Steric control of the nuclearity of metallamacrocycles: Formation of a hexanuclear gallium metalladiazamacrocycle and a hexadecanuclear manganese metalladiazamacrocycle

Article abstract of DOI:10.1039/b711686a

An S₆-symmetric hexanuclear gallium metalladiazamacrocycle, [Ga^III₆L²₆S₆] with a -(ΛΔ)(ΛΔ)- chiral sequence and an S ₈-symmetric hexadecanuclear manganese metalladiazamacrocycle,

Full text of DOI:10.1039/b711686a

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Steric control of the nuclearity of metallamacrocycles: formation of a
hexanuclear gallium metalladiazamacrocycle and a hexadecanuclear
manganese metalladiazamacrocycle†‡
a
a
a
a
b
c
Kyungjin Lee, Rohith P. John, Mira Park, Dohyun Moon, Hyeong-Cheol Ri, Ghyung Hwa Kim and
a
Myoung Soo Lah*
Received 31st July 2007, Accepted 30th October 2007
First published as an Advance Article on the web 16th November 2007
DOI: 10.1039/b711686a
III
2
An S
sequence and an S
6
-symmetric hexanuclear gallium metalladiazamacrocycle, [Ga
6
L
6
S ] with a –(KD)(KD)– chiral
6
III
2
8
-symmetric hexadecanuclear manganese metalladiazamacrocycle, [Mn 16
with a –(KKDD)(KKDD)– chiral sequence were prepared using the same N -trans-cinnamoyl-2-hydroxy-
L
16
16
S ]
2
2
3
-naphthoylhydrazide (H
3
L ) as a bridging pentadentate ligand between the metal centers for the
formation of a macrocyclic system.
Introduction
tate and tridentate binding modes around the metal center of
the ring alternates K and D, which leads to a –(KD)(KD)–
Metallamacrocycles that contain metal ions as ring constituents
have received attention from researchers over the past decade
because of their interesting molecular architectures, and their
potential applications for magnetic materials, electrolumines-
cence materials and sensors for small molecules. In addition,
metallamacrocycles could be used as supramolecular building
7–11
chiral sequence.
However, when a rigid but less sterically
demanding N-acyl side chain such as the 2-pentenoyl group
1
was introduced, the expanded dodecanuclear metalladiazamacro-
2
3−
cycle, [Mn12(tpeshz)12(DMF)12] (in which tpeshz is N-trans-2-
3
4
pentenoylsalicylhydrazidate), with –(KKDD)(KKDD)– chiral se-
12
quence was prepared, and this chiral sequence has led to a more
5
blocks for the construction of diverse metal–organic frameworks.
puckered macrocyclic ring conformation than that of the metalla-
diazamacrocycles with the –(KD)(KD)– chiral sequence. Half of the
N-acyl chains were directed to the outer region of the ring cavity
and the remaining half to the inner cavity region. When a rigid N-
Even though the metallamacrocycles usually formed via a cyclic
repeat of a ditopic metal node and a ditopic ligand node are
simple from a topological point of view, the control of the size and
nuclearity of macrocyclic ring systems is still challenging. The size
and nuclearity of a metallamacrocycle depend on the properties
acyl group with a sterically bulky phenyl end such as the cinnamoyl
1
group (H
3
L ) was introduced (Scheme 1), the resulting icosanu-
6
of the metal ion and the linker ligand between the metal ions.
1
clear metalladiazamacrocycle, [Mn20
L
20(DMSO)18(H
2
2
O) ], was
As potential pentadentate ligands, N-acyl salicylhydrazides
have led to various metalladiazamacrocycles depending on the
N-acyl side chains used, in which the pentadentate ligand serves
as a ditopic linker via a tridentate binding mode and a bidentate
severely puckered and the corresponding chiral sequence of
the metal center was somewhat complicated, forming the –
13
{
(KKDDK)(DDKKD)}{(KKDDK)(DDKKD)}– chiral sequence.
Four out of 20 ligands are in inverted conformation in the
7–13
binding mode on each side of the ligand.
