The Cu(I) thiocyanate complexes with N-allylquinolinium: Synthesis and crystal structures of [C9H7NC3H 5]Cu(SCN)2 and [C9H7NC 3H5]Cu2(SCN)3

Article abstract of DOI:10.1134/S1070328408100084

The crystals of [C₉H₇NC₃H ₅]Cu(SCN)₂ (I) and [C₉H₇NC ₃H₅]Cu₂(SCN)₃ (II) were obtained in the reaction of N-allylquinolinium bromide with CuSCN and NH₄SCN in a methanol solution. The crystals of I are triclinic: space group P¹, Z = 2, a = 8.619(2), b = 8.755(2), c = 10.463(3) A, α = 77.18(3), β = 69.95(3), γ = 79.38(3)°, V = 718.1(3) A³. The crystals of II are opthorhombic: space group P2₁2 ₁2₁, Z = 4, a = 5.744(2), b = 16.799(4), c = 17.980(5), V = 1735.9(9) A³. The structure of compound I is built of infinite linear {Cu(SCN)₂^-}_∞ anions and the N-allylquinolinium cations bonded additionally by relatively weak hydrogen contacts C-H...S. The [C₉H₇NC₃H ₅]⁺ cations are located between the corrugated layers of the {Cu₂(SCN)₃^-}_∞ anions in compound II. As in the case of the previously studied copper(I) halide complexes, the C=C bond of the allyl group in the N-allylquinolinium cation of complexes I, II does not interact with Cu(I).

Full text of DOI:10.1134/S1070328408100084

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2008, Vol. 34, No. 10, pp. 756–761. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © A.V. Pavlyuk, V. Kinzhybalo, T. Lis, M.G. Mys’kiv, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 10, pp. 764–769.
The Cu(I) Thiocyanate Complexes with N-Allylquinolinium:
Synthesis and Crystal Structures
of [C9H7NC3H5]Cu(SCN)2
and [C9H7NC3H5]Cu2(SCN)3
A. V. Pavlyuka,b, V. Kinzhybaloa, T. Lisa, and M. G. Mys’kivb
a Wroclaw University, Wroclaw, Poland.
b Franko National University, ul. Kirilla I Mefodiya 8, Lvov, 290005 Ukraine
E-mail: myskiv@franko.lviv.ua
Received October 18, 2007
Abstract—The crystals of [C9H7NC3H5]Cu(SCN)2 (I) and [C9H7NC3H5]Cu2(SCN)3 (II) were obtained in the
reaction of N-allylquinolinium bromide with CuSCN and NH4SCN in a methanol solution. The crystals of I are
triclinic: space group P1, Z = 2, a = 8.619(2), b = 8.755(2), c = 10.463(3) Å, α = 77.18(3), β = 69.95(3),
γ = 79.38(3)°, V = 718.1(3) Å3. The crystals of II are opthorhombic: space group P212121, Z = 4, a = 5.744(2),
b = 16.799(4), c = 17.980(5), V = 1735.9(9) Å3. The structure of compound I is built of infinite linear
{Cu(SCN)–2}∞ anions and the N-allylquinolinium cations bonded additionally by relatively weak hydrogen
contacts C–H…S. The [C9H7NC3H5]+ cations are located between the corrugated layers of the {Cu2(SCN)3–}∞
anions in compound II. As in the case of the previously studied copper(I) halide complexes, the C=C bond of
the allyl group in the N-allylquinolinium cation of complexes I, II does not interact with Cu(I).
DOI: 10.1134/S1070328408100084
The previous study of the complex formation of Buchner funnel with a mixture of benzene and hexane
copper(I) halides with N-allyl derivatives of mononi- (1 : 3).
trogen heterocycles showed that its nature depends on
Copper(I) thiocyanate was obtained by reacting the
the type of the halogen atom and basicity of the starting
aqueous solution of CuSO4 and NH4SCN. On stirring,
heterocycle [2]. The N-allylquinolinium catioans (pKa
the black-colored mixture turned quickly to the white
precipitate of CuSCN. The powder obtained was
washed with distilled water, methyl alcohol, and dried.
of quinoline is equal to 4.94) does not form the π-com-
plexes with Cu(I) halides, unlike the N-allyl derivatives
of pyridine and isoquinoline (the pKa values of the cor-
responding bases being equal to 5.20 and 5.40).
The
red
plates
of
the
complex
[C9H7NC3H5]Cu(SCN)2 (I) were synthesized from the
solution of N-allylquinolinium bromide, CuSCN, and
NH4SCN in methanol heated to 60°ë for 5 min. The yel-
low plates of the [C9H7NC3H5]Cu2(SCN)3 (II) crystals
were formed in the same vessel in two months.
On the other hand, the interaction of N-allylquino-
linium halides with copper pseudohalide CuCN gives
the novel heterocyclic cation [C24H21N2]+ [3].
In this connection it was interesting to study the
peculiarities of the reaction between the N-allylquino-
linium cation and CuSCN. This paper reports the
results of the X-ray diffraction study of the complex
formation in the system N-allylquinolinium bromide–
CuSCN–NH4SCN.
X-ray diffraction analysis. After the preliminary
study by the photomethod, the structures of I, II were
solved using the diffraction data arrays obtained on the
single-crystal KUMA KM4 CCD diffractometer (with
CCD detector, MoKα radiation, graphite monochroma-
tor, ω-scan mode, and low-temperature OXFORD Cry-
osystem unit). The reflection intensities were corrected
for the Lorentz and polarization factors. The X-ray dif-
fraction data were processed with the CrysAlis RED
EXPERIMENTAL
N-allylquinolinium bromide was prepared by heat- program [5]. The structures of I, II were solved by the
ing with refluxing of the chloroform solutions of the direct methods, the light atoms were localized from the
distilled quinoline and allyl bromide for 20 h [4]. The Fourier syntheses. The absorption correction was
crystalline salt obtained was filtered and washed on the applied by the analytical method [6]. The structure was
756

