208 DOI: 10.17344/acsi.2016.3116
Acta Chim. Slov. 2017, 64, 208-214
Scientific paper
Synthesis and Structure of [Cu(Hapn)]NO3]NO3, [Cu(Hapn)(H2O)2]SiF6, [Cu(Hapn)(H2O)BF4]BF4 • H2O and [Cu(Hapn)(NH2SO3)2] n-complexes (apn = 3-(prop-2-en-1-ylamino)propanenitrile)
Mykhailo Luk'yanov,1* Evgeny Goreshnik,2 Vasyl Kinzhybalo,3
and Marian Mys'kiv1
1 Department of Inorganic Chemistry, Ivan Franko National University of Lviv, Kyryla i Mefodiya Str., 6, 79005, Lviv, Ukraine
2 Department of Inorganic Chemistry and Technology, Jozef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia
3 Institute of Low Temperature and Structure Research, Okolna 2, Wroclaw, 50-422, Poland
* Corresponding author: E-mail: mishalukianov@gmail.com; Tel.: +380 32 23 94 506
Received: 29-11-2016
Abstract
Four copper(I) n-complexes: [Cu(Hapn)NO3]NO3 (1), [Cu(Hapn)(H2O)2]SiF6 (2), [Cu(Hapn)(H2O)BF4]BF4-H2O (3) and [Cu(Hapn)(NH2SO3)2] (4) were prepared using alternating-current electrochemical technique, starting from alcohol solutions of 3-(prop-2-en-1-ylamino)propanenitrile (apn) titrated with appropriate acid and copper(II) salts (Cu(NO3)2 • 3H2O, CuSiF6 • 4H2O, Cu(BF4)2 • 6H2O or Cu(NH2SO3)2 • xH2O, respectively). Obtained compounds were characterized by single-crystal X-ray diffraction and partially by IR spectroscopy. In the structures of complexes 1, 2 and 4 Cu(I) cation possesses a tetrahedral environment formed by the C=C bond of one organic cation Hapn, the N atom of cyano group from another Hapn moiety, and two O atoms (from NO3- anions in 1, from H2O molecules in 2) or N atoms (NH2SO3- anions in 4). In compound 3 strongly pronounced trigonal-pyramidal coordination environment of Cu(I) is formed by a mid-point of C=C-bond of one Hapn cation, nitrogen atom (of cyano group) of another Hapn unit, O atom of H2O molecule in the basal plane, and F atom of BF4- anion at the apical position.
Keywords: Copper(I); n-complex; aminonitrile derivative; crystal structure; coordination polymer
1. Introduction
For almost two centuries the attention of scientists within different branches has been paid to aminonitriles, ranging from a-aminonitriles discovered by A. Strecker as far as in 1850,1 to various P-, y-, o-, ra- aminonitriles obtained in our days.2 Representatives of this class are well-known not only as versatile intermediates in organic synthesis and in many other reactions,3,4 but also as reagents for synthesis of heterocyclic compounds,5 inhibitors of enzymes,6 precursors of peptides,7 amino-acids,8 which, in turn, exhibit antibiotic,9 antifungal,10 and other important biological and pharmacological properties.11,12 The coordination behaviour of aminonitriles in the complexation reactions with Cu(I) salts can be characteri-
zed on the basis of only several related,13,14 or closely related,15 compounds, though the matter under discussion is still relevant. It has been noticed that atoms of Cl or Br compete for space in coordination polyhedron with allyl groups and cyano group in the halide complexes of Cu(I) with diallylaminopropanenitrile (the tertiary amine N-atom is protonated).16,17 Still one of the two olefin bonds and ha-lide atoms have a priority, and CN-group (as well as the second C=C-bond) does not coordinate to the metal ion.
Generally speaking, there are few ways for apn-mo-iety to coordinate with Cu ions. Depending on the status (cation or molecular) of 3-(prop-2-en-1-ylamino)propanenitrile the number of active groups for coordination changes, which, in turn, influences the composition of coordination polyhedron of the Cu ion (other ligand moieties, such as sol-
vent molecules or anions, occupy usually the apical position of the coordination polyhedron) and complexity of the arisen inorganic component in a compound: from (CuCl)2 to (Cu2Cl3)nn-.16 Thus, being in molecular state, apn is coordinated to Cu with allyl- and amino- group and Cl- in the following sequence (C=C > NH >...), whereas C^N-group is not coordinated. Cationic form of apn provides these groups the same chance to be coordinated with the metal atom: C=C > C=N > Hal. In order to study a coordination ability of C=C-bond or C^N-group to the copper atom, the compounds with ionic copper salts have been studied.
