The synthesis and crystal structure determination of phenyl 2-(3,4-dihydro-1(2H)naphthalenylidine)hydrazinecarboxylate and Phenyl (2,4-dichlorophenyl-methylene)hydrazinecarboxylate

Article abstract of DOI:10.1007/s10870-010-9693-y

(E)-Phenyl 2-(3,4-dihydro-1(2H)-naphthalenylidine) hydrazinecarboxylate and (E)-phenyl (2,4-dichlorophenylmethylene) hydrazinecarboxylate were prepared by the condensation of 1-tetralone or 2,4-dichlorobenzaldehyde with phenyl hydrazinecarboxylate. Crysta

Full text of DOI:10.1007/s10870-010-9693-y

J Chem Crystallogr (2010) 40:541–545
DOI 10.1007/s10870-010-9693-y
ORIGINAL PAPER
The Synthesis and Crystal Structure Determination of Phenyl
2-(3,4-dihydro-1(2H)naphthalenylidine)hydrazinecarboxylate
and Phenyl (2,4-dichlorophenyl-methylene)hydrazinecarboxylate
•
Chandra Potter Amy M. Rhoden Smith
•
•
Clyde R. Metz William T. Pennington
•
•
Donald G. VanDerveer Charles F. Beam
Received: 18 July 2008 / Accepted: 7 January 2010 / Published online: 4 February 2010
Ó Springer Science+Business Media, LLC 2010
Abstract (E)-Phenyl 2-(3,4-dihydro-1(2H)-naphthalenyli-
dine)hydrazinecarboxylate and (E)-phenyl (2,4-dichloro-
phenylmethylene)hydrazinecarboxylate were prepared by
the condensation of 1-tetralone or 2,4-dichlorobenzaldehyde
with phenyl hydrazinecarboxylate. Crystals of C17H16N2O2
thiosemicarbazones and other hydrazones, indicates the
importance of knowing their exact structure [6–9]. They
have been used in stereochemical structure elucidation of a
variety of products some with biological application
potential [10–21], serving as a key component of ligand
complexes [22–26], for studying stereoselective conden-
sation reactions [27–29], and serving as a reactant in syn-
theses [30, 31], usually for heterocyclic compounds.
Phenyl hydrazinecarboxylate is a substituted hydrazine
that has received reasonable use since the first report
approximately 50 years ago. From a group of somewhat
less than 60 reports, one has involved X-ray crystal anal-
ysis of a heterocyclic compound made from it [32].
There are two reports dealing with the preparation of
carbophenoxyhydrazones from aldehydes and ketones,
where their preparation was one of the focal points of the
study. The earlier report deals with the 1:1 condensation
of phenyl hydrazinecarboxylate (phenyl carbazate) 2 with
several aldehydes and ketones employing ethanol as the
solvent and heating under reflux for several hours [33]. On
occasion a non-targeted second product resulted from a
second condensation of phenyl carbazate with the desired
carbophenoxyhydrazone. The recent report replaced etha-
nol with lower boiling solvent methanol, reduced the
condensation time to 20 min, which was aided by adding a
small amount of acetic acid [34]. By this modification a
single condensation product in higher yield resulted. Also,
there are no reports concerning an X-ray crystal analysis
for any of these compounds.
˚
3 are monoclinic, C2/c, a = 17.763(4) A, b = 8.353(2) A,
˚
3
˚
˚
c = 40.233(8) A, Z = 16, V = 5,839(2) A , R1 = 0.0448
and wR2 = 0.1104 for reflections with I [ 2r(I). Crystals of
C14H10N2O2Cl2 5 are orthorhombic, P212121, a = 8.288(3)
˚
A, b = 14.082(2) A, c = 23.788(5) A, Z = 8, V = 2,777(1)
˚
˚
3
A , R1 = 0.0815 and wR2 = 0.2006 for reflections with
˚
I [ 2r(I). The molecular packing in the crystal for both
compounds is the result of N–HÁÁÁO hydrogen bonding.
Keywords (E)-carbophenoxyhydrazones Á 1-Tetralone Á
2,4-Dichlorobenzaldehyde Á Phenyl hydrazinecarboxylate
Introduction
Hydrazones of numerous substitution types (e.g., phenyl-)
have recently been reviewed because of their potential for
many uses [1, 2], and as a result of the structural interest
alone in (E) and (Z) isomers, individual hydrazones have
received separate X-ray analyses [3–5]. The recent interest
in X-ray analysis of related imine link compounds, such as
C. Potter Á A. M. Rhoden Smith Á C. R. Metz Á C. F. Beam (&)
Department of Chemistry and Biochemistry,
College of Charleston, Charleston, SC 29424, USA
e-mail: beamc@cofc.edu
These hydrazones were easy to prepare and easy to
re-crystallize, which was followed by characterization with
absorption spectra, with support from combustion analysis.
