Synthesis and spectroscopic properties of diorganotin(IV) complexes of 2-quinaldate and crystal structures of (4-FC6H4CH 2)2Sn(2-quin)2 · 2CH3CN and {[(2-ClC6H4CH2)2SnCl(2-quin)] 2 · CH3OH}n

Article abstract of DOI:10.1016/j.jorganchem.2005.03.046

Twelve diorganotin(IV) complexes of 2-quinaldate R₂Sn(2-quin) ₂ and R₂SnCl(2-quin) have been synthesized by dealkyltion reactions of 2-quinaldic acid (2-quinH) with (R₃Sn)₂O (R = PhCH₂ 1, 2-ClC₆H₄CH₂ 2, 2-FC ₆H₄CH₂ 3, 4-FC₆H₄CH ₂ 4, 4-CNC₆H₄CH₂ 5, Ph 6, 2,4-Cl₂C₆H₃CH₂ 7) and R ₃SnCl (R = 2-ClC₆H₄CH₂ 8, 4-ClC ₆H₄CH₂ 9, 2-FC₆H₄CH ₂ 10, 4-FC₆H₄CH₂ 11, PhCH ₂ 12), and all the complexes have been characterized by elemental analysis, IR and multinuclear NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopies. The structures of (4-FC₆H ₄CH₂)₂Sn(2-quin)₂ · 2CH ₃CN (4) and {[(2-ClC₆H₄CH₂) ₂Sn(2-quin)Cl]₂ · CH₃OH}_n (8) have been determined by X-ray diffraction. Studies show that complex 4 is a monomer with the central tin atom six-coordinated in a skew-trapezoidal- bipyramidal geometry and complex 8 is a one-dimensional polymer with the tin atom six-coordinated. Studies also show that the nitrogen atoms of the 2-quin ligand are coordinating to the tin atoms for all of the 12 complexes.

Full text of DOI:10.1016/j.jorganchem.2005.03.046

Journal of Organometallic Chemistry 690 (2005) 3111–3117
www.elsevier.com/locate/jorganchem
Synthesis and spectroscopic properties of diorganotin(IV)
complexes of 2-quinaldate and crystal structures
of (4-FC6H4CH2)2Sn(2-quin)2 Æ 2CH3CN
and {[(2-ClC6H4CH2)2SnCl(2-quin)]2 Æ CH3OH}n
*
Han Dong Yin , Qi Bao Wang, Sheng Cai Xue
Department of Chemistry, Liaocheng University, Liaocheng 252059, China
Received 14 February 2005; revised 25 March 2005; accepted 25 March 2005
Available online 13 May 2005
Abstract
Twelve diorganotin(IV) complexes of 2-quinaldate R2Sn(2-quin)2 and R2SnCl(2-quin) have been synthesized by dealkyltion reac-
tions of 2-quinaldic acid (2-quinH) with (R3Sn)2O (R = PhCH2 1, 2-ClC6H4CH2 2, 2-FC6H4CH2 3, 4-FC6H4CH2 4, 4-CNC6H4CH2
5, Ph 6, 2,4-Cl2C6H3CH2 7) and R3SnCl (R = 2-ClC6H4CH2 8, 4-ClC6H4CH2 9, 2-FC6H4CH2 10, 4-FC6H4CH2 11, PhCH2 12), and
all the complexes have been characterized by elemental analysis, IR and multinuclear NMR (1H, 13C, 119Sn) spectroscopies. The
structures of (4-FC6H4CH2)2Sn(2-quin)2 Æ 2CH3CN (4) and {[(2-ClC6H4CH2)2Sn(2-quin)Cl]2 Æ CH3OH}n (8) have been determined
by X-ray diffraction. Studies show that complex 4 is a monomer with the central tin atom six-coordinated in a skew-trapezoidal-
bipyramidal geometry and complex 8 is a one-dimensional polymer with the tin atom six-coordinated. Studies also show that
the nitrogen atoms of the 2-quin ligand are coordinating to the tin atoms for all of the 12 complexes.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: Organotin complex; 2-Quinaldic acid; Synthesis; Crystal structure
1. Introduction
potential donor atom (e.g., N, O and S) available for
coordinating to tin, and that have led to new structural
modes of the organotin derivatives. We have previously
reported several unexpected products of organotin(IV)
complexes with pyridinylcarboxylic acids [14,15], which
can be assigned to dealkylation reactions as can be seen
in the literature [16–19]. As an extension of this study,
we synthesized another 12 diorganotin complexes of 2-
quinaldate by two quite different methods. Studies show
that whichever reaction we selected the final products
are diorganotin complexes of 2-quinaldate, which
strongly indicates that the steric bulk of the ligand 2-
quin plays a significant role in controlling the coordina-
tion geometry at tin regardless of the nature of the
tin-bound R groups. All the complexes have been char-
acterized by elemental analyses, IR and NMR (1H, 13C
Organotin(IV) complexes are widely used as biocides,
fungicides and as homogeneous catalysts in industry [1–
5]. Recently, pharmaceutical properties of organotin
complexes with carboxylic acid have been investigated
for their antitumor activity [6–9]. In general, the biocidal
activity of organotin complexes is greatly influenced by
the structure of the complex and the coordination num-
ber at the tin atoms [8–12]. Previous papers [5,13–15]
have reported the synthesis and X-ray crystal structure
determinations of several organotin complexes with car-
boxylic acids in which the R0 group has an additional
*
Corresponding author. Tel.:/fax: +866358239121.
E-mail address: handongyin@sohu.com (H.D. Yin).
0022-328X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.03.046

3112
H.D. Yin et al. / Journal of Organometallic Chemistry 690 (2005) 3111–3117
and 119Sn) spectra, and the results of this study are re-
ported herein.
ꢀ278. IR (KBr): tasym(OCO), 1671 cmꢀ1; tsym(OCO),
1329 cmꢀ1; t(Sn–C), 545 cmꢀ1; t(Sn–N), 474 cmꢀ1
;
t(Sn–O), 452 cmꢀ1
.
