Acta Cryst.(2002). E58, o623±o625 DOI: 10.1107/S160053680200819X Rodolfo Moreno-Fuquenet al. C6H6O2C6H6N2O3
o623
organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
The 1:1 complex of hydroquinone and
3-methy-4-nitropyridine 1-oxide
Rodolfo Moreno-Fuquen,a*
Angela Marcela MontanÄoaand
Reinaldo Atenciob
aDepartamento de QuõÂmica, Facultad de
Cien-cias, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, andbCentro de
QuõÂmica, Instituto Venezolano de Investiga-ciones, CientõÂficas IVIC, Apartado 21827, Caracas, Venezuela
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.002 AÊ
Rfactor = 0.043
wRfactor = 0.127
Data-to-parameter ratio = 11.6
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved
In the crystal structure of the title complex,
C6H6O2C6H6N2O3, the molecules are linked by intermole-cular hydrogen bonds between the OÐH and NÐO groups. The O atom of theN-oxide group of 3-methyl-4-nitropyridine 1-oxide acts as an acceptor for hydrogen bonds from OÐH groups of two symmetry-related hydroquinone molecules [O O 2.732 (2) and 2.810 (2) AÊ]. The angles between the rings of the 3-methyl-4-nitropyridine 1-oxide and two hydro-quinone molecules are 6.1 (3) and 0.6 (3). The crystal
structure exhibits overlap between the aromatic rings of the molecules in the [111] direction.
Comment
The design of organic crystals formed by non-covalent inter-molecular interactions has been one of the main goals of crystal engineering (Schmidt, 1971; Desiraju, 1995). This type of solid has attracted great interest because of its increasing technological applications (Lehn, 1990). The present work is part of a series of structural studies on molecular complexes, formed by hydrogen bonds, with potential non-linear optical applications (Moreno-Fuquenet al., 1998). The title molecular complex, (I), is formed by hydroquinone (HQ) (Lindemanet
al., 1981; Cambridge Structural Database refcode
HYQUIN05; Allen et al., 1991), which crystallizes in a centrosymmetric space group, and 3-methyl-4-nitropyridine 1-oxide (POM) (Hamzaouiet al., 1996; refcode MNPYDO03), whose non-linear optical response has already been reported (Zyss et al., 1981). Although the title complex is centrosym-metric, information about its crystal structure is important for the study of the general behavior of POM with respect to its formation of hydrogen-bond complexes. The title cocrystal is held together by hydrogen bonds between the OÐH groups of two different HQ molecules and the NÐO group of POM. The O O distances are 2.732 (2) AÊ for O1 O5 and 2.810 (2) AÊ for O1 O4. The O1 HO5ÐO5 angle is 156 (2) and the
O1 HO4ÐO4 angle is 168 (3). A view of the
hydrogen-bonded complex is shown in Fig. 1 and the unit cell contents are shown in Fig. 2.
organic papers
o624
Rodolfo Moreno-Fuquenet al. C6H6O2C6H6N2O3 Acta Cryst.(2002). E58, o623±o625 The presence of hydrogen bonds induces some changes inthe structure of the molecules in the complex with respect to the structures of the separate components. Thus, the CÐO bonds in (I) (Table 1) are 1.375 (2) and 1.371 (2) AÊ for C8Ð O4 and C11ÐO5, respectively, while in free hydroquinone, the bond length is 1.392 (4) AÊ. On the other hand, the bond lengths and angles for POM remain similar in the complex (Hamzaouiet al., 1996). The interplanar angles between the rings of POM and the two HQ molecules are 6.1 (3) and
0.6 (3). The aromatic rings of POM and HQ show an ABAB
disposition and are overlapped, with a mean distance between the rings of 3.47 (2) AÊ along the [111] direction. The complex consists of zigzag chains, with molecules linked by inter-molecular hydrogen bonds.
Experimental
Crystals of the title POM±HQ complex, (I), were obtained by slow evaporation from an equimolar solution of POM and HQ in aceto-nitrile. Orange±red crystals with a melting point of 384 (1) K were obtained. The initial reagents were purchased from Aldrich and were used without additional puri®cation.
