Supramolecular structures of three isomeric 2-chloro-N-(nitro­phen­yl)­nicotinamides

Souza, M.V.N. de; Vasconcelos, T.R.A.; Wardell, S.M.S.V.; Wardell, J.L.; Low, J.N.; Glidewell, C.

doi:10.1107/S0108270105003586

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 4| April 2005| Pages o204-o208

doi:10.1107/S0108270105003586

Supramolecular structures of three isomeric 2-chloro-N-(nitrophenyl)nicotinamides

Marcus V. N. de Souza,^a Thatyana R. A. Vasconcelos,^a Solange M. S. V. Wardell,^a James L. Wardell,^b John N. Low ^c and Christopher Glidewell ^d ^*

^aComplexo Tecnológico de Medicamentos Farmanguinhos, Av. Comandante Guaranys 447, Jacarepaguá, Rio de Janeiro, RJ, Brazil, ^bInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, ^cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 25 January 2005; accepted 1 February 2005; online 11 March 2005)

Molecules of 2-chloro-N-(2-nitrophenyl)nicotinamide, C₁₂H₈ClN₃O₃, are linked by two C—H⋯O hydrogen bonds into a chain of edge-fused $[R_{2}^{2}]$ (14) and $[R_{4}^{4}]$ (24) rings. In 2-chloro-N-(3-nitrophenyl)nicotinamide monohydrate, C₁₂H₈ClN₃O₃·H₂O, the molecules are linked by a combination of N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds into a chain of edge-fused rings containing two distinct types of $[R_{4}^{4}]$ (16) ring. In 2-chloro-N-(4-nitrophenyl)nicotinamide, C₁₂H₈ClN₃O₃, which crystallizes with Z′ = 2 in space group P2₁/n, the molecules are linked by two N—H⋯N hydrogen bonds into simple $[C_{2}^{2}]$ (12) chains.

Comment

We report here the molecular and supramolecular structures of three isomeric 2-chloro-N-(nitrophenyl)nicotinamides (Figs. 1–3 ). Of these isomers, the 3-nitrophenyl isomer, (II), crystallizes from acetone as a monohydrate, whereas the 2-nitrophenyl isomer, (I), crystallizes from the same solvent in the unsolvated form. The 4-nitrophenyl isomer, (III), crystallizes from ethanol with Z′ = 2 (Fig. 3).

In compounds (I) and (II), and in each of the independent molecules of (III), the central amide spacer unit is essentially planar, as demonstrated by the C—C—N—C torsion angles (Tables 1, 3 and 5). However, the torsion angles describing the conformations of the two rings relative to the spacer unit show some variations, particularly for the heteroaryl rings. The nitroaryl rings do not deviate significantly from the plane of the amide spacer unit, and in each molecule there is a short intramolecular C—H⋯O contact involving atom C26 in the aryl ring [atom C46 in molecule 2 of compound (III)] and the amide O atom (Tables 2, 4 and 6); this interaction may have some influence on the conformation. The planes of the nitro groups are all close to the planes of the adjacent aryl rings. The two independent molecules in (III) adopt very similar conformations so that for the selected asymmetric unit the two molecules are nearly enantiomeric (Table 5 and Fig. 3).

Within the spacer units, the backbone C—C—N angles are consistently significantly less than 120°, while the C—N—C angles are significantly greater than 120°. There is no evidence from the bond length in the nitroaniline fragments in compounds (I) and (III) of any bond fixation, such as is typically found in simple 2-nitro- and 4-nitroanilines. Thus, polarization of types (Ia) and (IIIa) cannot effectively compete with the normal polarization of the amide units in these compounds.

The molecules of (I) are linked into a chain of edge-fused rings by two C—H⋯O hydrogen bonds, involving both the carbonyl O and one of the nitro O atoms (Table 2). Atom C14 of the heteroaryl ring in the molecule at (x, y, z) acts as a hydrogen-bond donor to nitro atom O2 in the molecule at (−1 + x, y, z), so generating by translation a C(9) chain (Bernstein et al., 1995 ) running parallel to the [100] direction. At the same time, aryl atom C25 in the molecule at (x, y, z) acts as a donor to carbonyl atom O1 in the molecule at (−x, 1 − y, 1 − z), so forming a centrosymmetric $[R_{2}^{2}]$ (14) ring centred at (0, $[{1\over 2}]$ , $[{1\over 2}]$ ). The combination of these two motifs then generates a chain of centrosymmetric edge-fused rings along [100], with $[R_{2}^{2}]$ (14) rings centred at (n, $[{1\over 2}]$ , $[{1\over 2}]$ ) (n = zero or integer) and $[R_{4}^{4}]$ (24) rings centred at (n + $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ) (n = zero or integer) (Fig. 4). Two chains of this type pass through each unit cell, along the lines (x, 0, 0) and (x, $[{1\over 2}]$ , $[{1\over 2}]$ ), but there are no direction-specific interactions between adjacent chains.

The independent components in (II) are linked by a combination of O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds (Table 4) into a chain of edge-fused rings. Water atom O41 acts as a hydrogen-bond donor, via H41, to carbonyl atom O1 within the asymmetric unit. In addition, amine atom N21 at (x, y, z) acts as a hydrogen-bond donor to water atom O4 at (x, −1 + y, z), so generating by translation a $[C_{2}^{2}]$ (6) chain running parallel to the [010] direction, in which O—H⋯O hydrogen bonds alternate with N—H⋯O hydrogen bonds (Fig. 5). Two chains of this type, antiparallel to one another, pass through each unit cell, and these are linked by the O—H⋯N hydrogen bonds. Water atom O41 at (x, y, z) also acts as a hydrogen-bond donor, this time via H42, to ring atom N11 at (1 − x, 1 − y, −z), so generating a centrosymmetric $[R_{4}^{4}]$ (16) ring, centred at ( $[{1\over 2}]$ , $[{1\over 2}]$ , 0) (Fig. 5). The combination of these two motifs then generates a chain of centrosymmetric edge-fused rings along the line ( $[{1\over 2}]$ , y, 0), in which $[R_{4}^{4}]$ (16) rings containing O—H⋯O and O—H⋯N hydrogen bonds and centred at ( $[{1\over 2}]$ , n + $[{1\over 2}]$ , 0) (n = zero or integer) alternate with $[R_{4}^{4}]$ (16) rings containing N—H⋯O and O—H⋯N hydrogen bonds and centred at ( $[{1\over 2}]$ , n, 0) (n = zero or integer) (Fig. 5).

The hydrogen-bonded chains in compound (II) are linked by three distinct aromatic π–π stacking interactions, all of them centrosymmetric but some of them fairly weak, into a continuous three-dimensional array. The heteroaryl ring in the molecule at (x, y, z) is parallel to the corresponding ring in the molecule at (−x, 1 − y, −z), which itself forms part of the hydrogen-bonded chain along (− $[{1\over 2}]$ , y, 0); the interplanar spacing is 3.546 (2) Å, with a ring-centroid separation of 3.795 (2) Å, corresponding to a ring offset of 1.352 (2) Å. This interaction thus links the [010] chains into (001) sheets. In a similar fashion, the aryl rings of the molecules at (x, y, z) and (1 − x, −y, 1 − z), where the latter forms part of the hydrogen-bonded chain along ( $[{1\over 2}]$ , y, 1), are also parallel, with an interplanar spacing of 3.707 (2) Å, a ring-centroid separation of 3.917 (2) Å and a ring offset of 1.264 (2) Å. Finally, the aryl rings of the molecules at (x, y, z) and (−x, −y, 1 − z), which forms part of the hydrogen-bonded chain along (− $[{1\over 2}]$ , y, 1), are also parallel, with an interplanar spacing of 3.384 (2) Å, a ring-centroid separation of 3.793 (2) Å and a ring offset of 1.715 (2) Å. These latter interactions connect the (001) sheets, so linking all of the hydrogen-bonded chains into a continuous framework.

The two independent molecules in (III) are linked into simple chains by two N—H⋯N hydrogen bonds (Table 6). Amide atom N21 acts as a hydrogen-bond donor to ring atom N31 within the asymmetric unit; similarly, amide atom N41 at (x, y, z) acts as a donor to ring atom N11 at (−1 + x, y, z), so generating by translation a $[C_{2}^{2}]$ (12) chain running parallel to the [100] direction (Fig. 6). There are number of short C—H⋯O contacts within this chain (Table 6), although it is doubtful if any of them could be regarded as a hydrogen bond; it is likely that these contacts are simply adventitious consequences of the N—H⋯N hydrogen bonds. Two $[C_{2}^{2}]$ (12) chains, antiparallel to one another, pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

It is thus striking that modest changes in the geometric position of a single substituent are associated with significant changes in crystallization characteristics, in the direction-specific intermolecular interactions manifested and hence in the overall supramolecular structures; none of these changes is readily predictable.

Figure 1
The molecule of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
The molecular components of (II)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
The two independent molecules of (III)

, showing the atom-labelling schemes for (a) molecule 1 and (b) molecule 2. Displacement ellipsoids are drawn at the 30% probability level.

Figure 4
A stereoview of part of the crystal structure of (I)

, showing the formation of a chain of edge-fused rings along [100]. For clarity, H atoms not involved in the motifs shown have been omitted.

