Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102004511/gd1194sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004511/gd1194Isup2.hkl |
CCDC reference: 187926
dpkabz was synthesized from the reaction between p-aminobenzhydrazide and di-2-pyridyl ketone in refluxing ethanol/HCl solution, using a procedure similar to that reported for the synthesis of dpknph by Bakir & Abdur-Rashid (1999). When dpkabz was allowed to stand in ethanol/hexanes solution for several days at room temperature, yellow-brown crystals of dpkabz·H2O, (I), were obtained. A single-crystal was selected and mounted on a glass fibre using epoxy cement, and used for data collection.
With the exception of atoms H1 and H2, which were assigned from a difference Fourier map and refined freely, all H atoms were assigned by assuming idealized geometry, with C—H = 0.93 Å and N—H = 0.86 Å.
Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C18H15N5O·H2O | F(000) = 352 |
Mr = 335.37 | Dx = 1.308 Mg m−3 |
Triclinic, P1 | Melting point: 400 K |
a = 8.6648 (10) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.9630 (16) Å | Cell parameters from 46 reflections |
c = 11.1996 (11) Å | θ = 3.9–12.4° |
α = 91.083 (9)° | µ = 0.09 mm−1 |
β = 109.199 (5)° | T = 298 K |
γ = 109.571 (10)° | Octahedral, yellow-brown |
V = 851.21 (19) Å3 | 0.40 × 0.25 × 0.10 mm |
Z = 2 |
Bruker P4 diffractometer | 1820 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 32.5°, θmin = 2.0° |
2θ/ω scans | h = −1→13 |
Absorption correction: empirical (using intensity measurements) via ψ-scans (XSCANS; Bruker, 1996) | k = −14→14 |
Tmin = 0.957, Tmax = 0.991 | l = −16→16 |
7103 measured reflections | 3 standard reflections every 97 reflections |
6067 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.124 | w = 1/[σ2(Fo2) + (0.02P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max < 0.001 |
6067 reflections | Δρmax = 0.19 e Å−3 |
235 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0156 (15) |
C18H15N5O·H2O | γ = 109.571 (10)° |
Mr = 335.37 | V = 851.21 (19) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.6648 (10) Å | Mo Kα radiation |
b = 9.9630 (16) Å | µ = 0.09 mm−1 |
c = 11.1996 (11) Å | T = 298 K |
α = 91.083 (9)° | 0.40 × 0.25 × 0.10 mm |
β = 109.199 (5)° |
Bruker P4 diffractometer | 1820 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ-scans (XSCANS; Bruker, 1996) | Rint = 0.029 |
Tmin = 0.957, Tmax = 0.991 | 3 standard reflections every 97 reflections |
7103 measured reflections | intensity decay: none |
6067 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.124 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | Δρmax = 0.19 e Å−3 |
6067 reflections | Δρmin = −0.18 e Å−3 |
235 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The deepest hole, with an electron density of -0.18 e Å-3, appeared 0.77 Å from atom H5A. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.5842 (2) | 0.30151 (16) | 0.32922 (14) | 0.0743 (5) | |
