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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 10| October 2005| Pages o613-o616
doi:10.1107/S0108270105028799

Three isomeric (E)-nitro­benzaldehyde nitro­phenyl­hydrazones: chains of rings in isomorphous (E)-2-nitro­benzaldehyde 3-nitro­phenyl­hydrazone and (E)-3-nitro­benzaldehyde 2-nitro­phenyl­hydrazone, and centrosymmetric dimers in (E)-4-nitro­benz­aldehyde 2-nitro­phenyl­hydrazone

CROSSMARK_Color_square_no_text.svg
George Ferguson,a Christopher Glidewell,a* John N. Low,b Janet M. S. Skakleb and James L. Wardellc

aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 8 September 2005; accepted 12 September 2005; online 30 September 2005)

The isomeric compounds (E)-2-nitro­benzaldehyde 3-nitro­phenyl­hydrazone and (E)-3-nitro­benzaldehyde 2-nitro­phenyl­hydrazone, both C13H10N4O4, are isomorphous and effectively isostructural, and in both, the mol­ecules are disordered across centres of inversion in the space group P21/c. The mol­ecules are linked into complex chains of rings by N—H⋯O and C—H⋯O hydrogen bonds. In the isomeric compound (E)-4-nitro­benzaldehyde 2-nitro­phenyl­hydrazone, the fully ordered mol­ecules are linked by N—H⋯O hydrogen bonds into centrosymmetric dimers.

Comment

As part of our continuing studies of the supramolecular arrangements in imines and hydrazones, we report here the structures of three isomeric nitro­benzaldehyde nitro­phenyl hydrazones, (I)[link]–(III)[link], which we compare briefly with two further isomers, (IV)[link] and (V)[link] (see scheme) (Shan et al., 2004[Shan, S., Wang, X.-J., Hu, W.-X. & Xu, D.-J. (2004). Acta Cryst. E60, o1954-o1956.]; Wardell et al., 2005[Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o10-o14.]).

In isomers (I)[link] and (II)[link] (Figs. 1[link] and 2[link]), the mol­ecules are disordered over two sets of sites related by a centre of inversion, selected for the sake of convenience as that at ([{1\over 2}], [{1\over 2}], [{1\over 2}]). The asymmetric units for (I)[link] and (II)[link] were selected so that the coordinates of the atoms in the nitro groups were approximately the same. This then led to close correspondence between the coordinates for atoms C11–C16 in (I)[link] with those for atoms C16/C11–C15, respectively, in (II)[link]. Likewise, the coordinates for atoms N1, N2 and C27 in the reference asymmetric unit at (x, y, z) in (I)[link] closely correspond to those in (II)[link] for atoms C27, N2 and N1, respectively, at (1 − x, 1 − y, 1 − z). The unit-cell dimensions indicate that (I)[link] and (II)[link] are isomorphous, and the atom coordinates indicate that these compounds are effectively isostructural, but with atoms N1 and C27 inter­changed between (I)[link] and (II)[link] (Figs. 1[link] and 2[link]). By contrast, all atoms in isomer (III)[link] (Fig. 3[link]) are fully ordered in general positions. While all of the atoms in isomer (IV)[link] are fully ordered, in isomer (V)[link] the NH and CH sites in the central bridge are randomly scrambled, with the two heavy-atom sites each occupied by (0.5C + 0.5N) (Wardell et al., 2005[Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o10-o14.]).

[Scheme 1]

In each of isomers (I)[link]–(III)[link], the mol­ecules are essentially planar, and all have the E configuration at the C=N double bond. In (III)[link], the bond distances (Table 3[link]) show strong evidence for the development of the polarized quinonoid form, (IIIa)[link]. In particular, with the C11–C16 aryl ring, the C13—C14 and C15—C16 distances are significantly shorter than the remaining distances, the C11—C12 distance is the longest and the C12—N12 distance is short for its type, while the N12—O21 and N12—O22 distances are both long (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). By contrast, the C21–C26 aryl ring shows no evidence for the development of a quinonoid form. The structure of the isomer (IV)[link], which differs from (III)[link] by the notional reversal of the spacer fragment, has been determined both at 295 K (Shan et al., 2004[Shan, S., Wang, X.-J., Hu, W.-X. & Xu, D.-J. (2004). Acta Cryst. E60, o1954-o1956.]) and at 120 K (Wardell et al., 2005[Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o10-o14.]). The same phase is present at both temperatures and both structures show evidence for the development of the polarized form, (IVa)[link], although this was not remarked upon by Shan et al. (2004[Shan, S., Wang, X.-J., Hu, W.-X. & Xu, D.-J. (2004). Acta Cryst. E60, o1954-o1956.]).

In each of (I)[link] and (II)[link], there is a short intra­molecular X—H⋯O contact (Tables 1[link] and 2[link]), where X is atom C27 in (I)[link] and atom N1 in (II)[link]. We first discuss the inter­molecular hydrogen bonds on the assumption of local ordering and then consider the consequences of the disorder across inversion centres. In (I)[link], the mol­ecules are linked by the concerted action of three hydrogen bonds (Table 1[link]): atoms N1 and C27 in the mol­ecule at (x, y, z) both act as hydrogen-bond donors to atom O31 in the mol­ecule at (1 + x, −1 + y, z), while atom C16 at (x, y, z) similarly acts as donor to atom O32, also at (1 + x, −1 + y, z). Hence, this multi-point inter­action generates by translation a complex chain of rings running parallel to the [1[\overline{1}]0] direction (Fig. 1[link]). An entirely similar chain of rings is formed in compound (II)[link], where atoms N1 and C27 at (x, y, z) act as donors to atom O21 at (−x, 2 − y, 1 − z), while atom C15 acts as donor to atom O22 at (1 + x, −1 + y, z) (Fig. 2[link]). In each isomer, therefore, a given mol­ecule will form four hydrogen bonds with each of its neighbours within the [1[\overline{1}]0] chain, provided only that there is local ordering within the chain in question. The multi-point recognition makes it appear probable that, within a given chain, the mol­ecules are, in fact, ordered in this manner. Two chains of this type pass through each unit cell in (I)[link] and (II)[link], but there are no direction-specific inter­actions between adjacent chains. Accordingly, there is no necessity for the orientation of mol­ecules in adjacent chains to show any correlation.

The supramolecular structure of (III)[link], by contrast, is extremely simple. In addition to forming an intra­molecular hydrogen bond (Table 4[link]) which gives rise to an S(6) ring, amino atom N1 in the mol­ecule at (x, y, z) acts as hydrogen-bond donor to nitro atom O21 in the mol­ecule at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric dimer containing an S(6)R22(4)S(6) motif (Fig. 4[link]). There are no direction-specific inter­actions between adjacent dimers. In particular, C—H⋯π(arene) hydrogen bonds and aromatic π–π stacking inter­actions are both absent. The supramolecular structure of (III)[link] thus consists of isolated dimers.

