Syntheses and structural characterization of the one dimensional polymers: 1∞[ Rh2 (OAc)4 (NCPhCN)·S]; S=CH3COCH3, CH3OH, C2H5OH, C4H8O and C<sub

Article abstract of DOI:10.1016/S0277-5387(98)00213-7

The syntheses and characterization of five compounds obtained by the reaction of dirhodium (II)tetraacetate with 1,4-dicyanobenzene in different solvent systems are described. The structures of Rh₂ (OAc)₄ (NCPhCN)·CH₃COCH<

Full text of DOI:10.1016/S0277-5387(98)00213-7

Polyhedron Vol[ 06\ No[ 12Ð13\ pp[ 3968Ð3978\ 0887
Þ 0887 Elsevier Science Ltd
Pergamon
All rights reserved[ Printed in Great Britain
9166Ð4276:87 ,08[99¦9[99
\
PII] S9166!4276"87#99132!4
Syntheses and structural characterization of the
one dimensional polymers]
0
ꢀ ðRh1"OAc#3"NCPhCN#=SŁ^ SꢀCH2COCH2\
CH2OH\ C1H4OH\ C3H7O and C5H5
Tianyan Niu\ Jian Lu\ Gerardo Crisci and Allan J[ Jacobsonꢀ
Department of Chemistry\ University of Houston\ Houston\ TX 66193!4530\ U[S[A[
"Received 01 January 0887^ accepted 04 May 0887#
Abstract*The syntheses and characterization of _ve compounds obtained by the reaction of dirho!
dium"II#tetraacetate with 0\3!dicyanobenzene in di}erent solvent systems are described[ The structures of
Rh1"OAc#3"NCPhCN#=CH2COCH2 "0#\ Rh1"OAc#3"NCPhCN#=1CH2OH "1#\ Rh1"OAc#3"NCPhCN#=C3H7O
"3# and Rh1"OAc#3"NCPhCN#=C5H5 "4# were determined by single crystal X!ray di}raction[ All structures
contain one dimensional polymeric chain\ comprised of dirhodiumtetraacetate units bridged by 0\3!dicy!
anobenzene molecules[ Solvent molecules are located between the chains in each structure and three di}erent
packing arrangements of the polymer chains result from the inclusion of these di}erent solvent molecules[
Compounds 0\ 1 and 2 crystallize in space group C1:c with similar cell parameters[ Compound 3 also crystallizes
in the same space group\ but its structure is signi_cantly di}erent from those of 0\ 1 and 2[ Compound 4
¹
crystallizes in space group P0 and contains an unusual polymer chain structure[ Þ 0887 Elsevier Science Ltd[
All rights reserved
Keywords] coordination polymer^ one dimensional polymer chains^ dirhodiumtetraacetate^ 0\3!dicyanobenzene^
synthesis^ crystal structure
———————————————————————————————————————————————
INTRODUCTION
dimers with di}erent R groups\ for example\ Rh1"O1
CEt#3 ð04Ł or Rh1"O1CCF2#3 ð05\ 06Ł\ bridged by suit!
able organic ligands have also been reported[
The coordination chemistry of dinuclear tetra!car!
boxylates of the transition metals has been a focus
of several previous investigations[ Adducts such as
Cr1"OAc#3"py#1 ð0Ł and several polymers such as]
Cr1"OAc#3="pyz#1 ð0Ł\ Mo1"O1CCH2#3=L "Lꢁpyrazine\
3\3?!bipyridine\ 0\3!diazabicycloð1[1[1Łoctane# ð1Ł\
ðRu1"O1CC1H4#3"phz#ŁBF3 ð2Ł and Cu1"OAc#3"pyz# ð3Ł
have been studied in detail[ Several reactions of the
Rh"II# tetra!acetate dimer with organic or organ!
ometallic ligands have been reported ð4Ð7Ł[ With some
ligands\ for example bis"3!pyridinecarbonitrile# ð8Ł
and pyridine\ M1"O1CR#3L1 ð09Ł metal cluster com!
plexes are formed[ One and two dimensional polymers
Although extensive studies have focused on the for!
mation of coordination polymers of the Rh1"O1CR#3
dimer with linear!bidentate nitrogen ligands\ the role
of speci_c solvent molecules in the formation and
crystallization of such polymers has not been inves!
tigated[ In the present work\ we report the syntheses
and structures of compounds formed by the reaction
of Rh1"OAc#3 with 0\3!dicyanobenzene in di}erent
solvents[ Five new one dimensional coordination
polymers
have
been
obtained]
Rh1"OAc#3
"NCPhCN#=CH2COCH2 "0#\ Rh1"OAc#3"NCPhCN#
=1CH2OH "1#\ Rh1"OAc#3"NCPhCN#=xC1H4OH
"x30# "2#\ Rh1"OAc#3"NCPhCN#=C3H7O "3# and
Rh1"OAc#3"NCPhCN#=C5H5 "4#[
The structures of 0\ 1\ 3 and 4 were determined by
analyses of single crystal X!ray di}raction data[ The
polymers all consist of one dimensional chains of
Rh1"OAc#3 dimers bridged by 0\3!dicyanobenzene
ligands\ with the cavities between the chains _lled by
are
nomethyl#pyridine ð00Ł\ TCNE ð01Ł and 3!amino!4!
