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To examine the roles of competing inter­molecular inter­actions in differentiating the mol­ecular packing arrangements of some isomeric phenyl­hydrazones from each other, the crystal structures of five nitrile-halogen substituted phenyl­hydrazones and two nitro-halogen substituted phenyl­hydrazones have been determined and are described here: (E)-4-cyano­benzaldehyde 4-chloro­phenyl­hydrazone, C14H10ClN3, (Ia); (E)-4-cyano­benzaldehyde 4-bromo­phenyl­hydra­zone, C14H10BrN3, (Ib); (E)-4-cyano­benzaldehyde 4-iodo­phenyl­hydrazone, C14H10IN3, (Ic); (E)-4-bromo­benzaldehyde 4-cyano­phenyl­hydrazone, C14H10BrN3, (IIb); (E)-4-iodo­benzaldehyde 4-cyano­phenyl­hydrazone, C14H10IN3, (IIc); (E)-4-chloro­benzaldehyde 4-nitro­phenyl­hydrazone, C13H10ClN3O2, (III); and (E)-4-nitro­benzaldehyde 4-chloro­phenyl­hydrazone, C13H10ClN3O2, (IV). Both (Ia) and (Ib) are disordered (less than 7% of the molecules have the minor orientation in each structure). Pairs (Ia)/(Ib) and (IIb)/(IIc), related by a halogen exchange, are isomorphous, but none of the `bridge-flipped' isomeric pairs, viz. (Ib)/(IIb), (Ic)/(IIc) or (III)/(IV), is isomorphous. In the nitrile-halogen structures (Ia)-(Ic) and (IIb)-(IIc), only the bridge N-H group and not the bridge C-H group acts as a hydrogen-bond donor to the nitrile group, but in the nitro-halogen structures (III) (with Z' = 2) and (IV), both the bridge N-H group and the bridge C-H group inter­act with the nitro group as hydrogen-bond donors, albeit via different motifs. The occurrence here of the bridge C-H contact with a hydrogen-bond acceptor suggests the possibility that other pairs of `bridge-flipped' isomeric phenyl­hydrazones may prove to be isomorphous, regardless of the change from isomer to isomer in the position of the N-H group within the bridge.

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Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112026443/fg3255sup1.cif
Contains datablocks Ia, Ib, Ic, IIb, IIc, III, IV, global

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270112026443/fg3255Iasup2.hkl
Contains datablock Ia

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270112026443/fg3255Ibsup3.hkl
Contains datablock Ib

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270112026443/fg3255Icsup4.hkl
Contains datablock Ic

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270112026443/fg3255IIbsup5.hkl
Contains datablock IIb

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270112026443/fg3255IIcsup6.hkl
Contains datablock IIc

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270112026443/fg3255IIIsup7.hkl
Contains datablock III

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270112026443/fg3255IVsup8.hkl
Contains datablock IV

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Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112026443/fg3255Iasup9.cml
Supplementary material

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Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112026443/fg3255Ibsup10.cml
Supplementary material

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Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112026443/fg3255Icsup11.cml
Supplementary material

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Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112026443/fg3255IIbsup12.cml
Supplementary material

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Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112026443/fg3255IIcsup13.cml
Supplementary material

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Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112026443/fg3255IIIsup14.cml
Supplementary material

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Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112026443/fg3255IVsup15.cml
Supplementary material

CCDC references: 893498; 893499; 893500; 893501; 893502; 893503; 893504

Comment top

The analysis of intermolecular interactions for their potential utility in crystal engineering is a topic of ongoing interest. These have included the varieties of hydrogen bond ranging from the strong conventional type to the weak nonconventional type, as well as halogen–halogen contacts, halogen–nitrogen contacts and π stacking. For our part, we have been examining the role of interactions between the nitrile group and nearby halogen and H atoms in defining the solid-state molecular packing motifs assumed by pairs of molecules we have designated `bridge-flipped' isomers, molecules that differ only in the reversal of a bridge of atoms linking two major portions of the molecule (Ojala et al., 2007). Examples are readily identified among the benzylideneanilines (Ar1—CHN—Ar2 versus Ar1—NCH—Ar2; Ar = aryl) and phenylhydrazones (Ar1—CHN—NH—Ar2 versus Ar1—NH—NCH—Ar2; Ar = aryl). Pairs of bridge-flipped isomeric benzylideneanilines and phenylhydrazones may assume identical solid-state molecular packing arrangements by virtue of their closely similar space-filling requirements, although the number of reported isomorphous pairs is small (Ojala et al., 2007; Ferguson et al., 2005; Mocilak & Gallagher, 2011). Bridge-flipped isomers that happen not to be isomorphous offer a useful context for the comparison and analysis of molecular conformations, intermolecular interactions and packing motifs that differentiate the packing arrangements. In our studies, we have attempted to facilitate isomorphism by placing substituents on the molecules that would engage in similar intermolecular interactions in the two isomers. Similar motifs generated by these interactions, if packed in similar ways in the two isomers, should favour the formation of similar overall molecular packing arrangements. To date, we have focused primarily on the potential intermolecular Lewis acid–base interaction between the nitrile group and a halogen atom on a neighbouring molecule in the crystalline solid. Although this strategy in our own laboratory has yet to produce an isomorphous pair of bridge-flipped isomers, it has allowed us to examine the variety of motifs in which nitrile groups and halogen atoms engage, whether separately or with each other. In previous reports we have examined intermolecular interactions of this type primarily in bridge-flipped nitrile–halogen substituted benzylideneanilines (Ojala et al., 2009, 2001, 1999), where they play a significant role in defining the molecular packing arrangment. Here, we describe the interactions found in a group of bridge-flipped nitrile–halogen substituted phenylhydrazones.

Whether the potential nitrile–halogen intermolecular interaction can actually encourage isomorphism in phenylhydrazones is complicated by the presence of the N—H group in the phenylhydrazone bridge. This strong conventional hydrogen-bond donor, not present in the bridge of benzylideneanilines, could be expected to cause nitrile–halogen substituted bridge-flipped phenylhydrazones to assume different packing arrangements if the nitrile group were to hydrogen-bond to it rather than engage in Lewis acid–base interactions with the halogen atom. Reversal of the bridge from one isomer to the other would cause a substantial and probably structure-differentiating change in the position of the hydrogen-bonded groups. On the other hand, isomorphous pairs of bridge-flipped phenylhydrazones bearing hydrogen-bond acceptors are known, including the pair (E)-2-nitrobenzaldehyde 3-nitrophenylhydrazone [Cambridge Structural Database (CSD; Allen, 2002) refcode LAWCOC] and (E)-3-nitrobenzaldehyde 2-nitrophenylhydrazone (LAWJAV) (Ferguson et al., 2005) and the pair (E)-2-bromobenzaldehyde 4-cyanophenylhydrazone (RIFXOU) and (E)-4-cyanobenzaldehyde 2-bromophenylhydrazone (RIFXUA) (Ojala et al., 2007). In both these pairs, the hydrogen-bond acceptor (the nitro or nitrile group) is in contact (within the sum of the van der Waals radii) with both the N—H and C—H donors within the bridge; no clear preference for the stronger donor is shown by the acceptor. To find out how general this might be, and to examine what other structural motifs might be preferred given a choice among potential nitrile–hydrogen, nitrile–halogen and halogen–halogen contacts in the solid state, we have determined and describe here the crystal structures of the title cyanobenzaldehyde halophenylhydrazones, (Ia)–(Ic), and the halobenzaldehyde cyanophenylhydrazones, (IIb) and (IIc). [Regrettably, and in spite of our repeated efforts, we have not been successful in obtaining X-ray quality crystals of (IIa).]

Because one of the two previously published isomorphous pairs of bridge-flipped phenylhydrazones cited above (Ferguson et al., 2005) involves the nitro group rather than the nitrile group as the potential hydrogen-bond acceptor, we have extended our inquiry to nitro–halogen substituted phenylhydrazones in order to examine how discriminating the nitro group is as a potential acceptor of N—H versus C—H hydrogen bonds from phenylhydrazone bridges. We thus describe here, in addition to these nitrile–halogen substituted phenylhydrazones, the structures of the bridge-flipped isomeric pair of nitro–halogen (chlorine) substituted phenylhydrazones, (III) and (IV). None of the bridge-flipped isomeric pairs described here, whether nitrile- or nitro-substituted, proved to be isomorphous in our study, although several of the compounds related simply by the exchange of one halogen for another did; (Ia) and (Ib) are isomorphous, and (IIb) and (IIc) are isomorphous. Our purpose here is thus to determine which intermolecular interactions from an array of competing possibilities, including C N···H—N, CN···H—C, O—N—O···H—N, O—N—O···H—C, C N···X—C and C—X···X—C, are preferred in these structures and how these preferences differentiate the structures of these bridge-flipped isomers from each other.

Views of the isolated molecules of all seven title compounds are given in Figs. 1–7. All seven arylhydrazones possess the E configuration about the CN bond. All are nearly planar, with dihedral angles between the six-membered rings ranging from 7.31 (6)° in (Ia) to 25.38 (9)° in (IV). The conformational differences between the bridge-flipped isomers appear insufficient to explain completely their differences in crystal structure. The nitro groups in (III) and (IV) are essentially coplanar with the rings to which they are attached.

The packing arrangement assumed by both the cyanobenzaldehyde chlorophenylhydrazone, (Ia), and the cyanobenzaldehyde bromophenylhydrazone, (Ib), is shown in Fig. 8 for (Ia). Both structures show a small proportion [approximately 0.03 in (Ia) and 0.06 in (Ib)] of end-for-end disorder of the molecules; Fig. 8 shows the molecules as they are oriented in the major component of the disorder. The nitrile group in (Ia) and (Ib) is in contact with only the N—H group of the bridge and not with the C—H group (see Tables 1 and 2 for intermolecular N—H contact geometries). Even with this preference for the strong N—H donor over the weak C—H donor, the fact that the molecules are not locked into an entirely non-disordered pattern indicates that this particular interaction between the nitrile group and the bridge N—H may be relatively weak compared with other conventional hydrogen bonds. This is consistent with the observed donor-H···acceptor angle in these structures (Tables 1 and 2), which is unfavourable for strong hydrogen-bond formation (Wood et al., 2009). The nitrile group in (Ia) and (Ib) also engages in a centrosymmetric R22(10) motif (Bernstein et al., 1995) defined by C—H···NC (a ring C—H as opposed to a bridge C—H) contacts between the cyanobenzylidene moieties: for (Ia), H11···N3(-x, 2 - y, 1 - z) = 2.67 Å and C11—H11···N3(-x, 2 - y, 1 - z) = 144°; for (Ib), H11···N3(-x, 2 - y, 1 - z) = 2.66 Å and C11—H11···N3 (-x, 2 - y, 1 - z) = 144°. With respect to the halogen atoms, no close contacts of either the C—X···NC type or the C—X···X—C type are found. Instead, neighbouring molecules are connected by centrosymmetric interactions composed of C—H···X—C (a ring C—H) contacts involving the halophenylhydrazone moieties, defining an R22(8) motif: for (Ia), H3···Cl1(2 - x, 2 - y, -z) = 2.95 Å and C3—H3···Cl1(2 - x, 2 - y, -z) = 160°; for (Ib), H3···Br1(2 - x, 2 - y, -z) = 3.08 Å and C3—H3···Br1(2 - x, 2 - y, -z) = 160°. The halogen–hydrogen approach in (Ia) [Distance?] is closer than that in (Ib) [Distance?], which lies just outside the sum of the van der Waals radii [Value? Standard reference?] even though the Br atom is larger than the Cl atom. Our analysis has not revealed whether individual molecules assume disordered positions that would feature mixed cyclic motifs composed of both C—H···X—C and C—H···NC contacts, or whether instead entire chains of molecules are reversed and each cyclic motif is composed of only one kind of contact.

The hydrogen-bonded chain packing motif assumed by the cyanobenzaldehyde iodophenylhydrazone, (Ic), is shown in Fig. 9. As in (Ia) and (Ib), molecules of (Ic) are linked by an N—H···NC interaction, and no appreciable hydrogen bonding exists between the nitrile group and the bridge C—H. Iodine, as the strongest Lewis acid of the halogen atoms, may have offered the best opportunity for C—X···NC contacts, but these are excluded in (Ic) in favour of a strong N—H···NC contact that is more nearly linear than those in (Ia) and (Ib) (Table 3). In accord with this, the structure of (Ic) is ordered. Notably absent from the packing arrangement of (Ic) are the R22(10) motif defined by ring C—H···NC contacts and the R22(8) motif defined by ring C—H···X—C contacts present in (Ia) and (Ib), as are any C—X···X—C interactions involving the I atoms. Present instead are C—H···X—C approaches [Distance range?] just beyond the van der Waals contact distance [Value?] between centrosymmetrically related molecules, the I atom of one molecule being directed toward the cyanobenzylidene C—H group ortho to the bridge of its neighbour.

The hydrogen-bonded chain packing motif assumed by both the bromobenzaldehyde cyanophenylhydrazone, (IIb), and the iodobenzaldehyde cyanophenylhydrazone, (IIc), is shown in Fig. 10 for (IIc). The structure is ordered and the intermolecular approach distances indicate a preference for the N—H group over the bridge C—H group as the hydrogen-bond donor to the cyano group (Tables 4 and 5). The bridge flip relating (Ib) and (Ic) to (IIb) on one hand and to (IIc) on the other is accompanied by sharp differences in packing motifs. The R22(10) motif defined by ring C—H···NC contacts and the R22(8) motif defined by ring C—H···X—C contacts present in (Ib) [and in (Ia) but not in (Ic)] are absent from (IIb) and (IIc), but also absent from (IIb) and (IIc) are the rather long C—H···X—C approaches to the ortho C—H groups present in (Ic). Intermolecular contacts involving the Br atom of (IIb) and the I atom of (IIc) are not obvious C—H···X—C interactions but simply point the C—X bond towards the π cloud of the cyanophenylhydrazone ring of a neighbouring molecule, an interaction that may arise simply as a consequence of space-filling considerations, rather than as a directional interaction that would influence the packing pattern. Given the non-equivalence of the N—H and C—H groups as potential hydrogen-bond donors in (Ia)–(Ic) and (IIb)–(IIc), and the different positions of the N—H groups within the bridges of the bridge-flipped isomeric pairs (Ib)/(IIb) and (Ic)/(IIc), it is not surprising that these isomers assume different molecular packing arrangements.

