organic compounds
under PTC conditions gave the dialkylated product (4). Hydrolysis of
the coupling product was achieved by treating (4) in HCl/diethyl
ether/H2O solution at room temperature for a few hours to give the
title formamide derivative, (I). A similar procedure was used for the
synthesis of compound (II).
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.051
wR(F2) = 0.147
S = 0.88
4648 re¯ections
w = 1/[ꢅ2(Fo2) + (0.0772P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max = 0.001
3
Ê
Áꢆmax = 1.14 e A
3
Ê
0.74 e A
Áꢆmin
=
242 parameters
H-atom parameters constrained
Compound (I)
Crystal data
3
C19H19I2NO3
Mr = 563.15
Monoclinic, P21/n
Dx = 1.816 Mg m
Mo Kꢀ radiation
Cell parameters from 3103
re¯ections
Table 2
Hydrogen-bonding and short-contact geometry (A, ) for (II).
ꢀ
Ê
Ê
a = 13.982 (7) A
b = 8.922 (5) A
ꢃ = 2.3±26.2ꢀ
ꢄ = 3.07 mm
T = 293 (2) K
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Ê
1
Ê
c = 16.533 (8) A
N1ÐH1Á Á ÁO16
C2ÐH2BÁ Á ÁO19
C9ÐH9AÁ Á ÁO19
N1ÐH1Á Á ÁO16i
0.86
0.97
0.97
0.86
2.20
2.61
2.56
2.18
2.620 (4)
3.205 (5)
3.095 (6)
2.959 (5)
110
120
115
150
ꢂ = 92.976 (8)ꢀ
V = 2059.8 (18) A
Z = 4
3
Ê
Prism, colourless
0.76 Â 0.46 Â 0.29 mm
Data collection
Symmetry code: (i) 2 x; 1 y; z.
Bruker SMART APEX
diffractometer
! scans
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
Tmin = 0.203, Tmax = 0.472
32 912 measured re¯ections
4852 independent re¯ections
4008 re¯ections with I > 2ꢅ(I)
Rint = 0.036
ꢃ
max = 28.2ꢀ
The H atoms were ®xed geometrically at calculated positions
Ê
(NÐH = 0.86 A and CÐH = 0.93±0.97 A). The maximum electron-
Ê
h = 18 ! 18
k = 11 ! 11
l = 21 ! 21
Ê
Ê
density peaks are located 0.77 A from I6 and 1.09 A from Br12 in (I)
and (II), respectively.
Re®nement
For both compounds, data collection: SMART (Bruker, 1999); cell
re®nement: SAINT (Bruker, 1999); data reduction: SAINT;
program(s) used to solve structure: SHELXS97 (Sheldrick, 1997);
program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997);
molecular graphics: ORTEP-3 (Farrugia, 1999); software used to
prepare material for publication: SHELXL97.
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.056
wR(F2) = 0.160
S = 1.01
4852 re¯ections
w = 1/[ꢅ2(Fo2) + (0.0899P)2
+ 2.9260P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max < 0.001
3
Ê
Áꢆmax = 1.47 e A
3
Ê
0.58 e A
226 parameters
H-atom parameters constrained
Áꢆmin
=
This work was supported by the Council of Scienti®c and
Industrial Research and DST, India.
Table 1
Hydrogen-bonding and short-contact geometry (A, ) for (I).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA1593). Services for accessing these data are
described at the back of the journal.
N1ÐH1Á Á ÁO19i
C9ÐH9AÁ Á ÁO19
C9ÐH9BÁ Á ÁO17
C2ÐH2BÁ Á ÁO19
N1ÐH1Á Á ÁO16
0.86
0.97
0.97
0.97
0.86
2.26
2.53
2.57
2.51
2.23
2.975 (5)
3.080 (6)
2.896 (5)
3.133 (6)
2.643 (5)
141
116
100
122
110
References
1
2
1
2
Symmetry code: (i)
x; 12 y;
z.
Bruker (1999). SADABS, SMART and SAINT. Bruker AXS Inc., Madison,
Wisconsin, USA.
Damodharan, L., Shamaladevi, N., Pattabhi, V., Behera, M. & Kotha, S. (2002).
Acta Cryst. C58, o266±o267.
Compound (II)
Damodharan, L., Syed Ibrahim, B., Pattabhi, V., Halder, S. & Kotha, S. (2002).
Acta Cryst. E58, o1038±o1039.
Dewar, M. J. S. & Schmeizing, H. N. (1969). Tetrahedron, 38, 96±120.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838.
Formaggio, F., Crisma, M., Rossi, P., Scrimin, P., Kaptein, B., Broxterman, Q. B.,
Kamphuis, J. & Toniolo, C. (2000). Chem. Eur. J. 6, 4498±4504.
Hassel, O. & Roming, C. Q. (1962). Chem. Soc. Rev. pp. 1±18.
Karle, I. L., Balaji Rao, R., Prasad, S., Kaul, R. & Balaram, P. (1994). J. Am.
Chem. Soc. 116, 10355±10361.
Crystal data
3
C19H19Br2NO3
Mr = 469.17
Monoclinic, P21/n
a = 11.380 (3) A
b = 14.867 (3) A
Dx = 1.569 Mg m
Mo Kꢀ radiation
Cell parameters from 4648
re¯ections
Ê
Ê
Ê
ꢃ = 2.1±29.8ꢀ
ꢄ = 4.10 mm
T = 293 (2) K
1
c = 12.525 (3) A
ꢂ = 110.431 (4)ꢀ
3
Ê
V = 1985.8 (7) A
Z = 4
Irregular, colourless
0.43 Â 0.25 Â 0.18 mm
Kotha, S., Behera, M. & Vinod Kumar, R. (2002). Bioorg. Med. Chem. Lett. 12,
105±107.
Kotha, S. & Brahmachary, E. (1997). Bioorg. Med. Chem. Lett. 7, 2719±2722.
Kotha, S. & Brahmachary, E. (2000). J. Org. Chem. 65, 1359±1365.
Leser, J. & Rabinovich, D. (1978). Acta Cryst. B34, 2272±2280.
Ramesh, K. & Balaram, P. (1999). Bioorg. Med. Chem. 7, 105±107.
Scott, W. L., Zhou, C., Fang, Z. & O'Donnell, M. J. (1997). Tetrahedron Lett.
38, 3695±3698.
Data collection
Bruker CCD area-detector
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
Tmin = 0.272, Tmax = 0.526
17 080 measured re¯ections
4648 independent re¯ections
2163 re¯ections with I > 2ꢅ(I)
Rint = 0.092
ꢃ
max = 28.0ꢀ
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
È
h = 14 ! 14
k = 19 ! 19
l = 14 ! 16
Gottingen, Germany.
Studer, A. & Seebach, D. (1995). Liebigs Ann. Chem. pp. 217±222.
ꢁ
o218 Lakshminarasimhan Damodharan et al.
C19H19I2NO3 and C19H19Br2NO3
Acta Cryst. (2003). C59, o216±o218