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Logo of actae2this articlesearchopen accesssubmitActa Crystallographica Section E: Crystallographic CommunicationsActa Crystallographica Section E: Crystallographic Communications
 
Acta Crystallogr E Crystallogr Commun. 2017 July 1; 73(Pt 8): 1135–1139.
Published online 2017 July 7. doi:  10.1107/S2056989017009756
PMCID: PMC5598834

Syntheses and crystal structures of two adamantyl-substituted 1,2,4-triazole-5-thione N-Mannich bases

Abstract

In the title N-Mannich bases, 3-(adamantan-1-yl)-4-(4-fluoro­phen­yl)-1-[(4-phenyl­piperazin-1-yl)meth­yl]-4,5-di­hydro-1H-1,2,4-triazole-5-thione (C29H34FN5S) (I), and 3-(adamantan-1-yl)-4-(4-fluoro­phen­yl)-1-{[4-(2-meth­oxyphen­yl)piperazin-1-yl]-meth­yl}-4,5-di­hydro-1H-1,2,4-triazole-5-thione (C30H36FN5OS) (II), fluoro­phenyl, adamantane and piperazine moieties are linked to a planar triazole ring. There is an additional phenyl ring on the piperazine ring in (I) and a meth­oxy­phenyl ring in (II). In compound (I), the fluoro­phenyl and phenyl rings are inclined to the triazole ring by 86.55 (13) and 60.52 (12)°, respectively, and the two aryl rings are inclined to one another by 66.37 (13)°. In compound (II), the corresponding dihedral angles are 83.35 (13), 71.38 (15) and 11.97 (16)°, respectively. The crystal structure of (I) shows pairs of C—H(...)F hydrogen bonds forming inversion dimers, while in the crystal of compound (II), in addition to the C—H(...)F hydrogen bonds that generate chains parallel to the b axis, there are C—H(...)π inter­actions present that link the chains to form layers parallel to the ab plane.

Keywords: crystal structure, 1,2,4-triazole-5-thione, N-Mannich bases, adamantane, piperazine, biological activity, C—H(...)F hydrogen bonding: C—H(...)π inter­actions

Chemical context  

The incorporation of an adamantyl moiety into various bioactive mol­ecules results in compounds with relatively high lipophilicity, which in turn modifies the bioavailability and modulates the therapeutic indices through various mechanisms (Liu et al., 2011  ; Lamoureux & Artavia, 2010  ). Several adamantane-based drugs have been developed as anti­viral (Davies et al., 1964  ; Togo et al., 1968  ; Rosenthal et al., 1982  ; El-Emam et al., 2004  ; Burstein et al., 1999  ; Balzarini et al., 2009  ), anti-Parkinsonian (Schwab et al., 1969  ) and hypoglycaemic (Villhauer et al., 2003  ; Augeri et al., 2005  ) drugs. In addition, numerous adamantane-based analogues have promising anti­cancer (Sun et al., 2002  ), bactericidal (Protopopova et al., 2005  ; El-Emam et al., 2013  ; Kadi et al., 2010  ; Al-Abdullah et al.; 2014  ; Al-Deeb et al., 2006  ) and fungicidal (Omar et al., 2010  ) activities. In a continuation of our ongoing studies on the pharmacological and structural properties of adamantyl 1,2,4-triazole derivatives (Al-Abdullah et al., 2012  ; Al-Tamimi et al., 2014  ; El-Emam et al.; 2013  ; 2014  ), we report herein on the synthesis and crystal structures of the title adamantyl-substituted 1,2,4-triazole-5-thione N-Mannich bases, (I) and (II).

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Structural commentary  

The mol­ecular structures of the title compounds, (I) and (II), are illustrated in Figs. 1  and 2  , respectively. In both mol­ecules the piperazine rings have a chair conformation, with the N-bound substituents occupying equatorial positions. In (I), the fluoro­phenyl ring (C13–C18) and the phenyl ring (C24–C29) are inclined to the triazole ring (N1–N3/C11/C12) by 86.55 (13) and 60.52 (12)°, respectively. The two aryl rings are inclined to one another by 66.37 (13)°. In compound (II), the fluoro­phenyl ring (C13–C18) and the phenyl ring (C24–C29) are inclined to the triazole ring (N1–N3/C11/C12) by 83.35 (13) and 71.38 (15)°, respectively, while the two aryl rings are inclined to one another by only 11.97 (16)°. This difference in conformation is illustrated by the structural overlap diagram, shown in Fig. 3  .

Figure 1
The mol­ecular structure of compound (I), with the atom labelling and 30% probability displacement ellipsoids.
Figure 2
The mol­ecular structure of compound (II), with the atom labelling and 30% probability displacement ellipsoids.
Figure 3
A structural overlap of compounds (I) and (II) [colour code: (I) blue, (II) red].

Supra­molecular features  

In the crystal of compound (I), mol­ecules are linked by pairs of C—H(...)F hydrogen bonds, forming inversion dimers (Table 1  and Fig. 4  ). In compound (II), mol­ecules are linked by C—H(...)F hydrogen bonds, forming chains parallel to the b-axis direction. The chains are linked by C—H(...)π inter­actions, forming layers parallel to the ab plane (Table 2  and Fig. 5  ).

Figure 4
The crystal packing of compound (I), viewed along the c axis. The hydrogen bonds are shown as dashed lines (see Table 1  ), and only the H atoms involved in these inter­actions have been included.
Figure 5
The crystal packing of compound (II), viewed along the c axis, showing the C—H(...)F hydrogen bonds (dashed cyan lines) and some of the C—H(...)π inter­actions (dashed red lines); see Table 2  . ...
Table 1
Hydrogen-bond geometry (Å, °) for (I)
Table 2
Hydrogen-bond geometry (Å, °) for (II)

Database survey  

A search of the Cambridge Structural Database (Version 5.38, last update May 2017; Groom et al., 2016  ) for the 3-(adamantan-1-yl)-4-[(piperazin-1-yl) meth­yl]-1,2,4-triazole-3(3H)-thione moiety gave 14 hits. One compound, 3-(adamantan-1-yl)-4-phenyl-1-[(4-phenyl­piperazin-1-yl)meth­yl]-1H-1,2,4-triazole-5(4H)-thione (GAPWUR; Al-Abdullah et al., 2012  ), is very similar to compound (I). It has a phenyl ring substituent on the piperazine ring and a phenyl ring substituent on the triazole ring, which are inclined to one another by 72.4 (2)°, and by 89.0 (2) and 74.4 (2)°, respectively, to the triazole ring. In compound (I), the corresponding dihedral angles are 66.37 (13), 86.55 (13) and 60.52 (12)°, respectively. Two compounds have a 2-meth­oxy­phenyl ring substituent on the piperazine ring, viz. (3-(1-adamant­yl)-1-{[4-(2-meth­oxy­phen­yl)piperazin-1-yl]meth­yl}-4-methyl-1H-1,2,4-triazole-5(4H)-thione (YUPVIP; El-Emam et al., 2014  ), with a methyl substituent on the triazole ring, and 3-(adamantan-1-yl)-4-ethyl-1-{[4-(2-meth­oxy­phen­yl)piperazin-1-yl]meth­yl}-1H-1, 2,4-triazole-5(4H)-thione (RITMUE; Al-Tamimi et al., 2010  ) with an ethyl substituent on the triazole ring. In these two compounds the meth­oxy­phenyl rings are inclined to the triazole ring by 67.1 (1) and 59.4 (1)°, respectively. In compound (II), the corresponding dihedral angle is 71.38 (15)°.

