O6·C6H7NO | V = 1368.36 (4) Å3 |
Mr = 321.25 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.2223 (2) Å | µ = 0.13 mm−1 |
b = 6.3266 (1) Å | T = 123 K |
c = 23.4991 (4) Å | 0.20 × 0.15 × 0.08 mm |
β = 93.6067 (7)° |
Nonius KappaCCD diffractometer | 2759 reflections with I > 2σ(I) |
4607 measured reflections | Rint = 0.011 |
2973 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.31 e Å−3 |
2973 reflections | Δρmin = −0.22 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 | ||
C1 | 0.16145 (11) | 1.1161 (2) | 0.39689 (5) | 0.0163 (2) | |
C2 | 0.20254 (11) | 0.9265 (2) | 0.42280 (5) | 0.0166 (2) | |
H2 | 0.1608 | 0.8815 | 0.4557 | 0.020* | |
C3 | 0.30813 (11) | 0.8051 (2) | 0.39810 (5) | 0.0163 (2) | |
C4 | 0.36967 (11) | 0.8741 (2) | 0.34875 (5) | 0.0172 (2) | |
H4 | 0.4394 | 0.7931 | 0.3319 | 0.021* | |
C5 | 0.32487 (11) | 1.0659 (2) | 0.32531 (5) | 0.0171 (2) | |
C6 | 0.22033 (11) | 1.1908 (2) | 0.34819 (5) | 0.0172 (2) | |
H6 | 0.1911 | 1.3187 | 0.3317 | 0.021* | |
C7 | 0.36106 (11) | 0.5996 (2) | 0.42424 (5) | 0.0174 (2) | |
N1 | 0.05276 (10) | 1.2500 (2) | 0.42293 (4) | 0.0196 (2) | |
N2 | 0.39206 (10) | 1.1435 (2) | 0.27433 (4) | 0.0218 (2) | |
O1 | 0.01459 (10) | 1.2001 (2) | 0.46991 (4) | 0.0304 (2) | |
O2 | 0.00691 (10) | 1.40442 (14) | 0.39587 (4) | 0.0275 (2) | |
O3 | 0.29742 (9) | 0.55048 (13) | 0.47062 (4) | 0.0224 (2) | |
O4 | 0.45300 (9) | 0.49427 (13) | 0.40224 (4) | 0.0227 (2) | |
O5 | 0.47452 (10) | 1.0252 (2) | 0.25054 (4) | 0.0317 (2) | |
O6 | 0.36325 (10) | 1.3238 (2) | 0.25824 (4) | 0.0344 (2) | |
HO3 | 0.331 (2) | 0.419 (4) | 0.4857 (8) | 0.056 (6)* | |
C8 | 0.17946 (12) | 0.1770 (2) | 0.63476 (5) | 0.0205 (2) | |
H8 | 0.1177 | 0.2619 | 0.6547 | 0.025* | |
C9 | 0.23219 (12) | 0.2507 (2) | 0.58478 (5) | 0.0201 (2) | |
H9 | 0.2059 | 0.3843 | 0.5712 | 0.024* | |
C10 | 0.35938 (12) | −0.0678 (2) | 0.57380 (5) | 0.0178 (2) | |
H10 | 0.4197 | −0.1510 | 0.5528 | 0.021* | |
C11 | 0.30788 (12) | −0.1444 (2) | 0.62357 (5) | 0.0188 (2) | |
H11 | 0.3340 | −0.2796 | 0.6359 | 0.023* | |
C12 | 0.21739 (12) | −0.0228 (2) | 0.65585 (5) | 0.0187 (2) | |
C13 | 0.16328 (13) | −0.1040 (2) | 0.71072 (5) | 0.0253 (3) | |
H131 | 0.0869 | −0.0139 | 0.7225 | 0.030* | |
H132 | 0.2416 | −0.1050 | 0.7396 | 0.030* | |
H133 | 0.1267 | −0.2450 | 0.7051 | 0.030* | |
N3 | 0.32205 (10) | 0.12877 (15) | 0.55550 (4) | 0.0165 (2) | |
O7 | 0.37737 (9) | 0.19863 (13) | 0.50791 (3) | 0.0219 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0142 (5) | 0.0172 (5) | 0.0177 (5) | 0.0008 (4) | 0.0023 (4) | −0.0016 (4) |
C2 | 0.0159 (5) | 0.0177 (5) | 0.0163 (5) | −0.0011 (4) | 0.0022 (4) | 0.0004 (4) |
