Synthesis, Spectroscopy, and Structures of Mono- and Dinuclear Copper(I) Halide Complexes with 1,3-Imidazolidine-2-thiones

Article abstract of DOI:10.1002/zaac.201500162

Copper(I) halides with triphenyl phosphine and imidaozlidine-2-thiones (L-NMe, L-NEt, and L-NPh) in acetonitrile/methanol (or dichloromethane) yielded copper(I) mixed-ligand complexes: mononuclear, namely, [CuCl(κ¹-S-L-NMe)(PPh₃)₂] (1), [CuBr(κ¹-S-L-NMe)(PPh₃)₂] (2), [CuBr(κ¹-S-L-NEt)(PPh₃)₂] (5), [CuI(κ¹-S-L-NEt)(PPh₃)₂] (6), [CuCl(κ¹-S-L-NPh)(PPh₃)₂] (7), and [CuBr(κ¹-S-L-NPh)(PPh₃)₂] (8), and dinuclear, [Cu₂(κ¹-I)₂(μ-S-L-NMe)₂(PPh₃)₂] (3) and [Cu₂(μ-Cl)₂(κ¹-S-L-NEt)₂(PPh₃)₂] (4). All complexes were characterized with analytical data, IR and NMR spectroscopy, and X-ray crystallography. Complexes 2-4, 7, and 8 each formed crystals in the triclinic system with Pβar{1}$ space group, whereas complexes 1, 5, and 6 crystallized in the monoclinic crystal system with space groups P2₁/c, C2/c, and P2₁/n, respectively. Complex 2 has shown two independent molecules, [(CuBr(κ¹-S-L-NMe)(PPh₃)₂] and [CuBr(PPh₃)₂] in the unit cell. For X = Cl, the thio-ligand bonded to metal as terminal in complex 4, whereas for X = I it is sulfur-bridged in complex 3.

Full text of DOI:10.1002/zaac.201500162

Journal of Inorganic and General Chemistry
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ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
DOI: 10.1002/zaac.201500162
Synthesis, Spectroscopy, and Structures of Mono- and Dinuclear Copper(I)
Halide Complexes with 1,3-Imidazolidine-2-thiones
[
a]
[a]
[a]
[a]
Simran Walia, Supreet Kaur, Jaspreet Kaur, Amanpreet K. Sandhu,
[a]
[a]
[b]
Tarlok S. Lobana,* Geeta Hundal, and Jerry P. Jasinski
Keywords: 1-Methyl-imidazolidine-2-thione; 1-Ethyl-imidazolidine-2-thione; 1-Phenyl-imidazolidine-2-thione; Copper;
Structures
Abstract. Copper(I) halides with triphenyl phosphine and imidaozlid-
ine-2-thiones (l-NMe, l-NEt, and l-NPh) in acetonitrile/methanol formed crystals in the triclinic system with P1 space group, whereas
or dichloromethane) yielded copper(I) mixed-ligand complexes: mo- complexes 1, 5, and 6 crystallized in the monoclinic crystal system
troscopy, and X-ray crystallography. Complexes 2–4, 7, and 8 each
¯
(
1
nonuclear,
namely,
[CuCl(κ -S-l-NMe)(PPh
3
)
2
]
(1), with space groups P2
(5), shown two independent molecules, [(CuBr(κ -S-l-NMe)(PPh
] (7), and [CuBr(PPh ] in the unit cell. For X = Cl, the thio-ligand bonded to
(μ- metal as terminal in complex 4, whereas for X = I it is sulfur-bridged
1 1
/c, C2/c, and P2 /n, respectively. Complex 2 has
1
1
1
[
[
[
CuBr(κ -S-l-NMe)(PPh
CuI(κ -S-l-NEt)(PPh
CuBr(κ -S-l-NPh)(PPh
3
)
2
]
(2), [CuBr(κ -S-l-NEt)(PPh
3
)
2
]
3 2
) ] and
1
1
3
)
2
] (6), [CuCl(κ -S-l-NPh)(PPh
3
)
2
3 2
)
1
1
3
)
2
]
(8), and dinuclear, [Cu
2
(κ -I)
] (4). All
2
1
S-l-NMe)
2
(PPh
3
)
2
] (3) and [Cu
2
(μ-Cl)
2
(κ -S-l-NEt)
2
(PPh
3
)
2
in complex 3.
complexes were characterized with analytical data, IR and NMR spec-
Introduction
no similar mixed-ligand complexes with imidazolidine-2-
thiones are known.
The chemistry of heterocyclic-2-thiones has invited interest
of several researchers for a variety of reasons such as relevance
of their metal complexes in the biological systems,
satility of these organic bases to bind to metals in different
coordination patterns leading to the formation of a wide variety
We have observed that thio-ligand l-NH (Scheme 1) reacted
with copper(I) chloride / bromide in dimethylsulfoxide (or
[
1,2]
and ver-
II
2
DMF) and formed a sulfate bridged polymer, [Cu {κ -N,N-
1
2 3 5 2 2 2 n 2 3 5 2
[39]
(
N C H ) S}(μ-O,OSO )(κ -OH )] [(N C H ) S = 2,2Ј-thio-
di-2-imidazoline] involving C–S rupture.
Further reactions
of coordination compounds, ranging from mono- to poly-nu-
of l-NMe, l-NEt, and l-NPh with copper(I) chloride / bromide
in acetonitrile, dimethylsulfoxide (or DMF) also involved C–
S rupture but no product could be established except formation
of copper(II) sulfate. In this paper, results of reactions of thio-
ligands (l-NR, R = Me, Et, Ph) (Scheme 1) with copper(I)
clear.[
3–18]
Among heterocyclic-2-thiones, 1,3-imidazolidine-2-
thione and its derivatives have been used for the investigation
of their interaction with metals.
azolidine-2-thione and its derivatives with mono substitution
at one nitrogen (l-NR, R = H, Me, Et, nPr, iPr) with copper(I)
halides / pseudo halides have yielded trigonal planar com-
[
3–8]
The ligands, 1,3-imid-
halides carried out in the presence of PPh as co-ligand are
3
reported. New mixed-ligand copper(I) mono- and dinuclear
complexes 1–8 reported represent the first examples with imid-
azolidine-2-thiones.
