Azido- and thiocyanato-cobalt(II) complexes based pyrazole ligands

Azido- and thiocyanato-cobalt(II) complexes based pyrazole ligands

Polyhedron 78 (2014) 135–140 Contents lists available at ScienceDirect Polyhedron journal homepage: www.elsevier.com/locate/poly Azido- and thiocya...

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Polyhedron 78 (2014) 135–140

Contents lists available at ScienceDirect

Polyhedron journal homepage: www.elsevier.com/locate/poly

Azido- and thiocyanato-cobalt(II) complexes based pyrazole ligands Salah S. Massoud a,⇑, Marie Dubin a, Ashley E. Guilbeau a, Mark Spell b, Ramon Vicente c, Petra Wilfling d, Roland C. Fischer d, Franz A. Mautner e,⇑ a

Department of Chemistry, University of Louisiana at Lafayette, P.O. Box 44370, Lafayette, LA 70504, USA Department of Chemistry, Louisiana State University, Choppin Hall, Baton Rouge, LA 70803, USA c Department de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain d Institut für Anorganische Chemie, Technische Universität Graz, Stremayrgasse 9, A-8010 Graz, Austria e Institut für Physikalische and Theoretische Chemie, Technische Universität Graz, Stremayrgasse 9, A-8010 Graz, Austria b

a r t i c l e

i n f o

Article history: Received 22 February 2014 Accepted 14 April 2014 Available online 20 April 2014 Keywords: Cobalt Azido Thiocyanato Crystal structure Infrared UV-Visible

a b s t r a c t The reactions of pyrazole based ligands with Co(II) salts in the presence of NaN3 or NH4NCS afforded the cationic–anionic complexes [Co(bdmpzpy)2][Co(N3)4] (1) and [Co(bdmpzpy)2][Co(NCS)4].2CH3NO2 (2) containing tetrathiocyanato- and tetraazido-Co(II) complex anions as well as the mononuclear complexes [Co(bepza)(NCS)2] (3), [Co(tedmpza)(NCS)]ClO4½H2O (4) and [Co(tedmpza)(N3)]ClO4H2O (5) where bdmpzpy = 2,6-bis[(3,5-dimethyl-pyrazol-1H-yl)-methyl]pyridine, bepza = bis(ethyl-pyrazol-1H-yl)amine and tedmpza = tris(3,5-dimethyl-ethyl-pyrazol-1H-yl)amine. The complexes were structurally characterized by elemental microanalyses, IR and UV–Vis spectroscopy and by single crystal X-ray crystallography. Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction   Small pseudohalide ions such as N 3 , NCS and NCO and the larger molecular dicyanamide ion, N(CN) are versatile ligands that 2 can bind divalent transition metal ions (Mn2+, Co2+, Ni2+ and Cu2+) in a variety of ways. Aside from the ambidentate nature of the last three pseuohalide anions, this species have the ability to act as bridging ligands and hence assembling metal ions in extended network structures. The interaction of these pseudo halides and  especially N 3 and NCS with divalent paramagnetic metal ions, not only led to the construction of polynuclear and coordination polymers of interesting architectures design and diverse topology [1–23] but also, have led to the development of new magnetic molecular materials [1–22]. The magnetic coupling in these systems results from the electronic interaction between the paramagnetic  metal centers via the bridging N 3 or NCS ligand(s). Many bridging-azido coordination modes such as l21,3-N3 (end-to-end, EE), l21,1-N3 (end-on, EO), l31,1,3-N3 and l31,1,1-N3 [1–7,13] as well as multi-bridges l41,1,1,1-N3, l41,1,2,2-N3, and l61,1,1,3,3,3-N3 were reported [8–11]. Similar, bonding modes including l21,3-

⇑ Corresponding authors. Tel.: +1 337 482 5672; fax: +1 337 482 5676 (S.S. Massoud). Tel. +43 316 873 32270; fax: +43 316 4873 8225 (F.A. Mautner). E-mail addresses: [email protected] (S.S. Massoud), [email protected] (F.A. Mautner). http://dx.doi.org/10.1016/j.poly.2014.04.025 0277-5387/Ó 2014 Elsevier Ltd. All rights reserved.

