Organotin(IV) carboxylates based on amide carboxylic acids: Syntheses, crystal structures and characterizations

Article abstract of DOI:10.1016/j.jorganchem.2013.01.017

A series of organotin carboxylates based on amide carboxylic acids: (Ph₃Sn)(L¹)·C₇H₈ (1) (L ¹ = (1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-acetic acid), (Ph₃Sn)(L²) (2) (L² = 3-(1,3-dioxo-1H,3H- benzo[de]isoquinolin-2-yl)-benzoic acid), (Ph₃Sn)(L ³)·C₇H₈ (3) (L³ = N-phenyl-phthalamic acid), (n-Bu₂Sn)(L¹) ₂·C₇H₈ (4), (n-Bu₂Sn)(L ⁴)₂ (5) (L⁴ = 4-(1,3-dioxo-1,3-dihydro- isoindol-2-yl)-benzoic acid), [(n-Bu₂Sn)₂(L ²)O]₂·C₇H₈ (6), {[n-Bu ₂Sn(L⁵)]₂O}₂·C ₇H₈ (7) (L⁵ = 4-(1,3-dioxo-1H,3H-benzo[de] isoquinolin-2-yl)-benzoic acid) were synthesized with toluene being used as solvent in the reaction and characterized by elemental analysis, IR, ¹H and ¹³C NMR spectroscopy and X-ray crystallography diffraction analyses. Complexes 1-5 are monomers in which 1-3 are triphenlytin carboxylates while 4 and 5 are dibutyltin carboxylates possessing crystallographically imposed two-fold symmetry. Complexes 6 and 7 are dimeric carboxylate tetraorganodistannoxanes and show a "ladder-like" molecular structure. Ligands in 1-3 and 6 adopt unidentate chelating mode and in 4 and 5 they are bidentate, while for 7 both of the chelate coordination modes exist. Intermolecular hydrogen bonds and π?π interactions help complexes 1-7 build their respective supramolecular structures which are discussed in detail. It is found that amide carboxylic acids are apt to adopt various coordination modes and lead diverse molecular architectures for organotin carboxylates.

Full text of DOI:10.1016/j.jorganchem.2013.01.017

Journal of Organometallic Chemistry 729 (2013) 28e39
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Organotin(IV) carboxylates based on amide carboxylic acids: Syntheses, crystal
structures and characterizations
,
a
a
Xiao Xiao a, Xiao Han a, Zemin Mei b, Dongsheng Zhu a , Kuizhan Shao , Jingwen Liang ,
*
Min Tian a, Lin Xu a
a Department of Chemistry, Northeast Normal University, 5268 Renmin Street, Changchun 130024, PR China
b Department of Chemistry, Baicheng Normal University, 9 Zhongxing East Street, Baicheng 137000, PR China
a r t i c l e i n f o
a b s t r a c t
A series of organotin carboxylates based on amide carboxylic acids: (Ph3Sn)(L1)$C7H8 (1) (L1 ¼ (1,3-dioxo-
1H,3H-benzo[de]isoquinolin-2-yl)-acetic acid), (Ph3Sn)(L2) (2) (L2 ¼ 3-(1,3-dioxo-1H,3H-benzo[de]iso-
quinolin-2-yl)-benzoic acid), (Ph3Sn)(L3)$C7H8 (3) (L3 ¼ N-phenyl-phthalamic acid), (n-Bu2Sn)(L1)2$C7H8
Article history:
Received 25 December 2012
Received in revised form
18 January 2013
(4), (n-Bu2Sn)(L4)2 (5) (L4
¼
4-(1,3-dioxo-1,3-dihydro-isoindol-2-yl)-benzoic acid), [(n-Bu2Sn)2(L2)
Accepted 18 January 2013
O]2$C7H8 (6), {[n-Bu2Sn(L5)]2O}2$C7H8 (7) (L5 ¼ 4-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-yl)-benzoic
acid) were synthesized with toluene being used as solvent in the reaction and characterized by elemental
analysis, IR, 1H and 13C NMR spectroscopy and X-ray crystallography diffraction analyses. Complexes 1e5
are monomers in which 1e3 are triphenlytin carboxylates while 4 and 5 are dibutyltin carboxylates
possessing crystallographically imposed two-fold symmetry. Complexes 6 and 7 are dimeric carboxylate
tetraorganodistannoxanes and show a “ladder-like” molecular structure. Ligands in 1e3 and 6 adopt
unidentate chelating mode and in 4 and 5 they are bidentate, while for 7 both of the chelate coordination
Keywords:
Organotin carboxylate
Amide carboxylic acid
Self-assembly
Supramolecular structure
modes exist. Intermolecular hydrogen bonds and
p/p interactions help complexes 1e7 build their
respective supramolecular structures which are discussed in detail. It is found that amide carboxylic
acids are apt to adopt various coordination modes and lead diverse molecular architectures for organotin
carboxylates.
Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction
reacts with dibutyltin oxide [10e12]. To further understand the
coordination chemistry and explore the diversiform structures of
Self-assembly of organic ligands with organotin and the various
intriguing topologies of organotin carboxylates have been exten-
sively studied [1e4]. It is well known that the multidimensional
architectures of them can be controlled by adjusting the tin-R
groups, metal-to-ligand molar ratio and the type of organic li-
gands [5,6]. In addition to this, intermolecular interaction carries
the weight of generating various supramolecular structures [7e9].
It is found that the reaction of monocarboxylic acid with triphe-
nyltin hydroxide is inclined to produce mononuclear carboxylate,
however, di-, tetra-nuclear polymeric carboxylates with compli-
cated constructions are easily formed when monocarboxylic acid
organotin carboxylate, we have investigated novel carboxylate li-
gands which have one kind hetero atoms “nitrogen” (amide car-
boxylic acid) and synthesized seven new organotin carboxylates
herein.
2. Experimental section
2.1. General and instrumental
The reagents were used as supplied while the solvents were
purified according to standard procedures [13]. The melting point
was obtained with Kofler micro-melting point apparatus and was
uncorrected. Elemental analyses (C, H, N) were carried out on
a PerkineElmer PE 2400 CHN instrument. 1H and 13C NMR spectra
were recorded on a Varian Mercury operating at 300 and 75 MHz,
respectively. IR spectra (KBr pellets) were recorded on an Alpha
Centauri FI/IR spectrometer (400e4000 cmꢀ1 range).
* Corresponding author. Tel.: þ86 13009010567; fax: þ86 0431 85684009.
E-mail address: zhuds206@nenu.edu.cn (D. Zhu).
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.01.017