2. Experimental
2.2.3. (2-FC6H4CH2)2Sn(2-quin)2 (3)
The synthesis procedure of complex 3 was similar to
complex 1. The resulting solid was recrystallized from
dichloromethane and n-hexane to give colorless crystals.
Yield: 84.3%, m.p. 189–191 °C. Anal. Calc. for
C34H24F2N2O4Sn: C, 59.94; H, 3.53; N, 4.13; Sn,
17.42. Found: C, 60.21; H, 3.61; N, 4.08; Sn, 17.50%.
1H NMR (CDCl3): d 8.78 (d, 2H, H-3), 8.45 (d, 2H,
H-4), 8.29 (d, 2H, H-9), 8.07 (d, 2H, H-6), 7.96 (dd,
2H, H-8), 7.80 (dd, 2H, H-7), 6.210–7.46 (m, 8H, Ar–
H), 2.98 (s, 4H, JSn–H = 81 Hz, SnCH2). 13C NMR
(CDCl3): d 172 (COO), 152, 147, 136, 131, 129, 128,
126, 126, 125, 124, 123, 122, 121, 119, 113 (Ar–C), 33
2.1. Materials and methods
Triorganotin(IV) chloride and bis(triorganotin)(IV)
oxide were prepared by the methods described in the lit-
erature [20]. The melting points were obtained with Kol-
fer micro melting point apparatus and uncorrected. IR
spectra were recorded on a Nicolet-460 spectrophotom-
eter using KBr discs and sodium chloride optics. 1H, 13
C
and 119Sn NMR spectra were recorded on a Mercury
Plus-400 NMR spectrometer, chemical shifts were given
in ppm relative to Me4Si and Me4Sn in CDCl3 solvent.
Elemental analyses were performed in a PE-2400 II ele-
mental analyzer.
1
(CH2Ar, JSn–C = 763 Hz). 119Sn NMR (CDCl3): d
ꢀ276. IR (KBr): tasym(OCO), 1666 cmꢀ1; tsym(OCO),
1325 cmꢀ1; t(Sn–C), 523 cmꢀ1; t(Sn–N), 498 cmꢀ1
;
2.2. Syntheses of complexes
t(Sn–O), 459 cmꢀ1
.
2.2.1. (PhCH2)2Sn(2-quin)2 (1)
2.2.4. (4-FC6H4CH2)2Sn(2-quin)2 Æ 2CH3CN (4)
To a stirred solution of 2-quinaldic acid (0.692 g, 4.0
mmol) in benzene was added [(PhCH2)3Sn]2O (0.799 g,
1.0 mmol). The mixture was heated under reflux for
6–7 h and the solvent was removed by evaporation in
vacuo. The crude adduct was recrystallized from dichlo-
romethane and n-hexane to give colorless crystals. Yield:
87.52%, m.p. 183–185 °C. Anal. Calc. for C34H26N2-
O4Sn: C, 63.28; H, 4.06; N, 4.34; Sn, 18.40. Found: C,
The synthesis procedure of complex 4 was similar to
complex 1. The resulting solid was recrystallized from
acetonitrile to give colorless crystals. Yield: 83.7%,
m.p. 211–213 °C. Anal. Calc. for C38H30F2N4O4Sn: C,
59.79; H, 3.96; N, 7.34; Sn, 15.55. Found: C, 59.56; H,
1
3.88; N, 7.41; Sn, 15.51%. H NMR (CDCl3): d 8.72
(d, 2H, H-3), 8.45 (d, 2H, H-4), 8.30 (t, 2H, H-9), 8.09
(d, 2H, H-6), 8.01 (dd, 2H, H-8), 7.83 (dd, 2H, H-7),
6.24–7.41 (m, 8H, Ar–H), 2.99 (s, 4H, JSn–H = 82 Hz,
SnCH2). 13C NMR (CDCl3): d 174 (COO), 155, 146,
132, 130, 129, 128, 126, 126, 125, 124, 123, 122, 118
1
63.43; H, 4.12; N, 4.31; Sn, 18.37%. H NMR (CDCl3):
d 8.77 (d, 2H, H-3), 8.46 (d, 2H, H-4), 8.27 (d, 2H, H-9),
8.11 (d, 2H, H-6), 7.98 (dd, 2H, H-8), 7.85 (dd, 2H, H-
7), 6.24-7.25 (m, 10H, Ph–H), 2.96 (s, 4H, JSn–H = 87
Hz, SnCH2). 13C NMR (CDCl3): d 174 (COO), 149,
147, 135, 128, 128, 126, 125, 125, 122, 121, 117, 115,
1
(Ar–C), 32 (CH2Ar, JSn–C = 734 Hz). 119Sn NMR
(CDCl3): d ꢀ273. IR (KBr): tasym(OCO), 1669 cmꢀ1
483 cmꢀ1; t(Sn–O), 455.
;
t
sym(OCO), 1321 cmꢀ1; t(Sn–C), 543 cmꢀ1; t(Sn–N),
1
109 (Ar–C), 30 (CH2Ar, JSn–C = 728 Hz). 119Sn NMR
(CDCl3): d ꢀ262. IR (KBr): tasym(OCO), 1669 cmꢀ1
;
t
sym(OCO), 1321 cmꢀ1; t(Sn–C), 582 cmꢀ1; t(Sn–N),
2.2.5. (4-CNC6H4CH2)2Sn(2-quin)2 (5)
490 cmꢀ1; t(Sn–O), 469 cmꢀ1
.
The synthesis procedure of complex 5 was similar to
complex 1. The resulting solid was recrystallized from
dichloromethane and n-hexane to give colorless crystals.
Yield: 81.9%, m.p. 203–205 °C. Anal. Calc. for
C36H24N4O4Sn: C, 62.19; H, 3.48; N, 8.06; Sn, 17.07.
