Syntheses and characterization of copper(II) and cobalt(II) complexes with tris[2-(benzylamino)ethyl]amine

Article abstract of DOI:10.1135/cccc20021647

Two mononuclear complexes [Cu(NCS)(trenb)]ClO₄ (1) and [Co(NCS)(trenb)]Cl·H₂O (2), where trenb is tris[2-(benzylamino)ethyl]amine, were prepared and characterized by elemental analysis, IR, electronic and EPR spectra. Their crystal s

Full text of DOI:10.1135/cccc20021647

Copper(II) and Cobalt(II) Complexes
1647
SYNTHESES AND CHARACTERIZATION OF COPPER(II) AND COBALT(II)
COMPLEXES WITH TRIS[2-(BENZYLAMINO)ETHYL]AMINE
Yong-Shu XIEa1,b, Hui JIANGa2,b, Xue-Ting LIU , Zhong-Yuan ZHOU ,
b
c
b1,
b
Qing-Liang LIU * and Xiao-Long XU
a
State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei,
Anhui, 230026, P. R. China; e-mail: yshxie@ustc.edu.cn, hjiang@mail.ustc.edu.cn
Department of Chemistry, University of Science and Technology of China, Hefei, 230026,
1
2
b
c
1
P. R. China; e-mail: qliu@ustc.edu.cn
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University,
Hung Hom, Kowloon, Hong Kong, P. R. China
Received March 17, 2002
Accepted Septem ber 5, 2002
Two m on on uclear com plexes [Cu(NCS)(tren b)]ClO4 (1) an d [Co(NCS)(tren b)]Cl·H O (2),
2
wh ere tren b is tris[2-(ben zylam in o)eth yl]am in e, were prepared an d ch aracterized by elem en -
tal an alysis, IR, electron ic an d EPR spectra. Th eir crystal structures were determ in ed by X-ray
diffraction . Com plexes 1 an d 2 are both five-coordin ated with th eir m etal cen ters in th e dis-
torted trigon al-bipyram idal en viron m en t. Each m etal(II) ion coordin ates with th e tetra-
den tate tren b, an d on e isoth iocyan ate an ion . Th e two com plexes are n ot isostructural as
th ere are also a ch loride an d a water m olecule in th e asym m etric un it of 2. Besides balan c-
in g th e ch arge, th e ch lorides are also in volved in in tram olecular an d in term olecular h ydro-
gen bon ds with th e secon dary am in e groups, resultin g in a on e-dim en sion al ch ain structure.
UV-VIS spectrum an d EPR m easurem en t for 1 h ave un am biguously con firm ed th at th e
five-coordin ated structure is retain ed in solution , even in th e don atin g solven t such as DMF.
Keyw ord s: Copper(II) com plexes; Cobalt(II) com plexes; Crystal structure determ in ation ;
Tren derivative; Tripodal ligan ds; X-Ray diffraction .
Great in terest h as been focused on th e m etal com plexes of tripodal ligan ds,
especially to m odel fun ction s or spectroscopic features of m etalloen zym es1
an d to study th e factors th at cause various distortion s from regular stereo-
2
ch em istry . Som e of th em h ave been foun d to possess special features, such
3
as reversible bin din g of dioxygen , wh ich th rew som e ligh t on th e fun da-
m en tal step in m etalloen zym e redox reaction s. Th e ideas of utilizin g th em
in th e syn th eses of h igh ly sym m etrical m olecular cages, wh ich are poten -
4
tially suitable for m olecular recogn ition , are also con sidered . Am on g th e
tripodal ligan ds, tren (tris(2-am in oeth yl)am in e) attracted m uch atten tion ,
partly because of its ability to form un com m on five-coordin ated com plexes
Collect. Czech. Chem. Commun. (Vol. 67) (2002)
doi:10.1135/cccc20021647

1
648
Xie et al.:
5
with divalen t m etal ion s . However, in vestigation of th e com plexes of its
derivatives, in particular th e in vestigation of th e steric h in dran ce in duced
6
by th e m odification , was relatively scarce , bein g m ain ly lim ited to less
bulky groups such as m eth yl3 . Th us, we ch ose larger substituen t groups
to gain furth er in sigh t of com plexes of th e tren derivatives.
