4-Cyano­benzaldehyde isonicotinoylhydrazone monohydrate: a three-dimensional hydrogen-bonded ­framework structure

Souza, M.V.N. de; Wardell, S.M.S.V.; Wardell, J.L.; Low, J.N.; Glidewell, C.

doi:10.1107/S0108270107002788

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 63| Part 3| March 2007| Pages o166-o168

doi:10.1107/S0108270107002788

4-Cyanobenzaldehyde isonicotinoylhydrazone monohydrate: a three-dimensional hydrogen-bonded framework structure

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

^aInstituto de Tecnologia em Fármacos, Far-Manguinhos, FIOCRUZ, 21041-250 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 15 December 2006; accepted 18 January 2007; online 10 February 2007)

In the title compound, C₁₄H₁₀N₄O·H₂O, the molecular components are linked into a three-dimensional framework by three hydrogen bonds, one each of the O—H⋯O, O—H⋯N and N—H⋯O types, weakly augmented by two C—H⋯O hydrogen bonds.

Comment

As part of a more general study of isonicotinoylhydrazones (Wardell, de Souza, Ferreira et al., 2005 ; Wardell, de Souza, Wardell et al., 2005 ; Wardell et al., 2006 ; Low et al., 2006 ), we report here the molecular and supramolecular structure of the title compound, (I) (Fig. 1), which was crystallized from damp ethanol as a stoichiometric monohydrate.

The central spacer unit of the hydrazone component, between atoms C14 and C21 (Fig. 1), is effectively planar with an all-trans extended-chain conformation, as shown by the key torsion angles (Table 1); the two rings, on the other hand, are each rotated out of this plane, so that the hydrazone molecules have no internal symmetry and thus are chiral. While the bulk sample is racemic, in the absence of any inversion twinning, each crystal contains only a single enantiomer.

Within the selected asymmetric unit, the two independent molecular components are linked by an almost linear N—H⋯O hydrogen bond, weakly augmented by a C—H⋯O hydrogen bond (Fig. 1 and Table 2). These bimolecular units are then linked into a three-dimensional framework by one O—H⋯N and one O—H⋯O hydrogen bond, whose action may be weakly augmented by a second C—H⋯O hydrogen bond, although this augmentation is not essential to the framework formation. The formation of the framework is readily analysed in terms of three one-dimensional substructures, one formed by the inter-aggregate O—H⋯O hydrogen bond, one formed by the inter-aggregate O—H⋯N hydrogen bond and one involving both of these interactions. For the sake of simplicity, we shall omit any further consideration of the C—H⋯O hydrogen bonds, which are both likely to be weak, and which do not influence the overall dimensionality of the supramolecular structure.

In the first substructure, water atom O2 at (x, y, z) acts as a hydrogen-bond donor, via H2A, to carbonyl atom O1 at (1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z), so forming a C₂²(6) (Bernstein et al., 1995 ) chain running parallel to the [010] direction and generated by the 2₁ screw axis along ( $[1\over2]$ , y, $[1\over4]$ ) (Fig. 2). In the second substructure, water atom O2 at (x, y, z) acts as a hydrogen-bond donor, this time via H2B, to pyridyl atom N11 at ( $[{3\over 2}]$ − x, 1 − y, $[{1\over 2}]$ + z), so forming a C₂²(9) chain running parallel to the [001] direction and generated by the 2₁ screw axis along ( $[3\over4]$ , $[1\over2]$ , z) (Fig. 3). Each of these two chains involves only one type of inter-aggregate hydrogen bond; the alternation of the two types of inter-aggregate hydrogen bond generates a C₄⁴(15) chain running parallel to the [100] direction (Fig. 4). The combination of the two chain motifs, along [100], [010] and [001], is sufficient to link all the molecules into a single three-dimensional framework structure.

Figure 1
The independent molecular components of compound (I)

, showing the atom-labelling scheme and the N—H⋯O hydrogen bond within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.

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

, showing the formation of a C₂²(6) chain along [010] built from N—H⋯O and O—H⋯O hydrogen bonds only. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z) and (1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z), respectively.

Figure 3
Part of the crystal structure of compound (I)

, showing the formation of a C₂²(9) chain along [001] built from N—H⋯O and O—H⋯N hydrogen bonds only. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ( $[{3\over 2}]$ − x, 1 − y, − $[{1\over 2}]$ + z) and ( $[{3\over 2}]$ − x, 1 − y, $[{1\over 2}]$ + z), respectively.

