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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

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

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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)[link], which is a stoichiometric trihydrate (Fig. 1[link]), and we compare the supra­molecular aggregation in (I)[link] with that in the analogous compounds (II)[link], which crystallizes in an anhydrous form (Wardell, de Souza, Ferreira et al., 2005[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.]), and (III)[link], which crystallizes as a stoichiometric monohydrate (Wardell, de Souza, Wardell et al., 2005[Wardell, S. M. S. V., de Souza, M. V. N., Wardell, J. L., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o683-o689.]).

[Scheme 1]

The conformation of (I)[link] is very similar to those of (II)[link] and (III)[link]. 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[link]). The bond lengths and angles show no unexpected features.

In two of the three water mol­ecules in the structure of (I)[link], 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[link]) 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[link]). 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[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) 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[link]).

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[link]), 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)[link], 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 ππ stacking inter­action (Wardell, de Souza, Ferreira et al., 2005[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.]). 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[Wardell, S. M. S. V., de Souza, M. V. N., Wardell, J. L., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o683-o689.]). 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)[link] and (II)[link], those substituents play no direct role in that aggregation.

[Figure 1]
Figure 1
The independent mol­ecular components of compound (I)[link], 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]
Figure 2
A stereoview of part of the crystal structure of compound (I)[link], 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

  • Mr = 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

  • Dx = 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[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.949, Tmax = 0.998

  • 14799 measured reflections

  • 3563 independent reflections

  • 1982 reflections with I > 2σ(I)

  • Rint = 0.093

  • θmax = 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(Fo2) + (0.073P)2 + 0.1388P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.32 e Å−3

  • Δρmin = −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 DA 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⋯O3iv 1.03 1.89 2.917 (4) 174
O4—H4A⋯O1 0.97 1.87 2.811 (3) 163
O4—H4B⋯N11v 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)[link] 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 Uiso(H) = xUeq(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 Uiso(H) = 1.2Ueq(O).

Data collection: COLLECT (Nonius, 1999[Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[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.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and macro PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


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 ππ 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, NC—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).

Refinement top

Crystals of compound (I) are triclinic; the space group P1 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 Uiso(H) = kUeq(C,N), where k = 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 Uiso(H) = 1.2Ueq(O).

