(E)-N′-(4-Chlorobenzylidene)-,(E)-N′-(4-bromobenzylidene)- and (E)-N′-[4-(diethylamino)benzylidene]-derivatives of 4- hydroxybenzohydrazide

Article abstract of DOI:10.1107/S0108270112038462

The 4-chloro- [C₁₄H₁₁ClN₂O₂, (I)], 4-bromo- [C₁₄H₁₀BrN₂O₂, (II)] and 4-diethyl-amino- [C₁₈H₂₁N₃O₂, (III)] derivatives of benzyl-idene-4-hy-droxy-benzo-hydrazide, all crystallize in the same space group (P2₁/c), (I) and (II) also being isomorphous. In all three compounds, the conformation about the C=N bond is E. The molecules of (I) and (II) are relatively planar, with dihedral angles between the two benzene rings of 5.75 (12) and 9.81 (17)°, respectively. In (III), however, the same angle is 77.27 (9)°. In the crystal structures of (I) and (II), two-dimensional slab-like networks extending in the a and c directions are formed via N - H...O and O - H...O hydrogen bonds. The molecules stack head-to-tail via π-π interactions involving the aromatic rings [centroid-centroid distance = 3.7622 (14) A in (I) and 3.8021 (19) A in (II)]. In (III), undulating two-dimensional networks extending in the b and c directions are formed via N - H...O and O - H...O hydrogen bonds. The molecules stack head-to-head via π-π interactions involving inversion-related benzene rings [cen-troid-centroid distances = 3.6977 (12) and 3.8368 (11) A].

Full text of DOI:10.1107/S0108270112038462

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
compounds possess exceptional biological properties, espe-
cially for their potential pharmacological and antitumour
properties (Kucukguzel et al., 2006; Khattab, 2005; Karthi-
keyan et al., 2006; Okabe et al., 1993) and their antibacterial
activities (Cukurovali et al., 2002), or their uses in technology
and analytical chemistry (Kitaev, 1977). Recently, a number of
hydrazone compounds have been prepared and structurally
characterized (Abdul Alhadi et al., 2009; Mohd Lair et al.,
2009; Cao & Lu, 2009; Qu & Cao, 2009). Hydrazone
compounds have also been used as chelating ligands for the
spectrophotometric and fluorimetric determination of trace
metal ions (Katyal & Dutt, 1975; Galiano-Roth & Collum,
1988; Sugano et al., 2009).
ISSN 0108-2701
(E)-N0-(4-Chlorobenzylidene)-,
(E)-N0-(4-bromobenzylidene)- and
(E)-N0-[4-(diethylamino)benzylidene]-
derivatives of 4-hydroxybenzo-
hydrazide
Hydrazone derivatives can possess nonlinear optical (NLO)
properties because of their large molecular nonlinearities and
their remarkable propensity to form noncentrosymmetric
crystal systems (Serbutoviez et al., 1995). The chemistry of
2-hydroxybenzohydrazide and its derivatives has been studied
because of their multiple coordination environments (Chang,
2008; Huo et al., 2004). The presence of O and N atoms also
means that various hydrogen-bonding motifs can be formed,
which can lead to the formation of versatile supramolecular
architectures in the crystal structures. 4-Hydroxybenzo-
hydrazide has also been used to prepare a number of
compounds which have been shown to possess a variety of
biological activities, for example, antitumour (Patil et al., 2011;
Bhole & Bhusari, 2011), antibacterial (Rajput, 2012) and
antitubercular properties (Bhole et al., 2012).
Ashokkumar Subashini,a Kandasamy Ramamurthia* and
Helen Stoeckli-Evansb*
aCrystal Growth and Thin Film Laboratory, School of Physics, Bharathidasan
University, Tiruchirappalli, Tamil Nadu 620 024, India, and bInstitute of Physics,
ˆ
ˆ
University of Neuchatel, Rue Emile-Argand 11, CH-2000 Neuchatel, Switzerland
Correspondence e-mail: krmurthin@yahoo.co.in, helen.stoeckli-evans@unine.ch
Received 21 August 2012
Accepted 7 September 2012
Online 13 September 2012
The 4-chloro- [C14H11ClN2O2, (I)], 4-bromo- [C14H10BrN2O2,
(II)] and 4-diethylamino- [C18H21N3O2, (III)] derivatives of
benzylidene-4-hydroxybenzohydrazide, all crystallize in the
same space group (P21/c), (I) and (II) also being isomorphous.
In the present work, we report the synthesis and crystal
structures of three new Schiff base compounds formed by the
reaction of 4-hydroxybenzohydrazide with 4-chlorobenz-
aldehyde [(E)-N0-(4-chlorobenzylidene)-4-hydroxybenzohydra-
zide, (I)], 4-bromobenzaldehyde [(E)-N0-(4-bromobenzyl-
idene)-4-hydroxybenzohydrazide, (II)] and 4-diethylamino-
benzaldehyde {(E)-N0-[4-(dimethylamino)benzylidene]-4-hy-
droxybenzohydrazide, (III)}.
In all three compounds, the conformation about the C
N
bond is E. The molecules of (I) and (II) are relatively planar,
with dihedral angles between the two benzene rings of
5.75 (12) and 9.81 (17)ꢀ, respectively. In (III), however, the
same angle is 77.27 (9)ꢀ. In the crystal structures of (I) and
(II), two-dimensional slab-like networks extending in the a
and c directions are formed via N—Hꢁ ꢁ ꢁO and O—Hꢁ ꢁ ꢁO
hydrogen bonds. The molecules stack head-to-tail via ꢀ–ꢀ
interactions involving the aromatic rings [centroid–centroid
˚
˚
distance = 3.7622 (14) A in (I) and 3.8021 (19) A in (II)]. In
(III), undulating two-dimensional networks extending in the b
and c directions are formed via N—Hꢁ ꢁ ꢁO and O—Hꢁ ꢁ ꢁO
hydrogen bonds. The molecules stack head-to-head via ꢀ–ꢀ
interactions involving inversion-related benzene rings [cen-
˚
troid–centroid distances = 3.6977 (12) and 3.8368 (11) A].
Comment
The condensation reaction of aromatic aldehydes with
primary amines can be used to form a huge variety of Schiff
bases. Such compounds have been intensely studied due to
their ease of synthesis, versatile structures and wide applica-
tions (Sigman & Jacobsen, 1998; Akitsu & Einaga, 2006;
Pradeep, 2005; Butcher et al., 2005). Furthermore, Schiff bases
have also been employed as ligands for the complexation of
metal ions (Kumar et al., 2009). The excellent antibacterial and
antitumour properties of such compounds have attracted
much interest over the years (Hodnett & Mooney, 1970;
Bahner et al., 1968; Merchant & Chothia, 1970). Hydrazone
The molecular structure of (I) is illustrated in Fig. 1. The
two benzene rings, A (C1–C6) and B (C9–C14), are almost
coplanar, with a dihedral angle between the ring planes of
5.75 (12)ꢀ. The molecule has an E conformation about the
C8 N2 bond. The mean plane of the N2—N1—C7 O1
˚
segment [maximum deviation = 0.003 (2) A for atom O1] is
o408 # 2012 International Union of Crystallography
doi:10.1107/S0108270112038462
Acta Cryst. (2012). C68, o408–o412