Found: C, 62.37; H, 3.45; N, 8.11; Sn, 17.22%. 1H
NMR (CDCl3): d 8.79 (d, 2H, H-3), 8.45 (d, 2H, H-4),
8.30 (d, 2H, H-9), 8.09 (d, 2H, H-6), 8.01 (dd, 2H, H-
8), 7.83 (dd, 2H, H-7), 6.24–7.22 (m, 8H, Ar–H), 2.99
(s, 4H, JSn–H = 85 Hz, SnCH2). 13C NMR (CDCl3): d
171 (COO), 152, 137, 131, 130, 129, 128, 126, 126,
125, 124, 123, 122, 118 (Ar–C), 115 (CN), 32 (CH2Ar,
1JSn–C = 739 Hz). 119Sn NMR (CDCl3): d ꢀ289. IR
2.2.2. (2-Cl C6H4CH2)2Sn(2-quin)2 Æ CH2Cl2 (2)
The synthesis procedure of complex 2 was similar to
complex 1. The resulting solid was recrystallized from
dichloromethane and n-hexane to give colorless crystals.
Yield: 78.5%, m.p. 200–202 °C. Anal. Calc. for
C35H26Cl5N2O4Sn: C, 50.37; H, 3.14; N, 3.36; Sn,
14.22. Found: C, 49.86; H, 3.03; N, 3.42; Sn, 14.20%.
1H NMR ( CDCl3): d 8.84 (d, 2H, H-3), 8.44 (d, 2H,
H-4), 8.28 (d, 2H, H-9), 8.04 (d, 2H, H-6), 7.95 (dd,
2H, H-8), 7.78 (dd, 2H, H-7), 6.55–7.45 (m, 8H, Ar–
H), 3.02 (s, 4H, JSn–H = 80 Hz, SnCH2). 13C NMR
(CDCl3): d 172 (COO), 152, 147, 136, 132, 130, 128,
127, 126, 125, 125, 124, 122, 120, 117, 115 (Ar–C), 31
(KBr):
cmꢀ1; t(Sn–C), 538 cmꢀ1; t(Sn–N), 496 cmꢀ1; t(Sn–
O), 455 cmꢀ1
t ; tsym(OCO), 1383
asym(OCO), 1648 cmꢀ1
1
(CH2Ar, JSn–C = 775 Hz). 119Sn NMR (CDCl3): d
.

H.D. Yin et al. / Journal of Organometallic Chemistry 690 (2005) 3111–3117
3113
2.2.6. Ph2Sn(2-quin)2 (6)
from dichloromethane to give colorless crystals. Yield:
70%, m.p. 202–203 Anal. Calc. for
°C.
The synthesis procedure of complex 6 was similar to
complex 1. The resulting solid was recrystallized from
acetonitrile to give colorless crystals. Yield: 87.52%,
m.p. 217–219 °C. Anal. Calc. for C32H22N2O4Sn: C,
62.27; H, 3.59; N, 4.54; Sn, 19.23. Found: C, 62.14; H,
C25H20Cl5NO2Sn: C, 45.33; H, 3.04; N, 2.11; Sn,
17.92. Found: C, 45.28; H, 3.17; N, 2.13; Sn, 17.74%.
1H NMR (CDCl3): 8.50 (1H, d, H-3), 8.45 (1H, d, H-
4), 8.20 (1H, d, H-9), 7.90 (d, 2H, H-6), 7.81 (dd, 2H,
H-8), 7.73 (dd, 2H, H-7), 6.77-7.46 (8H, m, Ar–H),
3.13 (s, 4H, JSn–H = 85 Hz, SnCH2). 13C NMR (CDCl3):
d 173 (COO), 152, 147, 132, 134, 129, 127, 126, 125, 124,
122, 122, 121, 118 (Ar–C), 31 (CH2Ar, 1JSn–C = 680 Hz).
1
3.67; N, 4.43; Sn, 19.28%. H NMR (CDCl3): d 8.81
(d, 2H, H-3), 8.57 (d, 2H, H-4), 8.32 (d, 2H, H-9),
8.21 (d, 2H, H-6), 8.01 (dd, 2H, H-8), 7.93 (dd, 2H,
H-7), 6.80–7.67 (m, 10H, Ph–H). 13C NMR (CDCl3):
d 172 (COO), 148, 147, 135, 130, 130, 128, 126, 125,
119Sn NMR d ꢀ295. IR (KBr): tas(OCO), 1615 cmꢀ1
cmꢀ1; t(Sn–O), 457 cmꢀ1
.
;
125, 123, 122, 121, 117 (Ar–C, JSn–C = 631 Hz). 119Sn
ts(OCO), 1427 cmꢀ1; t(Sn–C), 548 cmꢀ1; t(Sn–N), 480
1
NMR (CDCl3): d ꢀ312. IR (KBr): tasym(OCO), 1667
cmꢀ1; tsym(OCO), 1335 cmꢀ1; t(Sn–C), 496 cmꢀ1
;
t(Sn–N), 483 cmꢀ1; t(Sn–O), 457 cmꢀ1
.
2.2.10. (2-FC6H4CH2)2SnCl(2-quin) (10)
The method of synthesis of the complex 10 was sim-
ilar as described for 8. The resulting solid was recrystal-
lized from dichloromethane and n-hexane to give
colorless crystals. Yield: 76.8%, m.p. 183–185 °C. Anal.
Calc. for C24H18ClF2NO2Sn: C, 52.94; H, 3.33; N, 2.57;
Sn, 21.80. Found: C, 53.26; H, 3.41; N, 2.51; Sn, 21.96%.
