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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 4| April 2005| Pages o216-o220
doi:10.1107/S0108270105004798

Three isomeric N-(nitro­phen­yl)­succinimides: isolated mol­ecules, hydrogen-bonded sheets and a hydrogen-bonded three-dimensional framework

CROSSMARK_Color_square_no_text.svg
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 9 February 2005; accepted 10 February 2005; online 11 March 2005)

Mol­ecules of N-(2-nitro­phen­yl)succinimide, C10H8N2O4, are linked into sheets by a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds. Mol­ecules of N-(3-nitro­phen­yl)­succinimide are linked into a three-dimensional framework by a combination of a two-centre C—H⋯O hydrogen bond and a three-centre C—H⋯(O)2 hydrogen bond. Mol­ecules of N-(4-nitro­phen­yl)succinimide which lie across twofold rotation axes in space group C2/c, participate in no direction-specific inter­molecular inter­actions.

Comment

We report here the structures of three isomeric N-(nitro­phen­yl)succinimides, (I)–(III)[link]. These compounds offer, within the compass of a small mol­ecular skeleton, a wide range of potential inter­molecular inter­actions, including C—H⋯O(carbon­yl/nitro) (each with aromatic and aliphatic C—H units as potential donors) and C—H⋯π(arene) hydrogen bonds, aromatic π–π stacking inter­actions, and dipolar carbon­yl–carbon­yl and nitro–nitro inter­actions.

In the 2-nitro and 3-nitro isomers (I)[link] and (II)[link] (Figs. 1[link] and 2[link]), the succinimide rings are effectively planar. However, in the 4-nitro isomer, (III)[link], where the mol­ecules lie across twofold rotation axes in space group C2/c, with the reference mol­ecule selected as one lying across the axis along ([{1\over 2}], y, [{3\over 4}]) (Fig. 3[link]), the succinimide rings are markedly puckered. The total puckering amplitude Q2 (Cremer & Pople, 1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]) is 0.161 (3) Å, and the ring-puckering parameter φ2 is 90.0 (9)° for the atom sequence N1—C1—C2—C2iii—C1iii [symmetry code: (iii) 1 − x, y, [{3\over 2}] − z], indicating a half-chair conformation for this ring. In isomers (I)–(III)[link], the dihedral angles between the mean planes of the two rings are 57.4 (2), 46.0 (2) and 39.1 (2)°, respectively, while the dihedral angles between the aryl rings and the nitro groups are 40.0 (2), 4.9 (2) and 23.2 (2)°, respectively. In isomers (I)[link] and (II)[link], the mol­ecules have point group C1, and in isomer (III)[link], the mol­ecular point group is C2; hence, in each isomer, the mol­ecules are chiral. Thus, for isomer (II)[link] in space group P21, each crystal contains just one enantiomer provided that inversion twinning is absent, although the bulk material is racemic. The bond distances and inter­bond angles in (I)–(III) show no unusual values.

[Scheme 1]

The mol­ecules of isomer (I)[link] (Fig. 1[link]) are linked into centrosymmetric dimers by a single C—H⋯O hydrogen bond, and these dimers are linked into sheets by a single C—H⋯π(arene) hydrogen bond (Table 1[link]). Aromatic π–π stacking inter­actions, on the other hand, are absent. Atom C3 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor to nitro atom O21 in the mol­ecule at (1 − x, 1 − y, 1 − z), so generating a centrosymmetric R22(16) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) dimer, centred at ([{1\over 2}], [{1\over 2}], [{1\over 2}]) (Fig. 4[link]). The atoms of type C2 in this dimer, at (x, y, z) and (1 − x, 1 − y, 1 − z), act as hydrogen-bond donors, respectively, to aryl rings C11–C16 in the mol­ecules at (1 − x, −[{1\over 2}] + y, [{3\over 2}] − z) and (x, [{3\over 2}] − y, −[{1\over 2}] + z), which themselves form parts of the dimers centred at ([{1\over 2}], 0, 1) and ([{1\over 2}], 1, 0), respectively. In a similar way, aryl rings C11–C16 in the mol­ecules at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms C2 in the mol­ecules at (1 − x, [{1\over 2}] + y, [{3\over 2}] − z) and (x, [{1\over 2}] − y, −[{1\over 2}] + z), respectively, which are themselves components of the dimers centred at ([{1\over 2}], 1, 1) and ([{1\over 2}], 0, 0). In this manner, a (100) sheet is generated (Fig. 5[link]).

There is a fairly short dipolar contact between carbon­yl atoms O1 at (x, y, z) and C4 at (1 − x, [{1\over 2}] + y, [{3\over 2}] − z) [O1⋯C4iv = 2.959 (2) Å, O1⋯O4iv = 3.193 (2) Å, C1—O1⋯C4iv = 148.7 (2)° and O1⋯C4iv—O4iv = 50.4 (2)°; symmetry code: (iv) 1 − x, [{1\over 2}] + y, [{3\over 2}] − z], corresponding to an inter­action part-way between the type I and type III motifs (Allen et al., 1998[Allen, F. H., Baalham, C. A., Lommerse, J. P. M. & Raithby, P. R. (1998). Acta Cryst. B54, 320-329.]). However, this inter­action occurs within a (100) sheet and hence does not affect the dimensionality of the supramol­ecular structure; there are, in fact, no direction-specific inter­actions between adjacent sheets.

The mol­ecules of (II)[link] are linked into a three-dimensional framework by a combination of one two-centre C—H⋯O hydrogen bond and one three-centre C—H⋯(O)2 hydrogen bond (Table 2[link]), and the formation of the framework is readily analysed and described by consideration of each of these inter­actions in turn. In the two-centre hydrogen bond, aromatic atom C16 in the mol­ecule at (x, y, z) acts as a donor to carbon­yl atom O4 in the mol­ecule at (−1 + x, y, z), so generating by translation a C(6) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) chain running parallel to the [100] direction (Fig. 6[link]).

In the three-centre hydrogen bond, which is planar, atom C3 in the mol­ecule at (x, y, z) acts as a donor, via H3A, to nitro atom O31 in the mol­ecule at (x, y, −1 + z) and to carbon­yl atom O1 in the mol­ecule at (−x, [{1\over 2}] + y, −z). The individual components of this three-centre system thus produce, respectively, a C(9) chain running parallel to the [001] direction and generated by translation, and a C(5) chain running parallel to the [010] direction and generated by the 21 screw axis along ([{1\over 4}], y, [{1\over 4}]). The action of the two components of this system, acting together, forms a (100) sheet in the form of a (4,4)-net (Batten & Robson, 1998[Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460-1494.]) built from a single type of R34(23) ring (Fig. 7[link]). The combination of the [100] chain (Fig. 6[link]) and the (100) sheet (Fig. 7[link]) suffices to generate the three-dimensional framework.