Figs. 11 and 12 show the two different packing arrangements assumed by the bridge-flipped isomers (III) and (IV), respectively. In both the chlorobenzaldehyde nitrophenylhydrazone, (III), and the nitrobenzaldehyde chlorophenylhydrazone, (IV), and in contrast with the nitrile-substituted phenylhydrazones discussed above, the geometries of the intermolecular approach indicate that both the N—H and C—H groups of the bridge act as hydrogen-bond donors. Although this equivalence might be expected to permit isomorphism between (III) and (IV), the packing arrangements of (III) and (IV) differ at least in part because the equivalence is expressed in the form of two different cyclic motifs. In (III), both molecules in the asymmetric unit engage in bridging interactions of the R22(8) type, involving both bridge hydrogen-bond donors and both nitro-group O atoms (Fig. 11), but in (IV) the bridging interactions are of the R21(6) type and involve only one of the two nitro-group O atoms (Fig. 12). In (III), the nitro O atom in contact with the bridge N—H is also in contact with the neighbouring ortho C—H group of the nitrophenylhydrazone ring; this motif is followed by both molecules in the asymmetric unit of (III). Contacts involving the Cl atom in (III) are exclusively of the C—H···X—C type, where the C—H group is part of the nitrophenylhydrazone ring. In (IV), the O atom not involved in the bridge interaction is in contact with a nitro group from a neighbouring molecule; this centrosymmetric nitro–nitro stacking interaction is not present in (III). The Cl atoms in (IV) are not involved in any contacts sufficiently directional to be noteworthy in terms of determining the molecular packing.

The four arylhydrazone structures published to date (Version 5.32 of the CSD) in which a nitrile group is present (other than the RIFXOU and RIFXUA structures already noted) bear no halogen atoms and thus lend no further insight into potential nitrile–halogen or halogen–halogen interactions in substituted phenylhydrazones, but three of them bear nitro groups and are relevant with respect to competition between nitrile and nitro groups as potential bridge hydrogen-bond acceptors. These structures show either a preference for the bridge N—H group as the hydrogen-bond donor or no interaction with the bridge atoms at all. Of the latter type, two are acetonitrile solvates that also bear nitro groups: 4-[(2,4-dinitrophenyl)hydrazonomethyl]phenol (BAFHIA; Szczesna & Urbanczyk-Lipkowska, 2002) and (E)-1-[3-(benzyloxy)-4-methoxybenzylidene]-2-(2,4-dinitrophenyl)hydrazine (DAYSOM; Shi, 2005). In BAFHIA, any hydrogen-bonding contact between the acetonitrile molecule and the bridge appears to be excluded in favour of a tight centrosymmetric hydrogen-bonding interaction in which a nitro group spans the HCN—NH group of the bridge. One of the nitro O atoms is within the van der Waals contact distance of both the C—H and N—H groups, while the other nitro O atom is within the van der Waals contact distance of only the C—H group. In DAYSOM, in contrast, no close contacts between the bridge atoms and either the acetonitrile molecule or either of the nitro groups are found. On the other hand, in the acetonitrile solvate (E)-1-[3-ethoxy-4-(4-methylbenzenesulfonyloxy)benzylidene-2-(4-nitrophenyl)hydrazine [Please balance brackets - closing ] missing] (NEQKEA; Chen & Yu, 2006), it is the nitrile group rather than the nitro group that acts as the hydrogen-bond acceptor towards the bridge atoms, the acetonitrile molecule interacting at hydrogen-bonding distance with only the bridge N—H and not with the bridge C—H. A clear preference by the nitrile group for the bridge N—H over the bridge C—H is also shown by the close approach between the nitrile group and the bridge N—H of 4-(phenylhydrazonomethyl)benzonitrile (CIQKOD; Wang & Ye, 2007), a system in which competition from a nitrile–halogen, halogen–halogen or any type of nitro interaction is impossible. This preference for the bridge N—H in CIQKOD suggests that the as yet unreported bridge-flipped isomer of CIQKOD will ultimately be found to assume a different molecular packing arrangement.

Of the various nitro–halogen substituted structures published thus far, that most closely related in molecular structure to (III) and (IV) is 4-iodobenzaldehyde 4-nitrophenylhydrazone (OMOLIL; Glidewell et al., 2004), although it is not isomorphous with either (III) or (IV). In OMOLIL, which differs from (III) only in the replacement of the Cl atom with an I atom, one of the nitro O atoms is in contact with both N—H and C—H groups, while the other O atom is in contact with only an iodobenzylidene ring C—H ortho to the bridge N—H. The differences between this motif and those observed in (III) and (IV) are subtle. In (III), one of the nitro O atoms is in contact with both the bridge N—H and the ring C—H ortho to it, but the O atom making only a single contact forms that contact with the bridge C—H. In (IV), as in OMOLIL and (III), one of the nitro O atoms is in contact with both the N—H and C—H groups of the bridge, but only in (IV) is the other O atom not in close van der Waals contact with any neighbouring atom. No directional contacts involving the I atom are apparent in OMOLIL.

In none of our structures do we observe a situation in which a hydrogen-bond acceptor in contact with the phenylhydrazone bridge C—H is not also in contact with the bridge N—H. The nitrile–halogen compounds show a preference for the N—H donor, while the nitro–halogen compounds treat the N—H and C—H donors equally. Hydrogen-bonding interactions with the bridge appear to be preferred over nitrile–halogen interactions. The limited number of examples we have examined here does not permit any firm conclusions to be drawn regarding how nitrile or nitro groups interact with the two potential hydrogen-bond donor groups of the phenylhydrazone bridge. On the other hand, the frequency with which no clear choice between these donor groups is made by potential hydrogen-bond acceptors may point towards the future identification of more isomorphous bridge-flipped phenylhydrazones than the two pairs identified thus far.

Related literature top

For related literature, see: Allen (2002); Bernstein et al. (1995); Chen & Yu (2006); Ferguson et al. (2005); Glidewell et al. (2004); Mocilak & Gallagher (2011); Ojala et al. (1999, 2001, 2007, 2009); Shi (2005); Szczesna & Urbanczyk-Lipkowska (2002); Wang & Ye (2007); Wood et al. (2009).

Experimental top

All of the phenylhydrazones described here were prepared by standard methods, i.e. reaction of a substituted benzaldehyde with a substituted phenylhydrazine (or the phenylhydrazine hydrochloride in the presence of a base) by brief heating in an ethanol solution. Obtained by this method were: (Ia) as yellow plates, m.p. 451–456 K; (Ib) as yellow prisms, m.p. 443–446 K; (Ic) as red needles, m.p. 421–422 K; (IIb) as brown prisms, m.p. 464–465 K; (IIc) as brown needles, m.p. 477–479 K; (III) as orange needles, m.p. 498–499 K; and (IV) as red needles, m.p. 423–427 K.

Refinement top

After initial refinement of (Ia), the presence of residual electron density near the nitrile group and (as a result) an anomalously short CN bond suggested a small amount of end-for-end disorder of the molecule. Attempts to refine the occupancy of the Cl atom over the two possible positions while applying geometric restraints to the nitrile group failed to yield a satisfactory geometry for that group, so only the two positions of the Cl atom were included in the final model, which refined with a final disorder of 0.03. A similar procedure was followed for (Ib), in which the disorder was found to be 0.06. In all structures, C-bound H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). N-bound H atoms were refined isotropically without constraints in (Ia), (Ib), (IIb) and (IV); in (Ic), (IIc) and (III) the N—H distance was restrained to 0.83(s.u.?) Å.

Structure description top

The analysis of intermolecular interactions for their potential utility in crystal engineering is a topic of ongoing interest. These have included the varieties of hydrogen bond ranging from the strong conventional type to the weak nonconventional type, as well as halogen–halogen contacts, halogen–nitrogen contacts and π stacking. For our part, we have been examining the role of interactions between the nitrile group and nearby halogen and H atoms in defining the solid-state molecular packing motifs assumed by pairs of molecules we have designated `bridge-flipped' isomers, molecules that differ only in the reversal of a bridge of atoms linking two major portions of the molecule (Ojala et al., 2007). Examples are readily identified among the benzylideneanilines (Ar1—CHN—Ar2 versus Ar1—NCH—Ar2; Ar = aryl) and phenylhydrazones (Ar1—CHN—NH—Ar2 versus Ar1—NH—NCH—Ar2; Ar = aryl). Pairs of bridge-flipped isomeric benzylideneanilines and phenylhydrazones may assume identical solid-state molecular packing arrangements by virtue of their closely similar space-filling requirements, although the number of reported isomorphous pairs is small (Ojala et al., 2007; Ferguson et al., 2005; Mocilak & Gallagher, 2011). Bridge-flipped isomers that happen not to be isomorphous offer a useful context for the comparison and analysis of molecular conformations, intermolecular interactions and packing motifs that differentiate the packing arrangements. In our studies, we have attempted to facilitate isomorphism by placing substituents on the molecules that would engage in similar intermolecular interactions in the two isomers. Similar motifs generated by these interactions, if packed in similar ways in the two isomers, should favour the formation of similar overall molecular packing arrangements. To date, we have focused primarily on the potential intermolecular Lewis acid–base interaction between the nitrile group and a halogen atom on a neighbouring molecule in the crystalline solid. Although this strategy in our own laboratory has yet to produce an isomorphous pair of bridge-flipped isomers, it has allowed us to examine the variety of motifs in which nitrile groups and halogen atoms engage, whether separately or with each other. In previous reports we have examined intermolecular interactions of this type primarily in bridge-flipped nitrile–halogen substituted benzylideneanilines (Ojala et al., 2009, 2001, 1999), where they play a significant role in defining the molecular packing arrangment. Here, we describe the interactions found in a group of bridge-flipped nitrile–halogen substituted phenylhydrazones.

Whether the potential nitrile–halogen intermolecular interaction can actually encourage isomorphism in phenylhydrazones is complicated by the presence of the N—H group in the phenylhydrazone bridge. This strong conventional hydrogen-bond donor, not present in the bridge of benzylideneanilines, could be expected to cause nitrile–halogen substituted bridge-flipped phenylhydrazones to assume different packing arrangements if the nitrile group were to hydrogen-bond to it rather than engage in Lewis acid–base interactions with the halogen atom. Reversal of the bridge from one isomer to the other would cause a substantial and probably structure-differentiating change in the position of the hydrogen-bonded groups. On the other hand, isomorphous pairs of bridge-flipped phenylhydrazones bearing hydrogen-bond acceptors are known, including the pair (E)-2-nitrobenzaldehyde 3-nitrophenylhydrazone [Cambridge Structural Database (CSD; Allen, 2002) refcode LAWCOC] and (E)-3-nitrobenzaldehyde 2-nitrophenylhydrazone (LAWJAV) (Ferguson et al., 2005) and the pair (E)-2-bromobenzaldehyde 4-cyanophenylhydrazone (RIFXOU) and (E)-4-cyanobenzaldehyde 2-bromophenylhydrazone (RIFXUA) (Ojala et al., 2007). In both these pairs, the hydrogen-bond acceptor (the nitro or nitrile group) is in contact (within the sum of the van der Waals radii) with both the N—H and C—H donors within the bridge; no clear preference for the stronger donor is shown by the acceptor. To find out how general this might be, and to examine what other structural motifs might be preferred given a choice among potential nitrile–hydrogen, nitrile–halogen and halogen–halogen contacts in the solid state, we have determined and describe here the crystal structures of the title cyanobenzaldehyde halophenylhydrazones, (Ia)–(Ic), and the halobenzaldehyde cyanophenylhydrazones, (IIb) and (IIc). [Regrettably, and in spite of our repeated efforts, we have not been successful in obtaining X-ray quality crystals of (IIa).]

Because one of the two previously published isomorphous pairs of bridge-flipped phenylhydrazones cited above (Ferguson et al., 2005) involves the nitro group rather than the nitrile group as the potential hydrogen-bond acceptor, we have extended our inquiry to nitro–halogen substituted phenylhydrazones in order to examine how discriminating the nitro group is as a potential acceptor of N—H versus C—H hydrogen bonds from phenylhydrazone bridges. We thus describe here, in addition to these nitrile–halogen substituted phenylhydrazones, the structures of the bridge-flipped isomeric pair of nitro–halogen (chlorine) substituted phenylhydrazones, (III) and (IV). None of the bridge-flipped isomeric pairs described here, whether nitrile- or nitro-substituted, proved to be isomorphous in our study, although several of the compounds related simply by the exchange of one halogen for another did; (Ia) and (Ib) are isomorphous, and (IIb) and (IIc) are isomorphous. Our purpose here is thus to determine which intermolecular interactions from an array of competing possibilities, including C N···H—N, CN···H—C, O—N—O···H—N, O—N—O···H—C, C N···X—C and C—X···X—C, are preferred in these structures and how these preferences differentiate the structures of these bridge-flipped isomers from each other.

Views of the isolated molecules of all seven title compounds are given in Figs. 1–7. All seven arylhydrazones possess the E configuration about the CN bond. All are nearly planar, with dihedral angles between the six-membered rings ranging from 7.31 (6)° in (Ia) to 25.38 (9)° in (IV). The conformational differences between the bridge-flipped isomers appear insufficient to explain completely their differences in crystal structure. The nitro groups in (III) and (IV) are essentially coplanar with the rings to which they are attached.

