33 卷 5 期
2014. 5
结
构 化 学 （JIEGOU HUAXUE）
Chinese J. Struct. Chem.
Vol. 33, No. 5
753─756
Synthesis and Crystal Structure of a New
Complex [Cu(C14H9O3)2(C5H5N)2(C2H5OH)2]①
HU Wei-Bing② SONG Nan-Nan
HUANG Meng FENG Fu TIAN Da-Ting
ZHOU Hong-Yan SONG Xin-Jian
(Key Laboratory of Biological Resources Protection and Utilization
of Hubei Province, Hubei Institute for Nationalities, Enshi 445000, China)
ABSTRACT
The title compound of Cu(C14H9O3)2(C5H5N)2(C2H5OH)2 (1) was synthesized via the hy-
drothermal reaction of CuCl2·2H2O and 9-hydroxy-fluorene-9-carboxylic acid (HHF) with pyridine, and
characterized by elemental analysis and infrared spectra. The crystal belongs to triclinic, space group P1 with a
= 8.8302(12), b = 10.1625(14), c = 12.2708(17) Å, α = 86.207(2), β = 69.562(2), γ = 64.932(2)º, V = 930.3(2)
Å3, Z = 1, Mr = 764.30, Dc = 1.364 g/cm3, F(000) = 399, S = 1.059 and μ(MoKα) = 0.644 mm-1. The final R =
0.0459 and wR = 0.1274 for 3414 observed reflections with I > 2σ(I). The copper atom is six-coordinated by
two oxygen atoms from two different 9-hydroxy-fluorene-9-carboxylate ligands, two pyridine nitrogen atoms
and two ethanol oxygen atoms, forming a distorted octahedral coordination geometry. The extensive O–H···O
hydrogen bonding connects the molecules to form a one-dimensional chain structure. Between adjacent
one-dimensional chains, a two-dimensional layered structure was formed by fluorene ring π-π packing
interaction. Between the layers, a three-dimensional structure was formed through the π-π packing interaction
of the pyridine ring. Moreover, the thermal stability and photoluminescent property of the complex has been
investigated.
Keywords: 9-hydroxy-fluorene-9-carboxylic acid, synthesis, crystal structure
1
INTRODUCTION
phototropism[5]. Moreover, the 9-hydroxy-fluorene9-carboxylic acid contain two different coordination
Fluorene and its derivatives are very useful com-
sites of hydroxyl and carboxyl, which were good
pounds due to their good optical property and high
potential building complex organization. At present,
luminescent efficiencies, and have received a lot of
relevant synthesis and structure chemical research of
attention
[1-4]
. Two hydrogen atoms in fluorene 9
it and metal ion are relatively less. In this paper, we
digit are replaced by hydroxyl and carboxyl that can
synthesize a novel compound of Cu(C14H9O3)2-
generate 9-hydroxy-fluorene-9-carboxylic acid. It
(C5H5N)2(C2H5OH)2 via the hydro- thermal reaction
has biological activity, and can delay the plant life
of CuCl2·2H2O and 9-hydroxyfluorene-9-carboxylic
and influence plant root gravitropism and stem
acid (HHF) with pyridine.
Received 8 October 2013; accepted 2 November 2013 (CCDC 921611)
① Supported by the Natural Science Foundation of Hubei Province (2012FFB01103), the Hubei Provincial Department of Education
(No. Q20131905), the Fund of Ethnic Affairs Commission of China (No. 12HBZ010), the Open Foundation of Key Laboratory
of Biologic Resources Protection and Utilization of Hubei Province, Forestry Key Disciplines (PKLHB1303) and the
Team Research for Excellent Mid-aged and Young Teachers of Higher Education of Hubei Province (T201006)
② Corresponding author. Tel: 15027224903, E-mail: [email protected]
HU W. B. et al.: Synthesis and Crystal Structure of a
New Complex [Cu(C14H9O3)2(C5H5N)2(C2H5OH)2]
754
2
No. 5
succeeding refinements. The data set was corrected
EXPERIMENTAL
by SADABS program; the structure was solved by
2. 1
direct methods and expanded by difference Fourier
Reagents and measurements
Infrared spectra were measured on a Nicolet 360
techniques with SHELXS-97[6]. The non-hydrogen
FT-IR instrument using KBr pellet in the 4000～400
atoms were refined anisotropically, and the hydro-
-1
cm range. Crystalline structure was measured on a
gen atoms were added according to the theoretical
BRUKER SMART APEX-CCD diffractometer. Ele-
models. The structure was refined by full-matrix
mental analysis was performed by Vario EL Ⅲ
least-squares method on F2 with SHELXL-97[7]. The
elementary analysis instrument. Melting point was
final refinement gave R = 0.0459, wR = 0.1274 (w =
measured on a XT4A Melting-Point Apparatus with
1/[σ2(Fo2) + (0.0799P)2 + 0.2724P], where P = (Fo2 +
Micrsocope and uncorrected. Other chemicals were
2Fc2)/3), S = 1.059, (ᇞ/σ)max = 0.000, (ᇞρ)max =
purchased from commercial sources and used
0.507 and (ᇞρ)min = –0.305 e/Å3.
