X-ray Structure Analysis Online 2013, VOL. 29
2013 © The Japan Society for Analytical Chemistry
33
X-ray Structure Analysis Online
Synthesis and Crystal Structure of a Chain Complex of Molybdenum(II)
Acetate and trans-1,2-Bis(4-pyridyl)ethylene in Relation to the N2-Adsorption
Property
Masahiro MIKURIYA,*† Shohei TAKADA,* Daisuke YOSHIOKA,* Hidekazu TANAKA,** and
Makoto HANDA**†
*Department of Chemistry and Research Center for Coordination Molecule-based Devices, School of Science
and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda 669-1337, Japan
**Department of Chemistry, Interdisciplinary Graduate School of Science and Engineering, Shimane
University, 1060 Nishikawatsu, Matsue 690-8504, Japan
The title compound, a chain adduct of molybdenum(II) acetate with trans-1,2-bis(4-pyridyl)ethylene (bpel),
catena(tetrakis(m-acetato-O,O¢)(m-trans-1,2-bis(4-pyridyl)ethylene-N,N¢)dimolybdenum(II)), [Mo2(CH3CO2)4(bpel)]n, was
synthesized, and the crystal structure was determined by the single-crystal X-ray diffraction method at 90 K. It
crystallizes in the triclinic space group P1 with a = 7.6144(15)Å, b = 8.4800(16)Å, c = 9.7140(19)Å, a = 99.026(3)˚, b =
112.749(3)˚, g = 103.210(3)˚, V = 541.72(18)Å3, Dx = 1.871 g/cm3, and Z = 1. The R1 [I > 2s(I)] and wR2 (all data)
values are 0.0336 and 0.0898, respectively, for all 2324 independent reflections. The molecule has a zigzag chain
structure with an alternating arrangement of Mo2(CH3CO2)4 and bpel [Mo–Mo 2.1038(5)Å, Mo–N 2.591(3)Å]. The
adsorption isotherm was investigated and no adsorption property was found for N2.
(Received June 25, 2013; Accepted July 13, 2013; Published on web August 10, 2013)
There has been much interest in the chemistry of chain
compounds of metal carboxylates with a lantern-like dinuclear
structure, because they may have unique properties, such as gasocclusion.1–4 We reported that chain compounds of rhodium(II)
carboxylates with N,N¢-bidentate ligands show adsorption
properties for nitrogen gas.5–8 Analogous chain compounds of
molybdenum(II) acetate can be expected to have an adsorption
property for nitrogen gas. Recently, we synthesized a chain
compound of molybdenum(II) acetate with 1,2-bis(4pyridyl)ethane (bpe) to make such a compound, because bpe has
two binding sites with an ethane-type orientation.9 However,
this compound did not show any adsorption property for N2,
because of a non-porous structure in the crystals. In this study,
we slightly modified the linking ligand to ethylene-type one,
N
CH 3
C
O
N
Mo
O
C
CH3
O
O
O
Mo
CH 3
C
O
O
C
O
CH 3
Fig. 1
Chemical structure of the title compound.
† To whom correspondence should be addressed.
