2,4-Dinitrophenylhydrazones of 2,4-dihydroxybenzaldehyde, 2,4-dihydroxyacetophenone and 2,4-dihydroxybenzophenone

Article abstract of DOI:10.1107/S0108270103027197

In 2,4-dihydroxybenzaldehyde 2,4-dinitrophenylhydrazone N,N-dimethylformamide solvate (or 4-[(2,4-dinitrophenyl)-hydrazonomethyl]benzene-1,3-diol N,N-dimethylformamide solvate}, C₁₃H₁₀N₄O₆·C ₃H_7<

Full text of DOI:10.1107/S0108270103027197

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
for a systematic variation of the chromophore structure to
study the resulting structure±property relationships. To this
end, three hydrazones were synthesized by coupling 2,4-di-
nitrophenylhydrazine (2,4-DNPH) with three carbonyl
compounds, namely, 2,4-dihydroxybenzaldehyde, 2,4-di-
hydroxyacetophenone and 2,4-dihydroxybenzophenone, to
yield hydrazones (X), (XI) and (XII), respectively.
ISSN 0108-2701
2
2
2
2
,4-Dinitrophenylhydrazones of
,4-dihydroxybenzaldehyde,
,4-dihydroxyacetophenone and
,4-dihydroxybenzophenone
a
a
Russell G. Baughman, * Kenneth L. Martin, ² Rajendra K.
b
b
Singh ³ and James O. Stoffer
a
Division of Science, Truman State University, Kirksville, MO 63501-4221, USA,
b
and Department of Chemistry, University of Missouri±Rolla, Rolla, MO 65409, USA
Correspondence e-mail: baughman@truman.edu
Received 7 August 2003
Accepted 26 November 2003
Online 10 January 2004
In 2,4-dihydroxybenzaldehyde 2,4-dinitrophenylhydrazone
N,N-dimethylformamide solvate {or 4-[(2,4-dinitrophenyl)-
hydrazonomethyl]benzene-1,3-diol N,N-dimethylformamide
solvate}, C H N O ÁC H NO, (X), 2,4-dihydroxyaceto-
1
3
10
4
6
3
7
phenone 2,4-dinitrophenylhydrazone N,N-dimethylformam-
ide solvate (or 4-{1-[(2,4-dinitrophenyl)hydrazono]ethyl}-
benzene-1,3-diol N,N-dimethylformamide solvate), C H -
To con®rm the structures of these three hydrazones, which
are part of a series of related compounds currently under
investigation [including compounds (I)±(IX), which are still in
progress], the single-crystal data for these compounds are
reported here. While each of the three compounds demon-
strates NLO properties, it should be noted that each crystal-
lizes in a centrosymmetric space group and that each molecule
lacks a center of symmetry.
1
4
12
N O ÁC H NO, (XI), and 2,4-dihydroxybenzophenone 2,4-di-
4
6
3
7
nitrophenylhydrazone N,N-dimethylacetamide solvate (or
-{[(2,4-dinitrophenyl)hydrazono]phenylmethyl}benzene-1,3-
diol N,N-dimethylacetamide solvate), C H N O ÁC H NO,
4
1
9
14
4
6
4
9
(
XII), the molecules all lack a center of symmetry, crystallize
in centrosymmetric space groups and have been observed to
exhibit non-linear optical activity. In each case, the hydrazone
skeleton is fairly planar, facilitated by the presence of two
intramolecular hydrogen bonds and some partial NÐN
double-bond character. Each molecule is hydrogen bonded
to one solvent molecule.
As seen in Figs. 1±3, all three compounds crystallize in a 1:1
ratio with solvent molecules [N,N-dimethylformamide (DMF)
for (X) and (XI), and N,N-dimethylacetamide (DMAc) for
(XII)], which accept a hydrogen bond at atom O7 from atom
H1A of the para-hydroxy group of the hydrazone. In each
case, across the C7 N1 bond, N2 is E to C4; simultaneously,
each R substituent at C7 is Z to N2. In each molecule, two
intramolecular hydrogen bonds, H2AÁ Á ÁN1 and H2BÁ Á ÁO3,
help to facilitate the planarity of each hydrazone.
Comment
Hydrazone derivatives are an attractive class of non-linear
optical (NLO) crystalline materials because of their large
molecular non-linearities and their remarkable propensity to
form non-centrosymmetric crystal systems (Serbutoviez et al.,
The 23-atom hydrazone skeleton [atoms O1±O6, N1±N4
and C1±C13, plus atom C14 for (XI) and (XII)] of (X) is the
most planar of the three compounds, as it has an r.m.s.
