2,4-Dimethyl­benzaldehyde isonicotinoylhydrazone trihydrate: a three-dimensional hydrogen-bonded framework structure

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

doi:10.1107/S0108270106020634

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 7| July 2006| Pages o444-o446

doi:10.1107/S0108270106020634

2,4-Dimethylbenzaldehyde isonicotinoylhydrazone trihydrate: a three-dimensional hydrogen-bonded framework structure

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

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, ^bInstituto de Tecnologia em Fármacos, Far-Manguinhos, FIOCRUZ, 21041-250 Rio de Janeiro, RJ, Brazil, ^cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 30 May 2006; accepted 31 May 2006; online 30 June 2006)

In the title compound, C₁₅H₁₅N₃O·3H₂O, two of the three water molecules exhibit disorder. The molecular components are linked into a three-dimensional framework by a combination of N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds.

Comment

We report here the structure of the title compound, (I), which is a stoichiometric trihydrate (Fig. 1), and we compare the supramolecular aggregation in (I) with that in the analogous compounds (II), which crystallizes in an anhydrous form (Wardell, de Souza, Ferreira et al., 2005 ), and (III), which crystallizes as a stoichiometric monohydrate (Wardell, de Souza, Wardell et al., 2005 ).

The conformation of (I) is very similar to those of (II) and (III). The central spacer unit is nearly coplanar with the substituted phenyl ring, with only the pyridyl ring significantly twisted away from coplanarity with the remainder of the molecule (Table 1). The bond lengths and angles show no unexpected features.

In two of the three water molecules in the structure of (I), viz. those containing atoms O2 and O3, the H atoms exhibit some disorder. This was modelled in each molecule in terms of one hydrogen site of full occupancy (labelled H2A and H3A) and two others each of 0.5 occupancy (labelled H2B/H2C and H3B/H3C). This disorder materially complicates the analysis of the supramolecular aggregation and, for the sake of convenience, we consider first the effect of those hydrogen bonds involving H-atom sites of unit occupancy, and then the disordered H-atom sites.

Within the selected asymmetric unit (Fig. 1) there are three hydrogen bonds, two of O—H⋯O type and one of N—H⋯O type, all involving fully occupied H-atom sites (Table 2). Two further hydrogen bonds with full-occupancy H atoms then link these aggregates into a chain of edge-fused rings. Water atom O2 at (x, y, z) acts as hydrogen-bond donor, via atom H2A, to water atom O4 at (−1 + x, y, z), so generating by translation a C₂²(8) (Bernstein et al., 1995 ) chain running parallel to the [100] direction. At the same time, water atom O4 at (x, y, z) acts as hydrogen-bond donor to ring atom N11 at (1 − x, 2 − y, 2 − z), so forming by inversion an R₄⁴(18) ring centred at ( $[{1 \over 2}]$ , 1, 1). The combination of these two motifs then generates a chain of edge-fused rings along (x, 1, 1), with R₄⁴(18) rings centred at (n + $[{1 \over 2}]$ , 1, 1) (n = zero or integer) and R₆⁶(22) rings centred at (n, 1, 1) (n = zero or integer) (Fig. 2).

Pairs of O2 water atoms and pairs of O3 water atoms are each related by centres of inversion, at (0, 1, $[{1 \over 2}]$ ) and (1, $[{1 \over 2}]$ , $[{1 \over 2}]$ ), respectively (Table 2), and for each pair of such O atoms the O—H⋯O contacts involving atoms H2C and H3C are almost linear. Hence, in each case, only one of the symmetry-related H-atom sites can be occupied; if both such sites were occupied, the corresponding H⋯H distances would be similar to the covalent bonding distance in molecular H₂. Thus, for example, if the site H2C at (x, y, z) is occupied, the sites H2B at (x, y, z) and H2C at (−x, 2 − y, 1 − z) must both be vacant, and conversely. Similar considerations apply to the sites H3B and H3C. To the extent that the sites H2B and H3B are occupied, they reinforce the [100] chain of rings. To the extent that the sites H2C and H3C are occupied, they link the [100] chains into a three-dimensional framework structure.