C3 | 0.0154 (5) | 0.0157 (5) | 0.0176 (5) | −0.0008 (4) | −0.0001 (4) | −0.0008 (4) |
C4 | 0.0148 (5) | 0.0194 (5) | 0.0174 (5) | 0.0008 (4) | 0.0016 (4) | −0.0022 (4) |
C5 | 0.0158 (5) | 0.0220 (5) | 0.0135 (5) | −0.0023 (4) | 0.0013 (4) | 0.0011 (4) |
C6 | 0.0165 (5) | 0.0169 (5) | 0.0179 (5) | −0.0006 (4) | −0.0010 (4) | 0.0014 (4) |
C7 | 0.0170 (5) | 0.0161 (5) | 0.0190 (5) | −0.0005 (4) | 0.0002 (4) | −0.0008 (4) |
N1 | 0.0181 (4) | 0.0189 (5) | 0.0221 (5) | 0.0025 (4) | 0.0043 (4) | 0.0009 (4) |
N2 | 0.0178 (5) | 0.0304 (6) | 0.0173 (5) | 0.0003 (4) | 0.0023 (4) | 0.0039 (4) |
O1 | 0.0338 (5) | 0.0301 (5) | 0.0294 (5) | 0.0090 (4) | 0.0181 (4) | 0.0072 (4) |
O2 | 0.0298 (5) | 0.0226 (4) | 0.0303 (5) | 0.0113 (4) | 0.0047 (4) | 0.0047 (4) |
O3 | 0.0237 (4) | 0.0196 (4) | 0.0245 (4) | 0.0050 (3) | 0.0070 (3) | 0.0065 (3) |
O4 | 0.0250 (4) | 0.0189 (4) | 0.0246 (5) | 0.0051 (3) | 0.0050 (3) | −0.0011 (3) |
O5 | 0.0317 (5) | 0.0394 (5) | 0.0255 (5) | 0.0057 (4) | 0.0140 (4) | 0.0017 (4) |
O6 | 0.0329 (5) | 0.0375 (5) | 0.0340 (5) | 0.0082 (4) | 0.0108 (4) | 0.0202 (4) |
C8 | 0.0195 (5) | 0.0209 (6) | 0.0213 (6) | 0.0035 (4) | 0.0041 (4) | −0.0021 (4) |
C9 | 0.0224 (5) | 0.0162 (5) | 0.0220 (6) | 0.0050 (4) | 0.0027 (4) | 0.0001 (4) |
C10 | 0.0176 (5) | 0.0148 (5) | 0.0208 (6) | 0.0018 (4) | 0.0007 (4) | −0.0017 (4) |
C11 | 0.0199 (5) | 0.0148 (5) | 0.0215 (6) | 0.0003 (4) | 0.0009 (4) | 0.0019 (4) |
C12 | 0.0165 (5) | 0.0207 (5) | 0.0189 (5) | −0.0021 (4) | 0.0010 (4) | 0.0002 (4) |
C13 | 0.0260 (6) | 0.0270 (6) | 0.0236 (6) | −0.0002 (5) | 0.0069 (5) | 0.0037 (5) |
N3 | 0.0180 (4) | 0.0161 (5) | 0.0155 (4) | 0.0011 (3) | 0.0018 (3) | 0.0004 (3) |
O7 | 0.0284 (4) | 0.0204 (4) | 0.0178 (4) | 0.0047 (3) | 0.0083 (3) | 0.0044 (3) |
C1—C6 | 1.381 (2) | N2—O5 | 1.2263 (14) |
C1—C2 | 1.387 (2) | O3—HO3 | 0.95 (2) |
C1—N1 | 1.4745 (14) | C8—C9 | 1.380 (2) |
C2—C3 | 1.3948 (15) | C8—C12 | 1.394 (2) |
C2—H2 | 0.930 | C8—H8 | 0.930 |
C3—C4 | 1.393 (2) | C9—N3 | 1.3518 (14) |
C3—C7 | 1.5062 (15) | C9—H9 | 0.930 |
C4—C5 | 1.385 (2) | C10—N3 | 1.3531 (14) |
C4—H4 | 0.930 | C10—C11 | 1.378 (2) |
C5—C6 | 1.381 (2) | C10—H10 | 0.930 |
C5—N2 | 1.4675 (14) | C11—C12 | 1.394 (2) |
C6—H6 | 0.930 | C11—H11 | 0.930 |
C7—O4 | 1.2187 (14) | C12—C13 | 1.502 (2) |
C7—O3 | 1.3074 (14) | C13—H131 | 0.960 |
N1—O1 | 1.2210 (13) | C13—H132 | 0.960 |
N1—O2 | 1.2265 (13) | C13—H133 | 0.960 |
N2—O6 | 1.2256 (14) | N3—O7 | 1.3335 (12) |
C6—C1—C2 | 123.32 (10) | O5—N2—C5 | 118.29 (10) |
C6—C1—N1 | 117.40 (10) | C7—O3—HO3 | 111.7 (12) |
C2—C1—N1 | 119.26 (10) | C9—C8—C12 | 120.98 (10) |
C1—C2—C3 | 118.15 (10) | C9—C8—H8 | 119.51 |
C1—C2—H2 | 120.92 | C12—C8—H8 | 119.51 |
