Hypercoordinated organotin(IV) halides containing 2-(Me2NCH 2)C6H4 groups: their solution behaviour and solid-state, hydrogen-bonding-based supramolecular architecture

Article abstract of DOI:10.1002/ejic.200501018

The hypercoordinated di- and triorganotin(IV) chlorides [{2-(Me ₂NCH₂)C₆H₄}₂SnCl ₂] (1a) and [{2-(Me₂NCH₂)C₆H ₄}-R₂SnCl] [R = Me (2a),

Full text of DOI:10.1002/ejic.200501018

FULL PAPER
DOI: 10.1002/ejic.200501018
Hypercoordinated Organotin(IV) Halides Containing 2-(Me2NCH2)C6H4
Groups: {2-(Me2NCH2)C6H4}2SnX2 (X = F, Cl, Br, I) and {2-(Me2NCH2)-
C6H4}R2SnX (R = Me, Ph; X = F, Cl, Br, I) and Their Solution Behaviour
and Solid-State, Hydrogen-Bonding-Based Supramolecular Architecture
Richard A. Varga,[a] Adina Rotar,[a] Markus Schürmann,[b] Klaus Jurkschat,[b] and
Cristian Silvestru*[a]
Keywords: Halides / Hydrogen bonding / Hypercoordination / Supramolecular chemistry / Tin
The hypercoordinated di- and triorganotin(IV) chlorides [{2-
(Me2NCH2)C6H4}2SnCl2] (1a) and [{2-(Me2NCH2)C6H4}-
R2SnCl] [R = Me (2a), Ph (3a)] were prepared by treating
SnCl4 or R2SnCl2 with [Li{2-(Me2NCH2)C6H4}]. Halide-ex-
change reactions between the organotin(IV) chlorides and
the appropriate potassium halides gave [{2-(Me2NCH2)-
C6H4}2SnX2] [X = F (1b), I (1d)], [{2-(Me2NCH2)C6H4}-
Me2SnX] [X = F (2b), Br (2c), I (2d)] and [{2-(Me2NCH2)-
C6H4}Ph2SnX] [X = F (3b), I (3d)]. Their solution behaviour
was investigated by multinuclear (1H, 13C, 19F and 119Sn)
NMR spectroscopy, including variable-temperature studies.
Single-crystal X-ray diffraction analyses revealed that the
strong intramolecular coordination of the nitrogen atom from
the pendant CH2NMe2 group to tin induces chirality. The in-
fluence of the identity and the number of the halogen atoms
and the organic substituents at tin is discussed in relation
with the hydrogen-bonding network, which results in dif-
ferent supramolecular architectures in the crystal.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
Introduction
available for the diorganotin() derivatives [{2-(Me2-
NCH2)C6H4}2SnX2], and no studies on the influence of the
identity and number of halogen atoms and organic substit-
uents on the association through hydrogen bonds in the so-
lid state have been reported. On the other hand, it has been
shown previously that intramolecular coordination of the
nitrogen atom to a metal atom in compounds containing a
[2-(Me2NCH2)C6H4]M moiety induces chirality at the me-
tal centre,[27–31] and therefore the crystals usually contain
1:1 mixtures of (R) and (S) isomers [with the C(1)–C(6)
aromatic ring and the N(1) atom as chiral plane and pilot
atom, respectively].[32] While this work was in progress the
molecular structures of the fluorides [{2-(Me2NCH2)-
C6H4}R2SnF] [R = Me (2bЈ), Ph (3bЈ)], which crystallise
in different space groups,[26] were reported, but no details
concerning the planar chirality induced by the intramolecu-
lar NǞSn interaction and the hydrogen-bond network in
the crystal were mentioned.
Several organotin() halides containing the [2-
(Me2NCH2)C6H4] group or related organic ligands have
been investigated so far both in solution and the solid state.
Single crystal X-ray diffraction studies have revealed, in all
cases, hypercoordinated structures obtained as a result of
strong intramolecular NǞSn interactions.[1–27] On the basis
of NMR spectroscopic data, octahedrally and trigonal bi-
pyramidally configured tin atoms were suggested in solu-
tion for the intramolecularly coordinated diorganotin diha-
lides [{2-(Me2NCH2)C6H4}2SnX2] and triorganotin halides
[{2-(Me2NCH2)C6H4}R2SnX] (X = halogen), respectively.
Single-crystal X-ray diffraction studies have confirmed the
hypercoordinated nature of [{2-(Me2NCH2)C6H4}-
Me2SnCl] (2a)[17] and [{2-(Me2NCH2)C6H4}Ph2SnX] [X =
Cl (3aЈ),[20] Br (3c)[3]), but no crystallographic data are
[a] Facultatea de Chimie si Inginerie Chimica, Universitatea Babes-
Bolyai,
Here we report the synthesis and spectroscopic charac-
terisation of some organotin() halides, as well as the crys-
tal and molecular structures of [{2-(Me2NCH2)-
C6H4}2SnX2] [X = Cl (1a), F (1b), I (1d)], [{2-(Me2NCH2)-
C6H4}Me2SnX] [X = Cl (2a), F (2b), Br (2c), I (2d)] and
[{2-(Me2NCH2)C6H4}Ph2SnX] [X = F (3b), I (3d)]. The dis-
cussion of the solid-state structure is focused on the hydro-
gen-bonding-based network between the isomers, which re-
sults in different supramolecular architectures in the crystal.
Str. Arany Janos Nr. 11, 400028 Cluj-Napoca, Romania,
Fax: +40-264-590-818
E-mail: cristi@chem.ubbcluj.ro
[b] Lehrstuhl für Anorganische Chemie II der Universität Dort-
mund,
44227 Dortmund, Germany,
Fax: +49-231-755-5048
E-mail: klaus.jurkschat@uni-dortmund.de
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Eur. J. Inorg. Chem. 2006, 1475–1486
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FULL PAPER
firmed for several compounds by simulation of the aromatic
region of the H NMR spectra using the gNMR program
Results and Discussion
1
The diorganotin() dihalides were prepared according to
Scheme 1. The ligand-redistribution reaction between [{2-
(Me2NCH2)C6H4}4Sn] and SnCl4 in the absence of a sol-
vent has proved to be an excellent alternative to the direct
synthesis from [Li{2-(Me2NCH2)C6H4}] and SnCl4 for the
preparation of 1a as it allows a better control of the stoichi-
ometry of the reagents. The halide-exchange reactions be-
tween the organotin() chlorides and the appropriate po-
tassium halides (Schemes 1 and 2) were performed accord-
ing to a modified literature procedure[33] in a two-layer sol-
vent system (H2O/MeOH/CH2Cl2).
(see Supporting Information).
The low-temperature 1H NMR spectra of the dior-
ganotin derivatives [{2-(Me2NCH2)C6H4}2SnX2] [X = Cl
(1a), F (1b) and I (1d)] are very similar (see Supporting
Information) to that reported for the dibromide analogue
1c,[6] i.e. an AB system and two singlet resonances in the
aliphatic region for the diastereotopic CH2 protons and the
CH3 groups at nitrogen, respectively. This is consistent with
a trans arrangement of the organic ligands and a cis ar-
rangement of the two coordinated nitrogen atoms and halo-
gen atoms in solution,[6] as subsequently proved by single-
crystal X-ray diffraction for compounds 1a, 1b and 1d (see
below). When the temperature is raised, the diorganotin di-
chloride 1a and the diorganotin diiodide 1d exhibit a sim-
ilar behaviour to the diorganotin dibromide 1c.[6,22] The two
singlets for the methyl protons of the NMe2 group coalesce
at 20 °C for 1a (∆G‡ = 13.8 kcalmol–1) and 0 °C for 1d (∆G‡
= 12.6 kcalmol–1) in CDCl3. This coalescence indicates that
the process involving NǞSn dissociation/recoordination,
with inversion at a three-coordinate nitrogen atom and ro-
tation of the Cmethylene–N bond, becomes fast on the NMR
timescale. The AB pattern for the methylene protons is re-
tained even at 60 °C, thus indicating configurational sta-
bility of the tin atom in the [{2-(Me2NCH2)C6H4}2SnX2]
derivatives containing heavier halogens. In contrast, co-
alescence of both the two resonances of the NMe2 group
(∆G‡ = 14.2 kcalmol–1) and the AB pattern of the CH2
group (∆G‡ = 14.3 kcalmol–1) is observed at 10 °C for the
diorganotin difluoride 1b in CDCl3. This suggests that ex-
change of the chloride by fluoride results in a considerable
decrease of the configurational stability of the tin atom in
1b compared to 1a. There is no indication for a cis–trans
equilibrium in solution such as that observed for
[{Me2N(CH2)3}2SnF2]·2H2O.[34]
Scheme 1. Synthesis of compounds 1a–1d.
Scheme 2. Synthesis of compounds 2a–2d, 3a, 3b and 3d.