1H NMR (CDCl3): d 8.58 (1H, d, H-3), 8.49 (1H, d, H-
4), 8.18 (1H, d, H-9), 7.90 (d, 2H, H-6), 7.85 (dd, 2H, H-
8), 7.70 (dd, 2H, H-7), 6.34–7.43 (m, 8H, Ar–H), 3.15 (s,
4H, JSn–H = 88 Hz, SnCH2). 13C NMR (CDCl3): d 173
(COO), 152, 147, 136, 131, 130, 128, 126, 126, 125,
124, 123, 122, 121, 119, 113 (Ar–C), 32 (CH2Ar,
1JSn–C = 682 Hz). 119Sn NMR (CDCl3): d ꢀ296. IR (KBr):
2.2.7. (2,4-Cl2C6H3CH2)2Sn(2-quin)2 (7)
The synthesis procedure of complex 7 was similar to
complex 1. The resulting solid was recrystallized from
acetonitrile to give colorless crystals. Yield: 84.3%,
m.p. 174–176 °C. Anal. Calc. for C34H22Cl4N2O4Sn:
C, 52.15; H, 2.83; N, 3.58; Sn, 15.16. Found: C, 52.39;
H, 2.96; N, 3.47; Sn, 15.31%. 1H NMR (CDCl3): d
8.77 (d, 2H, H-3), 8.52 (d, 2H, H-4), 8.33 (d, 2H, H-
9), 8.15 (d, 2H, H-6), 7.95 (dd, 2H, H-8), 7.89 (dd, 2H,
H-7), 6.53–7.62 (m, 6H, Ar–H), 2.98 (s, 4H, JSn–H = 81
Hz, SnCH2). 13C NMR (CDCl3): d 172 (COO), 150,
147, 136, 132, 130, 128, 127, 126, 125, 125, 124, 122,
1
120, 120, 118 (Ar–C), 34 (CH2Ar, JSn–C = 784 Hz).
119Sn NMR (CDCl3): d ꢀ284. IR (KBr): tasym(OCO),
t
asym(OCO), 1610 cmꢀ1; tsym(OCO), 1436 cmꢀ1; t(Sn–C),
536 cmꢀ1; t(Sn–N), 493 cmꢀ1; t(Sn–O), 451 cmꢀ1
.
1671 cmꢀ1; tsym(OCO), 1347 cmꢀ1; t(Sn–C), 573 cmꢀ1
;
t(Sn–N), 486 cmꢀ1; t(Sn–O), 463 cmꢀ1
.
2.2.11. (4-FC6H4CH2)2SnCl(2-quin) (11)
The method of synthesis of the complex 11 was similar
as described for 8. The resulting solid was recrystallized
from acetonitrile to give colorless crystals. Yield: 80.3%,
m.p. 193–195 °C. Anal. Calc. for C24H18ClF2NO2Sn: C,
52.94; H, 3.33; N, 2.57; Sn, 21.80. Found: C, 52.87; H,
2.2.8. {[(2-ClC6H4CH2)2SnCl(2-quin)]2 Æ CH3OH}n (8)
To a stirred solution of 2-quinaldic acid (0.173 g, 1.0
mmol) and Et3N (1.2 mmol) in benzene was added (2-
ClC6H4CH2)3SnCl (0.531 g, 1.0 mmol). The mixture
was heated under reflux for 1.5 h and the solvent was re-
moved by evaporation in vacuo. The crude adduct was
recrystallized from methanol. Yield: 67.1%, m.p. 179–
181 °C. Anal. Calc. for C49H40Cl6N2O5Sn2: C, 49.58;
H, 3.40; N, 2.36; Sn, 20.00. Found: C, 49.42; H, 3.37;
1
3.40; N, 2.63; Sn, 21.59%. H NMR (CDCl3): d 8.61
(1H, d, H-3), 8.45 (1H, d, H-4), 8.21 (1H, d, H-9), 7.93
(d, 2H, H-6), 7.85 (dd, 2H, H-8), 7.68 (dd, 2H, H-7),
6.27–7.43 (m, 8H, Ar–H), 3.02 (s, 4H, JSn–H = 89 Hz,
SnCH2). 13C NMR (CDCl3): d 173 (COO), 153, 147,
135, 131, 129, 128, 126, 126, 125, 124, 123, 122, 118
1
N, 2.41; Sn, 20.14%. H NMR (CDCl3): d 8.49 (d, 2H,
1
H-3), 8.41 (d, 2H, H-4), 8.10 (d, 2H, H-9), 7.85 (d,
2H, H-6), 7.76 (dd, 2H, H-8), 7.68 (dd, 2H, H-7),
6.87–7.43 (m, 8H, Ar–H), 3.12 (s, 4H, JSn–H = 88 Hz,
SnCH2). 13C NMR (CDCl3): d 173 (COO), 152, 147,
136, 131, 129, 128, 126, 126, 125, 124, 122, 122, 121,
(Ar–C), 32 (CH2Ar, JSn–C = 672 Hz). 119Sn NMR
(CDCl3): d ꢀ283. IR (KBr): tasym(OCO), 1617 cmꢀ1
486 cmꢀ1; t(Sn–O), 450.
;
t
sym(OCO), 1425 cmꢀ1; t(Sn–C), 538 cmꢀ1; t(Sn–N),
1
120, 118 (Ar–C), 31 (CH2Ar, JSn–C = 697 Hz). 119Sn
2.2.12. (PhCH2)2SnCl(2-quin) (12)
NMR (CDCl3): d ꢀ297. IR (KBr): tasym(OCO), 1625
The method of synthesis of the complex 12 was sim-
ilar as described for 8. The resulting solid was recrystal-
lized from acetonitrile to give colorless crystals. Yield:
80.5%, m.p. 187–188 °C. Anal. Calc. for C24H20Cl-
NO2Sn: C, 56.68; H, 3.96; N, 2.75; Sn, 23.34. Found:
C, 56.55; H, 4.02; N, 2.60; Sn, 23.61%. 1H NMR
(CDCl3): d 8.69 (1H, d, H-3), 8.46 (1H, d, H-4), 8.21
cmꢀ1; tsym(OCO), 1454 cmꢀ1; (Sn–C), 559 cmꢀ1; t(Sn–
N), 499 cmꢀ1; t(Sn–O), 453 cmꢀ1
.
