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Synthesis and structure of bis(dibenzoylmethane)copper(II)

Article  in  Journal of Chemical Crystallography · July 1999

DOI: 10.1023/A:1009543703278

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Journal of Chemical Crystallography, Vol. 29, No. 7, 1999

Synthesis and structure of bis(dibenzoylmethane)

copper(II)

Bao-Qing Ma,(1) Song Gao,(1)* Zhe-Ming Wang,(1) Chun-Sheng Liao,(1) Chun-Hua Yan,(1)
and Guang-Xian Xu(1)

Received April 7, 1999

Bis(dibenzoylmethane)copper Cu(dbm)2 has been synthesized and its structure determined

by x-ray diffraction. It crystallizes in the monoclinic system, space group C2/c, with a ⫽
25.936(3), b ⫽ 5.9806(8), c ⫽ 16.4908(16) Å, 웁 ⫽ 114.998(8)⬚, Z ⫽ 4, and V ⫽ 2318.3(4) Å3.
The Cu atom is located at a symmetry center and surrounded by four O atoms from two
dbm molecules to form a plane square coordination environment. On the a–c plane the
molecules are orderly arranged to result in a layered structure, and parallel to crystallographic
b-axis they form a molecular column due to the effect of aromatic stacking.

KEY WORDS: Copper complex; crystal structure; dibenzoylmethane complex.

Introduction Experimental

The chemical vapor deposition (CVD) of metals Materials

from metal-organic molecules is the subject of much
interest as a result of potential applications in the
microelectronics industry.1 The copper(II) 웁-diketo-
nate compounds are a good choice due to their high
vapor pressure. In the past, many copper 웁-diketo-
nate (R-COCH2COR⬘) compounds were synthesized
and structurally characterized by single crystal x-ray
diffraction, including symmetric (R u R⬘) and asym-
metric (R ⬆ R⬘) 웁-diketonate or mixed 웁-diketonate
ligands.2–10 In the case of dibenzoylmethane (dbm),
previous studies were mainly involved trivalent metal
Sc, Cr, Mn, Fe, Co, Ga, Al, Ln, etc.11–15 For divalent
metal ions, the structures are relatively limited. In
this paper, we report the synthesis and structural
characterization of the complex Cu(dbm)2.
(1)
State Key Laboratory of Rare Earth Materials Chemistry and
Applications, College of Chemistry and Molecular Engineering,
Peking University, Beijing 100871, P. R. China.
* To whom correspondence should be addressed.
CuCl2 ⭈ 2H2O, dibenzoylmethane and sodium
methoxide and analytic reagent are used without fur-
ther purification.
Synthesis
CuCl2 ⭈ 2H2O (1 mmol) dissolved in 10 mL meth-
anol was added to a 10 mL methanol solution con-
taining 2 mmol dbm. The mixture solution were ad-
justed to pH ⫽ 6 with methanol solution of sodium
methoxide and stirred for 4 h at room temperature.
The yellow-green precipite formed was filtered off
and washed with methanol (Yield: 42%). The prod-
ucts were recrystallized from CH2Cl2 at room temper-
ature and the plate-shaped single crystals suitable for
x-ray diffraction analysis were obtained after 5 days.
Calcd. for C30H22O4Cu: C, 70.59; H, 4.31. Found: C,
70.37; H, 3.98.

793
1074-1542/99/0700-0793$16.00/0  1999 Plenum Publishing Corporation
794 Ma, Gao, Wang, Liao, Yan, Xu

