Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010790/om6032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010790/om6032Isup2.hkl |
CCDC reference: 170900
Single crystals suitable for X-ray analysis were obtained by slow evaporation from an equimolecular solution of DNP and MEPNO in acetonitrile. Pale-yellow transparent prisms were obtained with a melting point of 418 (1) K.
The ring and methyl H atoms were added at calculated positions. The H atoms treated with a riding model with SHELXL97 (Sheldrick, 1997) defaults (C—H = 0.93–0.97 Å) and were not refined. The HO1 atom was found from a difference map and its coordinates were refined.
Data collection: Crysom Diffraction Software (Seifert, 1995); cell refinement: Crysom Diffractometer Software; data reduction: Crysom Diffractometer Software; program(s) used to solve structure: SHELXS97 (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.
C6H7NO2·C6H4N2O5 | F(000) = 320 |
Mr = 309.24 | Dx = 1.532 Mg m−3 |
Triclinic, P1 | Melting point: 418(1) K |
a = 6.7683 (5) Å | Cu Kα radiation, λ = 1.54180 Å |
b = 7.4976 (7) Å | Cell parameters from 25 reflections |
c = 14.4864 (2) Å | θ = 2.0–35.0° |
α = 87.92 (1)° | µ = 1.11 mm−1 |
β = 90.77 (1)° | T = 293 K |
γ = 114.18 (1)° | Transparent prisms, pale yellow |
V = 670.19 (8) Å3 | 0.22 × 0.16 × 0.15 mm |
Z = 2 |
Seifert diffractometer | Rint = 0.013 |
Radiation source: fine-focus sealed tube | θmax = 66.7°, θmin = 3.1° |
Graphite monochromator | h = −7→7 |
ω/2θ scans | k = −8→8 |
2329 measured reflections | l = 0→16 |
2229 independent reflections | 2 standard reflections every 150 reflections |
2060 reflections with I > 2σ(I) | intensity decay: 2.0% |
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)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0635P)2 + 0.3304P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
2229 reflections | Δρmax = 0.45 e Å−3 |
215 parameters | Δρmin = −0.29 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.029 (2) |
C6H7NO2·C6H4N2O5 | γ = 114.18 (1)° |
Mr = 309.24 | V = 670.19 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.7683 (5) Å | Cu Kα radiation |
b = 7.4976 (7) Å | µ = 1.11 mm−1 |
c = 14.4864 (2) Å | T = 293 K |
α = 87.92 (1)° | 0.22 × 0.16 × 0.15 mm |
β = 90.77 (1)° |
Seifert diffractometer | Rint = 0.013 |
2329 measured reflections | 2 standard reflections every 150 reflections |
2229 independent reflections | intensity decay: 2.0% |
2060 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.45 e Å−3 |
2229 reflections | Δρmin = −0.29 e Å−3 |
215 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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.0687 (3) | 0.4633 (2) | 0.23168 (10) | 0.0488 (4) | |
