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

Wardell, S.M.S.V.; Vasconcelos, T.R.A.; Souza, M.V.N. de; Wardell, J.L.; Low, J.N.; Glidewell, C.

doi:10.1107/S0108270106034974

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 10| October 2006| Pages o618-o624

doi:10.1107/S0108270106034974

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

Solange M. S. V. Wardell,^a Thatyana R. A. Vasconcelos,^a Marcus V. N. de Souza,^a James L. Wardell,^b John N. Low ^c and Christopher Glidewell ^d ^*

^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), 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 atoms Cl2 and C7 and/or N1, 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 hydrazine atom N2 is sharply pyramidal (Figs. 1–4 ), with sums of angles at N2 consistently less than 330°. In addition, amino atom N4 in compound (III) 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 ).

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 ( $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + 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 = $[3\over4]$ (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, $[{1\over 2}]$ + 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). The combination of the finite zero-dimensional substructure (Fig. 2) and the one-dimensional substructure (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 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), 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).

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); 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).

In (IV), the molecules are linked by a combination of N—H⋯O and N—H⋯N hydrogen bonds (Table 4) 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). 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). 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 pairs of isomers (I)/(II) and (IV)/(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.

Figure 1
A molecule of (I)

, with the atom-labelling scheme shown. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
A molecule of (II)

, with the atom-labelling scheme shown. Displacement ellipsoids are drawn at the 30% probability level.

Figure 3
The independent molecular components in (III)

, with the atom-labelling scheme shown. Displacement ellipsoids are drawn at the 30% probability level.

Figure 4
A molecule of (IV)

, with the atom-labelling scheme shown. Displacement ellipsoids are drawn at the 30% probability level.

Figure 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 ( $[{1\over 2}]$ + 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
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
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, $[{1\over 2}]$ + 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
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
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
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, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z) and (1 + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z), respectively.

Figure 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 (− $[{1\over 2}]$ + 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
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. 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
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 (− $[{1\over 2}]$ + 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
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.

Experimental

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 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).

Compound (I)

Crystal data

C₇H₆Cl₂N₂O
M_r = 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
D_x = 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 ) T_min = 0.700, T_max = 0.945
10109 measured reflections
1952 independent reflections
1661 reflections with I > 2σ(I)
R_int = 0.030
θ_max = 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(F_o²) + (0.035P)² + 0.3426P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.26 e Å⁻³

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

D—H⋯A	D—H	H⋯A	D⋯A	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)

Crystal data

C₇H₆Cl₂N₂O
M_r = 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
D_x = 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) T_min = 0.794, T_max = 0.978
8399 measured reflections
1813 independent reflections
1327 reflections with I > 2σ(I)
R_int = 0.065
θ_max = 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(F_o²) + (0.0401P)² + 0.717P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.36 e Å⁻³

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

D—H⋯A	D—H	H⋯A	D⋯A	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)

Crystal data

C₇H₈ClN₃O·H₂O
M_r = 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
D_x = 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) T_min = 0.874, T_max = 0.977
10045 measured reflections
2113 independent reflections
1700 reflections with I > 2σ(I)
R_int = 0.039
θ_max = 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(F_o²) + (0.0431P)² + 0.3314P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.29 e Å⁻³

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

D—H⋯A	D—H	H⋯A	D⋯A	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⋯O1W^iv	0.88	2.07	2.924 (2)	166
N4—H4B⋯O1^v	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)

Crystal data

C₇H₇N₃O₃
M_r = 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
D_x = 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) T_min = 0.944, T_max = 0.991
11674 measured reflections
1092 independent reflections
713 reflections with I > 2σ(I)
R_int = 0.146
θ_max = 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(F_o²) + (0.0501P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.040 (7)

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

D—H⋯A	D—H	H⋯A	D⋯A	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⋯O1^iv	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 [U_iso(H) = 1.2U_eq(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 [U_iso(H) = 1.2U_eq(N)] and O—H distances of 0.84–0.87 Å [U_iso(H) = 1.5U_eq(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.

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

Supporting information

Crystal structure: contains datablocks global, I, II, III, IV. DOI: 10.1107/S0108270106034974/gg3041sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106034974/gg3041Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270106034974/gg3041IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270106034974/gg3041IIIsup4.hkl

Structure factors: contains datablock IV. DOI: 10.1107/S0108270106034974/gg3041IVsup5.hkl

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).