In isomer (IV)[link], the close analogue of (III)[link], the mol­ecules are linked into complex sheets by a combination of one N—H⋯O hydrogen bond and three independent C—H⋯O hydrogen bonds (Wardell et al., 2005[Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o10-o14.]). In the earlier report on this compound (Shan et al., 2004[Shan, S., Wang, X.-J., Hu, W.-X. & Xu, D.-J. (2004). Acta Cryst. E60, o1954-o1956.]), the C—H⋯O hydrogen bonds were all overlooked; instead, those authors suggested the occurrence of π–π stacking inter­actions, but such inter­actions are, in fact, absent (Wardell et al., 2005[Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o10-o14.]). In the disordered isomer, (V)[link], an extensive series of N—H⋯O and C—H⋯O hydrogen bonds generates a three-dimensional framework structure, the formation of which is independent of the disorder (Wardell et al., 2005[Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o10-o14.]).

[Figure 1]
Figure 1
Part of the crystal structure of isomer (I)[link], showing the atom-labelling scheme and the formation of an ordered chain of rings along [1[\overline{1}]0]. Displacement ellipsoids are drawn at the 30% probability level. Atoms N1, N2 and C27 and their pendent H atoms have 0.5 occupancy, as do the H atoms bonded to atoms C11 and C16. Atoms marked with the suffixes a–e are at the symmetry positions (1 − x, 1 − y, 1 − z), (1 + x, −1 + y, z), (2 + x, −2 + y, z), (2 − x, −y, 1 − z) and (3 − x, −1 − y, 1 − z), respectively. For the sake of clarity, H atoms not involved in the motifs shown have been omitted, as has the unit-cell outline.
[Figure 2]
Figure 2
Part of the crystal structure of isomer (II)[link], showing the atom-labelling scheme and the formation of an ordered chain of rings along [1[\overline{1}]0]. Displacement ellipsoids are drawn at the 30% probability level. Atoms N1, N2 and C27 and their pendent H atoms have 0.5 occupancy, as do the H atoms bonded to atoms C11 and C12. Atoms marked with the suffixes a–e are at the symmetry positions (1 − x, 1 − y, 1 − z), (−x, 2 − y, 1 − z), (−1 + x, 1 + y, z), (−1 − x, 3 − y, 1 − z) and (−2 + x, 2 + y, z), respectively. For the sake of clarity, H atoms not involved in the motifs shown have been omitted, as has the unit-cell outline.
[Figure 3]
Figure 3
The mol­ecule of isomer (III)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4]
Figure 4
Part of the crystal structure of isomer (III)[link], showing the formation of a centrosymmetric dimer. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).

Experimental

Isomer (I)[link] was obtained by the reaction of equimolar quantities (2 mmol) of 2-nitro­benzaldehyde and 3-nitro­phenyl­hydrazine hydro­chloride in MeOH (20 ml). The reaction mixture was heated under reflux for 30 min and, after cooling, the solvent was removed under reduced pressure. The solid residue was recrystallized from methanol–1,2-dichloro­ethane (1:1 v/v). IR: 3295, 1616, 1573, 1566 cm−1. Isomers (II)[link] and (III)[link] were obtained from the reactions of equimolar quantities (2 mmol) of 2-nitro­phenyl­hydrazine and the appropriate nitro­benzaldehyde in MeOH (20 ml). The reaction mixtures were heated under reflux for 30 min and, after cooling, the solvents were removed under reduced pressure. Compounds (II)[link] and (III)[link] were obtained on recrystallization of the appropriate reaction residue from ethyl acetate. IR: for (II)[link], 3299, 1615, 1573, 1545 cm−1; for (III)[link], 3286, 1619, 1595, 1569 cm−1. Crystals of (II)[link] were very fragile, and attempts to cut small fragments from larger crystals consistently resulted in shattering.

Isomer (I)[link]

Crystal data

  • C13H10N4O4

  • Mr = 286.25

  • Monoclinic, P 21 /c

  • a = 5.9845 (2) Å

  • b = 5.5962 (2) Å

  • c = 19.1168 (6) Å

  • β = 104.558 (2)°

  • V = 619.67 (4) Å3

  • Z = 2

  • Dx = 1.534 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1415 reflections

  • θ = 4.3–27.5°

  • μ = 0.12 mm−1

  • T = 120 (2) K

  • Block, orange

  • 0.60 × 0.25 × 0.10 mm
Data collection

  • Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.942, Tmax = 0.988

  • 8294 measured reflections

  • 1415 independent reflections

  • 1286 reflections with I > 2σ(I)

  • Rint = 0.030

  • θmax = 27.5°

  • h = −7 → 7

  • k = −7 → 7

  • l = −23 → 24
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.064

  • wR(F2) = 0.149

  • S = 1.07

  • 1415 reflections

  • 111 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0204P)2 + 1.7995P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.22 e Å−3

  • Extinction correction: SHELXL97

  • Extinction coefficient: 0.089 (12)

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O31i 0.88 2.29 3.133 (5) 161
C16—H16⋯O32i 0.95 2.42 3.318 (3) 158
C27—H27⋯O31i 0.95 2.49 3.335 (5) 149
C27—H27⋯O31ii 0.95 2.13 2.698 (5) 117
Symmetry codes: (i) x+1, y-1, z; (ii) -x+1, -y+1, -z+1.

Isomer (II)[link]

Crystal data

  • C13H10N4O4

  • Mr = 286.25

  • Monoclinic, P 21 /c

  • a = 6.2280 (7) Å

  • b = 5.3947 (10) Å

  • c = 19.249 (4) Å

  • β = 106.847 (11)°

  • V = 618.98 (19) Å3

  • Z = 2

  • Dx = 1.536 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1415 reflections

  • θ = 3.5–27.6°

  • μ = 0.12 mm−1

  • T = 120 (2) K

  • Plate, red

  • 0.62 × 0.12 × 0.03 mm
Data collection

  • Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.947, Tmax = 0.997

  • 5521 measured reflections

  • 1415 independent reflections

  • 744 reflections with I > 2σ(I)

  • Rint = 0.077

  • θmax = 27.6°

  • h = −8 → 7

  • k = −7 → 6

  • l = −24 → 24
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.068

  • wR(F2) = 0.208

  • S = 1.04

  • 1415 reflections

  • 109 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0905P)2 + 0.3625P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.30 e Å−3

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O21 0.88 2.11 2.696 (6) 123
N1—H1⋯O21i 0.88 2.46 3.282 (6) 156
C15—H15⋯O22ii 0.95 2.52 3.379 (4) 151
C27—H27⋯O21i 0.95 2.35 3.268 (7) 163
Symmetry codes: (i) -x, -y+2, -z+1; (ii) x+1, y-1, z.

