organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Four substituted benzohydrazides: hydrogen-bonded structures in one, two and three dimensions

aInstituto de Tecnologia em Fármacos, Far-Manguinhos, FIOCRUZ, 21041-250 Rio de Janeiro, RJ, Brazil, bInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 16 August 2006; accepted 30 August 2006; online 21 September 2006)

The mol­ecules of 2,6-dichloro­benzohydrazide, C7H6Cl2N2O, are linked into simple chains by a single N—H⋯O hydrogen bond, while in the isomeric compound 2,4-dichloro­benzo­hydrazide, the mol­ecules are linked by N—H⋯N and N—H⋯O hydrogen bonds into complex sheets comprising an inner polar layer sandwiched between two non-polar layers. In 4-amino-2-chloro­benzohydrazide monohydrate, C7H8ClN3O·H2O, the components are linked into a three-dimensional framework by a combination of O—H⋯O, O—H⋯N, N—H⋯N and N—H⋯O hydrogen bonds, and in 2-nitro­benzohydrazide, C7H7N3O3, a three-dimensional framework is formed by a combination of N—H⋯N and N—H⋯O hydrogen bonds

Comment

As part of our general study of the supra­molecular structures of amine and hydrazine derivatives, we report here the mol­ecular and supra­molecular structures of four related benzohydrazides, namely isomeric 2,6-dichloro­benzohydrazide, (I)[link], and 2,4-dichloro­benzohydrazide, (II)[link], 4-amino-2-chloro­benzo­hydrazide, which crystallizes as a monohydrate, (III)[link], and 2-nitro­benzohydrazide, (IV)[link]. Compounds (I)[link] and (II)[link] were prepared straightforwardly by reaction of hydrazine with the methyl esters ArCOOCH3 to yield the corresponding hydrazines ArCONHNH2. By contrast, compound (III)[link] was obtained, on one occasion only, from the reaction of hydrazine with methyl 2-chloro-4-fluoro­benzoate; this reaction involves a nucleophilic displacement of the 4-fluoro substituent, and despite a number of attempts to reproduce this synthesis, we have been consistently unsuccessful.

The coordination at atoms C7 and N1 is effectively planar in each of compounds (I)–(IV) (Figs. 1[link]–4[link][link][link]), but the C1/C7/O1/N1/N2 planes make dihedral angles with the aryl rings of 78.0 (2)° in (I)[link], 38.5 (2)° in (II)[link], 63.9 (2)° in (III)[link] and 42.9 (2) in (IV)[link]. However, the orientations of the side chains differ markedly between compounds (II)[link] and (III)[link], with atom N1 syn to Cl2 in (II)[link] but anti in (III)[link] (Figs. 2[link] and 3[link]).

[Scheme 1]

The exocyclic bond angles in compound (II)[link] show some significant variations, including significant deviations from the idealized values of 120° (Table 5[link]). Thus, although the two independent exocyclic angles at atom C4 are identical within experimental uncertainty, those at atom C2 differ by more than 5°, while those at C1 differ by some 12°. The sense of these deviations suggests strongly repulsive inter­actions between atoms Cl2 and C7 and/or N1, possibly associated with the rather short intra­molecular H1⋯Cl2 contact in (II)[link] (Table 2[link]). By contrast, the corresponding angles in compounds (I)[link] and (III)[link], where there are no short intra­molecular contacts involving atom Cl2 (or Cl6), show no such features, while any such effect in compound (IV)[link] is very modest in magnitude.

In each compound, the coordination of hydrazine atom N2 is sharply pyramidal (Figs. 1[link]–4[link][link][link]), with sums of angles at N2 consistently less than 330°. In addition, amino atom N4 in compound (III)[link] is pyramidal, and the C4—N4 distance [1.395 (2) Å];] is identical to the mean values for C(aryl)—NH2 bonds with pyramidal N atoms and much longer than the corresponding mean value (1.355 Å) for such bonds with planar N atoms (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

In compound (I)[link], the mol­ecules are linked into simple chains by a single N—H⋯O hydrogen bond (Table 1[link]). Atom N1 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor to atom O1 in the mol­ecule at ([{1\over 2}] + x, [{3\over 2}] − y, [{1\over 2}] + z), so forming a C(4) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) chain running parallel to the [101] direction and generated by the n-glide plane at y = [3\over4] (Fig. 5[link]). Two such chains, related to one another by inversion and hence anti­parallel, pass through each unit cell, but there are no direction-specific inter­actions between adjacent chains. It is notable that the NH2 group in compound (I)[link] plays no part in the supra­molecular aggregation; there are no potential donor or acceptor atoms of any type within hydrogen-bonding range.

The mol­ecules of (II)[link] are linked by a combination of one N—H⋯N hydrogen bond and two N—H⋯O hydrogen bonds (Table 2[link]) into sheets whose formation is readily analysed in terms of two simple substructures. In the first of these substructures, paired N—H⋯N hydrogen bonds link the mol­ecules at (x, y, z) and (1 − x, 1 − y, 1 − z) into centrosymmetric R22(6) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) dimers (Fig. 6[link]). The second substructure is formed by the two N—H⋯O hydrogen bonds; atom N2 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor, via H2A and H2B, respectively, to atoms O1 in the mol­ecules at (1 − x, [{1\over 2}] + y, [{3\over 2}] − z) and (1 − x, −[{1\over 2}] + y, [{3\over 2}] − z), respectively, so forming a chain of edge-fused R22(10) rings running parallel to the [010] direction and generated by the 21 screw axis along ([1\over2], y, [3\over4]) (Fig. 7[link]). The combination of the finite zero-dimensional substructure (Fig. 2[link]) and the one-dimensional substructure (Fig. 3[link]) then leads to the formation of thick tripartite sheets, parallel to (100), in which a central polar layer is sandwiched between two non-polar layers with Cl atoms on the exterior faces (Fig. 8[link]).

The mol­ecules of (III)[link] are linked into a three-dimensional framework structure by a combination of O—H⋯O, O—H⋯N, N—H⋯N and N—H⋯O hydrogen bonds (Table 3[link]). The organic components are linked into sheets by one N—H⋯N and one N—H⋯O inter­action, and these sheets are linked into a continuous framework by means of the water mol­ecules. Paired N—H⋯N hydrogen bonds link the organic mol­ecules into centrosymmetric R22(16) dimers (Fig. 9[link]), and the reference dimer centred at ([{1\over 2}], [{1\over 2}], [{1\over 2}]) is linked by N—H⋯O hydrogen bonds to four similar dimers centred at ([1\over2], 0, 0), ([1\over2], 0, 1), ([1\over2], 1, 0) and ([1\over2], 1, 1), thereby generating a (100) sheet built from R22(16) and R66(28) rings alternating in a chessboard fashion (Fig. 9[link]).

The simplest description of the linking of the (100) sheets is in terms of one each of O—H⋯O and N—H⋯O hydrogen bonds. The O—H⋯O hydrogen bond lies within the selected asymmetric unit (Fig. 3[link]); in addition, atom N4 at (x, y, z) acts as a donor to water atom O1W at (−1 + x, [{3\over 2}] − y, −[{1\over 2}] + z), so forming a C22(10) chain running parallel to the [201] direction and generated by the c-glide plane at y = 0.75 (Fig. 10[link]).

In (IV)[link], the mol­ecules are linked by a combination of N—H⋯O and N—H⋯N hydrogen bonds (Table 4[link]) into a three-dimensional framework whose formation is readily analysed in terms of three one-dimensional substructures.

In the simplest of these substructures, which depends on the action of just one hydrogen bond, atom N2 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor, via H2A, to nitro atom O22 in the mol­ecule at (−[{1\over 2}] + x, [{1\over 2}] − y, 1 − z), so forming a simple C(8) chain running parallel to the [100] direction and generated by the 21 screw axis along (x, [1\over4], [1\over2]) (Fig. 11[link]). A second substructure is formed by the concerted action of the other two hydrogen bonds. Atom N2 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor to atom N2 in the mol­ecule at (1 − x, −[{1\over 2}] + y, [{1\over 2}] − z), so forming a C(2) chain running parallel to the [010] direction and generated by the 21 screw axis along ([1\over2], y, [1\over4]). At the same time, atom N1 in the mol­ecule at (x, y, z) acts as a donor to carbonyl atom O1 in the mol­ecule at (x, 1 + y, z), so generating by translation a C(4) chain along [010], and the combination of the two [010] chains generates a chain of edge-fused R33(10) rings (Fig. 12[link]). Finally, the combination of the two hydrogen bonds formed by the NH2 group generates a C22(10) chain running parallel to the [001] direction (Fig. 13[link]). The combination of [100], [010] and [001] chains then generates a single three-dimensional framework.