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

, showing the formation of a C₄⁴(15) chain along [100] built from N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms have been omitted.

Experimental

A mixture of 4-cyanobenzaldehyde and isonicotinoylhydrazine (10 mmol of each) in tetrahydrofuran (20 ml) was heated under reflux until thin-layer chromatography (on silica gel, with a chloroform/methanol mixture as eluant) indicated complete reaction (ca 4 h reaction time). The solution was cooled and the solvent was removed under reduced pressure; the residue was washed successively with cold ethanol and then diethyl ether, and the resulting solid product was recrystallized from reagent-grade ethanol (ethanol/water, 97:3 v/v) to give crystals of the monohydrate (I) suitable for single-crystal X-ray diffraction (yield 76%; m.p. 498–499 K). GC/MS m/z 250 [M]⁺. NMR (DMSO-d₆): δ(H) 7.83 (2H, d, J = 5.5 Hz, H13 and H15), 7.94 (4H, m, H22, H23, H25 and H26), 8.52 (1H, s, N=C—H), 8.80 (2H, d, J = 5.5 Hz, H12 and H16), 12.31 (1H, s, NH); δ(C) 161.9, 150.4, 147.0, 140.2, 138.4, 132.8, 127.8, 121.5, 118.6, 112.2. IR (KBr pellets, cm⁻¹): 3163 (NH), 2223 (CN), 1668 (C=O).

Crystal data

C₁₄H₁₀N₄O·H₂O
M_r = 268.28
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.9692 (2) Å
b = 12.3802 (5) Å
c = 14.5513 (7) Å
V = 1255.49 (9) Å³
Z = 4
D_x = 1.419 Mg m⁻³
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 120 (2) K
Needle, colourless
0.62 × 0.04 × 0.03 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.956, T_max = 0.997
14838 measured reflections
1664 independent reflections
1437 reflections with I > 2σ(I)
R_int = 0.069
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.107
S = 1.06
1664 reflections
181 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0426P)² + 0.6011P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Selected torsion angles (°)

C13—C14—C17—N17	28.8 (3)
C14—C17—N17—N27	176.7 (2)
C17—N17—N27—C27	179.0 (2)
N17—N27—C27—C21	179.9 (2)
N27—C27—C21—C22	168.0 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N17—H17⋯O2	0.90	1.95	2.845 (3)	174
O2—H2A⋯O1ⁱ	0.95	1.94	2.858 (3)	162
O2—H2B⋯N11ⁱⁱ	0.95	1.85	2.801 (3)	174
C13—H13⋯O2	0.95	2.44	3.122 (3)	129
C13—H13⋯O1ⁱ	0.95	2.51	3.243 (3)	134
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ .

The space group P2₁2₁2₁ was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C or N atoms were assigned C—H distances of 0.95 Å and N—H distances of 0.90 Å [U_iso(H) = 1.2U_eq(C,N)]; H atoms bonded to O atoms were permitted to ride at the positions derived from the difference maps, with O—H distances of 0.95 Å and U_iso(H) values of 1.5U_eq(O). In the absence of significant resonance scattering it was not possible to establish the absolute configuration of the molecules in the crystal selected for data collection, although this configuration has no chemical significance; accordingly, the Friedel equivalent reflections were merged prior to the final refinements.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270107002788/av3063sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270107002788/av3063Isup2.hkl

Comment top

As part of a more general study of isonicotinoylhydrazones (Wardell, de Souza, Ferreira et al., 2005; Wardell, de Souza, Wardell et al., 2005; Wardell et al., 2006; Low et al., 2006), we report here the molecular and supramolecular structure of the title compound, (I) (Fig. 1), which was crystallized from damp ethanol as a stoichiometric monohydrate.

The central spacer unit of the hydrazone component, between atoms C14 and C21 (Fig. 1), is effectively planar with an all-trans extended-chain conformation, as shown by the key torsion angles (Table 1); the two rings, on the other hand, are each rotated out of this plane, so that the hydrazone molecules have no internal symmetry, and thus are chiral. While the bulk sample is racemic, in the absence of any inversion twinning, each crystal contains only a single enantiomer.