Synthesis and crystallization  

The title compounds, (I) and (II), were synthesized via the reaction of 3-(adamantan-1-yl)-4-(4-fluoro­meth­yl)-4H-1,2,4-triazole-5-thiol (Al-Deeb et al., 2006  ) with the appropriate monosubstituted piperazie and a formaldehyde solution, as outlined in Fig. 6  .

Figure 6
Reaction schemes for the syntheses of compounds (I) and (II).

Compound (I): 1-Phenyl­piperazine (325 mg, 2 mmol) and a 37% formaldehyde solution (1 ml) were added to a solution of 3-(adamantan-1-yl)-4-(4-fluoro­meth­yl)-4H-1,2,4-triazole-5-thiol (659 mg, 2 mmol) in ethanol (10 ml), and the mixture was heated under reflux for 1 h then allowed to stand overnight. Cold water (3 ml) was slowly added and the mixture was stirred for 20 min. The precipitated crude product was filtered, washed with water, dried, and crystallized from ethanol to yield 846 mg (84%) of compound (I) as colourless plate-shaped crystals (m.p. 469–471 K). 1H NMR (700.17 MHz): δ 1.47–1.49 (m, 3H, adamantane-H), 1.60–1.62 (m, 3H, adamantane-H), 1.80 (s, 6H, adamantane-H), 1.89 (s, 3H, adamantane-H), 2.89–2.91 (m, 4H, piperazine-H), 3.14–3.15 (m, 4H, piperazine-H), 5.14 (s, 2H, CH2), 6.77–6.79 (m, 1H, Ar-H), 6.94 (d, 2H, Ar-H, J = 8.4 Hz), 7.20–7.22 (m, 2H, Ar-H), 7.41–7.49 (m, 4H, Ar-H). 13C NMR (125.76 MHz): δ 27.61, 36.07, 39.62, 39.74 (adamantane-C), 48.73, 50.30 (piperazine-C), 69.06 (CH2), 116.0, 116.78, 119.41, 129.37, 132.80, 133.10, 151.48, 156.28 (Ar-C), 162.17 (triazole C-3), 170.95 (C=S).

Compound (II): 1-(2-Meth­oxy­phen­yl)piperazine (385 mg, 2 mmol) and a 37% formaldehyde solution (1 ml) were added to a solution of 3-(adamantan-1-yl)-4-(4-fluoro­meth­yl)-4H-1,2,4-triazole-5-thiol (659 mg, 2 mmol) in ethanol (10 ml), and the mixture was heated under reflux for 1 h then allowed to stand overnight. The precipitated crude product was filtered, washed with cold ethanol, dried, and crystallized from ethanol to yield 865 mg (81%) of compound (II) as colourless block-like crystals (m.p. 462–464 K). 1H NMR (700.17 MHz): δ 1.49–1.50 (m, 3H, adamantane-H), 1.61–1.63 (m, 3H, adamantane-H), 1.83 (s, 6H, adamantane-H), 1.90 (s, 3H, adamantane-H), 2.89–2.90 (m, 4H, piperazine-H), 2.96–2.98 (m, 4H, piperazine-H), 3.78 (s, 3H, OCH3), 5.11 (s, 2H, CH2), 6.88–6.96 (m, 4H, Ar-H), 7.42–7.52 (m, 4H, Ar-H). 13C NMR (125.76 MHz): δ 27.61, 35.77, 36.07, 39.61 (adamantane-C), 50.54, 50.58 (piperazine-C), 55.65 (OCH3), 69.39 (CH2), 112.08, 116.78, 118.51, 121.23, 123.02, 132.79, 133.13, 141.53, 152.36, 156.32 (Ar-C), 162.17 (triazole C-3), 171.0 (C=S).

Suitable single crystals of compounds (I) and (II) were obtained by slow evaporation of CHCl3:EtOH solutions (1:1, 5 ml) at room temperature.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 3  .The C-bound H atoms were positioned geometrically and treated as riding atoms: C—H = 0.93–1.00 Å with U iso(H) = 1.5U eq(C-meth­yl) and 1.2U eq(C) for other H atoms.

Table 3
Experimental details

Supplementary Material

Crystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989017009756/su5368sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017009756/su5368Isup2.hkl

Structure factors: contains datablock(s) II. DOI: 10.1107/S2056989017009756/su5368IIsup3.hkl

CCDC references: 1559732, 1559731

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors extend their appreciation to the Deanship of Scientific Research and the Research Centre, College of Sciences, King Saud University for funding this research.

supplementary crystallographic information

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-[(4-phenylpiperazin-1-yl)methyl]-4,5-dihydro-1H-1,2,4-triazole-5-thione (I)   Crystal data

C29H34FN5SZ = 2
Mr = 503.67F(000) = 536
Triclinic, P1Dx = 1.281 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.4173 (5) ÅCell parameters from 9217 reflections
b = 10.9849 (5) Åθ = 2.5–23.7°
c = 12.0002 (6) ŵ = 0.16 mm1
α = 72.769 (2)°T = 296 K
β = 84.623 (2)°Plate, colourless
γ = 89.244 (2)°0.45 × 0.33 × 0.09 mm
V = 1305.66 (11) Å3

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-[(4-phenylpiperazin-1-yl)methyl]-4,5-dihydro-1H-1,2,4-triazole-5-thione (I)   Data collection

Bruker APEXII CCD diffractometer6011 independent reflections
Radiation source: fine-focus sealed tube3533 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.076
[var phi] and ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2012)h = −13→13
Tmin = 0.939, Tmax = 0.986k = −14→14
49580 measured reflectionsl = −15→15

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-[(4-phenylpiperazin-1-yl)methyl]-4,5-dihydro-1H-1,2,4-triazole-5-thione (I)   Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.163H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.065P)2 + 0.6113P] where P = (Fo2 + 2Fc2)/3
6007 reflections(Δ/σ)max < 0.001
325 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.25 e Å3
0 constraints

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-[(4-phenylpiperazin-1-yl)methyl]-4,5-dihydro-1H-1,2,4-triazole-5-thione (I)   Special details