Crystal data C6H6O2C6H6N2O3
Mr= 264.24 Triclinic,P1
a= 7.8593 (16) AÊ
b= 8.429 (3) AÊ
c= 9.039 (3) AÊ
= 84.39 (3)
= 89.92 (2)
= 88.91 (3)
V= 595.8 (3) AÊ3
Z= 2
Dx= 1.473 Mg mÿ3 MoKradiation Cell parameters from 25
re¯ections
= 8±20
= 0.12 mmÿ1
T= 293 (2) K
Irregular block, orange±red 0.200.140.14 mm Data collection
Rigaku AFC-7Sdiffractometer
!/2scans
2250 measured re¯ections 2091 independent re¯ections 1848 re¯ections withI> 2(I)
Rint= 0.015
max= 25.0
h=ÿ9!9
k=ÿ10!0
l=ÿ10!10 3 standard re¯ections
frequency: 150 min intensity decay: none
Re®nement Re®nement onF2
R[F2> 2(F2)] = 0.043
wR(F2) = 0.127
S= 1.04 2091 re¯ections 181 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.077P)2 + 0.1509P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.29 e AÊÿ3
min=ÿ0.22 e AÊÿ3
Extinction correction:SHELXL97 Extinction coef®cient: 0.034 (7)
Table 1
Selected geometric parameters (AÊ,).
C1ÐN1 1.346 (2)
C5ÐN1 1.346 (2)
N1ÐO1 1.3165 (17)
C8ÐO4 1.375 (2)
C11ÐO5 1.370 (2)
O4ÐHO4 0.82 (3)
O5ÐHO5 0.83 (2)
N1ÐC1ÐC2 119.55 (14) N1ÐC5ÐC4 122.49 (15) O1ÐN1ÐC5 120.00 (14) O1ÐN1ÐC1 119.01 (13) C5ÐN1ÐC1 120.98 (14) O4ÐC8ÐC7 117.43 (17)
O4ÐC8ÐC9i 122.79 (16)
O5ÐC11ÐC10 123.05 (15) O5ÐC11ÐC12 117.85 (14) C8ÐO4ÐHO4 106 (2) C11ÐO5ÐHO5 113.9 (16)
N1ÐC1ÐC2ÐC3 ÿ1.6 (3) C4ÐC5ÐN1ÐO1 ÿ179.30 (14) C2ÐC1ÐN1ÐO1 ÿ179.41 (14) C2ÐC1ÐN1ÐC5 1.6 (2)
C9ÐC7ÐC8ÐO4 ÿ178.64 (16) C12iiÐC10ÐC11ÐO5 178.54 (15)
O5ÐC11ÐC12ÐC10ii ÿ178.61 (15)
Symmetry codes: (i)ÿx;1ÿy;ÿz; (ii) 1ÿx;ÿy;1ÿz.
The ring and methyl H atoms were added at geometrically idea-lized positions and were allowed for as riding; CÐH = 0.93±0.96 AÊ, Uiso(H) = 1.2Ueqof the carrier atom. Hydroxyl atoms HO4 and HO5 Figure 1
AnORTEP-3 (Farrugia, 1997) plot of the title complex, with the atomic labeling scheme. Displacement ellipsoids are plotted at the 50% probability level.
Figure 2
were located from a Fourier difference map and their coordinates were re®ned.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell re®nement:MSC/AFC Diffractometer Control Software; data reduction:TEXSAN (Mole-cular Structure Corporation, 1995); program(s) used to solve struc-ture: SHELXS86 (Sheldrick, 1990); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) andZORTEP(Zsolnai, 1995); software used to prepare material for publication:SHELXL97.
RMF acknowledges Dr MartõÂn Martinez-Ripoll, of the Instituto de QuõÂmica Rocasolano, and CSIC of Spain for free access to the Cambridge Structural Database. The authors also thank the Universidad del Valle (Colombia) for partial ®nancial support. AMM acknowledges the Instituto Venezo-lano de Investigaciones Cientõ®cas (IVIC), Venezuela, for the diffraction analysis.
