Synthesis and crystal structure of (o-Diaminobenzene)2 Zn(OAc)2

Article abstract of DOI:10.1134/S107032840912001X

The treatment of o-diaminobenzene with Zn ( OAc )₂ ? 2H₂O in alcohol results in the formation of mononuclear bis(o-diaminobenzene)diacetate Zinc, Zn[C₈H₁₁N ₂O₂]₂. Its structure w

Full text of DOI:10.1134/S107032840912001X

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2009, Vol. 35, No. 12, pp. 871–873. © Pleiades Publishing, Ltd., 2009.
Synthesis and Crystal Structure
1
of (o-Diaminobenzene)2Zn(OAc)2
L. Meia,*, J. Lia, Z. S. Mingb, L. Q. Rongb, and L. X. Lianga
a Hefei University of Technology, Hefei 230009, P.R. China
b University of Science and Technology of China, Hefei 230009, P.R. China
*e-mail: luomei@pku.edu.cn; luomeihuahua@sohu.com
Received February 20, 2009
Abstract—The treatment of o-diaminobenzene with Zn(OAc)2 · 2H2O in alcohol results in the formation of
mononuclear bis(o-diaminobenzene)diacetate Zinc, Zn[C8H11N2O2]2. Its structure was determined by X-ray
diffraction analysis. The complex is also characterized by elemental analysis, 1H NMR and IR. The crystal is
monoclinic space group C2, parameters: a = 16.297(5), b = 4.775(3), c = 11.664(5) Å, β = 97.646(5)°, λ = 1.54184 Å,
V = 899.6(7) Å3, Z = 2, ρc = 1.476 g/cm3, Mr = 399.75, F(000) = 416.0, R1 = 0.0594, wR2 = 0.1439 for 995
observed reflections with I > 2σ(I).
DOI: 10.1134/S107032840912001X
1
INTRODUCTION
suitable for X-ray single crystal analysis, were
obtained. The yield of I was 37% (0.24 g).
The Zn–N complexes have been reported by many lit-
eratures [1–6], because they occupied an important posi-
tion in catalytic processes. For example, as the catalysts
they have showed high activities in the organic reaction
and polymerization [7, 8]. Inspired by their work, we first
synthesized the novel Zn–N complex with the simple one-
pot method. The crystal structure was obtained in the pro-
cess of recrystallization and characterized by elemental
analysis, 1H NMR and IR.
For Zn[C8H11N2O2]2
anal. calcd, %:
Found, %:
C, 48.07;
C, 48.20;
H, 5.55;
N, 14.02.
N, 14.13.
H, 5.636;
1H NMR (300 MHz, CDCl3; 27°C; δ, ppm): 6.46–
7.09 (s., 8H), 2.30–3.57 (s., 8H), 1.78–2.16 (s, 6H). IR
spectrum (KBr pellet; ν, cm–1): 3412, 3348, 3266, 3232,
3130, 3045, 2925, 2796, 2720, 2507, 1912, 1872, 1750,
1663, 1625, 1571, 1507, 1401, 1337, 1305, 1222, 1111,
1020, 935, 858, 741, 681, 655, 529, 481, 440.
EXPERIMENTAL
X-ray structure determination. A colorless block
monoclinic crystal of compound I approximating to
0.28 × 0.26 × 0.20 mm was selected for the data collec-
tion on a Gemini S Ultra diffractometer with graphite
monochromated MoKα radiation (λ = 1.54184 Å).
Reflections were collected in a range of 3.82° < θ < 62.79°
by using “multi-scan” techniques at 295 K,
C16H22N4O4Zn, M = 399.75, γ = 90°, V = monoclinic,
space group C2, a = 16.297(5), b= 4.775(3), c= 11.664(5) Å,
β = 97.646(5)°, V = 899.6(7) Å3, Z = 2, ρcalcd = 1.47 g/cm3,
the final R factor was R1 = 0.0594, 995 for reflections
with I0 > 2σ(I0), Rw = 0.1439 for all data, largest peak
and hole was 0.82 and –0.58 e Å–3, respectively. H
atoms on N(1) atom were fixed geometrically and con-
strained to ride on it parent atom, with N–H = 0.90 Å,
and with Uiso(H) = 1.2Ueq(N). H atoms on N(2) atom
were located in difference Fourier maps and refined iso-
tropically, with restrains of N–H = 0.90(4). The remaining
H atoms were positioned geometrically with C–H = 0.93
and 0.96 Å, for aromatic and methyl H atoms and con-
strained to ride on their parent atoms, with Uiso(H) =
The 1H NMR spectra were obtained using a Bruker
AM-300 spectrometer. Infrared spectra were recorded
on a Mattson Galaxy Series Spectrum-100 spectrome-
ter. Elemental analysis was performed on a VARIO
ELIII elemental analyzer. And crystal structure was
determined by Gemini S Ultra diffractometer.
Synthesis of bis(2-aminopyridine) zinc complex
(I). o-Diaminobenzene (0.3244 g, 3 mmol) was added
to an ethanolic solution (30 ml) of Zn(OAc)2 · 2H2O
(0.6575 g, 3 mmol) in dry ethanol 100-ml Schlenk flask
under free-water and free-oxygen conditions. The reac-
tion mixture was stirred vigorously while refluxing for
24 h and then filtered. The solution was slowly cooled
to room temperature, and a silver-gray solid slowly sep-
arated out. Recrystallizing the silver-gray solid with
dichloromethane, colorless block crystals, which were
1
The article is published in the original.
871