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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-[(4-phenylpiperazin-1-yl)methyl]-4,5-dihydro-1H-1,2,4-triazole-5-thione (I)   Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.97289 (7)0.79726 (7)0.53684 (7)0.0643 (2)
F10.9953 (2)0.2584 (2)0.8886 (2)0.1173 (9)
N10.74459 (18)0.67026 (17)0.62307 (16)0.0391 (5)
N20.59860 (19)0.80635 (18)0.54133 (17)0.0454 (5)
N30.7211 (2)0.85604 (18)0.50475 (17)0.0472 (5)
N40.7392 (2)1.01606 (19)0.30911 (17)0.0494 (5)
N50.7233 (2)0.9884 (2)0.08319 (18)0.0497 (5)
C10.3802 (2)0.6521 (3)0.6157 (2)0.0528 (7)
H1A0.36440.74280.60980.063*
H1B0.39330.64440.53530.063*
C20.2634 (3)0.5709 (3)0.6825 (3)0.0592 (7)
H2A0.18520.60030.640.071*
C30.2423 (3)0.5859 (3)0.8050 (3)0.0716 (9)
H3A0.2260.67640.79970.086*
H3B0.16610.53460.84860.086*
C40.3614 (3)0.5414 (3)0.8693 (2)0.0660 (8)
H4A0.34720.55160.94960.079*
C50.4791 (2)0.6218 (3)0.8034 (2)0.0514 (7)
H5A0.55590.59320.84630.062*
H5B0.46460.71230.79860.062*
C60.5025 (2)0.6083 (2)0.67938 (19)0.0365 (5)
C70.2865 (3)0.4317 (3)0.6911 (3)0.0669 (8)
H7A0.30070.42160.61170.08*
H7B0.21010.37950.73280.08*
C80.4048 (3)0.3872 (3)0.7577 (3)0.0606 (8)
H8A0.41970.29520.76470.073*
C90.5233 (2)0.4665 (2)0.6893 (2)0.0487 (6)
H9A0.53670.45570.610.058*
H9B0.60110.43620.73030.058*
C100.3844 (3)0.4035 (3)0.8797 (3)0.0727 (9)
H10A0.30930.35130.92450.087*
H10B0.46140.37440.92230.087*
C110.6145 (2)0.6934 (2)0.61309 (19)0.0381 (5)
C120.8141 (2)0.7769 (2)0.5529 (2)0.0442 (6)
C130.8086 (2)0.5622 (2)0.6933 (2)0.0393 (5)
C140.8596 (2)0.4721 (2)0.6427 (2)0.0505 (6)
H14A0.85110.48170.56240.061*
C150.9223 (3)0.3690 (3)0.7086 (3)0.0648 (8)
H15A0.95720.30580.67530.078*
C160.9332 (3)0.3597 (3)0.8221 (3)0.0700 (9)
C170.8867 (3)0.4476 (3)0.8746 (2)0.0679 (9)
H17A0.8970.43750.95460.081*
C180.8236 (2)0.5524 (3)0.8079 (2)0.0520 (7)
H18A0.79130.61640.84120.062*
C190.7401 (3)0.9915 (2)0.4322 (2)0.0548 (7)
H19A0.67161.04250.4590.066*
H19B0.82361.02230.44760.066*
C200.6161 (3)1.0001 (3)0.2677 (2)0.0530 (7)
H20A0.54841.04440.30390.064*
H20B0.59250.90840.29080.064*
C210.6245 (3)1.0548 (3)0.1353 (2)0.0530 (7)
H21A0.54031.04450.10690.064*
H21B0.64621.14690.11210.064*
C230.8397 (3)0.9514 (3)0.2571 (2)0.0574 (7)
H23A0.82030.85880.28140.069*
H23B0.92360.96440.28480.069*
C220.8475 (3)1.0037 (3)0.1250 (2)0.0585 (7)
H22A0.87221.09510.10060.07*
H22B0.91450.9580.08970.07*
C240.7295 (3)1.0128 (2)−0.0403 (2)0.0502 (6)
C250.8004 (3)0.9305 (3)−0.0903 (3)0.0678 (8)
H25A0.84230.8599−0.04170.081*
C260.8102 (4)0.9509 (4)−0.2097 (3)0.0820 (10)
H26A0.85840.8938−0.24260.098*
C270.7515 (4)1.0521 (4)−0.2813 (3)0.0837 (11)
H27A0.75991.066−0.36370.1*
C280.6804 (3)1.1335 (4)−0.2340 (3)0.0782 (10)
H28A0.63871.2036−0.28350.094*
C290.6692 (3)1.1139 (3)−0.1138 (3)0.0633 (8)
H29A0.61951.1706−0.08160.076*

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-[(4-phenylpiperazin-1-yl)methyl]-4,5-dihydro-1H-1,2,4-triazole-5-thione (I)   Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0496 (4)0.0660 (5)0.0691 (5)−0.0162 (3)0.0024 (3)−0.0092 (4)
F10.0819 (14)0.1034 (16)0.1216 (18)0.0377 (12)−0.0074 (12)0.0334 (13)
N10.0401 (11)0.0368 (11)0.0371 (11)−0.0016 (8)0.0025 (8)−0.0076 (8)
N20.0497 (12)0.0399 (11)0.0410 (11)0.0049 (9)0.0022 (9)−0.0058 (9)
N30.0543 (13)0.0385 (11)0.0415 (12)−0.0042 (10)0.0042 (9)−0.0030 (9)
N40.0572 (13)0.0475 (12)0.0411 (12)−0.0079 (10)−0.0001 (10)−0.0107 (9)
N50.0502 (13)0.0550 (13)0.0439 (12)0.0054 (10)−0.0022 (9)−0.0155 (10)
C10.0481 (15)0.0545 (16)0.0541 (16)0.0109 (12)−0.0079 (12)−0.0130 (13)
C20.0377 (14)0.0703 (19)0.074 (2)0.0088 (13)−0.0132 (13)−0.0255 (15)
C30.0447 (16)0.090 (2)0.085 (2)−0.0052 (15)0.0155 (15)−0.0409 (18)
C40.0536 (17)0.098 (2)0.0467 (16)−0.0167 (16)0.0137 (13)−0.0262 (16)
C50.0447 (14)0.0666 (17)0.0468 (15)−0.0077 (12)0.0044 (11)−0.0248 (13)
C60.0380 (12)0.0370 (12)0.0341 (12)0.0051 (10)0.0005 (9)−0.0114 (10)
C70.0460 (16)0.075 (2)0.089 (2)−0.0099 (14)−0.0048 (15)−0.0379 (17)
C80.0475 (15)0.0402 (15)0.093 (2)−0.0066 (12)−0.0009 (14)−0.0186 (14)
C90.0415 (14)0.0434 (14)0.0637 (17)0.0020 (11)−0.0014 (12)−0.0206 (12)
C100.0544 (18)0.081 (2)0.064 (2)−0.0212 (16)0.0055 (14)0.0049 (16)
C110.0438 (13)0.0378 (13)0.0320 (12)0.0050 (10)0.0003 (10)−0.0107 (10)
C120.0507 (15)0.0422 (14)0.0381 (13)−0.0036 (11)0.0031 (11)−0.0114 (11)
C130.0324 (12)0.0402 (13)0.0413 (14)−0.0017 (10)0.0008 (10)−0.0073 (10)
C140.0423 (14)0.0535 (16)0.0567 (16)0.0025 (12)−0.0017 (12)−0.0185 (13)
C150.0451 (16)0.0540 (18)0.092 (2)0.0079 (13)−0.0001 (15)−0.0185 (16)
C160.0418 (16)0.066 (2)0.079 (2)0.0101 (14)0.0003 (15)0.0128 (17)
C170.0473 (16)0.099 (2)0.0415 (16)0.0024 (16)−0.0036 (12)0.0037 (16)
C180.0403 (14)0.0688 (18)0.0453 (15)−0.0011 (12)0.0010 (11)−0.0160 (13)
C190.0785 (19)0.0372 (14)0.0445 (15)−0.0067 (13)−0.0011 (13)−0.0069 (11)
C200.0562 (16)0.0494 (15)0.0514 (16)0.0017 (12)0.0045 (12)−0.0148 (12)
C210.0516 (15)0.0584 (16)0.0490 (16)0.0068 (13)−0.0034 (12)−0.0164 (13)
C230.0482 (15)0.0715 (19)0.0477 (16)−0.0004 (13)−0.0034 (12)−0.0105 (13)
C220.0480 (16)0.076 (2)0.0475 (16)0.0016 (14)−0.0001 (12)−0.0136 (14)
C240.0522 (15)0.0520 (16)0.0479 (15)−0.0042 (12)−0.0024 (12)−0.0176 (12)
C250.076 (2)0.069 (2)0.063 (2)0.0030 (16)−0.0014 (16)−0.0289 (16)
C260.084 (2)0.103 (3)0.073 (2)−0.006 (2)0.0066 (19)−0.051 (2)
C270.086 (2)0.117 (3)0.0518 (19)−0.022 (2)−0.0013 (18)−0.031 (2)
C280.079 (2)0.094 (3)0.056 (2)−0.0078 (19)−0.0103 (17)−0.0124 (18)
C290.0690 (19)0.0678 (19)0.0543 (18)0.0011 (15)−0.0054 (14)−0.0200 (15)