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

	Fig. 1. A molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The independent molecular components in (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. A molecule of (IV), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	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.
	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).
	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 ($) or an ampersand (&) are at the symmetry positions (1 − x, 1/2 + y, 3/2 − z), (1 − x, −1/2 + y, 3/2 − z), (x, 1 + y, z) and (x, −1 + y, z), respectively.
	Fig. 8. A stereoview of part of the crystal structure of (II), showing the formation of a (100) sheet. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 9. A stereoview of part of the crystal structure of (III), showing the formation of a (100) sheet built from organic molecules only. For the sake of clarity, H atoms bonded to C or N atoms not involved in the motif shown have been omitted.
	Fig. 10. Part of the crystal structure of (III), showing the formation of a C²₂(10) chain along [201]. For the sake of clarity, H atoms bonded to C or N atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−1 + x, 3/2 − y, −1/2 + z) and (1 + x, 3/2 − y, 1/2 + z), respectively.
	Fig. 11. Part of the crystal structure of (IV), showing the formation of a C(8) chain along [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#) or an ampersand (&) are at the symmetry positions (−1/2 + x, 1/2 − y, 1 − z), (1/2 + x, 1/2 − y, 1 − z) and (−1 + x, y, z), respectively.
	Fig. 12. Part of the crystal structure of (IV), showing the formation of a chain of edge-fused R³₃(10) rings along [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*), a hash (#), a dollar sign ($), 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.
	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.
	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

C₇H₆Cl₂N₂O	F(000) = 416
M_r = 205.04	D_x = 1.600 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1952 reflections
a = 7.5511 (2) Å	θ = 2.8–27.5°
b = 14.4834 (4) Å	µ = 0.71 mm⁻¹
c = 8.3097 (3) Å	T = 120 K
β = 110.485 (2)°	Lath, colourless
V = 851.33 (5) Å³	0.54 × 0.36 × 0.08 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD diffractometer	1952 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1661 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 2.8°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −18→18
T_min = 0.700, T_max = 0.945	l = −9→10
10109 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.035P)² + 0.3426P] where P = (F_o² + 2F_c²)/3
1950 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₇H₆Cl₂N₂O	V = 851.33 (5) Å³
M_r = 205.04	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5511 (2) Å	µ = 0.71 mm⁻¹
b = 14.4834 (4) Å	T = 120 K
c = 8.3097 (3) Å	0.54 × 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)
T_min = 0.700, T_max = 0.945	R_int = 0.030
10109 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.05	Δρ_max = 0.35 e Å⁻³
1950 reflections	Δρ_min = −0.26 e Å⁻³
109 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.60402 (18)	0.65107 (9)	0.61322 (17)	0.0160 (3)
C7	0.42897 (19)	0.71038 (9)	0.56421 (18)	0.0167 (3)
O1	0.28941 (14)	0.69243 (8)	0.43709 (14)	0.0275 (3)
N1	0.44028 (16)	0.78201 (8)	0.66721 (16)	0.0189 (3)
N2	0.29431 (17)	0.84842 (9)	0.63530 (17)	0.0241 (3)
C2	0.61167 (19)	0.56620 (10)	0.69497 (18)	0.0179 (3)
Cl2	0.42081 (5)	0.53062 (3)	0.75093 (5)	0.02577 (12)
C3	0.7688 (2)	0.50903 (10)	0.7359 (2)	0.0213 (3)
C4	0.9214 (2)	0.53618 (10)	0.6905 (2)	0.0234 (3)
C5	0.9195 (2)	0.62007 (11)	0.6095 (2)	0.0224 (3)
C6	0.7624 (2)	0.67666 (10)	0.57392 (18)	0.0186 (3)
Cl6	0.76312 (5)	0.78292 (3)	0.47570 (5)	0.02700 (12)
H1	0.5387	0.7897	0.7553	0.023*
H2A	0.2521	0.8627	0.5223	0.029*
H2B	0.1951	0.8253	0.6605	0.029*
H3	0.7719	0.4522	0.7941	0.026*
H4	1.0282	0.4968	0.7152	0.028*
H5	1.0243	0.6385	0.5790	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0133 (6)	0.0178 (7)	0.0143 (7)	0.0001 (5)	0.0016 (5)	−0.0032 (5)
C7	0.0144 (6)	0.0167 (6)	0.0171 (7)	−0.0006 (5)	0.0032 (5)	0.0011 (5)
O1	0.0195 (5)	0.0265 (6)	0.0258 (6)	0.0028 (4)	−0.0055 (4)	−0.0058 (5)
N1	0.0121 (5)	0.0214 (6)	0.0192 (6)	0.0031 (4)	0.0005 (5)	−0.0033 (5)
N2	0.0177 (6)	0.0238 (6)	0.0278 (7)	0.0067 (5)	0.0042 (5)	−0.0005 (5)
C2	0.0153 (6)	0.0191 (7)	0.0181 (7)	−0.0021 (5)	0.0043 (5)	−0.0030 (6)
Cl2	0.02059 (18)	0.0259 (2)	0.0328 (2)	−0.00308 (13)	0.01184 (15)	0.00339 (15)
C3	0.0224 (7)	0.0163 (7)	0.0223 (8)	0.0012 (5)	0.0041 (6)	−0.0009 (6)
C4	0.0176 (7)	0.0208 (7)	0.0295 (8)	0.0043 (5)	0.0053 (6)	−0.0031 (6)
C5	0.0158 (7)	0.0251 (8)	0.0264 (8)	−0.0011 (5)	0.0076 (6)	−0.0046 (6)
C6	0.0189 (6)	0.0181 (7)	0.0176 (7)	−0.0002 (5)	0.0050 (5)	−0.0007 (6)
Cl6	0.0301 (2)	0.0225 (2)	0.0335 (2)	0.00196 (14)	0.01752 (17)	0.00690 (15)