Isomer (III)[link]

Crystal data

  • C13H10N4O4

  • Mr = 286.25

  • Monoclinic, P 21 /c

  • a = 17.9563 (16) Å

  • b = 3.7160 (2) Å

  • c = 22.0624 (17) Å

  • β = 124.406 (5)°

  • V = 1214.58 (16) Å3

  • Z = 4

  • Dx = 1.565 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 2795 reflections

  • θ = 3.9–27.7°

  • μ = 0.12 mm−1

  • T = 120 (2) K

  • Plate, orange

  • 0.36 × 0.34 × 0.02 mm
Data collection

  • Nonius KappaCCD area-detector diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.964, Tmax = 0.998

  • 20354 measured reflections

  • 2795 independent reflections

  • 1794 reflections with I > 2σ(I)

  • Rint = 0.077

  • θmax = 27.7°

  • h = −22 → 23

  • k = −4 → 4

  • l = −28 → 28
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.069

  • wR(F2) = 0.170

  • S = 1.08

  • 2795 reflections

  • 190 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0579P)2 + 1.5262P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.31 e Å−3

Table 3
Selected bond lengths (Å) for (III)[link]

C11—C12 1.421 (4)
C12—C13 1.395 (4)
C13—C14 1.368 (4)
C14—C15 1.392 (4)
C15—C16 1.370 (4)
C16—C11 1.410 (4)
C12—N12 1.437 (3)
N12—O21 1.250 (3)
N12—O22 1.231 (3)
C21—C22 1.405 (4)
C22—C23 1.380 (4)
C23—C24 1.386 (4)
C24—C25 1.375 (4)
C25—C26 1.388 (4)
C26—C21 1.397 (4)
C24—N24 1.470 (4)
N24—O41 1.219 (3)
N24—O42 1.232 (3)

Table 4
Hydrogen-bond geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O21 0.88 1.97 2.609 (3) 128
N1—H1⋯O21i 0.88 2.54 3.364 (3) 157
Symmetry code: (i) -x+1, -y+1, -z+1.

For each compound, the space group P21/c was uniquely assigned from the systematic absences. All H atoms were located in difference maps and subsequently treated as riding atoms, with distances C—H = 0.95 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N). It became apparent at an early stage that in each of (I)[link] and (II)[link] the mol­ecules were disordered over two sets of sites related by a centre of inversion, selected in each case as that at ([{1\over 2}], [{1\over 2}], [{1\over 2}]). Each isomer was then modelled using a single aryl ring with a single nitro substituent, all having unit occupancy, and an acyclic fragment –CH=N—NH– having 0.5 occupancy. The atom-labelling schemes (Figs. 1[link] and 2[link]) were such that atom N1 was bonded to atom C11, and the aryl ring was numbered to provide the lowest locant for the nitro group. The H-atom sites bonded to atoms C11 and C12 also have 0.5 occupancy.

For the three title isomers, data collection: COLLECT (Nonius, 1999[Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information

Crystal structure: contains datablocks global, I, II, III. DOI: 10.1107/S0108270105028799/sk1867sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105028799/sk1867Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105028799/sk1867IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270105028799/sk1867IIIsup4.hkl


Comment top

As part of our continuing studies of the supramolecular arrangements in imines and hydrazones, we report here the structures of three isomeric nitrobenzaldehyde nitrophenyl hydrazones, (I)–(II), which we compare briefly with two further isomers, (IV) and (V) (Shan et al., 2004; Wardell et al., 2005).

In compounds (I) and (II) (Figs. 1 and 2), the molecules are disordered over two sets of sites related by a centre of inversion, selected for the sake of convenience as that at (1/2, 1/2, 1/2). The asymmetric units for (I) and (II) were selected so that the coordinates of the atoms in the nitro groups were approximately the same. This then led to close correspondence between the coordinates for atoms C11–C16 in compound (I) with those for atoms C16/C11–C12 [C11/C16/C15/C14/C13/C12?], respectively, in compound (II). Likewise, the coordinates for atoms N1, N2 and C27 in the reference asymmetric unit at (x, y, z) in compound (I) closely correspond to those in compound (II) for atoms C27, N2 and N1, respectively, at (1 − x, 1 − y, 1 − z). The unit-cell dimensions indicate that compounds (I) and (II) are isomorphous, and the atom coordinates indicate that these compounds are effectively isostructural, but with atoms N1 and C27 interchanged between (I) and (II) (Figs. 1 and 2). By contrast, all atoms in compound (III) (Fig. 3) are fully ordered in general positions. While all of the atoms in isomer (IV) are fully ordered, in isomer (V) the NH and CH sites in the central bridge are randomly scrambled, with the two heavy-atom sites each occupied by (0.5 C+0.5 N) (Wardell et al., 2005).

In each of compounds (I)–(III), the molecules are essentially planar, and all have the (E) configuration at the C═N double bond. In compound (III), the bond distances (Table 3) show strong evidence for the development of the polarized quinonoid form, (IIIa). In particular, with the C11–C16 aryl ring, the C13—C14 and C15—C16 distances are significantly shorter than the remaining distances, while C11—C12 is the longest, and the C12—N12 distance is short for its type, while the N12—O21 and N12—O22 distances are both long (Allen et al., 1987). By contrast, the C21–C26 aryl ring shows no evidence for the development of a quinonoid form. The structure of the isomer (IV), which differs from (III) by the notional reversal of the spacer fragment, has been determined both at 295 K (Shan et al., 2004) and at 120 K (Wardell et al., 2005). The same phase is present at both temperatures and both structures show evidence for the development of the polarized form, (IVa), although this was not remarked upon by Shan et al. (2004).

In each of compounds (I) and (II), there is a short intramolecular X—H···O contact (Tables 1 and 2), where X is atom C27 in (I) and atom N1 in (II). We first discuss the intermolecular hydrogen bonds on the assumption of local ordering and then consider the consequences of the disorder across inversion centres. In compound (I), the molecules are linked by the concerted action of three hydrogen bonds (Table 1): atoms N1 and C27 in the molecule at (x, y, z) both act as hydrogen-bond donors to atom O31 in the molecule at (1 + x, −1 + y, z), while atom C16 at (x, y, z) similarly acts as donor to atom O32, also at (1 + x, −1 + y, z). Hence, this multi-point interaction generates by translation a complex chain of rings running parallel to the [110] direction (Fig. 1). An entirely similar chain of rings is formed in compound (II), where atoms N1 and C27 at (x, y, z) act as donors to atom O21 at (−x, 2 − y, 1 − z), while atom C15 acts as donor to atom O22 at (1 + x, −1 + y, z) (Fig. 2). In each compound, therefore, a given molecule will form four hydrogen bonds with each of its neighbours within the [110] chain, provided only that there is local ordering within the chain in question. The multi-point recognition makes it appear probable that, within a given chain, the molecules are, in fact, ordered in this manner. Two chains of this type pass through each unit cell in (I) and (II), but there are no direction-specific interactions between adjacent chains. Accordingly, there is no necessity for the orientation of molecules in adjacent chains to show any correlation.

