N-(2-Nitroxyethyl)isonicotinamide and its complexes Russ.Chem.Bull., Int.Ed., Vol. 50, No. 3, March, 2001
523
added to the pale-yellow precipitate of isonicotinoyl chloride
hydrochloride that formed. Then 2-nitroxyethylamine nitrate7
randil) (1.05 g, 5 mmol) in 60% aqueous alcohol (80 mL) at
2030 °C. The reaction mixture was stirred for 11 h. The
yellow precipitate that formed was filtered off, washed with
water and alcohol, and dried in air. Compound 4 was obtained
in a yield of 2.94 g (86%), m.p. >200 °C. Found (%): C, 27.78;
(
(
5.07 g, 3 mmol) and a solution of freshly distilled triethylamine
6 mL) in dichloroethane (12 mL) were successively added with
stirring at 510 °C. The reaction mixture was stirred at ∼ 20 °C
for 46 h and then water (40 mL) was added. The reaction
mixture was cooled to 05 °C. The precipitate that formed was
filtered off, washed with water, and dried in air. Compound 1
was obtained in a yield of 4.7 g (74%) with respect to isonicotinic
acid, m.p. 110111 °C (from dichloroethane). Found (%):
C, 45.38; H, 4.21; N, 19.87. C H N O . Calculated (%):
H, 2.36; N, 12.02; Cl, 9.98; Pt, 28.17. C16H18Cl N O Pt.
2
6
8
Calculated (%): C, 27.90; H, 2.61; N, 12.21; Cl, 10.32; Pt, 28.35.
IR (KBr), ν/cm1: 331 (PtCl), 761 (NO ); 867 (ONO );
2
2
1010 (CO); 1266 (CN, amide); 1280 and 1614 (ONO );
2
1
704, 740, 1398, 1492, and 1589 (CH and CC, Py). H NMR
(DMSO-d ), δ: 9.24 (br.m, 2 H, H(2), NH); 9.15 (br.d, 1 H,
8
9
3
4
6
1
C, 45.50; H, 4.29; N, 19.89. IR (KBr), ν/cm : 759 (NO ); 865
H(6), J = 4.8 Hz); 8.95 (br.t, 1 H, NH´, J = 6.1 Hz); 8.94
(br.d, 2 H, H(6´), H(2´), J = 6.7 Hz); 8.37 (br.d, 1 H, H(4),
J = 7.9 Hz); 7.78 (br.d, 2 H, H(3´), H(5´), J = 6.4 Hz); 7.64
2
(
ONO ); 1012 (CO); 1268 (CN, amide); 1274 and 1638
2
(
1
ONO ); 703, 738, 1420, and 1591 (CH and CC, Py).
2
H NMR (DMSO-d ), δ: 9.02 (br.t, 1 H, NH, J = 6.1 Hz);
(br.dd, 1 H, H(5), J = 4.8 and 8.0 Hz); 4.64 (br.m, 4 H, CH O,
6
2
8
.36 (br.d, 2 H, H(2), H(6), J = 6.4 Hz); 7.74 (br.d, 2 H, H(3),
H(5), J = 6.4 Hz); 4.67 (t, 2 H, CH O, J = 5.1 Hz); 3.63 (dt,
H, CH N, J = 5.6 and 5.1 Hz). Crystals suitable for X-ray
2
CH´O); 3.63 (br.m, 4 H, CH N, CH´N).
2
2
2
trans-[(2-Nitroxyethyl)isonicotinamide-N ´][(2-hydroxy-
ethyl)isonicotinamide-N]dichloropalladium(II) (6). An aqueous
solution of PdCl2 (40 mg mL1, 22.5 mL, 5.08 mmol) was
added with stirring to a solution of N-(2-nitroxyethyl)iso-
nicotinamide (1) (1.045 g, 4.95 mmol) and N-(2-hydroxy-
ethyl)isonicotinamide (0.822 g, 4.95 mmol) in a mixture of
alcohol (30 mL) and water (10 mL) at 2030 °C. Then
concentrated HCl was added to pH 22.5 and the reaction
mixture was stirred for 2 h. The yellow precipitate that formed
was filtered off, washed with water and alcohol, and dried in air.
2
2
diffraction study were prepared by slow crystallization from
dichloroethane.
trans-Bis[(2-nitroxyethyl)isonicotinamide-N]-dichloropal-
ladium(II) (2). Concentrated HCl (∼ 0.4 mL) was added to a
suspension of N-(2-nitroxyethyl)isonicotinamide (1) (2.39 g,
1
1.3 mmol) in water (120 mL) to pH 23 at 2030 °C. Then a
solution of PdCl2 (0.6 g, 5.65 mmol) in water (40 mL) was
added with stirring at the same temperature. The reaction
mixture was neutralized with an aqueous solution of sodium
carbonate to pH 6.06.5 and stirred for 12 h. The precipitate
that formed was filtered off, washed with water and alcohol, and
dried in air. Compound 2 was obtained in a yield of 3.3 g
Compound 6 was obtained in
m.p. >200 °C. Found (%): C, 34.51; H, 3.23; N, 12.57;
Cl, 12.39; Pd, 18.87. C16H19Cl N O Pd. Calculated (%):
a yield of 2.58 g (94%),
2
5
6
C, 34.64; H, 3.45; N, 12.64; Cl, 12.78; Pd 19.18. IR (KBr),
(
97%), m.p. >210 °C. Found (%): C, 31.92; H, 3.01; N, 14.10;
ν/cm1: 332 (PdCl), 761 (NO ); 867 (ONO ); 1010 (CO);
2
2
Cl, 11.63; Pd, 17.53. C16H18Cl N O Pd. Calculated (%): C,
1266 (CN, amide); 1280 and 1614 (ONO ); 704, 740, 1398,
2
6
8
2
3
2.05; H, 3.03; N, 14.01; Cl, 11.82; Pd, 17.74. IR (KBr),
1492, and 1589 (CH and CC, Py). 1H NMR (DMSO-d ),
6
1
ν/cm : 761 (NO ); 866 (ONO ); 1011 (CO); 1266 (CN,
δ: 9.20 (br.t, 1 H, NH, J = 6.1 Hz); 8.92 (br.m, 5 H, H(2) and
H(6), H(2´) and H(6´), NH´); 7.86 (br.m, 4 H, H(3) and H(5),
H(3´) and H(5´)); 4.79 (t, 1 H, OH, J = 3.1 Hz); 4.66 (t, 2 H,
CH O, J = 5.1 Hz); 3.64 (dt, 2 H, CH N, J = 5.1 and 5.6 Hz);
2
2
amide); 1280 and 1614 (ONO ); 704, 740, 1398, 1492, and
2
1
1
589 (CH and CC, Py). H NMR (DMSO-d ), δ: 9.21
6
(
br.t, 1 H, NH, J = 6.1 Hz); 8.93 (br.d, 2 H, H(2), H(6),
2
2
J = 6.4 Hz); 7.87 (br.d, 2 H, H(3), H(5), J = 6.4 Hz); 4.66 (t,
3.51 (dt, 2 H, CH´N, J = 5.1 and 5.6 Hz); 3.35 (dt, 2 H,
2
2
5
H, CH O, J = 5.1 Hz); 3.63 (td, 2 H, CH N, J = 5.6 and
.1 Hz). Crystals suitable for X-ray diffraction study were
CH´O, J = 3.1 and 5.1 Hz).