X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
29
Table 1
Crystal data and structure refinement parameters for 1e7.
1
2
3
4
5
6
7
Empirical formula
M
C35H23NO4Sn
640.23
Triclinic
C37H25NO4Sn
666.09
Monoclinic
C2/c
35.3105(16)
9.7150(4)
18.3051(8)
90.00
112.3770(10)
90.00
C39H33NO3Sn
682.35
Monoclinic
C2/c
31.094(2)
10.0610(7)
21.3427(15)
90.00
103.6560(10)
90.00
C79H76N4O16 Sn2
1574.82
Triclinic
C38H34N2O8Sn
765.36
Monoclinic
C2/c
16.1847(15)
7.2069(7)
28.821(3)
90.00
94.554(2)
90.00
C70H92N2O12Sn4
1628.22
Monoclinic
P21/n
11.728(3)
23.791(7)
13.941(4)
90.00
90.00
90.00
3889.7(19)
2
1.323
C122H128N4O18 Sn4
2413.04
Triclinic
Crystal system
Space group
P1
P1
P1
ꢀ
a (A)
8.7329(5)
9.1426(5)
19.8833(11)
92.0320(10)
90.0860(10)
111.6570(10)
1474.34(14)
2
11.3853(5)
11.8691(5)
14.0419(6)
97.9050(10)
104.7740(10)
104.4930(10)
1734.83(13)
1
13.2350(11)
14.0524(12)
16.6201(14)
80.1360(10)
88.6990(10)
63.7390(10)
2726.1(4)
1
ꢀ
b (A)
ꢀ
c (A)
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
3
ꢀ
V (A )
5806.6(4)
8
0.923
6488.0(8)
8
0.826
3351.2(6)
4
0.820
Z
m
(mmꢀ1
)
0.906
0.794
0.975
Reflections collected
Independent reflections
Rint
7483
5115
0.0136
1.044
15,149
5721
0.0254
1.052
18,748
5731
0.0541
0.966
9487
6678
0.0128
1.053
10,279
3273
0.0365
1.069
24,112
7726
0.0605
1.030
14,112
10,476
0.0164
1.047
Goodness-of-fit on F2
R1, wR2 [I > 2
R1, wR2 (all data)
s
(I)]
0.0339, 0.0945
0.0370, 0.0967
0.0259, 0.0634
0.0311, 0.0664
0.0383, 0.0722
0.0730, 0.0830
0.0395, 0.1052
0.0431, 0.1091
0.0381, 0.0831
0.0462, 0.0870
0.0921, 0.2464
0.1184, 0.2602
0.0398, 0.0983
0.0500, 0.1048
2.3. Syntheses
2.3.1. Syntheses of ligands
L3 is commercially available. L2, L4 and L5 were prepared by
a standard method reported in the literature [16]. The preparation
of L1 is similar to that of L2 and shown in Scheme 1.
Scheme 1. Synthesis of ligand L1.
L1: Benzo[de]isochromene-1,3-dione (3.96 g, 0.02 mol) and
glycine (1.50 g, 0.02 mol) were added into a three-neck flask with
40 mL DMF in it. The reaction mixture was stirred for 8 h in an oil-
bath at 90 ꢁC. After standing overnight, the mixture was filtrated to
get the pale yellow powder. After washed with ethanol till the filter
liquor turned colorless, the powder was recrystallized in a small
portion of DMF. Yield: 89.4%; mp: 270.8e273.4 ꢁC. 1H NMR
2.2. X-ray crystallography
Diffraction intensities for complexes 1e7 were collected on
a Bruker CCD Area Detector image plate diffractometer by using the
ꢀ
u
/4 scan technique with Mo-K
a
radiation (
l
¼ 0.71073 A). Ab-
(dimethyl sulfoxide-d6, ppm):
d 13.03 (s, 1H, COOH); 8.60 (d, 2H,
sorption corrections were applied by using multiscan techniques.
The structures were solved by direct methods with SHELXS-97 [14]
and refined using SHELXL-97 [15]. All non-hydrogen atoms were
refined with anisotropic temperature parameters; hydrogen atoms
were refined as rigid groups. Crystal data and refinement results for
complexes 1e7 are listed in Table 1.
J ¼ 7.2 Hz, AreH); 8.54 (d, 2H, J ¼ 7.1 Hz, AreH); 7.93 (dd, 2H, J ¼ 7.4,
7.0 Hz, AreH); 4.74 (s, 2H, eCH2e). 13C NMR (dimethyl sulfoxide-d6,
ppm):
d 179.81 (1C, COO); 173.50 (2C, C]O); 137.56 (2C), 135.25
(2C), 130.23 (1C), 127.76 (2C), 125.66 (1C), 121.85 (2C) (carbon
protons of aryl groups), 40.78 (1C, eCH2e).
Scheme 2. Syntheses of complexes 1e3.

30
X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
Scheme 3. Syntheses of complexes 4 and 5.
The syntheses of complexes 1e3 were shown in Scheme 2.
(6C, C17, C19, C23, C25, C29, C31), 127.51 (3C, C18, C24, C30), 125.30
(2C, C6, C10),124.98 (1C, C13),123.20 (2C, C4, C12) (carbonprotons of
aryl groups), 35.92 (1C, eCH2e).
2.3.2. Synthesis of (Ph3Sn)(L1)$C7H8 (1)
A mixture of triphenyltin hydroxide (0.367 g, 1 mmol) and L1
(0.255 g,1 mmol) was heated under reflux in toluene (50 mL) for 10 h
in a DeaneStark apparatus for azeotropic removal of the water
formed in the reaction. After cooling to room temperature, the so-
lution was filtered. The filtrate was gradually evaporated and the X-
ray quality colorless crystals were obtained. Yield: 75%; mp: 255.7e
258.0 ꢁC. Anal. Calcd for C32H23NO4Sn$C7H8: C, 67.26; N, 2.01; H,
4.49%. Found: C, 67.38; N, 2.08; H, 4.38%. IR (cmꢀ1): v(O]C) 1714;
2.3.3. Synthesis of (Ph3Sn)(L2) (2)
The preparation of 2 is similar to that of 1 except that L2 (0.317 g,
1 mmol) was used to replace L1. Yield: 78%; mp: 159.9e162.3 ꢁC.
Anal. Calcd for C37H25NO4Sn: C, 66.70; N, 2.10; H, 3.78%. Found: C,
66.59; N, 2.19; H, 3.83%. IR (cmꢀ1): v(O]C) 1704; vas(COO) 1658;
vs(COO) 1435; v(SneC) 585;
8.65 (s, 1H, AreH: H3); 8.30 (d, 2H, J ¼ 7.6 Hz, AreH: H10, H16);
n
(SneO) 440. 1H NMR (CDCl3, ppm):
d
vas(COO) 1598; vs(COO) 1393; v(SneC) 581;
n
(SneO) 437. 1H NMR
8.28 (d, 1H, J ¼ 7.5 Hz, AreH: H5); 7.89 (d, 2H, J ¼ 7.6 Hz, AreH: H12,
H14); 7.78 (d, 1H, J ¼ 7.5 Hz, AreH: H7); 7.68 (dd, 1H, J ¼ 7.8, 7.2 Hz,
AreH: H6); 7.63 (dd, 2H, J ¼ 7.1, 8.1 Hz, AreH: H11, H15); 7.35e7.50
(m, 15H, PheH). 13C NMR (CDCl3, ppm): 171.79 (1C, COO); 164.25
(2C, C]O); 138.19 (1C, C4), 136.96 (2C, C10, C16), 136.17 (2C, C12,
C14), 135.52 (1C, C2), 134.45 (1C, C13), 133.09 (1C, C6), 131.71 (2C,
C11, C15), 131.03 (2C, C9, C17), 130.21 (1C, C19), 129.31
(CDCl3, ppm): 8.37e8.31 (m, 4H, AreH: H5, H7, H9, H11); 7.66 (dd,
d
2H, J ¼ 7.6, 7.0 Hz, AreH: H6, H10); 7.25e7.28 (m,15H, PheH); 4.92 (s,
2H, eCH2e).13C NMR (CDCl3, ppm): 179.78(1C, COO); 167.79(2C, C]
O); 135.46 (2C, C5, C11), 133.69 (2C, C7, C9), 132.58 (1C, C8), 129.04
(3C,1J
¼ 424 Hz; 2J
¼ 19 Hz; 3J
¼
63 Hz,
119Sne13
C
119Sne13
C
119Sne13
C
C15, C21, C27), 128.82 (6C, C16, C20, C22, C26, C28, C32), 128.23
Scheme 4. Syntheses of complexes 6 and 7.