Figure 5
A stereoview of part of the crystal structure of (II)

, showing the formation of a chain of edge-fused rings along [010]. For clarity, H atoms bonded to C atoms have been omitted.

Figure 6
A stereoview of part of the crystal structure of (III)

, showing the formation of a $[C_{2}^{2}]$ (12) chain along [100]. For clarity, H atoms bonded to C atoms have been omitted.

Experimental

For the synthesis of each of compounds (I)–(III), a solution of 2-chloronicotinoyl chloride (5.68 mmol), the appropriate nitroaniline (5.78 mmol) and triethylamine (12 mmol) in anhydrous tetrahydrofuran (30 ml) was stirred at ambient temperature for 8 h; water (20 ml) and ethyl acetate (20 ml) were added, and the organic layer was separated. This was washed with a saturated aqueous Na(HCO₃) solution (2 × 20 ml), dried over sodium sulfate and the solvent removed. The resulting solids were purified by chromatography on alumina, with ethyl acetate and hexane (7:3 v/v) as eluant. Compounds (I) and (II) were recrystallized from acetone [m.p. 430–432 and 428–429 K (darkens at 407 K)], while compound (III) was recrystallized from ethanol (m.p. 479–481 K).

Compound (I)

Crystal data

C₁₂H₈ClN₃O₃
M_r = 277.66
Monoclinic, P 2₁ /c
a = 6.9964 (1) Å
b = 22.4244 (4) Å
c = 7.2085 (1) Å
β = 93.0910 (11)°
V = 1129.30 (3) Å³
Z = 4
D_x = 1.633 Mg m⁻³
Mo Kα radiation
Cell parameters from 2580 reflections
θ = 3.4–27.5°
μ = 0.35 mm⁻¹
T = 120 (2) K
Block, colourless
0.54 × 0.44 × 0.36 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.835, T_max = 0.886
13 129 measured reflections
2580 independent reflections
2355 reflections with I > 2σ(I)
R_int = 0.029
θ_max = 27.5°
h = −9 → 9
k = −29 → 28
l = −9 → 9

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.104
S = 1.19
2580 reflections
174 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0562P)² + 0.4042P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.47 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.078 (6)

Table 1
Selected geometric parameters (Å, °) for (I)

N21—C21	1.4052 (17)
C22—N22	1.4618 (18)

N21—C17—C13	114.40 (12)
C17—N21—C21	127.03 (12)

C12—C13—C17—N21	−62.93 (18)
C13—C17—N21—C21	178.88 (13)
C17—N21—C21—C22	−157.61 (14)
C21—C22—N22—O2	−15.1 (2)

Table 2
Hydrogen-bond parameters and short intramolecular contacts (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21⋯O2	0.88	2.01	2.6416 (16)	128
C14—H14⋯O2ⁱ	0.95	2.49	3.4084 (17)	162
C25—H25⋯O1ⁱⁱ	0.95	2.53	3.2921 (18)	137
C26—H26⋯O1	0.95	2.30	2.8771 (18)	119
Symmetry codes: (i) x-1, y, z; (ii) -x, -y+1, -z+1.

Compound (II)

Crystal data

C₁₂H₈ClN₃O₃·H₂O
M_r = 295.68
Triclinic, $[P{\overline 1}]$
a = 7.5607 (4) Å
b = 7.6518 (3) Å
c = 12.6775 (5) Å
α = 81.177 (3)°
β = 84.367 (2)°
γ = 61.172 (2)°
V = 634.69 (5) Å³
Z = 2
D_x = 1.547 Mg m⁻³
Mo Kα radiation
Cell parameters from 2891 reflections
θ = 3.3–27.6°
μ = 0.32 mm⁻¹
T = 120 (2) K
Block, colourless
0.2 × 0.2 × 0.2 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.926, T_max = 0.938
12 769 measured reflections
2891 independent reflections
2318 reflections with I > 2σ(I)
R_int = 0.028
θ_max = 27.6°
h = −9 → 9
k = −9 → 9
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.129
S = 1.08
2891 reflections
183 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.074P)² + 0.1161P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 3
Selected geometric parameters (Å, °) for (II)

N21—C21	1.4122 (18)
C23—N23	1.465 (2)

N21—C17—C13	114.31 (13)
C17—N21—C21	127.89 (13)

C12—C13—C17—N21	−123.99 (17)
C13—C17—N21—C21	−174.38 (15)
C17—N21—C21—C22	−178.35 (16)
C22—C23—N23—O2	3.2 (2)

Table 4
Hydrogen-bond parameters and short intramolecular contacts (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21⋯O4ⁱⁱⁱ	0.88	2.03	2.907 (2)	173
O4—H41⋯O1	0.85	2.07	2.916 (2)	173
O4—H42⋯N11^iv	0.88	2.06	2.935 (2)	170
C26—H26⋯O1	0.95	2.25	2.864 (2)	121
Symmetry codes: (iii) x, y-1, z; (iv) -x+1, -y+1, -z.

Compound (III)

Crystal data

C₁₂H₈ClN₃O₃
M_r = 277.66
Monoclinic, P 2₁ /n
a = 7.2385 (2) Å
b = 24.5094 (6) Å
c = 13.5018 (4) Å
β = 92.834 (2)°
V = 2392.44 (11) Å³
Z = 8
D_x = 1.542 Mg m⁻³
Mo Kα radiation
Cell parameters from 5494 reflections
θ = 2.9–27.6°
μ = 0.33 mm⁻¹
T = 120 (2) K
Block, colourless
0.2 × 0.1 × 0.1 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.945, T_max = 0.968
5494 measured reflections
5494 independent reflections
3366 reflections with I > 2σ(I)
R_int = 0.079
θ_max = 27.6°
h = −9 → 9
k = −31 → 30
l = −17 → 17

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.143
S = 1.00
5494 reflections
343 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.073P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 5
Selected geometric parameters (Å, °) for (III)

N21—C21	1.410 (3)
C24—N24	1.467 (3)
N41—C41	1.412 (3)
C44—N44	1.471 (3)

N21—C17—C13	114.8 (2)
C17—N21—C21	127.75 (19)
N41—C37—C33	114.6 (2)
C37—N41—C41	127.63 (19)

C12—C13—C17—N21	78.1 (3)
C13—C17—N21—C21	173.29 (19)
C17—N21—C21—C22	−179.8 (2)
C25—C24—N24—O13	−8.1 (3)
C32—C33—C37—N41	−71.5 (3)
C33—C37—N41—C41	−173.4 (2)
C37—N41—C41—C42	173.6 (2)
C43—C44—N44—O22	5.2 (3)

Table 6
Hydrogen-bond parameters and short intramolecular contacts (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21⋯N31	0.92	2.08	2.999 (3)	178
N41—H41⋯N11ⁱ	0.95	2.14	3.067 (3)	164
C22—H22⋯O11ⁱ	0.95	2.58	3.117 (3)	116
C23—H23⋯O11ⁱ	0.95	2.37	3.011 (3)	124
C26—H26⋯O11	0.95	2.25	2.861 (3)	121
C43—H43⋯O21ⁱ	0.95	2.57	3.166 (3)	121
C46—H46⋯O21	0.95	2.27	2.874 (3)	121
Symmetry code: (i) x-1, y, z.

For isomers (I) and (III), the space groups P2₁/c and P2₁/n were uniquely assigned from the systematic absences. Crystals of compound (II) are triclinic; space group P $[\overline{1}]$ was selected and confirmed by the successful structure analysis. All H atoms were located from difference maps. H atoms bonded to C atoms were treated as riding atoms, with C—H distances of 0.95 Å and U_iso(H) values of 1.2U_eq(C). H atoms bonded to N atoms were allowed to ride at the positions located from the difference maps, with N—H distances of 0.88–0.95 Å and U_iso(H) values of 1.2U_eq(N). H atoms bonded to atom O4 in (II) were allowed to ride at the positions located from the difference maps, with O—H distances of 0.85 and 0.88 Å and individual isotropic displacement parameters.

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

Supporting information

Crystal structure: contains datablocks global, I, II, III. DOI: 10.1107/S0108270105003586/sk1812sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105003586/sk1812Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105003586/sk1812IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270105003586/sk1812IIIsup4.hkl

Comment top

We report here the molecular and supramolecular structures of the three isomeric 2-chloro-N-(nitrophenyl)nicotinamides (Figs. 1–3). Of these isomers, the 3-nitrophenyl isomer, (II), crystallizes from acetone as a monohydrate, whereas the 2-nitrophenyl isomer, (I), crystallizes from the same solvent in unsolvated form. The 4-nitrophenyl isomer, (III), crystallizes from ethanol with Z' = 2 (Fig. 3).

In compounds (I) and (II), and in each of the independent molecules of (III), the central amide spacer unit is essentially planar, as demonstrated by the C—C—N—C torsional angles (Tables 1, 3 and 5). However, the torsion angles describing the conformations of the two rings relative to the spacer unit show some variations, particularly for the heteroaryl rings. The nitroaryl rings do not deviate significantly from the plane of the amide spacer unit, and in each molecule there is a short intramolecular C—H···O contact involving atom C26 in the aryl ring [C46 in molecule 2 of compound (III)] and the amide O atom (Tables 2, 4 and 6), which may have some influence of this conformation. The planes of the nitro groups are all close to the planes of the adjacent aryl rings. The two independent molecules in (III) adopt very similar conformations so that for the selected asymmetric unit the two molecules are nearly enantiomeric (Table 5 and Fig. 3).