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
[Figure 1] 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).
[Figure 2] 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·3H2OZ = 2
Mr = 307.35F(000) = 328
Triclinic, P1Dx = 1.316 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.6765 (7) ÅCell parameters from 3563 reflections
b = 9.0833 (6) Åθ = 3.0–27.6°
c = 11.2901 (9) ŵ = 0.10 mm1
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 anode1982 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.093
Detector resolution: 9.091 pixels mm-1θmax = 27.6°, θmin = 3.0°
ϕ and ω scansh = 1111
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1111
Tmin = 0.949, Tmax = 0.998l = 1414
14799 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.073P)2 + 0.1388P]
where P = (Fo2 + 2Fc2)/3
3563 reflections(Δ/σ)max < 0.001
200 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C15H15N3O·3H2Oγ = 65.147 (3)°
Mr = 307.35V = 775.41 (10) Å3
Triclinic, P1Z = 2
a = 8.6765 (7) ÅMo Kα radiation
b = 9.0833 (6) ŵ = 0.10 mm1
c = 11.2901 (9) ÅT = 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)
Tmin = 0.949, Tmax = 0.998Rint = 0.093
14799 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0640 restraints
wR(F2) = 0.173H-atom parameters constrained
S = 1.03Δρmax = 0.32 e Å3
3563 reflectionsΔρmin = 0.30 e Å3
200 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N110.2169 (3)1.0095 (3)0.9871 (2)0.0298 (5)
C120.1455 (3)1.0629 (3)0.8769 (2)0.0316 (6)
C130.2313 (3)1.0178 (3)0.7707 (2)0.0273 (6)
C140.4029 (3)0.9121 (3)0.7791 (2)0.0250 (6)
C150.4785 (3)0.8564 (3)0.8929 (2)0.0263 (6)
C160.3818 (3)0.9067 (3)0.9933 (2)0.0278 (6)
C170.5127 (3)0.8535 (3)0.6724 (2)0.0252 (6)
N170.4347 (3)0.8323 (2)0.58802 (18)0.0255 (5)
N270.5332 (3)0.7642 (2)0.49314 (18)0.0250 (5)
C270.4568 (3)0.7205 (3)0.4289 (2)0.0249 (6)
O10.6657 (2)0.8211 (2)0.66977 (17)0.0325 (5)
C210.5462 (3)0.6394 (3)0.3301 (2)0.0242 (6)
C220.4641 (3)0.5826 (3)0.2649 (2)0.0258 (6)
C2210.2828 (3)0.6044 (3)0.2934 (3)0.0331 (7)
C230.5569 (4)0.5033 (3)0.1726 (2)0.0297 (6)
C240.7251 (3)0.4794 (3)0.1434 (2)0.0285 (6)
C2410.8202 (4)0.3953 (3)0.0420 (3)0.0378 (7)
C260.7166 (3)0.6140 (3)0.3016 (2)0.0306 (6)
C250.8039 (4)0.5363 (3)0.2088 (2)0.0343 (7)
O20.0930 (2)0.8565 (2)0.58856 (16)0.0311 (5)
O30.9437 (2)0.6726 (2)0.50801 (17)0.0399 (5)
O40.8536 (2)0.9476 (2)0.76581 (17)0.0391 (5)
H120.02861.13630.87080.038*
H130.17441.05800.69470.033*
H150.59550.78430.90160.032*
H160.43500.86631.07080.033*
H170.32710.84850.59000.031*
H270.34030.74110.44580.030*
H22A0.27190.54650.37930.050*
H22B0.24840.55720.23860.050*
H22C0.20950.72380.28080.050*
H230.50270.46430.12810.036*
H24A0.82240.48040.03310.057*
H24B0.76320.33010.02560.057*
H24C0.93680.32060.06750.057*
H260.77270.65040.34670.037*
H250.91860.52190.18970.041*
H2A0.02150.88020.65880.037*
H2B0.09290.75330.58200.037*0.50
H2C0.01570.95010.53210.037*0.50
H3A0.82300.72730.53560.048*
H3B1.00070.66160.57760.048*0.50
H3C0.98410.54820.50850.048*0.50
H4A0.77450.90750.74690.047*
H4B0.82350.95920.84070.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0323 (13)0.0346 (12)0.0283 (12)0.0175 (11)0.0030 (10)0.0120 (10)