Herein , we report th e syn th eses, as well as spectroscopic an d structural
ch aracterization of Cu(II) an d Co(II) com plexes with a tripodal ligan d,
tris[2-(ben zylam in o)eth yl]am in e (Sch em e 1).
d,7
N
KSCN
NH Bn
NH Bn
Bn NH
N
HN Bn
+
M(II)
Bn
N
H
M
NCS
NH Bn
(M = Cu, Co; Bn = benzyl)
SCHEME 1
RESULTS AND DISCUSSION
Spectra
Th e IR spectra of th e title com plexes sh ow sh arp vibration ban ds due to
–
1
th e ν(CN) stretch in g. In com plex 1, th e stron g ban d lies at 2106 cm an d it
–
1
appears at 2059 cm in com plex 2. Oth er n oticeable ban ds appear at 3288
an d 3249 cm in 1 an d 3238 cm –1 in 2, wh ich belon g to th e ν(NH). Th e
bands at 1086 and 622 cm –1 are assigned to the perchlorate ion in com plex 1.
Featureless EPR spectra were observed for polycrystallin e sam ples of 1 at
room tem perature an d at 100 K. In DMF solution , an isotropic spectrum
con tain in g four h yperfin e lin es is observed at room tem perature, wh ile th e
spectrum at 100 K h as an axial sym m etry, exh ibitin g four h yperfin e peaks
–1
in th e perpen dicular region with g = 1.993, g = 2.195, g = 2.144, Aiso
=
|
|
⊥
iso
–
4
6
8.2 G, A = 113.3 G, A = 22.0 G (1 G = 10 T). Th e data m ostly fall in th e
⊥ ||
7
a
region reported except A , wh ich varies sign ifican tly in th e copper(II)
|
|
com plexes of tren an d its derivatives, m ain ly depen din g on th eir spin -orbit
couplin g con stan ts. Th e fact g⊥ > g|| con firm s a distorted trigon al-
1
8
bipyram idal stereoch em istry with a (d z
2
) groun d state in com plex 1 . Th e
g < 2.0 m ay result from th e “reversed axial” pattern th at copper(II) com -
|
|
plexes in th e trigon al-bipyram idal (TBP) geom etry with tripodal ligan ds
8
b,9
n orm ally display in th e frozen -solution EPR spectra
.
Collect. Czech. Chem. Commun. (Vol. 67) (2002)

Copper(II) and Cobalt(II) Complexes
1649
Th e electron ic spectra of com plexes 1 an d 2, m easured in DMF solution ,
are reported in Table I. Th e spectrum of 1 sh ows a sh arp ban d at 850 n m
an d an asym m etric h igh -en ergy sh oulder with th e m axim um at 676 n m ,
1
0
ch aracteristic of a distorted trigon al-bipyram idal CuN5 ch rom oph ore .
Th e two tran sition s are assign ed as (d , d x
2
−y2
) → d z
2
(lower en ergy) an d
xy
(
d , d ) → d . Com parin g to th e copper(II) com plexes of tren an d
z 2
yz
xz
tren Me , th e d-d ban ds both m ove to th e h igh er en ergy as th e bulkier
6
am in es in h ibit th e approach of adjacen t m olecules an d decrease th e axial
7
a
in teraction , resultin g in stron ger in -plan e bon din g . Th e two ban ds of 1
are obviously m ore in ten sive th an th ose of th e tren com plex, but a little
distin ction in in ten sity is foun d between 1 an d th e tren R (R = Me, Et) com -
6
plexes.