organic compounds
Figure 1
A view of the molecular structure of (I), showing the atom-numbering
scheme. Displacement ellipsoids are drawn at the 50% probability level.
Figure 3
A view of the molecular structure of (II), showing the atom-numbering
scheme. Displacement ellipsoids are drawn at the 50% probability level.
Figure 4
A view of the molecular structure of (III), showing the atom-numbering
scheme. Displacement ellipsoids are drawn at the 50% probability level.
In the crystal structure of (II), molecules are also linked by
N—Hꢁ ꢁ ꢁO and O—Hꢁ ꢁ ꢁO hydrogen bonds (Table 2) to form
two-dimensional slab-like networks propagating in the a and c
directions. These networks are slightly further apart than
those in (I), with the shortest C13—H13ꢁ ꢁ ꢁO2i [symmetry
1
2
1
2
˚
code: (i) ꢂx, y ꢂ , ꢂz + ] Hꢁ ꢁ ꢁA distance being 2.65 A,
˚
compared with 2.52 A in (I). Hence, no significant C—Hꢁ ꢁ ꢁO
interactions are present.
In (I) and (II), molecules stack head-to-tail via ꢀ–ꢀ inter-
actions involving the aromatic rings. The centroid–centroid
Figure 2
A view, along the c axis, of the crystal packing of (I). O—Hꢁ ꢁ ꢁO and N—
Hꢁ ꢁ ꢁO hydrogen bonds are shown as dashed lines (see Table 1 for
details). H atoms not involved in these interactions have been omitted for
clarity.
ii
˚
distance in (I) is 3.7622 (14) A [Cg1ꢁ ꢁ ꢁCg2 , where Cg1 and
Cg2 are the centroids of the C1–C6 and C9–C14 rings,
respectively; symmetry code: (ii) x ꢂ 1, ꢂy + 12, z ꢂ ]. In (II),
1
2
˚
the same distance is 3.8021 (19) A.
inclined to rings A and B by 28.51 (15) and 22.77 (15)ꢀ,
respectively, while the C7—N1—N2 C8 torsion angle is
166.6 (2)ꢀ.
In the crystal structure of (I), molecules are linked by N—
Hꢁ ꢁ ꢁO and O—Hꢁ ꢁ ꢁO hydrogen bonds (Table 1) to form two-
dimensional slab-like networks propagating in the a and c
directions (Fig. 2). These networks are linked via weak C—
Hꢁ ꢁ ꢁO interactions to form a three-dimensional structure
(Table 1).
The molecular structure of (II), illustrated in Fig. 3, is very
similar to that of (I) as they are isomorphous. Here the two
benzene rings, A (C1–C6) and B (C9–C14), are inclined to one
another by 9.81 (17)ꢀ. The mean plane of the N2—N1—
The molecular structure of (III) is illustrated in Fig. 4. The
molecule has an E conformation about the C8 N2 bond, with
the two benzene ring planes, A (C1–C6) and B (C9–C14),
inclined to one another by 77.27 (9)ꢀ, compared with 5.75 (12)ꢀ
in (I) and 9.81 (17)ꢀ in (II). The mean plane of the N2—N1—
˚
C7 O1 segment [maximum deviation = 0.015 (2) A for atom
N1] is inclined to rings A and B by 36.85 (11) and 40.57 (11)ꢀ,
respectively. Again, these angles are much larger than those
observed in (I) and (II), while the C7—N1—N2 C8 torsion
angle is smaller at 151.69 (17)ꢀ.
In the crystal structure of (III), molecules are linked by N—
Hꢁ ꢁ ꢁO and O—Hꢁ ꢁ ꢁO hydrogen bonds to form undulating
two-dimensional networks extending in the b and c directions.
These networks are stabilized by C—Hꢁ ꢁ ꢁO hydrogen bonds
(Fig. 5 and Table 3).
˚
C7 O1 segment [maximum deviation = 0.006 (3) A for atom
C7] is inclined to rings A and B by 28.29 (19) and 18.7 (2)ꢀ,
respectively, and the C7—N1—N2 C8 torsion angle is
169.0 (3)ꢀ.
In (III), the molecules stack head-to-head via ꢀ–ꢀ inter-
actions involving inversion-related benzene rings, with
ꢃ
Acta Cryst. (2012). C68, o408–o412
Subashini et al.
C14H11ClN2O2 and two analogues o409

organic compounds
˚
centroid distances vary between 3.6701 (11) A in (V) to
˚
3.9185 (7) A in (VII)].
Experimental
Compound (I) was prepared by the reaction of 4-hydroxybenzo-
hydrazide with 4-chlorobenzaldehyde (molar ratio 1:1) in methanol.
The reaction mixture was heated and refluxed for 4 h and then
filtered. Compounds (II) and (III) were prepared in the same
manner, using 4-hydroxybenzohydrazide and 4-bromobenzaldehyde
for (II), and 4-hydroxybenzohydrazide and 4-diethylaminobenz-
aldehyde for (III). In each case, crystals suitable for X-ray diffraction
analysis were formed by slow evaporation of the solvent at room
temperature over a period of several days.
Figure 5
Aview, along the c axis, of the crystal packing of (III). O—Hꢁ ꢁ ꢁO and N—
Hꢁ ꢁ ꢁO hydrogen bonds and C—Hꢁ ꢁ ꢁO interactions are shown as dashed
lines (see Table 3 for details). H atoms not involved in these interactions
have been omitted for clarity.
Compound (I)
Crystal data
3
˚
C14H11ClN2O2
Mr = 274.70
V = 1246.73 (16) A
Z = 4
centroid–centroid distances of 3.6977 (12) [Cg2ꢁ ꢁ ꢁCg2iii, Cg
defined as for (I); symmetry code: (iii) ꢂx, ꢂy + 2, ꢂz] and
Monoclinic, P21=c
Mo Kꢂ radiation
ꢃ = 0.31 mmꢂ1
T = 173 K
0.40 ꢄ 0.27 ꢄ 0.05 mm
˚
a = 7.4201 (6) A
˚
b = 24.1098 (14) A
iv
˚
3.8368 (11) A [Cg1ꢁ ꢁ ꢁCg1 ; symmetry code: (iv) ꢂx + 1, ꢂy + 1,
˚
c = 7.8614 (6) A
ꢁ = 117.566 (6)ꢀ
ꢂz].
A search of the Cambridge Structural Database (CSD,
Version 5.33, Update 3, May 2012; Allen, 2002) gave more
than 400 hits for the benzylidenebenzohydrazide substructure,
excluding metal complexes. Of these there were 59 hits for
benzylidene-4-hydroxybenzohydrazide and an even smaller
number for 4-substituted benzylidene-4-hydroxybenzo-
hydrazides. This last search included four compounds where
the substituent is comparable in size with those in (I)–(III).
They include the 4-nitro derivative, (IV) (Li & Ban, 2009b),
the 4-methoxy derivative, (V) (Shi, 2009), and the methanol
solvate of the 4-hydroxy derivative, (VI) (Li & Ban, 2009a),
which all crystallize in centrosymmetric space groups, and
finally the hemihydrate of the 4-dimethylamino derivative,
(VII) (Liu, 2010), which crystallizes in the chiral monoclinic
space group P21. Compound (III), the 4-diethylamino deri-
vative, was prepared in the hope that it too would crystallize in
a chiral or noncentrosymmetric space group, but this was not
to be the case.
Data collection
Stoe IPDS II diffractometer
Absorption correction: multi-scan
(MULABS in PLATON; Spek,
2009)
7727 measured reflections
2336 independent reflections
1698 reflections with I > 2ꢄ(I)
Rint = 0.060
Tmin = 0.879, Tmax = 1.000
Refinement
R[F2 > 2ꢄ(F2)] = 0.045
wR(F2) = 0.104
S = 1.02
2336 reflections
180 parameters
H atoms treated by a mixture of
independent and constrained
refinement
ꢂ3
˚
Áꢅmax = 0.19 e A
ꢂ3
˚
Áꢅmin = ꢂ0.29 e A
Compound (II)
Crystal data
3
˚
V = 1280.60 (19) A
Z = 4
C14H11BrN2O2
Mr = 319.16
Monoclinic, P21=c
Mo Kꢂ radiation
ꢃ = 3.21 mmꢂ1
T = 293 K
0.42 ꢄ 0.27 ꢄ 0.23 mm
In compounds (IV), (VI) and (VII), the molecules are
relatively planar, with the benzene ring planes being inclined
to one another by 2.54 (7), 7.21 (7) and 7.67 (13)ꢀ, respec-
tively. In (V) this same angle is larger, 46.56 (7)ꢀ, but still
smaller than that found for (III) [77.27 (9)ꢀ].
˚
a = 7.6046 (7) A
˚
b = 24.2250 (18) A
˚
c = 7.9230 (7) A
ꢁ = 118.673 (9)ꢀ
Data collection
In the crystal structures of (IV) and (V), O—Hꢁ ꢁ ꢁO and
N—Hꢁ ꢁ ꢁO hydrogen bonds lead to the formation of two-
dimensional networks, while for (VI) similar interactions lead
to the formation of a three-dimensional structure. Compound
(VII) crystallized with two independent molecules and one
water molecule per asymmetric unit, and the water molecule
links the two molecules via O—Hꢁ ꢁ ꢁO hydrogen bonds. These
units are then linked via N—Hꢁ ꢁ ꢁO and O—Hꢁ ꢁ ꢁO hydrogen
bonds to form a three-dimensional structure. As in the crystal
structures of (I)–(III), there are also weak ꢀ–ꢀ stacking
interactions in the crystal structures of (IV)–(VII) [centroid–
Stoe IPDS I diffractometer
Absorption correction: multi-scan
(MULABS in PLATON; Spek,
2009)
10103 measured reflections
2509 independent reflections
1626 reflections with I > 2ꢄ(I)
Rint = 0.054
Tmin = 0.783, Tmax = 1.000
Refinement
R[F2 > 2ꢄ(F2)] = 0.034
wR(F2) = 0.078
S = 0.94
2509 reflections
180 parameters
2 restraints
H atoms treated by a mixture of
independent and constrained
refinement
ꢂ3
˚
Áꢅmax = 0.45 e A
ꢂ3
˚
Áꢅmin = ꢂ0.46 e A
ꢃ
o410 Subashini et al. C14H11ClN2O2 and two analogues
Acta Cryst. (2012). C68, o408–o412