The supramolecular structure of compound (III), by contrast, is extremely simple. In addition to forming an intramolecular hydrogen bond (Table 4) which gives rise to an S(6) ring, the amino atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor to nitro atom O21 in the molecule at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric dimer containing an S(6)R22(4)S(6) motif (Fig. 4). There are no direction-specific interactions between adjacent dimers. In particular, C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are both absent. The supramolecular structure of compound (III) thus consists of isolated dimers.

In isomer (IV), the close analogue of (III), the molecules are linked into complex sheets by a combination of one N—H···O hydrogen bond and three independent C—H···O hydrogen bonds (Wardell et al., 2005). In the earlier report on this compound (Shan et al., 2004), the C—H···O hydrogen bonds were all overlooked; instead, those authors suggested the occurrence of π–π stacking interactions, but such interactions are, in fact, absent (Wardell et al., 2005). In the disordered isomer, (V), an extensive series of N—H···O and C—H···O hydrogen bonds generates a three-dimensional framework structure, the formation of which is independent of the disorder (Wardell et al., 2005).

Experimental top

Compound (I) was obtained by the reaction of equimolar quantities (2 mmol) of 2-nitrobenzaldehyde and 3-nitrophenylhydrazine hydrochloride in MeOH (20 ml). The reaction mixture was heated under reflux for 30 min and, after cooling the mixture, the solvent was removed under reduced pressure. The solid residue was recrystallized from methanol–1,2-dichloroethane (1:1 v/v). Analysis, IR: 3295, 1616, 1573, 1566 cm−1. Compounds (II) and (III) were obtained from the reactions of equimolar quantities (2 mmol) of 2-nitrophenylhydrazine and the appropriate nitrobenzaldehyde in MeOH (20 ml). The reaction mixtures were heated under reflux for 30 min and, after cooling the mixtures, the solvents were removed under reduced pressure. Compounds (II) and (III) were obtained on recrystallization of the appropriate reaction residue from ethyl acetate. Analysis, IR: for (II), 3299, 1615, 1573, 1545 cm−1; for (III), 3286, 1619, 1595, 1569 cm−1. Crystals of (II) were very fragile, and attempts to cut small fragments from larger crystals consistently resulted in shattering.

Refinement top

For each compound, the space group P21/c was uniquely assigned from the systematic absences. All H atoms were located in difference maps and subsequently treated as riding atoms, with distances C—H = 0.95 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N). It became apparent at an early stage that, in each of compounds (I) and (II), the molecules were disordered over two sets of sites related by a centre of inversion, selected in each case as that at (1/2, 1/2, 1/2). Each compound was then modelled using a single aryl ring with a single nitro substituent, all having unit occupancy, and an acyclic fragment –CH═N—NH– having occupancy 0.5. The atom-labelling schemes (Figs. 1 and 2) were such that atom N1 was bonded to atom C11, and the aryl ring was numbered to provide the lowest locant for the nitro group. The H-atom sites bonded to atoms C11 and C12 also have occupancy 0.5.

