π-Stacked hydrogen-bonded chains of rings in 2,4-difluoro­benzaldehyde isonicotinoylhydrazone and hydrogen-bonded sheets in 2,3-dichloro­benzaldehyde isonicotinoylhydrazone

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

doi:10.1107/S0108270105029136

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 10| October 2005| Pages o617-o620

doi:10.1107/S0108270105029136

π-Stacked hydrogen-bonded chains of rings in 2,4-difluorobenzaldehyde isonicotinoylhydrazone and hydrogen-bonded sheets in 2,3-dichlorobenzaldehyde isonicotinoylhydrazone

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

^aFundação Oswaldo Cruz, Far Manguinhos, Rua Sizenando Nabuco, 100 Manguinhos, 21041-250 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 13 September 2005; accepted 14 September 2005; online 30 September 2005)

The difluorinated ring in 2,4-difluorobenzaldehyde isonicotinoylhydrazone, C₁₃H₉F₂N₃O, (I), is disordered over two sets of sites with unequal occupancy. The molecules of (I) are linked by a combination of N—H⋯O and C—H⋯O hydrogen bonds into chains of rings, which are linked into sheets by a single π–π stacking interaction. In 2,3-dichlorobenzaldehyde isonicotinoylhydrazone, C₁₃H₉Cl₂N₃O, (II), the molecules are linked by a combination of N—H⋯N, C—H⋯N and C—H⋯O hydrogen bonds into sheets of R₄⁴(14) and R₄⁴(26) rings.

Comment

Tuberculosis is again a worldwide problem, due in part to the advent of multi-drug resistant strains and the association of tuberculosis with human immunodeficiency virus infection in AIDS. A first-line drug used in combination with other drugs

for the treatment of tuberculosis is isoniazid (isonicotinoylhydrazine). As part of a study of new derivatives of isoniazid, we now report the structures of 2,4-difluorobenzaldehyde isonicotinoylhydrazone, (I)

, and 2,3-dichlorobenzaldehyde isonicotinoylhydrazone, (II)

The leading torsion angles (Table 1) indicate that, while the molecules of compound (II) are nearly planar, in those of compound (I) not only is the central spacer unit between atoms C14 and C21 non-planar, but each of the rings, particularly the pyridyl ring, is twisted away from the mean plane of the adjacent spacer atoms.

Compound (I) (Fig. 1) exhibits orientational disorder of the difluorinated ring, such that one of the F atoms appears to be disordered over sites bonded to C22 and C26. The major conformer, with this F atom occupying the site designated F2, has occupancy 0.760 (3), while the minor conformer, with the disordered F atom occupying the site designated F6, has occupancy 0.240 (3).

The molecules of compound (I) are linked by a combination of N—H⋯O and C—H⋯O hydrogen bonds (Table 2) into a chain of rings, and these chains are linked into sheets by a single π–π stacking interaction. Atoms N17 and C27 in the molecule at (x, y, z) both act as hydrogen-bond donors to atom O1 in the molecule at ( $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z), so forming a C(4)C(7)[R₂¹(6)] chain of rings (Bernstein et al., 1995 ) running parallel to the [101] direction and generated by the n-glide plane at y = $[{1\over 4}]$ (Fig. 2).

The aryl ring in the molecule at (x, y, z) and the pyridyl ring in the molecules at ( $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z) and (− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z) are almost parallel, with a dihedral angle of only 0.6 (2)° between adjacent rings; the corresponding ring–centroid separations are 3.754 (2) Å, with an interplanar spacing of ca 3.394 Å and a ring offset of ca 1.60 Å. This interaction thus forms a chain parallel to the [10 $[\overline{1}]$ ] direction, which links the hydrogen-bonded [101] chains into an (010) sheet lying in the domain −0.01 < y < 0.51 (Fig. 3). A second such sheet, related to the first by inversion and generated by the n-glide plane at y = $[{3\over 4}]$ , lies in the domain 0.49 < y < 1.01, but there are no direction-specific interactions between adjacent (010 sheets.

The molecules of compound (II) (Fig. 4) are fully ordered, and they are linked into sheets by a combination of N—H⋯N, C—H⋯N and C—H⋯O hydrogen bonds. Atoms N17 and C13 in the molecule at (x, y, z) both act as hydrogen-bond donors to pyridyl atom N11 in the molecule at (1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z), so forming a C(4)C(7)[R₂¹(7)] chain of rings running parallel to the [010] direction and generated by the 2₁ screw axis along ( $[{1\over 2}]$ , y, $[{1\over 4}]$ ) (Fig. 5). In addition, atom C12 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O1 in the molecule at (x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z), so forming a C(6) chain running parallel to the [001] direction and generated by the c-glide plane at y = $[{3\over 4}]$ (Fig. 6). The combination of the [010] and [001] chains then generates a sheet parallel to (100) containing alternating R₄⁴(14) and R₄⁴(26) rings, where each type of ring is centrosymmetric (Fig. 7). There are no direction-specific interactions between adjacent sheets.

Figure 1
The major conformer (see Comment) of compound (I)

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

Figure 2
Part of the crystal structure of compound (I)

, showing the formation of a chain of rings along [101]. For the sake of clarity, only the major conformer is shown, and H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ( $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z) and (− $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z), respectively.

Figure 3
A stereoview of part of the crystal structure of compound (I)

, showing the formation of an (010) sheet of π-stacked [10 $[\overline{1}]$ ] chains. For the sake of clarity, only the major conformer is shown and H atoms not involved in the motifs shown have been omitted.