Therefore, we have undertaken the synthesis and crystal structure determination of copper(I)-n-complexes with 3-(prop-2-en-1-ylamino)propanenitrile.
2. Experimental
2. 1. Synthesis of 3-(prop-2-en-1-ylamino) propanenitrile (apn)
A mixture of 0.15 mol allylamine (11.2 mL) and 0.10 mol acrylonitrile (6.8 mL) was continuously stirred and cooled (5 h, 20 °C) preventing the temperature rising higher than 30 °C,18 then it was heated for 1 h in a water bath with a reflux condenser at 60 °C. The product (orange liquid) was purified by distillation in a vacuum of a water-jet pump (85 °C /40 mm Hg). The yield of apn was 88% (15 mL). IR (KBr) n 3315(w), 3077(m), 2977(m) 2912(s), 2837(s), 2247(s), 1642 (m), 1528(wv), 1465(s), 1419(s), 1118(s), 996(s), 922(vs) cm-1.
2. 2. Preparation of Complexes
Four crystalline copper(I) compounds with 3-(prop-2-en-1-ylamino)propanenitrile were prepared using alternating-current electrochemical syntheses.19 The density of crystals of 1-4 was determined by the flotation method in a chloroform-bromoform mixture (Table 1).
2. 2. 1. Preparation of [Cu(Hapn)NO3]NO3 (1)
The apn (4.8 mmol) in 2 mL of ethanol titrated by HNO3 to pH 5.5 was mixed with Cu(NO3)2 ■ 3H2O (4.3 mmol) in 2 mL of ethanol. The solution was placed into a small test-tube and copper-wire electrodes in cork were inserted. After applying U = 0.50 V of alternating-current tension (frequency 50 Hz, /init = 0.5 mA) for 16 h a starting coloured solution was discoloured and good quality colourless crystals of 1 appeared on the copper electrodes. Yield of complex 1 was 70%.
2. 2. 2. Preparation of [Cu(Hapn)(H2O)2]SiF6 (2)
The same synthesis (frequency 50 Hz, U = 0.55 V, Iinit = 0.54 mA), starting from CuSiF6 ■ 4H2O (3.8 mmol)
and 4 mL of methanolic solution of the apn (4.2 mmol), previously titrated with an aqueous solution of 19% H2Si-F6 to pH 3, resulted in a formation of good quality crystals of 2 in 12 h. Yield of the complex was 95%. IR (Nujol) n 3434(vs), 2953(vs), 2846(vs), 2260(w), 1642 (s), 1458(s), 1376(m), 1019(s), 953(w), 728(s) cm-1.
2. 2. 3. Preparation of [Cu(Hapn)(H2O)BF4]BF4 • H2O (3)
Good quality crystals of complex 3 were obtained in a similar way (alternating-current, U = 0.65 V, Iinit = 0.5 mA) starting from 4 mL of propanol solution of the 4 mmol of apn (titrated with HBF4 to pH = 4) and Cu(BF4)2 ■ 6H2O (4 mmol). Colourless prismatic crystals of compound 3 appeared on copper wire electrodes after 120 h. The yield was 60%.
2. 2. 4. Preparation of [Cu(Hapn)(NH2SO3)2] (4)
Colourless needle-like crystals of complex 4 appeared from a methanol solution (4 mL) of Cu(NH2SO3)2 ■ xH2O (4.1 mmol) and the apn (4.1 mmol) previously titrated with water solution of 50% NH2SO3H to pH 6.5 under conditions of the alternating-current electrochemical technique (U = 0.6 V, /init = 0.4 mA) during 7 days. A yield of 4 was 65%. IR (KBr) n 3787(vw), 3264(w), 2923(m), 2361(s), 1662(w), 1249(vs), 1203(vs), 1055(m), 787(w), 643(vw), 593(vw), 560(vw) cm-1.