organic compounds
Table 1
Hydrogen-bond geometry (A, ) for (I).
Data collection: X-AREA (Stoe & Cie, 2009) for (I) and (III);
EXPOSE in IPDS I Bedienungshandbuch (Stoe & Cie, 2004) for (II).
Cell refinement: X-AREA for (I) and (III); CELL in IPDS I
Bedienungshandbuch for (II). Data reduction: X-RED32 (Stoe & Cie,
2009) for (I) and (III); INTEGRATE in IPDS I Bedienungshandbuch
for (II). For all compounds, program(s) used to solve structure:
SHELXS97 (Sheldrick, 2008); program(s) used to refine structure:
SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek,
2009) and Mercury (Macrae et al., 2008); software used to prepare
material for publication: SHELXL97, PLATON and publCIF
(Westrip, 2010).
ꢀ
˚
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
N1—H1Nꢁ ꢁ ꢁO1i
O2—H2Oꢁ ꢁ ꢁO1ii
C13—H13ꢁ ꢁ ꢁO2iii
0.90 (3)
0.85 (3)
0.95
2.08 (3)
1.94 (3)
2.52
2.960 (2)
2.778 (2)
3.456 (3)
165 (3)
171 (3)
169
1
2
1
2
1
2
1
2
Symmetry codes: (i) x; ꢂy þ ; z ꢂ ; (ii) x ꢂ 1; y; z ꢂ 1; (iii) ꢂx; y ꢂ ; ꢂz þ .
Table 2
Hydrogen-bond geometry (A, ) for (II).
ꢀ
˚
AS thanks the University Grants Commission, India, for the
award of a Research Fellowship in Sciences for Meritorious
Students [File No. 4-1/2008 (BSR)]. HSE thanks the XRD
ˆ
Application Laboratory, CSEM, Neuchatel, for access to the
X-ray diffraction equipment.
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
N1—H1Nꢁ ꢁ ꢁO1i
0.84 (2)
0.79 (3)
2.19 (3)
2.02 (3)
2.983 (3)
2.788 (3)
158 (3)
164 (3)
O2—H2Oꢁ ꢁ ꢁO1ii
1
2
1
2
Symmetry codes: (i) x; ꢂy þ ; z ꢂ ; (ii) x ꢂ 1; y; z ꢂ 1.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: YF3017). Services for accessing these data are
described at the back of the journal.
Table 3
Hydrogen-bond geometry (A, ) for (III).
ꢀ
˚
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
N1—H1Nꢁ ꢁ ꢁO1i
N1—H1Nꢁ ꢁ ꢁO2ii
O2—H2Oꢁ ꢁ ꢁN2iii
C10—H10ꢁ ꢁ ꢁO2iv
0.87 (3)
0.87 (3)
0.93 (3)
0.95
2.21 (2)
2.41 (2)
1.86 (3)
2.60
2.859 (2)
3.119 (2)
2.780 (2)
3.496 (2)
131.6 (18)
138.6 (19)
174 (3)
158
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3
˚
V = 1697.6 (2) A
Z = 4
C18H21N3O2
Mr = 311.38
Monoclinic, P21=c
Mo Kꢂ radiation
ꢃ = 0.08 mmꢂ1
T = 173 K
0.45 ꢄ 0.28 ꢄ 0.10 mm
˚
a = 14.8338 (10) A
˚
b = 12.4571 (11) A
˚
c = 9.2935 (6) A
ꢁ = 98.687 (5)ꢀ
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Stoe IPDS II diffractometer
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Absorption correction: multi-scan
(MULABS in PLATON; Spek,
2009)
3199 independent reflections
2183 reflections with I > 2ꢄ(I)
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Qu, L.-Z. & Cao, G.-B. (2009). Acta Cryst. E65, o1705.
Rajput, S. S. (2012). Int. J. Pharm. Pharm. Sci. 4(2), 164–167.
Serbutoviez, C., Bosshard, C., Knopfle, G., Wyss, P., Pretre, P., Gunter, P.,
Schenk, K., Solari, E. & Chapuis, G. (1995). Chem. Mater. 7, 1198–1206.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Refinement
R[F2 > 2ꢄ(F2)] = 0.052
wR(F2) = 0.101
S = 1.01
3199 reflections
219 parameters
H atoms treated by a mixture of
independent and constrained
refinement
ꢂ3
˚
Áꢅmax = 0.17 e A
ꢂ3
˚
Áꢅmin = ꢂ0.17 e A
For all three compounds, the H atoms could be located in differ-
ence Fourier maps. The N- and O-bound H atoms were refined freely
for (I) and (III), but were refined with distance restraints for (II)
˚
[O—H = 0.82 (2) A and N—H = 0.86 (2) A]. C-bound H atoms were
˚
included in calculated positions and treated as riding atoms, with
˚
˚
C—H = 0.93 A for CH in (II) but 0.95 A in (I) and (III), 0.99 A for
˚
˚
CH2 and 0.98 A for CH3 H atoms, and with Uiso(H) = kUeq(C), where
k = 1.5 for CH3 H atoms or 1.2 otherwise.
ꢃ
Acta Cryst. (2012). C68, o408–o412
Subashini et al.
C14H11ClN2O2 and two analogues o411

organic compounds
Shi, D.-H. (2009). Acta Cryst. E65, o2107.
Sigman, M. S. & Jacobsen, E. N. (1998). J. Am. Chem. Soc. 120, 4901–4902.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Stoe & Cie (2004). IPDS I Bedienungshandbuch. Stoe & Cie GmbH,
Darmstadt, Germany.
Stoe & Cie (2009). X-AREA and X-RED32. Stoe & Cie GmbH, Darmstadt,
Germany.
Sugano, K., Hamada, H., Machida, M. & Ushio, H. (2009). J. Biomol. Screen. 6,
189–196.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
ꢃ
o412 Subashini et al. C14H11ClN2O2 and two analogues
Acta Cryst. (2012). C68, o408–o412

