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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

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

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, 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.]; 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.]; Wardell et al., 2006[Wardell, S. M. S. V., de Souza, M. V. N., Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. E62, o3361-o3363.]; Low et al., 2006[Low, J. N., Wardell, S. M. S. V., de Souza, M. V. N., Wardell, J. L. & Glidewell, C. (2006). Acta Cryst. C62, o444-o446.]), we report here the mol­ecular and supra­molecular structure of the title compound, (I)[link] (Fig. 1[link]), which was crystallized from damp ethanol as a stoichiometric monohydrate.

[Scheme 1]

The central spacer unit of the hydrazone component, between atoms C14 and C21 (Fig. 1[link]), is effectively planar with an all-trans extended-chain conformation, as shown by the key torsion angles (Table 1[link]); 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[link] and Table 2[link]). 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[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) chain running parallel to the [010] direction and generated by the 21 screw axis along ([1\over2], y, [1\over4]) (Fig. 2[link]). 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[link]). 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[link]). 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]
Figure 1
The independent mol­ecular components of compound (I)[link], 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]
Figure 2
Part of the crystal structure of compound (I)[link], 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]
Figure 3
Part of the crystal structure of compound (I)[link], 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]
Figure 4
A stereoview of part of the crystal structure of compound (I)[link], 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)[link] 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

  • Mr = 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

  • Dx = 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[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.956, Tmax = 0.997

  • 14838 measured reflections

  • 1664 independent reflections

  • 1437 reflections with I > 2σ(I)

  • Rint = 0.069

  • θmax = 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(Fo2) + (0.0426P)2 + 0.6011P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.25 e Å−3

  • Δρmin = −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 DA 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 [Uiso(H) = 1.2Ueq(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 Uiso(H) values of 1.5Ueq(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[Hooft, R. W. W. (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 PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


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, NC—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 (CO).

Refinement top

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. The 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 [Uiso(H) = 1.2Ueq(C,N)]; the H atoms bonded to O were permitted to ride at the positions derived from the difference maps, with O—H distances of 0.95 Å and Uiso(H) values of 1.5Ueq(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.