Figure 4
The molecule of compound (II)

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

Figure 5
Part of the crystal structure of compound (II)

, showing the formation of a chain of rings along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z) and (1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z), respectively.

Figure 6
Part of the crystal structure of compound (II)

, showing the formation of a C(6) chain along [001]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z) and (x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z), respectively.

Figure 7
A stereoview of part of the crystal structure of compound (II)

, showing the formation of a hydrogen-bonded (100) sheet. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Experimental

Equimolar mixtures of isoniazid (2 mmol) and the appropriate dihalobenzaldehyde (2 mmol) in tetrahydrofuran (20 ml) containing a catalytic amount of triethylamine were heated under reflux for 6 h in an atmosphere of dinitrogen. After cooling, the mixtures were concentrated under reduced pressure and the residues were purified by column chromatography on silica gel, eluting with a hexane–ethyl acetate gradient, to give pure samples of compounds (I) and (II). Crystallization from ethanol solutions gave crystals suitable for single-crystal X-ray diffraction. For (I), m.p. 501–503 K; for (II), m.p. 511–512 K. Spectroscopic analysis, for (I): ¹H NMR (DMSO-d₆): δ 12.43 (1H, s, NH), 8.82 (2H, d, J = 5.5 Hz), 8.67 (1H, s), 8.02 (1H, dd, J = 15.5 and 8.5 Hz), 7.85 (2H, d, J = 5.5 Hz), 7.40 (1H, dd, J = 9.5 and 11.0 Hz), 7.23 (1H, dd, J = 8.5 and 8.5 Hz); ¹³C NMR (DMSO-d₆): δ: 163.4 (dd, J = 13.2 and 250.5 Hz), 161.6, 161.1 (dd, J = 11.1 and 251.4 Hz), 150.4, 140.9, 140.1, 128.0 (d, J = 8.2 Hz), 121.4, 118.4 (d, J = 10.1 Hz), 112.7 (d, J = 21.9 Hz), 104.5 (t, J = 25.5 Hz); for (II): ¹H NMR (DMSO-d₆): δ 12.35 (1H, s, NH), 8.88 (1H, s), 8.79 (2H, d, J = 5.5 Hz), 7.98 (1H, d, J = 8.0 Hz), 7.83 (2H, d, J = 5.5 Hz), 7.71 (1H, d, J = 7.5 Hz), 7.45 (1H, dd, J = 7.5 and 8.0 Hz); ¹³C NMR (DMSO-d₆): δ 161.7, 150.4, 149.6, 144.6, 140.0, 133.7, 132.4, 131.8, 128.5, 125.6, 121.5; IR (KBr, ν, cm⁻¹), for (I): 3177 (NH) and 1654 (CO); for (II): 3188 (NH) and 1686 (CO).

Compound (I)

Crystal data

C₁₃H₉F₂N₃O
M_r = 261.23
Monoclinic, P 2₁ /n
a = 6.8859 (3) Å
b = 24.7258 (12) Å
c = 7.2582 (2) Å
β = 107.953 (2)°
V = 1175.61 (8) Å³
Z = 4
D_x = 1.476 Mg m⁻³
Mo Kα radiation
Cell parameters from 2658 reflections
θ = 3.2–27.5°
μ = 0.12 mm⁻¹
T = 120 (2) K
Block, colourless
0.60 × 0.35 × 0.10 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.946, T_max = 0.988
10256 measured reflections
2658 independent reflections
2231 reflections with I > 2σ(I)
R_int = 0.031
θ_max = 27.5°
h = −8 → 8
k = −32 → 30
l = −9 → 9

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.101
S = 1.07
2658 reflections
178 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.035P)² + 0.6726P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected torsion angles (°) for compounds (I) and (II)

	(I)	(II)
C13—C14—C17—N17	39.21 (19)	−1.9 (2)
C14—C17—N17—N27	178.39 (12)	−175.12 (12)
C17—N17—N27—C27	169.28 (13)	176.30 (13)
N17—N27—C27—C21	176.72 (12)	−178.28 (12)
N27—C27—C21—C22	168.76 (14)	−173.32 (13)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N17—H17⋯O1ⁱ	0.88	1.97	2.826 (2)	164
C27—H27⋯O1ⁱ	0.95	2.49	3.261 (2)	138
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Compound (II)

Crystal data

C₁₃H₉Cl₂N₃O
M_r = 294.13
Monoclinic, P 2₁ /c
a = 7.7369 (2) Å
b = 10.7764 (4) Å
c = 14.9091 (5) Å
β = 90.2400 (18)°
V = 1243.05 (7) Å³
Z = 4
D_x = 1.572 Mg m⁻³
Mo Kα radiation
Cell parameters from 2833 reflections
θ = 3.2–27.5°
μ = 0.52 mm⁻¹
T = 120 (2) K
Plate, colourless
0.30 × 0.10 × 0.07 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.861, T_max = 0.965
18370 measured reflections
2833 independent reflections
2466 reflections with I > 2σ(I)
R_int = 0.033
θ_max = 27.5°
h = −10 → 9
k = −13 → 13
l = −19 → 19

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.099
S = 1.15
2833 reflections
172 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0574P)² + 0.238P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 3
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N17—H17⋯N11ⁱ	0.88	2.22	3.079 (2)	164
C12—H12⋯O1ⁱⁱ	0.95	2.45	3.338 (2)	155
C13—H13⋯N11ⁱ	0.95	2.59	3.512 (2)	164
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

The space groups P2₁/n for (I) and P2₁/c for (II) were uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms, with distances C—H = 0.95 Å and N—H = 0.88 Å, and with U_iso(H) = 1.2U_eq(C,N). In compound (I), the disordered difluorinated ring was modelled using partially occupied hydrogen and fluorine sites adjacent to atoms C22 and C26, with the occupancies of the partially occupied hydrogen and partially occupied fluorine sites each constrained to sum to unity. The site-occupancy factors then refined to 0.760 (3) and 0.240 (3).

