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In 1-[5-(biphen­yl-2-yl)-1,3,4-thia­diazol-2-yl]methanaminium chloride, C15H14N3S+·Cl, the protonation occurs at the amine N atom. The outer phen­yl ring makes an angle of 88.0 (2)° with the plane through the inner benzene ring, and the planes of the thia­diazole ring and the attached benzene ring inter­sect at an angle of 165.5 (4)°. In addition to classical N—H...N and N—H...Cl hydrogen bonds producing chains parallel to the c axis, there are weak C—H...N and C—H...Cl hydrogen bonds. The hydrogen bonds and packing inter­actions result in hydro­philic and hydro­phobic planar areas in the crystal, perpendicular to the a axis. Stereochemical comparison with phenytoin shows that the two compounds may utilize similar mechanisms of action. 2-(Biphen­yl-4-yl)-5-[2-(1-methyl­ethyl­idene)hydrazino]-1,3,4-thia­diazole, C17H16N4S, where Z′ = 2, and the methanol solvate of its hydro­chloride salt, 5-(biphenyl-4-yl)-2-[2-(1-methyl­ethyl­idene)hydrazino]-1,3,4-thia­diazol-3-ium chloride methanol solvate, C17H17N4S+·Cl·CH3OH, adopt linear almost planar mol­ecular conformations. The para position of the outer phen­yl ring in these compounds precludes adoption of the phenytoin anticonvulsant stereochemistry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105015891/gd1394sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105015891/gd1394Isup2.hkl
Contains datablock I

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270105015891/gd1394IIsup3.hkl
Contains datablock II

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Structure factor file (CIF format) https://doi.org/10.1107/S0108270105015891/gd1394IIIsup4.hkl
Contains datablock III

CCDC references: 278558; 278559; 278560

Comment top

Pharmacological testing of a number of substituted 2-aryl-5-hydrazino-1,3,4-thiadiazoles, designed and synthesized as antihypertensives, showed them to possess anticonvulsant activity as well (Chapleo et al., 1986). Subsequently a series of aminoalkyl derivatives were synthesized in order to negate possible side effects of a free hydrazine group, and these derivatives were evaluated for anticonvulsant properties. The most promising of the series was the title compound, (I), chemically dissimilar from the well known anticonvulsants, such as carbamazepine, phenobarbital and phenytoin, but with a similar anticonvulsant profile (Stillings et al., 1986). We have elucidated the three-dimensional structure of this compound in an effort to identify structural determinants of its anticonvulsant activity and possible stereochemical correlations with other anticonvulsants. In addition, we have determined the structure of an inactive analogue in the series of 2-biphenyl-4-ylhydrazinothiadiazoles, in order to further identify conformational and stereochemical parameters responsible for activity and lack thereof. We obtained two crystalline forms of 2-biphenyl-4-yl-5-[2-(1-methylethylidene)hydrazino]-1,3,4-thiadiazole, from solutions of the hydrochloride salt, one unprotonated with two molecules in the asymmetric unit, (II), and the second, (III), as a hydrochloride containing a methanol solvent molecule.

In the active anticonvulsant compound (I) (Fig. 1), the bond distances and angles are within normal ranges. Protonation of the molecule occurs at N20 and the sum of the angles at this atom is 328.41°. The thiadiazole ring is planar. The plane of the outer phenyl ring is almost perpendicular [88.0 (2)° angle] to that of the inner phenyl ring, which, in turn, intersects the plane of the thiadiazole ring at an angle of 165.5 (4)°. N—H···Cl and N—H···N hydrogen bonds (Table 1) produce chains parallel to [001], and weak C—H···N and C—H···Cl hydrogen bonds along with van der Waals interactions contribute to the crystal packing. The molecules are packed in head-to-head and tail-to-tail fashion, creating distinct hydrophilic and hydrophobic regions running perpendicular to the unit cell a axis (Fig. 2).

The dissimilarity of the chemical structure of this molecule from any of the familiar anticonvulsant drugs has led to speculation about a different mode of action (Stillings et al., 1986). However, its comparable potency to phenytoin has led us to investigate stereochemical similarities in the two drugs. Accordingly, we have compared the two structures by a molecular superposition, which initially optimized the fit of the two carbonyl O atoms in phenytoin with atoms N4 and N20 in the title compound, and atom C5, the phenyl-substituted hydantoin C atom in phenytoin, with the thiadiazole ring S atom. Subsequently, two allowable phenyl group rotations were performed in the title compound, viz. 65° about the C7—C3 bond, followed by 80° about C8—C13. The resulting fit (Fig. 3) demonstrates that the two O and two N atoms in the molecules superpose closely, and the outer phenyl ring of the title compound is positioned very similarly to a phenytoin phenyl group. Since these features are the determinants of anticonvulsant activity in phenytoin (Camerman & Camerman, 1981) this is persuasive evidence that notwithstanding their different chemical structures, these similar stereochemical features may enable the thiadiazoles to exert their anticonvulsant activities, at least in part, through mechanisms similar to phenytoin.

In both (II) (Fig. 4) and (III) (Fig. 5), the bond distances and angles are within normal ranges. The two independent molecules in (II) are both roughly planar in overall conformation; the angles between planes of the two phenyl rings, the thiadiazole ring, and the five-membered hydrazine group are, respectively, 152.1 (2), 156.3 (2) and 170.0 (3)° for molecule A, and 143.9 (2), 178.5 (2) and 179.9 (2)° for molecule B. N—H···N hydrogen bonds (Table 2) connect the molecules, producing distinct dimers, and a weak C—H···N hydrogen bond along with van der Waals contacts contribute to the crystal packing of (II) (Fig. 6). In the crystal structure of (III), protonation occurs at the thiadiazole ring atom N4. The molecule is very nearly planar, with angles between the planes through the rings and the hydrazine group, beginning from the outer phenyl ring, of 170.6 (3), 178.7 (2) and 178.3 (2)°. The largest deviation from a plane taken through all the non-H atoms is 0.14 (1) Å for the outer phenyl ring atom C17. In addition to the hydrochloride molecule, the asymmetric unit also contains a methanol molecule, which donates a hydrogen bond to the Cl ion and accepts accepts one from the protonated atom N4 (Table 3). All intermolecular hydrogen bonding is through the Cl ion and the methanol molecule, resultng in infinite chains running parallel to the c axis. Because of the para relationship of the phenyl and thiadiazole substituents, molecular manipulations with these molecules could not give a conformation containing the stereochemical properties of the active anticonvulsants.