The nuclearity and
macrocycle. The less sterically-demanding phenoxyl part of the
ring size were controlled through the steric modulation of the
N-acyl side chains. With flexible linear or b-branched N-alkyl
groups, only 18-membered hexanuclear metalladiazamacrocycles
have been obtained regardless of the metal ions and the solvents
7,8
used. When the ligands of a-branched N-alkyl groups were
used, metalladiazamacrocycles with extended nuclearity have been
7,8
prepared. Metallamacrocycles of an octanuclear system have
been obtained with the least sterically bulky N-acyl group, the
9
N-isopropyl group. Increases in the steric volume of the N-
10
acyl group have led to either decanuclear or dodecanuclear
11
metalladiazamacrocycles. The chirality induced from the biden-
a
Department of Chemistry and Applied Chemistry, Hanyang Univer-
sity, Ansan, Kyunggi-do, 426-791, Korea. E-mail: mslah@hanyang.ac.kr;
Fax: +82 (0)31 436 8100; Tel: +82 (0)31 400 5496
Scheme 1 Schematic drawings of two pentadentate ditopic linker ligands
b
with partial numbering schemes. The tridentate and bidentate groups serve
Department of Physics, Kyungpook National University, Daegu, 702-701,
2
as a bridging domain that links two metal centers: an N -trans-cinnamoyl
Korea
c
group serves as a primary steric domain that controls the nuclearity and
size of the metallamacrocycle formed. An aroyl group of the ligand, either
a phenoyl or a naphthoyl group, serves as a secondary steric domain that
is related to the ligand conformation in the macrocyclic ring system.
Pohang Accelerator Laboratory, Pohang, Kyungbook, 790-784, Korea
†
CCDC reference numbers 644811–644812. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/b711686a
The HTML version of this article has been enhanced with colour images.
‡
This journal is © The Royal Society of Chemistry 2008
Dalton Trans., 2008, 131–136 | 131

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ligand is directed towards the inner side of the macrocycle and the
more sterically-demanding cinnamoyl part towards the outer side
of the macrocycle, to reduce the excessive steric repulsion around
the inner-core region of the cavity, which might be caused by the
ligand and manganese acetate tetrahydrate in dimethyl sulfoxide
(DMSO). The O1, N1, and O3 atoms bind to one manganese atom,
while O2 and N2 bind to the adjacent manganese in a back-to-back
fashion (Fig. 1), leading to a puckered S
8
-symmetric 48-membered
13
2
bulky phenyl end of the N-acyl side chain.
cyclic structure, [Mn16
L
16(DMSO)
8
(EtOH)
8
]·2(DMSO), 1, con-
In this study, we tried to modify the steric effect of the phenoxyl
group on the orientation of the ligand in the metallamacrocycle
on complexation with an octahedral metal ion such as manganese
or gallium.
sisting of 16 manganese metal ions and 16 ligands (Fig. 2a).
The complex with –(KKDD)(KKDD)– chiral sequence resem-
bles puckered dodecanuclear manganese metalladiazamacrocycle,
[Mn12(tpeshz)12(DMF)12], but extended further to a hexadecanu-
clear system. The Mn–Mn distances between the neighboring
manganese centers alternate between 4.869(5) and 4.906(5): how-
ever, the Mn–Mn–Mn interatomic angles are in the range from
Results and discussion
2
◦
◦
◦
We prepared a new pentadentate ligand, N -trans-cinnamoyl-3-
121.65(2) to 124.92(2) with an average value of 123.11(1) , which
is much smaller than the value in the ideal planar cyclohexadecane
2
hydroxy-2-naphthoylhydrazide (H
3
L ), in which the phenoxyl part
◦
of the ligand is replaced by the bulkier naphthoyl group to prevent
the inverted conformation in the metalladiazamacrocycle formed
structure (157.5 ) while closer to that for a puckered dodecanu-
◦
clear metalladiazamacrocycle (117.7 ).
(
Scheme 1). Dark-brown needle-shaped crystals were obtained by
Eight of the 16 ligands are directed toward the inner side of the
macrocycle and the remaining ligands towards the outer side, but
none of the ligands are in the inverted conformation, contrary
to the case of the highly puckered icosanuclear manganese
layering ethanol with the solution of equivalent amounts of the
1
13
metalladiazamacrocycle, [Mn20
L
20(DMSO)18(H
2
2
O) ], in which
four out of 20 ligands are in the inverted conformation. The
total steric volume of the eight cinnamoyl groups directed to
the inner cavity region is not large enough to fill the cavity
of the hexadecanuclear metalladiazamacrocycle, thereby leading
to the formation of solvent pockets around the central cavity.
