3,4,5-Trihydr-oxy-N'-(1H-indol-2-ylmethyl-idene)benzohydrazide-1H-indole-2-carbaldehyde azine-methanol (2/1/2).
ABSTRACT The title compound, 2C(16)H(13)N(3)O(4)·C(18)H(14)N(4)·2CH(4)O, was crystallized from the reaction between 3,4,5-trihydroxy-benzoyl-hydrazine and indole-2-carbaldehyde in a mixture of ethanol and methanol. The compound is a stoichiometric 2:1 cocrystal of the methanol-solvated reaction product, 3,4,5-trihydr-oxy-N'-(1H-indol-2-ylmethyl-idene)benzohydrazide and 1H-indole-2-carbaldehyde azine that arose unexpectedly during the synthesis. The former mol-ecules are linked by O-H⋯O hydrogen bonds and also by π-π stacking inter-actions between benzoyl-hydrazide rings into a two-dimensional network. The methanol solvent mol-ecules are hydrogen bonded to this network. The centrosymmetric azine mol-ecules are not engaged in hydrogen bonding.
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Article: A short history of SHELX.[Show abstract] [Hide abstract]
ABSTRACT: An account is given of the development of the SHELX system of computer programs from SHELX-76 to the present day. In addition to identifying useful innovations that have come into general use through their implementation in SHELX, a critical analysis is presented of the less-successful features, missed opportunities and desirable improvements for future releases of the software. An attempt is made to understand how a program originally designed for photographic intensity data, punched cards and computers over 10000 times slower than an average modern personal computer has managed to survive for so long. SHELXL is the most widely used program for small-molecule refinement and SHELXS and SHELXD are often employed for structure solution despite the availability of objectively superior programs. SHELXL also finds a niche for the refinement of macromolecules against high-resolution or twinned data; SHELXPRO acts as an interface for macromolecular applications. SHELXC, SHELXD and SHELXE are proving useful for the experimental phasing of macromolecules, especially because they are fast and robust and so are often employed in pipelines for high-throughput phasing. This paper could serve as a general literature citation when one or more of the open-source SHELX programs (and the Bruker AXS version SHELXTL) are employed in the course of a crystal-structure determination.Acta Crystallographica Section A Foundations of Crystallography 02/2008; 64(Pt 1):112-22. · 2.24 Impact Factor
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ABSTRACT: The two aromatic parts of the title compound, C(16)H(13)ClN(3)O(4), are connected through a conjugated -CH=N-NH-C(O)- fragment, giving an almost planar mol-ecule (r.m.s. deviation 0.08 Å). In the crystal structure, adjacent mol-ecules are linked by N-H⋯O and O-H⋯O hydrogen bonds into a three-dimensional network.Acta Crystallographica Section E Structure Reports Online 01/2008; 65(Pt 1):o169. · 0.35 Impact Factor
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ABSTRACT: The two aromatic parts of the title mol-ecule, C(16)H(12)BrN(3)O(4), are connected through a conjugated -CH=N-NH-C(O)- fragment to furnish an almost planar mol-ecule. Adjacent mol-ecules are linked by N-H⋯O and O-H⋯O hydrogen bonds into a three-dimensional network. An intramolecular O-H⋯O link also occurs.Acta Crystallographica Section E Structure Reports Online 01/2008; 64(Pt 11):o2108. · 0.35 Impact Factor
3,4,5-Trihydroxy-N0 0 0-(1H-indol-2-yl-
2-carbaldehyde azine–methanol (2/1/2)
Hamid Khaledi,a* Abeer A. Alhadi,aHapipah Mohd Ali,a
Ward T. Robinsonaand Mahmood A. Abdullab
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia,
andbDepartment of Molecular Medicine, University of Malaya, 50603 Kuala
Correspondence e-mail: firstname.lastname@example.org
Received 23 November 2009; accepted 6 December 2009
Key indicators: single-crystal X-ray study; T = 100 K; mean ?(C–C) = 0.006 A ˚;
R factor = 0.064; wR factor = 0.153; data-to-parameter ratio = 11.5.
