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The co-crystal C10H8N2O2·2C7H7NO2 owes its formation to an intermolecular hydrogen bond between the O—H and N—O groups; the O...O distance is 2.5796 (17) Å. The dihedral angle between the planes of the pyridyl N-oxide and amino­benzoic rings of the complex is 10.2 (1)°. An additional intermolecular C—H...O hydrogen bond is formed, giving rise to an eight-membered ring within the asymmetric unit. The structure is centrosymmetric about the mid-point of the bond joining the two pyridine rings. The crystal structure exhibits overlap between the aromatic rings of the mol­ecules in the [\overline 110] direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300552X/ac6032sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680300552X/ac6032Isup2.hkl
Contains datablock I

CCDC reference: 209962

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.044
  • wR factor = 0.146
  • Data-to-parameter ratio = 21.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The title compound, (I), was investigated as part of a study on D—H···A hydrogen bonding in system containing 4,4'-bipyridyl N,N-dioxide and hydrogen-bond donors (Thaimattam et al., 1998). Four molecular structures similar to (I) were found in the Cambridge Structural Database (Allen, 2002), namely 4,4'-bipyridine N,N'-dioxide urea clathrate, 4,4'-bipyridine N,N'-dioxide thiourea clathrate and 4,4'-bipyridine N,N'-dioxide dihydrate clathrate (Thaimattam et al., 1998), and 4-aminobenzoic acid (Lai & Marsh, 1967), and they were used as references to analyze the structural characteristics of complex (I).

The complex is held together by a strong intermolecular hydrogen bond (Emsley, 1984) between the O—H group of 4-aminobenzoic acid (PABA) molecule and the N—O group of 4,4'-bipyridyl N,N-dioxide (DIPNO) molecule. In the crystal, two acid components related by a centre of symmetry are linked to a centrosymmetric 4,4'-bipyridyl N,N-dioxide not only by the short O—H···O bonds but also by longer C5—H5.·O3 hydrogen bonds, giving rise to an eight-membered ring within the asymmetric unit. This results in an approximately linear chaining of the three molecules. The formation of these hydrogen bonds is probably related to the rotation of the carboxylic acid group around the C9—C12 bond [the dihedral angle between this group and the C6–C11 ring being 7.5 (1)°] and to the approximate planarity of the whole centrosymmetric unit. Selected hydrogen-bond O—H···O, N—H.·O and C—H.·O interactions are presented in Table 2. A perspective view of the DIPNO–PABA (1:2) adduct showing the atomic numbering scheme is given in Fig. 1. The dihedral angle formed by the planes which essentially contain the rings of DIPNO and PABA molecules is 10.2 (1)°. The values of bond lengths and other internal parameters of DIPNO are very close to values of structures reported in the literature (Thaimattam et al., 1998). The central C3—C3i bond length [1.475 (3) Å; symmetry code: (i) −x, −y, −z] is shorter than a normal C—C single-bond distance, showing that this C—C bond has probably a little π-bond character. The presence of a strong O—H.·O and other relatively weak C—H.·O intermolecular hydrogen bonds induces some structural changes in the donor complex. Indeed, the C9—C12, C12—O2 and C12—O3 bond lengths change from 1.471 (2), 1.320 (2) and 1.218 (2) Å in (I) to 1.455 (4), 1.295 (3) and 1.248 (5) Å in the PABA molecule. There are no unusual short intermolecular bonds in the crystal structure. The molecules of PABA and DIPNO(1/2 − x, −y, z − 1/2) are overlapped along the [110] direction at a distance of 3.454 (2) Å (Fig. 2). Additionally, hydrogen-bond interactions between atom N2 with atoms O3ii and O1iii of neighboring molecules [symmetry codes: (ii) ?, 1/2 − y, 1/2 + z; (iii) 1/2 + x, 1/2 − y, 1 − z] (please complete symmetry code) are observed (Fig. 3).