Eight solvent DMSO molecules are observed in these pockets,
four in each face of the macrocycle (Fig. 2b). The two different
sets of ligand orientations in the hexadecanuclear manganese
metallamacrocycle, resulting from the –(KKDD)(KKDD)– chiral
sequence, lead to slightly different sets of coordination geometries
around the metal center, while only one type of ligand orientation
in the hexanuclear gallium metallamacrocycle of –(KD)(KD)–
chiral sequence leads to one set of coordination geometry. There
are two sets of dihedral angles between the plane of the tridentate-
binding moiety and that of the bidentate-binding moiety of the
Fig. 1 An ORTEP diagram of the asymmetric unit of the 48-membered
hexadecanuclear manganese complex 1 drawn with 20%-probability
ellipsoids.
14
ligand in the hexadecanuclear manganese metallamacrocycle.
◦
One set of angles are in the range from 80.18(7) to 85.79(7) with
Fig. 2 (a) An ORTEP diagram of the 48-membered hexadecanuclear manganese complex 1. (b) Eight DMSO molecules reside at the solvent
pockets around the inner cavity region. The metallamacrocycle was presented using the green-stick model and the solvent DMSO molecules using
the Corey–Pauling–Koltun model.
1
32 | Dalton Trans., 2008, 131–136
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◦
an average value of 82.87 , and the other set of angles are in the
◦
◦
range from 88.90(7) to 89.64(6) with an average value of 89.03 .
However, only one set of dihedral angles were observed in the
hexanuclear gallium metallamacrocycle, ranging from 82.81(5) to
◦
◦
8
6.16(5) with an average value of 84.85 .
Allowing the mixed solution of the ligand and two equivalent
amounts of gallium nitrate hexahydrate in ethanol to stand led
to colorless block-shaped crystals. Fig. 3 shows the ORTEP dia-
2
gram of hexanuclear gallium metalladiazamacrocycle 2, [Ga
6
L
6
-
(
–
EtOH)
6
], in which the chiral sequence of the metallamacrocycle is
(KD)(KD)–. Compound 2 is isostructural with other hexanuclear
symmetry with all N-terminal groups
metallamacrocycles of S
6
directed to the inner core of the macrocycle. The neighboring
Ga–Ga interatomic distances are in the narrow range of 4.723(2)–
˚
4
.739(1) A, while the Ga–Ga–Ga angles in the 18-membered ring
◦
are in the range from 114.05(1) to 124.06(1) with an average
value of 117.39(6) . These values are slightly bigger than that for
a manganese hexanuclear metalladiazamacrocycle (115.2 ).
◦
Fig. 4 Ligand geometries showing the extent of bending in two different
viewing directions. The top drawings are parallel to the ligand plane and
the bottom drawings are perpendicular to the plane. a) The ligands of the
hexadecanuclear manganese metalladiazamacrocycle in the environment
of the least steric repulsion are planar. b) The ligands directed to the
inner-core region show some degree of bending caused by the repulsion
between the N-cinnamoyl groups. c) One of three ligands in the hexanuclear
gallium complex shows the largest deviation from the ideal planar
conformation.
◦
an alternative way to reduce excessive steric repulsion in the
metalladiazamacrocycle. The local geometry of the Jahn–Teller
distorted manganese(III) ion in the metalladiazamacrocycle might
be distorted to extend its nuclearity without severe destabilization
of the system when combined with the small bending of the ligands
1
0
to reduce the steric repulsion. Though gallium of d configuration
is known to have only a little geometry preference, it does not
prefer greater distortion in the dihedral angle between the planes
formed by the tridentate and bidentate chelation modes because
of short metal–ligand distance. The restriction in the dihedral
angles at the gallium center leads to a more regular octahedral
geometry, and results in a hexanuclear system of –(KD)(KD)–
chiral sequence, in which the ligands are bent to a larger extent to
reduce the severe steric repulsion between the bulky N-acyl groups.
Fig. 3 An ORTEP diagram of 18-membered hexanuclear gallium com-
plex 2.
◦
The severe bending (26.63 ) of one ligand observed in the gallium
metallamacrocycle (Fig. 4c) could be a consequence of the rigid
coordination environment of gallium(III) centers of the bidentate
and tridentate chelation modes that prefer a hexanuclear system.
