research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 72| Part 5| May 2016| Pages 652-655
doi:10.1107/S2056989016005600

Crystal structures of (Z)-5-[2-(benzo[b]thio­phen-2-yl)-1-(3,5-di­meth­­oxy­phen­yl)ethen­yl]-1H-tetra­zole and (Z)-5-[2-(benzo[b]thio­phen-3-yl)-1-(3,4,5-tri­meth­­oxy­phen­yl)ethen­yl]-1H-tetra­zole

CROSSMARK_Color_square_no_text.svg
Narsimha Reddy Penthala,a Jaishankar K. B. Yadlapalli,a Sean Parkinb and Peter A. Crooksa*

aDepartment of Pharmaceutical Sciences, College of Pharmacy, University of Arkansas for Medical Sciences, Little Rock, AR 72205, USA, and bDepartment of Chemistry, University of Kentucky, Lexington KY 40506, USA
*Correspondence e-mail: pacrooks@uams.edu

Edited by P. C. Healy, Griffith University, Australia (Received 24 March 2016; accepted 4 April 2016; online 8 April 2016)

(Z)-5-[2-(Benzo[b]thio­phen-2-yl)-1-(3,5-di­meth­oxy­phen­yl)ethen­yl]-1H-tetrazole methanol monosolvate, C19H16N4O2S·CH3OH, (I), was prepared by the reaction of (Z)-3-(benzo[b]thio­phen-2-yl)-2-(3,5-di­meth­oxy­phen­yl)acrylo­nitrile with tri­butyl­tin azide via a [3 + 2]cyclo­addition azide condensation reaction. The structurally related compound (Z)-5-[2-(benzo[b]thio­phen-3-yl)-1-(3,4,5-tri­meth­oxy­phen­yl)ethen­yl]-1H-tetra­zole, C20H18N4O3S, (II), was prepared by the reaction of (Z)-3-(benzo[b]thio­phen-3-yl)-2-(3,4,5-tri­meth­oxy­phen­yl)acrylo­nitrile with tri­butyl­tin azide. Crystals of (I) have two mol­ecules in the asymmetric unit (Z′ = 2), whereas crystals of (II) have Z′ = 1. The benzo­thio­phene rings in (I) and (II) are almost planar, with r.m.s deviations from the mean plane of 0.0084 and 0.0037 Å in (I) and 0.0084 Å in (II). The tetra­zole rings of (I) and (II) make dihedral angles with the mean planes of the benzo­thio­phene rings of 88.81 (13) and 88.92 (13)° in (I), and 60.94 (6)° in (II). The di­meth­oxy­phenyl and tri­meth­oxy­phenyl rings make dihedral angles with the benzo­thio­phene rings of 23.91 (8) and 24.99 (8)° in (I) and 84.47 (3)° in (II). In both structures, mol­ecules are linked into hydrogen-bonded chains. In (I), these chains involve both tetra­zole and methanol, and are parallel to the b axis. In (II), mol­ecules are linked into chains parallel to the a axis by N—H⋯N hydrogen bonds between adjacent tetra­zole rings.

CCDC references: 1472235; 1472234

1. Chemical context

We have reported on benzo­thio­phene cyano­combretastatin A-4 analogs (Penthala et al., 2013[Penthala, N. R., Sonar, V. N., Horn, J., Leggas, M., Yadlapalli, K. B. J. S. & Crooks, P. A. (2013). Med. Chem. Commun. 4, 1073-1078.]), and benzo­thio­phene triazol­ylcombretastatin A-4 analogs as promising anti-cancer agents (Penthala et al., 2015[Penthala, N. R., Madhukuri, L., Thakkar, S., Madadi, N. R., Lamture, G., Eoff, R. L. & Crooks, P. A. (2015). Med. Chem. Commun. 6, 1535-1543.]). Previously, we published the synthesis of triazolylcombretastatin A-4 analogs utilizing a [3 + 2]cyclo­addition azide condensation reaction with sodium azide in the presence of L-proline as catalyst (Penthala et al., 2014a[Penthala, N. R., Madadi, N. R., Janganati, V. & Crooks, P. A. (2014a). Tetrahedron Lett. 55, 5562-5565.]). In a continuation of our work on the chemical modification of the cyano group on the stilbene moiety of cyano­combretastatin A-4 analogs (Penthala et al., 2014a[Penthala, N. R., Madadi, N. R., Janganati, V. & Crooks, P. A. (2014a). Tetrahedron Lett. 55, 5562-5565.]), we have recently synthesized tetra­zolylcombretastatin A-4 analogs as potential anti-cancer agents (Penthala et al., 2016[Penthala, N. R., Bommagani, S., Yadlapalli, J. & Crooks, P. A. (2016). Tetrahedron Lett. 57, 1807-1810.]).

2. Structural commentary

Single crystal X-ray analysis was carried out to obtain the structural conformations of the tetra­zolylcombretastatin A-4 analogs (I)[link] and (II)[link] for the analysis of structure–activity relationships (SAR), the relevance of the geometry of the tetra­zole ring on the stilbene scaffold and to confirm the position of the hydrogen atom in the tetra­zole ring system. The single crystal X-ray structures of (I)[link] and (II)[link] are shown in Figs. 1[link] and 2[link], respectively.

[Scheme 1]
[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], with displacement ellipsoids drawn at the 50% probability level.
[Figure 2]
Figure 2
The mol­ecular structure of (II)[link], with displacement ellipsoids drawn at the 50% probability level.

The benzo­thio­phene rings are almost planar with r.m.s. deviations from the mean plane of 0.0084 and 0.0037 Å in (I)[link] and 0.0084 Å in (II)[link], with bond distances and angles comparable with those reported for other benzo­thio­phene derivatives (Sonar et al., 2007[Sonar, V. N., Parkin, S. & Crooks, P. A. (2007). Acta Cryst. C63, o743-o745.]; Penthala et al., 2014b[Penthala, N. R., Madadi, N. R., Bommagani, S., Parkin, S. & Crooks, P. A. (2014b). Acta Cryst. E70, 392-395.]). The tetra­zole rings make dihedral angles with the mean plane of the benzo­thio­phene rings of 88.81 (13) and 88.92 (13)° in (I)[link], and 60.94 (6)° in (II)[link]. The di­meth­oxy­phenyl ring in (I)[link] and tri­meth­oxy­phenyl ring in (II)[link] make dihedral angles with the benzo­thio­phene rings of 23.91 (8) and 24.99 (8)° in (I)[link] and 84.47 (3)° in (II)[link]. Bond lengths and angles in both (I)[link] and (II)[link] are, by and large, unremarkable.

3. Supra­molecular features

Hydrogen bonding and the mode of packing of (I)[link] is illus­trated in Fig. 3[link], and the mode of packing of (II)[link] is illustrated in Fig. 4[link]. In the structure of (I)[link], the mol­ecules are linked into hydrogen-bonded (Table 1[link]) chains parallel to the crystallographic b axis involving inter­action between tetra­zole–tetra­zole (N—H⋯N), tetra­zole–methanol (O—H⋯N and N—H⋯O), and methanol–methanol (O—H⋯O). These chains are bidirectional, as the hydrogen atoms on the tetra­zole rings and the methanol oxygen atom appear to be disordered over two positions. In the structure of (II)[link], the mol­ecules are linked into chains parallel to the a axis by inter­molecular N—H⋯N hydrogen bonds (Table 2[link]) between adjacent tetra­zole rings.

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1A—H1NA⋯N1Ai 0.88 1.91 2.787 (9) 176
N4A—H4NA⋯O1SB 0.88 1.87 2.736 (6) 168
N1B—H1NB⋯N1Bii 0.88 1.92 2.792 (9) 174
N4B—H4NB⋯O1SA 0.88 1.91 2.769 (6) 165
O1SA—H1SA⋯N4B 0.84 1.97 2.769 (6) 158
O1SA—H2SA⋯O1SAiii 0.84 1.81 2.646 (7) 177
O1SB—H1SB⋯N4A 0.84 1.90 2.736 (6) 176
Symmetry codes: (i) -x, -y, z; (ii) -x+1, -y+1, z; (iii) -x+1, -y, z.

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1N⋯N3i 0.91 (2) 2.65 (2) 3.3886 (19) 138.5 (16)
N1—H1N⋯N4i 0.91 (2) 1.85 (2) 2.7482 (19) 167.1 (18)
Symmetry code: (i) x-1, y, z.
[Figure 3]
Figure 3
Crystal packing of (I)[link], viewed down the c axis.
[Figure 4]
Figure 4
Crystal packing of (II)[link], viewed down the c axis.

4. Database survey

A search of the 2015 Cambridge Structural Database (Groom & Allen, 2014[Groom, C. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) for tetra­zole bonded via its carbon atom to another carbon atom yielded 255 hits. Of these, only two were bonded to an sp2 carbon atom, namely 5-(2H-chromen-3-yl)-1H-tetra­zole monohydrate (NEYCUR: Gawande et al., 2013[Gawande, S. D., Raihan, M. J., Zanwar, M. R., Kavala, V., Janreddy, D., Kuo, C.-W., Chen, M.-L., Kuo, T.-S. & Yao, C.-F. (2013). Tetrahedron, 69, 1841-1848.]) and (2Z,4E)-5-(di­methyl­amino)-2-(1H-tetra­zol-5-yl)penta-2,4-diene­nitrile methanol solvate (YUPPAB: Addicott et al., 2009[Addicott, C., Bernhardt, P. V. & Wentrup, C. (2009). Arkivoc, 10, 30-36.]). Neither NEYCUR nor YUPPAB have any particular similarity to compounds (I)[link] and (II)[link].