supplementary materials
supplementary materials
Acta Cryst. (2012). C68, o408–o412 [doi:10.1107/S0108270112038462]
(E)-N′-(4-Chlorobenzylidene)-, (E)-N′-(4-bromobenzylidene)- and (E)-N′-[4-(di-
ethylamino)benzylidene]- derivatives of 4-hydroxybenzohydrazide
Ashokkumar Subashini, Kandasamy Ramamurthi and Helen Stoeckli-Evans
(I) (E)-N′-(4-Chlorobenzylidene)-4-hydroxybenzohydrazide
Crystal data
C14H11ClN2O2
Mr = 274.70
F(000) = 568
Dx = 1.464 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 5627 reflections
θ = 1.7–26.1°
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 7.4201 (6) Å
b = 24.1098 (14) Å
c = 7.8614 (6) Å
β = 117.566 (6)°
V = 1246.73 (16) Å3
Z = 4
µ = 0.31 mm−1
T = 173 K
Plate, colourless
0.40 × 0.27 × 0.05 mm
Data collection
Stoe IPDS II
diffractometer
Radiation source: fine-focus sealed tube
Plane graphite monochromator
φ and ω scans
7727 measured reflections
2336 independent reflections
1698 reflections with I > 2σ(I)
Rint = 0.060
θ
max = 25.6°, θmin = 1.7°
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 2009)
h = −8→9
k = −26→29
l = −9→9
T
min = 0.879, Tmax = 1.000
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.045
wR(F2) = 0.104
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.02
2336 reflections
180 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.054P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.19 e Å−3
Δρmin = −0.29 e Å−3
Acta Cryst. (2012). C68, o408–o412
sup-1

supplementary materials
Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are
estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the
estimation of distances, angles and torsion angles
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Cl1
O1
0.90972 (10)
0.1887 (2)
−0.5023 (2)
0.1759 (3)
0.3041 (3)
−0.0290 (3)
−0.0411 (3)
−0.1951 (3)
−0.3424 (3)
−0.3281 (3)
−0.1714 (3)
0.1238 (3)
0.3126 (3)
0.4511 (3)
0.5956 (3)
0.7362 (3)
0.7304 (3)
0.5869 (4)
0.4478 (3)
0.156 (4)
0.01847 (3)
0.31605 (6)
0.39208 (7)
0.23805 (8)
0.20974 (7)
0.31607 (9)
0.37364 (9)
0.39843 (9)
0.36553 (9)
0.30811 (9)
0.28392 (9)
0.29075 (9)
0.15750 (9)
0.12285 (9)
0.14712 (9)
0.11509 (10)
0.05841 (10)
0.03248 (9)
0.06551 (9)
0.2231 (11)
0.39610
1.18343 (9)
0.56250 (19)
−0.2418 (2)
0.3947 (2)
0.5612 (2)
0.2243 (3)
0.2069 (3)
0.0461 (3)
−0.0969 (3)
−0.0849 (3)
0.0757 (3)
0.4069 (3)
0.5409 (3)
0.7012 (3)
0.8705 (3)
1.0174 (3)
0.9964 (3)
0.8322 (3)
0.6846 (3)
0.282 (4)
0.30580
0.0485 (2)
0.0288 (5)
0.0334 (5)
0.0262 (5)
0.0262 (5)
0.0237 (6)
0.0268 (6)
0.0293 (6)
0.0268 (6)
0.0281 (7)
0.0270 (6)
0.0246 (6)
0.0270 (6)
0.0273 (7)
0.0311 (7)
0.0335 (7)
0.0309 (7)
0.0372 (7)
0.0341 (7)
0.049 (8)*
0.0320*
O2
N1
N2
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
H1N
H2
0.05680
H2O
H3
−0.590 (5)
−0.20030
−0.42430
−0.16110
0.22810
0.3679 (13)
0.43770
−0.309 (4)
0.03330
0.067 (10)*
0.0350*
H5
0.28570
−0.18520
0.08430
0.0340*
H6
0.24460
0.0320*
H8
0.14090
0.42040
0.0320*
H10
H11
H13
H14
0.59730
0.18630
0.88490
0.0370*
0.83570
0.13200
1.13150
0.0400*
0.58350
−0.00680
0.82060
0.0450*
0.34880
0.04850
0.57040
0.0410*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Cl1
O1
O2
N1
0.0508 (4)
0.0294 (8)
0.0295 (8)
0.0267 (9)
0.0384 (4)
0.0264 (8)
0.0269 (8)
0.0262 (10)
0.0449 (4)
0.0163 (3)
0.0002 (6)
0.0024 (7)
0.0062 (8)
0.0126 (3)
0.0078 (7)
0.0047 (7)
0.0090 (8)
0.0144 (3)
−0.0029 (6)
0.0052 (7)
0.0026 (8)
0.0249 (8)
0.0325 (8)
0.0228 (9)
Acta Cryst. (2012). C68, o408–o412
sup-2

supplementary materials
N2
C1
0.0257 (9)
0.0273 (10)
0.0246 (11)
0.0250 (11)
0.0215 (11)
0.0282 (12)
0.0267 (12)
0.0202 (11)
0.0268 (12)
0.0276 (12)
0.0274 (12)
0.0208 (11)
0.0296 (13)
0.0298 (13)
0.0211 (12)
0.0268 (12)
0.0245 (9)
0.0053 (8)
0.0003 (8)
−0.0028 (8)
−0.0003 (9)
0.0030 (9)
0.0000 (9)
0.0018 (9)
−0.0012 (9)
0.0007 (9)
0.0006 (9)
0.0006 (10)
0.0027 (10)
0.0055 (10)
0.0022 (10)
−0.0020 (10)
0.0106 (7)
0.0126 (9)
0.0105 (9)
0.0148 (10)
0.0093 (9)
0.0087 (9)
0.0104 (9)
0.0106 (9)
0.0112 (9)
0.0130 (9)
0.0114 (10)
0.0077 (10)
0.0147 (10)
0.0170 (12)
0.0103 (10)
0.0049 (7)
−0.0001 (8)
−0.0022 (8)
0.0026 (9)
0.0052 (9)
−0.0011 (9)
−0.0005 (8)
0.0009 (9)
−0.0007 (9)
0.0030 (9)
−0.0008 (9)
0.0028 (10)
0.0080 (9)
0.0012 (10)
−0.0009 (10)
0.0231 (10)
0.0251 (11)
0.0316 (11)
0.0242 (10)
0.0260 (11)
0.0268 (11)
0.0211 (10)
0.0231 (10)
0.0242 (11)
0.0361 (12)
0.0318 (12)
0.0302 (12)
0.0432 (13)
0.0321 (12)
0.0252 (10)
0.0282 (11)
0.0343 (11)
0.0254 (10)
0.0274 (11)
0.0306 (11)
0.0257 (10)
0.0293 (11)
0.0307 (11)
0.0313 (11)
0.0311 (11)
0.0329 (12)
0.0436 (13)
0.0367 (12)
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
Geometric parameters (Å, º)
Cl1—C12
O1—C7
O2—C4
O2—H2O
N1—N2
N1—C7
N2—C8
N1—H1N
C1—C7
C1—C6
C1—C2
C2—C3
C3—C4
C4—C5
C5—C6
C8—C9
1.746 (2)
C9—C14
1.388 (3)
1.247 (3)
1.365 (3)
0.85 (3)
C9—C10
C10—C11
C11—C12
C12—C13
C13—C14
C2—H2
1.394 (3)
1.380 (3)
1.375 (3)
1.385 (3)
1.392 (3)
0.9500
1.390 (2)
1.344 (3)
1.275 (3)
0.90 (3)
C3—H3
0.9500
1.487 (3)
1.393 (3)
1.394 (3)
1.387 (3)
1.397 (3)
1.388 (3)
1.388 (3)
1.464 (3)
C5—H5
0.9500
C6—H6
0.9500
C8—H8
0.9500
C10—H10
C11—H11
C13—H13
C14—H14
0.9500
0.9500
0.9500
0.9500
C4—O2—H2O
N2—N1—C7
N1—N2—C8
N2—N1—H1N
C7—N1—H1N
C2—C1—C6
C2—C1—C7
C6—C1—C7
C1—C2—C3
C2—C3—C4
O2—C4—C3
O2—C4—C5
C3—C4—C5
C4—C5—C6
C1—C6—C5
108 (2)
Cl1—C12—C13
Cl1—C12—C11
C11—C12—C13
C12—C13—C14
C9—C14—C13
C1—C2—H2
C3—C2—H2
C2—C3—H3
C4—C3—H3
C4—C5—H5
C6—C5—H5
C1—C6—H6
C5—C6—H6
N2—C8—H8
C9—C8—H8
119.57 (18)
118.54 (17)
121.9 (2)
118.2 (2)
121.2 (2)
120.00
119.41 (16)
114.79 (16)
117.3 (18)
121.7 (17)
118.9 (2)
119.29 (19)
121.65 (19)
120.5 (2)
120.00
120.00
120.00
119.8 (2)
120.00
117.36 (19)
122.3 (2)
120.00
119.00
120.3 (2)
119.00
119.1 (2)
120.00
121.3 (2)
120.00
Acta Cryst. (2012). C68, o408–o412
sup-3