C3—C2—H2 | 120.92 | N3—C9—C8 | 120.03 (10) |
C4—C3—C2 | 120.37 (10) | N3—C9—H9 | 119.98 |
C4—C3—C7 | 118.13 (10) | C8—C9—H9 | 119.98 |
C2—C3—C7 | 121.49 (10) | N3—C10—C11 | 119.91 (10) |
C5—C4—C3 | 118.60 (10) | N3—C10—H10 | 120.04 |
C5—C4—H4 | 120.70 | C11—C10—H10 | 120.04 |
C3—C4—H4 | 120.70 | C10—C11—C12 | 121.20 (10) |
C6—C5—C4 | 122.99 (10) | C10—C11—H11 | 119.40 |
C6—C5—N2 | 117.86 (10) | C12—C11—H11 | 119.40 |
C4—C5—N2 | 119.14 (10) | C11—C12—C8 | 116.89 (10) |
C1—C6—C5 | 116.55 (10) | C11—C12—C13 | 121.39 (11) |
C1—C6—H6 | 121.72 | C8—C12—C13 | 121.72 (10) |
C5—C6—H6 | 121.72 | C12—C13—H131 | 109.47 |
O4—C7—O3 | 125.76 (10) | C12—C13—H132 | 109.47 |
O4—C7—C3 | 121.03 (10) | H131—C13—H132 | 109.47 |
O3—C7—C3 | 113.21 (9) | C12—C13—H133 | 109.47 |
O1—N1—O2 | 124.41 (10) | H131—C13—H133 | 109.47 |
O1—N1—C1 | 117.96 (9) | H132—C13—H133 | 109.47 |
O2—N1—C1 | 117.63 (9) | O7—N3—C9 | 121.12 (9) |
O6—N2—O5 | 123.77 (10) | O7—N3—C10 | 117.91 (9) |
O6—N2—C5 | 117.94 (10) | C9—N3—C10 | 120.97 (10) |
C6—C1—C2—C3 | −0.4 (2) | C2—C1—N1—O1 | 8.0 (2) |
N1—C1—C2—C3 | −178.46 (9) | C6—C1—N1—O2 | 9.7 (2) |
C1—C2—C3—C4 | −0.1 (2) | C2—C1—N1—O2 | −172.12 (10) |
C1—C2—C3—C7 | 178.70 (10) | C6—C5—N2—O6 | 7.4 (2) |
C2—C3—C4—C5 | 0.7 (2) | C4—C5—N2—O6 | −171.67 (10) |
C7—C3—C4—C5 | −178.12 (9) | C6—C5—N2—O5 | −173.13 (10) |
C3—C4—C5—C6 | −0.9 (2) | C4—C5—N2—O5 | 7.8 (2) |
C3—C4—C5—N2 | 178.15 (10) | C12—C8—C9—N3 | 0.0 (2) |
C2—C1—C6—C5 | 0.1 (2) | N3—C10—C11—C12 | 0.0 (2) |
N1—C1—C6—C5 | 178.27 (9) | C10—C11—C12—C8 | 1.3 (2) |
C4—C5—C6—C1 | 0.5 (2) | C10—C11—C12—C13 | −178.81 (11) |
N2—C5—C6—C1 | −178.57 (9) | C9—C8—C12—C11 | −1.3 (2) |
C4—C3—C7—O4 | −1.5 (2) | C9—C8—C12—C13 | 178.85 (11) |
C2—C3—C7—O4 | 179.74 (10) | C8—C9—N3—O7 | −178.25 (10) |
C4—C3—C7—O3 | 179.37 (10) | C8—C9—N3—C10 | 1.3 (2) |
C2—C3—C7—O3 | 0.59 (15) | C11—C10—N3—O7 | 178.29 (10) |
C6—C1—N1—O1 | −170.24 (10) | C11—C10—N3—C9 | −1.3 (2) |
Experimental details
Crystal data | |
Chemical formula | C7H4N2O6·C6H7NO |
Mr | 321.25 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 123 |
a, b, c (Å) | 9.2223 (2), 6.3266 (1), 23.4991 (4) |
β (°) | 93.6067 (7) |
V (Å3) | 1368.36 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.20 × 0.15 × 0.08 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4607, 2973, 2759 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.095, 1.05 |
No. of reflections | 2973 |
No. of parameters | 212 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.22 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Enraf-Nonius 1989), DENZO and COLLECT, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and ZORTEP (Zsolnai, 1995), SHELXL97.