E-mail: [email protected]
n
trans-1,2-bis(4-pyridyl)ethylene (bpel), to see any difference
from those of [Mo2(CH3CO2)4(bpe)]n, because the
corresponding rhodium(II) chain complex shows an adsorption
property for N2.5,6 The crystal structure of catena(tetrakis(mTable 1
Crystal and experimental data
Chemical formula: C20H22Mo2N2O8
Formula weight = 610.28
T = 90 K
Crystal system: triclinic
Space group: P1
a = 7.6144(15)Å
a = 99.026(3)˚
b = 8.4800(16)Å
b = 112.749(3)˚
c = 9.7140(19)Å
g = 103.210(3)˚
V = 541.72(18)Å3
Z=1
Dx = 1.871 g/cm3
Radiation: Mo Ka (l = 0.71073 Å)
m(Mo Ka) = 1.208 mm–1
F(0 0 0) = 304
Crystal size = 0.32 ¥ 0.10 ¥ 0.05 mm3
No. of reflections collected = 3161
No. of independent reflections = 2324
q range for data collection: 2.36 to 28.13˚
Data/Restraints/Parameters = 2324/0/145
Goodness-of-fit on F2 = 1.080
R indices [I > 2s(I)]: R1 = 0.0336, wR2 = 0.0884
R indices (all data): R1 = 0.0370, wR2 = 0.0898
(D/s)max = 0.001
(Dr)min = –0.686 eÅ–3
(Dr)max = 1.853 eÅ–3
Measurement: Bruker Smart APEX CCD diffractometer
Program system: SHELXTL
Structure determination: Direct methods (SHELXS-97)
Refinement: full matrix least-squares (SHELXL-97)
CCDC deposition number: 946731
34
X-ray Structure Analysis Online 2013, VOL. 29
C(4)i
C(3)i
C(1)i
C(9)ii
C(8)
C(6)ii
C(7)ii
N(1)ii
C(10)ii
C(10)
C(5)ii
C(5)
C(6)
C(2)i
Mo(1)i
O(2)i
N(1)
C(9)
O(1)i
O(2)
Mo(1)
C(7)
O(4)i
O(3)i
O(4)
C(8)ii
O(1)
C(2)
O(3)i
C(1)
C(3)
C(4)
Fig. 2 ORTEP view of the title compound. Hydrogen atoms are
omitted for clarity. The thermal ellipsoids are shown at the 50%
probability level. Symmetry code: (i) –x, 1–y, 1–z; (ii) 1–x, 2–y, –z.
Table 2
Selected bond distances (Å) and angles (˚)
Mo(1)-Mo(1)i
Mo(1)-O(2)
Mo(1)-O(4)
2.1038(5)
2.110(2)
2.124(2)
Mo(1)-O(1)
Mo(1)-O(3)
Mo(1)-N(1)
Mo(1)i-Mo(1)-N(1)
O(1)-Mo(1)-O(3)
O(2)-Mo(1)-O(3)
O(3)-Mo(1)-O(4)
N(1)-Mo(1)-O(2)
N(1)-Mo(1)-O(4)
171.81(6)
91.05(8)
88.60(9)
176.63(7)
94.04(9)
84.07(8)
O(1)-Mo(1)-O(2)
O(1)-Mo(1)-O(4)
O(2)-Mo(1)-O(4)
N(1)-Mo(1)-O(1)
N(1)-Mo(1)-O(3)
2.124(2)
2.114(2)
2.591(3)
176.75(7)
89.42(9)
90.75(9)
82.74(8)
92.68(8)
Symmetry code, (A), refers to the equivalent position (–x, 1–y, 1–z).
acetato-O,O¢)(m-trans-1,2-bis(4-pyridyl)ethylene-N,N¢)
dimolybdenum(II)), [Mo2(CH3CO2)4(bpel)]n, was determined by
X-ray crystallography, and the adsorption property was
examined for N2, which is the first example of a bpel adduct of
molybdenum(II) acetate, as shown in Fig. 1.
Molybdenum(II) acetate was prepared by a method described
in the literature.10 A 0.642 g (3.5 mmol) portion of bpel was
added to a solution of molybdenum(II) acetate (0.103 g, 0.24
mmol) in 5 cm3 of THF-hexane (1:1) under Ar, and the solution
was stirred for 4 h. The precipitate was collected, washed by
THF-hexane, and dried under vacuum. Yield, 0.080 g (54%).
Anal. Found: C, 38.38; H, 4.61; N, 4.44%. Calcd for
C20H22Mo2N2O8·1.5H2O·0.25C4H8O: C, 38.49; H, 4.15; N,
4.27%. IR (KBr, cm–1): 3049 (nCH(pyridyl)), 2924 (nCH3),
1602 (nC=N), 1523 (nasCOO), 1425 (nsCOO).
Diffuse
reflectance spectra: lmax 442 (d(Mo2) Æ d*(Mo2))nm. X-ray
quality crystals were grown by the slow diffusion of bpel in
hexane–liquid paraffin (1:1) with molybdenum(II) acetate in
THF.
X-ray diffraction data for these crystals were collected at 90 K
on a Bruker CCD X-ray diffractometer (SMART APEX) using
graphite-monochromated Mo-Ka radiation. Crystal data and
details concerning data collection are given in Table 1. The
structure was solved by direct methods, and refined by fullmatrix least-squares methods. Hydrogen atoms were inserted at
their calculated positions and included in a least-squares
calculation using a riding-atom model. All of the calculations
were carried out on a Pentium IV Windows 2000 computer
utilizing the SHELXTL software package.
