Download citation
Download citation
link to html
The title cocrystal, C6H7N1O2·C6H4N2O5, owes its formation to an intermolecular hydrogen bond between the O—H and N—O groups [O...O 2.461 (2) Å]. The angle between the planes of the rings of the mol­ecules is 88.82 (7)°. The crystal structure exhibits overlap between the rings of the mol­ecules in the [102] direction. The rings are stacked in the crystal, with a mean interplanar distance of 3.318 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010790/om6032sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010790/om6032Isup2.hkl
Contains datablock I

CCDC reference: 170900

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.045
  • wR factor = 0.132
  • Data-to-parameter ratio = 10.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 66.72 From the CIF: _reflns_number_total 2229 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2364 Completeness (_total/calc) 94.29% Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A perspective ORTEP-3 (Farrugia, 1997) view of the title molecular complex with the atomic numbering scheme. Displacement ellipsoids are plotted at the 50% probability level and H atoms are shown as spheres of arbitrary radii.
[Figure 2] Fig. 2. A ZORTEP (Zsolnai, 1995) plot of the packing showing the overlapped rings along the [102] direction.
(I) top
Crystal data top
C6H7NO2·C6H4N2O5F(000) = 320
Mr = 309.24Dx = 1.532 Mg m3
Triclinic, P1Melting point: 418(1) K
a = 6.7683 (5) ÅCu Kα radiation, λ = 1.54180 Å
b = 7.4976 (7) ÅCell parameters from 25 reflections
c = 14.4864 (2) Åθ = 2.0–35.0°
α = 87.92 (1)°µ = 1.11 mm1
β = 90.77 (1)°T = 293 K
γ = 114.18 (1)°Transparent prisms, pale yellow
V = 670.19 (8) Å30.22 × 0.16 × 0.15 mm
Z = 2
Data collection top
Seifert
diffractometer
Rint = 0.013
Radiation source: fine-focus sealed tubeθmax = 66.7°, θmin = 3.1°
Graphite monochromatorh = 77
ω/2θ scansk = 88
2329 measured reflectionsl = 016
2229 independent reflections2 standard reflections every 150 reflections
2060 reflections with I > 2σ(I) intensity decay: 2.0%
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)] = 0.045H 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 reflectionsΔρmax = 0.45 e Å3
215 parametersΔρmin = 0.29 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.029 (2)
Crystal data top
C6H7NO2·C6H4N2O5γ = 114.18 (1)°
Mr = 309.24V = 670.19 (8) Å3
Triclinic, P1Z = 2
a = 6.7683 (5) ÅCu Kα radiation
b = 7.4976 (7) ŵ = 1.11 mm1
c = 14.4864 (2) ÅT = 293 K
α = 87.92 (1)°0.22 × 0.16 × 0.15 mm
β = 90.77 (1)°
Data collection top
Seifert
diffractometer
Rint = 0.013
2329 measured reflections2 standard reflections every 150 reflections
2229 independent reflections intensity decay: 2.0%
2060 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.132H atoms treated by a mixture of independent and constrained refinement
S = 1.14Δρmax = 0.45 e Å3