Geometric parameters (Å, º) top

C1—C6	1.3952 (19)	C2—C3	1.388 (2)
C1—C2	1.396 (2)	C2—Cl2	1.7401 (14)
C1—C7	1.5080 (18)	C3—C4	1.389 (2)
C7—O1	1.2309 (17)	C3—H3	0.95
C7—N1	1.3284 (19)	C4—C5	1.387 (2)
N1—N2	1.4163 (16)	C4—H4	0.95
N1—H1	0.85	C5—C6	1.386 (2)
N2—H2A	0.90	C5—H5	0.95
N2—H2B	0.90	C6—Cl6	1.7429 (15)

C6—C1—C2	117.06 (12)	C1—C2—Cl2	119.59 (10)
C6—C1—C7	121.83 (12)	C2—C3—C4	118.93 (14)
C2—C1—C7	121.07 (12)	C2—C3—H3	120.5
O1—C7—N1	124.10 (13)	C4—C3—H3	120.5
O1—C7—C1	121.18 (13)	C5—C4—C3	120.76 (13)
N1—C7—C1	114.72 (12)	C5—C4—H4	119.6
C7—N1—N2	122.64 (12)	C3—C4—H4	119.6
C7—N1—H1	119.8	C6—C5—C4	118.97 (13)
N2—N1—H1	117.5	C6—C5—H5	120.5
N1—N2—H2A	108.6	C4—C5—H5	120.5
N1—N2—H2B	110.9	C5—C6—C1	122.18 (13)
H2A—N2—H2B	107.7	C5—C6—Cl6	118.63 (11)
C3—C2—C1	122.07 (13)	C1—C6—Cl6	119.19 (11)
C3—C2—Cl2	118.34 (11)

C6—C1—C7—O1	100.19 (17)	C1—C2—C3—C4	−1.5 (2)
C2—C1—C7—O1	−77.51 (19)	Cl2—C2—C3—C4	179.38 (11)
C6—C1—C7—N1	−79.22 (17)	C2—C3—C4—C5	1.7 (2)
C2—C1—C7—N1	103.07 (15)	C3—C4—C5—C6	−0.2 (2)
O1—C7—N1—N2	−3.4 (2)	C4—C5—C6—C1	−1.5 (2)
C1—C7—N1—N2	176.00 (12)	C4—C5—C6—Cl6	178.84 (12)
C6—C1—C2—C3	−0.1 (2)	C2—C1—C6—C5	1.6 (2)
C7—C1—C2—C3	177.72 (13)	C7—C1—C6—C5	−176.16 (13)
C6—C1—C2—Cl2	178.99 (10)	C2—C1—C6—Cl6	−178.72 (11)
C7—C1—C2—Cl2	−3.20 (19)	C7—C1—C6—Cl6	3.48 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.85	1.98	2.8246 (15)	172

Symmetry code: (i) x+1/2, −y+3/2, z+1/2.

(II) 2,4-Dichlorobenzohydrazide top

Crystal data top

C₇H₆Cl₂N₂O	F(000) = 416
M_r = 205.04	D_x = 1.707 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1950 reflections
a = 15.1188 (17) Å	θ = 2.9–27.5°
b = 3.8801 (4) Å	µ = 0.76 mm⁻¹
c = 13.6029 (14) Å	T = 120 K
β = 91.106 (6)°	Plate, colourless
V = 797.83 (15) Å³	0.32 × 0.30 × 0.03 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD diffractometer	1813 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1327 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.7°, θ_min = 3.0°
ϕ and ω scans	h = −17→19
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −4→5
T_min = 0.794, T_max = 0.978	l = −16→17
8399 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0401P)² + 0.717P] where P = (F_o² + 2F_c²)/3
1813 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₇H₆Cl₂N₂O	V = 797.83 (15) Å³
M_r = 205.04	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.1188 (17) Å	µ = 0.76 mm⁻¹
b = 3.8801 (4) Å	T = 120 K
c = 13.6029 (14) Å	0.32 × 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)
T_min = 0.794, T_max = 0.978	R_int = 0.065
8399 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.03	Δρ_max = 0.44 e Å⁻³
1813 reflections	Δρ_min = −0.36 e Å⁻³
109 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.28265 (17)	0.4675 (7)	0.64675 (18)	0.0171 (6)
C2	0.23079 (17)	0.5077 (7)	0.56096 (18)	0.0174 (6)
Cl2	0.27176 (5)	0.70300 (18)	0.45593 (5)	0.0232 (2)
C3	0.14354 (18)	0.4002 (7)	0.55600 (18)	0.0194 (6)
C4	0.10744 (17)	0.2413 (7)	0.63718 (19)	0.0187 (6)
Cl4	−0.00183 (4)	0.10534 (18)	0.63134 (5)	0.0245 (2)
C5	0.15681 (18)	0.1920 (7)	0.72318 (19)	0.0204 (6)
C6	0.24298 (18)	0.3089 (7)	0.72698 (18)	0.0183 (6)
C7	0.37502 (17)	0.5969 (7)	0.66526 (18)	0.0177 (6)
O1	0.39536 (12)	0.7165 (5)	0.74710 (13)	0.0232 (5)
N1	0.43400 (14)	0.5681 (6)	0.59380 (16)	0.0212 (5)
N2	0.52219 (14)	0.6877 (6)	0.60524 (15)	0.0206 (5)
H3	0.1089	0.4349	0.4978	0.023*
H5	0.1318	0.0803	0.7782	0.024*
H6	0.2766	0.2805	0.7862	0.022*
H1	0.4232	0.4890	0.5367	0.025*
H2A	0.5229	0.9039	0.6188	0.025*
H2B	0.5443	0.5863	0.6535	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0206 (14)	0.0147 (13)	0.0161 (13)	0.0018 (11)	0.0013 (10)	−0.0049 (10)
C2	0.0214 (15)	0.0157 (13)	0.0152 (13)	0.0022 (11)	0.0024 (10)	−0.0019 (11)
Cl2	0.0249 (4)	0.0273 (4)	0.0175 (3)	0.0003 (3)	0.0012 (3)	0.0038 (3)
C3	0.0214 (15)	0.0198 (14)	0.0169 (13)	0.0029 (12)	−0.0023 (11)	−0.0015 (11)
C4	0.0144 (14)	0.0189 (14)	0.0230 (14)	0.0008 (11)	0.0031 (10)	−0.0044 (11)
Cl4	0.0197 (4)	0.0269 (4)	0.0268 (4)	−0.0024 (3)	0.0012 (3)	−0.0016 (3)
C5	0.0222 (15)	0.0188 (14)	0.0203 (14)	0.0030 (12)	0.0051 (11)	0.0003 (11)
C6	0.0237 (15)	0.0166 (13)	0.0145 (12)	0.0033 (11)	0.0006 (11)	0.0002 (10)
C7	0.0196 (14)	0.0166 (13)	0.0168 (13)	0.0040 (11)	−0.0005 (11)	0.0031 (11)
O1	0.0214 (11)	0.0290 (11)	0.0189 (10)	0.0012 (9)	−0.0020 (8)	−0.0045 (9)
N1	0.0165 (12)	0.0296 (13)	0.0177 (11)	−0.0030 (11)	0.0008 (9)	−0.0041 (10)
N2	0.0153 (12)	0.0252 (13)	0.0211 (12)	−0.0026 (10)	−0.0013 (9)	0.0020 (10)

Geometric parameters (Å, º) top

C1—C6	1.398 (3)	C5—C6	1.379 (4)
C1—C2	1.402 (3)	C5—H5	0.95
C1—C7	1.501 (4)	C6—H6	0.95
C2—C3	1.384 (4)	C7—O1	1.239 (3)
C2—Cl2	1.741 (3)	C7—N1	1.336 (3)
C3—C4	1.386 (4)	N1—N2	1.418 (3)
C3—H3	0.95	N1—H1	0.85
C4—C5	1.389 (4)	N2—H2A	0.86
C4—Cl4	1.735 (3)	N2—H2B	0.83

C6—C1—C2	117.2 (2)	C4—C5—H5	120.7
C6—C1—C7	115.3 (2)	C5—C6—C1	122.3 (2)
C2—C1—C7	127.3 (2)	C5—C6—H6	118.8
C3—C2—C1	121.6 (2)	C1—C6—H6	118.8
C3—C2—Cl2	116.4 (2)	O1—C7—N1	121.8 (2)
C1—C2—Cl2	122.0 (2)	O1—C7—C1	119.3 (2)
C2—C3—C4	119.0 (2)	N1—C7—C1	118.8 (2)
C2—C3—H3	120.5	C7—N1—N2	122.2 (2)
C4—C3—H3	120.5	C7—N1—H1	125.2
C3—C4—C5	121.3 (2)	N2—N1—H1	112.6
C3—C4—Cl4	119.2 (2)	N1—N2—H2A	110.5
C5—C4—Cl4	119.5 (2)	N1—N2—H2B	107.1
C6—C5—C4	118.6 (2)	H2A—N2—H2B	106.9
C6—C5—H5	120.7

C6—C1—C2—C3	1.0 (4)	C4—C5—C6—C1	−1.5 (4)
C7—C1—C2—C3	−174.6 (2)	C2—C1—C6—C5	0.6 (4)
C6—C1—C2—Cl2	179.65 (19)	C7—C1—C6—C5	176.7 (2)
C7—C1—C2—Cl2	4.1 (4)	C6—C1—C7—O1	−35.3 (3)
C1—C2—C3—C4	−1.6 (4)	C2—C1—C7—O1	140.4 (3)
Cl2—C2—C3—C4	179.6 (2)	C6—C1—C7—N1	142.3 (2)
C2—C3—C4—C5	0.7 (4)	C2—C1—C7—N1	−42.0 (4)
C2—C3—C4—Cl4	−179.9 (2)	O1—C7—N1—N2	−3.2 (4)
C3—C4—C5—C6	0.8 (4)	C1—C7—N1—N2	179.3 (2)
Cl4—C4—C5—C6	−178.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2.

(III) 4-Amino-2-chlorobenzohydrazide monohydrate top

Crystal data top

C₇H₈ClN₃O·H₂O	F(000) = 424
M_r = 203.63	D_x = 1.470 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2203 reflections
a = 11.1667 (4) Å	θ = 2.9–27.5°
b = 6.9936 (3) Å	µ = 0.39 mm⁻¹
c = 12.7105 (4) Å	T = 120 K
β = 112.02 (6)°	Lath, yellow
V = 920.2 (4) Å³	0.36 × 0.18 × 0.06 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD diffractometer	2113 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1700 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ϕ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
T_min = 0.874, T_max = 0.977	l = −16→16
10045 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0431P)² + 0.3314P] where P = (F_o² + 2F_c²)/3
2113 reflections	(Δ/σ)_max = 0.001
121 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₇H₈ClN₃O·H₂O	V = 920.2 (4) Å³
M_r = 203.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.1667 (4) Å	µ = 0.39 mm⁻¹
b = 6.9936 (3) Å	T = 120 K
c = 12.7105 (4) Å	0.36 × 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)
T_min = 0.874, T_max = 0.977	R_int = 0.039
10045 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.06	Δρ_max = 0.25 e Å⁻³
2113 reflections	Δρ_min = −0.29 e Å⁻³
121 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.65533 (14)	0.7254 (2)	0.64723 (12)	0.0160 (3)
C2	0.62344 (15)	0.6112 (2)	0.72297 (12)	0.0161 (3)
Cl2	0.74464 (4)	0.53465 (6)	0.84824 (3)	0.02303 (14)
C3	0.49832 (15)	0.5517 (2)	0.70121 (12)	0.0161 (3)
C4	0.39897 (14)	0.6070 (2)	0.60043 (13)	0.0159 (3)
N4	0.27255 (12)	0.54521 (19)	0.57603 (11)	0.0183 (3)
C5	0.42930 (15)	0.7172 (2)	0.52236 (13)	0.0175 (3)
C6	0.55546 (15)	0.7739 (2)	0.54538 (13)	0.0177 (3)
C7	0.78903 (15)	0.8011 (2)	0.67535 (12)	0.0169 (3)
O1	0.84095 (11)	0.91309 (17)	0.75535 (9)	0.0224 (3)
N1	0.84701 (13)	0.7400 (2)	0.60755 (12)	0.0214 (3)
N2	0.97075 (13)	0.8042 (2)	0.61668 (12)	0.0258 (3)
O1W	1.05034 (11)	0.73568 (18)	0.92768 (10)	0.0284 (3)
H3	0.4799	0.4736	0.7545	0.021*
H4A	0.2148	0.6279	0.5350	0.022*
H4B	0.2561	0.5021	0.6413	0.022*
H5	0.3630	0.7536	0.4529	0.023*
H6	0.5745	0.8474	0.4907	0.023*
H1	0.8083	0.6666	0.5537	0.026*
H2A	1.0313	0.7487	0.6799	0.031*
H2B	0.9730	0.9215	0.6288	0.031*
H1W	0.9959	0.7983	0.8750	0.043*
H2W	1.0165	0.7207	0.9785	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0155 (8)	0.0161 (8)	0.0182 (7)	−0.0002 (6)	0.0083 (6)	−0.0024 (6)
C2	0.0169 (8)	0.0147 (7)	0.0167 (7)	0.0016 (6)	0.0065 (6)	−0.0017 (6)
Cl2	0.0184 (2)	0.0276 (2)	0.0204 (2)	−0.00095 (16)	0.00407 (16)	0.00689 (16)
C3	0.0190 (8)	0.0149 (7)	0.0170 (7)	−0.0006 (6)	0.0096 (6)	0.0000 (6)
C4	0.0147 (8)	0.0142 (7)	0.0206 (7)	−0.0006 (6)	0.0084 (6)	−0.0048 (6)
N4	0.0134 (7)	0.0213 (7)	0.0209 (6)	−0.0007 (5)	0.0073 (5)	0.0003 (6)
C5	0.0170 (8)	0.0185 (8)	0.0164 (7)	0.0024 (6)	0.0054 (6)	0.0003 (6)
C6	0.0203 (8)	0.0175 (8)	0.0179 (7)	0.0012 (6)	0.0102 (6)	0.0009 (6)
C7	0.0177 (8)	0.0179 (8)	0.0154 (7)	−0.0004 (6)	0.0065 (6)	0.0024 (6)
O1	0.0221 (6)	0.0261 (6)	0.0202 (6)	−0.0060 (5)	0.0093 (5)	−0.0062 (5)
N1	0.0150 (7)	0.0290 (8)	0.0227 (7)	−0.0074 (6)	0.0098 (6)	−0.0073 (6)
N2	0.0175 (7)	0.0339 (9)	0.0277 (8)	−0.0070 (6)	0.0104 (6)	−0.0048 (7)
O1W	0.0206 (6)	0.0384 (7)	0.0259 (6)	−0.0027 (5)	0.0083 (5)	0.0007 (5)

Geometric parameters (Å, º) top

C1—C2	1.396 (2)	C5—C6	1.385 (2)
C1—C6	1.397 (2)	C5—H5	0.95
C1—C7	1.495 (2)	C6—H6	0.95
C2—C3	1.383 (2)	C7—O1	1.2416 (19)
C2—Cl2	1.7428 (19)	C7—N1	1.328 (2)
C3—C4	1.398 (2)	N1—N2	1.4157 (19)
C3—H3	0.95	N1—H1	0.83
C4—C5	1.395 (2)	N2—H2A	0.92
C4—N4	1.395 (2)	N2—H2B	0.83
N4—H4A	0.88	O1W—H1W	0.84
N4—H4B	0.96	O1W—H2W	0.87

C2—C1—C6	117.16 (14)	C6—C5—H5	119.8
C2—C1—C7	121.84 (14)	C4—C5—H5	119.8
C6—C1—C7	120.93 (14)	C5—C6—C1	121.43 (15)
C3—C2—C1	122.29 (15)	C5—C6—H6	119.3
C3—C2—Cl2	118.07 (12)	C1—C6—H6	119.3
C1—C2—Cl2	119.62 (12)	O1—C7—N1	122.88 (15)
C2—C3—C4	119.66 (15)	O1—C7—C1	122.46 (14)
C2—C3—H3	120.2	N1—C7—C1	114.66 (14)
C4—C3—H3	120.2	C7—N1—N2	122.91 (14)
C5—C4—N4	120.55 (14)	C7—N1—H1	120.1
C5—C4—C3	118.93 (14)	N2—N1—H1	116.9
N4—C4—C3	120.45 (14)	N1—N2—H2A	108.2
C4—N4—H4A	112.7	N1—N2—H2B	106.7
C4—N4—H4B	114.2	H2A—N2—H2B	107.0
H4A—N4—H4B	112.5	H1W—O1W—H2W	105.6
C6—C5—C4	120.46 (15)

C6—C1—C2—C3	−1.8 (2)	C4—C5—C6—C1	−0.9 (2)
C7—C1—C2—C3	175.34 (14)	C2—C1—C6—C5	2.4 (2)
C6—C1—C2—Cl2	176.60 (11)	C7—C1—C6—C5	−174.82 (14)
C7—C1—C2—Cl2	−6.2 (2)	C2—C1—C7—O1	−63.0 (2)
C1—C2—C3—C4	−0.2 (2)	C6—C1—C7—O1	114.06 (17)
Cl2—C2—C3—C4	−178.68 (11)	C2—C1—C7—N1	117.46 (16)
C2—C3—C4—C5	1.8 (2)	C6—C1—C7—N1	−65.5 (2)
C2—C3—C4—N4	178.74 (14)	O1—C7—N1—N2	−3.2 (2)
N4—C4—C5—C6	−178.19 (14)	C1—C7—N1—N2	176.31 (14)
C3—C4—C5—C6	−1.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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···O1W^iv	0.88	2.07	2.924 (2)	166
N4—H4B···O1^v	0.96	2.09	3.015 (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) x−1, −y+3/2, z−1/2; (v) −x+1, y−1/2, −z+3/2.

(IV) 2-Nitrobenzohydrazide top

Crystal data top

C₇H₇N₃O₃	F(000) = 376
M_r = 181.16	D_x = 1.496 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1092 reflections
a = 12.5382 (10) Å	θ = 4.4–27.5°
b = 4.9867 (2) Å	µ = 0.12 mm⁻¹
c = 12.8637 (8) Å	T = 120 K
V = 804.29 (9) Å³	Lath, brown
Z = 4	0.63 × 0.13 × 0.08 mm

Data collection top

Bruker–Nonius KappaCCD diffractometer	1092 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	713 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.146
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 4.4°
ϕ and ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −6→6
T_min = 0.944, T_max = 0.991	l = −16→16
11674 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.088	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0501P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1092 reflections	Δρ_max = 0.23 e Å⁻³
119 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.040 (7)

Crystal data top

C₇H₇N₃O₃	V = 804.29 (9) Å³
M_r = 181.16	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 12.5382 (10) Å	µ = 0.12 mm⁻¹
b = 4.9867 (2) Å	T = 120 K
c = 12.8637 (8) Å	0.63 × 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)
T_min = 0.944, T_max = 0.991	R_int = 0.146
11674 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.088	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.03	Δρ_max = 0.23 e Å⁻³
1092 reflections	Δρ_min = −0.19 e Å⁻³
119 parameters

Special details top

Experimental. ?.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.8184 (2)	0.5658 (5)	0.3908 (2)	0.0229 (7)
C7	0.7043 (2)	0.5033 (5)	0.3640 (2)	0.0230 (7)
O1	0.67233 (16)	0.2693 (4)	0.36325 (18)	0.0314 (6)
N1	0.64395 (18)	0.7128 (5)	0.33887 (19)	0.0252 (6)
N2	0.5357 (2)	0.6803 (5)	0.3096 (2)	0.0289 (7)
C2	0.8692 (2)	0.4291 (5)	0.4714 (2)	0.0252 (7)
N21	0.8051 (2)	0.2721 (5)	0.5459 (2)	0.0287 (6)
O21	0.72326 (19)	0.3762 (4)	0.57959 (19)	0.0375 (6)
O22	0.83784 (17)	0.0504 (4)	0.57239 (19)	0.0402 (7)
C3	0.9773 (2)	0.4466 (6)	0.4904 (2)	0.0282 (7)
C4	1.0369 (3)	0.6181 (6)	0.4276 (3)	0.0309 (8)
C5	0.9886 (2)	0.7654 (6)	0.3515 (2)	0.0306 (7)
C6	0.8803 (3)	0.7365 (6)	0.3315 (2)	0.0283 (7)
H1	0.6722	0.8896	0.3398	0.030*
H2A	0.4929	0.6483	0.3692	0.035*
H2B	0.5340	0.5224	0.2683	0.035*
H3	1.0099	0.3455	0.5443	0.034*
H4	1.1117	0.6326	0.4378	0.037*
H5	1.0295	0.8889	0.3118	0.037*
H6	0.8485	0.8351	0.2764	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0238 (17)	0.0171 (13)	0.0279 (16)	0.0014 (14)	−0.0006 (14)	−0.0017 (13)
C7	0.0266 (17)	0.0189 (14)	0.0234 (16)	−0.0016 (13)	−0.0003 (14)	−0.0007 (13)
O1	0.0290 (12)	0.0181 (10)	0.0471 (13)	−0.0026 (9)	−0.0045 (10)	0.0018 (10)
N1	0.0200 (13)	0.0185 (11)	0.0372 (16)	−0.0013 (11)	−0.0041 (12)	0.0016 (11)
N2	0.0247 (15)	0.0244 (12)	0.0376 (15)	−0.0010 (12)	−0.0070 (12)	0.0008 (11)
C2	0.0258 (18)	0.0194 (14)	0.0303 (17)	−0.0013 (14)	0.0028 (15)	−0.0016 (13)
N21	0.0296 (15)	0.0252 (14)	0.0314 (15)	−0.0020 (13)	−0.0070 (12)	0.0032 (13)
O21	0.0323 (14)	0.0379 (13)	0.0424 (13)	0.0037 (11)	0.0091 (11)	0.0062 (12)
O22	0.0405 (15)	0.0277 (12)	0.0523 (15)	0.0015 (11)	−0.0056 (12)	0.0156 (12)
C3	0.0276 (19)	0.0228 (15)	0.0341 (18)	0.0023 (14)	−0.0033 (15)	−0.0029 (14)
C4	0.0230 (17)	0.0315 (16)	0.0383 (19)	−0.0027 (14)	0.0010 (17)	−0.0067 (16)
C5	0.0267 (17)	0.0315 (17)	0.0335 (16)	−0.0026 (15)	0.0041 (15)	0.0002 (16)
C6	0.0315 (17)	0.0237 (15)	0.0298 (17)	0.0000 (15)	−0.0015 (14)	0.0009 (14)

Geometric parameters (Å, º) top

C1—C6	1.382 (4)	C2—N21	1.475 (4)
C1—C2	1.396 (4)	N21—O22	1.228 (3)
C1—C7	1.504 (4)	N21—O21	1.229 (3)
C7—O1	1.234 (3)	C3—C4	1.393 (4)
C7—N1	1.330 (4)	C3—H3	0.95
N1—N2	1.418 (3)	C4—C5	1.365 (4)
N1—H1	0.95	C4—H4	0.95
N2—H2A	0.95	C5—C6	1.390 (4)
N2—H2B	0.95	C5—H5	0.95
C2—C3	1.380 (4)	C6—H6	0.95

C6—C1—C2	117.0 (3)	O22—N21—O21	124.2 (3)
C6—C1—C7	122.4 (3)	O22—N21—C2	118.4 (3)
C2—C1—C7	120.2 (3)	O21—N21—C2	117.4 (2)
O1—C7—N1	123.8 (3)	C2—C3—C4	117.6 (3)
O1—C7—C1	120.5 (3)	C2—C3—H3	121.2
N1—C7—C1	115.7 (2)	C4—C3—H3	121.2
C7—N1—N2	121.3 (2)	C5—C4—C3	120.6 (3)
C7—N1—H1	120.9	C5—C4—H4	119.7
N2—N1—H1	117.8	C3—C4—H4	119.7
N1—N2—H2A	110.2	C4—C5—C6	120.6 (3)
N1—N2—H2B	105.4	C4—C5—H5	119.7
H2A—N2—H2B	107.4	C6—C5—H5	119.7
C3—C2—C1	123.3 (3)	C1—C6—C5	120.7 (3)
C3—C2—N21	117.1 (3)	C1—C6—H6	119.6
C1—C2—N21	119.5 (3)	C5—C6—H6	119.6

C6—C1—C7—O1	132.2 (3)	C1—C2—N21—O22	137.6 (3)
C2—C1—C7—O1	−41.0 (4)	C3—C2—N21—O21	131.3 (3)
C6—C1—C7—N1	−45.7 (4)	C1—C2—N21—O21	−44.4 (4)
C2—C1—C7—N1	141.1 (3)	C1—C2—C3—C4	2.5 (4)
O1—C7—N1—N2	0.6 (5)	N21—C2—C3—C4	−173.0 (2)
C1—C7—N1—N2	178.4 (2)	C2—C3—C4—C5	1.0 (4)
C6—C1—C2—C3	−3.4 (4)	C3—C4—C5—C6	−3.5 (5)
C7—C1—C2—C3	170.1 (3)	C2—C1—C6—C5	0.9 (4)
C6—C1—C2—N21	172.0 (3)	C7—C1—C6—C5	−172.5 (3)
C7—C1—C2—N21	−14.5 (4)	C4—C5—C6—C1	2.5 (5)
C3—C2—N21—O22	−46.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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···O1^iv	0.95	2.43	3.269 (4)	148

Symmetry codes: (i) x, y+1, z; (ii) x−1/2, −y+1/2, −z+1; (iii) −x+1, y−1/2, −z+1/2; (iv) x+1/2, −y+1/2, −z+1.

Experimental details

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	C₇H₆Cl₂N₂O	C₇H₆Cl₂N₂O	C₇H₈ClN₃O·H₂O	C₇H₇N₃O₃
M_r	205.04	205.04	203.63	181.16
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/c	Monoclinic, P2₁/c	Orthorhombic, P2₁2₁2₁
Temperature (K)	120	120	120	120
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), 90	90, 91.106 (6), 90	90, 112.02 (6), 90	90, 90, 90
V (Å³)	851.33 (5)	797.83 (15)	920.2 (4)	804.29 (9)
Z	4	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.71	0.76	0.39	0.12
Crystal size (mm)	0.54 × 0.36 × 0.08	0.32 × 0.30 × 0.03	0.36 × 0.18 × 0.06	0.63 × 0.13 × 0.08

Data collection
Diffractometer	Bruker–Nonius KappaCCD diffractometer	Bruker–Nonius KappaCCD diffractometer	Bruker–Nonius KappaCCD diffractometer	Bruker–Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.700, 0.945	0.794, 0.978	0.874, 0.977	0.944, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	10109, 1952, 1661	8399, 1813, 1327	10045, 2113, 1700	11674, 1092, 713
R_int	0.030	0.065	0.039	0.146
(sin θ/λ)_max (Å⁻¹)	0.649	0.654	0.650	0.649

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 reflections	1950	1813	2113	1092
No. of parameters	109	109	121	119
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.26	0.44, −0.36	0.25, −0.29	0.23, −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···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.85	1.98	2.8246 (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···A	D—H	H···A	D···A	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+1/2, −z+3/2; (iii) −x+1, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) for (III) top

D—H···A	D—H	H···A	D···A	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···O1W^iv	0.88	2.07	2.924 (2)	166
N4—H4B···O1^v	0.96	2.09	3.015 (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) x−1, −y+3/2, z−1/2; (v) −x+1, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) for (IV) top

D—H···A	D—H	H···A	D···A	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···O1^iv	0.95	2.43	3.269 (4)	148

Symmetry codes: (i) x, y+1, z; (ii) x−1/2, −y+1/2, −z+1; (iii) −x+1, y−1/2, −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—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)

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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ISSN: 2053-2296

Volume 62| Part 10| October 2006| Pages o618-o624

doi:10.1107/S0108270106034974