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-[(4-phenylpiperazin-1-yl)methyl]-4,5-dihydro-1H-1,2,4-triazole-5-thione (I)   Geometric parameters (Å, º)

S1—C121.658 (3)C8—H8A1
F1—C161.358 (3)C9—H9A0.99
N1—C111.385 (3)C9—H9B0.99
N1—C121.389 (3)C10—H10A0.99
N1—C131.433 (3)C10—H10B0.99
N2—C111.303 (3)C13—C181.371 (3)
N2—N31.375 (3)C13—C141.383 (3)
N3—C121.346 (3)C14—C151.373 (4)
N3—C191.490 (3)C14—H14A0.95
N4—C191.422 (3)C15—C161.351 (5)
N4—C201.449 (3)C15—H15A0.95
N4—C231.452 (3)C16—C171.361 (5)
N5—C241.421 (3)C17—C181.389 (4)
N5—C211.453 (3)C17—H17A0.95
N5—C221.459 (3)C18—H18A0.95
C1—C21.530 (4)C19—H19A0.99
C1—C61.545 (3)C19—H19B0.99
C1—H1A0.99C20—C211.518 (3)
C1—H1B0.99C20—H20A0.99
C2—C71.519 (4)C20—H20B0.99
C2—C31.523 (4)C21—H21A0.99
C2—H2A1C21—H21B0.99
C3—C41.521 (4)C23—C221.513 (4)
C3—H3A0.99C23—H23A0.99
C3—H3B0.99C23—H23B0.99
C4—C101.501 (4)C22—H22A0.99
C4—C51.529 (4)C22—H22B0.99
C4—H4A1C24—C291.383 (4)
C5—C61.536 (3)C24—C251.394 (4)
C5—H5A0.99C25—C261.377 (4)
C5—H5B0.99C25—H25A0.95
C6—C111.511 (3)C26—C271.365 (5)
C6—C91.540 (3)C26—H26A0.95
C7—C81.528 (4)C27—C281.370 (5)
C7—H7A0.99C27—H27A0.95
C7—H7B0.99C28—C291.387 (4)
C8—C101.522 (4)C28—H28A0.95
C8—C91.539 (4)C29—H29A0.95
C11—N1—C12108.39 (19)N2—C11—N1110.2 (2)
C11—N1—C13130.57 (18)N2—C11—C6122.5 (2)
C12—N1—C13121.01 (19)N1—C11—C6127.21 (19)
C11—N2—N3105.12 (19)N3—C12—N1102.9 (2)
C12—N3—N2113.44 (18)N3—C12—S1130.23 (18)
C12—N3—C19125.9 (2)N1—C12—S1126.90 (19)
N2—N3—C19120.1 (2)C18—C13—C14120.9 (2)
C19—N4—C20116.2 (2)C18—C13—N1119.8 (2)
C19—N4—C23114.0 (2)C14—C13—N1119.3 (2)
C20—N4—C23110.5 (2)C15—C14—C13119.9 (3)
C24—N5—C21116.6 (2)C15—C14—H14A120.1
C24—N5—C22113.3 (2)C13—C14—H14A120.1
C21—N5—C22109.8 (2)C16—C15—C14118.1 (3)
C2—C1—C6110.4 (2)C16—C15—H15A120.9
C2—C1—H1A109.6C14—C15—H15A120.9
C6—C1—H1A109.6C15—C16—F1118.9 (3)
C2—C1—H1B109.6C15—C16—C17123.8 (3)
C6—C1—H1B109.6F1—C16—C17117.3 (3)
H1A—C1—H1B108.1C16—C17—C18118.2 (3)
C7—C2—C3109.6 (3)C16—C17—H17A120.9
C7—C2—C1109.9 (2)C18—C17—H17A120.9
C3—C2—C1109.2 (2)C13—C18—C17119.1 (3)
C7—C2—H2A109.4C13—C18—H18A120.5
C3—C2—H2A109.4C17—C18—H18A120.5
C1—C2—H2A109.4N4—C19—N3116.3 (2)
C4—C3—C2109.3 (2)N4—C19—H19A108.2
C4—C3—H3A109.8N3—C19—H19A108.2
C2—C3—H3A109.8N4—C19—H19B108.2
C4—C3—H3B109.8N3—C19—H19B108.2
C2—C3—H3B109.8H19A—C19—H19B107.4
H3A—C3—H3B108.3N4—C20—C21109.7 (2)
C10—C4—C3109.9 (3)N4—C20—H20A109.7
C10—C4—C5109.9 (2)C21—C20—H20A109.7
C3—C4—C5110.1 (3)N4—C20—H20B109.7
C10—C4—H4A109C21—C20—H20B109.7
C3—C4—H4A109H20A—C20—H20B108.2
C5—C4—H4A109N5—C21—C20109.2 (2)
C4—C5—C6110.0 (2)N5—C21—H21A109.8
C4—C5—H5A109.7C20—C21—H21A109.8
C6—C5—H5A109.7N5—C21—H21B109.8
C4—C5—H5B109.7C20—C21—H21B109.8
C6—C5—H5B109.7H21A—C21—H21B108.3
H5A—C5—H5B108.2N4—C23—C22109.7 (2)
C11—C6—C5109.46 (19)N4—C23—H23A109.7
C11—C6—C9113.41 (18)C22—C23—H23A109.7
C5—C6—C9108.6 (2)N4—C23—H23B109.7
C11—C6—C1108.72 (18)C22—C23—H23B109.7
C5—C6—C1108.15 (19)H23A—C23—H23B108.2
C9—C6—C1108.4 (2)N5—C22—C23110.3 (2)
C2—C7—C8108.9 (2)N5—C22—H22A109.6
C2—C7—H7A109.9C23—C22—H22A109.6
C8—C7—H7A109.9N5—C22—H22B109.6
C2—C7—H7B109.9C23—C22—H22B109.6
C8—C7—H7B109.9H22A—C22—H22B108.1
H7A—C7—H7B108.3C29—C24—C25118.1 (3)
C10—C8—C7110.3 (2)C29—C24—N5123.6 (2)
C10—C8—C9109.7 (2)C25—C24—N5118.3 (2)
C7—C8—C9109.1 (2)C26—C25—C24120.4 (3)
C10—C8—H8A109.2C26—C25—H25A119.8
C7—C8—H8A109.2C24—C25—H25A119.8
C9—C8—H8A109.2C27—C26—C25120.8 (3)
C8—C9—C6109.8 (2)C27—C26—H26A119.6
C8—C9—H9A109.7C25—C26—H26A119.6
C6—C9—H9A109.7C26—C27—C28119.8 (3)
C8—C9—H9B109.7C26—C27—H27A120.1
C6—C9—H9B109.7C28—C27—H27A120.1
H9A—C9—H9B108.2C27—C28—C29120.1 (3)
C4—C10—C8109.3 (2)C27—C28—H28A120
C4—C10—H10A109.8C29—C28—H28A120
C8—C10—H10A109.8C24—C29—C28120.8 (3)
C4—C10—H10B109.8C24—C29—H29A119.6
C8—C10—H10B109.8C28—C29—H29A119.6
H10A—C10—H10B108.3
C11—N2—N3—C12−0.5 (3)C11—N1—C12—N3−0.6 (2)
C11—N2—N3—C19−172.6 (2)C13—N1—C12—N3−178.6 (2)
C6—C1—C2—C7−59.7 (3)C11—N1—C12—S1178.75 (18)
C6—C1—C2—C360.6 (3)C13—N1—C12—S10.8 (3)
C7—C2—C3—C460.3 (3)C11—N1—C13—C18−83.5 (3)
C1—C2—C3—C4−60.2 (3)C12—N1—C13—C1894.0 (3)
C2—C3—C4—C10−60.7 (3)C11—N1—C13—C1499.5 (3)
C2—C3—C4—C560.4 (3)C12—N1—C13—C14−83.1 (3)
C10—C4—C5—C660.9 (3)C18—C13—C14—C152.3 (4)
C3—C4—C5—C6−60.2 (3)N1—C13—C14—C15179.3 (2)
C4—C5—C6—C11177.0 (2)C13—C14—C15—C16−0.6 (4)
C4—C5—C6—C9−58.7 (3)C14—C15—C16—F1−179.9 (3)
C4—C5—C6—C158.7 (3)C14—C15—C16—C17−0.8 (5)
C2—C1—C6—C11−178.1 (2)C15—C16—C17—C180.5 (5)
C2—C1—C6—C5−59.4 (3)F1—C16—C17—C18179.6 (2)
C2—C1—C6—C958.2 (3)C14—C13—C18—C17−2.5 (4)
C3—C2—C7—C8−59.2 (3)N1—C13—C18—C17−179.5 (2)
C1—C2—C7—C860.8 (3)C16—C17—C18—C131.2 (4)
C2—C7—C8—C1059.0 (3)C20—N4—C19—N369.5 (3)
C2—C7—C8—C9−61.5 (3)C23—N4—C19—N3−60.7 (3)
C10—C8—C9—C6−59.5 (3)C12—N3—C19—N4102.6 (3)
C7—C8—C9—C661.4 (3)N2—N3—C19—N4−86.3 (3)
C11—C6—C9—C8−179.9 (2)C19—N4—C20—C21168.6 (2)
C5—C6—C9—C858.2 (3)C23—N4—C20—C21−59.5 (3)
C1—C6—C9—C8−59.1 (3)C24—N5—C21—C20169.9 (2)
C3—C4—C10—C860.1 (3)C22—N5—C21—C20−59.5 (3)
C5—C4—C10—C8−61.2 (3)N4—C20—C21—N559.9 (3)
C7—C8—C10—C4−59.6 (3)C19—N4—C23—C22−168.7 (2)
C9—C8—C10—C460.6 (3)C20—N4—C23—C2258.3 (3)
N3—N2—C11—N10.1 (2)C24—N5—C22—C23−168.7 (2)
N3—N2—C11—C6176.33 (19)C21—N5—C22—C2359.0 (3)
C12—N1—C11—N20.3 (3)N4—C23—C22—N5−57.8 (3)
C13—N1—C11—N2178.0 (2)C21—N5—C24—C2915.0 (4)
C12—N1—C11—C6−175.7 (2)C22—N5—C24—C29−113.9 (3)
C13—N1—C11—C62.0 (4)C21—N5—C24—C25−165.1 (3)
C5—C6—C11—N2−97.1 (3)C22—N5—C24—C2566.0 (3)
C9—C6—C11—N2141.4 (2)C29—C24—C25—C260.5 (4)
C1—C6—C11—N220.8 (3)N5—C24—C25—C26−179.4 (3)
C5—C6—C11—N178.4 (3)C24—C25—C26—C270.4 (5)
C9—C6—C11—N1−43.0 (3)C25—C26—C27—C28−1.0 (5)
C1—C6—C11—N1−163.6 (2)C26—C27—C28—C290.7 (5)
N2—N3—C12—N10.7 (3)C25—C24—C29—C28−0.8 (4)
C19—N3—C12—N1172.3 (2)N5—C24—C29—C28179.1 (3)
N2—N3—C12—S1−178.63 (18)C27—C28—C29—C240.2 (5)
C19—N3—C12—S1−7.1 (4)