2. 3. Crystallography
The experimental details, crystallographic parameters and summaries of the data collection for 1-4 are presented in Table 1. Single crystals of 1-4 were preliminarily studied by the photo-method and then diffraction data were collected on a Rigaku AFC7R (for 1-2) or KU-MA-KM4/CCD (for 3-4) diffractometers with graphite monochromated Mo^a radiation (X = 0.71073 À). Corrections to the Lorentz and polarization factors were applied to reflection intensities. The X-ray experimental data were processed using the Rigaku Crystal Clear pro-gram,20 for compounds 1 and 2. The CrysAlisRED program was used for processing the X-ray data for complexes 3 and 4.21 An absorption correction was applied by the analytical method.22 Structures 1-4 were solved using direct methods and light atoms were revealed from the difference Fourier syntheses using the SHELX program package.23 Full-matrix least-squares refinements based on F2 were carried out for the positional and thermal parameters of all non-hydrogen atoms. Four fluorine atoms of SiF62- anion in 2 are split with roughly 50% s.o.f. The hydrogen atoms in structures 1-4 were revealed from the difference Fourier syntheses and refined in the riding model along with the non-hydrogen atoms (fixed C-H distances and with Uiso(H) equal to 1.2Ueq(C)). Hydrogen
Table 1. Crystallographic data and experimental details for structures 1—4
Compound
2
3
Empirical formula Formula weight Temperature (K) Space group
Unit cell dimensions (A, °)
a
b
c
a
P
Y
Volume (À3), Z Dc (g cm-3) Dm (g cm-3)
Absorption coefficient (mm ') F(000)
Measured reflections Independent reflections Observed reflections
[I > 2o(I)]
Goodness-of-fit on F2 Parameters refined Final R indices
[I > 2o(/)]
C6HnCuN4O6 298.73 200(2) P21/n
8.2341(4) 7.9905(3) 17.4008(8)
90 98.959(2) 90
1130.91(9), 4 1.755 1.73 1.96 608 4673 2552
2163 1.09 155 R1 = 0.049, wR2 = 0.134
C6H15CuN2O2F6Si 352.83 200(2) P21/c
8.5929(9) 9.7426(8) 15.2109(16) 90
103.448(4) 90
1238.5(2), 4 1.892 1.88 1.93 712 5091 2795
2542 1.12 204 R1 = 0.052, wR2 = 0.145
C6H15CuN2O2B2F8 384.36 100(2) P21/n
12.351(4) 12.351(4) 13.497(4)
90 97.98(3) 90
1420.9(7), 4 1.797 1.80 1.63 768 14002 4825
3266 0.99 226 R1 = 0.036, wR2 = 0.087
C12H30Cu2N8O12S4
733.76 100(2) PI
8.217(2) 9.018(3) 17.439(5) 91.93(3) 92.52(3) 90.21(3) 1290.3(6), 2 1.889 1.88 2.05 752 11271 8361
6055 1.00 343 R1 = 0.032, wR2 = 0.073
1
4
atoms of amino group and water were refined freely. The figures were prepared using DIAMOND 3.1 software.24
3. Results and Discussion
Analysis of the obtained new Cu(I) n-complexes proves that the type of anion influences strongly on a structure formation in these complexes.25'26
3. 1. Crystal Structure of [Cu(Hapn)NO3]NO3 Complex (1)
Complex [Cu(Hapn)NO3]NO3 (1) is formed with anion NO3- which is structurally related to halogenide ones. In this compound due to bridged functions of both Hapn and NO3- units the known [Cu(NO3)]2 inorganic fragments27-30 are interconnected with organic cations Hapn forming goffer chains in the direction [111] (Fig. 1). The
Figure 1. Infinite chains and hydrogen bonding in complex 1. Symmetry operations: (i) x + /2, -y + /2, z + '/2; (ii) -x + 2, -y, -z + 2.
angle between planes passing through two neighbouring inorganic linkers [Cu(NO3)]2 of the polymer is 67°. For comparison, the analogous angle between planes passing through two neighbouring inorganic units [CuCl]2 in the halide complex is 65°.16
The metal atom possesses a tetrahedral surrounding consisting of the middle (further m) of double C(5)=C(6)-bond, N (C^N-group) and 2 oxygen atoms from two NO3- anions. Lengths of the bonds are Cu-m 1.933(3), Cu-N 1.939(3), Cu-O(1) 2.102(2) and Cu-O(1)" 2.202(2) A (Table 2). The angle formed by three Cu atoms in the chain [Cu(Hapn)2+]n equals to 152°. The chain is not straight because of an influence of the non-coordinated NO3- anion, which forms N-H—O hydrogen bonds (Table 3).31
Table 2. Selected bond distances and angles for 1-4.