Th e spectral features of 2 are difficult to fully explain , sin ce th e spectra of
five-coordin ated cobalt(II) com plexes con siderably vary depen din g on th e
n ature of th e distortion 11. In com plex 2, th ere are broad ban ds at 606 an d
4
92 n m , associated with th e d-d tran sition s, with a sh oulder at a lower en -
1
2
ergy (756 n m ). Th e results are parallel to th e reported exam ples of th e
trigon al-bipyram idal geom etry of cobalt(II). Th e rem ain in g ban d m axim a
n ear or below 300 n m are due to th e in traligan d tran sition s as follows from
sim ilarities with th e absorban ce of th e “free” ligan d.
Structure Description
Th e perspective drawin gs for com plexes are sh own in Figs 1 an d 2. Selected
bon d len gth s an d bon d an gles are listed in Tables II an d III. Th e structure of
+
−
1
con sists of [Cu(NCS)(tren b)] cation an d ClO4 an ion . In th e cation , th e
copper(II) ion is in a distorted trigon al-bipyram idal geom etry with th ree
secon dary am in e groups of th e tren b ligan d form in g th e equatorial plan e
TABLE I
a
Sum m ary of electron ic spectral data
Com poun d
λm ax, n m (ε, dm 3 m ol–1 cm –1
)
Tren b·3HCl
281 (1500), 267 (6250)
1
2
850 (408), 676 (200), 287 (6240), 262 (4500)
756 (27), 606 (116), 492 (103), 306 (310), 264 (803)
a
Spectra recorded in DMF.
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650
Xie et al.:
O1
C11
O3
O2
C8
C7
O4
C9
C2
C6
C1
C5
C11
C10
C4
C3
N2
N1
C15
N3
C14
C19
C16
C13
Cu1
N5
C28
C12
C20
N4
C17
C18
C21
C22
S1
C27
C26
C23
C24
C25
FIG. 1
View of com plex [Cu(NCS)(tren b)]ClO4 (1) sh owin g th e n um berin g sch em e at th e 30% proba-
bility level with th e H atom s om itted for clarity
C18
C17
C27
C26
C25
C19
N1
C16
C24
C11
N4
C10
C23
C15
H4F
C12
C13
N3
C22
C8
C9
C20
C21
Co1
H3F
N2
C14
H2F
C11
N5
C7
C28
C5
C1
O1
S1
C4
C3
C2
FIG. 2
An ORTEP view of [Co(NCS)(tren b)]Cl·H O (2) sh owin g th e n um berin g sch em e. Th e th erm al
2
ellipsoids are at th e 10% probability level with th e H atom s om itted for clarity
Collect. Czech. Chem. Commun. (Vol. 67) (2002)

Copper(II) and Cobalt(II) Complexes
1651
–
an d with th e tertiary am in e an d NCS in th e apical position s. Th e square-
pyram idal com pon en t of structural in dex τ is 0.88 (for ideal square-
pyram idal an d trigon al-bipyram idal geom etries th e values are zero an d
1
3
un ity, respectively) . Th e axis N(1)–Cu–N(5) (an gle of 178.96(8)°) is
rough ly perpen dicular (90.76°) to th e equatorial plan e. Th e in terch elate
bon d an gles, such as N(1)–Cu–N(2) (84.15(7)°), agrees with th at of 84.1°
TABLE II
Selected bon d len gth s (in Å) an d bon d an gles (in °) for 1
Cu1–N5
Cu1–N2
Cu1–N4
N5–C28
1.928(2)
2.113(2)
2.107(2)
1.169(3)
Cu1–N3
Cu1–N1
S1–C28
2.152(2)
2.037(2)
1.618(3)
N5–Cu1–N2
N2–Cu1–N3
N2–Cu1–N4
N5–Cu1–N1
N3–Cu1–N1
C28–N5–Cu1
96.89(8)
113.78(8)
125.93(8)
178.96(8)
83.75(8)
175.5(2)
N5–Cu1–N3
N5–Cu1–N4
N3–Cu1–N4
N2–Cu1–N1
N4–Cu1–N1
N5–C28–S1
95.83(9)
94.44(9)
117.34(8)
84.15(7)
84.92(8)
178.4(2)
TABLE III
Selected bon d len gth s (in Å) an d bon d an gles (in °) for 2
Co1–N5
Co1–N2
Co1–N4
N5–C28
2.027(5)
2.087(5)