5. Synthesis and crystallization

The title compounds (I)[link] and (II)[link] were prepared by utilizing our recently reported literature procedure (Penthala et al., 2016[Penthala, N. R., Bommagani, S., Yadlapalli, J. & Crooks, P. A. (2016). Tetrahedron Lett. 57, 1807-1810.]). Recrystallization of the compounds from methanol afforded (I)[link] and (II)[link] as pale-yellow crystalline products which were suitable for X-ray analysis.

6. Refinement details

Crystal data, data collection and refinement details for both (I)[link] and (II)[link] are summarized in Table 3[link]. H atoms were found in difference Fourier maps and subsequently placed at idealized positions with constrained distances of 0.95 Å (R2Csp2H), 0.98 Å (RCH3), 0.84 Å (OH), 0.88 Å (Nsp2H). Uiso(H) values were set to either 1.2Ueq or 1.5Ueq (RCH3, OH) of the attached atom. Final models were checked using PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]), RT (Parkin, 2000[Parkin, S. (2000). Acta Cryst. A56, 157-162.]), and by checkCIF.

Table 3
Experimental details

  (I) (II)
Crystal data
Chemical formula C19H16N4O2S·CH4O C20H18N4O3S
Mr 396.46 394.44
Crystal system, space group Orthorhombic, P21212 Monoclinic, P21/c
Temperature (K) 90 90
a, b, c (Å) 18.2226 (4), 13.7954 (5), 15.5594 (5) 4.8888 (1), 24.6650 (6), 15.5956 (4)
α, β, γ (°) 90, 90, 90 90, 91.031 (1), 90
V (Å3) 3911.4 (2) 1880.25 (8)
Z 8 4
Radiation type Cu Kα Cu Kα
μ (mm−1) 1.72 1.78
Crystal size (mm) 0.21 × 0.15 × 0.12 0.10 × 0.08 × 0.02
 
Data collection
Diffractometer Bruker X8 Proteum Bruker X8 Proteum
Absorption correction Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.]) Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.])
Tmin, Tmax 0.720, 0.915 0.693, 0.897
No. of measured, independent and observed [I > 2σ(I)] reflections 51755, 7112, 6916 23250, 3337, 3138
Rint 0.038 0.037
(sin θ/λ)max (Å−1) 0.602 0.603
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.109, 1.10 0.034, 0.094, 1.13
No. of reflections 7112 3337
No. of parameters 514 259
H-atom treatment H-atom parameters constrained H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.33, −0.34 0.27, −0.31
Absolute structure Refined as an inversion twin –
Absolute structure parameter 0.50 (3) –
Computer programs: APEX2 and SAINT (Bruker, 2006[Bruker (2006). APEX2 and SAINT. 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.]), XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and CIFFIX (Parkin, 2013[Parkin, S. (2013). CIFFIX. https://xray.uky.edu/people/parkin/programs/ciffix .]).

Refinement of (I)[link] was hampered by the presence of pseudosymmetry. An alternative model using space group Pccn was also refined, but the overall quality of the refinement was not as good as the P21212 model given here. Indeed, the ADDSYM routine in PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) suggests a missing inversion centre and transformation to Pccn, but that model did not refine well (R1 > 9%). Other alternatives using space groups Pcc2, Pban, and Pna21 were much less satisfactory. Not surprisingly, the P21212 model was twinned by inversion, which was dealt with using standard SHELXL methods (TWIN and BASF commands).

The hydrogen on the tetra­zole ring was initially placed solely on the atoms labelled N1A and N1B. This assignment results in impossible clashes with symmetry equivalents about the twofold axis. Since there were suitable small difference map peaks for hydrogen atoms attached to atoms N4A and N4B as well as N1A and N1B, these hydrogen atoms were included as split over the two sites at half occupancy. Disorder of the tetra­zole ring hydrogen atoms in this way also requires that the hydroxyl hydrogen atoms of the methanol mol­ecules are disordered. Again, suitable (albeit small) difference map peaks were apparent. Further evidence for the disorder is that the distances C11A—N1A, C11A—N4A and C11B—N1B, C11B—N4B are all very similar, indicating that the C=N double bond and C—N single bond in these rings are scrambled. Not surprisingly, convergence of the OH hydrogen-atom positions was rather problematic.

Supporting information

CCDC references: 1472235; 1472234

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S2056989016005600/hg5472sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989016005600/hg5472Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S2056989016005600/hg5472IIsup3.hkl

checkCIF report


Chemical context top

We have reported on benzo­thio­phene cyano­combretastatin A-4 analogs (Penthala et al., 2013), and benzo­thio­phene triazolylcombretastatin A-4 analogs as promising anti-cancer agents (Penthala et al., 2015). Previously, we published the synthesis of triazolylcombretastatin A-4 analogs utilizing a [3+2]cyclo­addition azide condensation reaction with sodium azide in the presence of L-proline as catalyst (Penthala et al., 2014a). In a continuation of our work on the chemical modification of the cyano group on the stilbene moiety of cyano­combretastatin A-4 analogs (Penthala et al., 2014a), we have recently synthesized tetra­zolylcombretastatin A-4 analogs as potential anti-cancer agents (Penthala et al., 2016).

Structural commentary top

Single crystal X-ray analysis was carried out to obtain the structural conformations of the tetra­zolylcombretastatin A-4 analogs (I) and (II) for the analysis of structure–activity relationships (SAR), the relevance of the geometry of the tetra­zole ring on the stilbene scaffold and to confirm the position of the hydrogen atom in the tetra­zole ring system. The single crystal X-ray structures of (I) and (II) are shown in Figs. 1 and 2, respectively.

The benzo­thio­phene rings are almost planar with r.m.s. deviations from the mean plane of 0.0084 and 0.0037 Å in (I) and 0.0084 Å in (II), with bond distances and angles comparable with those reported for other benzo­thio­phene derivatives (Sonar et al., 2007; Penthala et al., 2014b). The tetra­zole rings make dihedral angles with the mean plane of the benzo­thio­phene rings of 88.81 (13) and 88.92 (13)° in (I), and 60.94 (6)° in (II). The di­meth­oxy­phenyl ring in (I) and tri­meth­oxy­phenyl ring in (II) make dihedral angles with the benzo­thio­phene rings of 23.91 (8) and 24.99 (8)° in (I) and 84.47 (3)° in (II). Bond lengths and angles in both (I) and (II) are, by and large, unremarkable.

Supra­molecular features top

Hydrogen bonding and the mode of packing of (I) is illustrated in Fig. 3, and the mode of packing of (II) is illustrated in Fig. 4. In the structure of (I), the molecules are linked into hydrogen-bonded (Table 1) chains parallel to the crystallographic b axis involving inter­action between tetra­zole–tetra­zole (N—H···N), tetra­zole–methanol (O—H···N and N—H···O), and methanol–methanol (O—H···O). These chains are bidirectional, as the hydrogen atoms on the tetra­zole rings and the methanol oxygen appear to be disordered over two positions. In the structure of (II), the molecules are linked into chains parallel to the a axis by inter­molecular N—H···N hydrogen bonds (Table 2) between adjacent tetra­zole rings.

Database survey top

\ A search of the 2015 Cambridge Structural Database (Groom & Allen, 2014) for tetra­zole bonded via its carbon atom to another carbon yielded 255 hits. Of these, only two were bonded to an sp2 carbon atom, namely 5-(2H-chromen-3-yl)-1H-tetra­zole monohydrate (NEYCUR: Gawande et al., 2013) and (2Z,4E)-5-(di­methyl­amino)-2-(1H-tetra­zol-5-yl)penta-2,4-\ diene­nitrile methanol solvate (YUPPAB: Addicott et al., 2009). Neither NEYCUR nor YUPPAB have any particular similarity to compounds (I) and (II).

Synthesis and crystallization top

The title compounds (I) and (II) were prepared by utilizing our recently reported literature procedure (Penthala et al., 2016). Recrystallization of the compounds from methanol afforded (I) and (II) as pale-yellow crystalline products which were suitable for X-ray analysis.

Refinement details top

Crystal data, data collection and refinement details for both (I) and (II) are summarized in Table 3. H atoms were found in difference Fourier maps and subsequently placed at idealized positions with constrained distances of 0.95 Å (R2Csp2H), 0.98 Å (RCH3), 0.84 Å (OH), 0.88 Å (Nsp2H). Uiso(H) values were set to either 1.2Ueq or 1.5Ueq (RCH3, OH) of the attached atom. Final models were checked using PLATON (Spek, 2009), RT (Parkin, 2000), and by checkCIF.

Refinement of (I) was hampered by the presence of pseudosymmetry. An alternative model using space group Pccn was also refined, but the overall quality of the refinement was not as good as the P21212 model given here. Indeed, the ADDSYM routine in PLATON (Spek, 2009) suggests a missing inversion centre and transformation to Pccn, but that model did not refine well (R1 > 9%). Other alternatives using space groups Pcc2, Pban, and Pna21 were much less satisfactory. Not surprisingly, the P21212 model was twinned by inversion, which was dealt with using standard SHELXL methods (TWIN and BASF commands).

The hydrogen on the tetra­zole ring was initially placed solely on the atoms labelled N1A and N1B. This assignment results in impossible clashes with symmetry equivalents about the twofold axis. Since there were suitable small difference map peaks for hydrogens attached to atoms N4A and N4B as well as N1A and N1B, these hydrogen atoms were included as split over the two sites at half occupancy. Disorder of the tetra­zole ring hydrogen atoms in this way also requires that the hydroxyl hydrogen atoms of the methanol molecules are disordered. Again, suitable (albeit small) difference map peaks were available. Further evidence for the disorder is that the distances C11A—N1A, C11A—N4A and C11B—N1B, C11B—N4B are all very similar, indicating that the C═N double bond and C—N single bond in these rings are scrambled. Not surprisingly, convergence of the OH hydrogen-atom positions was rather problematic.