The structural results presented here, in addition to identifying conformational and stereochemical features in (I) that are likely to be responsible for its anticonvulsant activity, also explain other structure–activity observations in the series of thiadiazoles tested (Chapleo et al., 1986; Stillings et al., 1986). Activity is abolished (i) when the outer phenyl ring is in the para position or (ii) as the alkylamine chain length is increased; our results show (i) superposition with the phenytoin phenyl ring is then not possible and (ii) the correspondence of the N atoms with phenytoin O atoms becomes problematic.

Experimental top

After extensive experiments to find proper crystallization conditions, crystals of (I) were produced by slow evaporation from a 6:3:1 ethyl acetate–methanol–ethanol mixture at 278 K. The crystals were small colourless needles. Crystallization experiments with 2-biphenyl-4-yl-5-[2-(1-methylethylidene)hydrazino]-1,3,4-thiadiazole hydrochloride resulted in two different products. A triclinic compound, (II), was obtained by slow evaporation from a 1:1 me thanol–dimethylformamide? mixture, and a monoclinic compound, (III), by slow evaporation from a 1:1 methanol–ethyl acetate mixture, both at room temperature. However, the quality of the crystals was poor for both (II) and (III), and tweaking the crystallization conditions proved unsuccessful.

Refinement top

Although all H atoms could be located from difference maps for the compounds (I), (II) and (III), they were allowed for as riding atoms, except for two H atoms in (III). For (I), the difference map indicated clearly that the protonation occurred at N20. One overall isotropic displacement parameter was refined for N20 H atoms [Uiso(H) = 0.13 (2) Å2] and another for the rest [0.082 (9) Å2]. The range of C—H distances is 0.93–0.97 Å. For (II), one overall isotropic displacement parameter was refined for outer phenyl ring H atoms [Uiso(H) = 0.063 (4) Å2], one for the inner phenyl ring [0.084 (5) Å2], one for the methyl groups [0.130 (6) Å2] and another for the H atom at N18 [0.128 (6) Å2]. The range of C—H distances was 0.93–0.96 Å. In the case of (III), one overall isotropic displacement parameter was refined for methyl groups H atoms [Uiso(H) = 0.081 (8) Å2] and another for the rest [0.141 (14) Å2]. The range of C—H distances was 0.93–0.96 Å. Atoms H1 in the water molecule and H4 at the protonated N4 atom were refined from the difference map locations. The N4—H4 distance is 1.02 (8) and the O1—H1 distamce is 0.75 (11) Å.

Computing details top

For all compounds, data collection: Picker Operating Manual (Picker, 1967); cell refinement: Picker Operating Manual; data reduction: DATRDN The X-ray System (Stewart, 1976); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 50% probability displacement elipsoids. H atoms are drawn as small circles of arbitrary radii.
[Figure 2] Fig. 2. A stereodiagram of the molecular packing and hydrogen-bond scheme for (I). Atoms are drawn as circles of arbitrary radii and hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. A stereodiagram showing superposition of the title compound after bond rotations and phenytoin (large circles, solid bonds).
[Figure 4] Fig. 4. The molecular structure of (II), showing 50% probability displacement elipsoids. H atoms are drawn as small circles of arbitrary radii and hydrogen bonds are shown as dashed lines.
[Figure 5] Fig. 5. The molecular structure of (III), showing 50% probability displacement elipsoids. H atoms are drawn as small circles of arbitrary radii.
[Figure 6] Fig. 6. A stereodiagram of the molecular packing and hydrogen-bond sheme of (II). Atoms are drawn as circles of arbitrary radii and hydrogen bonds are shown as dashed lines.
(I) 1-[5-(biphenyl-2-yl)-1,3,4-thiadiazol-2-yl]methanaminium chloride top
Crystal data top
C15H14N3S+·ClDx = 1.355 Mg m3
Mr = 303.80Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P212121Cell parameters from 32 reflections
a = 28.882 (6) Åθ = 21–47°
b = 9.198 (2) ŵ = 3.52 mm1
c = 5.605 (1) ÅT = 294 K
V = 1489.0 (5) Å3Needle, colourless
Z = 40.39 × 0.12 × 0.08 mm
F(000) = 632
Data collection top
PICKER FACS-1 four-circle
diffractometer
1138 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.000
Ni filtered radiation monochromatorθmax = 65.0°, θmin = 3.1°
ω?/2θ scanh = 033
Absorption correction: ψ scan
(North et al., 1968)
k = 010
Tmin = 0.630, Tmax = 0.753l = 06
1515 measured reflections3 standard reflections every 100 reflections
1515 independent reflections intensity decay: 2.7%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.057 w = 1/[σ2(Fo2) + 1.4774P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.124(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.26 e Å3
1515 reflectionsΔρmin = 0.23 e Å3
185 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0016 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), number of Friedel pairs?
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.02 (5)
Crystal data top
C15H14N3S+·ClV = 1489.0 (5) Å3
Mr = 303.80Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 28.882 (6) ŵ = 3.52 mm1
b = 9.198 (2) ÅT = 294 K
c = 5.605 (1) Å0.39 × 0.12 × 0.08 mm
Data collection top
PICKER FACS-1 four-circle
diffractometer
1138 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.000
Tmin = 0.630, Tmax = 0.7533 standard reflections every 100 reflections
1515 measured reflections intensity decay: 2.7%
1515 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.124Δρmax = 0.26 e Å3
S = 1.04Δρmin = 0.23 e Å3
1515 reflectionsAbsolute structure: Flack (1983), number of Friedel pairs?
185 parametersAbsolute structure parameter: 0.02 (5)
0 restraints
Special details top

Experimental. PICKER FACS-1 mechanical limit does not allow for data collection above θ = 65°