Within the spacer units, the backbone C—C—N angles are consistently significantly less than 120°, while the C—N—C angles are significantly greater than 120°. There is no evidence from the bond length in the nitroaniline fragments in compounds (I) and (III) for any bond fixation, such as is typically found in simple 2-nitro- and 4-nitroanilines. Thus polarization of types (Ia) and (IIIa) cannot effectively compete with the normal polarization of the amide units in these compounds.

The molecules of (I) are linked into a chain of edge-fused rings by two C—H···O hydrogen bonds, involving both the carbonyl O and one of the nitro O atoms (Table 2). Atom C14 of the heteroaryl ring in the molecule at (x, y, z) acts as a hydrogen-bond donor to nitro atom O2 in the molecule at (−1 + x, y, z), so generating by translation a C(9) chain (Bernstein et al., 1995) running parallel to the [100] direction. At the same time, aryl atom C25 in the molecule at (x, y, z) acts as a donor to carbonyl atom O1 in the molecule at (−x, 1 − y, 1 − z), so forming a centrosymmetric R₂²(14) ring centred at (0,1/2, 1/2). The combination of these two motifs then generates a chain of centrosymmetric edge-fused rings along [100], with R₂²(14) rings centred at (n,1/2, 1/2) (n = zero or integer) and R₄⁴(24) rings centred at (n + 1/2, 1/2, 1/2) (n = zero or integer) (Fig. 4). Two chains of this type pass through each unit cell, along the lines (x, 0, 0) and (x,1/2, 1/2), but there are no direction-specific interactions between adjacent chains.

The independent components in (II) are linked by a combination of O—H···O, O—H···N and N—H···O hydrogen bonds (Table 4) into a chain of edge-fused rings. Water atom O41 acts as a hydrogen-bond donor, via H41, to carbonyl atom O1 within the asymmetric unit. In addition, amine atom N21 at (x, y, z) acts as a hydrogen-bond donor to water atom O4 at (x, −1 + y, z), so generating by translation a C₂²(6) chain running parallel to the [010] direction, in which O—H···O hydrogen bonds alternate with N—H···O hydrogen bonds (Fig. 5). Two chains of this type, antiparallel to one another, pass through each unit cell, and these are linked by the O—H···N hydrogen bonds. Water atom O41 at (x, y, z) also acts as hydrogen-bond donor, this time via H42, to ring atom N11 at (1 − x, 1 − y, −z), so generating a centrosymmetric R₄⁴(16) ring, centred at (1/2, 1/2, 0) (Fig. 5). The combination of these two motifs then generates a chain of centrosymmetric edge-fused rings along the line (1/2, y, 0), in which R₄⁴(16) rings containing O—H···O and O—H···N hydrogen bonds and centred at (1/2, n + 1/2, 0) (n = zero or integer) alternate with R₄⁴(16) rings containing N—H···O and O—H···N hydrogen bonds and centred at (1/2, n, 0) (n = zero or integer) (Fig. 5).

The hydrogen-bonded chains in compound (II) are linked by three distinct aromatic π–π stacking interactions, all of them centrosymmetric but some of them fairly weak, into a continuous three-dimensional array. The heteroaryl ring in the molecule at (x, y, z) is parallel to the corresponding ring in the molecule at (−x, 1 − y, −z), which itself forms part of the hydrogen-bonded chain along (−0.5, y, 0); the interplanar spacing is 3.546 (2) Å, with a ring-centroid separation of 3.795 (2) Å, corresponding to a ring offset of 1.352 (2) Å. This interaction thus links the [010] chains into (001) sheets. In a similar fashion, the aryl rings of the molecules at (x, y, z) and (1 − x, −y, 1 − z), where the latter forms part of the hydrogen-bonded chain along (1/2, y, 1), are also parallel, with an interplanar spacing of 3.707 (2) Å, a ring-centroid separation of 3.917 (2) Å and a ring offset of 1.264 (2) Å. Finally, the aryl rings of the molecules at (x, y, z) and (−x, −y, 1 − z), which forms part of the hydrogen-bonded chain along (−0.5, y, 1), are also parallel, with an interplanar spacing of 3.384 (2) Å, a ring-centroid separation of 3.793 (2) Å and a ring offset of 1.715 (2) Å. These latter interactions connect the (001) sheets, so linking all of the hydrogen-bonded chains into a continuous framework.

The two independent molecules in (III) are linked into simple chains by two N—H···N hydrogen bonds (Table 6). Amide atom N21 acts as a hydrogen-bond donor to ring atom N31 within the asymmetric unit; similarly, amide atom N41 at (x, y, z) acts as a donor to ring atom N11 at (−1 + x, y, z), so generating by translation a C₂²(12) chain running parallel to the [100] direction (Fig. 6). There are number of short C—H···O contacts within this chain (Table 6), although it is doubtful if any of them could be regarded as a hydrogen bond; it is likely that these contacts are simply adventitious consequences of the N—H···N hydrogen bonds. Two C₂²(12) chains, antiparallel to one another, pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

It is thus striking that modest changes in the geometric position of a single substituent are associated with significant changes in crystallization characteristics, in the direction-specific intermolecular interactions manifested, and hence in the overall supramolecular structures; none of these changes is readily predictable.

Experimental top

For the synthesis of each of compounds (I)–(III), a solution of 2-chloronicotinoyl chloride (5.68 mmol), the appropriate nitroaniline (5.78 mmol) and triethylamine (12 mmol) in anhydrous tetrahydrofuran (30 ml) was stirred at ambient temperature for 8 h; water (20 ml) and ethyl acetate (20 ml) were added, and the organic layer was separated. This was washed with saturated aqueous Na[HCO₃] solution (2 × 20 ml) and dried over sodium sulfate, and then the solvent was removed. The resulting solids were purified by chromatography on alumina, with ethyl acetate and hexane (7:3, v/v) as eluant. Compounds (I) and (II) were recrystallized from acetone [m.p. 430–432 and 428–429 K (darkens at 407 K)]; compound (III) was recrystallized from ethanol (m.p. 479–481 K).

Computing details top

For all compounds, data collection: COLLECT (Hooft, 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

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular components of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The two independent molecules of (III), showing the atom-labelling scheme: (a) molecule 1 and (b) molecule 2. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a chain of edge-fused rings along [100]. For clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 5. A stereoview of part of the crystal structure of (II), showing the formation of a chain of edge-fused rings along [010]. For clarity, H atoms bonded to C atoms have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of (III), showing the formation of a C₂²(12) chain along [100]. For clarity, H atoms bonded to C atoms have been omitted.

(I) 2-Chloro-N-(2-nitrophenyl)nicotinamide top

Crystal data top

C₁₂H₈ClN₃O₃	F(000) = 568
M_r = 277.66	D_x = 1.633 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2580 reflections
a = 6.9964 (1) Å	θ = 3.4–27.5°
b = 22.4244 (4) Å	µ = 0.35 mm⁻¹
c = 7.2085 (1) Å	T = 120 K
β = 93.0910 (11)°	Block, colourless
V = 1129.30 (3) Å³	0.54 × 0.44 × 0.36 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2580 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	2355 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −29→28
T_min = 0.835, T_max = 0.886	l = −9→9
13129 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0562P)² + 0.4042P] where P = (F_o² + 2F_c²)/3
S = 1.19	(Δ/σ)_max = 0.001
2580 reflections	Δρ_max = 0.57 e Å⁻³
174 parameters	Δρ_min = −0.47 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.078 (6)

Crystal data top

C₁₂H₈ClN₃O₃	V = 1129.30 (3) Å³
M_r = 277.66	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.9964 (1) Å	µ = 0.35 mm⁻¹
b = 22.4244 (4) Å	T = 120 K
c = 7.2085 (1) Å	0.54 × 0.44 × 0.36 mm
β = 93.0910 (11)°