Our preliminary conclusions were that the (E)-isomer was
the predominant or exclusive isomer. Other reports from
this laboratory with other hydrazone types may support the
W. T. Pennington Á D. G. VanDerveer
Department of Chemistry, Clemson University,
Clemson, SC 29634, USA
123

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J Chem Crystallogr (2010) 40:541–545
predominance of this isomer [35]. If an X-ray analysis had
been undertaken during an earlier study, we may have been
able to explain the lower yields of heterocyclic products,
4,5-dihydrobenz[e]indazoles, because the carbomethoxyhyd-
razone of 2-tetralone used was possibly a mixture of (E) and
(Z) isomers. By contrast, 3,4-dihydrobenz[g]indazoles is pre-
pared in comparative higher yields from the (E) isomer of
1-tetralone carbomethoxyhydrazone under the same condi-
tions [36].
0.00954 mol), methanol (50 mL), and glacial acetic acid (10
drops) were mixed in an Erlenmeyer flask. The mixture was
gently heated at its boiling point for 30 min, and the reaction
volume was reduced to *25 mL. The solution was allowed
to sit and crystallization occurred. The resulting solid
was filtered to afford orange–white crystals, which were
recrystallized from methanol. Yield 2.21 g (83%); Mp
133–134 °C; IR (cm-1) 3203, 3033, 2925, 1747, 1716, and
1612; 1H NMR (CDCl3) d (ppm) 1.49 (m, 2H, CH2,
J = 6.3 Hz), 2.51 (t, 2H, CH2, J = 6.6 Hz), 2.75 (t, 2H,
CH2, J = 6.3 Hz), 7.12 (d, 1H, CH, J = 7.2 Hz), 7.23
(m, 5H), 7.37 (t, 2H, CH, J = 7.8 Hz), 8.20 (d, 1H, CH,
J = 7.2 Hz), and 8.35 (s, 1H, NH); 13C NMR (CDCl3)
d(ppm) 21.6, 25.2, 29.8, 121.7, 125.4, 125.8, 126.8, 128.4,
129.5, 132.1, 139.7, 150.4, 150.9, and 152.0; exact mass,
280.12, LCMS: [M ? H]? = 281.05; Anal. calcd. for
C17H16N2O2: C, 72.84; H, 5.75; N, 9.99. Found: C, 74.64;
H, 5.88; N, 10.03.
Experimental
Carbophenoxyhydrazones 3 and 5 were prepared by a 1:1
condensation of phenyl carbazate 2 with each carbonyl
compound, 1-tetralone 1 and 2,4-dichlorobenzaldehyde 4,
using methanol as the solvent, with the addition of a cat-
alytic amount of glacial acetic acid, and with a reflux
period of 30 min. No additional products resulted [22–26].
(E)-Phenyl 2-(3,4-dihydronaphthalen-1(2H)-ylidene)hydr-
azine carboxylate 3: 2 (1.45 g, 0.00954 mol), 1 (1.39 g,
(E)-Phenyl (2,4-dichlorophenylmethylene)hydrazinecarb-
oxylate 5: 54% yield (from 2 and 4), Mp 184–185 °C
(methanol or cyclohexane); IR (cm-1) 3200 b, 1712, 1587,
Table 1 Crystallographic data
for hydrazones 3 and 5
C17H16N2O2 3
C14H10N2O2Cl2 5
CCDC deposit number
Color/shape
695551
695552
Colorless/needle
0.60 9 0.31 9 0.12
Colorless/needle
0.28 9 0.12 9 0.07
C14H10N2O2Cl2
309.14
Crystal dimensions (mm)
Formula
C
17H16N2O2
Formula mass
T (°C)
Crystal system
280.32
-120
-120
Monoclinic
C2/c
Orthorhombic
P212121
Space group
˚
a (A)
17.763(4)
8.353(2)
40.233(8)
101.99(3)
5,839(2)
16
8.288(3)
˚
b (A)
14.082(2)
˚
c (A)
23.788(5)
b (°)
3
˚
V (A )
2,777(1)
8
Z
dcalc (g cm-3
)
1.275
1.479
˚
k (A)
0.71073
0.085
0.71073
0.469
l (mm-1
)
F(000)
2,368
1,264
h range (°)
Reflections collected
2.71–25.15
13,035
2.60–25.15
20,145
Miller indices
-21 B h B 21, -9 B k B 5,
-44 B l B 47
-9 B h B 7, -16 B k B 16,
-28 B l B 28
Unique reflections
4,991
4,960
Data, restraints, parameters
Final R indices I [ 2r (I)