X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
31
(3C, 1J
¼ 390 Hz; 2J
¼ 23 Hz; 3J
¼ 59 Hz,
256.3 ꢁC. Anal. Calcd for C70H92N2O12Sn4$C7H8: C, 53.75; N, 1.63;
H, 5.86%. Found: C, 53.68; N,1.61; H, 5.80%. IR (cmꢀ1): v(O]C) 1708;
119Sne13
C
119Sne13
C
119Sne13
C
C20, C26, C32), 128.95 (6C, C21, C25, C27, C31, C33, C37), 128.53
(6C, C22, C24, C28, C30, C34, C36), 128.05 (3C, C23, C29, C35), 127.08
(1C, C5), 126.58 (1C, C7), 122.66 (1C, C3) (carbon protons of aryl
groups).
vas(COO) 1583; vs(COO) 1352; v(SneC) 548;
(CDCl3, ppm):
8.71 (s, 2H, AreH: H3); 8.66 (d, 4H, J ¼ 7.4 Hz, AreH:
n
(SneO) 447. 1H NMR
d
H10, H16); 8.30 (d, 4H, J ¼ 7.5 Hz, AreH: H12, H14); 7.99 (d, 2H,
J ¼ 7.1 Hz, AreH: H5); 7.81 (dd, 4H, J ¼ 7.9, 6.9 Hz, AreH: H11, H15);
7.63 (dd, 2H, J ¼ 7.4, 6.8 Hz, AreH: H6); 7.20 (d, 2H, J ¼ 7.3 Hz, AreH:
H7); 1.72 (t,16H, J ¼ 7.0 Hz, BueH: eCH2e); 1.37e1.46 (m, 32H, Bue
H: eCH2e); 0.92 (t, 24H, J ¼ 6.8 Hz, BueH: eCH3). 13C NMR (CDCl3,
ppm): 173.03 (2C, COO), 164.17 (4C, C]O); 137.70 (2C, C4), 134.34
(4C, C10, C16), 133.85 (4C, C12, C14), 131.62 (2C, C2), 130.77 (2C,
C13), 129.59 (2C, C6), 129.04 (4C, C11, C15), 128.49 (4C, C9, C17),
128.23 (2C, C19), 127.06 (2C, C7), 125.31 (2C, C5), 122.70 (2C, C3)
(carbon protons of aryl groups), 27.49 (8C, eCH2e), 26.82 (8C, e
2.3.4. Synthesis of (Ph3Sn)(L3)$C7H8 (3)
The preparation of 3 is similar to that of 1 except that L3 (0.241 g,
1 mmol) was used to replace L1. Yield: 72%; mp: 150.1e152.8 ꢁC.
Anal. Calcd for C32H25NO3Sn$C7H8: C, 68.64; N, 2.05; H, 4.87%.
Found: C, 68.68; N, 2.08; H, 4.81%. IR (cmꢀ1): v(O]C) 1708; vas(COO)
1598; vs(COO) 1345; v(SneC) 571;
ppm):
n
(SneO) 443. 1H NMR (CDCl3,
d
8.07 (d, 1H, J ¼ 7.3 Hz, AreH: H7); 8.01 (s, 1H, NH); 7.97 (d,
1H, J ¼ 7.2 Hz, AreH: H4); 7.81 (dd,1H, J ¼ 6.9, 7.7 Hz, AreH: H5); 7.68
(dd, 1H, J ¼ 7.1, 7.3 Hz, AreH: H6); 7.61e7.34 (m, 20H, PheH). 13C
NMR (CDCl3, ppm): 172.01 (1C, COO); 168.90 (2C, C]O); 138.21 (1C,
C9), 137.78 (1C, C3), 137.23 (1C, C5), 136.59 (1C, C6), 132.09 (1C, C7),
131.32 (1C, C2), 130.19 (2C, C11, C13), 129.33 (1C, C4), 129.11 (3C,
CH2e), 13.63 (8C, eCH3), 8.01 (8C, eCH2e, 1J
¼ 618 Hz;
119Sne13
C
2J
¼ 31 Hz; 3J
¼ 81 Hz) (carbon protons of butyl
119Sne13
groups).
C
119Sne13
C
1J
¼ 402 Hz; 2J
¼ 22 Hz; 3J
¼ 60 Hz, C21,
2.3.8. Synthesis of {[n-Bu2Sn(L5)]2O}2$C7H8 (7)
119Sne13
C
119Sne13
C
119Sne13
C
C31, C41), 128.94 (6C, C22, C26, C32, C36, C42, C46), 128.47 (6C, C23,
C25, C33, C35, C43, C45),128.24 (3C, C24, C34, C44),124.16 (1C, C12),
119.92 (2C, C10, C14) (carbon protons of aryl groups).
The preparation of 7 is similar to that of 4 except that L5 (0.159 g,
0.5 mmol) was used to replace L1. Yield: 61.4%; mp: 254.1e256.9 ꢁC.
Anal. Calcd for C108H112N4O18Sn4$C7H8: C, 59.51; N, 2.41; H, 5.21%.
Found: C, 59.58; N, 2.48; H, 5.19%. IR (cmꢀ1): v(O]C) 1711; vas(COO)
The syntheses of complexes 4 and 5 were shown in Scheme 3.
2.3.5. Synthesis of (n-Bu2Sn)(L1)2$C7H8 (4)
The preparation of 4 is similar to that of 1 except that dibutyltin
oxide (0.124 g, 0.5 mmol) was used to replace triphenyltin hydrox-
ide. Yield: 69.5%; mp: 264.7e267.6 ꢁC. Anal. Calcd for
C36H34N2O8Sn$C7H8: C, 61.96; N, 3.36; H, 5.08%. Found: C, 61.89; N,
3.42; H, 5.12%. IR (cmꢀ1): v(O]C) 1705; vas(COO) 1589; vs(COO)
1390; v(SneC) 531; n d 8.47 (d,
(SneO) 435. 1H NMR (CDCl3, ppm):
4H, J ¼ 7.3 Hz, AreH: H5, H11, H19, H25); 8.13 (d, 4H, J ¼ 7.2 Hz, Are
H: H7, H13, H21, H27); 7.69 (dd, 4H, J ¼ 7.6, 7.0 Hz, AreH: H6, H12,
H20, H26); 4.97 (s, 4H, eCH2e); 1.75 (t, 4H, J ¼ 6.8 Hz, BueH: eCH2e
), 1.39e1.57 (m, 8H, BueH: eCH2e); 0.96 (t, 6H, J ¼ 6.9 Hz, BueH: e
CH3). 13C NMR (CDCl3, ppm): 178.10 (2C, COO), 163.25 (4C, C]O),
133.77 (4C, C5, C11, C19, C25), 130.68 (4C, C7, C13, C21, C27), 129.03
(2C, C8, C22), 128.22 (2C, C9, C23), 126.41 (4C, C6, C12, C20, C26),
121.40 (4C, C4, C10, C18, C24) (carbon protons of aryl groups), 41.48
(2C, eCH2e); 26.61 (2C, eCH2e), 26.38 (2C, eCH2e), 13.63 (2C, e
CH3), 7.05 (2C, eCH2e, 1J
¼ 767 Hz; 2J
¼ 35 Hz;
119Sne13
C
119Sne13
C
3J
¼ 89 Hz) (carbon protons of butyl groups).
119Sne13
C
2.3.6. Synthesis of (n-Bu2Sn)(L4)2 (5)
The preparation of 5 is similar to that of 4 except that L4 (0.267 g,
1 mmol) was used to replace L1. Yield: 63.7%; mp: 102.2e104.7 ꢁC.
Anal. Calcd for C38H34N2O8Sn: C, 59.63; N, 3.66; H, 4.48%. Found:
C, 59.68; N, 3.61; H, 4.46%. IR (cmꢀ1): v(O]C) 1711; vas(COO) 1605;
vs(COO) 1465; v(SneC) 582; n d 8.29 (d,
(SneO) 476. 1H NMR (CDCl3):
4H, J ¼ 7.0 Hz, AreH: H11, H14); 7.98 (d, 4H, J ¼ 6.9 Hz, AreH: H3,
H7); 7.83 (dd, 4H, J ¼ 6.8, 7.0 Hz, AreH: H12, H13); 7.62 (d, 4H,
J ¼ 7.0 Hz, AreH: H4, H6); 1.79 (t, 4H, J ¼ 6.8 Hz, BueH: eCH2e);
1.34e1.48 (m, 8H, BueH: eCH2e); 0.91 (t, 6H, J ¼ 6.7 Hz, BueH: e
CH3). 13C NMR (CDCl3, ppm): 175.27 (2C, COO), 166.81 (4C, C]O),
136.09 (2C, C5), 134.67 (4C, C10, C15), 131.58 (4C, C12, C13), 131.39
(4C, C3, C7),130.85 (2C, C11, C14),125.92 (4C, C2),123.94 (4C, C4, C6)
(carbon protons of aryl groups), 26.77 (2C, eCH2e), 26.30 (2C, e
CH2e), 13.61 (2C, eCH3), 7.95 (2C, eCH2e, 1J
¼ 664 Hz;
119Sne13
C
2J
¼ 34 Hz; 3J
¼ 88 Hz) (carbon protons of butyl
119Sne13
groups).
C
119Sne13
C
The syntheses of complexes 6 and 7 were shown in Scheme 4.
2.3.7. Synthesis of {[n-Bu2Sn(L2)]2O}2$C7H8 (6)
The preparation of 6 is similar to that of 4 except that L2 (0.079 g,
0.25 mmol) was used to replace L1. Yield: 66.4%; mp: 253.5e
Fig. 1. The molecular structures of complexes 1e3.