Data collection top

Nonius KappaCCD diffractometer	2580 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2355 reflections with I > 2σ(I)
T_min = 0.835, T_max = 0.886	R_int = 0.029
13129 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.19	Δρ_max = 0.57 e Å⁻³
2580 reflections	Δρ_min = −0.47 e Å⁻³
174 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.52679 (5)	0.284888 (15)	0.46820 (5)	0.02029 (15)
O1	0.08692 (16)	0.40079 (5)	0.48472 (16)	0.0251 (3)
O2	0.68027 (16)	0.36970 (4)	0.86260 (16)	0.0239 (3)
O3	0.89794 (16)	0.43787 (5)	0.86521 (19)	0.0323 (3)
N11	0.27639 (18)	0.20372 (5)	0.53499 (17)	0.0185 (3)
N21	0.34113 (17)	0.39216 (5)	0.69864 (17)	0.0172 (3)
N22	0.73074 (17)	0.42201 (5)	0.84092 (17)	0.0180 (3)
C12	0.3039 (2)	0.26202 (6)	0.53946 (18)	0.0154 (3)
C13	0.1696 (2)	0.30406 (6)	0.59056 (18)	0.0149 (3)
C14	−0.0066 (2)	0.28190 (6)	0.6405 (2)	0.0180 (3)
C15	−0.0387 (2)	0.22109 (7)	0.6399 (2)	0.0199 (3)
C16	0.1063 (2)	0.18371 (6)	0.5865 (2)	0.0205 (3)
C17	0.1949 (2)	0.37087 (6)	0.58400 (19)	0.0162 (3)
C21	0.3999 (2)	0.45183 (6)	0.71937 (18)	0.0151 (3)
C22	0.5865 (2)	0.46698 (6)	0.78843 (18)	0.0150 (3)
C23	0.6440 (2)	0.52602 (6)	0.81192 (19)	0.0180 (3)
C24	0.5170 (2)	0.57156 (6)	0.7690 (2)	0.0195 (3)
C25	0.3328 (2)	0.55773 (6)	0.6999 (2)	0.0190 (3)
C26	0.2747 (2)	0.49912 (6)	0.67514 (19)	0.0174 (3)
H14	−0.1043	0.3085	0.6748	0.022*
H15	−0.1573	0.2053	0.6752	0.024*
H16	0.0842	0.1419	0.5863	0.025*
H21	0.4055	0.3657	0.7669	0.021*
H23	0.7707	0.5349	0.8575	0.022*
H24	0.5548	0.6120	0.7863	0.023*
H25	0.2453	0.5891	0.6691	0.023*
H26	0.1482	0.4909	0.6275	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0150 (2)	0.0220 (2)	0.0240 (2)	0.00086 (12)	0.00233 (14)	−0.00109 (12)
O1	0.0258 (6)	0.0176 (5)	0.0305 (6)	0.0031 (4)	−0.0114 (5)	0.0001 (4)
O2	0.0228 (6)	0.0141 (5)	0.0340 (6)	0.0022 (4)	−0.0050 (5)	−0.0004 (4)
O3	0.0134 (6)	0.0306 (6)	0.0526 (8)	−0.0006 (4)	−0.0006 (5)	0.0048 (5)
N11	0.0195 (6)	0.0160 (6)	0.0194 (6)	0.0020 (5)	−0.0036 (5)	−0.0017 (4)
N21	0.0176 (6)	0.0124 (6)	0.0209 (6)	0.0009 (4)	−0.0043 (5)	0.0004 (4)
N22	0.0156 (6)	0.0201 (6)	0.0184 (6)	0.0016 (5)	0.0010 (5)	−0.0013 (5)
C12	0.0144 (7)	0.0174 (7)	0.0142 (6)	−0.0002 (5)	−0.0026 (5)	0.0002 (5)
C13	0.0155 (7)	0.0147 (6)	0.0139 (6)	0.0007 (5)	−0.0030 (5)	−0.0011 (5)
C14	0.0161 (7)	0.0198 (7)	0.0178 (7)	0.0005 (5)	−0.0004 (5)	−0.0025 (5)
C15	0.0180 (7)	0.0223 (7)	0.0190 (7)	−0.0047 (5)	−0.0010 (5)	0.0010 (5)
C16	0.0249 (8)	0.0151 (6)	0.0208 (7)	−0.0024 (6)	−0.0044 (6)	0.0006 (5)
C17	0.0163 (7)	0.0152 (6)	0.0169 (6)	0.0011 (5)	0.0005 (5)	−0.0021 (5)
C21	0.0179 (7)	0.0131 (6)	0.0141 (6)	−0.0005 (5)	0.0010 (5)	−0.0007 (5)
C22	0.0159 (7)	0.0155 (6)	0.0136 (6)	0.0021 (5)	0.0015 (5)	0.0002 (5)
C23	0.0186 (7)	0.0186 (7)	0.0167 (6)	−0.0038 (5)	0.0016 (5)	−0.0007 (5)
C24	0.0261 (8)	0.0142 (6)	0.0181 (7)	−0.0029 (5)	0.0016 (6)	0.0000 (5)
C25	0.0240 (8)	0.0144 (7)	0.0186 (7)	0.0027 (5)	0.0001 (6)	0.0008 (5)
C26	0.0170 (7)	0.0164 (7)	0.0187 (6)	0.0006 (5)	−0.0017 (5)	−0.0003 (5)

Geometric parameters (Å, º) top

N11—C12	1.3215 (18)	N21—H21	0.88
N11—C16	1.343 (2)	C21—C26	1.4011 (19)
C12—C13	1.3945 (19)	C21—C22	1.414 (2)
C12—Cl1	1.7453 (14)	C22—C23	1.3914 (19)
C13—C14	1.394 (2)	C22—N22	1.4618 (18)
C13—C17	1.5096 (18)	N22—O3	1.2262 (17)
C14—C15	1.382 (2)	N22—O2	1.2373 (16)
C14—H14	0.95	C23—C24	1.378 (2)
C15—C16	1.386 (2)	C23—H23	0.95
C15—H15	0.95	C24—C25	1.392 (2)
C16—H16	0.95	C24—H24	0.95
C17—O1	1.2141 (17)	C25—C26	1.3843 (19)
C17—N21	1.3664 (18)	C25—H25	0.95
N21—C21	1.4052 (17)	C26—H26	0.95

C12—N11—C16	116.98 (13)	C26—C21—N21	121.40 (13)
N11—C12—C13	125.17 (13)	C26—C21—C22	116.89 (12)
N11—C12—Cl1	114.49 (11)	N21—C21—C22	121.71 (12)
C13—C12—Cl1	120.31 (11)	C23—C22—C21	121.81 (13)
C14—C13—C12	116.41 (13)	C23—C22—N22	115.72 (12)
C14—C13—C17	117.95 (12)	C21—C22—N22	122.47 (12)
C12—C13—C17	125.51 (13)	O3—N22—O2	122.24 (12)
C15—C14—C13	119.78 (14)	O3—N22—C22	118.47 (12)
C15—C14—H14	120.1	O2—N22—C22	119.28 (12)
C13—C14—H14	120.1	C24—C23—C22	119.94 (14)
C14—C15—C16	118.47 (14)	C24—C23—H23	120.0
C14—C15—H15	120.8	C22—C23—H23	120.0
C16—C15—H15	120.8	C23—C24—C25	119.29 (13)
N11—C16—C15	123.18 (13)	C23—C24—H24	120.4
N11—C16—H16	118.4	C25—C24—H24	120.4
C15—C16—H16	118.4	C26—C25—C24	121.15 (13)
O1—C17—N21	125.81 (13)	C26—C25—H25	119.4
O1—C17—C13	119.77 (13)	C24—C25—H25	119.4
N21—C17—C13	114.40 (12)	C25—C26—C21	120.93 (13)
C17—N21—C21	127.03 (12)	C25—C26—H26	119.5
C17—N21—H21	116.5	C21—C26—H26	119.5
C21—N21—H21	116.5

C16—N11—C12—C13	−1.0 (2)	C17—N21—C21—C26	23.4 (2)
C16—N11—C12—Cl1	−179.28 (10)	C17—N21—C21—C22	−157.61 (14)
N11—C12—C13—C14	0.0 (2)	C26—C21—C22—C23	0.1 (2)
Cl1—C12—C13—C14	178.22 (10)	N21—C21—C22—C23	−178.94 (12)
N11—C12—C13—C17	−175.73 (13)	C26—C21—C22—N22	179.63 (12)
Cl1—C12—C13—C17	2.45 (18)	N21—C21—C22—N22	0.6 (2)
C12—C13—C14—C15	0.9 (2)	C23—C22—N22—O3	−14.27 (19)
C17—C13—C14—C15	177.02 (13)	C21—C22—N22—O3	166.17 (13)
C13—C14—C15—C16	−0.9 (2)	C23—C22—N22—O2	164.44 (13)
C12—N11—C16—C15	1.0 (2)	C21—C22—N22—O2	−15.1 (2)
C14—C15—C16—N11	−0.1 (2)	C21—C22—C23—C24	0.6 (2)
C14—C13—C17—O1	−57.32 (19)	N22—C22—C23—C24	−178.99 (12)
C12—C13—C17—O1	118.39 (16)	C22—C23—C24—C25	−0.9 (2)
C14—C13—C17—N21	121.36 (14)	C23—C24—C25—C26	0.5 (2)
C12—C13—C17—N21	−62.93 (18)	C24—C25—C26—C21	0.1 (2)
O1—C17—N21—C21	−2.5 (2)	N21—C21—C26—C25	178.59 (13)
C13—C17—N21—C21	178.88 (13)	C22—C21—C26—C25	−0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O2	0.88	2.01	2.6416 (16)	128
C14—H14···O2ⁱ	0.95	2.49	3.4084 (17)	162
C25—H25···O1ⁱⁱ	0.95	2.53	3.2921 (18)	137
C26—H26···O1	0.95	2.30	2.8771 (18)	119

Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z+1.