2.103(5)
1.162(7)
Co1–N3
Co1–N1
S1–C28
2.095(4)
2.214(5)
1.613(6)
N5–Co1–N2
N2–Co1–N3
N2–Co1–N4
N5–Co1–N1
N3–Co1–N1
C28–N5–Co1
102.2(2)
117.6(2)
115.8(2)
174.9(2)
80.9(2)
N5–Co1–N3
N5–Co1–N4
N3–Co1–N4
N2–Co1–N1
N4–Co1–N1
N5–C28–S1
101.4(2)
94.4(2)
118.9(2)
80.5(2)
80.5(2)
179.2(5)
154.5(5)
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Xie et al.:
1
4
in [Cu(NCS)(tren )](SCN) . Th e th ree out-of-plan e ch elate bite an gles im -
posed by th e ligan d lead to th e fact th at th e copper(II) ion is displayed by
–
0
.21 Å below th e equatorial plan e towards th e NCS . Th e equatorial plan e
is n ot strictly trian gular: on e of th e N(2)–Cu–N(4) an gle of 125.93(8)° is
sign ifican tly larger th an th e oth er two an d th e distan ce of th e Cu–N(3)
bon d (2.152(2) Å) opposite to th e an gle is lon ger th an th e oth er two Cu–N
bon ds. Th e Cu–N(tertiary am in e) distan ce (2.037(2) Å) is th e sh ortest of th e
four n itrogen atom s from tren b ligan d an d con sisten t with th e litera-
3
e,5,7b,10a,14
ture
. Th e axial com pression was com m on ly con sidered as a result
9
10a
of its d con figuration in th is stereoch em istry . Th e Cu–N(th iocyan ate)
bon d of 1.928(2) Å was even sh orter due to th e π-bon din g com pon en t an d
1
4
sim ilar to th at in [Cu(NCS)(tren )](SCN) .
Cation in com plex 2 is sim ilar to th at appearin g in 1, alth ough th e two
com plexes are n ot isostructural. Th e cobalt(II) ion is also in a distorted
trigon al-bipyram idal geom etry with its coordin ation en viron m en t in coin -
ciden ce with th at of 1. Th e pseudo-th ree-fold axis is align ed with
N(1)–Co–N(5) (174.9(2)°) an d is alm ost perpen dicular (89.84°) to th e equa-
torial plan e con tain in g th ree am in e n itrogen atom s, wh ich m ake alm ost an
equilateral trian gle. Th e cobalt(II) ion is about 0.34 Å out of th e plan e to-
–
wards th e NCS an d th e deviation is som ewh at larger th an th at of th e cop-
per(II) in com plex 1. However, th e Co–N bon d len gth s differ greatly from
th ose in 1: th e Co–N(tertiary am in e) distan ce (2.214(5) Å) is n ow dram ati-
cally lon ger th an th e oth er th ree n itrogen atom s from th e tren b ligan d
(
2.087(5)–2.103(5) Å), th ough still sim ilar to th e values foun d in litera-
1
5
ture . Th e oth er param eters are com m on .
Th e an gle M–N–C(th iocyan ate) (M m ean s m etal ion ) differs greatly in th e
two com plexes. Th e Co–N–C (154.6°) deviates m arkedly from th e pseudo-
th ree-fold axis th an th e an gle Cu–N–C (175.5°) does, an d th e values are dif-
feren t from th ose foun d in th e literature, such as 163.3° in [Cu(NCS)-
1
4
16
(
tren )](SCN) an d 163.4 an d 156.3° in octah edral [Ni(NCS) (tren )] . Th e
2
situation is com m on , as th e isoth iocyan ate ion can flexibly ch oose an y ap-
propriate coordin atin g direction after th e tripodal ligan d occupy th e apex
an d th e equatorial plan e of th e com plex. Th us th e steric h in dran ce m ay be
determ in an t. In com plex 2, th e strain of Co–N–C(isoth iocyan ate) bon ds
was caused by th e ben zyl groups, wh ich appears alleviative in com plex 1.