The magnitudes of the 119Sn chemical shifts for the dior-
ganotin halides 1a (s, δ = –260.7 ppm), 1b (t, δ =
–386.7 ppm) and 1d (δ = –346.9 ppm) at room temperature
are typical for six-coordinate diorganotin() species in
solution [cf. [{Me2N(CH2)3}2SnF2]·2H2O[34] (δ = –292.0
ppm in CD2Cl2) and [(8-Me2NC10H6)2SnI2][11] (δ = –361.9
ppm in C6D5CD3)]. The equivalence of the fluoride atoms
in 1b is reflected in a singlet 19F resonance surrounded by
All compounds were isolated as air-stable, colourless,
crystalline products. They are soluble in common organic
solvents, such as chloroform, methylene dichloride or ben-
zene.
Solution Behaviour
All compounds were investigated by multinuclear (1H,
13C, 119Sn) NMR spectroscopy in solution at room tem-
perature. For the organotin fluorides, the 19F NMR spectra
were also recorded.
1
tin satellites (δ = –181.5 ppm, JF,Sn = 2567/2683 Hz) and a
1
triplet 119Sn resonance (δ = –386.7 ppm, JF,Sn = 2663 Hz).
1
The H and 13C NMR spectra for the triorganotin ha-
lides [{2-(Me2NCH2)C6H4}Me2SnX] [X = Cl (2a), F (2b),
Br (2c), I (2d)] and [{2-(Me2NCH2)C6H4}Ph2SnX] [X = F
(3b), I (3d)] are very similar to those of benzyldimethylam-
ine, regardless of the nature of the halogen and the other
organic groups attached to tin. Two singlet resonances are
observed in the aliphatic region for the methylene and the
methyl protons, respectively, which is compatible either with
a tetrahedral or with a pentacoordinate structure (assuming
The assignments of the 1H and 13C resonances according a fast conformational change of the five-membered SnC3N
to the numbering scheme above were based on 2D experi- nonplanar chelate ring in solution, which gives averaged 1H
ments and tin–carbon coupling constants, and were con- NMR signals). The 13C NMR spectrum contains two sing-
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Eur. J. Inorg. Chem. 2006, 1475–1486

Hypercoordinated Organotin() Halides Containing 2-(Me2NCH2)C6H4 Groups
Table 1. Comparison of the solution NMR spectroscopic data for triorganotin() compounds (δ in ppm, J in Hz).[a]
FULL PAPER
Compound
119Sn
19F
[{2-(Me2NCH2)C6H4}2SnF2] (1b)
–386.7 (t)[b]
(1JF,Sn = 2663)
–260.7 (s)[b]
–26.7 (s)
–181.5 (s)
(1JF,Sn = 2567/2683)
[{2-(Me2NCH2)C6H4}2SnCl2] (1a)
[Ph2SnCl2][35]
[{2-(Me2NCH2)C6H4}2SnI2] (1d)
–346.9 (s)
–241.1 (s)
[Ph2SnI2][35]
[{2-(Me2NCH2)C6H4}Me2SnF] (2b)[c]
–52.7 (d)
–178.4 (s)
(1JF,Sn = 2039.3)
–52.3 (t)
(1JF,Sn = 1944.2/2034.6)
–137.4 (s)
[Me2PhSnF][33]
(1JF,Sn = 1340)
–53.0 (t, br)[d]
(1JF,Sn = 1334)
–49.5 (t)[e]
(1JF,Sn = 1235)
–48.7 (s)[b]
48.3 (s)
(1JF,Sn = 1255)
–139.0 (s)[d]
(1JF,Sn = 1260)
[{2-(Me2NCH2)C6H4}Me2SnCl] (2a)
[Me2PhSnCl][36]
[{2-(Me2NCH2)C6H4}Me2SnBr] (2c)
[{2-(Me2NCH2)C6H4}Me2SnI] (2d)
[Me2PhSnI][37]
–55.5 (s)
–72.8 (s)
–17.9 (s)
–197.6 (d)
(1JF,Sn = 2157)
–211.9 (t)[e]
(1JF,Sn = 1530)
–176.9 (s)
[{2-(Me2NCH2)C6H4}Ph2SnF] (3b)[f]
–182.4 (s)
(1JF,Sn = 2058.3/2154.0)
[Ph3SnF][38]
[{2-(Me2NCH2)C6H4}Ph2SnCl] (3a)[20]
[Ph3SnCl][39]
–44.8 (s)
[{2-(Me2NCH2)C6H4}Ph2SnI] (3d)
–199.5 (s)
–113.4 (s)
[Ph3SnI][39]
[a] Spectra recorded in CDCl3 at room temperature. [b] In CH2Cl2/[D6]acetone. [c] Ref.[26]: δ
= –53.8 ppm (1JF,Sn = 2023 Hz), δ
119Sn
19F
=
–178.8 ppm. [d] In C6D5CD3. [e] 119Sn MAS NMR spectroscopic data. [f] Ref.[26]: δ Sn = –198.6 ppm (1JF,Sn = 2141 Hz), δ F = –182.3 ppm.
119
19
let signals for the methylene and the methyl carbon atoms, C6H4}R2SnX] compounds exhibit intramolecular NǞSn
respectively, but the tin satellites are well resolved only for coordination in solution, which results in similar coordina-
2
the former; the magnitude of the JC,Sn (ca. 28–30 Hz) tion geometries to those found in the solid state (see below).
couplings is consistent with the presence of an intramolecu-
lar NǞSn coordination, i.e. a trigonal bipyramidal (C,N)-
C2SnX core. The major difference noted in the H NMR
Solid-State Structures
1
spectra of the two series of compounds is the downfield
The crystal and molecular structures of 1a, 1b,
shift of the resonance for the aromatic H-6 proton, which 1b·CH2Cl2, 1d, 2a, 2aЈ, 2b–2d, 3a, 3b and 3d were deter-
is a result of the intramolecular interaction of this proton mined by single-crystal X-ray diffraction. Crystals suitable
with the halogen atom.
for X-ray diffraction analysis were generally grown by sol-
The increase in the H-6 chemical shift follows the order vent diffusion from dichloromethane and n-hexane. Crys-
F Ͻ Cl Ͻ Br Ͻ I (δ = 7.97, 8.17, 8.26 and 8.31 ppm for the tals of the dichloromethane solvate of the diorganotin di-
triaryltin halides 2b, 2a, 2c and 2d, respectively). In addition fluoride [{2-(Me2NCH2)C6H4}2SnF2], namely 1b·CH2Cl2,
to the resonances assigned to the 2-(Me2NCH2)C6H4 li- were obtained from a CH2Cl2/n-hexane (approximately 1:3)
gand, the 1H and 13C NMR spectra for the [{2-(Me2NCH2)- mixture, and were measured immediately after removal
C6H4}R2SnX] derivatives also contain signals correspond- from solution. The crystal was stable enough for a suffic-
ing to equivalent methyl and phenyl groups, respectively.
iently good measurement, but they turned opaque within
A comparison of the 19F and 119Sn NMR parameters for two days in the air due to loss of the crystallisation solvent,
the diorganotin dihalides [{2-(Me2NCH2)C6H4}2SnX2] and as proved by 1H NMR spectroscopy. Crystals of [{2-
the triorganotin halides [{2-(Me2NCH2)C6H4}R2SnX] de- (Me2NCH2)C6H4}2SnF2] (1b), free of crystallisation sol-
scribed in this work and the related [Ph2SnX2], [Me2PhSnX] vent, were also obtained by slow crystallisation from a
and [Ph3SnX] derivatives is given in Table 1. The increase CH2Cl2/n-hexane (approximately 1:5) mixture. The trior-
of the coordination number at the metal atom in solution ganotin chloride [{2-(Me2NCH2)C6H4}Me2SnCl] crystal-
to six and five, respectively, is supported by the upfield shift lises in different forms from ethanol (2a; orthorhombic,
of the 119Sn chemical shift in the 2-(Me2NCH2)C6H4-con- space group Pbca) and n-hexane (2aЈ; orthorhombic, space
taining derivatives (X = Cl, Br, I) with respect to the corre- group Pna21. This form has also been reported by
sponding monomeric, tetrahedral [Ph2SnX2], [Me2PhSnX] Rippstein et al.[17] for crystals grown from CHCl3). Mono-
and [Ph3SnX] compounds.
clinic crystals (space group P21/n) with different unit-cell
In conclusion, the NMR spectroscopic data indicate that parameters were obtained for [{2-(Me2NCH2)C6H4}-
both [{2-(Me2NCH2)C6H4}2SnX2] and [{2-(Me2NCH2)- Ph2SnCl] when the compound was crystallised from tolu-
Eur. J. Inorg. Chem. 2006, 1475–1486
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FULL PAPER
ene[20] or CH2Cl2/n-hexane (3a); the first form contains one sponding atoms, Σcov(Sn,N) = 2.1 Å[40]]. This results in dif-
molecule in the unit cell[20] while the second one contains ferent coordination environments of the metal atom, i.e. oc-
two independent molecules. The crystals of [{2-(Me2NCH2)- tahedral (C,N)2SnX2 for 1a, 1b and 1d, and trigonal bipy-
C6H4}Ph2SnF] (3b; monoclinic, space group P21/n, which ramidal (C,N)C2SnX configurations for 2a–2d, 3b and 3d.
is different from the reported space group P21/c[26]) also
The (C,N)2SnX2 core in the [{2-(Me2NCH2)-
contain two independent molecules in the unit cell.