In the structure of isomer (III)[link] (Fig. 3[link]) there are neither hydrogen bonds of any type nor aromatic π–π stacking inter­actions or dipolar inter­actions; hence, the structure of (III)[link] consists of isolated mol­ecules.

It is of interest to compare the supramolecular structures of isomers (I)–(III)[link] with that of the isomeric C-(3-nitro­phen­yl)succinimide, (IV)[link] [Cambridge Structural Databse (CSD; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) refcode TANPUT (Kwiatkowski & Karolak-Wojciechowska, 1992[Kwiatkowski, W. & Karolak-Wojciechowska, J. (1992). Acta Cryst. C48, 204-206.])]. Compound (IV) crystallizes in the centrosymmetric space group P21/c, with Z′ = 2, so that equal numbers of the R and S enantiomers are present in each crystal. The supramolecular structure is dominated by two N—H⋯O hydrogen bonds, which generate C22(8) chains along [010]. Although no C—H⋯O hydrogen bonds were mentioned in the original report, analysis of the reported atomic coordinates using PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]) shows that the chains are, in fact, weakly linked into sheets by two such hydrogen bonds involving one nitro O atom and one carbon­yl O atom as acceptors; however, C—H⋯π(arene) hydrogen bonds and aromatic π–π stacking inter­actions are absent from the structure of (IV). We also note that, at 293 K, N-(4-nitro­phen­yl)maleimide, (V)[link] [CSD refcodes BEDWOX (Fruk & Graham, 2003[Fruk, L. & Graham, D. (2003). Heterocycles, 60, 2307-2313.]) and BEDWOX01 (Moreno-Fuquen et al., 2003[Moreno-Fuquen, R., Valencia, H., Abonia, R., Kennedy, A. R. & Graham, D. (2003). Acta Cryst. E59, o1717-o1718.])], is isostructural with (III)[link]. The structure of (V), like that of (III)[link], contains no direction-specific inter­molecular inter­actions, despite the different orientations of the C—H bonds in the heterocyclic ring of (V).

The inter­molecular inter­actions manifest in the structures of (I)–(III) are different in all three isomers. In (I)[link], the structure is determined by one C—H⋯O hydrogen bond and one C—H⋯π(arene) hydrogen bond; both inter­actions involve a CH2 donor rather than an aryl C—H bond as donor, and the C—H⋯O hydrogen bond has a nitro O-atom acceptor rather than the usual carbon­yl O-atom acceptor; however, the carbon­yl groups do participate in dipolar inter­actions. In isomer (II)[link], by contrast, where only C—H⋯O hydrogen bonds occur, both CH2 and aryl donors participate, and the three-centre hydrogen bond involves both nitro and carbon­yl O atoms as the acceptors. Likewise in (IV), the C—H⋯O hydrogen bonds involve both nitro and carbon­yl acceptors. In none of isomers (I)—(III)[link] is there any aromatic π–π stacking inter­actions, and these inter­actions are possibly precluded by the overall mol­ecular conformations. Perhaps the most surprising feature of the structures of isomers (I)–(III)[link] is the lack of any direction-specific inter­molecular inter­actions in isomer (III)[link].

Thus, each of the isomers (I)–(III)[link] exhibits a different range of inter­molecular inter­actions, and their supramolecular structures are all of different dimensionality, viz. two- and three-dimensional in (I)[link] and (II)[link], respectively, contrasted with isolated mol­ecules in (III)[link]. Such differences within a series of positional isomers are not yet readily predicta­ble, either heuristically or computationally.

[Figure 1]
Figure 1
The mol­ecule of (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
The mol­ecule of (II)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3]
Figure 3
The mol­ecule of (III)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level, and atoms marked with the suffix A are at the symmetry position (1 − x, y, [{3\over 2}] − z).
[Figure 4]
Figure 4
Part of the crystal structure of (I)[link], showing the formation of an R22(16) dimer centred at ([{1\over 2}], [{1\over 2}], [{1\over 2}]). Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 5]
Figure 5
A stereoview of part of the crystal structure of (I)[link], showing the formation of a (100) sheet built from C—H⋯O and C—H⋯π(arene) hydrogen bonds. For clarity, H atoms not involved in the motifs shown have been omitted
[Figure 6]
Figure 6
Part of the crystal structure of (II)[link], showing the formation, via a two-centre C—H⋯O hydrogen bond, of a C(6) chain along [100]. For clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−1 + x, y, z) and (1 + x, y, z), respectively.
[Figure 7]
Figure 7
A stereoview of part of the crystal structure of (II)[link], showing the formation, via a three-centre C—H⋯(O)2 hydrogen bond, of a (100) sheet. For clarity, H atoms not involved in the motifs shown have been omitted.

Experimental

For the preparation of compounds (I)–(III)[link], finely ground mixtures containing equimolar quantities of succinic anhydride and the appropriate nitro­aniline were heated in an oil bath at 473 K until effervescence ceased. The resulting solids were cooled to ambient temperature and dissolved in chloro­form. Activated charcoal was added and the mixtures were then heated under reflux for 10 min; this process was followed by filtration of the hot mixtures. After removal of the solvent under reduced pressure, crystallization of the solid products from ethanol gave crystals suitable for single-crystal X-ray diffraction.

Compound (I)

Crystal data

  • C10H8N2O4

  • Mr = 220.18

  • Monoclinic, P21/c

  • a = 8.3703 (2) Å

  • b = 8.2500 (1) Å

  • c = 14.1375 (3) Å

  • β = 101.0185 (10)°

  • V = 958.27 (3) Å3

  • Z = 4

  • Dx = 1.526 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 2192 reflections

  • θ = 3.5–27.5°

  • μ = 0.12 mm−1

  • T = 120 (2) K

  • Block, yellow

  • 0.15 × 0.15 × 0.10 mm
Data collection

  • Nonius KappaCCD 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 = 0.976, Tmax = 0.988

  • 12 771 measured reflections

  • 2192 independent reflections

  • 1846 reflections with I > 2σ(I)

  • Rint = 0.031

  • θmax = 27.5°

  • h = −10 → 10

  • k = −10 → 10

  • l = −18 → 18
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.114

  • S = 1.10

  • 2192 reflections

  • 146 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0646P)2 + 0.2225P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.35 e Å−3

  • Δρmin = −0.35 e Å−3

  • Extinction correction: SHELXL97

  • Extinction coefficient: 0.081 (7)

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

Cg is the centroid of the C11–C16 ring.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C3—H3B⋯O21i 0.99 2.42 3.253 (2) 141
C2—H2B⋯Cgii 0.99 2.75 3.638 (2) 149
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Compound (II)

Crystal data

  • C10H8N2O4

  • Mr = 220.18

  • Monoclinic, P21

  • a = 6.6318 (2) Å

  • b = 7.0944 (3) Å

  • c = 10.4260 (5) Å

  • β = 108.234 (2)°

  • V = 465.90 (3) Å3

  • Z = 2

  • Dx = 1.570 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1152 reflections

