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ISSN: 2056-9890

Crystal structure of a Zn complex with tereph­thalate and 1,6-bis­­(1,2,4-triazol-1-yl)hexa­ne

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aNikolaev Institute of Inorganic Chemistry, SB Russian Academy of Sciences, Akad. Lavrentiev prospekt 3, Novosibirsk 90, 630090 , Russian Federation, bDepartment of Natural Sciences, National Research University, Novosibirsk State University, Pirogova st. 2, Novosibirsk 90, 630090 , Russian Federation, and cDepartment of Biotechnology and Organic Chemistry, National Research Tomsk Polytechnic, University, 30 Lenin Ave., 634050, Tomsk, Russian Federation
*Correspondence e-mail: sukhikh@niic.nsc.ru

Edited by E. V. Boldyreva, Russian Academy of Sciences, Russia (Received 24 October 2017; accepted 30 November 2017; online 1 January 2018)

A new zinc coordination polymer with rigid benzene-1,4-di­carboxyl­ate (bdc) and flexible 1,6-bis­(1,2,4-triazol-1-yl)hexane (btrh), namely poly[[(μ2-benzene-1,4-di­carboxyl­ato)[μ2-1,6-bis­(1,2,4-triazol-1-yl)hexa­ne]zinc] di­methyl­form­amide monosolvate], [Zn(C8H4O4)(C10H16N6)]·C3H7NO, was synthesized. According to the single-crystal XRD analysis, the product crystallizes in the P-1 space group and has a layered structure. Analysis of the layered structure reveals {Zn(bdc)} chains which are connected by pairs of btrh ligands. The layers are packed tightly perpendicular to the [1-22] direction, separated by one non-disordered di­methyl­formamide solvent mol­ecule per formula unit. According to thermogravimetric analysis, the product completely loses this solvent at 453 K; the desolvated compound is stable up to 503 K. As a result of the lack of hydrogen-donor groups, hydrogen bonds are not observed in the structure of the complex; however, an inter­molecular C—H⋯π contact of 3.07 Å occurs.

1. Chemical context

Coordination polymers with flexible bitopic ligands have attracted great inter­est as prospective materials for gas separation, sensing materials, electrochemical devices or catalysis (Pettinari et al., 2016[Pettinari, C., Tăbăcaru, A. & Galli, S. (2016). Coord. Chem. Rev. 307, 1-31.]). One of the favoured classes of bitopic ligands are bis­(azol-1-yl) alkanes, which have been used for the preparation of various transition metals coordin­ation polymers with different topologies (Alkorta et al., 2017[Alkorta, I., Claramunt, R. M., Díez-Barra, E., Elguero, J., de la Hoz, A. & López, C. (2017). Coord. Chem. Rev. 339, 153-182.]; Pellei et al., 2017[Pellei, M., Santini, C., Marinelli, M., Trasatti, A. & Dias, H. V. R. (2017). Polyhedron, 125, 86-92.]; Manzano et al., 2016[Manzano, B. R., Jalón, F. A., Carrión, M. C. & Durá, G. (2016). Eur. J. Inorg. Chem. 2016, 2272-2295.]; Liu et al., 2012[Liu, Y.-Y., Li, J., Ma, J.-F., Ma, J.-C. & Yang, J. (2012). CrystEngComm, 14, 169-177.]). Bitopic bis­(azol-1-yl)alkanes have two separated metal-binding sites that allow them to form a wide variety of polymeric structures. Thus, coordination compounds based on these ligands could be applied in the design of various functional materials with a wide range of potential applications. Recently, we have synthesized three new Zn coordination polymers based on bis­(triazol-1-yl)propane and terephtalate anions (Semitut et al., 2017[Semitut, E. Y., Sukhikh, T. S., Filatov, E. Y., Anosova, G. A., Ryadun, A. A., Kovalenko, K. A. & Potapov, A. S. (2017). Cryst. Growth Des. 17, 5559-5567.]). By varying the conditions, it was possible to synthesize three different polymeric compounds, which have inter­esting luminescent properties. As part of our studies with the aim of preparing new coordination polymers with flexible bis­(triazol-1-yl)alkane ligands, we report herein the synthesis and crystal structure of [Zn(bdc)(btrh)]·DMF (bdc = benzene-1,4-di­carboxyl­ate, btrh = 1,6-bis­(1,2,4-triazol-1-yl)hexane, DMF = di­methyl­formamide).