The magnetic behavior of 1 is illustrated in Fig. 5 for the
It appears that the ligands in each metallamacrocycle were bent
from an ideal planar geometry to a different extent depending
on the environment of the ligands, even though all bonds are
conjugated (Fig. 4). In the manganese metallamacrocycle the
ligands with the N-acyl moiety directed to the inner side of
the macrocycle were bent more than the ligands with the N-
acyl moiety directed to the outer side. The bending angles for
range 3–300 K. The effective magnetic moment (l ) decreases
eff
slightly with decreasing temperature from 4.71 lB at 300 K
to 4.07 lB at 60 K. Below 60 K, it rapidly decreases and
reaches 1.51 lB at 3 K. This behavior is typical for a weakly
coupled antiferromagnetic system. Thus, by fitting the magnetic
susceptibility data at high temperatures, T > 60 K, to Curie–Weiss
expression, v(T) = C/[T + H], we obtained an effective coupling
eff
15
the ligands in the more sterically strained environment (17.72
◦
◦
and 16.44 ; see Fig. 4b) are ∼12 larger than those for the
ligands in less sterically strained or unstrained environments
3.23 and 6.17 ; see Fig. 4a). The average bending angle of the
ligands in the hexanuclear gallium complex (15.81 ) in the more
sterically strained environment is slightly larger than that of the
hexadecanuclear manganese complex (10.89 ). Interestingly, the
◦
(
constant J (−1.85 K) and an effective magnetic moment per
◦
metal ion leff (4.9 l ) for 1. This behavior is similar to those
B
9a,13
reported for the other similar metalladiazamacrocycles.
◦
◦
bending angles are found to be in a wide range, 6.79–26.63 , even
Conclusions
though there are no distinctive differences in the environment of
the three ligands of the crystallographic asymmetric unit. This
variation indicates some degree of ligand flexibility, which provides
We have prepared a hexanuclear gallium metallamacrocycle
and a hexadecanuclear manganese metallamacrocycle using
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Dalton Trans., 2008, 131–136 | 133

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magnetometer. Field-cooled magnetization data were collected at
H = 1000 Oe.
Ligand synthesis
2
2
N -trans-Cinnamoyl-2-hydroxy-3-naphthoylhydrazide (H
3
L ).
0
5
.62 mL (5.0 mmol) of trimethylacetyl chloride was added to
0 mL of chloroform solution at 0 C, containing 0.77 mL
◦
(5.5 mmol) of triethylamine and 0.78 g (5.25 mmol) of trans-
cinnamic acid, over a period of 15 minutes with stirring.
The solution was slowly brought to ambient temperature. An
equivalent amount of 3-hydroxy-2-naphthoic hydrazide (1.01 g,
5
mmol) was added to the solution and refluxed for a day. The
white precipitate obtained was filtered and washed with small
Fig. 5 Temperature dependence of the effective magnetic moment per
Mn ion (leff) and the inverse magnetic susceptibility (v ) for 1.
−
1
quantities of cold chloroform followed by water. Yield = 1.04 g
◦
(
62.9%). Mp = 280–281 C. Anal. calc. for C20
H
16
N
2
O : C 72.28,
3
1
H 4.85, N 8.43; Found: C 71.97, H 4.82, N 8.39%; H-NMR
(DMSO-d , d (ppm): 11.57 (s, 1H, OH), 11.09 (d, 1H, NH),
0.98 (d, 1H, NH), 8.57 (s, 1H, ArH), 7.94 (d, 1H, ArH), 7.78
d, 1H, ArH), 7.34–7.62 (m, 9H, ArH, –CH=CHPh), 6.85 (d,
2
2
6
N -trans-cinnamoyl-2-hydroxy-3-naphthoylhydrazide (H
3
L ) as a
1
(
diaza-bridging ditopic ligand in both compounds, where the
phenoxyl part of the ligand has been replaced by a naphthoyl
group to prevent the inverted conformation occurring in the
metalladiazamacrocycle formed. The size and nuclearity of the
metallamacrocycles were controlled via the modulation of
the steric repulsion between the ligands in the macrocyclic ring
system. The size and shape modulation of two domains of N-
acyl-aroylhydrazide, an N-acyl domain and an aroyl domain,
that are involved in the steric repulsion have led to an extremely
large 48-membered hexadecanuclear metalladiazamacrocycle with
a manganese ion and an 18-membered hexanuclear metalladiaza-
macrocycle with a gallium ion. With a metal ion of soft coor-
dination geometry such as Jahn–Teller distorted manganese(III)
the steric repulsion between the ligands could be reduced mainly
through the expansion of the ring system to hexadecanuclear
metallamacrocycle with –(KKDD)(KKDD)– chiral sequence. With
a gallium(III) ion of a relatively rigid coordination preference
caused by the two chelating binding modes around the metal
center, a hexanuclear metallamacrocyclic system with –(KD)(KD)–
chiral sequence was obtained in which steric repulsion between the
ligands was reduced via distortion of the ligand conformation.