32
X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
n
(SneO) 443. 1H NMR
Table 2
1629, 1551; vs(COO) 1412, 1377; v(SneC) 588;
(CDCl3, ppm):
8.65 (d, 8H, J ¼ 7.6 Hz, AreH: H15, H17, H35, H37);
ꢁ
ꢀ
Selected bond lengths (A) and angles ( ) for 1e3.
d
8.29 (d, 8H, J ¼ 7.4 Hz, AreH: H2, H8, H22, H28); 8.19 (d, 8H, J ¼ 7.6 Hz,
AreH: H4, H6, H24, H26); 7.82 (dd, 8H, J ¼ 7.1, 7.9 Hz, AreH: H3, H7,
H23, H27); 7.19 (d, 8H, J ¼ 7.4 Hz, AreH: H14, H18, H34, H38); 1.77 (t,
16H, J ¼ 6.9 Hz, BueH: eCH2e); 1.41e1.50 (m, 32H, BueH: eCH2e);
0.94 (t, 24H, J ¼ 6.7 Hz, BueH: eCH3). 13C NMR (CDCl3, ppm): 173.56
(4C, COO); 164.18 (8C, C]O),138.21 (4C, C13, C33),137.78 (8C, C2, C8,
C22, C28), 137.23 (8C, C4, C6, C24, C26), 134.41 (4C, C5, C25), 131.72
(8C, C15, C17, C35, C37),131.09 (8C, C3, C7, C23, C27), 128.55 (4C, C10,
C30), 127.05 (4C, C16, C36), 125.72 (8C, C1, C9, C21, C29), 122.68 (8C,
C14, C18, C34, C38) (carbon protons of aryl groups), 27.92 (8C, eCH2e
Complex 1
Bond lengths
Sn(1)eO(1)
Sn(1)eC(21)
2.050(2)
2.117(3)
Sn(1)eC(15)
Sn(1)eC(27)
2.118(3)
2.127(3)
Bond angles
O(1)eSn(1)eC(21)
O(1)eSn(1)eC(15)
O(1)eSn(1)eC(27)
108.79(11)
105.33(12)
98.06(11)
C(21)eSn(1)eC(15)
C(21)eSn(1)eC(27)
C(15)eSn(1)eC(27)
118.50(14)
110.54(13)
113.35(13)
Complex 2
Bond lengths
Sn(1)eO(1)
Sn(1)eC(20)
Bond angles
O(1)eSn(1)eC(20)
O(1)eSn(1)eC(32)
O(1)eSn(1)eC(26)
2.0597(14)
2.118(2)
Sn(1)eC(32)
Sn(1)eC(26)
2.121(2)
2.126(2)
), 26.87 (8C, eCH2e),13.71 (8C, eCH3), 8.20 (8C, eCH2e, 1J
¼
119Sne13
C
755 Hz; 2J
¼ 42 Hz; 3J
¼ 91 Hz) (carbon protons of
119Sne13
butyl groups).
C
119Sne13
C
113.05(7)
97.59(7)
108.24(7)
C(20)eSn(1)eC(32)
C(20)eSn(1)eC(26)
C(32)eSn(1)eC(26)
113.49(8)
114.26(8)
108.87(8)
3. Results and discussion
Complex 3
Bond lengths
Sn(1)eO(1)
2.059(2)
2.117(4)
Sn(1)eC(41)
Sn(1)eC(21)
2.123(4)
2.135(3)
3.1. IR spectra
Sn(1)eC(31)
Bond angles
Comparing the IR spectra of the free ligands with complexes 1e
7, the explicit feature is the absence of a broad band in the region
3400e2800 cmꢀ1, which appears in the free ligands owing to COOH
O(1)eSn(1)eC(31)
O(1)eSn(1)eC(41)
O(1)eSn(1)eC(21)
109.19(12)
113.79(12)
96.17(11)
C(31)eSn(1)eC(41)
C(31)eSn(1)eC(21)
C(41)eSn(1)eC(21)
113.06(13)
112.87(14)
110.64(14)
Fig. 2. 1D chain structures of complexes 1e3. Part of phenyl groups and H atoms are omitted for clarity.