C120.0298 (15)0.0369 (15)0.0326 (16)0.0136 (12)0.0014 (12)0.0160 (12)
C130.0264 (14)0.0345 (14)0.0253 (14)0.0130 (12)0.0012 (11)0.0124 (11)
C140.0290 (14)0.0283 (13)0.0238 (14)0.0163 (11)0.0025 (11)0.0094 (11)
C150.0282 (14)0.0265 (13)0.0276 (14)0.0129 (11)0.0013 (11)0.0086 (11)
C160.0378 (16)0.0288 (13)0.0224 (13)0.0185 (13)0.0017 (11)0.0065 (11)
C170.0305 (15)0.0280 (13)0.0215 (13)0.0134 (12)0.0009 (11)0.0099 (11)
N170.0236 (11)0.0327 (11)0.0225 (11)0.0111 (10)0.0006 (9)0.0111 (9)
N270.0270 (12)0.0290 (11)0.0196 (11)0.0103 (10)0.0036 (9)0.0105 (9)
C270.0259 (14)0.0265 (13)0.0220 (13)0.0106 (11)0.0007 (11)0.0052 (11)
O10.0271 (11)0.0444 (11)0.0333 (11)0.0155 (9)0.0016 (8)0.0199 (9)
C210.0286 (14)0.0235 (12)0.0203 (13)0.0115 (11)0.0010 (11)0.0043 (10)
C220.0301 (14)0.0246 (13)0.0210 (13)0.0089 (11)0.0040 (11)0.0047 (10)
C2210.0344 (16)0.0355 (15)0.0345 (15)0.0136 (13)0.0045 (12)0.0152 (12)
C230.0405 (17)0.0258 (13)0.0246 (14)0.0129 (12)0.0039 (12)0.0080 (11)
C240.0324 (15)0.0267 (13)0.0222 (13)0.0086 (12)0.0015 (11)0.0060 (11)
C2410.0411 (17)0.0401 (16)0.0349 (16)0.0147 (14)0.0041 (13)0.0183 (13)
C260.0325 (16)0.0347 (14)0.0278 (14)0.0148 (12)0.0009 (12)0.0104 (12)
C250.0327 (16)0.0387 (15)0.0331 (16)0.0153 (13)0.0062 (13)0.0131 (13)
O20.0271 (10)0.0358 (10)0.0309 (10)0.0107 (8)0.0024 (8)0.0137 (8)
O30.0334 (11)0.0458 (11)0.0421 (12)0.0121 (9)0.0054 (9)0.0222 (10)
O40.0385 (12)0.0609 (13)0.0317 (11)0.0276 (10)0.0098 (9)0.0252 (10)
Geometric parameters (Å, º) top
N11—C121.337 (3)C221—H22A0.98
N11—C161.338 (3)C221—H22B0.98
C12—C131.390 (3)C221—H22C0.98
C12—H120.95C23—C241.389 (4)
C13—C141.391 (3)C23—H230.95
C13—H130.95C24—C251.388 (4)
C14—C151.387 (3)C24—C2411.508 (3)
C14—C171.503 (3)C241—H24A0.98
C15—C161.380 (3)C241—H24B0.98
C15—H150.95C241—H24C0.98
C16—H160.95C26—C251.384 (3)
C17—O11.231 (3)C26—H260.95
C17—N171.338 (3)C25—H250.95
N17—N271.391 (3)O2—H2A0.95
N17—H170.88O2—H2B0.96
N27—C271.278 (3)O2—H2C0.96
C27—C211.460 (3)O3—H3A1.00
C27—H270.95O3—H3B0.95
C21—C261.402 (4)O3—H3C1.03
C21—C221.406 (3)O4—H4A0.97
C22—C231.398 (3)O4—H4B0.87
C22—C2211.501 (4)
C12—N11—C16116.8 (2)C22—C221—H22A109.5
N11—C12—C13124.2 (2)C22—C221—H22B109.5
N11—C12—H12117.9H22A—C221—H22B109.5
C13—C12—H12117.9C22—C221—H22C109.5
C12—C13—C14118.0 (2)H22A—C221—H22C109.5
C12—C13—H13121.0H22B—C221—H22C109.5
C14—C13—H13121.0C24—C23—C22122.6 (2)
C15—C14—C13118.3 (2)C24—C23—H23118.7
C15—C14—C17117.6 (2)C22—C23—H23118.7
C13—C14—C17124.1 (2)C25—C24—C23118.5 (2)
C16—C15—C14119.3 (2)C25—C24—C241120.5 (2)
C16—C15—H15120.3C23—C24—C241121.0 (2)
C14—C15—H15120.3C24—C241—H24A109.5
N11—C16—C15123.4 (2)C24—C241—H24B109.5
N11—C16—H16118.3H24A—C241—H24B109.5
C15—C16—H16118.3C24—C241—H24C109.5
O1—C17—N17124.25 (17)H24A—C241—H24C109.5
O1—C17—C14119.92 (17)H24B—C241—H24C109.5
N17—C17—C14115.7 (2)C25—C26—C21120.8 (2)
C17—N17—N27118.1 (2)C25—C26—H26119.6
C17—N17—H17126.1C21—C26—H26119.6
N27—N17—H17115.5C26—C25—C24120.5 (3)
C27—N27—N17114.6 (2)C26—C25—H25119.7
N27—C27—C21121.0 (2)C24—C25—H25119.7
N27—C27—H27119.5H2A—O2—H2B103.9