2229 reflectionsΔρmin = 0.29 e Å3
215 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.0687 (3)0.4633 (2)0.23168 (10)0.0488 (4)
HO10.084 (6)0.585 (6)0.194 (3)0.104 (12)*
O60.1267 (2)0.7653 (2)0.14150 (11)0.0544 (5)
C10.1427 (3)0.5002 (3)0.31659 (14)0.0373 (5)
C20.2529 (4)0.6919 (3)0.34742 (15)0.0436 (5)
H20.27580.79680.30640.046 (6)*
C30.3271 (3)0.7281 (3)0.43560 (15)0.0432 (5)
H30.40250.85610.45390.066 (8)*
C40.2892 (3)0.5726 (3)0.49809 (13)0.0361 (5)
C50.1780 (3)0.3818 (3)0.47268 (14)0.0369 (5)
H50.15030.27850.51520.056 (7)*
C60.1090 (3)0.3483 (3)0.38264 (14)0.0359 (5)
C70.0313 (3)0.7473 (3)0.00250 (15)0.0428 (5)
H70.08990.73970.02840.060 (7)*
C80.1945 (3)0.7488 (3)0.05902 (14)0.0414 (5)
H80.18460.74240.12270.048 (6)*
C90.3745 (3)0.7599 (3)0.01995 (14)0.0400 (5)
C100.3841 (3)0.7665 (3)0.07541 (15)0.0446 (5)
H100.50480.77180.10300.058 (7)*
C110.2169 (4)0.7654 (3)0.12868 (15)0.0433 (5)
H110.22330.77080.19250.061 (7)*
N10.0072 (3)0.1444 (3)0.35737 (13)0.0472 (5)
N20.3655 (3)0.6107 (3)0.59272 (12)0.0441 (5)
N30.0427 (3)0.7565 (2)0.08891 (12)0.0395 (4)
O20.0149 (4)0.0973 (3)0.28093 (14)0.0881 (7)
O30.1255 (3)0.0311 (3)0.41638 (14)0.0751 (6)
O40.4683 (3)0.7805 (3)0.61404 (12)0.0675 (6)
O50.3263 (3)0.4719 (3)0.64716 (11)0.0595 (5)
C120.5307 (4)0.7736 (4)0.16699 (16)0.0583 (7)
H1210.40780.88960.18630.058 (7)*
H1220.66030.77810.19260.092 (10)*
H1230.51460.66060.18830.064 (8)*
O70.5450 (2)0.7628 (3)0.06820 (11)0.0546 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0605 (10)0.0486 (9)0.0376 (9)0.0229 (7)0.0131 (7)0.0052 (7)
O60.0446 (9)0.0597 (10)0.0547 (10)0.0182 (7)0.0154 (7)0.0077 (8)
C10.0353 (10)0.0429 (11)0.0358 (11)0.0179 (8)0.0035 (8)0.0040 (8)
C20.0518 (12)0.0358 (10)0.0403 (12)0.0154 (9)0.0049 (9)0.0025 (9)
C30.0456 (11)0.0353 (11)0.0459 (13)0.0134 (9)0.0063 (9)0.0065 (9)
C40.0333 (10)0.0429 (11)0.0347 (11)0.0180 (8)0.0042 (8)0.0063 (8)
C50.0344 (10)0.0387 (10)0.0401 (12)0.0178 (8)0.0005 (8)0.0016 (8)
C60.0340 (10)0.0346 (10)0.0396 (11)0.0142 (8)0.0036 (8)0.0037 (8)
C70.0436 (12)0.0452 (11)0.0421 (13)0.0208 (9)0.0018 (9)0.0005 (9)
C80.0464 (12)0.0449 (11)0.0325 (11)0.0181 (9)0.0003 (9)0.0029 (8)
C90.0360 (10)0.0405 (11)0.0396 (12)0.0117 (8)0.0061 (8)0.0033 (8)
C100.0393 (11)0.0527 (12)0.0410 (12)0.0178 (9)0.0016 (9)0.0037 (9)
C110.0465 (12)0.0453 (11)0.0336 (12)0.0143 (9)0.0006 (9)0.0016 (9)
N10.0534 (11)0.0359 (9)0.0486 (12)0.0147 (8)0.0088 (9)0.0029 (8)
N20.0446 (10)0.0546 (11)0.0394 (10)0.0264 (9)0.0077 (8)0.0080 (9)
N30.0386 (9)0.0367 (9)0.0403 (10)0.0130 (7)0.0071 (7)0.0036 (7)
O20.135 (2)0.0522 (11)0.0615 (13)0.0207 (12)0.0018 (12)0.0219 (9)
O30.0844 (14)0.0424 (9)0.0786 (14)0.0065 (9)0.0020 (11)0.0044 (9)
O40.0895 (13)0.0553 (10)0.0572 (11)0.0282 (9)0.0294 (9)0.0219 (8)
O50.0710 (11)0.0678 (11)0.0397 (9)0.0290 (9)0.0072 (8)0.0026 (8)
C120.0542 (15)0.0689 (16)0.0441 (14)0.0181 (12)0.0145 (11)0.0020 (12)