[Scheme 1]

The btrh ligand (Fig. 1[link]) was prepared by the reaction of 1,2,4-triazole with 1,6-di­bromo­hexane in a superbasic dimeth­yl sulfoxide–potassium hydroxide medium using our modified procedure reported for bis­(triazol­yl)propane (Semitut et al., 2017[Semitut, E. Y., Sukhikh, T. S., Filatov, E. Y., Anosova, G. A., Ryadun, A. A., Kovalenko, K. A. & Potapov, A. S. (2017). Cryst. Growth Des. 17, 5559-5567.]). Our proposed procedure does not require the use of toxic solvents and gives higher yields compared to the literature procedure (Liu et al., 2012[Liu, Y.-Y., Li, J., Ma, J.-F., Ma, J.-C. & Yang, J. (2012). CrystEngComm, 14, 169-177.]). The title complex was prepared by the reaction of zinc nitrate, btrh and terephthalic acid under solvothermal conditions (368 K) in DMF. The product was formed after 48 h as a crystalline colourless solid of plate-like shape. The single crystal used for structure determination was collected from the filtered product. The polycrystalline compound was characterized by elemental (C, H, N) and powder XRD analysis (Fig. S1, Supporting information), indicating formation of this complex as a main phase.

[Figure 1]
Figure 1
Synthesis of 1,6-bis­(1,2,4-triazol-1-yl)hexane.

2. Thermal stability

The thermal stability of the synthesized coordination polymer was studied in oxidative O2/Ar (21%) atmosphere. Thermogravimetric measurements were carried out on a NETZSCH thermobalance TG 209 F1 Iris. Open Al2O3 crucibles were used (loads 7–10 mg, heating rate 10 K min−1). The thermal analysis of [Zn(btrh)(bdc)]·nDMF revealed that the synthesized compound has three thermolysis stages in an oxidative atmosphere (Fig. 2[link]). The first stage of thermolysis is the process of the loss of solvate mol­ecules that runs in the range of 373–453 K and has a well-defined step on the TG curve. The mass loss of solvate mol­ecules corresponds to a composition with n ≃ 1, which is in good agreement with the crystal data. The desolvated compound is stable up to 503 K. The second and third stages run in the ranges 503–573 and 633–773 K, respectively. The second stage corresponds to partial degradation of btrh and terephtalate and third to further decomposition and the burning process of the formed carbon products, resulting in the formation of ZnO according to powder XRD analysis.

[Figure 2]
Figure 2
Curves of thermal analysis for [Zn(btrh)(bdc)]·DMF in O2/Ar (21%) atmosphere; 1 TG, 2 DTG, 3 c-DTA.

3. Structural commentary

The structure is a 2D coordination polymer crystallizing in space group P[\overline{1}]. The central Zn atom has a distorted tetra­hedral environment comprising two oxygen and two nitro­gen atoms. It is coordinated by two crystallographically independent (bdc)2− ligands (halves), forming zigzag chains along the [210] direction, which are linked by btrh ligands (Fig. 3[link]). Contrary to our recently reported Zn complexes with 1,3-bis­(1,2,4-triazol-1-yl)propane containing a shorter alkyl bridge (Semitut et al., 2017[Semitut, E. Y., Sukhikh, T. S., Filatov, E. Y., Anosova, G. A., Ryadun, A. A., Kovalenko, K. A. & Potapov, A. S. (2017). Cryst. Growth Des. 17, 5559-5567.]), 1,3-bis­(pyrazol-1-yl)propane (Potapov et al., 2012[Potapov, A. S., Domina, G. A., Petrenko, T. V. & Khlebnikov, A. I. (2012). Polyhedron, 33, 150-157.]) and bis­(imidazol-1-yl)alkanes (Barsukova, Samsonenko et al., 2016[Barsukova, M. O., Samsonenko, D. G., Goncharova, T. V., Potapov, A. S., Sapchenko, S. A., Dybtsev, D. N. & Fedin, V. P. (2016). Russ. Chem. Bull. 65, 2914-2919.]; Barsukova, Goncharova et al., 2016[Barsukova, M., Goncharova, T., Samsonenko, D., Dybtsev, D. & Potapov, A. (2016). Crystals, 6, 132/1-132/15.]), the title compound is a 2D polymer, because the Zn atoms are connected by btrh ligands in pairs, not in chains, thus preventing the formation of a 3D net. Each Zn atom is linked with three others via (1) the first bdc2– ligand, (2) a second bdc2– ligand and (3) a pair of btrh ligands. The layers of the title compound are arranged perpendicular to the [1[\overline{2}]2] direction in such a way that the {Zn2(btrh)2} units lie between the hollows of neighboring layers (Figs. S2, S3).