Within the selected asymmetric unit, the two independent molecular components are linked by an almost linear N—H···O hydrogen bond, weakly augmented by a C—H···O hydrogen bond (Fig. 1 and Table 1). These bimolecular units are then linked into a three-dimensional framework by one O—H···N hydrogen bond and by one O—H···O hydrogen bond, whose action may be weakly augmented by a second C—H···O hydrogen bond, although this augmentation is not essential to the framework formation. The formation of the framework is readily analysed in terms of three one-dimensional substructures, one formed by the inter-aggregate O—H···O hydrogen bond, one formed by the inter-aggregate O—H···N hydrogen bond and one involving both of these interactions. For the sake of simplicity we shall omit any further consideration of the C—H···O hydrogen bonds, which are both likely to be weak, and which do not influence the overall dimensionality of the supramolecular structure.

In the first substructure, water atom O2 at (x, y, z) acts as a hydrogen-bond donor, via H2A, to the carbonyl atom O1 at (1 - x, -1/2 + y, 1/2 - z), so forming a C²₂(6) (Bernstein et al., 1995) chain running parallel to the [010] direction and generated by the 2₁ screw axis along (1/2, y, 1/4) (Fig. 2). In the second substructure, water atom O2 at (x, y, z) acts as a hydrogen-bond donor, this time via H2B, to the pyridyl atom N11 at (3/2 - x, 1 - y, 1/2 + z), so forming a C²₂(9) chain running parallel to the [001] direction and generated by the 2₁ screw axis along (3/4, 1/2, z) (Fig. 3). Each of these two chains involves only one type of inter-aggregate hydrogen bond; the alternation of the two types of inter-aggregate hydrogen bond generates a C⁴₄(15) chain running parallel to the [100] direction (Fig. 4). The combination of the two chain motifs, along [100], [010] and [001], is sufficient to link all the molecules into a single three-dimensional framework structure.

Related literature top

For related literature, see: Bernstein et al. (1995); Low et al. (2006); Wardell et al. (2006); Wardell, de Souza, Ferreira, Vasconcelos, Low & Glidewell (2005); Wardell, de Souza, Wardell, Low & Glidewell (2005).

Experimental top

A mixture of 4-cyanobenzaldehyde and isonicotinoylhydrazine (10 mmol of each) in tetrahydrofuran (20 ml) was heated under reflux, until thin-layer chromatography (on silica gel, with a chloroform/methanol mixture as eluant) indicated complete reaction (ca 4 h reaction time). The solution was cooled, and the solvent was removed under reduced pressure; the residue was washed successively with cold ethanol and then diethyl ether, and the resulting solid product was recrystallized from reagent-grade ethanol (ethanol/water, 97:3 v/v) to give crystals of the monohydrate (I) suitable for single-crystal X-ray diffraction (yield 76%, m.p. 498–499 K). GC/MS m/z 250 [M]⁺. NMR (DMSO-d₆): δ(H) 7.83 (2H, d, J = 5.5 Hz, H13 and H15), 7.94 (4H, m, H22, H23, H25 and H26), 8.52 (1H, s, N═C—H), 8.80 (2H, d, J = 5.5 Hz, H12 and H16), 12.31 (1H, s, NH); δ(C) 161.9, 150.4, 147.0, 140.2, 138.4, 132.8, 127.8, 121.5, 118.6, 112.2. IR (KBr pellets, cm^-1): 3163 (NH), 2223 (CN), 1668 (C═O).

Computing details top

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 independent molecular components of compound (I), showing the atom-labelling scheme and the N—H···O hydrogen bond within the selected asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of compound (I) showing the formation of a C²₂(6) chain along [010] built from N—H···O and O—H···O hydrogen bonds only. For the sake of clarity, the H atoms bonded to C atoms have been omitted. The 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. 3. Part of the crystal structure of compound (I), showing the formation of a C²₂(9) chain along [001] built from N—H···O and O—H···N hydrogen bonds only. For the sake of clarity, the H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (3/2 - x, 1 - y, -1/2 + z) and (3/2 - x, 1 - y, 1/2 + z) respectively.
	Fig. 4. A stereoview of part of the crystal structure of compound (I) showing the formation of a C⁴₄(15) chain along [100] built from N—H···O, O—H···O and O—H···N hydrogen bonds. For the sake of clarity, the H atoms bonded to C atoms have been omitted.