R indices all data
4991, 0, 387
4960, 0, 361
R1 = 0.0448, wR2 = 0.1104
R1 = 0.0519, wR2 = 0.1163
1.089
R1 = 0.0815, wR2 = 0.2006
R1 = 0.1187, wR2 = 0.2501
1.036
Goodness of fit on F2
-3
)
˚
Largest diff peak and hole (e A
0.194, -0.223
0.772, -0.491
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J Chem Crystallogr (2010) 40:541–545
543
1
and 756; H NMR (DMSO-d6): d (ppm), 7.22–7.31–7.38,
-40.0° to 90.0° at v = 45.0° and u = 0.0° for both
compounds; a second sweep was performed using x
oscillations from -40.0° to 70.0° at v = 45.0° and u =
90.0° for 3; -30.0° to 80.0° at v = 45.0° and u = 90.0°
for 5. The crystal-to-detector distance was 37.8890 mm for
3 and 27.5473 mm for 5. Details of the data collection are
reported in Table 1. Data were collected, processed, and
7.60–7.68, 7.95–7.97, and 8.51 (m, ArH); 13C NMR
(DMSO-d6) d (ppm) 114.6, 121.8, 125.6, 127.96, 128.0,
129.3, 130.5, 133.5, 134.9, 140.9, 150.3, and 151.8; exact
mass, 308.01, LCMS: [M ? H]? = 308.96. Anal. calcd. for
C14H10Cl2N2O2:C, 54.39; H, 3.26; N, 9.06. Found: C, 54.13:
H, 3.02; N, 8.94.
˚
Table 2 Selected bond distances (A), bond angles (°), and dihedral
Single Crystal X-ray Structure Determination
angles (°), C17H16N2O2 3
C1–O1, C1a–O1a
1.209(2), 1.206(2)
1.364(2), 1.365(2)
1.413(2), 1.411(2)
1.354(2), 1.351(2)
1.386(2), 1.383(2)
1.291(2), 1.288(2)
116.6(1), 116.1(1)
116.6(1), 116.5(1)
126.7(1), 127.7(1)
109.0(1), 108.8 (1)
121.1(1), 120.4 (1)
116.5(1), 117.4 (1)
124.9(1), 125.7 (1)
176.8(1), -177.8 (1)
-175.9(1), -179.4 (1)
-169.1(1), -177.3 (1)
170.7(1), -171.3 (1)
-58.8 (2), 67.4 (2)
Colorless crystals of C17H16N2O2 3 and C14H10N2O2Cl2 5
were recrystallized from methanol in order to give satis-
factory crystals for X-ray determination. Crystal data for
X-ray studies were collected at -120 °C for both com-
pounds on a Mercury CCD area detector coupled with a
Rigaku AFC8 diffractometer with graphite monochromated
Mo–K radiation. Data were collected in 0.50° oscillations
in x with 40 s exposures for 3 and 75 s exposures for 5.
A sweep of data was done using x oscillations from
C1–O2, C1a–O2a
O2–C2, O2a–C2a
N1–C1, N1a–C1a
N1–N2, N1a–N2a
N2–C8, N2a–C8a
C1–O2–C2, C1a–O2a–C2a
C1–N1–N2, C1a–N1a–N2a
O1–C1–N1, O1a–C1a–N1a
N1–C1–O2, N1a–C1a–O2a
O2–C2–C3, O2a–C2a–C3a
C8–N2–N1, C8a–N2a–N1a
N2–C8–C9, N2a–C8a–C9a
C8–N2–N1–C1, C1a–N1a–N2a–C8a
N1–N2–C8–C13, N1a–N2a–C8a–C13a
N2–N1–C1–O2, N2a–N1a–C1a–O2a
C2–O2–C1–N1, C2a–O2a–C1a–N1a
C1–O2–C2–C3, C1a–O2a–C2a–C3a
C15
C16
C4
C5
C6
C14
C13
C17
C12
C11
C3
C2
O1
C1
N2
C8
N1
O2
C10
C7
C15A
C9
C4A
C3A
C16A
O1A
C1A
C14A
C13A
C5A
N2A
C2A
O2A
C17A
C6A
C7A
˚
Table 3 Selected bond distances (A), bond angles (°), and dihedral
angles (°), C14H10N2O2Cl2 5
N1A
C12A
C11A
C8A
C9A
C1–O1, C1a–O1a
1.211(10), 1.192(10)
1.351(10), 1.367(9)
1.404(9), 1.400(9)
1.354(10), 1.346(9)
1.377(8), 1.383(9)
1.273(10), 1.280(9)
121.7(6), 120.2(6)
116.2(6), 115.5(6)
125.5(8), 127.1(7)
109.3(7), 107.9(6)
123.9(7), 124.5(7)
115.6(7), 116.2(7)
118.1(7), 118.5(7)
171.0(7), -167.5(7)
177.0(6), -174.5(7)
177.4(6), -178.5(6)
-173.1(6), 171.0(6)
31.6(11), -38.7(11)
C1–O2, C1a–O2a
C10A
O2–C2, O2a–C2a
N1–C1, N1a–C1a
Fig. 1 ORTEP diagram (50% ellipsoids for non-hydrogen atoms),
C17H16N2O2 3
N1–N2, N1a–N2a
N2–C8, N2a–C8a
C1–O2–C2, C1a–O2a–C2a
C1–N1–N2, C1a–N1a–N2a