C6H4}2SnX2] derivatives shows a trans-SnC2 fragment,
Selected molecular parameters are given in Tables 2, 3 while the N and X atoms are cis (Figure 1). This contrasts
and 4, and the molecular structures of representative com- with the molecular structure reported for the related
pounds 1b and 3d, with the atom numbering schemes, are [{Me2N(CH2)3}2SnF2]·2H2O,[34] which exhibits an all-trans
shown in Figures 1 and 2, respectively. The molecules of all octahedral (C,N)2SnX2 configuration. The difference in the
compounds investigated in this work feature a metal atom configuration of the octahedral environment of tin is re-
strongly coordinated by two or one nitrogen atoms of the flected in the lengthening and shortening of the Sn–F and
pendant arms trans to an Sn–halogen bond in diorganoti- Sn–N bond lengths, respectively, in 2b [Sn(1)–F(1) =
n() and triorganotin() halides, respectively [the Sn–N 1.9726(14), Sn(1)–F(2)
=
1.9774(13), Sn(1)–N(1)
=
distance exceeds the sum of the covalent radii for the corre- 2.5083(19) and Sn(1)–N(2) = 2.6064(18) Å] in comparison
Table 2. Selected bond lengths [Å] and angles [°] for [{2-(Me2NCH2)C6H4}2SnX2] compounds.
1a[a] (X = Cl)
1b (X = F)
1b·CH2Cl2 (X = F)
1d (X = I)
Sn(1)–C(1)
Sn(1)–C(10)
Sn(1)–X(1)
Sn(1)–X(2)
Sn(1)–N(1)
Sn(1)–N(2)
C(1)–Sn(1)–C(10)
X(1)–Sn(1)–N(1)
X(2)–Sn(1)–N(2)
C(1)–Sn(1)–N(1)
C(10)–Sn(1)–N(2)
N(1)–Sn(1)–N(2)
X(1)–Sn(1)–X(2)
2.1278(17)
2.119(2)
2.113(2)
2.109(6)
2.130(5)
1.988(3)
1.988(3)
2.601(5)
2.469(5)
154.8(2)
168.00(16)
166.83(16)
73.7(2)
2.142(6)
2.128(5)
2.8371(7)
2.8315(7)
2.572(5)
2.677(6)
156.3(2)
170.95(14)
170.62(12)
74.3(2)
2.4394(5)
1.9726(14)
1.9774(13)
2.5083(19)
2.6064(18)
154.86(8)
166.79(6)
167.53(6)
74.99(7)
2.6199(16)
152.22(9)
166.25(4)
73.77(6)
73.54(7)
103.86(6)
89.87(7)
75.26(19)
105.40(17)
88.30(18)
73.1(2)
102.39(18)
89.55(2)
108.54(7)
89.79(3)
[a] C(10) = C(1a), X(2) = X(1a), N(2) = N(1a); symmetry equivalent positions (–x, y, –z + 1/2) are indicated by an “a”.
Table 3. Selected bond lengths [Å] and angles [°] for [{2-(Me2NCH2)C6H4}Me2SnX] compounds.
2a[a] (X = Cl)
2aЈ[b] (X = Cl)
2b (X = F)
2c (X = Br)
2d (X = I)
Sn(1)–C(1)
Sn(1)–C(10)
Sn(1)–C(11)
Sn(1)–X(1)
2.129(3)
2.124(4)
2.115(4)
2.5250(16)
2.485(3)
168.11(7)
74.17(11)
123.73(14)
116.94(15)
117.71(16)
2.127(4)
2.144(5)
2.121(4)
2.5371(9)
2.488(3)
170.79(8)
75.55(13)
119.92(16)
116.13(18)
122.55(19)
2.123(3)
2.118(3)
2.120(3)
2.0187(17)
2.509(2)
167.45(9)
74.08(11)
118.91(13)
123.55(13)
115.75(15)
2.132(3)
2.110(4)
2.106(4)
2.6839(5)
2.445(3)
168.62(7)
74.76(12)
124.67(16)
116.02(17)
118.17(19)
2.135(4)
2.120(4)
2.133(5)
2.9367(5)
2.442(4)
170.45(9)
75.99(15)
129.5(2)
111.66(18)
117.2(2)
Sn(1)–N(1)
X(1)–Sn(1)–N(1)
C(1)–Sn(1)–N(1)
C(1)–Sn(1)–C(10)
C(1)–Sn(1)–C(11)
C(10)–Sn(1)–C(11)
[a] Crystals from ethanol. [b] Crystals from n-hexane.
Table 4. Selected bond lengths [Å] and angles [°] for [{2-(Me2NCH2)C6H4}Ph2SnX] compounds.
3a[a,b] (X = Cl)
3b[b] (X = F)
3d (X = I)
Sn(1)–C(1)
Sn(1)–C(10)
2.118(4)
2.130(4)
2.134(4)
2.126(4)
2.105(5)
2.121(4)
2.128(5)
2.132(5)
2.135(5)
2.132(5)
Sn(1)–C(16)
Sn(1)–X(1)
Sn(1)–N(1)
2.134(4)
2.4944(11)
2.538(4)
2.132(4)
2.4872(12)
2.509(3)
2.129(4)
2.008(3)
2.560(4)
2.132(4)
2.006(4)
2.521(4)
2.135(4)
2.8631(6)
2.496(4)
X(1)–Sn(1)–N(1)
C(1)–Sn(1)–N(1)
C(1)–Sn(1)–C(10)
C(1)–Sn(1)–C(16)
C(10)–Sn(1)–C(16)
169.73(10)
75.46(15)
116.85(16)
124.23(15)
116.28(16)
168.68(8)
74.86(14)
113.58(15)
126.56(16)
117.42(17)
167.53(14)
74.74(17)
117.34(18)
122.80(17)
117.61(18)
168.34(14)
74.88(18)
126.98(19)
112.10(17)
118.45(18)
171.56(10)
75.36(18)
114.09(19)
122.55(17)
121.29(19)
[a] Crystals from CH2Cl2/n-hexane. [b] Two independent molecules are present in the unit cell.
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Eur. J. Inorg. Chem. 2006, 1475–1486

Hypercoordinated Organotin() Halides Containing 2-(Me2NCH2)C6H4 Groups
FULL PAPER
crystals of the diorganotin() derivatives contain either
(SN1,RN2) and (RN1,SN2) isomers (for 1b) or (SN1,SN2) and
(RN1,RN2) isomers (for 1a and 1d) with respect to the two
chelate rings in a molecular unit. The discrete monomeric
molecular units are separated by normal van der Waals dis-
tances between heavy atoms.
However, a closer check of the crystal structures revealed
several intermolecular hydrogen-bonding interactions
shorter than the sum of the corresponding van der Waals
radii [i.e. ΣvdW(F,H) Ϸ 2.55, ΣvdW(Cl,H) Ϸ 3.0, ΣvdW(Br,H)
Ϸ 3.15 and ΣvdW(I,H) Ϸ 3.35 Å].[40] This results in different
supramolecular architectures that are presented in the sub-
sequent discussion taking into account the increasing de-
gree of association, with the common patterns summarised
in Table 5 (further details are available in the Supporting
Information). Thus, in the crystal of the fluoride 3b (space
group P21/n) pairs of isomers (S,S or R,R) of the two inde-
pendent molecules are associated through F(1)···H(34)aryl
contacts (2.50 Å). The short interatomic distance (2.56 Å)
between the F(2) atom and a methyl hydrogen of a neigh-
bouring dinuclear unit of the same type is at the limit of a
van der Waals contact. The crystal of 3bЈ (space group
P21/c[26]) contains polymeric chains of (S) and (R) isomers,
respectively, built through F(1)···H(17Ba)methylene interac-
tions (2.37 Å). Similar polymeric chains of (S) and (R) iso-
mers, respectively, were also found in the crystals of the
triorganotin chlorides 3a, 3aЈ[20] and the triorganotin iodide
3d. In contrast to the phenyl derivatives, the crystals of the
methyl analogues 2a (space group Pbca) and 2b contains
chains of alternating (S) and (R) isomers. There are no fur-
ther halogen–hydrogen contacts between the parallel poly-
meric chains.
Figure 1. ORTEP representation at 50% probability and atom-
numbering scheme for the isomer (RN1,SN2)-1b.
For compound 1b·CH2Cl2, alternating (RN1,SN2)- and
Figure 2. ORTEP representation at 30% probability and atom-
numbering scheme for the isomer (S)-3d. Hydrogens have been (SN1,RN2)-1b isomers are connected through F(2)···H-
omitted for clarity.
(7Ab)methylene interactions (2.52 Å) and further bridged by
CH2Cl2 molecules [F(1)···H(19A)solvent = 2.37, Cl(2a)···H-
with [{Me2N(CH2)3}2SnF2]·2H2O [Sn(1)–F(1) = 2.084(6) (8A)methyl = 2.94 Å], resulting in ribbon-like chains (Fig-
and Sn(1)–N(1) = 2.366(8) Å].[34]
ure 3), with no further inter-chain halogen–hydrogen con-
The molecular structures of the triorganotin halides [{2- tacts.
