Scholarly article on topic ' Contrasting three-dimensional framework structures in the isomeric pair 2-iodo- N -(2-nitrophenyl)benzamide and N -(2-iodophenyl)-2-nitrobenzamide '

Contrasting three-dimensional framework structures in the isomeric pair 2-iodo- N -(2-nitrophenyl)benzamide and N -(2-iodophenyl)-2-nitrobenzamide Academic research paper on "Chemical sciences"

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Academic research paper on topic " Contrasting three-dimensional framework structures in the isomeric pair 2-iodo- N -(2-nitrophenyl)benzamide and N -(2-iodophenyl)-2-nitrobenzamide "

Acta Crystallographica Section C

Crystal Structure Communications

ISSN 0108-2701

Contrasting three-dimensional framework structures in the isomeric pair 2-iodo-N-(2-nitrophenyl)benzamide and N-(2-iodophenyl)-2-nitro-benzamide

James L. Wardell,a Janet M. S. Skakle,b John N. Lowb and Christopher Glidewellc*

aInstituto de Química, Departamento de Química Inorgánica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland

Correspondence e-mail: cg@st-andrews.ac.uk

Received 20 September 2005 Accepted 21 September 2005 Online 11 October 2005

In 2-iodo-N-(2-nitrophenyl)benzamide, C13H9IN2O3, the molecules are linked into a three-dimensional framework structure by a combination of a C—H-O hydrogen bond, and iodo-nitro, carbonyl-carbonyl and aromatic n-n stacking interactions. In the isomeric compound N-(2-iodophenyl)-2-nitrobenzamide, the framework structure is built from N— H- • O, C—H- • O and C—H- • -n(arene) hydrogen bonds and an iodo-nitro interaction.

Comment

The isomeric benzamides 2-iodo-N-(2-nitrophenyl)benz-amide, (I), and N-(2-iodophenyl)-2-nitrobenzamide, (II), offer the possibility of a wide variety of potential intermolecular interactions. These include N—H---O and C— H---O hydrogen bonds, each with two possible types of acceptor O atoms (amide and nitro), C—H-- -n(arene) hydrogen bonds (again with two distinct acceptor rings), aromatic n-n stacking interactions, and two- or three-centre iodo-nitro interactions. We have recently reported that the supramolecular aggregation of 2-iodo-N-(4-nitrophenyl)-benzamide, (III), depends on a combination of N—H---O(carbonyl) and C—H- - -O(nitro) hydrogen bonds, together with weak n-n stacking interactions (Garden et al., 2005), and we now report the supramolecular structures for the isomers (I) and (II).

The molecules in (I) and (II) (Figs. 1 and 2, respectively) adopt conformations which have no internal symmetry, as shown by the leading torsion angles (Table 1). Accordingly, the molecules of (I) and (II) have no internal symmetry, and

hence they are chiral. Compound (I) crystallizes in the centrosymmetric space group PI, so that equal numbers of both enantiomers are present in each crystal, but compound (II) crystallizes in the non-centrosymmetric space group P212121; hence, in the absence of any inversion twinning, only one enantiomer is present in a given crystal of compound (II). The bond lengths and angles show no unusual values.

(i) (II)

The supramolecular structures formed by isomers (I) and (II) are both three-dimensional, but they are different not only in their detailed construction but also in the types of direction-specific intermolecular interactions which are active.

In compound (I) (Fig. 1), there is an intramolecular N— H- - -O hydrogen bond (Table 2), but the N—H bond plays no role in the intermolecular aggregation. This is instead determined by a combination of a C—H- - -O hydrogen bond, a two-centre iodo-nitro interaction and two aromatic n-n stacking interactions, which combine to generate a three-dimensional framework, the formation of which is readily analysed in terms of three one-dimensional substructures.

