Synthesis, spectrothermal behaviour and molecular structure of aquaorotatotriethanolaminenickel(II) monohydrate

Article abstract of DOI:10.1002/zaac.200500297

The aquaorotatotriethanolaminenickel(II) monohydrate, [Ni(HOr)(H ₂O)(tea)]·H₂O (1), was synthesized and characterized by means of elementel analysis, IR and UV-Vis. spectroscopy, magnetic susceptibility, thermal analysis and X-ray diffraction techniques. The nickel ion in [Ni(C₅H₂N₂O₄)(H ₂O)(N(C₂H₄OH)₃)] is chelated to the deprotonated N3 pyrimidine atom and to the carboxylate oxygen atom of the bidentate orotate dianion, and to the one nitrogen and two oxygen atoms of the tridentate triethanolamine molecule and its octahedral geometry is completed by an aqua ligand. It crystallizes in the monoclinic system, space group P2 ₁/c with lattice parameters a = 7.1528(5) A, b = 19.4903(14) A, c = 11.8085(8) A, β = 106.237(5)°, V = 1580.55(19) A³, Z = 4. An extensive three dimensional network of O _W-H...O, N-H...O and O-H...O hydrogen bonds, π-π and π-ring interactions are responsible for crystal stabilization. The decomposition reaction take places in the temperature range 20-1000°C in the static air atmosphere. Thermal decomposition of 1 proceeds in three stages.

Full text of DOI:10.1002/zaac.200500297

Synthesis, Spectrothermal Behaviour and Molecular Structure of
Aquaorotatotriethanolaminenickel(II) Monohydrate
a,
a
˙
b
b
b
Okan Zafer Ye s¸ ilel * Halis Ölmez , Ibrahim U c¸ ar , Ahmet Bulut , and Canan Kazak
Kurupelit, Samsun / Turkey, Ondokuz Mayıs University, Faculty of Arts and Sciences, a Department of Chemistry and b Department of
Physics
th
Received June 20 , 2005.
˚ ˚
with lattice parameters a ϭ 7.1528(5) A, b ϭ 19.4903(14) A, c ϭ
Abstract. The aquaorotatotriethanolaminenickel(II) monohydrate,
Ni(HOr)(H O)(tea)]·H O (1), was synthesized and characterized
by means of elementel analysis, IR and UV-Vis. spectroscopy, ma-
gnetic susceptibility, thermal analysis and X-ray diffraction techni-
˚
˚
3
[
2
2
11.8085(8) A, β ϭ 106.237(5)°, V ϭ 1580.55(19) A , Z ϭ 4. An
extensive three dimensional network of O -H...O, N-H...O and O-
w
H...O hydrogen bonds, π-π and π-ring interactions are responsible
for crystal stabilization. The decomposition reaction take places
in the temperature range 20-1000 °C in the static air atmosphere.
Thermal decomposition of 1 proceeds in three stages.
5 2 2 4 2 2 4 3
ques. The nickel ion in [Ni(C H N O )(H O)(N(C H OH) )] is che-
lated to the deprotonated N3 pyrimidine atom and to the carboxy-
late oxygen atom of the bidentate orotate dianion, and to the one
nitrogen and two oxygen atoms of the tridentate triethanolamine
molecule and its octahedral geometry is completed by an aqua li-
Keywords: Nickel; Orotato ligand; TEA ligand; Crystal structure;
gand. It crystallizes in the monoclinic system, space group P2
1
/c
IR spectroscopy; UV/Vis spectroscopy
1
Introduction
we report the preparation and crystal structure of the title
complex, incorporating both orotate and TEA ligand. To
study further the complexing properties of orotic acid we
In the last years, research in bioinorganic chemistry has re-
vealed the important role of metal ions in most biological
processes. Orotic acid (H Or, vitamin B13, Fig. 1. a) and
its metal complexes are closely related to the biologically
important pyrimidine bases [1, 2]. For these reasons, metal
orotates have recently attracted growing attention in medi-
cine. Furthermore, nickel, magnesium, palladium, and
platinum orotate complexes have been screened as thera-
peuctic agents for cancer [3Ϫ6]. Orotic acid and its anions,
2Ϫ
have prepared the new mixed-ligand orotato (HOr ) com-
3
II
plex of Ni with triethanolamine ligand and undertaken
their X-ray structural analysis.