Water atoms O2 and O3 at (x, y, z) are each part of the [100] chain along (x, 1, 1). These atoms act as hydrogen-bond donors, via atoms H2C and H3C, respectively, to water atoms O2 at (−x, 2 − y, 1 − z) and O3 at (2 − x, 1 − y, 1 − z), which themselves lie in the [100] chains along (x, 1, 0) and (x, 0, 0), respectively. Hence, propagation by translation and inversion of these two hydrogen bonds links all of the [100] chains into a three-dimensional framework structure. Although each of the H-atom sites involved has only 0.5 occupancy, averaged over the entire crystal, there is no necessary correlation between the H-atom occupancies at different local sites related by translation along [100]. Hence each [100] chain will be linked, at some points along its length, to four adjacent chains, so forming the framework structure.

In the anhydrous 2,4-difluoro analogue, (II), the molecules are linked by a combination of N—H⋯O and C—H⋯O hydrogen bonds, one of each type, into chains of rings, which are themselves further linked into sheets by a single π–π stacking interaction (Wardell, de Souza, Ferreira et al., 2005). In the 2,4-dinitro analogue, (IV), which crystallizes as a stoichiometric monohydrate with fully ordered H-atom sites, a combination of O—H⋯O, O—H⋯N, N–H⋯O and C—H⋯O hydrogen bonds links the molecular components into a three-dimensional framework structure (Wardell, de Souza, Wardell et al., 2005). The substituents in the aryl ring thus exert a considerable influence, not only upon the crystallization characteristics of the compounds, but also upon the supramolecular aggregation, even when, as in compounds (I) and (II), those substituents play no direct role in that aggregation.

Figure 1
The independent molecular components of compound (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds within the selected asymmetric unit are indicated by dashed lines. The H atoms bonded to atoms O2 and O3 are disordered (see Comment).

Figure 2
A stereoview of part of the crystal structure of compound (I)

, showing the formation of a chain of edge-fused R₄⁴(18) and R₆⁶(22) rings lying along [100]. For the sake of clarity, the water molecule containing atom O3 and the H atoms bonded to C atoms have been omitted. The H atoms bonded to atom O2 are disordered (see Comment).

Experimental

A mixture of equimolar quantities (10 mmol of each component) of 2,4-dimethylbenzaldehyde and isonicotinoylhydrazine (isoniazid) in tetrahydrofuran (20 ml) was heated under reflux for 6 h. The mixture was cooled and the solvent was removed under reduced pressure. The solid product was washed successively with cold ethanol and diethyl ether, and then recrystallized from ethanol (m.p. 426–428 K). CG/MS: m/z 253 [M]⁺; ¹H NMR (DMSO-d₆): δ 12.00 (1H, s, NH), 8.80 (2H, d, J = 5.5 Hz), 8.72 (1H, s, N=C—H), 7.84 (2H, d, J = 5.5 Hz), 7.77 (1H, d, J = 8.0 Hz), 7.12 (1H, d, J = 8.0 Hz), 7.09 (1H, s); ¹³C NMR (DMSO-d₆): δ 161.2, 150.2, 147.6, 140.4, 139.8, 136.9, 131.4, 129.2, 126.9, 126.4, 121.4, 20.8, 18.9; IR (KBr disk, ν, cm⁻¹): 3195 (NH), 1653 (CO).

Crystal data

C₁₅H₁₅N₃O·3H₂O
M_r = 307.35
Triclinic, $[P \overline 1]$
a = 8.6765 (7) Å
b = 9.0833 (6) Å
c = 11.2901 (9) Å
α = 73.870 (5)°
β = 82.182 (4)°
γ = 65.147 (3)°
V = 775.41 (10) Å³
Z = 2
D_x = 1.316 Mg m⁻³
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 120 (2) K
Plate, colourless
0.20 × 0.05 × 0.02 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.949, T_max = 0.998
14799 measured reflections
3563 independent reflections
1982 reflections with I > 2σ(I)
R_int = 0.093
θ_max = 27.6°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.173
S = 1.03
3563 reflections
200 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.073P)² + 0.1388P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected torsion angles (°)

