N-Methylpyridoxine and Its Diorganotin Complexes
FULL PAPER
operating under either EI conditions (direct insertion probe, 70 eV,
Synthesis of the Complexes
2
50 °C) or in FAB mode (m-nitrobenzyl alcohol, Xe, 8 eV; ca. 1.28
Ϫ15
ϫ 10
J); ions were identified by DS90 software and the data
[SnMe
yltin() oxide (0.51 g, 3.1 mmol) were added to a solution of pyri-
tope 1 Sn. IR spectra (KBr pellets or Nujol mulls) and Raman doxine (0.52 g, 3.1 mmol) in toluene/ethanol (3:1, v/v, 200 mL) and
2
(MePN؊H)]I (1): Methyl iodide (8 mL) and solid dimeth-
characterizing the metallated peaks were calculated using the iso-
20
spectra (polycrystalline samples) were recorded with a Bruker
IFS66V FT-IR spectrometer equipped with an FRA-106 Raman
accessory and are reported below using the following abbreviations:
the mixture was refluxed for 24 h. Water was then removed by azeo-
tropic distillation in a DeanϪStark funnel, and the resultant yellow
solid was filtered off, washed with diethyl ether and vacuum-dried.
vs ϭ very strong, s ϭ strong, m ϭ medium, w ϭ weak, sh ϭ Yield 96% (1.36 g). C11
3
H18INO Sn (457.9): calcd. C 28.8, H 4.0, N
2
shoulder, br ϭ broad. Mössbauer spectra were recorded at 80.0 K
3.1; found C 28.9, H 4.2, N 3.0. M.p. 205 °C. Λ
M
ϭ 57.2 S cm
mol . The main signals of metallated species in the EI spectrum
kept at room temperature and moved with a triangular velocity are at m/z (%) ϭ 302 (4.1) [Sn(MePNϪH)], 150 (30.8) [SnMe ], 135
(28.8) [SnMe] and 120 (46.9) [Sn]. In addition, the EI spectrum
shows signals for pyridoxine and its fragments, and the FAB spec-
2
trum exhibits signals at m/z (%) ϭ 664 (43.1) [SnMe (MePNϪH)] ,
in a Harwell cryostat; the Ca1 SnO
19m
source (15 mCi, NEN) was
Ϫ1
3
2
wave form; suitable computer programs were employed to fit Lor-
entzian lineshapes to the experimental data. Solid-state NMR spec-
tra were recorded with a Bruker AMX 300 spectrometer at
2
7
5.40 MHz using 7-mm o.d. zirconia rotors and the standard
2
332 (100) [SnMe (MePNϪH)] and 302 (10.0) [Sn(MePNϪH)]. IR
(Raman): ν˜ [cm ] ϭ 1619 w (1618 w), δ(OH); 1568 m (1568s),
Ϫ1
Bruker CPTOSS or CP LEV pulse programs at 3 and 4 kHz spin-
2
ning speeds, a contact time of 1 ms and a recycle delay of 5 s;
linewidths varied between 100 and 200 Hz, and chemical shifts are
1498 m (1483 w), 1451 s (1450 m), ν(ring); 1067s, 1017 m (1017 w),
ν(CO); 587 sh (587 w), νasym(SnϪC); 518 w (528vs), νsym(SnϪC);
1
13
referred to glycine (δ ϭ 176.3 ppm). H and C NMR spectra in 467 m (461 w), 427 m (425 w), ν(SnϪO). Mössbauer: I.S. ϭ 1.37,
Ϫ1
13
solution were recorded at room temperature with a Bruker AMX
00 operating at 300.14 and 75.40 MHz, respectively, by using 5-
mm o.d. tubes; chemical shifts are reported relative to TMS using
Q.S. ϭ 3.20, Γ ϭ 0.92 mm·s , A2/1 ϭ 1.00. C CP MAS NMR:
δ ϭ 159.0 [C(3)], 149.0 [C(2)], 143.6 [C(4)], 132.8 [C(6)], 132.8
3
[C(5)], 60.7 [C(7)], 57.4 [C(9)], 48.4 [C(10)], 16.5 [C(8)], 5.6, 1.8
1
13
1
the solvent signal [δ( H) ϭ 2.50 ppm; δ( C) ϭ 39.5 ppm] as refer-
[CϪSn] ppm. H NMR ([D
6
]DMSO, TMS): δ ϭ 8.05 [s, 1 H,
ence. 1 Sn NMR spectra were recorded at 186.50 MHz with a C(6)ϪH], 5.53 [t, J ϭ 5.2 Hz, 1 H, O(3)ϪH], 4.89 [s, J( H-
19
3
3
1
1
19Sn) ϭ 60.6 Hz, 2 H, C(9)ϪH], 4.55 [d, 3J ϭ 5.2 Hz, 2 H,
Bruker AMX 500 spectrometer by using 5-mm o.d. tubes and are
reported relative to external neat Sn(CH . Elemental analyses,
3 4
)
C(7)ϪH], 4.11 [s, 3 H, C(10)ϪH], 2.49 [s, 3 H, C(8)ϪH], 0.58 [s,
2
1
119/117
13
1
mass, IR, Raman and NMR spectra and X-ray data were obtained
at CACTUS, University of Santiago de Compostela.