C11 | 0.4877 (3) | 0.1993 (2) | 0.3790 (2) | 0.0963 (9) | |
H11A | 0.4935 | 0.2220 | 0.4617 | 0.116* | |
C12 | 0.3817 (3) | 0.0645 (2) | 0.3159 (2) | 0.0887 (8) | |
H12A | 0.3155 | −0.0020 | 0.3539 | 0.106* | |
C13 | 0.3755 (3) | 0.0300 (2) | 0.19650 (19) | 0.0810 (7) | |
H13A | 0.3052 | −0.0613 | 0.1511 | 0.097* | |
C14 | 0.4738 (3) | 0.13115 (19) | 0.14301 (17) | 0.0666 (6) | |
H14A | 0.4711 | 0.1083 | 0.0612 | 0.080* | |
C15 | 0.5769 (2) | 0.26686 (17) | 0.21077 (16) | 0.0531 (5) | |
C1 | 0.6862 (2) | 0.37739 (17) | 0.15655 (15) | 0.0489 (4) | |
N2 | 0.4948 (2) | 0.32413 (15) | −0.06348 (13) | 0.0577 (4) | |
C21 | 0.4712 (3) | 0.31476 (19) | −0.18867 (17) | 0.0658 (5) | |
H21A | 0.3584 | 0.2944 | −0.2470 | 0.079* | |
C22 | 0.6033 (3) | 0.3335 (2) | −0.23497 (18) | 0.0698 (6) | |
H22A | 0.5806 | 0.3278 | −0.3224 | 0.084* | |
C23 | 0.7696 (3) | 0.3607 (2) | −0.15089 (18) | 0.0682 (6) | |
H23A | 0.8616 | 0.3722 | −0.1799 | 0.082* | |
C24 | 0.7971 (3) | 0.37061 (18) | −0.02213 (17) | 0.0576 (5) | |
H24A | 0.9085 | 0.3880 | 0.0372 | 0.069* | |
C25 | 0.6590 (2) | 0.35461 (16) | 0.01796 (15) | 0.0484 (4) | |
N3 | 0.80950 (19) | 0.49946 (14) | 0.21342 (12) | 0.0500 (4) | |
N4 | 0.84465 (19) | 0.54217 (13) | 0.33902 (12) | 0.0511 (4) | |
H4A | 0.7931 | 0.4862 | 0.3828 | 0.061* | |
C2 | 0.9646 (2) | 0.67696 (18) | 0.39298 (15) | 0.0501 (4) | |
O2 | 1.05071 (18) | 0.75088 (13) | 0.33431 (11) | 0.0727 (4) | |
C31 | 0.9784 (2) | 0.72869 (17) | 0.52141 (14) | 0.0462 (4) | |
C32 | 1.0880 (3) | 0.86984 (18) | 0.57435 (16) | 0.0611 (5) | |
H32A | 1.1512 | 0.9263 | 0.5288 | 0.073* | |
C33 | 1.1049 (3) | 0.92749 (19) | 0.69182 (16) | 0.0650 (6) | |
H33A | 1.1790 | 1.0223 | 0.7244 | 0.078* | |
C34 | 1.0138 (3) | 0.84741 (18) | 0.76295 (15) | 0.0556 (5) | |
C35 | 0.9039 (3) | 0.70589 (18) | 0.71144 (15) | 0.0597 (5) | |
H35A | 0.8414 | 0.6494 | 0.7574 | 0.072* | |
C36 | 0.8871 (2) | 0.64892 (18) | 0.59283 (16) | 0.0571 (5) | |
H36A | 0.8124 | 0.5543 | 0.5598 | 0.068* | |
N5 | 1.0333 (2) | 0.90457 (17) | 0.88126 (13) | 0.0776 (6) | |
H5A | 1.1032 | 0.9917 | 0.9126 | 0.093* | |
H5B | 0.9758 | 0.8534 | 0.9244 | 0.093* | |
O1 | 0.8545 (3) | 0.76604 (18) | 1.05729 (18) | 0.0799 (5) | |
H1 | 0.738 (4) | 0.728 (3) | 1.038 (2) | 0.126 (11)* | |
H2 | 0.899 (4) | 0.738 (3) | 1.124 (3) | 0.144 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0835 (13) | 0.0663 (10) | 0.0572 (9) | −0.0013 (9) | 0.0348 (9) | −0.0001 (8) |
C11 | 0.112 (2) | 0.0878 (16) | 0.0662 (13) | −0.0082 (15) | 0.0481 (14) | 0.0050 (12) |
C12 | 0.0872 (18) | 0.0733 (14) | 0.0783 (15) | −0.0070 (13) | 0.0317 (14) | 0.0157 (12) |
C13 | 0.0945 (18) | 0.0521 (11) | 0.0692 (14) | 0.0049 (12) | 0.0171 (13) | 0.0112 (10) |