Ê
deviation of 0.061 A, with atoms O2 and C5 having the largest
Ê
deviations [0.137 (3) and 0.117 (3) A, respectively] from the
1
995). The current approach to the development of practical
NLO materials has focused on the use of a dihydroxy-func-
tionalized hydrazone chromophore that can be easily
synthesized and subsequently incorporated into a commercial
epoxy polymer system. The preliminary goal was to provide
plane. On the other hand, (XI) and (XII) display some
buckling. They have larger r.m.s. deviations (0.190 and
Ê
0.122 A, respectively), in part due to atoms with larger
deviations from the plane of the skeleton. For example, in
(XI), atoms O2 and O6 have deviations of 0.488 (2) and
²
Current address: Department of Chemistry, Berry College, Mt Berry,
GA 30149, USA.
Current address: General Electric Co., Lexan Technology, One Lexan Lane,
Ê
.491 (2) A, respectively, while in (XII), atoms O5 and C5
0
Ê
have deviations of 0.330 (3) and 0.180 (3) A, respectively,
from the 23-atom plane of the skeleton.
³
Mt Vernon, IN 47620, USA.
Acta Cryst. (2004). C60, o103±o106
DOI: 10.1107/S0108270103027197
# 2004 International Union of Crystallography o103

organic compounds
In the case of compound (X), even the solvent molecule is
coplanar with the plane of the hydrazone molecule; the r.m.s.
Ê
deviation for all non-H atoms is 0.081 A. However, neither
solvent molecule in compounds (XI) and (XII) is coplanar
with the hydrazone molecule (Figs. 2 and 3; Tables 3 and 5).
The phenyl substituent (C14±C19) in compound (XII) is
nearly perpendicular (Table 5) to the plane of the hydrazone
skeleton, likely due in large part to steric problems around C7.
While the intramolecular hydrogen bonding minimizes the
rotational freedom about the C4ÐC7 and N2ÐC8 bonds,
rotation about N1ÐN2 is also reduced. The average of the
C7 N1 bond lengths (Table 6) is ꢁ3ꢀ longer than the average
of 13 C N bond lengths (in PhC NH coordination
compounds) gleaned from the Cambridge Structural Database
(
CSD, Version 5.23; Allen, 2002). Similarly, the average of the
N1ÐN2 bond lengths (Table 6) is ꢁ20ꢀ shorter than the
average of ®ve NÐN bond lengths in hydrazine-solvated
compounds in the CSD. This likely implies some N1ÐN2
double-bond character, thus reducing rotational mobility. The
extent of this character changes as substituents vary on C7.
Figure 3
Ê
A view of the asymmetric unit of (XII), showing the atom-labeling
scheme. Displacement ellipsoids are drawn at the 50% probability level,
and signi®cant H atoms are labeled and drawn as small spheres of
arbitrary radii.
The variation of C7 N1 bond lengths is 0.020 A (ꢁ7ꢀ), while
Ê
that for N1ÐN2 is 0.015 A (ꢁ5ꢀ).
As seen in Table 6, some bond lengths near C7 are affected
signi®cantly (ꢂ3ꢀ) by changes in the R substituent on C7.
Speci®cally, increases in bond lengths are noted for C7 N1,
.
. .
C4ÐC7 and C4 C5, concomitant with decreases in the N1Ð
N2 and O2ÐC3 bond lengths as the R substituent changes
from ±H to ±CH to ±Ph. The effect of going from H to alkyl to
3
aromatic groups is felt as much as three bonds away from the
C7ÐR bond.
Experimental
The three title hydrazones were synthesized according to a known
procedure (Vogel, 1989) by mixing a solution of 2,4-DNPH in an
ethanol±tetrahydrofuran solvent mixture [1:1 for (X), 3:1 for (XI),
and 2:1 for (XII)] with the three dihydroxy±carbonyl compounds in a
Figure 1
1:1.05 molar ratio, with concentrated HCl as catalyst. The decom-
A view of the asymmetric unit of (X), showing the atom-labeling scheme.