NCS, l23,3-NCS, l21,1-NCS, l31,1,3-NCS and l31,3,3-NCS were also found in bridging-thiocyanato compounds [14–23]. The different bridging-azido, and -thiocyanato bonding modes were shown in references 1, 12 and 22, respectively. Azido and thiocyanato copper(II) and cobalt(II) complexes are probably among the most extensively studied complexes. Both metal ions are known to form five-coordinate species with stereochemical environment around the central metal ion ranges between trigonal bipyramidal (TBP) and square pyramidal (SP) [1,14a–c,15c,16,22–29] and octahedral or distorted octahedral geometry [1,3,4,5b,8,14a,22]. Bridging azido- and thiocyanato-copper(II) and cobalt(II) complexes are most likely formed when the coordinated coligand is bi-, tri- or linear tetra-dentate [1–22]. Monodentate-azido and –N bonded-thiocyanato complexes with TBP environment are produced with complexes of five-membered chelate rings that derived from tripodal-tetramine ligands [30,31], whereas the corresponding square-based pyramidal geometries are obtained with most ligands and with tripod amines with larger ring size [23–25,31]. Herein, A series of tri- and tripod tetradenate ligands based pyrazole namely bis(2-(pyrazol-1H-yl)ethyl)amine (bepza), 2,6-bis (3,5-dimethyl-pyrazol-1H-yl)methyl)pyridine (bdmpzpy) and tris (2-(3,5-dimethyl-pyrazol-1H-yl)ethyl)amine (tedmpza) (Scheme 1) were selected to study the coordination properties of azide and thiocyanate ions in Co(II) complexes that derived from these ligands.

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N N HN N

N N

N HN N

N N

N N

N

N N

N N

N

N

N

N

(bepza)

(bedmpza)

(tedmpza)

(bdmpzpy)

Scheme 1. Structure formulas of some pyrazole based ligands.

2. Experimental 2.1. Materials and physical measurements All materials used in this study were reagent grade quality. Infrared spectra were recorded on JASCO FT/IR-480 plus spectrometer as KBr pellets. The ligands bdmpzpy [25], bedmpza [24,32] and bepza [33] were synthesized and characterized according to the literature procedure. Electronic spectra were recorded using Agilent 8453 HP diode UV–Vis spectrophotometer. Elemental microanalyses were carried out by the Atlantic Microlaboratory, Norcross, Georgia USA Caution: Salts of perchlorate and azide salts are potentially explosive and should be handled with great care and in small quantities.

2.2. Synthesis of the compounds 2.2.1. Synthesis of the organic ligands The ligands bis(2-(pyrazol-1H-yl)ethyl)amine (bepza), 2,6bis(3,5-dimethyl-pyrazol-1H-yl)methyl)pyridine (bdmpzpy) and tris(2-(3,5-dimethyl-pyrazol-1H-yl)ethyl)amine (tedmpza) were synthesized as essentially described by literature methods [24,25,32–34]. Characterization of tedmpza: Selected IR bands (cm1): 1668, 1552, 1462, 1423, 1388. 1H NMR (DMSO-d6, 400 MHz, d in ppm): d = 2.03, 2.15 (each corresponds to 3H, s, – CH3), 3.04, 3.97 (each corresponds to 2H, t, CH2pz), 5.76 (1H, s, H4-pz). 13C NMR: (d6-DMSO, 100 MHz) d = 10.9, 13.7 (CH3), 39.5, 45.4 (CH2), 105.1, 139.4, 146.5 (pyrazole carbons).