2 Results and Discussion
The molar conductance value of the title complex (Λ
ϭ
M
Ϫ1
2
Ϫ1
2
4 ohm cm mol ) indicated that [Ni(HOr)(H O)(TEA)]·
Ϫ
2Ϫ
3Ϫ
2
H Or , HOr and Or , besides being biologically im-
2
H O (1) is a non electrolyte and exhibits an experimental
2
portant, are also interesting potentially multidentate li-
gands, especially above the deprotonation pH values, coord-
inating to metal-ions through the nitrogen atoms, the two
carbonyl oxygen and the carboxylate oxygen atoms. Exist-
ing studies of its coordination complexes demonstrate that
it occurs as a dianion coordinating often via the N atom
and carboxylic acid group so forming a five membered che-
late ring [7Ϫ11].
The triethanolamine ligand (TEA, Fig. 1. b) has a num-
ber of potantial donor sites which are high in electronega-
tivity, and a diversity of coordination modes. Although,
TEA usually acts as a N,O,OЈ-tridentate ligand in transition
metal complexes [12Ϫ14], a N, O, OЈ, OЉ-tetradentate li-
gand behavior has also been observed, especially towards
metal ions having large ionic radii [15Ϫ17]. In this paper,
magnetic moment value of 2.57 BM corresponding to two
unpaired electrons.
2.1 Uv-vis Spectra
The d-d transition spectrum in H O of 1 is compatible with
2
a distorted octahedral configuration. The λmax values of 1
are 392, 540, 900 nm and the corresponding ε values are
Ϫ1
Ϫ1
2
8, 16, 14 Lmol cm , respectively. These values were as-
3
3
3
3
3
signed to ν : A Ǟ T (P); ν : A Ǟ T , and ν : A
3
2g
1g
2
2g
1g
1
2g
3
Ǟ T dϪd transitions. The Δ values of 1 were calculated
as 11,111 cm since Δ ϭ ν for d complexes [18].
2g
o
Ϫ1
8
o
1
*
Dr. Okan Zafer Ye s¸ ilel
Department of Chemistry,
Faculty of Arts and Sciences,
Ondokuz Mayıs University
TRϪ55139, Kurupelit, Samsun / Turkey
Fax.: ϩ90 362 4576081
EϪmail: yesilel@omu.edu.tr
Fig. 1 (a) Orotic acid, (b) triethanolamine
DOI: 10.1002/zaac.200500297 Z. Anorg. Allg. Chem. 2005, 631, 3100Ϫ3103
3100
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

Aquaorotatotriethanolaminenickel(II) Monohydrate
Fig. 3 Molecular structure of 1
Fig. 2 Thermal decomposition of 1
the corresponding spectrum obtained under the same cir-
cumstances as the pure oxide.
2.2 IR Spectra
The strong and broad absorption band at 3545 cmϪ1 is at-
2.4 Crystallography
tributed to the ν(OH) vibration of water molecule in the IR
Ϫ1
spectrum of 1 complex. The bands at 3330-3150 cm are
A view of the molecule and its atom-numbering scheme are
shown in Figure 3 and selected bond lengths and bond
angels are given in Table 1. The title compound has a dis-
torted octahedral coordination comprised of atom N2 and
a carboxylate O atom from bidentate oratato ligand, atom
N1 and two O atom from TEA ligand and a aqua O atom.
Atoms N2 and O4 are bonded to Ni1 to form a five-mem-
bered chelate ring [N2-Ni1ϭ 2.085(2) and O4-Ni1ϭ
attributed to the stretching bands of the coordinated and
free hydroxyl groups of triethanolamine. The distinct weak
Ϫ1
band centered at 2955 cm can be assigned to the CH
stretching of TEA ligand. The carbonyl groups appear as
Ϫ1
two main bands at 1700 cm [νCϭO (acid) ϩ νC(2)ϭO] and
Ϫ1
1660 cm
[νC(6)ϭOϩνCϭC] in the free H Or molecule
3
[
1
1
19]. The carbonyl stretching modes in 1 were observed at
Ϫ1
˚
665 and 1648 cm . The disappearance of the band at
2.0291(13) A] two TEA O atoms [O2-Ni1ϭ2.090(2) and
Ϫ1
˚
431 cm , which was observed in the free orotic acid, was
O3-Ni1ϭ2.0906(14) A] form the equatorial plane, and aqua
˚
attributed to the deprotonation and coordination of N(3)
to the nickel ion. In the title complex, the orotate ligand is
coordinated as bidentate to Ni atom through the carboxylic
O, and N(3) from the pyrimidine ring.