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
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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.
[Figure 4] 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·H2OF(000) = 560
Mr = 268.28Dx = 1.419 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1664 reflections
a = 6.9692 (2) Åθ = 3.2–27.5°
b = 12.3802 (5) ŵ = 0.10 mm1
c = 14.5513 (7) ÅT = 120 K
V = 1255.49 (9) Å3Needle, colourless
Z = 40.62 × 0.04 × 0.03 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1664 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1437 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.069
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.2°
ϕ and ω scansh = 89
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1516
Tmin = 0.956, Tmax = 0.997l = 1816
14838 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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0426P)2 + 0.6011P]
where P = (Fo2 + 2Fc2)/3
1664 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C14H10N4O·H2OV = 1255.49 (9) Å3
Mr = 268.28Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.9692 (2) ŵ = 0.10 mm1
b = 12.3802 (5) ÅT = 120 K
c = 14.5513 (7) Å0.62 × 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)
Tmin = 0.956, Tmax = 0.997Rint = 0.069
14838 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.06Δρmax = 0.25 e Å3
1664 reflectionsΔρmin = 0.20 e Å3
181 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.5854 (3)0.87688 (14)0.25628 (12)0.0256 (4)
O20.6942 (3)0.49433 (16)0.34695 (13)0.0357 (5)
N110.6539 (3)0.60244 (19)0.00504 (14)0.0256 (5)
N170.6212 (3)0.72012 (18)0.33699 (13)0.0207 (5)
N240.5886 (4)0.94939 (19)0.91661 (16)0.0315 (6)
N270.6188 (3)0.77410 (18)0.42019 (14)0.0218 (5)
C120.5845 (4)0.5548 (2)0.08036 (17)0.0243 (6)
C130.5670 (4)0.6063 (2)0.16461 (16)0.0213 (5)
C140.6212 (4)0.7137 (2)0.17152 (15)0.0188 (5)
C150.6884 (4)0.7656 (2)0.09294 (16)0.0218 (6)
C160.7044 (4)0.7068 (2)0.01244 (17)0.0243 (6)
C170.6062 (3)0.77877 (19)0.25858 (16)0.0174 (5)
C210.6297 (4)0.7652 (2)0.58305 (18)0.0219 (6)
C220.6060 (4)0.7004 (2)0.66048 (17)0.0249 (6)
C230.5973 (4)0.7464 (2)0.74722 (19)0.0226 (6)
C240.6104 (4)0.8584 (2)0.75670 (17)0.0221 (6)
C250.6398 (4)0.9230 (2)0.67913 (17)0.0255 (6)
C260.6508 (4)0.8769 (2)0.59356 (17)0.0256 (6)
C270.6308 (4)0.7142 (2)0.49162 (17)0.0233 (5)
C2410.5978 (4)0.9089 (2)0.84602 (17)0.0232 (6)
H2A0.59420.44900.32500.054*
H2B0.74920.45760.39790.054*
H120.54480.48150.07600.029*
H130.51880.56870.21660.026*
H150.72250.83980.09460.026*
H160.75380.74220.04050.029*
H170.65020.64970.34340.025*
H220.59580.62420.65380.030*
H230.58240.70190.80000.027*
H250.65220.99900.68570.031*
H260.67270.92100.54120.031*
H270.64020.63800.48580.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0386 (11)0.0185 (8)0.0197 (9)0.0003 (8)0.0006 (9)0.0009 (7)
O20.0515 (14)0.0247 (10)0.0309 (11)0.0013 (11)0.0159 (10)0.0035 (9)
N110.0301 (12)0.0275 (11)0.0191 (10)0.0030 (10)0.0004 (10)0.0045 (9)
N170.0294 (12)0.0185 (10)0.0141 (10)0.0006 (10)0.0023 (9)0.0016 (8)
N240.0389 (14)0.0312 (12)0.0242 (12)0.0025 (12)0.0011 (11)0.0007 (11)
N270.0254 (12)0.0256 (11)0.0144 (10)0.0000 (10)0.0014 (9)0.0027 (9)
C120.0282 (14)0.0221 (12)0.0227 (13)0.0010 (12)0.0013 (11)0.0025 (11)
C130.0252 (13)0.0215 (12)0.0172 (12)0.0007 (11)0.0004 (10)0.0008 (10)
C140.0211 (13)0.0200 (12)0.0153 (11)0.0026 (10)0.0030 (10)0.0013 (10)
C150.0289 (14)0.0195 (12)0.0170 (12)0.0009 (11)0.0008 (11)0.0031 (10)
C160.0279 (14)0.0282 (14)0.0169 (12)0.0012 (12)0.0004 (11)0.0012 (11)
C170.0191 (12)0.0188 (11)0.0143 (11)0.0005 (11)0.0002 (10)0.0006 (10)
C210.0220 (13)0.0262 (13)0.0173 (12)0.0014 (11)0.0026 (10)0.0019 (10)
C220.0286 (14)0.0209 (12)0.0251 (13)0.0003 (12)0.0017 (12)0.0024 (11)