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

Supporting information

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S0108270105029136/sk1868sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105029136/sk1868Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105029136/sk1868IIsup3.hkl

Comment top

Tuberculosis is again a world-wide problem, due in part to the advent of multi-drug resistant strains and the association of tuberculosis with human immunodeficiency virus infection in AIDS. A first-line drug used in combination with other drugs for treatment of tuberculosis is isoniazid (isonitinoylhydrazine). As part of a study of new derivatives of isoniazid, we now report the structures of N-(isonicotinoyl)-2,4-difluorobenzaldehyde hydrazone, (I), and N-(isonicotinoyl)-2,3-dichlorobenzaldehyde hydrazone, (II).

The molecules of compound (I) are linked by a combination of N—H···O and C—H···O hydrogen bonds (Table 2) into a chain of rings, and these chains are linked into sheets by a single π–π stacking interaction. Atoms N17 and C27 in the molecule at (x, y, z) both act as hydrogen-bond donors to atom O1 in the molecule at (1/2 + x, 1/2 − y, 1/2 + z), so forming a C(4)C(7)[R₂¹(6)] chain of rings (Bernstein et al., 1995) running parallel to the [101] direction and generated by the n-glide plane at y = 1/4 (Fig. 2).

The aryl ring in the molecule at (x, y, z) and the pyridyl ring in the molecules at (1/2 + x, 1/2 − y, −1/2 + z) and (−1/2 + x, 1/2 − y, 1/2 + z) are almost parallel, with a dihedral angle of only 0.6 (2)° between adjacent rings. the corresponding ring–centroid separations are 3.754 (2) Å, with an interplanar spacing of ca 3.394 Å and a ring offset of ca 1.60 Å. This interaction thus forms a chain parallel to the [101] direction, which links the hydrogen-bonded [101] chains into an (010) sheet lying in the domain −0.01 < y < 0.51 (Fig. 3). A second such sheet, related to the first by inversion and generated by the n-glide plane at y = 3/4, lies in the domain 0.49 < y < 1.01, but there are no direction-specific interactions between adjacent (010 sheets.

The molecules of compound (II) (Fig. 4) are fully ordered, and they are linked into sheets by a combination of N—H···N, C—H···N and C—H···O hydrogen bonds. Atoms N17 and C13 in the molecule at (x, y, z) both act as hydrogen-bond donors to the pyridyl atom N11 in the molecule at (1 − x, −1/2 + y, 1/2 − z), so forming a C(4)C(7)[R₂¹(7)] chain of rings running parallel to the [010] direction and generated by the 2₁ screw axis along (1/2, y, 1/4) (Fig. 5). In addition, atom C12 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O1 in the molecule at (x, 3/2 − y, −1/2 + z), so forming C(6) chain running parallel to the [001] direction and generated by the c-glide plane at y = 3/4 (Fig. 6). The combination of the [010] and [001] chains then generates a sheet parallel to (100) containing alternating R₄⁴(14) and R₄⁴(26) rings, where each type of ring is centrosymmetric (Fig. 7). There are no direction-specific interactions between adjacent sheets.

Experimental top

Equimolar mixtures of isoniazid (2 mmol) and the appropriate dihalobenzaldehyde (2 mmol) in tetrahydrofuran (20 ml) containing a catalytic quantity of triethylamine were heated under reflux for 6 h in an atmosphere of dinitrogen. After cooling, the mixtures were concentrated under reduced pressure and the residues were purified by column chromatography on silica gel, eluting with hexane–ethyl acetate gradient, to give pure samples of compounds (I) and (II). Crystallization from ethanol solutions gave crystals suitable for single-crystal X-ray diffraction. For (I), m.p. 501–503 K; for (II), m.p. 511–512 K. Spectroscopic analysis, for (I): ¹H NMR (DMSO-d₆, δ, p.p.m.): 12.43 (1H, s, NH), 8.82 (2H, d, J = 5.5 Hz), 8.67 (1H, s), 8.02 (1H, dd, J = 15.5 and 8.5 Hz), 7.85 (2H, d, J = 5.5 Hz), 7.40 (1H, dd, J = 9.5 and 11.0 Hz), 7.23 (1H, dd, J= 8.5 and 8.5 Hz); ¹³C NMR (DMSO-d₆, δ, p.p.m.): 163.4 (dd, J = 13.2 and 250.5 Hz), 161.6, 161.1 (dd, J = 11.1 and 251.4 Hz) 150.4, 140.9, 140.1, 128.0 (d, J = 8.2 Hz), 121.4, 118.4 (d, J = 10.1 Hz), 112.7 (d, J = 21.9 Hz), 104.5 (t, J = 25.5 Hz); for (II): ¹H NMR (DMSO-d₆, δ, p.p.m.): 12.35 (1H, s, NH), 8.88 (1H, s), 8.79 (2H, d, J = 5.5 Hz), 7.98 (1H, d, J = 8.0 Hz), 7.83 (2H, d, J = 5.5 Hz), 7.71 (1H, d, J = 7.5 Hz), 7.45 (1H, dd, J = 7.5 and 8.0 Hz); ¹³C NMR (DMSO-d₆, δ, p.p.m.): 161.7, 150.4, 149.6, 144.6, 140.0, 133.7, 132.4, 131.8, 128.5, 125.6, 121.5; IR (KBr, ν, cm⁻¹), for (I): 3177 (NH) and 1654 (CO); for (II): 3188 (NH) and 1686 (CO).