  • θ = 3.2–27.4°

  • μ = 0.12 mm−1

  • T = 120 (2) K

  • Block, colourless

  • 0.40 × 0.35 × 0.30 mm
Data collection

  • Nonius KappaCCD diffractometer

  • φ scans, and ω scans with κ offsets

  • Absorption correction: multi-scan(SORTAV; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-37.], 1997[Blessing, R. H. (1997). J. Appl. Cryst. 30, 421-426.])Tmin = 0.947, Tmax = 0.964

  • 5403 measured reflections

  • 1152 independent reflections

  • 1067 reflections with I > 2σ(I)

  • Rint = 0.042

  • θmax = 27.4°

  • h = −8 → 8

  • k = −8 → 9

  • l = −12 → 13
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.031

  • wR(F2) = 0.078

  • S = 1.08

  • 1152 reflections

  • 146 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0485P)2 + 0.043P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.21 e Å−3

  • Extinction correction: SHELXL97

  • Extinction coefficient: 0.112 (14)

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

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C3—H3A⋯O31v 0.99 2.48 3.193 (2) 129
C3—H3A⋯O1vi 0.99 2.47 3.158 (3) 127
C16—H16⋯O4vii 0.95 2.37 3.162 (2) 141
Symmetry codes: (v) x, y, z-1; (vi) [-x, y+{\script{1\over 2}}, -z]; (vii) x-1, y, z.

Compound (III)

Crystal data

  • C10H8N2O4

  • Mr = 220.18

  • Monoclinic, C 2/c

  • a = 10.3731 (19) Å

  • b = 11.590 (2) Å

  • c = 7.9761 (18) Å

  • β = 108.135 (16)°

  • V = 911.3 (3) Å3

  • Z = 4

  • Dx = 1.605 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 1054 reflections

  • θ = 3.3–27.6°

  • μ = 0.13 mm−1

  • T = 120 (2) K

  • Lath, colourless

  • 0.25 × 0.11 × 0.03 mm
Data collection

  • Nonius KappaCCD 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 = 0.974, Tmax = 0.996

  • 9627 measured reflections

  • 1054 independent reflections

  • 690 reflections with I > 2σ(I)

  • Rint = 0.095

  • θmax = 27.6°

  • h = −13 → 13

  • k = −15 → 15

  • l = −10 → 10
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.058

  • wR(F2) = 0.167

  • S = 1.06

  • 1054 reflections

  • 75 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0889P)2 + 0.338P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.30 e Å−3

For isomer (I)[link], the space group P21/c was uniquely assigned from the systematic absences. For isomer (II)[link], the systematic absences permitted P21 and P21/m as possible space groups; since the unit-cell volume suggested Z = 2, space group P21 was selected and subsequently confirmed by the successful structure analysis. For isomer (III)[link], the systematic absences permitted C2/c and Cc as possible space groups; C2/c was selected and confirmed by the successful structure analysis. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 (aromatic) or 0.99 Å (CH2) and Uiso(H) values of 1.2Ueq(C). In the absence of any significant anomalous dispersion, the Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter for isomer (II)[link] was indeterminate (Flack & Bernardinelli, 2000[Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143-1148.]). Hence, it was not possible to determine the absolute configuration of the mol­ecules in the crystal selected for study (Jones, 1986[Jones, P. G. (1986). Acta Cryst. A42, 57.]); however, this configuration has no chemical significance. Accordingly, the Friedel pairs were merged prior to the final refinements. The data-to-parameter ratio for isomer (II)[link] is thus rather low, only 7.89, although the data set is 99.8% complete to θ = 27.43°.

For compounds (I) and (III), data collection: COLLECT (Hooft, 1999[Hooft, R. W. W. (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. For compound (II), data collection: KappaCCD Server Software (Nonius, 1997[Nonius (1997). KappaCCD Server Software. Windows 3.11 Version. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO–SMN (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.]); data reduction: DENZO–SMN. For all compounds, structure solution: 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.]); structure refinement: 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/S0108270105004798/sk1817sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105004798/sk1817Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105004798/sk1817IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270105004798/sk1817IIIsup4.hkl


Comment top

We report here the structures of the three isomeric N-(nitrophenyl)succinimides, (I)–(III). These compounds offer, within the compass of a small molecular skeleton, a wide range of potential intermolecular interactions, including C—H···O(carbonyl), C—H···O(nitro) (each with aromatic and aliphatic C—H units as potential donors) and C—H···π(arene) hydrogen bonds, aromatic π–π stacking interactions, and dipolar carbonyl···carbonyl and nitro···nitro interactions.

In the 2-nitro and 3-nitro isomers (I) and (II) (Figs. 1 and 2), the succinimide rings are effectively planar. However, in the 4-nitro isomer, (III), where the molecules lie across twofold rotation axes in space group C2/c, with the reference molecule selected as one lying across the axis along (1/2, y, 3/4) (Fig. 3), the succinimide rings are markedly puckered. The total puckering amplitude Q(2) (Cremer & Pople, 1975) is 0.161 (3) Å, and the ring-puckering parameter ϕ(2) is 90.0 (9)° for the atom-sequence N1—C1—C2—C2i—C1i [symmetry code: (i) 1 − x, y, 3/2, − z], indicating a half-chair conformation for this ring. In isomers (I)–(III), the dihedral angles between the mean planes of the two rings are 57.4 (2), 46.0 (2) and 39.1 (2)°, respectively, while the dihedral angles between the aryl rings and the nitro groups are 40.0 (2), 4.9 (2) and 23.2 (2)°, respectively. In isomers (I) and (II), the molecules have point group C1, and in isomer (III), the molecular point group is C2; hence, in each isomer the molecules are chiral. Thus for isomer (II), in space group P21, each crystal contains just one enantiomer provided that inversion twinning is absent, although the bulk material is racemic. The bond distances and interbond angles in (I)–(III) show no unusual values.

The molecules of isomer (I) (Fig. 1) are linked into centrosymmetric dimers by a single C—H···O hydrogen bond, and these dimers are linked into sheets by a single C—H···π(arene) hydrogen bond (Table 2). Aromatic π–π stacking interactions, on the other hand, are absent. Atom C3 in the molecule at (x, y, z) acts as a hydrogen-bond donor to nitro atom O21 in the molecule at (1 − x, 1 − y, 1 − z), so generating a centrosymmetric R22(16) (Bernstein et al., 1995) dimer, centred at (1/2, 1/2, 1/2) (Fig. 4). The atoms of type C2 in this dimer, at (x, y, z) and (1 − x, 1 − y, 1 − z), act as hydrogen-bond donors, respectively, to aryl rings C11–C16 in the molecules at (1 − x, −1/2 + y, 3/2 − z) and (x, 3/2 − y, −1/2 + z), which themselves form parts of the dimers centred at (1/2, 0, 1) and (1/2, 1, 0), respectively. In a similar way, aryl rings C11–C16 in the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms C2 in the molecules at (1 − x, 1/2 + y, 3/2 − z) and (x, 1/2 − y, −1/2 + z), respectively, which are themselves components of the dimers centred at (1/2, 1, 1) and (1/2, 0, 0). In this manner a (100) sheet is generated (Fig. 5).

