Bis{μ-2-[(2-carbamoylhydrazin-1-yl-idene)methyl]phenolato} bis-[chlorido-zinc(II)] methanol disolvate, with non-aromatic-aromatic π-π Stacking and N - H...Cl - Zn hydrogen bonding

Article abstract of DOI:10.1107/S0108270110033561

Centrosymmetric dimers of Zn^II with singly deprotonated 2-[(2-carbamoylhydrazin-1-yl-idene)meth-yl]phenolate, [Zn2(C₈H ₈N₃O₂)Cl2]·2CH₃OH, form an infinite one-dimensional hydrogen-bonded ch

Full text of DOI:10.1107/S0108270110033561

metal-organic compounds
˚
Acta Crystallographica Section C
Crystal Structure
Communications
gorized as short (Hꢀ ꢀ ꢀCl ꢂ 2.52 A), intermediate (2.52–
˚
˚
2.95 A) and long (2.95–3.15 A). It was reported that M—Cl in
complexes has the potential to interact with hydrogen-bond
donors in both a strong (i.e. short) and an anisotropic fashion.
To the best of our knowledge, non-aromatic–aromatic ꢀ–ꢀ
stacking has rarely been reported. In this work, the synthesis
and structural characterization of the title dinuclear ZnII
complex, (I), containing nonclassical N—Hꢀ ꢀ ꢀCl—ZnII
hydrogen bonding and ꢀ–ꢀ interactions that involve non-
aromatic groups, are discussed.
ISSN 0108-2701
Bis{l-2-[(2-carbamoylhydrazin-1-yl-
idene)methyl]phenolato}bis[chlorido-
zinc(II)] methanol disolvate, with non-
aromatic–aromatic p–p stacking and
N—Hꢀ ꢀ ꢀCl—Zn hydrogen bonding
Jing-lin Wang, Bin Liu and Bin-sheng Yang*
Key Laboratory of Chemical Biology and Molecular Engineering of the Ministry of
Education, Institute of Molecular Science, Shanxi University, Taiyuan, Shanxi
030006, People’s Republic of China
Correspondence e-mail: yangbs@sxu.edu.cn
Received 16 July 2010
Accepted 19 August 2010
Online 4 September 2010
Compound (I) is composed of centrosymmetric [Zn-
(HSSC)Cl]2 dimers {HSSC is 2-[(2-carbamoylhydrazin-1-yl-
idene)methyl]phenolate} (Fig. 1). Each HSSCꢁ ligand has a
deprotonated phenol group, which forms a one-atom bridge
between the two ZnII centres, and coordinates to one ZnII ion
through its N2 and O1 atoms. The Zn1ꢀ ꢀ ꢀZn1iv distance is
Centrosymmetric dimers of ZnII with singly deprotonated
2-[(2-carbamoylhydrazin-1-ylidene)methyl]phenolate, [Zn2-
(C8H8N3O2)Cl2]ꢀ2CH3OH, form an infinite one-dimensional
hydrogen-bonded chain which is further aggregated by non-
aromatic–aromatic ꢀ–ꢀ stacking and nonclassical N—Hꢀ ꢀ ꢀCl
hydrogen bonding.
˚
3.1317 (13) A [symmetry code: (iv) ꢁx + 1, ꢁy + 1, ꢁz + 1].
Atom Zn1 has a square-pyramidal coordination environment
and is situated slightly above the basal plane, which is formed
by N2 from azomethine (–CH N–), O1 from ureido (–NH—
CO—NH2) and O2 and O2iv from different phenol groups,
with the axial position occupied by one Clꢁ ion (Fig. 1). The
Zn—O(N,Cl) distances and related angles are all within
expected ranges (Casas et al., 2000). However, the structure of
Comment
In the past decade, the coordination-driven and conventional
hydrogen-bonding-directed self-assembly of high-symmetry
conglomerates has been studied extensively (Wei et al., 2009).
Noncovalent interactions have also been recognized as playing
a substantial role in a variety of chemical and biological
phenomena (Nishio, 2004). The understanding and utilization
of all types of noncovalent interactions, including ꢀ–ꢀ
stacking, are of fundamental importance for the further
development of supramolecular chemistry and the study and
prediction of crystal structures (Janiak, 2000). Dance &
Scudder (1995) suggested the concept of ‘molecular embrace’,
based on phenyl–phenyl intermolecular interactions, and
developed the embrace paradigm as an important and wide-
spread intermolecular motif and crystal engineering tool by
analysing the packing of molecules in crystals (Dance &
Scudder, 2009). Varied hydrogen-bond patterns, including
traditional and nonclassical versions, have been observed in
crystal packing, giving diverse supramolecular motifs (Casas et
´
al., 2004). Aullon et al. (1998) conducted a study based on the
Cambridge Structural Database (Allen, 2002) involving
hydrogen bonds containing M—Cl (M = transition metal),
C—Cl or Clꢁ and either HO or HN. The results indicated that
M—Cl moieties are good anisotropic hydrogen-bond accep-
tors. The D—Hꢀ ꢀ ꢀCl—M (D = O or N) contacts were cate-
Figure 1
The molecular structure of (I), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level and H
atoms are shown as small spheres of arbitrary radii. [Symmetry code: (iv)
ꢁx + 1, ꢁy + 1, ꢁz + 1.]
m280 # 2010 International Union of Crystallography
doi:10.1107/S0108270110033561
Acta Cryst. (2010). C66, m280–m282