The packing arrangement assumed by both the cyanobenzaldehyde chlorophenylhydrazone, (Ia), and the cyanobenzaldehyde bromophenylhydrazone, (Ib), is shown in Fig. 8 for (Ia). Both structures show a small proportion [approximately 0.03 in (Ia) and 0.06 in (Ib)] of end-for-end disorder of the molecules; Fig. 8 shows the molecules as they are oriented in the major component of the disorder. The nitrile group in (Ia) and (Ib) is in contact with only the N—H group of the bridge and not with the C—H group (see Tables 1 and 2 for intermolecular N—H contact geometries). Even with this preference for the strong N—H donor over the weak C—H donor, the fact that the molecules are not locked into an entirely non-disordered pattern indicates that this particular interaction between the nitrile group and the bridge N—H may be relatively weak compared with other conventional hydrogen bonds. This is consistent with the observed donor-H···acceptor angle in these structures (Tables 1 and 2), which is unfavourable for strong hydrogen-bond formation (Wood et al., 2009). The nitrile group in (Ia) and (Ib) also engages in a centrosymmetric R22(10) motif (Bernstein et al., 1995) defined by C—H···NC (a ring C—H as opposed to a bridge C—H) contacts between the cyanobenzylidene moieties: for (Ia), H11···N3(-x, 2 - y, 1 - z) = 2.67 Å and C11—H11···N3(-x, 2 - y, 1 - z) = 144°; for (Ib), H11···N3(-x, 2 - y, 1 - z) = 2.66 Å and C11—H11···N3 (-x, 2 - y, 1 - z) = 144°. With respect to the halogen atoms, no close contacts of either the C—X···NC type or the C—X···X—C type are found. Instead, neighbouring molecules are connected by centrosymmetric interactions composed of C—H···X—C (a ring C—H) contacts involving the halophenylhydrazone moieties, defining an R22(8) motif: for (Ia), H3···Cl1(2 - x, 2 - y, -z) = 2.95 Å and C3—H3···Cl1(2 - x, 2 - y, -z) = 160°; for (Ib), H3···Br1(2 - x, 2 - y, -z) = 3.08 Å and C3—H3···Br1(2 - x, 2 - y, -z) = 160°. The halogen–hydrogen approach in (Ia) [Distance?] is closer than that in (Ib) [Distance?], which lies just outside the sum of the van der Waals radii [Value? Standard reference?] even though the Br atom is larger than the Cl atom. Our analysis has not revealed whether individual molecules assume disordered positions that would feature mixed cyclic motifs composed of both C—H···X—C and C—H···NC contacts, or whether instead entire chains of molecules are reversed and each cyclic motif is composed of only one kind of contact.

The hydrogen-bonded chain packing motif assumed by the cyanobenzaldehyde iodophenylhydrazone, (Ic), is shown in Fig. 9. As in (Ia) and (Ib), molecules of (Ic) are linked by an N—H···NC interaction, and no appreciable hydrogen bonding exists between the nitrile group and the bridge C—H. Iodine, as the strongest Lewis acid of the halogen atoms, may have offered the best opportunity for C—X···NC contacts, but these are excluded in (Ic) in favour of a strong N—H···NC contact that is more nearly linear than those in (Ia) and (Ib) (Table 3). In accord with this, the structure of (Ic) is ordered. Notably absent from the packing arrangement of (Ic) are the R22(10) motif defined by ring C—H···NC contacts and the R22(8) motif defined by ring C—H···X—C contacts present in (Ia) and (Ib), as are any C—X···X—C interactions involving the I atoms. Present instead are C—H···X—C approaches [Distance range?] just beyond the van der Waals contact distance [Value?] between centrosymmetrically related molecules, the I atom of one molecule being directed toward the cyanobenzylidene C—H group ortho to the bridge of its neighbour.

The hydrogen-bonded chain packing motif assumed by both the bromobenzaldehyde cyanophenylhydrazone, (IIb), and the iodobenzaldehyde cyanophenylhydrazone, (IIc), is shown in Fig. 10 for (IIc). The structure is ordered and the intermolecular approach distances indicate a preference for the N—H group over the bridge C—H group as the hydrogen-bond donor to the cyano group (Tables 4 and 5). The bridge flip relating (Ib) and (Ic) to (IIb) on one hand and to (IIc) on the other is accompanied by sharp differences in packing motifs. The R22(10) motif defined by ring C—H···NC contacts and the R22(8) motif defined by ring C—H···X—C contacts present in (Ib) [and in (Ia) but not in (Ic)] are absent from (IIb) and (IIc), but also absent from (IIb) and (IIc) are the rather long C—H···X—C approaches to the ortho C—H groups present in (Ic). Intermolecular contacts involving the Br atom of (IIb) and the I atom of (IIc) are not obvious C—H···X—C interactions but simply point the C—X bond towards the π cloud of the cyanophenylhydrazone ring of a neighbouring molecule, an interaction that may arise simply as a consequence of space-filling considerations, rather than as a directional interaction that would influence the packing pattern. Given the non-equivalence of the N—H and C—H groups as potential hydrogen-bond donors in (Ia)–(Ic) and (IIb)–(IIc), and the different positions of the N—H groups within the bridges of the bridge-flipped isomeric pairs (Ib)/(IIb) and (Ic)/(IIc), it is not surprising that these isomers assume different molecular packing arrangements.

Figs. 11 and 12 show the two different packing arrangements assumed by the bridge-flipped isomers (III) and (IV), respectively. In both the chlorobenzaldehyde nitrophenylhydrazone, (III), and the nitrobenzaldehyde chlorophenylhydrazone, (IV), and in contrast with the nitrile-substituted phenylhydrazones discussed above, the geometries of the intermolecular approach indicate that both the N—H and C—H groups of the bridge act as hydrogen-bond donors. Although this equivalence might be expected to permit isomorphism between (III) and (IV), the packing arrangements of (III) and (IV) differ at least in part because the equivalence is expressed in the form of two different cyclic motifs. In (III), both molecules in the asymmetric unit engage in bridging interactions of the R22(8) type, involving both bridge hydrogen-bond donors and both nitro-group O atoms (Fig. 11), but in (IV) the bridging interactions are of the R21(6) type and involve only one of the two nitro-group O atoms (Fig. 12). In (III), the nitro O atom in contact with the bridge N—H is also in contact with the neighbouring ortho C—H group of the nitrophenylhydrazone ring; this motif is followed by both molecules in the asymmetric unit of (III). Contacts involving the Cl atom in (III) are exclusively of the C—H···X—C type, where the C—H group is part of the nitrophenylhydrazone ring. In (IV), the O atom not involved in the bridge interaction is in contact with a nitro group from a neighbouring molecule; this centrosymmetric nitro–nitro stacking interaction is not present in (III). The Cl atoms in (IV) are not involved in any contacts sufficiently directional to be noteworthy in terms of determining the molecular packing.

The four arylhydrazone structures published to date (Version 5.32 of the CSD) in which a nitrile group is present (other than the RIFXOU and RIFXUA structures already noted) bear no halogen atoms and thus lend no further insight into potential nitrile–halogen or halogen–halogen interactions in substituted phenylhydrazones, but three of them bear nitro groups and are relevant with respect to competition between nitrile and nitro groups as potential bridge hydrogen-bond acceptors. These structures show either a preference for the bridge N—H group as the hydrogen-bond donor or no interaction with the bridge atoms at all. Of the latter type, two are acetonitrile solvates that also bear nitro groups: 4-[(2,4-dinitrophenyl)hydrazonomethyl]phenol (BAFHIA; Szczesna & Urbanczyk-Lipkowska, 2002) and (E)-1-[3-(benzyloxy)-4-methoxybenzylidene]-2-(2,4-dinitrophenyl)hydrazine (DAYSOM; Shi, 2005). In BAFHIA, any hydrogen-bonding contact between the acetonitrile molecule and the bridge appears to be excluded in favour of a tight centrosymmetric hydrogen-bonding interaction in which a nitro group spans the HCN—NH group of the bridge. One of the nitro O atoms is within the van der Waals contact distance of both the C—H and N—H groups, while the other nitro O atom is within the van der Waals contact distance of only the C—H group. In DAYSOM, in contrast, no close contacts between the bridge atoms and either the acetonitrile molecule or either of the nitro groups are found. On the other hand, in the acetonitrile solvate (E)-1-[3-ethoxy-4-(4-methylbenzenesulfonyloxy)benzylidene-2-(4-nitrophenyl)hydrazine [Please balance brackets - closing ] missing] (NEQKEA; Chen & Yu, 2006), it is the nitrile group rather than the nitro group that acts as the hydrogen-bond acceptor towards the bridge atoms, the acetonitrile molecule interacting at hydrogen-bonding distance with only the bridge N—H and not with the bridge C—H. A clear preference by the nitrile group for the bridge N—H over the bridge C—H is also shown by the close approach between the nitrile group and the bridge N—H of 4-(phenylhydrazonomethyl)benzonitrile (CIQKOD; Wang & Ye, 2007), a system in which competition from a nitrile–halogen, halogen–halogen or any type of nitro interaction is impossible. This preference for the bridge N—H in CIQKOD suggests that the as yet unreported bridge-flipped isomer of CIQKOD will ultimately be found to assume a different molecular packing arrangement.

Of the various nitro–halogen substituted structures published thus far, that most closely related in molecular structure to (III) and (IV) is 4-iodobenzaldehyde 4-nitrophenylhydrazone (OMOLIL; Glidewell et al., 2004), although it is not isomorphous with either (III) or (IV). In OMOLIL, which differs from (III) only in the replacement of the Cl atom with an I atom, one of the nitro O atoms is in contact with both N—H and C—H groups, while the other O atom is in contact with only an iodobenzylidene ring C—H ortho to the bridge N—H. The differences between this motif and those observed in (III) and (IV) are subtle. In (III), one of the nitro O atoms is in contact with both the bridge N—H and the ring C—H ortho to it, but the O atom making only a single contact forms that contact with the bridge C—H. In (IV), as in OMOLIL and (III), one of the nitro O atoms is in contact with both the N—H and C—H groups of the bridge, but only in (IV) is the other O atom not in close van der Waals contact with any neighbouring atom. No directional contacts involving the I atom are apparent in OMOLIL.

In none of our structures do we observe a situation in which a hydrogen-bond acceptor in contact with the phenylhydrazone bridge C—H is not also in contact with the bridge N—H. The nitrile–halogen compounds show a preference for the N—H donor, while the nitro–halogen compounds treat the N—H and C—H donors equally. Hydrogen-bonding interactions with the bridge appear to be preferred over nitrile–halogen interactions. The limited number of examples we have examined here does not permit any firm conclusions to be drawn regarding how nitrile or nitro groups interact with the two potential hydrogen-bond donor groups of the phenylhydrazone bridge. On the other hand, the frequency with which no clear choice between these donor groups is made by potential hydrogen-bond acceptors may point towards the future identification of more isomorphous bridge-flipped phenylhydrazones than the two pairs identified thus far.

For related literature, see: Allen (2002); Bernstein et al. (1995); Chen & Yu (2006); Ferguson et al. (2005); Glidewell et al. (2004); Mocilak & Gallagher (2011); Ojala et al. (1999, 2001, 2007, 2009); Shi (2005); Szczesna & Urbanczyk-Lipkowska (2002); Wang & Ye (2007); Wood et al. (2009).