O1–C1–N1, O1a–C1a–N1a
N1–C1–O2, N1a–C1a–O2a
O2–C2–C3, O2a–C2a–C3a
C8–N2–N1, C8a–N2a–N1a
N2–C8–C9, N2a–C8a–C9a
C1–N1–N2–C8, C1a–N1a–N2a–C8a
N1–N2–C8–C9, N1a–N2a–C8a–C9a
N2–N1–C1–O2, N2a–N1a–C1a–O2a
C2–O2–C1–N1, C2a–O2a–C1a–N1a
C1–O2–C2–C3, C1a–O2a–C2a–C3a
C6
C4
C7
O2
C1
C5
N1
C8
Cl2
C13
C2
C14
C9
N2
C10
O2A
C3
O1
C12
Cl1
C11
C7A
Cl2A
C8A
N1A
C6A
C14A
C11A
C13A
Cl1A
C5A
C9A
C2A
C1A
O1A
N2A
C3A
C10A
C4A
C12A
Fig. 2 ORTEP diagram (50% ellipsoids for non-hydrogen atoms),
C14H10N2O2Cl2 5
123

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J Chem Crystallogr (2010) 40:541–545
H
O
N
O
O
C
N
C
O
H2N
+
N
O
H
3
2
1
H
C
H
C
H
N
O
O
N
C
O
2
+
Cl
Cl
Cl
Cl
4
5
Scheme 1 Preparation of carbophenoxyhydrazones: phenyl 2-(3,4-dihydro-1(2H)naphthalenylidine)hydrazinecarboxylate
(2,4-dichlorophenyl-methylene)hydrazinecarboxylate 5
3 and phenyl
corrected for Lorentz polarization and for absorption using
CrystalClear (Rigaku) [37, 38].
The O2, O1, C1, N1, N2, and C8 atoms for both 3 and 5 are
nearly planar which allows for extended pi bonding. The ring
containing C12–C17 for 3 is nearly coplanar (12.86°) with
these atoms and the ring containing C2–C7 is at an angle of
60.97° with these atoms. The rings in 5 containing C9–C14
and C2–C7 are nearly coplanar (14.36o) as are the rings
containing C9a–C14a and C2a–C7a (16.3o).
The non-hydrogen atoms were refined anisotropically.
Ideal hydrogen atom coordinates were calculated and the
hydrogen atoms were allowed to ride on their respective
carbon atoms. For hydrazone 3: the hydrogen atoms on N1
and N1a were found by difference. For hydrazone 5: the
hydrogen atoms on C8, C8a, N1, and N1a were located by
difference and then ideal coordinates were calculated and
these hydrogen atoms were allowed to ride on their respec-
tive atoms. The temperature factors of all hydrogen atoms
were varied isotropically with Uiso = 1.2 9 Uiso of the
carbon atom. Structure solution, refinement, and the calcu-
lation of derived results were performed using the SHELX-97
[39] package of computer programs. Neutral atom scattering
factors were those of Cromer and Waber [40, 41] and the real
and imaginary anomalous dispersion corrections were those
of Cromer [CCDC 695551 3 and 695552 5 contain the sup-
plementary crystallographic data for this paper. These data
can be obtained free of charge from the Cambridge Crys-
tallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif]. The molecular structure of C17H16N2O2 3 is
shown in Fig. 1 and C14H10N2O2Cl2 5 in Fig. 2. Selected
bond distances and angles for 3 are listed in Table 2 and for 5
in Table 3 (Scheme 1).
Crystal packing is the result of hydrogen bonding of
each molecule with two neighboring molecules: the
hydrogen atom on the N1 atom and the O1a atom in the
pair of molecules shown in Figs. 1 and 2, the O1 atom with
the hydrogen atom on N1a in a second neighboring mol-
ecule, and the hydrogen atom on N1a with the O1 atom in a
third neighboring molecule [37, 39].
Acknowledgments We wish to thank the following sponsors for
support: the Research Corporation, the National Science Foundation
grants CHE # 9708014 and # 0212699 for Research at Undergraduate
Institutions, and the United States Department of Agriculture,
NRICGP # 2003-35504-12853.
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