1
3
1
1
1
1
1
6
H, –CH=CHPh); C-NMR (DMSO-d
54.3, 141.0, 136.6, 135.3, 131.7, 130.6, 129.7, 129.6, 129.1, 128.4,
6
, d ppm): 164.3, 163.2,
−
1
27.5, 126.5, 124.6, 119.8, 119.4, 111.4; IR (KBr, cm ): 3171(br),
669(w), 1640(s), 1587(s), 1557(s), 1484(s), 1394(w), 1358(m),
209(m), 1019(w), 976(m), 912(w), 872(w), 852(w), 758(m),
90(m), 647(m), 600(w), 518(w), 475(w), 446(w).
Preparation of metallamacrocycles
2
[
Mn16
L
16(DMSO)
2
(EtOH)
6
(H
2
O) ]. 1: 16.6 mg (0.05 mmol)
8
2
of H
3
L was dissolved in 1.0 mL of DMSO in a 1.5 mL microtube
and 12.3 mg (0.05 mmol) of Mn(OAc)
2
·4H
2
O was dissolved
in 1 mL of DMSO in another 1.5 mL microtube. The two
solutions were mixed in a 15 mL vial and 10 mL of ethanol was
slowly added through the vial wall. The solution was allowed to
stand for 10 days, after which dark-brown needle-shaped crystals
were obtained. The product was filtered, washed with methanol
and ethanol successively and was freeze-dried before elemental
analysis. (14.2 mg, 67.6% yield). Elemental analysis data for
2
[
6
Mn16
L
16(DMSO)
2
(EtOH)
6
(H
2
O)
8
] (C336
H
272
N
32
O64Mn16
S
2
, fw =
725.16). Calc.: C 60.01, H 4.08, N 6.66, S 0.95%. Found: C 60.43,
−
1
H 3.63, N 6.91, S 1.12%. IR (KBr pellet, cm ): 3428(br), 3056(br),
631(s), 1593(s), 1513(s), 1453(s), 1400(s), 1367(s), 1261(m),
1171(w), 1108(w), 971(w), 914(w), 867(w), 802(w), 756(m), 680(w),
92(w), 551(w), 474(w), 429(w).
Note: Even though the crystal-structure analysis suggests that
Experimental
1
Materials
5
All reagents and solvents for syntheses were purchased from the
commercial sources and used as received.
[
the crystals contained at least 16 DMSO molecules, 16 water
molecules and 22 ethanol molecules as either ligating or structural
solvents per molecule of complex 1, the elemental analysis was
not consistent with the original content of the crystals, despite
several attempts. The compounds were found to lose some of the
coordinated solvent molecules during freeze-drying and exposure
to air and these were subsequently replaced by water molecules in
air.]
Instrumentation
Elemental analyses (C, H, N and S) were performed at the Elemen-
tal Analysis Laboratory of the Korean Basic Science Institute on
a CE Flash EA 1112 series elemental analyzer. Melting points
of well-ground solid samples were measured using a SANYO
Gallenkamp PLC melting-point apparatus. Infrared spectra were
−
1
2
2
recorded with KBr pellets in the range 4000–600 cm on a BioRad
FT-IR spectrometer. NMR spectra were obtained using a Varian-
[Ga
6
L
6
(EtOH)
4
(H
2
O)
2
]. 2: 8.3 mg (0.025 mmol) of H L was
3
added to 10 mL of ethanol in a 15 mL vial and was sonicated
for 5 minutes to form a suspension. In another vial 12.8 mg
3
00 spectrometer. Temperature-dependent magnetic-susceptibility
measurements were carried out on powdered samples between
(0.05 mmol) of Ga(NO
5 mL of ethanol to form a suspension. The contents of the two vials
3
)
3
·6H
2
O was sonicated for 30 minutes with
3
and 300 K using a Quantum Design MPMS-7XL SQUID
1
34 | Dalton Trans., 2008, 131–136
This journal is © The Royal Society of Chemistry 2008

View Article Online
were mixed in a 30 mL vial. When it was allowed to stand, it became
clear and yielded colorless block crystals. The product was filtered,
washed with small quantities of ethanol and freeze-dried before
full-matrix least-squares calculations with the SHELXTL-PLUS
software package.
