Crystal structure of 4,4′-dinitro-[1,1′-biphenyl]-2-amine
research communications
Crystal structure of 4,40 -dinitro-[1,10 -biphenyl]-2amine
ISSN 2056-9890
Md. Serajul Haque Faizi,a Ashanul Haque,a Necmi Dege,b Syed Imran Hasan,a
Mustafa Degec and Valentina A. Kalibabchukd*
Received 17 February 2017
Accepted 13 March 2017
Edited by H. Stoeckli-Evans, University of
Neuchâtel, Switzerland
Keywords: crystal structure; dinitro; biphenyl;
amine; biphenyl derivatives; hydrogen bonding.
CCDC reference: 1537734
Supporting information: this article has
supporting information at journals.iucr.org/e
a
Department of Chemistry, College of Science, Sultan Qaboos University, PO Box 36 Al-Khod 123, Muscat, Sultanate of ,
Oman, bOndokuz Mayıs University, Arts and Sciences Faculty, Department of Physics, 55139 Samsun, Turkey, cSpraying
Systems Company Turkey, Esentepe Mah. Kore Şehitleri Cad. Kaya Aldoğan Sok., Serhan apt. No. 3 Daire:3 Şişli ¤stanbul,
Turkey, and dDepartment of General Chemistry, O. O. Bohomolets National Medical University, Shevchenko Blvd. 13,
01601 Kiev, Ukraine. *Correspondence e-mail:
In the title biphenyl derivative, C12H9N3O4, the dihedral angle between the
benzene rings is 52.84 (10) . The nitro group attached to the benzene ring is
inclined to the ring by 4.03 (2) , while the nitro group attached to the aminosubstituted benzene ring is inclined to the ring by 8.84 (2) . In the crystal,
molecules are linked by two pairs of N—H O hydrogen bonds, forming chains
propagating along [101]. Within the chains, these N—H O hydrogen bonds
result in the formation of R22(20) and R22(14) ring motifs. The latter ring motif is
reinforced by a pair of C—H O hydrogen bonds, enclosing R12(6) ring motifs.
The chains are linked by a second C—H O hydrogen bond, forming a threedimensional supramolecular structure.
1. Chemical context
Biphenyl and its derivatives have been shown to play an
important role in fighting cancer and arteriosclerosis in
humans (Umeda et al., 2005). The dihedral angle between the
phenyl rings of biphenyl derivatives is associated with their
affinity for cellular target molecules and, therefore, can
correlate with their toxicity. The parent compound, biphenyl,
adopts a planar conformation in the solid state with a dihedral
angle of 0 (Trotter, 1961). The calculated dihedral angle for
biphenyl derivatives without ortho substituents is ca 41
(Shaikh et al., 2008). Deviations from the energetically most
favourable conformation are most likely the result of crystal
packing effects, which allow such compounds to adopt an
energetically favorable conformation in the solid state by
maximizing the lattice energy. Many research groups have
calculated the inter-ring torsion angle of biphenyl in the solid
state (Brock, 1980; Brock & Minton, 1989; Bastiansen &
Samdal, 1985), and in the gas phase (Bastiansen & Traetteberg, 1962). We report here a detailed description of the
molecular structure and supramolecular features of the title
biphenyl derivative, 4,40 -dinitro-[1,10 -biphenyl]-2-amine, (I).
550
https://doi.org/10.1107/S205698901700408X
Acta Cryst. (2017). E73, 550–552
research communications
Table 1
Hydrogen-bond geometry (Å, ).
D—H A
i
N2—H2B O1
N2—H2A O4ii
C6—H6 O1i
C9—H9 O3iii
Symmetry codes:
x; y þ 12; z þ 12.
Figure 1
The molecular structure of the title compound, with the atom labelling.
Displacement ellipsoids are drawn at the 40% probability level.