It is of inter­est briefly to compare the supra­molecular structures of the compounds reported here with those of some closely related analogues from the literature. A very brief report on the 4-chloro analogue, (V), stated that the structure is held together by two hydrogen bonds, one each of N—H⋯N and N—H⋯O types (Saraogi et al., 2002[Saraogi, I., Mruthyunjayaswamy, B. H. M., Ijare, O. B., Jadegoud, Y. & Guru Row, T. N. (2002). Acta Cryst. E58, o1341-o1342.]). While no discussion of the aggregation was given, the packing diagram provided appears to show a chain of edge-fused rings along [100]. However, re-examination of the structure using the published atomic coordinates shows that there are, in fact, three inter­molecular hydrogen bonds present, one of N—H⋯N type and two of N—H⋯O type, and these link the mol­ecules into complex sheets parallel to (100) in which all the Cl substituents lie on the two faces of the sheet (Fig. 14[link]), so that there are no direction-specific inter­actions between these sheets. Even the two hydrogen bonds listed in the original report (Saraogi et al., 2002[Saraogi, I., Mruthyunjayaswamy, B. H. M., Ijare, O. B., Jadegoud, Y. & Guru Row, T. N. (2002). Acta Cryst. E58, o1341-o1342.]) suffice to generate this type of (100) sheet. For the unsubstituted compound (VI), there is again only a very brief report with no discussion of the supra­molecular aggregation (Kallel et al., 1992[Kallel, A., Amor, B. H., Svoboda, I. & Fuess, H. (1992). Z. Kristallogr. 198, 137-138.]). Again, re-examination of the structure using coordinates as retrieved from the Cambridge Structural Database (Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]; refcode VOPJEP) shows that this compound forms exactly the same type of (100) sheet as the 4-chloro analogue (V), and that it is, indeed, isomorphous and effectively isostructural with compound (V), although this fact was not noted in the report on (V) (Saraogi et al., 2002[Saraogi, I., Mruthyunjayaswamy, B. H. M., Ijare, O. B., Jadegoud, Y. & Guru Row, T. N. (2002). Acta Cryst. E58, o1341-o1342.]). In compound (VII), which is isomeric with (IV)[link], the mol­ecules are linked into a three-dimensional framework of some complexity, built from a combination of N—H⋯O, N—H⋯N, C—H⋯O and C—H⋯N hydrogen bonds (Ratajczak et al., 2001[Ratajczak, H., Baran, J., Barnes, A. J., Barycki, J., Debrus, S., Latajka, Z., May, M. & Pietraszko, A. (2001). J. Mol. Struct. 596, 17-23.]).

The supra­molecular structures discussed here show the marked effects on the aggregation of the identity of the substituents on the aryl ring and, in the case of the pairs of isomers (I)[link]/(II)[link] and (IV)[link]/(VII) the strong influence of the orientation of the substituents, even when, as in (I)[link] and (II)[link], they play no direct role in the aggregation.

[Figure 1]
Figure 1
A mol­ecule of (I)[link], with the atom-labelling scheme shown. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
A mol­ecule of (II)[link], with the atom-labelling scheme shown. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3]
Figure 3
The independent mol­ecular components in (III)[link], with the atom-labelling scheme shown. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4]
Figure 4
A mol­ecule of (IV)[link], with the atom-labelling scheme shown. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 5]
Figure 5
Part of the crystal structure of (I)[link], showing the formation of a C(4) chain along [101]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ([{1\over 2}] + x, [{3\over 2}] − y, [{1\over 2}] + z) and (−[{1\over 2}] + x, [{3\over 2}] − y, −[{1\over 2}] + z), respectively.
[Figure 6]
Figure 6
Part of the crystal structure of (II)[link], showing the formation of a centrosymmetric R22(6) dimer. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 7]
Figure 7
Part of the crystal structure of (II)[link], showing the formation of a [010] chain of edge-fused R22(10) rings. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (1 − x, [{1\over 2}] + y, [{3\over 2}] − z), (1 − x, −[{1\over 2}] + y, [{3\over 2}] − z), (x, 1 + y, z) and (x, −1 + y, z), respectively.
[Figure 8]
Figure 8
A stereoview of part of the crystal structure of (II)[link], showing the formation of a (100) sheet. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 9]
Figure 9
A stereoview of part of the crystal structure of (III)[link], showing the formation of a (100) sheet built from organic mol­ecules only. For the sake of clarity, H atoms bonded to C or N atoms not involved in the motif shown have been omitted.
[Figure 10]
Figure 10
Part of the crystal structure of (III)[link], showing the formation of a C22(10) chain along [201]. For the sake of clarity, H atoms bonded to C or N atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−1 + x, [{3\over 2}] − y, −[{1\over 2}] + z) and (1 + x, [{3\over 2}] − y, [{1\over 2}] + z), respectively.
[Figure 11]
Figure 11
Part of the crystal structure of (IV)[link], showing the formation of a C(8) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#) or an ampersand (&) are at the symmetry positions (−[{1\over 2}] + x, [{1\over 2}] − y, 1 − z), ([{1\over 2}] + x, [{1\over 2}] − y, 1 − z) and (−1 + x, y, z), respectively.
[Figure 12]
Figure 12
Part of the crystal structure of (IV)[link], showing the formation of a chain of edge-fused R33(10) rings along [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($), an ampersand (&) or an `at' sign (@) are at the symmetry positions (1 − x, −[{1\over 2}] + y, [{1\over 2}] − z), (1 − x, −[{1\over 2}] + y, [{1\over 2}] − z), (x, −1 + y, z), (x, 1 + y, z) and (1 − x, −[{3\over 2}] + y, [{1\over 2}] − z), respectively.
[Figure 13]
Figure 13
Part of the crystal structure of (IV)[link], showing the formation of a C22(10) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (−[{1\over 2}] + x, [{1\over 2}] − y, 1 − z), (1 − x, [{1\over 2}] + y, [{1\over 2}] − z), ([{1\over 2}] − x, 1 − y, −[{1\over 2}] + z) and ([{1\over 2}] − x, 1 − y, [{1\over 2}] + z), respectively.
[Figure 14]
Figure 14
A stereoview of part of the crystal structure of (V), showing the formation of a sheet parallel to (100). The original atom coordinates (Saraogi et al., 2002[Saraogi, I., Mruthyunjayaswamy, B. H. M., Ijare, O. B., Jadegoud, Y. & Guru Row, T. N. (2002). Acta Cryst. E58, o1341-o1342.]) have been used. For the sake of clarity, H atoms bonded to C atoms have been omitted.

Experimental

A commercial sample (Aldrich) of compound (IV)[link] was recrystallized from ethanol. For the synthesis of compounds (I)–(III), a solution of the appropriate methyl ester [methyl 2,6-dichloro­benzoate for (I)[link], methyl 2,4-dichloro­benzoate for (II)[link] and methyl 2-chloro-4-fluoro­benzoate for (III)] and a fivefold molar excess of hydrazine hydrate in methanol was held at 353 K for 6–8 h. The mixtures were concentrated to dryness under reduced pressure, and the resulting solid products (I)–(III) were purified by washing successively with cold ethanol and diethyl ether, providing crystalline material suitable for single-crystal X-ray diffraction. (I)[link]: yield 71%, m.p. 415–417 K; NMR (DMSO-d6): δ(H) 9.74 (1H, s, NH), 7.50 (2H, d, J = 8.0 Hz, H3 and H5), 7.44 (1H, t, J = 8.0 Hz, H4), 4.63 (2H, s, NH2); δ(C) 162.8, 135.4, 131.7, 131.2, 128.1; IR (KBr disk, cm−1): 3312–3271 (NH2), 3209 (NH), 1644 (CO). (II)[link]: yield 66%, m.p. 413–414 K; NMR (DMSO-d6): δ(H) 9.63 (1H, s, NH), 7.69 (1H, d, J = 1.0 Hz, H3), 7.49 (1H, dd, J = 1.0 and 8.0 Hz, H5), 7.42 (1H, d, J = 8.0 Hz, H6), 4.55 (2H, s, NH2); δ(C) 164.7, 134.5, 134.4, 131.5, 130.4, 129.1, 127.2; IR (KBr disk, cm−1): 3310–3273 (NH2), 3211 (NH), 1646 (CO). (III)[link]: yield 70%, m.p. 446–447 K: NMR (DMSO-d6): δ(H) 9.58 (1H, s, NH), 7.94 (1H, d, J = 7.9 Hz, H6), 7.65 (1H, d, J = 1.0 Hz, H3), 6.92 (1H, dd, J = 1.0 and 7.9 Hz, H5), 7.21 (2H, s, NH2), 4.25 (2H, s, NH2); δ(C) 164.5, 142.3, 132.1, 127.3, 126.7, 117.1, 111.2; IR (KBr disk, cm−1): 3313–3274 (NH2), 3213 (NH), 1649 (CO).

Compound (I)[link]

Crystal data
  • C7H6Cl2N2O

  • Mr = 205.04

  • Monoclinic, P 21 /n

  • a = 7.5511 (2) Å

  • b = 14.4834 (4) Å

  • c = 8.3097 (3) Å

  • β = 110.485 (2)°

  • V = 851.33 (5) Å3

  • Z = 4

  • Dx = 1.600 Mg m−3

  • Mo Kα radiation

  • μ = 0.71 mm−1

  • T = 120 (2) K

  • Lath, colourless

  • 0.54 × 0.36 × 0.08 mm

Data collection
  • Bruker–Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.700, Tmax = 0.945

  • 10109 measured reflections

  • 1952 independent reflections

  • 1661 reflections with I > 2σ(I)

  • Rint = 0.030

  • θmax = 27.5°

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.072

  • S = 1.05

  • 1950 reflections

  • 109 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.035P)2 + 0.3426P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.35 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 0.85 1.98 2.8246 (15) 172
Symmetry code: (i) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}].