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.81358 (6)0.13170 (18)0.6209 (3)0.0599 (5)
S20.66324 (6)0.20081 (18)0.8072 (3)0.0581 (5)
C30.65843 (19)0.3542 (6)0.6324 (12)0.0433 (14)
N40.68978 (18)0.4511 (5)0.6867 (11)0.0539 (15)
N50.71895 (18)0.4097 (6)0.8659 (12)0.0567 (15)
C60.7097 (2)0.2823 (7)0.9427 (12)0.0514 (17)
C70.6242 (2)0.3858 (6)0.4469 (12)0.0464 (16)
C80.5832 (2)0.3043 (7)0.4146 (11)0.0429 (15)
C90.5509 (2)0.3550 (8)0.2542 (13)0.063 (2)
H90.52340.30380.23610.082 (8)*
C100.5579 (3)0.4798 (8)0.1177 (17)0.082 (3)
H100.53510.51240.01340.082 (8)*
C110.5989 (3)0.5536 (8)0.1402 (17)0.080 (3)
H110.60480.63450.04550.082 (8)*
C120.6311 (3)0.5077 (7)0.3022 (14)0.065 (2)
H120.65850.55960.31680.082 (8)*
C130.5746 (2)0.1628 (7)0.5363 (12)0.0462 (17)
C140.5938 (2)0.0364 (8)0.4437 (16)0.065 (2)
H140.61230.03940.30810.082 (8)*
C150.5848 (3)0.0938 (8)0.5569 (19)0.078 (3)
H150.59730.17940.49650.082 (8)*
C160.5579 (3)0.0984 (10)0.756 (2)0.085 (3)
H160.55250.18680.83130.082 (8)*
C170.5387 (3)0.0255 (11)0.8447 (17)0.083 (3)
H170.52030.02240.98090.082 (8)*
C180.5468 (2)0.1547 (9)0.7305 (13)0.063 (2)
H180.53290.23890.78770.082 (8)*
C190.7355 (2)0.2148 (8)1.1481 (13)0.063 (2)
H19A0.72400.25391.29730.082 (8)*
H19B0.73050.11061.14870.082 (8)*
N200.78506 (17)0.2451 (5)1.1271 (10)0.0522 (14)
H20A0.79580.20680.99220.13 (2)*
H20B0.79990.20621.25060.13 (2)*
H20C0.78960.34081.12590.13 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0809 (11)0.0521 (9)0.0467 (10)0.0051 (9)0.0090 (9)0.0030 (9)
S20.0618 (10)0.0495 (10)0.0629 (12)0.0139 (9)0.0161 (10)0.0158 (10)
C30.040 (3)0.040 (3)0.050 (4)0.002 (3)0.002 (3)0.004 (3)
N40.058 (3)0.045 (3)0.059 (4)0.011 (3)0.009 (3)0.013 (3)
N50.059 (3)0.053 (3)0.058 (4)0.012 (3)0.011 (3)0.012 (3)
C60.050 (4)0.049 (4)0.055 (4)0.011 (3)0.003 (3)0.017 (4)
C70.050 (4)0.042 (3)0.047 (4)0.001 (3)0.006 (3)0.000 (3)
C80.051 (4)0.044 (3)0.033 (4)0.008 (3)0.008 (3)0.003 (3)
C90.065 (4)0.056 (4)0.069 (5)0.001 (4)0.012 (4)0.014 (4)
C100.097 (6)0.062 (5)0.087 (6)0.016 (5)0.035 (6)0.019 (6)
C110.118 (7)0.047 (4)0.076 (6)0.010 (5)0.033 (6)0.011 (5)
C120.086 (5)0.045 (4)0.064 (5)0.009 (4)0.015 (5)0.004 (4)
C130.039 (3)0.051 (4)0.048 (4)0.004 (3)0.011 (3)0.009 (3)
C140.063 (5)0.052 (4)0.081 (6)0.013 (4)0.010 (4)0.002 (4)
C150.077 (6)0.046 (5)0.112 (8)0.005 (4)0.012 (6)0.008 (5)
C160.070 (6)0.071 (6)0.114 (8)0.027 (5)0.027 (6)0.036 (6)
C170.066 (5)0.107 (7)0.075 (6)0.022 (5)0.011 (5)0.026 (6)
C180.060 (4)0.071 (5)0.058 (5)0.005 (4)0.007 (4)0.002 (4)
C190.062 (4)0.076 (5)0.050 (4)0.018 (4)0.013 (4)0.028 (4)
N200.057 (3)0.050 (3)0.049 (3)0.006 (3)0.012 (3)0.002 (3)
Geometric parameters (Å, º) top
S2—C61.715 (7)C12—H120.93
S2—C31.723 (6)C13—C181.355 (9)
C3—N41.306 (7)C13—C141.388 (9)
C3—N41.306 (7)C14—C151.380 (10)
C3—C71.464 (8)C14—H140.93
N4—N51.365 (7)C15—C161.359 (12)
N5—C61.276 (8)C15—H150.93
N5—N41.365 (7)C16—C171.362 (11)
C6—C191.505 (9)C16—H160.93
C7—C81.413 (8)C17—C181.370 (10)
C7—C121.399 (9)C17—H170.93
C8—C91.377 (9)C18—H180.93
C8—C131.490 (8)C19—N201.462 (7)
C9—C101.394 (10)C19—H19A0.97
C9—H90.93C19—H19B0.97
C10—C111.372 (10)N20—H20A0.89
C10—H100.93N20—H20B0.89
C11—C121.365 (10)N20—H20C0.89
C11—H110.93
C6—S2—C387.5 (3)C18—C13—C14119.4 (7)
N4—C3—C7119.9 (5)C18—C13—C8121.0 (6)
N4—C3—C7119.9 (5)C14—C13—C8119.6 (6)
N4—C3—S2111.7 (5)C15—C14—C13118.7 (8)
N4—C3—S2111.7 (5)C15—C14—H14120.7
C7—C3—S2128.4 (5)C13—C14—H14120.7
C3—N4—N5114.1 (5)C14—C15—C16120.8 (8)
C6—N5—N4112.0 (6)C14—C15—H15119.6
C6—N5—N4112.0 (6)C16—C15—H15119.6
N5—C6—C19122.2 (6)C15—C16—C17120.5 (8)
N5—C6—S2114.6 (5)C15—C16—H16119.8
C19—C6—S2123.1 (5)C17—C16—H16119.8
C8—C7—C12118.0 (6)C18—C17—C16119.0 (8)
C8—C7—C3123.5 (6)C18—C17—H17120.5
C12—C7—C3118.4 (6)C16—C17—H17120.5
C9—C8—C7118.1 (6)C13—C18—C17121.6 (8)
C9—C8—C13118.8 (6)C13—C18—H18119.2
C7—C8—C13123.0 (5)C17—C18—H18119.2
C8—C9—C10122.7 (7)N20—C19—C6110.2 (5)
C8—C9—H9118.7N20—C19—H19A109.6
C10—C9—H9118.7C6—C19—H19A109.6
C11—C10—C9118.8 (7)N20—C19—H19B109.6
C11—C10—H10120.6C6—C19—H19B109.6
C9—C10—H10120.6H19A—C19—H19B108.1
C10—C11—C12119.7 (7)C19—N20—H20A109.5
C10—C11—H11120.1C19—N20—H20B109.5
C12—C11—H11120.1H20A—N20—H20B109.5
C11—C12—C7122.5 (7)C19—N20—H20C109.5
C11—C12—H12118.8H20A—N20—H20C109.5
C7—C12—H12118.8H20B—N20—H20C109.5
C6—S2—C3—N40.8 (5)C3—C7—C8—C9172.0 (6)
C6—S2—C3—N40.8 (5)C12—C7—C8—C13172.3 (6)
C6—S2—C3—C7179.0 (6)C3—C7—C8—C1311.3 (10)
C7—C3—N4—N40.0 (5)C7—C8—C9—C102.3 (10)
S2—C3—N4—N40.0 (6)C13—C8—C9—C10174.5 (7)
N4—C3—N4—N50 (100)C8—C9—C10—C111.4 (12)
C7—C3—N4—N5178.6 (5)C9—C10—C11—C123.0 (13)
S2—C3—N4—N50.2 (7)C10—C11—C12—C70.8 (12)
N4—N4—N5—C60.0 (16)C8—C7—C12—C112.9 (10)
C3—N4—N5—C60.7 (8)C3—C7—C12—C11173.6 (7)
C3—N4—N5—N40 (100)C9—C8—C13—C1881.9 (8)
N4—N5—C6—C19177.1 (6)C7—C8—C13—C18101.5 (7)
N4—N5—C6—C19177.1 (6)C9—C8—C13—C1495.4 (8)
N4—N5—C6—S21.3 (8)C7—C8—C13—C1481.3 (8)
N4—N5—C6—S21.3 (8)C18—C13—C14—C151.7 (10)
C3—S2—C6—N51.2 (6)C8—C13—C14—C15179.0 (7)
C3—S2—C6—C19176.9 (6)C13—C14—C15—C160.2 (12)
N4—C3—C7—C8164.8 (6)C14—C15—C16—C171.0 (13)
N4—C3—C7—C8164.8 (6)C15—C16—C17—C180.2 (13)
S2—C3—C7—C813.3 (9)C14—C13—C18—C172.9 (10)
N4—C3—C7—C1211.6 (9)C8—C13—C18—C17179.8 (7)
N4—C3—C7—C1211.6 (9)C16—C17—C18—C132.2 (12)
S2—C3—C7—C12170.3 (5)N5—C6—C19—N2042.0 (9)
C12—C7—C8—C94.3 (9)S2—C6—C19—N20142.7 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N20—H20A···Cl10.892.253.134 (6)170
N20—H20B···Cl1i0.892.223.070 (6)160
N20—H20C···N4ii0.892.032.906 (7)167
C19—H19B···Cl1iii0.972.573.492 (7)159
Symmetry codes: (i) x, y, z+1; (ii) x+3/2, y+1, z+1/2; (iii) x+3/2, y, z+1/2.
(II) 2-(Biphenyl-4-yl)-5-[2-(1-methylethylidene)hydrazino]-1,3,4-thiadiazole top
Crystal data top
C17H16N4SZ = 4
Mr = 308.40F(000) = 648
Triclinic, P1Dx = 1.309 Mg m3
a = 7.988 (2) ÅCu Kα radiation, λ = 1.54178 Å
b = 14.150 (3) ÅCell parameters from 32 reflections
c = 14.545 (3) Åθ = 27–53°
α = 74.77 (3)°µ = 1.84 mm1
β = 89.60 (2)°T = 294 K
γ = 80.79 (2)°Needle, colourless
V = 1564.8 (7) Å30.33 × 0.04 × 0.02 mm
Data collection top
PICKER FACS-1 four-circle
diffractometer
3511 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.073
Ni filtered radiation monochromatorθmax = 65.0°, θmin = 3.2°
ω?/2θ scanh = 90
Absorption correction: ψ scan
(North et al., 1968)
k = 1616
Tmin = 0.913, Tmax = 0.961l = 1717
5739 measured reflections3 standard reflections every 100 reflections
5322 independent reflections intensity decay: 3.1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073H-atom parameters constrained
wR(F2) = 0.177 w = 1/[σ2(Fo2) + (0.0632P)2 + 1.0582P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
5322 reflectionsΔρmax = 0.31 e Å3
406 parametersΔρmin = 0.28 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0033 (3)
Crystal data top
C17H16N4Sγ = 80.79 (2)°
Mr = 308.40V = 1564.8 (7) Å3
Triclinic, P1Z = 4
a = 7.988 (2) ÅCu Kα radiation
b = 14.150 (3) ŵ = 1.84 mm1
c = 14.545 (3) ÅT = 294 K
α = 74.77 (3)°0.33 × 0.04 × 0.02 mm
β = 89.60 (2)°
Data collection top
PICKER FACS-1 four-circle
diffractometer
3511 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.073
Tmin = 0.913, Tmax = 0.9613 standard reflections every 100 reflections
5739 measured reflections intensity decay: 3.1%
5322 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0730 restraints
wR(F2) = 0.177H-atom parameters constrained
S = 1.03Δρmax = 0.31 e Å3
5322 reflectionsΔρmin = 0.28 e Å3
406 parameters
Special details top