atom O1 [O1-Ni1ϭ2.085(2) A] and TEA N1 atom [N1-
˚
II
Ni1ϭ2.1389(18) A] are in the apical positions of the Ni
coordination octahedron. The equatorial plane is approxi-
˚
mately planar with r.m.s. deviation 0.0235 A and the largest
˚
deviation from the mean plane is 0.260(8) A for O4 atom.
All the N-Ni-N, N-Ni-O, and O-Ni-O bond angles deviate
significantly from 90° and 180° that is presumably as a re-
sult of the steric constraints arising from the shape of the
ligands. The angle subtended at the nickel atom by orotato
ligand is 80.08(6)°, which is in agreement with these pre-
viously reported for other orotato ligang contain nickel(II)
complexes [3, 10, 20].
2
.3 Thermal Analysis
Thermal decomposition of 1 proceeds in three stages
Fig. 2). The first stage is related to the dehydration of the
complex. The first peak, in the temperature range of 80-
35 °C, corresponds to the loss of one lattice water mol-
ecule and one coordinated water molecule (mass loss: exp.
.14 %; calcd. 9.05 %) by giving endothermic effect
(
1
In [Cu(HOr)(TEA)]·H O complex [17] the triethanolam-
2
9
II
ine acts as an N, O, OЈ, OЉ-tetradentate ligand (it forms
(
DTGmax: 116 °C). The anhydrous Ni complex is stable up
to 237 °C and starts to decompose with melting at 251 °C
DTA). The second stage of [Ni(HOr)(TEA)] is related to
˚
Table 1 Selected bond lengths /A and bond angles /°.
(
the decomposition of the neutral triethanolamine and orot-
ato ligands, in the temperature range of 237-384 °C. The
decomposition process is initially endothermic, an exother-
mic contribution is also observed on the DTA curve
Ni(1)-O(1)
Ni(1)-O(2)
Ni(1)-O(3)
Ni(1)-O(4)
O(4)-Ni(1)-N(2)
O(2)-Ni(1)-O(3)
N(2)-Ni(1)-N(1)
O(2)-Ni(1)-N(1)
O(4)-Ni(1)-O(1)
O(4)-Ni(1)-O(2)
O(1)-Ni(1)-O(2)
N(2)-Ni(1)-O(3)
2.085(2)
2.090(2)
2.091(1)
2.029(1)
80.08(6)
99.00(7)
101.04(6)
81.99(6)
90.76(6)
89.35(6)
82.70(7)
91.60(7)
Ni(1)-N(1)
Ni(1)-N(2)
2.139(2)
2.085(2)
O(1)-Ni(1)-O(3)
O(4)-Ni(1)-N(1)
O(1)-Ni(1)-N(1)
O(3)-Ni(1)-N(1)
N(2)-Ni(1)-O(1)
N(2)-Ni(1)-O(2)
O(4)-Ni(1)-O(3)
91.00(6)
97.08(5)
162.69(6)
83.48(6)
95.48(7)
169.26(6)
171.62(5)
(
DTGmax: 295 and 330 °C, respectively). In the third stage
the strong exothermic peak of the DTA curve (DTGmax
06 °C) is associated with the burning of the organic resi-
:
4
due. The overall weight loss (75.14 %, calc. 79.70 %) agrees
with the propose structure. The final decomposition prod-
uct, namely NiO, was identified by IR spectroscopy with
Z. Anorg. Allg. Chem. 2005, 631, 3100Ϫ3103
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
3101

˙
O. Z. Ye s¸ ilel, H. Ölmez, I. U c¸ ar, A. Bulut, C. Kazak
II
with Cu atom three five-membered chelate rings) while in
title complex the TEA acts as an N,O,OЈ-tridentate ligand.
II
This is apparently due to the different ionic radii of Cu
II
and Ni atoms. In the title compound, TEA ligand forms
with Ni ion two five-membered chelate rings [Ni1-O2-C1-
II
C2-N1 (A), Ni1-O3-C3-C4-N1(B)]. The dihedral angle be-
tween the A-B pair is 42.0(1)°.