"aminomethyl#!1!methylpyrimidine ð02Ł and
obtained
by
reactions
with
1!"ami!
K2Co"CN#5 ð03Ł[ Polymers containing Rh1"O1CR#3
ꢀ Author to whom correspondence should be addressed[
3968

3979
T[ Niu et al[
Rh1"OAc#3"NCPhCN#=C3H7O "3#[ The reaction
di}erent solvent molecules[ Packing of speci_c solvent
molecules and the chains determines the _nal crystal was carried out as described above for 0\ using THF
structure[ For 2\ only the unit cell dimensions and as the solvent in place of acetone[ Dark red diamond!
space group were determined and indicate that 2 is shaped plates formed in 6 days[ IR bands "cm−0#]
isostructural with 0 and 1[
2384 "s#\ 2311 "s#\ 2099 "w#\ 2943 "w#\ 1860 "w#\
1829 "w#\ 1744 "w#\ 1250 "w#\ 1123 "m#\ 0824 "w#\ 0477
"s#\ 0495 "w#\ 0326 "s#\ 0305 "s#\ 0245 "m#\ 0168 "w#\
0946 "m#\ 734 "s#\ 688 "w#\ 587 "s#\ 518 "w#\ 485 "w#\
450 "s#[
EXPERIMENTAL
Rea`ents and apparatus
Rh1"OAc#3"NCPhCN#=C5H5 "4#[ A solution of 0\3!
dicyanobenzene "4 mg\ 9[928 mmol# in 09 ml THF was
Rhodium"II#acetate "STREM Chemical# and 0\3!
dicyanobenzene "Aldrich# were used as received[ Ace!
tone\ methanol\ ethanol\ benzene and tetrahydrofuran
added to
a suspension of Rh1"OAc#3 "09 mg\
9[912 mmol# in 09 ml benzene[ The solid dissolved
completely after being stirred for 0 h[ Two distinct
habits of lilac coloured crystals were observed after a
week of slow evaporation[ The majority of the product
consisted of very large multifaceted blocks\ while the
remainder were square columns[ A square column
crystal was used for the data collection since the large
blocks appeared to be polycrystalline[ Subsequently\
a small fragment cut from a large block veri_ed that
it was indeed the same phase as the crystal used for
data collection[ IR bands "cm−0#] 2338 "s#\ 2313 "s#\
2985 "w#\ 2943 "w#\ 2994 "w#\ 1815 "w#\ 1289 "w#\ 1123
"m#\ 0477 "s#\ 0326 "s#\ 0305 "s#\ 0274 "m#\ 0245"m#\
0168"w#\ 0934"w#\ 734"m#\ 585"s#\ 518"w#\ 487"w#\
450"m#[
Ä
"THF# were dried over molecular sieves "3 A#[ Infra!
red data were collected on a Galaxy FTIR 4999 series
spectrometer\ using the KBr pellet method[ X!ray
powder di}raction measurements were carried out
using
a Scintag XDS 1999 automated powder
di}ractometer "Cu Ka radiation\ uÐu\ ~at plate
geometry#[ The Cerius 1 program ð07Ł was used to
simulate X!ray powder di}raction patterns from the
single crystal X!ray data[ Thermogravimetric analyses
were carried out by using a TA Instruments 1099
thermal analyzer in a ~owing nitrogen atmosphere at
a heating rate of 0>C:min[
Syntheses
All of the compounds show the expected IR stret!
ching
"0#[ cyanobenzene polymer and the speci_c solvent
Rh1"OAc#3 "09 mg\ 9[912 mmol# and 0\3!dicy! molecule[ Coordination of the dicyanobenzene is indi!
anobenzene "4 mg\ 9[928 mmol# were dissolved in cated by a CN stretching frequency at 1123 cm−0
frequencies
from
the
Rh1"OAc#3=di!
Rh1"OAc#3"NCPhCN#=CH2COCH2
\
14 ml acetone[ The solution was stirred for 29 min and which is slightly blue!shifted from the CN stretching
then slowly evaporated[ Dark red crystals in the form frequency "1121 cm−0# of neat 0\3!dicyanobenzene[
of long columns or thin plates crystallized from the
solution after 5 d[ IR bands "cm−0#] 2332 "s#\ 2981
"w#\ 2935 "w#\ 1875 "w#\ 1823 "w#\ 1285 "w#\ 1290 "w#\ Structure determinations
1123 "m#\ 0477 "s#\ 0495 "w#\ 0326 "s#\ 0306 "s#\ 0247
"m#\ 0168 "w#\ 0940 "w#\ 813 "w#\ 734 "m#\ 691 "s#\ 518
"w#\ 450 "m#[
For 0\ 2 and 4\ X!ray data were collected using a
Nicolet R2m:V automatic di}ractometer "graphite!