(II) 2-Chloro-N-(3-nitrophenyl)nicotinamide monohydrate top

Crystal data top

C₁₂H₈ClN₃O₃·H₂O	Z = 2
M_r = 295.68	F(000) = 304
Triclinic, P1	D_x = 1.547 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5607 (4) Å	Cell parameters from 2891 reflections
b = 7.6518 (3) Å	θ = 3.3–27.6°
c = 12.6775 (5) Å	µ = 0.32 mm⁻¹
α = 81.177 (3)°	T = 120 K
β = 84.367 (2)°	Block, colourless
γ = 61.172 (2)°	0.2 × 0.2 × 0.2 mm
V = 634.69 (5) Å³

Data collection top

Nonius KappaCCD diffractometer	2891 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	2318 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.3°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
T_min = 0.926, T_max = 0.938	l = −16→16
12769 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.074P)² + 0.1161P] where P = (F_o² + 2F_c²)/3
2891 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₁₂H₈ClN₃O₃·H₂O	γ = 61.172 (2)°
M_r = 295.68	V = 634.69 (5) Å³
Triclinic, P1	Z = 2
a = 7.5607 (4) Å	Mo Kα radiation
b = 7.6518 (3) Å	µ = 0.32 mm⁻¹
c = 12.6775 (5) Å	T = 120 K
α = 81.177 (3)°	0.2 × 0.2 × 0.2 mm
β = 84.367 (2)°

Data collection top

Nonius KappaCCD diffractometer	2891 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2318 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.938	R_int = 0.028
12769 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.08	Δρ_max = 0.27 e Å⁻³
2891 reflections	Δρ_min = −0.43 e Å⁻³
183 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.58252 (7)	0.28229 (7)	0.09351 (4)	0.05063 (18)
O1	0.2316 (3)	0.4034 (2)	0.26846 (10)	0.0603 (4)
O2	0.3065 (3)	−0.4763 (2)	0.56158 (12)	0.0656 (4)
O3	0.2362 (3)	−0.3722 (2)	0.71615 (10)	0.0633 (4)
N11	0.3821 (2)	0.2690 (2)	−0.05734 (11)	0.0429 (4)
N21	0.2574 (2)	0.09090 (19)	0.30122 (10)	0.0361 (3)
N23	0.2669 (2)	−0.3479 (2)	0.61966 (11)	0.0412 (3)
C12	0.3844 (3)	0.2642 (2)	0.04717 (12)	0.0354 (4)
C13	0.2435 (3)	0.2419 (2)	0.11982 (12)	0.0353 (4)
C14	0.0934 (3)	0.2215 (3)	0.07740 (14)	0.0434 (4)
C15	0.0853 (3)	0.2292 (3)	−0.03172 (14)	0.0482 (4)
C16	0.2316 (3)	0.2545 (3)	−0.09540 (13)	0.0479 (4)
C17	0.2453 (3)	0.2537 (2)	0.23712 (12)	0.0384 (4)
C21	0.2457 (2)	0.0631 (2)	0.41391 (11)	0.0320 (3)
C22	0.2681 (2)	−0.1225 (2)	0.46136 (12)	0.0337 (3)
C23	0.2491 (2)	−0.1538 (2)	0.57115 (12)	0.0348 (3)
C24	0.2096 (3)	−0.0094 (3)	0.63625 (13)	0.0455 (4)
C25	0.1907 (4)	0.1725 (3)	0.58779 (14)	0.0518 (5)
C26	0.2090 (3)	0.2107 (3)	0.47781 (13)	0.0429 (4)
O4	0.2818 (2)	0.7597 (2)	0.20376 (11)	0.0545 (4)
H14	−0.0043	0.2022	0.1235	0.052*
H15	−0.0181	0.2174	−0.0619	0.058*
H16	0.2252	0.2620	−0.1705	0.057*
H21	0.2743	−0.0102	0.2690	0.043*
H22	0.2958	−0.2257	0.4191	0.040*
H24	0.1960	−0.0345	0.7116	0.055*
H25	0.1645	0.2743	0.6307	0.062*
H26	0.1965	0.3368	0.4462	0.052*
H41	0.2596	0.6615	0.2265	0.090 (9)*
H42	0.3830	0.7389	0.1572	0.085 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0545 (3)	0.0588 (3)	0.0478 (3)	−0.0348 (2)	−0.0055 (2)	−0.0018 (2)
O1	0.1161 (13)	0.0478 (8)	0.0343 (6)	−0.0540 (8)	0.0103 (7)	−0.0075 (5)
O2	0.1015 (12)	0.0409 (7)	0.0608 (9)	−0.0413 (8)	0.0081 (8)	−0.0041 (6)
O3	0.0969 (12)	0.0604 (9)	0.0399 (7)	−0.0483 (8)	−0.0010 (7)	0.0115 (6)
N11	0.0582 (9)	0.0431 (8)	0.0307 (7)	−0.0280 (7)	0.0019 (6)	−0.0019 (6)
N21	0.0528 (8)	0.0319 (7)	0.0271 (6)	−0.0233 (6)	−0.0003 (6)	−0.0028 (5)
N23	0.0466 (8)	0.0394 (8)	0.0405 (8)	−0.0251 (7)	−0.0033 (6)	0.0048 (6)
C12	0.0454 (9)	0.0300 (7)	0.0315 (8)	−0.0195 (7)	−0.0015 (6)	0.0001 (6)
C13	0.0474 (9)	0.0297 (7)	0.0287 (7)	−0.0190 (7)	−0.0001 (6)	−0.0011 (6)
C14	0.0488 (10)	0.0458 (9)	0.0401 (9)	−0.0271 (8)	0.0000 (7)	−0.0022 (7)
C15	0.0564 (11)	0.0509 (10)	0.0430 (9)	−0.0291 (9)	−0.0113 (8)	−0.0028 (8)
C16	0.0708 (13)	0.0487 (10)	0.0293 (8)	−0.0323 (9)	−0.0066 (8)	−0.0020 (7)
C17	0.0533 (10)	0.0357 (8)	0.0295 (8)	−0.0248 (7)	0.0020 (7)	−0.0025 (6)
C21	0.0369 (8)	0.0338 (8)	0.0272 (7)	−0.0187 (6)	−0.0028 (6)	−0.0008 (6)
C22	0.0384 (8)	0.0311 (8)	0.0331 (8)	−0.0182 (7)	−0.0001 (6)	−0.0029 (6)
C23	0.0376 (8)	0.0340 (8)	0.0345 (8)	−0.0201 (7)	−0.0044 (6)	0.0040 (6)
C24	0.0683 (12)	0.0504 (10)	0.0267 (8)	−0.0360 (9)	−0.0035 (7)	−0.0003 (7)
C25	0.0875 (15)	0.0485 (10)	0.0332 (9)	−0.0426 (10)	−0.0004 (9)	−0.0079 (7)
C26	0.0670 (12)	0.0379 (9)	0.0329 (8)	−0.0326 (8)	−0.0026 (7)	−0.0017 (7)
O4	0.0750 (10)	0.0460 (7)	0.0529 (8)	−0.0375 (7)	0.0173 (7)	−0.0160 (6)

Geometric parameters (Å, º) top

Cl1—C12	1.7336 (17)	C21—C22	1.391 (2)
N11—C12	1.321 (2)	C21—C26	1.394 (2)
N11—C16	1.337 (2)	C22—C23	1.381 (2)
C12—C13	1.395 (2)	C22—H22	0.95
C13—C14	1.385 (2)	C23—C24	1.380 (2)
C13—C17	1.505 (2)	C23—N23	1.465 (2)
C14—C15	1.382 (2)	N23—O2	1.222 (2)
C14—H14	0.95	N23—O3	1.2251 (18)
C15—C16	1.377 (3)	C24—C25	1.378 (3)
C15—H15	0.95	C24—H24	0.95
C16—H16	0.95	C25—C26	1.387 (2)
C17—O1	1.224 (2)	C25—H25	0.95
C17—N21	1.347 (2)	C26—H26	0.95
N21—C21	1.4122 (18)	O4—H41	0.8492
N21—H21	0.88	O4—H42	0.8845

C12—N11—C16	117.10 (15)	C22—C21—C26	119.57 (14)
N11—C12—C13	124.66 (16)	C22—C21—N21	116.55 (13)
N11—C12—Cl1	115.73 (13)	C26—C21—N21	123.86 (14)
C13—C12—Cl1	119.60 (12)	C23—C22—C21	118.65 (14)
C14—C13—C12	116.42 (14)	C23—C22—H22	120.7
C14—C13—C17	121.49 (15)	C21—C22—H22	120.7
C12—C13—C17	121.96 (15)	C24—C23—C22	123.02 (14)
C15—C14—C13	120.17 (16)	C24—C23—N23	118.97 (14)
C15—C14—H14	119.9	C22—C23—N23	117.99 (14)
C13—C14—H14	119.9	O2—N23—O3	123.00 (15)
C16—C15—C14	118.00 (17)	O2—N23—C23	118.44 (14)
C16—C15—H15	121.0	O3—N23—C23	118.53 (14)
C14—C15—H15	121.0	C25—C24—C23	117.42 (15)
N11—C16—C15	123.61 (16)	C25—C24—H24	121.3
N11—C16—H16	118.2	C23—C24—H24	121.3
C15—C16—H16	118.2	C24—C25—C26	121.60 (16)
O1—C17—N21	124.71 (14)	C24—C25—H25	119.2
O1—C17—C13	120.95 (14)	C26—C25—H25	119.2
N21—C17—C13	114.31 (13)	C25—C26—C21	119.71 (15)
C17—N21—C21	127.89 (13)	C25—C26—H26	120.1
C17—N21—H21	116.1	C21—C26—H26	120.1
C21—N21—H21	116.1	H41—O4—H42	117.9