[
19–24]
plexes, [CuX(l-NR) ] (X = Cl, Br, I, NCS).
substitution at both nitrogen atoms {L-(NMe) } also formed a
The double
2
2
[
25]
[26,27]
similar three coordinate complex.
Dinuclear
or poly-
nuclear[
27,28]
complexes of 1,3-imidazolidine-2-thiones with
copper(I) halides are also reported. Several heterocyclic-2-
thiones such as pyridine-2-thione, pyrimidine-2-thione, thiazo-
lidine-2-thione etc. have formed mixed-ligand complexes such
[29–38]
as, [CuX(HL)(PPh ) ], with PPh as co-ligand,
whereas
3
2
3
Scheme 1. The imidazolidinethiones used as ligands.
*
Prof. Dr. T. S. Lobana
E-Mail: tarlokslobana@yahoo.co.in
[
[
a] Department of Chemistry
Guru Nanak Dev University
Amritsar-143 005, India
Experimental Section
b] Department of Chemistry
Keene State College
Materials and Techniques: The thio ligands, 1-methyl-imidazolidine-
2-thione (l-NMe) was prepared by the addition of carbon disulphide
Keene NH 03435–2001, USA
dropwise to a cooled solution of 1-methyl-ethylenediamine in ethanol
and water. The reaction mixture was heated under reflux (110 °C) for
1 h and conc. HCl was added. The mixture was heated under reflux
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201500162 or from the au-
thor.
Z. Anorg. Allg. Chem. 2015, 641, (10), 1728–1736
1728
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ARTICLE
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1
for a further period of 10 h. The reaction mixture was cooled and Synthesis of [Cu
stored in a freezer. The resulting precipitate were filtered off and a solution of copper(I) chloride (0.025 g, 0.25 mmol) in acetonitrile
washed with cold acetone to give the desired ligand. Similarly, 1-ethyl- was added PPh (0.132 g, 0.50 mmol). The reaction mixture was
imidazolidine-2-thione (l-NEt) and 1-phenyl-imidazolidine-2-thione stirred and mildly heated for 2 h, which yielded white precipitate. The
acetonitrile was removed and the precipitate suspended in CHCl . The
addition of thio-ligand l-NEt (0.032 g, 0.25 mmol) made a clear solu-
2 2 2 3 2
(μ-Cl) (κ -S-L-NEt) (PPh ) ] (4): Procedure (a): To
3
[
40]
(
l-NPh) were prepared.
Copper(I) halides were prepared by the re-
in the presence of stoichiometric
3
duction of CuSO ·5H O using SO
4
2
2
[
41]
amounts of corresponding NaCl, NaBr, or NaI in water. The melting tion which after filtration and addition of 1 mL of methanol was kept
point was determined with a Gallenkamp electrically heated apparatus. undisturbed for crystallization. Slow evaporation of solution at room
The IR spectra were recorded using KBr pellets with Varian 660 FT temperature yielded colorless prismatic crystals. Procedure (b): To a
–
1
IR and Perkin-Elmer FT IR Spectrometer in the 4000–200 cm range.
solution of CuCl (0.025 g, 0.25 mmol) in 10 mL of acetonitrile was
with a Bruker Avance added solid PPh (0.066 g, 0.25 mmol) followed by stirring for 2 h at
II 400 NMR spectrometer at 400 MHz and JEOL AL300 FT H NMR room temperature. To the precipitate formed was added l-NEt
1
The H NMR spectra were recorded in CDCl
3
3
1
at 300 MHz using TMS as an internal reference.
(0.032 g, 0.25mmol) and finally 1 mL dicholoromethane and the re-
sulting solution was filtered and kept undisturbed for crystallization.
Colorless crystals of compound 4 produced within 1 week (70%, M.p.
1
Synthesis of [CuCl(κ -S-
L-NMe)(PPh
3
)
2
] (1): To a solution of cop-
per(I) chloride (0.025 g, 0.25 mmol) in 10 mL of acetonitrile was 260–262 °C). C46
2 2 4 2 2
H50Cl Cu N P S : calcd.C 56.21; H 5.13; N 5.70%;
added PPh (0.132 g, 0.50 mmol). The solution was mildly heated and found: C 56.10; H 5.08; N 6.24%. IR (KBr, absorption bands): ν˜ =
3
stirred for a period of 2 h, which led to the formation of white precipi-
tate. The addition of the thio-ligand, l-NMe (0.029 g, 0.25 mmol)
ν(N–H), 3203 s; ν(C–H), 3049 w, 2970 w, 2886 w; ν(C–C) + ν(C–N)
+ δ(C–H), 1515 s, 1478 s, 1431s; 1380 w, 1360 w, 1321 s, 1282 s,
made the precipitate to dissolve and a clear solution was obtained. 1261 s, 1221 w, 1191 w; ν(C–S), 1126 w; ν(P–CPh), 1094 m; 1027 w,
After filtration, about 1 mL of methanol was added and the resulting
solution was kept undisturbed for slow evaporation at room tempera-
ture (10–15 d). This yielded colorless crystals of 1 (70%, M.p 155–
998 w, 943 w, 857 w, 786 w, 752 s, 696 s, 626 m, 609 m, 518 s, 502
s, 434 w cm .
–
1
1
Synthesis of [CuBr(κ -S-
per(I) bromide (0.025 g, 0.17 mmol) in 10 mL of acetonitrile was
added PPh (0.092 g, 0.35 mmol). The solution was stirred and mildly
3 2
L-NEt)(PPh ) ] (5): To a solution of cop-
1
57 °C).C40
C 65.39; H 5.20; N 3.52%. IR (KBr, absorption bands): ν˜ = ν(N–H),
072 s; ν(C–H), 3013 w, 2888 w; ν(C–C) + ν(C–N) + δ(C–H), 1517
s, 1480 m, 1434s; 1409 w, 1296 m, 1280 m, 1181 w, 1157 w; ν(C–S),
2 2
H38ClCuN SP : calcd.C 64.89; H 5.14; N 3.79%; found:
3
3
heated for 2 h, which formed precipitate and the addition of thio-ligand
l-NEt (0.023 g, 0.18 mmol) made a clear solution. After filtration,
1 mL of methanol was added and the resulting solution on slow evapo-
ration of solution at room temperature (10–15 d) yielded colorless
1
111 w; ν(P–CPh), 1092 s; 1027 w, 998 w, 744 s, 694 s, 632 w, 508 s,
–1
489 m cm .