Rh1"OAc#3"NCPhCN#=1CH2OH "1#[ A solution of monochromated Mo!Ka radiation#[ Data for 1 and 3
0\3!dicyanobenzene "04[1 mg\ 9[008 mmol# in THF were collected using an Enraf!Nonius CAD!3\ four
"29 ml# was added to a suspension of Rh1"OAc#3 circle di}ractometer also with Mo!Ka radiation[
"24 mg\ 9[97 mmol# in methanol "39 ml#[ The mixture
A
crystal
of
0
with
dimensions
was stirred for about 0 h at room temperature[ Slow 9[09×9[24×9[34 mm was mounted on a glass _ber
evaporation produced small\ red rod!shaped crystals and transferred to the di}ractometer[ The crystal was
in about 0 week in 84[8) yield[ The compound is cooled to 112 K in a stream of cold nitrogen gas[
insoluble in water\ but soluble in acetonitrile\ THF Lattice parameters were determined from the angles
and methanol[ IR bands "cm−0#] 2332 "s#\ 2989 "w#\ of 14 re~ections in the range 05[2>³1u³29[2>[ Crystal
2933 "w#\ 1829 "w#\ 1122 "w#\ 0480 "s#\ 0324 "s#\ 0305 data and details of the data collection and re_nement
"s#\ 0274 "m#\ 0241 "w#\ 0166 "w#\ 0108 "w#\ 0940 "w#\ are presented in Table 0[ Data were collected in vÐ1u
747 "w#\ 701 "w#\ 691 "m#\ 518 "w#\ 454 "w#[
mode[ Intensity data for 1275 re~ections "1010
Rh1"OAc#3"NCPhCN#=C1H4OH "2#[ The same pro! unique# were collected in the range 3>³1u³49>[ Two
cedure was used as described above for 0\ with ethanol standard re~ections were monitored after every two h
replacing acetone[ The dark red crystals were irregular or every 099 data collected and these showed a 01)
multifaceted prisms[ IR bands "cm−0#] 2336 "s#\ 2324 linear decay over the course of the experiment[ A
"s#\ 2987 "w#\ 2943 "w#\ 1252 "w#\ 1123 "m#\ 0477 "s#\ normalization factor as a function of X!ray exposure
0495 "w#\ 0326 "s#\ 0307 "s#\ 0247 "m#\ 0166 "w#\ 0940 time was applied to account for this[ During data
"w#\ 811 "w#\ 734 "m#\ 693 "s#\ 518 "w#\ 487 "w#\ 450 reduction\ Lorentz and polarization corrections and
"m#[
a semi!empirical absorption correction based on ten

One dimensional polymer chains
3970
Table 0[ Crystallographic data for 0\ 1\ 2\ 3 and 4
Solvent
Acetone "0#
Methanol "1#
Ethanol "2#d
THF "3#
Benzene "4#
Formula
FW
C08H11N1O8Rh1
517[10
C07H13N1O09Rh1
523[13
C19H13N1O8Rh1
531[12
C11H11N1O7Rh1
537[13
Ä
a "A#
12[011"6#
01[271"6#
7[407"2#
89
86[71"1#
89
12[002"2#
01[189"2#
7[492"0#
89
86[43"1#
89
12[225"7#
01[137"3#
7[416"2#
89
87[112
89
11[624"4#
7[051"09#
03[559"7#
89
005[05"1#
89
7[951"1#
7[399"1#
09[243"1#
84[05"1#
88[03"1#
007[07"1#
0
Ä
b "A#
Ä
c "A#
a ">#
b ">#
g ">#
Z
3
1305
3
3
3
2
Ä
V "A #
1284
1301
1331
488
Crystal system
Space group
T "K#
monoclinic
C1:c "No[ 04#
112
monoclinic
C1:c "No[ 04#
187
monoclinic
C1:c "No[ 04#
112
monoclinic
C1:c "No[ 04#
187
triclinic
¹
P0 "No[ 1#
112
9[60962
0[685
0[315
211
Ä
l "A#
9[60962
0[616
0[304
9[60962
0[659
0[320
9[60962
9[60962
0[636
0[391
Dcalc[ "g cm−2
#
m "Mo!Ka# "mm−0
F"999#
#
0137
0179
0179
Data collection\ u ">#
Index ranges
1[85 to 14[94
−16¾h¾16
9¾k¾03
−09¾l¾9
1179
1[86 to 13[87
−16¾h¾15
9¾k¾03
9¾l¾09
1158
1[99 to 16[80
−18¾h¾15
9¾k¾09
9¾l¾08
1603
1[79 to 14[94
9¾h¾8
−8¾k¾7
−01¾l¾00
1001
Re~ections collected
Independent re~ections
Number of parameters
R"F#a ")#c
1010
036
4[75
04[64
0853
032
3[64
02[03
1603
049
2[28
8[27
1091
087
0[66
3[21
wR1"F#b ")#c
−2
Ä
Drmax[\ Drmin "eA
#
0[673\ −1[232
0[946
0[017\ −0[285
0[013
9[639\ −0[077
0[938
9[416\ −9[242
9[882
Goodness!of!_t "F1#
a RꢁS>F9=−=Fc>:S=F9=[
b wR1ꢁðSðw"F1 −F1 #1Ł:Sðw"F1 #1ŁŁ0:1
[
9
c
9
c ðF9×3s"F9#Ł[
d Only unit cell determined[
re~ections having x values between 69 and 89> were 3³1u³49>[ A semi!empirical absorption correction
applied[ The structure was solved in space group C1:c based on c scans was applied to the data during data
by direct methods and standard di}erence Fourier reduction[ The structure was determined and re_ned
techniques using SHELXS!85 ð08Ł[ Re_nement on F1 in space group P0 using the same programs as 0[
¹
was carried out by full!matrix least!squares pro!