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-[(4-phenylpiperazin-1-yl)methyl]-4,5-dihydro-1H-1,2,4-triazole-5-thione (I)   Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
C22—H22B···F1i0.992.493.332 (4)142

Symmetry code: (i) −x+2, −y+1, −z+1.

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-{[4-(2-methoxyphenyl)piperazin-1-yl]methyl}-4,5-dihydro-1H-1,2,4-triazole-5-thione (II)   Crystal data

C30H36FN5OSF(000) = 1136
Mr = 533.7Dx = 1.283 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8790 reflections
a = 11.3074 (7) Åθ = 2.5–22.8°
b = 12.1576 (8) ŵ = 0.16 mm1
c = 20.4976 (13) ÅT = 293 K
β = 101.328 (2)°Block, colourless
V = 2762.9 (3) Å30.42 × 0.19 × 0.16 mm
Z = 4

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-{[4-(2-methoxyphenyl)piperazin-1-yl]methyl}-4,5-dihydro-1H-1,2,4-triazole-5-thione (II)   Data collection

Bruker APEXII CCD diffractometer6350 independent reflections
Radiation source: fine-focus sealed tube3203 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.134
[var phi] and ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2012)h = −14→14
Tmin = 0.965, Tmax = 0.975k = −15→15
67287 measured reflectionsl = −26→26

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-{[4-(2-methoxyphenyl)piperazin-1-yl]methyl}-4,5-dihydro-1H-1,2,4-triazole-5-thione (II)   Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0452P)2 + 0.8222P] where P = (Fo2 + 2Fc2)/3
6347 reflections(Δ/σ)max < 0.001
344 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = −0.22 e Å3
0 constraints

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-{[4-(2-methoxyphenyl)piperazin-1-yl]methyl}-4,5-dihydro-1H-1,2,4-triazole-5-thione (II)   Special details

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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-{[4-(2-methoxyphenyl)piperazin-1-yl]methyl}-4,5-dihydro-1H-1,2,4-triazole-5-thione (II)   Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.24167 (6)0.32667 (6)0.43345 (3)0.0608 (2)
F10.3856 (2)0.79567 (15)0.45842 (10)0.1199 (8)
O10.34615 (16)−0.06806 (14)0.77358 (8)0.0618 (5)
N10.19559 (16)0.42142 (14)0.54744 (10)0.0428 (5)
N30.13241 (17)0.25598 (15)0.53226 (9)0.0469 (5)
N20.10390 (17)0.28893 (15)0.59193 (10)0.0481 (5)
N40.18293 (18)0.05911 (15)0.54290 (9)0.0476 (5)
N50.35533 (17)−0.04464 (14)0.64472 (9)0.0439 (5)
C10.0665 (2)0.5658 (2)0.64261 (13)0.0583 (7)
H1A0.10870.60990.6150.07*
H1B−0.01370.55020.61740.07*
C20.0572 (3)0.6293 (2)0.70571 (14)0.0645 (8)
H2A0.0140.69840.69320.077*
C3−0.0100 (3)0.5635 (2)0.74851 (16)0.0755 (9)
H3A−0.09070.54760.72420.091*
H3B−0.01670.60530.78790.091*
C40.0574 (3)0.4566 (2)0.76852 (15)0.0750 (9)
H4A0.01350.41310.79620.09*
C50.0666 (3)0.3909 (2)0.70539 (14)0.0680 (8)
H5A0.10840.32210.71790.082*
H5B−0.01370.37390.68080.082*
C60.13488 (19)0.45742 (17)0.66124 (11)0.0412 (6)
C70.1822 (3)0.6551 (2)0.74427 (15)0.0741 (9)
H7A0.22540.69870.7170.089*
H7B0.17650.69750.78360.089*
C80.2498 (2)0.5495 (2)0.76445 (14)0.0688 (8)
H8A0.33050.56680.78970.083*
C90.2610 (2)0.4844 (2)0.70174 (13)0.0596 (7)
H9A0.30510.41680.71430.072*
H9B0.30540.52740.67480.072*
C100.1828 (3)0.4810 (3)0.80713 (14)0.0807 (9)
H10A0.22580.41270.81940.097*
H10B0.17790.52070.84760.097*
C110.14343 (19)0.39012 (18)0.60057 (11)0.0413 (6)
C120.1899 (2)0.33355 (19)0.50378 (12)0.0455 (6)
C130.2440 (2)0.52480 (18)0.53089 (11)0.0429 (6)
C140.3666 (2)0.5415 (2)0.54450 (13)0.0610 (7)
H14A0.41730.49020.56950.073*
C150.4142 (3)0.6341 (3)0.52107 (16)0.0785 (10)
H15A0.49690.64660.530.094*
C160.3373 (4)0.7071 (2)0.48460 (16)0.0740 (9)
C170.2163 (3)0.6944 (2)0.47141 (14)0.0666 (8)
H17A0.16620.74720.44740.08*
C180.1692 (2)0.60109 (19)0.49462 (12)0.0514 (6)
H18A0.08620.58970.48570.062*
C190.1079 (2)0.14220 (19)0.50729 (12)0.0550 (7)
H19A0.02460.12460.50830.066*
H19B0.11650.13990.46120.066*
C200.3118 (2)0.0819 (2)0.55064 (12)0.0541 (7)
H20A0.33220.1460.57880.065*
H20B0.33050.09830.50750.065*
C210.3869 (2)−0.0149 (2)0.58108 (12)0.0560 (7)
H21A0.3728−0.07720.5510.067*
H21B0.47190.00390.5880.067*
C220.2259 (2)−0.06913 (19)0.63489 (12)0.0505 (6)
H22A0.2053−0.08940.6770.061*
H22B0.2066−0.13070.60460.061*
C230.1536 (2)0.03040 (19)0.60675 (12)0.0483 (6)
H23A0.06810.01450.60110.058*
H23B0.17210.09180.63730.058*
C240.4291 (2)−0.12587 (18)0.68294 (12)0.0453 (6)
C250.5089 (2)−0.1917 (2)0.65777 (13)0.0592 (7)
H25A0.5185−0.18140.61420.071*
C260.5751 (3)−0.2730 (2)0.69618 (16)0.0722 (8)
H26A0.6289−0.3160.67830.087*
C270.5616 (2)−0.2903 (2)0.76022 (16)0.0686 (8)
H27A0.6031−0.34710.78520.082*
C280.4857 (2)−0.2226 (2)0.78764 (13)0.0591 (7)
H28A0.4781−0.23260.83160.071*
C290.4211 (2)−0.14002 (19)0.74968 (13)0.0482 (6)
C300.3295 (3)−0.0813 (2)0.83902 (13)0.0715 (8)
H30A0.2762−0.02510.84910.107*
H30B0.4059−0.07550.86910.107*
H30C0.295−0.15230.84370.107*

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-{[4-(2-methoxyphenyl)piperazin-1-yl]methyl}-4,5-dihydro-1H-1,2,4-triazole-5-thione (II)   Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0707 (5)0.0622 (4)0.0515 (4)0.0101 (4)0.0172 (3)−0.0018 (3)
F10.190 (2)0.0819 (13)0.1131 (15)−0.0717 (13)0.0917 (15)−0.0292 (11)
O10.0783 (13)0.0624 (12)0.0492 (11)0.0115 (10)0.0236 (9)0.0040 (9)
N10.0404 (11)0.0354 (11)0.0527 (12)0.0050 (9)0.0089 (9)−0.0016 (10)
N30.0552 (12)0.0383 (11)0.0467 (12)0.0066 (10)0.0083 (10)−0.0046 (10)
N20.0510 (12)0.0386 (12)0.0548 (13)0.0025 (9)0.0107 (10)−0.0056 (10)
N40.0623 (14)0.0379 (11)0.0429 (12)0.0048 (10)0.0111 (10)−0.0022 (9)
N50.0504 (12)0.0391 (11)0.0444 (12)0.0031 (9)0.0144 (9)0.0027 (9)
C10.0616 (17)0.0520 (16)0.0596 (17)0.0177 (13)0.0078 (13)−0.0084 (13)
C20.078 (2)0.0475 (15)0.0713 (19)0.0150 (14)0.0220 (17)−0.0104 (14)
C30.0684 (19)0.074 (2)0.093 (2)−0.0041 (16)0.0361 (17)−0.0302 (17)
C40.104 (2)0.0573 (18)0.080 (2)−0.0273 (17)0.059 (2)−0.0141 (16)
C50.087 (2)0.0501 (16)0.077 (2)−0.0167 (14)0.0416 (17)−0.0140 (14)
C60.0379 (13)0.0357 (13)0.0507 (14)0.0002 (10)0.0109 (11)−0.0047 (11)
C70.100 (2)0.0554 (18)0.073 (2)−0.0244 (17)0.0324 (18)−0.0197 (15)
C80.0542 (17)0.088 (2)0.0603 (18)−0.0096 (16)0.0028 (14)−0.0189 (16)
C90.0476 (15)0.0727 (18)0.0578 (17)0.0027 (13)0.0086 (13)−0.0064 (14)
C100.115 (3)0.075 (2)0.0538 (18)0.0137 (19)0.0211 (19)0.0017 (16)
C110.0348 (12)0.0383 (14)0.0496 (15)0.0037 (10)0.0055 (11)−0.0008 (11)
C120.0408 (13)0.0425 (14)0.0509 (15)0.0101 (11)0.0033 (12)0.0030 (12)
C130.0398 (14)0.0430 (14)0.0469 (14)−0.0009 (11)0.0110 (11)−0.0053 (11)
C140.0442 (16)0.0736 (19)0.0639 (18)−0.0019 (14)0.0076 (13)−0.0123 (15)
C150.062 (2)0.101 (3)0.078 (2)−0.037 (2)0.0290 (18)−0.036 (2)
C160.108 (3)0.0583 (19)0.068 (2)−0.038 (2)0.049 (2)−0.0253 (16)
C170.095 (2)0.0471 (17)0.0617 (19)−0.0013 (16)0.0260 (17)0.0011 (14)
C180.0515 (15)0.0464 (15)0.0565 (16)0.0025 (12)0.0112 (13)−0.0004 (13)
C190.0658 (17)0.0420 (15)0.0519 (16)0.0003 (12)−0.0017 (13)−0.0088 (12)
C200.0679 (18)0.0503 (15)0.0493 (16)0.0090 (13)0.0246 (13)0.0092 (12)
C210.0662 (17)0.0518 (16)0.0546 (16)0.0119 (13)0.0231 (14)0.0034 (13)
C220.0526 (16)0.0437 (14)0.0548 (16)−0.0053 (12)0.0095 (12)0.0005 (12)
C230.0492 (14)0.0427 (14)0.0539 (16)−0.0028 (11)0.0123 (12)−0.0019 (12)
C240.0510 (14)0.0332 (12)0.0514 (16)−0.0025 (11)0.0093 (12)−0.0007 (11)
C250.0704 (18)0.0520 (16)0.0562 (17)0.0172 (14)0.0147 (14)0.0009 (13)
C260.077 (2)0.0632 (19)0.078 (2)0.0246 (16)0.0208 (17)0.0007 (17)
C270.0634 (18)0.0545 (17)0.083 (2)0.0115 (14)0.0028 (16)0.0106 (16)
C280.0621 (17)0.0562 (16)0.0572 (17)−0.0057 (14)0.0073 (14)0.0131 (14)
C290.0474 (15)0.0418 (14)0.0559 (17)−0.0045 (11)0.0113 (13)0.0020 (12)
C300.083 (2)0.084 (2)0.0484 (17)−0.0038 (16)0.0137 (15)−0.0073 (15)