X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
33
ꢀ
ꢀ
group, indicating the removal of COOH protons and the formation
of SneO bonds through this site [1,17,18]. The Dn
intramolecular distances [Sn(1)/O(2) for 1: 2.943 A; 2: 2.950 A; 3:
ꢀ
(nasCOO ꢀ nsCOO)
2.735 A] although longer than SneO covalent bond length are much
shorter than the sum of the van der Waals radii of tin and oxygen
(3.7 A). They lie in the range of intramolecular SneO bond distances
of 2.61e3.02 A [29,30]. Therefore the oxygen atoms [O(2) of 1e3]
are involved in a weak coordinative interaction with tin along
one of the tetrahedral faces, and the structure distortion for the tin
atoms in complex 1e3 is best described as a capped tetrahedron.
Intermolecular H-bonds of complexes 1, 2 and 3 [1: C(2)e
H(2B)/O(4) (2.341 A), C(6)eH(6A) /O(4) (2.520 A), C(28)e
H(28A)/O(3) (2.552 A); 2: C(15)eH(15A)/O(4) (2.490 A); 3:
values for complexes 1e3 and 6 are 205, 223, 253 and 231 cmꢀ1
respectively larger than 200 cmꢀ1. This is representative of the
unidentate chelating mode for the carboxyl ligands in them [19e
21]. For complexes 4 and 5, they are 199 and 140 cmꢀ1 smaller
than 200 cmꢀ1, standing for the bidentate chelate coordination of
the carboxylate group. For 7, the values are 217 and 174 cmꢀ1
indicating both of the bidentate and unidentate chelate coordina-
tion modes exist in the carboxylate group. All of the coordination
modes proved by IR spectra of 1e7 are totally consistent with the X-
ray structures. A band in 531e588 cmꢀ1 region is assigned to the
stretching frequency associated with SneC bond [22,23]. A strong
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
C(11)eH(11A)/O(2) (2.564 A)] link them into 1D infinite chains
(Fig. 2). The oxygen atoms O(3), O(4) in 1 and O(4) in 2 are from
amide groups while O(2) in 3 is carboxylate oxygen atom. H(2B)
and H(28A) belong to methylene and butyl groups respectively in 1.
H(6A) of 1, H(15A) of 2 and H(11A) of 3 are from aromatic groups of
ligands. For 1, the adjacent planes of ligands (L1) in the chain are
band in 435e476 cmꢀ1 for complexes 1e7 is assigned to
indicative of a SneO coordinated structure [24,25].
n(SneO),
3.2. NMR spectra
almost paralleled with dihedral angle 1.49ꢁ. Distance between
interactions (offset face-to-face) exist
[31]. Besides these interactions, hydrogen bonds [1: C(10)e
H(10A)/O(2) (2.718 A), C(24)eH(24A)/O(1) (2.675 A); 2: C(36)e
H(36A)/O(2) (2.653 A), C(21)eH(21A)/O(3) (2.619 A); 3: N(1)e
H(1A)/O(3) (2.113 A)] also connect the chains into 2D networks
1H NMR spectra show that signal for COOH proton (12e14 ppm)
of free ligands is absent in the spectra of complexes 1e7. This in-
dicates carboxylate groups participate in the coordination to the Sn
atoms [17,18]. The expected integration and peak multiplicities for
the hydrogen protons on aromatic rings of ligands in 1e7 are also
observed. They appear almost in the same positions as in the ligand
at 8.71e7.19 ppm. The chemical shifts for “eCH2e” groups of L1 in 1
and 4, and “eNHe” group of L3 in 3 are at 4.92, 4.97 and 8.01 as
single peak respectively [26]. Signals for the hydrogen protons on
phenyl groups of tin in complexes 1e3 are revealed as multiplets at
7.25e7.61 ppm. Butyl groups of 4e7 can also be appropriately
attributed [8,18].
them is 3.461 A and
p/p
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
The carbon protons of all the complexes show a significant
downfield shift of carbon resonances compared with free ligands.
The shift is a consequence of electron density transfer from the
ligand to the acceptor Sn atoms [17]. Single resonances at 171.79e
179.78 and 163.25e168.90 ppm are attributed to COO and C]O
groups [8,17,18]. The carbon protons of phenyl groups in 1e3 pre-
sent four kinds of chemical environment, and give four peaks at
127.51e128.24, 128.23e128.53, 128.82e128.95 and 129.04e
129.31 ppm respectively. Chemical shifts for “eCH2e” of 1 and 4
are at 35.92 and 41.48 ppm [26]. The peaks of aromatic rings and
butyl groups can also be appropriately attributed. These data are
1
consistent with the structures of 1e7. For 1e3, with the JSneC
values being 390e424 Hz and by the use of the Holecek and
Lycka equation [27], CeSneC values of 110.9ꢁe114.0ꢁ were calcu-
lated, which correspond to the geometry of Sn atoms in 1e3
(108.87ꢁe118.50ꢁ). For 4e7, the values are 618e767 Hz, and Ce
SneC angles of 130.9ꢁe144.0ꢁ were calculated which are in
accord with the X-ray structures of them (129.20ꢁe149.61ꢁ).
3.3. Crystal structures
3.3.1. Crystal structures of 1e3
The molecular structures of 1e3 are shown in Fig. 1. Selected
bond lengths and angles are listed in Table 2. 1e3 exist as mono-
mers in the solid state with the tin atoms four coordinated. Each tin
atom demonstrates a distorted tetrahedral geometry coordinated
with one carboxylate oxygen atom from ligand and three carbon
atoms of phenyl groups. The related CeSneC angles of 1e3 among
108.87ꢁe118.50ꢁ and OeSneC angles sphering from 96.17ꢁ to
113.79ꢁ prove the distorted geometry. SneC bond lengths
ꢀ
[2.117(4)e2.135(3) A] are in the range of those found in other tri-
phenyltin carboxylates [12]. Strong chemical bonds exist between
carboxylate oxygen and tin atoms evidenced by the SneO bond
ꢀ
lengths [2.0500(2)e2.0597(14) A] which lie in the range of SneO
Fig. 3. 2D network structures of complexes 1e3. Only relevant C and H atoms are
covalent bond length reported [28]. In addition to that,
drawn for clarity.