For 1 and 3\ suitable crystals with dimensions
cedures using SHELXL!85 beta ð08Ł[ All nonhydrogen 9[20×9[00×9[09 and 9[04×9[2×9[2 mm\ respec!
atoms were re_ned with anisotropic thermal tively\ were mounted with epoxy glue on the tip of a
parameters[ Hydrogen atoms were included in cal! glass _ber and transferred to the di}ractometer[ 14
culated positions riding on their carrier atoms\ with re~ections were used to determine the unit cell and
_xed isotropic thermal parameters related to the value data were collected using the vÐ1u scan method in
of the equivalent isotropic thermal parameter of their both cases[ Intensities were corrected for Lorentz and
carrier atoms by a factor of 0[4 for the methyl hydro! polarization e}ects\ as well as for absorption "c
gen atoms and a factor of 0[1 for the other hydrogen scans#[ Intensities of three standard re~ections showed
atoms[ Weights were optimized in the _nal re_nement no variations greater than those predicted by counting
cycles[
statistics[ In both cases\ space group C1:c was chosen
The data collection and re_nement of 4 were carried and con_rmed by successful structure re_nement[ The
out in the same way as for 0[ A lilac square column structure solution and re_nement were carried out
with dimensions 9[97×9[01×9[39 mm was used[ similarly as the other compounds[ For 2\ only the
Twenty!_ve re~ections in the range 07>³1u³31> unit cell dimensions and space group were determined
were centered\ giving a triclinic cell[ Intensity data "112 K#[ Selected bond distances and angles for 0\ 1\
were collected in the vÐ1u mode with a range of 3 and 4 are given in Table 1[

3971
T[ Niu et al[
Ä
Table 1[ Selected bond distances "A# and angles "># for 0\ 1\ 3 and 4
Acetone "0#
Rh"0#ÐO"3#
Rh"0#ÐO"2#
Rh"0#ÐN"0#
O"0#ÐC"0#
O"2#ÐC"1#
N"0#ÐC"00#
C"1#ÐC"3#
1[918"3#
1[924"4#
1[128"4#
0[156"7#
0[149"7#
0[017"7#
0[400"00#
0[271"8#
0[242"09#
Rh"0#ÐO"0#
Rh"0#ÐO"1#
Rh"0#ÐRh"0#a
O"1#ÐC"1#a
O"3#ÐC"0#a
C"0#ÐC"2#
1[920"3#
1[938"4#
1[2809"09#
0[162"7#
0[155"7#
0[387"8#
0[337"7#
0[398"09#
C"00#ÐC"01#
C"01#ÐC"02#
C"01#ÐC"03#
C"02#ÐC"03#b
O"3#ÐRh"0#ÐO"0#
O"0#ÐRh"0#ÐO"2#
O"0#ÐRh"0#ÐO"1#
O"3#ÐRh"0#ÐN"0#
O"2#ÐRh"0#ÐN"0#
O"3#ÐRh"0#ÐRh"0#a
O"2#ÐRh"0#ÐRh"0#a
N"0#ÐRh"0#ÐRh"0#a
C"0#ÐO"0#ÐRh"0#
C"1#ÐO"2#ÐRh"0#
C"00#ÐN"0#ÐRh"0#
O"2#ÐC"1#ÐO"1#a
064[7"1#
89[3"1#
78[1"1#
80[1"1#
80[3"1#
76[81"02#
76[65"01#
067[6"1#
008[7"3#
019[1"3#
067[0"4#