Compound (II)[link]

Crystal data
  • C7H6Cl2N2O

  • Mr = 205.04

  • Monoclinic, P 21 /c

  • a = 15.1188 (17) Å

  • b = 3.8801 (4) Å

  • c = 13.6029 (14) Å

  • β = 91.106 (6)°

  • V = 797.83 (15) Å3

  • Z = 4

  • Dx = 1.707 Mg m−3

  • Mo Kα radiation

  • μ = 0.76 mm−1

  • T = 120 (2) K

  • Plate, colourless

  • 0.32 × 0.30 × 0.03 mm

Data collection
  • Bruker–Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.794, Tmax = 0.978

  • 8399 measured reflections

  • 1813 independent reflections

  • 1327 reflections with I > 2σ(I)

  • Rint = 0.065

  • θmax = 27.7°

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.101

  • S = 1.03

  • 1813 reflections

  • 109 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0401P)2 + 0.717P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.44 e Å−3

  • Δρmin = −0.36 e Å−3

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯Cl2 0.85 2.65 3.103 (2) 115
N1—H1⋯N2i 0.85 2.22 2.971 (3) 147
N2—H2A⋯O1ii 0.86 2.50 3.115 (3) 129
N2—H2B⋯O1iii 0.83 2.16 2.972 (3) 165
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) -x+1, [y-{\script{1\over 2}}], [-z+{\script{3\over 2}}].

Compound (III)[link]

Crystal data
  • C7H8ClN3O·H2O

  • Mr = 203.63

  • Monoclinic, P 21 /c

  • a = 11.1667 (4) Å

  • b = 6.9936 (3) Å

  • c = 12.7105 (4) Å

  • β = 112.02 (6)°

  • V = 920.2 (4) Å3

  • Z = 4

  • Dx = 1.470 Mg m−3

  • Mo Kα radiation

  • μ = 0.39 mm−1

  • T = 120 (2) K

  • Lath, yellow

  • 0.36 × 0.18 × 0.06 mm

Data collection
  • Bruker–Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.874, Tmax = 0.977

  • 10045 measured reflections

  • 2113 independent reflections

  • 1700 reflections with I > 2σ(I)

  • Rint = 0.039

  • θmax = 27.5°

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.091

  • S = 1.06

  • 2113 reflections

  • 121 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0431P)2 + 0.3314P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.29 e Å−3

Table 3
Hydrogen-bond geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1W—H1W⋯O1 0.84 1.99 2.822 (2) 169
O1W—H2W⋯N2i 0.87 2.01 2.871 (2) 170
N1—H1⋯N4ii 0.83 2.15 2.978 (2) 173
N2—H2B⋯O1Wiii 0.83 2.30 3.063 (2) 153
N4—H4A⋯O1Wiv 0.88 2.07 2.924 (2) 166
N4—H4B⋯O1v 0.96 2.09 3.015 (2) 161
Symmetry codes: (i) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]; (ii) -x+1, -y+1, -z+1; (iii) -x+2, [y+{\script{1\over 2}}], [-z+{\script{3\over 2}}]; (iv) [x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (v) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Compound (IV)[link]

Crystal data
  • C7H7N3O3

  • Mr = 181.16

  • Orthorhombic, P 21 21 21

  • a = 12.5382 (10) Å

  • b = 4.9867 (2) Å

  • c = 12.8637 (8) Å

  • V = 804.29 (9) Å3

  • Z = 4

  • Dx = 1.496 Mg m−3

  • Mo Kα radiation

  • μ = 0.12 mm−1

  • T = 120 (2) K

  • Lath, brown

  • 0.63 × 0.13 × 0.08 mm

Data collection
  • Bruker–Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.]) Tmin = 0.944, Tmax = 0.991

  • 11674 measured reflections

  • 1092 independent reflections

  • 713 reflections with I > 2σ(I)

  • Rint = 0.146

  • θmax = 27.5°

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.088

  • wR(F2) = 0.097

  • S = 1.03

  • 1092 reflections

  • 119 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0501P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.19 e Å−3

  • Extinction correction: SHELXL97

  • Extinction coefficient: 0.040 (7)

Table 4
Hydrogen-bond geometry (Å, °) for (IV)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 0.95 1.92 2.815 (3) 157
N2—H2A⋯O22ii 0.95 2.31 3.128 (3) 144
N2—H2B⋯N2iii 0.95 2.16 3.060 (3) 157
C3—H3⋯O1iv 0.95 2.43 3.269 (4) 148
Symmetry codes: (i) x, y+1, z; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]; (iii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1].

Table 5
Selected bond angles and torsion angles (°) for compounds (I)–(IV)

  (I) (II) (III) (IV)
C2—C1—C7 121.07 (12) 127.3 (2) 121.84 (14) 120.2 (3)
C6—C1—C7 121.83 (12) 115.3 (2) 120.93 (14) 122.4 (3)
C1—C2—Cl2/N21 119.59 (10) 122.0 (2) 119.62 (12) 119.5 (3)
C3—C2—Cl2/N21 118.34 (11) 116.4 (2) 118.07 (12) 117.1 (3)
C1—C6—Cl6 119.19 (11)
C5—C6—Cl6 118.63 (11)
         
C2—C1—C7—O1 −77.51 (19) 140.4 (3) −63.0 (2) −41.0 (4)
C2—C1—C7—N1 103.00 (15) −42.0 (4) 117.46 (16) 141.1 (3)
C1—C7—N1—N2 176.00 (12) 179.3 (2) 176.31 (14) 178.4 (2)

For compounds (I)–(IV), the space groups P21/n, P21/c, P21c and P212121, respectively, were uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were assigned C—H distances of 0.95 Å [Uiso(H) = 1.2Ueq(C)]. H atoms bonded to N or O atoms were permitted to ride at the X—H distances deduced from the difference maps, giving N—H distances of 0.83−0.96 Å [Uiso(H) = 1.2Ueq(N)] and O—H distances of 0.84–0.87 Å [Uiso(H) = 1.5Ueq(O)]. The crystals of compound (IV)[link] were consistently of poor quality, and this is reflected in the high merging index and the high final R values. In the absence of significant resonant scattering it was not possible to determine the absolute configuration of the mol­ecules in the crystal of (IV)[link] selected for data collection; accordingly, the Friedel equivalent reflections were merged prior to the final refinements.

Data collection: KappaCCD Server Software (Nonius, 1997[Nonius (1997). KappaCCD Server Software. Windows 3.11 Version. Nonius BV, Delft, The Netherlands.]) for (I); COLLECT (Hooft, 1999[Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.]) for (II), (III) and (IV). Cell refinement: DENZOSMN (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) for (I); DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT for (II), (III) and (IV). Data reduction: DENZOSMN for (I); DENZO and COLLECT for (II), (III) and (IV). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]) for (I); OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]) for (II), (III) and (IV). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]) for (I); OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]) for (II), (III) and (IV). For all compounds, molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

As part of our general study of the supramolecular structures of amine and hydrazine derivatives, we report here the molecular and supramolecular structures of four related benzohydrazides, namely the isomeric 2,6-dichlorobenzohydrazide, (I), and 2,4-dichlorobenzohydrazide, (II), 4-amino-2-chlorobenzohydrazide, which crystallizes as a monohydrate, (III), and 2-nitrobenzohydrazide, (IV). Compounds (I) and (II) were prepared straightforwardly by reaction of hydrazine with the methyl esters ArCOOCH3 to yield the corresponding hydrazines ArCONHNH2. By contrast, compound (III) was obtained, on one occasion only, from the reaction of hydrazine with methyl 2-chloro-4-fluorobenzoate; this reaction involves a nucleophilic displacement of the 4-fluoro substituent, and despite a number of attempts to reproduce this synthesis, we have been consistently unsuccessful.

The coordination at atoms C7 and N1 is effectively planar in each of compounds (I)–(IV) (Figs. 1–4), but the C1/C7/O1/N1/N2 planes make dihedral angles with the aryl rings of 78.0 (2)° in (I), 38.5 (2)° in (II), 63.9 (2)° in (III) and 42.9 (2) in (IV). However, the orientations of the side chains differ markedly between compounds (II) and (III), with atom N1 syn to Cl2 in (II) but anti in (III) (Figs. 2 and 3).

The exocyclic bond angles in compound (II) show some significant variations, including significant deviations from the idealized values of 120° (Table 5). Thus, although the two independent exocyclic angles at atom C4 are identical within experimental uncertainty, those at atom C2 differ by more than 5°, while those at C1 differ by some 12°. The sense of these deviations suggests strongly repulsive interactions between Cl2 and C7 and/or N1 and possibly associated with the rather short intramolecular H1···Cl2 contact in (II) (Table 2). By contrast, the corresponding angles in compounds (I) and (III), where there are no short intramolecular contacts involving atom Cl2 (or Cl6), show no such features, while any such effect in compound (IV) is very modest in magnitude.

In each compound the coordination of the hydrazine atoms N2 is sharply pyramidal (Figs. 1–4), with sums of angles at N2 consistently less than 330°. In addition, the amino atom N4 in compound (III) is pyramidal, and the C4—N4 distance, 1.395 (2) Å, is identical with the mean values for C(aryl)—NH2 bonds with pyramidal N atoms and much longer than the corresponding mean value, 1.355 Å, for such bonds with planar N atoms (Allen et al., 1987).

In compound (I), the molecules are linked into simple chains by a single N—H···O hydrogen bond (Table 1). Atom N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom O1 in the molecule at (1/2 + x, 3/2 − y, 1/2 + z), so forming a C(4) (Bernstein et al., 1995) chain running parallel to the [101] direction, and generated by the n-glide plane at y = 3/4 (Fig. 5). Two such chains, related to one another by inversion and hence antiparallel, pass through each unit cell, but there are no direction-specific interactions between adjacent chains. It is notable that the NH2 group in compound (I) plays no part in the supramolecular aggregation; there are no potential donor or acceptor atoms of any type within hydrogen-bonding range.

The molecules of (II) are linked by a combination of one N—H···N hydrogen bond and two N—H···O hydrogen bonds (Table 2) into sheets whose formation is readily analysed in terms of two simple substructures. In the first of these substructures, paired N—H···N hydrogen bonds link the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z) into centrosymmetric R22(6) (Bernstein et al., 1995) dimers (Fig. 6). The second substructure is formed by the two N—H···O hydrogen bonds; atom N2 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H2A and H2B, respectively, to atoms O1 in the molecules at (1 − x, 1/2 + y, 3/2 − z) and (1 − x, −1/2 + y, 3/2 − z), respectively, so forming a chain of edge-fused R22(10) rings running parallel to the [010] direction and generated by the 21 screw axis along (1/2, y, 3/4) (Fig. 7). The combination of the finite, zero-dimensional sub-structure (Fig. 2) and the one-dimensional sub-structure (Fig. 3) then leads to the formation of thick tripartite sheets, parallel to (100), in which a central polar layer is sandwiched between two non-polar layers with Cl atoms on the exterior faces (Fig. 8).

The molecules of (III) are linked into a three-dimensional framework structure by a combination of O—H···O, O—H···N, N—H···N and N—H···O hydrogen bonds (Table 3). The organic components are linked into sheets by one N—H···N and one N—H···O interactions, and these sheets are linked into a continuous framework by means of the water molecules. Paired N—H···N hydrogen bonds link the organic molecules into centrosymmetric R22(16) dimers (Fig. 9), and the reference dimer centred at (1/2, 1/2, 1/2) is linked by N—H···O hydrogen bonds to four similar dimers centred at (1/2, 0, 0), (1/2, 0, 1), (1/2, 1, 0) and (1/2, 1, 1), therefore generating a (100) sheet built from R22(16) and R66(28) rings alternating in chessboard fashion (Fig. 9).

The simplest description of the linking of the (100) sheets is in terms of one each of O—H···O and N—H···O hydrogen bonds. The O—H···O hydrogen bond lies within the selected asymmetric unit (Fig. 2); in addition, atom N4 at (x, y, z) acts as a donor to the water atom O1W at (−1 + x, 3/2 − y, −1/2 + z), so forming a C22(10) chain running parallel to he [201] direction and generated by the c-glide plane at y = 0.75 (Fig. 10).

In (IV), the molecules are linked by a combination of N—H···O and N—H···N hydrogen bonds (Table 5) into a three-dimensional framework whose formation is readily analysed in terms of three one-dimensional substructures.

In the simplest of these substructures, which depends on the action of just one hydrogen bond, atom N2 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H2A, to nitro atom O22 in the molecule at (−1/2 + x, 1/2 − y, 1 − z), so forming a simple C(8) chain running parallel to the [100] direction and generated by the 21 screw axis along (x, 1/4, 1/2) (Fig. 11). A second substructure is formed by the concerted action of the other two hydrogen bonds. Atom N2 in the molecule at (x, y, z) acts as a hydrogen-bond donor to atom N2 in the molecule at (1 − x, −1/2 + y, 1/2 − z), so forming a C(2) chain running parallel to the [010] direction and generated by the 21 screw axis along (1/2, y, 1/4). At the same time atom N1 in the molecule at (x, y, z) acts as a donor to carbonyl atom O1 in the molecule at (x, 1 + y, z), so generating by translation a C(4) chain along [010], and the combination of the two [010] chains generates a chain of edge-fused R33(10) rings (Fig. 12). Finally, the combination of the two hydrogen bonds formed by the NH2 group generates a C22(10) chain running parallel to the [001] direction (Fig. 13). The combination of [100], [010] and [001] chains then generates a single three-dimensional framework.

It is of interest briefly to compare the supramolecular structures of the compounds reported here with those of some closely related analogues from the literature. A very brief report on the 4-chloro analogue (V) stated that the structure is held together by two hydrogen bonds, one each of N—H···N and N—H···O types (Saraogi et al., 2002). While no discussion of the aggregation was given, the packing diagram provided appears to show a chain of edge-fused rings along [100]. However, re-examination of the structure using the published atomic coordinates shows that there are, in fact, three intermolecular hydrogen bonds present, one of N—H···N type and two of N—H···O type, and these link the molecules into complex sheets parallel to (100) in which all the Cl substituents lie on the two faces of the sheet (Fig. 14), so that there are no direction-specific interactions between these sheets. Even the two hydrogen bonds listed in the original report (Saraogi et al., 2002) suffice to generate this type of (100) sheet. For the unsubstituted compound (VI), there is again only a very brief report with no discussion of the supramolecular aggregation (Kallel et al., 1992). Again, re-examination of the structure using coordinates as retrieved from the Cambridge Structural Database (Allen, 2002; refcode VOPJEP) shows that this compound forms exactly the same type of (100) sheet as the 4-chloro analogue (V), and that it is, indeed. isomorphous and effectively isostructural with compound (V), although this fact was not noted in the report on (V) (Saraogi et al., 2002). In compound (VII), which is isomeric with (IV), the molecules are linked into a three-dimensional framework of some complexity, built from a combination of N—H···O, N—H···N, C—H···O and C—H···N hydrogen bonds (Ratajczak et al., 2001).

The supramolecular structures discussed here show the marked effects on the aggregation of the identity of the substituents on the aryl ring and, in the case of the two pairs of isomers (I) and (II), and (IV) and (VII), the strong influence of the orientation of the substituents, even when, as in (I) and (II), they play no direct role in the aggregation.

Experimental top

A commercial sample (Aldrich) of compound (IV) was recrystallized from ethanol. For the synthesis of compounds (I)–(III) a solution of the appropriate methyl ester [methyl 2,6-dichlorobenzoate for (I), methyl 2,4-dichlorobenzoate for (II) and methyl 2-chloro-4-fluorobenzoate for (III)] and a fivefold molar excess of hydrazine hydrate in methanol was held at 353 K for 6–8 h. The mixtures were concentrated to dryness under reduced pressure, and the resulting solid products (I)–(III) were purified by washing successively with cold ethanol and with diethyl ether, providing crystalline material suitable for single-crystal X-ray diffraction. (I): yield 71%, m.p. 415–417 K; NMR (DMSO-d6): δ(H) 9.74 (1H, s, NH), 7.50 (2H, d, J = 8.0 Hz, H3 and H5), 7.44 (1H, t, J = 8.0 Hz, H4), 4.63 (2H, s, NH2); δ(C) 162.8, 135.4, 131.7, 131.2, 128.1; IR (KBr disk, cm−1): 3312–3271 (NH2), 3209 (NH), 1644 (CO). (II): yield 66%, m.p. 413–414 K; NMR (DMSO-d6): δ(H) 9.63 (1H, s, NH), 7.69 (1H, d, J = 1.0 Hz, H3), 7.49 (1H, dd, J = 1.0 and 8.0 Hz, H5), 7.42 (1H, d, J = 8.0 Hz, H6), 4.55 (2H, s, NH2); δ(C) 164.7, 134.5, 134.4, 131.5, 130.4, 129.1, 127.2; IR (KBr disk, cm−1): 3310–3273 (NH2), 3211 (NH), 1646 (CO). (III): yield 70%, m.p. 446–447 K: NMR (DMSO-d6): δ(H) 9.58 (1H, s, NH), 7.94 (1H, d, J = 7.9 Hz, H6), 7.65 (1H, d, J = 1.0 Hz, H3), 6.92 (1H, dd, J = 1.0 and 7.9 Hz, H5), 7.21 (2H, s, NH2), 4.25 (2H, s, NH2); δ(C) 164.5, 142.3, 132.1, 127.3, 126.7, 117.1, 111.2; IR (KBr disk, cm−1): 3313–3274 (NH2), 3213 (NH), 1649 (CO).

Refinement top

For compounds (I)–(IV) the space groups P21/n, P21/c, P21c and P212121, respectively, were uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were assigned C—H distances of 0.95 Å [Uiso(H) = 1.2Ueq(C)]. H atoms bonded to N or O atoms were permitted to ride at the X—H distances deduced from the difference maps, giving N—H distances of 0.83 − 0.96 Å [Uiso(H) = 1.2Ueq(N)] and O—H distances of 0.84–0.87 Å [Uiso(H) = 1.5Ueq(O)]. The crystals of compound (IV) were consistently of poor quality, and this is reflected in the high merging index and the high final R values. In the absence of significant resonant scattering it was not possible to determine the absolute configuration of the molecules in the crystal of (IV) selected for data collection; accordingly the Friedel equivalent reflections were merged prior to the final refinements.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997) for (I); COLLECT (Hooft, 1999) for (II), (III), (IV). Cell refinement: DENZO–SMN (Otwinowski & Minor, 1997) for (I); DENZO (Otwinowski & Minor, 1997) and COLLECT for (II), (III), (IV). Data reduction: DENZO–SMN for (I); DENZO and COLLECT for (II), (III), (IV). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (I); OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997) for (II), (III), (IV). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (I); OSCAIL and SHELXL97 (Sheldrick, 1997) for (II), (III); OSCAIL & SHELXL97 (Sheldrick, 1997) for (IV). For all compounds, molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. A molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. The independent molecular components in (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4] Fig. 4. A molecule of (IV), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 5] Fig. 5. Part of the crystal structure of (I), showing the formation of a C(4) chain along [101]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 + x, 3/2 − y, 1/2 + z) and (−1/2 + x, 3/2 − y, −1/2 + z), respectively.
[Figure 6] Fig. 6. Part of the crystal structure of (II), showing the formation of a centrosymmetric R22(6) dimer. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 7] Fig. 7. Part of the crystal structure of (II), showing the formation of a [010] chain of edge-fused R22(10) rings. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (1 − x, 1/2 + y, 3/2 − z), (1 − x, −1/2 + y, 3/2 − z), (x, 1 + y, z) and (x, −1 + y, z), respectively.
[Figure 8] Fig. 8. A stereoview of part of the crystal structure of (II), showing the formation of a (100) sheet. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 9] Fig. 9. A stereoview of part of the crystal structure of (III), showing the formation of a (100) sheet built from organic molecules only. For the sake of clarity, H atoms bonded to C or N atoms not involved in the motif shown have been omitted.
[Figure 10] Fig. 10. Part of the crystal structure of (III), showing the formation of a C22(10) chain along [201]. For the sake of clarity, H atoms bonded to C or N atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−1 + x, 3/2 − y, −1/2 + z) and (1 + x, 3/2 − y, 1/2 + z), respectively.
[Figure 11] Fig. 11. Part of the crystal structure of (IV), showing the formation of a C(8) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#) or an ampersand (&) are at the symmetry positions (−1/2 + x, 1/2 − y, 1 − z), (1/2 + x, 1/2 − y, 1 − z) and (−1 + x, y, z), respectively.
[Figure 12] Fig. 12. Part of the crystal structure of (IV), showing the formation of a chain of edge-fused R33(10) rings along [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*), a hash (#), a dollar sign ($), an ampersand (&) or an `at' sign (@) are at the symmetry positions (1 − x, −1/2 + y, 1/2 − z), (1 − x, −1/2 + y, 1/2 − z), (x, −1 + y, z), (x, 1 + y, z) and (1 − x, −3/2 + y, 1/2 − z), respectively.
[Figure 13] Fig. 13. Part of the crystal structure of (IV), showing the formation of a C22(10) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (−1/2 + x, 1/2 − y, 1 − z), (1 − x, 1/2 + y, 1/2 − z), (1/2 − x, 1 − y, −1/2 + z) and (1/2 − x, 1 − y, 1/2 + z), respectively.
[Figure 14] Fig. 14. A stereoview of part of the crystal structure of (V), showing the formation of a sheet parallel to (100). The original atom coordinates (Saraogi et al., 2002) have been used. For the sake of clarity, H atoms bonded to C atoms have been omitted.
(I) 2,6-Dichlorobenzohydrazide top
Crystal data top
C7H6Cl2N2OF(000) = 416
Mr = 205.04Dx = 1.600 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1952 reflections
a = 7.5511 (2) Åθ = 2.8–27.5°
b = 14.4834 (4) ŵ = 0.71 mm1
c = 8.3097 (3) ÅT = 120 K
β = 110.485 (2)°Lath, colourless
V = 851.33 (5) Å30.54 × 0.36 × 0.08 mm
Z = 4
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1952 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1661 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.8°
ϕ and ω scansh = 99
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1818
Tmin = 0.700, Tmax = 0.945l = 910
10109 measured reflections
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) = 0.072H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.035P)2 + 0.3426P]
where P = (Fo2 + 2Fc2)/3
1950 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C7H6Cl2N2OV = 851.33 (5) Å3
Mr = 205.04Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.5511 (2) ŵ = 0.71 mm1
b = 14.4834 (4) ÅT = 120 K
c = 8.3097 (3) Å0.54 × 0.36 × 0.08 mm
β = 110.485 (2)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1952 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1661 reflections with I > 2σ(I)
Tmin = 0.700, Tmax = 0.945Rint = 0.030
10109 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.05Δρmax = 0.35 e Å3
1950 reflectionsΔρmin = 0.26 e Å3
109 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.60402 (18)0.65107 (9)0.61322 (17)0.0160 (3)
C70.42897 (19)0.71038 (9)0.56421 (18)0.0167 (3)
O10.28941 (14)0.69243 (8)0.43709 (14)0.0275 (3)
N10.44028 (16)0.78201 (8)0.66721 (16)0.0189 (3)
N20.29431 (17)0.84842 (9)0.63530 (17)0.0241 (3)
C20.61167 (19)0.56620 (10)0.69497 (18)0.0179 (3)
Cl20.42081 (5)0.53062 (3)0.75093 (5)0.02577 (12)
C30.7688 (2)0.50903 (10)0.7359 (2)0.0213 (3)
C40.9214 (2)0.53618 (10)0.6905 (2)0.0234 (3)
C50.9195 (2)0.62007 (11)0.6095 (2)0.0224 (3)
C60.7624 (2)0.67666 (10)0.57392 (18)0.0186 (3)
Cl60.76312 (5)0.78292 (3)0.47570 (5)0.02700 (12)
H10.53870.78970.75530.023*
H2A0.25210.86270.52230.029*
H2B0.19510.82530.66050.029*
H30.77190.45220.79410.026*
H41.02820.49680.71520.028*
H51.02430.63850.57900.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0133 (6)0.0178 (7)0.0143 (7)0.0001 (5)0.0016 (5)0.0032 (5)
C70.0144 (6)0.0167 (6)0.0171 (7)0.0006 (5)0.0032 (5)0.0011 (5)
O10.0195 (5)0.0265 (6)0.0258 (6)0.0028 (4)0.0055 (4)0.0058 (5)
N10.0121 (5)0.0214 (6)0.0192 (6)0.0031 (4)0.0005 (5)0.0033 (5)
N20.0177 (6)0.0238 (6)0.0278 (7)0.0067 (5)0.0042 (5)0.0005 (5)
C20.0153 (6)0.0191 (7)0.0181 (7)0.0021 (5)0.0043 (5)0.0030 (6)
Cl20.02059 (18)0.0259 (2)0.0328 (2)0.00308 (13)0.01184 (15)0.00339 (15)
C30.0224 (7)0.0163 (7)0.0223 (8)0.0012 (5)0.0041 (6)0.0009 (6)
C40.0176 (7)0.0208 (7)0.0295 (8)0.0043 (5)0.0053 (6)0.0031 (6)
C50.0158 (7)0.0251 (8)0.0264 (8)0.0011 (5)0.0076 (6)0.0046 (6)
C60.0189 (6)0.0181 (7)0.0176 (7)0.0002 (5)0.0050 (5)0.0007 (6)
Cl60.0301 (2)0.0225 (2)0.0335 (2)0.00196 (14)0.01752 (17)0.00690 (15)
Geometric parameters (Å, º) top
C1—C61.3952 (19)C2—C31.388 (2)
C1—C21.396 (2)C2—Cl21.7401 (14)
C1—C71.5080 (18)C3—C41.389 (2)
C7—O11.2309 (17)C3—H30.95
C7—N11.3284 (19)C4—C51.387 (2)
N1—N21.4163 (16)C4—H40.95
N1—H10.85C5—C61.386 (2)
N2—H2A0.90C5—H50.95
N2—H2B0.90C6—Cl61.7429 (15)
C6—C1—C2117.06 (12)C1—C2—Cl2119.59 (10)
C6—C1—C7121.83 (12)C2—C3—C4118.93 (14)
C2—C1—C7121.07 (12)C2—C3—H3120.5
O1—C7—N1124.10 (13)C4—C3—H3120.5
O1—C7—C1121.18 (13)C5—C4—C3120.76 (13)
N1—C7—C1114.72 (12)C5—C4—H4119.6
C7—N1—N2122.64 (12)C3—C4—H4119.6
C7—N1—H1119.8C6—C5—C4118.97 (13)
N2—N1—H1117.5C6—C5—H5120.5
N1—N2—H2A108.6C4—C5—H5120.5
N1—N2—H2B110.9C5—C6—C1122.18 (13)
H2A—N2—H2B107.7C5—C6—Cl6118.63 (11)
C3—C2—C1122.07 (13)C1—C6—Cl6119.19 (11)
C3—C2—Cl2118.34 (11)
C6—C1—C7—O1100.19 (17)C1—C2—C3—C41.5 (2)
C2—C1—C7—O177.51 (19)Cl2—C2—C3—C4179.38 (11)
C6—C1—C7—N179.22 (17)C2—C3—C4—C51.7 (2)
C2—C1—C7—N1103.07 (15)C3—C4—C5—C60.2 (2)
O1—C7—N1—N23.4 (2)C4—C5—C6—C11.5 (2)
C1—C7—N1—N2176.00 (12)C4—C5—C6—Cl6178.84 (12)
C6—C1—C2—C30.1 (2)C2—C1—C6—C51.6 (2)
C7—C1—C2—C3177.72 (13)C7—C1—C6—C5176.16 (13)
C6—C1—C2—Cl2178.99 (10)C2—C1—C6—Cl6178.72 (11)
C7—C1—C2—Cl23.20 (19)C7—C1—C6—Cl63.48 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.851.982.8246 (15)172
Symmetry code: (i) x+1/2, y+3/2, z+1/2.
(II) 2,4-Dichlorobenzohydrazide top
Crystal data top
C7H6Cl2N2OF(000) = 416
Mr = 205.04Dx = 1.707 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1950 reflections
a = 15.1188 (17) Åθ = 2.9–27.5°
b = 3.8801 (4) ŵ = 0.76 mm1
c = 13.6029 (14) ÅT = 120 K
β = 91.106 (6)°Plate, colourless
V = 797.83 (15) Å30.32 × 0.30 × 0.03 mm
Z = 4
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1813 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1327 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
Detector resolution: 9.091 pixels mm-1θmax = 27.7°, θmin = 3.0°
ϕ and ω scansh = 1719
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 45
Tmin = 0.794, Tmax = 0.978l = 1617
8399 measured reflections
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0401P)2 + 0.717P]
where P = (Fo2 + 2Fc2)/3
1813 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
C7H6Cl2N2OV = 797.83 (15) Å3
Mr = 205.04Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.1188 (17) ŵ = 0.76 mm1
b = 3.8801 (4) ÅT = 120 K
c = 13.6029 (14) Å0.32 × 0.30 × 0.03 mm
β = 91.106 (6)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1813 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1327 reflections with I > 2σ(I)
Tmin = 0.794, Tmax = 0.978Rint = 0.065
8399 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.101H-atom parameters constrained
S = 1.03Δρmax = 0.44 e Å3
1813 reflectionsΔρmin = 0.36 e Å3
109 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.28265 (17)0.4675 (7)0.64675 (18)0.0171 (6)
C20.23079 (17)0.5077 (7)0.56096 (18)0.0174 (6)
Cl20.27176 (5)0.70300 (18)0.45593 (5)0.0232 (2)
C30.14354 (18)0.4002 (7)0.55600 (18)0.0194 (6)
C40.10744 (17)0.2413 (7)0.63718 (19)0.0187 (6)
Cl40.00183 (4)0.10534 (18)0.63134 (5)0.0245 (2)
C50.15681 (18)0.1920 (7)0.72318 (19)0.0204 (6)
C60.24298 (18)0.3089 (7)0.72698 (18)0.0183 (6)
C70.37502 (17)0.5969 (7)0.66526 (18)0.0177 (6)
O10.39536 (12)0.7165 (5)0.74710 (13)0.0232 (5)
N10.43400 (14)0.5681 (6)0.59380 (16)0.0212 (5)
N20.52219 (14)0.6877 (6)0.60524 (15)0.0206 (5)
H30.10890.43490.49780.023*
H50.13180.08030.77820.024*
H60.27660.28050.78620.022*
H10.42320.48900.53670.025*
H2A0.52290.90390.61880.025*
H2B0.54430.58630.65350.025*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0206 (14)0.0147 (13)0.0161 (13)0.0018 (11)0.0013 (10)0.0049 (10)
C20.0214 (15)0.0157 (13)0.0152 (13)0.0022 (11)0.0024 (10)0.0019 (11)
Cl20.0249 (4)0.0273 (4)0.0175 (3)0.0003 (3)0.0012 (3)0.0038 (3)
C30.0214 (15)0.0198 (14)0.0169 (13)0.0029 (12)0.0023 (11)0.0015 (11)
C40.0144 (14)0.0189 (14)0.0230 (14)0.0008 (11)0.0031 (10)0.0044 (11)
Cl40.0197 (4)0.0269 (4)0.0268 (4)0.0024 (3)0.0012 (3)0.0016 (3)
C50.0222 (15)0.0188 (14)0.0203 (14)0.0030 (12)0.0051 (11)0.0003 (11)
C60.0237 (15)0.0166 (13)0.0145 (12)0.0033 (11)0.0006 (11)0.0002 (10)
C70.0196 (14)0.0166 (13)0.0168 (13)0.0040 (11)0.0005 (11)0.0031 (11)
O10.0214 (11)0.0290 (11)0.0189 (10)0.0012 (9)0.0020 (8)0.0045 (9)
N10.0165 (12)0.0296 (13)0.0177 (11)0.0030 (11)0.0008 (9)0.0041 (10)
N20.0153 (12)0.0252 (13)0.0211 (12)0.0026 (10)0.0013 (9)0.0020 (10)
Geometric parameters (Å, º) top
C1—C61.398 (3)C5—C61.379 (4)
C1—C21.402 (3)C5—H50.95
C1—C71.501 (4)C6—H60.95
C2—C31.384 (4)C7—O11.239 (3)
C2—Cl21.741 (3)C7—N11.336 (3)
C3—C41.386 (4)N1—N21.418 (3)
C3—H30.95N1—H10.85
C4—C51.389 (4)N2—H2A0.86
C4—Cl41.735 (3)N2—H2B0.83
C6—C1—C2117.2 (2)C4—C5—H5120.7
C6—C1—C7115.3 (2)C5—C6—C1122.3 (2)
C2—C1—C7127.3 (2)C5—C6—H6118.8
C3—C2—C1121.6 (2)C1—C6—H6118.8
C3—C2—Cl2116.4 (2)O1—C7—N1121.8 (2)
C1—C2—Cl2122.0 (2)O1—C7—C1119.3 (2)
C2—C3—C4119.0 (2)N1—C7—C1118.8 (2)
C2—C3—H3120.5C7—N1—N2122.2 (2)
C4—C3—H3120.5C7—N1—H1125.2
C3—C4—C5121.3 (2)N2—N1—H1112.6
C3—C4—Cl4119.2 (2)N1—N2—H2A110.5
C5—C4—Cl4119.5 (2)N1—N2—H2B107.1
C6—C5—C4118.6 (2)H2A—N2—H2B106.9
C6—C5—H5120.7
C6—C1—C2—C31.0 (4)C4—C5—C6—C11.5 (4)
C7—C1—C2—C3174.6 (2)C2—C1—C6—C50.6 (4)
C6—C1—C2—Cl2179.65 (19)C7—C1—C6—C5176.7 (2)
C7—C1—C2—Cl24.1 (4)C6—C1—C7—O135.3 (3)
C1—C2—C3—C41.6 (4)C2—C1—C7—O1140.4 (3)
Cl2—C2—C3—C4179.6 (2)C6—C1—C7—N1142.3 (2)
C2—C3—C4—C50.7 (4)C2—C1—C7—N142.0 (4)
C2—C3—C4—Cl4179.9 (2)O1—C7—N1—N23.2 (4)
C3—C4—C5—C60.8 (4)C1—C7—N1—N2179.3 (2)
Cl4—C4—C5—C6178.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl20.852.653.103 (2)115
N1—H1···N2i0.852.222.971 (3)147
N2—H2A···O1ii0.862.503.115 (3)129
N2—H2B···O1iii0.832.162.972 (3)165
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1/2, z+3/2; (iii) x+1, y1/2, z+3/2.
(III) 4-Amino-2-chlorobenzohydrazide monohydrate top
Crystal data top
C7H8ClN3O·H2OF(000) = 424
Mr = 203.63Dx = 1.470 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2203 reflections
a = 11.1667 (4) Åθ = 2.9–27.5°
b = 6.9936 (3) ŵ = 0.39 mm1
c = 12.7105 (4) ÅT = 120 K
β = 112.02 (6)°Lath, yellow
V = 920.2 (4) Å30.36 × 0.18 × 0.06 mm
Z = 4
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2113 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1700 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.3°
ϕ and ω scansh = 1414
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 99
Tmin = 0.874, Tmax = 0.977l = 1616
10045 measured reflections
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0431P)2 + 0.3314P]
where P = (Fo2 + 2Fc2)/3
2113 reflections(Δ/σ)max = 0.001
121 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C7H8ClN3O·H2OV = 920.2 (4) Å3
Mr = 203.63Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.1667 (4) ŵ = 0.39 mm1
b = 6.9936 (3) ÅT = 120 K
c = 12.7105 (4) Å0.36 × 0.18 × 0.06 mm
β = 112.02 (6)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer
2113 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1700 reflections with I > 2σ(I)
Tmin = 0.874, Tmax = 0.977Rint = 0.039
10045 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.06Δρmax = 0.25 e Å3
2113 reflectionsΔρmin = 0.29 e Å3
121 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.65533 (14)0.7254 (2)0.64723 (12)0.0160 (3)
C20.62344 (15)0.6112 (2)0.72297 (12)0.0161 (3)
Cl20.74464 (4)0.53465 (6)0.84824 (3)0.02303 (14)
C30.49832 (15)0.5517 (2)0.70121 (12)0.0161 (3)
C40.39897 (14)0.6070 (2)0.60043 (13)0.0159 (3)
N40.27255 (12)0.54521 (19)0.57603 (11)0.0183 (3)
C50.42930 (15)0.7172 (2)0.52236 (13)0.0175 (3)
C60.55546 (15)0.7739 (2)0.54538 (13)0.0177 (3)
C70.78903 (15)0.8011 (2)0.67535 (12)0.0169 (3)
O10.84095 (11)0.91309 (17)0.75535 (9)0.0224 (3)
N10.84701 (13)0.7400 (2)0.60755 (12)0.0214 (3)
N20.97075 (13)0.8042 (2)0.61668 (12)0.0258 (3)
O1W1.05034 (11)0.73568 (18)0.92768 (10)0.0284 (3)
H30.47990.47360.75450.021*
H4A0.21480.62790.53500.022*
H4B0.25610.50210.64130.022*
H50.36300.75360.45290.023*
H60.57450.84740.49070.023*
H10.80830.66660.55370.026*
H2A1.03130.74870.67990.031*
H2B0.97300.92150.62880.031*
H1W0.99590.79830.87500.043*
H2W1.01650.72070.97850.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0155 (8)0.0161 (8)0.0182 (7)0.0002 (6)0.0083 (6)0.0024 (6)
C20.0169 (8)0.0147 (7)0.0167 (7)0.0016 (6)0.0065 (6)0.0017 (6)
Cl20.0184 (2)0.0276 (2)0.0204 (2)0.00095 (16)0.00407 (16)0.00689 (16)
C30.0190 (8)0.0149 (7)0.0170 (7)0.0006 (6)0.0096 (6)0.0000 (6)
C40.0147 (8)0.0142 (7)0.0206 (7)0.0006 (6)0.0084 (6)0.0048 (6)
N40.0134 (7)0.0213 (7)0.0209 (6)0.0007 (5)0.0073 (5)0.0003 (6)
C50.0170 (8)0.0185 (8)0.0164 (7)0.0024 (6)0.0054 (6)0.0003 (6)
C60.0203 (8)0.0175 (8)0.0179 (7)0.0012 (6)0.0102 (6)0.0009 (6)
C70.0177 (8)0.0179 (8)0.0154 (7)0.0004 (6)0.0065 (6)0.0024 (6)
O10.0221 (6)0.0261 (6)0.0202 (6)0.0060 (5)0.0093 (5)0.0062 (5)
N10.0150 (7)0.0290 (8)0.0227 (7)0.0074 (6)0.0098 (6)0.0073 (6)
N20.0175 (7)0.0339 (9)0.0277 (8)0.0070 (6)0.0104 (6)0.0048 (7)
O1W0.0206 (6)0.0384 (7)0.0259 (6)0.0027 (5)0.0083 (5)0.0007 (5)
Geometric parameters (Å, º) top
C1—C21.396 (2)C5—C61.385 (2)
C1—C61.397 (2)C5—H50.95
C1—C71.495 (2)C6—H60.95
C2—C31.383 (2)C7—O11.2416 (19)
C2—Cl21.7428 (19)C7—N11.328 (2)
C3—C41.398 (2)N1—N21.4157 (19)
C3—H30.95N1—H10.83
C4—C51.395 (2)N2—H2A0.92
C4—N41.395 (2)N2—H2B0.83
N4—H4A0.88O1W—H1W0.84
N4—H4B0.96O1W—H2W0.87
C2—C1—C6117.16 (14)C6—C5—H5119.8
C2—C1—C7121.84 (14)C4—C5—H5119.8
C6—C1—C7120.93 (14)C5—C6—C1121.43 (15)
C3—C2—C1122.29 (15)C5—C6—H6119.3
C3—C2—Cl2118.07 (12)C1—C6—H6119.3
C1—C2—Cl2119.62 (12)O1—C7—N1122.88 (15)
C2—C3—C4119.66 (15)O1—C7—C1122.46 (14)
C2—C3—H3120.2N1—C7—C1114.66 (14)
C4—C3—H3120.2C7—N1—N2122.91 (14)
C5—C4—N4120.55 (14)C7—N1—H1120.1
C5—C4—C3118.93 (14)N2—N1—H1116.9
N4—C4—C3120.45 (14)N1—N2—H2A108.2
C4—N4—H4A112.7N1—N2—H2B106.7
C4—N4—H4B114.2H2A—N2—H2B107.0
H4A—N4—H4B112.5H1W—O1W—H2W105.6
C6—C5—C4120.46 (15)
C6—C1—C2—C31.8 (2)C4—C5—C6—C10.9 (2)
C7—C1—C2—C3175.34 (14)C2—C1—C6—C52.4 (2)
C6—C1—C2—Cl2176.60 (11)C7—C1—C6—C5174.82 (14)
C7—C1—C2—Cl26.2 (2)C2—C1—C7—O163.0 (2)
C1—C2—C3—C40.2 (2)C6—C1—C7—O1114.06 (17)
Cl2—C2—C3—C4178.68 (11)C2—C1—C7—N1117.46 (16)
C2—C3—C4—C51.8 (2)C6—C1—C7—N165.5 (2)
C2—C3—C4—N4178.74 (14)O1—C7—N1—N23.2 (2)
N4—C4—C5—C6178.19 (14)C1—C7—N1—N2176.31 (14)
C3—C4—C5—C61.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O10.841.992.822 (2)169
O1W—H2W···N2i0.872.012.871 (2)170
N1—H1···N4ii0.832.152.978 (2)173
N2—H2B···O1Wiii0.832.303.063 (2)153
N4—H4A···O1Wiv0.882.072.924 (2)166
N4—H4B···O1v0.962.093.015 (2)161
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x+1, y+1, z+1; (iii) x+2, y+1/2, z+3/2; (iv) x1, y+3/2, z1/2; (v) x+1, y1/2, z+3/2.
(IV) 2-Nitrobenzohydrazide top
Crystal data top
C7H7N3O3F(000) = 376
Mr = 181.16Dx = 1.496 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1092 reflections
a = 12.5382 (10) Åθ = 4.4–27.5°
b = 4.9867 (2) ŵ = 0.12 mm1
c = 12.8637 (8) ÅT = 120 K
V = 804.29 (9) Å3Lath, brown
Z = 40.63 × 0.13 × 0.08 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1092 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode713 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.146
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 4.4°
ϕ and ω scansh = 1616
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 66
Tmin = 0.944, Tmax = 0.991l = 1616
11674 measured reflections
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)] = 0.088H-atom parameters constrained
wR(F2) = 0.097 w = 1/[σ2(Fo2) + (0.0501P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1092 reflectionsΔρmax = 0.23 e Å3
119 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.040 (7)
Crystal data top
C7H7N3O3V = 804.29 (9) Å3
Mr = 181.16Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 12.5382 (10) ŵ = 0.12 mm1
b = 4.9867 (2) ÅT = 120 K
c = 12.8637 (8) Å0.63 × 0.13 × 0.08 mm
Data collection top
Bruker–Nonius KappaCCD
diffractometer
1092 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
713 reflections with I > 2σ(I)
Tmin = 0.944, Tmax = 0.991Rint = 0.146
11674 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0880 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.03Δρmax = 0.23 e Å3
1092 reflectionsΔρmin = 0.19 e Å3
119 parameters
Special details top

Experimental. ?.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8184 (2)0.5658 (5)0.3908 (2)0.0229 (7)
C70.7043 (2)0.5033 (5)0.3640 (2)0.0230 (7)
O10.67233 (16)0.2693 (4)0.36325 (18)0.0314 (6)
N10.64395 (18)0.7128 (5)0.33887 (19)0.0252 (6)
N20.5357 (2)0.6803 (5)0.3096 (2)0.0289 (7)
C20.8692 (2)0.4291 (5)0.4714 (2)0.0252 (7)
N210.8051 (2)0.2721 (5)0.5459 (2)0.0287 (6)
O210.72326 (19)0.3762 (4)0.57959 (19)0.0375 (6)
O220.83784 (17)0.0504 (4)0.57239 (19)0.0402 (7)
C30.9773 (2)0.4466 (6)0.4904 (2)0.0282 (7)
C41.0369 (3)0.6181 (6)0.4276 (3)0.0309 (8)
C50.9886 (2)0.7654 (6)0.3515 (2)0.0306 (7)
C60.8803 (3)0.7365 (6)0.3315 (2)0.0283 (7)
H10.67220.88960.33980.030*
H2A0.49290.64830.36920.035*
H2B0.53400.52240.26830.035*
H31.00990.34550.54430.034*
H41.11170.63260.43780.037*
H51.02950.88890.31180.037*
H60.84850.83510.27640.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0238 (17)0.0171 (13)0.0279 (16)0.0014 (14)0.0006 (14)0.0017 (13)
C70.0266 (17)0.0189 (14)0.0234 (16)0.0016 (13)0.0003 (14)0.0007 (13)
O10.0290 (12)0.0181 (10)0.0471 (13)0.0026 (9)0.0045 (10)0.0018 (10)
N10.0200 (13)0.0185 (11)0.0372 (16)0.0013 (11)0.0041 (12)0.0016 (11)
N20.0247 (15)0.0244 (12)0.0376 (15)0.0010 (12)0.0070 (12)0.0008 (11)
C20.0258 (18)0.0194 (14)0.0303 (17)0.0013 (14)0.0028 (15)0.0016 (13)
N210.0296 (15)0.0252 (14)0.0314 (15)0.0020 (13)0.0070 (12)0.0032 (13)
O210.0323 (14)0.0379 (13)0.0424 (13)0.0037 (11)0.0091 (11)0.0062 (12)
O220.0405 (15)0.0277 (12)0.0523 (15)0.0015 (11)0.0056 (12)0.0156 (12)
C30.0276 (19)0.0228 (15)0.0341 (18)0.0023 (14)0.0033 (15)0.0029 (14)
C40.0230 (17)0.0315 (16)0.0383 (19)0.0027 (14)0.0010 (17)0.0067 (16)
C50.0267 (17)0.0315 (17)0.0335 (16)0.0026 (15)0.0041 (15)0.0002 (16)
C60.0315 (17)0.0237 (15)0.0298 (17)0.0000 (15)0.0015 (14)0.0009 (14)
Geometric parameters (Å, º) top
C1—C61.382 (4)C2—N211.475 (4)
C1—C21.396 (4)N21—O221.228 (3)
C1—C71.504 (4)N21—O211.229 (3)
C7—O11.234 (3)C3—C41.393 (4)
C7—N11.330 (4)C3—H30.95
N1—N21.418 (3)C4—C51.365 (4)
N1—H10.95C4—H40.95
N2—H2A0.95C5—C61.390 (4)
N2—H2B0.95C5—H50.95
C2—C31.380 (4)C6—H60.95
C6—C1—C2117.0 (3)O22—N21—O21124.2 (3)
C6—C1—C7122.4 (3)O22—N21—C2118.4 (3)
C2—C1—C7120.2 (3)O21—N21—C2117.4 (2)
O1—C7—N1123.8 (3)C2—C3—C4117.6 (3)
O1—C7—C1120.5 (3)C2—C3—H3121.2
N1—C7—C1115.7 (2)C4—C3—H3121.2
C7—N1—N2121.3 (2)C5—C4—C3120.6 (3)
C7—N1—H1120.9C5—C4—H4119.7
N2—N1—H1117.8C3—C4—H4119.7
N1—N2—H2A110.2C4—C5—C6120.6 (3)
N1—N2—H2B105.4C4—C5—H5119.7
H2A—N2—H2B107.4C6—C5—H5119.7
C3—C2—C1123.3 (3)C1—C6—C5120.7 (3)
C3—C2—N21117.1 (3)C1—C6—H6119.6
C1—C2—N21119.5 (3)C5—C6—H6119.6
C6—C1—C7—O1132.2 (3)C1—C2—N21—O22137.6 (3)
C2—C1—C7—O141.0 (4)C3—C2—N21—O21131.3 (3)
C6—C1—C7—N145.7 (4)C1—C2—N21—O2144.4 (4)
C2—C1—C7—N1141.1 (3)C1—C2—C3—C42.5 (4)
O1—C7—N1—N20.6 (5)N21—C2—C3—C4173.0 (2)
C1—C7—N1—N2178.4 (2)C2—C3—C4—C51.0 (4)
C6—C1—C2—C33.4 (4)C3—C4—C5—C63.5 (5)
C7—C1—C2—C3170.1 (3)C2—C1—C6—C50.9 (4)
C6—C1—C2—N21172.0 (3)C7—C1—C6—C5172.5 (3)
C7—C1—C2—N2114.5 (4)C4—C5—C6—C12.5 (5)
C3—C2—N21—O2246.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.951.922.815 (3)157
N2—H2A···O22ii0.952.313.128 (3)144
N2—H2B···N2iii0.952.163.060 (3)157
C3—H3···O1iv0.952.433.269 (4)148
Symmetry codes: (i) x, y+1, z; (ii) x1/2, y+1/2, z+1; (iii) x+1, y1/2, z+1/2; (iv) x+1/2, y+1/2, z+1.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC7H6Cl2N2OC7H6Cl2N2OC7H8ClN3O·H2OC7H7N3O3
Mr205.04205.04203.63181.16
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/cMonoclinic, P21/cOrthorhombic, P212121
Temperature (K)120120120120
a, b, c (Å)7.5511 (2), 14.4834 (4), 8.3097 (3)15.1188 (17), 3.8801 (4), 13.6029 (14)11.1667 (4), 6.9936 (3), 12.7105 (4)12.5382 (10), 4.9867 (2), 12.8637 (8)
α, β, γ (°)90, 110.485 (2), 9090, 91.106 (6), 9090, 112.02 (6), 9090, 90, 90
V3)851.33 (5)797.83 (15)920.2 (4)804.29 (9)
Z4444
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.710.760.390.12
Crystal size (mm)0.54 × 0.36 × 0.080.32 × 0.30 × 0.030.36 × 0.18 × 0.060.63 × 0.13 × 0.08
Data collection
DiffractometerBruker–Nonius KappaCCD
diffractometer
Bruker–Nonius KappaCCD
diffractometer
Bruker–Nonius KappaCCD
diffractometer
Bruker–Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.700, 0.9450.794, 0.9780.874, 0.9770.944, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
10109, 1952, 1661 8399, 1813, 1327 10045, 2113, 1700 11674, 1092, 713
Rint0.0300.0650.0390.146
(sin θ/λ)max1)0.6490.6540.6500.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.072, 1.05 0.046, 0.101, 1.03 0.035, 0.091, 1.06 0.088, 0.097, 1.03
No. of reflections1950181321131092
No. of parameters109109121119
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.260.44, 0.360.25, 0.290.23, 0.19

Computer programs: KappaCCD Server Software (Nonius, 1997), COLLECT (Hooft, 1999), DENZO–SMN (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO–SMN, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), OSCAIL & SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.851.982.8246 (15)171.5
Symmetry code: (i) x+1/2, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl20.852.653.103 (2)115
N1—H1···N2i0.852.222.971 (3)147
N2—H2A···O1ii0.862.503.115 (3)129
N2—H2B···O1iii0.832.162.972 (3)165
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1/2, z+3/2; (iii) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O10.841.992.822 (2)169
O1W—H2W···N2i0.872.012.871 (2)170
N1—H1···N4ii0.832.152.978 (2)173
N2—H2B···O1Wiii0.832.303.063 (2)153
N4—H4A···O1Wiv0.882.072.924 (2)166
N4—H4B···O1v0.962.093.015 (2)161
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x+1, y+1, z+1; (iii) x+2, y+1/2, z+3/2; (iv) x1, y+3/2, z1/2; (v) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.951.922.815 (3)157
N2—H2A···O22ii0.952.313.128 (3)144
N2—H2B···N2iii0.952.163.060 (3)157
C3—H3···O1iv0.952.433.269 (4)148
Symmetry codes: (i) x, y+1, z; (ii) x1/2, y+1/2, z+1; (iii) x+1, y1/2, z+1/2; (iv) x+1/2, y+1/2, z+1.
Selected bond angles and torsion angles (°) for compounds (I)–(IV) top
Parameter(I)(II)(III)(IV)
C2—C1—C7121.07 (12)127.3 (2)121.84 (14)120.2 (3)
C6—C1—C7121.83 (12)115.3 (2)120.93 (14)122.4 (3)
C1—C2—Cl2/N21119.59 (10)122.0 (2)119.62 (12)119.5 (3)
C3—C2—Cl2/N21118.34 (11)116.4 (2)118.07 (12)117.1 (3)
C1—C6—Cl6119.19 (11)
C5—C6—Cl6118.63 (11)
C2—C1—C7—O1-77.51 (19)140.4 (3)-63.0 (2)-41.0 (4)
C2—C1—C7—N1103.00 (15)-42.0 (4)117.46 (16)141.1 (3)
C1—C7—N1—N2176.00 (12)179.3 (2)176.31 (14)178.4 (2)
 

Acknowledgements

X-ray data were collected at the EPSRC National Crystallography Service, University of Southampton, England; the authors thank the staff of the Service for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

References

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