Crystal Structures and Raman Spectra of cis-[SnCl4(H2O)2]·2H2O,
cis-[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O, and
[HL][SnCl5(H2O)]·2.5H2O (Lⴝ3-acetyl-5-benzyl-1-phenyl-4,5-dihydro1,2,4-triazine-6-one oxime, C18H18N4O2)
Abdel-Fattah Shihada1,*, Ahmad S. Abushamleh1, and Frank Weller2
1
2
Zarqa/Jordan, Department of Chemistry, Faculty of Sciences and Arts, Hashemite University
Marburg, Fachbereich Chemie der Philipps-Universität
Received January 6th, 2004.
Dedicated to Professor Werner Massa on the Occasion of his 60th Birthday
Abstract.
The
complexes
cis-[SnCl4(H2O)2]·2H2O
(1),
[Sn2Cl6(OH)2(H2O)2]·4H2O (3), and [HL][SnCl5(H2O)]·2.5H2O (4)
were isolated from a CH2Cl2 solution of equimolar amounts of
SnCl4 and the ligand L (L⫽3-acetyl-5-benzyl-1-phenyl-4,5-dihydro1,2,4-triazine-6-one oxime,C18H18N4O2) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a ⫽
2402.5(1) pm, b ⫽ 672.80(4) pm, c ⫽ 1162.93(6) pm, β ⫽
93.787(6)° and Z ⫽ 8. 4 was found to crystallize monoclinic in the
space group P21, with lattice parameters a ⫽ 967.38(5) pm, b ⫽
1101.03(6) pm, c ⫽ 1258.11(6) pm, β ⫽ 98.826(6)° and Z ⫽ 2. The
cell data for the reinvestigated structures are: [SnCl4(H2O)2]·3H2O
(2): a ⫽ 1227.0(2) pm, b ⫽ 994.8(1) pm, c ⫽ 864.0(1) pm, β ⫽
103.86(1)°, with space group C2/c and Z ⫽ 4; 3: a ⫽ 961.54(16) pm,
b ⫽ 646.29(7) pm, c ⫽ 1248.25(20) pm, β ⫽ 92.75(1)°, space group
P21/c and Z ⫽ 4.
Keywords: Tin; Crystal structure; Raman spectra; Aquapentachlorostannate; Diaquatetrachlorotin dihydrate
Kristallstrukturen und Ramanspektren von cis-[SnCl4(H2O)2]·2H2O, cis[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O und [HL][SnCl5(H2O)]·2.5H2O
(Lⴝ3-acetyl-5-benzyl-1-phenyl-4,5-dihydro-1,2,4-triazin-6-on oxim, C18H18N4O2)
Inhaltsübersicht. Die Komplexe cis-[SnCl4(H2O)2]·2H2O (1),
[Sn2Cl6(OH]2(H2O)2]·4H2O (3) und [HL][SnCl5(H2O)]·2.5H2O (4)
wurden aus einer Lösung äquimolarer Mengen von SnCl4 und dem
Liganden L (L⫽ 3-acetyl-5-benzyl-1-phenyl-4,5,dihydro-1,2,4-triazin-6-on oxim, C18H18N4O2) in CH2Cl2 in Gegenwart von Wasser
isoliert. (Kristallstrukturdaten s. Abstract).
1 Introduction
same complex with the solvates CHCl3 [5] or CH3CN·1/2
C6H14 [6] show the water molecules in cis positions within
the octahedral [SnCl4(H2O)2] units. Octahedra with trans
water molecules have been found in [SnCl4(H2O) 2]·15crown-5 at 120 K [7]. Hydrogen bonding in these complexes
links together crown ethers, uncoordinated water and
[SnCl4(H2O)2] octahedra. The crown ethers act as secondsphere ligands. Octahedral [SnCl4(H2O)2] units with cis
water molecules are also found in [SnX4(H2O)2]·2diox (X⫽
Cl, Br) [8] and [SnCl4(H2O)2]·C3H6(CO2Et)2 [9] according
to X-ray crystallographic studies.
One crystal of [Sn2Cl6(OH)2(H2O)2]·4H2O (3) was found
in a sample of SnCl4·5H2O (2). The similar
[Sn2Cl6(OH)2(H2O)2]·3diox has been obtained from a hot
dioxane solution of an aged commercial sample of
SnCl2·2H2O [3] and as the product of the attempted recrystallization of SnCl2.diox from dioxane [10].