C14 | 0.0813 (15) | 0.0472 (10) | 0.0579 (11) | 0.0094 (10) | 0.0224 (11) | 0.0045 (9) |
C15 | 0.0573 (12) | 0.0476 (9) | 0.0484 (10) | 0.0125 (9) | 0.0181 (9) | 0.0036 (8) |
C1 | 0.0532 (11) | 0.0435 (9) | 0.0465 (9) | 0.0135 (9) | 0.0177 (9) | 0.0018 (7) |
N2 | 0.0586 (11) | 0.0576 (9) | 0.0501 (8) | 0.0157 (8) | 0.0167 (8) | 0.0029 (7) |
C21 | 0.0698 (15) | 0.0672 (12) | 0.0505 (11) | 0.0211 (11) | 0.0131 (10) | 0.0047 (9) |
C22 | 0.0914 (18) | 0.0659 (12) | 0.0477 (11) | 0.0193 (12) | 0.0289 (12) | 0.0002 (9) |
C23 | 0.0759 (16) | 0.0656 (12) | 0.0645 (12) | 0.0142 (11) | 0.0388 (12) | −0.0022 (10) |
C24 | 0.0553 (12) | 0.0557 (10) | 0.0550 (11) | 0.0112 (9) | 0.0207 (9) | −0.0032 (8) |
C25 | 0.0508 (11) | 0.0408 (9) | 0.0475 (9) | 0.0087 (8) | 0.0184 (9) | −0.0021 (7) |
N3 | 0.0542 (10) | 0.0496 (8) | 0.0424 (7) | 0.0146 (7) | 0.0170 (7) | −0.0015 (6) |
N4 | 0.0598 (10) | 0.0441 (8) | 0.0414 (7) | 0.0083 (7) | 0.0191 (7) | −0.0011 (6) |
C2 | 0.0512 (11) | 0.0477 (9) | 0.0469 (9) | 0.0109 (9) | 0.0194 (9) | −0.0002 (8) |
O2 | 0.0834 (11) | 0.0608 (8) | 0.0597 (8) | −0.0048 (7) | 0.0402 (8) | −0.0085 (6) |
C31 | 0.0474 (11) | 0.0442 (9) | 0.0423 (9) | 0.0112 (8) | 0.0159 (8) | 0.0022 (7) |
C32 | 0.0694 (14) | 0.0497 (10) | 0.0551 (10) | 0.0028 (10) | 0.0302 (10) | 0.0008 (8) |
C33 | 0.0778 (15) | 0.0487 (10) | 0.0546 (11) | 0.0010 (10) | 0.0290 (10) | −0.0065 (8) |
C34 | 0.0659 (13) | 0.0524 (10) | 0.0434 (9) | 0.0145 (10) | 0.0205 (9) | 0.0016 (8) |
C35 | 0.0716 (14) | 0.0547 (10) | 0.0495 (10) | 0.0106 (10) | 0.0297 (10) | 0.0081 (8) |
C36 | 0.0643 (13) | 0.0430 (9) | 0.0532 (10) | 0.0057 (9) | 0.0217 (10) | 0.0021 (8) |
N5 | 0.1009 (15) | 0.0698 (10) | 0.0504 (9) | 0.0089 (10) | 0.0354 (9) | −0.0076 (7) |
O1 | 0.0798 (13) | 0.0870 (11) | 0.0781 (11) | 0.0231 (10) | 0.0409 (10) | 0.0291 (9) |
N1—C15 | 1.340 (2) | C24—H24A | 0.9300 |
N1—C11 | 1.344 (2) | N3—N4 | 1.3643 (16) |
C11—C12 | 1.363 (3) | N4—C2 | 1.3675 (19) |
C11—H11A | 0.9300 | N4—H4A | 0.8600 |
C12—C13 | 1.354 (3) | C2—O2 | 1.2260 (18) |
C12—H12A | 0.9300 | C2—C31 | 1.472 (2) |
C13—C14 | 1.372 (2) | C31—C36 | 1.384 (2) |
C13—H13A | 0.9300 | C31—C32 | 1.391 (2) |
C14—C15 | 1.381 (2) | C32—C33 | 1.368 (2) |
C14—H14A | 0.9300 | C32—H32A | 0.9300 |
C15—C1 | 1.478 (2) | C33—C34 | 1.382 (2) |
C1—N3 | 1.2957 (19) | C33—H33A | 0.9300 |
C1—C25 | 1.492 (2) | C34—N5 | 1.3668 (19) |
N2—C25 | 1.340 (2) | C34—C35 | 1.391 (2) |
N2—C21 | 1.345 (2) | C35—C36 | 1.377 (2) |
C21—C22 | 1.366 (3) | C35—H35A | 0.9300 |
C21—H21A | 0.9300 | C36—H36A | 0.9300 |
C22—C23 | 1.368 (3) | N5—H5A | 0.8600 |
C22—H22A | 0.9300 | N5—H5B | 0.8600 |
C23—C24 | 1.378 (2) | O1—H1 | 0.90 (3) |
C23—H23A | 0.9300 | O1—H2 | 0.83 (3) |
C24—C25 | 1.374 (2) | ||
C15—N1—C11 | 117.43 (16) | N2—C25—C24 | 122.71 (16) |
N1—C11—C12 | 124.1 (2) | N2—C25—C1 | 116.05 (16) |
N1—C11—H11A | 118.0 | C24—C25—C1 | 121.17 (17) |