HO1 | 0.084 (6) | 0.585 (6) | 0.194 (3) | 0.104 (12)* | |
O6 | 0.1267 (2) | 0.7653 (2) | 0.14150 (11) | 0.0544 (5) | |
C1 | 0.1427 (3) | 0.5002 (3) | 0.31659 (14) | 0.0373 (5) | |
C2 | 0.2529 (4) | 0.6919 (3) | 0.34742 (15) | 0.0436 (5) | |
H2 | 0.2758 | 0.7968 | 0.3064 | 0.046 (6)* | |
C3 | 0.3271 (3) | 0.7281 (3) | 0.43560 (15) | 0.0432 (5) | |
H3 | 0.4025 | 0.8561 | 0.4539 | 0.066 (8)* | |
C4 | 0.2892 (3) | 0.5726 (3) | 0.49809 (13) | 0.0361 (5) | |
C5 | 0.1780 (3) | 0.3818 (3) | 0.47268 (14) | 0.0369 (5) | |
H5 | 0.1503 | 0.2785 | 0.5152 | 0.056 (7)* | |
C6 | 0.1090 (3) | 0.3483 (3) | 0.38264 (14) | 0.0359 (5) | |
C7 | −0.0313 (3) | 0.7473 (3) | −0.00250 (15) | 0.0428 (5) | |
H7 | 0.0899 | 0.7397 | −0.0284 | 0.060 (7)* | |
C8 | −0.1945 (3) | 0.7488 (3) | −0.05902 (14) | 0.0414 (5) | |
H8 | −0.1846 | 0.7424 | −0.1227 | 0.048 (6)* | |
C9 | −0.3745 (3) | 0.7599 (3) | −0.01995 (14) | 0.0400 (5) | |
C10 | −0.3841 (3) | 0.7665 (3) | 0.07541 (15) | 0.0446 (5) | |
H10 | −0.5048 | 0.7718 | 0.1030 | 0.058 (7)* | |
C11 | −0.2169 (4) | 0.7654 (3) | 0.12868 (15) | 0.0433 (5) | |
H11 | −0.2233 | 0.7708 | 0.1925 | 0.061 (7)* | |
N1 | −0.0072 (3) | 0.1444 (3) | 0.35737 (13) | 0.0472 (5) | |
N2 | 0.3655 (3) | 0.6107 (3) | 0.59272 (12) | 0.0441 (5) | |
N3 | −0.0427 (3) | 0.7565 (2) | 0.08891 (12) | 0.0395 (4) | |
O2 | 0.0149 (4) | 0.0973 (3) | 0.28093 (14) | 0.0881 (7) | |
O3 | −0.1255 (3) | 0.0311 (3) | 0.41638 (14) | 0.0751 (6) | |
O4 | 0.4683 (3) | 0.7805 (3) | 0.61404 (12) | 0.0675 (6) | |
O5 | 0.3263 (3) | 0.4719 (3) | 0.64716 (11) | 0.0595 (5) | |
C12 | −0.5307 (4) | 0.7736 (4) | −0.16699 (16) | 0.0583 (7) | |
H121 | −0.4078 | 0.8896 | −0.1863 | 0.058 (7)* | |
H122 | −0.6603 | 0.7781 | −0.1926 | 0.092 (10)* | |
H123 | −0.5146 | 0.6606 | −0.1883 | 0.064 (8)* | |
O7 | −0.5450 (2) | 0.7628 (3) | −0.06820 (11) | 0.0546 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0605 (10) | 0.0486 (9) | 0.0376 (9) | 0.0229 (7) | −0.0131 (7) | −0.0052 (7) |
O6 | 0.0446 (9) | 0.0597 (10) | 0.0547 (10) | 0.0182 (7) | −0.0154 (7) | 0.0077 (8) |
C1 | 0.0353 (10) | 0.0429 (11) | 0.0358 (11) | 0.0179 (8) | −0.0035 (8) | −0.0040 (8) |
C2 | 0.0518 (12) | 0.0358 (10) | 0.0403 (12) | 0.0154 (9) | −0.0049 (9) | 0.0025 (9) |
C3 | 0.0456 (11) | 0.0353 (11) | 0.0459 (13) | 0.0134 (9) | −0.0063 (9) | −0.0065 (9) |
C4 | 0.0333 (10) | 0.0429 (11) | 0.0347 (11) | 0.0180 (8) | −0.0042 (8) | −0.0063 (8) |
C5 | 0.0344 (10) | 0.0387 (10) | 0.0401 (12) | 0.0178 (8) | 0.0005 (8) | 0.0016 (8) |
C6 | 0.0340 (10) | 0.0346 (10) | 0.0396 (11) | 0.0142 (8) | −0.0036 (8) | −0.0037 (8) |
C7 | 0.0436 (12) | 0.0452 (11) | 0.0421 (13) | 0.0208 (9) | 0.0018 (9) | 0.0005 (9) |