The structure of the complex [Sn2Cl6(OH)2(H2O)2] consists of centrosymmetric dimeric molecules with the tin
atoms linked through two OH bridges leading to Sn2O2
four-membered rings. The tin atoms are hexa-coordinated
with fac-octahedral SnCl3(OH)2(H2O) units [3]. The com-
It has been suggested on the basis of Raman spectra that
the hydrates of tin(IV) chloride SnCl4·xH2O (x⫽2,3,4,5 and
8) have trans-[SnCl4(H2O)2] structural entities in the liquid
state [1]. Similar results are concluded from 35Cl nuclear
quadrupole resonance spectra (NQR) of SnCl4·2H2O and
SnCl4·3H2O in the solid state [2]. However, an X-ray diffraction
study
of
SnCl4·5H2O
shows
cis[SnCl4(H2O)2]·3H2O structure, in which the cis-octahedral
units are linked to a three-dimensional network through hydrogen bonds involving lattice water [3].
Several diaquatetrachlorotin(IV) complexes with crown
ethers have been isolated and characterized. Crystal structures of [SnCl4(H2O)2]·18-crown-6·2H2O [4] and of the
* Prof. Dr. Abdel-Fattah Shihada.
Department of Chemistry,
Faculty of Sciences and Arts, Hashemite University,
P.O.Box: 150459, Zarqa, 13115 Jordan.
Fax: 009625-3826613.
E-mail: [email protected]
Z. Anorg. Allg. Chem. 2004, 630, 841⫺847
DOI: 10.1002/zaac.200400007
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
841
A.-F. Shihada, A. S. Abushamleh, F. Weller
plexes
[Sn2Cl6(OH)2(thf)2]·2thf
[11,12]
and
[Sn2Cl4Br2(OH)2(thf)2]·2thf [13] show similar structures
with OH bridges and Sn2O2 four-membered rings.
The octrahedral [SnCl5(H2O)]⫺ anion has been identified
by X-ray diffraction studies in [PPh4][SnCl5(H2O)] [14],
[C6H13N2][SnCl5(H2O)]·H2O [15] (C6H13N2⫹ ⫽ 4,5-dihydro-3,5,5-trimethylpyrazolium), [H2L⬘]2[SnCl5(H2O)]2 ·
H2O · MeCN [16] (HL⬘ ⫽ 1,4,7,10,13-pentaoxa-16-azacyclooctadecane), [C5H5Mo(CO)(NO)(PPh3)(SnCl3)][SnCl5(H2O)] [17] and [Mo(CO)4{Ph2P(CH2)2PPh2}(SnCl3)][SnCl5(H2O)] [18].
We report here the crystal structures of SnCl4·4H2O (1),
[HL][SnCl5(H2O)]·2.5H2O (4), along with our structural investigations
of
SnCl4·5H2O
(2)
as
well
as
[Sn2Cl6(OH)2(H2O)2]·4H2O (3) in which more accurate results have been achieved. The Raman spectra of 1, 2, 3, and
4 in the solid state are given and discussed.
2 Results and Discussion
In an attempt to study the behavior of the ligand L (L⫽3acetyl-5-benzyl-1-phenyl-4,5-dihydro-1,2,4-triazine-6-one
oxime,C18H18N4O2) towards SnCl4, crystals of 1, 3, and 4
were isolated from a solution of equimolar amounts of both
reactants in not previously dehydrated CH2Cl2. It is well
established that the oxime ligand reacts with M(OAc)2 (M⫽
Ni,Pd) to form stable complexes in which the ligand behaves as bidentate chelating agent [19, 20].
Hydrates of tin(IV) chloride SnCl4·xH2O (x ⫽ 2,3,4,5
and 8) have been prepared by the reaction of SnCl4 with
water in the proper molar ratio [1, 2]. The hydrate SnCl4 ·
2H2O was accidentally isolated during recrystallization of
[Sn2Cl8{µ-C3H6(CO2Et)2}2]·2CH2Cl2 in dichloromethane
[9]. The tendency of SnCl4 to form the octahedral
[SnCl4(H2O)2] moiety in the presence of moisture [4⫺9] can
be taken as an indication for the considerable stability of
such entity.