Computing details top

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

Figures top

	Fig. 1. The major conformer (see text) of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of compound (I), showing the formation of a chain of rings along [101]. For the sake of clarity, only the major conformer is shown, and H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 + x, 1/2 − y, 1/2 + z) and (−1/2 + x, 1/2 − y, −1/2 + z), respectively.
	Fig. 3. A stereoview of part of the crystal structure of compound (I), showing the formation of an (010) sheet of π-stacked [101] chains. For the sake of clarity, only the major conformer is shown, and H atoms not involved in the motifs shown have been omitted.
	Fig. 4. The molecule of compound (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 5. Part of the crystal structure of compound (II), showing the formation of a chain of rings along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 − x, −1/2 + y, 1/2 − z) and (1 − x, 1/2 + y, 1/2 − z), respectively.
	Fig. 6. Part of the crystal structure of compound (II), showing the formation of a C(6) chain along [001]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, 3/2 − y, −1/2 + z) and (x, 3/2 − y, 1/2 + z), respectively.
	Fig. 7. A stereoview of part of the crystal structure of compound (II), showing the formation of a hydrogen-bonded (100) sheet. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

(I) 2,4-difluorobenzaldehyde isonicotinoylhydrazone top

Crystal data top

C₁₃H₉F₂N₃O	F(000) = 536
M_r = 261.23	D_x = 1.476 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2658 reflections
a = 6.8859 (3) Å	θ = 3.2–27.5°
b = 24.7258 (12) Å	µ = 0.12 mm⁻¹
c = 7.2582 (2) Å	T = 120 K
β = 107.953 (2)°	Block, colourless
V = 1175.61 (8) Å³	0.60 × 0.35 × 0.10 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	2658 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	2231 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −32→30
T_min = 0.946, T_max = 0.988	l = −9→9
10256 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.035P)² + 0.6726P] where P = (F_o² + 2F_c²)/3
2658 reflections	(Δ/σ)_max = 0.001
178 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₃H₉F₂N₃O	V = 1175.61 (8) Å³
M_r = 261.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.8859 (3) Å	µ = 0.12 mm⁻¹
b = 24.7258 (12) Å	T = 120 K
c = 7.2582 (2) Å	0.60 × 0.35 × 0.10 mm
β = 107.953 (2)°