Experimental. PICKER FACS-1 mechanical limit does not allow for data collection above θ = 65°

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S1A0.70342 (15)0.53858 (8)0.54529 (7)0.0623 (3)
C2A0.7435 (5)0.4100 (3)0.5699 (3)0.0584 (10)
N3A0.6791 (5)0.3651 (3)0.6480 (2)0.0669 (10)
N4A0.5935 (5)0.4292 (3)0.6957 (2)0.0647 (10)
C5A0.5949 (5)0.5215 (3)0.6508 (3)0.0556 (10)
C6A0.8407 (5)0.3556 (3)0.5077 (3)0.0550 (10)
C7A0.9155 (6)0.2582 (3)0.5451 (3)0.0727 (13)
H7A0.90910.22900.60990.063 (4)*
C8A0.9998 (6)0.2033 (3)0.4883 (3)0.0720 (13)
H8A1.04990.13790.51570.063 (4)*
C9A1.0110 (5)0.2438 (3)0.3909 (3)0.0553 (10)
C10A0.9384 (5)0.3415 (3)0.3545 (3)0.0582 (10)
H10A0.94620.37100.28980.063 (4)*
C11A0.8537 (5)0.3975 (3)0.4111 (3)0.0577 (10)
H11A0.80570.46340.38410.063 (4)*
C12A1.0942 (5)0.1820 (3)0.3293 (3)0.0574 (10)
C13A1.1004 (7)0.0806 (3)0.3526 (4)0.0859 (16)
H13A1.05230.04920.40840.084 (5)*
C14A1.1772 (8)0.0249 (4)0.2942 (4)0.1014 (19)
H14A1.17930.04340.31110.084 (5)*
C15A1.2494 (7)0.0682 (4)0.2129 (4)0.0840 (15)
H15A1.30150.02970.17450.084 (5)*
C16A1.2453 (6)0.1683 (3)0.1874 (3)0.0717 (12)
H16A1.29370.19860.13130.084 (5)*
C17A1.1689 (6)0.2251 (3)0.2456 (3)0.0632 (11)
H17A1.16760.29330.22820.084 (5)*
N18A0.5265 (5)0.5999 (2)0.6847 (3)0.0645 (10)
H18A0.49160.59220.74180.128 (16)*
N19A0.5170 (5)0.6924 (2)0.6213 (2)0.0634 (9)
C20A0.4472 (6)0.7672 (3)0.6490 (3)0.0648 (11)
C21A0.3744 (6)0.7648 (3)0.7436 (3)0.0738 (13)
H21A0.26540.74410.74570.130 (6)*
H21B0.36190.82990.75380.130 (6)*
H21C0.44890.71890.79260.130 (6)*
C22A0.4402 (8)0.8661 (4)0.5793 (4)0.0968 (18)
H22A0.50850.85910.52610.130 (6)*
H22B0.48270.91060.60950.130 (6)*
H22C0.32490.89230.55720.130 (6)*
S1B0.31252 (14)0.42651 (7)1.03061 (7)0.0559 (3)
C2B0.2084 (5)0.5477 (3)0.9873 (3)0.0521 (9)
N3B0.2241 (5)0.5850 (3)0.8966 (2)0.0633 (9)
N4B0.3217 (4)0.5193 (2)0.8544 (2)0.0607 (9)
C5B0.3739 (5)0.4346 (3)0.9147 (3)0.0512 (9)
C6B0.1102 (5)0.6037 (3)1.0477 (3)0.0520 (9)
C7B0.0919 (5)0.5619 (3)1.1441 (3)0.0583 (10)
H7B0.14390.49701.17200.063 (4)*
C8B0.0028 (5)0.6155 (3)1.1994 (3)0.0582 (10)
H8B0.01480.58511.26350.063 (4)*
C9B0.0797 (5)0.7127 (3)1.1617 (3)0.0545 (10)
C10B0.0599 (6)0.7540 (3)1.0647 (3)0.0617 (11)
H10B0.11110.81911.03710.063 (4)*
C11B0.0333 (6)0.7015 (3)1.0083 (3)0.0628 (11)
H11B0.04470.73160.94410.063 (4)*
C12B0.1736 (5)0.7715 (3)1.2214 (3)0.0575 (10)
C13B0.2709 (6)0.7281 (3)1.2960 (3)0.0704 (12)
H13B0.27600.66081.30870.084 (5)*
C14B0.3594 (6)0.7833 (4)1.3513 (3)0.0786 (14)
H14B0.42330.75301.40070.084 (5)*
C15B0.3536 (7)0.8819 (4)1.3338 (4)0.0827 (15)
H15B0.41570.91951.37010.084 (5)*
C16B0.2550 (8)0.9261 (4)1.2619 (4)0.0876 (16)
H16B0.24730.99301.25130.084 (5)*
C17B0.1677 (7)0.8713 (3)1.2058 (3)0.0739 (13)
H17B0.10390.90231.15660.084 (5)*
N18B0.4722 (4)0.3567 (2)0.8927 (2)0.0612 (9)
H18B0.50540.35990.83580.128 (16)*
N19B0.5159 (5)0.2723 (2)0.9661 (2)0.0623 (9)
C20B0.6075 (6)0.1977 (3)0.9470 (3)0.0657 (11)
C21B0.6716 (6)0.1926 (3)0.8515 (3)0.0753 (13)
H21D0.57920.18950.81120.130 (6)*
H21E0.75600.13440.85870.130 (6)*
H21F0.72090.25060.82340.130 (6)*
C22B0.6555 (8)0.1076 (4)1.0282 (4)0.108 (2)
H22D0.61020.12061.08580.130 (6)*
H22E0.77690.09121.03520.130 (6)*
H22F0.61020.05301.01600.130 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S1A0.0745 (8)0.0553 (6)0.0564 (6)0.0097 (5)0.0134 (5)0.0145 (5)
C2A0.061 (3)0.061 (3)0.053 (2)0.008 (2)0.003 (2)0.015 (2)
N3A0.081 (3)0.061 (2)0.054 (2)0.0020 (19)0.0140 (18)0.0135 (17)
N4A0.082 (3)0.054 (2)0.056 (2)0.0035 (18)0.0178 (18)0.0159 (16)