Apparently presence of moisture in the reaction mixture
of SnCl4 with the ligand L afforded the hydrate 1 under the
applied conditions. The formation of [Sn2Cl6(OH)2(H2O)2]
· 4H2O (3) and [HL][SnCl5(H2O)]·2.5H2O (4) can be referred to the partial hydrolysis of [SnCl4(H2O)2]·2H2O (1),
which causes cleavage of a Sn-Cl bond and generates
H3O⫹Cl⫺. The resulting [SnCl3(OH)(H2O)]·2H2O dimerizes to give [Sn2Cl6(OH)2(H2O)2]·4H2O (3) whereas
H3O⫹Cl⫺ protonates the ligand L and forms
[HL][SnCl5(H2O)], crystallizing with2.5 water molecules (4)
in the presence of SnCl4, all pointed out by the following
reaction scheme:
[SnCl4(H2O)2]·2H2O (1) ⫹ 2H2O 씮 [SnCl3(OH)(H2O)]·2H2O
⫹ H3O⫹Cl⫺
2[SnCl3(OH)(H2O)]·2H2O 씮 [Sn2Cl6(OH)2(H2O)2]·4H2O (3)
SnCl4 ⫹ L ⫹ H3O⫹Cl⫺ 씮 [HL][SnCl5(H2O)] (4)
The related complex with a dihydropyrazolium cation
[C6H13N2][SnCl5(H2O)]·H2O [15] is generated by treatment
842
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
of [C6H13N2]2[SnCl6] with hexafluoroacetone trihydrate, a
reaction in which a Cl⫺ ion is replaced by an H2O molecule.
Furthermore, partial hydrolysis of SnCl3L⬘ during an attempted
recrystallization
in
acetonitrile,
gave
[H2L⬘]2[SnCl5(H2O)]2·H2O·MeCN [16]. The analogous
tin(IV)
complexes
[Sn2Cl6(OH)2(thf)2]·2thf
and
[MCl2(thf)4][SnCl5(thf)] (M⫽V or Cr) were formed by the
influence of moisture during recrystallization of
[SnCl4(thf)2] and by chloride transfer in the reactions of
[MCl3(thf)3] with [SnCl4(thf)2] in thf, respectively [12]. It is
worth noting that the Sn-O(thf) bond length in
[Sn2Cl6(OH)2(thf)2] [11,12] and [Sn2Cl4Br2(OH)2(thf)2] [13]
is longer than Sn-O(H2O) in [Sn2X6(OH)2(H2O)2](X⫽
Cl,Br) [3] indicating that water bonds to tin more strongly
than does thf [13].
Raman spectra
Table 1 lists the observed Raman frequencies of the complexes 1, 2, 3 and 4 with the relative intensities and assignments.
The Raman frequencies of cis-[SnCl4(H2O)2]·2H2O (1)
and cis-[SnCl4(H2O)2]·3H2O (2) in the solid state are assigned by comparison with Raman spectra ofSnCl4·xH2O
in the liquid state [1], with the vibrational spectra of complexes containing the cis-[SnCl4(H2O)2] moiety [4, 21, 22]
and with cis-[SnCl4L⬙2] complexes (L⬙ ⫽ OPCl2NHCH3
[23], Me2CO, C6H5NO, Me2SO [24]).
The Raman spectra of cis-[SnCl4(H2O)2]·3H2O (2) and
cis-[SnCl4(OPCl2NHCH3)2] [23] exhibit the four expected
frequencies due to ν(Sn-Cl) required by cis-[SnCl4O2] skeleton with C2v local symmetry (2A1, 1B1, 1B2), whereas that
of cis-[SnCl4(H2O)2]·2H2O (1) displays three of the four vibrations. The strongest and characteristic ν(Sn-Cl) band appears at 332, 329, 351, 318, cm⫺1 in the Raman spectrum
of 1, 2, 3, and 4, respectively. Apparently an increasing
number of oxygen atoms bonded to the tin atom causes a
shift of this characteristic mode to higher frequencies.
The bands at 450, 422 cm⫺1 in the Raman spectrum of 1
and at 449, 421 cm⫺1 in the Raman spectrum of 2 are assigned to ν(SnO) vibrations. These vibrations display at 443,
402 cm-1 in the Raman spectra of 3 and 4, respectively. The
region of 395 to 465 cm⫺1 is given for tin-oxygen frequencies in SnCl4 adducts with aldehydes [25].
The Raman spectrum of 3 shows a band at 482 cm⫺1
assigned to ν(Sn-O-Sn). Such vibrations appear in the range
480-530 cm⫺1 for dimeric tin compounds containing bridging oxygen atoms [13, 26].