Table 1. Crystal Data and Structure Refinement for Cu(dbm)2

Compound Cu(C6H5COCHCOC6H5)2
CCDC deposit no. CCDC-1003/5603
Color/Shape Brown/plate
Empirical formula C30H22CuO4
Formula weight 510.02
Temperature 293(2) K
Wavelength 0.71073 Å
Crystal system Monoclinic
Space group C2/c
Unit cell dimensions
a ⫽ 25.936(3) Å 움 ⫽ 90⬚
b ⫽ 5.9806(8) Å 웁 ⫽ 114.998(8)⬚
c ⫽ 16.4908(16) Å 웂 ⫽ 90⬚
Volume 2318.3(4) Å3
Z 4
Calculated density 1.461 mg/cm3
Absorption coefficient 0.978 mm⫺1
F(000) 1052
Crystal size 0.34 ⫻ 0.18 ⫻ 0.08 mm3
Theta range for data collection 1.73 to 26.99⬚
Limiting indices 0 ⬍ ⫽ h ⬍ ⫽ 32, 0 ⬍ ⫽ k ⬍ ⫽ 7, ⫺21 ⬍ ⫽ l ⬍ ⫽ 19
Reflections collected/unique 2584/2530 [R(int) ⫽ 0.0490]
Completeness to theta ⫽ 26.99 99.9%
Max. and min. transmission 0.996 and 0.7949
Refinement method Full-matrix least-squares on F 2
Data/restraints/parameters 2530/0/160
Goodness-of-fit on F 2 0.980
Final R indices [I ⬎ 2␴(I)] R1 ⫽ 0.0683, wR2 ⫽ 0.1215
R indices (all data) R1 ⫽ 0.1566, wR2 ⫽ 0.1483
Largest diff. peak and hole 0.353 and ⫺0.500 e Å⫺3

Data collection and structure refinement

A crystal with dimensions 0.34 mm ⫻ 0.18
mm ⫻ 0.08 mm was chosen and mounted on a Nonius
CAD4 Mach3 diffractometer. Unit cell parameters Table 2. Atomic Coordinates (⫻104) and Equivalent Isotropic and
Displacement Parameters (Å2 ⫻ 103) for Cu(dbm)2
were determined from 25 reflections in the range
9.98⬚ ⬍ ␪ ⬍ 13.93⬚. The data were reduced by the x y z U(eq)
MoLEN program. The structure was solved by direct
method using the SHELXS97 program and refined by Cu(1) 0 0 0 38(1)
full-matrix least-squares on F 02 using the SHELXL97 O(1) ⫺357(1) ⫺2630(6) 148(2) 41(1)
program with anisotropic temperature factors for all O(2) 679(1) ⫺551(5) 1060(2) 43(1)
C(1) ⫺392(2) ⫺7666(9) 1333(3) 43(1)
nonhydrogen atoms: All hydrogen atoms were placed C(2) ⫺775(2) ⫺9284(9) 1299(3) 46(1)
in calculated positions. The crystal data and structure C(3) ⫺1332(2) ⫺9134(10) 679(4) 54(2)
refinement appear in Table 1. Positional parameters C(4) ⫺1492(2) ⫺7375(10) 105(4) 57(2)
of nonhydrogen atoms of the complex are listed in C(5) ⫺1116(2) ⫺5734(9) 138(3) 49(2)
Table 2. C(6) ⫺556(2) ⫺5846(8) 768(3) 34(1)
C(7) ⫺161(2) ⫺3994(9) 802(3) 36(1)
C(8) 381(2) ⫺3819(9) 1510(3) 41(1)
C(9) 777(2) ⫺2186(8) 1591(3) 34(1)
Results and discussion C(10) 1365(2) ⫺2292(8) 2330(3) 35(1)
C(11) 1747(2) ⫺614(9) 2387(3) 49(2)
The ORTEP drawing is shown in Fig. 1. Selected C(12) 2294(2) ⫺655(10) 3056(3) 59(2)
bond lengths and angles are given in Table 3. C(13) 2469(2) ⫺2330(11) 3676(4) 57(2)
C(14) 2091(2) ⫺3970(10) 3632(4) 56(2)
The Cu atom is located at a symmetry center C(15) 1548(2) ⫺3975(10) 2954(3) 49(1)
and surrounded by four O atoms from two dbm mole-
Bis(dibenzoylmethane) copper (II) 795