C8 | 0.0464 (12) | 0.0449 (11) | 0.0325 (11) | 0.0181 (9) | −0.0003 (9) | −0.0029 (8) |
C9 | 0.0360 (10) | 0.0405 (11) | 0.0396 (12) | 0.0117 (8) | −0.0061 (8) | −0.0033 (8) |
C10 | 0.0393 (11) | 0.0527 (12) | 0.0410 (12) | 0.0178 (9) | 0.0016 (9) | −0.0037 (9) |
C11 | 0.0465 (12) | 0.0453 (11) | 0.0336 (12) | 0.0143 (9) | −0.0006 (9) | −0.0016 (9) |
N1 | 0.0534 (11) | 0.0359 (9) | 0.0486 (12) | 0.0147 (8) | −0.0088 (9) | −0.0029 (8) |
N2 | 0.0446 (10) | 0.0546 (11) | 0.0394 (10) | 0.0264 (9) | −0.0077 (8) | −0.0080 (9) |
N3 | 0.0386 (9) | 0.0367 (9) | 0.0403 (10) | 0.0130 (7) | −0.0071 (7) | 0.0036 (7) |
O2 | 0.135 (2) | 0.0522 (11) | 0.0615 (13) | 0.0207 (12) | 0.0018 (12) | −0.0219 (9) |
O3 | 0.0844 (14) | 0.0424 (9) | 0.0786 (14) | 0.0065 (9) | −0.0020 (11) | 0.0044 (9) |
O4 | 0.0895 (13) | 0.0553 (10) | 0.0572 (11) | 0.0282 (9) | −0.0294 (9) | −0.0219 (8) |
O5 | 0.0710 (11) | 0.0678 (11) | 0.0397 (9) | 0.0290 (9) | −0.0072 (8) | 0.0026 (8) |
C12 | 0.0542 (15) | 0.0689 (16) | 0.0441 (14) | 0.0181 (12) | −0.0145 (11) | 0.0020 (12) |
O7 | 0.0417 (9) | 0.0794 (11) | 0.0429 (9) | 0.0254 (8) | −0.0089 (7) | −0.0025 (8) |
O1—C1 | 1.317 (2) | C8—C9 | 1.384 (3) |
O1—HO1 | 1.01 (4) | C8—H8 | 0.9300 |
O6—N3 | 1.348 (2) | C9—O7 | 1.349 (2) |
O6—HO1 | 1.45 (4) | C9—C10 | 1.387 (3) |
C1—C6 | 1.407 (3) | C10—C11 | 1.364 (3) |
C1—C2 | 1.407 (3) | C10—H10 | 0.9300 |
C2—C3 | 1.361 (3) | C11—N3 | 1.346 (3) |
C2—H2 | 0.9300 | C11—H11 | 0.9300 |
C3—C4 | 1.389 (3) | N1—O2 | 1.204 (3) |
C3—H3 | 0.9300 | N1—O3 | 1.226 (3) |
C4—C5 | 1.377 (3) | N2—O5 | 1.223 (2) |
C4—N2 | 1.455 (3) | N2—O4 | 1.223 (2) |
C5—C6 | 1.376 (3) | N3—O6 | 1.348 (2) |
C5—H5 | 0.9300 | C12—O7 | 1.433 (3) |
C6—N1 | 1.462 (3) | C12—H121 | 0.9600 |
C7—N3 | 1.333 (3) | C12—H122 | 0.9600 |
C7—C8 | 1.370 (3) | C12—H123 | 0.9600 |
C7—H7 | 0.9300 | ||
C1—O1—HO1 | 113 (2) | O7—C9—C8 | 124.52 (19) |
N3—O6—HO1 | 112.8 (14) | O7—C9—C10 | 116.83 (19) |
O1—C1—C6 | 121.31 (18) | C8—C9—C10 | 118.65 (19) |
O1—C1—C2 | 122.46 (19) | C11—C10—C9 | 120.1 (2) |
C6—C1—C2 | 116.20 (18) | C11—C10—H10 | 119.9 |
C3—C2—C1 | 121.89 (19) | C9—C10—H10 | 119.9 |
C3—C2—H2 | 119.1 | N3—C11—C10 | 120.1 (2) |
C1—C2—H2 | 119.1 | N3—C11—H11 | 120.0 |
C2—C3—C4 | 119.54 (19) | C10—C11—H11 | 120.0 |
C2—C3—H3 | 120.2 | O2—N1—O3 | 123.8 (2) |
C4—C3—H3 | 120.2 | O2—N1—C6 | 119.37 (19) |
C5—C4—C3 | 121.31 (18) | O3—N1—C6 | 116.86 (19) |
C5—C4—N2 | 118.98 (18) | O5—N2—O4 | 122.90 (18) |
C3—C4—N2 | 119.71 (18) | O5—N2—C4 | 118.65 (18) |
C6—C5—C4 | 118.22 (18) | O4—N2—C4 | 118.45 (18) |
C6—C5—H5 | 120.9 | C7—N3—C11 | 120.84 (18) |
C4—C5—H5 | 120.9 | C7—N3—O6 | 119.31 (18) |
C5—C6—C1 | 122.81 (18) | C11—N3—O6 | 119.79 (18) |