Structural results
[SnCl4(H2O)2]·2H2O (1) crystallizes monoclinic in the space
group Cc. There are two SnCl4(H2O)2 octahedra with cispositioned water ligands in the asymmetric unit, which are
linked by two additional crystal water molecules each, forming infinite chains running roughly along space diagonal
[11̄1] and its c translated equivalent (see Fig. 1). At the
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 841⫺847
Crystal Structures and Raman Spectra of cis-[SnCl4(H2O)2]·2H2O
Table 1 Raman frequencies of 1, 2, 3, and 4 in the region of 500 to 100 cm⫺1
cis-[SnCl4(H2O)2]·2H2O (1)
cis-[SnCl4(H2O)2]·3H2O (2)
450 w
422 vw
449 w
421 vw
[Sn2Cl6(OH)2(H2O)2]·4H2O (3)
[HL][SnCl5(H2O)]·2.5H2O (4)
482 vw
443 vw
402 vw
355 vw
332 vs
308 w
284 w
274 w
395 vw
351 vw
329 vs
305 vw
163 m
350 vw
318 vs
321 m
310 m
289 vw
285 w
冧
δ(SnO2)
δ(SnClO)
254 w
冧
δ(SnClO)
δ(SnCl2)
274 m
219 w
199 vw
159 m
141 vw
113 m
冧
ν(Sn-O)
351 vs
247 vw
203 vw
191 vw
冧
ν(Sn-O-Sn)
206 w-m
191 vw
166 w
155 w
138 s
131 vs
118 m
167 s
156 w
131 s
115 s
ν(Sn-Cl)
Figure 1 Projection [31] of the unit cell of 1 along the b-axis, showing the numbering scheme. Hydrogen bonding is pointed out by ----(O···O) and ᎏᎏ (Cl···O).
point of their closest approach these chains are cross-linked
via hydrogen bond O(4)-H(41)···O(7) ⫺ another bridge
(O(2)-H(22)···O(6)) connects chains of neighbouring unit
cells in b direction, all resulting in a three-dimensional network. Direction of the chains and order of the units in them
is determined by the diagonal glide plane. The O···O distances (see table 2) indicate asymmetric hydrogen bonds
[27]. Actually most of the hydrogen atom positions can be
located in the difference Fourier synthesis (site of H(52) is
Z. Anorg. Allg. Chem. 2004, 630, 841⫺847
zaac.wiley-vch.de
calculated). Additional bridging within the three-dimensional network is exerted by weak Cl···H bonds
Cl(1)···H(61), Cl(8)···H(32), Cl(4)···H(11), and, in b axis direction Cl(3)···H(72) and Cl(7)···H(51) (see table 2).
The structure of [SnCl4(H2O)2]·3H2O (2) was correctly,
yet, as basing on film data, not with ultimate exactness determined by Barnes et al. [3]. It crystallizes monoclinic in
the space group C2/c. The diffractometer data allowed refinement to a degree where all hydrogen atom sites could
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
843
A.-F. Shihada, A. S. Abushamleh, F. Weller
Table 2 Bond lengths/pm and angles/° in 1 also showing O···O and
O···Cl hydrogen bonding.
Molecule 1
Molecule 2
Sn(1)-O(1)
Sn(1)-O(2)
Sn(1)-Cl(1)
Sn(1)-Cl(2)
Sn(1)-Cl(3)
Sn(1)-Cl(4)
214.8(3)
212.6(3)
237.68(12)
236.79(11)
239.12(10)
239.00(11)
Sn(2)-O(3)
Sn(2)-O(4)
Sn(2)-Cl(7)
Sn(2)-Cl(6)
Sn(2)-Cl(8)
Sn(2)-Cl(5)
213.2(3)
212.3(3)
238.10(10)
236.26(11)
238.47(10)
239.49(12)
O(1)···O(6)
O(6)···O(5)
O(5)···O(3)
O(2)···O(6)
265.5(5)
275.4(6)
259.4(5)
266.1(5)
O(4)···O(8)
O(8)···O(7)
O(7)···O(2)
O(7)···O(4)
265.3(5)
298.9(5)
269.0(5)
268.9(5)
Cl(1)···O(6)
Cl(4)···O(1)
324.9(4)
327.4(4)
Cl(3)···O(7)
Cl(7)···O(5)
Cl(8)···O(3)
324.7(4)
323.8(4)
324.9(4)
O(2)-Sn(1)-O(1)
O(2)-Sn(1)-Cl(2)
O(1)-Sn(1)-Cl(2)
O(2)-Sn(1)-Cl(1)
O(1)-Sn(1)-Cl(1)
Cl(2)-Sn(1)-Cl(1)