Computing details top

For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. Part of the crystal structure of compound (I), showing the atom-labelling scheme and the formation of an ordered chain of rings along [110]. Displacement ellipsoids are drawn at the 30% probability level. Atoms N1, N2 and C27 and their pendent H atoms have occupancy 1/2, as do the H atoms bonded to atoms C11 and C16. Atoms marked with the suffixes a–e are at the symmetry positions (1 − x, 1 − y, 1 − z), (1 + x, −1 + y, z), (2 + x, −2 + y, z), (2 − x, −y, 1 − z) and (3 − x, −1 − y, 1 − z), respectively. For the sake of clarity, H atoms not involved in the motifs shown have been omitted, as has the unit-cell outline.
[Figure 2] Fig. 2. Part of the crystal structure of compound (II), showing the atom-labelling scheme and the formation of an ordered chain of rings along [110]. Displacement ellipsoids are drawn at the 30% probability level. Atoms N1, N2 and C27 and their pendent H atoms have occupancy 1/2, as do the H atoms bonded to atoms C11 and C12. Atoms marked with the suffixes a–e are at the symmetry positions (1 − x, 1 − y, 1 − z), (−x, 2 − y, 1 − z), (−1 + x, 1 + y, z), (−1 − x, 3 − y, 1 − z) and (−2 + x, 2 + y, z), respectively. For the sake of clarity, H atoms not involved in the motifs shown have been omitted, as has the unit-cell outline.
[Figure 3] Fig. 3. The molecule of compound (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4] Fig. 4. Part of the crystal structure of compound (III), showing the formation of a centrosymmetric dimer. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
(I) 2-Nitrobenzaldehyde 3-nitrophenylhydrazone top
Crystal data top
C13H10N4O4F(000) = 296
Mr = 286.25Dx = 1.534 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1415 reflections
a = 5.9845 (2) Åθ = 4.3–27.5°
b = 5.5962 (2) ŵ = 0.12 mm−1
c = 19.1168 (6) ÅT = 120 K
β = 104.558 (2)°Block, orange
V = 619.67 (4) Å30.60 × 0.25 × 0.10 mm
Z = 2
Data collection top
Nonius KappaCCD area-detector
diffractometer		1415 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode1286 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 4.3°
ϕ and ω scansh = −7→7
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −7→7
Tmin = 0.942, Tmax = 0.988l = −23→24
8294 measured reflections
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)] = 0.064H-atom parameters constrained
wR(F2) = 0.149 w = 1/[σ2(Fo2) + (0.0204P)2 + 1.7995P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1415 reflectionsΔρmax = 0.24 e Å−3
111 parametersΔρmin = −0.22 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.089 (12)
Crystal data top
C13H10N4O4V = 619.67 (4) Å3
Mr = 286.25Z = 2
Monoclinic, P21/cMo Kα radiation
a = 5.9845 (2) ŵ = 0.12 mm−1
b = 5.5962 (2) ÅT = 120 K
c = 19.1168 (6) Å0.60 × 0.25 × 0.10 mm
β = 104.558 (2)°
Data collection top
Nonius KappaCCD area-detector
diffractometer		1415 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1286 reflections with I > 2σ(I)
Tmin = 0.942, Tmax = 0.988Rint = 0.030
8294 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0640 restraints
wR(F2) = 0.149H-atom parameters constrained
S = 1.07Δρmax = 0.24 e Å−3
1415 reflectionsΔρmin = −0.22 e Å−3
111 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O31−0.1887 (3)0.8431 (4)0.43869 (10)0.0298 (5)
O32−0.4466 (3)0.7503 (4)0.34233 (12)0.0363 (6)
N10.4510 (7)0.2491 (8)0.4389 (2)0.0188 (9)0.50
N20.5531 (7)0.4005 (8)0.4928 (2)0.0176 (9)0.50
N13−0.2584 (4)0.7171 (4)0.38563 (11)0.0213 (5)
C110.2337 (4)0.2959 (5)0.39702 (13)0.0198 (6)
C120.1116 (4)0.4918 (5)0.41351 (13)0.0188 (5)
C13−0.1153 (4)0.5182 (5)0.37179 (13)0.0186 (5)
C14−0.2180 (4)0.3638 (5)0.31671 (13)0.0209 (6)
C15−0.0907 (4)0.1734 (5)0.30107 (13)0.0220 (6)
C160.1348 (4)0.1399 (5)0.34160 (13)0.0216 (6)
C270.7587 (8)0.3420 (9)0.5287 (3)0.0186 (10)0.50
H10.52470.12010.43070.023*0.50
H110.39260.29220.42180.024*0.50
H120.18320.59960.45080.023*0.50
H14−0.37320.38780.29000.025*
H15−0.15720.06650.26290.026*
H160.22200.00870.33120.026*
H270.82660.19660.51870.022*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O310.0323 (11)0.0288 (11)0.0263 (10)0.0069 (9)0.0038 (8)−0.0050 (9)
O320.0229 (10)0.0388 (13)0.0395 (12)0.0133 (9)−0.0061 (8)−0.0011 (10)
N10.0128 (18)0.022 (2)0.020 (2)0.0050 (16)0.0012 (15)−0.0027 (17)
N20.0143 (19)0.021 (2)0.0163 (18)−0.0015 (16)0.0024 (15)−0.0009 (16)
N130.0178 (10)0.0258 (12)0.0203 (10)0.0038 (9)0.0046 (8)0.0043 (9)
C110.0166 (11)0.0221 (13)0.0189 (11)0.0016 (10)0.0013 (9)0.0019 (10)
C120.0197 (12)0.0208 (12)0.0148 (11)−0.0001 (10)0.0024 (9)0.0014 (9)
C130.0176 (12)0.0197 (12)0.0193 (11)0.0028 (10)0.0062 (9)0.0033 (10)
C140.0166 (11)0.0258 (13)0.0193 (11)−0.0011 (10)0.0023 (9)0.0032 (10)
C150.0222 (12)0.0231 (13)0.0198 (12)−0.0023 (10)0.0036 (10)−0.0016 (10)
C160.0233 (12)0.0204 (12)0.0213 (12)0.0021 (10)0.0059 (10)−0.0011 (10)
C270.017 (2)0.018 (2)0.020 (2)0.0006 (18)0.0028 (18)−0.0015 (19)
Geometric parameters (Å, º) top
N1—N21.355 (6)C12—H120.95
N1—C111.370 (4)C13—C141.381 (4)
N1—H10.88C13—N131.469 (3)
N2—C271.291 (6)N13—O311.219 (3)
C27—C12i1.503 (5)N13—O321.233 (3)
C27—H270.95C14—C151.386 (4)
C11—C161.386 (4)C14—H140.95
C11—C121.397 (4)C15—C161.390 (3)
C11—H110.95C15—H150.95
C12—C131.399 (3)C16—H160.95
N2—N1—C11120.3 (4)C13—C12—H12123.4
N2—N1—H1119.8C14—C13—C12123.4 (2)
C11—N1—H1119.8C14—C13—N13116.3 (2)
N2—N1—H11108.4C12—C13—N13120.3 (2)
H1—N1—H11127.2O31—N13—O32122.4 (2)
C27—N2—N1115.6 (4)O31—N13—C13119.7 (2)
N2—C27—C12i118.8 (4)O32—N13—C13118.0 (2)
N2—C27—H27120.6C13—C14—C15118.8 (2)
C12i—C27—H27120.6C13—C14—H14120.6
N1—C11—C16119.1 (3)C15—C14—H14120.6
N1—C11—C12119.5 (3)C14—C15—C16119.5 (2)
C16—C11—C12121.3 (2)C14—C15—H15120.2
C16—C11—H11123.3C16—C15—H15120.2
C12—C11—H11114.8C11—C16—C15120.6 (2)
C11—C12—C13116.2 (2)C11—C16—H16119.7
C11—C12—H12120.3C15—C16—H16119.7
C11—N1—N2—C27−179.4 (4)C12—C13—N13—O31−8.4 (3)
N1—N2—C27—C12i176.5 (4)C14—C13—N13—O32−8.8 (3)
N2—N1—C11—C16179.1 (3)C12—C13—N13—O32171.5 (2)
N2—N1—C11—C12−4.5 (5)C12—C13—C14—C15−0.6 (4)
N1—C11—C12—C13−175.5 (3)N13—C13—C14—C15179.7 (2)
C16—C11—C12—C130.9 (4)C13—C14—C15—C161.0 (4)
C11—C12—C13—C14−0.4 (4)N1—C11—C16—C15175.9 (3)
C11—C12—C13—N13179.3 (2)C12—C11—C16—C15−0.5 (4)
C14—C13—N13—O31171.3 (2)C14—C15—C16—C11−0.5 (4)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O31ii0.882.293.133 (5)161
C16—H16···O32ii0.952.423.318 (3)158
C27—H27···O31ii0.952.493.335 (5)149
C27—H27···O31i0.952.132.698 (5)117
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y−1, z.