References
Allen, F. H., Davies, J. E., Galloy, J. J., Johnson, O., Kennard, O., Macrae, C. F., Mitchell, E. M., Mitchell, G. F., Smith, J. M. & Watson, D. G. (1991).J. Chem. Inf. Comput. Sci.31, 187±204.
Desiraju, G. R. (1995).Angew. Chem. Int. Ed. Engl.34, 2311±2327. Hamzaoui, F., Baert, F. & Zyss, J. (1996).J. Mater. Chem.6, 1123±1130. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.
Lehn, J. M. (1990).Angew. Chem. Int. Ed. Engl.29, 1304±1319.
Lindeman, S. V., Shklover, V. E. & Struchkov, Yu. T. (1981).Cryst. Struct. Commun.10, 1173±1179.
Molecular Structure Corporation (1993).MSC/AFC Diffractometer Control Software. Version 5.1.0. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.
Molecular Structure Corporation (1995). TEXSAN/TEXRAY.MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.
Moreno-Fuquen, R., De Almeida Santos, R. H. & Ribeiro de Castro, E. V. (1998).Acta Cryst.C54, 517±519.
Schmidt, G. M. J. (1971).Pure Appl. Chem.27, 647±678. Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.
Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Zsolnai, L. (1995).ZORTEP. University of Heidelberg, Germany. Zyss, J., Chemla, D. S. & Nicoud, J. F. (1981).J. Chem. Phys.74, 4800±4810.
supporting information
sup-1 Acta Cryst. (2002). E58, o623–o625
supporting information
Acta Cryst. (2002). E58, o623–o625 [https://doi.org/10.1107/S160053680200819X]
The 1:1 complex of hydroquinone and 3-methy-4-nitropyridine 1-oxide
Rodolfo Moreno-Fuquen, Angela Marcela Monta
ñ
o and Reinaldo Atencio
(I)
Crystal data C6H6O2·C6H6N2O3 Mr = 264.24 Triclinic, P1 Hall symbol: -P 1 a = 7.8593 (16) Å b = 8.429 (3) Å c = 9.039 (3) Å α = 84.39 (3)° β = 89.92 (2)° γ = 88.91 (3)° V = 595.8 (3) Å3
Z = 2 F(000) = 276 Dx = 1.473 Mg m−3 Melting point: 384(1) K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections θ = 8–20°
µ = 0.12 mm−1 T = 293 K
Irregular_block, orange–red 0.20 × 0.14 × 0.14 mm
Data collection Rigaku AFC-7S
diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω/2θ scans
2250 measured reflections 2091 independent reflections 1848 reflections with I > 2σ(I)
Rint = 0.015
θmax = 25.0°, θmin = 2.3° h = −9→9
k = −10→0 l = −10→10
3 standard reflections every 150 min intensity decay: none
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.043 wR(F2) = 0.127 S = 1.04 2091 reflections 181 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.077P)2 + 0.1509P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001 Δρmax = 0.29 e Å−3 Δρmin = −0.22 e Å−3
