Different intermolecular inter-actions in azido-[2-(diphenyl-phosphino)- benzaldehyde semicarbazonato-2 P,N 1,O]nickel(II)

Article abstract of DOI:10.1107/S0108270109021970

The title compound, [Ni(C20H17N3OP)(N3)], is the first complex with a semicarbazide-based ligand having a P atom as one of the donors. The influence of the P atom on the deformation of the coordination geometry of the Ni ^II ion is evident but l

Full text of DOI:10.1107/S0108270109021970

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
of the extent of the deformation of the metal coordination
environment caused by different donor sets, as well as the
effect on the manner of intermolecular association. According
to a survey of the Cambridge Structural Database (CSD,
Version 3.2; Allen, 2002), among the 201 crystal structures
containing the fragment (I) (see scheme), there are only six
which have a P atom as the X2 donor coordinated to a metal
ISSN 0108-2701
Different intermolecular interactions
in azido[2-(diphenylphosphino)-
benzaldehyde semicarbazonato-
j2P,N1,O]nickel(II)
ˇ
atom (Brceski et al., 2004; Castineiras & Pedrido, 2008; Abram
et al., 2000; Argay et al., 2000; Leovac et al., 1996; You et al.,
1997). The title complex, [NiL(N3)] [HL = 2-(diphenyl-
phosphino)benzaldehyde semicarbazone], (II), represents the
first complex with a semicarbazone-based ligand (X1 = O)
which, besides the standard N- and O-atom donors, involves a
P atom as the third donor in the coordination environment of
the metal.
a
a
´
´
Sladjana B. Novakovic, * Goran A. Bogdanovic, Ilija D.
b
c
ˇ
Brceski and Vukadin M. Leovac
a
ˇ
‘Vinca’ Institute of Nuclear Sciences, Laboratory of Theoretical Physics and
Condensed Matter Physics, PO Box 522, 11001 Belgrade, Serbia, bFaculty of
Chemistry, University of Belgrade, Studentski trg 16, 11000 Belgrade, Serbia, and
cDepartment of Chemistry, Faculty of Sciences, University of Novi Sad, Trg Dositeja
´
Obradovica 3, 21000 Novi Sad, Serbia
Correspondence e-mail: snovak@vinca.rs
Received 28 April 2009
Accepted 9 June 2009
Online 24 June 2009
The title compound, [Ni(C20H17N3OP)(N3)], is the first
complex with a semicarbazide-based ligand having a P atom
as one of the donors. The influence of the P atom on the
deformation of the coordination geometry of the NiII ion is
evident but less expressed than in the cases of complexes with
analogous seleno- and thiosemicarbazide ligands. The torsion
angles involving the two bonds formed by the P atom within
the six-membered chelate ring have the largest values [C—P—
Ni—N = 24.3 (2)ꢀ and C—C—P—Ni = ꢁ24.2 (4)ꢀ], suggesting
that the P atom considerably influences the conformation of
the ring. Two types of N—Hꢂ ꢂ ꢂN hydrogen bond connect the
complex units into chains.
In the crystal structure of (II), the NiII centre occupies a
distorted square-planar environment formed by atoms P1, N1
and O1 of the deprotonated semicarbazone ligand and azide
atom N4 (Fig. 1). While in the cases of the complexes with
equivalent Se and S ligands, [NiL0(NCS)] [HL0 = 2-(di-
phenylphosphino)benzaldehyde selenosemicarbazone], (III)
(Brceski et al., 2004), and [NiL (py)]NO3 [HL00 = 2-(di-
phenylphosphino)benzaldehyde thiosemicarbazone and py is
pyridine] (Leovac et al., 1996), considerable deviation of the P
atom from the mean planes defined by Ni1 and the rest of the
coordinated atoms has been reported [0.494 (3) and
00
ˇ
Comment
Semicarbazones, thiosemicarbazones and selenosemicarba-
zones and their metal complexes have been the subject of
extensive investigations because of their potential pharma-
˚
´
cological properties (Beraldo & Gambino, 2004; Gomez-
0.683 (3) A, respectively], in the present case, for the same
reference plane, the deviation of P1 is less expressed and equal
Quiroga & Navarro Ranninger, 2004). Besides their relevance
for biological studies, the structural diversity of these ligands,
their good complexation abilities and the variety of their
coordination modes have prompted the development of a very
rich structural chemistry related to these compounds (Camp-
˚
to 0.079 (4) A. If the mean reference plane is defined by atoms
O1, N1, P1 and N4, the metal atom is significantly displaced by
˚
0.069 (2) A, which is somewhat smaller than the displacement
of the P1 atom from the mean plane through atoms O1, N1, N4
and Ni1.
´
bell, 1975; Padhye & Kauffman, 1985; West et al., 1991, 1993;
Fanning, 1991; Dittes et al., 1997; Casas et al., 2000). The
similarity in composition and structure which can be attained
by the analogous semi-, thiosemi- and selenosemicarbazone
ligands offers an opportunity for an investigation of the
changes in metal–ligand bonding when the donor set is partly
modified by a donor of different van der Waals radius (O, S
and Se, respectively; Bondi, 1964). It also allows a comparison
Selected geometric parameters for (II) are given in Table 1.
It is worth noting that three metal–ligand bonds (one Ni—O
and two Ni—N) have almost identical lengths, while Ni—P is
longer, as expected. Comparison of this geometry with related
Ni complexes having Se and S ligands points to substantial
˚
shortening of the Ni1—P1 bond by 0.048 (1) and 0.041 (6) A,
respectively. Similarly, the Ni1—N1 bond in (II) is on average
Acta Cryst. (2009). C65, m263–m265
doi:10.1107/S0108270109021970
# 2009 International Union of Crystallography m263