014[1"6#
O"3#ÐRh"0#ÐO"2#
O"3#ÐRh"0#ÐO"1#
O"2#ÐRh"0#ÐO"1#
O"0#ÐRh"0#ÐN"0#
O"1#ÐRh"0#ÐN"0#
O"0#ÐRh"0#ÐRh"0#a
O"1#ÐRh"0#ÐRh"0#a
78[5"1#
89[3"1#
064[7"1#
82[0"1#
81[8"1#
76[74"01#
77[90"01#
C"1#aÐO"1#ÐRh"0#
C"0#aÐO"3#ÐRh"0#
O"0#ÐC"0#ÐO"3#a
N"0#ÐC"00#ÐC"01#
007[6"3#
008[8"3#
013[4"5#
068[0"6#
CH2OH "1#
RhÐO"2#
RhÐO"1#
1[913"3#
1[938"4#
1[125"3#
0[137"6#
0[151"6#
0[011"6#
0[264"7#
0[281"7#
0[388"8#
RhÐO"0#
1[922"3#
1[949"3#
1[2809"7#
0[154"6#
0[135"6#
0[351"6#
0[280"8#
0[408"7#
RhÐO"3#
RhÐN
RhÐRhc
O"0#ÐC"00#
O"2#ÐC"00#c
NÐC"0#
O"1#ÐC"02#
O"3#ÐC"02#c
C"0#ÐC"1#
C"1#ÐC"2#
C"00#ÐC"01#
C"1#ÐC"3#d
C"2#ÐC"3#
C"02#ÐC"03#
O"2#ÐRhÐO"0#
O"0#ÐRhÐO"1#
O"0#ÐRhÐO"3#
O"2#ÐRhÐN
064[37"03#
78[3"1#
89[9"1#
O"2#ÐRhÐO"1#
O"2#ÐRhÐO"3#
O"1#ÐRhÐO"3#
O"0#ÐRhÐN
89[0"1#
89[0"1#
064[3"1#
82[1"1#
80[2"1#
O"1#ÐRhÐN
81[3"1#
O"3#ÐRhÐN
81[0"1#
O"2#ÐRhÐRhc
O"1#ÐRhÐRhc
NÐRhÐRhc
76[65"00#
76[84"00#
068[99"02#
008[1"3#
019[0"3#
068[1"6#
014[0"5#
O"0#ÐRhÐRhc
O"3#ÐRhÐRhc
C"00#ÐO"0#ÐRh
C"00#cÐO"2#ÐRh
C"0#ÐNÐRh
76[63"00#
76[49"00#
008[4"3#
008[5"2#
066[7"4#
014[4"4#
C"02#ÐO"1#ÐRh
C"02#cÐO"3#ÐRh
NÐC"0#ÐC"1#
O"3#cÐC"02#ÐO"1#
O"0#ÐC"00#ÐO"2#c
THF "3#
Rh"0#ÐO"3#
Rh"0#ÐO"0#
Rh"0#ÐN"0#
O"0#ÐC"0#
1[918"2#
1[939"2#
1[115"2#
0[152"3#
0[147"3#
0[039"4#
0[495"5#
0[263"4#
0[265"4#
0[295"02#
Rh"0#ÐO"1#
Rh"0#ÐO"2#
Rh"0#ÐRh"0#a
O"1#ÐC"1#
1[928"2#
1[939"2#
1[2729"09#
0[154"4#
0[142"3#
0[378"4#
0[323"3#
0[277"4#
0[390"00#
0[31"1#
O"2#ÐC"0#a
N"0#ÐC"00#
C"1#ÐC"2#
O"3#ÐC"1#a
C"0#ÐC"3#
C"00#ÐC"01#
C"1#ÐC"03#
O"10#ÐC"10#
C"11#ÐC"11#f
C"01#ÐC"02#
C"02#ÐC"03#e
C"10#ÐC"11#g
O"3#ÐRh"0#ÐO"1#
O"1#ÐRh"0#ÐO"0#
O"1#ÐRh"0#ÐO"2#
O"3#ÐRh"0#ÐN"0#
064[87"8#
78[83"00#
78[75"00#
80[26"01#
O"3#ÐRh"0#ÐO"0#
O"3#ÐRh"0#ÐO"2#
O"0#ÐRh"0#ÐO"2#
O"1#ÐRh"0#ÐN"0#
78[36"01#
89[34"01#
065[95"8#
81[53"01#
"continued#

One dimensional polymer chains
3972
Table 1*continued
O"0#ÐRh"0#ÐN"0#
O"3#ÐRh"0#ÐRh"0#a
O"0#ÐRh"0#ÐRh"0#a
N"0#ÐRh"0#ÐRh"0#a
O"2#aÐC"0#ÐO"0#
O"0#ÐC"0#ÐC"3#
82[86"01#
O"2#ÐRh"0#ÐN"0#
O"1#ÐPh"0#ÐRh"0#a
O"2#ÐRh"0#ÐRh"0#a
C"00#ÐN"0#ÐRh"0#
O"2#a"C0#ÐC"3#
78[85"00#
76[73"6#
76[83"6#
057[6"2#
006[7"2#
014[6"2#
005[2"3#
095[3"02#
095[9"7#
77[06"7#
77[02"7#
066[74"7#
014[6"2#
005[5"2#
006[8"3#
067[1"3#
095[3"8#
O"3#a"C1#ÐO"1#
O"3#aÐC"1#ÐC"2#
O"1#ÐC"1#ÐC"2#
N"0#ÐC"00#ÐC"01#
C"10#fÐO"10#ÐC"10#
"C10#hÐC"11#ÐC"11#f
C"11#gÐC"10#ÐO"10#
Benzene "4#
RhÐO"2#i
RhÐO"0#
1[9237"03#
1[9259"01#
1[126"1#
0[153"1#
0[152"1#
0[026"2#
0[492"2#
0[279"2#