The title compound, 2C16H13N3O4?C18H14N4?2CH4O, was
crystallized from the reaction between 3,4,5-trihydroxy-
benzoylhydrazine and indole-2-carbaldehyde in a mixture of
ethanol and methanol. The compound is a stoichiometric
2:1 cocrystal of the methanol-solvated reaction product, 3,4,5-
and 1H-indole-2-carbaldehyde azine that arose unexpectedly
during the synthesis. The former molecules are linked by O—
H???O hydrogen bonds and also by ?–? stacking interactions
between benzoylhydrazide rings into a two-dimensional
network. The methanol solvent molecules are hydrogen
bonded to this network. The centrosymmetric azine molecules
are not engaged in hydrogen bonding.
For the crystal structures of some compounds similar to 3,4,5-
see: Khaledi et al. (2008a,b, 2009a,b). For the structure of 1H-
indole-2-carbaldehyde azine, see: Rizal et al. (2008). For the
biological activity of gallic acid (3,4,5-trihydroxybenzoic acid)
derivatives see: Arunkumar et al. (2006); Saxena et al. (2008).
a = 7.4642 (15) A˚
b = 12.791 (2) A˚
c = 25.079 (5) A˚
? = 95.918 (3)?
? = 95.166 (4)?
? = 101.451 (4)?
V = 2319.3 (8) A˚3
Z = 2
Mo K? radiation
? = 0.10 mm?1
T = 100 K
0.50 ? 0.12 ? 0.03 mm
Bruker APEXII CCD
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin= 0.952, Tmax= 0.997
10985 measured reflections
7939 independent reflections
4029 reflections with I > 2?(I)
R[F2> 2?(F2)] = 0.064
wR(F2) = 0.153
S = 0.98
H atoms treated by a mixture of
independent and constrained
??max= 0.30 e A˚?3
??min= ?0.32 e A˚?3
Hydrogen-bond geometry (A˚,?).
Symmetry codes: (i) ?x þ 2;?y;?z þ 1; (ii) x;y ? 1;z; (iii) ?x þ 1;?y þ 1;?z þ 1;
(iv) ?x þ 1;?y;?z þ 1; (v) ?x þ 3;?y þ 1;?z þ 1.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT
(Bruker, 2007); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-
SEED (Barbour, 2001) and Mercury (Macrae et al., 2008); software
used to prepare material for publication: publCIF (Westrip, 2009).
The authors thank the University of Malaya for funding this
study (FRGS grant FP009/2008 C).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: OM2302).
Acta Cryst. (2010). E66, o105–o106 doi:10.1107/S1600536809052465 Khaledi et al.
Acta Crystallographica Section E
Arunkumar, S., Ramalakshmi, N., Saraswathy, T. & Aruloly, L. (2006). Indian
J. Heterocycl. Chem. 16, 29–32.
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
Khaledi, H., Mohd Ali, H. & Ng, S. W. (2008a). Acta Cryst. E64, o2108.
Khaledi, H., Mohd Ali, H. & Ng, S. W. (2008b). Acta Cryst. E64, o2481.
Khaledi, H., Mohd Ali, H. & Ng, S. W. (2009a). Acta Cryst. E65, o169.
Khaledi, H., Saharin, S. M., Mohd Ali, H., Robinson, W. T. & Abdulla, M. A.
(2009b). Acta Cryst. E65, o1920.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P.,
Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P.
A. (2008). J. Appl. Cryst. 41, 466–470.
Rizal, M. R., Ali, H. M. & Ng, S. W. (2008). Acta Cryst. E64, o555.
Saxena, H. O., Faridi, U., Srivastava, S., Kumar, J. K., Darokar, M. P., Luqman,
S., Chanotiya, C. S., Krishna, V., Negi, A. S. & Khanuja, S. P. S. (2008).
Bioorg. Med. Chem. Lett. 18, 3914–3918.
Sheldrick, G. M. (1996). SADABS. University of Go ¨ttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Westrip, S. P. (2009). publCIF. In preparation.
Khaledi et al.
Acta Cryst. (2010). E66, o105–o106
Acta Cryst. (2010). E66, o105-o106 [ doi:10.1107/S1600536809052465 ]
H. Khaledi, A. A. Alhadi, H. Mohd Ali, W. T. Robinson and M. A. Abdulla
Gallic acid (3,4,5-trihydroxybenzoic acid) derivatives have been studied for various biological activities including antican-
cer (Saxena et al., 2008), antioxidant and antimicrobial activity (Arunkumar et al., 2006). In order to prepare a new deriv-
ative of gallic acid, the reaction between 3,4,5-trihydroxybenzoylhydrazine and indole-2-carboxaldehyde was carried out
to synthesize the related gallichydrazone; 3,4,5-trihydroxy-N'-[(1H-indol-2-yl)methylidene]benzoylhydrazide. However, a
crystal suitable for X-ray diffraction was unexpectedly obtained during the synthesis.