Distance	(A)	Angle	(°)
1a			
Cu-N1	1.939(3)
Cu-mi	1.933(3)
Cu-O1	2.102(2)
Cu-O1ii	2.202(2)
N1-C1	1.129(4)
C5-C6	1.361(4) 2b
Cu-N1i	1.987(3)
Cu-O1w	2.003(3)
Cu-m	1.936(3)
Cu-O2w	2.239(3)
C5-C6	1.363(5)
N1-C1	1.132(5)
3
Cu-N1	1.946(2)
Cu-O1w	1.992(2)
Cu-mi	1.893(5)
N1-C1	1.132(2)
C5-C6	1.364(3)
4
Cu1-N11i	1.990(2)	N11i-Cu1-N1	106.2(7)
Cu1-N1	2.061(2)	N11i-Cu1-N2	92.2(7)
Cu1-m1	1.977(7)	N1-Cu1-N2	99.2(7)
Cu1-N2	2.275(9)	N11i-Cu1-m1	117.4(6)
C16-C15	1.352(3)	N2-Cu1-m1	110.3(5)
C11-N11	1.134(3)	C11-N11-Cu1i	176.1(8)
Cu2-N3	2.039(8)	N3-Cu2-N4	104.6(7)
Cu2-N4	2.143(9)	N3-Cu2-N21ii	96.6(7)
Cu2-m2	1.971(7)	N21ii-Cu2-N4	93.9(8)
Cu2-N21ii	2.130(2)	N4-Cu2-m2	111.1(5)
C26-C25	1.352(3)	N3-Cu2-m2	130.5(6)
C21-N21	1.138(3)	C21-N21-Cu2ii	165.8(8)
m - middle point of C5=C6 (in 4: C15=C16 and C25=C26) double bond. Symmetry codes: " (i) x + /, -y + /, z + /; (ii) -x + 2, -y, -z + 2; b (i) -x + 1, y - /, -z - /; (ii) -x + 1, y + /, -z - /; c (i) -x + /, y - /, -z + /; (iii) - x + 1.5, y - /, -z + /; d (i) -x + 1, -y + 1, -z; (ii) -x + 2, -y, -z + 1.
Table 3. Geometry of selected hydrogen bonds in 1-4.
Atoms involved	Distances, A		Angle, deg	
D-H-A	D-H	H-A	D-A	D-H-A
1a				
N2-H1N-O5i	0.90	2.48	3.116(4)	128
N2-H1N-O6i	0.90	1.94	2.798(2)	159
N2-H2N-O5	0.90	1.94	2.807(4)	161
2b				
N2-H1N-F1	0.90	1.89	2.784(8)	174
O1w-H2w1-F2i	0.97	1.70	2.661(1)	170
N2-H2N-F2ii	0.90	1.95	2.812(5)	160
O2w-H2w2-F1	0.96	2.39	3.259(6)	151
3c				
O1w-H1w1-F4i
N2-H1N-O2w"
O1w-H2w1-F5iii
N2-H2N-F1
O2w-H1w2-F7iv
O2w-H2w2-F8
4d
N1-H1B-O21i	0.92	2.02	2.919(1)	165
N2-H2A-O31	0.92	1.93	2.820(8)	162
N2-H2B-O12"	0.92	2.07	2.992(1)	176
N3-H3B-O43iii	0.92	2.01	2.925(2)	173
N22-H2N2-O42iv	0.92	1.81	2.730(3)	178
N4-H4B-O32ii	0.92	2.07	2.992(6)	177
Symmetry codes: a (i) /2 - x, y - /2, /2 - z; b (i) —x, 1 - y, —z; (ii) 1 -x, y - /, -z; c (i) -x, -y, 1 - z; (ii) x - /, / - y, z- /; (iii) x - 1, y, z; (iv) 1.5 - x, / + y, / - z; d (i) 2 - x, -y, -z; (ii) x - 1, y, z; (iii) 1 -x, 1 - y, 1 - z; (iv) -x, 1 - y, 1 - z.
3. 2. Crystal Structure of [Cu(Hapn)(H2O)2] SiF6 Complex (2)
In following two complexes 2 and 3 water molecules act as co-ligands. The structure of the compound 2 consists of infinite metal-organic spiral-like ribbons of [Cu(Hapn)(H2O)2]2+ composition. The angle between three neighbouring copper atoms is 63°. Located between mentioned ribbons SiF62- anions are bound to metal-organic fragment via O-H -F and N-H -F hydrogen bonds (Fig. 2). Despite the existence of Cu1 complexes with hexaflourosilicate-anion with the direct CuI-F-Si-F5 bond,32 SiF62--anion does not enter the internal coordination sphere of the metal. Tetrahedral coordination polyhedron of copper(I) ion is formed by a mid-point of C(5) = C(6) bond, one nitrogen (C=N) and two O (H2O molecules) atoms. Respective bond lengths are Cu-m 1.936(3), Cu-N(1)' 1.987(3), Cu-O(1w) 2.003(3) and Cu-O(2w) 2.239(3) À (Table 2). A system of hydrogen bonds is much more developed in the given complex (table 2) in comparison with 1. This promotes relatively dense packing of metal-organic chains and the inorganic anions.
C6i-Cu-C5i	38.8(2)
N1-Cu-O1	104.8(2)
N1-C1-C2	177.1(4)
N1-Cu-O1ii	101.0(2)
O1-Cu-O1ii	71.9(1)
mi-Cu-N1	132.6(1)
N1i-Cu-O1w	107.1(2)
N1i-Cu-m	118.5(9)
N1i-Cu-O2w	95.9(2)
O1w-Cu-O2w	93.7(1)
C1-N1-Cuii	162.9(3)
N1-C1-C2	178.4(4)
N1-Cu-O1w	99.7(7)
O1w-Cu-mi	129.1(5)
C1-N1-Cu	169.7(8)
N1-C1-C2	177.7(2)
O1w-Cu-F8iii	89.1(6)
0.73	1.99	2.710(6)	169
0.86	1.88	2.725(2)	168
0.72	2.01	2.716(1)	169
0.96	1.96	2.755(1)	139
0.92	1.95	2.834(9)	160
0.84	2.09	2.827(3)	146
3. 3. Crystal Structure of [Cu(Hapn)(H2O) BF4]BF4 • H2O Complex (3)
In the complex 3 water molecules and BF4- anions (apart from the active centers of Hapn) are included in
the internal coordination sphere of Cu. The presence of BF4- anions promotes transformation of coordination polyhedron of the metal from tetrahedron to trigonal pyramid formed by m of (C=C)-bond, N (C^N-group) and O (H2O) atoms in the basal plane. Fluorine atom
Figure 3. Cu(I) coordination in 3. Structure fragment of complex 3. Symmetry operations: (i) —x + /2, y - /2, -z + '/2; (ii) -x+ 1, - y + 1, -z; (iii) - x + 1.5, y - /2, -z + /2. (80% probability displacement ellipsoids).
from BF4- anion occupies the apical position (Cu-F(8)"' 2.640(2) A) of coordination polyhedron. Atom of Cu is somewhat (A = 0.03 A) removed from the (m, N, O) plane.
Another crystallographically independent H2O molecule and BF4-anion are not coordinated to copper® and fixed in a crystal space by relatively strong hydrogen bonds. As one can see from Figure 3, the structure 3 is similar to 2, but separate fragments of coordination polymer due to the Hapn flexibility demonstrate bulbous chain structure (the angle between three atoms of Cu [Cu(Hapn)2+]n equals to 59°). Since one distance of Cu-O(1w) equals to 1.992(2) A, and the other opposite Cu-O(1w)" is equal to 2.900(2) A, one may regard from a certain distance (Cu(H2O))2 moiety as dimeric fragment and Cu(I) polyhedron as a trigonal bipyramid.
4. Conclusions
Flexibility of Hapn allows using it as a convenient tool in a construction of coordination compounds. In all the above-mentioned compounds Hapn totally realizes its coordination abilities attaching to the metal atom with (C=C)-bond of allyl- and N atom of cyano-group. The protonated N-amine atom being deprived of its donor ability participates actively in a formation of strong N-H-X hydrogen bonds (Table 2). On the other hand, the combination of Hapn with ionic copper(I) salts (CuNO3, Cu2Si-F6, CuBF4, CuSO3NH2) promotes an effective interaction of both n- and o-ligands with the central atom, which serve to a formation of stable frameworks.
5. Supplementary Material
3. 4. Crystal Structure of
[Cu(Hapn)(NH2SO3)2] Complex (4)
As in complexes 1 and 2, in the compound 4 coordination polyhedra for both independent Cu(I) ions possess tetrahedral shape. The Cu(1) environment comprises of the mid-point of C(15)=C(16) bond (ml), N(11) atom from CN-group and two nitrogen atoms from two NH2SO3- anions. The Cu(2) polyhedron involves m2 (C(25) =2 C(326)), N(21) (C=N) and N(3) and N(4) (NH2SO3-) centers. Bonds lengths: Cu(1)-m1 1.977(7), Cu(1)-N(1iy 1.990(2), Cu(1)-N(1) 2.061(8) and Cu1-N(2) 2.275(9) A; Cu(2)-m2 1.971(7), Cu(2)-N(21)" 2.130(2), Cu(2)-N(3) 2.039(8) and Cu(2)-N(4) 2.143(9) A.
The main structural feature of the complex 4 is the appearance of [Cu(Hapn)]2 rings (Fig. 4). Two closest rings are tilted by 72° and linked with H-bonds among inorganic anions and organic cations (N(2)-H(2A)-O(31) 1.93 A etc. Table. 3).
CCDC 913397 (1), 913398 (2), 913399 (3) and 913400 (4) contain the supplementary crystallographic data for this article. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033; E-mail: deposit@ccdc.cam. ac.uk).
6. References
1.	A. Strecker, Ann. Chem. Pharm. 1850, 75, 27-45. https://doi.org/10.1002/jlac.18500750103
2.	V. Chhiba, M. L. Bode, K. Mathiba, W. Kwezi, D. Brady, J. Mol. Catal. B: Enz. 2012, 76, 68-74. https://doi.org/10.1016Zj.molcatb.2011.12.005
3.	D. Enders, J. P. Shilvock, Chem. Soc. Rev. 2000, 29, 359373. https://doi.org/10.1039/a908290e
4.	E. Rafiee, A. Azad, M. Joshaghani, Lett. Org. Chem. 2007, 4,
Figure 4. Copper(I) coordination in 4 and [Cu(Hapn)]2. Symmetry operation: (i) -x + 1, -y + 1, -z; (80% probability displacement ellipsoids).
60-63. https://doi.org/10.2174/157017807780037478
5.	E. C. Taylor, J. G. Berger, J. Org. Chem. 1967, 32, 23762378. https://doi.org/10.1021/jo01283a003
6.	S.-S. Tang, P. C. Trackman, H. M. Kagang, J. Biol. Chem. 1983, 258, 4331-4338.
7.	G. Cardillo, C. Tomasini, Chem. Soc. Rev. 1996, 25, 117128. https://doi.org/10.1039/CS9962500117
8.	M. Preiml, K. Hillmayer, N. Klempier, Tetrahedron Lett. 2003, 44, 5057-5059.
https://doi.org/10.1016/S0040-4039(03)01136-5
9.	S. G. Davies, O. Ichihara, I. Lenoir, I. A. S. Walters, J. Chem. Soc. Perkin Trans. 1 1994, 11, 1411-1415. https://doi.org/10.1039/P19940001411
10.	F. Theil, S. Ballschuh, Tetrahedron Asymmetry 1996, 7, 3565-3572.
https://doi.org/10.1016/S0957-4166(96)00465-X
11.	D. Steinhuebel, Y. Sun, K. Matsumura, N. Sayo, T. Saito, J. Am. Chem. Soc. 2009, 131, 11316-11317. https://doi.org/10.1021/ja905143m
12.	M. Liu, M.P. Sibi, Tetrahedron 2002, 58, 7991-8035. https://doi.org/10.1016/S0040-4020(02)00991-2
13.	A. Albinati, M. L. Carraro, S. Gross, M. Rancan, S. Rizzato, E. Tondello, A. Venzo, Eur. J. Inorg. Chem. 2009, 35, 53465351. https://doi.org/10.1002/ejic.200900620
14.	Y. E. Filinchuk, V. V. Olijnik, V. N. Davydov, Russ. J. Coord. Chem. 1997, 23, 843-845.
15.	E. A.Goreshnik, V. V.Oliinik, Russ. J. Inorg.Chem. 1996, 41, 206-208.
16.	M. Y. Luk'yanov, A. V. Pavlyuk, M. G. Mys'kiv, Russ. J. Coord. Chem. 2012, 38, 86-91 (Koord. Khimiya 2012, 38, 92-97).