[Figure 3]
Figure 3
Displacement ellipsoid plot of a single layer of the coordination polymer showing ellispoids drawn at the 50% probability level.

4. Supra­molecular features

Layers of the complex are packed tightly, revealing only one DMF solvent mol­ecule per formula unit. Analysis of the residual electron-density map clearly indicates the presence of a not or very slightly disordered DMF mol­ecule (Fig. S4). After refining DMF, only one peak of 0.60 e Å−3 (attributed to a C atom of occupancy ca 0.15) is observed, while the densities of other peaks coincide with those of holes (ca ±0.3 e Å−3). Thus, the DMF mol­ecule is rather not disordered. Besides disorder, atomic displacement parameters that are larger than those for other atoms can be due to partial loss of the solvent during the experiment. DMF mol­ecules are located in the channel voids, which occupy 26.4% of the structure (Fig. S5). As a result of the lack of H-donor groups, hydrogen bonds are not observed in the structure of the complex; however, inter­molecular C—H⋯π contacts of 3.07 Å (Table 1[link]) occur between the aromatic rings of bdc ligands (Fig. S6). These contacts connect neighbouring layers.

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C24–C26/C241–C26i ring.

D—H⋯A D—H H⋯A DA D—H⋯A
C36ii—H36iiCg 0.93 3.07 3.95 149
Symmetry codes: (i) 2 - x, 1 - y, - z; (ii) x+1, y+1, z.

5. Database survey

A database survey showed that the majority of the known structures of polymers with flexible bis­(azol-1-yl)alkanes are compounds based on relatively short linkers (from methane to penta­ne) but that the number of polymers based on longer linkers (having a CH2-chain higher than six) is relatively low. The lack of structural information on long flexible ligands can be due to the fact that it is more difficult to obtain single crystals of good quality for these compounds. Such ligands tend to form inter­penetrated polymers with disorder and a variety of modifications. A search of the Cambridge Structural Database (CSD, Version 5.38, update May 2017; Groom et al., 2016[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]) for compounds containing btrh and any metal gave 51 hits, of which only one contains both btrh and bdc ligands (refcode ETAKAM; Zhang et al., 2011[Zhang, P., Li, D.-S., Zhao, J., Wu, Y.-P., Li, C., Zou, K. & Lu, J. Y. (2011). J. Coord. Chem. 64, 13, 2329-2341.]). This Cd polymer also has a 2D structure, but the {Cd(bdc)} chains are linear and are inter­sected by {Cd(btrh)} chains. Thus, contrary to our case, the two central metal atoms are connected by only one btrh ligand.

6. Synthesis and crystallization

Starting materials and experimental procedures

The starting reagents used for the synthesis of the coordination compound – Zn(NO3)2·6H2O (chemical grade), dimethyl formamide (analytical grade) and terephthalic acid (analytical grade) – were used as received.

NMR spectra were recorded on a Bruker AV300 instrument operating at 300 MHz for 1H and 75 MHz for 13C, solvent residual peaks were used as inter­nal standard. Elemental analyses were carried out on a Eurovector EuroEA 3000 analyser. Infrared (IR) spectra of solid samples as KBr pellets were recorded on a FT-801 spectrometer (4000–550 cm−1). The powder XRD data were collected with a DRON RM4 powder diffractometer equipped with a Cu Kα source (λ = 1.5418 Å) and graphite monochromator for the diffracted beam.

Synthesis of compound [Zn(btrh)(bdc)]·nDMF

35.2 mg (0.16 mmol) of btrh ligand and 4.0 ml of Zn(NO3)2·6H2O (0.04 M) were added to 0.4 ml of a DMF solution of H2bdc (0.4 M) in a glass vial. The resulting mixture was stirred for several minutes at room temperature for total ligand dissolution and placed into an oven at 368 K. After heating for 48 h, the vial was cooled to room temperature. Plate-like colourless crystals formed on the bottom of the vial; they where filtered and washed twice with 5 ml of DMF and dried in a vacuum. The yield was 39 mg (53%). IR bands, cm−1: 3115, 2948, 2861, 1680, 1611, 1530, 1499, 1437, 1391, 1345, 1287, 1217, 1136, 1098, 1017, 1001, 947, 905, 878, 828, 750, 743, 673, 642, 577. Elemental analysis: found, %: C 48.5, H 5.9, N 18.9; calculated ([Zn(btrh)(bdc)]·DMF), %: C 48.2, H 5.2, N 18.8.

Synthesis of 1,6-bis­(1,2,4-triazol-1-yl)hexane (btrh)

A suspension of 2.76 g (40 mmol) of 1,2,4-triazole and 4.48 g (80 mmol) of powdered KOH in 15 ml of DMSO was stirred vigorously at 353 K for 30 min. The reaction flask was then immersed into a cold water bath and, after cooling to room temperature, 4.88 g (20 mmol) of 1,6-di­bromo­hexane in 10 ml of DMSO were added dropwise over 30 min. After the addition was complete, the reaction mixture was stirred overnight at 353 K. It was then quenched with 200 ml of water and extracted with 1-butanol (5 × 20 ml), the extract was then washed with water (2 ×10 ml). Evaporation of solvents from the extract on a rotary evaporator and recrystallization from isopropyl alcohol gave 3.83 g (87%) of the product as colourless crystals. 1H NMR (CDCI3), δ, ppm: 1.24 (t, 4H, γ-CH2, J = 7 Hz), 1.79 (q, 4H, β-CH2, J = 7 Hz), 4.06 (t, 4H, α-CH2, J = 7 Hz), 7.83 (s, 2H, H3-Tr), 8.08 (s, 2H, H5-Tr). 13C NMR (CDCI3), δ, ppm: 25.6 (γ-CH2), 29.3 (β-CH2), 49.2 (α –CH2), 142.7 (Tr-C3), 151.6 (Tr-C5).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. H atoms were refined as riding atoms (C—H = 0.97 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms and C—H = 0.93 Å 1.2Ueq(C) for all others. Methyl H atoms were refined as rotating groups.

Table 2
Experimental details

Crystal data
Chemical formula [Zn(C8H4O4)(C10H16N6)]·C3H7NO
Mr 522.86
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 298
a, b, c (Å) 9.7803 (6), 10.4481 (5), 13.3708 (8)
α, β, γ (°) 101.438 (2), 101.015 (2), 109.073 (2)
V3) 1216.41 (12)
Z 2
Radiation type Mo Kα
μ (mm−1) 1.06
Crystal size (mm) 0.1 × 0.05 × 0.02
 
Data collection
Diffractometer Bruker APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2012[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.665, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections 12157, 4293, 2999
Rint 0.049
(sin θ/λ)max−1) 0.595
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.118, 1.00
No. of reflections 4293
No. of parameters 309
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.60, −0.33
Computer programs: APEX2 and SAINT (Bruker, 2012[Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Supporting information


Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[[(µ2-benzene-1,4-dicarboxylato)[µ2-1,6-bis(1,2,4-triazol-1-yl)hexane]zinc] dimethylformamide monosolvate] top
Crystal data top
[Zn(C8H4O4)(C10H16N6)]·C3H7NOZ = 2
Mr = 522.86F(000) = 544
Triclinic, P1Dx = 1.428 Mg m3
a = 9.7803 (6) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.4481 (5) ÅCell parameters from 2516 reflections
c = 13.3708 (8) Åθ = 2.3–22.4°
α = 101.438 (2)°µ = 1.06 mm1
β = 101.015 (2)°T = 298 K
γ = 109.073 (2)°Plate, colourless
V = 1216.41 (12) Å30.1 × 0.05 × 0.02 mm
Data collection top
Bruker APEXII CCD
diffractometer
2999 reflections with I > 2σ(I)
φ and ω scansRint = 0.049
Absorption correction: multi-scan
(SADABS; Bruker, 2012)
θmax = 25.0°, θmin = 2.2°
Tmin = 0.665, Tmax = 0.745h = 1111
12157 measured reflectionsk = 129
4293 independent reflectionsl = 1515
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.118 w = 1/[σ2(Fo2) + (0.062P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
4293 reflectionsΔρmax = 0.60 e Å3
309 parametersΔρmin = 0.33 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.55113 (4)0.42735 (4)0.19802 (3)0.04413 (17)
O210.6685 (3)0.4028 (3)0.0983 (2)0.0588 (7)
O220.8610 (3)0.5441 (3)0.2351 (2)0.0751 (9)
O310.3399 (3)0.3182 (3)0.1154 (3)0.0745 (9)
O320.3836 (4)0.1533 (3)0.1758 (3)0.0911 (11)
N1110.6118 (3)0.4320 (3)0.3513 (2)0.0476 (7)
N1130.6160 (4)0.3855 (4)0.5075 (3)0.0749 (11)
N1140.7283 (4)0.5081 (3)0.5193 (3)0.0586 (9)
N1211.4483 (3)1.3736 (3)0.7898 (2)0.0464 (7)
N1231.4969 (4)1.1793 (4)0.7385 (3)0.0701 (10)
N1241.4569 (3)1.1841 (3)0.8295 (3)0.0504 (8)
C230.8065 (4)0.4779 (4)0.1401 (3)0.0486 (9)
C240.9064 (4)0.4885 (3)0.0678 (3)0.0436 (9)
C251.0606 (4)0.5593 (4)0.1062 (3)0.0654 (12)
H251.10320.60040.17880.078*
C261.1517 (4)0.5703 (4)0.0403 (3)0.0637 (11)
H261.25510.61860.06880.076*
C330.3002 (4)0.1957 (4)0.1235 (3)0.0540 (10)
C340.1434 (4)0.0945 (4)0.0602 (3)0.0473 (9)
C350.0949 (4)0.0457 (4)0.0597 (3)0.0544 (10)
H350.15840.07730.10020.065*
C360.0471 (4)0.1389 (4)0.0003 (3)0.0547 (10)
H360.07810.23310.00030.066*
C1120.5502 (5)0.3442 (4)0.4054 (4)0.0674 (12)
H1120.46700.26050.37290.081*
C1150.7231 (5)0.5337 (4)0.4267 (3)0.0596 (11)
H1150.78940.61320.41580.071*
C1221.4891 (5)1.2946 (4)0.7177 (3)0.0658 (12)
H1221.51001.31990.65770.079*
C1251.4289 (4)1.2994 (4)0.8595 (3)0.0496 (9)
H1251.39991.32470.92040.060*
C1310.8254 (6)0.5943 (5)0.6262 (3)0.0807 (14)
H13A0.82790.53260.67140.097*
H13B0.78100.65840.65540.097*
C1320.9823 (5)0.6778 (4)0.6292 (3)0.0662 (12)
H13C0.98120.73430.57970.079*
H13D1.03170.61460.60760.079*
C1331.0684 (5)0.7730 (4)0.7397 (3)0.0656 (12)
H13E1.07440.71460.78710.079*
H13F1.01180.82840.76290.079*
C1341.2262 (5)0.8728 (4)0.7510 (3)0.0628 (11)