Th ere are also a ch loride an d a water m olecule in th e crystal un it of 2. Be-
sides balan cin g th e ch arge, th e ch loride also weakly in teracts with th ree h y-
drogen atom s from secon dary am in e groups. It is clear th at ch loride
in teracts with H(2F) an d H(4F) atom (th e distan ces are 2.639 an d 2.713 Å,
respectively) but n ot H(3F) (about 6.14 Å), wh ich always in teracts with th e
Collect. Czech. Chem. Commun. (Vol. 67) (2002)

Copper(II) and Cobalt(II) Complexes
1653
ch loride in th e adjacen t m olecule (2.488 Å), as Fig. 3 sh ows. Th us, th e crys-
tal un its can be con sidered as bein g con n ected via weak in teraction s
between ch lorides an d h ydrogen atom s to give a on e-dim en sion al ch ain .
Th e water m olecule in teracts with th e ch loride with th e Cl···O distan ce of
2
.473 Å. Th e un usual sh ort Cl···O bon d m ay owe to th e effect of th e very
stron g h ydrogen bon ds, wh ich n orm ally sh orten th e relative distan ce
1
7
sh arply . However, com parable data con cern in g Cl···H–O h ydrogen bon ds
are rare due to th e h eavy effects of th e th erm al vibration artifacts1
.
7b
Th ough direct eviden ce is un available, th e h ydrogen of th e water m ay be
presum ed to delocalize to som e exten t an d be in an equilibrium state with
ch loride an d oxygen . Th us th e water m olecule is also adm itted as a m em ber
of th e on e-dim en sion al ch ain .
EXPERIMENTAL
General Comments
All th e reagen ts were com m ercially available an d were used with out furth er purification .
1
6
H NMR spectra were recorded on a Bruker DMX-500 spectrom eter in DMSO-d solution s at
98 K. Ch em ical sh ifts (δ, ppm ) are given relative to in tern al tetram eth ylsilan e. IR spectra
2
(
4
–
1
waven um bers in cm ) were m easured on a Bruker Vector-22 spectrom eter (ran ge 400–
000 cm ). Electron ic spectra were obtain ed on a Sh im adzu UV-3100 UV-VIS-NIR recordin g
–
1
3
–1
–1
spectroph otom eter (λm ax in n m ,
ε
in dm m ol
cm
) in th e ran ge 200–900 n m .
Microan alyses of C, H an d N were carried out with a VARIO ELIII elem en tal an alyzer.
EPR studies were perform ed with a Bruker ER200D-SRC spectrom eter at X-ban d (9.46 GHz).
Safety n ote! Perch lorate salts of m etal com plexes with organ ic ligan ds are poten tially ex-
plosive. On ly a sm all am oun t of th e m aterial sh ould be prepared an d h an dled with extrem e
care.