For two of the substructures, the basic building block is a hydrogen-bonded dimer. Aryl atom C25 in the molecule at (x, y, z) acts as donor to amide atom O17 in the molecule at (1 — x, 1 — y, 1 — z), so generating a centrosymmetric ^2(14) dimer centred at (2,1,1) (Fig. 3). These dimers are linked into two distinct chains by aromatic n-n stacking interactions.

Because of the near planarity of the molecules in compound (I), the C11-C16 ring at (x, y, z) is nearly parallel to the C21-C26 rings in the molecules at (—x, —y, 1 — z) and (—x, 1 — y,

Figure 1

The molecule of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

o634 © 2005 International Union of Crystallography DOI: 10.1107/S0108270105030180 Acta Cryst. (2005). C61, o634-o638

1 — z), with dihedral angles between adjacent planes of only 5.2 (2)°. For the molecules at (x, y, z) and (— x, —y, 1 — z), the corresponding ring-centroid separation is 3.827 (2) A, with an interplanar spacing of ca 3.49 A and a ring offset of ca 1.57 A. The molecules at (x, y, z) and (—x, —y, 1 — z) are components of the hydrogen-bonded dimers centred at (1, 1) and (——2), respectively, so that propagation by inversion of these two interactions generates a ^-stacked chain of rings running parallel to the [110] direction (Fig. 4). For the mol-

Figure 2

The molecule of compound (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 3

Part of the crystal structure of compound (I), showing the formation of a cyclic ^2(14) dimer. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 — x, 1 — y, 1 — z).

ecules at (x, y, z) and (— x, 1 — y,l — z), which are components of the hydrogen-bonded dimers centred at (1,1,1) and (—2' 2' 2)' respectively, the ring-centroid separation is 3.808 (2) A, with an interplanar separation of ca 3.52 A and a ring offset of ca 1.45 A. This interaction thus generates a ^-stacked chain of rings running parallel to the [100] direction (Fig. 5).

The final substructure depends solely on a two-centre iodo-nitro interaction, with 112- • -022' = 3.4101 (16) A and C12 — 112- • -022' = 159.71 (6)° [symmetry code: (i) x, y, —1 + z], so forming a C(9) chain (Starbuck etal., 1999) running parallel to the [001] direction (Fig. 6). The combination of [100], [110] and [001] chains then generates a three-dimensional structure,

Figure 4

A stereoview of part of the crystal structure of compound (I), showing the formation of a ^-stacked chain of hydrogen-bonded dimers along [110]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Figure 5

A stereoview of part of the crystal structure of compound (I), showing the formation of a ^-stacked chain of hydrogen-bonded dimers along [100]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Acta Cryst. (2005). C61, o634-o638

Wardell et al. • Two isomers ofC13H9IN203 o635

which is augmented by a carbonyl-carbonyl interaction of type II (Allen et al., 1998). The carbonyl groups in the molecules at (x, y, z) and (—x, 1 — y, 1 — z) are strictly parallel, with 017---C17" = 2.976 (2) A and C17-017---C17" = 92.8 (2)° [symmetry code: (ii) —x, 1 — y, 1 — z].

The molecules of compound (II) (Fig. 2) are linked into a three-dimensional framework structure by a combination of N-H- • O, C-H- • O and C-H- • -Tr(arene) hydrogen bonds (Table 3) and a two-centre iodo-nitro interaction. The

Figure 6

Part of the crystal structure of compound (I), showing the formation of an [001] chain built from iodo-nitro interactions. For the sake of clarity, H atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, y, —1 + z) and (x, y, 1 + z), respectively.

formation of this framework is readily analysed in terms of three one-dimensional substructures. In the first substructure, amide atom N1 in the molecule at (x, y, z) acts as hydrogen-bond donor to carbonyl atom 017 in the molecule at (—2 + y, | — y, 1 — z), so forming the C(4) (Bernstein et al., 1995) motif characteristic of simple amides running parallel to the [100] direction and generated by the 21 screw axis along (x, 4, 2) (Fig. 7).