2
2
2
X-ray diffraction study of compounds 1, 2, and 3. Crys-
tals of compound 1 are monoclinic, mol. weight 211.18,
a = 9.155(1) Å, b = 11.454(1) Å, c = 9.902(1) Å, β = 111.09(9)°,
prepared by crystallization from CH NO .
cis-Bis[(2-nitroxyethyl)isonicotinamide-N]dichloropla-
tinum(II) (3). A solution of N-(2-nitroxyethyl)isonicotinamide
3
2
3
3
V = 968.85(9) Å , d = 1.447(5) g cm , λ = 0.7107 Å,
(
(
(
1) (2.1 g, 10 mmol) in a mixture of alcohol (80 mL) and water
30 mL) was added with stirring to a solution of Na PtCl
1.915 g, 5 mmol) in water (75 mL) at 2030 °C. The reaction
µ = 0.110 mm1, space group P2 /ñ, Z = 4; 1931 reflections
1
with I > 2σ(I) were measured in the region sin(θ/λ) ≤ 0.63.
2
4
Crystals of complex 2 are triclinic, mol. weight
mixture was stirred for 14 h. The precipitate that formed was
filtered off, washed with water and alcohol, and dried in air.
Compound 3 was obtained in a yield of 2.52 g (73.7%),
m.p. >214 °C. Found (%): C, 27.63; H, 2.54; N, 12.08;
Cl, 10.11; Pt, 28.04. C16H18Cl N O Pt. Calculated (%):
599.98, à = 14.890(15) Å, b = 7.968(7) Å, c = 4.844(6) Å,
3
α = 81.51 (9)°, β = 84.22(9)°, γ = 82.93(7)°, V = 562.20(8) Å ,
3
1
d = 1.771(7) g cm , λ = 1.5418 Å, µ = 2.330 mm , space
group P1, Z = 1; 1936 reflections with I > 2σ(I) were measured
in the region sin(θ/λ) ≤ 0.63.
2
6
8
C, 27.90; H, 2.61; N, 12.21; Cl, 10.32; Pt, 28.35. IR (KBr),
Crystals of complex 3 are orthorhombic, mol. weight 688.52,
ν/cm1: 337, 347 (PtCl), 761 (NO ); 867 (ONO ); 1010
à = 26.692(8) Å, b = 9.801(2) Å, c = 10.057(2) Å,
2
2
3
3
(
7
(
CO); 1266 (CN, amide); 1280 and 1614 (ONO ); 704,
V = 2631.10(10) Å , d = 1.737(8) g cm , λ = 0.7107 Å,
2
40, 1398, 1492, and 1589 (CH and CC, Py). 1H NMR
DMSO-d ), δ: 9.13 (br.t, 1 H, NH, J = 6.1 Hz); 8.94 (br.d,
µ = 9.358 mm1, space group Pñ2 n, Z = 4; 1450 reflections
1
with I > 2σ(I) were measured in the region sin(θ/λ) ≤ 0.59.
The intensities of the observed independent reflections (1931
(1), 1936 (2), and 1450 (3)) were measured on a four-circle
KM-4 diffractometer (KUMA-Diffraction, Poland) using the
ω/2θ scanning technique. The structures of 1, 2, and 3 were
solved by the direct method with the use of the SHELX-97
program package.
6
2
H, H(2) and H(6), J = 6.4 Hz); 7.78 (br.d, 2 H, H(3) and
H(5), J = 6.4 Hz); 4.63 (t, 2 H, CH O, J = 5.1 Hz); 3.61 (td,
2
2
H, CH N, J = 5.1 and 5.6 Hz). Crystals suitable for X-ray
2
diffraction study were prepared by crystallization from a 1 : 1
CH ) COCH CN mixture.
(
3
2
3
trans-[(2-Nitroxyethyl)isonicotinamide-N´][(2-nitroxy-
ethyl)nicotinamide-N]dichloroplatinum(II) (4). A solution of
Na PtCl (1.915 g, 5 mmol) in water (60 mL) was added with
An attempt to solve the structure of complex 2 in the space
group Ð1 failed. Hence, we solved and refined the structure of
2
4
stirring to a solution of N-(2-nitroxyethyl)isonicotinamide (1)
1.05 g, 5 mmol) and N-(2-nitroxyethyl)nicotinamide8 (nico-
complex 2 in the space group P1. It should be noted that the
central portion of complex 2 has a local center of symmetry.
(