FIG. 3
Molecular packin g in structure of [Co(NCS)(tren b)]Cl·H O (2). Th e figure sh ows th e weak in -
2
teraction s N–H···Cl resultin g in a on e-dim en sion al ch ain
Collect. Czech. Chem. Commun. (Vol. 67) (2002)

1
654
Xie et al.:
Syntheses
Tris[2-(ben zylam in o)eth yl]am in e Trih ydroch loride (tren b·3HCl)
To a stirred solution of 15.5 m l of 98% ben zaldeh yde (0.15 m ol) in eth an ol (25 m l) was
added tris(2-am in oeth yl)am in e (7.6 m l, 0.05 m ol). After refluxin g for 4 h , potassium
boroh ydride (5.5 g) in a m orsel of water was added over 15 m in . Th e origin al yellow color
slowly faded. Wh en th e evolution of th e gas slacken ed, th e solution was cooled an d th en
acidified with con c. h ydroch loric acid to pH 3. Th e am oun t of th e wh ite precipitate reduced
by addin g 4 M KOH solution un til pH about 9. After filtration , th e solution was extracted
with 3 × 50 m l ch loroform an d th e organ ic ph ase was dried (Na SO ) an d evaporated to dry-
2
4
n ess. Th e residual oil was dissolved in 50 m l eth an ol an d pH of th e solution was adjusted by
con cen trated h ydroch loric acid to stron g acidic. A soft wh ite powder was obtain ed. Th e
solid was wash ed with eth an ol an d th en dried in vacuo. Yield 10.5 g (40%). For C27H39Cl N
3
4
(
526.0) calculated: 61.43% C, 7.45% H, 10.72 % N; foun d: 61.65% C, 7.47% H, 10.65% N.
IR (KBr): ν(h ydroch loride) 2500–2900 br, 1456 s, 1434 m , 1371 m , 1021 m com posite, 744 s,
1
6
+
6
94 s. H NMR (DMSO-d ): 9.54 apparen t s, 6 H (-NH ); 7.42 apparen t t, 9 H (Ar-H); 7.65 ap-
2
+
paren t t, 6 H (Ar-H); 4.22 apparen t s, 6 H (ArCH -); 3.12 apparen t s, 6 H (-NH CH -); 2.80
2
2
2
apparen t t, 6 H (>NCH -).
2
[
Cu(NCS)(tren b)]ClO4 (1)
A m eth an olic solution (10 m l) of Cu(ClO ) ·6H O (0.074 g, 0.20 m m ol) was added dropwise
4
2
2
to a stirred solution of tren b·3HCl (0.083 g, 0.16 m m ol) in m eth an ol (40 m l). Th en th e m ix-
ture was m ade stron gly alkalin e with 4 M aqueous NaOH (0.30 m l). Fin ally, KSCN (0.038 g,
0
.40 m m ol) dissolved in a sm all volum e of water was added slowly. Th e clear green -blue
solution was refluxed for 3 h , filtered to rem ove a sm all quan tity of a precipitate an d left
un disturbed at room tem perature. After a few m on th s, crystals suitable for X-ray an alysis
were filtered off, wash ed several tim es with water–eth an ol (1 : 1, v/v) an d air-dried. Yield
0
.026 g (25%). Th e an alysis for th e bulk m aterial was con sisten t with th e form ula proposed.
For C28H36ClCuN O S (637.7) calculated: 52.74% C, 5.69% H, 10.98% N; foun d: 52.46% C,
5
4
5
1
.37% H, 10.71% N. IR (KBr): ν(NH) 3288 m , 3249 m , 2923 m ; ν(CN) 2106 s, 1455 m ,
343 w, 1203 w, 1086 br, 988 s, 830 w, 746 s, 705 s, 622 m .
[
Co(NCS)(tren b)]Cl·H O (2)
2
A m eth an olic solution (10 m l) of Co(OAc) ·4H O (0.074 g, 0.20 m m ol) was added dropwise
2
2
to a stirred solution of tren b·3HCl (0.083 g, 0.16 m m ol) in m eth an ol (40 m l). Th e dark blue
solution darken ed after a solution of KSCN (0.038 g, 0.40 m m ol) in a sm all volum e of water
was slowly added. A m ass of green crystals was grown from th e rosy solution on ly after
evaporation of som e solven t. Th e crystallin e product was collected by filtration , wash ed
with water–eth an ol (1 : 1, v/v) an d dried in th e air. Yield 0.024 g (21%). Th e an alysis of
th e bulk m aterial was con sisten t with th e form ula proposed. For C28H38ClCoN SO (587.1)
5
calculated: 57.28% C, 6.52% H, 11.93% N; foun d: 57.34% C, 6.53% H, 11.78% N. IR (KBr):
3
1
418 m ; ν(NH) 3238 w, 3079 m , 2947 w; ν(CN) 2060 s, 1495 m , 1454 m , 1345 m , 1207 w,
077 m , 1044 w, 1003 m , 960 w, 851 w, 742 m , 702 s, 625 m .