The second substructure arises from the co-operative action of two fairly weak interactions. Aryl atom C24 in the molecule at (x, y, z) acts as hydrogen-bond donor to amide atom 017 in the molecule at (1 — x, —2 + y, | — z), while atom C24 at (1 — x, —1 + y, | — z) in turn acts as donor to atom 017 at (x,

Figure 8

A stereoview of part of the crystal structure of compound (II), showing the formation of a chain of edge-fused rings along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Figure 7

Part of the crystal structure of compound (II), showing the formation of a hydrogen-bonded C(4) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (—1 + y, 2 — y, 1 — z) and (2 + y, 2 — y, 1 — z), respectively.

Figure 9

Part of the crystal structure of compound (II), showing the formation of a hydrogen-bonded chain along [001]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 — x, 1 — y, 2 + z) and (2 — x, 1 — y, —2 + z), respectively.

1 + y, z), so forming a C(8) chain running parallel to the [010] direction (Fig. 8). At the same time, atoms 122 at (x, y, z) and 022 at (x, 1 + y, z) form a two-centre iodo-nitro interaction, with I- • -0m = 3.3677 (17) A and C-I- • -0m = 159.71 (6)° [symmetry code: (iii) x, 1 + y, z], so forming a C(9) chain (Starbuck et al., 1999). The combination of these two interactions then generates a chain of edge-fused -i(19) rings generated by the 21 screw axis along (1, y, |) (Fig. 8).

The third one-dimensional substructure in (II) is built from a single C-H- • -jr(arene) hydrogen bond. Aryl atom C23 in the molecule at (x, y, z) acts as donor to the C11-C16 ring in the molecule at (1 — x, 1 — y, | + z), so forming a chain running parallel to the [001] direction and generated by the 21 screw axis along (4, z) (Fig. 9). The combination of the chains along [100], [010] and [001] suffices to generate a continuous three-dimensional framework.

In conclusion, for the two isomeric title compounds, (I) and (II), the difference between their molecular structures can be regarded as a simple reversal of the amidic function -NH-C0- between (I) and (II), yet they manifest very different ranges of direction-specific intermolecular interactions with consequently very different supramolecular structures.

Experimental

The title amides were obtained by reaction of equimolar mixtures (2 mmol of each) of 2-XC6H4C0Cl and 2-YC6H4NH2 [for (I), X = I and Y = N02; for (II), X = N02 and Y = I] in chloroform (50 ml). After heating each mixture under reflux for 1 h, the solvent was removed under reduced pressure and the resulting solid residues were recrystallized from ethanol, yielding crystals suitable for single-crystal X-ray diffraction.

Compound (I)

Crystal data

C13H9IN203 Mr = 368.12 Triclinic, P1 a = 7.2773 (2) A b = 7.62070 (10) A c = 11.6821 (3) A a = 100.248 (2)° P = 107.7770 (10)° y = 92.529 (2)° V = 603.73 (2) A3

Data collection

Nonius KappaCCD area-detector

diffractometer p and ú scans

Absorption correction: multi-scan (SADABS; Sheldrick, 2003) Tmin = 0.465, Tmax = 0.901 12249 measured reflections

Refinement

Refinement on F2 R[F2 > 2ff(F2)] = 0.018 wR(F2) = 0.045 S = 1.07 2759 reflections 172 parameters

H-atom parameters constrained

Table 1

Selected torsion angles (°) for compounds (I) and (II).

(I) (II)

C11 — C17—N1 — C21 -168.48 (17) -173.38 (16)

C12—C11 — C17—N1 -149.64 (18) 76.1 (2)

C22—C21—N1 — C17 147.54 (19) -143.98 (19)

C11 — C12—N12—021 12.0 (3)

C21 — C22—N22—021 16.7 (3)

Table 2

Hydrogen-bond geometry (A, °) for (I).

D—H- ■ -A D—H H-A D-A D — H^ ■ A

N1 — H1- ■ -021 0.88 2.11 2.649 (2) 119

C25 — H25- ■ ■017i 0.95 2.38 3.312 (3) 168

C26—H26- ■ -017 0.95 2.34 2.883 (3) 116

Symmetry code: (i) — x + 1, — y + 1, —z + 1.