17
elemental analysis. (6.5 mg, 59.2% yield). Elemental analysis data
2
for [Ga
6
L
6
(EtOH)
4
(H
2
O)
2
] (C128
H
106
N
12
O24Ga
6
, fw = 2614.64).
Crystal structure determination for
Calc.: C 58.80, H 4.09, N 6.43%. Found: C 59.20, H 3.85, N 6.87%.
IR (KBr pellet, cm ): 3390(br), 3054(br), 1634(s), 1597(s), 1525(s),
2
[Mn16
L
16(DMSO)
8
(EtOH)
8
]·8DMSO·14EtOH·16H
2
O, 1
−
1
An asymmetric unit of hexadecanuclear metallamacrocycle con-
sists of four manganese and four ligand units with two DMSO
and two ethanol molecules coordinated to the available solvent
coordination sites. Among the coordinated solvents one ethanol
and one DMSO are disordered. The asymmetric unit also contains
two DMSO molecules, one of which is disordered, four ethanol
sites (three of them fully occupied, two of which are disordered
and one half occupied) contributing three and a half ethanol
molecules, and six partial-occupancy water sites with an overall
contribution of four molecules. All non-hydrogen atoms except
those of the non-coordinating structural solvent molecules were
refined anisotropically and those of the remaining structural
solvents were refined isotropically with the exception of two
DMSO molecules. Hydrogen atoms of the main macrocyclic
structural unit were assigned isotropic displacement coefficients
U(H) = 1.2U(C) or 1.5U(Cmethyl), and their coordinates were
allowed to ride on their respective atoms. One of the ethanol sites
with severe disorder was refined with geometry restraints during
the least-squares refinement. The refinement converged to a final
R1 = 0.0979, and wR2 = 0.2785 for 10 238 reflections of I > 2r(I).
The structure refinement was further performed after modification
1
1
5
502(s), 1455(s), 1413(s), 1327(m), 1262(m), 1228(m), 1176(w),
151(w), 1038(w), 970(w), 915(w), 866(w), 807(w), 754(w), 665(w),
79(w), 479(w).
[
Note: Even though the crystal-structure analysis suggests that
the crystals contained at least 15 ethanol molecules as either
ligating or structural solvents per molecule of complex 2, the
elemental analysis was not consistent with the original content of
the crystals, despite several attempts. The compounds were found
to lose some of the coordinated solvent molecules during freeze-
drying and exposure to air and these were subsequently replaced
by water molecules in air.]
Crystallographic studies
The crystals were coated with paratone oil because they lose
crystallinity on exposure to air. The diffraction data were measured
˚
with synchrotron radiation (k = 0.70000 A) on a 4AMXW
ADSC Quantum-210 detector with a Pt-coated Si double-crystal
monochromator at the Pohang Accelerator Laboratory, Korea.