C13—C14—C17—N17	−32.8 (3)
C14—C17—N17—N27	−174.39 (19)
C17—N17—N27—C27	168.3 (2)
N17—N27—C27—C21	−176.9 (2)
N27—C27—C21—C22	176.1 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N17—H17⋯O2	0.88	2.00	2.878 (3)	172
O2—H2A⋯O4ⁱ	0.95	1.77	2.711 (2)	168
O2—H2B⋯O3ⁱ	0.96	2.08	2.877 (3)	139
O2—H2C⋯O2ⁱⁱ	0.96	1.86	2.801 (3)	167
O3—H3A⋯O1	1.00	2.02	2.900 (3)	146
O3—H3B⋯O2ⁱⁱⁱ	0.95	2.26	2.877 (3)	122
O3—H3C⋯O3^iv	1.03	1.89	2.917 (4)	174
O4—H4A⋯O1	0.97	1.87	2.811 (3)	163
O4—H4B⋯N11^v	0.87	2.01	2.872 (3)	172
Symmetry codes: (i) x-1, y, z; (ii) -x, -y+2, -z+1; (iii) x+1, y, z; (iv) -x+2, -y+1, -z+1; (v) -x+1, -y+2, -z+2.

Crystals of compound (I) are triclinic; the space group P $[\overline{1}]$ was selected and confirmed by the structure analysis. H atoms bonded to C or N atoms were located in a difference map and then treated as riding atoms, with C—H = 0.95 (aromatic) or 0.98 Å (methyl), and N—H = 0.88 Å, and with U_iso(H) = xU_eq(C,N), where x = 1.5 for the methyl groups and 1.2 for all other H atoms bonded to C or N atoms. The H atoms of the water molecules were located in a difference map, and those bonded to atoms O2 and O3 were modelled as two H atoms of full occupancy (H2A and H3A) and four with occupancy 0.5 (H2B/H2C and H3B/H3C). These H atoms were all permitted to ride at the O—H distances (0.87–1.03 Å) found from the difference map, with U_iso(H) = 1.2U_eq(O).

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 macro PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270106020634/sk3031sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106020634/sk3031Isup2.hkl

Comment top

We report here the structure of the title compound, (I), which is a stoichiometric trihydrate (Fig. 1), and we compare the supramolecular aggregation in (I) with that in the analogous compounds (II), which crystallizes in an anhydrous form (Wardell, de Souza, Ferreira et al., 2005), and (III), which crystallizes as a stoichiometric monohydrate (Wardell, de Souza, Wardell et al., 2005).

The conformation of (I) is very similar to those of (II) and (III). The central spacer unit is nearly co-planar with the substituted phenyl ring, with only the pyridyl ring significantly twisted away from co-planarity with the remainder of the molecule (Table 1). The bond lengths and angles show no unexpected features.

In two of the three water molecules in the structure of (I), those containing atoms O2 and O3, the H atoms exhibit some disorder. This was modelled in each molecule in terms of one H site of full occupancy (labelled H2A and H3A) and two others each of 0.5 occupancy (labelled H2B/H2C and H3B/H3C). This disorder materially complicates the analysis of the supramolecular aggregation and, for the sake of convenience, we consider first the effect of those hydrogen bonds involving H-atom sites of unit occupancy, and then the disordered H-atom sites.

Within the selected asymmetric unit (Fig. 1) there are three hydrogen bonds, two of O—H···O type and one of N—H···O type, all involving fully occupied H-atom sites (Table 2). Two further hydrogen bonds with full-occupancy H atoms then link these aggregates into a chain of edge-fused rings. Water atom O2 at (x, y, z) acts as hydrogen-bond donor, via atom H2A, to water atom O4 at (−1 + x, y, z), so generating by translation a C²₂(8) (Bernstein et al., 1995) chain running parallel to the [100] direction. At the same time, water atom O4 at (x, y, z) acts as hydrogen-bond donor to ring atom N11 at (1 − x, 2 − y, 2 − z), so forming by inversion an R⁴₄(18) ring centred at (1/2, 1, 1). The combination of these two motifs then generates a chain of edge-fused rings along (x, 1, 1), with R⁴₄(18) rings centred at (n + 1/2, 1, 1) (n = zero or integer) and R⁶₆(22) rings centred at (n, 1, 1) (n = zero or integer) (Fig. 2).