1
crystals of 5 (67%, M.p 182–184 °C). C41
1.63; H 5.01; N 3.51%; found : C 61.41; H 5.17; N 3.96%. IR (KBr,
absorption bands): ν˜ = ν(N–H), 3196 s; ν(C–H), 3068 m, 3046 m,
2 2
H40BrCuN P S: calcd.C
Synthesis of [CuBr(κ -S-
per(I) bromide (0.025 g, 0.17 mmol) in acetonitrile was added PPh
0.091 g, 0.35 mmol). The reaction mixture on stirring and mild heat-
3 2
L-NMe)(PPh ) ] (2): To a solution of cop-
6
3
(
3000 w, 2975 m, 2928 w, 2885 w; ν(C–C) + ν(C–N) + δ(C–H),
ing for a period of 2 h yielded white precipitate. The acetonitrile sol-
vent was removed and the precipitate suspended in chloroform. To the
suspension, the thio-ligand l-NMe (0.0202 g, 0.17 mmol) was added
and a clear solution obtained was filtered. After filtration 1 mL of
methanol was added and the solution was kept undisturbed for
crystallization. Slow evaporation of solution at room temperature
1512 s, 1479 s, 1433 s, 1356 w, 1377 w, 1321 m, 1280 s, 1264 s, 1180
m, 1155 w; ν(C–S), 1124w; ν(P–CPh), 1095s; 1073 w, 1028 m, 998 w,
9
5
43 w, 913 w, 841 w, 785 w, 748 s, 741 s, 694 s, 627 m, 607 m,
13 s, 505 s, 493 s, 444 w, 431 w cm .
–
1
1
Synthesis of [CuI(κ -S-
L-NEt)(PPh
3
)
2
] (6): To a solution of copper(I)
yielded colorless prismatic crystals of
72 °C).C40 38BrCuN S: calcd.C 61.30; H 4.85; N 3.58%; found:
C 61.40; H 4.61; N 3.70%. IR (KBr, absorption bands): ν˜ = ν(N–H),
211 s; ν(C–H), 3050 w, 2997 w, 2964 w, 2927 w, 2886 w; ν(C–C) +
ν(C–N) + δ(C–H), 1541 s, 1514 s, 1477 m, 1434 s, 1404 w, 1330 m,
290s, 1179 w, 1154 w; ν(C–S), 1108 s; ν(P–CPh), 1094s; 1021 w, 998
w, 957 w, 919w, 858 w, 749 s, 698 s, 640 w, 567 w, 520 m, 502 s,
2 (69%, M.p. 270–
iodide (0.025 g, 0.13 mmol) in 10 mL of acetonitrile was added PPh
3
2
H
2 2
P
(
0.069 g, 0.26 mmol). The solution was stirred and mildly heated for
2
h and to the precipitate thio-ligand l-NEt (0.017g, 0.13 mmol) was
3
added. A clear solution obtained was filtered, 1 mL of methanol was
added and slow evaporation of solution at room temperature
1
(
C
10–15 d) yielded colorless crystals of 6 (65%, M.p. 179–181°C).
38CuIN S: calcd. C 58.34; H 4.51; N 3.32%; found: C 58.10;
41
H
2 2
P
–
1
4
38 w cm .
H 4.65; N 3.44%. IR (KBr, absorption bands): ν˜ = : ν(N–H) 3261 m;
ν(C–H) 3048 m, 2974 w, 2961 w, 2928 w, 2884 w; ν(C–C) + ν(C–N)
1
Synthesis of [Cu
copper(I) iodide (0.025 g, 0.13 mmol) in 10 mL of acetonitrile, PPh
0.069 g, 0.26 mmol) was added. The solution on stirring and mild
heating for 2 h gave precipitate and addition of the thio-ligand l-NMe
0.015g, 0.13 mmol) made a clear solution which was filtered. After
2 2 2 3 2
(κ -I) (μ-S-L-NMe) (PPh ) ] (3): To a solution of
+
δ(C–H), 1518 s, 1506 s, 1478 s, 1433 s, 1379 w, 1357 w, 1320 m,
3
1
1
5
282 s, 1256 s, 1153 w; ν(C–S), 1125 m; ν(P–CPh) 1092 s; 1072 m,
(
026 m, 997 m, 945 w, 857 w, 791 w, 746 s, 696 s, 624 m, 517 s,
–1
02 s cm .
(
1
filtration, 1 mL of methanol was added and the resulting solution was Synthesis [CuCl(κ -S-
L-NPh)(PPh
3
)
2
] (7): Procedure (a): To a solu-
kept undisturbed for crystallization. The slow evaporation of solution
at room temperature (10–15 d) yielded colorless crystals of 3 (65%, nitrile was added PPh
M.p 162–164 °C).C44 : calcd.C 46.40; H 4.04; N and mildly heated for 2 h which yielded white precipitate and after
.92%; found : C 46.20; H 4.10; N 5.20%. IR (KBr, absorption removal of acetonitrile solvent, 5 mL CHCl was added. To this sus-
bands): ν˜ = ν(N–H) 3257 m; ν(C–H), 3048 m, 3017 w, 3002 w, 2952 pension was added thio-ligand l-NPh (0.045 g, 0.25 mmol). A clear
tion of copper(I) chloride (0.025 g, 0.25 mmol) in 10 mL of aceto-
3
(0.132 g, 0.50 mmol). The solution was stirred
2 2 4 2 2
H46Cu I N P S
4
3
w, 2886 w; ν(C–N)+δ(C–H), 1529 s, 1507 s, 1478 s, 1433 s; 1407 m,
solution obtained was filtered and 1 mL of methanol was added to the
solution. Slow evaporation of solution at room temperature (10–15 d)
1
1
5
331 m, 1295 s, 1184 w, 1153w; ν(C = S), 1110 m; ν(P–CPh), 1092 s;
026 m, 998 w, 958 w, 918 w, 853 w, 746 s, 638 w, 618 w, 517 s, yielded colorless crystals. Procedure (b): To a solution of CuCl
–
1
01 s cm .
(0.025 g, 0.25 mmol) in 10 mL of acetonitrile was added solid PPh
3
Z. Anorg. Allg. Chem. 2015, 1728–1736
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ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
(0.066 g, 0.25 mmol) followed by stirring for 2 h at room temperature. preparing the mixed ligand complexes (molar ratio used:
To the precipitate formed was added l-NPh (0.045 g, 0.25 mmol) and
finally 1 mL dicholoromethane and the resulting solution was filtered
and kept undisturbed for crystallization. Colorless crystals of 7 (68%,
Cu:PPh :thio-ligand 1:2:1). Scheme 2 shows the formation of
mono-nuclear complexes (1, 2, 5–8) and Scheme 3 that of di-
nuclear complexes (3, 4). The preferred order of reaction used
3
2 2
M.p 174–184°C) were produced within one week. C45H40ClCuN P S:
is initially reacting a copper(I) halide with PPh followed by
3
calcd.C 67.35; H 4.99; N 3.49%; found: C 67.15; H 5.03; N 3.62%.
IR (KBr, absorption bands): ν˜ = ν(N–H) 3184 s; ν(C–H) 3051 s, 3001
w, 2955 w, 2894 w; ν(C–N)+δ(C–H) 1584 m, 1596 m, 1511 s, 1499
s, 1453 w, 1434 s, 1340 w, 1305 m, 1288 m, 1267 m, 1248 s, 1199 w,
the addition of a thio-ligand in situ [Scheme 2, route (i) for 1,
5
, 6, 8; Scheme 3 , route (i) for 3]. In case the mixed ligand
complex is not obtained, acetonitrile is removed after initially
and then the precipitate
028 m, 999 m, 949 m, 900 w, 848 w, 757 s, 746 s, 694 s, 665 m, is suspended in chloroform followed by the reaction with a
1
185 w, 1157 w; ν(C–S), 1120 w; ν(P–CPh), 1093 s; 1071 w, 1041 w, binding a copper(I) halide with PPh
3
1
6
–1
35 w, 618 w, 551 s, 518 s, 503 s, 422 w, 442 w cm .
thio-ligand [Scheme 2, route (ii) for 2, 7]. The addition of
small amount of methanol/dichloroform helped in crystalli-
zation. The chloro bridged dinuclear complex 4 was obtained
1
Synthesis of [CuBr(κ -S-
L-NPh)(PPh
3
)
2
] (8): To a solution of cop-
per(I) bromide (0.025 g, 0.17 mmol) in 10 mL of acetonitrile was
added PPh (0.092 g, 0.35 mmol). The solution was stirred and mildly
heated for 2 h and to the precipitate thio-ligand l-NPh (0.031 g,
by using 1:2:1 molar ratio (Cu:PPh :thio-ligand) through route
3
3
(ii) and using 1:1:1 molar ratio through route (iii) (see Scheme
3
). It was found that reaction of copper(I) chloride with PPh3
0
1
.17 mmol) was added. A clear solution obtained was filtered and
mL of methanol was added. Slow evaporation of solution at room and l-NPh in 1:1:1 molar ratio in CH
CN/CH Cl [route (iii)]
2 2
3
temperature (10–15 d) yielded colorless crystals of 8 (62%, M.p 175– also gave the same mononuclear complex 7 as obtained by
77 °C). C45 S: calcd. C 63.81; H 4.73; N 3.31%; found: route (ii) (Scheme 2).
C 63.50; H 4.50; N 3.10%. IR (KBr, absorption bands): ν˜ = ν(N–H)
1
2 2
H40BrCuN P
3
1
1
1
117 s; ν(C–H) 3050 s, 3002 w, 2957 w, 2895 w, 1596 m, 1584 m,
498 s, 1478 s, 1453 w, 1433 s, 1339 w, 1328 w, 1298 m, 1287 m,
251 s, 1184 w; ν(C–S), 1157 w; ν(P–CPh) 1092 s; 1071 w, 1026 m,
038 w, 998 m, 972 w, 947 w, 899 w, 849 w, 824 w, 746 s, 693 s, 634
–1
w, 618 w, 550 s, 518 s, 502 s, 442 w, 421 w cm .
X-ray Crystallography: The single crystals of compounds were
mounted on glass fibers and data were collected with an Xcalibur, Eos,
Gemini (1, 4, 7, 8) and a Bruker APEX-II CCD (2, 3, 5, 6) dif-
fractometer, equipped with a graphite monochromator and Mo-K
ation (λ = 0.71073 Å; 2–8,) and Cu-K radiation (λ = 1.54178 Å; 1).
The unit cell dimensions and intensity data were measured at 173(2) K
for 1, 4, 7, 8) and 296(2) K (for 2, 3, 5, 6). The data collection,
cell refinement were processed with CrysAlisPro and data reduction
α
radi-
α
(
Scheme 2. Synthesis of complexes (i) CH
3
CN/MeOH (1, 5, 6, 8), (ii)
CN/CH Cl (7).
(
a) CH CN, (b) CHCl /MeOH (2, 7), and (iii) CH
3
3
3
2
2
[
42]
processed with CrysAlisRED (1, 4, 7, 8).
The data for other com-
pounds (2, 3, 5, 6) collected with Bruker APEX2, while cell refinement
and data reduction carried out with Bruker SAINT (cell refinement,
[
43]
data reduction, data collection).
The structures were solved by di-
[
44,45]
rect methods using the program SHELXS97, SIR-92 and refined
by full-matrix least-squares techniques against F using SHELXL-
2
[46]
97
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-1054767 (1), CCDC-1054547 (2), CCDC-1054550
(
3), CCDC-1054551 (4), CCDC-1054548 (5), CCDC-1054549 (6),
CCDC-1054552 (7), and CCDC-1054553 (8) (Fax: +44-1223-336-
33; E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk)
Scheme 3. Synthesis of dinuclear complexes: (i) CH
3
CN/MeOH (3),
Cl (4).
(
ii) (a) CH CN, (b) CHCl /MeOH, and (iii) CH CN/CH
3
3
3
2
2
0
All complexes have shown the ν(N–H) bands in the region
Supporting Information (see footnote on the first page of this article):
3070–3265 cm–1 which are medium to strong in intensity and
reveal that the thio ligands are binding to central metal atoms
as neutral ligands. These bands either move to low energy re-
gion (1, 7, 8) or to high energy region (2–6) relative to the
uncoordinated thio ligands [ν(N–H), 3196 m, l-NMe; 3188 m,
l-NEt; 3203 s, l-NPh]. Likewise the ν(C–S) bands in the free
More details about ligands and X-ray packing figures.
Results and Discussion
Synthesis and IR spectroscopy
The imidazolidine-2-thione based thio-ligands, l-NMe, ligands occur in the region 1178 to 1200 cm–1 [ν(C–S), 1200
l-NEt and l-NPh, were reacted with copper(I) halides (X = Cl, s, l-NMe; 1199 s, l-NEt; 1178 m, l-NPh], which shift to low
–1
Br, I) and triphenylphosphine (PPh ) in acetonitrile for energy region (1100–1160 cm ) in complexes which support
3
Z. Anorg. Allg. Chem. 2015, 1728–1736
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that the thio ligands are coordinating through its thione sulfur complexes fall in two categories: four coordinated mononu-
to central metal atoms as neutral ligand. The ν(P–C ) bands clear (1, 2, 5–8) and dinuclear (3 and 4). The geometric param-
Ph
–
1
in the region 1090 to 1100 cm showed the presence of coor- eters are briefly discussed below.
dinated PPh in complexes. The above IR data support coordi-
3
nation of thio ligands and PPh as neutral ligands through sul-
fur and phosphorus respectively (see Experimental Section and
3
Mononuclear Complexes
Supporting Information for more IR details).
1
In complex [CuCl(κ -S-l-NMe)(PPh ) ] (1), the thio-ligand
3
2
l-NMe is bonded to the central copper(I) metal through its
sulfur donor atom at Cu–S bond length of 2.4154(6) Å. Cop-
Crystal and Molecular Structures
Complexes 2–4, 7, and 8 each formed crystals in the triclinic per(I) is also bonded to P donor atoms of two PPh ligands at
3
¯
system with P1 space group, the other complexes 1, 5 and 6 Cu–P distances of 2.2865(5) and 2.2967(5) Å, and to one
each crystallized in monoclinic crystal system with space chloride anion at Cu–Cl distance of 2.3440(5) Å (Table 2). The
groups P2 /c, C2/c, and P2 /n respectively (Table 1). Most of bond angles lie in the range of 98.92(2) to 121.92(2)°, which
1
1
Table 1. Crystallographic data for complexes 1–8.
1
2
3
4
Empirical formula
C
40
H38ClCuN
2
P
2
S
C
40
H38BrCuN
2
P
2
S·C36
H30BrCuP
2
C
44
H46Cu
2
I
2
N
4
P
2
S
2
46 2 2 4 2 2
C H50Cl Cu N P S
M
T /K
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
739.72
173(2)
monoclinic
1452.17
296(2)
1137.83
296(2)
982.94
173(2)
triclinic
P1
9.1060(6)
10.1794(9)
13.4004(10)
79.020(7)
73.800(7)
70.193(7)
1115.90(16)
1
triclinic
triclinic
¯
¯
¯
P2
1
/c
P1
P1
14.3620(5)
10.1350(3)
24.5148(9)
90
91.901(3)
90
3566.4(2)
4
1.378
9.8946(6)
17.6174(11)
19.9244(13)
84.274(3)
88.539(4)
79.225(3)
3394.8(4)
2
9.609(3)
9.824(3)
13.756(5)
102.644(16)
90.783(17)
116.723(14)
1122.3(7)
1
γ /°
V /Å3
Z
–3
Dcalcd. /g·cm
1.421
1.973
1.683
2.523
1.463
1.267
–1
μ /mm
3.186
F(000)
1536
1484
564
508
Reflections collected
Unique reflections
Data/ restraints / parameters
Reflections with [I Ͼ 2σ(I)]
R (reflections)
23241
64016
21651
12365
6907 (Rint, 0.0429)
6907 / 0 / 430
6151
0.0362 (6151)
0.0968(6907)
17307 (Rint, 0.0444)
17307/ 0 / 784
10623
0.0401(10623)
0.0894(17307)
0.543 and –0.755
6171 (Rint, 0.0335)
6171/ 0 / 257
5347
0.0270 (5347)
0.0685(6171)
0.511 and –0.788
7273 (Rint, 0.0338)
7273/ 0 / 263
6094
0.0374(6094)
0.0968 (7273)
0.452 and –0.447
WR2 (reflections)
Largest diff. peak and hole /e·Å–3 0.484 and –0.343
5
6
7
8
Empirical formula
C
41
H40BrCuN
2
P
2
S
C
41
H
38CuIN
2
P
2
S
C
45
H40ClCuN
2
P
2
S
45 2 2
C H40BrCuN P S
M
T /K
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
798.21
296(2)
monoclinic
C2/c
35.917(3)
12.8242(10)
17.6358(13)
90
113.559(4)
90
7446.1(10)
8
843.19
296(2)
monoclinic
801.80
173(2)
triclinic
846.24
173(2)
triclinic
¯
¯
P2
1
/n
P1
P1
12.9335(9)
21.4828(11)
14.5224(9)
90
104.301(2)
90
3910.0(4)
4
1.432
10.2292(5)
12.8630(7)
15.3861(8)
75.944(4)
79.403(4)
79.235(4)
1908.79(17)
2
10.3251(5)
12.8502(6)
15.4540(7)
76.242(4)
79.258(4)
79.566(4)
1936.52(16)
2
γ /°
V /Å3
Z
–3
Dcalcd. /g·cm
1.424
1.834
1.395
0.816
1.451
1.767
–1
μ /mm
1.514
F(000)
3280
1704
832
868
Reflections collected
Unique reflections
Data/ restraints / parameters
Reflens.with [I Ͼ 2σ(I)]
R (reflections)
53991
40770
25980
25461
13386 (Rint, 0.0611)
13386/ 0 / 433
7783
0.0407(7783)
0.0999 (13386)
0.337 and –0.560
10150 (Rint, 0.0465)
10150/ 0 / 434
6344
0.0408(6344)
0.0982(10150)
0.597 and –0.416
12653 (Rint, 0.0362)
12653 / 0 / 470
10191
0.0389(10191)
0.0996(12653)
0.617 and –0.490
12864 (Rint, 0.0391)
12864/ 0 / 470
9596
0.0422(9596)
0.0868(12864)
0.512 and –0.503
2
wR (reflections)
–3
Largest diff. peak and hole /e·Å
Z. Anorg. Allg. Chem. 2015, 1728–1736
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suggest distorted tetrahedral arrangement of complex 1 (Fig- mononuclear complexes lie in the usual range, ca. 121–
ure 1). The bonding pattern of other mononuclear complexes 126°.[
29–38]
1
is similar except that there is difference in anions (Br, 2, 5, 8;
Complex [(CuBr(κ -S-l-NMe)(PPh ) .CuBr(PPh ) ] (2) has
3
2
3 2
I, 6, Cl, 7) and thio ligands, which alter bond lengths and two different four and three coordinated independent
angles around the central metal atoms (Figure 2, Figure 3, Fig- molecules in the unit cell. The latter moiety CuBr(PPh ) has
3
2
ure 4, Figure 5, and Figure 6). The P–Cu–P bond angles of the two PPh ligands and a bromide bonded to a central metal
3
Table 2. Bond parameters /Å,° of complexes 1–8.
1
1
[
CuCl(κ -S-l-NMe)(PPh
3
)
2
] (1)
2.3440(5)
2.4154(6)
2.2865(5)
2.2967(5)
1.697(2)
108.759(19)
103.99(2)
112.92(2)
110.76(2)
121.17(2)
98.92(2)
[CuBr(κ -S-l-NMe)(PPh
3
)
2
] (2)
a)
b)
a)
b)
Cu1–Cl1
Cu1–Br1 ; Cu2–Br2
2.4821(4) ; 2.3331(4)
a)
a)
Cu1–S1
Cu1–P1
Cu1–P2
S1–C37
Cu1–S1
2.3976(7)
a)
b)
b)
a)
b)
b)
Cu1–P1 ; Cu2–P3
2.2718(7) ; 2.2626(7)
a)
a)
Cu1–P2 ; Cu2–P4
2.2877(7) ; 2.2638(7)
a)
a)
S1–C37
1.687(3)
110.05(2)
a)
a)
Cl1–Cu1–S1
P1–Cu1–S1
P2–Cu1–S1
P1–Cu1–Cl1
P1–Cu1–P2
P2–Cu1–Cl1
Cu1–S1–C37
Br1–Cu1–S1
P1–Cu1–S1
P2–Cu1–S1
P1–Cu1–Br1 ; P3–Cu2–Br2
P1–Cu1–P2 ; P3–Cu2–P4
P2–Cu1–Br1 ; P4–Cu2–Br2
Cu1–S1–C37
a)
a)
109.50(3)
a)
a)
98.66(3)
a)
b)
a)
b)
b)
102.46(2) ; 115.73(2)
a)
b)
a)
125.26(3) ; 128.98(3)
a)
b)
a)
b)
110.61(2) ; 115.26(2)
a)
a)
110.52(7)
109.81(9)
1
[Cu
2
I
2
(μ-S-l-NMe)
2
(PPh
3
)
2
] (3)
[Cu
2
(μ-Cl)
2
(κ -S-l-NEt)
2
(PPh
3
)
2
] (4)
Cu1–I1
Cu1–S1
Cu1–S1
Cu1–P1
2.5743(10)
2.3935(9)
2.4789(8)
2.2489(10)
1.711(2)
Cu1–Cl1
Cu1–Cl1
Cu1–S1
Cu1–P1
S1–C19
Cu1–Cl1–Cu1
Cl1–Cu1–Cl1
Cl1–Cu1–S1
Cl1–Cu1–S1
P1–Cu1–S1
2.3913(5)
2.5060(5)
2.3127(5)
2.2380(5)
1.7079(17)
84.312(16)
95.687(16)
114.451(17)
105.460(17)
114.738(18)
109.786(17)
114.453(17)
110.20(6)
S1–C19
Cu1–S1–Cu1
S1–Cu1–S1
I1–Cu1–S1
I1–Cu1–S1
P1–Cu1–S1
P1–Cu1–S1
P1–Cu1–I1
Cu1–S1–C19
92.07(3)
87.93(3)
115.32(2)
105.45(3)
108.32(3)
120.04(3)
116.67(3)
113.32(7)
P1–Cu1–Cl1
P1–Cu1–Cl1
Cu1–S1–C19
1
1
[
CuBr(κ -S-l-NEt)(PPh
3
)
2
] (5)
2.4845(4)
[CuI(κ -S-l-NEt)(PPh
3
)
2
] (6)
Cu1–Br1
Cu1–I1
2.6733(4)
2.3785(9)
2.2958(8)
2.2864(8)
2.2864(8)
112.44(2)
102.99(3)
108.95(3)
105.45(2)
103.20(2)
123.91(3)
110.21(11)
Cu1–S1
Cu1–P1
Cu1–P2
S1–C37
S1–Cu1–Br1
P1–Cu1–S1
P2–Cu1–S1
P1–Cu1- Br1
P2–Cu1–Br1
P2–Cu1–P1
C37–S1–Cu1
2.3868(6)
2.2966(6)
2.2750(6)
1.701(2)
111.199(18)
101.98(2)
103.93(2
105.367(17)
107.825(16)
126.14(2)
110.00(7)
Cu1–S1
Cu1–P1
Cu1–P2
S1–C37
S1–Cu1–I1
P1–Cu1–S1
P2–Cu1–S1
P1–Cu1–I1
P2–Cu1–I1
P2–Cu1–P1
C37–S1–Cu1
1
1
[
CuCl(κ -S-l-NPh)(PPh
3
)
2
] (7)
[CuBr(κ -S-l-NPh)(PPh
3
)
2
] (8)
Cu1–Cl1
Cu1–S1
Cu1–P1
2.3297(4)
2.4448(5)
2.2626(4)
Cu1–Br1
Cu1–S1
S1–C1
2.4510(3)
2.4342(5)
1.692(2)
Cu1–P2
S1–C1
2.2824(4)
Cu1–P1
Cu1–P2
2.2634(5)
2.2802(5)
105.373(16)
103.60(2)
106.951(19)
105.518(16)
108.427(17)
125.381(19)
102.94(7)
1.6944(16)
103.874(16)
102.955(16)
106.218(16)
108.102(16)
108.964(17)
124.703(16)
101.87(6)
Cl1–Cu1–S1
P1–Cu1–S1
P2–Cu1–S1
P1–Cu1–Cl1
P2–Cu1–Cl1
P1–Cu1–P2
C1–S1–Cu1
S1–Cu1–Br1
P1–Cu1–S1
P2–Cu1–S1
P1–Cu1–Br1
P2–Cu1–Br1
P1–Cu1–P2
C1–S1–Cu1
a) Refers to parameters of molecule 1. b) Refers to parameters of molecule 2.
Z. Anorg. Allg. Chem. 2015, 1728–1736
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1
3 2
Figure 1. Molecular structure of [CuCl(κ -S-l-NMe)(PPh ) ] (1).
Figure 3. Molecular structure of [CuBr(κ1-S-l-NEt)(PPh3)2] (5).
1
Figure 2. Molecular structure of [(CuBr(κ -S-l-NMe)(PPh
3
)
2
).
3 2
CuBr(PPh ) ] (2).
atom and angles around the metal atom (115–129°) suggest a
distorted trigonal planar arrangement. A related thio ligand,
1
3 2
Figure 4. Molecular structure of [CuI(κ -S-l-NEt)(PPh ) ] (6).
1,3-imidazoline-2-thione (LЈ-NH) is reported to yield mononu-
clear copper(I) complexes, [CuX(LЈ-NH)(PPh ) ] (X = Br, I)
3
2
similar to monomer 1 as well as a mixed coordinate complex
ure 7).[48,49] The unequal Cu–S distances, 2.3935(9),
2.4789(8) Å suggest that Cu S core forms a parallelogram.
1
[
2
(CuCl(κ -S-LЈ-NH)(PPh ) .CuCl(PPh ) ] similar to complex
3 2 3 2
2
2
[
47]
.
The bond parameters of complexes under study are sim-
ilar to those reported for LЈ-NH ligand and other heterocy-
clic-2-thiones.[
The angles around the central copper atoms vary in the range
of ca. 88 to 120° suggesting distorted tetrahedral arrangement
of each central metal atom. The angles of Cu S core, namely,
[47]
29–38]
2
2
Cu–S–Cu, 92.07(3)° and S–Cu–S, 87.93(3)° are much different
from usually observed ideal values of ca. Cu–S–Cu, 70° and
S–Cu–S 109° shown by parallelograms of such Cu S
Dinuclear Complexes
2
2
Complex [Cu I (μ-S-l-NMe) (PPh ) ] (3) has each cop- cores.[
48,49]
2
2
2
3 2
1
per(I) ion bonded to two bridging S, one P and one I donor
species at Cu–S, Cu–P and Cu–I bond lengths of 2.3935(9), each copper metal atom bonded to two bridging Cl, one P and
.4789(8); 2.2489(10) and 2.5743(10) Å, respectively (Fig- one S atoms at bond lengths of 2.3913(5), 2.5060(5); 2.2380(5)
The second dimer [Cu (μ-Cl) (κ -S-l-NEt) (PPh ) ] (4) has
2 2 2 3 2
2
Z. Anorg. Allg. Chem. 2015, 1728–1736
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Figure 7. Molecular structure of [Cu
2
I
2
2 3 2
(μ-S-l-NMe) (PPh ) ] (3).
1
3 2
Figure 5. Molecular structure of [CuCl(κ -S-l-NPh)(PPh ) ] (7).
1
1
Figure 6. Molecular structure of [CuBr(κ -S-l-NPh)(PPh
3
)
2
] (8).
Figure 8. Molecular structure of [Cu (μ-Cl) (κ -S-l-NEt) (PPh ) ]
2
2
2
3 2
(
4).
and 2.3127(5) Å, respectively (Figure 8). The Cu–S distance is
short as thio ligand l-NEt is terminally bonded unlike μ-S
bridging by l-NMe in 3. The angles around the central copper
atoms vary in the range of ca. 95 to 115° suggesting distorted
tetrahedral arrantgement of each central metal atom. It is
atoms were bridging two silver atoms. In this context complex
[
52]
4
(X = Cl) shows the same halogen bridging behavior. How-
ever, this trend appears to be reversed in complex 3 (X = I)
due to the presence of bulky iodide, which has favored ter-
minal bonding.