Displacement ellipsoids are drawn at the 50% probability level, and
signi®cant H atoms are labeled and drawn as small spheres of arbitrary
radii.
position points (>523 K for each of the three hydrazones) were
determined on a Thermal Analysis differential scanning calorimeter
�
1
at a heating rate of 10 K min . Crystals suitable for diffraction
analysis were grown by slow evaporation of a saturated solution in
DMF for hydrazones (X) and (XI), and in DMAc for hydrazone
(XII). Each crystal was placed into a capillary and sealed with mother
liquor.
Compound (X)
Crystal data
C
13
H
10
N
4
O
6
ÁC
3
H
7
NO
Mo Kꢂ radiation
Cell parameters from 49
re¯ections
M = 391.35
r
Monoclinic, P2 =c
1
Ê
a = 19.697 (4) A
ꢃ
ꢃ = 7.8±17.5
ꢄ = 0.12 mm
T = 293 (2) K
Ê
b = 7.152 (1) A
� 1
Figure 2
Ê
c = 12.949 (3) A
ꢃ
Aview of the asymmetric unit of (XI), showing the atom-labeling scheme.
Displacement ellipsoids are drawn at the 50% probability level, and
signi®cant H atoms are labeled and drawn as small spheres of arbitrary
radii.
ꢁ = 100.34 (2)
Block cut from a larger crystal,
red±orange
0.50 Â 0.39 Â 0.13 mm
Ê
3
V = 1794.5 (6) A
Z = 4
�
x
D = 1.448 Mg m
3
ꢀ
o104 Russell G. Baughman et al.
Three 2,4-dinitrophenylhydrazones
Acta Cryst. (2004). C60, o103±o106

organic compounds
Data collection
Table 2
Hydrogen-bonding geometry (A, ) for (XI).
Ê
ꢃ
Siemens P4 diffractometer
ꢃ/2ꢃ scans
h = � 23 ! 23
k = � 8 ! 2
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
3
3
1
504 measured re¯ections
119 independent re¯ections
774 re¯ections with I > 2ꢀ(I)
l = 0 ! 15
3 standard re¯ections
every 50 re¯ections
intensity decay: 2.3%
O1ÐH1AÁ Á ÁO7
O2ÐH2AÁ Á ÁN1
N2ÐH2BÁ Á ÁO3
0.82
0.82
0.86
1.86
1.88
1.94
2.677 (3)
2.590 (2)
2.590 (2)
175
146
131
R
int = 0.013
ꢃ
ꢃ
max = 25.0
Re®nement
Table 3
Selected r.m.s. deviations (A) and dihedral angle ( ) for (XI).
Ê
ꢃ
2
Re®nement on F
2
(Á/ꢀ)max < 0.001
Áꢅmax = 0.21 e A
2
Ê
� 3
R[F > 2ꢀ(F )] = 0.051
wR(F ) = 0.137
S = 1.01
2
Ê
� 3
Plane 1
r.m.s. deviation
Plane 2
DMF
r.m.s. deviation
0.004
Angle
Áꢅmin = � 0.16 e A
Extinction correction: SHELXL97
(Sheldrick, 1997)
Extinction coef®cient: 0.0059 (11)
Hydrazone
Hydrazone + C14
0.194
0.190
3
2
110 re¯ections
58 parameters
85.3 (1)
H-atom parameters constrained
2
2
o
2
) + (0.0658P) ]
w = 1/[ꢀ (F
where P = (F
2 2
+ 2F
c
o
)/3
Compound (XII)
Crystal data
C
19
H
14
N
4
O
6
ÁC
4
H
9
NO
Z = 2
�
3
Table 1
Hydrogen-bonding geometry (A, ) for (X).