(Me2NCH2)C6H4}R2SnX] (2a–2d, 3b and 3d) are very sim-
Polymeric chains of (S) and (R) isomers, respectively,
ilar. One representative is shown in Figure 2. The tin–nitro- built through I(1)···H(7Ba)methylene interactions (3.16 Å),
gen distances are not dramatically affected by the identity are also found in the crystal of the triorganotin iodide 2d,
of the halogen atom trans to the nitrogen atom. The Sn(1) but in this case additional I(1)···H(10Ac)Sn–methyl contacts
atom is displaced from the equatorial plane defined by C(1), (3.29 Å) between chains of the same isomers result in a 2D
C(10) and C(16) (Figure 2) in the direction of the X(1) supramolecular architecture. The crystal consists of layers
atom, which means that the X–Sn–C angles are larger than alternating in the sequence -R-R-S-S-R-R-S-S-, with no
the N–Sn–C angles.
further inter-layer contacts. The triorganotin chloride 2aЈ
As a result of the intramolecular coordination of the ni- (space group Pna21) and the triorganotin bromide 2c also
trogen to the tin atom a five-membered SnC3N ring is form polymeric chains, but in this case they are built from
formed. This ring is not planar but is folded along the alternating (S) and (R) isomers [Cl(1)···H(8Bb)N–methyl
Sn(1)···Cmethylene axis, with the nitrogen atom lying above 2.81 Å for 2aЈ; Br(1)···H(9Bb)N–methyl = 3.02 Å for 2c]. For
the best plane defined by Sn(1), C(1), C(2) and C(methy- 2aЈ, weak inter-chain contacts [Cl(1)···H(8Cc)N–methyl
=
=
lene). This induces planar chirality at the metal atom,[27–31] 2.98 Å] result in a 2D network with a honeycomb motif
and all compounds reported here crystallise as racemates. (Figure 4, a) in which each molecule is linked to four neigh-
The crystals of the triorganotin() derivatives (2a, 2aЈ, 2b– bouring molecules (two isomers of a different type for the
2d, 3a, 3aЈ, 3b, 3bЈ and 3d) contain 1:1 mixtures of (R) and polymeric chain and two isomers of the same type for the
(S) isomers, with the C(1)–C(6) aromatic ring and the N(1) parallel chains). For 2c, the weak inter-chain contacts be-
atom as chiral plane and pilot atom, respectively.[32] The tween the halogen and an aromatic hydrogen atom [Br(1)···
Eur. J. Inorg. Chem. 2006, 1475–1486
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FULL PAPER
Table 5. Structural patterns of the hydrogen-bonding-based supramolecular architectures in the crystals of [{2-(Me2NCH2)C6H4}2SnX2]
and [{2-(Me2NCH2)C6H4}R2SnX].
Compound
[R = 2-(Me2NCH2)C6H4] patterns
Supramolecular architecture
X···H [Å]
1D architectures
[RPh2SnF] (3b)
dinuclear associations between isomers of the same intermolecular
type of two independent molecules;
F(1)–H(34)aryl
2.50
no further intermolecular contacts
chains of (S) and (R) isomers
no inter-chain contacts
chains of (S) and (R) isomers
(with alternating independent molecules 1 and 2);
no inter-chain contacts
chains of (S) and (R) isomers
no inter-chain contacts
chains of (S) and (R) isomers
no inter-chain contacts
chains of alternating (S) and (R) isomers;
no inter-chain contacts
chains of alternating (S) and (R) isomers;
no inter-chain contacts
ribbon-like chains of alternating
(RN1,SN2)- and (SN1,RN2) isomers,
connected through CH2Cl2 molecules;
no inter-chain contacts
[RPh2SnF] (3bЈ)[26]
[RPh2SnCl] (3a)
intra-chain
F(1)–H(17Ba)methylene 2.37
intra-chain
intra-chain
Cl(1)–H(34b)aryl
Cl(2a)–H(9A)methyl
2.88
2.92
[RPh2SnCl] (3aЈ)[20]
[RPh2SnI] (3d)
intra-chain
intra-chain
intra-chain
Cl(1)–H(20a)aryl
I(1)–H(19a)aryl
2.89
3.11
[RMe2SnCl] (2a)
[RMe2SnF] (2b)
Cl(1)–H(9Cb)N–methyl 2.95
intra-chain
intra-chain
intra-chain
intra-chain
intra-chain
F(1)–H(10Bb)Sn–methyl 2.47
F(1)–H(9Ab)N–methyl
F(2)–H(7Ab)methylene
F(1)–H(19A)solvent
Cl(2a)–H(8A)methyl
2.52
2.52
2.37
2.94
[R2SnF2]·CH2Cl2
(1b·CH2Cl2)
2D Architectures
[RMe2SnI] (2d)
chains of (S) and (R) isomers
contacts between parallel chains, resulting in a layer inter-chain
intra-chain
I(1)–H(7Ba)methylene
I(1)–H(10Ac)Sn–methyl 3.29
3.16
network;
no inter-layer contacts
chains of (RN1,SN2) and (SN1,RN2
isomers
[R2SnF2] (1b)
)
intra-chain
inter-chain
F(2)–H(12a)aryl
F(1)–H(7Ad)methylene
2.38
2.47
contacts between parallel chains, resulting in a layer
network;
no inter-layer contacts
chain of alternating (S) and (R) isomers;
contacts between parallel chains, resulting in a layer inter-chain
network;
no inter-layer contacts
chain of alternating (S) and (R) isomers;
contacts between parallel chains, resulting in a layer inter-chain
[RMe2SnCl] (2aЈ)
[RMe2SnBr] (2c)
intra-chain
Cl(1)–H(8Bb)N–methyl
Cl(1)–H(8Cc)N–methyl
2.81
2.98
intra-chain
Br(1)–H(9Bb)N–methyl 3.02
Br(1)–H(4d)aryl
3.15
network;
no inter-layer contacts
3D architectures
[R2SnCl2] (1a)
alternating layers of (SN1,SN2) and
(RN1,RN2) isomers, respectively;
inter-layer contacts leading to a 3D
supramolecular architecture
chain of alternating (SN1,SN2) and
(RN1,RN2) isomers;
intra-layer
inter-layer
Cl(1)–H(4aЈ)aryl
Cl(1)–H(6fЈ)aryl
2.81
2.94
[R2SnI2] (1d)
intra-chain
inter-chain
I(2)–H(9Ca)methyl
I(2)–H(8Ac)methyl
I(1)–H(14f)aryl
3.15
3.26
3.32
contacts between parallel chains, resulting in a layer inter-layer
network;
inter-layer contacts leading to a 3D supramolecular
architecture
H(4d)aryl = 3.15 Å, at the limit of a van der Waals contact] mers [F(2)–H(12a)aryl = 2.38 Å] are connected through
lead to a different two-dimensional motif, with rings built F(1)–H(7Ad)methylene (2.47 Å) interactions. The overall layer
from two molecules [(R)- and (S)-2c isomers] and four network resembles that observed in the crystal of the trior-
molecules [(R)-(R)-(S)-(S)-2c isomers], respectively (Fig- ganotin iodide 2d, with both fluorine atoms being involved
ure 4, b). In both cases there are no further contacts be- in weak hydrogen-bonding interactions.
tween the parallel layers.
Three-dimensional
supramolecular
architectures
In contrast to 1b·CH2Cl2, the crystal structure of the di- (Table 5) were found for the diorganotin dihalides 1a and
organotin difluoride 1b consists of layers in which alternat- 1d. Thus, in the crystal of the diorganotin diiodide 1d there
ing polymeric chains of (RN1,SN2)- and (SN1,RN2)-1b iso- are parallel chains built from alternating (SN1,SN2) and
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Hypercoordinated Organotin() Halides Containing 2-(Me2NCH2)C6H4 Groups
FULL PAPER
Figure 3. Polymeric associations in the crystal of compound
1b·CH2Cl2 based on halogen–hydrogen contacts (only hydrogens
involved in such contacts are shown) [symmetry-equivalent atoms
(x, 2 – y, 0.5 + z) and (x, 2 – y, –0.5 + z) are labelled as “a” and
“b”].
Figure 5. View of supramolecular architectures based on hydrogen
bonding (only hydrogen atoms involved in intermolecular interac-
tions are shown): (a) the layer network of (SN1,SN2) and (RN1,RN2
)
isomers in the crystal of 1d [symmetry equivalent atoms (–0.5 + x,
1.5 – y, 0.5 + z), (0.5 + x, 1.5 – y, –0.5 + z), (0.5 – x, –0.5 + y, 1.5 –
z) and (0.5 – x, 0.5 + y, 1.5 – z) are labelled as “a”, “b”, “c” and
“d”, respectively]; (b) the layer network of (SN1,SN2) isomers in the
crystal of 1a [symmetry equivalent atoms (0.5 + x, 0.5 + y, z), (0.5
+ x, –0.5 + y, z), (–0.5 + x, –0.5 + y, z) and (–0.5 + x, 0.5 + y, z)
are labelled as “a”, “b”, “c” and “d”, respectively]; (c) 3D supramo-
lecular structure in the crystal of 1a [symmetry equivalent atoms
(–x, 1 – y, 1 – z) and (0.5 – x, 0.5 – y, –z) are labelled as “e” and
“f”, respectively].