17.	M. Luk'yanov, V. Kinzhybalo, E. Goreshnik, O. Pavlyuk, M. Mys'kiv, Chem. Met. Alloys. 2012, 5, 66-76.
18.	Houben-Weil. Methoden der organischen Chemie, Stuttgart: Georg Thieme 1949,4.
19.	B. M. Mykhalichko, M. G. Mys'kiv. Ukraine Patent UA25450A, Bull. N. 6 1998.
20.	Crystal Clear. Woodlands (Texas, USA): Rigaku Corporation (1999).
21.	CrysAlis RED. Version 1.171.31.8, Oxford: Oxford Diffraction Ltd. (2007).
22.	R. C. Clark, J. S. Reid, Acta Crystallogr., Sect. A: Found. Crystallogr. 1995, 51, 887-897. https://doi.org/10.1107/S0108767395007367
23.	G. M. Sheldrick, Acta Cryst., Sect. A: Found. Crystallogr. 2008, A64, 112-122.
https://doi.org/10.1107/S0108767307043930
24.	DIAMOND v3.1. Crystal Impact GbR, Bonn, Germany (2004-2005).
25.	E. Goreshnik, M. Mys'kiv, J. Chem. Crystallogr. 2010, 40, 381-383.https://doi.org/10.1007/s10870-009-9666-1
26.	M.Y. Luk'yanov, A.V. Pavlyuk, E. A. Goreshnik, M. G. Mys'kiv, Russ. J. Coord. Chem. 2012, 38, 639-645. (Koord. Khimiya 2012, 38, 663-670).
27.	S. P. Neo, Z.-Y. Zhou, T. C. W. Mak, T. S. A. Hor, J. Chem. Soc., Dalton Trans. 1994, 23, 3451-3458. https://doi.org/10.1039/DT9940003451
28.	R. D. Hart, G. A. Bowmaker, J. D. Kildea, E. N. de Silva, B. W. Skelton, A. H. White, Aust. J. Chem. 1997, 50, 604-620. https://doi.org/10.1071/C96041
29.	E. A. Goreshnik, M. G. Mys'kiv, Acta. Chim. Slov. 2011, 58, 772-775.
30.	Y. Slyvka, E. Goreshnik, N. Pokhodylo, O. Pavlyuk, M. Mys'kiv, Acta. Chim. Slov. 2016, 63, 399-405. https://doi.org/10.17344/acsi.2016.2486
31.	G. R. Desiraju, Angew. Chem. Int. Ed. 2011, 50, 52-59. https://doi.org/10.1002/anie.201002960
32.	E. A. Goreshnik, Y. I. Slyvka, M. G. Mys'kiv, Inorg. Chim. Acta 2011, 377, 177-180. https://doi.org/10.1016Zj.ica.2011.08.008
Povzetek
Pripravili smo štiri bakrove(I) n-komplekse: [Cu(Hapn)NO3]NO3 (1), [Cu(Hapn)(H2O)2]SiF6 (2), [Cu(Hapn) (H2O)BF4]BF4-H2O (3) in [Cu(Hapn)(NH2SO3)2] (4) z uporabo elektrokemijske tehnike z izmenično napetostjo iz alkoholnih raztopin 3-(prop-2-en-1-ilamino)propannitrila (apn) titriranega z ustrezno kislino ter z bakrovo(II) soljo (Cu(NO3)2 • 3H2O, CuSiF6 • 4H2O, Cu(BF4)2 • 6H2O ali Cu(NH2SO3)2 • xH2O). Pripravljene spojine smo okarakterizira-li z monokristalno rentgensko difrakcijo in delno z IR spektroskopijo. Pri strukturah 1, 2 in 4 ima Cu(I) kation te-traedrično razporeditev ligandov, ki nastane z C=C vezjo enega organskega kationa Hapn, N atoma ciano skupine iz drugega Hapn liganda ter dveh O atomom (iz NO3- aniona pri 1, iz H2O molekule pri 2) oziroma N atoma (anion NH2SO3- pri 4). Pri spojini 3 je prisotna trigonala-piramidalna koordinacija Cu(I) s sredinsko točko C=C-vezi enega Hapn kationa, N atoma (iz ciano skupine) drugega Hapn liganda in O atoma molekule H2O v osnovni ravnini ter s F atomom iz BF4- aniona v navpični legi.