S. D´ıaz et al. / Journal of Organometallic Chemistry 610 (2000) 25–30
29
4.10. X-ray crystal structure determination of 1
3: IR (KBr): 3200, 2900, 1650, 1490, 1444, 1200, 740,
1
700 cm−1. H-NMR (DMSO-d6, 200 MHz): l (ppm):
Intensity data for 1 were collected on a Nonius-
C6H5, 7.4–7.2 (m, 15H); NH, 3.8 (m, 2H); CH (LꢀCys),
Mach3 diffractometer equipped with
a
graphite
2.9 (dd, J=4.4, 8.4 Hz, 1H); CH2ꢀS, 2.5–2.2 (m, 2H);
CH2/CH, 1.9–1.5 (m, 14 H); CH3, 1.3–0.8 (m, 18H);
CHꢀB, 0.8 (broad s, 2H). 13C-NMR (DMSO-d6, 50
MHz): l (ppm): 169.2 (CꢁO), 144.1, 129.1, 128.1, 126.8,
,
monochromated Mo–Ka radiation (u=0.71073 A) us-
ing an ꢀ/2q scan technique to a maximum value of 58°.
Crystals are orthorhombic of space group P212121 with
one molecule (C30H34BNO2S; formula weight, 483.44)
per unit cell. Unit-cell parameters were obtained from a
least-squares fit to automatically centered settings for 25
66.1 (C), 53.1 (CH)(
(CH), 40.3 (CH2), 37.9 (CH2), 33.7 (CH2)(
L
ꢀCys), 47.4 (CH), 47.1 (CH), 41.3
ꢀCys), 27.6
L
(CH3), 23.6 (CH3), 23.4 (CH),20.7 (CH3). MS: 243
(100), 228 (13), 215 (9),165 (89), 119 (6), 77 (3). Elem.
Anal.: C42H54BNO2S (647.30) requires: C, 77.86; H,
8.41; N, 2.16; found: C, 77.45; H, 8.29; N, 2.38%.
4: IR (KBr): 3380, 3058, 1731, 1660, 1546, 1202, 1144,
reflections: a=9.952(5), b=14.4933(7), c=18.633(9)
3
A; V=2687.6(14) A , Z=4, Dcalc=1.190 g cm−3
.
,
,
Data were corrected for Lorentz-polarization effects
and for linear decay of the two periodically measured
reference reflections. No absorption correction was nec-
essary (v=1.47 cm−1). The structure was solved by a
combination of direct methods and Fourier synthesis
740, 701 cm−1 1H-NMR (DMSO-d6, 200 MHz): l
.
(ppm): NH, 8.3 (2H); NH, 8.2 (2H); C6H5, 7.3–7.2 (15
H); CH, 4.4 (1H); CH, 3.8 (1H); CH2 (Gly), 3.7 (2H);
and then refined by full-matrix least-squares (SHELXL
-
CH2 (L
ꢀCys)/CH2, 2.5–2.3 (4H); CH2, 2.0 (2H). 13C-
97, G.M. Sheldrick, Program for the refinement of
Crystal Structures from Diffraction data, University of
Go¨ttingen, Germany, 1997). All non-hydrogen atoms
were refined with anisotropic thermal parameters. The
hydrogen atoms were included in their calculated posi-
tions except H1 and H2 which were located in the
difference-Fourier map and refined isotropically.
Weights were optimized in the final refinement cycles.
Refinement of 324 parameters against 6448 intensity
data converged at wR2=0.1333 and R1=0.0572; S=
1.068. Maximum and minimum residual electron densi-
NMR (DMSO-d6, 50 MHz): l (ppm): 170.8 (CꢁO),
170.7 (CꢁO), 170.0 (CꢁO), 144.2 (C), 129.0 (CH), 128.0
(CH), 126.7 (CH), 65.8 (C), 51.8 (CH), 51.4 (CH), 40.8
(CH2), 33.9 (CH2), 30.6 (CH2), 26.1 (CH2). MALDI–
TOF MS calculated: 550.3 (M+H)+; found: 550.6.
5: IR (KBr): 3270, 2930, 2844, 1709, 1533, 1256, 1217,
740, 701 cm−1 1H-NMR (DMSO-d6, 300 MHz): l
.
(ppm): NH, 8.3 (3H); C6H5, 7.4–7.2 (15H); NH, 6.4
(1H); NH, 6.1 (1H); CH, 4.4 (1H); CH, 3.7 (1H); CH2
(Gly), 3.5 (2H); CH2 ( ꢀCys)/CH2, 2.4 (4H); CH2, 2.0
L
(2H); CH2 boron, 1.9–1.3 (12H); CHꢀB, 0.5 (1H);
CHꢀB, 0.4 (1H). 13C-NMR (DMSO-d6, 75 MHz): l
(ppm): 173.6 (CꢁO), 171.9 (CꢁO), 171.1 (CꢁO), 170.3
(CꢁO), 144.5 (C), 129.3 (CH), 128.2 (CH), 127.0 (CH),
66.0 (C), 54.2 (CH), 51.5 (CH), 40.9 (CH2), 34.2 (CH2),
31.9 (CH2), 31.4 (CH2), 31.0 (CH2), 26.6 (CH2), 24.5
(CH2), 24.1 (CH2), 23.7 (CH), 22.5 (CH). MALDI–
TOF MS calculated: 692.2 (M+Na)+; found: 692.3.
6: IR (KBr): 3400, 2921, 2847, 1706, 1530, 1445, 1211,
ties are 0.202 and −0.163 e A−3
.
4.11. Characterization data
1: 1H-NMR (CDCl3, 200 MHz): l (ppm): C6H5,
7.5–7.2 (m, 15H); NH, 3.6 (broad s, 1H); NH, 3.4
(broad s, 1H); CH ( ꢀCys), 3.14 (quint, 1H); CH2ꢀS,
L
3.00 (d, J=6.2 Hz, 2H); CH2, 2.0–1.2 (m, 12H); CHꢀB,
0.35 (broad s,2H). 13C-NMR (DMSO-d6, 75 MHz): l
(ppm): 172.0 (CꢁO), 144.3 (C), 129.4 (CH), 128.4 (CH),
743, 701 cm−1 1H-NMR (DMSO-d6, 300 MHz): l
.
(ppm): NH, 8.3 (3H); C6H5, 7.3–7.2 (15H); NH, 6.2
(1H); NH, 5.4 (1H); CH, 4.4 (1H); CH, 3.7 (1H); CH2
127.1 (CH), 66.7 (C), 53.9 (CH)(
L
ꢀCys), 31.9
(CH2)(
L
ꢀCys), 31.5 (CH2), 31.4 (CH2), 30.8 (CH2), 30.7
(Gly), 3.3 (2H); CH2 (LꢀCys)/CH2, 2.4 (4H); CH2, 2.0
(CH2), 24.5 (CH2), 24.1 (CH2), 23.2 (CH), 21.9 (CH).
(2H); CH2 boron, 1.8–0.8 (20H); CHꢀB, 0.3 (2H).
13C-NMR (DMSO-d6, 75 MHz): l (ppm): 173.8 (CꢁO),
172.1 (CꢁO), 171.0 (CꢁO), 170.2 (CꢁO), 144.4 (C), 129.2
(CH),128.2 (CH),126.9 (CH), 66.0 (C), 54.8 (CH), 51.5
(CH), 40.9 (CH2), 34.1 (CH2), 32.0 (CH2), 29.2/28.6
(CH2), 28.2/27.8 (CH2), 27.5/27.1 (CH2), 26.8 (CH2),
23.2 (CH). MALDI–TOF MS calculated: 749.3 (M+
H+Na)+; found: 750.9.
2: IR (KBr): 3218, 3060, 2923, 1646, 1489, 1444, 1388,
742, 699 cm−1 1H-NMR (DMSO-d6, 200 MHz): l
.
(ppm): C6H5, 7.4–7.2 (m, 15H); NH, 3.4 (m, 2H); CH
ꢀCys), 2.9 (dd, J=4.0 Hz, 8.4, 1H); CH2ꢀS, 2.6–2.3
(L
(m, 2H); CH2, 1.8–1.0 (m, 20H); CHꢀB, 0.3 (broad
s,2H). 13C-NMR (DMSO-d6, 75 MHz): l (ppm): 168.7
(CꢁO), 144.4 (C), 129.3 (CH), 128.3 (CH), 126.9 (CH),
66.3 (C), 53.4 (CH)(
L
ꢀCys), 35.6 (CH2), 33.5
7: IR (KBr): 3425, 3217, 2933, 1641, 1498, 1450, 1204,
(CH2)( ꢀCys), 28.2 (CH), 25.5 (CH2), 23.9 (CH2). MS:
L
743, 700 cm−1 1H-NMR (DMSO-d6, 300 MHz): l
.
243 (100), 228 (12), 215 (8), 165 (83), 115 (5), 77 (3).
Elem. Anal.: C34H42BNO2S (539.21) requires: C, 75.67;
H, 7.85; N, 2.59; Found: C, 75.45; H, 7.59; N, 2.78%.
MALDI–TOF MS calculated: 562.2 (M+Na)+;
found: 561.9.
(ppm): NH, 8.4 (1H); NH, 8.2 (2H); C6H5, 7.4–7.2
(15H); NH, 6.2 (1H); NH, 5.2 (1H); CH, 4.4 (1H); CH2
(Gly)/CH, 3.7 (3H); CH2 ( ꢀCys)/CH2, 2.4 (4H); CH2,
L
2.1 (2H); CH2/CH boron, 1.9–1.2 (14H); CH3, 1.1 (6H);
CH3, 1.06 (3H); CH3, 1.0 (3H); CH3, 0.9 (d,