Data collection top

Nonius KappaCCD area-detector diffractometer	2658 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2231 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.988	R_int = 0.031
10256 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.07	Δρ_max = 0.25 e Å⁻³
2658 reflections	Δρ_min = −0.28 e Å⁻³
178 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
F2	0.8073 (2)	0.45076 (5)	0.56591 (17)	0.0346 (4)	0.760 (3)
F4	0.72835 (17)	0.50298 (4)	−0.07066 (15)	0.0403 (3)
F6	0.6083 (6)	0.32559 (14)	0.0544 (5)	0.0317 (13)	0.240 (3)
O1	0.51293 (16)	0.19391 (4)	0.41215 (14)	0.0219 (2)
N11	0.7884 (2)	0.10916 (5)	1.06980 (18)	0.0258 (3)
N17	0.72223 (19)	0.25953 (5)	0.58717 (16)	0.0192 (3)
N27	0.68464 (18)	0.29395 (5)	0.42872 (17)	0.0189 (3)
C12	0.7607 (2)	0.16247 (6)	1.0840 (2)	0.0238 (3)
C13	0.7125 (2)	0.19749 (6)	0.9274 (2)	0.0198 (3)
C14	0.6889 (2)	0.17639 (6)	0.74432 (19)	0.0169 (3)
C15	0.7128 (2)	0.12117 (6)	0.7257 (2)	0.0187 (3)
C16	0.7642 (2)	0.08966 (6)	0.8920 (2)	0.0235 (3)
C17	0.6327 (2)	0.21063 (5)	0.56489 (19)	0.0180 (4)
C21	0.7347 (2)	0.38328 (6)	0.3252 (2)	0.0174 (3)
C22	0.7742 (2)	0.43710 (6)	0.3791 (2)	0.0236 (3)
C23	0.7718 (3)	0.47825 (6)	0.2506 (2)	0.0286 (4)
C24	0.7276 (2)	0.46374 (6)	0.0597 (2)	0.0261 (3)
C25	0.6819 (2)	0.41167 (7)	−0.0066 (2)	0.0266 (3)
C26	0.6863 (2)	0.37187 (6)	0.1282 (2)	0.0226 (3)
C27	0.7506 (2)	0.34208 (6)	0.4739 (2)	0.0181 (3)
H12	0.7751	0.1771	1.2086	0.029*
H13	0.6958	0.2351	0.9447	0.024*
H15	0.6944	0.1053	0.6023	0.022*
H16	0.7835	0.0520	0.8790	0.028*
H17	0.8159	0.2677	0.6969	0.023*
H27	0.8111	0.3512	0.6064	0.022*
H22	0.8046	0.4460	0.5124	0.028*	0.240 (3)
H23	0.7993	0.5147	0.2919	0.034*
H25	0.6485	0.4034	−0.1406	0.032*
H26	0.6555	0.3356	0.0855	0.038*	0.760 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F2	0.0587 (9)	0.0227 (6)	0.0207 (7)	−0.0062 (6)	0.0096 (6)	−0.0055 (5)
F4	0.0542 (7)	0.0306 (5)	0.0370 (6)	0.0013 (5)	0.0155 (5)	0.0180 (4)
F6	0.053 (3)	0.0194 (19)	0.023 (2)	−0.0074 (17)	0.0115 (18)	−0.0032 (15)
O1	0.0240 (6)	0.0197 (5)	0.0173 (5)	−0.0013 (4)	−0.0005 (4)	−0.0002 (4)
N11	0.0278 (7)	0.0274 (7)	0.0213 (6)	0.0004 (5)	0.0061 (5)	0.0057 (5)
N17	0.0215 (6)	0.0182 (6)	0.0143 (6)	−0.0023 (5)	0.0001 (5)	0.0024 (4)
N27	0.0192 (6)	0.0190 (6)	0.0175 (6)	0.0002 (5)	0.0041 (5)	0.0042 (5)
C12	0.0249 (8)	0.0293 (8)	0.0172 (7)	−0.0025 (6)	0.0065 (6)	−0.0008 (6)
C13	0.0198 (7)	0.0194 (7)	0.0201 (7)	−0.0011 (5)	0.0060 (6)	−0.0022 (5)
C14	0.0130 (7)	0.0192 (7)	0.0176 (7)	−0.0011 (5)	0.0034 (5)	0.0013 (5)
C15	0.0182 (7)	0.0189 (7)	0.0183 (7)	−0.0011 (5)	0.0048 (5)	−0.0018 (5)
C16	0.0246 (8)	0.0193 (7)	0.0262 (8)	0.0006 (6)	0.0073 (6)	0.0023 (6)
C17	0.0159 (9)	0.0202 (9)	0.0164 (9)	0.0005 (7)	0.0029 (7)	0.0004 (7)
C21	0.0139 (6)	0.0186 (7)	0.0194 (7)	0.0005 (5)	0.0048 (5)	0.0016 (5)
C22	0.0276 (8)	0.0228 (7)	0.0205 (7)	−0.0017 (6)	0.0073 (6)	−0.0026 (6)
C23	0.0351 (9)	0.0180 (7)	0.0335 (9)	−0.0016 (6)	0.0120 (7)	0.0010 (6)
C24	0.0264 (8)	0.0234 (7)	0.0285 (8)	0.0027 (6)	0.0086 (7)	0.0112 (6)
C25	0.0295 (8)	0.0311 (8)	0.0186 (7)	−0.0004 (7)	0.0064 (6)	0.0031 (6)
C26	0.0240 (8)	0.0206 (7)	0.0227 (7)	−0.0038 (6)	0.0064 (6)	−0.0016 (6)
C27	0.0163 (7)	0.0204 (7)	0.0164 (7)	0.0004 (5)	0.0034 (5)	0.0002 (5)

Geometric parameters (Å, º) top

N11—C16	1.339 (2)	C27—C21	1.4631 (19)
N11—C12	1.340 (2)	C27—H27	0.95
C12—C13	1.386 (2)	C21—C22	1.390 (2)
C12—H12	0.95	C21—C26	1.393 (2)
C13—C14	1.3895 (19)	C22—F2	1.3465 (19)
C13—H13	0.95	C22—C23	1.377 (2)
C14—C15	1.387 (2)	C22—H22	0.95
C14—C17	1.5006 (19)	C23—C24	1.372 (2)
C15—C16	1.388 (2)	C23—H23	0.95
C15—H15	0.95	C24—F4	1.3564 (17)
C16—H16	0.95	C24—C25	1.377 (2)
C17—O1	1.2315 (17)	C25—C26	1.382 (2)
C17—N17	1.3442 (18)	C25—H25	0.95
N17—N27	1.3894 (16)	C26—F6	1.307 (4)
N17—H17	0.88	C26—H26	0.95
N27—C27	1.2799 (18)

C16—N11—C12	116.74 (13)	N27—C27—H27	119.4
N11—C12—C13	123.73 (14)	C21—C27—H27	119.4
N11—C12—H12	118.1	C22—C21—C26	116.53 (13)
C13—C12—H12	118.1	C22—C21—C27	119.69 (13)
C12—C13—C14	118.54 (14)	C26—C21—C27	123.76 (13)
C12—C13—H13	120.7	F2—C22—C23	117.36 (14)
C14—C13—H13	120.7	F2—C22—C21	118.76 (14)
C15—C14—C13	118.70 (13)	C23—C22—C21	123.80 (14)
C15—C14—C17	118.54 (12)	C23—C22—H22	118.1
C13—C14—C17	122.74 (13)	C21—C22—H22	118.1
C14—C15—C16	118.32 (13)	C24—C23—C22	116.34 (14)
C14—C15—H15	120.8	C24—C23—H23	121.8
C16—C15—H15	120.8	C22—C23—H23	121.8
N11—C16—C15	123.96 (14)	F4—C24—C23	118.06 (14)
N11—C16—H16	118.0	F4—C24—C25	118.32 (14)
C15—C16—H16	118.0	C23—C24—C25	123.61 (14)
O1—C17—N17	124.42 (13)	C24—C25—C26	117.74 (14)
O1—C17—C14	120.92 (12)	C24—C25—H25	121.1
N17—C17—C14	114.65 (12)	C26—C25—H25	121.1
C17—N17—N27	119.34 (11)	F6—C26—C25	114.62 (19)
C17—N17—H17	119.8	F6—C26—C21	122.42 (19)
N27—N17—H17	120.4	C25—C26—C21	121.94 (14)
C27—N27—N17	113.36 (11)	C25—C26—H26	119.1
N27—C27—C21	121.22 (13)	C21—C26—H26	119.0