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-{[4-(2-methoxyphenyl)piperazin-1-yl]methyl}-4,5-dihydro-1H-1,2,4-triazole-5-thione (II)   Geometric parameters (Å, º)

S1—C121.661 (2)C8—H8A0.98
F1—C161.364 (3)C9—H9A0.97
O1—C291.374 (3)C9—H9B0.97
O1—C301.400 (3)C10—H10A0.97
N1—C121.387 (3)C10—H10B0.97
N1—C111.390 (3)C13—C181.372 (3)
N1—C131.438 (3)C13—C141.374 (3)
N3—C121.342 (3)C14—C151.375 (4)
N3—N21.384 (3)C14—H14A0.93
N3—C191.482 (3)C15—C161.358 (4)
N2—C111.309 (3)C15—H15A0.93
N4—C191.425 (3)C16—C171.351 (4)
N4—C231.454 (3)C17—C181.377 (3)
N4—C201.461 (3)C17—H17A0.93
N5—C241.424 (3)C18—H18A0.93
N5—C211.464 (3)C19—H19A0.97
N5—C221.468 (3)C19—H19B0.97
C1—C21.528 (3)C20—C211.512 (3)
C1—C61.537 (3)C20—H20A0.97
C1—H1A0.97C20—H20B0.97
C1—H1B0.97C21—H21A0.97
C2—C31.500 (4)C21—H21B0.97
C2—C71.510 (4)C22—C231.510 (3)
C2—H2A0.98C22—H22A0.97
C3—C41.522 (4)C22—H22B0.97
C3—H3A0.97C23—H23A0.97
C3—H3B0.97C23—H23B0.97
C4—C101.511 (4)C24—C251.380 (3)
C4—C51.541 (4)C24—C291.399 (3)
C4—H4A0.98C25—C261.388 (3)
C5—C61.531 (3)C25—H25A0.93
C5—H5A0.97C26—C271.367 (4)
C5—H5B0.97C26—H26A0.93
C6—C111.507 (3)C27—C281.385 (4)
C6—C91.538 (3)C27—H27A0.93
C7—C81.509 (4)C28—C291.387 (3)
C7—H7A0.97C28—H28A0.93
C7—H7B0.97C30—H30A0.96
C8—C101.514 (4)C30—H30B0.96
C8—C91.536 (3)C30—H30C0.96
C29—O1—C30118.5 (2)N1—C11—C6127.1 (2)
C12—N1—C11108.77 (18)N3—C12—N1103.03 (19)
C12—N1—C13119.51 (19)N3—C12—S1128.71 (18)
C11—N1—C13131.62 (19)N1—C12—S1128.26 (18)
C12—N3—N2113.44 (18)C18—C13—C14120.0 (2)
C12—N3—C19125.4 (2)C18—C13—N1119.7 (2)
N2—N3—C19121.01 (19)C14—C13—N1119.8 (2)
C11—N2—N3105.01 (19)C13—C14—C15119.9 (3)
C19—N4—C23114.40 (19)C13—C14—H14A120.1
C19—N4—C20113.73 (19)C15—C14—H14A120.1
C23—N4—C20110.29 (18)C16—C15—C14118.4 (3)
C24—N5—C21116.26 (18)C16—C15—H15A120.8
C24—N5—C22113.26 (18)C14—C15—H15A120.8
C21—N5—C22109.82 (19)C17—C16—C15123.3 (3)
C2—C1—C6109.8 (2)C17—C16—F1118.6 (4)
C2—C1—H1A109.7C15—C16—F1118.0 (3)
C6—C1—H1A109.7C16—C17—C18118.0 (3)
C2—C1—H1B109.7C16—C17—H17A121
C6—C1—H1B109.7C18—C17—H17A121
H1A—C1—H1B108.2C13—C18—C17120.3 (3)
C3—C2—C7109.5 (2)C13—C18—H18A119.8
C3—C2—C1110.6 (2)C17—C18—H18A119.8
C7—C2—C1109.6 (2)N4—C19—N3115.62 (19)
C3—C2—H2A109N4—C19—H19A108.4
C7—C2—H2A109N3—C19—H19A108.4
C1—C2—H2A109N4—C19—H19B108.4
C2—C3—C4109.2 (2)N3—C19—H19B108.4
C2—C3—H3A109.8H19A—C19—H19B107.4
C4—C3—H3A109.8N4—C20—C21111.4 (2)
C2—C3—H3B109.8N4—C20—H20A109.4
C4—C3—H3B109.8C21—C20—H20A109.4
H3A—C3—H3B108.3N4—C20—H20B109.4
C10—C4—C3110.0 (2)C21—C20—H20B109.4
C10—C4—C5109.3 (2)H20A—C20—H20B108
C3—C4—C5109.2 (3)N5—C21—C20110.12 (19)
C10—C4—H4A109.4N5—C21—H21A109.6
C3—C4—H4A109.4C20—C21—H21A109.6
C5—C4—H4A109.4N5—C21—H21B109.6
C6—C5—C4110.3 (2)C20—C21—H21B109.6
C6—C5—H5A109.6H21A—C21—H21B108.2
C4—C5—H5A109.6N5—C22—C23109.88 (18)
C6—C5—H5B109.6N5—C22—H22A109.7
C4—C5—H5B109.6C23—C22—H22A109.7
H5A—C5—H5B108.1N5—C22—H22B109.7
C11—C6—C5108.80 (19)C23—C22—H22B109.7
C11—C6—C1111.76 (19)H22A—C22—H22B108.2
C5—C6—C1108.2 (2)N4—C23—C22109.52 (19)
C11—C6—C9110.99 (18)N4—C23—H23A109.8
C5—C6—C9108.4 (2)C22—C23—H23A109.8
C1—C6—C9108.60 (19)N4—C23—H23B109.8
C8—C7—C2109.8 (2)C22—C23—H23B109.8
C8—C7—H7A109.7H23A—C23—H23B108.2
C2—C7—H7A109.7C25—C24—C29117.8 (2)
C8—C7—H7B109.7C25—C24—N5123.5 (2)
C2—C7—H7B109.7C29—C24—N5118.7 (2)
H7A—C7—H7B108.2C24—C25—C26121.4 (3)
C7—C8—C10110.0 (2)C24—C25—H25A119.3
C7—C8—C9109.2 (2)C26—C25—H25A119.3
C10—C8—C9109.4 (2)C27—C26—C25120.3 (3)
C7—C8—H8A109.4C27—C26—H26A119.9
C10—C8—H8A109.4C25—C26—H26A119.9
C9—C8—H8A109.4C26—C27—C28119.5 (3)
C8—C9—C6110.0 (2)C26—C27—H27A120.2
C8—C9—H9A109.7C28—C27—H27A120.2
C6—C9—H9A109.7C27—C28—C29120.2 (3)