O70.0417 (9)0.0794 (11)0.0429 (9)0.0254 (8)0.0089 (7)0.0025 (8)
Geometric parameters (Å, º) top
O1—C11.317 (2)C8—C91.384 (3)
O1—HO11.01 (4)C8—H80.9300
O6—N31.348 (2)C9—O71.349 (2)
O6—HO11.45 (4)C9—C101.387 (3)
C1—C61.407 (3)C10—C111.364 (3)
C1—C21.407 (3)C10—H100.9300
C2—C31.361 (3)C11—N31.346 (3)
C2—H20.9300C11—H110.9300
C3—C41.389 (3)N1—O21.204 (3)
C3—H30.9300N1—O31.226 (3)
C4—C51.377 (3)N2—O51.223 (2)
C4—N21.455 (3)N2—O41.223 (2)
C5—C61.376 (3)N3—O61.348 (2)
C5—H50.9300C12—O71.433 (3)
C6—N11.462 (3)C12—H1210.9600
C7—N31.333 (3)C12—H1220.9600
C7—C81.370 (3)C12—H1230.9600
C7—H70.9300
C1—O1—HO1113 (2)O7—C9—C8124.52 (19)
N3—O6—HO1112.8 (14)O7—C9—C10116.83 (19)
O1—C1—C6121.31 (18)C8—C9—C10118.65 (19)
O1—C1—C2122.46 (19)C11—C10—C9120.1 (2)
C6—C1—C2116.20 (18)C11—C10—H10119.9
C3—C2—C1121.89 (19)C9—C10—H10119.9
C3—C2—H2119.1N3—C11—C10120.1 (2)
C1—C2—H2119.1N3—C11—H11120.0
C2—C3—C4119.54 (19)C10—C11—H11120.0
C2—C3—H3120.2O2—N1—O3123.8 (2)
C4—C3—H3120.2O2—N1—C6119.37 (19)
C5—C4—C3121.31 (18)O3—N1—C6116.86 (19)
C5—C4—N2118.98 (18)O5—N2—O4122.90 (18)
C3—C4—N2119.71 (18)O5—N2—C4118.65 (18)
C6—C5—C4118.22 (18)O4—N2—C4118.45 (18)
C6—C5—H5120.9C7—N3—C11120.84 (18)
C4—C5—H5120.9C7—N3—O6119.31 (18)
C5—C6—C1122.81 (18)C11—N3—O6119.79 (18)
C5—C6—N1117.07 (18)O7—C12—H121109.5
C1—C6—N1120.10 (18)O7—C12—H122109.5
N3—C7—C8121.3 (2)H121—C12—H122109.5
N3—C7—H7119.3O7—C12—H123109.5
C8—C7—H7119.3H121—C12—H123109.5
C7—C8—C9119.0 (2)H122—C12—H123109.5
C7—C8—H8120.5C9—O7—C12117.89 (18)
C9—C8—H8120.5
O1—C1—C2—C3179.4 (2)C8—C9—C10—C111.1 (3)
C6—C1—C2—C31.4 (3)C9—C10—C11—N30.4 (3)
C1—C2—C3—C41.5 (3)C5—C6—N1—O2145.8 (2)
C2—C3—C4—C50.0 (3)C1—C6—N1—O235.3 (3)
C2—C3—C4—N2179.12 (19)C5—C6—N1—O335.2 (3)
C3—C4—C5—C61.5 (3)C1—C6—N1—O3143.7 (2)
N2—C4—C5—C6179.35 (17)C5—C4—N2—O50.8 (3)
C4—C5—C6—C11.6 (3)C3—C4—N2—O5178.40 (18)
C4—C5—C6—N1179.54 (17)C5—C4—N2—O4178.40 (19)
O1—C1—C6—C5177.87 (18)C3—C4—N2—O42.4 (3)
C2—C1—C6—C50.2 (3)C8—C7—N3—C110.7 (3)
O1—C1—C6—N10.9 (3)C8—C7—N3—O6176.45 (18)
C2—C1—C6—N1179.00 (18)C10—C11—N3—C70.5 (3)
N3—C7—C8—C90.1 (3)C10—C11—N3—O6176.70 (18)
C7—C8—C9—O7179.84 (19)C8—C9—O7—C126.1 (3)
C7—C8—C9—C100.8 (3)C10—C9—O7—C12174.6 (2)
O7—C9—C10—C11179.54 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—HO1···O61.01 (4)1.45 (4)2.461 (2)175 (3)

Experimental details

Crystal data
Chemical formulaC6H7NO2·C6H4N2O5
Mr309.24
Crystal system, space groupTriclinic, 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)
V3)670.19 (8)
Z2
Radiation typeCu Kα
µ (mm1)1.11
Crystal size (mm)0.22 × 0.16 × 0.15
Data collection
DiffractometerSeifert
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2329, 2229, 2060
Rint0.013
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.132, 1.14
No. of reflections2229
No. of parameters215
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—HO1···O61.01 (4)1.45 (4)2.461 (2)175 (3)
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds