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

Article abstract of DOI:10.1107/S0108270106034974

The molecules of 2,6-dichlorobenzohydrazide, C₇H ₆Cl₂N₂O, are linked into simple chains by a single N-H...O hydrogen bond, while in the isomeric compound 2,4-dichlorobenzo-hydrazide, the molecules are linked by

Full text of DOI:10.1107/S0108270106034974

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
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).
ISSN 0108-2701
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. Lowc
and Christopher Glidewelld*
a
Â
Instituto de Tecnologia em Farmacos, Far-Manguinhos, FIOCRUZ, 21041-250 Rio
b
Â
Â
Ã
de Janeiro, RJ, Brazil, Instituto de Quõmica, Departamento de Quõmica Inorganica,
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 NÐHÁ Á ÁO hydrogen
bond, while in the isomeric compound 2,4-dichlorobenzo-
hydrazide, the molecules are linked by NÐHÁ Á ÁN and NÐ
HÁ Á ÁO hydrogen bonds into complex sheets comprising an
inner polar layer sandwiched between two non-polar layers. In
4-amino-2-chlorobenzohydrazide monohydrate, C7H8ClN3OÁ-
H2O, the components are linked into a three-dimensional
framework by a combination of OÐHÁ Á ÁO, OÐHÁ Á ÁN, NÐ
HÁ Á ÁN and NÐHÁ Á ÁO hydrogen bonds, and in 2-nitro-
benzohydrazide, C7H7N3O3, a three-dimensional framework
is formed by a combination of NÐHÁ Á ÁN and NÐHÁ Á ÁO
hydrogen bonds
The exocyclic bond angles in compound (II) show some
signi®cant variations, including signi®cant deviations from the
idealized values of 120ꢀ (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 5ꢀ, while those at C1 differ by some 12ꢀ. The sense of
these deviations suggests strongly repulsive interactions
between atoms Cl2 and C7 and/or N1, possibly associated with
Comment
As part of our general study of the supramolecular structures
of amine and hydrazine derivatives, we report here the mol-
ecular and supramolecular structures of four related benzo-
hydrazides, namely isomeric 2,6-dichlorobenzohydrazide, (I),
and 2,4-dichlorobenzohydrazide, (II), 4-amino-2-chlorobenzo-
hydrazide, 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 hydra-
zines ArCONHNH2. By contrast, compound (III) was
obtained, on one occasion only, from the reaction of hydrazine
with methyl 2-chloro-4-¯uorobenzoate; this reaction involves
a nucleophilic displacement of the 4-¯uoro substituent, and
despite a number of attempts to reproduce this synthesis, we
have been consistently unsuccessful.
Figure 1
A molecule of (I), with the atom-labelling scheme shown. Displacement
ellipsoids are drawn at the 30% probability level.
o618 # 2006 International Union of Crystallography
DOI: 10.1107/S0108270106034974
Acta Cryst. (2006). C62, o618±o624

organic compounds
the rather short intramolecular H1Á Á ÁCl2 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 330ꢀ. In addition, amino atom N4 in
compound (III) is pyramidal, and the C4ÐN4 distance
C(4) (Bernstein et al., 1995) chain running parallel to the [101]
direction and generated by the n-glide plane at y = 34 (Fig. 5).
Two such chains, related to one another by inversion and
hence antiparallel, pass through each unit cell, but there are
no direction-speci®c 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
NÐHÁ Á ÁN hydrogen bond and two NÐHÁ Á ÁO hydrogen
bonds (Table 2) into sheets whose formation is readily
analysed in terms of two simple substructures. In the ®rst of
these substructures, paired NÐHÁ Á ÁN hydrogen bonds link
Ê
[1.395 (2) A] is identical to the mean values for C(aryl)ÐNH2
bonds with pyramidal N atoms and much longer than the
Ê
corresponding mean value (1.355 A) for such bonds with
planar N atoms (Allen et al., 1987).
In compound (I), the molecules are linked into simple
chains by a single NÐHÁ Á ÁO 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 (12 + x, 23 y, 21 + z), so forming a
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 NÐHÁ Á ÁO
hydrogen bonds; atom N2 in the molecule at (x, y, z) acts as a
hydrogen-bond donor, via H2A and H2B, respectively, to
Figure 4
A molecule of (IV), 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 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 (12 + x, 23 y, 12 + z) and ( 21 + x, 23 y,
Figure 3
The independent molecular components in (III), with the atom-labelling
scheme shown. Displacement ellipsoids are drawn at the 30% probability
level.
1
+ z), respectively.
2
ꢁ
Acta Cryst. (2006). C62, o618±o624
Wardell et al.
C7H6Cl2N2O, C7H8ClN3OÁH2O and C7H7N3O3 o619

organic compounds
atoms O1 in the molecules at (1 x, 12 + y, 23 z) and (1 x,
molecules. Paired NÐHÁ Á ÁN hydrogen bonds link the organic
molecules into centrosymmetric R22(16) dimers (Fig. 9), and
the reference dimer centred at (12, 21, 21 ) is linked by NÐHÁ Á ÁO
hydrogen bonds to four similar dimers centred at (12, 0, 0),
(12, 0, 1), (21, 1, 0) and (12, 1, 1), thereby generating a (100) sheet
built from R22(16) and R66(28) rings alternating in a chessboard
fashion (Fig. 9).
1
3
+ y,
z), respectively, so forming a chain of edge-fused
2
2
R22(10) rings running parallel to the [010] direction and
generated by the 21 screw axis along (12, y, ) (Fig. 7). The
3
4
combination of the ®nite 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 OÐHÁ Á ÁO, OÐ
HÁ Á ÁN, NÐHÁ Á ÁN and NÐHÁ Á ÁO hydrogen bonds (Table 3).
The organic components are linked into sheets by one NÐ
HÁ Á ÁN and one NÐHÁ Á ÁO interaction, and these sheets are
linked into a continuous framework by means of the water
The simplest description of the linking of the (100) sheets is
in terms of one each of OÐHÁ Á ÁO and NÐHÁ Á ÁO hydrogen
bonds. The OÐHÁ Á ÁO hydrogen bond lies within the selected
asymmetric unit (Fig. 3); in addition, atom N4 at (x, y, z) acts
3
2
1
2
as a donor to water atom O1W at ( 1 + x,
y,
+ 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).
Figure 6
Figure 8
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).
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 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
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.
1
3
1
3
positions (1 x, + y,
(x, 1 + y, z), respectively.
z), (1 x,
+ y,
2
z), (x, 1 + y, z) and
2
2
2
ꢁ
o620 Wardell et al. C7H6Cl2N2O, C7H8ClN3OÁH2O and C7H7N3O3
Acta Cryst. (2006). C62, o618±o624

organic compounds
In (IV), the molecules are linked by a combination of NÐ
HÁ Á ÁO and NÐHÁ Á ÁN 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
1
2
1
2
O22 in the molecule at ( + x,
simple C(8) chain running parallel to the [100] direction and
y, 1 z), so forming a
1
1
generated by the 21 screw axis along (x, , ) (Fig. 11). A
4
2
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
1
2
1
2
at (1
x,
+ y,
z), so forming a C(2) chain running
parallel to the [010] direction and generated by the 21 screw
axis along (12, y, 14 ). 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 brie¯y to compare the supramolecular
structures of the compounds reported here with those of some
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
1
1
2
ampersand (&) are at the symmetry positions ( + x,
(12 + x,
y, 1
z),
2
y, 1 z) and ( 1 + x, y, z), respectively.
1
2
Figure 12
Figure 10
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
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, 32 y,
1
1
1
at the symmetry positions (1 x,
(x, 1 + y, z), (x, 1 + y, z) and (1 x,
+ y,
z), (1 x,
+ y, 12 z), respectively.
2
+ y, 12 z),
2
2
2
1
3
3
+ z) and (1 + x,
y, 12 + z), respectively.
2
2
ꢁ
Acta Cryst. (2006). C62, o618±o624
Wardell et al.
C7H6Cl2N2O, C7H8ClN3OÁH2O and C7H7N3O3 o621

organic compounds
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 NÐ
HÁ Á ÁN and NÐHÁ Á ÁO 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 NÐ
HÁ Á ÁN type and two of NÐHÁ Á ÁO 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-speci®c interactions between these
sheets. Even the two hydrogen bonds listed in the original
report (Saraogi et al., 2002) suf®ce 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 NÐHÁ Á ÁO, NÐHÁ Á ÁN, CÐHÁ Á ÁO and CÐ
HÁ Á ÁN 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 in¯uence of the
orientation of the substituents, even when, as in (I) and (II),
they play no direct role in the aggregation.
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-¯uoro-
benzoate for (III)] and a ®vefold molar excess of hydrazine hydrate in
methanol was held at 353 K for 6±8 h. The mixtures were concen-
trated to dryness under reduced pressure, and the resulting solid
products (I)±(III) were puri®ed 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): ꢀ(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); ꢀ(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):
ꢀ(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);
ꢀ(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): ꢀ(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); ꢀ(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).
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 ( 12 + x,
1
2
y, 1 z), (1 x, 12 + y, 21 z), (21 x, 1 y, 21 + z) and (12 x, 1 y,
+ z), respectively.
1
2
Compound (I)
Crystal data
C7H6Cl2N2O
Mr = 205.04
Z = 4
Dx = 1.600 Mg m
Mo Kꢂ radiation
ꢃ = 0.71 mm
T = 120 (2) K
Lath, colourless
0.54 Â 0.36 Â 0.08 mm
3
Monoclinic, P21=n
1
Ê
a = 7.5511 (2) A
Figure 14
Ê
b = 14.4834 (4) A
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.
Ê
c = 8.3097 (3) A
ꢁ = 110.485 (2)ꢀ
3
Ê
V = 851.33 (5) A
ꢁ
o622 Wardell et al. C7H6Cl2N2O, C7H8ClN3OÁH2O and C7H7N3O3
Acta Cryst. (2006). C62, o618±o624

organic compounds
Data collection
Compound (III)
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.700, Tmax = 0.945
10109 measured re¯ections
1952 independent re¯ections
1661 re¯ections with I > 2ꢄ(I)
Rint = 0.030
Crystal data
C7H8ClN3OÁH2O
Z = 4
Dx = 1.470 Mg m
3
ꢅmax = 27.5ꢀ
Mr = 203.63
Monoclinic, P21=c
Mo Kꢂ radiation
1
Ê
a = 11.1667 (4) A
ꢃ = 0.39 mm
T = 120 (2) K
Ê
b = 6.9936 (3) A
Ê
c = 12.7105 (4) A
Lath, yellow
0.36 Â 0.18 Â 0.06 mm
ꢁ = 112.02 (6)ꢀ
Re®nement
3
Ê
V = 920.2 (4) A
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.028
wR(F2) = 0.072
S = 1.05
1950 re¯ections
109 parameters
H-atom parameters
constrained
w = 1/[ꢄ2(F2o) + (0.035P)2
+ 0.3426P]
Data collection
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max < 0.001
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.874, Tmax = 0.977
10045 measured re¯ections
2113 independent re¯ections
1700 re¯ections with I > 2ꢄ(I)
Rint = 0.039
3
Ê
Áꢆmax = 0.35 e A
3
Ê
0.26 e A
Áꢆmin
=
ꢅmax = 27.5ꢀ
Table 1
Hydrogen-bond geometry (A, ) for (I).
Re®nement
ꢀ
Ê
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.035
wR(F2) = 0.091
S = 1.06
2113 re¯ections
w = 1/[ꢄ2(F2o) + (0.0431P)2
+ 0.3314P]
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
2.8246 (15)
DÐHÁ Á ÁA
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max = 0.001
N1ÐH1Á Á ÁO1i
0.85
1.98
172
3
Ê
Áꢆmax = 0.25 e A
3
Symmetry code: (i) x ‡ 12; y ‡ 23; z ‡ 21.
Ê
0.29 e A
121 parameters
H-atom parameters constrained
Áꢆmin
=
Table 3
Hydrogen-bond geometry (A, ) for (III).
ꢀ
Ê
Compound (II)
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Crystal data
C7H6Cl2N2O
Mr = 205.04
Z = 4
Dx = 1.707 Mg m
Mo Kꢂ radiation
ꢃ = 0.76 mm
T = 120 (2) K
Plate, colourless
0.32 Â 0.30 Â 0.03 mm
O1WÐH1WÁ Á ÁO1
O1WÐH2WÁ Á ÁN2i
N1ÐH1Á Á ÁN4ii
0.84
0.87
0.83
0.83
0.88
0.96
1.99
2.01
2.15
2.30
2.07
2.09
2.822 (2)
2.871 (2)
2.978 (2)
3.063 (2)
2.924 (2)
3.015 (2)
169
170
173
153
166
161
3
Monoclinic, P21=c
1
N2ÐH2BÁ Á ÁO1Wiii
N4ÐH4AÁ Á ÁO1Wiv
N4ÐH4BÁ Á ÁO1v
Ê
a = 15.1188 (17) A
Ê
b = 3.8801 (4) A
Ê
c = 13.6029 (14) A
ꢁ = 91.106 (6)ꢀ
V = 797.83 (15) A
Symmetry codes: (i) x; y ‡ 23; z ‡ 21; (ii) x ‡ 1; y ‡ 1; z ‡ 1; (iii) x ‡ 2, y ‡ 12,
3
Ê
z ‡ 32; (iv) x 1; y ‡ 23; z 12; (v) x ‡ 1; y
;
z ‡ 32.
1
2
Data collection
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.794, Tmax = 0.978
8399 measured re¯ections
1813 independent re¯ections
1327 re¯ections with I > 2ꢄ(I)
Rint = 0.065
ꢅmax = 27.7ꢀ
Compound (IV)
Crystal data
C7H7N3O3
Mr = 181.16
Orthorhombic, P212121
Z = 4
Dx = 1.496 Mg m
Mo Kꢂ radiation
ꢃ = 0.12 mm
T = 120 (2) K
Lath, brown
0.63 Â 0.13 Â 0.08 mm
3
Re®nement
1
Ê
a = 12.5382 (10) A
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.046
wR(F2) = 0.101
S = 1.03
1813 re¯ections
109 parameters
H-atom parameters
constrained
w = 1/[ꢄ2(F2o) + (0.0401P)2
+ 0.717P]
Ê
b = 4.9867 (2) A
Ê
c = 12.8637 (8) A
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max < 0.001
3
Ê
V = 804.29 (9) A
3
Ê
Áꢆmax = 0.44 e A
Data collection
3
Ê
0.36 e A
Áꢆmin
=
Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.944, Tmax = 0.991
11674 measured re¯ections
1092 independent re¯ections
713 re¯ections with I > 2ꢄ(I)
Rint = 0.146
Table 2
Hydrogen-bond geometry (A, ) for (II).
ꢅmax = 27.5ꢀ
ꢀ
Ê
Re®nement
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.088
wR(F2) = 0.097
S = 1.03
1092 re¯ections
w = 1/[ꢄ2(F2o) + (0.0501P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max < 0.001
N1ÐH1Á Á ÁCl2
N1ÐH1Á Á ÁN2i
N2ÐH2AÁ Á ÁO1ii
N2ÐH2BÁ Á ÁO1iii
0.85
0.85
0.86
0.83
2.65
2.22
2.50
2.16
3.103 (2)
2.971 (3)
3.115 (3)
2.972 (3)
115
147
129
165
3
Ê
Áꢆmax = 0.23 e A
3
Ê
0.19 e A
Áꢆmin
Extinction correction: SHELXL97
=
Symmetry codes: (i) x ‡ 1; y ‡ 1; z ‡ 1; (ii) x ‡ 1; y ‡ 12; z ‡ 23; (iii) x ‡ 1,
119 parameters
H-atom parameters constrained
1
2
Extinction coef®cient: 0.040 (7)
y
,
z ‡ 32.
ꢁ
Acta Cryst. (2006). C62, o618±o624
Wardell et al.
C7H6Cl2N2O, C7H8ClN3OÁH2O and C7H7N3O3 o623

organic compounds
Table 4
Hydrogen-bond geometry (A, ) for (IV).
(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 re®ne
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).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N1ÐH1Á Á ÁO1i
0.95
0.95
0.95
0.95
1.92
2.31
2.16
2.43
2.815 (3)
3.128 (3)
3.060 (3)
3.269 (4)
157
144
157
148
N2ÐH2AÁ Á ÁO22ii
N2ÐH2BÁ Á ÁN2iii
C3ÐH3Á Á ÁO1iv
1
2
1
Symmetry codes: (i) x; y ‡ 1; z; (ii) x
;
y ‡ 12; z ‡ 1; (iii) x ‡ 1; y
;
2
z ‡ 12; (iv)
x ‡ 12; y ‡ 12; z ‡ 1.
Table 5
X-ray data were collected at the EPSRC National Crystal-
lography 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 ®nancial support.
Selected bond angles and torsion angles (ꢀ) for compounds (I)±(IV).
(I)
(II)
(III)
(IV)
C2ÐC1ÐC7
C6ÐC1ÐC7
C1ÐC2ÐCl2/N21
C3ÐC2ÐCl2/N21
C1ÐC6ÐCl6
121.07 (12)
121.83 (12)
119.59 (10)
118.34 (11)
119.19 (11)
118.63 (11)
127.3 (2)
115.3 (2)
122.0 (2)
116.4 (2)
±
121.84 (14)
120.93 (14)
119.62 (12)
118.07 (12)
±
120.2 (3)
122.4 (3)
119.5 (3)
117.1 (3)
±
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GG3041). Services for accessing these data are
described at the back of the journal.
C5ÐC6ÐCl6
±
±
±
C2ÐC1ÐC7ÐO1
C2ÐC1ÐC7ÐN1
C1ÐC7ÐN1ÐN2
77.51 (19)
103.00 (15)
176.00 (12)
140.4 (3)
42.0 (4)
179.3 (2)
63.0 (2)
117.46 (16)
176.31 (14)
41.0 (4)
141.1 (3)
178.4 (2)
References
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absences. All H atoms were located in difference maps and then
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Ê
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Ê
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Ê
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quality, and this is re¯ected in the high merging index and the high
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È
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ꢁ
o624 Wardell et al. C7H6Cl2N2O, C7H8ClN3OÁH2O and C7H7N3O3
Acta Cryst. (2006). C62, o618±o624