2.2.9. (4-ClC6H4CH2)2SnCl(2-quin) Æ CH2Cl2 (9)
The method of synthesis of the complex 9 was similar
as described for 8. The resulting solid was recrystallized

3114
H.D. Yin et al. / Journal of Organometallic Chemistry 690 (2005) 3111–3117
Table 1
Crystallographic data of complexes 4 and 8
occurs and as a result we have obtained 12 diorgano-
tin(IV) complexes of 2-quinaldate. We assumed that it
may result from the steric bulk of the 2-quin ligand as
have studied in the previous report [14–19], in order to
confirm our assumption we have done further research
by devising another reaction shown in Scheme 1. Studies
show that whichever reaction we selected the final prod-
ucts are diorganotin complexes of 2-quinaldate, which
strongly indicates that the coordination number at tin
is dominated by the 2-quin ligand. And studies also
show that the structure of the molecule have something
to do with the reaction conditions and tin-bound R
groups. The existence of H2O or Et3N Æ HCl facilitates
the dealkyltion reaction. Based on these studies, we
raised possible mechanisms for all of the 12 complexes,
which are shown in Scheme 1.
4
6
Empirical formula
M
C38H30F2N4O4Sn C49H40Cl6N2O5Sn2
1186.91
293(2)
763.35
298(2)
T (K)
Crystal system
Space group
Unit cell dimensions
Monoclinic
P21/c
Monoclinic
P21/n
˚
a (A)
10.071(5)
23.682(13)
14.626(8)
99.912(7)
3436(3)
4
12.613(13)
20.10(2)
20.33(2)
103.865(17)
5005(9)
4
˚
b (A)
˚
c (A)
b (°)
3)
˚
V (A
Z
Dcalc (Mg mꢀ3
F(000)
l (mmꢀ1
)
1.475
1544
0.801
1.575
2360
)
1.365
24414
Reflections collected
Unique data
Data/restraints/parameters 6057/18/466
17790
6057
8422
8422/134/589
0.6046, 0.5428
3.2. IR and NMR studies
Maximum/minimum
transmission
GOF
0.7561, 0.6763
The infrared spectra of diorganotin(IV) complexes
with carboxylic acid have been recorded and some
important assignments are shown above. The Dm (mas
(CO2) ꢀ ms(CO2)) value is used to determine the nature
of bonding of carboxylate to tin(IV) complexes accord-
ing to the previous report [21]. It is generally believed
that the difference in Dm between asymmetric masym(CO2)
and symmetric msym(CO2) absorption frequencies below
200 cmꢀ1 for the bidentate carboxylate moiety, but
greater than 200 cmꢀ1 for the unidentate carboxylate
moiety [22]. Study shows that the values of Dm of the
complex 1–7 are between 265 and 348 cmꢀ1 and this
strongly indicate that these complexes adopt unidentate
carboxylate structure [23,24]. The value of Dm of com-
plexes 8–12 are 171–194 cmꢀ1, and this shows that com-
plexes 8–12 adopt the bidentate carboxylate, which
accords with the result of the X-ray diffraction study
for complex 8. Compared with the free ligand the new
occurrence of the bands in the region of 474 and 499
cmꢀ1 for all the 12 complexes were assigned to the Sn–
N vibrations, which provides prove for the existence of
Sn–N bonds for all of the 12 complexes, and the bands
in the region of 450 and 469 cmꢀ1 were assigned to the
Sn–O vibrations according to the literature [14,15].
Chemical shifts d(1H) and d(13C) inherent to ligand
atoms and organic radicals bound to Sn in complexes
1–12 are assigned by comparison with the spectra of
the free ligand, 2-quinaldic acid as well as of the com-
plex [R2SnCl2(2-quin)]ꢀ(HNEt3)+ [24]. Signal integra-
tions indicate the stoichiometry R2Sn(2-quin)2 and
R2SnCl(2-quin).
1.055
0.874
R1, wR2[I > 2r(I)]
R1, wR2 (all data)
Largest difference peak,
0.0348, 0.0778
0.0517, 0.0845
0.358, ꢀ0.811
0.0669, 0.1302
0.1495, 0.1609
0.854, ꢀ0.413
ꢀ3
˚
hole (e A
)
(1H, d, H-9), 7.85 (d, 2H, H-6), 7.72 (dd, 2H, H-8), 7.64
(dd, 2H, H-7), 6.46-7.32 (m, 10H, Ph–H), 2.94 (s, 4H,
JSn–H = 87 Hz, SnCH2). 13C NMR (CDCl3): d 172
(COO), 150, 148, 135, 128, 128, 126, 125, 124, 122,
1
121, 117, 115, 110 (Ar–C), 31 (CH2Ar, JSn–C = 658
Hz). 119Sn NMR (CDCl3): d ꢀ285. IR (KBr): tasym(O-
CO), 1615 cmꢀ1; tsym(OCO), 1430 cmꢀ1; t(Sn–C), 587
cmꢀ1; t(Sn–N), 483 cmꢀ1; t(Sn–O), 465 cmꢀ1
.
2.3. X-ray crystallography
Crystallographic data and refinement details are gi-
ven in Table 1. All X-ray crystallographic data were col-
lected on a Bruker smart-1000 CCD diffractometer with
˚
graphite monochromated Mo Ka (0.71073 A) radiation
and the u–x scan technique. The structures were solved
by direct method and difference Fourier map using
SHELXL-97 program, and refined by full-matrix least-
squares on F2. All non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were located at calcu-
lated positions and refined isotropically.
