Bis(5-amino-3-methyl-1-phenyl-1H-pyrazol-4-yl)-3,4,5-trimethoxyphenylmethane: sheets built from N-H...N and N-H...O hydrogen bonds

# 2004 International Union of Crystallography Printed in Great Britain ± all rights reserved In molecules of the title compound, C30H32N6O3, there is an intramolecular NÐH N hydrogen bond [H N = 2.28 AÊ , N N = 3.194 (3) AÊ and NÐH N = 167 ]. The molecules are linked by an NÐH O hydrogen bond [H O = 2.37 AÊ , N O = 3.255 (3) AÊ and NÐH O = 154 ] into C(10) chains along [100], and by an intermolecular NÐH N hydrogen bond [H N = 2.06 AÊ , N N = 2.958 (3) AÊ and NÐH N = 155 ] into C(8) chains along [001]; these chains combine to generate (010) sheets.

two sites, while that bonded to N13 is fully ordered. This disorder, and the orientations of these phenyl rings relative to the adjacent pyrazole rings, also rule out any internal molecular symmetry. The molecules of (I) are accordingly chiral in the solid state, although this chirality probably has no chemical signi®cance; however, the centrosymmetric space group accommodates equal numbers of the two enantiomers.
Within the trimethoxyphenyl unit, the methoxy groups based on O33 and O35 are almost coplanar with the adjacent benzene ring, whereas the C34ÐO34ÐC341 unit is nearly orthogonal to this ring. Associated with this difference, the exocyclic bond angles at C33 and C35 show the usual pattern of differences between the angles cisoid and transoid to the methyl group (Seip & Seip, 1973;Ferguson et al., 1996;Patterson et al., 1998;Abonia et al., 2003), while the two exocyclic angles at C34 are nearly identical. In addition, the bond O34ÐC34 is marginally longer than the bonds O33Ð C33 and O35ÐC35, again a stereoelectronic consequence of the different conformations of the methoxy substituents.
The corresponding bond distances within the two independent pyrazole units are very similar, and all are typical of their types (Allen et al., 1987): the CÐC bonds connecting the central atom C1 to the pyrazole units are markedly shorter than that to the trimethoxyphenyl ring.
The amino atoms N12 and N22 act respectively as double and single donors of hydrogen bonds, while N22 in addition acts as a single acceptor (Table 2). Within the molecule, N12 acts as hydrogen-bond donor, via H12A, to atom N22, forming an S(8) motif (Bernstein et al., 1995). Two intermolecular hydrogen bonds link the molecules into sheets, and the formation of the sheet is most readily analysed in terms of two simple one-dimensional substructures.
Amino atom N12 in the molecule at (x, y, z) acts as hydrogen-bond donor, via H12B, to methoxy atom O34 in the molecule at (1 + x, y, z), generating by translation a C(10) chain running parallel to the [100] direction (Fig. 2). In the second substructure, amino atom N22 in the molecule at (x, y, z) acts as hydrogen-bond donor, via H22A, to ring atom N14 in the molecule at (x, y, 1 + z), thus generating by translation a C(8) chain running parallel to the [001] direction (Fig. 3). Atom N22 acts only as a single donor of hydrogen bonds, and three are no other potential acceptors within hydrogenbonding distance. It may be noted here, ®rstly, that the intramolecular NÐHÁ Á ÁN hydrogen bond is likely to be an important in¯uence on the overall molecular conformation and, secondly, that the pattern of the intermolecular hydrogen bonds is itself suf®cient to preclude the possibility of any intramolecular symmetry.
The combination of the [100] and [001] chains generates a (010) sheet in the form of a (4,4)-net (Batten & Robson, 1998). Four sheets of this type pass through each unit cell, in the domains 0 < y < 0.25, 0.25 < y < 0.50, 0.50 < y < 0.75 and 0.75 < 1. 00 The molecule of compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. For the sake of clarity, only one orientation of the disordered phenyl ring is shown.

Figure 2
Part of the crystal structure of compound (I), showing the formation of a C(10) chain along [100]. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x À 1, y, z) and (1 + x, y, z), respectively. For the sake of clarity, H atoms bonded to C atoms have been omitted and only one orientation of the disordered phenyl ring is shown.
interactions in the structure and, despite the presence of three independent aryl rings, there are neither XÐHÁ Á Á%(arene) hydrogen bonds (X = C or N) nor aromatic %±% stacking interactions.
À6.5 (4) C12ÐN13ÐC131ÐC132 45.9 (3) C22ÐN23ÐC23AÐC23B À63.5 (4) Table 2 Hydrogen-bonding geometry (A Ê , ). All H atoms were located in difference maps and those bonded to carbon were then treated as riding atoms, with distances CÐH = 0.95 (aromatic), 0.98 (methyl) or 1.00 A Ê (aliphatic CH), and with U iso (H) =  For the sake of clarity, H atoms bonded to C atoms have been omitted and only one orientation of the disordered phenyl ring is shown.

Figure 3
Part of the crystal structure of compound (I), showing the formation of a C(8) chain along [001]. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, y, z À 1) and (x, y, 1 + z), respectively. For the sake of clarity, H atoms bonded to C atoms have been omitted and only one orientation of the disordered phenyl ring is shown.
1.2U eq (C), or 1.5U eq (C) for the methyl groups. The H atoms bonded to nitrogen were allowed to ride on their parent atoms at the distances deduced from the difference maps, with U iso (H) = 1.2U eq (N); the NÐH distances were in the range 0.93±0.96 A Ê . It became apparent at an early stage that the phenyl ring bonded to N23 was disordered. When this was modelled using two sets of atom sites, the re®ned occupancies of the two sets were identical within experimental uncertainty, and hence they were subsequently ®xed at 0.50. There is some indication from the displacement parameters that this ring might, indeed, be disordered over more than two sites, although no static disorder model could be found which was superior to the two-site model. Nonetheless, it was found desirable to treat both components of this disordered ring as planar rigid hexagons.
X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants which have provided computing facilities for this work. JC thanks the Consejerõ Âa de Educacio Â n y Ciencia (Junta de Andalucõ Âa, Spain) and the Universidad de Jae Â n for ®nancial support. JP and JQ thank COLCIENCIAS and the Universidad de Valle for ®nancial support.