C12—C11—H11A | 118.0 | C1—N3—N4 | 119.37 (14) |
C13—C12—C11 | 118.2 (2) | N3—N4—C2 | 117.83 (13) |
C13—C12—H12A | 120.9 | N3—N4—H4A | 121.1 |
C11—C12—H12A | 120.9 | C2—N4—H4A | 121.1 |
C12—C13—C14 | 119.37 (19) | O2—C2—N4 | 120.86 (15) |
C12—C13—H13A | 120.3 | O2—C2—C31 | 122.73 (15) |
C14—C13—H13A | 120.3 | N4—C2—C31 | 116.37 (15) |
C13—C14—C15 | 119.91 (18) | C36—C31—C32 | 117.11 (15) |
C13—C14—H14A | 120.0 | C36—C31—C2 | 125.10 (14) |
C15—C14—H14A | 120.0 | C32—C31—C2 | 117.77 (15) |
N1—C15—C14 | 121.02 (16) | C33—C32—C31 | 121.50 (16) |
N1—C15—C1 | 117.77 (15) | C33—C32—H32A | 119.2 |
C14—C15—C1 | 121.20 (15) | C31—C32—H32A | 119.2 |
N3—C1—C15 | 128.82 (14) | C32—C33—C34 | 121.22 (16) |
N3—C1—C25 | 111.42 (14) | C32—C33—H33A | 119.4 |
C15—C1—C25 | 119.76 (14) | C34—C33—H33A | 119.4 |
C25—N2—C21 | 116.57 (17) | N5—C34—C33 | 121.06 (16) |
N2—C21—C22 | 123.7 (2) | N5—C34—C35 | 120.96 (17) |
N2—C21—H21A | 118.1 | C33—C34—C35 | 117.98 (15) |
C22—C21—H21A | 118.1 | C36—C35—C34 | 120.42 (17) |
C21—C22—C23 | 119.08 (18) | C36—C35—H35A | 119.8 |
C21—C22—H22A | 120.5 | C34—C35—H35A | 119.8 |
C23—C22—H22A | 120.5 | C35—C36—C31 | 121.78 (15) |
C22—C23—C24 | 118.3 (2) | C35—C36—H36A | 119.1 |
C22—C23—H23A | 120.9 | C31—C36—H36A | 119.1 |
C24—C23—H23A | 120.9 | C34—N5—H5A | 120.0 |
C25—C24—C23 | 119.58 (19) | C34—N5—H5B | 120.0 |
C25—C24—H24A | 120.2 | H5A—N5—H5B | 120.0 |
C23—C24—H24A | 120.2 | H1—O1—H2 | 106 (3) |
C15—N1—C11—C12 | −1.0 (4) | N3—C1—C25—C24 | 50.9 (2) |
N1—C11—C12—C13 | 1.3 (4) | C15—C1—C25—C24 | −129.45 (19) |
C11—C12—C13—C14 | −0.5 (4) | C15—C1—N3—N4 | −3.7 (3) |
C12—C13—C14—C15 | −0.4 (3) | C25—C1—N3—N4 | 175.92 (14) |
C11—N1—C15—C14 | 0.0 (3) | C1—N3—N4—C2 | −174.31 (16) |
C11—N1—C15—C1 | −178.45 (19) | N3—N4—C2—O2 | −7.4 (3) |
C13—C14—C15—N1 | 0.7 (3) | N3—N4—C2—C31 | 170.29 (15) |
C13—C14—C15—C1 | 179.12 (19) | O2—C2—C31—C36 | −178.64 (18) |
N1—C15—C1—N3 | 10.7 (3) | N4—C2—C31—C36 | 3.7 (3) |
C14—C15—C1—N3 | −167.73 (19) | O2—C2—C31—C32 | 3.1 (3) |
N1—C15—C1—C25 | −168.84 (18) | N4—C2—C31—C32 | −174.54 (16) |
C14—C15—C1—C25 | 12.7 (3) | C36—C31—C32—C33 | 0.0 (3) |
C25—N2—C21—C22 | 0.4 (3) | C2—C31—C32—C33 | 178.35 (18) |
N2—C21—C22—C23 | 1.3 (3) | C31—C32—C33—C34 | 0.2 (3) |
C21—C22—C23—C24 | −1.1 (3) | C32—C33—C34—N5 | 178.85 (19) |
C22—C23—C24—C25 | −0.7 (3) | C32—C33—C34—C35 | 0.0 (3) |
C21—N2—C25—C24 | −2.4 (2) | N5—C34—C35—C36 | −179.14 (18) |
C21—N2—C25—C1 | 174.85 (14) | C33—C34—C35—C36 | −0.3 (3) |
C23—C24—C25—N2 | 2.5 (3) | C34—C35—C36—C31 | 0.4 (3) |
C23—C24—C25—C1 | −174.55 (15) | C32—C31—C36—C35 | −0.3 (3) |
N3—C1—C25—N2 | −126.34 (17) | C2—C31—C36—C35 | −178.52 (18) |
C15—C1—C25—N2 | 53.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···N1 | 0.86 | 2.01 | 2.656 (2) | 131 |
N5—H5B···O1 | 0.86 | 2.13 | 2.979 (2) | 168 |
C14—H14A···N2 | 0.93 | 2.57 | 3.048 (2) | 112 |