4-Cyanobenzaldehyde isonicotinoylhydrazone monohydrate top

Crystal data top

C₁₄H₁₀N₄O·H₂O	F(000) = 560
M_r = 268.28	D_x = 1.419 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1664 reflections
a = 6.9692 (2) Å	θ = 3.2–27.5°
b = 12.3802 (5) Å	µ = 0.10 mm⁻¹
c = 14.5513 (7) Å	T = 120 K
V = 1255.49 (9) Å³	Needle, colourless
Z = 4	0.62 × 0.04 × 0.03 mm

Data collection top

Bruker–Nonius KappaCCD diffractometer	1664 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1437 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ϕ and ω scans	h = −8→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −15→16
T_min = 0.956, T_max = 0.997	l = −18→16
14838 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0426P)² + 0.6011P] where P = (F_o² + 2F_c²)/3
1664 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₄H₁₀N₄O·H₂O	V = 1255.49 (9) Å³
M_r = 268.28	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.9692 (2) Å	µ = 0.10 mm⁻¹
b = 12.3802 (5) Å	T = 120 K
c = 14.5513 (7) Å	0.62 × 0.04 × 0.03 mm

Data collection top

Bruker–Nonius KappaCCD diffractometer	1664 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1437 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.997	R_int = 0.069
14838 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	Δρ_max = 0.25 e Å⁻³
1664 reflections	Δρ_min = −0.20 e Å⁻³
181 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.5854 (3)	0.87688 (14)	0.25628 (12)	0.0256 (4)
O2	0.6942 (3)	0.49433 (16)	0.34695 (13)	0.0357 (5)
N11	0.6539 (3)	0.60244 (19)	0.00504 (14)	0.0256 (5)
N17	0.6212 (3)	0.72012 (18)	0.33699 (13)	0.0207 (5)
N24	0.5886 (4)	0.94939 (19)	0.91661 (16)	0.0315 (6)
N27	0.6188 (3)	0.77410 (18)	0.42019 (14)	0.0218 (5)
C12	0.5845 (4)	0.5548 (2)	0.08036 (17)	0.0243 (6)
C13	0.5670 (4)	0.6063 (2)	0.16461 (16)	0.0213 (5)
C14	0.6212 (4)	0.7137 (2)	0.17152 (15)	0.0188 (5)
C15	0.6884 (4)	0.7656 (2)	0.09294 (16)	0.0218 (6)
C16	0.7044 (4)	0.7068 (2)	0.01244 (17)	0.0243 (6)
C17	0.6062 (3)	0.77877 (19)	0.25858 (16)	0.0174 (5)
C21	0.6297 (4)	0.7652 (2)	0.58305 (18)	0.0219 (6)
C22	0.6060 (4)	0.7004 (2)	0.66048 (17)	0.0249 (6)
C23	0.5973 (4)	0.7464 (2)	0.74722 (19)	0.0226 (6)
C24	0.6104 (4)	0.8584 (2)	0.75670 (17)	0.0221 (6)
C25	0.6398 (4)	0.9230 (2)	0.67913 (17)	0.0255 (6)
C26	0.6508 (4)	0.8769 (2)	0.59356 (17)	0.0256 (6)
C27	0.6308 (4)	0.7142 (2)	0.49162 (17)	0.0233 (5)
C241	0.5978 (4)	0.9089 (2)	0.84602 (17)	0.0232 (6)
H2A	0.5942	0.4490	0.3250	0.054*
H2B	0.7492	0.4576	0.3979	0.054*
H12	0.5448	0.4815	0.0760	0.029*
H13	0.5188	0.5687	0.2166	0.026*
H15	0.7225	0.8398	0.0946	0.026*
H16	0.7538	0.7422	−0.0405	0.029*
H17	0.6502	0.6497	0.3434	0.025*
H22	0.5958	0.6242	0.6538	0.030*
H23	0.5824	0.7019	0.8000	0.027*
H25	0.6522	0.9990	0.6857	0.031*
H26	0.6727	0.9210	0.5412	0.031*
H27	0.6402	0.6380	0.4858	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0386 (11)	0.0185 (8)	0.0197 (9)	0.0003 (8)	−0.0006 (9)	−0.0009 (7)
O2	0.0515 (14)	0.0247 (10)	0.0309 (11)	−0.0013 (11)	−0.0159 (10)	0.0035 (9)
N11	0.0301 (12)	0.0275 (11)	0.0191 (10)	0.0030 (10)	−0.0004 (10)	−0.0045 (9)
N17	0.0294 (12)	0.0185 (10)	0.0141 (10)	0.0006 (10)	−0.0023 (9)	−0.0016 (8)
N24	0.0389 (14)	0.0312 (12)	0.0242 (12)	0.0025 (12)	0.0011 (11)	−0.0007 (11)
N27	0.0254 (12)	0.0256 (11)	0.0144 (10)	0.0000 (10)	−0.0014 (9)	−0.0027 (9)
C12	0.0282 (14)	0.0221 (12)	0.0227 (13)	0.0010 (12)	−0.0013 (11)	−0.0025 (11)
C13	0.0252 (13)	0.0215 (12)	0.0172 (12)	−0.0007 (11)	−0.0004 (10)	0.0008 (10)
C14	0.0211 (13)	0.0200 (12)	0.0153 (11)	0.0026 (10)	−0.0030 (10)	−0.0013 (10)
C15	0.0289 (14)	0.0195 (12)	0.0170 (12)	0.0009 (11)	−0.0008 (11)	0.0031 (10)
C16	0.0279 (14)	0.0282 (14)	0.0169 (12)	0.0012 (12)	0.0004 (11)	0.0012 (11)
C17	0.0191 (12)	0.0188 (11)	0.0143 (11)	−0.0005 (11)	0.0002 (10)	0.0006 (10)
C21	0.0220 (13)	0.0262 (13)	0.0173 (12)	0.0014 (11)	−0.0026 (10)	−0.0019 (10)
C22	0.0286 (14)	0.0209 (12)	0.0251 (13)	−0.0003 (12)	−0.0017 (12)	0.0024 (11)
C23	0.0237 (13)	0.0238 (13)	0.0204 (13)	0.0003 (11)	0.0018 (12)	0.0040 (10)
C24	0.0219 (14)	0.0247 (13)	0.0196 (12)	0.0012 (11)	−0.0042 (11)	−0.0011 (10)
C25	0.0339 (16)	0.0200 (12)	0.0225 (12)	−0.0022 (11)	−0.0028 (12)	0.0013 (10)
C26	0.0324 (15)	0.0241 (13)	0.0203 (12)	−0.0017 (12)	−0.0040 (11)	0.0052 (10)
C27	0.0285 (14)	0.0202 (12)	0.0214 (12)	0.0007 (11)	−0.0001 (11)	−0.0021 (11)
C241	0.0251 (13)	0.0235 (13)	0.0210 (13)	−0.0001 (11)	0.0003 (11)	0.0040 (11)