without further purification.
2. 2
3 RESULTS AND DISCUSSION
Synthesis of the title complex
An ethanolic solution (20 mL) of 9-hydroxyfluorene-9-carboxylic acid (0.5 mmol) was mixed
In order to confirm the configuration of the
with copper chloride dihydrate (0.5 mmol) at room
product, a single crystal of the title compound was
temperature with continuous stirring. After 1 h,
cultured for X-ray diffraction analysis. The selected
pyridine (1 mL) was added to the mixture slowly,
bond lengths and bond angles are shown in Tables 1
then the solution was filtered. An ethanolic solution
and 2, respectively. Table 3 shows the hydrogen-
of the mixture was stood at room temperature. Upon
bonding interaction distance. The crystal structure of
slowly evaporating ethanol from the solution, blue
the title compound is revealed in Fig. 1. Fig. 1 shows
crystals suitable for X-ray diffraction analysis were
that the copper atom is six-coordinated by two
isolated one week later. m.p. 131～133 ℃. Anal.
oxygen atoms from two different 9-hydroxy-fluo-
Calcd. (%). for Cu(C14H9O3)2(C5H5N)2(C2H5OH)2:
rene-9-carboxylate ligands, two pyridine nitrogen
C, 65.97; H, 5.24; N, 3.66. Found (%): C, 66.13; H,
atoms and two ethanol oxygen atoms, forming a
5.31; N, 3.57. IR(KBr) v: 3412(-OH), 3063,
distorted octahedral coordination geometry. In the
3021(Ar-H), 2965(-CH3), 2872(-CH2), 1631(C=O)
crystal structure, the bond length of C(6)–C(7) is
-1
1.461(5) Å, in good agreement with the corres-
cm .
2. 3
Crystal structure determination
ponding value obtained in case of the related fluo-
A blue single crystal of the title compound with
rene derivatives. The extensive O–H···O hydrogen
dimensions of 0.23mm × 0.20mm × 0.20mm was
bonding connects the molecules to form a one-
chosen for X-ray diffraction analysis performed on a
dimensional chain structure (Fig. 2). Between adja-
BRUKER
diffractometer
cent one-dimensional chains, a two-dimensional
equipped with a graphite-monochromatic MoKa
layered structure was formed by fluorene ring π-π
radiation (λ = 0.71073 Å) at 296(2) K. A total of
packing interaction (Fig. 3). Between the layers, a
6766 reflections were collected in the range of
three-dimensional structure was further generated
1.78<θ<25.50º by using a ψ-ω scan mode with 3414
through π-π packing interaction of the pyridine ring
independent ones (Rint = 0.0232), in which 3155
(Fig. 4).
SMART
APEX-CCD
with I > 2σ(I) were observed and used in the
2014
Vol. 33
结
构
化
学（JIEGOU HUAXUE）Chinese J.
Table 1.
Bond
Dist.
Struct. Chem.
755
Selected Bond lengths (Å)
Bond
Dist.
Cu(1)–O(2)
1.9699(16)
C(14)–O(3)
1.234(3)
C(15)–N(1)
Cu(1)–N(1)
2.022(2)
C(1)–C(9)
1.527(4)
C(14)–O(2)
1.258(3)
Cu(1)–O(4)
2.417(2)
C(9)–O(1)
1.412(3)
C(6)–C(7)
1.461(5)
Cu(1)–O(2)#1
1.9700(16)
Cu(1)–O(4)#1
2.417(2)
C(19)–N(1)
1.338(3)
Cu(1)–N(1)#1
2.022(2)
C(3)–C(4)
1.376(7)
C(21)–O(4)
1.445(8
Table 2.