The orotato ligand in the complex is essentially planar
˚
r.m.s. deviation is 0.0144 A), with a slight deviation from
(
planarity arising from the non-zero torsion angle between
the carboxylate group and the ring [N2-C8-C7-O4: 1.8(2)°].
This torsion angle indicated that distortion in orotato li-
II
gand caused by coordination to Ni metal ion is even
smaller than in uncoordinated orotic acid 5.9(4)° [21] and
5
.0(2) [22]. Of all the N-C bonds in the uracyclic ring of the
Fig. 4 Crystal packing and hydrogen bonds in 1
˚
orotato ligand, N2-C11 [1.349(2) A] and N2-C8
˚
[
1.360(2) A] are the shortest. This indicates a significantly
π-electron delocalization within the C9-C8-N2-C11 skel-
eton.
Ring A is oriented such that the perpendicular distance
i
˚
from A to A is 3.384 A, the closest interatomic distance
For the exocyclic atoms O6 and O7, the C10ϭO6
i
˚
being C8...C10 [3.391(13) A, symmetry code: (i) Ϫx, 1Ϫy,
˚
˚
[
[
1.247(2) A] bond distance is shorter than the C11-O7
˚
Ϫz]. The distance between the ring centroids is 3.754(3) A.
1.263(2) A] bond length. This situation is apparently due
Additionally, there is also π-ring interaction between the
atoms C5 and H14 of the tridentate TEA ligand and five
membered chelate ring (Ni-O4-C7-C8-N2, ring B). For the
C-H...Cg contact (Cg is the center of the chelate ring), the
distance between the chelate centroid and the nearest meth-
to the strong intra-molecular hydrogen bonding interaction
between atom H2 of the O3 atom and exocyclic atom O7
˚
[
Fig 4; O3...O7ϭ2.656(3) A].
The orotate anion seems to have a degree of elasticity
involving coordination to metal centers. In complex of
˚
ylene H atom is 2.571 A. The perpendicular distance be-
2
Ϫ
II
II
II
HOr with Ni [10, 20], Cu [23], Zn [7], the C8-N2-C11
angle is smaller [117.33(14)°, 118.9(11)°, 118.25(15),
˚
Table 2 Hydrogen-bonding geometry /A
1
17.9(2)°, and 118.1(4)°, respectively] than that found in or-
otic acid [122.8(3) [24], 123.07(14) [22]; 122.8(3) [21]]. This
shrinkage of the C8-N2-C11 angle is due to the metal coor-
dination at N2, which causes widening of the adjacent N2-
C11-N3 and N2-C8-C9 angles to 119.0(2) and 124.9(2)°,
respectively [115.15(14) and 120.8(2)°, respectively, in [22].
In the oratato molecule the carboxylate C-O distancs also
display some variability, depending on their environment.
D-H
d(D-H) d(H..A) <DHA d(D..A)
A
O8-H19 0.809
N3-H18 0.835
O3-H2 0.790
O2-H1 0.821
O9-H22 0.987
O1-H4 0.873
O1-H3 0.864
O9-H20 1.007
1.976
2.063
1.880
1.837
1.910
2.218
1.787
1.780
167.66 2.772
174.65 2.895
167.29 2.656
162.12 2.630
175.72 2.895
156.62 3.039
165.93 2.633
166.80 2.770
O4 [Ϫxϩ1, Ϫyϩ1, Ϫzϩ1]
O6 [Ϫx-1, Ϫyϩ1, Ϫz]
O7
O9
O7 [xϩ1, Ϫyϩ1/2, zϩ1/2]
O7 [xϩ1, y, z]
O6 [Ϫx, Ϫyϩ1, Ϫz]
O5 [Ϫxϩ1, yϪ1/2, Ϫzϩ1/2]
II
When unligated or when bound to Ni or Li [10, 20], two
C-O length are practically equal. However, in title complex
the C-O distances are significantly different each other [C7-
˚
II
O4 ϭ 1.271(2); C7-O5 ϭ 1.226(2) A]. Similarly, in the Co ,
II
II
2Ϫ
Table 3 Crystal data and structure refinement for 1
Cu [11] and Mg [8] complexes of HOr , the carboxylate
group is asymmetric [C-O; 1.278(2)-1.223(3), 1.27(4)-
Empirical formula
Formula weight
Crystal system
Space group
11 21 3 9
C H N O Ni
˚
1.240(4), and 1.262(2)-1.243(2) A, respectively].