metal-organic compounds
Figure 1
A view of the molecule of (II), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii.
Figure 2
A segment of the crystal packing of (II), viewed approximately along the
c axis, displaying two chains of molecules generated by N—Hꢂ ꢂ ꢂN
hydrogen bonds separated by regions of accumulated phenyl rings. See
Table 2 for symmetry codes.
˚
0.024 (7) A shorter than those in the previously characterized
complexes. This finding suggests that the presence of the O
atom as a donor instead of S or Se induces stronger binding of
the ligand in general.
Coordination of the tridentate ligand to the metal atom in
(II) results in the formation of two fused chelate rings, one
five-membered (semicarbazide) and the other six-membered
[(2-diphenylphosphino)benzaldehyde]. The five-membered
chelate ring is nearly planar, with an r.m.s. deviation of the
Both of these interactions connect centrosymmetrically
related molecules into two types of dimers and further into
chain of dimers (Fig. 2). The stronger N3—H3Bꢂ ꢂ ꢂN2
hydrogen bond engages the semicarbazide parts of a neigh-
bouring complex molecule, forming a cyclic centrosymmetric
1
R22(8) motif (Etter, 1990) centred at (0, 0, ). In the second
2
dimer, the same N3 atom acts as a hydrogen-bond donor via
atom H3A to terminal azide N6 atom. This pair of interactions
therefore results in a centrosymmetric macrocyclic R22(16)
˚
constituent atoms of 0.057 A. The six-membered ring, on the
other hand, exhibits considerable deviation of its atoms from
1
1
the mean plane (0.136 A). The ring-puckering parameters
defined for the atom sequence P1—C4—C3—C2—N1—Ni1
motif, centred at (12, , ). In the further arrangement of (II),
˚
2 2
neighbouring chains of dimers mutually orient their
diphenylphosphine groups (Fig. 2), probably giving rise to C—
Hꢂ ꢂ ꢂꢁ interactions, as some of the perpendicular distances
ꢀ
ꢀ
˚
are ꢀ = 62.0 (8) , ’ = ꢁ20.1 (8) and Q = 0.337 (3) A (Cremer
& Pople, 1975). A similar deformation of the six-membered
chelate ring containing the P atom was observed and
˚
from H atoms to phenyl ring planes do not exceed 2.8 A
ˇ
explained in more detail in a previous report (Brceski et al.,
2004), and it has also been described in other structural
(Desiraju & Steiner, 1999). It should also be mentioned that in
the crystal packing of the complex units, the chelate rings
which represent widely delocalized systems have a parallel
arrangement, resulting in very weak ꢁ-stacking interactions.
The mean planes of these rings are at a distance of 3.7 A from
˚
each other and the shortest distance of 3.42 A was observed
ˇ
´
´
reports (Draskovic et al., 2006; Bogdanovic et al., 1998). The P
atom is the only atom in the chelate ligand which has four
bonds and these bonds are in a distorted tetrahedral
arrangement. The Ni—P1—C4 angle of 111.95 (13)ꢀ is in
contrast with the planar form of the ring, which requires a
wider angle of about 125ꢀ. Considering also that atoms N1, C2,
C3 and C4 are sp2-hybridized and prefer a planar geometry,
the most pronounced deformation of the corresponding
chelate ring is evident in the torsion angles involving the two
bonds formed by P1, viz. C—P—Ni—N = 24.3 (2) and C—C—
P—Ni = ꢁ24.2 (4)ꢀ. The other torsion angles within this
chelate ring are below 12ꢀ. The torsion angles involving P1 in
(II) are, however, smaller than in (III) [29.6 (1) and 27.1 (1)ꢀ,
respectively] and [NiL00(py)]NO3 [31.5 (2) and 25.1 (2)ꢀ,
respectively].
˚
between atoms C3 and O1 (see Fig. S1 in the supplementary
material).
Probably the most interesting result concerning the crystal
structures of (II) and complexes with analogous ligands is
obtained by comparison of the intermolecular interactions in
(II) and (III). Although the coordination environments of the
corresponding Ni atoms in (II) and (III) differ in half the
atoms [P, N, O and azide N in (II), and P, N, Se and thiocyanate
N in (III)], and in (III) the voluminous Se atom takes the place
of the much smaller O-atom donor, these two complexes
arrange in very similar ways (see Fig. S2 in the supplementary
material). Complex (III) also displays two main structural
motifs, R22(8), which here involves the N-atom donors and
The crystal structure arrangement of (II) is dominated by
two relatively strong N—Hꢂ ꢂ ꢂN hydrogen bonds (Table 2).
ꢃ
´
m264 Novakovic et al. [Ni(C20H17N3OP)(N3)]
Acta Cryst. (2009). C65, m263–m265

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
acceptors from the analogous selenosemicarbazide fragment,
and the larger R22(16) motif, where the role of the acceptor is
delegated to the S atom of the linear thiocyanate ligand.
Finally, as in the case of (II), the bulky diphenylphosphine
groups tend to accumulate in separate regions.
ꢀ
˚
Ni1—N1
Ni1—N4
Ni1—O1
Ni1—P1
P1—C4
1.871 (3)
1.872 (4)
1.872 (3)
2.1306 (11)
1.799 (4)
1.811 (4)
P1—C9
N1—C2
N1—N2
N2—C1
N3—C1
O1—C1
1.826 (4)
1.285 (5)
1.401 (5)
1.327 (6)
1.335 (6)
1.297 (5)
P1—C15
Experimental
N1—Ni1—O1
N4—Ni1—O1
N1—Ni1—P1
N4—Ni1—P1
O1—Ni1—P1
N1—Ni1—N4
84.20 (14)
92.28 (15)
94.74 (11)
88.49 (13)
175.49 (11)
174.91 (17)
C4—P1—Ni1
C15—P1—Ni1
C9—P1—Ni1
C4—P1—C15
C4—P1—C9
C15—P1—C9
111.95 (13)
117.29 (15)
110.42 (13)
106.06 (18)
105.94 (19)
104.32 (19)
A mixture of 2-(diphenylphosphino)benzaldehyde semicarbazone
(100 mg) and Ni(NO3)2ꢂ6H2O (100 mg) was dissolved in MeOH
(6 ml) with heating. To this solution, a warm solution of NaN3 (35 mg)
in MeOH (4 ml) was added. Awhite snow-like precipitate was readily
formed which, after 24 h, transformed into red single crystals of
complex (II). The crystals were filtered off and washed with MeOH
(yield 140 mg).
Table 2
Hydrogen-bond geometry (A, ).
ꢀ
˚
Crystal data
D—Hꢂ ꢂ ꢂA
D—H
Hꢂ ꢂ ꢂA
Dꢂ ꢂ ꢂA
D—Hꢂ ꢂ ꢂA
[Ni(C20H17N3OP)(N3)]
Mr = 447.08
Triclinic, P1
ꢄ = 67.556 (19)ꢀ
N3—H3Bꢂ ꢂ ꢂN2i
0.86
0.86
2.27
2.44
3.051 (7)
3.254 (8)
152
158
3
˚
V = 964.7 (4) A
Z = 2
N3—H3Aꢂ ꢂ ꢂN6ii
˚
a = 8.8700 (15) A
˚
Mo Kꢂ radiation
ꢅ = 1.11 mmꢁ1
T = 293 K
0.30 ꢄ 0.28 ꢄ 0.25 mm
Symmetry codes: (i) ꢁx þ 2; ꢁy; ꢁz þ 1; (ii) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.
b = 10.004 (3) A
˚
c = 12.870 (2) A
ꢂ = 69.993 (19)ꢀ
ꢃ = 70.598 (14)ꢀ
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ꢃ
´
Acta Cryst. (2009). C65, m263–m265
Novakovic et al.
[Ni(C20H17N3OP)(N3)] m265