3. Results and discussion
1
The H NMR of complexes 1–5, and 7–12 show that
3.1. Syntheses
the chemical shifts of the protons of methylene on the
benzyl group exhibit signals about 2.94–3.15 ppm as sin-
gle with 119Sn satellites, the coupling constant JSn–H is
equal 80–89 Hz. The signals at 7.48–8.84 ppm as muti-
pliplicity for all the 12 complexes are assigned to the
We treated (R3Sn)2O and 2-quinH in a 1:2 stoichiom-
etry in benzene and hoped to get triorganotin complexes
of 2-quinaldate. To our surprise, dealkylation reaction

H.D. Yin et al. / Journal of Organometallic Chemistry 690 (2005) 3111–3117
3115
(R3Sn)2O + 2-quinH
R3Sn(2-quin) + H2O
+ RH
R2Sn(OH)(2-quin)
2-quinH
R2Sn(2-quin)2 + H2O
R= PhCH2 1, 2-ClC6H4CH2 2, 2-FC6H4CH2 3, 4-FC6H4CH2 4, 4-CNC6H4CH2 5, Ph 6, 2,4-Cl2C6H3CH2 7;
NEt3
.
(ArCH2)3SnCl + 2-quinH
(ArCH2)3Sn(2-quin) + NEt3 HCl
-ArCH3
(ArCH2)2SnCl(2-quin)
Ar=2-ClC6H4CH2 8, 4-ClC6H4CH2 9, 2-FC6H4CH2 10, 4-FC6H4CH2 11, PhCH2 12
6
4
5
7
8
3
COO
10
N
2
9
1
2-quin
Scheme 1.
protons of 2-quin ligand, which is shifting slightly to the
low field compared with the free ligand.
In the 13C NMR spectra of complexes 1–12, chemical
shifts are similar to the free ligands. The 13C NMR data
show a slightly downfield shift of all carbon resonances
compared with the free ligand in complexes 1–12, which
could be interpreted in terms of Sn–N interactions.
Previous studies show that for most methyl derivatives
there have a relationship between the 1J(119Sn–13C)
values and the Me–Sn–C angle [25,26], on this base we
assumed that there must some relationship between
benzyltin derivatives and the C–Sn–C angle. The
1
sequence of the J(119Sn–13C) values for complexes 1–7
is 7 > 2 ꢁ 3 > 5ꢁ 4 > 1 > 6, which accords to the
sequences of the stereo-constraints, 2,4-Cl2C6H3CH2 >
2-ClC6H4CH2 ꢁ 2-FC6H4CH2 > 4-CNC6H4CH2 ꢁ 4-
FC6H4CH2 > C6H4CH2 > Ph, so does complexes 8–12.
It is reported that in the alkyltin carboxylates, four-
coordinate tin has d(119Sn) values range from +200 to
ꢀ60 ppm, five-coordinate tin from ꢀ90 to ꢀ190 ppm,
and six-coordinate tin from ꢀ200 to ꢀ400 ppm [27].
On this base, the 119Sn NMR values for complexes 1–7
in the region ꢀ262 and ꢀ312 ppm as one broad sharp
signal indicate that in solution the tin atoms of these
complexes are six-coordinate, which suggest that the
Sn–N interaction probably survives in solution as well
in the solid state. The 119Sn NMR values for complexes
8–12 in the region ꢀ283 and ꢀ297 ppm also show that
both the Sn–N interaction and the intermolecular Sn–
O interaction survive in solution. And their structures
are similar to those diorganotin complexes of 2-quinal-
date that have been reported [13].
Fig. 1. Molecular structure of complex 4.
Fig. 2. Molecular structure of complex 8.
dimensional chain work of complex 8 is shown in Fig. 3.
All hydrogen atoms have been omitted for the purpose
of clarity. Tables 2 and 3, respectively, list selected bond
lengths and angles for complexes 4 and 8.
3.3. Structural studies
The crystal structure and unit cell of complexes 4 and
8 are shown in Figs. 1 and 2, respectively, and the one-

3116
H.D. Yin et al. / Journal of Organometallic Chemistry 690 (2005) 3111–3117
mary bonds: two to the p-fluorobenzyl carbon atoms,
and two to the oxygen atoms of two carboxylates. In
addition, there exists a coordination interaction between
tin and nitrogen atoms. The Sn–N bond length 2.516(2)
˚
˚
A for Sn(1)–N(1) and 2.505(3) A for Sn(1)–N(2) is simi-
lar to that of the corresponding distances found in
˚
Me2Sn(2-quin)2 (2.594(3), 2.473(4) A) and Cy2Sn(2-pi-
˚
c)2(OH2) Æ MeOH (2.550(3), 2.495(3) A) [13], it is longer
than that of found in Me2Sn(2-quin)2 showing above,
but it is much shorter than the sum of the van der Waals
Fig. 3. One-dimensional chain work of complex 8.
˚
radii of tin and nitrogen, 3.74 A [28]. The two 2-quin li-
Table 2
gands are bidentate coordinating to the tin atom using
one carboxylate oxygen atom and the nitrogen atom,
thus providing five-membered chelate rings with bite an-
gles of 70.26(9)° for O(1)–Sn(1)–N(1) and 70.99(8)° for
O(3)–Sn(1)–N(2). Thus the geometry at tin becomes
skew-trapezoidal-bipyramidal with two p-fluorobenzyl
carbon atoms in axial sites and two oxygen atoms and
two nitrogen atoms occupying the equatorial position.