There is a fairly short dipolar contact between carbonyl atoms O1 at (x, y, z) and C4 at (1 − x, 1/2 + y, 1.5 − z) [O1···C4i = 2.959 (2) Å, O1···O4i = 3.193 (2) Å, C1—O1···C4i = 148.7 (2)° and O1···C4i—O4i = 50.4 (2)°; symmetry code: (i) 1 − x, 1/2 + y, 3/2 − z)], corresponding to an interaction part-way between the type I and type III motifs (Allen et al., 1998). However, this interaction occurs within a (100) sheet and hence does not affect the dimensionality of the supramolecular structure; there are, in fact, no direction-specific interactions between adjacent sheets.

The molecules of (II) are linked into a three-dimensional framework by a combination of one two-centre C—H···O hydrogen bond and one three-centre C—H···(O)2 hydrogen bond (Table 2), and the formation of the framework is readily analysed and described by consideration of each of these interactions in turn. In the two-centre hydrogen bond, aromatic atom C16 in the molecule at (x, y, z) acts as a donor to carbonyl atom O4 in the molecule at (−1 + x, y, z), so generating by translation a C(6) (Bernstein et al., 1995) chain running parallel to the [100] direction (Fig. 6).

In the three-centre hydrogen bond, which is planar, atom C3 in the molecule at (x, y, z) acts as a donor, via H3A, to nitro atom O31 in the molecule at (x, y, −1 + z) and to carbonyl atom O1 in the molecule at (−x, 1/2 + y, −z). The individual components of this three-centre system thus produce, respectively, a C(9) chain running parallel to the [001] direction and generated by translation, and a C(5) chain running parallel to the [010] direction and generated by the 21 screw axis along (1/4, y, 1/4). The action of the two components of this system, acting together, forms a (100) sheet in the form of a (4,4)-net (Batten & Robson, 1998) built from a single type of R34(23) ring (Fig. 7). The combination of the [100] chain (Fig. 6) and the (100) sheet (Fig. 7) suffices to generate the three-dimensional framework.

In the structure of isomer (III) (Fig. 3) there are no hydrogen bonds of any type nor any aromatic π–π stacking interactions or dipolar interactions; hence, the structure of (III) consists of isolated molecules.

It is of interest to compare the supramolecular structures of isomers (I)–(III) with that of the isomeric C-(3-nitrophenyl)succinimide, (IV) [Cambridge Structural Databse (CSD; Allen, 2002) reference code TANPUT; Kwiatkowski & Karolak-Wojciechowska, 1992]. Compound (IV) crystallizes in the centrosymmetric space group P21/c, with Z' = 2, so that equal numbers of the R and S enantiomers are present in each crystal. The supramolecular structure is dominated by two N—H···O hydrogen bonds, which generate C22(8) chains along [010]. Although no C—H···O hydrogen bonds were mentioned in the original report, analysis of the reported atomic coordinates using PLATON (Spek, 2003) shows that the chains are, in fact, weakly linked into sheets by two such hydrogen bonds, involving one nitro O atom and one carbonyl O atom as acceptors; however, C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are absent from the structure of (IV). We also note that at 293 K, N-(4-nitrophenyl)maleimide, (V) [CSD refcodes BEDWOX (Fruk & Graham, 2003) and BEDWOX01 (Moreno-Fuquen et al., 2003)], is isostructural with (III). The structure of (V), like that of (III), contains no direction-specific intermolecular interactions, despite the different orientations of the C—H bonds in the heterocyclic ring of (V).

The intermolecular interactions manifest in the structures of isomers (I)–(III) are different in all three isomers. In (I), the structure is determined by one C—H···O hydrogen bond and one C—H···π(arene) hydrogen bond; both interactions involve a CH2 donor rather than an aryl C—H bond as donor, and the C—H···O hydrogen bond has a nitro O acceptor rather than the usual carbonyl O acceptor; however, the carbonyl groups do participate in dipolar interactions. In isomer (II), by contrast, where only C—H···O hydrogen bonds occur, both CH2 and aryl donors participate, and the three-centre hydrogen bond involves both nitro and carbonyl O atoms as the acceptors. Likewise in (IV), the C—H···O hydrogen bonds involve both nitro and carbonyl acceptors. In none of the isomers (I)—(III) are there any aromatic π–π stacking interactions, and these interactions are possibly precluded by the overall molecular conformations. Perhaps the most surprising feature of the structures of isomers (I)–(III) is the lack of any direction-specific intermolecular interactions in isomer (III).

Thus, each of the isomers (I)–(III) exhibits a different range of intermolecular interactions, and their supramolecular structures are all of different dimensionality, viz. two- and three-dimensional in (I) and (II), respectively, contrasted with isolated molecules in (III). Such differences within a series of positional isomers are not yet readily predictable, either heuristically or computationally.

Experimental top

For the preparation of compounds (I) - (III), finely ground mixtures containing equimolar quantities of succinic anhydride and the appropriate nitroaniline were heated in an oil bath at 473 K until effervescence ceased. The resulting solids were cooled to ambient temperature and dissolved in chloroform. Activated charcoal was added and the mixtures were then heated under reflux for 10 min; this process was followed by filtration of the hot mixtures. After removal of the solvent under reduced pressure, crystallization of the solid products from ethanol gave crystals suitable for single-crystal X-ray diffraction.

Refinement top

For isomer (I), the space group P21/c was uniquely assigned from the systematic absences. For isomer (II), the systematic absences permitted P21 and P21/m as possible space groups: since the unit-cell volume suggested Z = 2, space group P21 was selected and subsequently confirmed by the successful structure analysis. For isomer (III), the systematic absences permitted C2/c and Cc as possible space groups; C2/c was selected and confirmed by the successful structure analysis. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.95 Å (aromatic) or 0.99 Å (CH2), and with Uiso(H) values of 1.2Ueq(C). In the absence of any significant anomalous dispersion, the Flack (1983) parameter for isomer (II) was indeterminate (Flack & Bernardinelli, 2000). Hence it was not possible to determine the absolute configuration of the molecules in the crystal selected for study (Jones, 1986); however, this configuration has no chemical significance. Accordingly, the Friedel pairs were merged prior to the final refinements. The data-to-parameter ratio for isomer (II) is thus rather low, only 7.89, although the data set is 99.8% complete to θ = 27.43°.

Computing details top

Data collection: COLLECT (Hooft, 1999) for (I), (III); KappaCCD Server Software (Nonius, 1997) for (II). Cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT for (I), (III); DENZO–SMN (Otwinowski & Minor, 1997) for (II). Data reduction: DENZO and COLLECT for (I), (III); DENZO–SMN for (II). Program(s) used to solve structure: OSCAIL (McArdle , 2003) and SHELXS97 (Sheldrick, 1997) for (I); OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997) for (II), (III). For all compounds, 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. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. The molecule of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level, and the atoms marked 'A' are at the symmetry position (1 − x, y, 1.5 − z).
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation of an R22(16) dimer centred at (1/2, 1/2, 1/2). Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a (100) sheet built from C—H···O and C—H···π(arene) hydrogen bonds. For clarity, the H atoms not involved in the motifs shown have been omitted
[Figure 6] Fig. 6. Part of the crystal structure of (II), showing the formation, by the two-centre C—H···O hydrogen bond, of a C(6) chain along [100]. For clarity, the H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−1 + x, y, z) and (1 + x, y, z), respectively.
[Figure 7] Fig. 7. A stereoview of part of the crystal structure of (II), showing the formation, by the three-centre C—H···(O)2 hydrogen bond, of a (100) sheet. For clarity, the H atoms not involved in the motifs shown have been omitted.
(I) N-(2-Nitrophenyl)succinimide top
Crystal data top
C10H8N2O4F(000) = 456
Mr = 220.18Dx = 1.526 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2192 reflections
a = 8.3703 (2) Åθ = 3.5–27.5°
b = 8.2500 (1) ŵ = 0.12 mm−1
c = 14.1375 (3) ÅT = 120 K
β = 101.0185 (10)°Block, yellow
V = 958.27 (3) Å30.15 × 0.15 × 0.10 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer		2192 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1846 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.5°
ϕ and ω scansh = −10→10
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −10→10
Tmin = 0.976, Tmax = 0.988l = −18→18
12771 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)] = 0.043H-atom parameters constrained
wR(F2) = 0.114 w = 1/[σ2(Fo2) + (0.0646P)2 + 0.2225P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
2192 reflectionsΔρmax = 0.35 e Å−3
146 parametersΔρmin = −0.35 e Å−3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.081 (7)
Crystal data top
C10H8N2O4V = 958.27 (3) Å3
Mr = 220.18Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.3703 (2) ŵ = 0.12 mm−1
b = 8.2500 (1) ÅT = 120 K
c = 14.1375 (3) Å0.15 × 0.15 × 0.10 mm
β = 101.0185 (10)°
Data collection top
Nonius KappaCCD
diffractometer		2192 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1846 reflections with I > 2σ(I)
Tmin = 0.976, Tmax = 0.988Rint = 0.031
12771 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.114H-atom parameters constrained
S = 1.10Δρmax = 0.35 e Å−3
2192 reflectionsΔρmin = −0.35 e Å−3
146 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.56943 (12)0.28051 (12)0.69420 (7)0.0184 (3)
C10.41560 (15)0.31944 (15)0.71194 (9)0.0222 (3)
O10.39277 (12)0.39518 (13)0.78109 (7)0.0327 (3)
C20.29142 (16)0.25421 (17)0.62910 (10)0.0269 (3)
C30.38899 (16)0.16599 (16)0.56392 (9)0.0242 (3)
C40.56402 (16)0.19965 (15)0.60632 (9)0.0202 (3)
O40.68351 (12)0.16841 (11)0.57385 (7)0.0261 (3)
C110.71852 (15)0.32760 (15)0.75413 (9)0.0180 (3)
C120.83386 (15)0.41825 (15)0.71784 (9)0.0202 (3)
N120.79528 (14)0.48594 (14)0.62029 (8)0.0260 (3)
O210.65761 (13)0.54083 (13)0.59282 (7)0.0363 (3)
O220.90292 (14)0.48825 (14)0.57244 (7)0.0377 (3)
C130.98520 (16)0.45331 (17)0.77271 (10)0.0257 (3)
C141.01968 (16)0.40293 (18)0.86802 (10)0.0276 (3)
C150.90492 (17)0.31608 (17)0.90600 (9)0.0261 (3)
C160.75611 (16)0.27618 (15)0.84926 (9)0.0216 (3)
H2A0.22730.34370.59380.032*
H2B0.21600.17860.65270.032*
H3A0.36680.04810.56330.029*
H3B0.36090.20760.49710.029*
H131.06400.51080.74560.031*
H141.12200.42800.90730.033*
H150.92850.28350.97160.031*
H160.67980.21360.87550.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0169 (5)0.0193 (5)0.0189 (5)−0.0024 (4)0.0033 (4)−0.0024 (4)
C10.0190 (6)0.0204 (6)0.0274 (7)−0.0008 (5)0.0054 (5)0.0009 (5)
O10.0232 (5)0.0396 (6)0.0367 (6)0.0013 (4)0.0091 (4)−0.0131 (5)
C20.0206 (6)0.0274 (7)0.0308 (7)−0.0030 (5)0.0005 (5)0.0005 (5)
C30.0267 (7)0.0209 (6)0.0227 (6)−0.0048 (5)−0.0009 (5)0.0009 (5)
C40.0264 (7)0.0157 (6)0.0183 (6)−0.0033 (5)0.0039 (5)0.0006 (5)
O40.0295 (5)0.0269 (5)0.0237 (5)−0.0026 (4)0.0097 (4)−0.0046 (4)
C110.0174 (6)0.0177 (6)0.0190 (6)0.0008 (4)0.0037 (5)−0.0033 (5)
C120.0215 (6)0.0201 (6)0.0195 (6)−0.0002 (5)0.0049 (5)−0.0018 (5)
N120.0318 (6)0.0232 (6)0.0231 (6)−0.0082 (5)0.0052 (5)0.0005 (4)
O210.0372 (6)0.0326 (6)0.0359 (6)−0.0017 (5)−0.0012 (5)0.0125 (4)
O220.0460 (7)0.0423 (6)0.0291 (5)−0.0147 (5)0.0180 (5)−0.0003 (5)
C130.0194 (6)0.0268 (7)0.0316 (7)−0.0027 (5)0.0064 (5)−0.0040 (5)
C140.0193 (6)0.0309 (7)0.0297 (7)0.0016 (5)−0.0026 (5)−0.0056 (6)
C150.0284 (7)0.0277 (7)0.0203 (6)0.0062 (6)−0.0001 (5)−0.0018 (5)
C160.0240 (6)0.0212 (6)0.0207 (6)0.0012 (5)0.0066 (5)−0.0004 (5)
Geometric parameters (Å, º) top
N1—C11.3955 (16)C11—C121.3942 (17)
N1—C41.4033 (15)C12—C131.3837 (18)
N1—C111.4219 (15)C12—N121.4655 (16)
C1—O11.2059 (16)N12—O221.2259 (15)
C1—C21.5087 (18)N12—O211.2299 (16)
C2—C31.5276 (19)C13—C141.3868 (19)
C2—H2A0.99C13—H130.95
C2—H2B0.99C14—C151.386 (2)
C3—C41.4991 (18)C14—H140.95
C3—H3A0.99C15—C161.3861 (19)
C3—H3B0.99C15—H150.95
C4—O41.2054 (16)C16—H160.95
C11—C161.3878 (17)
C1—N1—C4113.19 (10)C16—C11—C12118.42 (12)
C1—N1—C11124.40 (10)C16—C11—N1120.30 (11)
C4—N1—C11122.24 (10)C12—C11—N1121.19 (11)
O1—C1—N1124.02 (12)C13—C12—C11122.01 (12)
O1—C1—C2128.44 (12)C13—C12—N12117.47 (11)
N1—C1—C2107.51 (11)C11—C12—N12120.47 (11)
C1—C2—C3105.65 (10)O22—N12—O21124.27 (12)
C1—C2—H2A110.6O22—N12—C12118.18 (12)
C3—C2—H2A110.6O21—N12—C12117.52 (11)
C1—C2—H2B110.6C12—C13—C14118.70 (12)
C3—C2—H2B110.6C12—C13—H13120.6
H2A—C2—H2B108.7C14—C13—H13120.6
C4—C3—C2105.36 (10)C15—C14—C13120.02 (12)
C4—C3—H3A110.7C15—C14—H14120.0
C2—C3—H3A110.7C13—C14—H14120.0
C4—C3—H3B110.7C14—C15—C16120.75 (12)
C2—C3—H3B110.7C14—C15—H15119.6
H3A—C3—H3B108.8C16—C15—H15119.6
O4—C4—N1123.37 (12)C15—C16—C11120.03 (12)
O4—C4—C3128.82 (12)C15—C16—H16120.0
N1—C4—C3107.80 (11)C11—C16—H16120.0
C4—N1—C1—O1−176.61 (12)C4—N1—C11—C1252.59 (17)
C11—N1—C1—O1−1.3 (2)C16—C11—C12—C132.14 (19)
C4—N1—C1—C21.84 (14)N1—C11—C12—C13−174.33 (12)
C11—N1—C1—C2177.18 (11)C16—C11—C12—N12−175.27 (11)
O1—C1—C2—C3−178.89 (14)N1—C11—C12—N128.25 (18)
N1—C1—C2—C32.74 (14)C13—C12—N12—O2239.62 (17)
C1—C2—C3—C4−5.92 (13)C11—C12—N12—O22−142.85 (12)
C1—N1—C4—O4173.23 (12)C13—C12—N12—O21−138.47 (13)
C11—N1—C4—O4−2.22 (19)C11—C12—N12—O2139.06 (17)
C1—N1—C4—C3−5.77 (14)C11—C12—C13—C14−3.1 (2)
C11—N1—C4—C3178.77 (11)N12—C12—C13—C14174.41 (11)
C2—C3—C4—O4−171.84 (13)C12—C13—C14—C151.4 (2)
C2—C3—C4—N17.09 (13)C13—C14—C15—C161.1 (2)
C1—N1—C11—C1661.24 (17)C14—C15—C16—C11−2.0 (2)
C4—N1—C11—C16−123.82 (13)C12—C11—C16—C150.44 (18)
C1—N1—C11—C12−122.35 (13)N1—C11—C16—C15176.95 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3B···O21i0.992.423.253 (2)141
C2—H2B···Cgii0.992.753.638 (2)149
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2.
(II) N-(3-Nitrophenyl)succinimide top
Crystal data top
C10H8N2O4F(000) = 228
Mr = 220.18Dx = 1.570 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1152 reflections
a = 6.6318 (2) Åθ = 3.2–27.4°
b = 7.0944 (3) ŵ = 0.12 mm−1
c = 10.4260 (5) ÅT = 120 K
β = 108.234 (2)°Block, colourless
V = 465.90 (3) Å30.40 × 0.35 × 0.30 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer		1152 independent reflections
Radiation source: rotating anode1067 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
ϕ scans, and ω scans with κ offsetsθmax = 27.4°, θmin = 3.2°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)		h = −8→8
Tmin = 0.947, Tmax = 0.964k = −8→9
5403 measured reflectionsl = −12→13
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)] = 0.031H-atom parameters constrained
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.0485P)2 + 0.043P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1152 reflectionsΔρmax = 0.22 e Å−3
146 parametersΔρmin = −0.21 e Å−3
1 restraintExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.112 (14)
Crystal data top
C10H8N2O4V = 465.90 (3) Å3
Mr = 220.18Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.6318 (2) ŵ = 0.12 mm−1
b = 7.0944 (3) ÅT = 120 K
c = 10.4260 (5) Å0.40 × 0.35 × 0.30 mm
β = 108.234 (2)°
Data collection top
Nonius KappaCCD
diffractometer		1152 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)		1067 reflections with I > 2σ(I)
Tmin = 0.947, Tmax = 0.964Rint = 0.042
5403 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0311 restraint
wR(F2) = 0.078H-atom parameters constrained
S = 1.08Δρmax = 0.22 e Å−3
1152 reflectionsΔρmin = −0.21 e Å−3
146 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1−0.0774 (2)0.1798 (2)0.12597 (15)0.0287 (4)
O40.5317 (2)0.5258 (2)0.21968 (14)0.0237 (3)
O310.5687 (2)0.4665 (2)0.79705 (13)0.0297 (4)
O320.7367 (2)0.3479 (2)0.66840 (14)0.0276 (4)
N10.2263 (2)0.3593 (2)0.20348 (15)0.0175 (4)
N130.5760 (2)0.4110 (2)0.68743 (15)0.0205 (4)
C10.0784 (3)0.2473 (3)0.10809 (19)0.0204 (4)
C20.1516 (3)0.2310 (3)−0.01408 (18)0.0232 (4)
C30.3605 (3)0.3371 (3)0.02054 (19)0.0215 (4)
C40.3916 (3)0.4221 (3)0.15678 (19)0.0180 (4)
C110.2143 (3)0.4001 (3)0.33495 (18)0.0171 (4)
C120.3956 (3)0.3791 (3)0.44531 (18)0.0174 (4)
C130.3814 (3)0.4252 (3)0.57126 (18)0.0183 (4)