Structure description top

We have reported on benzo­thio­phene cyano­combretastatin A-4 analogs (Penthala et al., 2013), and benzo­thio­phene triazolylcombretastatin A-4 analogs as promising anti-cancer agents (Penthala et al., 2015). Previously, we published the synthesis of triazolylcombretastatin A-4 analogs utilizing a [3+2]cyclo­addition azide condensation reaction with sodium azide in the presence of L-proline as catalyst (Penthala et al., 2014a). In a continuation of our work on the chemical modification of the cyano group on the stilbene moiety of cyano­combretastatin A-4 analogs (Penthala et al., 2014a), we have recently synthesized tetra­zolylcombretastatin A-4 analogs as potential anti-cancer agents (Penthala et al., 2016).

Single crystal X-ray analysis was carried out to obtain the structural conformations of the tetra­zolylcombretastatin A-4 analogs (I) and (II) for the analysis of structure–activity relationships (SAR), the relevance of the geometry of the tetra­zole ring on the stilbene scaffold and to confirm the position of the hydrogen atom in the tetra­zole ring system. The single crystal X-ray structures of (I) and (II) are shown in Figs. 1 and 2, respectively.

The benzo­thio­phene rings are almost planar with r.m.s. deviations from the mean plane of 0.0084 and 0.0037 Å in (I) and 0.0084 Å in (II), with bond distances and angles comparable with those reported for other benzo­thio­phene derivatives (Sonar et al., 2007; Penthala et al., 2014b). The tetra­zole rings make dihedral angles with the mean plane of the benzo­thio­phene rings of 88.81 (13) and 88.92 (13)° in (I), and 60.94 (6)° in (II). The di­meth­oxy­phenyl ring in (I) and tri­meth­oxy­phenyl ring in (II) make dihedral angles with the benzo­thio­phene rings of 23.91 (8) and 24.99 (8)° in (I) and 84.47 (3)° in (II). Bond lengths and angles in both (I) and (II) are, by and large, unremarkable.

Hydrogen bonding and the mode of packing of (I) is illustrated in Fig. 3, and the mode of packing of (II) is illustrated in Fig. 4. In the structure of (I), the molecules are linked into hydrogen-bonded (Table 1) chains parallel to the crystallographic b axis involving inter­action between tetra­zole–tetra­zole (N—H···N), tetra­zole–methanol (O—H···N and N—H···O), and methanol–methanol (O—H···O). These chains are bidirectional, as the hydrogen atoms on the tetra­zole rings and the methanol oxygen appear to be disordered over two positions. In the structure of (II), the molecules are linked into chains parallel to the a axis by inter­molecular N—H···N hydrogen bonds (Table 2) between adjacent tetra­zole rings.

\ A search of the 2015 Cambridge Structural Database (Groom & Allen, 2014) for tetra­zole bonded via its carbon atom to another carbon yielded 255 hits. Of these, only two were bonded to an sp2 carbon atom, namely 5-(2H-chromen-3-yl)-1H-tetra­zole monohydrate (NEYCUR: Gawande et al., 2013) and (2Z,4E)-5-(di­methyl­amino)-2-(1H-tetra­zol-5-yl)penta-2,4-\ diene­nitrile methanol solvate (YUPPAB: Addicott et al., 2009). Neither NEYCUR nor YUPPAB have any particular similarity to compounds (I) and (II).

Synthesis and crystallization top

The title compounds (I) and (II) were prepared by utilizing our recently reported literature procedure (Penthala et al., 2016). Recrystallization of the compounds from methanol afforded (I) and (II) as pale-yellow crystalline products which were suitable for X-ray analysis.

Refinement details top

Crystal data, data collection and refinement details for both (I) and (II) are summarized in Table 3. H atoms were found in difference Fourier maps and subsequently placed at idealized positions with constrained distances of 0.95 Å (R2Csp2H), 0.98 Å (RCH3), 0.84 Å (OH), 0.88 Å (Nsp2H). Uiso(H) values were set to either 1.2Ueq or 1.5Ueq (RCH3, OH) of the attached atom. Final models were checked using PLATON (Spek, 2009), RT (Parkin, 2000), and by checkCIF.

Refinement of (I) was hampered by the presence of pseudosymmetry. An alternative model using space group Pccn was also refined, but the overall quality of the refinement was not as good as the P21212 model given here. Indeed, the ADDSYM routine in PLATON (Spek, 2009) suggests a missing inversion centre and transformation to Pccn, but that model did not refine well (R1 > 9%). Other alternatives using space groups Pcc2, Pban, and Pna21 were much less satisfactory. Not surprisingly, the P21212 model was twinned by inversion, which was dealt with using standard SHELXL methods (TWIN and BASF commands).

The hydrogen on the tetra­zole ring was initially placed solely on the atoms labelled N1A and N1B. This assignment results in impossible clashes with symmetry equivalents about the twofold axis. Since there were suitable small difference map peaks for hydrogens attached to atoms N4A and N4B as well as N1A and N1B, these hydrogen atoms were included as split over the two sites at half occupancy. Disorder of the tetra­zole ring hydrogen atoms in this way also requires that the hydroxyl hydrogen atoms of the methanol molecules are disordered. Again, suitable (albeit small) difference map peaks were available. Further evidence for the disorder is that the distances C11A—N1A, C11A—N4A and C11B—N1B, C11B—N4B are all very similar, indicating that the C═N double bond and C—N single bond in these rings are scrambled. Not surprisingly, convergence of the OH hydrogen-atom positions was rather problematic.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and CIFFIX (Parkin, 2013).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. The molecular structure of (II), with displacement ellipsoids drawn at the 50% probability level.
[Figure 3] Fig. 3. Crystal packing of (I), viewed down the c axis.
[Figure 4] Fig. 4. Crystal packing of (II), viewed down the c axis.
(I) (Z)-5-[2-(Benzo[b]thiophen-2-yl)-1-(3,5-dimethoxyphenyl)ethenyl]-1H-tetrazole methanol monosolvate top
Crystal data top
C19H16N4O2S·CH4ODx = 1.346 Mg m−3
Mr = 396.46Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P21212Cell parameters from 9871 reflections
a = 18.2226 (4) Åθ = 4.9–68.2°
b = 13.7954 (5) ŵ = 1.72 mm−1
c = 15.5594 (5) ÅT = 90 K
V = 3911.4 (2) Å3Irregular block, pale yellow
Z = 80.21 × 0.15 × 0.12 mm
F(000) = 1664
Data collection top
Bruker X8 Proteum
diffractometer		7112 independent reflections
Radiation source: fine-focus rotating anode6916 reflections with I > 2σ(I)
Detector resolution: 5.6 pixels mm-1Rint = 0.038
φ and ω scansθmax = 68.2°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)		h = −21→17
Tmin = 0.720, Tmax = 0.915k = −16→15
51755 measured reflectionsl = −18→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.109 w = 1/[σ2(Fo2) + (0.0327P)2 + 4.5187P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
7112 reflectionsΔρmax = 0.33 e Å−3
514 parametersΔρmin = −0.34 e Å−3
0 restraintsAbsolute structure: Refined as an inversion twin
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.50 (3)
Crystal data top
C19H16N4O2S·CH4OV = 3911.4 (2) Å3
Mr = 396.46Z = 8
Orthorhombic, P21212Cu Kα radiation
a = 18.2226 (4) ŵ = 1.72 mm−1
b = 13.7954 (5) ÅT = 90 K
c = 15.5594 (5) Å0.21 × 0.15 × 0.12 mm
Data collection top
Bruker X8 Proteum
diffractometer		7112 independent reflections
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)		6916 reflections with I > 2σ(I)
Tmin = 0.720, Tmax = 0.915Rint = 0.038
51755 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.109Δρmax = 0.33 e Å−3
S = 1.10Δρmin = −0.34 e Å−3
7112 reflectionsAbsolute structure: Refined as an inversion twin
514 parametersAbsolute structure parameter: 0.50 (3)
0 restraints
Special details top

Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat.

Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

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.