C5—C6—N1 | 117.07 (18) | O7—C12—H121 | 109.5 |
C1—C6—N1 | 120.10 (18) | O7—C12—H122 | 109.5 |
N3—C7—C8 | 121.3 (2) | H121—C12—H122 | 109.5 |
N3—C7—H7 | 119.3 | O7—C12—H123 | 109.5 |
C8—C7—H7 | 119.3 | H121—C12—H123 | 109.5 |
C7—C8—C9 | 119.0 (2) | H122—C12—H123 | 109.5 |
C7—C8—H8 | 120.5 | C9—O7—C12 | 117.89 (18) |
C9—C8—H8 | 120.5 | ||
O1—C1—C2—C3 | 179.4 (2) | C8—C9—C10—C11 | 1.1 (3) |
C6—C1—C2—C3 | 1.4 (3) | C9—C10—C11—N3 | −0.4 (3) |
C1—C2—C3—C4 | −1.5 (3) | C5—C6—N1—O2 | −145.8 (2) |
C2—C3—C4—C5 | 0.0 (3) | C1—C6—N1—O2 | 35.3 (3) |
C2—C3—C4—N2 | −179.12 (19) | C5—C6—N1—O3 | 35.2 (3) |
C3—C4—C5—C6 | 1.5 (3) | C1—C6—N1—O3 | −143.7 (2) |
N2—C4—C5—C6 | −179.35 (17) | C5—C4—N2—O5 | −0.8 (3) |
C4—C5—C6—C1 | −1.6 (3) | C3—C4—N2—O5 | 178.40 (18) |
C4—C5—C6—N1 | 179.54 (17) | C5—C4—N2—O4 | 178.40 (19) |
O1—C1—C6—C5 | −177.87 (18) | C3—C4—N2—O4 | −2.4 (3) |
C2—C1—C6—C5 | 0.2 (3) | C8—C7—N3—C11 | 0.7 (3) |
O1—C1—C6—N1 | 0.9 (3) | C8—C7—N3—O6 | −176.45 (18) |
C2—C1—C6—N1 | 179.00 (18) | C10—C11—N3—C7 | −0.5 (3) |
N3—C7—C8—C9 | −0.1 (3) | C10—C11—N3—O6 | 176.70 (18) |
C7—C8—C9—O7 | 179.84 (19) | C8—C9—O7—C12 | −6.1 (3) |
C7—C8—C9—C10 | −0.8 (3) | C10—C9—O7—C12 | 174.6 (2) |
O7—C9—C10—C11 | −179.54 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—HO1···O6 | 1.01 (4) | 1.45 (4) | 2.461 (2) | 175 (3) |
Experimental details
Crystal data | |
Chemical formula | C6H7NO2·C6H4N2O5 |
Mr | 309.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.7683 (5), 7.4976 (7), 14.4864 (2) |
α, β, γ (°) | 87.92 (1), 90.77 (1), 114.18 (1) |
V (Å3) | 670.19 (8) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 1.11 |
Crystal size (mm) | 0.22 × 0.16 × 0.15 |
Data collection | |
Diffractometer | Seifert diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2329, 2229, 2060 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.132, 1.14 |
No. of reflections | 2229 |
No. of parameters | 215 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.45, −0.29 |
Computer programs: Crysom Diffraction Software (Seifert, 1995), Crysom Diffractometer Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and ZORTEP (Zsolnai, 1995), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—HO1···O6 | 1.01 (4) | 1.45 (4) | 2.461 (2) | 175 (3) |
Continuing an ongoing study of the properties of molecular complexes formed from various pyridine N-oxide derivatives and several hydrogen-bond donors, and particularly to complement the crystallographic information avalaible on compounds based on 4-methoxypyridine N-oxide (MEPNO), to analyse the type of hydrogen-bond in the title complex and to study its non-linear optical properties, the crystal structure determination of MEPNO and 2,4-dinitrophenol (DNP) was undertaken.