O(2)-Sn(1)-Cl(4)
O(1)-Sn(1)-Cl(4)
Cl(2)-Sn(1)-Cl(4)
Cl(1)-Sn(1)-Cl(4)
O(2)-Sn(1)-Cl(3)
O(1)-Sn(1)-Cl(3)
Cl(2)-Sn(1)-Cl(3)
Cl(1)-Sn(1)-Cl(3)
Cl(4)-Sn(1)-Cl(3)
81.46(12)
93.94(9)
175.40(9)
87.42(9)
85.84(10)
93.83(4)
169.32(9)
88.22(9)
96.38(5)
94.59(5)
82.72(9)
86.60(10)
93.00(4)
168.37(4)
93.99(4)
O(4)-Sn(2)-O(3)
O(4)-Sn(2)-Cl(6)
O(3)-Sn(2)-Cl(6)
O(4)-Sn(2)-Cl(8)
O(3)-Sn(2)-Cl(8)
Cl(6)-Sn(2)-Cl(8)
O(4)-Sn(2)-Cl(5)
O(3)-Sn(2)-Cl(5)
Cl(6)-Sn(2)-Cl(5)
Cl(8)-Sn(2)-Cl(5)
O(4)-Sn(2)-Cl(7)
O(3)-Sn(2)-Cl(7)
Cl(6)-Sn(2)-Cl(7)
Cl(7)-Sn(2)-Cl(8)
Cl(7)-Sn(2)-Cl(5)
85.44(14)
91.60(10)
176.94(11)
84.00(9)
85.58(9)
94.89(4)
172.76(10)
87.48(11)
95.50(4)
93.94(4)
86.39(9)
84.44(10)
94.62(4)
166.65(4)
94.45(4)
Figure 2 Unit cell of 2 as an a-axis projection [31]. Atom numbering
is given for an asymmetric unit.
Table 3 Bond lengths/pm and angles/° in 2. Comparison of selected
bonding parameters with the data of [3].
be taken from the difference Fourier synthesis. 16-membered rings consisting of lattice and complex water connect
the SnCl4(H2O)2 molecules to zigzag chains along the z
axis, which are linked to layers in the yz plane by weak
Cl···H bridges Cl(2)···H(3) (see Fig. 2). These layers are
joined by bifurcating bridges Cl(1)···H(22) and
Cl(2)···H(22) to form a three-dimensional polymer [3].
Table 3 shows a comparison of the most important bonding
parameters of 2.
A hydrolysis product ofthe SnCl4 hydrate is the dimeric
complex [Sn2Cl6(OH)2(H2O)2] (3) (see above). As outlined
in [3] it crystallizes monoclinic in space group P21/n with
dimeric units, generated by centres of symmetry and
stacked in the direction of the b axis. Again refinement of
diffractometer data allowed location of all hydrogen positions ⫺ so helical chains of water molecules consisting of
complex and crystal water can be shown flanking the stacks
(Fig. 3). The sequence in the water helix is ···H(21)-O(2)H(22)···O(4)···H(31)-O(3)···H(21)- with “lone” hydrogen
atoms at O3 and O4, which weakly bond to adjacent and
neighbouring dimers via chlorine ligands (Cl(2)···H(42),
Cl(1)···H(32)). An additional strong hydrogen bond occurs
between O(3) and H(1)-O(1) (see table 4 for bonding parameters of 3).
The organic ligand L, involved in the hydrolysis of the
hydrated SnCl4 molecules is readily protonated at nitrogen
atom N(2) forming an imonium cation, whereas the Cl⫺
ion, cleaved by hydrolysis, substitutes a water molecule in
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 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
Sn-O(1)
Sn-Cl(1)
Sn-Cl(2)
O(1)-Sn-O(1⬘)
O(1)-Sn-Cl(1)
O(1⬘)-Sn-Cl(1)
O(1)-Sn-Cl(2)
O(1)-Sn-Cl(2⬘)
Cl(1-Sn-Cl(1⬘)
Cl(2)-Sn-Cl(2⬘)
Cl(1)-Sn-Cl(2)
Cl(1)-Sn-Cl(2⬘)
O(1)···O(2)
O(1)···O(2)
O(2)···O(3)
Cl(1)···O(2)
Cl(2)···O(3)
Cl(1)···O(3)
2
[3]
211.49(17)
238.26(7)
238.24(6)
79.86(10)
87.05(5)
86.41(5)
90.87(5)
170.67(5)
171.47(3)
98.41(3)
92.02(2)
93.54(2)
270.7(2)
267.4(2)
274.0(3)
326.6(2)
338.4(3)
319.5(1)
209.8(14)
240.1(4)
238.3(5)
78.1(8)
86.5(3)
86.0(4)
91.9(4)
169.7(6)
170.4(4)
98.2(3)
92.3(3)
94.0(3)
275(2)
271(2)
278(2)
331(2)
322(2)
Equivalent atoms El’ are generated by the symmetry transformation ⫺x, y,
1
/2⫹z.