398.03
monoclinic
P2 /c
Extensive hydrogen bonding, π-π, and π-ring interactions
1
give the structure of 1 three dimensional character. Two or-
atato molecules are joined by two N3-H18...O6 hydrogen
bonds (Fig. 4; Table 2), which leads to the formation of a
centrocymmetric dimer of 1 in the crystal unit cell. The hy-
droxyl H atoms of TEA ligand, aqua and water molecules
are also form intermolecular hydrogen bonding interac-
tions, through carboxylate O5 and exocyclic carbonyl atoms
O6 and O7 (see Table 3. for details). All the hydrogen atoms
of water molecule rotationally disordered, with a site-occu-
pancy factors of 0.86, 0.68, and 0.47, respectively. Intermo-
lecular π-π contact occurs between the two-symmetry re-
lated uracilate rings (ringA) of neighbouring molecules.
˚
Unit cell dimensions /A, °
a/A˚
7.1528(5)
19.4903(14)
11.8085(8)
106.237(5)
1580.55(19)
1.673
˚
b/A
˚
c/A
β/°
˚
3
Volume /A
Ϫ3
D /g.cm
c
Z
4
Reflections collected
Independent refls
Observ.ref [I > 2σ (I)]
Data/restr/params
Goodn.-of-fit on F
Final R indices [I > 2σ (I)]
12505
3127 [R(int) ϭ 0.0385]
2734
3127/8/253
1.044
R1ϭ0.0266, wR2ϭ0.0716
R1ϭ0.0310, wR2ϭ0.0732
2
Final R indices (all data)
3102
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 3100Ϫ3103

Aquaorotatotriethanolaminenickel(II) Monohydrate
tween the atom H14 and the center of the chelate ring is
˚
[3] M. Sabat, D. Zglinska, B. Jezowska-Trzebiatowska, Acta
Crystallogr. 1980, B36, 1187.
2
.554 A, and the C-H...Cg angle is 111°.
[
[
4] A. Karipides, B. Thomas, Acta Crystallogr. 1986, C42, 1705.
5] P. Castan, E. Colacio-Rodriguez, A. L. Beauchamp, S. Cros,
S. Wimmer, J. Inorg. Biochem. 1990, 38, 225.
3
Experimental Section
3
.1 Preparation of 1
[6] O. Kumberger, J. Riede, H. Schmidbaur, Z. Naturforsch. 1993,
8b, 961.
7] I. Mutikainen, Inorg. Chim. Acta 1987, 136, 155.
[8] I. Mutikainen, R. Hämäläinen, M. Klinga, O. Orama, U.
Turpeinen, Acta Crystallogr. 1996, C52, 2480.
4
A solution of triethanolamine (0.37 g, 2.5 mmol) in methanol
10 mL) was added drop wisely upon stirring to a solution of
Ni(HOr)(H O) ]·H O [20] (0.76 g, 2.5 mmol) in distilled water
30 mL). The solution was heated to 60 °C in a temperature-con-
[
(
[
(
2
4
2
trolled bath and stirring for 6 h at 60 °C. The reaction mixture was
then cooled to room temperature. The green crystals formed were
filtered and washed with 10 mL of cold distilled water and meth-
[9] O. Z. Ye s¸ ilel, F. Tezcan, H. Ölmez, H. Pa s¸ aog;ablu, O.
Büyükgüngör, Z. Anorg. Allg. Chem. 2005, 631, 2497.
[10] R. Wysoki n´ ski, B. Morzyk-Ociepa, T. Głowiak, D. Michalska,
J. Mol. Struc. 2002, 606, 241.
anol and dried in vacuo. Anal. Calc. for C11
21 3 9
H N O Ni: C, 33.20;
H, 5.32; N; 10.56. Found: C, 33.32; H, 5.48; N, 10.78 %.
[
11] H. ;.I c¸ budak, H. Ölmez, O. Z. Ye s¸ ilel, F. Arslan, P. Naumov,
G. Jovanovski, A. R. Ibrahim, A. Usman, H. K. Fun, S. Chan-
trapromma, S. W. Ng, J. Mol. Struc. 2003, 657, 255.