2.2.2. Synthesis of [Co(bdmpzpy)2][Co(N3)4] (1) To a mixture containing cobalt(II) chloride hexahydrate (0.140 g, 0.500 mmol) and 2,6-bis[(3,5-dimethyl-pyrazol-1H-yl)methyl]pyridine (0.150 g, 0.500 mmol) in 5 mL methanol, NaN3 (0.066 g, 1.00 mmol) dissolved in H2O (10 mL) was added. The solution was heated on a steam-bath for 5 min, filtered while hot through Celite and then allowed to stand at room temperature. The large blue chunks of compound which separated after 3 days were collected by filtration and washed with Et2O (yield: 0.175 g, 80%). Recrystallized from absolute CH3OH afforded shiny blue single crystals suitable for X-ray structural determination. Characterization: Anal. Calc. for C34H42Co2N22 (876.38 g/mol): C, 46.60; H, 4.83; N, 35.16. Found C, 46.47; H, 4.71; N, 34.96%. Selected IR bands (KBr, cm1): 2083 (s), 2045 (vs), 1605 (m), 1574 (m), 1553 (s), 1468 (s), 1430 (m) 1389 (w), 1362 (w). UV–Vis. spectrum {kmax, nm (saturated)}: in CH3CN: 329, 571, 655, 690.

2.2.3. Synthesis of [Co(bmdmpzpy)2][Co(NCS)4]2CH3NO2 (2) This complex was prepared using a similar procedure as that described for 1, except NH4NCS was used instead of NaN3 (overall yield: 83%). Suitable single crystals for X-ray structural determination were obtained by recrystallization from MeOH/CH3NO2. Characterization: Anal. Calc. for solvent free C38H42Co2N14S4 (940.50 g/mol): C, 48.53; H, 4.50; N, 20.85. Found: C, 48.41; H, 4.52; N, 20.77%. Selected IR bands (KBr, cm1): 2063 (vsb), 1605 (s), 1575 (m), 1554 (s), 1468 (s), 1428 (s), 1387 (m). UV–Vis spectrum {kmax, nm (emax, M1 cm1)}: in CH3CN: 465 (sh), 495 (33), 590 (sh), 626 (648). 2.2.4. Synthesis of [Co(bepza)(NCS)2] (3) A mixture of CoCl26H2O (0.140 g, 0.500 mmol), bis(ethyl-1Hpyrazol-yl)amine, bepza (0.102 g, 0.500 mmol) and NH4NCS (0.076 g, 1.00 mmol) were dissolved in MeOH (20 mL). The mixture was heated on a steam-bath for 5 min, followed by filtration through Celite. Upon standing at room temperature purple crystalline compound was separated. This was collected by filtration, washed with Et2O and dried in air (overall yield: 0.166 g, 87%). Single crystals suitable for X-ray structure determination were obtained from dilute methanolic solution. Characterization: Anal. Calc. for C12H15CoN7S2 (380.35 g/mol): C, 37.89; H, 3.98; N, 25.78. Found: C, 37.71; H, 3.96; N, 25.82%. Selected IR bands (KBr, cm1): 3218 (w), 2104 (vs), 2079 (vs). UV–Vis. spectrum {kmax, nm (saturated solution)} in CH3CN: 485 (sh), 502, 582 (sh), 620. 2.2.5. Synthesis of [Co(tedmpza)(NCS)]ClO4½H2O (4) A mixture of Co(ClO4)26H2O (0.185 g, 0.50 mmol) and tris(3,5dimethyl-ethyl-1H-pyrazol-yl)amine, tedmpza (0.150 g, 0.50 mmol) was dissolved in MeOH (10 mL). To this mixture NH4NCS (0.036 g, 0.50 mmol) dissolved in H2O (10 mL) was added. The resulting purple solution was heated on a steam-bath for 5 min, filtered through Celite and then allowed to stand at room temperature. After three days, the shiny violet needles which separated were collected by filtration, washed with Et2O, propan-2-ol and dried in air (overall yield: 0.190 g, 63%). Characterization: Anal. Calc. for C22H33ClCoN8O4S (599.74 g/mol): C, 43.41; H, 5.63; N, 18.41. Found: C, 43.67; H, 5.53; N, 18.45%. Selected IR bands (KBr, cm1): 3449 (w,b), 2081 (vs), 1094 (s). UV–Vis. spectrum {kmax, nm (emax, M1 cm1)}: in CH3CN: 477 (sh), 506 (126), 611 (179), 800 (31,b). 2.2.6. Synthesis of [Co(tedmpza)(N3)]ClO4H2O (5) The complex was synthesized using a procedure similar to that described for 1 except Co(ClO4)26H2O was used instead of CoCl26H2O. It was isolated after three days upon standing at room temperature as large dark blue chunks containing some