The sum of the angles subtended at tin atom in the trigo-
nal plane is 359.96°, so that the Sn(1), O(1), O(3), N(1)
and N(2) atoms are in the same plane, and the mean devi-
˚
Selected bond distances (A) and angles (°) for complex 4
Sn(1)–O(3)
Sn(1)–O(1)
Sn(1)–C(21)
Sn(1)–C(28)
Sn(1)–N(2)
Sn(1)–N(1)
F(1)–C(25)
F(2)–C(32)
2.086(2)
2.090(2)
2.152(3)
2.159(3)
2.505(3)
2.516(2)
1.371(4)
1.368(4)
N(1)–C(2)
N(1)–C(10)
N(2)–C(12)
N(2)–C(20)
O(1)–C(1)
O(2)–C(1)
O(3)–C(11)
1.325(4)
1.366(4)
1.320(4)
1.366(4)
1.292(4)
1.221(4)
1.303(4)
O(3)–Sn(1)–O(1)
O(3)–Sn(1)–C(21)
O(1)–Sn(1)–C(21)
O(3)–Sn(1)–C(28)
O(1)–Sn(1)–C(28)
C(21)–Sn(1)–C(28)
O(3)–Sn(1)–N(2)
O(1)–Sn(1)–N(2)
77.94(9)
103.43(11)
99.80(11)
99.96(12)
101.40(11)
151.15(14)
70.99(8)
C(21)–Sn(1)–N(1)
C(28)–Sn(1)–N(1)
N(2)–Sn(1)–N(1)
C(21)–Sn(1)–N(2)
C(28)–Sn(1)–N(2)
O(3)–Sn(1)–N(1)
O(1)–Sn(1)–N(1)
81.79(10)
87.21(11)
140.77(8)
86.14(11)
85.74(11)
148.19(8)
70.26(9)
˚
ation for these atoms from the plane is 0.0112 A.
Study shows that in this complex there exists intermo-
lecular non-bonding Fꢂ ꢂ ꢂF interaction similar to that of
the Clꢂ ꢂ ꢂCl interaction in our previous report [29]. The
148.89(8)
˚
Fꢂ ꢂ ꢂF bond distance is 2.877 A, which is considerably
shorter than the sum of the van der Waals radii of twice
the fluorin atoms and should be considered as weak
non-bonding interaction [28], thus the complex become
a weakly-bridged one-dimensional chain polymer as
can be seen in Fig. 2.
Table 3
˚
Selected bond distances (A) and angles (°) for complex 8
Sn(1)–O(1)
Sn(1)–C(28)
Sn(1)–C(21)
Sn(1)–O(4A)
Sn(1)–Cl(1)
Sn(1)–N(1)
2.097(6)
2.174(9)
2.177(9)
2.434(7)
2.436(3)
2.462(7)
Sn(2)–O(3)
Sn(2)–C(35)
Sn(2)–C(42)
Sn(2)–N(2)
Sn(2)–O(2)
Sn(2)–Cl(2)
2.107(6)
2.146(9)
2.153(9)
2.394(7)
2.421(7)
2.454(3)
While complex 8 is a polymer with the structural unit
containing two distinct tin atoms with small differences
in bond lengths and bond angles as shown in Fig. 2,
both of the tin atoms are six-coordinate axially by two
oxygen atoms and equatorially by one chlorine atom,
one nitrogen atom and two tin-bound o-chlorobenzyl
carbon atoms. The carboxylate groups are bidentate
with one each oxygen atom to the intramolecular and
the intermolecular tin atoms, thus the complex becomes
a one-dimensional chain polymer as shown in Fig. 3.
O(1)–Sn(1)–C(28)
O(1)–Sn(1)–C(21)
C(28)–Sn(1)–C(21)
O(1)–Sn(1)–O(4A)
C(28)–Sn(1)–O(4A)
C(21)–Sn(1)–O(4A)
O(1)–Sn(1)–Cl(1)
C(28)–Sn(1)–Cl(1)
C(21)–Sn(1)–Cl(1)
O(4A)–Sn(1)–Cl(1)
O(1)–Sn(1)–N(1)
C(28)–Sn(1)–N(1)
C(21)–Sn(1)–N(1)
O(4A)–Sn(1)–N(1)
Cl(1)–Sn(1)–N(1)
100.0(3)
C(35)–Sn(2)–O(2)
C(42)–Sn(2)–O(2)
N(2)–Sn(2)–O(2)
O(3)–Sn(2)–Cl(2)
C(35)–Sn(2)–Cl(2)
C(42)–Sn(2)–Cl(2)
N(2)–Sn(2)–Cl(2)
O(2)–Sn(2)–Cl(2)
O(3)–Sn(2)–C(35)
O(3)–Sn(2)–C(42)
C(35)–Sn(2)–C(42)
O(3)–Sn(2)–N(2)
C(35)–Sn(2)–N(2)
C(42)–Sn(2)–N(2)
O(3)–Sn(2)–O(2)
79.8(3)
80.2(3)
101.0(3)
154.9(4)
175.0(3)
79.1(3)
107.9(2)
90.0(2)
95.2(3)
81.1(4)
95.4(3)
89.62(17)
98.0(3)
95.8(3)
163.50(18)
88.62(17)
100.0(3)
100.3(3)
157.1(4)
73.5(3)
˚
The Sn–O bond distances 2.097(6) A for Sn(1)–O(1),
˚
2.434(7) A for Sn(1)–O(4A), 2.107(6) A for Sn(2)–O(3)
˚
˚
85.7(2)
72.6(2)
and 2.421(7) A for Sn(2)–O(2) are similar to that of
the corresponding distances found in [nBu3Sn(O-
COCH2C8H5N-3)]n [30]. The Sn–Cl bond lengths are
86.9(3)
86.3(4)
88.4(3)
87.2(3)
178.6(3)
˚
˚
2.436(3) A for Sn(1)–Cl(1) and 2.454(3) A for Sn(2)–
Cl(2) lie in the range of the normal covalent radii
112.1(3)
162.18(18)
˚
2.37–2.60 A [31]. The bond angles 175.0(3) A for
˚
˚
O(1)–Sn(1)–O(4A) and 178.6(3) A for O(3)–Sn(2)–O(2)
3.3.1. Structures of [(4-F-PhCH2)2Sn(2-quin)2] Æ
2(CH3CN) (4) and {[(2-Cl-PhCH2)2Sn(2-quin)Cl]2 Æ
(CH3OH)}n (8)
Complex 4 is a monomer as can be seen in Fig. 1. In
the structure of the complex, the tin atom forms four pri-
indicate that the geometry at both tin atoms become dis-
torted octahedral. The sum of the angles subtended at
Sn(1) and Sn(2) atoms in the equatorial plane are 367°
and 366.2°, respectively, which shows that the Sn(1),
Cl(1), C(21), C(28) and the Sn(2), Cl(2), C(42), C(35)

H.D. Yin et al. / Journal of Organometallic Chemistry 690 (2005) 3111–3117
3117
[7] S. Wilson, L. Dzon, A. Reed, M. Pruitt, M.M. Whalen, Appl.