supplementary materials
N1—C7—C1
O1—C7—C1
O1—C7—N1
N2—C8—C9
C8—C9—C10
C8—C9—C14
C10—C9—C14
C9—C10—C11
C10—C11—C12
115.78 (18)
121.5 (2)
C9—C10—H10
C11—C10—H10
C10—C11—H11
C12—C11—H11
C12—C13—H13
C14—C13—H13
C9—C14—H14
C13—C14—H14
120.00
120.00
120.00
120.00
121.00
121.00
119.00
119.00
122.62 (19)
120.78 (19)
120.38 (19)
120.84 (19)
118.7 (2)
120.9 (2)
119.1 (2)
C7—N1—N2—C8
N2—N1—C7—O1
N2—N1—C7—C1
N1—N2—C8—C9
C6—C1—C2—C3
C7—C1—C2—C3
C2—C1—C6—C5
C7—C1—C6—C5
C2—C1—C7—O1
C2—C1—C7—N1
C6—C1—C7—O1
C6—C1—C7—N1
C1—C2—C3—C4
C2—C3—C4—O2
C2—C3—C4—C5
166.6 (2)
1.2 (4)
O2—C4—C5—C6
C3—C4—C5—C6
C4—C5—C6—C1
−174.0 (2)
3.2 (4)
−174.4 (2)
176.1 (2)
1.4 (4)
0.0 (4)
N2—C8—C9—C10
N2—C8—C9—C14
C8—C9—C10—C11
C14—C9—C10—C11
C8—C9—C14—C13
C10—C9—C14—C13
C9—C10—C11—C12
C10—C11—C12—Cl1
C10—C11—C12—C13
Cl1—C12—C13—C14
C11—C12—C13—C14
C12—C13—C14—C9
−8.9 (4)
174.2 (2)
−175.4 (2)
1.6 (4)
−173.5 (2)
−2.3 (4)
172.4 (2)
26.1 (4)
176.2 (2)
−0.8 (4)
−1.1 (4)
179.9 (2)
−0.3 (4)
−179.1 (2)
1.0 (4)
−158.2 (2)
−148.6 (2)
27.1 (3)
1.8 (4)
173.2 (2)
−4.2 (4)
−0.5 (4)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1N···O1i
O2—H2O···O1ii
C13—H13···O2iii
0.90 (3)
0.85 (3)
0.95
2.08 (3)
1.94 (3)
2.52
2.960 (2)
2.778 (2)
3.456 (3)
165 (3)
171 (3)
169
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x−1, y, z−1; (iii) −x, y−1/2, −z+1/2.
(II) (E)-N′-(4-Bromobenzylidene)-4-hydroxybenzohydrazide
Crystal data
C14H11BrN2O2
Mr = 319.16
F(000) = 640
Dx = 1.655 Mg m−3
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 7.6046 (7) Å
b = 24.2250 (18) Å
c = 7.9230 (7) Å
β = 118.673 (9)°
V = 1280.60 (19) Å3
Z = 4
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 6613 reflections
θ = 2.5–26.0°
µ = 3.21 mm−1
T = 293 K
Rod, colourless
0.42 × 0.27 × 0.23 mm
Acta Cryst. (2012). C68, o408–o412
sup-4