0[271"2#
0[288"09#
0[239"00#
0[288"00#
RhÐO"3#
1[9259"03#
1[9258"02#
1[2776"3#
0[159"1#
0[154"1#
0[491"1#
0[335"2#
0[278"2#
0[225"09#
0[260"09#
0[396"00#
RhÐO"1#i
RhÐN"0#
RhÐRhi
O"0#ÐC"0#
O"2#ÐC"2#
N"0#ÐC"4#
C"2#ÐC"3#
C"5#ÐC"7#b
C"6#ÐC"7#
C"8#ÐC"09#
C"8?#ÐC"09?#
C"09?#ÐC"00?#
O"1#ÐC"0#
O"3#ÐC"2#
C"0#ÐC"1#
C"4#ÐC"5#
C"5#ÐC"6#
C"8#ÐC"00#j
C"09#ÐC"00#
C"8?#ÐC"00?#j
O"2#iÐRhÐO"3#
O"3#ÐRhÐO"0#
O"3#ÐRhÐO"1#i
O"2#iÐRhÐN"0#
O"0#ÐRhÐN"0#
O"2#iÐRhÐRhi
O"0#ÐRhÐRhi
N"0#ÐRhÐRhi
C"0#ÐO"1#ÐRhi
C"2#ÐO"3#ÐRh
O"1#ÐC"0#ÐO"0#
N"0#ÐC"4#ÐC"5#
065[90"4#
89[33"4#
78[52"4#
87[21"5#
81[92"4#
76[89"3#
076[86"3#
062[67"3#
008[06"00#
008[95"01#
014[6"1#
065[1"1#
O"2#iÐRhÐO"0#
O"2#iÐRhÐO"1#i
O"0#ÐRhÐO"1#i
O"3#ÐRhÐN"0#
O"1#iÐRhÐN"0#
O"3#ÐRhÐRhi
O"1#iÐRhÐRhi
C"0#ÐO"0#ÐRh
C"2#ÐO"2#ÐRhi
C"4#ÐN"0#ÐRh
O"2#ÐC"2#ÐO"3#
78[73"4#
78[71"4#
064[87"4#
74[54"5#
80[88"4#
77[02"3#
77[90"3#
008[07"00#
008[28"01#
049[5"1#
014[4"1#
Symmetry transformations used to generate equivalent atoms]a−x¦0:1\ −y¦0:1\ −z^ b−x¦0\
−y¦0\ −z¦0^ c−x¦0:1\ −y¦2:1\ −z^ d−x¦0\ −y¦1\ −z¦0^ e−x¦0\ −y\ −z¦0^ f−x¦0\
i
j
y\ −z¦0:1^ g−x¦0\ y−0\ −z¦0:1^ h−x¦0\ y¦0\ −z¦0:1^ −x\ −y¦0\ −z¦1^ −x\ −y\
−z¦0[
RESULTS AND DISCUSSION
Preparation
The characteristics of the compounds obtained
reactions[ The structure and composition of the _nal
products were insensitive to changes in the stoi!
chiometry of the reactants[
from the reaction of rhodium"II#acetate dimer with Structures
0\3!dicyanobenzene vary with the di}erent solvents
used[ Two methods were used for the synthesis of the
All of the polymeric structures contain one dimen!
_ve compounds[ 0\ 2 and 3 were synthesized with only sional chains comprised of rhodiumacetate dimers
one type of solvent[ The solvent served to dissolve the bridged by 0\3!dicyanobenzene "see Fig[ 0 for 0#[ Each
starting materials and was subsequently incorporated compound has di}erent solvent molecules located
into the structure within a channel formed by stacking between the polymer chains and each solvent causes
of the polymer chains[ For 1 and 4\ two types of signi_cant variations in the crystal structures that are
solvents were involved in the synthesis[ One served to adopted[
dissolve the starting material and the other one was
Figure 0 shows the local coordination of compound
incorporated into the structure[ THF was used as the 0 with the atoms labelled[ Figures 1 and 2 show di}er!