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well-shaped rectangle single crystals (overall yield: 0.252 g, 84%). Characterization: Anal. Calc. for C21H35ClCoN10O5 (601.70 g/mol): C, 41.90; H, 5.86; N, 23.28. Found: C, 41.97; H, 5.89; N, 23.22%. Selected IR bands (KBr, cm1): 3495 (w,b), 2066 (vs), 1092 (vs). UV–Vis. spectrum {kmax, nm (emax, M1 cm1)}: in CH3CN: 350 (1440), 525 (145), 653 (154). 2.3. X-ray crystal structure analysis The X-ray single-crystal data of the compounds were collected on a Bruker-AXS APEX (compounds 2 and 3) and SMART CCD (compounds 1, 4 and 5) diffractometer at 100(2) K. The crystallographic data, conditions retained for the intensity data collection and some features of the structure refinements are listed in Table 1. The intensities were collected with Mo Ka radiation (k = 0.71073 Å). Data processing, Lorentz-polarization and absorption corrections were performed using SAINT, APEX and the SADABS computer programs [35]. The structures were solved by direct methods and refined by full-matrix least-squares methods on F2, using the SHELXTL [36] program package. All non-hydrogen atoms were refined anisotropically. The hydrogen atoms were located from difference Fourier maps, assigned with isotropic displacement factors and included in the final refinement cycles by use HFIX (parent C atoms) or DFIX (parent O atoms) utility of the SHELXTL program package. Lattice water molecule in 4 has occupancy of 0.50. Molecular plots were performed with the Mercury program [37].

characterized by elemental microanalyses, IR and UV–Vis. spectroscopy as well as by single crystal X-ray diffraction. The mono-thiocyanato and mono-azido complexes 4 and 5, respectively and the dithiocyanto complex 3 are expected in regard to the tripodal tetrdentate nature of tedmpza and the tridentate nature of bepza (Scheme 1). Attempts made to synthesize the azidoCo(II) complex using bepza were unsuccessful. However, the isolation of the tetra-azido and tetra-thiocyanato complexes 1 and 2, respectively from the sterically hindered bdmpzpy were unpredictable. Structurally characterized complexes similar to the dithiocyanato complex 3 were obtained with bis(2-(3,5-dimethyl-pyrazol-1H-yl)ethyl)amine (bedmpza), [Co(bedmpza)(X)2] (X = NCS or N 3 ) and bis(3,5-dimethylpyrazol-1H-yl)methane) (bdmpzm), [Co(bdmpzm)(NCS)2] [1,24,25]. However, the corresponding reactions of bedmpza with Cu2+ ion afforded the dithiocyanato complex [Cu(bedmpza)(NCS)2] and the bridged-EO-azido dimer [Cu(bedmpza)(l1,1-N3)]2(ClO4)2 [1,25]. With some triedentate ligands such as Et2dien (N,N-diethyltriethylenetriamine) dinuclear doubly bridged EE-azido and EE-Thiocyanato complexes were obtained with Cu(II) [38]. Mono-azido and mono-thiocyanato Cu(II) and Co(II) complexes are well established when the blocking ligand is a tripod tetraamine [23–25,30,31]. Cobalt(II) complexes containing tetrathiocyanato or tetraazido complex anions do not seem to be unusual and a number of similar complexes have been reported and structurally characterized [39]. 3.2. IR and UV–Vis spectra of the complexes

3. Results and discussion 3.1. Synthesis of the complexes The reactions of equimolar amounts of methanolic solution of Co(II) salts with the ligands based pyrazolyl groups namely tris(2,5-dimethyl-ethyl-pyrazol-1H-yl)amine (tedmpza), bis(ethyl-pyrazol-1H-yl)amine (bepza) and 2,6-bis[(3,5-dimethylpyrazol-1H-yl)-methyl]pyridine (bdmpzpy) in presence of NaN3 or NH4NCS afforded three categories of complexes: [Co(bdmpzpy)2] [Co(X)4].nCH3NO2 (1: X = N n = 0; 2: X = NCS, n = 2), 3, [Co(bepza)(NCS)2] (3), and [Co(tedmpza)(X)]ClO4nH2O (4: X = NCS, n = ½; 5: X = N 3 , n = 1). The isolated complexes were