J( H-
Sn) ϭ 87.0/84.4 Hz, 6 H, CH
]DMSO, TMS): δ ϭ 158.9 [C(3)], 145.1 [C(2)], 142.4
C(4)], 134.9 [C(6)], 130.8 [C(5)], 58.6 [C(7)], 57.9 [C(9)], 45.7
3
ϪSn] ppm. C{ H}
NMR ([D
6
[
[
1
13 119
C(10)], 12.6 [C(8)], 6.1 [ J( C- Sn) ϭ 780.5 Hz, (CϪSn)] ppm.
Synthesis of [HMePN]I and MePN
1
19
6 3 4
Sn NMR {[D ]DMSO, Sn(CH ) }: δ ϭ Ϫ170.2 ppm. Crystals
suitable for X-ray study were obtained by crystallization from
methanol.
[
HMePN]I: This compound was prepared by a published pro-
[
23]
cedure as follows. Methyl iodide (8 mL) was added to a solution
of pyridoxine (0.52 g, 3.1 mmol) in benzene/ethanol (12:1, v/v, 260
mL). The resultant solution was refluxed overnight, affording small
crystals, and then concentrated to one-third of its volume; the crys-
tals formed were filtered off, washed with diethyl ether to remove
traces of hydriodic acid, and recrystallized from absolute ethanol
as well-shaped single crystals. IR (Raman) : ν˜ [cm ] ϭ 1644 w
(
(
2
[SnEt (MePN؊H)]I (2): Methyl iodide (8 mL) and solid diethyl-
tin() oxide (0.59 g, 3.1 mmol) were added to a solution of pyridox-
ine (0.52 g, 3.1 mmol) in toluene/ethanol (3:1, v/v, 200 mL). After
refluxing for 24 h, water was removed by azeotropic distillation in
a DeanϪStark funnel and the resultant yellow solid was filtered off
Ϫ1
3
and vacuum-dried. Yield 97% (1.46 g). C13H22INO Sn (485.9):
1643 m), δ(OH); 1579 m (1583s), 1530 m (1525 w), 1460 vs
calcd. C 32.1, H 2.9, N 4.5; found C 32.4, H 2.8, N 4.5. M.p. 239
1
3
1461sh), ν(ring); 1064 s (1061 m), 1015 s (1015 w), ν(CO). C CP
2
Ϫ1
°
C. Λ
in the EI spectrum are at m/z (%) ϭ 302 (71.5) [Sn(MePNϪH)], 178
10.0) [SnEt ], 149 (36.6) [SnEt] and 120 (30.1) [Sn]. Also, the EI
spectrum shows signals for pyridoxine and its fragments, and the
FAB spectrum has signals at m/z (%) 720 (26.6)
(MePNϪH)] and 302 (18.3)
M
ϭ 73.8 S cm mol . The main signals of metallated species
MAS NMR (see III for numbering): δ ϭ 152.5 [C(3)], 143.4 [C(2)],
34.5 [C(6)], 133.2 [C(4)], 131.9 [C(5)], 62.2 [C(7)], 58.4 [C(9)], 47.7
1
[
[
4
(
2
1
C(10)], 15.8 [C(8)] ppm. H NMR ([D
s, 1 H, C(6)ϪH], 5.65 [s, br, 1 H, O(3)ϪH], 4.80 [s, 2 H, C(9)ϪH],
.68 [s, 2 H, C(7)ϪH], 4.23 [s, 3 H, C(10)ϪH], 2.59 [s, 3 H,
6
]DMSO, TMS): δ ϭ 8.43
ϭ
[
[
1
(
SnEt
Sn(MePNϪH)]. IR (Raman): ν˜ [cm ] ϭ 1619 w (1618 w), δ(OH);
564 m (1568s), 1501 w (1500 w), 1455 s (1456 m), ν(ring); 1068 s
1064 w), 1029 m (1033 w), ν(CO); 541 m (545 w), νasym(SnϪC); 500
2 2 2
(MePNϪH)] , 360 (100) [SnEt
13
1
C(8)ϪH] ppm. C{ H} NMR ([D
[
[
6
]DMSO, TMS): δ ϭ 152.6
Ϫ1
C(3)], 144.4 [C(2)], 139.7 [C(6)], 138.2 [C(4)], 134.9 [C(5)], 58.0
C(7)], 56.5 [C(9)], 46.6 [C(10)], 13.8 [C(8)] ppm.
w (502 vs), νsym(SnϪC); 462 m (456 w), 435 m (428 w), ν(SnϪO).
Ϫ1
[
MePN]: This compound was prepared from [HMePN]I by reac-
Mössbauer: I.S. ϭ 1.49, Q.S. ϭ 3.21, Γ ϭ 0.85 mm·s , A2/1 ϭ 1.08.
[23]
Ϫ1
13
tion with silver carbonate.
IR (Raman): ν˜ [cm ] ϭ 1653 w,
C CP MAS NMR: δ ϭ 158.9 [C(3)], 147.1 [C(2)], 141.8 [C(4)],
δ(OH); 1558 vs (1556 s), 1498 vs (1480 w), 1467 s (1453 m), ν(ring); 133.9 [C(6)], 133.9 [C(5)], 54.1 [C(7)], 54.1 [C(9)], 46.5 [C(10)], 14.0
1
1
066 m (1066 w), 1020 vs, ν(CO). 13C CP MAS NMR: δ ϭ 161.9
6
[C(8)], 9.7 [C(α)ϪSn] ppm. H NMR ([D ]DMSO, TMS): δ ϭ 8.07
3
3
1
[
[
C(3)], 146.9 [C(2)], 139.2 [C(6)], 134.3 [C(4)], 123.0 [C(5)], 58.4 [s, 1 H, C(6)ϪH], 5.53 [t, J ϭ 5.2 Hz, 1 H, O(3)ϪH], 4.91 [s, J( H-
1
119
3
C(7)], 53.8 [C(9)], 44.7 [C(10)], 12.1 [C(8)] ppm. H NMR
Sn) ϭ 47.7 Hz, 2 H, C(9)ϪH], 4.55 [d, J ϭ 5.1 Hz, 2 H,
3
([D
6
]DMSO, TMS): δ ϭ 7.36 [s, 1 H, C(6)ϪH], 5.27 [t, J ϭ 5.2 Hz, C(7)ϪH], 4.13 [s, 3 H, C(10)ϪH], 2.53 [s, 3 H, C(8)ϪH], 1.29 [m,
3
1
119/117
1
[
H, O(3)ϪH], 4.58 [s, 2 H, C(9)ϪH], 4.38 [d, 2 H, C(7)ϪH], 3.95 4 H, CH(α)ϪSn], 1.16 [t, J( H-
Sn) ϭ 135.0/128.5 Hz, 6 H,
]DMSO, TMS): δ ϭ 159.3
]DMSO, TMS): δ ϭ 165.9 [C(3)], 142.0 [C(2)], 136.8 [C(6)], [C(3)], 144.5 [C(2)], 142.0 [C(4)], 134.7 [C(6)], 130.2 [C(5)], 59.5
34.6 [C(4)], 121.6 [C(5)], 58.8 [C(7)], 58.0 [C(9)], 45.0 [C(10)], 11.9 [C(7)], 57.7 [C(9)], 45.4 [C(10)], 17.7 [C(β)ϪSn], 12.2 [C(8)], 9.6
C(8)] ppm.
s, 3 H, C(10)ϪH], 2.36 [s, 3 H, C(8)ϪH] ppm. 13C{ H} NMR
1
CH(β)ϪSn] ppm. C{ H} NMR ([D
6
13
1
([D
6
1
[
1
19
[C(α)ϪSn] ppm. Sn NMR {[D
6
]DMSO, Sn(CH
3
)
4
}: δ ϭ Ϫ209.5
Eur. J. Inorg. Chem. 2003, 2790Ϫ2797
www.eurjic.org
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2795