Organometal. Chem 19 (2004) 554.
atoms are almost co-planar. The mean deviations from
˚
the plane are 0.3259 and 0.3035 A. Studies show that
the dihedral angels formed by the two planes is 6.6°, and
this indicates that the above eight atoms also are almost
in the same plane.
[8] M. Gielen, Appl. Organometal. Chem. 16 (2002) 481.
[9] M. Gielen, M. Biesemans, R. Willem, Appl. Organometal. Chem.
19 (2005) 440.
[10] K.C. Molloy, T.G. Purcell, E. Hahn, H. Schumann, J.J. Zucker-
man, Organometallics 5 (1986) 85.
[11] K.C. Molloy, K. Quill, I.W. Nowell, J. Chem. Soc., Dalton
Trans. (1987) 101.
4. Supplementary material
[12] R.R. Holmes, Acc. Chem. Res. 22 (1989) 190;
J. Otera, T. Yano, R. Owawara, Organometallics 5 (1986) 1167.
[13] D. Dakternieks, A. Duthie, D.R. Smyth, C.P.D. Stapleton,
E.R.T. Tiekink, Organometallics 22 (2003) 4599.
[14] H.D. Yin, C.H. Wang, Y. Wang, C.L. Ma, J.X. Shao, Chem. J.
Chin. Univ. 24 (2003) 68.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Center, CCDC No. 250004 for complex 4 and
CCDC No. 228447 for complex 8. Copies of this infor-
mation may be obtained from The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223
336 033; e-mail: deposit@ccdc.cam.ac.uk).
[15] H.D. Yin, C.H. Wang, C.L. Ma, H.X. Fang, Chin. J. Chem. 21
(2003) 452.
[16] K.C.K. Swamy, M.A. Said, S. Nagabrahmanandachari, D.M.
Poojary, J. Chem. Soc., Dalton Trans. (1998) 1645.
[17] V. Chandrasekhar, V. Bhaskar, A. Steiner, S. Zacchini, Organo-
metallics 21 (2002) 4528.
[18] V. Chandrasekhar, S. Nagendran, K. Gopal, A. Steiner, S.
Zacchini, Chem. Commun. (2003) 862.
Acknowledgments
[19] T.S. Basu Baul, K.S. Singh, A. Lycka, M. Holcapek, A. Linden,
J. Organomet. Chem. 690 (2005) 1581.
We acknowledge the National Natural Foundation
PR China (20271025) and the Shandong Province Sci-
ence Foundation (L2003B01), and the state Key Labo-
ratory of Crystal Materials, Shandong University, PR
China.
[20] (a) K. Sisido, Y. Takeda, Z. Kinugawa, J Am. Chem. Soc. 82
(1960) 434;
(b) Q.L. Xie, X.H. Xu, D.K. Zhang, Acta Chim. Sinica 50 (1992)
508.
[21] B.Y.K. Ho, J.J. Zuckerman, Inorg. Chem. 12 (1973) 1552.
[22] X.N. Fang, X.Q. Song, Q.L. Xie, J. Organomet. Chem. 619
(2001) 43.
[23] S.P. Narula, S.K. Bharadwaj, Y. Sharda, D.C. Povey, G.W.
Smith, J. Organomet. Chem. 430 (1992) 167.
References
[24] H.D. Yin, Q.B. Wang, S.C. Xue, J. Organomet. Chem. 690 (2005)
831.
[1] B. Jousseaume, V. Guillou, N. Noiret, M. Pereyre, J.M. France,
J. Organomet. Chem. 450 (1993) 97.
[25] T.P. Lockhart, W.F. Manders, Inorg. Chem. 25 (1986) 892.
[26] J. Holecek, A. Lycka, Inorg. Chim. Acta 118 (1986) L15.
[27] S.G. Eoh, S.H. Ang, J.P.D. Declercq, Polyhedron 16 (1997) 3729.
[28] A. Bondi, J. Phys. Chem. 68 (1964) 441.
[2] A.G. Davies, P.J. Smith, in: G. Wilkinson (Ed.), Comprehensive
Organometallic Chemistry, vol. 2, Pergamon Press, Oxford, 1982,
p. 519.
[29] H.D. Yin, M. Hong, Chin. Inorg. Chem. 20 (2004) 297.
[30] Q.L. Xie, X.K. Yao, R.J. Wang, Z.G. Zhang, J.M. Hu, Acta
Chim. Sinica 49 (1991) 723.
[3] J.A. Zubita, J.J. Zuckerman, Inorg. Chem. 24 (1987) 251.
[4] G.K. Sandhu, R. Gupta, S.S. Sandhu, R.V. Parish, Polyhedron 4
(1985) 81.
[31] F.H. Allen, S.A. Bellard, M.D. Brice, B.A. Cartwright, A.
Doubleday, H. Higgs, T. Hummelink, B.G. Hummelink-Peters,
O. Kennard, W.D.S. Motherwell, J.R. Rogers, D.G. Watson,
Acta Crystallogr., Sect. B 35 (1979) 2331.
[5] C.S. Parulekar, V.K. Jain, T.K. Das, A.R. Gupta, B.F. Hoskins,
E.R.T. Tiekink, J. Organomet. Chem. 372 (1989) 193.
[6] M. Gielen, A.M. Khloufi, M. Biesmans, R. Kayser, Appl.
Organometal. Chem. 7 (1993) 201.