(II) 3-Nitrobenzaldehyde 2-nitrophenylhydrazone top
Crystal data top
C13H10N4O4F(000) = 296
Mr = 286.25Dx = 1.536 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1415 reflections
a = 6.2280 (7) Åθ = 3.5–27.6°
b = 5.3947 (10) ŵ = 0.12 mm−1
c = 19.249 (4) ÅT = 120 K
β = 106.847 (11)°Plate, red
V = 618.98 (19) Å30.62 × 0.12 × 0.03 mm
Z = 2
Data collection top
Nonius KappaCCD area-detector
diffractometer		1415 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode744 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.077
Detector resolution: 9.091 pixels mm-1θmax = 27.6°, θmin = 3.5°
ϕ and ω scansh = −8→7
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −7→6
Tmin = 0.947, Tmax = 0.997l = −24→24
5521 measured reflections
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)] = 0.068Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.208H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0905P)2 + 0.3625P]
where P = (Fo2 + 2Fc2)/3
1415 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.24 e Å−3
0 restraintsΔρmin = −0.30 e Å−3
Crystal data top
C13H10N4O4V = 618.98 (19) Å3
Mr = 286.25Z = 2
Monoclinic, P21/cMo Kα radiation
a = 6.2280 (7) ŵ = 0.12 mm−1
b = 5.3947 (10) ÅT = 120 K
c = 19.249 (4) Å0.62 × 0.12 × 0.03 mm
β = 106.847 (11)°
Data collection top
Nonius KappaCCD area-detector
diffractometer		1415 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		744 reflections with I > 2σ(I)
Tmin = 0.947, Tmax = 0.997Rint = 0.077
5521 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0680 restraints
wR(F2) = 0.208H-atom parameters constrained
S = 1.04Δρmax = 0.24 e Å−3
1415 reflectionsΔρmin = −0.30 e Å−3
109 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O21−0.1660 (4)0.8644 (5)0.44227 (13)0.0396 (7)
O22−0.4434 (4)0.7607 (5)0.35056 (13)0.0432 (8)
N10.2348 (8)0.6358 (10)0.4693 (3)0.0253 (12)0.50
N20.4566 (7)0.5792 (10)0.5045 (3)0.0257 (13)0.50
N12−0.2507 (4)0.7293 (5)0.38996 (15)0.0333 (7)
C110.1037 (5)0.4953 (6)0.41451 (17)0.0312 (9)
C12−0.1197 (5)0.5262 (6)0.37373 (17)0.0291 (8)
C13−0.2236 (5)0.3686 (7)0.31694 (18)0.0317 (9)
C14−0.1032 (5)0.1774 (7)0.29945 (17)0.0320 (9)
C150.1177 (5)0.1419 (7)0.33987 (18)0.0328 (9)
C160.2211 (5)0.2968 (7)0.39653 (18)0.0359 (9)
C270.5502 (9)0.7246 (13)0.5564 (3)0.0291 (15)0.50
H10.17590.76870.48300.030*0.50
H110.17330.60530.45300.037*0.50
H13−0.37650.39270.29040.038*
H14−0.17100.07050.26000.038*
H150.19980.00770.32830.039*
H160.37310.26880.42340.043*0.50
H270.46320.85900.56520.035*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O210.0426 (14)0.0410 (16)0.0316 (14)0.0016 (11)0.0047 (11)−0.0045 (12)
O220.0284 (13)0.0506 (18)0.0436 (16)0.0057 (12)−0.0006 (12)−0.0004 (12)
N10.022 (3)0.027 (3)0.024 (3)0.004 (2)0.003 (2)−0.002 (2)
N20.015 (3)0.037 (4)0.021 (3)0.000 (2)−0.001 (2)−0.004 (3)
N120.0304 (16)0.0405 (19)0.0262 (16)0.0003 (14)0.0037 (13)0.0026 (14)
C110.0336 (18)0.036 (2)0.0198 (17)−0.0084 (16)0.0005 (14)0.0037 (16)
C120.0264 (17)0.032 (2)0.0293 (19)0.0011 (15)0.0090 (15)0.0056 (15)
C130.0241 (16)0.040 (2)0.0288 (19)−0.0037 (15)0.0048 (14)0.0027 (16)
C140.0292 (17)0.037 (2)0.0255 (19)−0.0022 (15)0.0010 (15)−0.0010 (16)
C150.0305 (18)0.037 (2)0.032 (2)0.0034 (15)0.0097 (16)0.0055 (16)
C160.0241 (17)0.049 (2)0.0296 (19)−0.0041 (16)−0.0007 (14)0.0113 (18)
C270.017 (3)0.037 (4)0.034 (4)0.005 (3)0.007 (3)0.003 (3)
Geometric parameters (Å, º) top
N1—C111.362 (6)C12—N121.453 (4)
N1—N21.384 (6)N12—O211.231 (3)
N1—H10.88N12—O221.232 (3)
N2—C271.271 (8)C13—C141.373 (5)
C27—C16i1.454 (6)C13—H130.95
C27—H270.95C14—C151.383 (4)
C11—C121.395 (4)C14—H140.95
C11—C161.395 (5)C15—C161.377 (5)
C11—H110.95C15—H150.95
C12—C131.388 (5)C16—H160.95
C11—N1—N2123.0 (5)O21—N12—C12119.2 (3)
C11—N1—H1118.5O22—N12—C12118.6 (3)
N2—N1—H1118.5C14—C13—C12119.4 (3)
N2—N1—H11141.9C14—C13—H13120.3
C27—N2—N1114.4 (5)C12—C13—H13120.3
N2—C27—C16i125.8 (5)C13—C14—C15119.4 (3)
N2—C27—H27117.1C13—C14—H14120.3
C16i—C27—H27117.1C15—C14—H14120.3
N1—C11—C12130.2 (4)C16—C15—C14121.5 (3)
N1—C11—C16112.3 (3)C16—C15—H15119.3
C12—C11—C16117.4 (3)C14—C15—H15119.3
C12—C11—H11121.3C15—C16—C11120.2 (3)
C16—C11—H11121.3C15—C16—C27i126.5 (4)
C13—C12—C11122.1 (3)C11—C16—C27i113.3 (4)
C13—C12—N12118.0 (3)C15—C16—H16119.9
C11—C12—N12120.0 (3)C11—C16—H16119.9
O21—N12—O22122.2 (3)
C11—N1—N2—C27−177.0 (5)C11—C12—N12—O22175.9 (3)
N1—N2—C27—C16i178.1 (5)C11—C12—C13—C14−0.7 (5)
N2—N1—C11—C12−179.8 (4)N12—C12—C13—C14178.9 (3)
N2—N1—C11—C16−2.4 (6)C12—C13—C14—C151.6 (5)
N1—C11—C12—C13176.8 (4)C13—C14—C15—C16−1.2 (5)
C16—C11—C12—C13−0.5 (5)C14—C15—C16—C11−0.1 (5)
N1—C11—C12—N12−2.8 (6)C14—C15—C16—C27i178.7 (4)
C16—C11—C12—N12179.9 (3)N1—C11—C16—C15−176.9 (3)
C13—C12—N12—O21176.5 (3)C12—C11—C16—C150.9 (5)
C11—C12—N12—O21−3.9 (4)N1—C11—C16—C27i4.2 (5)
C13—C12—N12—O22−3.7 (4)C12—C11—C16—C27i−178.0 (4)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O210.882.112.696 (6)123
N1—H1···O21ii0.882.463.282 (6)156
C15—H15···O22iii0.952.523.379 (4)151
C27—H27···O21ii0.952.353.268 (7)163
Symmetry codes: (ii) −x, −y+2, −z+1; (iii) x+1, y−1, z.
(III) 4-Nitrobenzaldehyde 2-nitrophenylhydrazone top
Crystal data top
C13H10N4O4F(000) = 592
Mr = 286.25Dx = 1.565 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2795 reflections
a = 17.9563 (16) Åθ = 3.9–27.7°
b = 3.7160 (2) ŵ = 0.12 mm−1
c = 22.0624 (17) ÅT = 120 K
β = 124.406 (5)°Plate, orange
V = 1214.58 (16) Å30.36 × 0.34 × 0.02 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer		2795 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode1794 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.077
Detector resolution: 9.091 pixels mm-1θmax = 27.7°, θmin = 3.9°
ϕ and ω scansh = −22→23
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −4→4
Tmin = 0.964, Tmax = 0.998l = −28→28
20354 measured reflections
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)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0579P)2 + 1.5262P]
where P = (Fo2 + 2Fc2)/3
2795 reflections(Δ/σ)max < 0.001
190 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C13H10N4O4V = 1214.58 (16) Å3
Mr = 286.25Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.9563 (16) ŵ = 0.12 mm−1
b = 3.7160 (2) ÅT = 120 K
c = 22.0624 (17) Å0.36 × 0.34 × 0.02 mm
β = 124.406 (5)°
Data collection top
Nonius KappaCCD area-detector
diffractometer		2795 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1794 reflections with I > 2σ(I)
Tmin = 0.964, Tmax = 0.998Rint = 0.077
20354 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0690 restraints
wR(F2) = 0.170H-atom parameters constrained