M
r
= 481.46
Triclinic, P1
D
x
= 1.343 Mg m
Ê
ꢃ
Mo Kꢂ radiation
Cell parameters from 50
re¯ections
ꢃ = 6.3±20.7
ꢄ = 0.10 mm
T = 293 (2) K
Parallelepiped, red±orange
0.50 Â 0.38 Â 0.38 mm
Ê
Ê
a = 7.8155 (9) A
b = 11.549 (2) A
Ê
c = 13.904 (2) A
ꢂ = 100.38 (1)
ꢁ = 95.80 (1)
ꢆ = 102.74 (1)
V = 1191.0 (3) A
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
ꢃ
ꢃ
� 1
O1ÐH1AÁ Á ÁO7
O2ÐH2AÁ Á ÁN1
N2ÐH2BÁ Á ÁO3
0.82
0.82
0.86
1.83
1.97
1.96
2.626 (3)
2.691 (3)
2.603 (3)
163
146
131
ꢃ
ꢃ
Ê
3
Data collection
Siemens P4 diffractometer
ꢃ/2ꢃ scans
h = � 1 ! 9
k = � 13 ! 13
Compound (XI)
5
4
2
472 measured re¯ections
175 independent re¯ections
517 re¯ections with I > 2ꢀ(I)
l = � 16 ! 16
3 standard re¯ections
every 50 re¯ections
intensity decay: 1.7%
Crystal data
�
x
= 1.418 Mg m
Mo Kꢂ radiation
3
Rint = 0.013
ꢃ
C
14
H
12
N
4
O
6
ÁC
3
H
7
NO
D
ꢃ
max = 25.1
M
r
= 405.37
Triclinic, P1
Cell parameters from 50
re¯ections
Re®nement
Ê
a = 7.928 (1) A
Ê
b = 9.146 (1) A
ꢃ
2
ꢃ = 9.6±18.8
Re®nement on F
2
(Á/ꢀ)max < 0.001
Ê
c = 14.362 (2) A
� 1
2
Ê
� 3
Áꢅmax = 0.51 e A
ꢄ = 0.11 mm
T = 293 (2) K
R[F > 2ꢀ(F )] = 0.057
wR(F ) = 0.171
ꢃ
2
Ê
� 3
ꢂ = 104.45 (1)
ꢁ
ꢆ = 108.80 (1)
V = 949.1 (2) A
Z = 2
Áꢅmin = � 0.25 e A
ꢃ
= 91.04 (1)
Block cut from a larger crystal,
red±orange
0.54 Â 0.43 Â 0.31 mm
S = 1.04
4153 re¯ections
Extinction correction: SHELXL97
(Sheldrick, 1997)
Extinction coef®cient: 0.025 (4)
ꢃ
Ê
3
322 parameters
H-atom parameters constrained
2
2
2
w = 1/[ꢀ (F
o
) + (0.0921P)
+
0.1171P]
2
2
Data collection
c
where P = (Fo + 2F )/3
Siemens P4 diffractometer
ꢃ/2ꢃ scans
h = � 3 ! 9
k = � 10 ! 10
Table 4
Hydrogen-bonding geometry (A, ) for (XII).
4
3
2
336 measured re¯ections
310 independent re¯ections
207 re¯ections with I > 2ꢀ(I)
l = � 17 ! 17
Ê
ꢃ
3 standard re¯ections
every 50 re¯ections
intensity decay: 1.5%
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
R
int = 0.011
ꢃ
ꢃ
max = 25.1
O1ÐH1AÁ Á ÁO7
O2ÐH2AÁ Á ÁN1
N2ÐH2BÁ Á ÁO3
0.82
0.82
0.86
1.82
1.90
1.95
2.630 (3)
2.623 (3)
2.600 (3)
172
146
131
Re®nement
2
Re®nement on F
2
(Á/ꢀ)max < 0.001
Áꢅmax = 0.18 e A
2
Ê
� 3
R[F > 2ꢀ(F )] = 0.047
wR(F ) = 0.142
S = 1.01
2
Ê
� 3
Table 5
Selected r.m.s. deviations (A) and dihedral angles ( ) for (XII).
Áꢅmin = � 0.16 e A
Ê
ꢃ
Extinction correction: SHELXL97
(Sheldrick, 1997)
Extinction coef®cient: 0.026 (4)
3
2
298 re¯ections
68 parameters
Plane 1
r.m.s. deviation
Plane 2
r.m.s. deviation
Angle
H-atom parameters constrained
2
2
2
Hydrazone
Hydrazone
Hydrazone + C14
0.109
0.109
0.122
C14±C19
DMAc
0.002
0.031
84.04 (7)
44.7 (1)
w = 1/[ꢀ (F
o
) + (0.0747P)
+ 0.1707P]
where P = (F
2
o
2
c
+ 2F
)/3
ꢀ
Acta Cryst. (2004). C60, o103±o106
Russell G. Baughman et al.
Three 2,4-dinitrophenylhydrazones o105

organic compounds
Table 6
Selected interatomic distances (A) for compounds (X)±(XII); the effects
ment. The percentage decay of the three standards was calculated as
the average of their ꢀ(I) values.
Ê
of changing R at C7 from ±H to ±CH
3
to ±Ph.