[SnCl4(H2O)2] to give the anion [SnCl5(H2O)]⫺. The ion
pair crystallizes with excess water as 4. In the crystals of
space group P21 the cations are linked to chains along the
21 axis by >N-H---O⫽C< bonds with O---N distance
277 pm. The atoms C(3), N(1), N(2), C(1), and N(3) of the
heterocyclic ring do not deviate much from their best plane
(maximum N(1) with 6.4 pm) ⫺ sp3 carbon atom C(2),
however, elevates 36.3 pm above this plane. Essential bonding parameters of the organic ligand may be taken from
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 841⫺847
Crystal Structures and Raman Spectra of cis-[SnCl4(H2O)2]·2H2O
Table 5 Comparison of the [Cl5Sn(H2O)]⫺ anion in 4 with related
salts.
4
[14]
[15]
Sn-O(3)
Sn-Cl(1)(trans)
Sn-Cl(2)
Sn-Cl(3)
Sn-Cl(4)
Sn-Cl(5)
219.7(4)
238.8(1)
237.6(1)
242.8(1)
240.7(1)
237.5(1)
224(1)
235.5(3)
216.5(4)
237.1(2)
238.6(2)
236.1(2)-243.6(1)
O(3)-Sn-Cl(1)
O(3)-Sn-Cl(2-5)
177.7(1)
84.2(1)-87.5(1)
180
85.56(6)
177.2(1)
83.6(1)-88.5(1)
冧
Figure 3 SCHAKAL [31] perspective view of a section of a stack
of dimers of 3. For clarity only one of the ClᎏO bonds is indicated.
Atoms of the asymmetric unit are numbered.
Table 4 Selected bond lengths/pm and angles/° for 3. Comparison
with the earlier determination [3] and with similar compounds.
3
[3]
[11]
[13]
Sn-O(1)
Sn-O(1⬘)
Sn-O(2)
Sn-Cl(1)
SnCl(2)
SnCl(3)
206.3(2)
208.1(2)
213.5(2)
238.65(7)
236.98(6)
234.26(6)
205.6(10)
208.6(11)
213.0(12)
236.3(6)
235.6(4)
237.1(4)
203.1(8)
210(1)
224.5(8)(thf)
235.6(5)
235.6(4)
234.3(4)
206.6(4)
208.6(5)
221.1(4)(thf)
O(1)-Sn-O(1⬘)
O(1)-Sn-O(2)
Cl(1)-Sn-Cl(2)
Cl(2)-Sn-Cl(3)
Cl(3)-Sn-Cl(1)
O(1)-Sn-Cl(2)
O(1⬘)-Sn-Cl((3)
O(2)-Sn-Cl(1)
71.81(8)
86.83(7)
95.12(2)
101.02(2)
94.77(3)
89.49(5)
96.66(5)
179.13(5)
71.7(5)
86.9(5)
95.6(2)
98.4(2)
93.5(2)
93.6(3)
95.3(3)
177.0(4)
O(1)···O(3)
O(3)···O(2)
O(2)···O(4)
O(3)···O(4)
Cl(1)···O(3)
Cl(2)···O(4)
273.0(3)
265.6(3)
271.1(3)
284.0(3)
331.9(2)
330.4(2)
277(2)
267(2)
267(2)
287(2)
334(2)
334(2)
table 5. Tied to the oxime groups of the chains via three
lattice water molecules the site of one of whichis occupied
only with 50 % probability are the anions (see Fig. 4). In
them the equatorial chlorine atoms are slightly bent
towards the complex water molecule due to its lower sterical
demand. A comparison of bond lengths and angles with
Z. Anorg. Allg. Chem. 2004, 630, 841⫺847
zaac.wiley-vch.de
Figure 4 Section of a chain of substituted heterocycles with flanking
[Cl5SnOH2]⫺ anions in perspective view [31]. Atom numbering is
given for the chain, the oxime ligand, and the anion.
Table 6 Selected bond lengths/pm and angles/° of the organic ligand in 4 and hydrogen bonding O···O and O···N distances.
