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organic compounds
2,4-Dimethylbenzaldehyde isonicotinoylhydrazone trihydrate: a three-dimensional hydrogen-bonded framework structure
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
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 ) 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, 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, 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, ) and (1,
,
), 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) ![]() |
![]() | Figure 2 A stereoview of part of the crystal structure of compound (I) ![]() |
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
|
Refinement
|
|
|
Crystals of compound (I) are triclinic; the P
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); cell 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
10.1107/S0108270106020634/sk3031sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S0108270106020634/sk3031Isup2.hkl
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).
Crystals of compound (I) are triclinic; the 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) = 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).
PData collection: COLLECT (Nonius, 1999); cell
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).C15H15N3O·3H2O | Z = 2 |
Mr = 307.35 | F(000) = 328 |
Triclinic, P1 | Dx = 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 |
Nonius KappaCCD area-detector diffractometer | 3563 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 1982 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.093 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.6°, θmin = 3.0° |
ϕ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −11→11 |
Tmin = 0.949, Tmax = 0.998 | l = −14→14 |
14799 measured reflections |
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(Fo2) + (0.073P)2 + 0.1388P] where P = (Fo2 + 2Fc2)/3 |
3563 reflections | (Δ/σ)max < 0.001 |
200 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C15H15N3O·3H2O | γ = 65.147 (3)° |
Mr = 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)° |
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 = 0.998 | Rint = 0.093 |
14799 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.173 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.32 e Å−3 |
3563 reflections | Δρmin = −0.30 e Å−3 |
200 parameters |
x | y | z | Uiso*/Ueq | 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* |
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) |
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) |
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···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. |
Experimental details
Crystal data | |
Chemical formula | C15H15N3O·3H2O |
Mr | 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) |
Tmin, Tmax | 0.949, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14799, 3563, 1982 |
Rint | 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 |
Δρmax, Δρmin (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).
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) |
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···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. |
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
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Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
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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.