For all three compounds, data collection: P3/P4-PC Diffractometer
Program (Siemens, 1991); cell re®nement: P3/P4-PC Diffractometer
Program; data reduction: XDISK (Siemens, 1991); program(s) used
to solve structure: SHELXS86 (Sheldrick, 1990a); program(s) used to
re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL/PC (Sheldrick, 1990b); software used to prepare material
for publication: SHELXTL/PC and SHELXL97.
Bond (X) (XI) (XII)
Change², Á/s.u.(X)³ Range§, R/s.u.(X)
³
Ê
Á (A)
Ê
R (A)
O1ÐC1 1.358 (3) 1.358 (3) 1.352 (3) � 0.006
O2ÐC3 1.362 (3) 1.347 (3) 1.351 (3) � 0.009
2.0
3.0
2.0
3.3
7.7
0.006
0.015
0.007
0.011
0.030
0.006
0.020
0.015
0.011
0.003
0.009
2.0
5.0
2.3
3.7
10.0
2.0
6.7
5.0
3.7
1.0
2.3
.
. .
C3 C4 1.408 (3) 1.415 (3) 1.414 (4) 0.006
C4 C5 1.386 (3) 1.397 (3) 1.396 (3) 0.010
C4ÐC7 1.439 (3) 1.469 (3) 1.462 (3) 0.023
.
. .
C7ÐC14
1.496 (3) 1.502 (3) 0.006} 2.0²²
David B. Hall, Northwestern University, Evanston, IL,
USA, is thanked for NLO analyses.
C7 N1 1.283 (3) 1.303 (3) 1.302 (3) 0.019
N1ÐN2 1.386 (3) 1.372 (2) 1.371 (3) � 0.015
N2ÐC8 1.343 (3) 1.354 (3) 1.348 (3) 0.005
N3ÐC13 1.447 (3) 1.450 (3) 1.447 (3) � 0.000
N4ÐC11 1.459 (4) 1.452 (3) 1.461 (4) 0.002
6.3
5.0
1.7
0.0
0.5
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: LN1175). Services for accessing these data are
described at the back of the journal.
²
Á for (XII)� (X) } Á for (XII)� (XI) ²² Á/s.u.(XI) ³ s.u.(X) is the s.u. in the
bond length for (X) § Range = maximum value � minimum value.
References
In all three cases, the approximate positions of the two hydroxy H
atoms were ®rst obtained from a difference map. These atoms were
then placed in `ideal' positions and re®ned as a rotating group. Bond
Allen, F. H. (2002). Acta Cryst. B58, 380±388.
Serbutoviez, C., Bosshard, C., Knop¯e, G., Wyss, P., Pretre, P., Gunter, P.,
Schenk, K., Solari, E. & Chapuis, G. (1995). Chem. Mater. 7, 1198±1206.
Sheldrick, G. M. (1990a). Acta Cryst. A46, 467±473.
Sheldrick, G. M. (1990b). SHELXTL/PC. Release 4.1. Siemens Analytical
X-ray Instruments Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997). SHELXL97. University of G oÈ ttingen, Germany.
Siemens (1991). P3/P4-PC Diffractometer Program (Version 4.23) and XDISK
(Version 4.20.2PC). Siemens Analytical X-ray Instruments Inc., Madison,
Wisconsin, USA.
Ê
lengths were constrained (AFIX 43) at 0.93 A for aromatic CÐH,
Ê
Ê
0
.96 A (AFIX 137) for methyl CÐH, 0.86 A (AFIX 43) for NÐH
Ê
and 0.82 A (AFIX 147) for OÐH. Uiso(H) values were ®xed at 1.5Ueq
for OH and methyl H atoms, and 1.2Ueq for all other H atoms. In the
®
nal stages of re®nement for all three compounds, a few very small or
negative F values were deemed to be in strong disagreement with
their F values. The corresponding nine, 12, and 22 re¯ections for (X),
XI), and (XII), respectively, were eliminated from the ®nal re®ne-
o
Vogel, A. I. (1989). Vogel's Textbook of Practical Organic Chemistry, 5th ed.,
revised by B. S. Furniss, A. J. Hannaford, P. W. G. Smith & A. R. Tatchell,
pp. 1257±1258. New York: John Wiley & Sons Inc.
c
(
ꢀ
o106 Russell G. Baughman et al.
Three 2,4-dinitrophenylhydrazones
Acta Cryst. (2004). C60, o103±o106