Figure 4. View of the layer network based on intermolecular hydro-
gen bonding (only hydrogens involved in intermolecular interac-
tions are shown) in the crystals of (a) 2aЈ [symmetry-equivalent
atoms (1.5 – x, 0.5 + y, 0.5 + z), (1.5 – x, –0.5 + y, –0.5 + z), (1.5 –
x, –0.5 + y, 0.5 + z) and (1.5 – x, 0.5 + y, –0.5 + z) are labelled
“a”, “b”, “c” and “d”, respectively] and (b) 2c [symmetry-equiva-
lent atoms (–0.5 + x, y, 0.5 – z), (0.5 + x, y, 0.5 – z), (0.5 – x, –y,
0.5 + z) and (0.5 – x, –y, –0.5 + z) are labelled “a”, “b”, “c” and
“d”, respectively].
Eur. J. Inorg. Chem. 2006, 1475–1486
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R. A. Varga, A. Rotar, M. Schürmann, K. Jurkschat, C. Silvestru
FULL PAPER
was removed in vacuo. The solid residue was recrystallised from
CH2Cl2/n-hexane to give 6.1 g (81%) of the title compound as
colourless crystals.
(RN1,RN2) isomers through I···Hmethyl contacts [I(2)–H-
(9Ca)methyl
= 3.15 Å]. Inter-chain contacts [I(2)···H-
(8Ac)methyl = 3.26 Å] result in a similar layer network to
that observed for 2aЈ (Figure 5, a). Additional weak, inter-
layer contacts between I(1) and an aromatic proton [I(1)···
H(14f)aryl = 3.32 Å] lead to a 3D network. By contrast, in
the crystal of the diorganotin dichloride 1a only aromatic
protons are involved in hydrogen bonding. The molecules
are associated into layers built of the same type of isomer
[Cl(1)···H(4aЈ)aryl = 2.81 Å] (Figure 5, b) and alternating
parallel layers of (SN1,SN2) or (RN1,RN2) isomers are
bridged through weak Cl(1)···H(6fЈ)aryl (2.94 Å) interac-
tions (Figure 5, c).
Procedure 2: SnCl4 (0.437 g, 1.68 mmol) was added to [{2-
(Me2NCH2)C6H4}4Sn] (1.1 g, 1.68 mmol) under inert atmosphere
and the mixture was slowly heated whilst stirring until a homogen-
eous melt was obtained. The heating was maintained for 15 min
and then the reaction mixture was cooled to room temperature.
Recrystallisation from a CH2Cl2/n-hexane mixture (approximately
1:4) provided 1.2 g (78%) of 1a as colourless crystals (m.p. 257–
259 °C). 1H NMR (CDCl3, 300 MHz, 20 °C): δ = 2.22 (br. s, 12 H,
NCH3), AB spin system with δA = 3.37 and δB = 4.07 (2JH,H
=
14.1 Hz, 4 H, CH2N), 7.18 (m, 2 H, 3-H), 7.41 (m, 4 H, 4,5-H),
3
8.22 (m, JH,Sn = 108 Hz, 2 H, 6-H) ppm. 1H NMR (CDCl3,
300 MHz, 60 °C): δ = 2.21 (br. s, 12 H, NCH3), AB spin system
3
with δA = 3.38 and δB = 4.04 (br. s, 4 H, CH2N), 7.17 (d, JH,H
=
6.9 Hz, 2 H, 3-H), 7.52 (m, 4 H, 4,5-H), 8.25 (d, 3JH,H = 6.3, 3JH,Sn
= 108 Hz, 2 H, 6-H) ppm. H NMR (300 MHz, CDCl3, –60 °C): δ
Conclusion
1
3
3
= 2.05 (s, JH,Sn = 39 Hz, 6 H, NCH3), 2.55 (s, JH,Sn = 39 Hz, 6
The hypercoordinated di- and triorganotin() halides
H, NCH3), AB spin system with δA = 3.39 and δB = 4.14 (2JH,H
=
[{2-(Me2NCH2)C6H4}2SnX2],
[{2-(Me2NCH2)C6H4}-
14.2, 3JH,Sn = 39 Hz, 4 H, CH2N), 7.19 (d, JH,H = 6.6 Hz, 2 H, 3-
3
Me2SnX] and [{2-(Me2NCH2)C6H4}Ph2SnX] (X = F, Cl,
Br, I) have been prepared and their solutions investigated
by multinuclear NMR spectroscopy, including variable-
temperature studies. Single-crystal X-ray structure analyses
have revealed that the strong intramolecular coordination
of the nitrogen atom from the pendant CH2NMe2 group to
tin induces planar chirality and the compounds crystallise
as racemates. The influence of the identity and number of
halogen atoms and organic substituents attached to the tin
atoms is reflected in different supramolecular architectures
based on hydrogen-bonding networks.
3
3
H), 7.41 (m, 4 H, 4,5-H), 8.19 (d, JH,H = 6.8, JH,Sn = 110 Hz, 2
H, 6-H) ppm. 13C NMR (CDCl3, 100.6 MHz, 20 °C): δ = 46.78
2
3
(br. s, NCH3), 63.80 (s, JC,Sn = 42.8 Hz, CH2N), 127.85 (s, JC,Sn
= 97.1/99.3 Hz, C-3), 128.18 (s, JC,Sn = 104.8/107.6 Hz, C-5),
130.16 (s, JC,Sn = 19.1 Hz, C-4), 135.47 (s, JC,Sn = 61.3 Hz, C-6),
140.79 (s, JC,Sn = 62.8 Hz, C-2; JC,Sn = 1167.1/1221.3 Hz, C-1)
ppm. 119Sn NMR (CH2Cl2/[D6]acetone, 149.2 MHz, 20 °C): δ = –
260.7 ppm (s). C18H24Cl2N2Sn (458.00): calcd. C 47.21, H 5.28, N
6.12; found C 47.34, H 5.43, N 5.84.
3
4
2
2
1
Synthesis of [{2-(Me2NCH2)C6H4}2SnF2] (1b): Dichloromethane
was added to a suspension of 1a (0.3 g, 0.65 mmol) in MeOH
(20 mL) until the solid compound dissolved. An aqueous solution
of KF (0.2 g, 3.44 mmol) was then added and the mixture was
stirred for 3 h at room temperature. The organic layer was sepa-
rated and the water solution was washed twice with 5 mL of
CH2Cl2. The combined organic layers were dried with anhydrous
Na2SO4. The latter was filtered, the solvent was removed in vacuo
and the obtained white solid residue was recrystallised from a
CH2Cl2/n-hexane mixture to give 1b (0.25 g, 90%; m.p. 213–
215 °C). Colourless crystals suitable for single-crystal X-ray diffrac-
tion were obtained by slow crystallisation from a CH2Cl2/n-hexane
Experimental Section
General Remarks: All manipulations were carried out under argon
1
using dried solvents freshly distilled prior to use. The H and 13C
NMR spectra were recorded with Bruker Avance DRX 400 (includ-
ing 2D experiments), Bruker Avance 300 and Bruker DPX 200 in-
struments. The 19F NMR were recorded with Bruker Avance DRX
400 and Bruker DPX 300, and 119Sn NMR were obtained using
Bruker DPX 400 and Varian Unity 300 instruments. Variable-tem-
perature 1H NMR studies were performed with a Varian Unity 300
(compound 1a) and a Varian Gemini 300S (compound 1b). The
chemical shifts are reported in ppm relative to the residual peak of
solvent (CHCl3; δ1H = 7.26, δ13C = 77.0 ppm for 1H and 13C, CFCl3
for 19F and neat SnMe4 for 119Sn). Starting materials such as SnCl4,
BuSnCl3, Ph2SnCl2, Me2SnCl2 KX (X = F, Br, I), N,N-dimethylbe-
nzylamine and n-butyllithium were commercially available. The
1
(approximately 1:5) mixture. H NMR (CDCl3, 400 MHz, 20 °C):
δ = 2.24 (br. s, 12 H, NCH3), 3.66 (br. s, 4 H, CH2N), 7.16 (m, 2
3
H, 3-H), 7.38 (m, 4 H, 4,5-H), 8.08 (m, JH,Sn = 92.2 Hz, 2 H, 6-
H) ppm. 1H NMR (CDCl3, 300 MHz, 55 °C): δ = 2.24 (s, 12 H,
NCH3), 3.66 (s, 4 H, CH2N), 7.17 (m, 2 H, 3-H), 7.39 (m, 4 H, 4,5-
3
1
H), 8.09 (m, JH,Sn = 91.5 Hz, 2 H, 6-H) ppm. H NMR (CDCl3,
300 MHz, –55 °C): δ = 2.10 (s, 6 H, NCH3), 2.42 (s, 6 H, NCH3),
AB spin system with δA = 3.53 and δB = 3.82 (2JH,H = 14.3 Hz, 4
H, CH2N), 7.17 (m, 2 H, 3-H), 7.38 (m, 4 H, 4,5-H), 8.05 (m, 3JH,Sn
= 93.3 Hz, 2 H, 6-H) ppm. 13C NMR (CDCl3, 100.6 MHz, 20 °C):
compounds
[Li{2-(Me2NCH2)C6H4}],[41]
[{2-(Me2NCH2)
C6H4}4Sn][17] and [{2-(Me2NCH2)C6H4}Ph2SnCl] (3a)[20] were pre-
2
pared according to the literature methods.