S = 1.08Δρmax = 0.25 e Å−3
2795 reflectionsΔρmin = −0.31 e Å−3
190 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O210.58067 (12)0.6313 (6)0.51862 (10)0.0299 (5)
O220.72540 (13)0.6652 (6)0.57542 (10)0.0316 (5)
O41−0.05385 (15)1.3148 (7)0.02928 (12)0.0511 (7)
O42−0.10049 (15)1.0647 (8)0.09054 (14)0.0566 (8)
N10.47229 (14)0.8944 (6)0.38680 (11)0.0205 (5)
N20.39114 (15)0.9854 (6)0.32429 (11)0.0225 (5)
N120.64900 (15)0.7228 (6)0.52058 (11)0.0214 (5)
N24−0.04001 (17)1.1624 (7)0.08371 (14)0.0357 (7)
C110.55111 (17)0.9737 (7)0.39357 (13)0.0188 (6)
C120.63777 (18)0.8951 (7)0.45759 (13)0.0193 (6)
C130.71669 (18)0.9779 (7)0.46240 (14)0.0217 (6)
C140.71247 (19)1.1358 (8)0.40452 (15)0.0233 (6)
C150.62839 (18)1.2127 (7)0.34086 (14)0.0220 (6)
C160.55016 (18)1.1400 (7)0.33569 (14)0.0213 (6)
C210.22943 (18)0.9782 (7)0.26158 (14)0.0210 (6)
C220.21069 (18)1.1358 (8)0.19648 (14)0.0232 (6)
C230.12273 (19)1.1935 (8)0.13793 (15)0.0256 (6)
C240.05384 (18)1.0972 (8)0.14555 (15)0.0264 (7)
C250.06954 (19)0.9461 (8)0.20868 (15)0.0276 (7)
C260.15813 (18)0.8871 (8)0.26730 (15)0.0239 (6)
C270.32166 (18)0.9025 (7)0.32442 (14)0.0230 (6)
H10.47390.78440.42280.025*
H130.77370.92430.50610.026*
H140.76621.19230.40770.028*
H150.62521.31770.30020.026*
H160.49391.20310.29210.026*
H220.25901.20320.19270.028*
H230.10971.29660.09350.031*
H250.02070.88330.21210.033*
H260.17030.78440.31150.029*
H270.33040.78860.36650.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O210.0233 (11)0.0434 (13)0.0239 (10)−0.0017 (10)0.0139 (9)0.0079 (9)
O220.0224 (11)0.0464 (14)0.0218 (10)0.0030 (10)0.0098 (9)0.0083 (10)
O410.0314 (13)0.0719 (19)0.0329 (12)0.0047 (13)0.0078 (10)0.0213 (13)
O420.0227 (12)0.075 (2)0.0571 (16)−0.0030 (13)0.0137 (12)0.0224 (14)
N10.0190 (12)0.0260 (13)0.0156 (10)0.0003 (10)0.0092 (9)0.0040 (10)
N20.0223 (12)0.0246 (13)0.0184 (11)0.0013 (10)0.0102 (10)−0.0004 (10)
N120.0201 (12)0.0251 (13)0.0183 (11)−0.0002 (10)0.0104 (10)−0.0004 (10)
N240.0257 (14)0.0342 (16)0.0324 (14)−0.0002 (12)0.0075 (12)0.0047 (12)
C110.0215 (14)0.0173 (14)0.0192 (13)−0.0020 (11)0.0124 (11)−0.0027 (11)
C120.0248 (14)0.0155 (14)0.0175 (12)−0.0001 (11)0.0119 (11)−0.0008 (11)
C130.0206 (14)0.0214 (15)0.0189 (13)−0.0009 (12)0.0086 (11)−0.0023 (11)
C140.0240 (15)0.0229 (16)0.0292 (15)−0.0028 (12)0.0187 (13)−0.0021 (12)
C150.0279 (15)0.0213 (15)0.0202 (13)−0.0023 (12)0.0158 (12)−0.0007 (11)
C160.0246 (15)0.0201 (15)0.0165 (12)0.0007 (12)0.0099 (11)0.0002 (11)
C210.0239 (14)0.0171 (14)0.0226 (13)−0.0002 (12)0.0135 (12)−0.0020 (11)
C220.0238 (15)0.0231 (15)0.0248 (14)0.0011 (12)0.0149 (12)0.0013 (12)
C230.0299 (16)0.0233 (15)0.0207 (13)0.0004 (13)0.0126 (12)0.0008 (12)
C240.0184 (14)0.0251 (16)0.0256 (14)0.0026 (12)0.0064 (12)0.0000 (12)
C250.0263 (16)0.0241 (16)0.0315 (16)−0.0001 (13)0.0157 (14)0.0012 (13)
C260.0241 (15)0.0260 (16)0.0226 (13)−0.0002 (13)0.0137 (12)0.0020 (12)
C270.0270 (15)0.0214 (15)0.0198 (13)0.0012 (12)0.0126 (12)−0.0004 (11)
Geometric parameters (Å, º) top
N1—N21.367 (3)C14—H140.95
N1—C111.368 (3)C15—H150.95
N1—H10.88C16—H160.95
N2—C271.287 (3)C21—C221.405 (4)
C27—C211.466 (4)C22—C231.380 (4)
C27—H270.95C23—C241.386 (4)
C11—C121.421 (4)C24—C251.375 (4)
C12—C131.395 (4)C25—C261.388 (4)
C13—C141.368 (4)C26—C211.397 (4)
C14—C151.392 (4)C24—N241.470 (4)
C15—C161.370 (4)N24—O411.219 (3)
C16—C111.410 (4)N24—O421.232 (3)
C12—N121.437 (3)C22—H220.95
N12—O211.250 (3)C23—H230.95
N12—O221.231 (3)C25—H250.95
C13—H130.95C26—H260.95
N2—N1—C11120.3 (2)C15—C16—C11121.6 (2)
N2—N1—H1119.9C15—C16—H16119.2
C11—N1—H1119.9C11—C16—H16119.2
C27—N2—N1114.9 (2)C26—C21—C22119.4 (3)
N2—C27—C21122.0 (2)C26—C21—C27118.1 (2)
N2—C27—H27119.0C22—C21—C27122.5 (2)
C21—C27—H27119.0C23—C22—C21120.6 (3)
N1—C11—C16120.9 (2)C23—C22—H22119.7
N1—C11—C12123.3 (2)C21—C22—H22119.7
C16—C11—C12115.9 (2)C22—C23—C24118.3 (3)
C13—C12—C11121.7 (2)C22—C23—H23120.8
C13—C12—N12116.3 (2)C24—C23—H23120.8
C11—C12—N12122.0 (2)C25—C24—C23122.8 (3)
O22—N12—O21120.9 (2)C25—C24—N24118.6 (3)
O22—N12—C12119.8 (2)C23—C24—N24118.6 (3)
O21—N12—C12119.3 (2)O41—N24—O42123.6 (3)
C14—C13—C12120.4 (2)O41—N24—C24118.6 (3)
C14—C13—H13119.8O42—N24—C24117.7 (3)
C12—C13—H13119.8C24—C25—C26118.6 (3)
C13—C14—C15119.1 (3)C24—C25—H25120.7
C13—C14—H14120.5C26—C25—H25120.7
C15—C14—H14120.5C25—C26—C21120.3 (3)
C16—C15—C14121.3 (2)C25—C26—H26119.9
C16—C15—H15119.3C21—C26—H26119.9
C14—C15—H15119.3
C11—N1—N2—C27−179.1 (2)C12—C11—C16—C151.4 (4)
N1—N2—C27—C21−179.5 (2)N2—C27—C21—C26−178.4 (3)
N2—N1—C11—C16−1.9 (4)N2—C27—C21—C221.9 (4)
N2—N1—C11—C12178.4 (2)C26—C21—C22—C23−1.4 (4)
N1—C11—C12—C13179.6 (3)C27—C21—C22—C23178.3 (3)
C16—C11—C12—C13−0.1 (4)C21—C22—C23—C241.0 (4)
N1—C11—C12—N120.3 (4)C22—C23—C24—C25−0.3 (4)
C16—C11—C12—N12−179.4 (2)C22—C23—C24—N24179.2 (3)
C13—C12—N12—O221.9 (4)C25—C24—N24—O41176.0 (3)
C11—C12—N12—O22−178.8 (2)C23—C24—N24—O41−3.5 (4)
C13—C12—N12—O21−177.7 (2)C25—C24—N24—O42−2.8 (4)
C11—C12—N12—O211.7 (4)C23—C24—N24—O42177.7 (3)
C11—C12—C13—C14−0.6 (4)C23—C24—C25—C260.0 (4)
N12—C12—C13—C14178.7 (2)N24—C24—C25—C26−179.5 (3)
C12—C13—C14—C150.0 (4)C24—C25—C26—C21−0.4 (4)
C13—C14—C15—C161.3 (4)C22—C21—C26—C251.1 (4)
C14—C15—C16—C11−2.1 (4)C27—C21—C26—C25−178.6 (3)
N1—C11—C16—C15−178.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O210.881.972.609 (3)128
N1—H1···O21i0.882.543.364 (3)157
Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC13H10N4O4C13H10N4O4C13H10N4O4
Mr286.25286.25286.25
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)120120120
a, b, c (Å)5.9845 (2), 5.5962 (2), 19.1168 (6)6.2280 (7), 5.3947 (10), 19.249 (4)17.9563 (16), 3.7160 (2), 22.0624 (17)
β (°) 104.558 (2) 106.847 (11) 124.406 (5)
V (Å3)619.67 (4)618.98 (19)1214.58 (16)
Z224
Radiation typeMo KαMo KαMo Kα
µ (mm−1)0.120.120.12
Crystal size (mm)0.60 × 0.25 × 0.100.62 × 0.12 × 0.030.36 × 0.34 × 0.02
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer		Nonius KappaCCD area-detector
diffractometer		Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)		Multi-scan
(SADABS; Sheldrick, 2003)		Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.942, 0.9880.947, 0.9970.964, 0.998
No. of measured, independent and
observed [I > 2σ(I)] reflections		8294, 1415, 1286 5521, 1415, 744 20354, 2795, 1794
Rint0.0300.0770.077
(sin θ/λ)max (Å−1)0.6500.6510.654
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.064, 0.149, 1.07 0.068, 0.208, 1.04 0.069, 0.170, 1.08
No. of reflections141514152795
No. of parameters111109190
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.24, −0.220.24, −0.300.25, −0.31