Geometric parameters (Å, º) top

N11—C12	1.336 (3)	C27—C21	1.473 (4)
N11—C16	1.344 (3)	C27—H27	0.95
C12—C13	1.387 (3)	C21—C22	1.393 (4)
C12—H12	0.95	C21—C26	1.399 (4)
C13—C14	1.386 (4)	C22—C23	1.386 (4)
C13—H13	0.95	C22—H22	0.95
C14—C15	1.392 (3)	C23—C24	1.397 (3)
C14—C17	1.505 (3)	C23—H23	0.95
C15—C16	1.383 (3)	C24—C25	1.398 (3)
C15—H15	0.95	C24—C241	1.445 (4)
C16—H16	0.95	C25—C26	1.372 (4)
C17—O1	1.224 (3)	C25—H25	0.95
C17—N17	1.356 (3)	C26—H26	0.95
N17—N27	1.383 (3)	C241—N24	1.145 (3)
N17—H17	0.90	O2—H2A	0.95
N27—C27	1.279 (3)	O2—H2B	0.95

C12—N11—C16	117.0 (2)	N27—C27—C21	119.0 (2)
N11—C12—C13	123.6 (2)	N27—C27—H27	120.5
N11—C12—H12	118.2	C21—C27—H27	120.5
C13—C12—H12	118.2	C22—C21—C26	119.6 (2)
C14—C13—C12	118.8 (2)	C22—C21—C27	119.0 (2)
C14—C13—H13	120.6	C26—C21—C27	121.5 (2)
C12—C13—H13	120.6	C23—C22—C21	120.3 (2)
C13—C14—C15	118.3 (2)	C23—C22—H22	119.8
C13—C14—C17	123.7 (2)	C21—C22—H22	119.8
C15—C14—C17	117.9 (2)	C22—C23—C24	119.7 (2)
C16—C15—C14	118.7 (2)	C22—C23—H23	120.2
C16—C15—H15	120.7	C24—C23—H23	120.2
C14—C15—H15	120.7	C23—C24—C25	119.9 (2)
N11—C16—C15	123.5 (2)	C23—C24—C241	121.0 (2)
N11—C16—H16	118.2	C25—C24—C241	119.2 (2)
C15—C16—H16	118.2	C26—C25—C24	120.2 (2)
O1—C17—N17	124.3 (2)	C26—C25—H25	119.9
O1—C17—C14	121.1 (2)	C24—C25—H25	119.9
N17—C17—C14	114.6 (2)	C25—C26—C21	120.3 (2)
C17—N17—N27	118.5 (2)	C25—C26—H26	119.8
C17—N17—H17	128.6	C21—C26—H26	119.8
N27—N17—H17	112.3	N24—C241—C24	179.6 (3)
C27—N27—N17	115.5 (2)	H2A—O2—H2B	106.0