metal-organic compounds
Figure 3
The arrangement of one-dimensional staircase chains in the ab plane.
Hydrogen-bonding interactions are represented by dashed lines. H atoms
not involved in hydrogen bonding have been omitted.
Figure 2
(a) The one-dimensional staircase structure of (I) formed by N1—
H1ꢀ ꢀ ꢀCl1(x ꢁ 1, y, z) hydrogen bonds and extending along the a axis.
Hydrogen-bonding interactions are represented by dashed lines. For
clarity, H atoms not involved in hydrogen bonding have been omitted. (b)
A drawing of the non-aromatic–aromatic ꢀ–ꢀ contacts between adjacent
dimers in the one-dimensional staircase chain.
the HSSCꢁ ligand is slightly twisted, with an angle of 13.5 (3)ꢃ
between the ureido plane (C1/O1/N1/N3) and the benzene
group (C3–C8) to accommodate the geometric requirements
of coordination about ZnII, and to accommodate noncovalent
interactions.
The ꢀ-electron density is delocalized in neutral H2SSC,
especially when an aromatic group is bound to the azomethine
C atom (Casas et al., 2000). Compared with free H2SSC, the
related bond lengths of the C2—N2—N1—C1—O1—N3
backbone are almost unvaried in the dimer of (I) (Table 1). In
addition, compared with conventional localized bond lengths
Figure 4
The two-dimensional net structure of (I) formed by hydrogen-bonding
interactions (dashed lines), showing the formation of an (010) sheet. For
clarity, H atoms not involved in hydrogen bonding have been omitted.
˚
˚
of C—N = 1.472 (5) A in RNH2, N—N = 1.451 (5) A in
˚
R2NNH2 and C O = 1.145 (10) A in carbonyls (Dean 1999),
the corresponding single bonds are shorter and the double
bonds are longer in (I). Thus, it is reasonable to conclude that
HSSCꢁ maintains a considerably delocalized ꢀ system in the
dimer of (I).
The dimers of (I) are assembled through intermolecular
N1—H1ꢀ ꢀ ꢀCl1iii interactions [Table 2; symmetry code: (iii)
x ꢁ 1, y, z] and non-aromatic–aromatic ꢀ–ꢀ interactions to
form an infinite one-dimensional hydrogen-bond-supported
chain. This one-dimensional chain has the form of a staircase
propagating in the direction of the shortest lattice parameter
parallel, being related by a centre of symmetry, and are at a
˚
distance of 3.618 (7) A.
The one-dimensional chains pack into two-dimensional
sheets in which neighbouring chains are related by a b-axis
translation (Fig. 3). Between adjacent chains there are van der
Waals contacts between HSSC groups, but their relative
disposition is substantially slipped so that no ꢀ–ꢀ interaction
exists.
More significantly, the one-dimensional chains stack in a
side-by-side fashion along the c axis to form two-dimensional
sheets of parallel staircases, which are held together through
hydrogen bonds to form aggregates, the basic units of which lie
parallel to (010) (Fig. 4). Hydrogen bonding mediates the
formation of a chain of fused rings parallel to the a axis of the
unit cell, with alternating R44(12) and R24(8) rings [see Bern-
stein et al. (1995) for hydrogen-bonding motifs]. These
hydrogen-bonded rings also involve the methanol solvent
molecules (Table 2).
´
(a axis; Fig. 2a). According to the study of Aullon et al. (1998),
the H1ꢀ ꢀ ꢀCl1iii distance of 2.33 A indicates strong hydrogen-
˚
bonding interactions in the one-dimensional chains. Within
one staircase-like chain, the HSSCꢁ ligand is in contact with
that at (ꢁx, ꢁy + 1, ꢁz + 1) in a head-to-tail fashion, with ꢀ–ꢀ
interactions that appear to extend the entire length of the
ligand (Fig. 2b). Specifically, non-aromatic ureido and
azomethine and aromatic phenol groups participate in ꢀ-
stacking. The best planes of the two contacting ligands are
ꢄ
Acta Cryst. (2010). C66, m280–m282
Wang et al.
[Zn2(C8H8N3O2)Cl2]ꢀ2CH4O m281