34
X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
Fig. 6. The molecular structures of complexes 4 and 5.
electrons are from the phenyl ring of toluene and phenyl group on
tin atom. In the stacking format of 2 (Fig. 5), each pair of the net-
works are connected with each other by p/p interactions with the
plane of aromatic rings of ligands face-to-face. Compared the su-
pramolecular structures of 1 and 2 (Figs. 4 and 5), it is found that
though ligands L1 and L2 contain the same part in structure (benzo
Fig. 4. 2D networks of complexes 1 and 3 interact with free toluene. Part of phenyl
groups and H atoms are omitted for clarity.
[de]isoquinoline-1,3-dione), there are more
p/p interactions
among layers of the 2D networks in 1. That is caused by the steric
hindrance from rigid construction of ligand L2.
(Fig. 3). O(3), O(4) in 2 are derived from the amide groups. O(1),
O(2) of 1 and O(2) of 2 are the carboxylate oxygens and that H(24A)
in 1, H(36A), H(21A) of 2 are from the phenyl groups on tin. H(10A)
of 1, H(15A) in 2 are hydrogen atoms of aromatic ring. For 3, N(1),
H(1A) and O(3) are all from amide group. With the H-bonds,
complex 3 forms two kinds of irregular ring (A and B). A is 28-
membered while B is 24-membered. In the crystal lattice of 1 and
3, free toluene molecules are situated on both sides of the network
3.3.2. Crystal structures of 4 and 5
The molecular structures of complexes 4 and 5 are shown in
Fig. 6. Selected bond lengths and angles are given inTable 3. Both the
Table 3
ꢁ
ꢀ
Selected bond lengths (A) and angles ( ) for 4 and 5.
and stabilized by edge-to-face
p/p interactions (Fig. 4). The pi
Complex 4
Bond lengths
SneO(1)
SneO(5)
SneC(33)
2.136(2)
2.140(2)
2.119(3)
SneO(2)
2.552(3)
2.130(4)
SneC(29)
Bond angles
O(1)eSneO(5)
O(1)eSneO(2)
O(5)eSneO(2)
C(33)eSneC(29)
C(33)eSneO(1)
80.93(8)
55.01(8)
135.83(8)
146.41(14)
101.33(11)
C(29)eSneO(1)
C(33)eSneO(5)
C(29)eSneO(5)
C(33)eSneO(2)
C(29)eSneO(2)
103.05(12)
99.32(12)
107.02(13
87.60(11)
87.77(13)
Complex 5
Bond lengths
Sn(1)eO(1)
Sn(1)eO(2)
2.113(2)
2.511(2)
Sn(1)eC(21)
Sn(1)eC(1)
2.109(3)
2.663(3)
Bond angles
O(1)eSn(1)eO(2)
O(1)eSn(1)eO(2)#1
O(1)eSn(1)eO(1)#1
O(2)eSn(1)eO(2)#1
C(21)#1eSn(1)eC(21)
C(21)#1eSn(1)eC(1)
C(21)eSn(1)eC(1)
C(1)eSn(1)eC(1)#1
56.04(7)
140.25(7)
84.62(11)
163.66(10)
133.79(18)
94.69(11)
100.24(11)
141.40(14)
O(2)eSn(1)eC(1)#1
C(21)#1eSn(1)eO(1)
C(21)eSn(1)eO(1)
C(21)#1eSn(1)eO(2)
C(21)eSn(1)eO(2)
O(1)eSn(1)eC(1)
168.45(9)
103.67(10)
110.13(10)
86.81(10)
86.80(10)
28.43(9)
O(1)eSn(1)eC(1)#1
O(2)eSn(1)eC(1)
112.99(9)
27.65(8)
Fig. 5. Packing configuration of complex 2. Only relevant atoms are drawn for clarity.

X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
35
ꢀ
crystal structures of 4 and 5 are composed of discrete molecules in
which six-coordinated Sn atoms are bonded by two n-butyl groups
and two ligands (L1 and L4). The CeSneC angles of 4 (146.43ꢁ) and 5
(133.80ꢁ) are in the range of 122.6ꢁe156.9ꢁ found for the dio-
rganotin complexes in which the organo substituents neither adopt
cis- nor trans-geometries on the tin atom [32], and the OeSneO
angles of them are 53.50ꢁ [O(5)eSneO(6)], 55.01ꢁ [O(1)eSneO(2)]
for 4 and 56.04ꢁ [O(1)eSn(1)eO(2) and O(1A)eSn(1)eO(2A)] for
5. The carboxylate groups of ligands coordinate with tin in an ani-
sobidentate mode and form two types of SneO bond distances: the
interactions (2.887 A) (significantly shorter than the sum of the van
der Waals radii for tin and oxygen atoms) help the molecules
compose
a
Sn2O2 distannoxane unit [Sn/O(6)/Sn/O(6)
ꢀ
ꢀ
2.632 A ꢂ 2.887 A] which is highly distorted as evidenced by the
difference in OeSneO bond angle 63.24ꢁ and SneOeSn bond angle
116.78ꢁ. Through these Sn/O interactions, the chains build a 2D
network. Considering the above, the coordination geometry of tin
atom is best described as a skew-pentagonal bipyramid.
Intermolecular H-bonds also help the molecules form a 3D ar-
chitecture. As shown in Fig. S2, H(12A) from aromatic ring and O(7)
of amide group are interacted with each other via C(12)eH(12A)/
ꢀ
short SneO distance (2.113e2.140 A) [SneO(1) and SneO(5) for 4;
ꢀ
ꢀ
Sn(1)eO(1) and Sn(1)eO(1A) for 5] and long ones (2.511e2.632 A)
O(7) bonds with reasonable distance 2.47 A. Besides that, C(2)e
ꢀ
ꢀ
[SneO(2) and SneO(6) for 4; Sn(1)eO(2) and Sn(1)eO(2A) for 5].
This coordination mode is also reflected in the disparity of the
associated carboxylate CeO bonds: the CeO bond distances for the
H(2A)/O(2) (2.62 A) and C(16)eH(16A)/O(3) (2.64 A) bonds are
also formed. H(2A) and H(16A) are from the methylene groups. O(2)
is carboxylate oxygen atom and O(3) is from amide group. With
these H-bonds, the molecular structure can be described as a 3D
architecture with large cavities occupied by free toluene molecules
(Fig. S2).
ꢀ
weakly coordinated oxygen atoms (1.229e1.245 A) are shorter than
ꢀ
the ones with the strong bonds (1.281e1.291 A). This type of
structure and relevant bond lengths and angles are close to the
complexes reported in the literature [6,10,11]. The geometry of tin
atom in both 4 and 5 is best described as a skew-trapezoidal
bipyramid or bicapped tetrahedron. For the flexibility of L1 in 4,
two naphthalene rings in the structure are almost paralleled with
For complex 5, intermolecular
aromatic rings of ligands make the structure demonstrate as a zig-
zag chain (Fig. S3). Except that, the hydrogen bonds C(6)eH(6A)/
O(4) (2.575 A) and C(7)eH(7A)/O(4) (2.695 A) extend the chains
into different directions around. H(6A) and H(7A) are from the ar-
omatic ring of ligand while O(4) is from the amide group. With the
connections mentioned above, the molecules form a kind of
intermolecular cavity (A) [Fig. 8(a)] and present a 3D architecture as
it can be seen in Fig. 8(b). Fig. 8(c) shows the 3D pack configuration
on ac-plane.
p/p interactions between the
ꢀ
ꢀ
the dihedral angle 3.50ꢁ and distance 6.86 A, which makes the
ꢀ
molecule demonstrate as an “U” shape. While L4 in 5 is rigid, this
leads to the small radian in the line of the molecule structure.
In 4, intermolecular p/p interactions as shown in Fig. S1 arrange
the molecules staggered up and down and link into a 1D infinite
chain. In Fig. 7, an extensive set of weak intermolecular Sn/O(6)
Fig. 7. 2D structure of 4. Butyl groups and H atoms are omitted for clarity.

36
X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
Fig. 8. 3D structure of 5. Only relevant C and H atoms are drawn for clarity.
3.3.3. Crystal structures of 6 and 7
the center Sn2O2 ring is bound by three Bu2Sn units. Therefore
these oxygen atoms are three-coordinated and adopt planar
trigonal geometry. Tin atoms in 6 and 7 are all pentacoordinated
coordinated by three oxygen and two carbon atoms of butyl
groups. They can be divided into two types in each of the com-
plexes by chemical environments. In 6, three O atoms connected
The crystal structures of 6 and 7 are shown in Fig. 9. Selected
bond lengths and angles are listed in Table 4. The dominating
structural form of 6 and 7 is dimeric tetraorganodistannoxane
which is composed of a central planar (Bu2Sn)2O2 four-membered
ring and two peripheral Bu2Sn units. Each bridging oxygen atom of

X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
37
from different carboxylate groups and the other is m3-O atom [O(1)
and O(1A)]. While Sn(2) and Sn(2A) are chelated with two m3-O
and a carboxylate O atom. The SneO bonds formed are among
ꢀ
2.008(6)e2.261(2) A. Together with two bonds to butyl groups, the
Sn atoms can be viewed as a distorted trigonal bipyramid with the
axial angles OeSneO [6: 147.3(3)ꢁ and 152.7(3)ꢁ; 7: 168.67(9)ꢁ and
170.43(10)ꢁ]. Besides the bonds mentioned above, intramolecular
ꢀ
Sn/O bonds [6: Sn(1)/O(2) and Sn(1A)/O(2A) (2.943 A); 7:
ꢀ
Sn(2)/O(2) and Sn(2A)/O(2A) (2.743 A)] should be taken into
account. Thus the coordination of Sn(1) in 6 and Sn(2) in 7 can also
be described as distorted tetragonal bipyramid with four equato-
rial oxygen atoms and two axial carbon atoms and the stannoxane
framework in the constructures (Sn4O4) of 6 and 7 seems like
a short “ladder”. All the relevant bond lengths and distances are
similar to those found in this type of structures [12,22,23]. The
molecular structure of 6 can be revealed as a “ladder” skeleton
enclosed by two invert ligands L2 with monodentate chelating,
while the skeleton in 7 is rounded by four ligands L5 extending
into two flanks adopting mono- and bi-dentate coordination
modes alternately.
Comparing the structures of 6 and 7, two more ligands chelate
with the molecular center frame employing bidentate coordination
mode. This is due to the constructures of ligands L2 and L5. Meta-
benzo[de]isoquinoline-1,3-dione group of L2 obstructs other ligand
to coordinate with Sn(2) and Sn(2A) in 6, while the para of L5
without this hindrance permits more coordination. In 7, two
bidentate ligands make the distances between the coordinated tin
atoms [Sn(1) and Sn(2A); Sn(1A) and Sn(2)] shorter than those of
Sn(1)/Sn(2) and Sn(1A)/Sn(2A) in 6. Consequently the ‘ladder’
structure of 7 is more distorted. Distances of Sn(2)/O(2) and
Sn(2A)/O(2A) are beyond the rage of SneO covalent bond length,
which relieves the tensile force of the stannoxane center unite. For
this reason, the CeSneC angles across the stannoxane center in 7
[139.38(18)ꢁ and 149.61(18)ꢁ] are larger than those in 6 [129.2(5)ꢁ
and 134.7(7)ꢁ].
Fig. 9. The molecular structures of complexes 6 and 7.
with Sn(1) and Sn(1A) are m3-O from Sn2O2 moiety, m2-O [O(6) and
O(6A)] and carboxylate O atom respectively. While for Sn(2) and
Sn(2A), two of the three O atoms are m3-O of Sn2O2 ring and the
other one is m2-O atom. In 7, for Sn(1) and Sn(1A), two of them are
Table 4
ꢁ
ꢀ
Selected bond lengths (A) and angles ( ) for 6 and 7.
Complex 6
Bond lengths
Complexes 6 and 7 have one-dimensional chain structure
(Fig. 10) linked by hydrogen bonds [6: C(14)eH(14A)/O(2)
Sn(1)eO(5)
Sn(1)eO(1)
Sn(2)eO(5)
Sn(1)eC(21)
Sn(2)eC(35)
Bond angles
2.008(6)
2.154(7)
2.126(6)
2.145(15)
2.117(13)
Sn(1)eO(6)#1
O(5)eSn(2)#1
Sn(2)eO(6)
Sn(1)eC(25)
Sn(2)eC(31)
2.237(8)
2.043(6)
2.146(8)
2.086(14)
2.084(13)
ꢀ
ꢀ
(2.630 A); 7: C(3)eH(3A)/O(8) (2.680 A)]. H(14A) of 6 and H(3A)
in 7 are from the aromatic rings. O(2) is carboxylate oxygen and
O(8) is derived from the amide group. Intermolecular rings (6: A; 7:
B) are constructed by these bonds. A is 40-membered and B is 44-
membered. In Fig. S4, it can be seen that cavity B is like a channel
made up by four L5 ligands which are pairwise paralleled. Two free
O(5)eSn(1)eO(1)
O(1)eSn(1)eO(6)#1
O(5)#1eSn(2)eO(6)
O(5)eSn(1)eC(25)
C(25)eSn(1)eO(1)
C(25)eSn(1)eO(6)#1
O(5)#1eSn(2)eC(31)
C(31)eSn(2)eO(5)
C(31)eSn(2)eO(6)
C(25)eSn(1)eC(21)
80.6(3)
152.7(3)
73.5(3)
113.0(6)
97.7(6)
94.6(5)
116.2(4)
96.1(4)
96.8(4)
134.7(7)
O(5)eSn(1)eO(6)#1
O(5)#1eSn(2)eO(5)
O(5)eSn(2)eO(6)
O(5)eSn(1)eC(21)
C(21)eSn(1)eO(1)
C(21)eSn(1)eO(6)#1
O(5)#1eSn(2)eC(35)
C(35)eSn(2)eO(5)
C(35)eSn(2)eO(6)
C(31)eSn(2)eC(35)
72.2(3)
73.9(3)
147.3(3)
111.4(4)
97.4(5)
91.0(5)
114.5(5)
96.4(5)
98.4(5)
129.2(5)
toluene molecules are located in B stabilized by the
p/p in-
teractions with the aromatic groups of ligands L5.
On the both sides of 1D chain of complex 6, H(11A), H(14A),
H(15A) of aromatic groups and O(4), O(3) from amide groups are
ꢀ
connected by the H-bonds C(11)eH(11A)/O(4) (2.522 A), C(14)e
ꢀ
ꢀ
H(14A)/O(3) (2.663 A) and C(15)eH(15A)/O(3) (2.336 A)
(Fig. S5). These bonds extend the chain into four different directions
and help to build the 3D architecture of 6 which is filled with large
Complex 7
Bond lengths
ꢀ
cavities (Fig. 11). For 7, C(24)eH(24A)/O(6) (2.612 A) and C(26)e
H(26A)/O(6) (2.468 A) link the chains into a 2D network, and
Sn(1)eO(1)
Sn(1)eO(2)
2.018(2)
2.171(3)
2.219(3)
2.045(2)
2.184(2)
Sn(2)eO(4)
Sn(1)eC(41)
Sn(1)eC(51)
Sn(2)eC(71)
Sn(2)eC(61)
2.261(2)
2.124(4)
2.122(5)
2.143(4)
2.125(4)
ꢀ
Sn(1)eO(5)#1
Sn(2)eO(1)#1
intermolecular irregular rings C and D are formed as shown in
Fig. S6. H(24A), H(26A) are from aromatic rings of ligands and O(6)
is from amide group.
Sn(2)eO(1)
Bond angles
It can be seen from complexes 1 and 4, 2 and 6 that, even if
complexes contain the same ligands and obtained under reflux in
the same solvent, different organotins will lead different molecular
structures. Simple monomers 1 and 2 are obtained when ligands L1
and L2 react with triphenyltin hydroxide, while bicapped structure
4 and “ladder” like architecture 6 are built when they coordinate
with dibutyltin oxide. And the relevant SneO bonds in 1 and 2
(triphenyltin carboxylate) are shorter than those in 4 and 6 (dibu-
tyltin carboxylate).
O(1)eSn(1)eO(2)
O(1)eSn(1)eO(5)#1
O(2)eSn(1)eO(5)#1
O(1)#1eSn(2)eO(1)
O(1)#1eSn(2)eO(4)
O(1)eSn(2)eO(4)
O(1)eSn(1)eC(51)
O(1)eSn(1)eC(41)
C(51)eSn(1)eO(2)
C(61)eSn(2)eO(4)
79.89(10)
90.67(10)
170.43(10)
76.37(10)
92.31(9)
168.67(9)
112.01(16)
108.51(14)
94.2(2)
C(41)eSn(1)eO(2)
C(51)eSn(1)eO(5)#1
C(41)eSn(1)eO(5)#1
O(1)#1eSn(2)eC(61)
O(1)#1eSn(2)eC(71)
C(61)eSn(2)eO(1)
C(71)eSn(2)eO(4)
C(71)eSn(2)eO(1)
C(61)eSn(2)eC(71)
C(51)eSn(1)eC(41)
95.51(14)
87.9(2)
88.91(14)
104.03(14)
106.35(15)
93.89(14)
89.99(13)
93.64(13)
149.61(18)
139.38(18)
88.32(14)