C16—N11—C12—C13	1.1 (2)	C17—N21—C21—C22	−178.35 (16)
C16—N11—C12—Cl1	179.74 (13)	C17—N21—C21—C26	3.2 (3)
N11—C12—C13—C14	0.7 (2)	C26—C21—C22—C23	1.3 (2)
Cl1—C12—C13—C14	−177.87 (12)	N21—C21—C22—C23	−177.24 (14)
N11—C12—C13—C17	−175.17 (15)	C21—C22—C23—C24	−0.3 (3)
Cl1—C12—C13—C17	6.2 (2)	C21—C22—C23—N23	178.16 (14)
C12—C13—C14—C15	−1.7 (2)	C24—C23—N23—O2	−178.33 (17)
C17—C13—C14—C15	174.18 (16)	C22—C23—N23—O2	3.2 (2)
C13—C14—C15—C16	0.9 (3)	C24—C23—N23—O3	3.6 (2)
C12—N11—C16—C15	−2.0 (3)	C22—C23—N23—O3	−174.91 (16)
C14—C15—C16—N11	1.0 (3)	C22—C23—C24—C25	−0.6 (3)
C14—C13—C17—O1	−118.0 (2)	N23—C23—C24—C25	−179.00 (17)
C12—C13—C17—O1	57.7 (2)	C23—C24—C25—C26	0.4 (3)
C14—C13—C17—N21	60.3 (2)	C24—C25—C26—C21	0.5 (3)
C12—C13—C17—N21	−123.99 (17)	C22—C21—C26—C25	−1.4 (3)
O1—C17—N21—C21	3.8 (3)	N21—C21—C26—C25	176.98 (18)
C13—C17—N21—C21	−174.38 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O4ⁱ	0.88	2.03	2.907 (2)	173
O4—H41···O1	0.85	2.07	2.916 (2)	173
O4—H42···N11ⁱⁱ	0.88	2.06	2.935 (2)	170
C26—H26···O1	0.95	2.25	2.864 (2)	121

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z.

(III) 2-Chloro-N-(4-nitrophenyl)nicotinamide top

Crystal data top

C₁₂H₈ClN₃O₃	F(000) = 1136
M_r = 277.66	D_x = 1.542 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5494 reflections
a = 7.2385 (2) Å	θ = 2.9–27.6°
b = 24.5094 (6) Å	µ = 0.33 mm⁻¹
c = 13.5018 (4) Å	T = 120 K
β = 92.834 (2)°	Block, colourless
V = 2392.44 (11) Å³	0.2 × 0.1 × 0.1 mm
Z = 8

Data collection top

Nonius KappaCCD diffractometer	5494 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	3366 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 2.9°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −31→30
T_min = 0.945, T_max = 0.968	l = −17→17
5494 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.073P)²] where P = (F_o² + 2F_c²)/3
5494 reflections	(Δ/σ)_max = 0.001
343 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₁₂H₈ClN₃O₃	V = 2392.44 (11) Å³
M_r = 277.66	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.2385 (2) Å	µ = 0.33 mm⁻¹
b = 24.5094 (6) Å	T = 120 K
c = 13.5018 (4) Å	0.2 × 0.1 × 0.1 mm
β = 92.834 (2)°

Data collection top

Nonius KappaCCD diffractometer	5494 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	3366 reflections with I > 2σ(I)
T_min = 0.945, T_max = 0.968	R_int = 0.079
5494 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.00	Δρ_max = 0.29 e Å⁻³
5494 reflections	Δρ_min = −0.44 e Å⁻³
343 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl12	0.93279 (9)	0.69680 (2)	0.66272 (4)	0.02873 (18)
O11	1.0754 (3)	0.83940 (7)	0.74087 (16)	0.0480 (6)
O12	0.2074 (3)	0.99261 (6)	0.58346 (13)	0.0319 (4)
O13	0.4593 (2)	1.04072 (6)	0.58583 (12)	0.0287 (4)
N11	1.0557 (3)	0.66161 (7)	0.83516 (14)	0.0217 (4)
N21	0.7716 (3)	0.81689 (7)	0.75206 (13)	0.0196 (4)
N24	0.3761 (3)	0.99758 (7)	0.59832 (14)	0.0238 (5)
C12	1.0031 (3)	0.70646 (9)	0.78670 (16)	0.0197 (5)
C13	1.0065 (3)	0.75853 (9)	0.82673 (17)	0.0211 (5)
C14	1.0703 (4)	0.76385 (9)	0.92505 (18)	0.0249 (6)
C15	1.1218 (3)	0.71762 (9)	0.97860 (18)	0.0234 (5)
C16	1.1114 (3)	0.66747 (9)	0.93093 (17)	0.0225 (5)
C17	0.9547 (4)	0.80889 (9)	0.76783 (18)	0.0231 (5)
C21	0.6817 (3)	0.86260 (8)	0.70840 (16)	0.0187 (5)
C22	0.4896 (3)	0.86073 (8)	0.70096 (16)	0.0205 (5)
C23	0.3897 (3)	0.90496 (8)	0.66402 (16)	0.0196 (5)
C24	0.4841 (3)	0.95029 (8)	0.63428 (16)	0.0209 (5)
C25	0.6744 (3)	0.95342 (9)	0.64081 (16)	0.0221 (5)
C26	0.7754 (3)	0.90911 (8)	0.67751 (16)	0.0208 (5)
Cl32	0.42948 (9)	0.69468 (2)	0.66056 (4)	0.03089 (19)
O21	0.5793 (3)	0.54792 (7)	0.73644 (15)	0.0400 (5)
O22	−0.2799 (3)	0.39905 (8)	0.54869 (15)	0.0512 (6)
O23	−0.0226 (3)	0.35435 (7)	0.53995 (14)	0.0524 (6)
N31	0.5494 (3)	0.72622 (7)	0.83614 (15)	0.0242 (5)
N41	0.2759 (3)	0.57478 (7)	0.72771 (14)	0.0214 (4)
N44	−0.1105 (4)	0.39612 (9)	0.55726 (16)	0.0404 (6)
C32	0.4996 (3)	0.68234 (9)	0.78379 (17)	0.0210 (5)
C33	0.5028 (3)	0.62914 (9)	0.81950 (17)	0.0218 (5)
C34	0.5620 (3)	0.62221 (9)	0.91846 (18)	0.0280 (6)
C35	0.6082 (4)	0.66748 (10)	0.97554 (19)	0.0287 (6)
C36	0.5993 (3)	0.71837 (9)	0.93195 (18)	0.0252 (6)
C37	0.4570 (4)	0.57985 (9)	0.75576 (18)	0.0248 (6)
C41	0.1888 (3)	0.53077 (8)	0.67670 (17)	0.0213 (5)
C42	−0.0027 (3)	0.53272 (9)	0.66533 (17)	0.0230 (5)
C43	−0.1021 (4)	0.48949 (9)	0.62399 (17)	0.0283 (6)
C44	−0.0050 (4)	0.44408 (9)	0.59327 (17)	0.0290 (6)
C45	0.1850 (4)	0.44203 (9)	0.60068 (18)	0.0313 (6)
C46	0.2844 (4)	0.48558 (9)	0.64170 (18)	0.0276 (6)
H14	1.0784	0.7988	0.9552	0.030*
H15	1.1633	0.7202	1.0463	0.028*
H16	1.1454	0.6357	0.9679	0.027*
H21	0.7004	0.7897	0.7781	0.024*
H22	0.4268	0.8289	0.7213	0.025*
H23	0.2584	0.9040	0.6593	0.023*
H25	0.7357	0.9855	0.6204	0.027*
H26	0.9067	0.9103	0.6817	0.025*
H34	0.5706	0.5867	0.9465	0.034*
H35	0.6453	0.6636	1.0436	0.034*
H36	0.6301	0.7493	0.9718	0.030*
H41	0.1867	0.5974	0.7573	0.026*
H42	−0.0664	0.5642	0.6863	0.028*
H43	−0.2333	0.4908	0.6168	0.034*
H45	0.2481	0.4108	0.5777	0.038*
H46	0.4157	0.4848	0.6460	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl12	0.0339 (4)	0.0296 (3)	0.0221 (3)	0.0024 (3)	−0.0040 (3)	−0.0013 (2)
O11	0.022 (12)	0.0402 (10)	0.0830 (15)	0.0017 (9)	0.0082 (10)	0.0358 (11)
O12	0.0296 (12)	0.0295 (9)	0.0360 (11)	0.0089 (8)	−0.0043 (9)	0.0025 (8)
O13	0.0431 (12)	0.0152 (8)	0.0278 (10)	0.0015 (8)	0.0014 (8)	0.0011 (7)
N11	0.0213 (12)	0.0192 (9)	0.0246 (11)	0.0012 (8)	0.0022 (9)	0.0010 (8)
N21	0.0194 (12)	0.0159 (9)	0.0236 (11)	−0.0022 (8)	0.0023 (9)	0.0041 (8)
N24	0.0329 (14)	0.0200 (10)	0.0185 (10)	0.0050 (9)	0.0002 (9)	−0.0013 (8)
C12	0.0140 (13)	0.0236 (12)	0.0216 (12)	0.0005 (10)	0.0030 (10)	−0.0002 (10)
C13	0.0168 (13)	0.0212 (11)	0.0259 (13)	0.0007 (10)	0.0052 (10)	0.0034 (10)
C14	0.0308 (16)	0.0173 (11)	0.0267 (13)	−0.0013 (10)	0.0033 (11)	−0.0031 (10)
C15	0.0257 (15)	0.0227 (12)	0.0219 (12)	−0.0003 (10)	0.0011 (10)	−0.0007 (10)
C16	0.0222 (14)	0.0206 (11)	0.0245 (13)	0.0012 (10)	0.0002 (10)	0.0050 (10)
C17	0.0231 (15)	0.0191 (11)	0.0272 (13)	−0.0001 (10)	0.0037 (11)	0.0034 (10)
C21	0.0223 (14)	0.0145 (10)	0.0193 (12)	0.0014 (9)	0.0000 (10)	0.0002 (9)
C22	0.0227 (15)	0.0160 (11)	0.0229 (12)	−0.0018 (10)	0.0033 (10)	−0.0003 (9)
C23	0.0195 (14)	0.0204 (11)	0.0187 (11)	0.0028 (10)	−0.0003 (10)	−0.0017 (9)
C24	0.0280 (15)	0.0156 (11)	0.0189 (12)	0.0052 (10)	0.0010 (10)	−0.0003 (9)
C25	0.0274 (15)	0.0175 (11)	0.0216 (12)	−0.0009 (10)	0.0035 (11)	0.0025 (9)
C26	0.0199 (14)	0.0190 (11)	0.0235 (12)	−0.0020 (10)	0.0022 (10)	0.0016 (10)
Cl32	0.0333 (4)	0.0331 (3)	0.0260 (3)	−0.0046 (3)	−0.0020 (3)	0.0083 (3)
O21	0.0231 (11)	0.0329 (10)	0.0639 (14)	0.0050 (8)	0.0024 (9)	−0.0160 (9)
O22	0.0585 (16)	0.0476 (12)	0.0461 (13)	−0.0264 (11)	−0.0118 (11)	−0.0019 (10)
O23	0.0890 (18)	0.0268 (10)	0.0423 (12)	−0.0114 (11)	0.0113 (11)	−0.0117 (9)
N31	0.0204 (12)	0.0223 (10)	0.0301 (12)	−0.0031 (8)	0.0032 (9)	0.0039 (9)
N41	0.0218 (12)	0.0164 (9)	0.0262 (11)	0.0022 (8)	0.0033 (9)	−0.0013 (8)
N44	0.070 (2)	0.0267 (12)	0.0239 (12)	−0.0172 (13)	0.0011 (12)	−0.0025 (10)
C32	0.0126 (13)	0.0255 (12)	0.0250 (13)	−0.0004 (10)	0.0018 (10)	0.0041 (10)
C33	0.0150 (13)	0.0220 (11)	0.0286 (13)	−0.0001 (10)	0.0029 (10)	0.0028 (10)
C34	0.0280 (16)	0.0218 (12)	0.0339 (14)	0.0027 (10)	−0.0005 (12)	0.0061 (11)
C35	0.0262 (16)	0.0318 (13)	0.0276 (13)	0.0023 (11)	−0.0034 (11)	0.0024 (11)
C36	0.0185 (14)	0.0251 (12)	0.0320 (14)	−0.0020 (10)	−0.0006 (11)	−0.0015 (11)
C37	0.0238 (15)	0.0203 (12)	0.0303 (14)	0.0010 (11)	0.0019 (11)	0.0012 (10)
C41	0.0278 (15)	0.0183 (11)	0.0181 (12)	−0.0012 (10)	0.0029 (10)	0.0028 (9)
C42	0.0272 (15)	0.0200 (11)	0.0217 (13)	0.0016 (10)	0.0015 (10)	0.0019 (10)
C43	0.0350 (17)	0.0292 (13)	0.0205 (13)	−0.0066 (12)	0.0009 (11)	0.0035 (11)
C44	0.0451 (19)	0.0234 (12)	0.0184 (13)	−0.0117 (12)	0.0018 (12)	0.0006 (10)
C45	0.051 (2)	0.0196 (12)	0.0243 (14)	0.0033 (12)	0.0070 (12)	−0.0022 (10)
C46	0.0294 (16)	0.0250 (12)	0.0289 (14)	0.0035 (11)	0.0062 (11)	0.0000 (11)