872
MEI et al.
Table 1. Selected bond distances and bond angles for complex I Table 2. Hydrogen bond distances and angles for the complex
Distance, Å
Bond
d, Å
Angle
ω, deg
Angle
Contact D–H···A
DHA, deg
D–H
H···A
2.08
D···A
Zn(1)–O(1)
Zn(1)–N(1)
O(1)–C(1)
O(2)–C(1)
N(1)–C(4)
N(2)–C(9)
1.9619
2.0522
1.3153
1.2084
1.4487
1.3723
O(1)Zn(1)O(1)
O(1)Zn(1)N(1)
N(1)Zn(1)N(1)
C(1)O(1)Zn(1)
C(4)N(1)Zn(1)
O(2)C(1)O(1)
O(2)C(1)C(2)
O(1)C(1)C(2)
99.70
101.55
106.44
111.71
115.33
121.12
122.23
116.64
N(2)–H(1B)···O(1) 0.90
2.948(8) 162(1)
N(2)–H(2D)···O(2) 0.90(2) 2.20(2) 3.091(9) 170(9)
NH2
NH2
Zn
NH2
+ Zn(OAc)2 · 2H2O
NH2
OAc
OAc
NH2
NH2
Several interesting observations can be made about the
structure from Fig. 1. The complex I was composed of
two o-diaminobenzene, and Zn(OAc)2 cores, around
the zinc ion is N(1), N(2), O(1) and O(3), with these
atoms forming a tetrahedron with the zinc ion in the
center. The C(4)–C(9) atoms are coplanar. The bond
lengths C–C are in range of 1.368–1.400 Å, and the
CCC angles are nearly 120°. The bond distance C(1)–
O(2) 1.208 Å, indicating some double-bond characters.
Four o-diaminobenzene molecules, and two Zn(OAc)2
cores are connected together to construct a hydrogen-
xUeq(C), where x = 1.2 for aromatic H and x = 1.5 for
methyl H atoms. The structure was solved by full-
matrix least squares on F2 using the SHELXTL pro-
gram [9–11]. Selected bond distances and bond angles
are listed in Table 1.
The atomic coordinates and other parameters of
structure I have been deposited with the Cambridge
Crystallographic Data Center (no. 730209;
deposit@ccdc.cam.ac.uk).
z
RESULTS AND DISCUSSION
The synthetic route of compound I can be summa-
rized as follows:
N2
N1
C9
C8
y
C4
Zn1
x
C7
C5
C6
O1
C1
O2
C2
Fig. 1. Crystal structure of complex I.
Fig. 2. Packing structure of complex I.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 35 No. 12 2009

SYNTHESIS AND CRYSTAL STRUCTURE
873
5. Chen, F.T., Tang, G.R., and Jin, G.X., J. Org. Chem.,
bonded dinuclear structure (Fig. 2). The hydrogen-
bond distance N···O of are given in Table 2.
2007, vol. 692, p. 3435.
6. Sumanta, K.P., Rojalin, S., and Vadivelu, M., Polyhe-
dron, 2008, vol. 27, p. 805.
In conclusion, crystalline of Zn[C8H11N2O2]2 was
synthesized with a simple, one-pot method. Research is
going toward the application to organic reactions such
as the Henry reaction and cyaosilylation reaction.
7. Chakraborty, D. and Chen, E.Y.X., Organometallics,
2003, vol. 22, p. 769.
8. Yu, K. and Jones, C.W., Organometallics, 2003, vol. 22,
p. 2571.
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