metal-organic compounds
Table 1
Selected bond lengths (A).
Experimental
˚
2-[(2-Carbamoylhydrazin-1-ylidene)methyl]phenol (H2SSC) was
prepared by the reaction of semicarbazide hydrochloride with 2-hy-
droxybenzaldehyde in a 1:1 molar ratio in water. Analysis calculated
for H2SSC: C 53.63, H 5.06, N 23.45%; found: C 53.74, H 5.065, N
22.97%. IR (KBr): ꢁ(OH) 3472 cmꢁ1, ꢁ(C O) 1697 cmꢁ1, ꢁ(C N)
1622 cmꢁ1, ꢁ(C—O) 1267 cmꢁ1. H2SSC (0.179 g, 1 mmol) and ZnCl2
(0.136 g, 1 mmol) were dissolved separately in methanol (20 ml).
These solutions were mixed in a flask and stirred for ꢅ3 h. A milky
white precipitate was obtained from the resulting reaction solution,
separated by filtration, washed with methanol and tetrahydrofuran,
and dried. The filtrate was allowed to stand at room temperature and
colourless single crystals of (I) were grown by slow evaporation over
a period of about four weeks. Analysis calculated for Zn(HSSC)Cl: C
34.44, H 2.89, N 15.06%; found: C 34.32, H 2.91, N 15.02%. IR (KBr):
C1—N1
N1—N2
C2—N2
1.362 (7)
1.391 (6)
1.288 (7)
C1—N3
C1—O1
1.336 (7)
1.246 (6)
Table 2
Hydrogen-bond geometry (A, ).
ꢃ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N3—H3Aꢀ ꢀ ꢀO3
N3—H3Bꢀ ꢀ ꢀO3i
O3—H3ꢀ ꢀ ꢀO1ii
N1—H1ꢀ ꢀ ꢀCl1iii
0.86
0.86
0.82
0.86
2.08
2.27
2.13
2.33
2.929 (7)
3.040 (8)
2.923 (6)
3.175 (5)
170
150
163
166
Symmetry codes: (i) ꢁx; ꢁy þ 1; ꢁz; (ii) ꢁx þ 1; ꢁy þ 1; ꢁz; (iii) x ꢁ 1; y; z.
ꢁ(C O) 1665, ꢁ(C N) 1600, ꢁ(C—O) 1275 cmꢁ1
.
Crystal data
The authors thank the National Natural Science Foundation
of the People’s Republic of China (grant Nos. 20771068 and
20901048) and the Natural Science Foundation of Shanxi
Province (grant No. 2010011011-1).
[Zn2(C8H8N3O2)Cl2]ꢀ2CH4O
ꢄ = 76.003 (1)ꢃ
V = 633.04 (15) A
Z = 1
Mo Kꢂ radiation
ꢅ = 2.15 mmꢁ1
T = 298 K
0.38 ꢆ 0.20 ꢆ 0.10 mm
3
˚
Mr = 622.07
Triclinic, P1
˚
a = 6.9061 (8) A
˚
b = 8.3585 (12) A
˚
c = 11.7666 (16) A
ꢂ = 75.066 (1)ꢃ
ꢃ = 80.565 (2)ꢃ
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FA3235). Services for accessing these data are
described at the back of the journal.
Data collection
Bruker SMART CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
Tmin = 0.496, Tmax = 0.814
3291 measured reflections
2179 independent reflections
1602 reflections with I > 2ꢆ(I)
Rint = 0.051
References
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155 parameters
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˚
Áꢇmax = 0.78 e A
ꢁ3
˚
2179 reflections
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˚
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˚
˚
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m282 Wang et al. [Zn2(C8H8N3O2)Cl2]ꢀ2CH4O
Acta Cryst. (2010). C66, m280–m282