C2—C3 | 1.3948 (15) | C7—O3 | 1.3074 (14) |
C3—C4 | 1.393 (2) | C9—N3 | 1.3518 (14) |
C3—C7 | 1.5062 (15) | C10—N3 | 1.3531 (14) |
C7—O4 | 1.2187 (14) | N3—O7 | 1.3335 (12) |
C4—C3—C7 | 118.13 (10) | O3—C7—C3 | 113.21 (9) |
C2—C3—C7 | 121.49 (10) | O7—N3—C9 | 121.12 (9) |
O4—C7—O3 | 125.76 (10) | O7—N3—C10 | 117.91 (9) |
C4—C3—C7—O4 | −1.5 (2) | C4—C5—N2—O5 | 7.8 (2) |
C6—C1—N1—O2 | 9.7 (2) |
The para-methylpyridine N-oxide molecule (PPNO) represents an interesting system which tends to form molecular complexes with diverse hydrogen-bond donors (Moreno-Fuquen et al., 1995). The synthesis and characterization of the title PPNO and 3,5-dinitrobENZOic acid (DNBA) complex, (I), have a twofold purpose: (a) to enrich the crystallographic information on compounds based on the PPNO and (b) to analyze the type of hydrogen bond in the title complex, (I).
The DNBA–PPNO adduct with the adopted atom-numbering scheme is shown in Fig. 1. The molecular complex owes its formation to a strong hydrogen bond (Emsley, 1984) between the O7 atom of the N-oxide group of PPNO and the O3 atom of the DNBA carboxylic group. The O7···O3 distance is 2.487 (1) Å and the angle O7···HO3—O3 is 176 (2)°. The O3—HO3 and O7···HO3 distances are 0.95 (2) and 1.54 (2) Å, respectively. The dihedral angle formed by the planes of the rings of the component molecules is 7.40 (7)°.
The structure of pyridine oxide component is close to that found in a number of structures involving pyridine oxide derivatives, e.g. 4-methylpyridine N-oxide [Morris et al., 1998; Cambridge Structural Database (Allen et al., 1991) refcode NUSCAF], 4,4'-dimethyl-2,2'-bipyridine 1,1'-dioxide (Kanno & Iijima, 1997; TUDREP), 3,5-dinitrobENZOic acid (Domenicano et al., 1990; CUKCAM10) and 3-methyl-nitropyridine-1-oxide 3,5-dinitrobENZOic acid (Bochuan et al., 1995; FAFTAH). The N3—O7 bond length changes from 1.3335 (12) Å in (I) to 1.309 and 1.301 Å, respectively, in the NUSCAF and TUDREP structures. The C3—C7, O4—C7 and O3—C7 bond lengths in the CUKCAM10 structure change from 1.4837 (8), 1.2357 (7) and 1.2844 (5) Å to 1.5062 (15), 1.2187 (14) and 1.3074 (14) Å, respectively, in the title complex. The latter changes in bond lengths may be explained by the formation of intermolecular hydrogen bond in the title complex. The structural behavior of DNBA moiety in the title complex is very close to the structure of the same moiety in the FAFTAH structure.
The rings of the complex are stacked in the crystal along the b axis (Fig. 2). Resulting stacks exhibit overlap between the aromatic rings with a mean interplanar distance of 3.136 (1) Å.