Experimental top

Single yellow crystals of the DIPNO–PABA (1:2) [m.p. 453 (1) K] suitable for X-ray analysis were obtained by slow evaporation from an equimolecular solution of DIPNO and PABA in methanol. Initial reagents were purchased from Aldrich and were used without additional purification.

Refinement top

All H atoms, with the exception of the carboxyl atom HO2, were added at geometrically idealized positions and were allowed for as riding; C—H = 0.86–0.93 Å and Uiso(H)= 1.2Ueq of the carrier atom. Hydroxyl atom HO2 was located from a Fourier difference map and its coordinates were refined.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); 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.

Figures top
[Figure 1] Fig. 1. An ORTEP-3 (Farrugia, 1997) plot of the title complex, with the atomic labelling scheme. Displacement ellipsoids are plotted at the 50% probability level. H atoms are shown as spheres of an arbitrary radius.
[Figure 2] Fig. 2. A ZORTEP (Zsolnai, 1995) diagram of (I), showing the overlap between the molecules along the [110] direction.
[Figure 3] Fig. 3. A ZORTEP (Zsolnai, 1995) view of (I), showing additional hydrogen bonds. Hydrogen-bonding interactions are indicated by dashed lines.
(I) top
Crystal data top
C10H8N2O2·2C7H7NO2Dx = 1.383 Mg m3
Mr = 462.46Melting point: 453(1) K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 11.188 (1) Åθ = 9–18°
b = 12.138 (2) ŵ = 0.10 mm1
c = 16.354 (2) ÅT = 293 K
V = 2220.9 (5) Å3Regular block, yellow
Z = 40.22 × 0.18 × 0.12 mm
F(000) = 968
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.026
Radiation source: fine-focus sealed tubeθmax = 30.4°, θmin = 2.5°
Graphite monochromatorh = 015
ω/2θ scansk = 017
6757 measured reflectionsl = 2323
3350 independent reflections3 standard reflections every 120 min
2057 reflections with I > 2σ(I) intensity decay: 1.9%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0639P)2 + 0.5535P]
where P = (Fo2 + 2Fc2)/3
3350 reflections(Δ/σ)max < 0.001
158 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C10H8N2O2·2C7H7NO2V = 2220.9 (5) Å3
Mr = 462.46Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 11.188 (1) ŵ = 0.10 mm1
b = 12.138 (2) ÅT = 293 K
c = 16.354 (2) Å0.22 × 0.18 × 0.12 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.026
6757 measured reflections3 standard reflections every 120 min
3350 independent reflections intensity decay: 1.9%
2057 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.146H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.22 e Å3
3350 reflectionsΔρmin = 0.20 e Å3
158 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
O10.00584 (14)0.05247 (12)0.29335 (7)0.0715 (4)