δ = 46.09 (br. s, NCH3), 64.10 (s, JC,Sn = 48.4 Hz, CH2N), 127.31
3
3
(s, JC,Sn = 96.7 Hz, C-3), 127.93 (s, JC,Sn = 99.3 Hz, C-5), 129.97
Synthesis of [{2-(Me2NCH2)C6H4}2SnCl2] (1a). Procedure 1: A sus-
pension of [Li{2-(Me2NCH2)C6H4}] [prepared as above from
nBuLi in n-hexane (24.6 mL, 1.6 , 20% excess) and
Me2NCH2C6H5 (4.43 g, 32.8 mmol) in 200 mL of anhydrous n-hex-
ane] in anhydrous toluene (150 mL) was added dropwise, whilst
stirring, to a cooled (–78 °C) solution of SnCl4 (4.27 g, 16.4 mmol)
in 300 mL of toluene (300 mL). After all the suspension had been
added, the reaction mixture was stirred for 1 h at –78 °C, and then
allowed to reach room temperature overnight. The reaction mixture
was filtered under inert atmosphere and the solvent of the filtrate
4
2
(s, JC,Sn = 17.6 Hz, C-4), 136.30 (s, JC,Sn = 49.5 Hz, C-6), 139.23
(t, 3JC,F = 22.5 Hz, C-1), 141.04 (s, 2JC,Sn = 66.7 Hz, C-2) ppm. 19
F
=
1
NMR (CDCl3, 282.38 MHz, 20 °C): δ = –181.5 ppm (s, JF,Sn
2567/2683 Hz). 119Sn NMR (CH2Cl2/[D6]acetone, 149.2 MHz,
1
20 °C): δ = –386.7 ppm (t, JF,Sn = 2663 Hz). C18H24F2N2Sn
(425.09): calcd. C 50.86, H 5.69, N 6.59; found C 50.58, H 5.33, N
6.37.
Synthesis of [{2-(Me2NCH2)C6H4}2SnI2] (1d): A saturated aqueous
solution of NH4I (20 mL) was added to a solution of 1a (0.79 g,
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Hypercoordinated Organotin() Halides Containing 2-(Me2NCH2)C6H4 Groups
1.73 mmol) in CH2Cl2 (20 mL)/EtOH (4 mL) and the reaction mix-
FULL PAPER
4
2
64.6 Hz, C-5), 129.24 (s, JC,Sn = 12.8 Hz, C-4), 137.19 (s, JC,Sn
=
=
3
2
ture was stirred for 10 h at room temperature. The organic layer 38.2 Hz, C-6), 141.32 (d, JC,F = 21.7 Hz, C-1), 142.04 (s, JC,Sn
was separated and the water solution was washed twice with 5 mL
of CH2Cl2. The organic solution was separated and dried with an-
hydrous Na2SO4. The latter was filtered, the solvent was removed
in vacuo and the solid residue was recrystallised from a CH2Cl2/n-
hexane mixture to give 1d as colourless crystals (0.66 g, 60%; m.p.
238 °C). 1H NMR (CDCl3, 300 MHz, 20 °C): δ = 2.23 (br. s, 12 H,
39.4 Hz, C-2) ppm. 19F NMR (CDCl3, 376.5 MHz, 20 °C): δ =
–178.4 ppm (s, JF,Sn = 1944.2/2034.6 Hz). 119Sn NMR (CDCl3,
1
1
111.9 MHz, 20 °C): δ = –52.7 ppm (d, JF,Sn = 2039.3 Hz).
C11H18FNSn (301.96): calcd. C 43.75, H 6.01, N 4.64; found C
43.41, H 5.79, N 4.41.
Synthesis of [{2-(Me2NCH2)C6H4}Me2SnBr] (2c): An aqueous
solution of KBr (0.93 g, 7.85 mmol) was added to a solution of 2a
(0.5 g, 1.57 mmol) in CH2Cl2 (30 mL) and the reaction mixture was
stirred for 3 h at room temperature. The organic layer was sepa-
rated and the water solution was washed twice with 10 mL of
CH2Cl2. The organic solution was dried with anhydrous Na2SO4.
The solvent was removed in vacuo and the obtained pale brown-
red residue was recrystallised from a CH2Cl2/n-hexane mixture to
give 2c (0.52 g, 91%) [m.p. 136–138 °C (dec); ref.[2] white solid, 136–
137 °C]. Colourless crystals suitable for single-crystal X-ray diffrac-
NCH3), AB spin system with δA = 3.19 and δB = 4.22 (2JH,H
=
12.7 Hz, 4 H, CH2N), 7.13 (d, 3JH,H = 6.9 Hz, 2 H, 3-H), 7.37 (dd,
3JH,H = 7.4 Hz, 2 H, 4-H), 7.47 (dd, JH,H = 7.5 Hz, 2 H, 5-H),
8.19 (d, JH,H = 7.2, JH,Sn = 111.9 Hz, 2 H, 6-H) ppm. H NMR
(CDCl3, 300 MHz, 50 °C): δ = 2.21 (s, JH,Sn = 39.1 Hz, 12 H,
3
3
3
1
3
NCH3), AB spin system with δA = 3.24 and δB = 4.16 (br. s, 4 H,
3
3
CH2N), 7.12 (d, JH,H = 7.3 Hz, 2 H, 3-H), 7.37 (dd, JH,H
=
3
7.4 Hz, 2 H, 4-H), 7.47 (dd, JH,H = 7.5 Hz, 2 H, 5-H), 8.21 (d,
3JH,H = 7.3, JH,Sn = 111.9 Hz, 2 H, 6-H) ppm. 1H NMR
3
3
(300 MHz, CDCl3, –50 °C): δ = 1.96 (s, JH,Sn = 39.2 Hz, 6 H,
tion were obtained from a CH2Cl2/n-hexane (approximately 1:4)
3
NCH3), 2.63 (s, JH,Sn = 38.8 Hz, 6 H, NCH3), AB spin system
solution. 1H NMR (CDCl3, 200 MHz, 20 °C): δ = 0.87 (s, JH,Sn
=
2
with δA = 3.17 and δB = 4.30 (2JH,H = 14.2 Hz, 4 H, CH2N), 7.13
63.5/66.4 Hz, 6 H, SnCH3), 2.32 (s, 6 H, NCH3), 3.64 (s, 2 H,
(d, JH,H = 7.2 Hz, 2 H, 3-H), 7.37 (dd, 3JH,H = 7.4 Hz, 2 H, 4-H),
3
3
CH2N), 7.12 (m, 1 H, 3-H), 7.35 (m, 2 H, 4,5-H), 8.26 (m, JH,Sn
3
3
3
7.46 (dd, JH,H = 7.4 Hz, 2 H, 5-H), 8.15 (d, JH,H = 7.4, JH,Sn
=
= 68.5 Hz, 1 H, 6-H) ppm. 13C NMR (CDCl3, 50.3 MHz, 20 °C):
115.3 Hz, 2 H, 6-H) ppm. 13C NMR (CDCl3, 100.6 MHz, 20 °C):
1
δ = 1.02 (s, JC,Sn = 483.1/505.1 Hz, SnCH3), 45.22 (s, NCH3),
2
δ = 46.90 (br. s, NCH3), 62.80 (s, JC,Sn = 35.6 Hz, CH2N), 128.02
2
3
64.74 (s, JC,Sn = 28.1 Hz, CH2N), 126.46 (s, JC,Sn = 58.9 Hz, C-
(s, 3JC,Sn = 104.1 Hz, C-5), 128.22 (s, 3JC,Sn = 90.8 Hz, C-3), 130.29
3), 127.89 (s, 3JC,Sn = 67.6 Hz, C-5), 129.39 (s, C-4), 138.22 (s, 2JC,Sn
4
2
(s, JC,Sn = 18.2 Hz, C-4), 135.73 (s, JC,Sn = 67.1 Hz, C-6), 138.17
(s, C-1), 140.51 (s, C-2) ppm. 119Sn NMR (CDCl3, 111.9 MHz,
20 °C): δ = –346.9 ppm (s). C18H24I2N2Sn (640.90): calcd. C 33.73,
H 3.77, N 4.37; found C 33.42, H 3.53, N 4.12.
2
= 44.7 Hz, C-6), 139.54 (s, C-1), 141.58 (s, JC,Sn = 37 Hz, C-2).
119Sn NMR (CDCl3, 149.2 MHz, 20 °C): δ = –55.5 ppm (s).
C11H18BrNSn (362.86): calcd. C 36.41, H 5.00, N 3.86; found C
36.11, H 5.21, N 3.67.
Synthesis of [{2-(Me2NCH2)C6H4}Me2SnCl] (2a): A suspension of
[Li{2-(Me2NCH2)C6H4}] [prepared as above from nBuLi in n-hex-
ane (17.6 mL, 1.6 , 20% excess) and Me2NCH2C6H5 (3.18 g,
23.5 mmol) in 50 mL of anhydrous n-hexane] in anhydrous toluene
(50 mL) was added dropwise, whilst stirring, to a cooled (–78 °C)
solution of Me2SnCl2 (5.17 g, 23.5 mmol) in 150 mL of toluene
(300 mL). After all the suspension had been added the reaction
mixture was stirred for 1 h at –78 °C, and then allowed to reach
room temperature overnight. The reaction mixture was filtered un-
der inert atmosphere and the solvent was removed in vacuo. The
white solid residue was recrystallised from CH2Cl2/n-hexane to give
2a (5.2 g, 69%) as colourless crystals (m.p. 119–121 °C; ref.[12] 120–
Synthesis of [{2-(Me2NCH2)C6H4}Me2SnI] (2d): Same procedure as
for 1b, using 2a (0.2 g, 0.63 mmol) and KI (0.52 g, 3.14 mmol).