The IR spectra of the azido complex 1 display very strong absorption bands located at 2083, and 2045, whereas the corresponding complex 5 displayed a band at 2066 cm1 due to the asymmetric stretching vibration, mas(N3) of the coordinated mono-dentate azido group(s). The thiocyanato compounds 2, 3 and 4 display the corresponding mas(C„N) frequencies over the range 2060–2100 cm1 which is most likely consistent with Nbonded thiocyanate. In general, the S-bonded thiocyanate complexes show mas(C„N) at higher frequencies (2110–2140 cm1), whereas in N-bonded complexes, the mas(C„N) frequencies absorb at mas < 2110 cm1 [24,30,31]. These assignments were also confirmed by X-ray (Section 3.3). Complexes [Co(tedmpza)(NCS)]

Table 1 Crystallographic data and processing parameters. Compound

1

2

3

4

5

Empirical formula Formula mass System Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z l (mm1) Dcalc (Mg/m3) Crystal size (mm) h max (°) Data collected Unique reflection/Rint Parameters Goodness-of-Fit (GOF) on F2 R1/wR2 (all data) Residual extrema (e/Å3)

C34H42Co2N22 876.76 triclinic  P1

C40H48Co2N16O4S4 1063.08 monoclinic P21/c 24.2948(10) 19.5577(9) 21.7427(9) 90 108.465(2) 90 9799.2(7) 8 0.905 1.441 0.24  0.19  0.14 26.40 315 234 20087/0.0507 1209 1.043 0.0287/0.0729 0.69/0.42

C12H15CoN7S2 380.38 monoclinic P21/c 7.9108(4) 13.3019(6) 15.0116(7) 90 94.718(2) 90 1574.30(13) 4 1.362 1.605 0.28  0.20  0.12 33.00 51 464 5918/0.0324 203 0.968 0.0223/0.0547 0.55/0.32

C22H34ClCoN8O4.50S 609.02 monoclinic P21/c 10.5958(9) 9.1347(8) 29.0112(18) 90 98.902(18) 90 2774.2(4) 4 0.836 1.458 0.42  0.22  0.16 26.35 21 501 5656/0.0632 355 1.180 0.0428/0.0952 0.50/0.34

C21H35ClCoN10O5 601.97 monoclinic P21/c 8.8830(11) 14.1315(15) 21.6017(18) 90 98.339(18) 90 2683.0(5) 4 0.792 1.490 0.45  0.45  0.40 26.34 20 995 5470/0.0227 355 1.056 0.0375/0.0990 0.78/0.42

10.0601(15) 12.8437(18) 15.573(2) 88.441(8) 77.673(8) 82.152(7) 1948.0(5) 2 0.910 1.495 0.26  0.23  0.16 26.00 52 441 7624/0.0341 531 1.042 0.0394/0.1012 0.81/0.69

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Table 2 UV–Vis in CH3CN solution and IR stretching mas(C„N) and mas(N3) spectral data of the thiocyanato and azido complexes 1–5. Complex a

[Co(bdmpzpy)2][Co(N3)4] (1) [Co(bmdmpzpy)2][Co(NCS)4] (2) b [Co(bepza)(NCS)2] (3)a [Co(tedmpza)(NCS)]ClO4½H2O (4) [Co(tedmpza)(N3)]ClO4H2O (5) a b

UV–Vis {kmax, nm (emax, M1 cm1)}

mas(C„N)/mas(N3) (cm1)

329, 571, 655, 690 465 (sh), 495 (33), 590 (sh), 626 (648) 485 (sh), 502, 582 (sh), 620 477 (sh), 506 (126), 611 (179), 800 (31,b) 350 (1440), 525 (145), 653 (154)

2083, 2045 2063 2104, 2079 2081 2066

Saturated solution. Free solvent complex.

ClO4½H2O (4) and [Co(tedmpza)(N3)]ClO4H2O (5) display a sharp single band of strong intensity at 1094 and 1092 cm1, respectively attributable to the Cl–O stretching vibration of the perchlorate counter ions. The presence of lattice water in the two complexes was confirmed by appearance of a broad weak band around 3500 cm1 assigned to the t (O-H) stretching frequency of lattice H2O. The acetonitrile visible spectral features of the complexes under investigation show some general similarities. The complexes exhibit two strong bands over the wavelength regions 490–570 and 610–690 nm with occasional shoulder around 465–485 nm region. These features are most likely attributable to the presence of fivecoordinate species in solution. The very intense bands observed at 690 and 626 nm in complexes 1 and 2, respectively may reflect the tetrahedral geometry of the tetra-thiocyanato or the tetraazido complex anions [40]. Selected IR and electronic spectral data of complexes 1–5 are collected in Table 2. 3.3. Description of the structures 3.3.1. [Co(bdmpzpy)2][Co(N3)]4) (1) and [Co(bdmpzpy)2][Co(NCS)4]2CH3NO2 (2) The asymmetric unit of the crystal structure of 1 contains a [Co(bdmpzpy)2]2+ complex cation and a [Co(N3)]2 4 anion, whereas the asymmetric unit of 2 is formed by two crystallographically indenpendent [Co(bdmpzpy)2]2+ complex cations, two [Co(NCS)]24 anions and four CH3NO2 solvent molecules. Perspective views of representative pairs of complex ions together with partial atom numbering schemes are depicted in Figs. 1 and 2, respectively, and selected bond parameters are presented in Table S1. The bdmpzpy blocking ligands are pairwise ligated by three of their N donor atoms to CoII centers in the [Co(bdmpzpy)2]2+ complex cations to form slightly distorted octahedra with mer arrangement. The CoN6 chromophores have Co–N bond distances in the range from 2.1282(17) to 2.2184(17) Å, and transoid N–Co–N bond angles are in the range from 171.80(8)° to 179.60(6)°. In the [Co(N3)]2 4 complex anion of 1 four terminal azido groups are arranged tetra-

Fig. 1. Perspective view of 1 with the atom numbering scheme.

Fig. 2. Perspective view of a [Co(bdmpzpy)2]2+ cation and [Co(NCS)]2 4 anion of 2 with the atom numbering scheme.

hedrally around the Co(2) center. The Co(2)–N, Co(2)–N–N and N– N–N bond parameters vary from 1.992(3) to 2.114(3) Å, from 118.7(4)° to 132.5(2)° and from 169.6(7)° to 177.6(3)°, respectively. The azide groups have asymmetric N–N bond distances with mean D(N–N) of 0.054 Å. In the [Co(NCS)]24 complex anions of 2 four terminal N-thiocyanato groups are arranged tetrahedrally around each CoII center. The N–Co–N tetrahedral bond angles range from 102.27(8)° to 116.78(8)°. The Co–N, N–C and C–S bond lengths vary from 1.9433(19) to 1.973(2) Å, 1.160(3) to 1.167(3) Å, and from 1.621(2) to 1.632(2) Å, respectively. The Co–N–S, and N– C–S bond angles vary from 162.4(2)° to 176.38(19)° and from 177.8(2)° to 179.6(2)°, respectively. The shortest Co  Co separations are 7.3014(12) Å in 1 and 6.8497(5) Å in 2, respectively.

3.3.2. [Co(bepza)(NCS)2] (3) The crystal structure of 3 consists of neutral monomeric [Co(bepza)(NCS)2] complexes. A perspective view with the atom numbering scheme is illustrated in Fig. 3 and selected bond parameters are summarized in Table S2. The cobalt center is penta-coordinated by the three N donor atoms of the bepza amine ligand and two N atoms of the terminal thiocyanato ligands. The coordination polyhedron may be described as distorted square pyramid with

Fig. 3. Perspective view of 3 with the atom numbering scheme.

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s = 0.20

[N(1)–Co(1)–N(7) = 177.35(3)°, N(3)–Co(1)– N(5) = 165.38(3)°] [41]. The apical site in the CoN5 chromophore of 3 is occupied by N(6) atom of NCS group [Co(1)– N(6) = 2.0439(9) Å]. The basal Co–N bonds vary from 2.0805(8) to 2.1833(8) Å, and Co(1) center deviates by 0.158 Å from its basal N4 plane. The N–C and C–S bond lengths and the Co–N–C and N– C–S bond angles for the terminal thiocyanato ligands are 1.1627(12) and 1.1664(13) Å; 1.6270(11) and 1.6438(10) Å; 172.98(9) and 161.10(8)°, 177.70(9)° and 178.98(10)°, respectively. The shortest Co  Co separation is 5.8608(4) Å.