Compound (II)

Crystal data

c13h9in2o3

Mr = 368.12 Orthorhombic, P212121 a = 8.8908 (2) A b = 9.7468 (2) A c = 15.0112 (2) A V = 1300.82 (4) A3 Z = 4

Dx = 1.880 Mg m-3 Data collection

Nonius KappaCCD area-detector

diffractometer p and a scans

Absorption correction: multi-scan (SADABS; Sheldrick, 2003) Tmin = 0.439, Tmat = 0.791 18237 measured reflections 2970 independent reflections

Refinement

Refinement on F2 R[F2 > 2a(F2)] = 0.017 wR(F2) = 0.036 S = 1.08 2970 reflections 173 parameters

H-atom parameters constrained w = 1/[ct2(Fo2) + (0.0148P)2 + 0.3804P] where P = (Fo2 + 2Fc2)/3

Table 3

Hydrogen-bond geometry (A, °) for (II).

Cgl is the centroid of the C11-C16 ring.

D-H-A D—H H^ ■ A D-A D — H^ ■■A

N1-H1- ■ ■017i 0.88 1.94 2.792 (2) 161

C24-H24- ■ ■017ii 0.95 2.54 3.321 (3) 140

C23-H23- ■ ■Cg1iii 0.95 2.94 3.846 (2) 160

Symmetry codes: (i) x - z +1. -1 -y +1, -z- h 1; (ii) -x + 1, y - -h -z + 3; (iii) - -x + -y - + 1,

Dx = 2.025 Mg m~3

Mo Ka radiation

Cell parameters from 2759

reflections G = 3.6-27.5° ¡1 = 2.66 mm-1 T = 120 (2) K Plate, yellow 0.34 x 0.20 x 0.04 mm

2759 independent reflections 2646 reflections with I > 2o(I) Rint = 0.023

^max _ 27-5

h = —9 ^ 9 k = —9 ^ 9 I = —15 ^ 15

w = 1/[ff2(fo2) + (0.0212P)2 + 0.5992P] where P = (Fo2 + 2fc2)/3 (A/<r)max = 0.001 Apmax= 1.18 e^A Apmin = -0.65 e A~3

Mo Ka radiation

Cell parameters from 2970

reflections G = 4.1-27.5° 1 = 2.47 mm-1 T = 120 (2) K Rod, colourless 0.40 x 0.10 x 0.10 mm

2906 reflections with I > 2<r(I)

Rnt = 0.028

^max = 27-5 h = —10 ^ 11 k = —12 ^ 12 I ^19 18

(A/ff)max = 0.001 Apmax = 0.47 e À 3 Apmin = -0.49 e À-3 Extinction correction: SHELXL97

(Sheldrick, 1997) Extinction coefficient: 0.0129 (4) Àbsolute structure: Flack (1983),

with 1249 Friedel pairs Flack parameter: -0.001 (13)

Acta Cryst. (2005). C61, o634-o638

Wardell et al. • Two isomers of C13H9IN203 o637

Crystals of compound (I) are triclinic. The space group PI was selected and confirmed by the subsequent structure analysis. For compound (II), the space group P212:L2:L was uniquely determined from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 A and N — H = 0.88 A, and with t/iso(H) = 1.2Ueq(C,N). The absolute configuration of the molecules in the crystal of (II) selected for data collection was established by use of the Flack (1983) parameter, although this configuration has no chemical significance.

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

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

Supplementary data for this paper are available from the IUCr electronic archives (Reference: SK1872). Services for accessing these data are described at the back of the journal.

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/ni. £ngZ. 34, 1555-1573. Ferguson, G. (1999). PÄPXAPPA. University of Guelph, Canada. Flack, H. D. (1983). Acia Crysi. A39, 876-881.

Garden, S. J., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2005).

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