THE Cu(I) THIOCYANATE COMPLEXES WITH N-ALLYLQUINOLINIUM
757
Table 1. The crystallographic characteristics and the details of the experiment for single crystals of [C9H7NC3H5]Cu(SCN)2 (I) and
[C9H7NC3H5]Cu2(SCN)3 (II)
Value
Parameter
I
II
M
349.9
471.6
P212121
Space group
P1
8.619(2)
8.755(2)
10.463(3)
77.18(3)
69.95(3)
79.38(3)
718.1(3)
2
a, Å
5.744(2)
b, Å
16.799(4)
c, Å
17.980(5)
α, deg
90
β, deg
90
γ, deg
V, Å3
90
1735.0(9)
4
Z
ρ(calcd.), g/cm3
F(000)
Crystal size, mm
1.618
1.805
356
944
0.07 × 0.16 × 0.54
1.80
0.06 × 0.27 × 0.34
2.82
µ
Mo, mm–1
T, K
100(2)
29.0
240(2)
36.7
θ
max, deg
Number of reflections
Independent reflections with F ≥ 2σF*
Number of refined parameters
10307
19572
6074
5899
181
217
1/[σ2(Fe2xp) + (0.039P)2]
Weighting scheme, w**
1/[σ2(Fe2xp) (0.026P)2]
R
0.035
0.085
0.048
0.074
wR
GOOF
0.94
1.00
∆ρmax/∆ρmin, eÅ–3
The Fleck parameter
0.64/–0.42
0.56/–0.43
0.02(1)
* With correction for the Loretz and polarization factors, absorption.
** R = (F2exp + 2Fe2xp)/3.
solved with the SHELX program package [7]. The
hydrogen atoms located from the Fourier syntheses
were refined in the rider model together with non-
hydrogen atoms.
RESULTS AND DISCUSSION
The crystal structure of complex I is built of the
polymer inorganic anions {Cu(SCN)–2}∞ and the
N-allylquinolinium cations (Fig. 1). The Cu(I) atom has
the distorted tetrahedral coordination surrounding of
The crystallographic parameters and details of the
X-ray diffraction experiment are given in Table 1; the
coordinates of non-hydrogen atoms and the thermal two N and two S atoms. The SCN– ions use their coor-
factors are listed in Table 2; the main bond lengths and dinating capacity in full and act as the linking units
bond angles are presented in Table 3.
between the metal atoms, which leads to the formation
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 10 2008

758
PAVLYUK et al.
Table 2. The coordinates of non-hydrogen atoms the their Table 3. The main bond lengths and bond angles in struc-
thermal parameters (Ueq) in structures I, II
tures I, II
Atom
x
y
z
Ueq, Å2*
Bond
d, Å
Angle
ω, deg
I
I
Cu(1)–N(21)i 1.957(2) N(21)iCu(1)N(31) 126.23(6)
Cu(1)–N(31) 1.960(2) N(21)iCu(1)S(31)ii 108.22(5)
Cu(1)–S(31)ii 2.3898(7) N(31)Cu(1)S(31)ii 103.80(5)
Cu(1)–S(21) 2.457(1) N(21)iCu(1)S(21) 103.75(5)
Cu(1)
0.00156(3) –0.01059(3) 0.25095(2) 0.01971(7)
S(21) –0.24268(6) 0.13763(5) 0.39340(5) 0.0197(1)
C(21) –0.1831(2) 0.1118(2) 0.5315(2) 0.0154(3)
N(21) –0.1404(2) 0.0890(2) 0.6288(2) 0.0191(3)
S(31)
C(31)
N(31)
N(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
0.09124(5) 0.23185(5) –0.21168(5) 0.01807(9)
0.0772(2) 0.1675(2) –0.04753(2) 0.0162(3)
0.0674(2) 0.1215(2) 0.0679(2) 0.0185(3)
0.3158(2) 0.2594(2) 0.2388(2) 0.0164(3)
0.4285(2) 0.1430(2) 0.2695(2) 0.0204(4)
0.5647(2) 0.0852(2) 0.1682(2) 0.0221(4)
0.5846(2) 0.1485(2) 0.0324(2) 0.0211(4)
0.4832(2) 0.3411(2) –0.1411(2) 0.0205(3)
0.3701(2) 0.4638(2) –0.1715(2) 0.0228(4)
0.2372(2) 0.5204(2) –0.0648(2) 0.0221(4)
0.2152(2) 0.4556(2) 0.0710(2) 0.0189(3)
0.3311(2) 0.3293(2) 0.1038(2) 0.0166(3)
0.4674(2) 0.2717(2) –0.0028(2) 0.0174(3)
0.1740(2) 0.3129(2) 0.3573(2) 0.0216(4)
0.2012(2) 0.4612(2) 0.3915(2) 0.0214(4)
0.2811(3) 0.4598(2) 0.4785(2) 0.0283(4)
II
S(21)–C(21) 1.650(2) N(31)Cu(1)S(21)
106.38(5)
C(21)–N(21) 1.163(2) S(31)iiCu(1)S(21) 107.37(3)
N(21)–Cu(1)i 1.957(2) C(21)S(21)Cu(1)
S(31)–C(31) 1.654(2) N(21)C(21)S(21)
97.81(6)
178.1(2)
S(31)–Cu(1)ii 2.3898(7) C(21)N(21)Cu(1)i 159.7(2)
C(31)–N(31) 1.164(2) C(31)S(31)Cu(1)ii
C(12)–C(11) 1.499(3) N(31)C(31)S(31)
97.74(7)
179.7(2)
C(13)–C(12) 1.312(3) C(31)N(31)Cu(1) 158.0(1)
C(11)–N(1)
N(1)–C(2)
N(1)–C(9)
1.502(2) C(13)C(12)C(11)
1.338(2) C(12)C(11)N(1)
1.380(2) C(11)N(1)C(2)
C(2)N(1)C(9)
122.4(2)
111.8(2)
117.3(2)
121.2(2)
II
Cu(1)–S(31)vi 2.2894(9) S(31)viCu(1)S(41) 104.61(3)
Cu(1)–S(21)iii 2.4792(10) N(41)Cu(1)S(21)iv 103.53(8)
Cu(1)–S(41) 2.4007(9) S(31)viCu(1)S(21)iv 114.20(3)
Cu(1)–N(41) 1.956(3) N(41)Cu(1)S(31)vi 124.99(7)
Cu(1)
Cu(2)
N(21)
C(21)
S(21)
N(31)
0.03877(6) 0.21377(2) 0.22169(2) 0.0309(1)
0.29209(7) 0.38328(2) 0.26671(3) 0.0449(2)
0.5963(5) 0.3640(1) 0.3083(2) 0.0340(7)
0.7740(5) 0.3351(2) 0.3210(2) 0.0243(6)
1.0281(1) 0.29183(4) 0.33866(4) 0.0286(2)
0.1072(5) 0.4774(1) 0.2540(2) 0.0351(7)
Cu(2)–S(41) 2.5222(10) N(41)Cu(1)S(41)
Cu(2)–S(21)iii 2.5164(10) S(41)Cu(1)S(21)iv
Cu(2)–N(31) 1.918(3) N(31)Cu(2)N(21) 133.4(1)
Cu(2)–N(21) 1.929(3) N(31)Cu(2)S(21)iv 103.32(9)
N(21)–C(21) 1.153(4) N(21)Cu(2)S(21)iv 104.11(9)
C(21)–S(21) 1.661(3) N(31)Cu(2)S(41)
N(31)–C(31) 1.164(4) N(21)Cu(2)S(41)
C(31)–S(31) 1.645(3) S(21)ivCu(2)S(41)
N(41)–C(41)iv 1.155(4) Cu(1)iiiS(21)Cu(2)iii 82.64(3)
C(41)–S(41) 1.661(3) C(31)S(31)Cu(1)v 105.1(1)
107.60(8)
98.68(3)
111.60(9)
102.95(8)
94.57(3)
C(31) –0.0315(6) 0.5274(2) 0.2605(2) 0.0259(7)
S(31) –0.2353(1) 0.59562(4) 0.26919(5) 0.0298(2)
N(41) –0.2758(4) 0.2261(1) 0.1816(2) 0.0294(6)
C(41)
S(41)
N(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
0.5460(6) 0.2548(2) 0.1686(2) 0.0249(7)
0.2925(1) 0.29844(4) 0.15098(4) 0.0259(2)
0.2951(5) 0.5463(1) 0.0493(2) 0.0302(6)
0.1318(6) 0.5565(2) –0.0024(2) 0.0405(9)
0.1114(7) 0.5061(2) –0.0631(2) 0.0479(10)
0.2630(7) 0.4450(2) –0.0703(2) 0.0404(9)
0.6026(7) 0.3702(2) –0.0235(2) 0.0409(9)
0.7726(7) 0.3611(2) 0.0282(2) 0.0426(9)
0.7867(6) 0.4138(2) 0.0881(2) 0.0366(8)
0.6341(6) 0.4753(2) 0.0968(2) 0.0324(8)
0.4564(6) 0.4848(2) 0.0440(2) 0.0249(6)
0.4378(6) 0.4325(2) –0.0176(2) 0.0313(7)
0.3102(6) 0.6040(2) 0.1117(2) 0.0382(8)
0.4867(6) 0.6677(2) 0.0975(2) 0.0393(8)
0.5958(7) 0.6800(2) 0.0364(2) 0.0486(10)
C(11)–N(1)
1.486(4) C(41)S(41)Cu(1)
99.8(1)
95.3(1)
84.11(3)
C(11)–C(12) 1.496(5) C(41)S(41)Cu(2)
C(12)–C(13) 1.281(5) Cu(1)S(41)Cu(2)
C(31)N(31)Cu(2) 164.3(3)
C(41)ivN(41)Cu(1) 159.5(2)
C(21)S(21)Cu(1)iii 95.2(1)
C(21)S(21)Cu(2)iii 99.5(1)
C(21)N(21)Cu(2) 161.8(2)
C(13)C(12)C(11)
C(12) C(11)N(1)
N(21)C(21)S(21)
N(31)C(31)S(31)
N(41)iiiC(41)S(41) 178.4(3)
C(9)N(1)C(11)
126.3(3)
112.2(3)
178.9(3)
177.8(3)
119.8(3)
i
ii
iii
* Ueq = 1/3
U a*a*(a a ).
ij i j i j
∑∑
* The symmetry transformations: –x, –y, –z + 1; –x, –y, –z; x + 1,
iv
v
vi
i
j
y, z; x – 1, y, z; –x, y + 0.5, –z + 0.5; –x, y – 0.5, –z + 0.5.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 10 2008