Computing details top

For all compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of (Ia), showing the atom-numbering scheme in the major orientation of the disorder. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The molecular structure of (Ib), showing the atom-numbering scheme in the major orientation of the disorder. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. The molecular structure of (Ic), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 4] Fig. 4. The molecular structure of (IIb), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 5] Fig. 5. The molecular structure of (IIc), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 6] Fig. 6. The two molecules in the asymmetric unit of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 7] Fig. 7. The molecular structure of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 8] Fig. 8. The molecular packing in (Ia) and (Ib), shown for the major component of disordered (Ia). For clarity, only the H atoms in the bridge and others involved in intermolecular contacts are shown. Dashed lines indicate contacts at or shorter than the sum of the van der Waals radii. The bridge N—H participates in a weak hydrogen bond, but the bridge C—H does not participate in hydrogen bonding (see Tables 1 and 2 for N—H contact geometries). Centrosymmetric close-contact motifs shown here are defined by paired C—X···H—C interactions, where X = Cl in (Ia) and X = Br in (Ib) [the R22(8) motif], and paired CN···H—C interactions [the R22(10) motif]; see Comment for contact geometries. [Symmetry codes: (i) x + 1, y, z; (ii) -x, -y + 2, -z + 1; (iii) -x + 2, -y + 2, -z.]
[Figure 9] Fig. 9. The hydrogen-bonded chain motif (dashed lines) defined by the N—H···NC interaction in the cyanobenzaldehyde iodophenylhydrazone (Ic); see Table 3 for contact geometry. For clarity, only the H atom involved in hydrogen bonding, the N—H atom, is shown; the bridge C—H is not involved in any hydrogen-bonding motifs. [Symmetry codes: (i) -x, y + 1/2, -z + 1/2; (ii) x, y + 1, z.]
[Figure 10] Fig. 10. The hydrogen-bonded chain motif (dashed lines) defined by the N—H···NC interaction in the iodobenzaldehyde cyanophenylhydrazone (IIc); see Table 5 for contact geometry. A corresponding hydrogen-bonded chain motif is observed in the bromo analogue (IIb) (contact geometry given in Table 4). For clarity, only the H atom involved in hydrogen bonding, the N—H atom, is shown; as in (Ic) (Fig. 9), the bridge C—H is not involved in any hydrogen-bonding motifs. [Symmetry codes: (i) x, -y + 3/2, z - 1/2; (ii) x, -y + 3/2, z + 1/2.]
[Figure 11] Fig. 11. The molecular packing in (III), showing the R22(8) hydrogen-bonding interaction (dashed lines) between the nitro group and the bridge N—H and C—H groups. For clarity, only the H atoms of the bridge are shown. See Table 6 for contact geometries. [Symmetry codes: (i) x - 1, y + 1, z; (ii) x, y - 1, z; (iii) x + 1/2, -y + 1, z + 1/2; (iv) x - 1/2, -y + 2, z + 1/2.]
[Figure 12] Fig. 12. The molecular packing in (IV), showing the R21(6) interaction (dashed lines) between one O atom of the nitro group and both the bridge N—H and C—H groups of a neighbouring molecule. Also shown as a dashed line is the 3.002 (2) Å approach between atom O1 and the N atom of the nitro group of a neighbouring molecule, an interaction in which O1 engages instead of hydrogen bonding with the molecular bridge. For clarity, only the H atoms of the bridge are shown. See Table 7 for contact geometries. [Symmetry codes: (i) -x + 5/2, y - 1/2, -z + 1/2; (ii) -x + 5/2, y + 1/2, -z + 1/2; (iii) x - 1/2, -y + 1/2, z + 1/2; (iv) -x + 2, -y + 1, -z + 1.]
(Ia) (E)-4-cyanobenzaldehyde 4-chlorophenylhydrazone top
Crystal data top
C14H10ClN3F(000) = 528
Mr = 255.70Dx = 1.396 Mg m3
Monoclinic, P21/nMelting point = 451–456 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 10.7246 (10) ÅCell parameters from 3716 reflections
b = 7.1767 (6) Åθ = 2.8–25.0°
c = 16.3492 (15) ŵ = 0.30 mm1
β = 104.779 (1)°T = 173 K
V = 1216.72 (19) Å3Plate, yellow
Z = 40.50 × 0.50 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2154 independent reflections
Radiation source: fine-focus sealed tube1952 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω scans per φθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1212
Tmin = 0.894, Tmax = 1.000k = 88
11510 measured reflectionsl = 1919
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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H atoms treated by a mixture of independent and constrained refinement
S = 1.13 w = 1/[σ2(Fo2) + (0.0365P)2 + 0.2987P], P = (Fo2 + 2Fc2)/3
2154 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C14H10ClN3V = 1216.72 (19) Å3
Mr = 255.70Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.7246 (10) ŵ = 0.30 mm1
b = 7.1767 (6) ÅT = 173 K
c = 16.3492 (15) Å0.50 × 0.50 × 0.10 mm
β = 104.779 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2154 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1952 reflections with I > 2σ(I)
Tmin = 0.894, Tmax = 1.000Rint = 0.027
11510 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.080H atoms treated by a mixture of independent and constrained refinement
S = 1.13Δρmax = 0.16 e Å3
2154 reflectionsΔρmin = 0.17 e Å3
172 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl10.81863 (4)1.09092 (5)0.04948 (2)0.04344 (15)0.9669 (12)
Cl1A0.020 (2)1.065 (2)0.3845 (12)0.032 (4)*0.0331 (12)
C10.69784 (12)0.96031 (18)0.19029 (8)0.0302 (3)
C20.81968 (13)0.90738 (18)0.18230 (9)0.0325 (3)
H20.87720.84360.22740.039*
C30.85700 (13)0.94691 (19)0.10946 (9)0.0346 (3)
H30.94000.91110.10440.042*
C40.77251 (13)1.03919 (19)0.04366 (9)0.0331 (3)
C50.65171 (13)1.09237 (19)0.05032 (9)0.0343 (3)
H50.59461.15600.00490.041*
C60.61411 (13)1.05271 (19)0.12323 (9)0.0334 (3)
H60.53081.08860.12770.040*
C70.38895 (13)0.95124 (18)0.35319 (8)0.0301 (3)
C80.29058 (13)1.03183 (19)0.28922 (9)0.0330 (3)
H80.30861.07120.23800.040*
C90.16883 (13)1.05405 (19)0.30017 (9)0.0342 (3)
H90.10301.10820.25650.041*
C100.14167 (13)0.99703 (18)0.37549 (8)0.0305 (3)
C110.23750 (13)0.91580 (19)0.43940 (9)0.0342 (3)
H110.21900.87570.49040.041*
C120.36004 (14)0.89413 (19)0.42772 (9)0.0339 (3)
H120.42570.83930.47130.041*
C130.51839 (13)0.92277 (18)0.34294 (8)0.0322 (3)
H130.58480.87990.38940.039*
C140.0146 (2)1.0235 (3)0.38803 (12)0.0356 (5)
H2N0.7239 (16)0.885 (2)0.3088 (11)0.050 (5)*
N10.54374 (10)0.95508 (16)0.27155 (7)0.0316 (3)
N20.66378 (11)0.91805 (17)0.26445 (8)0.0349 (3)
N30.08499 (15)1.0452 (2)0.39733 (8)0.0429 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0513 (3)0.0415 (2)0.0400 (2)0.00337 (16)0.01611 (17)0.00427 (16)
C10.0288 (7)0.0262 (7)0.0325 (7)0.0028 (5)0.0024 (6)0.0046 (5)
C20.0296 (7)0.0310 (7)0.0335 (7)0.0030 (5)0.0017 (6)0.0018 (6)
C30.0305 (7)0.0337 (7)0.0391 (8)0.0018 (6)0.0076 (6)0.0049 (6)
C40.0375 (8)0.0275 (7)0.0334 (7)0.0036 (6)0.0074 (6)0.0035 (6)
C50.0332 (7)0.0317 (7)0.0341 (7)0.0005 (6)0.0012 (6)0.0009 (6)
C60.0271 (7)0.0326 (7)0.0383 (8)0.0002 (6)0.0044 (6)0.0018 (6)
C70.0323 (7)0.0251 (6)0.0305 (7)0.0011 (5)0.0036 (6)0.0028 (5)
C80.0345 (7)0.0358 (7)0.0281 (7)0.0018 (6)0.0069 (6)0.0034 (6)
C90.0326 (7)0.0350 (7)0.0317 (7)0.0029 (6)0.0023 (6)0.0036 (6)
C100.0309 (7)0.0277 (7)0.0322 (7)0.0018 (5)0.0069 (6)0.0011 (6)
C110.0366 (8)0.0334 (7)0.0320 (7)0.0009 (6)0.0079 (6)0.0048 (6)
C120.0345 (7)0.0332 (7)0.0310 (7)0.0035 (6)0.0027 (6)0.0054 (6)
C130.0316 (7)0.0309 (7)0.0306 (7)0.0009 (5)0.0015 (6)0.0001 (6)
C140.0403 (13)0.0315 (10)0.0315 (9)0.0004 (9)0.0026 (8)0.0020 (7)
N10.0270 (6)0.0299 (6)0.0358 (6)0.0005 (5)0.0044 (5)0.0029 (5)
N20.0269 (6)0.0423 (7)0.0335 (7)0.0037 (5)0.0037 (5)0.0017 (5)
N30.0373 (8)0.0504 (8)0.0387 (8)0.0028 (7)0.0053 (6)0.0030 (6)
Geometric parameters (Å, º) top
Cl1—C41.7567 (14)C8—C91.372 (2)
C1—N21.3861 (18)C8—H80.95
C1—C61.3949 (19)C9—C101.3969 (19)
C1—C21.3986 (19)C9—H90.95
C2—C31.379 (2)C10—C111.3929 (19)
C2—H20.95C10—C141.442 (3)
C3—C41.385 (2)C11—C121.384 (2)
C3—H30.95C11—H110.95
C4—C51.381 (2)C12—H120.95
C5—C61.382 (2)C13—N11.2852 (18)
C5—H50.95C13—H130.95
C6—H60.95C14—N31.127 (3)
C7—C121.3935 (19)N1—N21.3482 (16)
C7—C81.4065 (19)N2—H2N0.871 (17)
C7—C131.4546 (19)
N2—C1—C6122.08 (12)C9—C8—H8120
N2—C1—C2118.90 (12)C7—C8—H8120
C6—C1—C2119.02 (13)C8—C9—C10120.03 (12)
C3—C2—C1120.58 (13)C8—C9—H9120
C3—C2—H2120C10—C9—H9120
C1—C2—H2120C11—C10—C9120.27 (12)
C2—C3—C4119.49 (13)C11—C10—C14119.46 (13)
C2—C3—H3120C9—C10—C14120.27 (14)
C4—C3—H3120C12—C11—C10119.23 (13)
C5—C4—C3120.78 (13)C12—C11—H11120
C5—C4—Cl1119.15 (11)C10—C11—H11120
C3—C4—Cl1120.07 (11)C11—C12—C7121.23 (13)
C4—C5—C6119.80 (13)C11—C12—H12119
C4—C5—H5120C7—C12—H12119
C6—C5—H5120N1—C13—C7120.56 (12)
C5—C6—C1120.32 (13)N1—C13—H13120
C5—C6—H6120C7—C13—H13120
C1—C6—H6120N3—C14—C10179.5 (2)
C12—C7—C8118.64 (12)C13—N1—N2118.06 (11)
C12—C7—C13119.42 (12)N1—N2—C1120.18 (11)
C8—C7—C13121.93 (12)N1—N2—H2N120.1 (11)
C9—C8—C7120.60 (13)C1—N2—H2N118.9 (11)
C12—C7—C13—N1172.28 (12)C13—N1—N2—C1176.38 (12)
C8—C7—C13—N16.5 (2)C6—C1—N2—N14.40 (19)
C7—C13—N1—N2176.95 (11)C2—C1—N2—N1175.13 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N3i0.871 (17)2.471 (17)3.1345 (19)133.5 (14)
Symmetry code: (i) x+1, y, z.
(Ib) (E)-4-cyanobenzaldehyde 4-bromophenylhydrazone top
Crystal data top
C14H10BrN3F(000) = 600
Mr = 300.16Dx = 1.601 Mg m3
Monoclinic, P21/nMelting point = 443–446 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 10.6804 (8) ÅCell parameters from 2250 reflections
b = 7.3150 (6) Åθ = 2.6–25.0°
c = 16.5427 (13) ŵ = 3.28 mm1
β = 105.500 (1)°T = 173 K
V = 1245.43 (17) Å3Prism, yellow
Z = 40.40 × 0.30 × 0.08 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2205 independent reflections
Radiation source: fine-focus sealed tube1975 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω scans per φθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1212
Tmin = 0.778, Tmax = 1.000k = 88
8153 measured reflectionsl = 1919
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.13 w = 1/[σ2(Fo2) + (0.026P)2 + 0.8669P], P = (Fo2 + 2Fc2)/3
2205 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.30 e Å3
1 restraintΔρmin = 0.33 e Å3
Crystal data top
C14H10BrN3V = 1245.43 (17) Å3
Mr = 300.16Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.6804 (8) ŵ = 3.28 mm1
b = 7.3150 (6) ÅT = 173 K
c = 16.5427 (13) Å0.40 × 0.30 × 0.08 mm
β = 105.500 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2205 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1975 reflections with I > 2σ(I)
Tmin = 0.778, Tmax = 1.000Rint = 0.024
8153 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0281 restraint
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.13Δρmax = 0.30 e Å3
2205 reflectionsΔρmin = 0.33 e Å3
172 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.81199 (3)1.09158 (4)0.053034 (17)0.04084 (11)0.9352 (13)
Br1A0.0346 (7)1.0609 (9)0.3861 (4)0.0352 (17)*0.0648 (13)
C10.6932 (2)0.9558 (3)0.19291 (14)0.0283 (5)
C20.8140 (2)0.8998 (3)0.18434 (15)0.0325 (5)
H20.87140.83350.22840.039*
C30.8507 (2)0.9402 (3)0.11214 (15)0.0335 (5)
H30.93320.90280.10660.040*
C40.7659 (2)1.0357 (3)0.04811 (15)0.0314 (5)
C50.6459 (2)1.0917 (3)0.05576 (15)0.0334 (5)
H50.58871.15790.01160.040*
C60.6096 (2)1.0513 (3)0.12772 (15)0.0323 (5)
H60.52691.08890.13280.039*
C70.3864 (2)0.9473 (3)0.35430 (14)0.0296 (5)
C80.2873 (2)1.0261 (3)0.29064 (15)0.0321 (5)
H80.30481.06400.23980.039*
C90.1653 (2)1.0489 (3)0.30122 (15)0.0336 (5)
H90.09861.10210.25770.040*
C100.1387 (2)0.9942 (3)0.37580 (15)0.0300 (5)
C110.2359 (2)0.9147 (3)0.43944 (15)0.0342 (5)
H110.21820.87630.49010.041*
C120.3584 (2)0.8923 (3)0.42795 (15)0.0339 (5)
H120.42480.83830.47130.041*
H130.58260.87170.39000.041*
C130.5160 (2)0.9170 (3)0.34427 (15)0.0316 (5)
C140.0128 (4)1.0207 (5)0.38820 (19)0.0400 (9)
H2N0.719 (3)0.869 (4)0.3084 (19)0.048 (8)*
N10.54088 (18)0.9510 (3)0.27366 (12)0.0304 (4)
N20.65998 (19)0.9120 (3)0.26620 (13)0.0348 (5)
N30.0881 (3)1.0436 (4)0.39812 (16)0.0445 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.05031 (19)0.03846 (17)0.03563 (17)0.00253 (13)0.01474 (12)0.00395 (12)
C10.0275 (12)0.0254 (12)0.0303 (12)0.0027 (9)0.0047 (9)0.0037 (9)
C20.0294 (12)0.0328 (13)0.0323 (12)0.0033 (10)0.0029 (10)0.0003 (10)
C30.0299 (12)0.0330 (13)0.0373 (13)0.0010 (10)0.0082 (10)0.0045 (11)
C40.0375 (13)0.0272 (12)0.0289 (12)0.0036 (10)0.0080 (10)0.0039 (10)
C50.0337 (12)0.0307 (13)0.0319 (13)0.0010 (10)0.0022 (10)0.0001 (10)
C60.0279 (12)0.0324 (13)0.0353 (13)0.0009 (10)0.0062 (10)0.0021 (10)
C70.0321 (12)0.0251 (12)0.0303 (12)0.0007 (9)0.0061 (10)0.0035 (10)
C80.0339 (13)0.0356 (13)0.0264 (12)0.0026 (10)0.0070 (10)0.0019 (10)
C90.0331 (13)0.0342 (13)0.0291 (12)0.0023 (10)0.0010 (10)0.0019 (10)
C100.0284 (12)0.0281 (12)0.0327 (13)0.0021 (10)0.0070 (10)0.0016 (10)
C110.0364 (13)0.0334 (13)0.0328 (13)0.0005 (11)0.0094 (10)0.0059 (11)
C120.0356 (13)0.0326 (13)0.0313 (12)0.0039 (10)0.0050 (10)0.0054 (10)
C130.0300 (12)0.0326 (13)0.0289 (12)0.0029 (10)0.0025 (9)0.0002 (10)
C140.047 (2)0.0363 (18)0.0337 (16)0.0015 (16)0.0056 (15)0.0010 (12)
N10.0275 (10)0.0302 (11)0.0321 (11)0.0012 (8)0.0053 (8)0.0027 (8)
N20.0265 (11)0.0445 (12)0.0312 (11)0.0037 (10)0.0039 (9)0.0011 (10)
N30.0372 (15)0.0550 (17)0.0405 (15)0.0044 (12)0.0092 (12)0.0035 (11)
Geometric parameters (Å, º) top
Br1—C41.910 (2)C8—C91.370 (3)
C1—N21.389 (3)C8—H80.95
C1—C61.391 (3)C9—C101.397 (3)
C1—C21.396 (3)C9—H90.95
C2—C31.385 (3)C10—C111.393 (3)
C2—H20.95C10—C141.427 (5)
C3—C41.385 (3)C11—C121.380 (4)
C3—H30.95C11—H110.95
C4—C51.384 (4)C12—H120.95
C5—C61.379 (3)C13—N11.289 (3)
C5—H50.95C13—H130.95
C6—H60.95C14—N31.145 (6)
C7—C121.389 (3)N1—N21.341 (3)
C7—C81.402 (3)N2—H2N0.87 (3)
C7—C131.455 (3)
N2—C1—C6122.1 (2)C9—C8—H8120
N2—C1—C2118.7 (2)C7—C8—H8120
C6—C1—C2119.2 (2)C8—C9—C10120.2 (2)
C3—C2—C1120.5 (2)C8—C9—H9120
C3—C2—H2120C10—C9—H9120
C1—C2—H2120C11—C10—C9120.0 (2)
C4—C3—C2119.3 (2)C11—C10—C14119.3 (2)
C4—C3—H3120C9—C10—C14120.7 (2)
C2—C3—H3120C12—C11—C10119.2 (2)
C5—C4—C3120.8 (2)C12—C11—H11120
C5—C4—Br1118.59 (18)C10—C11—H11120
C3—C4—Br1120.59 (18)C11—C12—C7121.4 (2)
C6—C5—C4119.8 (2)C11—C12—H12119
C6—C5—H5120C7—C12—H12119
C4—C5—H5120N1—C13—C7120.4 (2)
C5—C6—C1120.5 (2)N1—C13—H13120
C5—C6—H6120C7—C13—H13120
C1—C6—H6120N3—C14—C10179.4 (4)
C12—C7—C8118.8 (2)C13—N1—N2118.20 (19)
C12—C7—C13119.4 (2)N1—N2—C1120.1 (2)
C8—C7—C13121.8 (2)N1—N2—H2N120.4 (19)
C9—C8—C7120.4 (2)C1—N2—H2N119.3 (19)
C12—C7—C13—N1173.5 (2)C13—N1—N2—C1176.4 (2)
C8—C7—C13—N14.7 (4)C6—C1—N2—N14.5 (3)
C7—C13—N1—N2176.7 (2)C2—C1—N2—N1174.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···Br1Ai0.87 (3)2.96 (3)3.508 (7)123 (2)
N2—H2N···N3i0.87 (3)2.54 (3)3.129 (3)126 (2)
Symmetry code: (i) x+1, y, z.
(Ic) (E)-4-cyanobenzaldehyde 4-iodophenylhydrazone top
Crystal data top
C14H10IN3F(000) = 672
Mr = 347.15Dx = 1.703 Mg m3
Monoclinic, P21/cMelting point = 421–422 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 8.9757 (11) ÅCell parameters from 2767 reflections
b = 20.547 (2) Åθ = 2.3–25.0°
c = 7.3703 (9) ŵ = 2.35 mm1
β = 95.137 (2)°T = 173 K
V = 1353.8 (3) Å3Needle, red
Z = 40.50 × 0.15 × 0.13 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2405 independent reflections
Radiation source: fine-focus sealed tube2164 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω scans per φθmax = 25.1°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1010
Tmin = 0.801, Tmax = 1.000k = 2424
13201 measured reflectionsl = 88
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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.058H atoms treated by a mixture of independent and constrained refinement
S = 1.12 w = 1/[σ2(Fo2) + (0.0226P)2 + 1.1577P], P = (Fo2 + 2Fc2)/3
2405 reflections(Δ/σ)max = 0.002
167 parametersΔρmax = 0.77 e Å3
1 restraintΔρmin = 0.39 e Å3
Crystal data top
C14H10IN3V = 1353.8 (3) Å3
Mr = 347.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.9757 (11) ŵ = 2.35 mm1
b = 20.547 (2) ÅT = 173 K
c = 7.3703 (9) Å0.50 × 0.15 × 0.13 mm
β = 95.137 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2405 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
2164 reflections with I > 2σ(I)
Tmin = 0.801, Tmax = 1.000Rint = 0.027
13201 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0251 restraint
wR(F2) = 0.058H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.77 e Å3
2405 reflectionsΔρmin = 0.39 e Å3
167 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.74920 (2)0.150156 (10)1.13709 (3)0.04832 (9)
C10.4021 (3)0.10285 (13)0.6064 (4)0.0320 (6)
C20.4425 (3)0.16714 (13)0.6487 (4)0.0356 (6)
H20.40310.20160.57280.043*
C30.5393 (3)0.18096 (14)0.7999 (4)0.0370 (6)
H30.56540.22480.82910.044*
C40.5981 (3)0.13074 (14)0.9086 (4)0.0338 (6)
C50.5620 (3)0.06666 (13)0.8652 (4)0.0344 (6)
H50.60480.03230.93890.041*
C60.4641 (3)0.05273 (13)0.7153 (4)0.0345 (6)
H60.43890.00880.68640.041*
C70.0666 (3)0.04326 (13)0.2884 (3)0.0306 (6)
C80.1367 (3)0.09687 (13)0.3759 (4)0.0343 (6)
H80.22580.09080.45380.041*
C90.0778 (3)0.15846 (13)0.3503 (4)0.0359 (6)
H90.12570.19450.41150.043*
C100.0521 (3)0.16786 (14)0.2344 (4)0.0348 (6)
C110.1230 (3)0.11516 (14)0.1448 (4)0.0369 (7)
H110.21070.12160.06470.044*
C120.0641 (3)0.05317 (14)0.1735 (4)0.0350 (6)
H120.11320.01700.11430.042*
C130.1281 (3)0.02220 (13)0.3185 (4)0.0325 (6)
H130.08390.05830.25340.039*
C140.1104 (3)0.23303 (15)0.2109 (4)0.0399 (7)
H2N0.260 (4)0.1243 (13)0.413 (5)0.057 (11)*
N10.2419 (2)0.03021 (10)0.4333 (3)0.0328 (5)
N20.2986 (3)0.09102 (11)0.4582 (3)0.0371 (6)
N30.1553 (3)0.28451 (13)0.1952 (4)0.0540 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.05096 (14)0.04358 (14)0.04772 (14)0.00131 (9)0.01059 (9)0.00726 (9)
C10.0328 (15)0.0258 (13)0.0374 (15)0.0002 (11)0.0042 (12)0.0001 (11)
C20.0402 (16)0.0235 (13)0.0428 (16)0.0022 (11)0.0013 (13)0.0064 (12)
C30.0405 (16)0.0242 (14)0.0463 (17)0.0037 (12)0.0030 (13)0.0012 (13)
C40.0308 (14)0.0342 (15)0.0358 (15)0.0015 (11)0.0001 (12)0.0032 (12)
C50.0328 (14)0.0249 (14)0.0453 (16)0.0004 (11)0.0016 (12)0.0049 (12)
C60.0344 (15)0.0250 (14)0.0440 (16)0.0007 (11)0.0024 (12)0.0008 (12)
C70.0330 (14)0.0315 (14)0.0277 (13)0.0031 (11)0.0054 (11)0.0015 (11)
C80.0341 (15)0.0355 (15)0.0325 (14)0.0014 (12)0.0025 (12)0.0002 (12)
C90.0400 (16)0.0311 (15)0.0356 (15)0.0024 (12)0.0022 (12)0.0037 (12)
C100.0385 (16)0.0326 (15)0.0333 (15)0.0036 (12)0.0034 (12)0.0039 (12)
C110.0330 (15)0.0416 (17)0.0352 (15)0.0001 (12)0.0016 (12)0.0025 (13)
C120.0349 (15)0.0360 (15)0.0332 (14)0.0043 (12)0.0011 (12)0.0005 (12)
C130.0376 (15)0.0288 (14)0.0312 (14)0.0041 (12)0.0029 (12)0.0013 (11)
C140.0401 (17)0.0385 (18)0.0403 (16)0.0020 (13)0.0007 (13)0.0056 (13)
N10.0342 (13)0.0258 (12)0.0383 (12)0.0002 (9)0.0021 (10)0.0024 (10)
N20.0420 (14)0.0238 (13)0.0437 (14)0.0005 (10)0.0064 (11)0.0017 (11)
N30.0609 (18)0.0376 (16)0.0606 (18)0.0056 (13)0.0104 (14)0.0076 (13)
Geometric parameters (Å, º) top
I1—C42.104 (3)C8—C91.378 (4)
C1—N21.391 (4)C8—H80.95
C1—C61.391 (4)C9—C101.396 (4)
C1—C21.398 (4)C9—H90.95
C2—C31.380 (4)C10—C111.393 (4)
C2—H20.95C10—C141.443 (4)
C3—C41.382 (4)C11—C121.388 (4)
C3—H30.95C11—H110.95
C4—C51.387 (4)C12—H120.95
C5—C61.379 (4)C13—N11.277 (3)
C5—H50.95C13—H130.95
C6—H60.95C14—N31.134 (4)
C7—C81.397 (4)N1—N21.355 (3)
C7—C121.399 (4)N2—H2N0.824 (18)
C7—C131.463 (4)
N2—C1—C6121.9 (2)C9—C8—H8120
N2—C1—C2118.8 (2)C7—C8—H8120
C6—C1—C2119.3 (3)C8—C9—C10120.0 (3)
C3—C2—C1120.4 (3)C8—C9—H9120
C3—C2—H2120C10—C9—H9120
C1—C2—H2120C11—C10—C9120.3 (3)
C2—C3—C4119.7 (3)C11—C10—C14121.3 (3)
C2—C3—H3120C9—C10—C14118.5 (3)
C4—C3—H3120C12—C11—C10119.3 (3)
C3—C4—C5120.4 (3)C12—C11—H11120
C3—C4—I1120.5 (2)C10—C11—H11120
C5—C4—I1119.0 (2)C11—C12—C7120.9 (3)
C6—C5—C4120.1 (3)C11—C12—H12120
C6—C5—H5120C7—C12—H12120
C4—C5—H5120N1—C13—C7119.1 (2)
C5—C6—C1120.1 (3)N1—C13—H13120
C5—C6—H6120C7—C13—H13120
C1—C6—H6120N3—C14—C10178.9 (3)
C8—C7—C12118.9 (3)C13—N1—N2118.5 (2)
C8—C7—C13120.5 (2)N1—N2—C1118.9 (2)
C12—C7—C13120.6 (2)N1—N2—H2N125 (3)
C9—C8—C7120.6 (3)C1—N2—H2N114 (3)
C8—C7—C13—N13.8 (4)C13—N1—N2—C1167.4 (3)
C12—C7—C13—N1175.4 (2)C6—C1—N2—N18.8 (4)
C7—C13—N1—N2179.3 (2)C2—C1—N2—N1170.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N3i0.82 (2)2.21 (2)3.035 (4)177 (3)
Symmetry code: (i) x, y+1/2, z+1/2.
(IIb) (E)-4-bromobenzaldehyde 4-cyanophenylhydrazone top
Crystal data top
C14H10BrN3F(000) = 600
Mr = 300.16Dx = 1.560 Mg m3
Monoclinic, P21/cMelting point = 464–465 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.7963 (6) ÅCell parameters from 3313 reflections
b = 9.8952 (8) Åθ = 2.4–24.9°
c = 16.5695 (13) ŵ = 3.20 mm1
β = 91.070 (1)°T = 173 K
V = 1278.05 (17) Å3Prism, brown
Z = 40.35 × 0.25 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2250 independent reflections
Radiation source: fine-focus sealed tube2050 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω scans per φθmax = 25.1°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 99
Tmin = 0.778, Tmax = 1.000k = 1111
12087 measured reflectionsl = 1919
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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.058H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0265P)2 + 0.6825P], P = (Fo2 + 2Fc2)/3
2250 reflections(Δ/σ)max = 0.001
167 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
C14H10BrN3V = 1278.05 (17) Å3
Mr = 300.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.7963 (6) ŵ = 3.20 mm1
b = 9.8952 (8) ÅT = 173 K
c = 16.5695 (13) Å0.35 × 0.25 × 0.10 mm
β = 91.070 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2250 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
2050 reflections with I > 2σ(I)
Tmin = 0.778, Tmax = 1.000Rint = 0.028
12087 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.058H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.40 e Å3
2250 reflectionsΔρmin = 0.40 e Å3
167 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.33275 (3)0.05579 (2)0.334131 (14)0.04304 (10)
C10.6555 (2)0.38513 (19)0.47078 (11)0.0258 (4)
C20.6398 (2)0.3875 (2)0.38691 (11)0.0298 (4)
H20.69560.45660.35750.036*
C30.5441 (2)0.2905 (2)0.34558 (12)0.0321 (4)
H30.53450.29270.28840.038*
C40.4632 (2)0.1910 (2)0.38881 (12)0.0306 (4)
C50.4753 (3)0.1868 (2)0.47260 (12)0.0328 (4)
H50.41810.11810.50170.039*
C60.5710 (2)0.2832 (2)0.51286 (11)0.0304 (4)
H60.57980.28050.57010.036*
C70.8899 (2)0.60323 (19)0.70449 (10)0.0241 (4)
C80.7983 (2)0.52408 (19)0.75872 (11)0.0261 (4)
H80.71880.45850.73920.031*
C90.8236 (2)0.54138 (19)0.84064 (11)0.0275 (4)
H90.76260.48670.87750.033*
C100.9385 (2)0.63908 (18)0.86964 (11)0.0250 (4)
C111.0264 (2)0.72022 (19)0.81566 (11)0.0282 (4)
H111.10290.78790.83530.034*
C121.0026 (2)0.70259 (19)0.73403 (11)0.0277 (4)
H121.06280.75810.69740.033*
C130.7586 (2)0.4883 (2)0.51210 (11)0.0269 (4)
H130.81440.55560.48130.032*
C140.9680 (2)0.65794 (19)0.95459 (11)0.0278 (4)
H2N0.916 (3)0.649 (2)0.5950 (13)0.031 (6)*
N10.77477 (19)0.48937 (16)0.58926 (9)0.0258 (3)
N20.8758 (2)0.58758 (17)0.62203 (10)0.0283 (4)
N30.9944 (2)0.67822 (17)1.02184 (10)0.0365 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.03524 (14)0.04233 (15)0.05128 (16)0.00198 (9)0.00644 (10)0.01822 (10)
C10.0243 (9)0.0270 (10)0.0260 (9)0.0062 (8)0.0037 (7)0.0016 (8)
C20.0304 (10)0.0330 (10)0.0260 (10)0.0027 (8)0.0014 (8)0.0006 (8)
C30.0308 (10)0.0401 (12)0.0251 (10)0.0052 (9)0.0042 (8)0.0051 (8)
C40.0240 (9)0.0323 (11)0.0353 (11)0.0046 (8)0.0040 (8)0.0097 (8)
C50.0319 (11)0.0306 (11)0.0360 (11)0.0008 (8)0.0008 (8)0.0007 (8)
C60.0327 (10)0.0339 (11)0.0244 (10)0.0029 (9)0.0018 (8)0.0002 (8)
C70.0254 (9)0.0235 (9)0.0232 (9)0.0048 (8)0.0019 (7)0.0005 (7)
C80.0260 (10)0.0244 (10)0.0277 (10)0.0013 (7)0.0011 (8)0.0042 (7)
C90.0296 (10)0.0271 (10)0.0259 (10)0.0013 (8)0.0038 (8)0.0004 (7)
C100.0266 (10)0.0248 (10)0.0236 (9)0.0035 (8)0.0005 (7)0.0037 (7)
C110.0298 (10)0.0242 (9)0.0304 (10)0.0031 (8)0.0034 (8)0.0020 (8)
C120.0316 (10)0.0262 (10)0.0252 (10)0.0046 (8)0.0004 (8)0.0016 (8)
C130.0273 (10)0.0272 (10)0.0262 (10)0.0024 (8)0.0023 (7)0.0030 (8)
C140.0300 (10)0.0241 (10)0.0293 (11)0.0002 (8)0.0028 (8)0.0033 (8)
N10.0267 (8)0.0257 (8)0.0249 (8)0.0025 (7)0.0039 (6)0.0010 (6)
N20.0346 (9)0.0273 (9)0.0228 (8)0.0057 (7)0.0035 (7)0.0020 (7)
N30.0475 (11)0.0351 (10)0.0269 (9)0.0023 (8)0.0022 (8)0.0054 (7)
Geometric parameters (Å, º) top
Br1—C41.9006 (19)C8—C91.379 (3)
C1—C21.393 (3)C8—H80.95
C1—C61.398 (3)C9—C101.397 (3)
C1—C131.461 (3)C9—H90.95
C2—C31.389 (3)C10—C111.392 (3)
C2—H20.95C10—C141.434 (3)
C3—C41.377 (3)C11—C121.373 (3)
C3—H30.95C11—H110.95
C4—C51.390 (3)C12—H120.95
C5—C61.376 (3)C13—N11.282 (2)
C5—H50.95C13—H130.95
C6—H60.95C14—N31.147 (2)
C7—N21.377 (2)N1—N21.358 (2)
C7—C81.398 (3)N2—H2N0.82 (2)
C7—C121.400 (3)
C2—C1—C6118.43 (18)C9—C8—H8120
C2—C1—C13119.54 (17)C7—C8—H8120
C6—C1—C13122.02 (17)C8—C9—C10120.23 (17)
C3—C2—C1121.12 (19)C8—C9—H9120
C3—C2—H2119C10—C9—H9120
C1—C2—H2119C11—C10—C9119.89 (16)
C4—C3—C2118.98 (18)C11—C10—C14118.92 (17)
C4—C3—H3121C9—C10—C14121.18 (17)
C2—C3—H3121C12—C11—C10120.04 (17)
C3—C4—C5121.18 (18)C12—C11—H11120
C3—C4—Br1120.09 (14)C10—C11—H11120
C5—C4—Br1118.73 (15)C11—C12—C7120.39 (17)
C6—C5—C4119.30 (19)C11—C12—H12120
C6—C5—H5120C7—C12—H12120
C4—C5—H5120N1—C13—C1121.06 (18)
C5—C6—C1120.98 (18)N1—C13—H13120
C5—C6—H6120C1—C13—H13120
C1—C6—H6120N3—C14—C10177.2 (2)
N2—C7—C8122.82 (17)C13—N1—N2116.76 (16)
N2—C7—C12117.63 (17)N1—N2—C7120.81 (16)
C8—C7—C12119.55 (16)N1—N2—H2N122.5 (15)
C9—C8—C7119.85 (17)C7—N2—H2N115.7 (15)
C2—C1—C13—N1179.60 (18)C13—N1—N2—C7174.85 (17)
C6—C1—C13—N10.3 (3)C8—C7—N2—N12.4 (3)
C1—C13—N1—N2178.74 (16)C12—C7—N2—N1177.12 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N3i0.82 (2)2.19 (2)3.006 (2)173 (2)
Symmetry code: (i) x, y+3/2, z1/2.
(IIc) (E)-4-iodobenzaldehyde 4-cyanophenylhydrazone top
Crystal data top
C14H10IN3F(000) = 672
Mr = 347.15Dx = 1.739 Mg m3
Monoclinic, P21/cMelting point = 477–479 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.9108 (8) ÅCell parameters from 3772 reflections
b = 10.0376 (11) Åθ = 2.4–27.5°
c = 16.6958 (18) ŵ = 2.40 mm1
β = 90.871 (2)°T = 173 K
V = 1325.6 (2) Å3Needle, brown
Z = 40.50 × 0.25 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3047 independent reflections
Radiation source: fine-focus sealed tube2735 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
ω scans per φθmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1010
Tmin = 0.775, Tmax = 1.000k = 1313
15523 measured reflectionsl = 2121
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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0311P)2 + 1.1484P], P = (Fo2 + 2Fc2)/3
3047 reflections(Δ/σ)max < 0.001
167 parametersΔρmax = 0.92 e Å3
1 restraintΔρmin = 0.50 e Å3
Crystal data top
C14H10IN3V = 1325.6 (2) Å3
Mr = 347.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.9108 (8) ŵ = 2.40 mm1
b = 10.0376 (11) ÅT = 173 K
c = 16.6958 (18) Å0.50 × 0.25 × 0.15 mm
β = 90.871 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3047 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
2735 reflections with I > 2σ(I)
Tmin = 0.775, Tmax = 1.000Rint = 0.038
15523 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0251 restraint
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.92 e Å3
3047 reflectionsΔρmin = 0.50 e Å3
167 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.33066 (2)0.050029 (18)0.334559 (11)0.03736 (8)
C10.6600 (3)0.3910 (2)0.47557 (14)0.0264 (5)
C20.6447 (3)0.3935 (3)0.39216 (15)0.0310 (5)
H20.69890.46200.36280.037*
C30.5508 (3)0.2968 (3)0.35140 (15)0.0316 (5)
H30.54100.29930.29460.038*
C40.4724 (3)0.1977 (3)0.39398 (15)0.0290 (5)
C50.4848 (3)0.1943 (3)0.47758 (15)0.0324 (5)
H50.42950.12620.50670.039*
C60.5777 (3)0.2904 (3)0.51740 (15)0.0310 (5)
H60.58570.28820.57420.037*
C70.8951 (3)0.6050 (2)0.70653 (14)0.0249 (5)
C80.8052 (3)0.5271 (2)0.76038 (15)0.0275 (5)
H80.72780.46180.74110.033*
C90.8290 (3)0.5450 (2)0.84207 (15)0.0286 (5)
H90.76890.49110.87870.034*
C100.9411 (3)0.6421 (2)0.87068 (14)0.0261 (5)
C111.0281 (3)0.7219 (2)0.81678 (15)0.0282 (5)
H111.10290.78900.83610.034*
C121.0059 (3)0.7038 (2)0.73560 (14)0.0283 (5)
H121.06570.75820.69910.034*
C130.7623 (3)0.4930 (3)0.51613 (15)0.0274 (5)
H130.81660.55970.48540.033*
C140.9695 (3)0.6616 (2)0.95514 (15)0.0296 (5)
H2N0.914 (3)0.651 (2)0.5980 (15)0.029 (8)*
N10.7796 (3)0.4936 (2)0.59272 (12)0.0267 (4)
N20.8803 (3)0.5900 (2)0.62476 (12)0.0292 (4)
N30.9949 (3)0.6814 (2)1.02117 (13)0.0388 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.03313 (11)0.03624 (12)0.04255 (12)0.00186 (7)0.00510 (8)0.01277 (7)
C10.0267 (12)0.0273 (12)0.0252 (11)0.0035 (9)0.0037 (9)0.0019 (9)
C20.0356 (14)0.0320 (13)0.0253 (12)0.0026 (11)0.0027 (10)0.0011 (10)
C30.0356 (13)0.0361 (14)0.0228 (11)0.0013 (11)0.0032 (10)0.0032 (10)
C40.0264 (12)0.0295 (12)0.0308 (12)0.0029 (10)0.0040 (10)0.0083 (10)
C50.0367 (14)0.0308 (13)0.0295 (12)0.0021 (11)0.0004 (10)0.0021 (10)
C60.0348 (13)0.0333 (13)0.0247 (12)0.0004 (11)0.0039 (10)0.0007 (10)
C70.0288 (12)0.0221 (11)0.0238 (11)0.0033 (9)0.0036 (9)0.0009 (9)
C80.0292 (12)0.0264 (12)0.0270 (12)0.0026 (9)0.0014 (10)0.0038 (9)
C90.0311 (13)0.0286 (13)0.0262 (12)0.0023 (10)0.0022 (10)0.0005 (9)
C100.0300 (12)0.0239 (11)0.0244 (11)0.0049 (10)0.0011 (9)0.0037 (9)
C110.0308 (12)0.0241 (12)0.0294 (12)0.0019 (9)0.0038 (10)0.0011 (9)
C120.0329 (13)0.0254 (12)0.0264 (12)0.0042 (10)0.0035 (10)0.0016 (9)
C130.0301 (12)0.0262 (12)0.0256 (11)0.0008 (10)0.0058 (9)0.0020 (10)
C140.0331 (13)0.0237 (12)0.0319 (13)0.0007 (10)0.0015 (10)0.0039 (10)
N10.0286 (10)0.0243 (10)0.0271 (10)0.0007 (9)0.0056 (8)0.0019 (8)
N20.0361 (12)0.0281 (11)0.0232 (10)0.0070 (9)0.0055 (9)0.0024 (9)
N30.0528 (15)0.0355 (12)0.0281 (11)0.0047 (11)0.0040 (10)0.0057 (9)
Geometric parameters (Å, º) top
I1—C42.099 (2)C8—C91.386 (3)
C1—C61.395 (4)C8—H80.95
C1—C21.396 (3)C9—C101.397 (3)
C1—C131.465 (3)C9—H90.95
C2—C31.393 (4)C10—C111.394 (3)
C2—H20.95C10—C141.438 (3)
C3—C41.376 (4)C11—C121.376 (3)
C3—H30.95C11—H110.95
C4—C51.398 (3)C12—H120.95
C5—C61.378 (4)C13—N11.284 (3)
C5—H50.95C13—H130.95
C6—H60.95C14—N31.135 (3)
C7—N21.377 (3)N1—N21.358 (3)
C7—C81.394 (4)N2—H2N0.804 (17)
C7—C121.405 (3)
C6—C1—C2118.6 (2)C9—C8—H8120
C6—C1—C13122.2 (2)C7—C8—H8120
C2—C1—C13119.2 (2)C8—C9—C10120.2 (2)
C3—C2—C1120.8 (2)C8—C9—H9120
C3—C2—H2120C10—C9—H9120
C1—C2—H2120C11—C10—C9119.8 (2)
C4—C3—C2119.5 (2)C11—C10—C14118.9 (2)
C4—C3—H3120C9—C10—C14121.3 (2)
C2—C3—H3120C12—C11—C10120.2 (2)
C3—C4—C5120.6 (2)C12—C11—H11120
C3—C4—I1120.55 (18)C10—C11—H11120
C5—C4—I1118.88 (19)C11—C12—C7120.2 (2)
C6—C5—C4119.5 (2)C11—C12—H12120
C6—C5—H5120C7—C12—H12120
C4—C5—H5120N1—C13—C1120.9 (2)
C5—C6—C1121.0 (2)N1—C13—H13120
C5—C6—H6120C1—C13—H13120
C1—C6—H6120N3—C14—C10177.4 (3)
N2—C7—C8122.8 (2)C13—N1—N2116.6 (2)
N2—C7—C12117.6 (2)N1—N2—C7120.6 (2)
C8—C7—C12119.6 (2)N1—N2—H2N121 (2)
C9—C8—C7119.9 (2)C7—N2—H2N116 (2)
C6—C1—C13—N10.2 (4)C13—N1—N2—C7174.6 (2)
C2—C1—C13—N1179.8 (2)C8—C7—N2—N12.2 (4)
C1—C13—N1—N2178.4 (2)C12—C7—N2—N1177.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N3i0.80 (2)2.22 (2)3.021 (3)177 (3)
Symmetry code: (i) x, y+3/2, z1/2.
(III) (E)-4-chlorobenzaldehyde 4-nitrophenylhydrazone top
Crystal data top
C13H10ClN3O2F(000) = 568
Mr = 275.69Dx = 1.427 Mg m3
Monoclinic, PnMelting point = 498–499 K
Hall symbol: P -2yacMo Kα radiation, λ = 0.71073 Å
a = 9.7426 (8) ÅCell parameters from 2410 reflections
b = 6.1015 (5) Åθ = 2.4–26.6°
c = 21.7139 (18) ŵ = 0.30 mm1
β = 96.175 (1)°T = 173 K
V = 1283.28 (18) Å3Needle, orange
Z = 40.50 × 0.20 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
5458 independent reflections
Radiation source: fine-focus sealed tube4595 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ω scans per φθmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1112
Tmin = 0.877, Tmax = 1.000k = 77
11862 measured reflectionsl = 2727
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.126 w = 1/[σ2(Fo2) + (0.0714P)2 + 0.3497P], P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
5458 reflectionsΔρmax = 0.45 e Å3
350 parametersΔρmin = 0.19 e Å3
4 restraintsAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.59 (6)
Crystal data top
C13H10ClN3O2V = 1283.28 (18) Å3
Mr = 275.69Z = 4
Monoclinic, PnMo Kα radiation
a = 9.7426 (8) ŵ = 0.30 mm1
b = 6.1015 (5) ÅT = 173 K
c = 21.7139 (18) Å0.50 × 0.20 × 0.15 mm
β = 96.175 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
5458 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
4595 reflections with I > 2σ(I)
Tmin = 0.877, Tmax = 1.000Rint = 0.023
11862 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.126Δρmax = 0.45 e Å3
S = 1.06Δρmin = 0.19 e Å3
5458 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
350 parametersAbsolute structure parameter: 0.59 (6)
4 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.20232 (8)0.08377 (15)0.56869 (4)0.0517 (2)
Cl1A0.55441 (9)1.36931 (16)0.18876 (4)0.0575 (3)
C10.4061 (3)0.3903 (5)0.41299 (13)0.0320 (6)
C20.3035 (3)0.5039 (5)0.44031 (14)0.0381 (7)
H20.27620.64570.42570.046*
C30.2411 (3)0.4106 (5)0.48876 (15)0.0403 (7)
H30.17120.48740.50730.048*
C40.2820 (3)0.2072 (5)0.50915 (12)0.0363 (6)
C50.3838 (4)0.0896 (5)0.48332 (15)0.0408 (7)
H50.41070.05200.49830.049*
C60.4449 (3)0.1845 (5)0.43524 (14)0.0411 (7)
H60.51490.10670.41710.049*
C70.7036 (3)0.4145 (5)0.25264 (13)0.0345 (6)
C80.7641 (3)0.2132 (5)0.26790 (14)0.0385 (7)
H80.74090.13520.30320.046*
C90.8586 (3)0.1271 (5)0.23122 (14)0.0387 (7)
H90.90050.01110.24080.046*
C100.8912 (3)0.2450 (5)0.18048 (13)0.0377 (7)
C110.8344 (3)0.4464 (5)0.16488 (13)0.0359 (6)
H110.85930.52440.12990.043*
C120.7389 (3)0.5335 (5)0.20198 (14)0.0372 (6)
H120.69840.67290.19260.045*
C130.4658 (3)0.4919 (5)0.36107 (13)0.0357 (6)
H130.43320.63120.34640.043*
C1A0.3428 (3)1.0758 (4)0.03349 (13)0.0332 (6)
C2A0.3054 (3)1.2847 (5)0.05634 (14)0.0410 (7)
H2A0.23551.36560.03910.049*
C3A0.3713 (4)1.3734 (5)0.10453 (15)0.0426 (8)
H3A0.34641.51510.12010.051*
C4A0.4710 (3)1.2574 (5)0.12918 (13)0.0385 (7)
C5A0.5094 (3)1.0488 (5)0.10753 (15)0.0412 (7)
H5A0.57890.96870.12530.049*
C6A0.4443 (3)0.9611 (5)0.05967 (13)0.0354 (6)
H6A0.46990.81930.04450.042*
C7A0.2956 (3)0.5702 (5)0.12952 (13)0.0357 (6)
C8A0.3996 (3)0.4326 (5)0.11286 (15)0.0395 (7)
H8A0.44510.46360.07730.047*
C9A0.4358 (3)0.2485 (5)0.14917 (14)0.0403 (7)
H9A0.50610.15200.13860.048*
C10A0.3684 (3)0.2087 (5)0.20041 (14)0.0370 (6)
C11A0.2684 (3)0.3449 (5)0.21882 (14)0.0396 (7)
H11A0.22580.31470.25530.047*
C12A0.2307 (3)0.5292 (5)0.18260 (15)0.0400 (7)
H12A0.16140.62590.19410.048*
C13A0.2779 (3)0.9907 (5)0.01923 (13)0.0326 (6)
H13A0.20481.06990.03460.039*
N10.5614 (3)0.3964 (4)0.33497 (11)0.0365 (5)
N20.6065 (3)0.5063 (4)0.28652 (11)0.0383 (6)
H2N0.562 (3)0.625 (4)0.2753 (16)0.046*
N30.9871 (3)0.1509 (5)0.14072 (13)0.0451 (6)
N1A0.3190 (3)0.8099 (4)0.04478 (11)0.0370 (5)
N2A0.2541 (3)0.7515 (4)0.09497 (12)0.0401 (6)
H2NA0.188 (3)0.827 (5)0.1053 (16)0.048*
N3A0.4076 (3)0.0165 (4)0.23823 (13)0.0454 (6)
O11.0140 (3)0.2538 (4)0.09540 (11)0.0533 (6)
O21.0355 (3)0.0315 (4)0.15493 (14)0.0613 (7)
O1A0.3474 (3)0.0176 (4)0.28414 (12)0.0617 (7)
O2A0.5004 (3)0.1004 (4)0.22202 (14)0.0598 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0492 (5)0.0702 (6)0.0371 (4)0.0129 (4)0.0116 (3)0.0099 (4)
Cl1A0.0632 (6)0.0727 (6)0.0375 (4)0.0201 (5)0.0092 (4)0.0131 (4)
C10.0324 (15)0.0348 (14)0.0298 (14)0.0002 (11)0.0085 (11)0.0003 (11)
C20.0388 (17)0.0364 (15)0.0398 (16)0.0024 (12)0.0072 (13)0.0035 (12)
C30.0341 (16)0.0537 (18)0.0349 (15)0.0014 (14)0.0110 (13)0.0013 (13)
C40.0349 (16)0.0488 (17)0.0255 (13)0.0118 (13)0.0042 (11)0.0028 (12)
C50.047 (2)0.0388 (16)0.0369 (16)0.0044 (13)0.0082 (14)0.0075 (12)
C60.0456 (18)0.0443 (17)0.0349 (15)0.0090 (14)0.0109 (13)0.0070 (12)
C70.0361 (15)0.0320 (14)0.0341 (14)0.0024 (11)0.0019 (11)0.0019 (11)
C80.0411 (17)0.0360 (15)0.0374 (14)0.0017 (13)0.0007 (12)0.0103 (12)
C90.0402 (17)0.0319 (15)0.0435 (16)0.0025 (13)0.0021 (13)0.0021 (12)
C100.0372 (16)0.0377 (16)0.0375 (16)0.0001 (12)0.0007 (12)0.0048 (13)
C110.0372 (16)0.0380 (15)0.0320 (13)0.0012 (12)0.0009 (12)0.0031 (12)
C120.0351 (16)0.0295 (14)0.0466 (17)0.0024 (12)0.0026 (13)0.0064 (12)
C130.0385 (16)0.0342 (14)0.0349 (14)0.0062 (12)0.0067 (12)0.0062 (12)
C1A0.0360 (16)0.0319 (14)0.0305 (14)0.0017 (11)0.0018 (12)0.0039 (11)
C2A0.0474 (19)0.0360 (15)0.0397 (16)0.0072 (13)0.0059 (14)0.0045 (12)
C3A0.059 (2)0.0319 (15)0.0350 (16)0.0078 (13)0.0019 (15)0.0090 (12)
C4A0.0432 (18)0.0461 (16)0.0259 (13)0.0143 (14)0.0032 (12)0.0051 (12)
C5A0.0366 (17)0.0503 (18)0.0372 (16)0.0006 (14)0.0063 (13)0.0002 (13)
C6A0.0394 (16)0.0338 (14)0.0325 (14)0.0016 (12)0.0016 (12)0.0048 (11)
C7A0.0352 (16)0.0349 (14)0.0371 (14)0.0011 (11)0.0041 (12)0.0008 (11)
C8A0.0411 (17)0.0420 (16)0.0371 (15)0.0002 (13)0.0123 (13)0.0012 (12)
C9A0.0388 (17)0.0372 (16)0.0459 (17)0.0079 (13)0.0097 (14)0.0065 (13)
C10A0.0388 (16)0.0304 (13)0.0413 (16)0.0013 (12)0.0024 (13)0.0019 (12)
C11A0.0425 (17)0.0392 (16)0.0389 (15)0.0016 (13)0.0135 (13)0.0007 (13)
C12A0.0388 (16)0.0382 (15)0.0452 (16)0.0094 (13)0.0147 (13)0.0012 (13)
C13A0.0287 (14)0.0333 (14)0.0366 (14)0.0055 (11)0.0075 (11)0.0041 (11)
N10.0409 (14)0.0352 (12)0.0338 (11)0.0043 (10)0.0065 (10)0.0060 (10)
N20.0423 (15)0.0355 (13)0.0396 (13)0.0089 (11)0.0152 (11)0.0102 (10)
N30.0395 (15)0.0489 (16)0.0473 (15)0.0002 (12)0.0060 (12)0.0079 (12)
N1A0.0387 (14)0.0387 (13)0.0352 (12)0.0024 (11)0.0113 (10)0.0040 (10)
N2A0.0424 (15)0.0367 (13)0.0443 (13)0.0109 (11)0.0183 (11)0.0100 (11)
N3A0.0508 (17)0.0345 (14)0.0507 (16)0.0014 (12)0.0041 (13)0.0032 (12)
O10.0549 (15)0.0617 (15)0.0454 (13)0.0031 (11)0.0145 (11)0.0060 (11)
O20.0587 (16)0.0480 (14)0.0806 (18)0.0206 (12)0.0231 (13)0.0007 (13)
O1A0.0785 (19)0.0505 (14)0.0581 (15)0.0062 (13)0.0162 (13)0.0180 (12)
O2A0.0603 (16)0.0415 (13)0.0777 (18)0.0185 (12)0.0080 (13)0.0123 (12)
Geometric parameters (Å, º) top
Cl1—C41.748 (3)C2A—C3A1.394 (4)
Cl1A—C4A1.740 (3)C2A—H2A0.95
C1—C61.383 (4)C3A—C4A1.357 (5)
C1—C21.400 (4)C3A—H3A0.95
C1—C131.461 (4)C4A—C5A1.394 (5)
C2—C31.392 (4)C5A—C6A1.382 (4)
C2—H20.95C5A—H5A0.95
C3—C41.363 (4)C6A—H6A0.95
C3—H30.95C7A—N2A1.373 (4)
C4—C51.391 (5)C7A—C8A1.393 (4)
C5—C61.383 (4)C7A—C12A1.396 (4)
C5—H50.95C8A—C9A1.396 (4)
C6—H60.95C8A—H8A0.95
C7—N21.378 (4)C9A—C10A1.373 (4)
C7—C81.387 (4)C9A—H9A0.95
C7—C121.392 (4)C10A—C11A1.372 (4)
C8—C91.384 (4)C10A—N3A1.459 (4)
C8—H80.95C11A—C12A1.399 (4)
C9—C101.381 (4)C11A—H11A0.95
C9—H90.95C12A—H12A0.95
C10—C111.375 (4)C13A—N1A1.279 (4)
C10—N31.456 (4)C13A—H13A0.95
C11—C121.400 (4)N1—N21.360 (3)
C11—H110.95N2—H2N0.865 (18)
C12—H120.95N3—O11.219 (4)
C13—N11.281 (4)N3—O21.235 (4)
C13—H130.95N1A—N2A1.365 (3)
C1A—C6A1.383 (4)N2A—H2NA0.841 (18)
C1A—C2A1.402 (4)N3A—O1A1.227 (4)
C1A—C13A1.461 (4)N3A—O2A1.232 (4)
C6—C1—C2118.8 (3)C4A—C3A—H3A120
C6—C1—C13122.6 (3)C2A—C3A—H3A120
C2—C1—C13118.6 (3)C3A—C4A—C5A121.4 (3)
C3—C2—C1120.5 (3)C3A—C4A—Cl1A120.0 (2)
C3—C2—H2120C5A—C4A—Cl1A118.6 (3)
C1—C2—H2120C6A—C5A—C4A118.6 (3)
C4—C3—C2118.8 (3)C6A—C5A—H5A121
C4—C3—H3121C4A—C5A—H5A121
C2—C3—H3121C5A—C6A—C1A121.3 (3)
C3—C4—C5122.4 (3)C5A—C6A—H6A119
C3—C4—Cl1119.7 (3)C1A—C6A—H6A119
C5—C4—Cl1118.0 (2)N2A—C7A—C8A121.6 (3)
C6—C5—C4118.2 (3)N2A—C7A—C12A117.6 (3)
C6—C5—H5121C8A—C7A—C12A120.9 (3)
C4—C5—H5121C7A—C8A—C9A119.0 (3)
C5—C6—C1121.3 (3)C7A—C8A—H8A121
C5—C6—H6119C9A—C8A—H8A121
C1—C6—H6119C10A—C9A—C8A119.1 (3)
N2—C7—C8122.1 (3)C10A—C9A—H9A121
N2—C7—C12116.9 (3)C8A—C9A—H9A121
C8—C7—C12121.1 (3)C11A—C10A—C9A123.0 (3)
C9—C8—C7119.4 (3)C11A—C10A—N3A118.3 (3)
C9—C8—H8120C9A—C10A—N3A118.6 (3)
C7—C8—H8120C10A—C11A—C12A118.3 (3)
C10—C9—C8119.1 (3)C10A—C11A—H11A121
C10—C9—H9121C12A—C11A—H11A121
C8—C9—H9121C7A—C12A—C11A119.6 (3)
C11—C10—C9122.7 (3)C7A—C12A—H12A120
C11—C10—N3118.2 (3)C11A—C12A—H12A120
C9—C10—N3119.0 (3)N1A—C13A—C1A120.3 (3)
C10—C11—C12118.2 (3)N1A—C13A—H13A120
C10—C11—H11121C1A—C13A—H13A120
C12—C11—H11121C13—N1—N2115.4 (2)
C7—C12—C11119.5 (3)N1—N2—C7120.6 (2)
C7—C12—H12120N1—N2—H2N116 (2)
C11—C12—H12120C7—N2—H2N123 (2)
N1—C13—C1121.1 (3)O1—N3—O2123.8 (3)
N1—C13—H13119O1—N3—C10118.9 (3)
C1—C13—H13119O2—N3—C10117.3 (3)
C6A—C1A—C2A119.0 (3)C13A—N1A—N2A114.9 (2)
C6A—C1A—C13A122.1 (2)N1A—N2A—C7A120.8 (2)
C2A—C1A—C13A118.9 (3)N1A—N2A—H2NA120 (3)
C3A—C2A—C1A119.7 (3)C7A—N2A—H2NA119 (3)
C3A—C2A—H2A120O1A—N3A—O2A124.3 (3)
C1A—C2A—H2A120O1A—N3A—C10A118.3 (3)
C4A—C3A—C2A120.0 (3)O2A—N3A—C10A117.4 (3)
C6—C1—C13—N12.5 (5)C11—C10—N3—O2179.0 (3)
C2—C1—C13—N1179.0 (3)C9—C10—N3—O20.5 (4)
C6A—C1A—C13A—N1A3.5 (5)C1A—C13A—N1A—N2A177.7 (3)
C2A—C1A—C13A—N1A173.4 (3)C13A—N1A—N2A—C7A174.9 (3)
C1—C13—N1—N2178.9 (3)C8A—C7A—N2A—N1A3.7 (4)
C13—N1—N2—C7176.4 (3)C12A—C7A—N2A—N1A175.7 (3)
C8—C7—N2—N13.2 (4)C11A—C10A—N3A—O1A1.5 (4)
C12—C7—N2—N1176.9 (3)C9A—C10A—N3A—O1A179.6 (3)
C11—C10—N3—O10.4 (4)C11A—C10A—N3A—O2A177.9 (3)
C9—C10—N3—O1178.8 (3)C9A—C10A—N3A—O2A0.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2A—H2NA···O2i0.84 (2)2.11 (2)2.930 (4)164 (4)
N2—H2N···O2Aii0.87 (2)2.09 (2)2.911 (3)159 (3)
C13A—H13A···O1i0.952.643.583 (4)170
C13—H13···O1Aii0.952.623.559 (4)169
Symmetry codes: (i) x1, y+1, z; (ii) x, y+1, z.
(IV) (E)-4-nitrobenzaldehyde 4-chlorophenylhydrazone top
Crystal data top
C13H10ClN3O2F(000) = 568
Mr = 275.69Dx = 1.434 Mg m3
Monoclinic, P21/nMelting point = 423–427 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 6.1260 (7) ÅCell parameters from 2311 reflections
b = 16.404 (2) Åθ = 3.0–25.3°
c = 12.9510 (16) ŵ = 0.30 mm1
β = 101.091 (2)°T = 173 K
V = 1277.1 (3) Å3Needle, red
Z = 40.50 × 0.23 × 0.08 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2426 independent reflections
Radiation source: fine-focus sealed tube1730 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
ω scans per φθmax = 25.7°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 77
Tmin = 0.869, Tmax = 1.000k = 2019
13035 measured reflectionsl = 1515
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0635P)2 + 0.2059P], P = (Fo2 + 2Fc2)/3
2426 reflections(Δ/σ)max < 0.001
176 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C13H10ClN3O2V = 1277.1 (3) Å3
Mr = 275.69Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.1260 (7) ŵ = 0.30 mm1
b = 16.404 (2) ÅT = 173 K
c = 12.9510 (16) Å0.50 × 0.23 × 0.08 mm
β = 101.091 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2426 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1730 reflections with I > 2σ(I)
Tmin = 0.869, Tmax = 1.000Rint = 0.039
13035 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.24 e Å3
2426 reflectionsΔρmin = 0.22 e Å3
176 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.18962 (10)0.34124 (4)0.69229 (5)0.0550 (2)
C10.7104 (3)0.30131 (12)0.49396 (15)0.0381 (5)
C20.6031 (3)0.23538 (13)0.52947 (16)0.0412 (5)
H20.63990.18150.51210.049*
C30.4436 (3)0.24766 (13)0.58977 (16)0.0429 (5)
H30.37150.20240.61450.052*
C40.3890 (3)0.32631 (13)0.61414 (16)0.0398 (5)
C50.4909 (3)0.39216 (13)0.57811 (16)0.0418 (5)
H50.45010.44590.59420.050*
C60.6528 (3)0.38040 (13)0.51846 (16)0.0413 (5)
H60.72450.42590.49420.050*
C71.2172 (3)0.39209 (12)0.28158 (15)0.0372 (5)
C81.1158 (3)0.46781 (13)0.25853 (17)0.0423 (5)
H80.98540.48070.28470.051*
C91.2022 (3)0.52403 (13)0.19841 (16)0.0421 (5)
H91.13070.57500.18160.051*
C101.3950 (3)0.50485 (12)0.16299 (15)0.0367 (5)
C111.5009 (3)0.43097 (13)0.18543 (16)0.0404 (5)
H111.63410.41920.16100.049*
C121.4110 (3)0.37454 (13)0.24375 (16)0.0413 (5)
H121.48120.32310.25850.050*
C131.1243 (3)0.33085 (13)0.34199 (16)0.0400 (5)
H131.18710.27770.34920.048*
H2N0.927 (4)0.2384 (16)0.4326 (17)0.051 (7)*
N10.9585 (3)0.34764 (10)0.38574 (13)0.0403 (4)
N20.8737 (3)0.28665 (12)0.43564 (15)0.0436 (5)
N31.4899 (3)0.56458 (11)0.10106 (14)0.0423 (4)
O11.6707 (2)0.55056 (9)0.07763 (12)0.0478 (4)
O21.3830 (3)0.62751 (9)0.07438 (14)0.0548 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0494 (4)0.0657 (4)0.0529 (4)0.0012 (3)0.0173 (3)0.0083 (3)
C10.0381 (11)0.0393 (11)0.0358 (11)0.0017 (9)0.0044 (9)0.0000 (9)
C20.0481 (12)0.0332 (11)0.0418 (12)0.0006 (9)0.0071 (10)0.0000 (9)
C30.0446 (12)0.0440 (13)0.0393 (11)0.0054 (10)0.0059 (9)0.0031 (10)
C40.0365 (11)0.0451 (13)0.0365 (11)0.0003 (9)0.0034 (9)0.0018 (9)
C50.0423 (11)0.0384 (12)0.0431 (12)0.0055 (9)0.0044 (9)0.0023 (10)
C60.0451 (12)0.0353 (12)0.0427 (12)0.0023 (9)0.0066 (10)0.0025 (9)
C70.0352 (10)0.0405 (12)0.0345 (11)0.0013 (9)0.0031 (8)0.0028 (9)
C80.0351 (11)0.0407 (12)0.0520 (13)0.0007 (9)0.0106 (10)0.0010 (10)
C90.0377 (11)0.0365 (11)0.0519 (13)0.0022 (9)0.0082 (10)0.0004 (10)
C100.0369 (11)0.0374 (12)0.0351 (11)0.0049 (9)0.0051 (9)0.0015 (9)
C110.0378 (11)0.0435 (12)0.0407 (11)0.0026 (9)0.0094 (9)0.0019 (9)
C120.0440 (12)0.0382 (12)0.0420 (12)0.0061 (9)0.0088 (9)0.0019 (9)
C130.0389 (11)0.0402 (12)0.0401 (11)0.0025 (9)0.0059 (9)0.0011 (9)
N10.0417 (10)0.0400 (10)0.0391 (10)0.0026 (8)0.0074 (8)0.0022 (8)
N20.0484 (11)0.0355 (11)0.0497 (11)0.0038 (9)0.0166 (9)0.0047 (8)
N30.0430 (10)0.0392 (10)0.0438 (10)0.0040 (8)0.0057 (8)0.0058 (8)
O10.0425 (9)0.0534 (10)0.0502 (9)0.0052 (7)0.0154 (7)0.0021 (7)
O20.0544 (10)0.0406 (9)0.0705 (11)0.0004 (7)0.0147 (8)0.0108 (8)
Geometric parameters (Å, º) top
Cl1—C41.747 (2)C8—C91.377 (3)
C1—N21.386 (3)C8—H80.95
C1—C21.389 (3)C9—C101.383 (3)
C1—C61.397 (3)C9—H90.95
C2—C31.378 (3)C10—C111.379 (3)
C2—H20.95C10—N31.456 (3)
C3—C41.384 (3)C11—C121.375 (3)
C3—H30.95C11—H110.95
C4—C51.373 (3)C12—H120.95
C5—C61.383 (3)C13—N11.285 (3)
C5—H50.95C13—H130.95
C6—H60.95N1—N21.348 (2)
C7—C81.395 (3)N2—H2N0.86 (3)
C7—C121.398 (3)N3—O11.226 (2)
C7—C131.455 (3)N3—O21.236 (2)
N2—C1—C2118.85 (19)C7—C8—H8120
N2—C1—C6121.71 (19)C8—C9—C10118.7 (2)
C2—C1—C6119.44 (19)C8—C9—H9121
C3—C2—C1120.40 (19)C10—C9—H9121
C3—C2—H2120C11—C10—C9121.83 (19)
C1—C2—H2120C11—C10—N3119.05 (18)
C2—C3—C4119.6 (2)C9—C10—N3119.11 (18)
C2—C3—H3120C12—C11—C10119.01 (19)
C4—C3—H3120C12—C11—H11121
C5—C4—C3120.7 (2)C10—C11—H11121
C5—C4—Cl1120.05 (17)C11—C12—C7120.72 (19)
C3—C4—Cl1119.29 (17)C11—C12—H12120
C4—C5—C6120.12 (19)C7—C12—H12120
C4—C5—H5120N1—C13—C7120.90 (19)
C6—C5—H5120N1—C13—H13120
C5—C6—C1119.75 (19)C7—C13—H13120
C5—C6—H6120C13—N1—N2117.55 (18)
C1—C6—H6120N1—N2—C1121.17 (18)
C8—C7—C12118.76 (19)N1—N2—H2N118.6 (15)
C8—C7—C13121.72 (18)C1—N2—H2N120.2 (15)
C12—C7—C13119.51 (18)O1—N3—O2122.91 (18)
C9—C8—C7120.93 (19)O1—N3—C10119.07 (17)
C9—C8—H8120O2—N3—C10118.02 (18)
C8—C7—C13—N17.5 (3)C6—C1—N2—N110.9 (3)
C12—C7—C13—N1173.68 (18)C11—C10—N3—O15.9 (3)
C7—C13—N1—N2176.50 (18)C9—C10—N3—O1173.59 (18)
C13—N1—N2—C1173.27 (18)C11—C10—N3—O2174.08 (18)
C2—C1—N2—N1169.65 (18)C9—C10—N3—O26.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O2i0.86 (3)2.17 (3)3.021 (3)170 (2)
C13—H13···O2i0.952.723.510 (3)141
Symmetry code: (i) x+5/2, y1/2, z+1/2.

Experimental details

(Ia)(Ib)(Ic)(IIb)
Crystal data
Chemical formulaC14H10ClN3C14H10BrN3C14H10IN3C14H10BrN3
Mr255.70300.16347.15300.16
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/nMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)173173173173
a, b, c (Å)10.7246 (10), 7.1767 (6), 16.3492 (15)10.6804 (8), 7.3150 (6), 16.5427 (13)8.9757 (11), 20.547 (2), 7.3703 (9)7.7963 (6), 9.8952 (8), 16.5695 (13)
β (°) 104.779 (1) 105.500 (1) 95.137 (2) 91.070 (1)
V3)1216.72 (19)1245.43 (17)1353.8 (3)1278.05 (17)
Z4444
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.303.282.353.20
Crystal size (mm)0.50 × 0.50 × 0.100.40 × 0.30 × 0.080.50 × 0.15 × 0.130.35 × 0.25 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detectorBruker SMART CCD area-detectorBruker SMART CCD area-detectorBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Multi-scan
(SADABS; Bruker, 2000)
Multi-scan
(SADABS; Bruker, 2000)
Multi-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.894, 1.0000.778, 1.0000.801, 1.0000.778, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
11510, 2154, 1952 8153, 2205, 1975 13201, 2405, 2164 12087, 2250, 2050
Rint0.0270.0240.0270.028
(sin θ/λ)max1)0.5960.5950.5960.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.080, 1.13 0.028, 0.068, 1.13 0.025, 0.058, 1.12 0.023, 0.058, 1.06
No. of reflections2154220524052250
No. of parameters172172167167
No. of restraints0110
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.16, 0.170.30, 0.330.77, 0.390.40, 0.40
Absolute structure????
Absolute structure parameter????


(IIc)(III)(IV)
Crystal data
Chemical formulaC14H10IN3C13H10ClN3O2C13H10ClN3O2
Mr347.15275.69275.69
Crystal system, space groupMonoclinic, P21/cMonoclinic, PnMonoclinic, P21/n
Temperature (K)173173173
a, b, c (Å)7.9108 (8), 10.0376 (11), 16.6958 (18)9.7426 (8), 6.1015 (5), 21.7139 (18)6.1260 (7), 16.404 (2), 12.9510 (16)
β (°) 90.871 (2) 96.175 (1) 101.091 (2)
V3)1325.6 (2)1283.28 (18)1277.1 (3)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm1)2.400.300.30
Crystal size (mm)0.50 × 0.25 × 0.150.50 × 0.20 × 0.150.50 × 0.23 × 0.08
Data collection
DiffractometerBruker SMART CCD area-detectorBruker SMART CCD area-detectorBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Multi-scan
(SADABS; Bruker, 2000)
Multi-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.775, 1.0000.877, 1.0000.869, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
15523, 3047, 2735 11862, 5458, 4595 13035, 2426, 1730
Rint0.0380.0230.039
(sin θ/λ)max1)0.6500.6490.610
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.068, 1.05 0.046, 0.126, 1.06 0.041, 0.118, 1.07
No. of reflections304754582426
No. of parameters167350176
No. of restraints140
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.92, 0.500.45, 0.190.24, 0.22
Absolute structure?Flack (1983), with how many Friedel pairs??
Absolute structure parameter?0.59 (6)?

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N3i0.871 (17)2.471 (17)3.1345 (19)133.5 (14)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···Br1Ai0.87 (3)2.96 (3)3.508 (7)123 (2)
N2—H2N···N3i0.87 (3)2.54 (3)3.129 (3)126 (2)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (Ic) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N3i0.82 (2)2.21 (2)3.035 (4)177 (3)
Symmetry code: (i) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (IIb) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N3i0.82 (2)2.19 (2)3.006 (2)173 (2)
Symmetry code: (i) x, y+3/2, z1/2.
Hydrogen-bond geometry (Å, º) for (IIc) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···N3i0.80 (2)2.22 (2)3.021 (3)177 (3)
Symmetry code: (i) x, y+3/2, z1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N2A—H2NA···O2i0.84 (2)2.11 (2)2.930 (4)164 (4)
N2—H2N···O2Aii0.87 (2)2.09 (2)2.911 (3)159 (3)
C13A—H13A···O1i0.952.643.583 (4)170
C13—H13···O1Aii0.952.623.559 (4)169
Symmetry codes: (i) x1, y+1, z; (ii) x, y+1, z.
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···O2i0.86 (3)2.17 (3)3.021 (3)170 (2)
C13—H13···O2i0.952.723.510 (3)141
Symmetry code: (i) x+5/2, y1/2, z+1/2.
 

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