N10.00521 (12)0.03725 (11)0.21317 (7)0.0498 (3)
C10.06048 (16)0.10416 (14)0.16603 (10)0.0537 (4)
H10.10440.16060.19000.064*
C20.06367 (15)0.09039 (13)0.08308 (10)0.0506 (4)
H20.11000.13780.05160.061*
C30.00058 (12)0.00731 (11)0.04476 (8)0.0378 (3)
C40.06638 (16)0.06063 (14)0.09572 (9)0.0548 (4)
H40.11020.11820.07320.066*
C50.06824 (17)0.04477 (16)0.17887 (10)0.0604 (5)
H50.11360.09130.21170.072*
N20.37505 (15)0.33076 (15)0.67973 (9)0.0688 (5)
HN210.35060.31160.72750.083*
HN220.42620.38320.67460.083*
O20.13107 (12)0.03202 (10)0.41001 (7)0.0593 (3)
HO20.105 (2)0.007 (2)0.3615 (14)0.084 (7)*
O30.22365 (13)0.15164 (12)0.32868 (6)0.0683 (4)
C60.33268 (14)0.27774 (14)0.61185 (9)0.0482 (4)
C70.37289 (14)0.30819 (14)0.53363 (9)0.0491 (4)
H70.42830.36480.52800.059*
C80.33072 (13)0.25479 (13)0.46541 (8)0.0455 (3)
H80.35820.27580.41400.055*
C90.24761 (14)0.16980 (12)0.47180 (8)0.0422 (3)
C100.20820 (15)0.13959 (13)0.54979 (9)0.0482 (3)
H100.15300.08280.55540.058*
C110.25001 (15)0.19266 (14)0.61827 (9)0.0512 (4)
H110.22270.17140.66960.061*
C120.20161 (14)0.11742 (13)0.39705 (8)0.0461 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0988 (10)0.0777 (9)0.0379 (6)0.0287 (8)0.0023 (6)0.0031 (6)
N10.0583 (8)0.0512 (7)0.0400 (6)0.0064 (6)0.0022 (6)0.0072 (5)
C10.0625 (10)0.0504 (8)0.0481 (8)0.0175 (7)0.0051 (7)0.0051 (7)
C20.0547 (9)0.0506 (8)0.0466 (7)0.0167 (7)0.0004 (6)0.0084 (6)
C30.0344 (6)0.0367 (6)0.0422 (7)0.0006 (5)0.0002 (5)0.0077 (5)
C40.0657 (10)0.0548 (9)0.0440 (8)0.0244 (8)0.0024 (7)0.0052 (7)
C50.0735 (11)0.0638 (10)0.0439 (8)0.0277 (9)0.0039 (8)0.0089 (7)
N20.0718 (10)0.0901 (12)0.0447 (7)0.0115 (9)0.0033 (7)0.0134 (8)
O20.0802 (8)0.0535 (7)0.0442 (6)0.0097 (6)0.0040 (6)0.0031 (5)
O30.0837 (9)0.0850 (9)0.0362 (5)0.0195 (7)0.0002 (5)0.0044 (6)
C60.0464 (8)0.0574 (9)0.0407 (7)0.0109 (7)0.0005 (6)0.0038 (6)
C70.0467 (8)0.0544 (8)0.0463 (8)0.0009 (7)0.0005 (6)0.0023 (7)
C80.0465 (7)0.0513 (8)0.0386 (6)0.0071 (7)0.0033 (6)0.0078 (6)
C90.0462 (7)0.0442 (7)0.0362 (6)0.0104 (6)0.0003 (6)0.0037 (5)
C100.0537 (8)0.0485 (8)0.0424 (7)0.0015 (7)0.0029 (6)0.0064 (6)
C110.0583 (9)0.0585 (9)0.0368 (6)0.0065 (7)0.0065 (7)0.0046 (6)
C120.0500 (8)0.0489 (8)0.0394 (7)0.0082 (7)0.0003 (6)0.0032 (6)
Geometric parameters (Å, º) top
O1—N11.3243 (16)C4—C51.373 (2)
O1—O22.5796 (17)C4—H40.9300
O2—HO20.90 (2)N2—C61.368 (2)
N2—O3i2.975 (2)O2—C121.320 (2)
N2—HN210.8600O3—C121.2180 (17)
N2—O1ii3.095 (2)C6—C111.390 (2)
N2—HN220.8600C6—C71.405 (2)
C5—O33.273 (2)C7—C81.374 (2)
C5—H50.9300C7—H70.9300
N1—C11.3394 (19)C8—C91.393 (2)
N1—C51.343 (2)C8—H80.9300
C1—C21.367 (2)C9—C101.398 (2)
C1—H10.9300C9—C121.471 (2)
C2—C31.388 (2)C10—C111.374 (2)
C2—H20.9300C10—H100.9300
C3—C41.384 (2)C11—H110.9300
C3—C3iii1.475 (3)