THE Cu(I) THIOCYANATE COMPLEXES WITH N-ALLYLQUINOLINIUM
759
H(3)
C(3)
H(4)
H(13b)
C(4)
H(13a)
H(5)
H(2)
C(2)
C(10)
C(5)
C(13)
C(9)
H(12)
C(12)
H(6)
x
N(1)
C(11)
C(6)
y
iii
H(11b)
S(21)
z
C(8)
C(7)
H(8)
H(7)
iii
H(11a)
C(21)
iii
N(21)
i
S(21)
Cu(1)
N(31)
C(31)
N(21)
S(31)
i
C(21)
C(21)
i
i
N(21)
Cu(1)
Cu
S
S(21)
i
S(31)
i
ii
C(31)
i
N(21)
N(31)
ii
C
C(21)
N
H
ii
S(21)
Fig. 1. The fragment of the [C H NC H ]Cu(SCN) (I) structure.
9
7
3
5
2
Cu
S
C
N
H
y
z
x
Fig. 2. The packing of the structural units in compound I.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 10 2008

760
PAVLYUK et al.
Table 4. The geometrical parameters of the short interionic
contacts (H···S < 3.0 Å ) in structures I, II*
Cu(2) atom involves two S and two N atoms (as in the
case of I), while the Cu(1) tetrahedron is formed by
three S atoms and one N atom (Fig. 3). The S atom of
one of the crystallographically independent thiocyanate
anion enters the coordination sphere of two metal
atoms thus forming the corrugated ribbons of
Distance, Å
the DHA
D–H···A bond
angle, deg
D–H H···A
D···A
{Cu2(SCN)–2}∞. The analogous topological units were
I
C(8)–H(8)···S(31)vii 0.95
C(3)–H(3)···S(31)viii 0.95
2.81 3.617(2)
2.81 3.746(2)
143
169
previously described for [(1,10-diaza-18-crown-
6)Cu2(SCN)2] [9] and [(4,4'-Bipy)Cu2(SCN)2] (4,4'-
Bipy is 4,4'-bipyridine) [10]. However, in structure II,
the second SCN– ion unites separate ribbons into infi-
II
C(8)–H(8)···S(31)iii 0.94
C(7)–H(7)···S(41)iii 0.94
2.85 3.776(4)
2.91 3.670(4)
2.96 3.804(4)
168
138
nite walls of {Cu2(SCN)–3}∞, perpendicular to [001]
(Fig. 4). The voids between the anions are filled with
the N-allylquinolinium cation. In the absence of the
π-interaction with the Cu(I) atom, the allyl group of the
cation is slightly disordered, which appears as the imag-
inary shortening of the ë=ë distance to 1.282(5) Å. The
lacking additional bonding by the intermolecular con-
tacts provide the relatively free rotation of the allyl
group and thus the unique for the N-allyl derivatives
conformation of the N-allylquinolinium cation. The
comparison of the torsion angles (τ) CH2=CH–CH2–N,
which describe the spatial location of the allyl group
relative to a plane of the quinoline nucleus, for
21 known compounds [11] showed that the value of
τ lies in the interval 80°–140°, except for the complexes
[Cu{4-H2N–C5H4N(C3H5)}Cl2] [12] and II. In the latter
C(5)–H(5)···S(41)ix
0.94
150
iii
vii
* The symmetry transformations: x + 1, y, z;
–x, –y + 1, –z;
viii
ix
–x + 1, –y, –z; x + 0.5, –y + 0.5, –z.
of the infinite inorganic chains directed along [001]
(Fig. 2). The N-allylquinolinium cations lying between
isolated polyanions form almost planar layers parallel
to the fragments {Cu(SCN)–2}∞. The structure is stabi-
lized also by sufficiently weak hydrogen contacts
C−H···S [8] (H···S 2.81 Å, Table 4).
Complex II has somewhat different structure. The
distorted tetrahedral coordination surrounding of the
H(13b)
C(13)
H(12)
H(13a)
C(12)
S(31)
H(11b)
C(2)
H(2)
H(3)
C(3)
C(11)
H(11a)
C(31)
N(31)
iii
N(1)
H(8)
C(7)
C(4)
Cu(2)
N(21)
iii
C(9)
C(21)
C(8)
iii
S(21)
H(7)
C(10)
iii
H(4)
S(41)
iii
C(41)
C(5)
C(6)
H(6)
iii
H(5)
N(41)
N(21)
C(21)
S(21)
y
Cu
S(41)
Cu(1)
C(41)
x
z
N(41)
S
C
iν
S(31)
N
H
iν
C(31)
iν
N(31)
Fig. 3. The fragment of the [C H NC H ]Cu (SCN) (II) structure.
9
7
3
5
2
3
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 34 No. 10 2008

THE Cu(I) THIOCYANATE COMPLEXES WITH N-ALLYLQUINOLINIUM
761
Cu
S
C
N
H
z
x
y
Fig. 4. The packing of the structural units in compound II.
3. Pavlyuk, O., Lis, T., and Mys’kiv, M., Z. Anorg. Allg.
Chem., 2005, vol. 631, no. 10, p. 1893.
cases, one of the two terminal H atoms of the allyl
group is additionally bonded, respectively, with the
pyridine and quinoline nucleus via the C–H…π contact
[13]. In the structure of compound II, the H(13‡)···M
distance (M is the pyridine nucleus center) is 3.03,
H(13‡)···N – 2.50 Å, the angle C(13)−H(13a)···M is
equal to 128°.
4. Weygand, C. and Hilgetag, G., Organisch-Chemische
Experimentierkunst, Leipzig: Barth, 1964.
5. CrysAlis RED. Oxford Diffraction Ltd. Version
1.171.31.8 (release 12-01- 2007 CrysAlis171.NET).
6. Clark, R.C. and Reid, J.S., Acta Crystallogr., Sect. A:
Found. Crystallogr, 1995, vol. 51, no. 6, p. 887.
7. Sheldrick, G., SHELXL-97. Program for Refinement of
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ACKNOWLEDGMENTS
A.V. Pavlyuk is grateful to the Foundation “Kasa im J.
Mianowskiego—Fundacja Popierania Nauki” for
financial support.
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Bond, Oxford: Oxford Univ., 1999.
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