H13G1.28580.81860.73190.075*
H13H1.22220.93020.70250.075*
C1351.3004 (5)0.9675 (4)0.8631 (3)0.0636 (12)
H13I1.23581.01600.88230.076*
H13J1.30560.90830.91000.076*
C1361.4545 (5)1.0756 (4)0.8842 (3)0.0654 (12)
H13K1.49531.12040.96000.078*
H13L1.51911.02900.86170.078*
O1S1.2093 (8)1.1555 (6)0.4821 (6)0.225 (4)
N3S1.1710 (7)0.9340 (5)0.4102 (4)0.1045 (16)
C2S1.2272 (11)1.0486 (9)0.4748 (8)0.179 (4)
H2S1.30171.05320.53180.215*
C4S1.1971 (10)0.8107 (8)0.4102 (7)0.175 (4)
H4SA1.28290.83030.46800.263*
H4SB1.21590.77570.34430.263*
H4SC1.11040.74110.41810.263*
C5S1.0403 (15)0.9099 (11)0.3279 (8)0.261 (7)
H5SA0.96040.91460.35860.392*
H5SB1.00940.81830.27900.392*
H5SC1.06370.98070.29090.392*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0345 (2)0.0472 (3)0.0430 (3)0.00801 (18)0.01047 (19)0.00923 (18)
O210.0449 (16)0.0665 (17)0.0534 (18)0.0082 (13)0.0217 (14)0.0061 (13)
O220.0524 (18)0.100 (2)0.052 (2)0.0115 (16)0.0196 (16)0.0013 (17)
O310.0462 (17)0.0557 (18)0.097 (3)0.0006 (13)0.0069 (16)0.0137 (16)
O320.061 (2)0.070 (2)0.104 (3)0.0154 (16)0.0199 (19)0.0029 (18)
N1110.0452 (18)0.0493 (17)0.0420 (19)0.0111 (14)0.0116 (16)0.0114 (15)
N1130.070 (3)0.078 (2)0.053 (3)0.000 (2)0.008 (2)0.0255 (19)
N1140.055 (2)0.061 (2)0.045 (2)0.0058 (17)0.0104 (17)0.0148 (16)
N1210.0449 (18)0.0446 (17)0.0431 (19)0.0117 (14)0.0118 (15)0.0077 (15)
N1230.093 (3)0.069 (2)0.063 (3)0.041 (2)0.037 (2)0.0171 (19)
N1240.0488 (19)0.0504 (19)0.046 (2)0.0174 (15)0.0054 (16)0.0093 (15)
C230.045 (2)0.055 (2)0.051 (3)0.0197 (19)0.021 (2)0.016 (2)
C240.038 (2)0.046 (2)0.043 (2)0.0121 (16)0.0134 (18)0.0102 (17)
C250.042 (2)0.092 (3)0.040 (3)0.011 (2)0.008 (2)0.001 (2)
C260.032 (2)0.093 (3)0.048 (3)0.008 (2)0.010 (2)0.006 (2)
C330.039 (2)0.056 (3)0.060 (3)0.017 (2)0.017 (2)0.002 (2)
C340.036 (2)0.045 (2)0.054 (3)0.0101 (16)0.0138 (18)0.0059 (17)
C350.041 (2)0.051 (2)0.065 (3)0.0149 (18)0.008 (2)0.0133 (19)
C360.048 (2)0.042 (2)0.068 (3)0.0121 (18)0.014 (2)0.0144 (19)
C1120.061 (3)0.063 (3)0.058 (3)0.001 (2)0.009 (2)0.022 (2)
C1150.061 (3)0.059 (2)0.048 (3)0.007 (2)0.017 (2)0.017 (2)
C1220.072 (3)0.071 (3)0.054 (3)0.024 (2)0.026 (2)0.015 (2)
C1250.044 (2)0.053 (2)0.047 (2)0.0171 (18)0.0098 (18)0.0097 (19)
C1310.087 (4)0.083 (3)0.044 (3)0.006 (3)0.008 (3)0.010 (2)
C1320.054 (3)0.074 (3)0.056 (3)0.022 (2)0.003 (2)0.001 (2)
C1330.071 (3)0.057 (2)0.052 (3)0.016 (2)0.002 (2)0.008 (2)
C1340.060 (3)0.065 (3)0.055 (3)0.026 (2)0.005 (2)0.006 (2)
C1350.076 (3)0.055 (2)0.049 (3)0.021 (2)0.001 (2)0.0133 (19)
C1360.077 (3)0.057 (2)0.054 (3)0.028 (2)0.003 (2)0.012 (2)
O1S0.253 (8)0.094 (4)0.257 (8)0.083 (4)0.056 (6)0.012 (4)
N3S0.146 (5)0.079 (3)0.084 (4)0.049 (3)0.020 (3)0.013 (3)
C2S0.214 (10)0.096 (6)0.187 (9)0.047 (6)0.008 (8)0.017 (6)