Geometric parameters (Å, º) top

N11—C12	1.326 (3)	N31—C32	1.327 (3)
N11—C16	1.343 (3)	N31—C36	1.340 (3)
C12—C13	1.386 (3)	C32—C33	1.390 (3)
C12—Cl12	1.741 (2)	C32—Cl32	1.742 (2)
C13—C14	1.390 (3)	C33—C34	1.393 (3)
C13—C17	1.506 (3)	C33—C37	1.510 (3)
C14—C15	1.385 (3)	C34—C35	1.383 (3)
C14—H14	0.95	C34—H34	0.95
C15—C16	1.388 (3)	C35—C36	1.379 (3)
C15—H15	0.95	C35—H35	0.95
C16—H16	0.95	C36—H36	0.95
C17—O11	1.219 (3)	C37—O21	1.220 (3)
C17—N21	1.346 (3)	C37—N41	1.352 (3)
N21—C21	1.410 (3)	N41—C41	1.412 (3)
N21—H21	0.9237	N41—H41	0.9536
C21—C22	1.390 (3)	C41—C42	1.387 (3)
C21—C26	1.400 (3)	C41—C46	1.400 (3)
C22—C23	1.382 (3)	C42—C43	1.383 (3)
C22—H22	0.95	C42—H42	0.95
C23—C24	1.375 (3)	C43—C44	1.391 (3)
C23—H23	0.95	C43—H43	0.95
C24—C25	1.378 (3)	C44—C45	1.375 (4)
C24—N24	1.467 (3)	C44—N44	1.471 (3)
N24—O12	1.234 (3)	N44—O22	1.228 (3)
N24—O13	1.233 (2)	N44—O23	1.234 (3)
C25—C26	1.387 (3)	C45—C46	1.387 (3)
C25—H25	0.95	C45—H45	0.95
C26—H26	0.95	C46—H46	0.95

C12—N11—C16	116.86 (18)	C32—N31—C36	116.83 (19)
N11—C12—C13	124.9 (2)	N31—C32—C33	125.2 (2)
N11—C12—Cl12	115.14 (16)	N31—C32—Cl32	115.27 (16)
C13—C12—Cl12	119.93 (17)	C33—C32—Cl32	119.55 (18)
C12—C13—C14	117.2 (2)	C32—C33—C34	116.5 (2)
C12—C13—C17	123.4 (2)	C32—C33—C37	123.6 (2)
C14—C13—C17	119.33 (19)	C34—C33—C37	119.83 (19)
C15—C14—C13	119.3 (2)	C35—C34—C33	119.4 (2)
C15—C14—H14	120.3	C35—C34—H34	120.3
C13—C14—H14	120.3	C33—C34—H34	120.3
C14—C15—C16	118.4 (2)	C36—C35—C34	118.9 (2)
C14—C15—H15	120.8	C36—C35—H35	120.6
C16—C15—H15	120.8	C34—C35—H35	120.6
N11—C16—C15	123.2 (2)	N31—C36—C35	123.1 (2)
N11—C16—H16	118.4	N31—C36—H36	118.4
C15—C16—H16	118.4	C35—C36—H36	118.4
O11—C17—N21	125.3 (2)	O21—C37—N41	125.8 (2)
O11—C17—C13	119.8 (2)	O21—C37—C33	119.6 (2)
N21—C17—C13	114.8 (2)	N41—C37—C33	114.6 (2)
C17—N21—C21	127.75 (19)	C37—N41—C41	127.63 (19)
C17—N21—H21	113.5	C37—N41—H41	119.8
C21—N21—H21	118.6	C41—N41—H41	110.7
C22—C21—C26	120.2 (2)	C42—C41—C46	119.8 (2)
C22—C21—N21	116.32 (19)	C42—C41—N41	116.6 (2)
C26—C21—N21	123.4 (2)	C46—C41—N41	123.5 (2)
C23—C22—C21	120.3 (2)	C43—C42—C41	121.0 (2)
C23—C22—H22	119.9	C43—C42—H42	119.5
C21—C22—H22	119.9	C41—C42—H42	119.5
C24—C23—C22	118.7 (2)	C42—C43—C44	118.2 (2)
C24—C23—H23	120.6	C42—C43—H43	120.9
C22—C23—H23	120.6	C44—C43—H43	120.9
C23—C24—C25	122.4 (2)	C45—C44—C43	121.8 (2)
C23—C24—N24	118.1 (2)	C45—C44—N44	119.7 (2)
C25—C24—N24	119.5 (2)	C43—C44—N44	118.4 (3)
O12—N24—O13	123.31 (19)	O22—N44—O23	123.6 (2)
O12—N24—C24	118.87 (19)	O22—N44—C44	118.9 (2)
O13—N24—C24	117.8 (2)	O23—N44—C44	117.5 (3)
C24—C25—C26	119.1 (2)	C44—C45—C46	119.9 (2)
C24—C25—H25	120.4	C44—C45—H45	120.1
C26—C25—H25	120.4	C46—C45—H45	120.1
C25—C26—C21	119.3 (2)	C45—C46—C41	119.2 (2)
C25—C26—H26	120.3	C45—C46—H46	120.4
C21—C26—H26	120.3	C41—C46—H46	120.4

