1,3-Bis(4-methylphenyl)triazene, 1-(4-chlorophenyl)-3-(4-fluorophenyl)- triazene and 1-(4-fluorophenyl)-3-(4-methylphenyl)triazene

Article abstract of DOI:10.1107/S0108270105004373

The title 4,4′-disubstituted diphenyl-1,3-triazines, C ₁₄H₁₅N₃, (I), C₁₂H ₉ClFN₃, (II), and C₁₃H₁₂FN ₃, (III), each contain a triazene group (-N=N-NH-) having an extended conformation. The dihedral angles between the two benzene rings in (I), (II) and (III) are 4.3, 3.4 and 6.5°, respectively. The molecules are almost entirely planar, with maximum deviations from the mean planes of 0.1087 (2), -0.1072 (7) and 0.1401 (3) A, respectively. In each compound, the molecules are linked by N-H...N hydrogen bonds to form chains and pack similarly in the crystal structures.

Full text of DOI:10.1107/S0108270105004373

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
1,3-Bis(4-methylphenyl)triazene, (I), 1-(4-chlorophenyl)-3-
(4-¯uorophenyl)triazene, (II), and 1-(4-¯uorophenyl)-3-(4-
methylphenyl)triazene, (III), differ only in the substituents at
atoms C4 and C10; these substituents are methyl groups in (I),
Cl and F atoms in (II), and a methyl group and an F atom in
(III). The angle between the benzene rings is 4.28 (1)ꢀ for (I),
3.42 (4)ꢀ for (II) and 6.53 (2)ꢀ for (III). These angles are in
close agreement with the value observed in another open-ring
intermediate in the synthesis of triazane [6.2 (2)ꢀ; Zhang et al.,
1999].
ISSN 0108-2701
1,3-Bis(4-methylphenyl)triazene,
1-(4-chlorophenyl)-3-(4-fluorophenyl)-
triazene and 1-(4-fluorophenyl)-
3-(4-methylphenyl)triazene
Nevzat Karadayõ,a* SËukriye CËakmak,b Mustafa
È
OdabaËsogÆlub and Orhan Buyukgungorc
È
È È
È
aIndustrial Electronics Program, Samsun Vocational School of Higher Education,
Ondokuz Mayõs University, TR-55139 Samsun, Turkey, bDepartment of Chemistry,
Faculty of Arts and Sciences, Ondokuz Mayõs University, TR-55139 Samsun, Turkey,
and cDepartment of Physics, Faculty of Arts and Sciences, Ondokuz
Mayõs University, TR-55139 Samsun, Turkey
The molecular structures of (I), (II) and (III) are shown in
Fig. 1, and the geometric parameters are compared in Table 1.
For (I), within the limits of uncertainty, the bond lengths and
angles of the two methylphenyl rings are in agreement with
one another. The N3 N2 bond is longer than the value
expected for a double bond, the N2ÐN1 bond is shorter than
expected for a single bond, and the C1ÐN1 and C7ÐN3
bonds are both short for single CarÐN bonds. These values
(Table 1) are in good agreement with those found in related
Correspondence e-mail: nevzatk@omu.edu.tr
Received 25 June 2004
Accepted 8 February 2005
Online 23 April 2005
The title 4,40-disubstituted diphenyl-1,3-triazines, C14H15N3,
(I), C12H9ClFN3, (II), and C13H12FN3, (III), each contain a
triazene group (±N NÐNH±) having an extended conforma-
tion. The dihedral angles between the two benzene rings in (I),
(II) and (III) are 4.3, 3.4 and 6.5ꢀ, respectively. The molecules
are almost entirely planar, with maximum deviations from the
Ê
mean planes of 0.1087 (2), 0.1072 (7) and 0.1401 (3) A,
respectively. In each compound, the molecules are linked by
NÐHÁ Á ÁN hydrogen bonds to form chains and pack similarly
in the crystal structures.
Comment
Triazene compounds containing a diazoamine group have
important industrial and medical applications. The substituted
triazenes (RN NÐNH±) ®nd wide-ranging applications as
initiators of radical polymerization (Rapta et al., 1996), as
ef®cient chelating agents (Leman et al., 1992; Cotton et al.,
1992) and as antitumor drugs (Wilman, 1988). These
compounds, characterized by having a diazoamine group,
commonly adopt the trans con®guration in the ground state.