known that the C–S double bond length is 1.62°A, whereas
the C–S single bond length is 1.81 Å.[
50,51]
A comparison of
C–S bond lengths observed in different complexes (Table 2)
reveals a variation from 1.687 to 1.711 Å, which suggests a
considerable double bond character in this bond. Complex 3
Proton NMR Spectroscopy
1
Table 3 gives H NMR spectroscopic data of complexes 1–
shows the longest C–S bond due to Cu–S–Cu bridging occur- 8. The most sensitive protons of thio ligands to coordination
ring in this complex. are –NH protons, while ring protons are generally less affected
It was observed recently by our group that the ligands under except in complex 2. Thus complexes 1, 2, 4–8 showed NH
discussion formed dinuclear complexes with silver(I) chloride/ signals in the region 7.72 to 9.87 ppm, significantly to low
bromide and each thio ligand was terminal and only halogen field relative to the uncoordinated ligands (6.09 to 6.53 ppm),
Z. Anorg. Allg. Chem. 2015, 1728–1736
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Table 3. H NMR spectroscopic data (δ in ppm) of complexes 1–8.a)
1
Compound
Ring + N–R protons
PPh
3
Compound
Ring + N–R protons
PPh
3
1
8.64 s (NH)
7.44 m (12 H, o-H),
7.36 m (6 H, p-H),
7.30 m (12 H, m-H)
5
8.36 s (NH)
7.44 m (12 H, o-H),
7.36 m (6 H, p-H),
7.28 m (12 H, m-H)
4
4
3
3
3
.65 m (C H
.59 m (C H
2
),
),
3.61 m (C H
2
),
5
5
2
3.55 m (C H
2
2
,N-CH ),
.07 s (CH
3
)
3
1.41 t (CH )
2
3
4
8.55 s (NH)
7.39 m (12 H, o-H),
7.35 m (6 H, p-H),
7.30 m (12 H, m-H)
6
7
8
7.72 s (NH)
7.44 m (12 H, o-H),
7.36 m (6 H, p-H),
), 7.28 m (12 H, m-H)
4
4
3
3
3
.68 m (C H
.57 m (C H
.01 m (CH
2
),
),
3.62 m (C H
2
),
5
5
2
3.55 m (C H
2
, N-CH
2
3
)
1.15 t (CH
3
)
6.03 s (NH)
5.85 m (12 H, o-H),
5.77 m (6 H, p-H),
5.69 m (12 H, m-H)
9.87 s (NH)
7.44 m (14 H, o-H),b)
7.36 m (6 H, p-H),
4
4
2
1
1
.04 m (C H
2
),
),
4.08 t (C H
2
),
),
5
5
b)
.94 m (C H
2
3.76 t (C H
2
7.28 m (14 H, m-H)
.45 s (CH
3
)
7.40 m (p-H, N–Ph)
b)
9.31 s (NH)
7.51 m (12 H, o-H),
7.40 m (18 H, m-H and, p-H)
9.13 s (NH)
7.43 m (14 H, o-H),
7.36 m (7 H, p-H),
7.26 m (14 H, m-H)
.72 bs (C4,5H
.60 q (N–CH
.21t (CH
),
),
4.01 t (C H
4
),
)
b)
3
3
1
2
2
5
b)
2
3.65 t (C H
2
3
)
4
5
L-NMe
L-Net
L-NPh
6.09s (NH), 3.72 m (C H
2
), 3.58m (C H
2
), 3.15 s (CH
3
)
4
5
6.09 s(NH),3.68 m (C H
2
, N-CH ), 1.20 t (CH
2
), 3.58 m (C H
2
3
)
4
5
6.53s (NH), 4.19m (C H
2
), 3.76m (C H ), 7.59m (o-H, N–Ph),7.43 m (m-H, N–Ph), 7.27 m (p-H, N–Ph)
2
a) Proton NMR spectra of 1, 3–8 recorded in CDCl
3
and that of 2 in CDCl + D [DMSO]. b) Incorporate N–Ph hydrogen signals.
3
6
Table 4. Intramolecular N/H···halogen contacts /Å.
Compound
X
d(X–H)
d(H–X), van
Δd
1
d(N–X)
d(N–X), van d(N–X)
Δd
2
der Waals
der Waals
1
2
3
4
5
6
7
8
Cl
Br
I
Cl
Br
I
2.291
2.711
2.913
2.403
2.509
2.848
2.528
2.677
2.9
3.0
3.15
2.9
3.0
3.15
2.9
0.609
0.289
0.237
0.497
0.491
0.302
0.372
0.323
3.097
3.362
3.608
3.222
3.336
3.635
3.145
3.294
3.25
3.35
3.5
3.25
3.35
3.5
3.097
3.362
3.608
3.222
3.336
3.635
3.145
3.294
0.153
–0.012
–0.108
0.028
0.014
–0.135
0.105
Cl
Br
3.25
3.35
3.0
0.056
except complex 2, in which this signal is unaffected as well as formed: mononuclear tetrahedral [CuX(L-NR)(PPh ) ], halo-
3
2
4
5
1
its ring proton signals (C H , C H , N-Me) moved to high gen- and sulfur-bridged dimers, [Cu (μ-Cl) (κ -S-L-
2
2
2
2
field. Further, it can be seen that for –NH signas, the magni- NEt) (PPh ) ] and [Cu I (μ-S-L-NMe) (PPh ) ]. In silver(I)
2
3 2
2 2
2
3 2
tude of shift varies in the order : Cl Ͼ Br Ͼ I. It is added here halide (chloride/bromide) complexes of this class of thio li-
that X-ray crystallography has shown that there is an intramo- gands with PPh as a co-ligand, it was found that halogen
3
lecular interaction involving the N–H···X(halogen) moiety. bridging was favored over sulfur bridging,[ and this trend
From Table 4 it can be seen that d(H···X) and d(N···X) dis- continues with copper(I) chloride, though with copper(I) iod-
tances are less than the sum of van der Waals radii of atoms ide, the trend is reversed. It is added here that pyridine-2-
52]
participating in these bonds for X = Cl and Br and are more thione has displayed essentially sulfur-bridging in its dinuclear
for X = I. These interactions decrease with the decrease of complexes.[
49]
Reaction of copper(I) chloride/bromide with
electronegativity of a halogen. The ring protons (C4,5H ) ap- thio ligands under discussion in the absence of PPh involved
2
3
peared as triplets in 7 and 8, while these are multiplets in other C–S rupture forming copper(II) sulfate, but other products
complexes (1–6), due to lack of resolution/interference of could not be identified. The binding of copper(I) chloride/
N–Me and N–Et protons. The o-, m- and p-hydrogen atoms of bromide to PPh followed by binding to sulfur of thio ligands
3
PPh show signals in separate regions, and also incorporate has yielded stable mixed-ligand copper(I) complexes.
3
N–Ph signals of the l-NPh ligand coordinated to central metal
atoms for complexes 7 and 8.
Acknowledgements
Conclusions
Financial assistance in the form of Emeritus Scientist Grant (21(0904)/
2-EMR-II) to T. S. Lobana, from the Council of Scientific and Indus-
trial Research (CSIR), New Delhi is gratefully acknowledged. J. P. J
1
A series of mixed ligand mono- and dinuclear complexes of
copper(I) halides with imidazolidine-2-thiones and PPh (as
3
acknowledges the NSF-MRI program (grant No. CHE-1039027) for
co-ligand) 1–8 are synthesized, which represent first examples funds to purchase the X-ray diffractometer. Authors thank the re-
of this class of thio ligands. Three types of complexes are viewers for useful comments which improved the quality of paper.
Z. Anorg. Allg. Chem. 2015, 1728–1736
1735
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
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Zeitschrift für anorganische und allgemeine Chemie
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Received: March 21, 2015
Published Online: June 18, 2015
Z. Anorg. Allg. Chem. 2015, 1728–1736
1736
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim