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Volume 68 
Part 9 
Pages o327-o331  
September 2012  

Received 14 June 2012
Accepted 2 July 2012
Online 1 August 2012

Hydrogen bonding in cyclic imides and amide carboxylic acid derivatives from the facile reaction of cis-cyclohexane-1,2-carboxylic anhydride with o- and p-anisidine and m- and p-aminobenzoic acids

aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
Correspondence e-mail: g.smith@qut.edu.au

The structures of the open-chain amide carboxylic acid rac-cis-2-[(2-methoxyphenyl)carbamoyl]cyclohexane-1-carboxylic acid, C15H19NO4, (I), and the cyclic imides rac-cis-2-(4-methoxyphenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, C15H17NO3, (II), chiral cis-3-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)benzoic acid, C15H15NO4, (III), and rac-cis-4-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)benzoic acid monohydrate, C15H15NO4·H2O, (IV), are reported. In the amide acid (I), the phenylcarbamoyl group is essentially planar [maximum deviation from the least-squares plane = 0.060 (1) Å for the amide O atom] and the molecules form discrete centrosymmetric dimers through intermolecular cyclic carboxy-carboxy O-H...O hydrogen-bonding interactions [graph-set notation R22(8)]. The cyclic imides (II)-(IV) are conformationally similar, with comparable benzene ring rotations about the imide N-Car bond [dihedral angles between the benzene and isoindole rings = 51.55 (7)° in (II), 59.22 (12)° in (III) and 51.99 (14)° in (IV)]. Unlike (II), in which only weak intermolecular C-H...Oimide hydrogen bonding is present, the crystal packing of imides (III) and (IV) shows strong intermolecular carboxylic acid O-H...O hydrogen-bonding associations. With (III), these involve imide O-atom acceptors, giving one-dimensional zigzag chains [graph-set C(9)], while with the monohydrate (IV), the hydrogen bond involves the partially disordered water molecule which also bridges molecules through both imide and carboxy O-atom acceptors in a cyclic R44(12) association, giving a two-dimensional sheet structure. The structures reported here expand the structural database for compounds of this series formed from the facile reaction of cis-cyclohexane-1,2-dicarboxylic anhydride with substituted anilines, in which there is a much larger incidence of cyclic imides compared to amide carboxylic acids.

Comment

The 1:1 stoichiometric reaction of cis-cyclohexane-1,2-dicarboxylic anhydride (cis-CHDC anhydride) with substituted anilines has been found to give both open-chain amide carboxylic acids or more commonly cyclic imides under mild reaction conditions (Smith & Wermuth, 2012a[Smith, G. & Wermuth, U. D. (2012a). Acta Cryst. C68, o253-o256.]). These products are analogous to the phthalanilic acids and phthalimides formed in the reactions of phthalic anhydride with anilines (Perry & Parveen, 2001[Perry, C. J. & Parveen, Z. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 512-521.]). We previously reported the structure of the amide acid from the reaction of cis-CHDC anhydride with 3-fluoroaniline and the isomeric cyclic imides from the parallel reactions with 2- and 4-fluoroaniline (Smith & Wermuth, 2012a[Smith, G. & Wermuth, U. D. (2012a). Acta Cryst. C68, o253-o256.]), which are among only the very few crystallographically characterized examples of these compounds.

[Scheme 1]

The parallel reaction of 2-methoxyaniline (o-anisidine), 4-methoxyaniline (p-anisidine), 3-carboxyaniline (m-aminobenzoic acid) and 4-carboxyaniline (p-aminobenzoic acid) with cis-CHDC anhydride under common mild reaction conditions in 50% ethanol-water solution yielded, respectively, the open-chain amide carboxylic acid racemic cis-2-[(2-methoxyphenyl)carbamoyl]cyclohexane-1-carboxylic acid, (I)[link], and the cyclic imides racemic 2-(4-methoxyphenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, (II)[link], chiral 3-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)benzoic acid, (III)[link], and racemic 4-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)benzoic acid monohydrate, (IV)[link] (Figs. 1[link]-4[link][link][link]), and the structures are reported here.

In the racemic amide acid (I)[link] (Fig. 1[link]), the phenylcarbamoyl group is essentially planar [C21-C11-N11-C12 torsion angle = 175.18 (12)°], with a maximum deviation from the least-squares plane of 0.060 (1) Å for the amide O atom. The conformation is stabilized by intramolecular N11-H...O211(methoxy) and aromatic C61-H...O12(carbonyl) interactions [H...O = 2.6003 (14) and 2.8812 (17) Å, respectively]. The carboxy group on the cyclohexane ring is almost parallel to the C1-C3 bond [C1-C2-C22-O22 torsion angle = 173.17 (10)°] and the methoxy group is close to being coplanar with the benzene ring [C11-C21-O211-C211 torsion angle = 173.23 (11)°]. The molecules form discrete centrosymmetric dimers through classical intermolecular cyclic carboxy-carboxy O-H...O hydrogen-bonding interactions (Table 1[link]) [graph-set notation R22(8); Etter et al., 1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]] (Fig. 5[link]). The amide group is not involved in intermolecular interactions, which is unlike the 4-chloro-substituted analogue in which the amide group links hydrogen-bonded carboxylic acid chains into a two-dimensional sheet structure (Smith & Wermuth, 2012b[Smith, G. & Wermuth, U. D. (2012b). J. Chem. Crystallogr. In the press.]).

The cyclic imides (II)[link] and (IV)[link] (Figs. 2[link] and 4[link]) are racemic, while compound (III)[link] is chiral. However, the absolute configurations for the two chiral centres in (III)[link] were not determined, being arbitrarily assigned (C8S and C9R). Conformationally, compounds (II)-(IV) are similar, with comparable ring rotations about the imide N-Car bond [minimum torsion angles C1/C3-N2-C11-C21 = -56.72 (18)° for (II)[link], 61.8 (3)° for (III)[link] and -53.8 (3)° for (IV)]. These correspond to dihedral angles of 51.55 (7), 59.22 (12) and 51.99 (14)°, respectively, between the benzene ring and the plane of the isoindole ring, in which distortion results in either atom C8 or C9 showing a maximum deviation of 0.157 (1) Å in (II)[link], 0.139 (2) Å in (III)[link] and 0.131 (3) Å in (IV)[link]. These values compare closely to those of 0.152 (1) and 0.149 (1) Å for the 2- and 4-fluoro analogues, respectively (Smith & Wermuth, 2012a[Smith, G. & Wermuth, U. D. (2012a). Acta Cryst. C68, o253-o256.]), and 0.153 (3) and 0.138 (4) Å for the 4-bromo- and 3-carboxy-4-hydroxy-substituted analogues, respectively (Smith & Wermuth, 2012b[Smith, G. & Wermuth, U. D. (2012b). J. Chem. Crystallogr. In the press.]). In (III)[link] and (IV)[link], the carboxy substituent groups are close to being coplanar with the attached benzene rings [C21-C31-C311-O32 = -172.2 (2)° in (III)[link] and C31-C41-C411-O42 = -177.3 (3)° in (IV)].

Unlike the structure of (II)[link], in which there are only weak aromatic C-H...Oimide hydrogen-bonding interactions (Table 2[link]), the crystal packing of both imides (III)[link] and (IV)[link] shows strong intermolecular O-H...O hydrogen-bonding interactions involving carboxy groups. In (III)[link], these are with imide O-atom acceptors (Table 3[link]), giving one-dimensional zigzag chains [C(9)] which extend along (010) (Fig. 6[link]). In the monohydrate (IV)[link], the para-carboxy group forms a hydrogen bond with the partially disordered water molecule [O1W, occupancy factor = 0.81 (1); O2W, occupancy factor = 0.19 (1)], both components of which also act as donors to both imide and carboxy O-atom acceptors (Table 4[link]). These interactions give an R44(12) ring motif and extend the structure into a two-dimensional sheet (Fig. 7[link]).

The structures reported here expand the structural database for compounds of this series, formed in the facile reaction of cis-CHDC anhydride with substituted anilines, among which there is a much larger incidence of cyclic imides compared to amide carboxylic acids [currently 8:3, among known examples, which, apart from our previously reported structures, include the imide from the reaction with 5-benzyloxy-2,4-dichloroaniline (Wang et al., 2005[Wang, N.-X., Luo, Y.-P., Chen, Q. & Yang, G.-F. (2005). Acta Cryst. E61, o2081-o2082.]) and those from the reactions with 4-bromoaniline and 5-aminosalicylic acid (Smith & Wermuth, 2012b[Smith, G. & Wermuth, U. D. (2012b). J. Chem. Crystallogr. In the press.])]. However, there are no apparent structural features which might allow a definitive prediction of the preferred reaction product.