N(1)-C(3)
N(1)-N(2)
C(2)-C(3)
C(2)-N(3)
N(3)-C(1)
N(2)-C(1)
N(1)-C11
C(3)-O(1)
C(1)-C(4)
N(4)-C(4)
N(4)-O(2)
134.7(5)
139.7(5)
151.9(6)
145.6(6)
131.7(5)
131.3(5)
142.6(4)
121.2(5)
147.5(6)
130.1(6)
138.2(6)
O(1)···N(2)
277.0(5)
O(3)···O(4)
O(2)···O(4)
O(2)···O(5)
O(4)···O(6)
N(4)···O(6)
295.5(7)
266.9(7)
288.0(9)
247.4(15)
280.0(13)
C(3)-N(1)-N(2)
C(1)-N(2)-N(1)
N(3)-C(1)-N(2)
C(1)-N(3)-C(2)
N(3)-C(2)-C(3)
N(1)-C(3)-C(2)
120.9(3)
121.8(3)
119.8(4)
122.2(4)
111.0(3)
117.2(4)
O(1)-C(3)-N(1)
O(1)-C(3)-C(2)
122.4(4)
120.4(4)
N(4)-C(4)-C(5)
C(5)-C(4)-C(1)
N(4)-C(4)-C(1)
C(4)-N(4)-O(2)
125.4(5)
121.4(5)
113.2(4)
112.1(4)
C(3)-N(1)-C(11)
N(2)-N(1)-C(11)
124.0(3)
115.0(3)
N(2)-C(1)-C(4)
N(3)-C(1)-C(4)
118.9(4)
121.3(4)
N(3)-C(2)-C(6)
C(3)-C(2)-C(6)
C(21)-C(6)-C(2)
111.2(4)
111.1(4)
112.3(3)
those in other compounds containing this anion is made in
table 6.
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
845
A.-F. Shihada, A. S. Abushamleh, F. Weller
Table 7 Crystal data, measurement and structure refinement details for 1, 2, 3, and 4.
1
Formula
Empirical formula
Formula weight
Crystal system
Space group
a / pm
b / pm
c / pm
β / deg
V / m3 x 10⫺30
Cell determination
ρcalc / Mg x m⫺3
Z
F(000)
µ ( MoKα ) / cm⫺1
Diffractometer type
Wavelength / pm
T/K
Scan mode
hkl range
Theta range for data coll.
Reflections collected
Independent reflections
Reflections used for refinement
Observed reflections
Absorption correction
Flack parameter
Programs used
Solution
Refinement
refined parameters
wR2 [all reflections]
R1 [I>2sigma(I)]
(shift/error)max
ρfin (max/min) / eÅ⫺1
2
3
4
[Cl4Sn(H2O)2] · 2 H2O
[Cl4Sn(H2O)2] · 3 H2O
[Cl3Sn(H2O)OH]2 · 4 H2O [LH][Cl5Sn(H2O)] · 2.5 H2O
H10Cl4O5Sn
H14Cl6O8Sn2
C18H26Cl5N4O5.5Sn
H8Cl4O4Sn
332.55
350.57
592.20
682.29
monoclinic
monoclinic
monoclinic
monoclinic
Cc
C2/c
P21/n
P21
2402.5(1)
1227.0(2)
961.5(2)
967.4(1)
672.8(1)
994.8(1)
646.3(1)
1101.0(1)
1162.9(1)
864.0(1)
1248.2(2)
1258.1(1)
93.787(6)
103.85(1)
92.75
98.826(6)
1875.7
1023.9(2)
774.8(2)
1324.2(1)
5000 reflections
2000 reflections
5000 reflections
5000 reflections
2.355
2.274
2.538
1.691
8
4
2
2
1264
672
560
674
38.2
35.12
42.74
15.05
IPDS I (Stoe)
IPDS II (Stoe)
IPDS I (Stoe)
IPDS II (Stoe)
71.073
71.073
71.073
71.073
203(2)
193(2)
193(2)
193(2)
phi-scans
omega-scans
phi-scans
omega-scans
⫺29ⱕhⱕ29, ⫺8ⱕkⱕ8, ⫺15ⱕhⱕ15, ⫺12ⱕkⱕ12,
⫺11ⱕhⱕ11, ⫺8ⱕkⱕ8,
⫺11ⱕhⱕ11, ⫺13ⱕkⱕ13,
⫺14ⱕlⱕ14
⫺10ⱕlⱕ10
⫺15ⱕlⱕ15
⫺15ⱕlⱕ15
3.14° to 25.87°
2.67° to 26.25°
2.61° to26.22°
2.13° to 25.92°
7363
7255
7299
11281
1035 [Rint ⫽ 0.0444]
1535 [R ⫽ 0.0591]
5111 [Rint ⫽ 0.0483]
3573 [Rint ⫽ 0.0281]
3573
1035
1535
5111
3513 [I > 2σ(I)]
1000 [I > 2σ(I)]
1409 [I > 2σ(I)]
4343 [I > 2σ(I)]
numerical
empirical, equivalent reflections numerical
Empirical, equivalent reflections
0.15(2)
⫺0.02(2)
SHELXS-97[29], SHELXL-97[29], PLATON[30], SCHAKAL[31], XCAD4[28]
Direct methods/difmap
full-matrix least squares on F2
208
68
102
298
0.0563
0.0497
0.0441
0.0659
0.0223
0.0190
0.0179
0.0309
⫺0.185
⫺0.001
0.010
0.001
0.391/⫺0.579
0.417/⫺0.517
0.623/⫺0.704
0.571/⫺0.619
3 Experimental
X-ray structural investigations
The anhydrous SnCl4 andSnCl4·5H2O were commercial products
and were used without further purification. The Raman spectra
were obtained using a Jobin Yvon Labram HR 800 instrument with
632.8 nm helium neon laser excitation.
