Synthesis and characterization of new copper(I) complexes containing thione derivatives of 1,2,4-triazine. Crystal structure of [Cu(PPh3) 2(ATTO)]NO3 (ATTO = 4-amino-1,2,4-triazin-3(2H)-thione-5- one)

Article abstract of DOI:10.1002/zaac.200480012

The reaction of 4-amino-1,2,4-triazin-3(2H)-thione-5-one (ATTO, 1) with [Cu(PPh₃)₂]NO₃ in ethanol led to the complex [Cu(PPh₃)₂(ATTO)]NO₃ (2). 2 was characterized by elemental analyses, IR, ¹H NMR and Raman spectroscopy. A single-crystal X-ray diffraction of compound 2 revealed that ATTO acts as a bidentate ligand via its nitrogen and sulfur atoms. Crystal data for 2 at 20°C: space group P2₁/n with a = 975.7(1), b = 1533.5(2), c = 2504.2(3) pm, β = 92.25(1)°, Z = 4, R₁ = 0.0632.

Full text of DOI:10.1002/zaac.200480012

Synthesis and Characterization of New Copper(I) Complexes Containing
Thione Derivatives of 1,2,4-Triazine. Crystal Structure of
[Cu(PPh3)2(ATTO)]NO3 (ATTO ؍ 4-amino-1,2,4-triazin-3(2H)-thione-5-one)
Mohammad Yazdanbakhsha, Mohammad Hakimib, Majid M. Heravic,*, Mitra Ghassemzadehd, and
Bernhard Neumüllere
a Mashhad/Iran, Ferdowsi University of Mashhad, Department of Chemistry
b Fariman/Iran, Payam noor University, Department of Chemistry
c Tehran/Iran, Azzahra University, Department of Chemistry, d Chemistry and Chemical Engineering Research Center of Iran
e Marburg, Fachbereich Chemie der Universität
Received January 23rd, 2004.
Abstract. The reaction of 4-amino-1,2,4-triazin-3(2H)-thione-5-one
(ATTO, 1) with [Cu(PPh3)2]NO3 in ethanol led to the complex
[Cu(PPh3)2(ATTO)]NO3 (2). 2 was characterized by elemental
bidentate ligand via its nitrogen and sulfur atoms. Crystal data for
2 at 20 °C: space group P21/n with a ϭ 975.7(1), b ϭ 1533.5(2),
c ϭ 2504.2(3) pm, β ϭ 92.25(1)°, Z ϭ 4, R1 ϭ 0.0632.
1
analyses, IR, H NMR and Raman spectroscopy. A single-crystal
X-ray diffraction of compound 2 revealed that ATTO acts as a
Keywords: Copper; Triazine-thione; Crystal structure
Copper is definitely an essential element of many life processes in
higher organisms, but its biological relevance and prevalence was
recognized when the bio-inorganic chemistry have been developed
[1]. Many attention has been paid to copper(I) complexes because
of their participation in certain biochemical redox reactions [2] and
provide suitable models for the representation of several enzymatic
sites [3]. In our investigation in the study of coordination chemistry
of copper group metals, recently, we have reported the reaction of
4-amino-6-methyl-1,2,4-triazine-3(2H)-thione-5-one
(AMTTO)
with silver(I), copper(I) and copper(II) ions and showed that the
AMTTO acts an an bidentate ligand and chelates the metals atoms
via its sulfur and hydrazinic nitrogen atoms. We have also studied
the behavior of the synthesized complexes against triphenylphos-
phane as nucleophil agent [4]. In this communication we wish to
report the reaction of ATTO (1) Ϫ another member of the 1,2,4-
thiotrizine family Ϫ with copper(I) ion.
According to the crystal structural data of 2, the CuI complex con-
sists of [Cu(PPh3)2(ATTO)]ϩ cations and NO3-anions without sym-
metry (C1) [5]. The ligand chelates the copper atom through its
sulfur and hydrazine nitrogen atom (Fig. 1) forming a five mem-
bered ring. Two triphenylphosphane molecules are also bound to
the central atom. The Cu-S distance of 235.0(2) pm is consistent
with the distances usually found for tetrahedrally coordinated cop-
per(I) ions with thione-S donors [6] and is longer than the observed
range of 222 Ϫ 233 pm for tricoordinated copper(I) ions, respec-
tively [7]. The Cu-P bond distances, mean 227.95 pm, lie in the
range observed for copper(I) complexes (227.7 Ϫ 230.7 pm) [8].The
Cu-N bond length (214.9(5) pm) is rather weak, indicated by the
distances of reference complexes [9], exhibiting values of 198.1 Ϫ
210.7 pm, and lie in the observed range for the three coordinated
copper(I) complex such as [Cu(AMTTO)2]Cl (coordination num-
ber (c.n.) 2ϩ2; Cu-N: 217.9(4) pm), [Cu2{SC6H4(CH2NMe2)-
Fig. 1 Molecular structure of 2.
2}(C6H2Me3-2,4,6)]2 (c.n. 3, Cu-N: 214.3(2) and 213.0(2) pm) and
[Cu3{SC6H3(CH2NMe2)-2-Cl-3}2(C6H2Me3-2,4,6)(PPh3)] (c.n. 3,
Cu-N: 215.0(4) and 218.7(4) pm) [10]. Important for the charac-
terization of the coordination sphere in 2 are the angles S1-Cu1-
P1 (109.10(6)°), S1-Cu1-P2 (108.96(6)°), P1-Cu1-P2 (121.18(6)°),
and S1-Cu1-N2 (82.4(1)°). Therefore, according to the observed
bond angles, the structure of 3 can be described as distorted tetra-
hedral Ϫ compressing the S1-Ag1-N1 angle by the two bulky tri-
phenylphosphane molecules Ϫ and in quoting the bond distances
(weak Cu-N bond) it can be described as 3ϩ1 coordination.
2 contains three intramolecular hydrogen bondings (N2-H1···O1a:
279.3(6) pm, N2-H1···O2b: 296.0(6) pm and N2-H2···O4c:
300.8(6) pm; always N···O distance given) and one intermolecular
hydrogen bridge (N4-H3···O2: 276.3(6) pm), leading to layers of
cations and anions (Fig. 2) parallel to (010).
* Dr. Majid M. Heravi
Department of Chemistry, School of Sciences
Azzahra University, Vanak, Tehran / Iran
E-mail: mmheravi@azzahra.ac.ir
Z. Anorg. Allg. Chem. 2004, 630, 627Ϫ629
DOI: 10.1002/zaac.200480012
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
In der gedruckten Version war der DOI falsch. Richtig muss es heißen: DOI: 10.1002/zaac.200480012 627

M. Yazdanbakhsh, M. Hakimi, M. M. Heravi, M. Ghassemzadeh, B. Neumüller
Table 1 Selected bond lengths/pm and angles/° of 2
Cu1-S1
Cu1-P1
Cu1-P2
Cu1-N2
S1-C1
N1-N2
N1-C1
N1-C2
N3-C3
N3-N4
O2-N5
O3-N5
O4-N5
235.0(2)
226.2(2)
229.7(2)
214.9(5)
166.4(5)
142.0(6)
136.3(6)
139.5(6)
128.6(7)
135.0(6)
122.9(6)
123.0(6)
122.7(6)
S1-Cu1-P1
S1-Cu1-P2
S1-Cu1-N2
P1-Cu1-P2
P1-Cu1-N2
P2-Cu1-N2
Cu1-S1-C1
Cu1-N2-N1
O3-N5-O4
O2-N5-O3
O2-N5-O4
109.10(6)
108.96(6)
82.4(1)
121.18(6)
107.1(1)
120.9(1)
96.6(2)
113.0(3)
121.2(6)
118.3(6)
120.3(6)
Preparation of 2: an ethanol solution (10 mL) of 1 (1 mmol) was
added to an ethanol suspension (40 mL) of [Cu(PPh3)2]NO3
(0.15 g, 1 mmol) and was stirred for 1.5 hrs at 50 °C under nitrogen
atmosphere. The solid crude was filtered off and the filtrate was
kept at 20 °C. After 24 hrs yellowish crystals of 2 suitable for X-
ray diffraction study were isolated.
Yield: 0.77 g (97 %), mp.: 218 °C.
Elemental analysis: C39H34CuN5O4P2S (794.29) C 59.01 (calcd.
58.98), H 4.28 (4.31), N 8.79 (8.82), Cu 8.03 (8.00) %.
IR (KBr disc; cmϪ1): 3325 (νasNH2, sh), 3233 (νsNH2, m), 3133 (νNH, m),
3050 (ν CH(Ph), m), 3000 (νCH, w), 2965 (νCH, w), 2936 (νsCH(Ph), w),
1718 (νCO, vs), 1670 (δNH2, w), 1631 (νCN, sh), 1591 (νCN, s), 1553 (s),
1544 (vw), 1520 (νCC(Ph), m), 1481 (δasNO3, s), 1431 (s), 1413 (sh), 1384
(δsNO3, m), 1349(w), 1311 (sh), 1302 (νCC(Ph), s), 1216 (νCC(Ph) ϩ δCH,
w), 1191 (∆CH, s), 1158 (νCC(Ph), w), 1115 (w), 1094 (ρNH2, s), 1042
(ΠCH3, m-w), 1028 (ΠCH3, w), 1018 (ΠCH3, m-w), 992 (νCp, w), 979
(νCCH, w), 925 (νCCH ϩ ρNH2, w), 879 (γCH(Ph), w), 850 (δNO3, vw),
826 (m-w), 746 (∆Ph, s), 696 (ΓPh, s)
Fig. 2 View of the unit cell of 2 in direction [001].
Far-IR (CsI disc, cmϪ1): 681 (w), 670 (w), 650 (ρNO3, m), 630 (w), 619 (ΓPh,
w), 602 (∆Ph, s), 540 (ΓPh, ms), 530 (s), 518(ΓPh, s), 503 (∆Ph, w), 478 (s),
452 (m), 426 (m), 403 (νCuN, w), 370 (νCuS, w), 334 (νCuP, w), 280 (∆Ph,
m), 251 (∆Ph, m).
The hydrogen bridges between the nitrate ion and the complex cat-
ion cause no elongation in the N-O bond distances in the planar
anion (N-O: 122.9(6)°, 123.0(6)° and 122.7(6)° pm) and the bond
angles are very close to the ideal value of 120° (118.3(6)°, 121.2(6)°,
and 120.3(6)°).
Raman (crystalline, cmϪ1): 3323 (νasNH2, w), 3230 (νsNH2, w), 3139 (νNH,
w), 3046 (νCH(Ph), w), 3002 (νCH, w), 2966 (νCH, sh), 2952 (w), 2930
(νCH(Ph), w), 2921 (νCH(Ph), w), 1714 (νCO, w), 1631 (νCOϩδNH2, sh),
1603 (m), 1591 (νCN, s), 1566 (νCCϩνCOϩνCN), s), 1545 (νCC(Ph), m),
1511 (νCC(Ph)ϩδCH), w), 1485 (δasNO3, m), 1464 (νCCϩδCH, m), 1430
(ms), 1408 (m), 1369 (s), 1343 (sh), 1336 (s), 1321 (m), 1303 (νCC(Ph), mw),
1217 (w), 1250 (m), 1215 (νCC(Ph)ϩδCH, w), 1191 (∆CH, s), 1153
(νCC(Ph), sh), 1147 (ms), 1135 (w), 1116 (νring(Ph), w), 1105 (mw), 1076 (m),
1064 (sh), 1042 (ΠCH3, mw), 1023 (ΠCH3, mw), 987 (νCP, s), 975 (νCCH,
w), 928 (νCCHϩρNH2, m-s), 862 (γCH(Ph), m), 842 (δNO3, w), 796 (w),
776 (γCH(Ph), s), 748 (∆Ph, w), 690 (ΓPh, w), 676 (w), 653 (ρNO3, m), 620
(ΓPh, mw), 560 (m), 535 (m), 518 (m), 497 (∆Ph, s), 474 (w), 462 (w), 406
(νCuN, mw), 398 (mw), 372 (νCuS, m), 330 (νCuP, w), 273 (∆Ph, w), 250
(∆Ph, mw, 203 (ΓPh, m).
The far-infrared spectrum of 2 shows three absorptions at 403, 370
and 334 cmϪ1, which can be assigned to νCuN, νCuS and νCuP
[11]. The corresponding vibrations on the Raman spectrum are ob-
served at 406, 372 and 330 cmϪ1. The N-O asymmetric strechting
mode (EЈ) and the out-of-plane deformation mode (AЈ2) of the ni-
trate anion are presented at 1384 cmϪ1 and 850 cmϪ1 in the IR
spectrum and at 1485 cmϪ1 and 842 cmϪ1 in the Raman spectrum.
The NH, CϭO and CϭN vibrations have been observed at 3325,
3133, 1718 and 1591 cmϪ1 in IR spectrum and at 3323, 3139, 1714
and 1591 cmϪ1 in the Raman spectrum, respectively.
1H NMR (DMSO-d6): δ ϭ 7.01 Ϫ 7.63 (br, 32 H, NH2, CH-phenyl), 7.99 (s,
1 H, CH-imine), 14.51 (br, 1 H, NH, exchangeable with D2O).
13C NMR (DMSO-d6): δ ϭ 38.8 Ϫ 40.8, 129.0, 129.2, 129.4, 129.5, 130.5,
131.9, 132.3, 132.6, 133.0, 133.5, 133.7, 139.7, 150.6 and 170.1.
Experimental
All chemicals and solvents were purchased from Fluka and used
after purification and drying of the solvents using standard meth-
ods [12]. All preparative operations were performed under nitrogen.
1 was prepared according to literature [13]. The IR spectra were
obtained on a Shimatzu 4300 and far-IR on a Perkin-Elmer 230
(nujol mulls, KBr discs for the range 4000-400 cmϪ1 and CsI disks
for the range 800Ϫ200 cmϪ1). The Raman spectra were measured
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1
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