C5A0.062 (3)0.055 (2)0.052 (2)0.0063 (19)0.0080 (19)0.0200 (19)
C6A0.059 (2)0.055 (2)0.052 (2)0.0056 (19)0.0017 (19)0.0180 (19)
C7A0.102 (4)0.059 (3)0.045 (2)0.006 (2)0.009 (2)0.005 (2)
C8A0.098 (4)0.049 (2)0.057 (3)0.010 (2)0.001 (2)0.007 (2)
C9A0.056 (2)0.053 (2)0.054 (2)0.0066 (19)0.0028 (19)0.0110 (18)
C10A0.072 (3)0.049 (2)0.051 (2)0.007 (2)0.012 (2)0.0088 (18)
C11A0.065 (3)0.046 (2)0.057 (2)0.0042 (19)0.008 (2)0.0083 (18)
C12A0.057 (2)0.059 (3)0.055 (2)0.001 (2)0.0021 (19)0.018 (2)
C13A0.109 (4)0.058 (3)0.086 (3)0.010 (3)0.035 (3)0.012 (2)
C14A0.133 (5)0.058 (3)0.121 (5)0.016 (3)0.045 (4)0.038 (3)
C15A0.097 (4)0.075 (3)0.085 (4)0.005 (3)0.022 (3)0.036 (3)
C16A0.079 (3)0.073 (3)0.063 (3)0.002 (2)0.013 (2)0.024 (2)
C17A0.078 (3)0.050 (2)0.058 (2)0.001 (2)0.005 (2)0.0154 (19)
N18A0.082 (3)0.049 (2)0.060 (2)0.0001 (17)0.0108 (19)0.0168 (16)
N19A0.078 (2)0.0475 (19)0.064 (2)0.0066 (17)0.0111 (18)0.0157 (16)
C20A0.075 (3)0.056 (2)0.063 (3)0.008 (2)0.006 (2)0.018 (2)
C21A0.089 (3)0.067 (3)0.071 (3)0.007 (2)0.014 (3)0.031 (2)
C22A0.142 (5)0.063 (3)0.079 (3)0.007 (3)0.028 (3)0.014 (3)
S1B0.0650 (7)0.0478 (6)0.0520 (6)0.0033 (5)0.0084 (5)0.0116 (4)
C2B0.056 (2)0.050 (2)0.051 (2)0.0085 (18)0.0030 (18)0.0142 (18)
N3B0.070 (2)0.060 (2)0.057 (2)0.0016 (18)0.0088 (17)0.0176 (17)
N4B0.067 (2)0.057 (2)0.0533 (19)0.0055 (17)0.0049 (17)0.0146 (16)
C5B0.055 (2)0.043 (2)0.055 (2)0.0045 (17)0.0014 (18)0.0143 (17)
C6B0.053 (2)0.054 (2)0.052 (2)0.0108 (18)0.0037 (18)0.0183 (18)
C7B0.063 (3)0.048 (2)0.060 (3)0.0045 (19)0.005 (2)0.0130 (19)
C8B0.070 (3)0.053 (2)0.050 (2)0.007 (2)0.011 (2)0.0114 (18)
C9B0.055 (2)0.053 (2)0.056 (2)0.0099 (19)0.0049 (19)0.0164 (19)
C10B0.075 (3)0.046 (2)0.056 (2)0.005 (2)0.002 (2)0.0079 (19)
C11B0.075 (3)0.056 (2)0.053 (2)0.003 (2)0.002 (2)0.0114 (19)
C12B0.063 (3)0.051 (2)0.054 (2)0.0043 (19)0.0009 (19)0.0142 (18)
C13B0.084 (3)0.055 (3)0.074 (3)0.010 (2)0.018 (3)0.022 (2)
C14B0.088 (4)0.074 (3)0.072 (3)0.001 (3)0.018 (3)0.023 (3)
C15B0.094 (4)0.075 (3)0.074 (3)0.012 (3)0.015 (3)0.026 (3)
C16B0.125 (5)0.050 (3)0.082 (3)0.005 (3)0.016 (3)0.020 (2)
C17B0.101 (4)0.050 (2)0.063 (3)0.002 (2)0.017 (3)0.007 (2)
N18B0.073 (2)0.053 (2)0.054 (2)0.0025 (17)0.0085 (17)0.0140 (16)
N19B0.072 (2)0.052 (2)0.055 (2)0.0020 (17)0.0093 (17)0.0071 (16)
C20B0.072 (3)0.052 (2)0.068 (3)0.003 (2)0.010 (2)0.010 (2)
C21B0.082 (3)0.067 (3)0.075 (3)0.009 (2)0.007 (3)0.028 (2)
C22B0.146 (6)0.066 (3)0.090 (4)0.018 (3)0.031 (4)0.004 (3)
Geometric parameters (Å, º) top
S1A—C2A1.736 (4)C22A—H22C0.96
S1A—C5A1.737 (4)S1B—C5B1.732 (4)
C2A—N3A1.295 (5)S1B—C2B1.735 (4)
C2A—C6A1.477 (5)C2B—N3B1.300 (5)
N3A—N4A1.377 (5)C2B—C6B1.474 (5)
N4A—C5A1.299 (5)N3B—N4B1.381 (4)
N4A—N3A1.377 (5)N4B—C5B1.294 (5)
C5A—N4A1.299 (5)C5B—N18B1.356 (5)
C5A—N18A1.365 (5)C6B—C7B1.387 (5)
C6A—C7A1.379 (5)C6B—C11B1.393 (5)
C6A—C11A1.384 (5)C7B—C8B1.386 (5)
C7A—C8A1.379 (6)C7B—H7B0.93
C7A—H7A0.930C8B—C9B1.382 (5)
C8A—C9A1.390 (5)C8B—H8B0.93
C8A—H8A0.93C9B—C10B1.396 (5)
C9A—C10A1.375 (5)C9B—C12B1.476 (5)
C9A—C12A1.492 (5)C10B—C11B1.383 (5)
C10A—C11A1.388 (5)C10B—H10B0.93
C10A—H10A0.93C11B—H11B0.93
C11A—H11A0.93C12B—C17B1.379 (6)
C12A—C13A1.377 (6)C12B—C13B1.396 (6)
C12A—C17A1.387 (5)C13B—C14B1.379 (6)
C13A—C14A1.381 (7)C13B—H13B0.93
C13A—H13A0.93C14B—C15B1.359 (6)
C14A—C15A1.353 (7)C14B—H14B0.93
C14A—H14A0.93C15B—C16B1.381 (7)
C15A—C16A1.363 (6)C15B—H15B0.93
C15A—H15A0.93C16B—C17B1.380 (6)
C16A—C17A1.388 (6)C16B—H16B0.93
C16A—H16A0.93C17B—H17B0.93
C17A—H17A0.93N18B—N19B1.374 (4)
N18A—N19A1.379 (4)N18B—H18B0.86