3.3.3. [Co(tedmpza)(NCS)](ClO4).0.5H2O (4) and [Co(tedmpza)(N3)](ClO4)H2O (5) Perspective views together with the atom numbering scheme for crystal structures of 4 and 5 are presented in Figs. 4 and 5, respectively, and selected bond parameters are given in Table S2. Both structures consist of [Co(tedmpza)X]+ (X = NCS (4) or N 3 (5) complex cations, ClO-4 counter anions and lattice water molecules. Their CoN5 chromophores have distorted TBP geometry (s = 0.87 for 4 and 0.86 for 5) [41]. The equatorial sites are occupied by the three N-donor atoms of tedmpza blocking ligand, [Co–N bonds ranges from 2.0145(17) to 2.0637(19) Å]. The two axial sites are occupied by ammine N of tedmpza ligand and by N atom of the terminal pseudohalide group [(4): Co(1)–N(8) = 2.3476(19), Co(1)–N(7) = 2.019(2) Å, N(8)–Co(1)–N(7) = 176.70(7)°; (5): Co(1)–N(1) = 2.4000(16), Co(1)–N(8) = 2.0580(17) Å, N(1)– Co(1)–N(8) = 175.22(6)°]. The terminal pseudohalides have the

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following bond parameters: (4): N(7)–C(16) = 1.159(3), C(16)– (S1) = 1.635(2) Å, Co(1)–N(7)–C(16) = 176.6(2), N(7)–C(16)–S(1) = 178.9(2)°; (5): N(8)–N(9) = 1.185(2), N(9)–N(10) = 1.165(2) Å, Co(1)–N(8)–N(9) = 133.85(15), N(8)–N(9)–N(10) = 176.9(2)°. Hydrogen bonds of type O–H  O are formed between lattice water molecules and oxygen atoms of perchlorate counter ions, further a hydrogen bond of type O–H  N is observed in case of 5 between O(5) and N(10) atom of azide group (Table S3). 4. Conclusions Reactions of linear tridendate and tripod tetraamine pyrazole containing ligands bepza and tedmpza with Co(II) salts and N 3 or NCS anions resulted in the formation of the expected mononuclear five-coordinate complexes [Co(bepza)(NCS)2] (3), [Co(tedmpza)(NCS)]ClO4½H2O (4) and [Co(tedmpza)(NCS)]ClO4H2O (5) as it has been indicated in the introduction. The corresponding reactions with the sterically hindered 2,6-bis[(3,5-dimethyl-pyrazol-1H-yl)-methyl]pyridine (bdmpzpy) ligand, led to the isolation of tetraazido and tetrathiocyanato [Co(bdmpzpy)2][Co(N3)4] (1) and [Co(bdmpzpy)2][Co(NCS)4]2CH3NO2 (2) cationic-anionic compounds. The formation of this class of compounds is unpredictable because some of these complexes were isolated with Co(II) complex cations containing small simple ligands such as ethylenediamie, 10 H,100 H-2,20 -imidazole, 2,20 -bis((4R)-phenyl-1,3-oxazoline) and pyridinoacetate [39c,42] and others have been isolated with more complex ligands [43]. Thus, the isolation of Co(II)-cationic[Co(NCS)4]2 anionic systems is most likely attributed to the limited solubility of these compounds compared to the other possible products in the reaction. Acknowledgments This research was financially supported by the Department of Chemistry, UL Lafayette. FAM thanks Dr. J. Baumgartner (TU-Graz) for assistance. Appendix A. Supplementary data

Fig. 4. Perspective view of 4 with the atom numbering scheme.

CCDC 986657–986661 contains the supplementary crystallographic data for 1–5. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected] Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/ 10.1016/j.poly.2014.04.025. References

Fig. 5. Perspective view of 5 with the atom numbering scheme.

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