1.266(5) Å, slightly shorter than that of free ligand

Fig. 1. ORTEP view of Cu(dbm)2 (50% probability for the thermal
ellipsoids).
cules, leading to a planar square coordination envi-
ronment. The CuUO(1) and CuUO(2) bond dis-
tances are 1.892(3) and 1.914(3) Å, respectively, in
agreement with that of other copper complexes with
웁-diketonates.2–10,16 The O(1)UCuUO(2) bond angle
(92.88(13)⬚) is close to 90⬚. The bond lengths of
O(1)UC(7) and O(2)UC(9) are 1.274(5) and
(1.284, 1.292 Å).17 This may be contributed by a back-
bonding effect from the 3d orbital of the Cu atom,
which makes the CUO bond stronger.
The O(1)UC(7)UC(8)UC(9)UO(2) atoms
are almost coplanar with a maximum deviation of
0.0283(32) Å. The dihedral angles between this plane
and two of the terminal phenyl rings (C(1)UC(6))
and (C(10)UC(15)) are 9.96(30) and 4.98(33)⬚, re-
spectively, suggesting the phenyl rings with their low
twisting angles participate in the 앟 delocalization of
the 웁-diketonate enol ring.
In the molecular packing diagram (Fig. 2), indi-
vidual molecules are arranged orderly along the a-c
plane, giving rise to a layered structure. The neigh-
boring interlayer distance is 5.9806 Å, which is equal
to the length of the b axis. In the b viewing direction,
the molecules overlap completely, due to the effect
of aromatic stacking, yielding a molecular column
(Fig. 3). This kind of conjugation effect will reduce
the energy of the system and stabilize crystal
packing.18
Conclusions
A new compound, Cu(dbm)2, was synthesized
and characterized by x-ray diffraction analysis. In the
complex, the Cu atom is located at a symmetry center
and has a planar square coordination environment.

Table 3. Selected Bond Lengths [Å] and Angles [⬚] for Cu(dmb)2

Bond distances
Cu(1)UO(1) 1.892(3) Cu(1)UO(2) 1.914(3)
O(1)UC(7) 1.274(5) O(2)UC(9) 1.266(5)
C(1)UC(2) 1.370(6) C(1)UC(6) 1.378(7)
C(2)UC(3) 1.377(7) C(3)UC(4) 1.358(7)
C(4)UC(5) 1.370(7) C(5)UC(6) 1.384(6)
C(6)UC(7) 1.494(7) C(7)UC(8) 1.400(6)
C(8)UC(9) 1.382(6) C(9)UC(10) 1.499(6)
C(10)UC(15) 1.372(7) C(10)UC(11) 1.386(6)
C(11)UC(12) 1.381(6) C(12)UC(13) 1.365(7)
C(13)UC(14) 1.366(8) C(14)UC(15) 1.380(6)
Bond angles
O(1)UCu(1)UO(2) 92.88(13) C(7)UO(1)UCu(1) 126.9(3)
C(9)UO(2)UCu(1) 127.1(3) C(2)UC(1)UC(6) 121.2(5)
C(1)UC(2)UC(3) 120.0(5) C(4)UC(3)UC(2)1 119.0(5)
C(3)UC(4)UC(5) 121.7(5) C(4)UC(5)UC(6) 119.9(5)
C(1)UC(6)UC(5) 118.2(5) C(1)UC(6)UC(7) 123.3(4)
C(5)UC(6)UC(7) 118.5(4) O(1)UC(7)UC(8) 123.9(5)
O(1)UC(7)UC(6) 114.9(4) C(8)UC(7)UC(6) 121.1(4)
C(9)UC(8)UC(7) 125.2(5) O(2)UC(9)UC(8) 123.8(4)
O(2)UC(9)UC(10) 115.6(4) C(8)UC(9)UC(10) 120.6(4)
C(15)UC(10)UC(11) 118.0(4) C(15)UC(10)UC(9) 123.4(5)
(11)UC(10)UC(9) 118.6(4) C(12)UC(11)UC(10) 120.3(5)
C(13)UC(12)UC(11) 121.0(5) C(12)UC(13)UC(14) 118.9(5)
C(13)UC(14)UC(15) 120.6(5) C(10)UC(15)UC(14) 121.1(5)
Fig. 2. A layered packing diagram in the a–c projection.
796
Fig. 3. Stereoscopic drawing of molecular packing along the b
direction.
Due to the effect of aromatic packing, the molecules
form a molecular column along the b direction.
Acknowledgments
Financial support by the National Natural Sci-
ence Foundation of China (No. 29771001 and
View publication stats
Ma, Gao, Wang, Liao, Yan, Xu
29525101), National Key Project for Fundamental
Research, and Founder Corporation Group Founda-
tion of Peking University is greatly appreciated.
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