[Figure 1]
Figure 1
The molecular conformation and atom-labelling scheme for (I)[link]. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2]
Figure 2
The molecular conformation and atom-labelling scheme for (II)[link]. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 3]
Figure 3
The molecular conformation and atom-labelling scheme for (III)[link]. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 4]
Figure 4
The molecular conformation and atom-labelling scheme for (IV)[link]. Displacement ellipsoids are drawn at the 40% probability level. The water molecule of solvation is disordered over two sites [O1W, occupancy factor = 0.81 (1); O2W, occupancy factor = 0.19 (1)]. Inter-species hydrogen bonds are shown as dashed lines.
[Figure 5]
Figure 5
The centrosymmetric hydrogen-bonded dimers in the structure of (I)[link], showing hydrogen-bonding interactions as dashed lines. Non-associative H atoms have been omitted. For symmetry code (i), see Table 1[link].
[Figure 6]
Figure 6
The one-dimensional hydrogen-bonded chain structures in (III)[link], viewed down the a-cell direction of the unit cell, showing hydrogen-bonding interactions as dashed lines. Non-associative H atoms have been omitted. For symmetry code (i), see Table 3[link].
[Figure 7]
Figure 7
The two-dimensional hydrogen-bonded structure in (IV)[link], viewed approximately down the a-cell direction of the unit cell, showing hydrogen-bonding interactions as dashed lines. Non-associative H atoms have been omitted as has the minor-component O2W water molecule. For symmetry codes, see Table 4[link].

Experimental

The title compounds were synthesized by heating together under reflux for 15 min 1 mmol quantities of cis-cyclohexane-1,2-dicarboxylic anhydride and o-anisidine [for (I)], p-anisidine [for (II)], m-aminobenzoic acid [for (III)] and p-aminobenzoic acid [for (IV)] in ethanol-water (50 ml, 1:1 v/v). After volume reduction to 30 ml, the hot-filtered solutions were allowed to evaporate to incipient dryness at room temperature over a period of several weeks, giving either colourless plates [of (I)-(III)] or fine needles [of (IV)] from which specimens were cleaved for structural analyses.

Compound (I)[link]

Crystal data
  • C15H19NO4

  • Mr = 277.31

  • Triclinic, [P \overline 1]

  • a = 7.3557 (4) Å

  • b = 8.3630 (4) Å

  • c = 11.7128 (6) Å

  • [alpha] = 100.453 (4)°

  • [beta] = 97.232 (4)°

  • [gamma] = 104.042 (4)°

  • V = 676.40 (6) Å3

  • Z = 2

  • Mo K[alpha] radiation

  • [mu] = 0.10 mm-1

  • T = 200 K

  • 0.45 × 0.30 × 0.18 mm

Data collection
  • Oxford Diffraction Gemini-S CCD-detector diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.975, Tmax = 0.980

  • 8079 measured reflections

  • 2640 independent reflections

  • 2082 reflections with I > 2[sigma](I)

  • Rint = 0.024

Refinement
  • R[F2 > 2[sigma](F2)] = 0.035

  • wR(F2) = 0.087

  • S = 1.03

  • 2640 reflections

  • 189 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • [Delta][rho]max = 0.18 e Å-3

  • [Delta][rho]min = -0.20 e Å-3

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

D-H...A D-H H...A D...A D-H...A
O22-H22...O21i 0.94 (2) 1.76 (2) 2.6866 (14) 173 (2)
Symmetry code: (i) -x, -y+1, -z+1.

Compound (II)[link]

Crystal data
  • C15H17NO3

  • Mr = 259.30

  • Monoclinic, P 21 /n

  • a = 11.7119 (5) Å

  • b = 6.6705 (3) Å

  • c = 17.2898 (8) Å

  • [beta] = 109.482 (5)°

  • V = 1273.42 (11) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 0.09 mm-1

  • T = 200 K

  • 0.40 × 0.25 × 0.12 mm

Data collection
  • Oxford Diffraction Gemini-S CCD-detector diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.929, Tmax = 0.981

  • 8552 measured reflections

  • 2498 independent reflections

  • 1959 reflections with I > 2[sigma](I)

  • Rint = 0.024

Refinement
  • R[F2 > 2[sigma](F2)] = 0.035

  • wR(F2) = 0.088

  • S = 1.09

  • 2498 reflections

  • 172 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 0.18 e Å-3

  • [Delta][rho]min = -0.17 e Å-3

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

D-H...A D-H H...A D...A D-H...A
C21-H21...O3i 0.93 2.56 3.2205 (15) 128
C51-H51...O1ii 0.93 2.46 3.2914 (17) 149
Symmetry codes: (i) x, y+1, z; (ii) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Compound (III)[link]

Crystal data
  • C15H15NO4

  • Mr = 273.28

  • Orthorhombic, P 21 21 21

  • a = 6.4958 (2) Å

  • b = 12.5236 (4) Å

  • c = 16.1281 (6) Å

  • V = 1312.03 (8) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 0.10 mm-1

  • T = 200 K

  • 0.45 × 0.12 × 0.08 mm

Data collection
  • Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.980, Tmax = 0.990