They are also known to undergo reversible changes in double-
bond con®guration as a result of photoinduced and thermally
induced trans±cis±trans isomerization (Baro et al., 1983; Le
Fevre & Liddicoet, 1951; Barra & Chen, 2000). Photochromic
materials of this type are of interest for potential applications,
among others, in molecular electronic devices (Martin et al.,
1995). The results of the present X-ray analysis are in agree-
ment with those of the structure analyses of similar substituted
Figure 1
È
triazenes (Anulewicz, 1997; Zhang et al., 1999; Horner et al.,
ORTEP-3 (Farrugia, 1997) drawings of the title compounds, showing the
atomic numbering schemes and 50% probability displacement ellipsoids
for (a) (I), (b) (II) and (c) (III).
2004, 2002). In this paper, we report the structures of the three
title 4,40-disubstituted diphenyl-1,3-triazines.
Acta Cryst. (2005). C61, o303±o305
DOI: 10.1107/S0108270105004373
# 2005 International Union of Crystallography o303

organic compounds
Experimental
Compounds (I) (m.p. 388±389 K), (II) (m.p. 402±403 K) and (III)
È
(m.p. 385±386 K) were prepared as described by Horner et al. (2004)
using 4-methylaniline, 4-¯uoroaniline and 4-chloroaniline as starting
materials. The products were recrystallized from tetrahydrofuran
(THF) and well shaped crystals were obtained by slow evaporation of
an n-hexane/THF (1:1 v/v) solution.
Compound (I)
Crystal data
3
C14H15N3
Mr = 225.29
Monoclinic, P21=n
Ê
a = 14.4024 (19) A
Dx = 1.209 Mg m
Mo Kꢁ radiation
Cell parameters from 3402
ꢂ = 1.8±28.6ꢀ
1
Ê
Ê
b = 4.8171 (4) A
ꢃ = 0.07 mm
T = 296 (2) K
c = 17.840 (2) A
ꢀ = 91.510 (11)ꢀ
Plate, light brown
0.44 Â 0.29 Â 0.09 mm
3
Ê
V = 1237.3 (3) A
Z = 4
Figure 2
A perspective view of the packing in (I). The relationship between the
Data collection
molecules in (II) and (III) is similar. Hydrogen bonds are shown as
1
Stoe IPDS-II diffractometer
! scans
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
Tmin = 0.976, Tmax = 0.994
2184 measured re¯ections
2184 independent re¯ections
1091 re¯ections with I > 2ꢄ(I)
ꢂmax = 25.0ꢀ
3
dashed lines. [Symmetry code: (i) 32 x, y
,
z.]
2
2
h = 17 ! 17
compounds (Anulewicz, 1997; Walton et al., 1991; Zhang et al.,
1999). The dihedral angles between the two benzene rings and
the C1ÐN1ÐN2ÐN3 and N1ÐN2ÐN3ÐC7 torsion angles
are 177.21 (15) and 177.97 (14)ꢀ, respectively, showing the
near coplanarity of the whole molecule. The crystal structure
of (I) has been reported by Kondrashev (1964). [The b axis of
the monoclinic cell lies along the axis of the needle-shaped
crystals. The development of the four planes hkl (k = 0±3) and
of the planes hk0 was obtained with a Weissenberg goni-
ometer, and from these the space group P21/n was established.
From the rotation X-ray photograph and the development of
h0l, taken with NaCl as standard, the following lattice para-
k = 0 ! 5
l = 0 ! 21
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.033
wR(F2) = 0.066
S = 0.99
2184 re¯ections
194 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[ꢄ2(F2o) + (0.0204P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max = 0.003
3
Ê
Áꢅmax = 0.10 e A
3
Ê
0.10 e A
Áꢅmin
Extinction correction: SHELXL97
=
Extinction coef®cient: 0.0063 (11)
Ê
Ê
meters were determined: a = 17.83 (2) A, b = 4.83 (1) A, c =
Compound (II)
ꢀ
Ê
14.40 (2) A and ꢀ = 88.40 (10) .] The molecular structures of
(II) and (III) are similar to that of (I), with small differences
for some bond lengths due to the presence of the F and Cl
atoms attached to the benzene rings (Figs. 1b and 1c). The
Crystal data
3
C12H9ClFN3
Mr = 249.67
Dx = 1.353 Mg m
Mo Kꢁ radiation
Cell parameters from 4244
re¯ections
Monoclinic, P21=n
Ê
Ê
Ê
Ê
N3 N2 bond lengths [1.2777 (17) A in (I) and 1.280 (3) A in
a = 14.500 (3) A
b = 4.7385 (5) A
ꢂ = 1.8±24.4ꢀ
ꢃ = 0.30 mm
T = 296 (2) K
Ê
(III)] are somewhat shorter than the value of 1.317 (8) A in
(II).
Molecules of (I), (II) and (III) pack similarly in the unit cell,
as shown in Fig. 2, and all have intermolecular NÐHÁ Á ÁN
hydrogen bonds (Table 2). These hydrogen bonds are some-
what longer than the analogous interaction in the spiral of the
ꢀ modi®cation of 3-(4-bromophenyl)-1-phenyltriazine, (IV)
1
Ê
c = 17.848 (3) A
ꢀ = 92.298 (16)ꢀ
Ê
V = 1225.3 (4) A
Z = 4
3
Plate, brown
0.50 Â 0.29 Â 0.06 mm
Data collection
Stoe IPDS-II diffractometer
! scans
978 re¯ections with I > 2ꢄ(I)
Rint = 0.078
ꢂmax = 25.0ꢀ
Ê
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
Tmin = 0.886, Tmax = 0.981
8654 measured re¯ections
2157 independent re¯ections
(3.206 A; Omel'chenko & Kondrashev, 1973). This difference
is due to the different packing characters, where in the case of
h = 17 ! 17
k = 5 ! 5
the ¯at parallel molecules the smallest NÐHÁ Á ÁN distance
l = 21 ! 21
Ê
should be 3.60 A. The shortening is achieved as a result of
strong bending of the molecules of (IV), which form dimers in
which the molecules are bent towards one another, and of the
deviation of the N atoms from the plane of the molecule to the
same side; this con®guration provides additional evidence for
the existence of strong interaction between the molecules in
the dimer (Omel'chenko & Kondrashev, 1973).
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.087
wR(F2) = 0.253
S = 1.08
2157 re¯ections
154 parameters
H-atom parameters constrained
w = 1/[ꢄ2(F2o) + (0.1152P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max < 0.001
3
Ê
Áꢅmax = 0.33 e A
3
Ê
0.44 e A
Áꢅmin
=
ꢁ
o304 Karadayõ et al. C14H15N3, C12H9ClFN3 and C13H12FN3
Acta Cryst. (2005). C61, o303±o305

organic compounds
Table 2
Hydrogen-bonding geometry (A, ).
Compound (III)
ꢀ
Ê
Crystal data
3
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C13H12FN3
Mr = 229.26
Monoclinic, P21=n
a = 13.683 (3) A
b = 4.7712 (6) A
Dx = 1.316 Mg m
Mo Kꢁ radiation
(I)
(II)
(III)
N1ÐH1Á Á ÁN3i
N1ÐH1Á Á ÁN3i
N1ÐH1Á Á ÁN3i
0.99 (2)
0.86
0.86
2.31 (2)
2.39
2.38
3.242 (2)
3.223 (8)
3.211 (3)
158.1 (15)
163
164
Cell parameters from 3288
re¯ections
Ê
Ê
Ê
ꢂ = 1.8±27.7ꢀ
1
3
2
1 3
Symmetry code: (i)
x; y
;
2 2
z.
c = 17.742 (4) A
ꢃ = 0.09 mm
T = 296 (2) K
ꢀ = 92.512 (18)ꢀ
3
Ê
V = 1157.2 (4) A
Z = 4
Plate, brown
0.50 Â 0.28 Â 0.06 mm
1.2Ueq(C,N)]. For (III), the methyl H atoms and those attached to
atoms C3 and N1 were re®ned with ®xed displacement parameters
[Uiso(H) = 1.5Ueq(methyl C) and 1.2Ueq(C,N)] using a riding model
Data collection
Ê
(methyl CÐH = 0.96 A and C3ÐH3 = 0.93 A). All other H atoms
Ê
were re®ned freely [CÐH = 0.88 (3)±0.97 (3) A and Uiso(H) =
Ê
0.063 (9)±0.116 (14) A].
Ê
Stoe IPDS-II diffractometer
! scans
6441 measured re¯ections
2019 independent re¯ections
757 re¯ections with I > 2ꢄ(I)
Rint = 0.081
ꢂmax = 25.0ꢀ
h = 16 ! 16
k = 5 ! 5
l = 21 ! 21
For all three compounds, data collection: X-AREA (Stoe & Cie,
2002); cell re®nement: X-AREA; data reduction: X-RED32 (Stoe &
Cie, 2002); structure solution: SHELXS97 (Sheldrick, 1997); structure
re®nement: SHELXL97 (Sheldrick, 1997); molecular graphics:
ORTEP-3 (Farrugia, 1997) and PLUTON (Spek, 1997); publication
software: WinGX (Farrugia, 1999).
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.052
wR(F2) = 0.110
S = 0.85
2019 re¯ections
183 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[ꢄ2(F2o) + (0.0316P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max = 0.009
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: TA1464). Services for accessing these data are
described at the back of the journal.
3
Ê
Áꢅmax = 0.15 e A
3
Ê
0.16 e A
Áꢅmin
=
Table 1
Comparative selected geometric parameters (A, ).
ꢀ
Ê
References
(F)a
(I)
(II)
(III)
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C1ÐC2
C1ÐC6
C7ÐC8
C7ÐC12
C4ÐC14
C10ÐC13
Cl1ÐC4
1.334 (4)
1.378 (4)
1.399 (5)
1.386 (5)
1.385 (5)
±
1.332 (2)
1.375 (2)
1.390 (2)
1.366 (2)
1.381 (2)
1.507 (2)
1.516 (2)
±
1.321 (7)
1.359 (10)
1.415 (10)
1.361 (9)
1.388 (9)
±
1.316 (3)
1.370 (4)
1.408 (4)
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±
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±
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È
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N3ÐN2ÐN1
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C2ÐC1ÐN1
N1ÐC1ÐC6
C8ÐC7ÐN3
C12ÐC7ÐN3
119.0 (3)
112.9 (2)
111.9 (3)
118.6 (3)
121.1 (3)
115.9 (3)
125.0 (3)
120.35 (17)
112.07 (15)
112.65 (14)
118.56 (17)
122.71 (18)
115.97 (17)
125.41 (18)
119.2 (6)
110.9 (6)
111.8 (5)
119.3 (7)
122.1 (7)
116.5 (6)
126.4 (6)
121.4 (3)
112.4 (3)
112.1 (2)
119.9 (3)
120.6 (3)
117.0 (3)
126.5 (3)
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N3ÐC7ÐC8ÐC9
N1ÐN2ÐN3ÐC7
C1ÐN1ÐN2ÐN3
179.9 (3)
179.1 (3)
178.8 (3)
179.0 (3)
177.64 (18)
179.17 (17)
177.97 (14)
177.21 (15)
176.8 (7)
178.7 (6)
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177.5 (5)
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È
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For (I), the methyl H atoms were re®ned using a riding model, with
Ê
®xed CÐH distances of 0.96 A [Uiso(H) = 1.5Ueq(C)]. All other H
Ê
atoms were re®ned freely [CÐH = 0.922 (17)±1.001 (19) A and
2
Uiso(H) = 0.063 (6)±0.096 (7) A ]. For (II), all H atoms were re®ned
Ê
Ê
using a riding model, with ®xed CÐH distances of 0.93 A [Uiso(H) =
ꢁ
Acta Cryst. (2005). C61, o303±o305
Karadayõ et al.
C14H15N3, C12H9ClFN3 and C13H12FN3 o305