solvent but was not observed in the _nal structures[ ent views of the spatial relationship between the linear
Excess 0\3!dicyanobenzene was used in all of the _ve chains[ In Fig[ 1\ the acetate ligands have been omitted

3973
T[ Niu et al[
plane\ Fig[ 2[ Part of the extended structure of 0 is
shown in Fig[ 2[ The intersections of the chains de_ne
channels in the structure that are occupied by the
solvent molecules[
The acetone molecules in 0 are severely disordered
and are di.cult to locate in di}erence maps[ One
acetone molecule was re_ned with an occupancy fac!
tor of 9[165\ while four additional atom sites des!
ignated as carbon were also located and re_ned with
_xed occupancies of 9[2[ From thermogravimetric
analysis data "see Section 2[2#\ one acetone molecule
per dirhodium unit is present[
The arrangement of the polymer chains in the struc!
ture of 1 is the same as in 0[ Adjacent chains are
oriented at an angle of 45[9> with respect to each
other\ when projected on the ab plane[ This angle is
essentially the same as observed in 0 "45[2>#[ The aver!
age RhÐO\ RhÐN and RhÐRh bond distances in the
two compounds are the same within errors[ The meth!
anol solvent molecules in 1 are also disordered[ The
positions of two methanol molecules could be re_ned\
albeit with high thermal parameters[ The exact num!
ber of methanol molecules could not be determined
from the X!ray data\ however thermogravimetric
analysis indicates that two methanol molecules per
dirhodium unit are present[
Fig[ 0[ Ortep drawing of the local coordination of 0 with
thermal ellipsoids at the 49) probability level\ the solvent
acetone is not shown[
for clarity[ The dinuclear Rh3¦ carboxylate core
1
Ä
remains intact\ with a RhÐRh distance of 1[280"0# A[
The RhÐO distances range from 1[918"3# to
Ä
1[938"4# A[ The octahedral coordination sphere of Rh
is completed by axial coordination to the nitrogen
Ä
atom of the organic ligand at a distance of 1[128"4# A[
The RhÐNÐC linkage is nearly linear\ with an angle of
067[0"4#>[ The chains stack together with an average
Ä
In 3\ the THF solvent molecules are ordered and a
signi_cant change in the arrangement of the polymeric
chains ðFig[ 3"a#Ð"c#Ł is observed[ In 0 and 1 the chains
are nearly linear\ but in 3 the CÐNÐRh angle is reduced
separation of 2[7 A\ Fig[ 1[ The phenylrings from the
alternating chains are not parallel to each other and
the closest contact between adjacent phenylrings is
Ä
2[448 A "C01 from one ring and C03 from another
ring#[ Adjacent chains are oriented at an angle of 45[2> to 057[6"2#>[ The RhÐRhÐN and NÐCÐC angles in 3
Ä
with respect to each other when projected on the ab are still close to 079>[ The NÐRh distance ð1[115"2# AŁ
Fig[ 1[ View of the structure of 0 showing the stacking of the chains[ For clarity\ the acetate groups of the Rh dimer are not
shown[

One dimensional polymer chains
3974
Fig[ 2[ Projection of the structure of 0 along c[ Disordered acetone molecules are shown between the chains[
Fig[ 3[ "a# View of the structure of 3 showing the stacking of the chains and the THF molecules[ For clarity\ the acetate
groups of the Rh dimer are not shown[ "b# Local coordination of 3 showing the attraction between oxygen of the THF and
the phenylrings in the chains[ For clarity\ the acetate groups of the Rh dimer are not shown[ The dotted lines indicate the
closest contact between the THF and phenylrings[ "c# View of the structure of 3 showing the attraction between oxygen of
the THF and the phenylrings in the chains[ For clarity\ the acetate groups of the Rh dimer are not shown[ The dotted lines
indicate the closest contact between the THF and phenylrings[
is similar to the distance in 0 and 1[ The change in an angle of 28[49> "projected on ab plane#[ The
angle at the N atom\ however\ imparts a slight zigzag arrangement of THF molecules between adjacent
geometry to the chains as can be seen in Fig[ 3[ The chains suggests a weak interaction through the oxygen
stacking of the polymer chains in 3 is similar to that lone electron pairs[ This interaction may be respon!
observed in 0 and 1\ but the alternating chains make sible for reducing the dihedral angle between the

3975
T[ Niu et al[
Fig[ 3*continued[
chains by ½06>[ The distances between the THF oxy! molecules that sandwich each phenylring in the chain
gen atom and the chains "O10ÐC03 and O10ÐC01# are are parallel to each other and are separated by a dis!