C140.1965 (3)0.4874 (3)0.59194 (19)0.0216 (4)
C150.0176 (3)0.5039 (3)0.4795 (2)0.0221 (4)
C160.0254 (3)0.4619 (3)0.35155 (19)0.0206 (4)
H2A0.04610.2876−0.09400.028*
H2B0.17200.0971−0.03380.028*
H3A0.35420.4365−0.04720.026*
H3B0.47850.25000.02320.026*
H120.52470.33480.43480.021*
H140.19220.51780.67980.026*
H15−0.11240.54470.49060.027*
H16−0.09800.47530.27540.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0239 (7)0.0299 (8)0.0311 (8)−0.0098 (6)0.0069 (6)−0.0030 (6)
O40.0195 (6)0.0282 (8)0.0245 (7)−0.0030 (6)0.0086 (5)−0.0021 (6)
O310.0362 (8)0.0368 (9)0.0170 (7)−0.0076 (7)0.0098 (6)−0.0076 (7)
O320.0221 (7)0.0371 (9)0.0224 (7)0.0032 (6)0.0052 (6)0.0007 (7)
N10.0151 (7)0.0204 (8)0.0164 (8)−0.0005 (6)0.0040 (6)0.0001 (6)
N130.0245 (8)0.0203 (8)0.0170 (8)−0.0041 (7)0.0070 (6)−0.0012 (6)
C10.0199 (8)0.0186 (9)0.0195 (9)0.0011 (8)0.0017 (7)0.0005 (8)
C20.0278 (9)0.0247 (10)0.0143 (9)0.0008 (8)0.0026 (7)−0.0004 (8)
C30.0259 (9)0.0224 (9)0.0178 (9)0.0035 (8)0.0093 (7)0.0023 (8)
C40.0165 (8)0.0187 (9)0.0193 (9)0.0040 (7)0.0063 (6)0.0035 (7)
C110.0202 (8)0.0160 (9)0.0168 (9)−0.0021 (7)0.0082 (6)−0.0013 (7)
C120.0187 (8)0.0160 (9)0.0190 (9)0.0007 (7)0.0080 (7)−0.0006 (7)
C130.0206 (8)0.0163 (9)0.0178 (8)−0.0024 (7)0.0059 (7)−0.0007 (7)
C140.0280 (9)0.0189 (10)0.0221 (9)−0.0026 (8)0.0139 (7)−0.0027 (8)
C150.0204 (8)0.0224 (9)0.0283 (11)0.0011 (8)0.0144 (7)0.0006 (9)
C160.0192 (8)0.0204 (10)0.0226 (9)0.0001 (7)0.0070 (7)0.0030 (8)
Geometric parameters (Å, º) top
N1—C11.404 (2)C11—C161.388 (2)
C1—O11.205 (2)C12—C131.385 (3)
C1—C21.503 (3)C12—H120.95
C2—C31.518 (3)C13—C141.382 (2)
N1—C41.404 (2)C13—N131.471 (2)
C4—O41.206 (2)C14—C151.388 (3)
C4—C31.497 (3)C14—H140.95
N1—C111.427 (2)C15—C161.384 (3)
C2—H2A0.99C15—H150.95
C2—H2B0.99C16—H160.95
C3—H3A0.99N13—O311.224 (2)
C3—H3B0.99N13—O321.228 (2)
C11—C121.388 (2)
C1—N1—C11123.97 (15)C12—C11—C16120.81 (16)
C4—N1—C11123.54 (15)C12—C11—N1118.69 (15)
O1—C1—N1123.90 (17)C16—C11—N1120.50 (16)
O1—C1—C2128.35 (18)C13—C12—C11117.55 (16)
N1—C1—C2107.75 (16)C13—C12—H12121.2
C1—C2—C3105.85 (15)C11—C12—H12121.2
C1—N1—C4112.46 (15)C14—C13—C12123.37 (16)
N1—C4—C3108.07 (15)C14—C13—N13119.06 (15)
C4—C3—C2105.66 (15)C12—C13—N13117.55 (15)
C1—C2—H2A110.6C13—C14—C15117.47 (16)
C3—C2—H2A110.6C13—C14—H14121.3
C1—C2—H2B110.6C15—C14—H14121.3
C3—C2—H2B110.6C16—C15—C14121.06 (16)
H2A—C2—H2B108.7C16—C15—H15119.5
C4—C3—H3A110.6C14—C15—H15119.5
C2—C3—H3A110.6C15—C16—C11119.72 (16)
C4—C3—H3B110.6C15—C16—H16120.1
C2—C3—H3B110.6C11—C16—H16120.1
H3A—C3—H3B108.7O31—N13—O32123.91 (15)
O4—C4—N1123.89 (18)O31—N13—C13117.80 (15)
O4—C4—C3128.03 (17)O32—N13—C13118.28 (14)
C4—N1—C1—O1−179.21 (19)C4—N1—C11—C16133.62 (19)
C11—N1—C1—O12.7 (3)C16—C11—C12—C13−1.1 (3)
C11—N1—C1—C2−177.47 (17)N1—C11—C12—C13178.07 (16)
O1—C1—C2—C3−177.9 (2)C11—C12—C13—C141.0 (3)
N1—C1—C2—C32.2 (2)C11—C12—C13—N13−177.31 (17)
C4—N1—C1—C20.7 (2)C12—C13—C14—C15−0.1 (3)
C1—C2—C3—C4−4.1 (2)N13—C13—C14—C15178.27 (17)
N1—C4—C3—C24.5 (2)C13—C14—C15—C16−0.9 (3)
C1—N1—C4—C3−3.3 (2)C14—C15—C16—C110.8 (3)
C1—N1—C4—O4177.09 (19)C12—C11—C16—C150.3 (3)
C11—N1—C4—O4−4.8 (3)N1—C11—C16—C15−178.92 (18)
C11—N1—C4—C3174.81 (16)C14—C13—N13—O31−4.4 (3)
C2—C3—C4—O4−175.9 (2)C12—C13—N13—O31174.01 (18)
C1—N1—C11—C12132.34 (19)C14—C13—N13—O32176.95 (18)
C4—N1—C11—C12−45.6 (3)C12—C13—N13—O32−4.6 (2)
C1—N1—C11—C16−48.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O31i0.992.483.193 (2)129
C3—H3A···O1ii0.992.473.158 (3)127
C16—H16···O4iii0.952.373.162 (2)141
Symmetry codes: (i) x, y, z−1; (ii) −x, y+1/2, −z; (iii) x−1, y, z.
(III) N-(4-Nitrophenyl)phthalimide top
Crystal data top
C10H8N2O4F(000) = 456
Mr = 220.18Dx = 1.605 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1054 reflections
a = 10.3731 (19) Åθ = 3.3–27.6°
b = 11.590 (2) ŵ = 0.13 mm−1
c = 7.9761 (18) ÅT = 120 K
β = 108.135 (16)°Lath, colourless
V = 911.3 (3) Å30.25 × 0.11 × 0.03 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer		1054 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode690 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.095
Detector resolution: 9.091 pixels mm-1θmax = 27.6°, θmin = 3.3°
ϕ and ω scansh = −13→13
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −15→15
Tmin = 0.974, Tmax = 0.996l = −10→10
9627 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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.167H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0889P)2 + 0.338P]
where P = (Fo2 + 2Fc2)/3
1054 reflections(Δ/σ)max < 0.001
75 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.30 e Å−3
Crystal data top
C10H8N2O4V = 911.3 (3) Å3
Mr = 220.18Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.3731 (19) ŵ = 0.13 mm−1
b = 11.590 (2) ÅT = 120 K
c = 7.9761 (18) Å0.25 × 0.11 × 0.03 mm
β = 108.135 (16)°
Data collection top
Nonius KappaCCD
diffractometer		1054 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		690 reflections with I > 2σ(I)