16
The HKL2000 (Ver. 0.98.694) was used for data collection,
cell refinement, reduction and absorption correction. Both the
crystal structures were solved by direct methods and refined by
of the data for electron density, except for the two well-defined
3
˚
DMSO molecules of the free solvent region (6754.1 A , 30.3%)
Table 1 Crystal data and structure refinement for 1 and 2
1
2
Empirical formula
Formula weight/gmol
Temperature/K
Mn16
7758.75
103(2)
C
368
H
344
N
32
O
72
S
16
6 150 169 12 33.5
Ga C H N O
3094.29
99(2)
−
1
Wavelength/A˚
0.70000
0.70000
Crystal system
Space group
Tetragonal
P4/n
a = 39.134(6), a = 90
b = 39.134(6), b = 90
c = 14.553(3), c = 90
22 288(6)
Monoclinic
P2 /n
a = 16.918(3), a = 90
b = 27.325(6), b = 107.05(3)
c = 16.928(3), c = 90
7482(3)
1
◦
Unit cell dimensions (length/ A˚ , angle/ )
Volume/ A˚ 3
Z
2
2
−
3
Densitycalcd/mg m
1.156
0.577
1.374
1.143
−
1
Absorption coefficient/mm
F(000)
8016
3214
3
Crystal size/mm
0.20 × 0.10 × 0.10
1.56 to 30.42
−56 ≤ h ≤ 56, −56 ≤ k ≤ 56,
0.20 × 0.20 × 0.10
◦
h range for data collection/
Index ranges
1.47 to 30.44
0 ≤ h ≤ 24, −39 ≤ k ≤ 39,
−24 ≤ l ≤ 23
−
21 ≤ l ≤ 0
Reflections collected
125 699
41 821
Independent reflections
35 175 [R(int) = 0.0685]
23 484 [R(int) = 0.0511]
◦
Completeness to h = 30.42 (%)
99.5
98.8
Absorption correction
Empirical
Full-matrix least-squares on F
35 175/0/1169
Empirical
Full-matrix least-squares on F
23 484/3/959
2
2
Refinement method
Data/restraints/parameters
2
Goodness-of-fit on F
0.794
1.024
Final R indices [I > 2r(I)]
R indices (all data)
Largest diff. peak and hole (e A˚
R1 = 0.0737, wR2 = 0.2024
R1 = 0.1872, wR2 = 0.2437
0.609 and −0.553
R1 = 0.0589, wR2 = 0.1717
R1 = 0.0905, wR2 = 0.1924
1.114 and −0.935
−
3
)
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Dalton Trans., 2008, 131–136 | 135

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1
8
with the SQUEEZE routine of PLATON, which led to better
refinement and data convergence.
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18.
2
Crystal structure determination for [Ga
EtOH·0.5H O, 2
6
L
6
(EtOH)
6
]·
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2
H. Courtney and G. R. Newkome, Dalton Trans., 2006, 3518–3522;
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An asymmetric unit of hexanuclear metallamacrocycle consists
of three gallium and three ligand units with three ethanol
molecules coordinated to the available solvent coordination sites.
Among the coordinated solvents, one ethanol is disordered. The
asymmetric unit also contains five ethanol sites (three of them
fully occupied, one of which is disordered and the other two
sites are partially occupied) with an overall contribution of four
and a half ethanol molecules, and one partial-occupancy water
site. All non-hydrogen atoms except one carbon from the ethanol
solvent and one partially-occupied water molecule were refined
anisotropically. The hydrogen atoms attached to the coordi-
nated ethanol molecules were identified from difference Fourier
analysis and were assigned isotropic displacement coefficients
U(H) = 1.5U(Ohydroxyl). The rest of the hydrogen atoms were
assigned isotropic displacement coefficients U(H) = 1.2U(C) or
1
4
2
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6
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(
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1
.5U(Cmethyl/Ohydroxyl), and their coordinates were allowed to ride
on their respective atoms. One free ethanol site is disordered
and was refined with geometry restraints during the least-squares
refinement.
A summary of the crystal and intensity data for 1 and 2 is given
in Table 1.
7
3
599–3602; (b) B. Kwak, H. Rhee and M. S. Lah, Polyhedron, 2000,
9, 1985–1994; (c) I. Kim, B. Kwak and M. S. Lah, Inorg. Chim. Acta,
1
CCDC 644811–644812.†
2001, 317, 12–20.
8
9
S. Lin, S.-X. Liu, J.-Q. Huang and C.-C. Lin, J. Chem. Soc., Dalton
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Acknowledgements
This work was supported by KRF (KRF-2005-070-C00068),
KOSEF (R01-2007-000-10167-0) and CBMH. The authors also
acknowledge PAL for beam line use (2007-1041-08).
1
1
0 S.-X. Liu, S. Lin, B.-Z. Lin, C.-C. Lin and J.-Q. Huang, Angew. Chem.,
Int. Ed., 2001, 40, 1084–1087.
1 R. P. John, J. Park, D. Moon, K. Lee and M. S. Lah, Chem. Commun.,
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006, 3699–3701.
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1
2 R. P. John, K. Lee and M. S. Lah, Chem. Commun., 2004, 2660–2661.
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Notes and references
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1
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36 | Dalton Trans., 2008, 131–136
This journal is © The Royal Society of Chemistry 2008