2. Structural commentary
The molecular structure of the title compound (I), is illustrated in Fig. 1. The dihedral angle between the two rings of
the biphenyl unit is 52.84 (10) . The nitro group (N3/O3/O4) is
inclined to the benzene ring (C7–C12) to which it is attached
by 4.03 (2) . The nitro group (N1/O1/O2) is inclined to the
amino-substituted benzene ring (C1–C6), to which it is
attached, by 8.84 (2) . The amino N atom, N2, lies in the plane
of the C1–C6 benzene ring, and the N2—C5 bond length of
1.375 (3) Å clearly indicates a single bond. The C1—N1
distance of 1.466 (3) Å is slightly less than the C10—N3 bond
distance of 1.477 (3) Å, which indicates that the 2-amino
group containing a benzene ring (C1–C6) is more conjugated
with the nitro group (N1/O1/O2) than is the other nitro group
(N3/O3/O4) with respect to the C7–C12 benzene ring. The
bond length of the C4—C7 bridge is 1.482 (3) Å, which indicates a single bond, and is similar to the same bond length of
1.494 (2) Å reported for dimethyl 2,20 -dinitrobiphenyl-4,40 dicarboxylate (Lehane et al., 2014), and ca 1.493 Å observed in
2,20 -dinitrobiphenyl (Sekine et al., 1994).
(i)
D—H
H A
D A
D—H A
0.92 (2)
0.89 (2)
0.93
0.93
2.36 (2)
2.50 (2)
2.54
2.57
3.229 (3)
3.345 (3)
3.308 (3)
3.496 (3)
157 (2)
157 (2)
140
174
x þ 1; y þ 1; z þ 2;
(ii)
x; y þ 1; z þ 1;
(iii)
3. Supramolecular features
In the crystal, molecules are linked by two pairs of N—H O
hydrogen bonds, forming chains propagating along the [101]
direction. Within the chains, these N—H O hydrogen bonds
result in the formation of R22 (20) and R22 (14) ring motifs
(Table 1 and Fig. 2). The latter ring motif is reinforced by a
pair of C—H O hydrogen bonds, enclosing R12 (6) ring motifs
(Table 1 and Fig. 2). The chains are linked by a second C—
H O hydrogen bond (Table 1), forming a three-dimensional
supramolecular structure, as illustrated in Figs. 3 and 4.
Figure 3
A view along the b axis of the crystal packing of (I). Hydrogen bonds are
shown as dashed lines (see Table 1) and, for clarity, only H atoms H2A,
H2B, H6 and H9 have been included.
Figure 2
Figure 4
A view of the N—H O and C—H O hydrogen bonds (dashed lines;
see Table 1), in the crystal of (I), forming chains that propagate along
[101].
A view along the a axis of the crystal packing of (I). Hydrogen bonds are
shown as dashed lines (see Table 1) and, for clarity, only H atoms H2A,
H2B, H6 and H9 have been included.
Acta Cryst. (2017). E73, 550–552
Faizi et al. C12H9N3O4
551
research communications
Table 2
suitable for single-crystal X-ray analysis, were grown by slow
evaporation of a solution in ethanol.
Experimental details.
Crystal data
Chemical formula
Mr
Crystal system, space group
Temperature (K)
a, b, c (Å)
( )
V (Å3)
Z
Radiation type
(mm1)
Crystal size (mm)
Data collection
Diffractometer
Absorption correction
Tmin, Tmax
No. of measured, independent and
observed [I > 2(I)] reflections
Rint
(sin /)max (Å1)
Refinement
R[F 2 > 2(F 2)], wR(F 2), S
No. of reflections
No. of parameters
No. of restraints
H-atom treatment
3
max, min (e Å )
C12H9N3O4
259.22
Monoclinic, P21/c
296
14.2940 (11), 7.0352 (6),
11.6043 (9)
99.437 (6)
1151.15 (16)
4
Mo K
0.12
0.34 0.20 0.07
Acknowledgements
The authors are grateful to the Ondokuz Mayıs University,
Arts and Sciences Faculty, Department of Physics, 55139
Samsun, Turkey for X-ray the data collection.
0.044
0.646
Funding information
0.040, 0.092, 0.81
2566
180
2
H atoms treated by a mixtu (...truncated)