Single crystals of 1, 3, and 4 were used as yielding from the reactions described above, whereas 2, being a commercial product (Riedel), was taken unchanged from the bottle. All crystals, the colourless blocks of 1, the cubelets of 2, the flat needles of 3, as well as
the yellow needles of 4 were handled in oil, mounted on glass
threads, and measured at ⫺70 °C (1) and ⫺80 °C (2, 3, and 4) on
Stoe diffractometers IPDS I (1, 3) and IPDS II (2, 4) (see table 7
for crystal and experimental details and for structure solution and
refinement). After data reduction [28] the data were corrected for
absorption basing on equivalent reflections (2, 4) and numerically
(1, 3). The structures were solved by direct methods [29] ⫺ refinement of the models was done by successive refinement cycles and
difference Fourier syntheses [29]. Except for 4, where water hydrogen atoms have been left out completely, they were found in the
difmaps and refined with equal O-H distances and isotropic thermal parameters. A search of the non-centrosymmetric structures of
1 and 4 for overlooked symmetry did not give any result [30]. In 4
the Flack parameter (see table 7) indicates correctness of the absolute structure, whereas in the refinement of the structure of 1 a
Flack parameter significantly deviating from zero hints presence of
the structure in two orientations related by inversion in a ratio of
(1-x)/x with x⫽Flack parameter [32].
Preparation of SnCl4 · 4H2O (1)
[Sn2Cl6(OH)2(H2O)2] · 4H2O (3) and
[HL][SnCl5(H2O)] · 2.5H2O (4)
A solution of an equimolar amounts (1 mmol) of SnCl4 and 3acetyl-5-benzyl-1-phenyl-4,5-dihydro-1,2,4-triazine-6-one oxime in
not previously dehydrated CH2Cl2 (50 mL) was set aside for several
days in a closed flask at ambient temperature. To allow partial
evaporation of the solvent the stopper was replaced with a drying
tube filled with silica gel. After few days, white crystals of
SnCl4·4H2O (1) separated on the flask walls, which were obtained
by decantation into another flask. These were dried and kept in a
closed tube. The flask with the mother liquor was equipped with
drying tube and set aside. After several days, crystals of
[Sn2Cl6(OH)2(H2O)2]·4H2O (3) were sublimed around the flask
neck and a crystalline mixture of [Sn2Cl6(OH)2(H2O)2]·4H2O (3)
and [HL][SnCl5(H2O)]·2.5H2O (4) was precipitated. The sublimate
and the crystalline mixture were isolated and preserved separately
in closed tubes.
846
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
Crystallographic data (excluding structure factors) have been deposited with the Fachinformationszentrum Karlsruhe, D-76344
Eggenstein-Leopoldshafen (Germany) under the depositary num-
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2004, 630, 841⫺847
Crystal Structures and Raman Spectra of cis-[SnCl4(H2O)2]·2H2O
bers CSD-413632 (1), -413631 (2), and -413630 (3), and with the
Cambridge Crystallographic Data Centre as supplementary publication nr. CCDC-228475 (4). Details are available from the FIZ,
quoting the depositary number, the names of the authors, and citation of the paper, and, free of charge, on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax: (⫹44) 1223/
336033; e-mail:[email protected]).
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 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
847