C16—N11—C12—C13	1.9 (4)	C36—N31—C32—C33	−2.9 (4)
C16—N11—C12—Cl12	179.80 (17)	C36—N31—C32—Cl32	178.23 (17)
N11—C12—C13—C14	0.1 (4)	N31—C32—C33—C34	0.5 (4)
Cl12—C12—C13—C14	−177.70 (18)	Cl32—C32—C33—C34	179.39 (18)
N11—C12—C13—C17	176.7 (2)	N31—C32—C33—C37	−175.8 (2)
Cl12—C12—C13—C17	−1.1 (3)	Cl32—C32—C33—C37	3.1 (3)
C12—C13—C14—C15	−1.8 (4)	C32—C33—C34—C35	1.9 (4)
C17—C13—C14—C15	−178.5 (2)	C37—C33—C34—C35	178.3 (2)
C13—C14—C15—C16	1.4 (4)	C33—C34—C35—C36	−1.9 (4)
C12—N11—C16—C15	−2.3 (4)	C32—N31—C36—C35	2.9 (4)
C14—C15—C16—N11	0.7 (4)	C34—C35—C36—N31	−0.6 (4)
C12—C13—C17—O11	−103.9 (3)	C32—C33—C37—O21	110.5 (3)
C14—C13—C17—O11	72.7 (3)	C34—C33—C37—O21	−65.7 (3)
C12—C13—C17—N21	78.1 (3)	C32—C33—C37—N41	−71.5 (3)
C14—C13—C17—N21	−105.4 (3)	C34—C33—C37—N41	112.3 (3)
O11—C17—N21—C21	−4.6 (4)	O21—C37—N41—C41	4.4 (4)
C13—C17—N21—C21	173.29 (19)	C33—C37—N41—C41	−173.4 (2)
C17—N21—C21—C22	−179.8 (2)	C37—N41—C41—C42	173.6 (2)
C17—N21—C21—C26	−2.7 (3)	C37—N41—C41—C46	−3.9 (4)
C26—C21—C22—C23	−0.7 (3)	C46—C41—C42—C43	3.1 (3)
N21—C21—C22—C23	176.54 (19)	N41—C41—C42—C43	−174.5 (2)
C21—C22—C23—C24	0.5 (3)	C41—C42—C43—C44	−0.5 (3)
C22—C23—C24—C25	−0.6 (3)	C42—C43—C44—C45	−1.7 (3)
C22—C23—C24—N24	−178.02 (19)	C42—C43—C44—N44	174.8 (2)
C23—C24—N24—O12	−9.6 (3)	C45—C44—N44—O22	−178.2 (2)
C25—C24—N24—O12	172.9 (2)	C43—C44—N44—O22	5.2 (3)
C23—C24—N24—O13	169.4 (2)	C45—C44—N44—O23	3.8 (3)
C25—C24—N24—O13	−8.1 (3)	C43—C44—N44—O23	−172.8 (2)
C23—C24—C25—C26	0.8 (3)	C43—C44—C45—C46	1.4 (4)
N24—C24—C25—C26	178.19 (19)	N44—C44—C45—C46	−175.1 (2)
C24—C25—C26—C21	−0.9 (3)	C44—C45—C46—C41	1.1 (4)
C22—C21—C26—C25	0.9 (3)	C42—C41—C46—C45	−3.3 (3)
N21—C21—C26—C25	−176.1 (2)	N41—C41—C46—C45	174.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···N31	0.92	2.08	2.999 (3)	178
N41—H41···N11ⁱ	0.95	2.14	3.067 (3)	164
C22—H22···O11ⁱ	0.95	2.58	3.117 (3)	116
C23—H23···O11ⁱ	0.95	2.37	3.011 (3)	124
C26—H26···O11	0.95	2.25	2.861 (3)	121
C43—H43···O21ⁱ	0.95	2.57	3.166 (3)	121
C46—H46···O21	0.95	2.27	2.874 (3)	121

Symmetry code: (i) x−1, y, z.

Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₁₂H₈ClN₃O₃	C₁₂H₈ClN₃O₃·H₂O	C₁₂H₈ClN₃O₃
M_r	277.66	295.68	277.66
Crystal system, space group	Monoclinic, P2₁/c	Triclinic, P1	Monoclinic, P2₁/n
Temperature (K)	120	120	120
a, b, c (Å)	6.9964 (1), 22.4244 (4), 7.2085 (1)	7.5607 (4), 7.6518 (3), 12.6775 (5)	7.2385 (2), 24.5094 (6), 13.5018 (4)
α, β, γ (°)	90, 93.0910 (11), 90	81.177 (3), 84.367 (2), 61.172 (2)	90, 92.834 (2), 90
V (Å³)	1129.30 (3)	634.69 (5)	2392.44 (11)
Z	4	2	8
Radiation type	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.35	0.32	0.33
Crystal size (mm)	0.54 × 0.44 × 0.36	0.2 × 0.2 × 0.2	0.2 × 0.1 × 0.1

Data collection
Diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.835, 0.886	0.926, 0.938	0.945, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	13129, 2580, 2355	12769, 2891, 2318	5494, 5494, 3366
R_int	0.029	0.028	0.079
(sin θ/λ)_max (Å⁻¹)	0.651	0.651	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.104, 1.19	0.044, 0.129, 1.08	0.051, 0.143, 1.00
No. of reflections	2580	2891	5494
No. of parameters	174	183	343
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.47	0.27, −0.43	0.29, −0.44

Computer programs: COLLECT (Hooft, 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).

Selected geometric parameters (Å, º) for (I) top

N21—C21	1.4052 (17)	C22—N22	1.4618 (18)

N21—C17—C13	114.40 (12)	C17—N21—C21	127.03 (12)

C12—C13—C17—N21	−62.93 (18)	C17—N21—C21—C22	−157.61 (14)
C13—C17—N21—C21	178.88 (13)	C21—C22—N22—O2	−15.1 (2)

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O2	0.88	2.01	2.6416 (16)	128
C14—H14···O2ⁱ	0.95	2.49	3.4084 (17)	162
C25—H25···O1ⁱⁱ	0.95	2.53	3.2921 (18)	137
C26—H26···O1	0.95	2.30	2.8771 (18)	119

Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z+1.

Selected geometric parameters (Å, º) for (II) top

N21—C21	1.4122 (18)	C23—N23	1.465 (2)

N21—C17—C13	114.31 (13)	C17—N21—C21	127.89 (13)

C12—C13—C17—N21	−123.99 (17)	C17—N21—C21—C22	−178.35 (16)
C13—C17—N21—C21	−174.38 (15)	C22—C23—N23—O2	3.2 (2)

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O4ⁱ	0.88	2.03	2.907 (2)	173
O4—H41···O1	0.85	2.07	2.916 (2)	173
O4—H42···N11ⁱⁱ	0.88	2.06	2.935 (2)	170
C26—H26···O1	0.95	2.25	2.864 (2)	121

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z.

Selected geometric parameters (Å, º) for (III) top

N21—C21	1.410 (3)	N41—C41	1.412 (3)
C24—N24	1.467 (3)	C44—N44	1.471 (3)

N21—C17—C13	114.8 (2)	N41—C37—C33	114.6 (2)
C17—N21—C21	127.75 (19)	C37—N41—C41	127.63 (19)

C12—C13—C17—N21	78.1 (3)	C32—C33—C37—N41	−71.5 (3)
C13—C17—N21—C21	173.29 (19)	C33—C37—N41—C41	−173.4 (2)
C17—N21—C21—C22	−179.8 (2)	C37—N41—C41—C42	173.6 (2)
C25—C24—N24—O13	−8.1 (3)	C43—C44—N44—O22	5.2 (3)

Hydrogen-bond geometry (Å, º) for (III) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···N31	0.92	2.08	2.999 (3)	178
N41—H41···N11ⁱ	0.95	2.14	3.067 (3)	164
C22—H22···O11ⁱ	0.95	2.58	3.117 (3)	116
C23—H23···O11ⁱ	0.95	2.37	3.011 (3)	124
C26—H26···O11	0.95	2.25	2.861 (3)	121
C43—H43···O21ⁱ	0.95	2.57	3.166 (3)	121
C46—H46···O21	0.95	2.27	2.874 (3)	121

Symmetry code: (i) 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. JLW thanks CNPq and FAPERJ for financial support.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
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. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 4| April 2005| Pages o204-o208

doi:10.1107/S0108270105003586

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search term		doi		Advanced search
Author		volume	page

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

Supramolecular structures of three isomeric 2-chloro-N-(nitro­phen­yl)­nicotinamides

Comment

Experimental

Compound (I)

Crystal data

Data collection

Refinement

Compound (II)

Crystal data

Data collection

Refinement

Compound (III)

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Supramolecular structures of three isomeric 2-chloro-N-(nitrophenyl)nicotinamides