C4S0.199 (9)0.149 (7)0.189 (9)0.099 (7)0.052 (7)0.017 (6)
C5S0.345 (17)0.179 (10)0.186 (10)0.104 (10)0.075 (12)0.026 (8)
Geometric parameters (Å, º) top
Zn1—O211.950 (3)C36—H360.9300
Zn1—O311.969 (3)C112—H1120.9300
Zn1—N1112.008 (3)C115—H1150.9300
Zn1—N121i2.052 (3)C122—H1220.9300
O21—C231.263 (4)C125—H1250.9300
O22—C231.236 (4)C131—H13A0.9700
O31—C331.244 (5)C131—H13B0.9700
O32—C331.222 (5)C131—C1321.485 (6)
N111—C1121.340 (5)C132—H13C0.9700
N111—C1151.315 (5)C132—H13D0.9700
N113—N1141.344 (4)C132—C1331.509 (5)
N113—C1121.309 (5)C133—H13E0.9700
N114—C1151.314 (5)C133—H13F0.9700
N114—C1311.472 (5)C133—C1341.513 (6)
N121—Zn1i2.052 (3)C134—H13G0.9700
N121—C1221.348 (5)C134—H13H0.9700
N121—C1251.327 (5)C134—C1351.510 (5)
N123—N1241.343 (4)C135—H13I0.9700
N123—C1221.311 (5)C135—H13J0.9700
N124—C1251.324 (4)C135—C1361.492 (6)
N124—C1361.462 (5)C136—H13K0.9700
C23—C241.495 (5)C136—H13L0.9700
C24—C251.382 (5)O1S—C2S1.174 (8)
C24—C26ii1.376 (5)N3S—C2S1.208 (9)
C25—H250.9300N3S—C4S1.393 (8)
C25—C261.363 (5)N3S—C5S1.432 (10)
C26—C24ii1.376 (5)C2S—H2S0.9300
C26—H260.9300C4S—H4SA0.9600
C33—C341.508 (5)C4S—H4SB0.9600
C34—C351.383 (5)C4S—H4SC0.9600
C34—C36iii1.374 (5)C5S—H5SA0.9600
C35—H350.9300C5S—H5SB0.9600
C35—C361.379 (5)C5S—H5SC0.9600
C36—C34iii1.374 (5)
O21—Zn1—O31105.00 (12)N124—C125—N121110.0 (4)
O21—Zn1—N111124.42 (12)N124—C125—H125125.0
O21—Zn1—N121i104.47 (12)N114—C131—H13A108.7
O31—Zn1—N111118.44 (13)N114—C131—H13B108.7
O31—Zn1—N121i98.53 (12)N114—C131—C132114.2 (4)
N111—Zn1—N121i101.66 (12)H13A—C131—H13B107.6
C23—O21—Zn1110.9 (2)C132—C131—H13A108.7
C33—O31—Zn1110.0 (3)C132—C131—H13B108.7
C112—N111—Zn1131.6 (3)C131—C132—H13C109.6
C115—N111—Zn1126.1 (3)C131—C132—H13D109.6
C115—N111—C112102.1 (3)C131—C132—C133110.3 (4)
C112—N113—N114102.6 (3)H13C—C132—H13D108.1
N113—N114—C131119.8 (3)C133—C132—H13C109.6
C115—N114—N113109.4 (3)C133—C132—H13D109.6
C115—N114—C131130.7 (4)C132—C133—H13E108.5
C122—N121—Zn1i128.6 (3)C132—C133—H13F108.5
C125—N121—Zn1i128.2 (3)C132—C133—C134115.3 (4)
C125—N121—C122102.5 (3)H13E—C133—H13F107.5
C122—N123—N124102.6 (3)C134—C133—H13E108.5
N123—N124—C136121.4 (3)C134—C133—H13F108.5
C125—N124—N123110.2 (3)C133—C134—H13G109.4
C125—N124—C136128.4 (4)C133—C134—H13H109.4
O21—C23—C24116.7 (3)H13G—C134—H13H108.0
O22—C23—O21123.9 (4)C135—C134—C133111.3 (4)
O22—C23—C24119.4 (3)C135—C134—H13G109.4
C25—C24—C23121.5 (4)C135—C134—H13H109.4
C26ii—C24—C23121.3 (3)C134—C135—H13I108.1
C26ii—C24—C25117.1 (3)C134—C135—H13J108.1
C24—C25—H25119.2H13I—C135—H13J107.3
C26—C25—C24121.7 (4)C136—C135—C134116.8 (4)
C26—C25—H25119.2C136—C135—H13I108.1
C24ii—C26—H26119.4C136—C135—H13J108.1
C25—C26—C24ii121.2 (4)N124—C136—C135113.0 (3)
C25—C26—H26119.4N124—C136—H13K109.0
O31—C33—C34117.3 (4)N124—C136—H13L109.0
O32—C33—O31123.2 (4)C135—C136—H13K109.0
O32—C33—C34119.4 (4)C135—C136—H13L109.0
C35—C34—C33120.5 (3)H13K—C136—H13L107.8
C36iii—C34—C33120.8 (3)C2S—N3S—C4S130.5 (8)
C36iii—C34—C35118.7 (3)C2S—N3S—C5S116.7 (7)
C34—C35—H35119.8C4S—N3S—C5S112.0 (6)
C36—C35—C34120.4 (3)O1S—C2S—N3S134.7 (10)
C36—C35—H35119.8O1S—C2S—H2S112.7
C34iii—C36—C35120.8 (3)N3S—C2S—H2S112.7
C34iii—C36—H36119.6N3S—C4S—H4SA109.5
C35—C36—H36119.6N3S—C4S—H4SB109.5
N111—C112—H112122.6N3S—C4S—H4SC109.5
N113—C112—N111114.8 (4)H4SA—C4S—H4SB109.5
N113—C112—H112122.6H4SA—C4S—H4SC109.5
N111—C115—H115124.4H4SB—C4S—H4SC109.5
N114—C115—N111111.1 (4)N3S—C5S—H5SA109.5
N114—C115—H115124.4N3S—C5S—H5SB109.5
N121—C122—H122122.6N3S—C5S—H5SC109.5
N123—C122—N121114.8 (4)H5SA—C5S—H5SB109.5
N123—C122—H122122.6H5SA—C5S—H5SC109.5
N121—C125—H125125.0H5SB—C5S—H5SC109.5
Zn1—O21—C23—O228.3 (5)C24—C25—C26—C24ii0.1 (7)
Zn1—O21—C23—C24170.1 (2)C26ii—C24—C25—C260.1 (7)
Zn1—O31—C33—O320.1 (5)C33—C34—C35—C36178.3 (4)
Zn1—O31—C33—C34176.8 (3)C34—C35—C36—C34iii0.5 (7)
Zn1—N111—C112—N113176.0 (3)C36iii—C34—C35—C360.5 (7)
Zn1—N111—C115—N114176.7 (3)C112—N111—C115—N1140.3 (5)
Zn1i—N121—C122—N123170.8 (3)C112—N113—N114—C1150.6 (5)
Zn1i—N121—C125—N124171.3 (2)C112—N113—N114—C131176.1 (4)
O21—C23—C24—C25175.2 (3)C115—N111—C112—N1130.0 (5)
O21—C23—C24—C26ii5.7 (5)C115—N114—C131—C13236.4 (7)
O22—C23—C24—C256.4 (5)C122—N121—C125—N1240.1 (4)
O22—C23—C24—C26ii172.7 (4)C122—N123—N124—C1250.6 (4)
O31—C33—C34—C35175.8 (4)C122—N123—N124—C136178.1 (3)
O31—C33—C34—C36iii3.0 (6)C125—N121—C122—N1230.5 (5)
O32—C33—C34—C351.0 (6)C125—N124—C136—C13583.2 (5)
O32—C33—C34—C36iii179.8 (4)C131—N114—C115—N111175.5 (4)
N113—N114—C115—N1110.6 (5)C131—C132—C133—C134175.0 (4)
N113—N114—C131—C132149.1 (4)C132—C133—C134—C135177.6 (3)
N114—N113—C112—N1110.4 (5)C133—C134—C135—C136177.4 (3)
N114—C131—C132—C133174.5 (4)C134—C135—C136—N12466.5 (5)
N123—N124—C125—N1210.4 (4)C136—N124—C125—N121177.7 (3)
N123—N124—C136—C13599.8 (5)C4S—N3S—C2S—O1S177.8 (11)
N124—N123—C122—N1210.7 (5)C5S—N3S—C2S—O1S9.0 (19)
C23—C24—C25—C26179.3 (4)
Symmetry codes: (i) x+2, y+2, z+1; (ii) x+2, y+1, z; (iii) x, y, z.
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C24–C26/C24i–C26i ring.
D—H···AD—HH···AD···AD—H···A
C36iv—H36iv···Cg0.933.073.95149
Symmetry code: (iv) x+1, y+1, z.
 

Funding information

This study was supported by the Russian Science Foundation, grant No. 15–13-10023 and the X-ray structure analysis was carried out with support from the Ministry of Education and Science of the Russian Federation (a project of the Joint Laboratories of the Siberian Branch of the Russian Academy of Sciences and the National Research Universities).

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