Pairs of water atoms O2 and pairs of water atoms O3 are each related by centres of inversion, at (0, 1, 1/2) and (1, 1/2, 1/2), respectively (Table 2), and for each pair of such O atoms the O—H···O contacts involving atoms H2C and H3C are almost linear. Hence in each case, only one of the symmetry-related H-atom sites can be occupied; if both such sites were occupied, the corresponding H···H distances would be similar to the covalent bonding distance in molecular H₂. Thus, for example, if the site H2C at (x, y, z) is occupied, the sites H2B at (x, y, z) and H2C at (−x, 2 − y, 1 − z) must both be vacant, and conversely. Similar considerations apply to the sites H3B and H3C. To the extent that the sites H2B and H3B are occupied, they reinforce the [100] chain of rings. To the extent that the sites O2C and O3C are occupied, they link the [100] chains into a three-dimensional framework structure.

Water atoms O2 and O3 at (x, y, z) are each part of the [100] chain along (x, 1, 1). These atoms act as hydrogen-bond donors, via atoms H2C and H3C, respectively, to water atoms O2 at (−x, 2 − y, 1 − z) and O3 at (2 − x, 1 − y, 1 − z), respectively, which themselves lie in the [100] chains along (x, 1, 0) and (x, 0, 0), respectively. Hence, propagation by translation and inversion of these two hydrogen bonds links all of the [100] chains into a three-dimensional framework structure. Although each of the H-atom sites involved has only 0.5 occupancy, averaged over the entire crystal, there is no necessary correlation between the H-atom occupancies at different local sites related by translation along [100]. Hence each [100] chain will be linked, at some points along its length, to four adjacent chains, so forming the framework structure.

In the anhydrous 2,4-difluoro analogue, (II), the molecules are linked by a combination of N—H···O and C—H···O hydrogen bonds, one of each type, into chains of rings, which are themselves further linked into sheets by a single π–π stacking interaction (Wardell, de Souza, Ferreira et al., 2005). In the 2,4-dinitro analogue, (IV), which crystallizes as a stoichiometric monohydrate with fully ordered H-atom sites, a combination of O—H···O, O—H···N, N–H···O and C—H···O hydrogen bonds links the molecular components into a three-dimensional framework structure (Wardell, de Souza, Wardell et al., 2005). The substituents in the aryl ring thus exert a considerable influence, not only upon the crystallization characteristics of the compounds, but also upon the supramolecular aggregation, even when, as in compounds (I) and (II), those substituents play no direct role in that aggregation.

Experimental top

A mixture of equimolar quantities (10 mmol of each component) of 2,4-dimethylbenzaldehyde and isonicotinoylhydrazine (isoniazid) in tetrahydrofuran (20 ml) was heated under reflux for 6 h. The mixture was cooled and the solvent was removed under reduced pressure. The solid product was washed successively with cold ethanol and diethyl ether, and then recrystallized from ethanol (m.p. 426–428 K). CG/MS: m/z 253 [M]⁺; ¹H NMR (DMSO-d₆, δ, p.p.m.): 12.00 (1H, s, NH), 8.80 (2H, d, J = 5.5 Hz), 8.72 (1H, s, N═C—H), 7.84 (2H, d, J = 5.5 Hz), 7.77 (1H, d, J = 8.0 Hz), 7.12 (1H, d, J = 8.0 Hz), 7.09 (1H, s); ¹³C NMR (DMSO-d₆, δ, p.p.m.): 161.2, 150.2, 147.6, 140.4, 139.8, 136.9, 131.4, 129.2, 126.9, 126.4, 121.4, 20.8, 18.9; IR (KBr disk, ν, cm⁻¹): 3195 (NH), 1653 (CO).

Computing details top

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 macro PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The independent molecular components of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the ??% probability level [Please complete] and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds within the selected asymmetric unit are indicated by dashed lines. The H atoms bonded to atoms O2 and O3 are disordered (see text).
	Fig. 2. A stereoview of part of the crystal structure of compound (I), showing the formation of a chain of edge-fused R⁴₄(18) and R⁶₆(22) rings lying along [100]. For the sake of clarity, the water molecule containing O3 and the H atoms bonded to C atoms have been omitted. The H atoms bonded to atom O2 are disordered (see text).