N5—H5A···O1i | 0.86 | 2.32 | 3.086 (2) | 149 |
O1—H1···N2ii | 0.90 (3) | 2.03 (3) | 2.880 (3) | 158 (2) |
O1—H2···O2iii | 0.83 (3) | 2.26 (3) | 3.043 (2) | 158 (3) |
O1—H2···N3iii | 0.83 (3) | 2.57 (3) | 3.193 (2) | 133 (3) |
C23—H23A···O2iv | 0.93 | 2.55 | 3.325 (2) | 142 |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+1, −z+1; (iii) x, y, z+1; (iv) −x+2, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C18H15N5O·H2O |
Mr | 335.37 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.6648 (10), 9.9630 (16), 11.1996 (11) |
α, β, γ (°) | 91.083 (9), 109.199 (5), 109.571 (10) |
V (Å3) | 851.21 (19) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.25 × 0.10 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ-scans (XSCANS; Bruker, 1996) |
Tmin, Tmax | 0.957, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7103, 6067, 1820 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.756 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.124, 0.95 |
No. of reflections | 6067 |
No. of parameters | 235 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.18 |
Computer programs: XSCANS (Bruker, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
C15—C1 | 1.478 (2) | C2—O2 | 1.2260 (18) |
C1—N3 | 1.2957 (19) | C2—C31 | 1.472 (2) |
C1—C25 | 1.492 (2) | C34—N5 | 1.3668 (19) |
N3—N4 | 1.3643 (16) | O1—H1 | 0.90 (3) |
N4—C2 | 1.3675 (19) | O1—H2 | 0.83 (3) |
C15—N1—C11 | 117.43 (16) | C1—N3—N4 | 119.37 (14) |
N1—C11—C12 | 124.1 (2) | N3—N4—C2 | 117.83 (13) |
N3—C1—C15 | 128.82 (14) | O2—C2—N4 | 120.86 (15) |
N3—C1—C25 | 111.42 (14) | O2—C2—C31 | 122.73 (15) |
C15—C1—C25 | 119.76 (14) | N4—C2—C31 | 116.37 (15) |
C25—N2—C21 | 116.57 (17) | H1—O1—H2 | 106 (3) |
N2—C21—C22 | 123.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···N1 | 0.86 | 2.01 | 2.656 (2) | 131 |
N5—H5B···O1 | 0.86 | 2.13 | 2.979 (2) | 168 |
C14—H14A···N2 | 0.93 | 2.57 | 3.048 (2) | 112 |
N5—H5A···O1i | 0.86 | 2.32 | 3.086 (2) | 149 |
O1—H1···N2ii | 0.90 (3) | 2.03 (3) | 2.880 (3) | 158 (2) |
O1—H2···O2iii | 0.83 (3) | 2.26 (3) | 3.043 (2) | 158 (3) |
O1—H2···N3iii | 0.83 (3) | 2.57 (3) | 3.193 (2) | 133 (3) |
C23—H23A···O2iv | 0.93 | 2.55 | 3.325 (2) | 142 |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+1, −z+1; (iii) x, y, z+1; (iv) −x+2, −y+1, −z. |
Hydrazones and their metal compounds have been studied for their physical properties, reactivity patterns and applications in a variety of processes, including nonlinear optics and molecular sensing (Bakir et al., 2000, Bakir, 2002a,b,c; Pan et al., 1997). We have been interested in the chemistry of di-2-pyridyl ketone and its oxime and hydrazone derivatives, and have reported on the structures of Re compounds of the type fac-Re(CO)3(L—L)Cl, where L—L is di-2-pyridyl ketone p-nitrophenylhydrazone (dpknph), di-2-pyridyl ketone 2,4-dinitrophenylhydrazone (dpkdnph), di-2-pyridyl ketone phenylhydrazone (dpkphh) or di-2-pyridyl oxime (dpkoxime) (Bakir & McKenzie, 1997a,b; Bakir & Abdur-Rashid, 1999; Bakir, 1999, 2001a,b, 2002a,b,c). Structural studies on the optical sensor di-2-pyridyl ketone benzoylhydrazone (dpkbz) revealed a network of non-covalent interactions that may account for its optosensing behaviour (Bakir & Brown, 2002). Here, we report on the structure of di-2-pyridyl ketone p-aminobenzoylhydrazone hydrate, dpkabz·H2O, (I). \sch
The molecular structure of (I) is shown in Fig. 1, and selected bond distances and angles are given in Table 1. The p-aminobenzoylhydrazone moiety and the N1 pyridine ring are coplanar, and orthogonal to the N2 pyridine ring. The orthogonality of the pyridine rings is similar to what is observed in dpkhydrazones such as dpkbz and di-2-pyridyl ketone 2-pyridylhydrazone (dpkph) (Bakir & Brown, 2002; Ishak et al., 1984). The bond distances and angles are normal, and similar to those reported for dpkbz and other related compounds. For example, in dpkbz, C═N, N—N and C═O bond distances of 1.30 (2), 1.36 (2) and 1.22 (2) Å, respectively, and N—N═C, O═C—N and O═C—C bond angles of 120.6 (2), 123.6 (2) and 122.2 (2)°, respectively, were reported by Bakir & Brown (2002).
The packing of the molecules of (I) (Fig. 2) shows a web of dpkabz·H2O units interlocked via a network of classical and non-classical hydrogen bonds (Fig. 3, Table 2). The coordination about the O atom of the solvated water molecule is tetrahedral (Fig. 3a), with two H atoms from the p-amino groups and the two water H atoms occupying the coordination around O. Each solvated water molecule interlocks four dpkabz molecules through a web of classical hydrogen bonds of the type O—H···X, where X is O or N (Table 2, Fig. 3a), and each dpkabz molecule is hydrogen-bonded to adjacent dpkabz molecules through a network of non-classical hydrogen bonds of the type O···H—C (Fig. 3 b). The bond distances and angles of these hydrogen bonds are of the same order as those reported for dpkbzh and fac-Re(CO)3(dpknph)Cl.dmso (dmso is dimethyl sulfoxide) and other compounds containing such bonds (Bakir, 2001b; Bakir & Brown, 2002; Braga et al., 1998; Glusker et al., 1994). For example, hydrogen-bond parameters of 0.82, 1.88 and 2.68 Å, and 164° were reported for O···H—O in fac-Re(CO)3(dpkO,OH)Cl [dpkO,OH is hydroxybis(2-pyridyl)methanolato; Bakir, 2002c], and parameters of 1.00, 2.50 and 3.24 Å, and 130.6° were observed for the soft non-classical C—H···O hydrogen bond in dpkbz (Bakir & Brown, 2002).
Due to their convenient synthesis, rich physico-chemical properties and application in a variety of processes, work is in progress to prepare a series of di-2-pyridyl ketone hydrazones and their metal compounds to explore their solid-state structures and electro-optical properties.