C16—N11—C12—C13	−0.9 (2)	N27—C27—C21—C26	−13.0 (2)
N11—C12—C13—C14	0.7 (2)	C26—C21—C22—F2	175.32 (14)
C12—C13—C14—C15	0.6 (2)	C27—C21—C22—F2	−6.3 (2)
C12—C13—C14—C17	178.76 (13)	C26—C21—C22—C23	−1.3 (2)
C13—C14—C15—C16	−1.6 (2)	C27—C21—C22—C23	177.04 (15)
C17—C14—C15—C16	−179.82 (13)	F2—C22—C23—C24	−176.81 (15)
C12—N11—C16—C15	−0.2 (2)	C21—C22—C23—C24	−0.1 (2)
C14—C15—C16—N11	1.4 (2)	C22—C23—C24—F4	−178.56 (14)
C15—C14—C17—O1	37.62 (19)	C22—C23—C24—C25	1.7 (3)
C13—C14—C17—O1	−140.55 (14)	F4—C24—C25—C26	178.55 (14)
C15—C14—C17—N17	−142.61 (14)	C23—C24—C25—C26	−1.7 (3)
C13—C14—C17—N17	39.21 (19)	C24—C25—C26—F6	168.8 (2)
O1—C17—N17—N27	−1.9 (2)	C24—C25—C26—C21	0.1 (2)
C14—C17—N17—N27	178.39 (12)	C22—C21—C26—F6	−166.5 (2)
C17—N17—N27—C27	169.28 (13)	C27—C21—C26—F6	15.2 (3)
N17—N27—C27—C21	176.72 (12)	C22—C21—C26—C25	1.3 (2)
N27—C27—C21—C22	168.76 (14)	C27—C21—C26—C25	−176.98 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17···O1ⁱ	0.88	1.97	2.826 (2)	164
C27—H27···O1ⁱ	0.95	2.49	3.261 (2)	138

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

(II) 2,3-dichlorobenzaldehyde isonicotinoylhydrazone top

Crystal data top

C₁₃H₉Cl₂N₃O	F(000) = 600
M_r = 294.13	D_x = 1.572 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2833 reflections
a = 7.7369 (2) Å	θ = 3.2–27.5°
b = 10.7764 (4) Å	µ = 0.52 mm⁻¹
c = 14.9091 (5) Å	T = 120 K
β = 90.2400 (18)°	Plate, colourless
V = 1243.05 (7) Å³	0.30 × 0.10 × 0.07 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	2833 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode	2466 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ϕ and ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
T_min = 0.861, T_max = 0.965	l = −19→19
18370 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0574P)² + 0.238P] where P = (F_o² + 2F_c²)/3
2833 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₁₃H₉Cl₂N₃O	V = 1243.05 (7) Å³
M_r = 294.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7369 (2) Å	µ = 0.52 mm⁻¹
b = 10.7764 (4) Å	T = 120 K
c = 14.9091 (5) Å	0.30 × 0.10 × 0.07 mm
β = 90.2400 (18)°

Data collection top

Nonius KappaCCD area-detector diffractometer	2833 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2466 reflections with I > 2σ(I)
T_min = 0.861, T_max = 0.965	R_int = 0.033
18370 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.15	Δρ_max = 0.42 e Å⁻³
2833 reflections	Δρ_min = −0.49 e Å⁻³
172 parameters

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

	x	y	z	U_iso*/U_eq
Cl2	0.04940 (5)	0.24580 (4)	0.42803 (2)	0.02352 (14)
Cl3	−0.10886 (5)	0.09016 (3)	0.58410 (3)	0.02128 (13)
O1	0.51413 (15)	0.78229 (11)	0.53171 (7)	0.0230 (3)
N11	0.63516 (16)	0.99082 (12)	0.23853 (9)	0.0196 (3)
N17	0.39121 (15)	0.64469 (12)	0.43497 (8)	0.0161 (3)
N27	0.32647 (16)	0.57712 (11)	0.50549 (9)	0.0168 (3)
C12	0.5589 (2)	0.88125 (15)	0.22055 (10)	0.0199 (3)
C13	0.5094 (2)	0.79782 (15)	0.28652 (10)	0.0191 (3)
C14	0.53873 (18)	0.82704 (14)	0.37632 (10)	0.0151 (3)
C15	0.62092 (19)	0.93893 (15)	0.39518 (11)	0.0185 (3)
C16	0.6659 (2)	1.01645 (15)	0.32536 (11)	0.0209 (3)
C17	0.48243 (19)	0.74973 (13)	0.45513 (11)	0.0162 (3)
C21	0.15624 (18)	0.40883 (13)	0.55589 (10)	0.0150 (3)
C22	0.06857 (18)	0.29789 (14)	0.53716 (10)	0.0158 (3)
C23	−0.00409 (19)	0.22879 (14)	0.60658 (10)	0.0167 (3)
C24	0.0077 (2)	0.26876 (15)	0.69431 (11)	0.0220 (3)
C25	0.0932 (2)	0.37925 (16)	0.71337 (11)	0.0249 (4)
C26	0.1665 (2)	0.44816 (15)	0.64513 (11)	0.0197 (3)
C27	0.23389 (18)	0.48333 (14)	0.48410 (10)	0.0163 (3)
H12	0.5380	0.8600	0.1596	0.024*
H13	0.4560	0.7215	0.2706	0.023*
H15	0.6458	0.9617	0.4554	0.022*
H16	0.7220	1.0924	0.3395	0.025*
H17	0.3793	0.6147	0.3804	0.019*
H24	−0.0420	0.2212	0.7413	0.026*
H25	0.1012	0.4076	0.7736	0.030*
H26	0.2248	0.5234	0.6591	0.024*
H27	0.2157	0.4622	0.4229	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl2	0.0362 (3)	0.0209 (2)	0.0135 (2)	−0.00425 (15)	−0.00043 (16)	−0.00294 (14)
Cl3	0.0249 (2)	0.0160 (2)	0.0230 (2)	−0.00380 (14)	0.00022 (15)	0.00012 (14)
O1	0.0329 (6)	0.0217 (6)	0.0143 (6)	−0.0044 (5)	−0.0022 (5)	0.0003 (5)
N11	0.0241 (7)	0.0165 (7)	0.0182 (7)	−0.0001 (5)	0.0005 (5)	0.0018 (5)
N17	0.0207 (6)	0.0152 (6)	0.0124 (6)	−0.0001 (5)	0.0011 (5)	0.0024 (5)
N27	0.0174 (6)	0.0162 (7)	0.0167 (7)	0.0014 (5)	0.0011 (5)	0.0032 (5)
C12	0.0260 (8)	0.0187 (8)	0.0148 (8)	−0.0005 (6)	−0.0003 (6)	−0.0015 (6)
C13	0.0243 (8)	0.0159 (8)	0.0171 (8)	−0.0025 (6)	−0.0009 (6)	−0.0009 (6)
C14	0.0150 (7)	0.0140 (7)	0.0163 (8)	0.0029 (5)	0.0000 (5)	0.0016 (6)
C15	0.0220 (7)	0.0181 (8)	0.0153 (8)	−0.0004 (6)	−0.0025 (6)	−0.0008 (6)
C16	0.0243 (8)	0.0187 (8)	0.0198 (8)	−0.0038 (6)	−0.0017 (6)	−0.0003 (6)
C17	0.0173 (7)	0.0145 (8)	0.0168 (8)	0.0024 (5)	−0.0002 (6)	0.0014 (6)
C21	0.0154 (7)	0.0150 (7)	0.0148 (7)	0.0036 (5)	0.0006 (5)	0.0012 (6)
C22	0.0173 (7)	0.0171 (8)	0.0130 (7)	0.0033 (6)	−0.0019 (5)	−0.0010 (6)
C23	0.0169 (7)	0.0143 (7)	0.0187 (8)	0.0011 (6)	0.0001 (6)	0.0003 (6)
C24	0.0264 (8)	0.0234 (8)	0.0162 (8)	−0.0026 (6)	0.0037 (6)	0.0017 (6)
C25	0.0337 (9)	0.0265 (9)	0.0147 (8)	−0.0060 (7)	0.0013 (7)	−0.0034 (7)
C26	0.0233 (8)	0.0181 (8)	0.0175 (8)	−0.0029 (6)	0.0002 (6)	−0.0023 (6)
C27	0.0176 (7)	0.0166 (8)	0.0146 (7)	0.0032 (6)	0.0004 (5)	0.0004 (6)

Geometric parameters (Å, º) top

N11—C16	1.344 (2)	N27—C27	1.2785 (19)
N11—C12	1.346 (2)	C27—C21	1.469 (2)
C12—C13	1.388 (2)	C27—H27	0.95
C12—H12	0.95	C21—C26	1.398 (2)
C13—C14	1.393 (2)	C21—C22	1.402 (2)
C13—H13	0.95	C22—C23	1.395 (2)
C14—C15	1.391 (2)	C22—Cl2	1.7270 (15)
C14—C17	1.506 (2)	C23—C24	1.380 (2)
C15—C16	1.381 (2)	C23—Cl3	1.7318 (16)
C15—H15	0.95	C24—C25	1.391 (2)
C16—H16	0.95	C24—H24	0.95
C17—O1	1.2183 (19)	C25—C26	1.383 (2)
C17—N17	1.3667 (19)	C25—H25	0.95
N17—N27	1.3751 (17)	C26—H26	0.95
N17—H17	0.88