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sup-2 Acta Cryst. (2002). E58, o623–o625
Special details
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)
x y z Uiso*/Ueq
C1 0.3953 (2) 0.55619 (19) 0.68901 (18) 0.0419 (4)
H1 0.4661 0.4711 0.6696 0.050*
C2 0.4149 (2) 0.6282 (2) 0.81648 (18) 0.0421 (4)
H2 0.4973 0.5907 0.8856 0.051*
C3 0.3119 (2) 0.75697 (19) 0.84251 (17) 0.0381 (4)
C4 0.1868 (2) 0.81540 (18) 0.74227 (18) 0.0374 (4)
C5 0.1717 (2) 0.73451 (19) 0.61632 (18) 0.0395 (4)
H5 0.0886 0.7683 0.5465 0.047*
C6 0.0674 (2) 0.9538 (2) 0.7568 (2) 0.0536 (5)
H61 −0.0163 0.9587 0.6792 0.064*
H62 0.1303 1.0509 0.7487 0.064*
H63 0.0119 0.9406 0.8517 0.064*
N1 0.27269 (17) 0.60914 (15) 0.59155 (14) 0.0374 (3)
N2 0.3422 (2) 0.82778 (19) 0.98195 (17) 0.0524 (4)
O1 0.25402 (17) 0.53780 (15) 0.46953 (13) 0.0515 (4)
O2 0.2858 (3) 0.9599 (2) 0.99536 (19) 0.0919 (6)
O3 0.4255 (3) 0.7501 (2) 1.07750 (17) 0.0854 (6)
C7 −0.1063 (2) 0.6283 (2) 0.02089 (19) 0.0456 (4)
H7 −0.1782 0.7146 0.0344 0.055*
C8 0.0043 (2) 0.5704 (2) 0.13225 (18) 0.0428 (4)
C9 −0.1105 (2) 0.5577 (2) −0.11172 (18) 0.0447 (4)
H9 −0.1851 0.5970 −0.1868 0.054*
C10 0.4654 (2) 0.11298 (18) 0.59675 (17) 0.0398 (4)
H10 0.4426 0.1891 0.6623 0.048*
C11 0.3716 (2) 0.11380 (18) 0.46727 (18) 0.0386 (4)
C12 0.4074 (2) −0.00009 (19) 0.37064 (17) 0.0409 (4)
H12 0.3453 −0.0004 0.2832 0.049*
O4 0.0002 (2) 0.64284 (19) 0.26215 (16) 0.0637 (4)
HO4 0.080 (4) 0.605 (3) 0.312 (3) 0.087 (9)*
O5 0.24142 (17) 0.22086 (16) 0.43064 (16) 0.0564 (4)
HO5 0.250 (3) 0.306 (3) 0.469 (3) 0.063 (6)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.0490 (9) 0.0359 (8) 0.0404 (9) 0.0105 (7) 0.0005 (7) −0.0042 (7)
C2 0.0474 (9) 0.0399 (9) 0.0382 (8) 0.0047 (7) −0.0072 (7) −0.0009 (7)
C3 0.0452 (9) 0.0369 (8) 0.0333 (8) −0.0041 (7) −0.0009 (6) −0.0085 (6)
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sup-3 Acta Cryst. (2002). E58, o623–o625
C5 0.0434 (9) 0.0374 (8) 0.0378 (8) 0.0055 (7) −0.0055 (7) −0.0059 (7)
C6 0.0532 (11) 0.0480 (10) 0.0619 (11) 0.0125 (8) −0.0072 (9) −0.0196 (8)
N1 0.0481 (8) 0.0348 (7) 0.0301 (7) 0.0026 (6) 0.0007 (5) −0.0075 (5)
N2 0.0635 (10) 0.0530 (9) 0.0430 (8) 0.0006 (7) −0.0097 (7) −0.0174 (7)
O1 0.0726 (9) 0.0487 (7) 0.0355 (6) 0.0105 (6) −0.0046 (6) −0.0185 (5)
O2 0.1312 (16) 0.0763 (11) 0.0748 (11) 0.0353 (10) −0.0339 (10) −0.0477 (9)
O3 0.1185 (14) 0.0848 (11) 0.0555 (9) 0.0190 (10) −0.0414 (9) −0.0232 (8)
C7 0.0523 (10) 0.0404 (9) 0.0436 (9) 0.0070 (7) −0.0031 (7) −0.0026 (7)
C8 0.0520 (10) 0.0417 (9) 0.0350 (8) −0.0026 (7) −0.0025 (7) −0.0043 (7)