Collect. Czech. Chem. Commun. (Vol. 67) (2002)

Copper(II) and Cobalt(II) Complexes
1655
X-Ray Crystallography
Sin gle crystals were m oun ted on a glass fiber. All m easurem en ts were m ade with a Rigaku
RAXIS-IV im age plate area detector with graph ite-m on och rom atized MoKα radiation . Th e
data were collected at th e tem peratures listed in Table IV an d corrected for Loren tz an d po-
larization effects. A correction for secon dary extin ction was applied. Th e structure was
solved by direct m eth ods an d expan ded usin g Fourier tech n iques. Th e n on -h ydrogen atom s
were refin ed an isotropically. Hydrogen atom s were in cluded but n ot refin ed. Th e fin al cycle
TABLE IV
Crystal data an d structure refin em en t for 1 an d 2
Com poun d
1
2
Molecular form ula
Form ula weigh t
Crystal color an d h abit
Crystal dim en sion , m m
System space group
T, K
C28H36ClCuN O S
C28H36ClCoN OS
5
4
5
637.67
585.06
blue, plate
dark red, prism
0.28 × 0.20 × 0.20
orth orh om bic, Pbac
291(2)
0.22 × 0.20 × 0.12
m on oclin ic, P2 /c
1
294(2)
a, Å; α, °
11.3134(15); 90
29.246(4); 113.379(3)
9.8149(13); 90
2980.8(7); 4
1.421
14.729(3); 90
16.039(3); 90
25.214(5); 90
5956.2(20); 8
1.305
b, Å; β, °
c, Å; γ, °
3
V, Å , Z
–
3
D , g cm
c
F(000); µ(MoKα), m m –1
1332; 0.934
1.0–27.5
2456; 0.765
2.0–25.2
θ ran ge, °
hkl ran ge
–12/14, –37/36, –12/12
6840
–19/19, –20/0, –32/32
5964
No. of un ique diffraction s
No. of observed diffraction sa
No. of param eters
3463
3213
358
347
b
R, wR for observed diffraction s , %
4.84, 13.53
10.77, 16.40
0.0529
7.93, 14.70
21.82, 18.49
0.0824
b
R, wR for all data , %
Rin t
GOF for all datac
0.823
1.099
Residual electron den sity, e Å–3
0.816/–0.505
0.289/–0.564
a
Diffraction s with I > 2σ(I). R(F) = Σ||F | – |F ||/Σ|F |, wR(F ) = [Σ(w(F − F ) )/(Σw(F )) ]1/2.
b
2
2
o
2
c
2
2
o
2
o
c
o
c
2
2
2
1/2
GOF = [Σ(w(Fo − F ) )/(N
– Nparam s)]
diffrs
.
c
Collect. Czech. Chem. Commun. (Vol. 67) (2002)

1
656
Xie et al.:
of full-m atrix least-squares refin em en t was based on observed reflection s (I > 2.00σ(I)) an d
1
8
variable param eters. All calculation s were perform ed usin g SHELX97 software package
.
Abbreviated crystal data are sum m arized in Table IV. CCDC 183909 (for structure 1) an d
CCDC 183908 (for structure 2) con tain th e supplem en tary crystallograph ic data for th is pa-
per. Th ese data can be obtain ed free of ch arge via www.ccdc.cam .ac.uk/con ts/retrievin g.h tm l
(
or from th e Cam bridge Crystallograph ic Data Cen tre, 12, Un ion Road, Cam bridge, CB2 1EZ,
UK; fax: +44 1223 336033; or deposit@ccdc.cam .ac.uk).
This work was financially supported by the National Science Foundation of Anhui Province
(
No. 01045408).
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