C21—C27—H27119.5H2A—O2—H2C93.6
C26—C21—C22119.6 (2)H2B—O2—H2C111.0
C26—C21—C27119.9 (2)H3A—O3—H3B100.2
C22—C21—C27120.5 (2)H3A—O3—H3C115.2
C23—C22—C21118.0 (2)H3B—O3—H3C99.9
C23—C22—C221120.5 (2)H4A—O4—H4B103.2
C21—C22—C221121.5 (2)
C16—N11—C12—C130.3 (4)N27—C27—C21—C262.3 (4)
N11—C12—C13—C140.9 (4)N27—C27—C21—C22176.1 (2)
C12—C13—C14—C150.6 (4)C26—C21—C22—C230.5 (3)
C12—C13—C14—C17179.6 (2)C27—C21—C22—C23178.9 (2)
C13—C14—C15—C160.2 (4)C26—C21—C22—C221179.0 (2)
C17—C14—C15—C16179.7 (2)C27—C21—C22—C2210.6 (4)
C12—N11—C16—C150.6 (4)C21—C22—C23—C240.1 (4)
C14—C15—C16—N110.8 (4)C221—C22—C23—C24179.6 (2)
C15—C14—C17—O129.7 (3)C22—C23—C24—C250.1 (4)
C13—C14—C17—O1150.5 (2)C22—C23—C24—C241179.2 (2)
C15—C14—C17—N17147.1 (2)C22—C21—C26—C251.1 (4)
C13—C14—C17—N1732.8 (3)C27—C21—C26—C25179.6 (2)
O1—C17—N17—N272.2 (3)C21—C26—C25—C241.2 (4)
C14—C17—N17—N27174.39 (19)C23—C24—C25—C260.5 (4)
C17—N17—N27—C27168.3 (2)C241—C24—C25—C26179.8 (2)
N17—N27—C27—C21176.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N17—H17···O20.882.002.878 (3)172
O2—H2A···O4i0.951.772.711 (2)168
O2—H2B···O3i0.962.082.877 (3)139
O2—H2C···O2ii0.961.862.801 (3)167
O3—H3A···O11.002.022.900 (3)146
O3—H3B···O2iii0.952.262.877 (3)122
O3—H3C···O3iv1.031.892.917 (4)174
O4—H4A···O10.971.872.811 (3)163
O4—H4B···N11v0.872.012.872 (3)172
Symmetry codes: (i) x1, 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 formulaC15H15N3O·3H2O
Mr307.35
Crystal system, space groupTriclinic, 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)
V3)775.41 (10)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.20 × 0.05 × 0.02
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.949, 0.998
No. of measured, independent and
observed [I > 2σ(I)] reflections
14799, 3563, 1982
Rint0.093
(sin θ/λ)max1)0.653
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.064, 0.173, 1.03
No. of reflections3563
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—N1732.8 (3)N17—N27—C27—C21176.9 (2)
C14—C17—N17—N27174.39 (19)N27—C27—C21—C22176.1 (2)
C17—N17—N27—C27168.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N17—H17···O20.882.002.878 (3)172
O2—H2A···O4i0.951.772.711 (2)168
O2—H2B···O3i0.962.082.877 (3)139
O2—H2C···O2ii0.961.862.801 (3)167
O3—H3A···O11.002.022.900 (3)146
O3—H3B···O2iii0.952.262.877 (3)122
O3—H3C···O3iv1.031.892.917 (4)174
O4—H4A···O10.971.872.811 (3)163
O4—H4B···N11v0.872.012.872 (3)172
Symmetry codes: (i) x1, 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

First citationBernstein, 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
First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
First citationMcArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.  Google Scholar
First citationNonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationOtwinowski, 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
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWardell, 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
First citationWardell, 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

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