  • 4693 measured reflections

  • 1728 independent reflections

  • 1395 reflections with I > 2[sigma](I)

  • Rint = 0.024

Refinement
  • R[F2 > 2[sigma](F2)] = 0.038

  • wR(F2) = 0.086

  • S = 1.10

  • 1728 reflections

  • 185 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • [Delta][rho]max = 0.18 e Å-3

  • [Delta][rho]min = -0.18 e Å-3

Table 3
Hydrogen-bond geometry (Å, °) for (III)[link]

D-H...A D-H H...A D...A D-H...A
O31-H31...O1i 0.89 (3) 1.84 (3) 2.682 (2) 156 (3)
Symmetry code: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}].

Compound (IV)[link]

Crystal data
  • C15H15NO4·H2O

  • Mr = 291.30

  • Monoclinic, P 21 /n

  • a = 13.077 (2) Å

  • b = 6.6713 (7) Å

  • c = 16.432 (2) Å

  • [beta] = 97.982 (13)°

  • V = 1419.6 (3) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 0.10 mm-1

  • T = 200 K

  • 0.30 × 0.10 × 0.08 mm

Data collection
  • Oxford Diffraction Gemini-S CCD-detector diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]) Tmin = 0.813, Tmax = 0.980

  • 9649 measured reflections

  • 2790 independent reflections

  • 1374 reflections with I > 2[sigma](I)

  • Rint = 0.055

Refinement
  • R[F2 > 2[sigma](F2)] = 0.052

  • wR(F2) = 0.132

  • S = 0.85

  • 2790 reflections

  • 194 parameters

  • H-atom parameters constrained

  • [Delta][rho]max = 0.34 e Å-3

  • [Delta][rho]min = -0.20 e Å-3

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

D-H...A D-H H...A D...A D-H...A
O41-H41...O1Wi 0.90 1.71 2.609 (3) 179
O1W-H11W...O1 0.83 2.08 2.894 (3) 167
O1W-H12W...O42ii 0.82 1.94 2.754 (3) 172
O2W-H21W...O1 0.90 2.10 2.991 (12) 179
O2W-H22W...O42iii 0.90 2.33 3.233 (12) 178
Symmetry codes: (i) [x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]; (ii) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) [x+{\script{1\over 2}}], [-y+{\script{1\over 2}}, z-{\script{1\over 2}}].

Amide and/or carboxylic acid H atoms in (I)[link], (III)[link] and (IV)[link] were located by difference methods and in (I)[link] and (III)[link] both their positional and isotropic displacement parameters were refined. For (IV)[link], these H atoms were allowed to ride in the refinement, with Uiso(H) = 1.5Ueq(O). Other H atoms in all structures were allowed to ride in the refinement, with Uiso(H) = 1.2Ueq(O). Other H atoms in all structures were included in the respective refinements at calculated positions (C-H = 0.93-0.98 Å), with Uiso(H) = 1.2Ueq(C), using a riding-model approximation. The water molecule of solvation in (IV)[link] was found to be disordered over two adjacent sites [O...O = 1.458 (12) Å], with occupancy factors determined as 0.81 (1) (O1W) and 0.19 (1) (O2W). The occupancies were subsequently fixed and the minor component was refined isotropically. In chiral (III)[link], in the absence of a suitable heavy atom, Friedel pairs (1062) were merged, the relative configuration of the chiral centres (C8S and C9R) being arbitrarily assigned.

For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2010[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO. Program(s) used to solve structure: SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]) for (I), (III) and (IV); SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) for (II). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) within WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: PLATON.


Supplementary data for this paper are available from the IUCr electronic archives (Reference: BM3120 ). Services for accessing these data are described at the back of the journal.


Acknowledgements

The authors acknowledge financial support from the Australian Research Council and the Science and Engineering Faculty, Queensland University of Technology.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.  [CrossRef] [ISI] [details]
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.  [CrossRef] [ISI] [details]
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.  [CrossRef] [ChemPort] [details]
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.
Perry, C. J. & Parveen, Z. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 512-521.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Smith, G. & Wermuth, U. D. (2012a). Acta Cryst. C68, o253-o256.  [CSD] [CrossRef] [details]
Smith, G. & Wermuth, U. D. (2012b). J. Chem. Crystallogr. In the press.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.  [ISI] [CrossRef] [details]
Wang, N.-X., Luo, Y.-P., Chen, Q. & Yang, G.-F. (2005). Acta Cryst. E61, o2081-o2082.  [CrossRef] [details]


Acta Cryst (2012). C68, o327-o331   [ doi:10.1107/S0108270112030168 ]