Tmin = 0.974, Tmax = 0.996Rint = 0.095
9627 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.167H-atom parameters constrained
S = 1.06Δρmax = 0.25 e Å−3
1054 reflectionsΔρmin = −0.30 e Å−3
75 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.50000.3039 (2)0.75000.0312 (7)
C10.3822 (3)0.2363 (2)0.7179 (3)0.0317 (6)
O10.27027 (16)0.27500 (13)0.6969 (2)0.0361 (5)
C20.4229 (2)0.11216 (19)0.7119 (3)0.0346 (6)
C110.50000.4274 (3)0.75000.0286 (8)
C120.4011 (2)0.4868 (2)0.6205 (3)0.0318 (6)
C130.4002 (2)0.6061 (2)0.6206 (3)0.0320 (6)
C140.50000.6629 (3)0.75000.0303 (8)
N140.50000.7896 (2)0.75000.0332 (7)
O410.44363 (17)0.84004 (14)0.6103 (2)0.0394 (5)
H2A0.39370.08310.58910.042*
H2B0.38200.06320.78370.042*
H120.33430.44550.53200.038*
H130.33270.64790.53390.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0323 (16)0.0273 (14)0.0343 (16)0.0000.0108 (13)0.000
C10.0342 (14)0.0313 (13)0.0297 (13)−0.0023 (11)0.0100 (10)0.0021 (10)
O10.0322 (10)0.0338 (10)0.0442 (11)−0.0003 (7)0.0146 (8)0.0014 (7)
C20.0374 (14)0.0278 (13)0.0406 (14)−0.0030 (10)0.0148 (12)0.0001 (11)
C110.0296 (18)0.0231 (16)0.0372 (18)0.0000.0164 (15)0.000
C120.0307 (13)0.0288 (13)0.0365 (14)−0.0022 (10)0.0116 (11)−0.0030 (10)
C130.0327 (13)0.0316 (13)0.0335 (13)0.0027 (10)0.0128 (11)0.0033 (10)
C140.0339 (19)0.0241 (17)0.0367 (19)0.0000.0168 (15)0.000
N140.0318 (16)0.0330 (16)0.0374 (18)0.0000.0146 (14)0.000
O410.0467 (12)0.0302 (10)0.0416 (10)0.0021 (8)0.0141 (8)0.0055 (8)
Geometric parameters (Å, º) top
N1—C11.406 (3)C11—C121.390 (3)
N1—C111.431 (4)C12—C131.383 (3)
C1—O11.207 (3)C12—H120.95
C1—C21.505 (3)C13—C141.380 (3)
C2—C2i1.524 (5)C13—H130.95
C2—H2A0.99C14—N141.467 (4)
C2—H2B0.99N14—O411.233 (2)
C1—N1—C1i112.3 (3)C12—C11—N1119.67 (15)
C1—N1—C11123.86 (13)C13—C12—C11119.9 (2)
C1i—N1—C11123.86 (14)C13—C12—H12120.1
O1—C1—N1124.2 (2)C11—C12—H12120.1
O1—C1—C2128.2 (2)C14—C13—C12118.3 (2)
N1—C1—C2107.6 (2)C14—C13—H13120.9
C1—C2—C2i104.89 (13)C12—C13—H13120.9
C1—C2—H2A110.8C13—C14—C13i123.0 (3)
C1—C2—H2B110.8C13—C14—N14118.48 (15)
H2A—C2—H2B108.8O41i—N14—O41123.3 (3)
C12i—C11—C12120.7 (3)O41—N14—C14118.34 (14)
C1i—N1—C1—O1175.7 (3)C12i—C11—C12—C13−0.41 (15)
C11—N1—C1—O1−4.3 (3)N1—C11—C12—C13179.59 (15)
C1i—N1—C1—C2−5.42 (12)C11—C12—C13—C140.8 (3)
C11—N1—C1—C2174.58 (12)C12—C13—C14—C13i−0.40 (15)
O1—C1—C2—C2i−167.5 (3)C12—C13—C14—N14179.60 (15)
N1—C1—C2—C2i13.7 (3)C13—C14—N14—O41i156.63 (14)
C1—N1—C11—C12i137.66 (16)C13—C14—N14—O41−23.37 (14)
C1—N1—C11—C12−42.34 (16)
Symmetry code: (i) −x+1, y, −z+3/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC10H8N2O4C10H8N2O4C10H8N2O4
Mr220.18220.18220.18
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21Monoclinic, C2/c
Temperature (K)120120120
a, b, c (Å)8.3703 (2), 8.2500 (1), 14.1375 (3)6.6318 (2), 7.0944 (3), 10.4260 (5)10.3731 (19), 11.590 (2), 7.9761 (18)
β (°) 101.0185 (10) 108.234 (2) 108.135 (16)
V (Å3)958.27 (3)465.90 (3)911.3 (3)
Z424
Radiation typeMo KαMo KαMo Kα
µ (mm−1)0.120.120.13
Crystal size (mm)0.15 × 0.15 × 0.100.40 × 0.35 × 0.300.25 × 0.11 × 0.03
Data collection
DiffractometerNonius KappaCCD
diffractometer		Nonius KappaCCD
diffractometer		Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)		Multi-scan
(SORTAV; Blessing, 1995, 1997)		Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.976, 0.9880.947, 0.9640.974, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections		12771, 2192, 1846 5403, 1152, 1067 9627, 1054, 690
Rint0.0310.0420.095
(sin θ/λ)max (Å−1)0.6500.6480.652
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.114, 1.10 0.031, 0.078, 1.08 0.058, 0.167, 1.06
No. of reflections219211521054
No. of parameters14614675
No. of restraints010
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.35, −0.350.22, −0.210.25, −0.30

Computer programs: COLLECT (Hooft, 1999), KappaCCD Server Software (Nonius, 1997), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO–SMN (Otwinowski & Minor, 1997), DENZO and COLLECT, DENZO–SMN, OSCAIL (McArdle , 2003) and SHELXS97 (Sheldrick, 1997), 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
C3—H3B···O21i0.992.423.253 (2)141
C2—H2B···Cgii0.992.753.638 (2)149
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O31i0.992.483.193 (2)129
C3—H3A···O1ii0.992.473.158 (3)127
C16—H16···O4iii0.952.373.162 (2)141
Symmetry codes: (i) x, y, z−1; (ii) −x, y+1/2, −z; (iii) x−1, y, z.
 

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants which have provided computing facilities for this work. JLW thanks CNPq and FAPERJ for financial support.

References

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Journal logoSTRUCTURAL
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ISSN: 2053-2296
Volume 61| Part 4| April 2005| Pages o216-o220
doi:10.1107/S0108270105004798
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