C230.0237 (13)0.0238 (13)0.0204 (13)0.0003 (11)0.0018 (12)0.0040 (10)
C240.0219 (14)0.0247 (13)0.0196 (12)0.0012 (11)0.0042 (11)0.0011 (10)
C250.0339 (16)0.0200 (12)0.0225 (12)0.0022 (11)0.0028 (12)0.0013 (10)
C260.0324 (15)0.0241 (13)0.0203 (12)0.0017 (12)0.0040 (11)0.0052 (10)
C270.0285 (14)0.0202 (12)0.0214 (12)0.0007 (11)0.0001 (11)0.0021 (11)
C2410.0251 (13)0.0235 (13)0.0210 (13)0.0001 (11)0.0003 (11)0.0040 (11)
Geometric parameters (Å, º) top
N11—C121.336 (3)C27—C211.473 (4)
N11—C161.344 (3)C27—H270.95
C12—C131.387 (3)C21—C221.393 (4)
C12—H120.95C21—C261.399 (4)
C13—C141.386 (4)C22—C231.386 (4)
C13—H130.95C22—H220.95
C14—C151.392 (3)C23—C241.397 (3)
C14—C171.505 (3)C23—H230.95
C15—C161.383 (3)C24—C251.398 (3)
C15—H150.95C24—C2411.445 (4)
C16—H160.95C25—C261.372 (4)
C17—O11.224 (3)C25—H250.95
C17—N171.356 (3)C26—H260.95
N17—N271.383 (3)C241—N241.145 (3)
N17—H170.90O2—H2A0.95
N27—C271.279 (3)O2—H2B0.95
C12—N11—C16117.0 (2)N27—C27—C21119.0 (2)
N11—C12—C13123.6 (2)N27—C27—H27120.5
N11—C12—H12118.2C21—C27—H27120.5
C13—C12—H12118.2C22—C21—C26119.6 (2)
C14—C13—C12118.8 (2)C22—C21—C27119.0 (2)
C14—C13—H13120.6C26—C21—C27121.5 (2)
C12—C13—H13120.6C23—C22—C21120.3 (2)
C13—C14—C15118.3 (2)C23—C22—H22119.8
C13—C14—C17123.7 (2)C21—C22—H22119.8
C15—C14—C17117.9 (2)C22—C23—C24119.7 (2)
C16—C15—C14118.7 (2)C22—C23—H23120.2
C16—C15—H15120.7C24—C23—H23120.2
C14—C15—H15120.7C23—C24—C25119.9 (2)
N11—C16—C15123.5 (2)C23—C24—C241121.0 (2)
N11—C16—H16118.2C25—C24—C241119.2 (2)
C15—C16—H16118.2C26—C25—C24120.2 (2)
O1—C17—N17124.3 (2)C26—C25—H25119.9
O1—C17—C14121.1 (2)C24—C25—H25119.9
N17—C17—C14114.6 (2)C25—C26—C21120.3 (2)
C17—N17—N27118.5 (2)C25—C26—H26119.8
C17—N17—H17128.6C21—C26—H26119.8
N27—N17—H17112.3N24—C241—C24179.6 (3)
C27—N27—N17115.5 (2)H2A—O2—H2B106.0
C16—N11—C12—C131.6 (4)C17—N17—N27—C27179.0 (2)
N11—C12—C13—C141.1 (4)N17—N27—C27—C21179.9 (2)
C12—C13—C14—C150.9 (4)N27—C27—C21—C22168.0 (3)
C12—C13—C14—C17179.0 (2)N27—C27—C21—C2611.6 (4)
C13—C14—C15—C162.2 (4)C26—C21—C22—C232.0 (4)
C17—C14—C15—C16179.6 (2)C27—C21—C22—C23177.6 (2)
C12—N11—C16—C150.2 (4)C21—C22—C23—C240.6 (4)
C14—C15—C16—N111.8 (4)C22—C23—C24—C252.5 (4)
C13—C14—C17—O1152.4 (3)C22—C23—C24—C241178.7 (2)
C15—C14—C17—O125.7 (4)C23—C24—C25—C261.7 (4)
C13—C14—C17—N1728.8 (3)C241—C24—C25—C26179.5 (3)
C15—C14—C17—N17153.1 (2)C24—C25—C26—C211.0 (4)
O1—C17—N17—N272.1 (4)C22—C21—C26—C252.8 (4)
C14—C17—N17—N27176.7 (2)C27—C21—C26—C25176.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N17—H17···O20.901.952.845 (3)174
O2—H2A···O1i0.951.942.858 (3)162
O2—H2B···N11ii0.951.852.801 (3)174
C13—H13···O20.952.443.122 (3)129
C13—H13···O1i0.952.513.243 (3)134
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+3/2, y+1, z+1/2.

Experimental details

Crystal data
Chemical formulaC14H10N4O·H2O
Mr268.28
Crystal system, space groupOrthorhombic, P212121
Temperature (K)120
a, b, c (Å)6.9692 (2), 12.3802 (5), 14.5513 (7)
V3)1255.49 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.62 × 0.04 × 0.03
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.956, 0.997
No. of measured, independent and
observed [I > 2σ(I)] reflections
14838, 1664, 1437
Rint0.069
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.107, 1.06
No. of reflections1664
No. of parameters181
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—N1728.8 (3)N17—N27—C27—C21179.9 (2)
C14—C17—N17—N27176.7 (2)N27—C27—C21—C22168.0 (3)
C17—N17—N27—C27179.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N17—H17···O20.901.952.845 (3)174
O2—H2A···O1i0.951.942.858 (3)162
O2—H2B···N11ii0.951.852.801 (3)174
C13—H13···O20.952.443.122 (3)129
C13—H13···O1i0.952.513.243 (3)134
Symmetry codes: (i) x+1, y1/2, 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

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