Recrystallisation from a CH2Cl2/n-hexane (approximately 1:3) mix-
ture gave 2d (0.21 g, 82%) as pale-yellow crystals (m.p. 105–
1
2
107 °C). H NMR (CDCl3, 300 MHz, 20 °C): δ = 1.05 (s, JH,Sn
=
63.2/65.0 Hz, 6 H, SnCH3), 2.34 (s, 6 H, NCH3), 3.65 (s, 2 H,
3
CH2N), 7.11 (d, JH,H = 7.0 Hz, 1 H, 3-H), 7.35 (m, 2 H, 4,5-H),
3
3
8.30 (d, JH,H = 6.6, JH,Sn = 71.2 Hz, 1 H, 6-H) ppm. 13C NMR
1
(CDCl3, 75.5 MHz, 20 °C): δ = 3.18 (s, JC,Sn = 470.1/492.0 Hz,
SnCH3), 45.42 (s, NCH3), 64.84 (s, 2JC,Sn = 26.9 Hz, CH2N), 126.54
3
3
(s, JC,Sn = 58.9 Hz, C-3), 128.03 (s, JC,Sn = 69.4 Hz, C-5), 129.58
(s, JC,Sn = 13.7 Hz, C-4), 138.26 (s, JC,Sn = 664.0/694.8 Hz, C-1),
139.62 (s, JC,Sn = 46.2 Hz, C-6), 141.40 (s, JC,Sn = 35.8 Hz, C-2)
ppm. 119Sn NMR (CDCl3, 111.9 MHz, 20 °C): δ = –72.8 ppm (s).
C11H18INSn (409.87): calcd. C 32.24, H 4.43, N 3.42; found C
32.11, H 4.25, N 3.33.
3
1
1
2
123 °C). H NMR (CDCl3, 200 MHz, 20 °C): δ = 0.73 (s, JH,Sn
=
2
2
64.1/67.0 Hz, 6 H, SnCH3), 2.29 (s, 6 H, NCH3), 3.62 (s, 2 H,
3
CH2N), 7.12 (m, 1 H, 3-H), 7.32 (m, 2 H, 4,5-H), 8.17 (m, JH,Sn
= 67.2 Hz, 1 H, 6-H) ppm. 13C NMR (CDCl3, 50.3 MHz, 20 °C):
1
δ = –0.28 (s, JC,Sn = 492.4/515.4 Hz, SnCH3), 45.15 (s, NCH3),
2
3
64.78 (s, JC,Sn = 28.8 Hz, CH2N), 126.46 (s, JC,Sn = 59.1 Hz, C-
3), 127.88 (s, 3JC,Sn = 67.2 Hz, C-5), 129.32 (s, 4JC,Sn = 13.2 Hz, C-
4), 137.60 (s, 2JC,Sn = 42.9 Hz, C-6), 140.28 (s, C-1), 141.78 (s, 2JC,Sn
Synthesis of [{2-(Me2NCH2)C6H4}Ph2SnF] (3b): Same procedure as
for 1b, using 3a (0.25 g, 0.56 mmol) and KF (0.164 g, 2.82 mmol).
Recrystallisation from a CH2Cl2/n-hexane (approximately 1:3) mix-
ture gave 3b (0.21 g, 87%) as colourless crystals (m.p. 161–163 °C).
1H NMR (CDCl3, 400 MHz, 20 °C): δ = 1.97 (s, 6 H, NCH3), 3.56
=
38.6 Hz, C-2) ppm. 119Sn NMR (CH2Cl2/[D6]acetone,
149.2 MHz, 20 °C): δ = –48.7 ppm (s). C11H18ClNSn (318.41):
calcd. C 41.49, H 5.70, N 4.40; found C 41.23, H 5.61, N 4.53.
3
(s, 2 H, CH2N), 7.20 (d, JH,H = 7.2 Hz, 1 H, 3-H), 7.44 (m, 8 H,
3
Synthesis of [{2-(Me2NCH2)C6H4}Me2SnF] (2b): Same procedure
4,5-H + C6H5-meta,para), 7.72 (m, JH,Sn = 61.1 Hz, 4 H, C6H5-
as for 1b, using 2a (0.25 g, 0.78 mmol) and KF (0.228 g, ortho), 8.31 (d, JH,H = 7.0, JH,Sn = 64.4 Hz, 1 H, 6-H) ppm. 13C
3
3
3.92 mmol). Recrystallisation from CH2Cl2/n-hexane (approxi-
NMR (CDCl3, 100.6 MHz, 20 °C): δ = 45.76 (s, NCH3), 64.82 (s,
3
mately 1:3) mixture gave 2b (0.21 g, 89%) as colourless crystals 2JC,Sn = 31.2 Hz, CH2N), 127.03 (s, JC,Sn = 64.6 Hz, C-3), 128.05
1
3
3
(m.p. 92–94 °C). H NMR (CDCl3, 400 MHz, 20 °C): δ = 0.56 (d,
(s, JC,Sn = 68.7 Hz, C-5), 128.75 (s, JC,Sn = 67.5 Hz, C6H5-meta),
2
3JH,F = 3.7, JH,Sn = 64.8/67.2 Hz, 6 H, SnCH3), 2.28 (s, 6 H, 129.53 (s, 4JC,Sn = 13.5 Hz, C6H5-para), 129.93 (s, 4JC,Sn = 13.1 Hz,
2
2
NCH3), 3.59 (s, 2 H, CH2N), 7.12 (m, 1 H, 3-H), 7.32 (m, 2 H, 4,5-
C-4), 136.03 (s, JC,Sn = 44.8 Hz, C6H5-ortho), 138.34 (s, JC,Sn =
3
3
H), 7.97 (m, JH,Sn = 60.4 Hz, 1 H, 6-H) ppm. 13C NMR (CDCl3,
39.1 Hz, C-6), 140.29 (d, JC,F = 15.5 Hz, C6H5-ipso), 142.88 (s,
2JC,Sn = 44.3 Hz, C-2) ppm; the resonance for C-1 is overlapped by
the resonance of C-6. 19F NMR (CDCl3, 376.5 MHz, 20 °C): δ =
2
1
100.6 MHz, 20 °C): δ = –3.67 (d, JC,F = 16.7, JC,Sn = 507.7/
2
531.3 Hz, SnCH3), 45.16 (s, NCH3), 64.91 (s, JC,Sn = 30.3 Hz,
CH2N), 126.47 (s, JC,Sn = 58.3 Hz, C-3), 127.83 (s, JC,Sn
3
3
1
=
–182.4 ppm (s, JF,Sn = 2058.3/2154.0 Hz). 119Sn NMR (CDCl3,
Eur. J. Inorg. Chem. 2006, 1475–1486
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1483

R. A. Varga, A. Rotar, M. Schürmann, K. Jurkschat, C. Silvestru
FULL PAPER
1
111.9 MHz, 20 °C):
δ
=
–197.6 ppm (d, JF,Sn
=
2157 Hz). 236 °C). 1H NMR (CDCl3, 300 MHz, 20 °C): δ = 1.87 (s, 6 H,
3
C21H22FNSn (426.10): calcd. C 59.20, H 5.20, N 3.29; found C
58.96, H 5.05, N 3.07.
NCH3), 3.56 (s, 2 H, CH2N), 7.18 (d, JH,H = 7.3 Hz, 1 H, 3-H),
3
7.40 (m, 7 H, 4-H + C6H5-meta,para), 7.53 (dd, JH,H = 7.5 Hz, 1
H, 5-H), 7.72 (m, 3JH,Sn = 65.3 Hz, 4 H, C6H5-ortho), 8.60 (d, 3JH,H
3
Synthesis of [{2-(Me2NCH2)C6H4}Ph2SnI] (3d): Same procedure as = 7.1, JH,Sn = 75.1 Hz, 1 H, 6-H) ppm. 13C NMR (CDCl3,
2
for 1b, using 3a (0.2 g, 0.45 mmol) and KI (0.375 g, 2.26 mmol). 75.4 MHz, 20 °C): δ = 45.84 (s, NCH3), 64.64 (s, JC,Sn = 25.8 Hz,
3
3
Recrystallisation from a CH2Cl2/n-hexane (approximately 1:4) mix-
CH2N), 127.19 (s, JC,Sn = 62.1 Hz, C-3), 128.29 (s, JC,Sn =
3
ture gave 3d (0.22 g, 91%) as pale-yellow crystals (m.p. 235– 74.2 Hz, C-5), 128.85 (s, JC,Sn = 69.3 Hz, C6H5-meta), 129.35 (s,
Table 6. Crystallographic data for compounds 1a, 1b, 1b·CH2Cl2 and 1d.