O1—N1—C1119.23 (13)C12—O2—HO2108.8 (15)
O1—N1—C5120.95 (13)N2—C6—C11121.24 (14)
O1—HO2—O2157 (2)N2—C6—C7120.26 (16)
N2—HN21—O3i145.6C11—C6—C7118.49 (14)
N2—HN22—O1ii153.8C8—C7—C6120.34 (15)
C5—H5—O3158.4C8—C7—H7119.8
C1—N1—C5119.82 (13)C6—C7—H7119.8
N1—C1—C2120.75 (15)C7—C8—C9121.19 (13)
N1—C1—H1119.6C7—C8—H8119.4
C2—C1—H1119.6C9—C8—H8119.4
C1—C2—C3121.55 (14)C8—C9—C10118.23 (13)
C1—C2—H2119.2C8—C9—C12119.44 (12)
C3—C2—H2119.2C10—C9—C12122.30 (14)
C4—C3—C2115.87 (13)C11—C10—C9120.87 (15)
C5—C4—C3121.37 (15)C11—C10—H10119.6
C5—C4—H4119.3C9—C10—H10119.6
C3—C4—H4119.3C10—C11—C6120.88 (14)
N1—C5—C4120.64 (14)C10—C11—H11119.6
N1—C5—H5119.7C6—C11—H11119.6
C4—C5—H5119.7O3—C12—O2122.43 (15)
C6—N2—HN21120.0O3—C12—C9123.00 (15)
C6—N2—HN22120.0O2—C12—C9114.53 (13)
HN21—N2—HN22120.0
O1—N1—C1—C2179.64 (17)C7—C8—C9—C100.3 (2)
C5—N1—C1—C20.4 (3)C7—C8—C9—C12177.87 (14)
N1—C1—C2—C30.1 (3)C8—C9—C10—C110.3 (2)
C1—C2—C3—C40.6 (2)C12—C9—C10—C11177.81 (14)
C2—C3—C4—C50.8 (3)C9—C10—C11—C60.0 (2)
O1—N1—C5—C4179.45 (18)N2—C6—C11—C10179.78 (16)
C1—N1—C5—C40.2 (3)C7—C6—C11—C100.2 (2)
C3—C4—C5—N10.4 (3)C8—C9—C12—O37.4 (2)
N2—C6—C7—C8179.79 (15)C10—C9—C12—O3170.65 (16)
C11—C6—C7—C80.2 (2)C10—C9—C12—O27.3 (2)
C6—C7—C8—C90.0 (2)C8—C9—C12—O2174.67 (14)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1/2, y+1/2, z+1; (iii) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—HO2···O10.90 (2)1.73 (2)2.580 (2)157 (2)
N2—HN21···O3i0.862.232.975 (2)146
N2—HN22···O1ii0.862.303.095 (2)154
C5—H5···O30.932.393.273 (2)158
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC10H8N2O2·2C7H7NO2
Mr462.46
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)293
a, b, c (Å)11.188 (1), 12.138 (2), 16.354 (2)
V3)2220.9 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.22 × 0.18 × 0.12
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6757, 3350, 2057
Rint0.026
(sin θ/λ)max1)0.712
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.146, 1.02
No. of reflections3350
No. of parameters158
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.22, 0.20

Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and ZORTEP (Zsolnai, 1995), SHELXL97.

Selected geometric parameters (Å, º) top
O1—N11.3243 (16)C3—C3i1.475 (3)
O1—N1—C1119.23 (13)O3—C12—O2122.43 (15)
O1—N1—C5120.95 (13)O3—C12—C9123.00 (15)
N2—C6—C7120.26 (16)O2—C12—C9114.53 (13)
C8—C9—C12—O2174.67 (14)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—HO2···O10.90 (2)1.73 (2)2.580 (2)157 (2)
N2—HN21···O3ii0.862.232.975 (2)146
N2—HN22···O1iii0.862.303.095 (2)154
C5—H5···O30.932.393.273 (2)158
Symmetry codes: (ii) x, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z+1.
 

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