N18A—H18A0.86N19B—C20B1.277 (5)
N19A—C20A1.276 (5)C20B—C21B1.491 (6)
C20A—C21A1.484 (6)C20B—C22B1.493 (6)
C20A—C22A1.490 (6)C21B—H21D0.96
C21A—H21A0.96C21B—H21E0.96
C21A—H21B0.96C21B—H21F0.96
C21A—H21C0.96C22B—H22D0.96
C22A—H22A0.96C22B—H22E0.96
C22A—H22B0.96C22B—H22F0.96
C2A—S1A—C5A86.24 (19)C5B—S1B—C2B86.22 (18)
N3A—C2A—C6A122.4 (4)N3B—C2B—C6B122.7 (4)
N3A—C2A—S1A114.0 (3)N3B—C2B—S1B114.1 (3)
C6A—C2A—S1A123.6 (3)C6B—C2B—S1B123.2 (3)
C2A—N3A—N4A113.3 (3)C2B—N3B—N4B112.7 (3)
C5A—N4A—N3A111.9 (3)C5B—N4B—N3B112.0 (3)
C5A—N4A—N3A111.9 (3)N4B—C5B—N18B124.5 (4)
N4A—C5A—N18A123.9 (4)N4B—C5B—S1B114.9 (3)
N4A—C5A—S1A114.6 (3)N18B—C5B—S1B120.6 (3)
N18A—C5A—S1A121.4 (3)C7B—C6B—C11B118.2 (4)
C7A—C6A—C11A118.1 (4)C7B—C6B—C2B121.9 (4)
C7A—C6A—C2A119.6 (4)C11B—C6B—C2B119.9 (4)
C11A—C6A—C2A122.3 (4)C6B—C7B—C8B121.0 (4)
C6A—C7A—C8A121.3 (4)C6B—C7B—H7B119.5
C6A—C7A—H7A119.3C8B—C7B—H7B119.5
C8A—C7A—H7A119.3C9B—C8B—C7B121.7 (4)
C7A—C8A—C9A121.2 (4)C9B—C8B—H8B119.1
C7A—C8A—H8A119.4C7B—C8B—H8B119.1
C9A—C8A—H8A119.4C8B—C9B—C10B116.7 (4)
C10A—C9A—C8A117.0 (4)C8B—C9B—C12B121.8 (4)
C10A—C9A—C12A122.3 (4)C10B—C9B—C12B121.4 (4)
C8A—C9A—C12A120.7 (4)C11B—C10B—C9B122.3 (4)
C9A—C10A—C11A122.2 (4)C11B—C10B—H10B118.8
C9A—C10A—H10A118.9C9B—C10B—H10B118.8
C11A—C10A—H10A118.9C10B—C11B—C6B120.0 (4)
C6A—C11A—C10A120.1 (4)C10B—C11B—H11B120.0
C6A—C11A—H11A119.9C6B—C11B—H11B120.0
C10A—C11A—H11A119.9C17B—C12B—C13B117.5 (4)
C13A—C12A—C17A117.3 (4)C17B—C12B—C9B121.1 (4)
C13A—C12A—C9A121.9 (4)C13B—C12B—C9B121.3 (4)
C17A—C12A—C9A120.8 (4)C14B—C13B—C12B121.2 (4)
C12A—C13A—C14A120.9 (5)C14B—C13B—H13B119.4
C12A—C13A—H13A119.6C12B—C13B—H13B119.4
C14A—C13A—H13A119.6C15B—C14B—C13B120.3 (5)
C15A—C14A—C13A121.1 (5)C15B—C14B—H14B119.9
C15A—C14A—H14A119.5C13B—C14B—H14B119.9
C13A—C14A—H14A119.5C14B—C15B—C16B119.6 (5)
C14A—C15A—C16A119.7 (5)C14B—C15B—H15B120.2
C14A—C15A—H15A120.2C16B—C15B—H15B120.2
C16A—C15A—H15A120.2C17B—C16B—C15B120.3 (5)
C15A—C16A—C17A119.8 (4)C17B—C16B—H16B119.9
C15A—C16A—H16A120.1C15B—C16B—H16B119.9
C17A—C16A—H16A120.1C12B—C17B—C16B121.1 (5)
C16A—C17A—C12A121.2 (4)C12B—C17B—H17B119.5
C16A—C17A—H17A119.4C16B—C17B—H17B119.5
C12A—C17A—H17A119.4C5B—N18B—N19B116.6 (3)
C5A—N18A—N19A115.6 (3)C5B—N18B—H18B121.7
C5A—N18A—H18A122.2N19B—N18B—H18B121.7
N19A—N18A—H18A122.2C20B—N19B—N18B117.7 (3)
C20A—N19A—N18A117.5 (4)N19B—C20B—C21B126.1 (4)
N19A—C20A—C21A126.2 (4)N19B—C20B—C22B116.6 (4)
N19A—C20A—C22A116.2 (4)C21B—C20B—C22B117.2 (4)
C21A—C20A—C22A117.6 (4)C20B—C21B—H21D109.5
C20A—C21A—H21A109.5C20B—C21B—H21E109.5
C20A—C21A—H21B109.5H21D—C21B—H21E109.5
H21A—C21A—H21B109.5C20B—C21B—H21F109.5
C20A—C21A—H21C109.5H21D—C21B—H21F109.5
H21A—C21A—H21C109.5H21E—C21B—H21F109.5
H21B—C21A—H21C109.5C20B—C22B—H22D109.5
C20A—C22A—H22A109.5C20B—C22B—H22E109.5
C20A—C22A—H22B109.5H22D—C22B—H22E109.5
H22A—C22A—H22B109.5C20B—C22B—H22F109.5
C20A—C22A—H22C109.5H22D—C22B—H22F109.5
H22A—C22A—H22C109.5H22E—C22B—H22F109.5
H22B—C22A—H22C109.5
C5A—S1A—C2A—N3A0.3 (4)C5B—S1B—C2B—N3B0.3 (3)
C5A—S1A—C2A—C6A179.7 (4)C5B—S1B—C2B—C6B179.5 (4)
C6A—C2A—N3A—N4A179.9 (4)C6B—C2B—N3B—N4B180.0 (4)
S1A—C2A—N3A—N4A0.7 (5)S1B—C2B—N3B—N4B0.2 (5)
C2A—N3A—N4A—C5A0.7 (6)C2B—N3B—N4B—C5B0.9 (5)
N3A—N4A—C5A—N18A176.7 (4)N3B—N4B—C5B—N18B179.8 (4)
N3A—N4A—C5A—S1A0.4 (5)N3B—N4B—C5B—S1B1.2 (5)
C2A—S1A—C5A—N4A0.0 (4)C2B—S1B—C5B—N4B0.8 (3)
C2A—S1A—C5A—N18A176.5 (4)C2B—S1B—C5B—N18B179.6 (4)
N3A—C2A—C6A—C7A22.5 (7)N3B—C2B—C6B—C7B178.6 (4)
S1A—C2A—C6A—C7A158.1 (4)S1B—C2B—C6B—C7B1.2 (6)
N3A—C2A—C6A—C11A154.6 (4)N3B—C2B—C6B—C11B1.7 (6)
S1A—C2A—C6A—C11A24.7 (6)S1B—C2B—C6B—C11B178.5 (3)
C11A—C6A—C7A—C8A0.7 (7)C11B—C6B—C7B—C8B1.1 (6)
C2A—C6A—C7A—C8A176.6 (5)C2B—C6B—C7B—C8B179.2 (4)
C6A—C7A—C8A—C9A0.6 (8)C6B—C7B—C8B—C9B1.3 (7)
C7A—C8A—C9A—C10A1.6 (7)C7B—C8B—C9B—C10B1.0 (6)
C7A—C8A—C9A—C12A176.6 (5)C7B—C8B—C9B—C12B177.0 (4)
C8A—C9A—C10A—C11A1.4 (7)C8B—C9B—C10B—C11B0.7 (7)
C12A—C9A—C10A—C11A176.7 (4)C12B—C9B—C10B—C11B177.3 (4)
C7A—C6A—C11A—C10A0.8 (6)C9B—C10B—C11B—C6B0.5 (7)
C2A—C6A—C11A—C10A176.3 (4)C7B—C6B—C11B—C10B0.8 (6)
C9A—C10A—C11A—C6A0.2 (7)C2B—C6B—C11B—C10B179.6 (4)
C10A—C9A—C12A—C13A151.2 (5)C8B—C9B—C12B—C17B143.0 (4)
C8A—C9A—C12A—C13A26.9 (7)C10B—C9B—C12B—C17B34.9 (6)
C10A—C9A—C12A—C17A28.8 (6)C8B—C9B—C12B—C13B36.7 (6)
C8A—C9A—C12A—C17A153.1 (4)C10B—C9B—C12B—C13B145.4 (4)
C17A—C12A—C13A—C14A0.4 (8)C17B—C12B—C13B—C14B0.8 (7)
C9A—C12A—C13A—C14A179.6 (5)C9B—C12B—C13B—C14B179.5 (4)
C12A—C13A—C14A—C15A0.4 (10)C12B—C13B—C14B—C15B0.1 (8)
C13A—C14A—C15A—C16A0.5 (10)C13B—C14B—C15B—C16B1.7 (8)
C14A—C15A—C16A—C17A0.7 (8)C14B—C15B—C16B—C17B2.4 (8)
C15A—C16A—C17A—C12A0.7 (7)C13B—C12B—C17B—C16B0.0 (7)
C13A—C12A—C17A—C16A0.6 (7)C9B—C12B—C17B—C16B179.7 (5)
C9A—C12A—C17A—C16A179.5 (4)C15B—C16B—C17B—C12B1.6 (8)
N4A—C5A—N18A—N19A170.6 (4)N4B—C5B—N18B—N19B179.9 (4)
S1A—C5A—N18A—N19A13.3 (5)S1B—C5B—N18B—N19B1.3 (5)
C5A—N18A—N19A—C20A177.1 (4)C5B—N18B—N19B—C20B179.5 (4)
N18A—N19A—C20A—C21A0.0 (7)N18B—N19B—C20B—C21B0.4 (7)
N18A—N19A—C20A—C22A179.5 (4)N18B—N19B—C20B—C22B179.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N18A—H18A···N4B0.862.263.022 (5)147
N18B—H18B···N4A0.862.182.990 (5)157
C21B—H21F···N3A0.962.633.312 (6)129
(III) 5-(biphenyl-4-yl)-2-[2-(1-methylethylidene)hydrazino]-1,3,4-thiadiazol-3-ium chloride methanol solvate top
Crystal data top
C17H17N4S+·Cl·CH4OF(000) = 792
Mr = 376.90Dx = 1.339 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
a = 7.472 (3) ÅCell parameters from 32 reflections
b = 16.437 (4) Åθ = 18–41°
c = 15.532 (2) ŵ = 2.96 mm1
β = 101.41 (2)°T = 294 K
V = 1869.9 (9) Å3Needle, colourless
Z = 40.21 × 0.05 × 0.03 mm
Data collection top
PICKER FACS-1 four-circle
diffractometer
1725 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.000
Ni filtered radiation monochromatorθmax = 65.1°, θmin = 4.0°
θ/2θ scanh = 08
Absorption correction: ψ scan
(North et al., 1968)
k = 190
Tmin = 0.835, Tmax = 0.912l = 1817
3167 measured reflections3 standard reflections every 100 reflections
3167 independent reflections intensity decay: 1.8%
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)] = 0.092Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.264H atoms treated by a mixture of independent and constrained refinement
S = 0.89 w = 1/[σ2(Fo2) + (0.1328P)2 + 4.9564P]
where P = (Fo2 + 2Fc2)/3
3167 reflections(Δ/σ)max = 0.001
237 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C17H17N4S+·Cl·CH4OV = 1869.9 (9) Å3
Mr = 376.90Z = 4
Monoclinic, P21/cCu Kα radiation
a = 7.472 (3) ŵ = 2.96 mm1
b = 16.437 (4) ÅT = 294 K
c = 15.532 (2) Å0.21 × 0.05 × 0.03 mm
β = 101.41 (2)°
Data collection top
PICKER FACS-1 four-circle
diffractometer
1725 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.000
Tmin = 0.835, Tmax = 0.9123 standard reflections every 100 reflections
3167 measured reflections intensity decay: 1.8%
3167 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0920 restraints
wR(F2) = 0.264H atoms treated by a mixture of independent and constrained refinement
S = 0.89Δρmax = 0.28 e Å3
3167 reflectionsΔρmin = 0.29 e Å3
237 parameters
Special details top