The title complex is the first organic molecular complex with MEPNO as a precursor. Other series of molecular complexes with nitropyridine N-oxide as a precursor have been reported (Moreno-Fuquen et al., 2000). The crystal structure of free MEPNO has not been reported. Several organometallic structures where MEPNO forms diverse complexes are reported in the literature. From the Cambridge Structural Database (CSD; Allen et al., 1991), the molecular parameters of three structures, namely, bis(4-methoxypyridine N-oxide)dichlorocopper (CSD refcode PIJDUH; Le Fur et al., 1993), trifluorobis(4-methoxypyridine N-oxide)antimony(III) hydrate (FMXPSB; Dewan et al., 1975) and free 2,4-dinitrophenol (DNOPHL01; Iwasaki & Kawano, 1977), may be used as a reference to analyse the behaviour of the present complex. A displacement ellipsoid plot of the hydrogen-bonded complex with the atomic numbering scheme is shown in Fig. 1.
In the title complex, the DNP and MEPNO molecules are held together by a strong intermolecular hydrogen bond (Emsley, 1984) between the O1 atom of the phenol group of the DNP molecule and nitroxide O6 atom of the MEPNO molecule. The O1···O6 distance is 2.462 (2) Å and the O1—HO1···O6 angle is 176 (4)°. The O1—HO1 and HO1···O6 distances are 1.01 (4) and 1.46 (4) Å, respectively. If one compares the molecular parameters of the title complex with those of PIJDUH, FMXPSB and DNOPHL01, the C7—C8 bond length changes from 1.371 (3) Å in the title system to 1.395 (9) Å in MSXPSB, and the C9—C10 bond length changes from 1.387 (3) Å in the title complex to 1.412 (8) Å in PIJDUH. The C1—O1 and C4—N2 bond lengths change from 1.319 (2) and 1.454 (2) Å, respectively, in the title complex to 1.343 (5) and 1.484 (3) Å in DNOPHL01. The other bond lengths and angles agree well with those reported for PIJDUH, FMXPSB and DNOPHL01. A dihedral angle of 88.82 (7)° formed by the least-squares planes containing the phenyl rings of MEPNO and DNP is shown by the title complex. The nitro O5—N2—O4 and O2—N1—O3 groups form dihedral angles of 2.06 (4) and 35.71 (3)°, respectively, with the DNP ring. The pyridine ring is planar, with the C12 and O6 atoms lying 0.082 (1) and 0.071 (1) Å out of this plane; these distances are similar to those reported for the pyridine N-oxide ligand (Horrocks et al., 1968). The crystal structure exhibits overlap between the rings of the molecules in the [102] direction. The molecules of the title complex are overlapped in the crystal with the MEPNO ring at a mean interplanar distance of 3.318 (2) Å from the other MEPNO ring at -x, 1 - y, 1 - z. The presence of a centre of symmetry in the crystal inhibits the SHG response.