C8—C9—H9B109.7C27—C28—H28A119.9
C6—C9—H9B109.7C29—C28—H28A119.9
H9A—C9—H9B108.2O1—C29—C28123.7 (2)
C4—C10—C8109.2 (2)O1—C29—C24115.7 (2)
C4—C10—H10A109.8C28—C29—C24120.6 (2)
C8—C10—H10A109.8O1—C30—H30A109.5
C4—C10—H10B109.8O1—C30—H30B109.5
C8—C10—H10B109.8H30A—C30—H30B109.5
H10A—C10—H10B108.3O1—C30—H30C109.5
N2—C11—N1109.73 (19)H30A—C30—H30C109.5
N2—C11—C6123.1 (2)H30B—C30—H30C109.5
C12—N3—N2—C110.7 (2)C11—N1—C12—S1−178.65 (17)
C19—N3—N2—C11176.39 (19)C13—N1—C12—S14.6 (3)
C6—C1—C2—C3−60.5 (3)C12—N1—C13—C1888.6 (3)
C6—C1—C2—C760.3 (3)C11—N1—C13—C18−87.3 (3)
C7—C2—C3—C4−60.2 (3)C12—N1—C13—C14−83.7 (3)
C1—C2—C3—C460.6 (3)C11—N1—C13—C14100.5 (3)
C2—C3—C4—C1060.1 (3)C18—C13—C14—C15−0.7 (4)
C2—C3—C4—C5−59.9 (3)N1—C13—C14—C15171.5 (2)
C10—C4—C5—C6−60.3 (3)C13—C14—C15—C16−0.2 (4)
C3—C4—C5—C660.2 (3)C14—C15—C16—C171.5 (4)
C4—C5—C6—C11179.3 (2)C14—C15—C16—F1−176.4 (2)
C4—C5—C6—C1−59.1 (3)C15—C16—C17—C18−2.0 (4)
C4—C5—C6—C958.5 (3)F1—C16—C17—C18176.0 (2)
C2—C1—C6—C11178.4 (2)C14—C13—C18—C170.3 (4)
C2—C1—C6—C558.6 (3)N1—C13—C18—C17−172.0 (2)
C2—C1—C6—C9−58.8 (3)C16—C17—C18—C131.0 (4)
C3—C2—C7—C860.3 (3)C23—N4—C19—N375.5 (3)
C1—C2—C7—C8−61.2 (3)C20—N4—C19—N3−52.4 (3)
C2—C7—C8—C10−59.4 (3)C12—N3—C19—N4104.2 (3)
C2—C7—C8—C960.7 (3)N2—N3—C19—N4−71.0 (3)
C7—C8—C9—C6−59.9 (3)C19—N4—C20—C21−172.94 (19)
C10—C8—C9—C660.6 (3)C23—N4—C20—C2157.0 (2)
C11—C6—C9—C8−178.1 (2)C24—N5—C21—C20−172.6 (2)
C5—C6—C9—C8−58.6 (3)C22—N5—C21—C2057.1 (3)
C1—C6—C9—C858.7 (3)N4—C20—C21—N5−56.0 (3)
C3—C4—C10—C8−59.0 (3)C24—N5—C22—C23168.36 (19)
C5—C4—C10—C861.0 (3)C21—N5—C22—C23−59.8 (2)
C7—C8—C10—C458.6 (3)C19—N4—C23—C22171.58 (19)
C9—C8—C10—C4−61.4 (3)C20—N4—C23—C22−58.7 (2)
N3—N2—C11—N10.3 (2)N5—C22—C23—N460.5 (2)
N3—N2—C11—C6−177.88 (18)C21—N5—C24—C25−13.9 (3)
C12—N1—C11—N2−1.1 (2)C22—N5—C24—C25114.7 (3)
C13—N1—C11—N2175.1 (2)C21—N5—C24—C29165.9 (2)
C12—N1—C11—C6177.0 (2)C22—N5—C24—C29−65.5 (3)
C13—N1—C11—C6−6.8 (4)C29—C24—C25—C263.0 (4)
C5—C6—C11—N2−3.9 (3)N5—C24—C25—C26−177.2 (2)
C1—C6—C11—N2−123.3 (2)C24—C25—C26—C270.6 (4)
C9—C6—C11—N2115.2 (2)C25—C26—C27—C28−3.1 (4)
C5—C6—C11—N1178.3 (2)C26—C27—C28—C292.0 (4)
C1—C6—C11—N158.8 (3)C30—O1—C29—C28−2.9 (3)
C9—C6—C11—N1−62.6 (3)C30—O1—C29—C24176.8 (2)
N2—N3—C12—N1−1.3 (2)C27—C28—C29—O1−178.5 (2)
C19—N3—C12—N1−176.79 (19)C27—C28—C29—C241.7 (4)
N2—N3—C12—S1178.75 (16)C25—C24—C29—O1176.1 (2)
C19—N3—C12—S13.3 (3)N5—C24—C29—O1−3.7 (3)
C11—N1—C12—N31.4 (2)C25—C24—C29—C28−4.2 (3)
C13—N1—C12—N3−175.31 (18)N5—C24—C29—C28176.1 (2)

3-(Adamantan-1-yl)-4-(4-fluorophenyl)-1-{[4-(2-methoxyphenyl)piperazin-1-yl]methyl}-4,5-dihydro-1H-1,2,4-triazole-5-thione (II)   Hydrogen-bond geometry (Å, º)

Cg1 and Cg8 are the centroids of rings (N1–N3/C11/C12) and (C24–C29), respectively.

D—H···AD—HH···AD···AD—H···A
C21—H21A···F1i0.972.473.407 (3)162
C18—H18A···Cg1ii0.932.813.661152
C9—H9A···Cg8iii0.972.803.697155

Symmetry codes: (i) x, y−1, z; (ii) −x, −y, −z; (iii) −x+1, y−1/2, −z+1/2.

Funding Statement

This work was funded by Spanish Ministerio de Economía y Competitividad grants MINECO-13-MAT2013–40950-R, MAT2016–78155-C2–1-R, and BES-2011–046948. Gobierno del Principado de Asturias grant GRUPIN14–060. FEDER grant .

This paper was supported by the following grant(s):

Spanish Ministerio de Economía y Competitividad MINECO-13-MAT2013–40950-RMAT2016–78155-C2–1-RBES-2011–046948 to .
Gobierno del Principado de Asturias GRUPIN14–060.
FEDER .

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Articles from Acta Crystallographica Section E: Crystallographic Communications are provided here courtesy of International Union of Crystallography