3.2 Materials and measurements
[
[
12] B. Sen, R. L. Dotson, J. Inorg. Nucl. Chem. 1970, 32, 2707.
13] H. I c¸ budak, V. T. Yilmaz, H. Ölmez, J. Thermal Anal. 1995,
All chemicals used were analytical reagent products. Elemental
analysis for C, H and N was carried out at the TÜBITAK Marm-
ara Research Centre. Magnetic susceptibility measurement at room
temperature was performed using a Sherwood Scientific MXI
model Gouy magnetic balance. The UV-vis. spectrum was obtained
44, 605.
[14] I. U c¸ ar, O. Z. Ye s¸ ilel, A. Bulut, H. I c¸ budak, H. Ölmez, C.
Kazak, Acta Crystallogr. 2004, E60, m322.
Ϫ3
for the aqueous solution of the complex (10 M) with a Unicam
[15] B. Chiswell, E. D. McKenzie, L. F. Lindoy, Comprehensive Co-
ordination Chemistry, Vol. 4, edited by G. Wilkinson, R. D. Gil-
lard and J. A. McCleverty, Oxford: Pergamon Press. 1997, pp.
1Ϫ122.
[16] I. U c¸ ar, O. Z. Ye s¸ ilel, A. Bulut, H. I c¸ budak, H. Ölmez, C.
Kazak, Acta Crystallogr. 2004, C60, m392.
UV2 spectrometer in the range 900-190 nm. The IR spectrum was
Ϫ1
recorded in the 4000Ϫ500 cm region with a Mattson 1000 FT-
IR spectrometer using KBr pellets. TG8110 thermal analyzer was
used to record simultaneous TG, DTG and DTA curves in static
Ϫ1
air atmosphere at a heating rate of 10 Kmin in the temperature
2 3
range 20-1000 °C using platinum crucibles. Highly sintered α-Al O
[
[
[
[
17] H. Ölmez, H. I c¸ budak, O. Z. Ye s¸ ilel, C. Arıcı, D. Ülkü, Z.
Ϫ1
was used as a reference and the DTG sensitivity was 0.05 mgs
.
Kristallogr. 2004, 219, 300.
18] D. Sutton, Electronic Spectra of Transition Metal Complexes,
McGraw-Hill, London, 1968, pp. 208.
19] G. Maistralis, A. Koutsodimou, N. Katsaros, Transition Met.
Chem. 2000, 25, 166.
20] I. U c¸ ar, A. Bulut, O. Z. Ye s¸ ilel, H. Ölmez, O. Büyükgüngör,
Acta Crystallogr. 2004, C60, m563.
Conductivity was measured by using a Crison conductimeter,
model 522.
3.3 Crystallographic analysis
Data collection were performed on a STOE IPDSII image plate
˚
detector using Mo K radiation (λ ϭ0.71019 A). Intensity data
α
were collected in the θ range 1.88-26.00° and 296 K. Details of
crystal structures are given in Table 3. Data collection: Stoe X-
AREA [25]. Cell refinement: Stoe X-AREA [25]. Data reduction:
Stoe X-RED [25]. The structure was solved by direct-methods
using SIR97 [26] and anisotropic displacement parameters were ap-
plied to non-hydrogen atoms in a full-matrix least-squares refine-
[21] L. R. Falvello, D. Ferrer, T. Soler, M. Tom a´ s, Acta Crystallogr.
2003, C59, m149.
[22] A. Bulut, H. I c¸ budak, O. Z. Ye s¸ ilel, H. Ölmez, O.
Büyükgüngör, Acta Crystallogr. 2003, E59, m736.
[23] I. Mutikainen, P. Lumme, Acta Crystallogr. 1980, B36, 2233.
[
[
[
24] F. Takusagawa, A. Shimada, Bull. Chem. Soc. Jpn. 1973, 46,
011.
25] Stoe & Cie. X-area (version 1.18) and X-red32 (version 1.04).
Stoe & Cie, Darmstadt, Germany, 2002.
26] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C.
Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori,
R. Spagna, J. Appl. Cryst. 1999, 32, 115.
2
ment based on F using SHELXL-97 [27]. All hydrogen atoms ex-
2
cept bounded to O5 (water) atom were positioned geometrically
and refined by a riding model with Uiso 1.2 times that of attached
atoms. Molecular drawings were obtained using ORTEP-III [28].
References
[
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