Ä
Ä
2[270 and 2[323 A\ respectively[ The bridging tance of 7[350 A[ The phenylring in the chain and the
geometry is symmetric because THF lies on a crys! benzenering are not parallel and the closest contact
Ä
tallographic two!fold axis[
between them is 2[372 A "C5ÐC8#\ while the distance
A di}erent structure is observed when benzene mol! from C4 of the cyanide group to C8 of the benzenering
Ä
ecules are trapped between the polymer chains[ Crys! is 2[241 A[ The spacing between the phenylrings is too
tals of 0\ 1\ 2 and 3 all have the same dark red color\ large to imply any strong electronic interaction[ The
while crystals of 4 are lilac[ In 4\ all of the chains in benzene molecules are disordered over two di}erent
the crystal are parallel to each other "Figure 4#[ Every positions\ rotated at roughly 29> to each other about
polymeric chain zigzags as in 3\ with a CÐNÐRh angle a common crystallographic inversion center[ Analysis
of 049[5"1#>\ which is much further from linear than of the isotropic thermal parameters showed a 49)
the corresponding angle in 3 ð057[6"2#>Ł[ The benzene occupancy for each orientation[

One dimensional polymer chains
3976
Fig[ 4[ "a# View of the structure of 4 showing the stacking of the chains and the benzene molecules[ For clarity\ the acetate
groups of the Rh dimer are not shown and only one position of the disordered benzene molecule is shown[ "b# Local
coordination of 4 showing the attraction between the benzene molecules and the phenylrings in the chains[ The dotted lines
indicate the closest contact between the benzene molecule with the chains[ "c# View of the structure of 4 along a showing the
stacking of the chains[
All _ve crystal structures have solvent {{channels|| The structure of 3\ suggests some interaction between
leading directly to the surface] 0\ 1\ 2 and 3 have the oxygen lone pair electrons in THF and the chains\
channels along the c axis\ while 4 has a channel along whereas in 4 the benzene molecules may have some
a[ In TGA measurements on heating\ acetone\ meth! pÐp interactions with the phenylrings in the chain[
anol and ethanol are all removed near their boiling
points[ However\ THF and benzene are lost at tem!
peratures signi_cantly higher than their boiling points Thermo`ravimetric analysis
and the removal of the solvent molecules is not well
resolved in temperature from the temperature at
Each of 0\ 1\ 2\ 3 and 4 was heated to 399>C in
which the dicyanobenzene molecules are removed[ nitrogen to determine the solvent contents and ther!
The TGA data suggest some weak interaction between mal stabilities "Figure 5#[ For 0\ the _rst two weight
the solvent molecules and the frameworks of 3 and 4[ losses at T³007>C corresponded to the loss of one

3977
T[ Niu et al[
Fig[ 4*continued[
molecule of acetone "observed 8[56)\ calculated corresponding to the four acetate groups was similar
8[14)#[ From 007 to 064>C\ a second weight loss to the value observed for the other compounds[ The
corresponded to removal of one dicyanobenzene mol! thermal decomposition of 4 showed three!steps in the
ecule "observed 10[88)\ calculated 19[39)#[ The _nal weight loss below 067>C\ the total weight loss cor!
weight loss occurred between 116 and 135>C and cor! responded to the removal of one benzene and one
responded to the loss of the four acetate groups[ No dicyanobenzene molecule "observed 20[70)\ cal!
further decomposition was observed above 135>C[ X! culated 20[71)#[ The remaining weight losses was
ray powder di}raction con_rmed that the black resi! similar to other compounds[
due was pure Rh "observed 20[19)\ calculated
21[65)#[ Interestingly the original shape of the crystal
was preserved after decomposition[
The thermal decomposition behaviors of 1 and 2
3[ CONCLUSIONS
were similar to that of 0[ In both cases\ the loss of
solvent molecules was completed at relatively low tem!
Five new one dimensional coordination polymers
formed by dirhodium"II#tetraacetate bridged by 0\3!
perature "51>C for 1 and 002>C for 2#[ The weight
dicyanobenzene have been synthesized and char!
losses corresponding to the loss of dicyanobenzene
acterized[ Each compound has a di}erent solvent mol!
ecule _lling the cavities between the polymeric chains[
The type of solvent apparently plays an important
molecules and the four acetate groups occurred in
similar temperature ranges in 1 and 2 and they were
not signi_cantly di}erent from those of 0[ The solvent
role in the crystallization process and determines the
losses indicated a composition of two methanol mol!
separation and orientation of the polymeric chains[
We are currently investigating other solvents that can
be introduced between the chains and further work
will focus on studying the extensions to 1D and 2D
polymers by using multifunctional organic bridging
ligands[
ecules per dirhodium unit per unit cell in 1 and one
ethanol molecule per dirhodium unit per unit cell in
2[
Compound 3 showed no thermal decomposition
until 099>C[ This temperature is signi_cantly higher
than observed for 0\ 1 and 2\ which lose solvent mol!
ecules immediately on heating[ The removal of THF
and the dicyanobenzene molecules were not well
resolved in temperature but the sum of the losses
"observed 20[24)\ calculated 20[07)# indicated only
Acknowled`ements*We thank the National Science Foun!
dation "DMR!8103793# and the Robert A[ Welch Foun!
dation for support of this work and Dr James Korp for help
one THF molecule per formula unit[ The weight loss with crystallography[

One dimensional polymer chains
3978
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