Bond
Dist.
1.340(3)
Selected Bond Angles (°)
Angle
( º)
Angle
( º)
Angle
(º)
O(2)–Cu(1)–O(2)#1
180.00(8)
N(1)–Cu(1)–O(4)
89.64(9)
O(2)#1–Cu(1)–O(4)
91.99(7)
O(2)–Cu(1)–N(1)#1
89.54(8)
O(4)#1–Cu(1)–O(4)
180.00(13)
C(5)–C(6)–C(7)
131.6(4)
O(2)#1–Cu(1)–N(1)#1
90.46(8)
O(2)–C(14)–C(9)
115.0(2)
C(1)–C(6)–C(7)
109.0(3)
O(2)–Cu(1)–N(1)
90.46(8)
C(2)–C(1)–C(9)
129.0(3)
C(13)–C(7)–C(8)
118.7(4)
O(2)#1–Cu(1)–N(1)
89.54(8)
O(1)–C(9)–C(14)
110.1(2)
C(13)–C(7)–C(6)
132.3(3)
N(1)#1–Cu(1)–N(1)
179.999
O(3)–C(14)–O(2)
127.0(2)
O(1)–C(9)–C(8)
111.9(2)
O(2)–Cu(1)–O(4)#1
88.01(7)
N(1)#1–Cu(1)–O(4)#1
90.36(9)
O(1)–C(9)–C(1)
112.9(2)
O(2)–Cu(1)–O(4)
91.99(7)
C(2)–C(3)–C(4)
119.6(4)
Table 3. Hydrogen-bond Geometry (Å, °)
D–H···A
D–H
D···A
D–H···A
O(4)–H(4A1)···O(3)#1
0.82
2.13
H···A
2.706(3)
127.6
O(4)–H(4A1)···O(3)
0.82
2.13
2.706(3)
127.6
O(1)–H(1)···O(3)#2
0.809(10)
2.15(4)
2.622(3)
117(4)
O(1)–H(1)···O(3)
0.809(10)
2.38(3)
3.029(3)
138(4)
Symmetry codes: #1: –x+1, –y+2, –z+2; #2: –x+2, –y+1, –z+2
Fig. 1.
Molecular structure of the title complex
Fig. 3. Two-dimensional layered structure of the title complex
Fig. 2.
One-dimensional chain structure of the title complex
Fig. 4. Three-dimensional structure of the title complex
HU W. B. et al.: Synthesis and Crystal Structure of a
New Complex [Cu(C14H9O3)2(C5H5N)2(C2H5OH)2]
756
3. 1
Thermal analyses
Thermal stability of the title complex was exa-
No. 5
Owning to their potential applications in chemical
photochemistry, sensors, and electroluminescent (EL)
mined by TG analysis under N2 atmosphere in the
display, luminescent metal-organic frameworks are
temperature range of 30～500 ℃ (Fig. 5). TG curve
receiving much attention[8]. In this work, the
of the title complex illustrates that the first weight
luminescence properties of compound 1 and the
loss occurring between 135 and 220 ℃ is 13.07%
ligand
due to the removal of two ethanol molecules (92/764
(HHF) were investigated under ambient temperature
= 12.04%). At the same time, in the range of 220～
(Fig. 6). For 1, the emission bands at 460 nm (λex =
315 ℃, there is a 54.68% weight loss owing to the
316 nm) are observed. The ligand of 9-hydroxy-
release of two 9-hydroxy-fluorene-9-carboxylic acid
fluorene-9-carboxylic acid (HHF) exhibits emission
molecules (450/764 = 58.90%) and a 54.68% weight
band at 491 nm (λex = 332 nm). According to the
loss in the 315 ～ 375 ℃ range because of the
reported literatures, the emission band of 1 may be
decomposition of pyridine ligands.
interpreted as a ligand-to-metal charge transition
3. 2
(LMCT)[9].
Photoluminescent property
Fig. 5.
TG curve of title complex
of
Fig. 6.
9-hydroxy-fluorene-9-carboxylic
acid
Luminescent spectra at room temperature
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