1a
1b
1b·CH2Cl2
1d
Empirical formula
Formula mass
C18H24Cl2N2Sn
457.98
C18H24F2N2Sn
425.08
C18H24F2N2Sn·CH2Cl2 C18H24I2N2Sn
510.01
640.88
Crystal system
Space group
monoclinic
C2/c
monoclinic
P21/n
monoclinic
Cc
monoclinic
P21/n
a [Å]
b [Å]
c [Å]
α [°]
16.9910(4)
8.0759(1)
14.5798(4)
90
9.4178(13)
16.101(2)
12.2211(17)
90
12.9347(16)
12.7973(16)
13.4533(17)
90
10.0711(10)
13.7642(14)
15.1918(15)
90
β [°]
105.9252(11)
90
1980.0(3)
4
1.581
920
111.560(2)
90
1723.6(4)
4
1.638
856
102.312(2)
90
2175.7(5)
4
1.557
1024
96.531(2)
90
2092.2(4)
4
2.035
1208
γ [°]
V [Å3]
Z
Dcalcd. [gcm–3]
F(000)
Crystal size [mm]
µ(Mo-Kα) [mm–1]
θ range [°]
0.25×0.15×0.13
1.607
3.79–27.45
8700
2201 (Rint = 0.0330) 3778 (Rint = 0.0201)
107
0.40×0.31×0.18
1.503
2.19–27.10
10414
0.32×0.20×0.10
1.442
2.26–26.37
8549
4259 (Rint = 0.0349)
239
0.44×0.20×0.20
4.174
2.00–26.37
16388
4274 (Rint = 0.0392)
212
multi-scan (SAINT)
0.0465
No. of reflections collected
No. of independent reflections
No. of parameters
Absorption correction
R1 [I Ͼ 2σ(I)]
wR2
213
none
multi-scan (Bruker SAINT) multi-scan (SAINT)
0.0240
0.0529
1.080
0.0211
0.0452
1.006
0.0381
0.0816
1.023
0.767/–0.700
0.1068
1.157
1.277/–1.382
GOF on F2
Residual electron density [eÅ–3]
0.370/–0.601
0.408/–0.334
Table 7. Crystallographic data for compounds 2a, 2aЈ and 2b–2d.
2a
2aЈ
2b
2c
2d
Empirical formula
C11H18ClNSn
318.40
orthorhombic
Pbca
13.993(9)
12.973(9)
14.687(10)
90
C11H18ClNSn
318.40
orthorhombic
Pna21
17.155(3)
11.2080(19)
7.0150(12)
90
C11H18FNSn
301.97
monoclinic
P21/n
9.5956(8)
12.7844(12)
11.3157(10)
90
C11H18BrNSn
362.86
C11H18INSn
409.85
monoclinic
P21/n
7.1685(10)
7.5197(11)
26.236(4)
90
Formula mass
Crystal system
Space group
a [Å]
b [Å]
c [Å]
orthorhombic
Pbca
14.1705(13)
13.0368(12)
14.6525(14)
90
α [°]
β [°]
90
90
2666(3)
8
1.586
90
90
1348.8(4)
4
1.568
111.521(2)
90
1291.4(2)
4
1.553
600
90
90
2706.9(4)
8
1.781
90.067(2)
90
1414.3(4)
4
1.925
776
γ [°]
V [Å3]
Z
Dcalcd. [gcm–3
F(000)
]
1264
632
1408
Crystal size [mm]
0.13×0.21×0.23
2.084
2.55–26.37
19522
0.42×0.37×0.17
2.084
2.17–26.37
10378
0.24×0.29×0.53
1.957
2.4–26.4
7352
0.25×0.22×0.17
4.808
2.54–26.37
20438
0.37×0.21×0.08
3.959
1.55–26.37
10856
µ(Mo-Kα) [mm–1
θ range [°]
]
No. of reflections collected
No. of independent reflections
No. of parameters
Absorption correction
R1 [I Ͼ 2σ(I)]
2716 (Rint = 0.0372) 2727 (Rint = 0.0220) 2623 (Rint = 0.0174) 2763 (Rint = 0.0362) 2876 (Rint = 0.0519)
131 131 131 131 132
multi-scan (SAINT) multi-scan (SAINT) multi-scan (SAINT) multi-scan (SAINT) multi-scan (SAINT)
0.0315
0.0217
0.0260
0.0317
0.0354
wR2
0.0620
1.100
0.522/–0.470
0.0447
1.092
0.218/–0.408
0.0588
1.060
0.476/–0.202
0.0715
1.101
0.534/–0.602
0.0752
1.116
0.701/–0.762
GOF on F2
Residual electron density [eÅ–3
]
1484
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 1475–1486

Hypercoordinated Organotin() Halides Containing 2-(Me2NCH2)C6H4 Groups
Table 8. Crystallographic data for compounds 3a, 3b and 3d.
FULL PAPER
3a
3b
3d
Empirical formula
Formula mass
C21H22ClNSn
442.54
C21H22FNSn
426.09
C21H22INSn
533.99
Crystal system
Space group
monoclinic
P21/n
monoclinic
P21/n
monoclinic
P21/n
a [Å]
b [Å]
c [Å]
α [°]
9.2370(15)
24.215(4)
17.832(3)
90
9.2868(7)
23.5553(17)
17.8373(13)
90
8.8090(15)
15.875(3)
15.058(3)
90
β [°]
97.558(3)
90
3954.1(11)
8
1.487
1776
99.7480(10)
90
3845.6(5)
8
1.472
1712
92.636(3)
90
2103.5(6)
4
1.686
1032
γ [°]
V [Å3]
Z
Dcalcd. [gcm–3]
F(000)
Crystal size [mm]
µ(Mo-Kα) [mm–1]
θ range [°]
0.24×0.23×0.18
1.429
1.43–26.35
31134
8068 (Rint = 0.0424)
220
multi-scan (SAINT)
0.0444
0.20×0.19×0.04
1.339
1.45–26.38
30497
7877 (Rint = 0.0411)
437
multi-scan (SAINT)
0.0457
0.22×0.15×0.14
2.684
1.87–26.37
16667
4292 (Rint = 0.0438)
219
multi-scan (SAINT)
0.0425
No. of reflections collected
No. of independent reflections
No. of parameters
Absorption correction
R1 [I Ͼ 2σ(I)]
wR2
0.0933
1.195
1.161/–0.509
0.1091
1.026
2.576/–0.921
0.0830
1.058
0.797/–0.874
GOF on F2
Residual electron density [eÅ–3]
4
4JC,Sn = 13.7 Hz, C6H5-para), 130.20 (s, JC,Sn = 14.2 Hz, C-4),
Acknowledgments
2
135.18 (s, JC,Sn = 45.8 Hz, C6H5-ortho), 135.23 (s, C-1), 140.80 (s,
2JC,Sn = 50.3 Hz, C-6), 142.32 (s, JC,Sn = 38.4 Hz, C-2), 142.36 (s,
2
This work was supported by the National University Research
Council of Romania [a CNCSIS grant (AT-23/552/2004) and a
CERES Project (contract no. 32/12.11.2004). We thank the
National Center for X-ray Diffraction (“Babes-Bolyai” University,
Cluj-Napoca) for performing the single-crystal X-ray diffraction
studies.
1JC,Sn
=
705.1/737.9 Hz, C6H5-ipso). 119Sn NMR (CDCl3,
111.9 MHz, 20 °C): δ = –199.5 ppm (s). C21H22INSn (534.01):
calcd. C 47.23, H 4.15, N 2.62; found C 47.01, H 3.88, N 2.45.
X-ray Crystallographic Study: The crystal structure measurement
and refinement data for 1a, 1b, 1b·CH2Cl2, 1d, 2a, 2aЈ, 2b–2d, 3a,
3b and 3d are given in Tables 6, 7 and 8. Data for 1a were collected
with a Nonius KappaCCD diffractometer (University of Dort-
mund) at 291 K. For all the other compounds the data were col-
lected using a SMART APEX diffractometer (“Babes-Boyai” Uni-
versity) at 297 K. In both cases a graphite monochromator was
used to produce a wavelength (Mo-Kα) of 0.71073 Å. The struc-
tures were solved by direct methods (full-matrix least-squares on
F2). All non-hydrogen atoms were refined with anisotropic thermal
parameters. For structure solving and refinement the SHELX-97
software package was used.[42] The drawings were created with the
Diamond program by Crystal Impact GbR.[43]
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CCDC-231308 (for 1a), -230620 (for 1b), -230621 (for 1b·CH2Cl2),
-285103 (for 1d), -215229 (for 2a), -215230 (for 2aЈ), -215224 (for
2b), -230622 (for 2c), -215380 (for 2d), -215228 (for 3a), -215226
(for 3b) and -215227 (for 3d) contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Supporting Information Available (for details see the footnote on
the first page of this article): Figure S1 (variable-temperature 1H
NMR spectra for 1a and 1b, in CDCl3 solution), Figures S2–S8
(simulation of the aromatic region of the1H NMR spectra for 1a,
1b, 2a–2d and 4b, respectively) and Figures S9–S43 (details of the
different supramolecular architectures based on hydrogen-bonding
networks in the crystals of investigated compounds).
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Received: November 15, 2005
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