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S1A−0.14677 (5)0.17392 (8)0.08523 (7)0.0251 (2)
O1A0.27407 (16)0.0780 (3)−0.00263 (19)0.0339 (8)
O2A0.25387 (16)0.1201 (3)0.2996 (2)0.0318 (8)
N1A−0.00422 (19)0.1008 (3)−0.0368 (2)0.0246 (8)
H1NA−0.00120.0373−0.03380.030*0.5
N2A−0.0252 (2)0.1531 (3)−0.1071 (2)0.031 (1)
N3A−0.0231 (2)0.2448 (3)−0.0848 (3)0.0349 (10)
N4A−0.00020 (19)0.2525 (3)−0.0020 (3)0.0287 (8)
H4NA0.00620.30630.02740.034*0.5
C1A−0.0953 (2)0.1363 (3)0.1756 (3)0.0223 (9)
C2A−0.1397 (2)0.1174 (3)0.2428 (3)0.0231 (9)
H2A−0.12140.09730.29710.028*
C3A−0.2158 (2)0.1295 (3)0.2268 (3)0.0239 (9)
C4A−0.2763 (2)0.1176 (3)0.2813 (3)0.0244 (9)
H4A−0.26880.09800.33910.029*
C5A−0.3458 (2)0.1339 (3)0.2521 (3)0.0277 (10)
H5A−0.38650.12490.28940.033*
C6A−0.3574 (2)0.1642 (3)0.1660 (3)0.0273 (10)
H6A−0.40600.17420.14570.033*
C7A−0.2992 (2)0.1793 (3)0.1117 (3)0.0270 (9)
H7A−0.30680.20220.05480.032*
C8A−0.2287 (2)0.1604 (3)0.1415 (3)0.0226 (9)
C9A−0.0161 (2)0.1270 (3)0.1772 (3)0.0204 (8)
H9A0.00360.10980.23160.025*
C10A0.0341 (2)0.1385 (3)0.1153 (3)0.0211 (9)
C11A0.0106 (2)0.1620 (4)0.0259 (3)0.0225 (9)
C12A0.1135 (2)0.1267 (3)0.1272 (3)0.0224 (9)
C13A0.1443 (2)0.1325 (3)0.2116 (3)0.0234 (9)
H13A0.11430.14630.26000.028*
C14A0.2187 (2)0.1177 (3)0.2212 (3)0.0233 (9)
C15A0.2651 (2)0.1003 (3)0.1514 (3)0.0271 (10)
H15A0.31630.09150.15940.033*
C16A0.2347 (2)0.0964 (3)0.0717 (3)0.0268 (10)
C17A0.1596 (2)0.1100 (3)0.0598 (3)0.0264 (10)
H17A0.14010.10770.00320.032*
C18A0.3507 (2)0.0617 (4)0.0066 (3)0.0377 (12)
H18A0.37330.11800.03440.057*
H18B0.37280.0520−0.05010.057*
H18C0.35880.00390.04200.057*
C19A0.2093 (3)0.1288 (4)0.3753 (3)0.0335 (11)
H19A0.18450.19190.37520.050*
H19B0.24040.12360.42650.050*
H19C0.17250.07690.37590.050*
S1B0.63976 (5)0.33164 (8)0.41542 (7)0.0245 (2)
O1B0.21860 (16)0.4196 (3)0.5019 (2)0.0393 (9)
O2B0.23920 (16)0.3710 (3)0.2009 (2)0.0306 (7)
N1B0.49906 (19)0.3988 (3)0.5359 (2)0.0250 (8)
H1NB0.49690.46250.53320.030*0.5
N2B0.5193 (2)0.3455 (3)0.6043 (2)0.0321 (10)
N3B0.5154 (2)0.2549 (3)0.5866 (3)0.0332 (9)
N4B0.49224 (19)0.2483 (3)0.5038 (3)0.0260 (8)
H4NB0.48480.19400.47540.031*0.5
C1B0.5881 (2)0.3683 (3)0.3263 (3)0.0218 (9)
C2B0.6327 (2)0.3889 (3)0.2573 (3)0.0244 (9)
H2B0.61440.40950.20310.029*
C3B0.7093 (2)0.3762 (3)0.2746 (3)0.0215 (9)
C4B0.7694 (2)0.3905 (3)0.2191 (3)0.0252 (9)
H4B0.76250.41140.16150.030*
C5B0.8392 (2)0.3730 (3)0.2517 (3)0.0247 (9)
H5B0.88060.38190.21530.030*
C6B0.8503 (2)0.3429 (3)0.3357 (3)0.0271 (10)
H6B0.89890.33210.35560.032*
C7B0.7919 (2)0.3283 (3)0.3910 (3)0.0261 (9)
H7B0.79960.30760.44850.031*
C8B0.7214 (2)0.3451 (3)0.3595 (3)0.0253 (9)
C9B0.5091 (2)0.3757 (4)0.3228 (3)0.0233 (9)
H9B0.48950.39230.26810.028*
C10B0.4590 (2)0.3625 (3)0.3856 (3)0.0211 (9)
C11B0.4828 (2)0.3364 (3)0.4728 (3)0.0221 (9)
C12B0.3782 (2)0.3708 (3)0.3707 (3)0.0200 (8)
C13B0.3489 (2)0.3638 (3)0.2897 (3)0.0224 (9)
H13B0.37990.35130.24190.027*
C14B0.2740 (2)0.3750 (3)0.2778 (3)0.0261 (10)
C15B0.2278 (2)0.3939 (3)0.3476 (3)0.0249 (9)
H15B0.17650.40190.33900.030*
C16B0.2576 (2)0.4008 (3)0.4304 (3)0.0261 (10)
C17B0.3329 (2)0.3884 (3)0.4430 (3)0.0233 (9)
H17B0.35340.39180.49910.028*
C18B0.1415 (2)0.4338 (4)0.4934 (3)0.0382 (12)
H18D0.13220.48970.45600.057*
H18E0.12000.44570.55010.057*
H18F0.11920.37580.46810.057*
C19B0.2836 (3)0.3658 (4)0.1264 (3)0.0357 (12)
H19D0.32180.41570.12920.054*
H19E0.25310.37640.07530.054*
H19F0.30650.30170.12300.054*
C1SA0.4356 (4)0.1141 (5)0.3215 (5)0.069 (2)
H1S10.38500.11650.34280.103*
H1S20.43990.06320.27790.103*
H1S30.44860.17680.29610.103*
O1SA0.4839 (2)0.0935 (2)0.3908 (3)0.0400 (9)
H1SA0.47640.13300.43100.060*0.5
H2SA0.49550.03460.38970.060*0.5
C1SB0.0583 (3)0.3839 (4)0.1772 (5)0.065 (2)
H1S40.07890.44380.20090.098*
H1S50.09820.34220.15670.098*
H1S60.03050.34990.22190.098*
O1SB0.0113 (2)0.4064 (3)0.1081 (2)0.0391 (9)
H1SB0.00670.35760.07630.059*0.5
H2SB0.03270.44460.07430.059*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0254 (4)0.0331 (6)0.0167 (5)−0.0001 (4)0.0001 (4)0.0019 (5)
O1A0.0268 (15)0.061 (2)0.0140 (15)0.0078 (15)0.0072 (13)0.0040 (16)
O2A0.0265 (14)0.049 (2)0.0195 (15)0.0074 (14)−0.0059 (13)−0.0006 (15)
N1A0.0252 (17)0.036 (2)0.0126 (17)0.0037 (15)−0.0012 (15)0.0035 (16)
N2A0.0258 (17)0.050 (3)0.0170 (19)0.0041 (18)0.0003 (14)0.0097 (18)
N3A0.0286 (18)0.051 (3)0.025 (2)0.0004 (18)0.0037 (17)0.016 (2)
N4A0.0268 (18)0.0291 (19)0.0302 (19)0.0012 (15)0.0000 (17)0.0062 (16)
C1A0.0254 (19)0.023 (2)0.019 (2)−0.0022 (16)0.0013 (16)0.0030 (18)
C2A0.033 (2)0.022 (2)0.015 (2)−0.0017 (18)−0.0008 (17)−0.0009 (17)
C3A0.027 (2)0.020 (2)0.024 (2)−0.0053 (17)−0.0029 (17)−0.0007 (18)
C4A0.036 (2)0.022 (2)0.015 (2)−0.0051 (18)0.0026 (18)0.0012 (18)
C5A0.024 (2)0.029 (2)0.030 (2)−0.0031 (17)0.0077 (18)−0.004 (2)
C6A0.026 (2)0.030 (2)0.026 (2)0.0005 (19)−0.0021 (16)−0.004 (2)
C7A0.029 (2)0.028 (2)0.024 (2)0.0006 (18)−0.0023 (17)−0.0014 (19)
C8A0.029 (2)0.021 (2)0.018 (2)−0.0023 (17)0.0012 (16)−0.0041 (18)
C9A0.029 (2)0.020 (2)0.0124 (19)−0.0040 (18)−0.0033 (15)0.0030 (17)
C10A0.0253 (19)0.018 (2)0.020 (2)0.0006 (16)−0.0028 (17)−0.0017 (18)
C11A0.0185 (18)0.033 (2)0.016 (2)0.0016 (18)0.0017 (15)0.0023 (19)
C12A0.0260 (19)0.021 (2)0.020 (2)−0.0018 (17)−0.0037 (16)0.0065 (19)
C13A0.0245 (19)0.023 (2)0.022 (2)0.0034 (16)0.0028 (17)0.0009 (19)
C14A0.034 (2)0.026 (2)0.0104 (19)0.0022 (18)−0.0048 (16)0.0036 (18)
C15A0.023 (2)0.028 (2)0.030 (2)0.0047 (19)0.0015 (18)0.005 (2)
C16A0.031 (2)0.033 (2)0.017 (2)0.0018 (19)0.0050 (18)0.0025 (19)
C17A0.027 (2)0.027 (2)0.025 (2)0.0001 (18)0.0028 (17)0.0067 (19)
C18A0.028 (2)0.053 (3)0.032 (3)0.007 (2)0.008 (2)0.016 (2)
C19A0.037 (2)0.050 (3)0.013 (2)0.008 (2)−0.0022 (18)−0.004 (2)
S1B0.0225 (4)0.0342 (6)0.0167 (5)−0.0002 (4)−0.0002 (4)0.0009 (5)
O1B0.0211 (14)0.065 (2)0.0322 (19)0.0067 (16)0.0042 (14)0.0094 (18)
O2B0.0268 (14)0.0429 (19)0.0220 (15)0.0032 (14)−0.0041 (13)−0.0040 (15)