supplementary materials
Data collection
Stoe IPDS I
10103 measured reflections
diffractometer
2509 independent reflections
1626 reflections with I > 2σ(I)
Rint = 0.054
Radiation source: fine-focus sealed tube
Graphite monochromator
φ rotation scans
θ
max = 26.0°, θmin = 3.1°
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 2009)
h = −9→9
k = −29→29
l = −9→9
T
min = 0.783, Tmax = 1.000
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.034
wR(F2) = 0.078
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 0.94
2509 reflections
180 parameters
2 restraints
Primary atom site location: structure-invariant
direct methods
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0383P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.45 e Å−3
Δρmin = −0.46 e Å−3
Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are
estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the
estimation of distances, angles and torsion angles
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is
used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based
on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Br1
O1
O2
N1
N2
C1
0.91542 (6)
0.1703 (3)
−0.5204 (3)
0.1521 (3)
0.2816 (3)
−0.0515 (4)
−0.0637 (4)
−0.2154 (4)
−0.3638 (4)
−0.3507 (4)
−0.1950 (4)
0.1012 (4)
0.2956 (4)
0.4356 (4)
0.5727 (4)
0.7139 (5)
0.7165 (4)
0.01798 (1)
0.31403 (7)
0.38918 (9)
0.23619 (10)
0.20835 (9)
0.31330 (10)
0.37043 (11)
0.39459 (11)
0.36263 (11)
0.30585 (11)
0.28173 (11)
0.28873 (11)
0.15655 (11)
0.12286 (11)
0.14700 (12)
0.11593 (12)
0.05989 (11)
1.19850 (5)
0.5594 (3)
−0.2416 (3)
0.3944 (3)
0.5592 (3)
0.2231 (4)
0.2042 (4)
0.0444 (4)
−0.0976 (4)
−0.0841 (4)
0.0758 (4)
0.4048 (4)
0.5400 (4)
0.7001 (4)
0.8713 (4)
1.0172 (4)
0.9937 (4)
0.0724 (1)
0.0440 (6)
0.0520 (7)
0.0394 (7)
0.0380 (7)
0.0338 (8)
0.0391 (8)
0.0455 (9)
0.0384 (8)
0.0413 (9)
0.0406 (8)
0.0349 (8)
0.0398 (9)
0.0375 (8)
0.0479 (9)
0.0516 (10)
0.0461 (10)
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
Acta Cryst. (2012). C68, o408–o412
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supplementary materials
C13
C14
H1N
H2
0.5815 (5)
0.4415 (5)
0.123 (4)
0.03210
0.03438 (12)
0.06631 (12)
0.2219 (11)
0.39240
0.8286 (4)
0.6821 (5)
0.288 (3)
0.30080
−0.308 (4)
0.03100
−0.18180
0.08460
0.42160
0.88730
1.13100
0.81530
0.56850
0.0542 (11)
0.0530 (10)
0.043 (9)*
0.0470*
H2O
H3
−0.595 (4)
−0.21900
−0.44580
−0.18650
0.21470
0.3659 (10)
0.43280
0.049 (10)*
0.0550*
H5
0.28400
0.0500*
H6
0.24340
0.0490*
H8
0.14000
0.0480*
H10
H11
H13
H14
0.56860
0.18490
0.0570*
0.80710
0.13260
0.0620*
0.58400
−0.00370
0.04940
0.0650*
0.34880
0.0640*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Br1
O1
O2
N1
N2
C1
0.0706 (2)
0.0577 (2)
0.0638 (2)
0.0282 (10)
0.0421 (12)
0.0261 (12)
0.0304 (12)
0.0284 (14)
0.0346 (15)
0.0493 (18)
0.0329 (15)
0.0347 (15)
0.0382 (16)
0.0326 (15)
0.0361 (16)
0.0356 (15)
0.0410 (17)
0.0375 (17)
0.0500 (19)
0.057 (2)
0.0230 (2)
0.0120 (2)
0.0203 (2)
0.0452 (11)
0.0457 (12)
0.0429 (13)
0.0357 (12)
0.0323 (15)
0.0352 (14)
0.0457 (16)
0.0344 (14)
0.0367 (15)
0.0403 (15)
0.0328 (14)
0.0349 (15)
0.0353 (14)
0.0522 (18)
0.0523 (18)
0.0451 (17)
0.060 (2)
0.0426 (10)
0.0423 (12)
0.0398 (13)
0.0402 (13)
0.0346 (13)
0.0351 (13)
0.0308 (14)
0.0393 (15)
0.0378 (15)
0.0312 (13)
0.0354 (14)
0.0399 (16)
0.0364 (13)
0.0337 (14)
0.0459 (17)
0.0404 (16)
0.0307 (14)
0.0381 (15)
0.0005 (9)
0.0049 (9)
−0.0044 (9)
0.0085 (10)
0.0022 (11)
0.0074 (10)
0.0013 (11)
−0.0025 (12)
0.0064 (13)
0.0050 (12)
−0.0022 (12)
−0.0035 (12)
0.0015 (12)
−0.0003 (12)
0.0065 (12)
0.0019 (13)
−0.0002 (14)
0.0098 (14)
0.0049 (14)
−0.0024 (15)
0.0050 (10)
0.0103 (11)
0.0070 (10)
0.0009 (11)
−0.0056 (12)
−0.0006 (12)
0.0021 (12)
0.0018 (12)
0.0001 (12)
−0.0016 (11)
0.0016 (12)
0.0030 (12)
0.0043 (13)
0.0010 (14)
0.0075 (13)
0.0046 (14)
−0.0031 (14)
0.0002 (10)
0.0090 (11)
0.0097 (10)
0.0098 (12)
0.0067 (12)
0.0143 (14)
0.0093 (12)
0.0053 (13)
0.0091 (13)
0.0126 (12)
0.0103 (13)
0.0129 (12)
0.0089 (15)
0.0062 (14)
0.0207 (15)
0.0162 (17)
0.0104 (15)
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
0.0520 (18)
0.0510 (19)
Geometric parameters (Å, º)
Br1—C12
O1—C7
O2—C4
O2—H2O
N1—N2
N1—C7
N2—C8
N1—H1N
C1—C7
C1—C6
C1—C2
1.897 (3)
C9—C14
1.380 (4)
1.239 (3)
1.353 (4)
0.79 (3)
C9—C10
C10—C11
C11—C12
C12—C13
C13—C14
C2—H2
1.383 (4)
1.366 (4)
1.372 (4)
1.363 (4)
1.376 (5)
0.9300
1.377 (3)
1.344 (4)
1.275 (3)
0.84 (2)
C3—H3
0.9300
1.473 (4)
1.384 (4)
1.390 (4)
C5—H5
0.9300
C6—H6
0.9300
C8—H8
0.9300
Acta Cryst. (2012). C68, o408–o412
sup-6

supplementary materials
C2—C3
C3—C4
C4—C5
C5—C6
C8—C9
1.369 (4)
1.386 (4)
1.380 (4)
1.382 (4)
1.454 (4)
C10—H10
C11—H11
C13—H13
C14—H14
0.9300
0.9300
0.9300
0.9300
C4—O2—H2O
N2—N1—C7
N1—N2—C8
N2—N1—H1N
C7—N1—H1N
C2—C1—C6
C2—C1—C7
C6—C1—C7
C1—C2—C3
C2—C3—C4
O2—C4—C3
O2—C4—C5
C3—C4—C5
C4—C5—C6
C1—C6—C5
N1—C7—C1
O1—C7—C1
O1—C7—N1
N2—C8—C9
C8—C9—C10
C8—C9—C14
C10—C9—C14
C9—C10—C11
C10—C11—C12
106 (2)
Br1—C12—C13
Br1—C12—C11
C11—C12—C13
C12—C13—C14
C9—C14—C13
C1—C2—H2
120.2 (2)
118.1 (2)
121.7 (3)
118.4 (3)
121.4 (3)
120.00
120.00
120.00
120.00
120.00
120.00
119.00
119.00
119.00
119.00
120.00
120.00
120.00
120.00
121.00
121.00
119.00
119.00
120.1 (2)
115.6 (2)
118.4 (19)
120.6 (18)
118.3 (3)
119.2 (2)
122.3 (2)
120.5 (3)
120.6 (3)
117.6 (2)
122.8 (3)
119.6 (3)
119.4 (3)
121.4 (2)
116.0 (2)
121.9 (2)
122.1 (3)
121.1 (3)
120.7 (2)
120.9 (3)
118.3 (3)
120.9 (3)
119.2 (3)
C3—C2—H2
C2—C3—H3
C4—C3—H3
C4—C5—H5
C6—C5—H5
C1—C6—H6
C5—C6—H6
N2—C8—H8
C9—C8—H8
C9—C10—H10
C11—C10—H10
C10—C11—H11
C12—C11—H11
C12—C13—H13
C14—C13—H13
C9—C14—H14
C13—C14—H14
C7—N1—N2—C8
N2—N1—C7—O1
N2—N1—C7—C1
N1—N2—C8—C9
C6—C1—C2—C3
C7—C1—C2—C3
C2—C1—C6—C5
C7—C1—C6—C5
C2—C1—C7—O1
C2—C1—C7—N1
C6—C1—C7—O1
C6—C1—C7—N1
C1—C2—C3—C4
C2—C3—C4—O2
C2—C3—C4—C5
169.0 (3)
1.4 (5)
O2—C4—C5—C6
C3—C4—C5—C6
C4—C5—C6—C1
−174.4 (3)
3.2 (5)
−174.9 (3)
176.4 (3)
0.7 (5)
0.0 (5)
N2—C8—C9—C10
N2—C8—C9—C14
−7.2 (5)
175.9 (3)
−175.3 (3)
1.7 (5)
−173.9 (3)
−1.9 (5)
172.5 (3)
25.6 (5)
C8—C9—C10—C11
C14—C9—C10—C11
C8—C9—C14—C13
C10—C9—C14—C13
C9—C10—C11—C12
C10—C11—C12—Br1
C10—C11—C12—C13
Br1—C12—C13—C14
C11—C12—C13—C14
C12—C13—C14—C9
176.0 (4)
−1.0 (6)
−1.2 (5)
179.7 (3)
−0.1 (6)
−179.0 (3)
0.8 (6)
−158.2 (3)
−148.8 (3)
27.5 (5)
2.6 (5)
173.2 (3)
−4.6 (5)
−0.2 (6)
Acta Cryst. (2012). C68, o408–o412
sup-7