C16—N11—C12	116.60 (13)	C27—N27—N17	115.68 (13)
N11—C12—C13	123.31 (14)	N27—C27—C21	118.74 (14)
N11—C12—H12	118.3	N27—C27—H27	120.6
C13—C12—H12	118.3	C21—C27—H27	120.6
C12—C13—C14	119.37 (14)	C26—C21—C22	118.26 (14)
C12—C13—H13	120.3	C26—C21—C27	120.40 (14)
C14—C13—H13	120.3	C22—C21—C27	121.33 (13)
C15—C14—C13	117.55 (14)	C23—C22—C21	120.23 (14)
C15—C14—C17	117.07 (13)	C23—C22—Cl2	119.48 (12)
C13—C14—C17	125.33 (14)	C21—C22—Cl2	120.29 (11)
C16—C15—C14	119.25 (14)	C24—C23—C22	120.75 (14)
C16—C15—H15	120.4	C24—C23—Cl3	118.81 (12)
C14—C15—H15	120.4	C22—C23—Cl3	120.44 (12)
N11—C16—C15	123.89 (15)	C23—C24—C25	119.38 (15)
N11—C16—H16	118.1	C23—C24—H24	120.3
C15—C16—H16	118.1	C25—C24—H24	120.3
O1—C17—N17	123.12 (14)	C26—C25—C24	120.36 (15)
O1—C17—C14	120.92 (13)	C26—C25—H25	119.8
N17—C17—C14	115.93 (13)	C24—C25—H25	119.8
C17—N17—N27	117.38 (13)	C25—C26—C21	121.01 (15)
C17—N17—H17	124.0	C25—C26—H26	119.5
N27—N17—H17	118.4	C21—C26—H26	119.5

C16—N11—C12—C13	1.4 (2)	N27—C27—C21—C26	7.4 (2)
N11—C12—C13—C14	0.0 (2)	N27—C27—C21—C22	−173.32 (13)
C12—C13—C14—C15	−1.4 (2)	C26—C21—C22—C23	−0.8 (2)
C12—C13—C14—C17	176.01 (14)	C27—C21—C22—C23	180.00 (13)
C13—C14—C15—C16	1.4 (2)	C26—C21—C22—Cl2	179.17 (11)
C17—C14—C15—C16	−176.26 (13)	C27—C21—C22—Cl2	−0.08 (19)
C12—N11—C16—C15	−1.4 (2)	C21—C22—C23—C24	0.6 (2)
C14—C15—C16—N11	0.0 (2)	Cl2—C22—C23—C24	−179.36 (12)
C15—C14—C17—O1	−2.8 (2)	C21—C22—C23—Cl3	−178.73 (11)
C13—C14—C17—O1	179.78 (15)	Cl2—C22—C23—Cl3	1.35 (18)
C15—C14—C17—N17	175.51 (13)	C22—C23—C24—C25	0.0 (2)
C13—C14—C17—N17	−1.9 (2)	Cl3—C23—C24—C25	179.32 (13)
O1—C17—N17—N27	3.1 (2)	C23—C24—C25—C26	−0.4 (3)
C14—C17—N17—N27	−175.12 (12)	C24—C25—C26—C21	0.2 (2)
C17—N17—N27—C27	176.30 (13)	C22—C21—C26—C25	0.4 (2)
N17—N27—C27—C21	−178.28 (12)	C27—C21—C26—C25	179.65 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17···N11ⁱ	0.88	2.22	3.079 (2)	164
C12—H12···O1ⁱⁱ	0.95	2.45	3.338 (2)	155
C13—H13···N11ⁱ	0.95	2.59	3.512 (2)	164

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+3/2, z−1/2.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₃H₉F₂N₃O	C₁₃H₉Cl₂N₃O
M_r	261.23	294.13
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/c
Temperature (K)	120	120
a, b, c (Å)	6.8859 (3), 24.7258 (12), 7.2582 (2)	7.7369 (2), 10.7764 (4), 14.9091 (5)
β (°)	107.953 (2)	90.2400 (18)
V (Å³)	1175.61 (8)	1243.05 (7)
Z	4	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.12	0.52
Crystal size (mm)	0.60 × 0.35 × 0.10	0.30 × 0.10 × 0.07

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.946, 0.988	0.861, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	10256, 2658, 2231	18370, 2833, 2466
R_int	0.031	0.033
(sin θ/λ)_max (Å⁻¹)	0.649	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.101, 1.07	0.031, 0.099, 1.15
No. of reflections	2658	2833
No. of parameters	178	172
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.28	0.42, −0.49

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

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

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17···O1ⁱ	0.88	1.97	2.826 (2)	164
C27—H27···O1ⁱ	0.95	2.49	3.261 (2)	138

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

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

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17···N11ⁱ	0.88	2.22	3.079 (2)	164
C12—H12···O1ⁱⁱ	0.95	2.45	3.338 (2)	155
C13—H13···N11ⁱ	0.95	2.59	3.512 (2)	164

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+3/2, z−1/2.

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

Parameter	(I)	(II)
C13-C14-C17-N17	39.21 (19)	-1.9 (2)
C14-C17-N17-N27	178.39 (12)	-175.12 (12)
C17-N17-N27-C27	169.28 (13)	176.30 (13)
N17-N27-C27-C21	176.72 (12)	-178.28 (12)
N27-C27-C21-C22	168.76 (14)	-173.32 (13)

Acknowledgements

The X-ray data were collected at the EPSRC X-Ray Crystallographic 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.

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
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands. 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

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ISSN: 2053-2296

Volume 61| Part 10| October 2005| Pages o617-o620

doi:10.1107/S0108270105029136

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

π-Stacked hydrogen-bonded chains of rings in 2,4-di­fluoro­benzaldehyde isonicotinoylhydrazone and hydrogen-bonded sheets in 2,3-di­chloro­benzaldehyde isonicotinoylhydrazone

Comment

Experimental

Compound (I)

Crystal data

Data collection

Refinement

Compound (II)

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

π-Stacked hydrogen-bonded chains of rings in 2,4-difluorobenzaldehyde isonicotinoylhydrazone and hydrogen-bonded sheets in 2,3-dichlorobenzaldehyde isonicotinoylhydrazone