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O31i0.882.293.133 (5)161
C16—H16···O32i0.952.423.318 (3)158
C27—H27···O31i0.952.493.335 (5)149
C27—H27···O31ii0.952.132.698 (5)117
Symmetry codes: (i) x+1, y−1, z; (ii) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O210.882.112.696 (6)123
N1—H1···O21i0.882.463.282 (6)156
C15—H15···O22ii0.952.523.379 (4)151
C27—H27···O21i0.952.353.268 (7)163
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1, y−1, z.
Selected bond lengths (Å) for (III) top
C11—C121.421 (4)C21—C221.405 (4)
C12—C131.395 (4)C22—C231.380 (4)
C13—C141.368 (4)C23—C241.386 (4)
C14—C151.392 (4)C24—C251.375 (4)
C15—C161.370 (4)C25—C261.388 (4)
C16—C111.410 (4)C26—C211.397 (4)
C12—N121.437 (3)C24—N241.470 (4)
N12—O211.250 (3)N24—O411.219 (3)
N12—O221.231 (3)N24—O421.232 (3)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O210.881.972.609 (3)128
N1—H1···O21i0.882.543.364 (3)157
Symmetry code: (i) −x+1, −y+1, −z+1.
 

Acknowledgements

The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton; the authors thank the staff for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
 First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
 First citationMcArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.  Google Scholar
 First citationNonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
 First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
 First citationShan, S., Wang, X.-J., Hu, W.-X. & Xu, D.-J. (2004). Acta Cryst. E60, o1954–o1956.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
 First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationWardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o10–o14.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 10| October 2005| Pages o613-o616
doi:10.1107/S0108270105028799
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