supplementary materials
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1N···O1i
O2—H2O···O1ii
0.84 (2)
0.79 (3)
2.19 (3)
2.02 (3)
2.983 (3)
2.788 (3)
158 (3)
164 (3)
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x−1, y, z−1.
(III) (E)-N′-[4-(Diethylamino)benzylidene]-4-hydroxybenzohydrazide
Crystal data
C18H21N3O2
Mr = 311.38
F(000) = 664
Dx = 1.218 Mg m−3
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 14.8338 (10) Å
b = 12.4571 (11) Å
c = 9.2935 (6) Å
β = 98.687 (5)°
V = 1697.6 (2) Å3
Z = 4
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 7297 reflections
θ = 1.4–26.1°
µ = 0.08 mm−1
T = 173 K
Rod, pale yellow
0.45 × 0.28 × 0.10 mm
Data collection
Stoe IPDS II
diffractometer
Radiation source: fine-focus sealed tube
Plane graphite monochromator
φ and ω scans
15142 measured reflections
3199 independent reflections
2183 reflections with I > 2σ(I)
Rint = 0.084
θ
max = 25.6°, θmin = 1.4°
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 2009)
h = −18→16
k = −15→15
l = −10→11
T
min = 0.868, Tmax = 1.000
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.052
wR(F2) = 0.101
S = 1.01
3199 reflections
Hydrogen site location: inferred from
neighbouring sites
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0447P)2]
where P = (Fo2 + 2Fc2)/3
219 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
(Δ/σ)max < 0.001
Δρmax = 0.17 e Å−3
Δρmin = −0.17 e Å−3
Extinction correction: SHELXL97 (Sheldrick,
2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.0104 (15)
Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are
estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the
estimation of distances, angles and torsion angles
Refinement. The OH and NH H atoms were located in a difference electron-density map and were freely refined. The C-
bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.95, 0.98, and 0.99 Å for CH
(aromatic), CH3, and CH2 H atoms, respectively, with Uiso(H) = kUeq(parent C atom), where k = 1.5 for CH3 H atoms and
k = 1.2 for all other H atoms.
Acta Cryst. (2012). C68, o408–o412
sup-8

supplementary materials
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
O1
0.37129 (10)
0.68902 (9)
0.32947 (11)
0.25433 (11)
−0.15693 (12)
0.46596 (13)
0.49401 (13)
0.56761 (13)
0.61606 (13)
0.58960 (13)
0.51494 (13)
0.38654 (13)
0.18532 (13)
0.09977 (13)
0.08837 (14)
0.00461 (14)
−0.07410 (14)
−0.06237 (14)
0.02219 (14)
−0.16867 (17)
−0.1747 (2)
−0.23686 (15)
−0.28938 (19)
0.3387 (15)
0.46180
0.68546 (10)
0.43456 (11)
0.71351 (12)
0.77393 (12)
0.95604 (13)
0.61330 (14)
0.52351 (15)
0.46261 (15)
0.49196 (14)
0.58214 (14)
0.64178 (15)
0.67424 (14)
0.77041 (15)
0.82317 (14)
0.89382 (15)
0.93608 (15)
0.91120 (15)
0.84009 (16)
0.79891 (16)
1.02374 (18)
0.9610 (3)
0.93648 (18)
0.8349 (2)
0.7028 (17)
0.50400
0.38111 (15)
0.13423 (16)
0.13930 (19)
0.16470 (18)
0.1157 (2)
0.2188 (2)
0.3038 (2)
0.2779 (2)
0.1666 (2)
0.0819 (2)
0.1072 (2)
0.2546 (2)
0.0636 (2)
0.0758 (2)
0.1890 (2)
0.2029 (2)
0.1033 (2)
−0.0101 (3)
−0.0234 (2)
0.2394 (3)
0.3783 (3)
0.0067 (3)
0.0302 (4)
0.050 (3)
0.38080
0.0282 (5)
0.0269 (5)
0.0216 (5)
0.0221 (5)
0.0348 (6)
0.0204 (6)
0.0231 (6)
0.0237 (6)
0.0208 (6)
0.0237 (6)
0.0225 (6)
0.0194 (6)
0.0235 (6)
0.0232 (6)
0.0252 (6)
0.0282 (7)
0.0266 (6)
0.0331 (7)
0.0313 (7)
0.0466 (9)
0.0738 (12)
0.0441 (8)
0.0685 (13)
0.036 (6)*
0.0280*
O2
N1
N2
N22
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
H1N
H2
H2O
H3
0.704 (2)
0.381 (2)
0.203 (3)
0.33570
0.068 (9)*
0.0280*
0.58520
0.40100
H5
0.62290
0.60270
0.00670
0.0290*
H6
0.49670
0.70260
0.04820
0.0270*
H8
0.19050
0.73160
−0.02280
0.25790
0.0280*
H10
H11
H13
H14
H15A
H15B
H16A
H16B
H16C
H17A
H17B
H18A
H18B
H18C
0.13990
0.91300
0.0300*
−0.00040
0.98330
0.28150
0.0340*
−0.11370
0.82010
−0.07880
−0.10260
0.21410
0.0400*
0.02780
0.75250
0.0380*
−0.22500
1.06670
0.0560*
−0.11670
1.07430
0.25790
0.0560*
−0.11820
0.92040
0.40650
0.1110*
−0.22640
0.91120
0.36130
0.1110*
−0.18350
1.01090
0.45650
0.1110*
−0.21700
0.93250
−0.09020
0.00560
0.0530*
−0.27860
0.99860
0.0530*
−0.24850
0.77290
0.03380
0.1030*
−0.33970
0.82600
−0.05020
0.12220
0.1030*
−0.31380
0.84030
0.1030*
Acta Cryst. (2012). C68, o408–o412
sup-9