38
X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
Fig. 10. 1D chain structures of complexes 6 and 7. Butyl groups and part of H atoms are omitted for clarity.
Fig. 11. 3D structure of 6. Only relevant C and H atoms are drawn for clarity.
4. Conclusion
charge from The Cambridge Crystallographic Data Centre via www.
cccdc.cam.ac.uk/data-request/cif.
In summary, a series of organotin(IV) carboxylates complexes
based on amide carboxylic acids have been synthesized. They
demonstrate diverse molecular structures and possess esthetic
supramolecular architectures which supplement the group of
organotin carboxylate to help us know better.
Appendix B. Supplementary data
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.jorganchem.2013.
01.017.
Acknowledgments
References
We acknowledged the Postdoctoral Science Foundation P.R.
China (No. 2005038561).
[1] C. Ma, Q. Wang, R. Zhang, Inorg. Chem. 47 (2008) 7060e7061.
[2] M. Gielen, M. Biesemans, R. Willem, Appl. Organomet. Chem. 19 (2005)
440e450.
[3] G. Zheng, J. Ma, Z. Su, L. Yan, J. Yang, Y. Li, J. Liu, Angew. Chem., Int. Ed. 43
(2004) 2409e2411.
Appendix A. Supplementary material
[4] M. Gielen, M. Biesemans, R. Willem, E.R.T. Tiekink, Eur. J. Inorg. Chem. 3 (2004)
445e451.
[5] V. Chandrasekhar, K. Gopal, P. Thilagar, Acc. Chem. Res. 40 (2007) 420e434.
[6] S. Shahzadi, S. Ali, J. Iran. Chem. Soc. 5 (2008) 16e28.
[7] C. Ma, S. Zhang, R. Zhang, J. Organomet. Chem. 701 (2012) 43e50.
CCDC 916676, 850159, 827596, 916677, 835953, 916678 and
827594 for complexes 1e7 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of

X. Xiao et al. / Journal of Organometallic Chemistry 729 (2013) 28e39
39
[8] X. Xiao, D. Du, M. Tian, X. Han, J. Liang, D. Zhu, L. Xu, J. Organomet. Chem. 715
(2012) 54e63.
[22] M. Sun, B. Ruan, Q. Zhang, Z. Liu, S. Li, J. Wu, B. Jin, J. Yang, S. Zhang, Y. Tian,
J. Organomet. Chem. 696 (2011) 3180e3185.
[9] V. Chandrasekhar, C. Mohapatra, R.J. Butcher, Cryst. Growth Des. 12 (2012)
3285e3295.
[23] M. Iqbal, S. Ali, N. Muhammad, M. Parvez, P. Langer, A. Villinger, J. Organomet.
Chem. 723 (2013) 214e223.
[10] R. Zhang, J. Sun, C. Ma, J. Organomet. Chem. 690 (2005) 4366e4372.
[11] H. Yin, H. Liu, M. Hong, J. Organomet. Chem. 713 (2012) 11e19.
[12] E.R.T. Tiekink, Appl. Organomet. Chem. 5 (1991) 1e23.
[13] D.D. Perrin, W.L.F. Armarego, D.R. Perrin, Purification of Laboratory Chemicals,
second ed., Pergamon, Oxford, 1980.
[24] F. Benetollo, G.G. Lobbia, M. Mancini, M. Pellei, C. Santini, J. Organomet. Chem.
690 (2005) 1994e2001.
[25] M. Hanif, M. Hussain, S. Alia, M.H. Bhatti, M.S. Ahmed, B. Mirza, H.S. Evans,
Polyhedron 29 (2010) 613e619.
[26] E. Navarro, C. Alemán, J. Puiggalí, Macromolecules 31 (1998) 408e416.
[27] T.P. Lockhart, W.F. Manders, E.M. Holt, J. Am. Chem. Soc. 108 (1986)
6611e6616.
[14] G.M. Sheldrick, SHELXS-97, A Program for Automatic Solution of Crystal
Structure, University of Gottingen, Germany, 1997.
[15] G.M. Sheldrick, SHELXL-97,
A
Program for Crystal Structure Refinement,
[28] J.F. Vollano, R.O. Day, D.N. Rau, V. Chandrasekhar, R.R. Holmes, Inorg. Chem. 23
(1984) 3153e3160.
University of Gottingen, Germany, 1997.
[16] D. Singh, J.B. Baruah, Tetrahedron Lett. 49 (2008) 4374e4377.
[17] D. Du, Z. Jiang, C. Liu, A.M. Sakho, D. Zhu, L. Xu, J. Organomet. Chem. 696
(2011) 2549e2558.
[18] W. Li, D. Du, S. Liu, C. Zhu, A.M. Sakho, D. Zhu, L. Xu, J. Organomet. Chem. 695
(2010) 2153e2159.
[19] H.D. Yin, C. Wang, C. Ma, D. Wang, J. Organomet. Chem. 689 (2004) 246e251.
[20] R. Zhang, Q. Zhang, Y. Shi, C. Ma, J. Organomet. Chem. 691 (2006) 1668e1672.
[21] H. Yin, M. Hong, M. Yang, J. Cui, J. Mol. Struct. 984 (2010) 383e388.
[29] K.C. Molloy, T.G. Purcell, K. Quill, I.W. Nowell, J. Organomet. Chem. 267 (1984)
237e247.
[30] A.R. Forrester, S.J. Garden, R.A. Howie, J.L. Wardell, J. Chem. Soc., Dalton Trans.
17 (1992) 2615e2621.
[31] V. Chandrasekhar, K. Gopal, S. Nagendran, P. Singh, A. Steiner, S. Zacchini,
J.F. Bickley, Chem.dEur. J. 11 (2005) 5437e5448.
[32] S.W. Ng, C. Wei, V.G.K. Das, E.R.T. Tiekink, J. Organomet. Chem. 334 (1987)
295e305.