The molecular structure drawn by ORTEP is shown in Fig. 2.
Selected bond distances and angles are given in Table 2. The
crystal structure consists of chain molecules made up by an
alternating arrangement of Mo2(CH3CO2)4 and bpel molecules.
The asymmetric unit contains one-half of the dinuclear unit and
the bpel molecule with a crystallographic inversion center at the
midpoint of the Mo(1)–Mo(1)i bond and the center of the bpel
moiety, respectively. The Mo(1)–Mo(1)i distance is 2.1038(5)Å,
which is in the range of 2.09 – 2.11 Å, found in the majority of
dinuclear molybdenum(II) carboxylates.9,10 The coordination
geometry around the Mo(1) atom is a distorted octahedron. One
apical position is occupied by the nitrogen atom N(1) of the
bpel molecule. The Mo(1) atom is 0.061(1)Å below the basal
plane formed by O(1)–O(2)–O(3)–O(4) towards the molybdenum
atom Mo(1)i, suggesting strong metal–metal bonding in the
dinuclear molybdenum(II) acetate core. The basal bond
distances of the Mo and basal O atoms are 2.110(2) – 2.124(2)Å,
which are comparable to those found in molybdenum(II) acetate
and their chain compounds.9,10 The apical Mo(1)–N(1) distance
is 2.591(3)Å, which is also in the usual range as apical bonding
for those of molybdenum(II) carboxylate adducts.9,10 The
Mo(1)i–Mo(1)–N(1) angle is 171.81(6)˚, resulting in a zigzag
chain molecule. It is to be noted that the crystal structure is
similar to that of [Mo2(CH3CO2)4(bpe)]n, (Fig. 3S).9 We
measured the adsorption isotherm of N2 (77 K) for the present
compound (Fig. 4S). The adsorption isotherm showed that the
present compound did not adsorb N2 gas, and the specific
surface area, SBET, was less than 1 m2 g–1, although the SBET value
(0.61 m2 g–1) was two-times larger than that of
[Mo2(CH3CO2)4(bpe)]n (SBET = 0.25 m2 g–1), in accordance with
the fact that the crystal possesses no porous structure.
Acknowledgements
The present work was partially supported by MEXT-Supported
Program for the Strategic Research Foundation at Private
Universities from the Ministry of Education, Culture, Sports,
Science and Technology (MEXT).
References
1. M. Mikuriya, D. Yoshioka, and M. Handa, Coord. Chem.
Rev., 2006, 250, 2194.
2. M. Mikuriya, Bull. Jpn. Soc. Coord. Chem., 2008, 52, 17.
3. R. Nukada, W. Mori, S. Takamizawa, M. Mikuriya, M.
Handa, and H. Naono, Chem. Lett., 1999, 367.
4. W. Mori, H. Hoshino, Y. Nishimoto, and S. Takamizawa,
Chem. Lett., 1999, 331.
5. M. Mikuriya, J. Yamamoto, D. Yoshioka, H. Tanaka, and
M. Handa, in “New Trends in Coordination, Bioinorganic
and Applied Inorganic Chemistry”, ed. by M. Melnik, P.
Segra, and M. Tatarko, Slovak University of Technology
Press, Blatislava, 2011, 311.
6. M. Mikuriya, J. Yamamoto, D. Yoshioka, H. Tanaka, and
M. Handa, X-ray Struc. Anal. Online, 2011, 27, 27.
7. M. Mikuriya, J. Yamamoto, K. Ouchi, D. Yoshioka, H.
Tanaka, and M. Handa, X-ray Struc. Anal. Online, 2013,
29, 7.
8. M. Mikuriya, K. Ouchi, Y. Nakanishi, D. Yoshioka, H.
Tanaka, and M. Handa, X-ray Struc. Anal. Online, 2013,
29, 21.
9. M. Mikuriya, N. Kaihara, J. Yamamoto, S. Takada, D.
Yoshioka, H. Tanaka, and M. Handa, X-ray Struc. Anal.
Online, 2013, 29, 31.
10. M. Handa, M. Mikuriya, T. Kotera, K. Yamada, T. Nakao,
H. Matsumoto, and K. Kasuga, Bull. Chem. Soc. Jpn.,
1995, 68, 2567.