A view of the title structure is illustrated in Fig. 1. The asymmetric unit contains two molecules of the gallic hydrazone
with different conformation. In one of them, (I), the aromatic rings are nearly coplanar [dihedral angle = 11.00 (0.16) °],
similar to the related previously reported structures (Khaledi et al., 2008a, 2008b, 2009a, 2009b), whereas in the other one,
(II), they are highly twisted with respect to each other, the dihedral angle between the two ring planes being 52.43 (0.11)
°. The crystal structure is an infinite two-dimensional, hydrogen bonded, network of gallic hydrazone molecules (Fig. 2)
with methanol solvate molecules. In addition, π–π interactions between aromatic rings occur. The benzoylhydrazide rings of
molecule (I) and the symmetry-related planes at (-x+2, -y, -z+1 and -x+1, -y, -z + 1) are arranged in an antiparallel manner
above each other in an infinite one dimensional chain with centroid separations of 3.783 (2) Å and 3.973 (2) Å alternatively.
The benzoylhydrazide ring of molecule (II) and the symmetry-related plane at (-x + 2, -y + 1, -z + 1) also interact with
one another through π–π stacking, with a centroid-centroid distances of 3.703 (2) Å, leading to a dimer. The framework
is interdigitated with solvate azine molecules (Fig. 4) in the ratio of one for every two hydrazone molecules. The azine
constituent, which is an unexpected decomposition product of the reaction, is almost planar [maximum deviation 0.21 (1)
A°] with a trans configuration about N—N single bond, similar to its indole-3-carbaldehyde analogue (Rizal et al., 2008).
A solution of indole-2-carboxaldehyde (0.725 g, 5 mmol) in methanol (20 ml) was added to a solution of 3,4,5-trihydroxy-
benzoylhydrazine (0.92 g, 5 mmol) in ethanol (60 ml). Furthermore, 1 ml of acetic acid was added and the mixture was
refluxed for 4 h. The solution was then cooled and filtered to remove the unreacted hydrazide.The filtrate was set aside at
room temperature overnight and crystals of the title compound were collected.
C-bound hydrogen atoms were placed at calculated positions (C–H 0.95 Å), and were treated as riding on their parent carbon
atoms, with U(H) set to 1.2Ueq(C). The nitrogen- and oxygen-bound H atoms were located in a difference Fourier map, and
were refined with distance restraints of N–H 0.88±0.01 and O–H 0.84±0.01 Å.
Fig. 1. Perspective view of one crystal chemical unit of the title compound defining the atom
labelling scheme and showing 40% probability displacement ellipsoids.
Fig. 2. Packing view looking down the crystallographic α unit cell edge and showing all the
links, between electronegative O and N atoms, which are within the range for normal hydro-
Fig. 3. A view of the intermolecular π–π interactions between gallic hydrazone molecules. H
atoms have been omitted for clarity. [Symmetry codes: (i) -x + 2, -y, -z + 1; (ii) -x + 1, -y, -z +
1; (iii) -x + 2, -y + 1, -z + 1.]
Fig. 4. Packing view looking down the crystallographic b unit cell edge thus emphasizing the
two-dimensional extension of the polymeric network and the interdigitation with hydrazine
3,4,5-Trihydroxy-N'-(1H-indol-2-ylmethylidene)benzohydrazide– 1H-indole-2-carbaldehyde azine–methanol (2/
Mr = 973.00
Z = 2
F(000) = 1020
Dx = 1.393 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 754 reflections
θ = 2.5–20.7°
µ = 0.10 mm−1
T = 100 K
0.50 × 0.12 × 0.03 mm
Hall symbol: -P 1
a = 7.4642 (15) Å
b = 12.791 (2) Å
c = 25.079 (5) Å
α = 95.918 (3)°
β = 95.166 (4)°
γ = 101.451 (4)°
V = 2319.3 (8) Å3
Bruker APEXII CCD
7939 independent reflections