supplementary materials
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O1
0.0318 (8)
0.0232 (8)
0.0194 (9)
0.0184 (9)
0.0216 (10)
0.0182 (10)
0.0206 (10)
0.0239 (11)
0.0163 (10)
0.0217 (11)
0.0219 (11)
0.0200 (10)
0.0243 (11)
0.0199 (11)
0.0240 (11)
0.0289 (12)
0.0229 (11)
0.0211 (11)
0.0282 (12)
0.0364 (14)
0.082 (2)
0.0329 (8)
0.0293 (8)
0.0256 (8)
0.0232 (8)
0.0315 (9)
0.0211 (9)
0.0295 (10)
0.0247 (10)
0.0238 (10)
0.0266 (10)
0.0217 (9)
0.0172 (9)
0.0233 (10)
0.0221 (9)
0.0251 (10)
0.0259 (10)
0.0212 (10)
0.0324 (11)
0.0296 (11)
0.0405 (13)
0.080 (2)
0.0207 (8)
0.0297 (8)
0.0202 (9)
0.0255 (9)
0.0523 (12)
0.0211 (10)
0.0196 (10)
0.0222 (11)
0.0221 (10)
0.0243 (11)
0.0240 (11)
0.0211 (11)
0.0233 (11)
0.0277 (11)
0.0261 (11)
0.0311 (12)
0.0368 (12)
0.0434 (14)
0.0358 (13)
0.0664 (18)
0.070 (2)
0.0077 (6)
0.0084 (6)
0.0044 (7)
0.0005 (7)
0.0072 (8)
−0.0006 (8)
0.0000 (8)
0.0017 (8)
0.0004 (8)
−0.0023 (8)
0.0005 (8)
−0.0036 (7)
0.0009 (8)
0.0009 (8)
0.0012 (8)
0.0049 (9)
0.0025 (8)
0.0029 (9)
0.0007 (9)
0.0171 (11)
0.0156 (18)
0.0045 (10)
−0.0101 (13)
0.0067 (7)
0.0091 (7)
0.0046 (8)
0.0064 (8)
0.0085 (9)
0.0006 (8)
0.0044 (9)
0.0027 (9)
0.0023 (9)
0.0079 (9)
0.0035 (9)
0.0035 (9)
0.0050 (9)
0.0044 (9)
0.0024 (9)
0.0084 (10)
0.0083 (10)
−0.0024 (10)
0.0037 (10)
0.0188 (14)
0.046 (2)
−0.0007 (6)
0.0052 (6)
−0.0003 (7)
0.0013 (7)
0.0036 (9)
−0.0011 (8)
0.0014 (8)
0.0027 (8)
−0.0047 (8)
0.0045 (8)
0.0026 (8)
−0.0012 (8)
0.0003 (8)
0.0014 (8)
0.0004 (8)
−0.0009 (9)
0.0078 (8)
−0.0034 (10)
−0.0059 (9)
−0.0057 (12)
−0.0014 (17)
0.0070 (12)
0.0098 (16)
O2
N1
N2
N22
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
0.0222 (12)
0.0394 (16)
0.0361 (12)
0.0489 (16)
0.0726 (19)
0.115 (3)
0.0031 (13)
0.0048 (17)
Geometric parameters (Å, º)
O1—C7
O2—C4
O2—H2O
N1—C7
N1—N2
N2—C8
N22—C12
N22—C17
N22—C15
N1—H1N
C1—C2
1.238 (2)
C13—C14
1.378 (3)
1.368 (2)
0.93 (3)
C15—C16
C17—C18
C2—H2
1.523 (4)
1.519 (3)
0.9500
0.9500
0.9500
0.9500
0.9500
0.9500
0.9500
0.9500
0.9500
0.9900
0.9900
0.9800
0.9800
0.9800
0.9900
0.9900
0.9800
0.9800
1.353 (3)
1.394 (2)
1.281 (3)
1.370 (3)
1.459 (3)
1.457 (3)
0.87 (3)
C3—H3
C5—H5
C6—H6
C8—H8
C10—H10
C11—H11
C13—H13
C14—H14
C15—H15A
C15—H15B
C16—H16A
C16—H16B
C16—H16C
C17—H17A
C17—H17B
C18—H18A
C18—H18B
1.396 (3)
1.481 (3)
1.399 (3)
1.380 (3)
1.395 (3)
1.394 (3)
1.383 (3)
1.449 (3)
1.401 (3)
1.395 (3)
1.373 (3)
C1—C7
C1—C6
C2—C3
C3—C4
C4—C5
C5—C6
C8—C9
C9—C10
C9—C14
C10—C11
Acta Cryst. (2012). C68, o408–o412
sup-10

supplementary materials
C11—C12
C12—C13
1.411 (3)
1.408 (3)
C18—H18C
0.9800
C4—O2—H2O
N2—N1—C7
N1—N2—C8
C12—N22—C17
C15—N22—C17
C12—N22—C15
C7—N1—H1N
N2—N1—H1N
C2—C1—C6
109.9 (18)
118.80 (16)
115.33 (16)
121.23 (17)
117.58 (18)
121.18 (18)
122.0 (15)
119.2 (15)
118.61 (17)
117.57 (17)
123.81 (16)
121.18 (17)
119.68 (17)
119.84 (17)
122.65 (16)
117.50 (17)
120.10 (17)
120.58 (17)
121.94 (18)
115.55 (16)
122.46 (17)
122.64 (17)
119.67 (17)
123.38 (17)
116.83 (18)
121.66 (18)
121.67 (17)
116.49 (19)
121.27 (17)
122.23 (18)
121.2 (2)
C4—C3—H3
120.00
120.00
120.00
120.00
120.00
119.00
119.00
119.00
119.00
119.00
119.00
119.00
119.00
119.00
119.00
109.00
109.00
109.00
109.00
C4—C5—H5
C6—C5—H5
C1—C6—H6
C5—C6—H6
N2—C8—H8
C9—C8—H8
C9—C10—H10
C11—C10—H10
C10—C11—H11
C12—C11—H11
C12—C13—H13
C14—C13—H13
C9—C14—H14
C13—C14—H14
N22—C15—H15A
N22—C15—H15B
C16—C15—H15A
C16—C15—H15B
C2—C1—C7
C6—C1—C7
C1—C2—C3
C2—C3—C4
C3—C4—C5
O2—C4—C3
O2—C4—C5
C4—C5—C6
C1—C6—C5
O1—C7—N1
N1—C7—C1
H15A—C15—H15B
C15—C16—H16A
C15—C16—H16B
C15—C16—H16C
H16A—C16—H16B
H16A—C16—H16C
H16B—C16—H16C
N22—C17—H17A
N22—C17—H17B
C18—C17—H17A
C18—C17—H17B
H17A—C17—H17B
C17—C18—H18A
C17—C18—H18B
C17—C18—H18C
H18A—C18—H18B
H18A—C18—H18C
H18B—C18—H18C
108.00
110.00
109.00
110.00
109.00
109.00
109.00
109.00
109.00
109.00
109.00
108.00
109.00
109.00
109.00
109.00
109.00
110.00
O1—C7—C1
N2—C8—C9
C8—C9—C14
C8—C9—C10
C10—C9—C14
C9—C10—C11
C10—C11—C12
C11—C12—C13
N22—C12—C11
N22—C12—C13
C12—C13—C14
C9—C14—C13
N22—C15—C16
N22—C17—C18
C1—C2—H2
C3—C2—H2
C2—C3—H3
122.11 (19)
113.6 (2)
114.8 (2)
119.00
119.00
120.00
C7—N1—N2—C8
−151.69 (17)
4.0 (3)
C6—C1—C7—N1
C1—C2—C3—C4
C2—C3—C4—O2
C2—C3—C4—C5
O2—C4—C5—C6
C3—C4—C5—C6
C4—C5—C6—C1
N2—C8—C9—C10
38.6 (3)
1.1 (3)
N2—N1—C7—O1
N2—N1—C7—C1
−178.50 (15)
176.26 (16)
−5.5 (3)
−179.31 (17)
−0.3 (3)
178.40 (17)
−0.6 (3)
0.8 (3)
N1—N2—C8—C9
C15—N22—C12—C11
C15—N22—C12—C13
C17—N22—C12—C11
C17—N22—C12—C13
175.8 (2)
175.44 (18)
−3.2 (3)
8.8 (3)
Acta Cryst. (2012). C68, o408–o412
sup-11

supplementary materials
C12—N22—C15—C16
C17—N22—C15—C16
C12—N22—C17—C18
C15—N22—C17—C18
C6—C1—C2—C3
C7—C1—C2—C3
C2—C1—C6—C5
C7—C1—C6—C5
C2—C1—C7—O1
C2—C1—C7—N1
C6—C1—C7—O1
−76.9 (3)
102.2 (2)
85.6 (3)
N2—C8—C9—C14
−167.07 (18)
−175.07 (18)
0.9 (3)
C8—C9—C10—C11
C14—C9—C10—C11
C8—C9—C14—C13
C10—C9—C14—C13
C9—C10—C11—C12
C10—C11—C12—N22
C10—C11—C12—C13
N22—C12—C13—C14
C11—C12—C13—C14
C12—C13—C14—C9
−93.5 (2)
−0.9 (3)
174.72 (19)
−1.4 (3)
−179.77 (17)
0.0 (3)
−0.5 (3)
−178.18 (18)
0.6 (3)
178.71 (18)
34.9 (3)
177.67 (19)
−1.1 (3)
−142.64 (18)
−143.90 (19)
1.5 (3)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1N···O1i
N1—H1N···O2ii
O2—H2O···N2iii
C10—H10···O2iv
0.87 (3)
0.87 (3)
0.93 (3)
0.95
2.21 (2)
2.41 (2)
1.86 (3)
2.60
2.859 (2)
3.119 (2)
2.780 (2)
3.496 (2)
131.6 (18)
138.6 (19)
174 (3)
158
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+1/2.
Acta Cryst. (2012). C68, o408–o412
sup-12