N1B0.0236 (17)0.031 (2)0.0200 (19)0.0006 (14)0.0013 (16)−0.0029 (17)
N2B0.0260 (18)0.052 (3)0.0183 (19)0.0023 (18)0.0002 (14)0.0063 (19)
N3B0.0288 (18)0.045 (2)0.025 (2)0.0006 (17)−0.0004 (17)0.012 (2)
N4B0.0288 (18)0.0294 (19)0.0198 (17)−0.0002 (15)−0.0006 (15)0.0044 (15)
C1B0.026 (2)0.023 (2)0.016 (2)0.0008 (17)−0.0020 (15)−0.0066 (17)
C2B0.0201 (19)0.025 (2)0.028 (2)−0.0035 (17)0.0008 (17)0.0008 (19)
C3B0.027 (2)0.022 (2)0.016 (2)−0.0023 (17)0.0010 (16)−0.0013 (18)
C4B0.026 (2)0.022 (2)0.028 (2)−0.0029 (17)0.0007 (18)0.0005 (19)
C5B0.025 (2)0.028 (2)0.021 (2)−0.0074 (17)0.0018 (17)−0.0008 (19)
C6B0.0210 (18)0.029 (2)0.031 (2)−0.0004 (18)−0.0029 (16)−0.002 (2)
C7B0.029 (2)0.030 (2)0.019 (2)−0.0010 (19)−0.0023 (16)−0.0011 (19)
C8B0.0221 (19)0.029 (2)0.024 (2)−0.0014 (17)−0.0006 (16)0.0004 (19)
C9B0.025 (2)0.024 (2)0.020 (2)0.0000 (18)−0.0028 (17)−0.0047 (19)
C10B0.025 (2)0.022 (2)0.017 (2)0.0004 (16)0.0008 (16)0.0007 (17)
C11B0.0200 (18)0.024 (2)0.022 (2)−0.0014 (18)0.0021 (15)0.0006 (18)
C12B0.0215 (18)0.021 (2)0.017 (2)0.0015 (16)0.0018 (16)−0.0012 (18)
C13B0.0259 (19)0.024 (2)0.017 (2)0.0009 (16)−0.0008 (17)0.0019 (18)
C14B0.024 (2)0.0194 (19)0.035 (3)−0.0005 (17)−0.0026 (18)−0.001 (2)
C15B0.0230 (19)0.030 (2)0.021 (2)0.0012 (18)−0.0025 (17)0.0029 (19)
C16B0.0230 (19)0.028 (2)0.028 (2)0.0013 (17)0.0040 (17)0.0082 (19)
C17B0.026 (2)0.031 (2)0.0124 (18)0.0000 (18)0.0008 (15)0.0010 (17)
C18B0.025 (2)0.061 (3)0.029 (2)0.009 (2)0.0073 (19)0.011 (2)
C19B0.029 (2)0.049 (3)0.029 (3)0.006 (2)−0.0046 (19)−0.007 (2)
C1SA0.070 (4)0.045 (4)0.091 (6)0.008 (3)−0.055 (4)−0.004 (4)
O1SA0.0391 (17)0.0270 (18)0.054 (2)0.0036 (15)−0.0169 (17)−0.0028 (17)
C1SB0.062 (4)0.033 (3)0.101 (6)0.001 (3)−0.051 (4)−0.002 (4)
O1SB0.0427 (18)0.0318 (19)0.043 (2)0.0008 (16)−0.0132 (16)−0.0011 (17)
Geometric parameters (Å, º) top
S1A—C8A1.742 (4)N1B—C11B1.339 (6)
S1A—C1A1.768 (4)N1B—N2B1.346 (5)
O1A—C16A1.385 (5)N1B—H1NB0.8800
O1A—C18A1.422 (5)N2B—N3B1.281 (6)
O2A—C14A1.379 (5)N3B—N4B1.360 (6)
O2A—C19A1.437 (5)N4B—C11B1.319 (6)
N1A—C11A1.317 (6)N4B—H4NB0.8800
N1A—N2A1.365 (5)C1B—C2B1.376 (6)
N1A—H1NA0.8800C1B—C9B1.444 (6)
N2A—N3A1.313 (7)C2B—C3B1.433 (6)
N3A—N4A1.358 (6)C2B—H2B0.9500
N4A—C11A1.337 (7)C3B—C8B1.406 (6)
N4A—H4NA0.8800C3B—C4B1.408 (6)
C1A—C2A1.348 (6)C4B—C5B1.391 (6)
C1A—C9A1.449 (6)C4B—H4B0.9500
C2A—C3A1.418 (6)C5B—C6B1.386 (6)
C2A—H2A0.9500C5B—H5B0.9500
C3A—C4A1.400 (7)C6B—C7B1.383 (6)
C3A—C8A1.413 (6)C6B—H6B0.9500
C4A—C5A1.364 (6)C7B—C8B1.395 (6)
C4A—H4A0.9500C7B—H7B0.9500
C5A—C6A1.419 (7)C9B—C10B1.351 (6)
C5A—H5A0.9500C9B—H9B0.9500
C6A—C7A1.372 (6)C10B—C11B1.469 (6)
C6A—H6A0.9500C10B—C12B1.494 (5)
C7A—C8A1.389 (6)C12B—C13B1.372 (6)
C7A—H7A0.9500C12B—C17B1.416 (6)
C9A—C10A1.338 (6)C13B—C14B1.386 (6)
C9A—H9A0.9500C13B—H13B0.9500
C10A—C12A1.469 (6)C14B—C15B1.400 (7)
C10A—C11A1.491 (6)C15B—C16B1.400 (6)
C12A—C17A1.363 (6)C15B—H15B0.9500
C12A—C13A1.431 (6)C16B—C17B1.398 (6)
C13A—C14A1.378 (6)C17B—H17B0.9500
C13A—H13A0.9500C18B—H18D0.9800
C14A—C15A1.396 (6)C18B—H18E0.9800
C15A—C16A1.359 (6)C18B—H18F0.9800
C15A—H15A0.9500C19B—H19D0.9800
C16A—C17A1.394 (6)C19B—H19E0.9800
C17A—H17A0.9500C19B—H19F0.9800
C18A—H18A0.9800C1SA—O1SA1.421 (7)
C18A—H18B0.9800C1SA—H1S10.9800
C18A—H18C0.9800C1SA—H1S20.9800
C19A—H19A0.9800C1SA—H1S30.9800
C19A—H19B0.9800O1SA—H1SA0.8400
C19A—H19C0.9800O1SA—H2SA0.8400
S1B—C8B1.733 (4)C1SB—O1SB1.409 (6)
S1B—C1B1.750 (4)C1SB—H1S40.9800
O1B—C16B1.345 (5)C1SB—H1S50.9800
O1B—C18B1.425 (5)C1SB—H1S60.9800
O2B—C14B1.355 (6)O1SB—H1SB0.8400
O2B—C19B1.415 (6)O1SB—H2SB0.8400
C8A—S1A—C1A91.3 (2)C11B—N4B—N3B108.9 (4)
C16A—O1A—C18A116.9 (4)C11B—N4B—H4NB125.5
C14A—O2A—C19A117.7 (3)N3B—N4B—H4NB125.5
C11A—N1A—N2A108.2 (4)C2B—C1B—C9B122.9 (4)
C11A—N1A—H1NA125.9C2B—C1B—S1B111.2 (3)
N2A—N1A—H1NA125.9C9B—C1B—S1B125.9 (3)
N3A—N2A—N1A106.8 (4)C1B—C2B—C3B113.7 (4)
N2A—N3A—N4A109.6 (4)C1B—C2B—H2B123.1
C11A—N4A—N3A106.2 (4)C3B—C2B—H2B123.1
C11A—N4A—H4NA126.9C8B—C3B—C4B119.8 (4)
N3A—N4A—H4NA126.9C8B—C3B—C2B111.5 (4)
C2A—C1A—C9A124.6 (4)C4B—C3B—C2B128.6 (4)
C2A—C1A—S1A110.8 (3)C5B—C4B—C3B117.6 (4)
C9A—C1A—S1A124.6 (3)C5B—C4B—H4B121.2
C1A—C2A—C3A115.3 (4)C3B—C4B—H4B121.2
C1A—C2A—H2A122.4C6B—C5B—C4B121.9 (4)
C3A—C2A—H2A122.4C6B—C5B—H5B119.1
C4A—C3A—C8A118.2 (4)C4B—C5B—H5B119.1
C4A—C3A—C2A130.4 (4)C7B—C6B—C5B121.3 (4)
C8A—C3A—C2A111.4 (4)C7B—C6B—H6B119.4
C5A—C4A—C3A120.6 (4)C5B—C6B—H6B119.4
C5A—C4A—H4A119.7C6B—C7B—C8B117.8 (4)
C3A—C4A—H4A119.7C6B—C7B—H7B121.1
C4A—C5A—C6A120.1 (4)C8B—C7B—H7B121.1
C4A—C5A—H5A120.0C7B—C8B—C3B121.6 (4)
C6A—C5A—H5A120.0C7B—C8B—S1B126.7 (4)
C7A—C6A—C5A120.8 (4)C3B—C8B—S1B111.7 (3)
C7A—C6A—H6A119.6C10B—C9B—C1B129.6 (4)
C5A—C6A—H6A119.6C10B—C9B—H9B115.2
C6A—C7A—C8A118.6 (4)C1B—C9B—H9B115.2
C6A—C7A—H7A120.7C9B—C10B—C11B120.1 (4)
C8A—C7A—H7A120.7C9B—C10B—C12B123.0 (4)
C7A—C8A—C3A121.7 (4)C11B—C10B—C12B116.9 (4)
C7A—C8A—S1A127.1 (3)N4B—C11B—N1B107.2 (4)
C3A—C8A—S1A111.2 (3)N4B—C11B—C10B127.0 (4)
C10A—C9A—C1A131.2 (4)N1B—C11B—C10B125.8 (4)
C10A—C9A—H9A114.4C13B—C12B—C17B120.9 (4)
C1A—C9A—H9A114.4C13B—C12B—C10B121.3 (4)
C9A—C10A—C12A124.7 (4)C17B—C12B—C10B117.7 (4)
C9A—C10A—C11A120.1 (4)C12B—C13B—C14B119.9 (4)
C12A—C10A—C11A115.1 (4)C12B—C13B—H13B120.0
N1A—C11A—N4A109.2 (4)C14B—C13B—H13B120.0
N1A—C11A—C10A127.6 (4)O2B—C14B—C13B125.1 (4)
N4A—C11A—C10A123.2 (4)O2B—C14B—C15B114.3 (4)
C17A—C12A—C13A118.3 (4)C13B—C14B—C15B120.6 (5)
C17A—C12A—C10A121.9 (4)C14B—C15B—C16B119.6 (4)
C13A—C12A—C10A119.8 (4)C14B—C15B—H15B120.2
C14A—C13A—C12A118.5 (4)C16B—C15B—H15B120.2
C14A—C13A—H13A120.8O1B—C16B—C17B115.2 (4)
C12A—C13A—H13A120.8O1B—C16B—C15B124.7 (4)
C13A—C14A—O2A123.3 (4)C17B—C16B—C15B120.1 (4)
C13A—C14A—C15A122.5 (4)C16B—C17B—C12B118.8 (4)
O2A—C14A—C15A114.2 (4)C16B—C17B—H17B120.6
C16A—C15A—C14A118.0 (4)C12B—C17B—H17B120.6
C16A—C15A—H15A121.0O1B—C18B—H18D109.5
C14A—C15A—H15A121.0O1B—C18B—H18E109.5
C15A—C16A—O1A124.0 (4)H18D—C18B—H18E109.5
C15A—C16A—C17A121.1 (4)O1B—C18B—H18F109.5
O1A—C16A—C17A114.9 (4)H18D—C18B—H18F109.5
C12A—C17A—C16A121.7 (4)H18E—C18B—H18F109.5
C12A—C17A—H17A119.2O2B—C19B—H19D109.5
C16A—C17A—H17A119.2O2B—C19B—H19E109.5
O1A—C18A—H18A109.5H19D—C19B—H19E109.5
O1A—C18A—H18B109.5O2B—C19B—H19F109.5
H18A—C18A—H18B109.5H19D—C19B—H19F109.5
O1A—C18A—H18C109.5H19E—C19B—H19F109.5
H18A—C18A—H18C109.5O1SA—C1SA—H1S1109.5
H18B—C18A—H18C109.5O1SA—C1SA—H1S2109.5
O2A—C19A—H19A109.5H1S1—C1SA—H1S2109.5
O2A—C19A—H19B109.5O1SA—C1SA—H1S3109.5
H19A—C19A—H19B109.5H1S1—C1SA—H1S3109.5
O2A—C19A—H19C109.5H1S2—C1SA—H1S3109.5
H19A—C19A—H19C109.5C1SA—O1SA—H1SA109.5
H19B—C19A—H19C109.5C1SA—O1SA—H2SA109.5
C8B—S1B—C1B91.9 (2)O1SB—C1SB—H1S4109.5
C16B—O1B—C18B118.0 (4)O1SB—C1SB—H1S5109.5
C14B—O2B—C19B117.2 (3)H1S4—C1SB—H1S5109.5
C11B—N1B—N2B106.8 (4)O1SB—C1SB—H1S6109.5
C11B—N1B—H1NB126.6H1S4—C1SB—H1S6109.5
N2B—N1B—H1NB126.6H1S5—C1SB—H1S6109.5
N3B—N2B—N1B110.4 (4)C1SB—O1SB—H1SB109.5
N2B—N3B—N4B106.7 (4)C1SB—O1SB—H2SB109.5
C11A—N1A—N2A—N3A−0.6 (4)C11B—N1B—N2B—N3B−0.8 (5)
N1A—N2A—N3A—N4A0.9 (5)N1B—N2B—N3B—N4B0.4 (5)
N2A—N3A—N4A—C11A−0.8 (5)N2B—N3B—N4B—C11B0.2 (5)
C8A—S1A—C1A—C2A−1.1 (4)C8B—S1B—C1B—C2B0.5 (4)
C8A—S1A—C1A—C9A178.9 (4)C8B—S1B—C1B—C9B179.6 (4)
C9A—C1A—C2A—C3A−178.9 (4)C9B—C1B—C2B—C3B−179.6 (4)
S1A—C1A—C2A—C3A1.1 (5)S1B—C1B—C2B—C3B−0.4 (5)
C1A—C2A—C3A—C4A−179.1 (5)C1B—C2B—C3B—C8B0.1 (6)
C1A—C2A—C3A—C8A−0.4 (6)C1B—C2B—C3B—C4B179.9 (4)
C8A—C3A—C4A—C5A1.1 (7)C8B—C3B—C4B—C5B−0.1 (7)
C2A—C3A—C4A—C5A179.7 (5)C2B—C3B—C4B—C5B−180.0 (5)
C3A—C4A—C5A—C6A−0.7 (7)C3B—C4B—C5B—C6B−0.3 (7)
C4A—C5A—C6A—C7A−1.2 (7)C4B—C5B—C6B—C7B0.4 (8)
C5A—C6A—C7A—C8A2.6 (7)C5B—C6B—C7B—C8B−0.1 (7)
C6A—C7A—C8A—C3A−2.2 (7)C6B—C7B—C8B—C3B−0.3 (7)
C6A—C7A—C8A—S1A−180.0 (4)C6B—C7B—C8B—S1B179.7 (4)
C4A—C3A—C8A—C7A0.4 (7)C4B—C3B—C8B—C7B0.4 (7)
C2A—C3A—C8A—C7A−178.5 (4)C2B—C3B—C8B—C7B−179.7 (4)
C4A—C3A—C8A—S1A178.4 (3)C4B—C3B—C8B—S1B−179.6 (4)
C2A—C3A—C8A—S1A−0.4 (5)C2B—C3B—C8B—S1B0.3 (5)
C1A—S1A—C8A—C7A178.8 (5)C1B—S1B—C8B—C7B179.6 (5)
C1A—S1A—C8A—C3A0.8 (3)C1B—S1B—C8B—C3B−0.4 (4)
C2A—C1A—C9A—C10A176.3 (5)C2B—C1B—C9B—C10B−176.6 (5)
S1A—C1A—C9A—C10A−3.6 (8)S1B—C1B—C9B—C10B4.3 (8)
C1A—C9A—C10A—C12A179.7 (5)C1B—C9B—C10B—C11B−0.1 (8)
C1A—C9A—C10A—C11A−2.2 (8)C1B—C9B—C10B—C12B−178.6 (5)
N2A—N1A—C11A—N4A0.0 (4)N3B—N4B—C11B—N1B−0.7 (5)
N2A—N1A—C11A—C10A178.6 (4)N3B—N4B—C11B—C10B179.4 (4)
N3A—N4A—C11A—N1A0.5 (4)N2B—N1B—C11B—N4B0.9 (4)
N3A—N4A—C11A—C10A−178.2 (3)N2B—N1B—C11B—C10B−179.2 (4)
C9A—C10A—C11A—N1A−90.9 (5)C9B—C10B—C11B—N4B−90.0 (6)
C12A—C10A—C11A—N1A87.3 (5)C12B—C10B—C11B—N4B88.6 (5)
C9A—C10A—C11A—N4A87.5 (5)C9B—C10B—C11B—N1B90.1 (5)
C12A—C10A—C11A—N4A−94.3 (5)C12B—C10B—C11B—N1B−91.3 (5)
C9A—C10A—C12A—C17A159.7 (5)C9B—C10B—C12B—C13B19.7 (7)
C11A—C10A—C12A—C17A−18.4 (6)C11B—C10B—C12B—C13B−158.9 (4)
C9A—C10A—C12A—C13A−20.2 (7)C9B—C10B—C12B—C17B−159.0 (5)
C11A—C10A—C12A—C13A161.6 (4)C11B—C10B—C12B—C17B22.5 (6)
C17A—C12A—C13A—C14A−2.2 (6)C17B—C12B—C13B—C14B0.7 (7)
C10A—C12A—C13A—C14A177.7 (4)C10B—C12B—C13B—C14B−177.9 (4)
C12A—C13A—C14A—O2A−178.9 (4)C19B—O2B—C14B—C13B−7.5 (7)
C12A—C13A—C14A—C15A2.0 (7)C19B—O2B—C14B—C15B171.4 (5)
C19A—O2A—C14A—C13A6.4 (7)C12B—C13B—C14B—O2B179.0 (4)
C19A—O2A—C14A—C15A−174.5 (4)C12B—C13B—C14B—C15B0.3 (7)
C13A—C14A—C15A—C16A−1.2 (7)O2B—C14B—C15B—C16B−179.3 (4)
O2A—C14A—C15A—C16A179.7 (4)C13B—C14B—C15B—C16B−0.4 (7)
C14A—C15A—C16A—O1A−178.8 (4)C18B—O1B—C16B—C17B179.5 (5)
C14A—C15A—C16A—C17A0.5 (7)C18B—O1B—C16B—C15B−0.2 (7)
C18A—O1A—C16A—C15A0.5 (7)C14B—C15B—C16B—O1B179.3 (4)
C18A—O1A—C16A—C17A−178.9 (4)C14B—C15B—C16B—C17B−0.4 (7)
C13A—C12A—C17A—C16A1.7 (7)O1B—C16B—C17B—C12B−178.4 (4)
C10A—C12A—C17A—C16A−178.3 (4)C15B—C16B—C17B—C12B1.3 (7)
C15A—C16A—C17A—C12A−0.8 (8)C13B—C12B—C17B—C16B−1.4 (7)
O1A—C16A—C17A—C12A178.6 (4)C10B—C12B—C17B—C16B177.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1NA···N1Ai0.881.912.787 (9)176
N4A—H4NA···O1SB0.881.872.736 (6)168
N1B—H1NB···N1Bii0.881.922.792 (9)174
N4B—H4NB···O1SA0.881.912.769 (6)165
O1SA—H1SA···N4B0.841.972.769 (6)158
O1SA—H2SA···O1SAiii0.841.812.646 (7)177
O1SB—H1SB···N4A0.841.902.736 (6)176
Symmetry codes: (i) −x, −y, z; (ii) −x+1, −y+1, z; (iii) −x+1, −y, z.
(II) (Z)-5-[2-(Benzo[b]thiophen-3-yl)-1-(3,4,5-trimethoxyphenyl)ethenyl]-1H-tetrazole top
Crystal data top
C20H18N4O3SF(000) = 824
Mr = 394.44Dx = 1.393 Mg m−3
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
a = 4.8888 (1) ÅCell parameters from 9924 reflections
b = 24.6650 (6) Åθ = 3.4–68.3°
c = 15.5956 (4) ŵ = 1.78 mm−1
β = 91.031 (1)°T = 90 K
V = 1880.25 (8) Å3Plate, colourless
Z = 40.10 × 0.08 × 0.02 mm
Data collection top
Bruker X8 Proteum
diffractometer		3337 independent reflections
Radiation source: fine-focus rotating anode3138 reflections with I > 2σ(I)
Detector resolution: 5.6 pixels mm-1Rint = 0.037
φ and ω scansθmax = 68.5°, θmin = 3.4°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)		h = −5→2
Tmin = 0.693, Tmax = 0.897k = −29→29
23250 measured reflectionsl = −18→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: mixed
wR(F2) = 0.094H atoms treated by a mixture of independent and constrained refinement
S = 1.13 w = 1/[σ2(Fo2) + (0.0391P)2 + 1.3628P]
where P = (Fo2 + 2Fc2)/3
3337 reflections(Δ/σ)max = 0.005
259 parametersΔρmax = 0.27 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C20H18N4O3SV = 1880.25 (8) Å3
Mr = 394.44Z = 4
Monoclinic, P21/cCu Kα radiation
a = 4.8888 (1) ŵ = 1.78 mm−1
b = 24.6650 (6) ÅT = 90 K
c = 15.5956 (4) Å0.10 × 0.08 × 0.02 mm
β = 91.031 (1)°
Data collection top
Bruker X8 Proteum
diffractometer		3337 independent reflections
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)		3138 reflections with I > 2σ(I)
Tmin = 0.693, Tmax = 0.897Rint = 0.037
23250 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.094H atoms treated by a mixture of independent and constrained refinement
S = 1.13Δρmax = 0.27 e Å−3
3337 reflectionsΔρmin = −0.31 e Å−3
259 parameters
Special details top

Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat.

Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

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.

Refinement. Refinement progress was checked using Platon (Spek, 2009) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.58440 (8)0.92397 (2)0.22030 (3)0.02003 (13)
N10.5809 (3)0.76447 (5)0.36657 (9)0.0158 (3)
H1N0.397 (4)0.7636 (8)0.3563 (12)0.019*
N20.6748 (3)0.78140 (6)0.44376 (9)0.0189 (3)
N30.9385 (3)0.78051 (6)0.44059 (9)0.0188 (3)
N41.0187 (3)0.76305 (5)0.36194 (9)0.0167 (3)
C10.7332 (3)0.86078 (7)0.22620 (11)0.0195 (3)
H10.87710.85220.26570.023*
C20.6269 (3)0.82413 (7)0.1694 (1)0.0169 (3)
C30.4172 (3)0.84839 (7)0.11505 (10)0.0162 (3)
C40.2612 (3)0.82496 (7)0.04825 (10)0.0185 (3)
H40.28850.78810.03270.022*
C50.0676 (3)0.85608 (7)0.00545 (11)0.0225 (4)
H5−0.03730.8405−0.04010.027*
C60.0238 (3)0.91033 (7)0.02841 (12)0.0230 (4)
H6−0.11080.9310−0.00180.028*
C70.1728 (3)0.93419 (7)0.09405 (11)0.0207 (4)
H70.14220.97090.10980.025*
C80.3703 (3)0.90284 (7)0.13672 (11)0.0178 (3)
C90.7039 (3)0.76681 (6)0.1624 (1)0.0165 (3)
H90.70030.75150.10650.020*
C100.7788 (3)0.73397 (6)0.22705 (10)0.0148 (3)
C110.7926 (3)0.75371 (6)0.31634 (10)0.0134 (3)
C120.8405 (3)0.67535 (6)0.21635 (10)0.0154 (3)
C131.0177 (3)0.65742 (6)0.15372 (10)0.0161 (3)
H131.10990.68270.11860.019*
C141.0588 (3)0.60179 (7)0.14293 (10)0.0167 (3)
C150.9205 (3)0.56460 (7)0.19391 (11)0.0175 (3)
C160.7445 (3)0.58324 (7)0.25707 (11)0.0170 (3)
C170.7064 (3)0.63845 (7)0.26888 (10)0.0166 (3)
H170.58940.65110.31260.020*
O11.2285 (2)0.57947 (5)0.08429 (8)0.0210 (3)
C181.3890 (3)0.61614 (7)0.03497 (11)0.0211 (4)
H18A1.26770.63930.00020.032*
H18B1.50880.5955−0.00270.032*
H18C1.50060.63870.07360.032*
O20.9650 (2)0.50992 (5)0.18551 (8)0.0236 (3)
C190.8111 (4)0.48639 (8)0.11584 (12)0.0308 (4)
H19A0.61540.49240.12460.046*
H19B0.84760.44740.11340.046*
H19C0.86500.50330.06190.046*
O30.6211 (2)0.54394 (5)0.30402 (8)0.0226 (3)
C200.4227 (3)0.56095 (7)0.36440 (11)0.0220 (4)
H20A0.51060.58410.40790.033*
H20B0.34360.52910.39210.033*
H20C0.27760.58140.33460.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0226 (2)0.0163 (2)0.0211 (2)0.00207 (14)−0.00164 (16)−0.00240 (15)
N10.0109 (7)0.0222 (7)0.0142 (7)0.0006 (5)0.0001 (5)−0.0018 (5)
N20.0157 (7)0.0246 (7)0.0163 (7)0.0013 (5)0.0004 (5)−0.0026 (6)
N30.0158 (7)0.0242 (7)0.0163 (7)0.0007 (5)−0.0002 (5)−0.0029 (6)
N40.0143 (7)0.0214 (7)0.0143 (7)0.0004 (5)−0.0001 (5)−0.0016 (5)
C10.0197 (8)0.0197 (8)0.0189 (9)0.0015 (6)−0.0017 (6)0.0008 (6)
C20.0166 (8)0.0197 (8)0.0146 (8)0.0012 (6)0.0033 (6)0.0019 (6)
C30.0144 (7)0.0191 (8)0.0153 (8)0.0000 (6)0.0042 (6)0.0028 (6)
C40.0181 (8)0.0199 (8)0.0176 (8)−0.0011 (6)0.0023 (6)0.0000 (6)
C50.0184 (8)0.0282 (9)0.0207 (9)−0.0025 (7)−0.0022 (6)0.0010 (7)
C60.0154 (8)0.0263 (9)0.0271 (10)0.0026 (7)−0.0013 (7)0.0054 (7)
C70.0174 (8)0.0177 (8)0.0272 (9)0.0020 (6)0.0035 (6)0.0025 (7)
C80.0163 (8)0.0193 (8)0.0180 (8)−0.0004 (6)0.0038 (6)0.0007 (6)
C90.0163 (8)0.0189 (8)0.0142 (8)−0.0003 (6)0.0014 (6)−0.0019 (6)
C100.0104 (7)0.0184 (8)0.0157 (8)−0.0010 (6)0.0015 (6)−0.0016 (6)
C110.0124 (7)0.0135 (7)0.0144 (8)0.0004 (5)0.0005 (6)0.0007 (6)
C120.0125 (7)0.0178 (8)0.0158 (8)0.0000 (6)−0.0034 (6)−0.0011 (6)
C130.0143 (7)0.0179 (8)0.0162 (8)−0.0005 (6)−0.0012 (6)0.0014 (6)
C140.0138 (7)0.0207 (8)0.0155 (8)0.0020 (6)−0.0012 (6)−0.0026 (6)
C150.0174 (8)0.0165 (8)0.0186 (8)0.0020 (6)−0.0026 (6)−0.0011 (6)
C160.0158 (8)0.0185 (8)0.0168 (8)−0.0023 (6)−0.0015 (6)0.0021 (6)
C170.0150 (7)0.0205 (8)0.0142 (8)0.0010 (6)−0.0001 (6)−0.0015 (6)
O10.0206 (6)0.0196 (6)0.0231 (7)0.0018 (4)0.0073 (5)−0.0023 (5)
C180.0174 (8)0.0254 (9)0.0206 (9)−0.0004 (6)0.0047 (6)−0.0008 (7)
O20.0285 (6)0.0152 (6)0.0270 (7)0.0027 (5)0.0005 (5)−0.0012 (5)
C190.0457 (11)0.0204 (9)0.0266 (10)−0.0074 (8)0.0069 (8)−0.0056 (7)
O30.0267 (6)0.0173 (6)0.0242 (7)−0.0021 (5)0.0084 (5)0.0021 (5)
C200.0212 (8)0.0234 (9)0.0216 (9)−0.0028 (7)0.0049 (7)0.0010 (7)
Geometric parameters (Å, º) top
S1—C11.7218 (17)C10—C121.487 (2)
S1—C81.7371 (17)C12—C131.389 (2)
N1—C111.336 (2)C12—C171.396 (2)
N1—N21.3470 (19)C13—C141.397 (2)
N1—H1N0.91 (2)C13—H130.9500
N2—N31.2911 (19)C14—O11.3622 (19)
N3—N41.3641 (19)C14—C151.396 (2)
N4—C111.324 (2)C15—O21.373 (2)
C1—C21.362 (2)C15—C161.397 (2)
C1—H10.9500C16—O31.362 (2)
C2—C31.448 (2)C16—C171.387 (2)
C2—C91.467 (2)C17—H170.9500
C3—C41.404 (2)O1—C181.431 (2)
C3—C81.405 (2)C18—H18A0.9800
C4—C51.381 (2)C18—H18B0.9800
C4—H40.9500C18—H18C0.9800
C5—C61.403 (3)O2—C191.433 (2)
C5—H50.9500C19—H19A0.9800
C6—C71.378 (3)C19—H19B0.9800
C6—H60.9500C19—H19C0.9800
C7—C81.396 (2)O3—C201.427 (2)
C7—H70.9500C20—H20A0.9800
C9—C101.339 (2)C20—H20B0.9800
C9—H90.9500C20—H20C0.9800
C10—C111.476 (2)
C1—S1—C890.97 (8)C13—C12—C17120.70 (15)
C11—N1—N2109.29 (13)C13—C12—C10121.24 (14)
C11—N1—H1N131.7 (12)C17—C12—C10118.02 (14)
N2—N1—H1N119.0 (12)C12—C13—C14119.34 (15)
N3—N2—N1106.55 (12)C12—C13—H13120.3
N2—N3—N4110.08 (12)C14—C13—H13120.3
C11—N4—N3106.69 (13)O1—C14—C15115.07 (14)
C2—C1—S1114.20 (13)O1—C14—C13124.64 (15)
C2—C1—H1122.9C15—C14—C13120.29 (15)
S1—C1—H1122.9O2—C15—C14120.79 (15)
C1—C2—C3111.37 (15)O2—C15—C16119.41 (15)
C1—C2—C9126.31 (15)C14—C15—C16119.73 (15)
C3—C2—C9122.31 (15)O3—C16—C17124.42 (15)
C4—C3—C8118.88 (15)O3—C16—C15115.42 (14)
C4—C3—C2129.32 (15)C17—C16—C15120.16 (15)
C8—C3—C2111.79 (15)C16—C17—C12119.76 (15)
C5—C4—C3119.22 (16)C16—C17—H17120.1
C5—C4—H4120.4C12—C17—H17120.1
C3—C4—H4120.4C14—O1—C18116.88 (13)
C4—C5—C6120.87 (16)O1—C18—H18A109.5
C4—C5—H5119.6O1—C18—H18B109.5
C6—C5—H5119.6H18A—C18—H18B109.5
C7—C6—C5121.07 (16)O1—C18—H18C109.5
C7—C6—H6119.5H18A—C18—H18C109.5
C5—C6—H6119.5H18B—C18—H18C109.5
C6—C7—C8118.00 (16)C15—O2—C19112.84 (13)
C6—C7—H7121.0O2—C19—H19A109.5
C8—C7—H7121.0O2—C19—H19B109.5
C7—C8—C3121.96 (16)H19A—C19—H19B109.5
C7—C8—S1126.42 (13)O2—C19—H19C109.5
C3—C8—S1111.62 (12)H19A—C19—H19C109.5
C10—C9—C2126.42 (15)H19B—C19—H19C109.5
C10—C9—H9116.8C16—O3—C20117.28 (13)
C2—C9—H9116.8O3—C20—H20A109.5
C9—C10—C11121.21 (14)O3—C20—H20B109.5
C9—C10—C12123.84 (15)H20A—C20—H20B109.5
C11—C10—C12114.88 (13)O3—C20—H20C109.5
N4—C11—N1107.39 (14)H20A—C20—H20C109.5
N4—C11—C10126.03 (14)H20B—C20—H20C109.5
N1—C11—C10126.58 (14)
C11—N1—N2—N3−0.48 (17)C9—C10—C11—N4−107.56 (19)
N1—N2—N3—N4−0.08 (17)C12—C10—C11—N475.24 (19)
N2—N3—N4—C110.61 (17)C9—C10—C11—N173.8 (2)
C8—S1—C1—C2−1.09 (14)C12—C10—C11—N1−103.42 (18)
S1—C1—C2—C32.01 (18)C9—C10—C12—C1349.6 (2)
S1—C1—C2—C9−177.01 (13)C11—C10—C12—C13−133.26 (15)
C1—C2—C3—C4179.11 (16)C9—C10—C12—C17−127.84 (17)
C9—C2—C3—C4−1.8 (3)C11—C10—C12—C1749.29 (19)
C1—C2—C3—C8−2.11 (19)C17—C12—C13—C140.7 (2)
C9—C2—C3—C8176.95 (14)C10—C12—C13—C14−176.67 (14)
C8—C3—C4—C50.4 (2)C12—C13—C14—O1−179.49 (14)
C2—C3—C4—C5179.09 (15)C12—C13—C14—C150.8 (2)
C3—C4—C5—C6−0.6 (2)O1—C14—C15—O22.1 (2)
C4—C5—C6—C70.2 (3)C13—C14—C15—O2−178.17 (14)
C5—C6—C7—C80.4 (3)O1—C14—C15—C16178.98 (14)
C6—C7—C8—C3−0.6 (2)C13—C14—C15—C16−1.3 (2)
C6—C7—C8—S1179.37 (13)O2—C15—C16—O3−2.4 (2)
C4—C3—C8—C70.2 (2)C14—C15—C16—O3−179.38 (14)
C2—C3—C8—C7−178.70 (14)O2—C15—C16—C17177.21 (14)
C4—C3—C8—S1−179.77 (12)C14—C15—C16—C170.3 (2)
C2—C3—C8—S11.32 (17)O3—C16—C17—C12−179.17 (14)
C1—S1—C8—C7179.83 (15)C15—C16—C17—C121.2 (2)
C1—S1—C8—C3−0.18 (12)C13—C12—C17—C16−1.7 (2)
C1—C2—C9—C1034.3 (3)C10—C12—C17—C16175.75 (14)
C3—C2—C9—C10−144.62 (16)C15—C14—O1—C18−175.64 (14)
C2—C9—C10—C11−0.3 (2)C13—C14—O1—C184.6 (2)
C2—C9—C10—C12176.63 (14)C14—C15—O2—C19−81.92 (19)
N3—N4—C11—N1−0.88 (17)C16—C15—O2—C19101.17 (17)
N3—N4—C11—C10−179.75 (14)C17—C16—O3—C205.4 (2)
N2—N1—C11—N40.86 (17)C15—C16—O3—C20−174.98 (14)
N2—N1—C11—C10179.73 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···N3i0.91 (2)2.65 (2)3.3886 (19)138.5 (16)
N1—H1N···N4i0.91 (2)1.85 (2)2.7482 (19)167.1 (18)
Symmetry code: (i) x−1, y, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1A—H1NA···N1Ai0.881.912.787 (9)175.5
N4A—H4NA···O1SB0.881.872.736 (6)168.4
N1B—H1NB···N1Bii0.881.922.792 (9)173.7
N4B—H4NB···O1SA0.881.912.769 (6)164.5
O1SA—H1SA···N4B0.841.972.769 (6)157.7
O1SA—H2SA···O1SAiii0.841.812.646 (7)176.8
O1SB—H1SB···N4A0.841.902.736 (6)175.8
Symmetry codes: (i) −x, −y, z; (ii) −x+1, −y+1, z; (iii) −x+1, −y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···N3i0.91 (2)2.65 (2)3.3886 (19)138.5 (16)
N1—H1N···N4i0.91 (2)1.85 (2)2.7482 (19)167.1 (18)
Symmetry code: (i) x−1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC19H16N4O2S·CH4OC20H18N4O3S
Mr396.46394.44
Crystal system, space groupOrthorhombic, P21212Monoclinic, P21/c
Temperature (K)9090
a, b, c (Å)18.2226 (4), 13.7954 (5), 15.5594 (5)4.8888 (1), 24.6650 (6), 15.5956 (4)
α, β, γ (°)90, 90, 9090, 91.031 (1), 90
V (Å3)3911.4 (2)1880.25 (8)
Z84
Radiation typeCu KαCu Kα
µ (mm−1)1.721.78
Crystal size (mm)0.21 × 0.15 × 0.120.10 × 0.08 × 0.02
Data collection
DiffractometerBruker X8 ProteumBruker X8 Proteum
Absorption correctionMulti-scan
(SADABS; Krause et al., 2015)		Multi-scan
(SADABS; Krause et al., 2015)
Tmin, Tmax0.720, 0.9150.693, 0.897
No. of measured, independent and
observed [I > 2σ(I)] reflections		51755, 7112, 6916 23250, 3337, 3138
Rint0.0380.037
(sin θ/λ)max (Å−1)0.6020.603
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.109, 1.10 0.034, 0.094, 1.13
No. of reflections71123337
No. of parameters514259
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.33, −0.340.27, −0.31
Absolute structureRefined as an inversion twin?
Absolute structure parameter0.50 (3)?

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and CIFFIX (Parkin, 2013).

 

Acknowledgements

The authors gratefully acknowledge the Arkansas Research Alliance for financial support, the UAMS sub award to PNR and SA from NIA Claude Pepper Center grant P30-AG028718 (J. Wei, P.I.) and the NIH/National Institute of General Medical Sciences (P20GM109005) for a COBRE award.

References

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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 72| Part 5| May 2016| Pages 652-655
doi:10.1107/S2056989016005600
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