C16—N11—C12—C13	−1.6 (4)	C17—N17—N27—C27	179.0 (2)
N11—C12—C13—C14	1.1 (4)	N17—N27—C27—C21	179.9 (2)
C12—C13—C14—C15	0.9 (4)	N27—C27—C21—C22	168.0 (3)
C12—C13—C14—C17	179.0 (2)	N27—C27—C21—C26	−11.6 (4)
C13—C14—C15—C16	−2.2 (4)	C26—C21—C22—C23	2.0 (4)
C17—C14—C15—C16	179.6 (2)	C27—C21—C22—C23	−177.6 (2)
C12—N11—C16—C15	0.2 (4)	C21—C22—C23—C24	0.6 (4)
C14—C15—C16—N11	1.8 (4)	C22—C23—C24—C25	−2.5 (4)
C13—C14—C17—O1	−152.4 (3)	C22—C23—C24—C241	178.7 (2)
C15—C14—C17—O1	25.7 (4)	C23—C24—C25—C26	1.7 (4)
C13—C14—C17—N17	28.8 (3)	C241—C24—C25—C26	−179.5 (3)
C15—C14—C17—N17	−153.1 (2)	C24—C25—C26—C21	1.0 (4)
O1—C17—N17—N27	−2.1 (4)	C22—C21—C26—C25	−2.8 (4)
C14—C17—N17—N27	176.7 (2)	C27—C21—C26—C25	176.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17···O2	0.90	1.95	2.845 (3)	174
O2—H2A···O1ⁱ	0.95	1.94	2.858 (3)	162
O2—H2B···N11ⁱⁱ	0.95	1.85	2.801 (3)	174
C13—H13···O2	0.95	2.44	3.122 (3)	129
C13—H13···O1ⁱ	0.95	2.51	3.243 (3)	134

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀N₄O·H₂O
M_r	268.28
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	120
a, b, c (Å)	6.9692 (2), 12.3802 (5), 14.5513 (7)
V (Å³)	1255.49 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.62 × 0.04 × 0.03

Data collection
Diffractometer	Bruker–Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.956, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	14838, 1664, 1437
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.107, 1.06
No. of reflections	1664
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.20

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 torsion angles (º) top

C13—C14—C17—N17	28.8 (3)	N17—N27—C27—C21	179.9 (2)
C14—C17—N17—N27	176.7 (2)	N27—C27—C21—C22	168.0 (3)
C17—N17—N27—C27	179.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17···O2	0.90	1.95	2.845 (3)	174
O2—H2A···O1ⁱ	0.95	1.94	2.858 (3)	162
O2—H2B···N11ⁱⁱ	0.95	1.85	2.801 (3)	174
C13—H13···O2	0.95	2.44	3.122 (3)	129
C13—H13···O1ⁱ	0.95	2.51	3.243 (3)	134

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

Acknowledgements

X-ray data were collected at the EPSRC National Crystallography 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
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Low, J. N., Wardell, S. M. S. V., de Souza, M. V. N., Wardell, J. L. & Glidewell, C. (2006). Acta Cryst. C62, o444–o446. Web of Science CSD CrossRef CAS IUCr Journals 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
Wardell, S. M. S. V., de Souza, M. V. N., Ferreira, M. de L., Vasconcelos, T. R. A., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o617–o620. CSD CrossRef CAS IUCr Journals Google Scholar
Wardell, S. M. S. V., de Souza, M. V. N., Wardell, J. L., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o683–o689. CSD CrossRef CAS IUCr Journals Google Scholar
Wardell, S. M. S. V., de Souza, M. V. N., Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. E62, o3361–o3363. CSD CrossRef IUCr Journals Google Scholar

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ISSN: 2053-2296

Volume 63| Part 3| March 2007| Pages o166-o168

doi:10.1107/S0108270107002788

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

4-Cyano­benzaldehyde isonicotinoylhydrazone monohydrate: a three-dimensional hydrogen-bonded ­framework structure

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-Cyanobenzaldehyde isonicotinoylhydrazone monohydrate: a three-dimensional hydrogen-bonded framework structure