2,4-Dimethylbenzaldehyde isonicotinoylhydrazone trihydrate top

Crystal data top

C₁₅H₁₅N₃O·3H₂O	Z = 2
M_r = 307.35	F(000) = 328
Triclinic, P1	D_x = 1.316 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6765 (7) Å	Cell parameters from 3563 reflections
b = 9.0833 (6) Å	θ = 3.0–27.6°
c = 11.2901 (9) Å	µ = 0.10 mm⁻¹
α = 73.870 (5)°	T = 120 K
β = 82.182 (4)°	Plate, colourless
γ = 65.147 (3)°	0.20 × 0.05 × 0.02 mm
V = 775.41 (10) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	3563 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1982 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.093
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.0°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
T_min = 0.949, T_max = 0.998	l = −14→14
14799 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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.073P)² + 0.1388P] where P = (F_o² + 2F_c²)/3
3563 reflections	(Δ/σ)_max < 0.001
200 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₅H₁₅N₃O·3H₂O	γ = 65.147 (3)°
M_r = 307.35	V = 775.41 (10) Å³
Triclinic, P1	Z = 2
a = 8.6765 (7) Å	Mo Kα radiation
b = 9.0833 (6) Å	µ = 0.10 mm⁻¹
c = 11.2901 (9) Å	T = 120 K
α = 73.870 (5)°	0.20 × 0.05 × 0.02 mm
β = 82.182 (4)°

Data collection top

Nonius KappaCCD area-detector diffractometer	3563 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1982 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.998	R_int = 0.093
14799 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.03	Δρ_max = 0.32 e Å⁻³
3563 reflections	Δρ_min = −0.30 e Å⁻³
200 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
N11	0.2169 (3)	1.0095 (3)	0.9871 (2)	0.0298 (5)
C12	0.1455 (3)	1.0629 (3)	0.8769 (2)	0.0316 (6)
C13	0.2313 (3)	1.0178 (3)	0.7707 (2)	0.0273 (6)
C14	0.4029 (3)	0.9121 (3)	0.7791 (2)	0.0250 (6)
C15	0.4785 (3)	0.8564 (3)	0.8929 (2)	0.0263 (6)
C16	0.3818 (3)	0.9067 (3)	0.9933 (2)	0.0278 (6)
C17	0.5127 (3)	0.8535 (3)	0.6724 (2)	0.0252 (6)
N17	0.4347 (3)	0.8323 (2)	0.58802 (18)	0.0255 (5)
N27	0.5332 (3)	0.7642 (2)	0.49314 (18)	0.0250 (5)
C27	0.4568 (3)	0.7205 (3)	0.4289 (2)	0.0249 (6)
O1	0.6657 (2)	0.8211 (2)	0.66977 (17)	0.0325 (5)
C21	0.5462 (3)	0.6394 (3)	0.3301 (2)	0.0242 (6)
C22	0.4641 (3)	0.5826 (3)	0.2649 (2)	0.0258 (6)
C221	0.2828 (3)	0.6044 (3)	0.2934 (3)	0.0331 (7)
C23	0.5569 (4)	0.5033 (3)	0.1726 (2)	0.0297 (6)
C24	0.7251 (3)	0.4794 (3)	0.1434 (2)	0.0285 (6)
C241	0.8202 (4)	0.3953 (3)	0.0420 (3)	0.0378 (7)
C26	0.7166 (3)	0.6140 (3)	0.3016 (2)	0.0306 (6)
C25	0.8039 (4)	0.5363 (3)	0.2088 (2)	0.0343 (7)
O2	0.0930 (2)	0.8565 (2)	0.58856 (16)	0.0311 (5)
O3	0.9437 (2)	0.6726 (2)	0.50801 (17)	0.0399 (5)
O4	0.8536 (2)	0.9476 (2)	0.76581 (17)	0.0391 (5)
H12	0.0286	1.1363	0.8708	0.038*
H13	0.1744	1.0580	0.6947	0.033*
H15	0.5955	0.7843	0.9016	0.032*
H16	0.4350	0.8663	1.0708	0.033*
H17	0.3271	0.8485	0.5900	0.031*
H27	0.3403	0.7411	0.4458	0.030*
H22A	0.2719	0.5465	0.3793	0.050*
H22B	0.2484	0.5572	0.2386	0.050*
H22C	0.2095	0.7238	0.2808	0.050*
H23	0.5027	0.4643	0.1281	0.036*
H24A	0.8224	0.4804	−0.0331	0.057*
H24B	0.7632	0.3301	0.0256	0.057*
H24C	0.9368	0.3206	0.0675	0.057*
H26	0.7727	0.6504	0.3467	0.037*
H25	0.9186	0.5219	0.1897	0.041*
H2A	0.0215	0.8802	0.6588	0.037*
H2B	0.0929	0.7533	0.5820	0.037*	0.50
H2C	0.0157	0.9501	0.5321	0.037*	0.50
H3A	0.8230	0.7273	0.5356	0.048*
H3B	1.0007	0.6616	0.5776	0.048*	0.50
H3C	0.9841	0.5482	0.5085	0.048*	0.50
H4A	0.7745	0.9075	0.7469	0.047*
H4B	0.8235	0.9592	0.8407	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N11	0.0323 (13)	0.0346 (12)	0.0283 (12)	−0.0175 (11)	0.0030 (10)	−0.0120 (10)
C12	0.0298 (15)	0.0369 (15)	0.0326 (16)	−0.0136 (12)	0.0014 (12)	−0.0160 (12)
C13	0.0264 (14)	0.0345 (14)	0.0253 (14)	−0.0130 (12)	−0.0012 (11)	−0.0124 (11)
C14	0.0290 (14)	0.0283 (13)	0.0238 (14)	−0.0163 (11)	0.0025 (11)	−0.0094 (11)
C15	0.0282 (14)	0.0265 (13)	0.0276 (14)	−0.0129 (11)	−0.0013 (11)	−0.0086 (11)
C16	0.0378 (16)	0.0288 (13)	0.0224 (13)	−0.0185 (13)	−0.0017 (11)	−0.0065 (11)
C17	0.0305 (15)	0.0280 (13)	0.0215 (13)	−0.0134 (12)	−0.0009 (11)	−0.0099 (11)
N17	0.0236 (11)	0.0327 (11)	0.0225 (11)	−0.0111 (10)	0.0006 (9)	−0.0111 (9)
N27	0.0270 (12)	0.0290 (11)	0.0196 (11)	−0.0103 (10)	0.0036 (9)	−0.0105 (9)
C27	0.0259 (14)	0.0265 (13)	0.0220 (13)	−0.0106 (11)	−0.0007 (11)	−0.0052 (11)
O1	0.0271 (11)	0.0444 (11)	0.0333 (11)	−0.0155 (9)	0.0016 (8)	−0.0199 (9)
C21	0.0286 (14)	0.0235 (12)	0.0203 (13)	−0.0115 (11)	0.0010 (11)	−0.0043 (10)
C22	0.0301 (14)	0.0246 (13)	0.0210 (13)	−0.0089 (11)	−0.0040 (11)	−0.0047 (10)
C221	0.0344 (16)	0.0355 (15)	0.0345 (15)	−0.0136 (13)	−0.0045 (12)	−0.0152 (12)
C23	0.0405 (17)	0.0258 (13)	0.0246 (14)	−0.0129 (12)	−0.0039 (12)	−0.0080 (11)
C24	0.0324 (15)	0.0267 (13)	0.0222 (13)	−0.0086 (12)	0.0015 (11)	−0.0060 (11)
C241	0.0411 (17)	0.0401 (16)	0.0349 (16)	−0.0147 (14)	0.0041 (13)	−0.0183 (13)
C26	0.0325 (16)	0.0347 (14)	0.0278 (14)	−0.0148 (12)	−0.0009 (12)	−0.0104 (12)
C25	0.0327 (16)	0.0387 (15)	0.0331 (16)	−0.0153 (13)	0.0062 (13)	−0.0131 (13)
O2	0.0271 (10)	0.0358 (10)	0.0309 (10)	−0.0107 (8)	0.0024 (8)	−0.0137 (8)
O3	0.0334 (11)	0.0458 (11)	0.0421 (12)	−0.0121 (9)	0.0054 (9)	−0.0222 (10)
O4	0.0385 (12)	0.0609 (13)	0.0317 (11)	−0.0276 (10)	0.0098 (9)	−0.0252 (10)

Geometric parameters (Å, º) top

N11—C12	1.337 (3)	C221—H22A	0.98
N11—C16	1.338 (3)	C221—H22B	0.98
C12—C13	1.390 (3)	C221—H22C	0.98
C12—H12	0.95	C23—C24	1.389 (4)
C13—C14	1.391 (3)	C23—H23	0.95
C13—H13	0.95	C24—C25	1.388 (4)
C14—C15	1.387 (3)	C24—C241	1.508 (3)
C14—C17	1.503 (3)	C241—H24A	0.98
C15—C16	1.380 (3)	C241—H24B	0.98
C15—H15	0.95	C241—H24C	0.98
C16—H16	0.95	C26—C25	1.384 (3)
C17—O1	1.231 (3)	C26—H26	0.95
C17—N17	1.338 (3)	C25—H25	0.95
N17—N27	1.391 (3)	O2—H2A	0.95
N17—H17	0.88	O2—H2B	0.96
N27—C27	1.278 (3)	O2—H2C	0.96
C27—C21	1.460 (3)	O3—H3A	1.00
C27—H27	0.95	O3—H3B	0.95
C21—C26	1.402 (4)	O3—H3C	1.03
C21—C22	1.406 (3)	O4—H4A	0.97
C22—C23	1.398 (3)	O4—H4B	0.87
C22—C221	1.501 (4)

C12—N11—C16	116.8 (2)	C22—C221—H22A	109.5
N11—C12—C13	124.2 (2)	C22—C221—H22B	109.5
N11—C12—H12	117.9	H22A—C221—H22B	109.5
C13—C12—H12	117.9	C22—C221—H22C	109.5
C12—C13—C14	118.0 (2)	H22A—C221—H22C	109.5
C12—C13—H13	121.0	H22B—C221—H22C	109.5
C14—C13—H13	121.0	C24—C23—C22	122.6 (2)
C15—C14—C13	118.3 (2)	C24—C23—H23	118.7
C15—C14—C17	117.6 (2)	C22—C23—H23	118.7
C13—C14—C17	124.1 (2)	C25—C24—C23	118.5 (2)
C16—C15—C14	119.3 (2)	C25—C24—C241	120.5 (2)
C16—C15—H15	120.3	C23—C24—C241	121.0 (2)
C14—C15—H15	120.3	C24—C241—H24A	109.5
N11—C16—C15	123.4 (2)	C24—C241—H24B	109.5
N11—C16—H16	118.3	H24A—C241—H24B	109.5
C15—C16—H16	118.3	C24—C241—H24C	109.5
O1—C17—N17	124.25 (17)	H24A—C241—H24C	109.5
O1—C17—C14	119.92 (17)	H24B—C241—H24C	109.5
N17—C17—C14	115.7 (2)	C25—C26—C21	120.8 (2)
C17—N17—N27	118.1 (2)	C25—C26—H26	119.6
C17—N17—H17	126.1	C21—C26—H26	119.6
N27—N17—H17	115.5	C26—C25—C24	120.5 (3)
C27—N27—N17	114.6 (2)	C26—C25—H25	119.7
N27—C27—C21	121.0 (2)	C24—C25—H25	119.7
N27—C27—H27	119.5	H2A—O2—H2B	103.9
C21—C27—H27	119.5	H2A—O2—H2C	93.6
C26—C21—C22	119.6 (2)	H2B—O2—H2C	111.0
C26—C21—C27	119.9 (2)	H3A—O3—H3B	100.2
C22—C21—C27	120.5 (2)	H3A—O3—H3C	115.2
C23—C22—C21	118.0 (2)	H3B—O3—H3C	99.9
C23—C22—C221	120.5 (2)	H4A—O4—H4B	103.2
C21—C22—C221	121.5 (2)

C16—N11—C12—C13	0.3 (4)	N27—C27—C21—C26	−2.3 (4)
N11—C12—C13—C14	−0.9 (4)	N27—C27—C21—C22	176.1 (2)
C12—C13—C14—C15	0.6 (4)	C26—C21—C22—C23	−0.5 (3)
C12—C13—C14—C17	−179.6 (2)	C27—C21—C22—C23	−178.9 (2)
C13—C14—C15—C16	0.2 (4)	C26—C21—C22—C221	179.0 (2)
C17—C14—C15—C16	−179.7 (2)	C27—C21—C22—C221	0.6 (4)
C12—N11—C16—C15	0.6 (4)	C21—C22—C23—C24	−0.1 (4)
C14—C15—C16—N11	−0.8 (4)	C221—C22—C23—C24	−179.6 (2)
C15—C14—C17—O1	−29.7 (3)	C22—C23—C24—C25	0.1 (4)
C13—C14—C17—O1	150.5 (2)	C22—C23—C24—C241	−179.2 (2)
C15—C14—C17—N17	147.1 (2)	C22—C21—C26—C25	1.1 (4)
C13—C14—C17—N17	−32.8 (3)	C27—C21—C26—C25	179.6 (2)
O1—C17—N17—N27	2.2 (3)	C21—C26—C25—C24	−1.2 (4)
C14—C17—N17—N27	−174.39 (19)	C23—C24—C25—C26	0.5 (4)
C17—N17—N27—C27	168.3 (2)	C241—C24—C25—C26	179.8 (2)
N17—N27—C27—C21	−176.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17···O2	0.88	2.00	2.878 (3)	172
O2—H2A···O4ⁱ	0.95	1.77	2.711 (2)	168
O2—H2B···O3ⁱ	0.96	2.08	2.877 (3)	139
O2—H2C···O2ⁱⁱ	0.96	1.86	2.801 (3)	167
O3—H3A···O1	1.00	2.02	2.900 (3)	146
O3—H3B···O2ⁱⁱⁱ	0.95	2.26	2.877 (3)	122
O3—H3C···O3^iv	1.03	1.89	2.917 (4)	174
O4—H4A···O1	0.97	1.87	2.811 (3)	163
O4—H4B···N11^v	0.87	2.01	2.872 (3)	172

Symmetry codes: (i) x−1, y, z; (ii) −x, −y+2, −z+1; (iii) x+1, y, z; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅N₃O·3H₂O
M_r	307.35
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	8.6765 (7), 9.0833 (6), 11.2901 (9)
α, β, γ (°)	73.870 (5), 82.182 (4), 65.147 (3)
V (Å³)	775.41 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.05 × 0.02

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.949, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	14799, 3563, 1982
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.173, 1.03
No. of reflections	3563
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.30

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 macro PRPKAPPA (Ferguson, 1999).

Selected torsion angles (º) top

C13—C14—C17—N17	−32.8 (3)	N17—N27—C27—C21	−176.9 (2)
C14—C17—N17—N27	−174.39 (19)	N27—C27—C21—C22	176.1 (2)
C17—N17—N27—C27	168.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17···O2	0.88	2.00	2.878 (3)	172
O2—H2A···O4ⁱ	0.95	1.77	2.711 (2)	168
O2—H2B···O3ⁱ	0.96	2.08	2.877 (3)	139
O2—H2C···O2ⁱⁱ	0.96	1.86	2.801 (3)	167
O3—H3A···O1	1.00	2.02	2.900 (3)	146
O3—H3B···O2ⁱⁱⁱ	0.95	2.26	2.877 (3)	122
O3—H3C···O3^iv	1.03	1.89	2.917 (4)	174
O4—H4A···O1	0.97	1.87	2.811 (3)	163
O4—H4B···N11^v	0.87	2.01	2.872 (3)	172

Symmetry codes: (i) x−1, y, z; (ii) −x, −y+2, −z+1; (iii) x+1, y, z; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y+2, −z+2.

Acknowledgements

The X-ray data were collected at the EPSRC National Crystallography Service, University of Southampton, England: 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
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

© 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 62| Part 7| July 2006| Pages o444-o446

doi:10.1107/S0108270106020634

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

2,4-Di­methyl­benzaldehyde isonicotinoylhydrazone trihydrate: a three-dimensional hydrogen-bonded framework structure

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2,4-Dimethylbenzaldehyde isonicotinoylhydrazone trihydrate: a three-dimensional hydrogen-bonded framework structure