C9 0.0491 (9) 0.0465 (10) 0.0371 (9) 0.0039 (7) −0.0095 (7) 0.0017 (7)
C10 0.0513 (9) 0.0345 (8) 0.0347 (8) −0.0008 (7) −0.0068 (7) −0.0089 (6)
C11 0.0451 (9) 0.0318 (8) 0.0389 (8) 0.0002 (6) −0.0091 (7) −0.0030 (6)
C12 0.0512 (9) 0.0384 (9) 0.0336 (8) −0.0001 (7) −0.0126 (7) −0.0054 (6)
O4 0.0850 (11) 0.0638 (9) 0.0447 (8) 0.0164 (8) −0.0149 (7) −0.0203 (6)
O5 0.0631 (8) 0.0441 (7) 0.0636 (8) 0.0154 (6) −0.0277 (6) −0.0170 (6)
Geometric parameters (Å, º)
C1—N1 1.346 (2) C7—C8 1.377 (3)
C1—C2 1.364 (2) C7—C9 1.390 (2)
C1—H1 0.930 C7—H7 0.930
C2—C3 1.380 (2) C8—O4 1.375 (2)
C2—H2 0.930 C8—C9i 1.379 (3)
C3—C4 1.388 (2) C9—C8i 1.379 (3)
C3—N2 1.468 (2) C9—H9 0.930
C4—C5 1.389 (2) C10—C12ii 1.379 (2)
C4—C6 1.499 (2) C10—C11 1.384 (2)
C5—N1 1.346 (2) C10—H10 0.930
C5—H5 0.930 C11—O5 1.370 (2)
C6—H61 0.960 C11—C12 1.385 (2)
C6—H62 0.960 C12—C10ii 1.379 (2)
C6—H63 0.960 C12—H12 0.930
N1—O1 1.3165 (17) O4—HO4 0.82 (3)
N2—O2 1.208 (2) O5—HO5 0.83 (2)
N2—O3 1.216 (2)
N1—C1—C2 119.55 (14) O2—N2—O3 123.45 (16)
N1—C1—H1 120.2 O2—N2—C3 118.86 (16)
C2—C1—H1 120.2 O3—N2—C3 117.68 (16)
C1—C2—C3 119.77 (15) C8—C7—C9 120.02 (17)
C1—C2—H2 120.1 C8—C7—H7 120.0
C3—C2—H2 120.1 C9—C7—H7 120.0
C2—C3—C4 121.64 (15) O4—C8—C7 117.43 (17)
C2—C3—N2 116.19 (15) O4—C8—C9i 122.79 (16)
C4—C3—N2 122.18 (15) C7—C8—C9i 119.76 (17)
C3—C4—C5 115.54 (15) C8i—C9—C7 120.22 (16)
C3—C4—C6 126.99 (15) C8i—C9—H9 119.9
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sup-4 Acta Cryst. (2002). E58, o623–o625
N1—C5—C4 122.49 (15) C12ii—C10—C11 120.49 (15)
N1—C5—H5 118.8 C12ii—C10—H10 119.8
C4—C5—H5 118.8 C11—C10—H10 119.8
C4—C6—H61 109.5 O5—C11—C10 123.05 (15)
C4—C6—H62 109.5 O5—C11—C12 117.85 (14)
H61—C6—H62 109.5 C10—C11—C12 119.09 (15)
C4—C6—H63 109.5 C10ii—C12—C11 120.42 (14)
H61—C6—H63 109.5 C10ii—C12—H12 119.8
H62—C6—H63 109.5 C11—C12—H12 119.8
O1—N1—C5 120.00 (14) C8—O4—HO4 106 (2)
O1—N1—C1 119.01 (13) C11—O5—HO5 113.9 (16)
C5—N1—C1 120.98 (14)
N1—C1—C2—C3 −1.6 (3) C2—C1—N1—C5 1.6 (2)
C1—C2—C3—C4 0.5 (3) C2—C3—N2—O2 163.02 (19)
C1—C2—C3—N2 −179.68 (15) C4—C3—N2—O2 −17.1 (3)
C2—C3—C4—C5 0.8 (2) C2—C3—N2—O3 −16.0 (3)
N2—C3—C4—C5 −179.09 (14) C4—C3—N2—O3 163.90 (18)
C2—C3—C4—C6 −179.82 (16) C9—C7—C8—O4 −178.64 (16)
N2—C3—C4—C6 0.3 (3) C9—C7—C8—C9i −0.1 (3)
C3—C4—C5—N1 −0.9 (2) C8—C7—C9—C8i 0.1 (3)
C6—C4—C5—N1 179.66 (15) C12ii—C10—C11—O5 178.54 (15)
C4—C5—N1—O1 −179.30 (14) C12ii—C10—C11—C12 −0.2 (3)
C4—C5—N1—C1 −0.3 (2) O5—C11—C12—C10ii −178.61 (15)
C2—C1—N1—O1 −179.41 (14) C10—C11—C12—C10ii 0.2 (3)