Experimental. PICKER FACS-1 mechanical limit does not allow for data collection above θ = 65°

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.5415 (3)0.64738 (12)0.18004 (13)0.0703 (7)
S10.6729 (3)0.56449 (11)0.38191 (11)0.0542 (5)
C20.7528 (9)0.5380 (4)0.4918 (4)0.0470 (16)
N30.8075 (8)0.5983 (4)0.5431 (3)0.0539 (15)
N40.7871 (9)0.6695 (4)0.4975 (4)0.0525 (15)
C50.7188 (10)0.6644 (4)0.4125 (5)0.0518 (18)
C60.7569 (10)0.4538 (4)0.5235 (4)0.0488 (17)
C70.7003 (12)0.3892 (5)0.4675 (5)0.065 (2)
H70.65950.39910.40790.081 (8)*
C80.7034 (11)0.3112 (5)0.4983 (5)0.062 (2)
H80.66350.26940.45880.081 (8)*
C90.7640 (9)0.2920 (5)0.5866 (4)0.0506 (18)
C100.8208 (13)0.3581 (5)0.6400 (5)0.074 (3)
H100.86270.34870.69960.081 (8)*
C110.8192 (13)0.4357 (5)0.6106 (5)0.077 (3)
H110.86090.47730.65000.081 (8)*
C120.7693 (9)0.2083 (4)0.6203 (4)0.0457 (16)
C130.6887 (11)0.1425 (5)0.5695 (5)0.0584 (19)
H130.62890.15190.51190.081 (8)*
C140.6954 (11)0.0650 (5)0.6019 (5)0.062 (2)
H140.64220.02280.56580.081 (8)*
C150.7799 (11)0.0485 (5)0.6872 (5)0.065 (2)
H150.78310.00420.70920.081 (8)*
C160.8590 (12)0.1116 (5)0.7390 (5)0.067 (2)
H160.91380.10150.79710.081 (8)*
C170.8590 (11)0.1899 (5)0.7064 (5)0.060 (2)
H170.91930.23090.74190.081 (8)*
N180.6907 (9)0.7266 (4)0.3581 (4)0.0580 (16)
H180.64470.72040.30320.081 (8)*
N190.7393 (8)0.8025 (4)0.3940 (4)0.0571 (16)
C200.7119 (10)0.8634 (4)0.3414 (5)0.0559 (19)
C210.6321 (12)0.8598 (5)0.2461 (5)0.074 (2)
H21A0.71800.83510.21560.141 (14)*
H21B0.60480.91390.22410.141 (14)*
H21C0.52200.82820.23690.141 (14)*
C220.7675 (13)0.9458 (5)0.3799 (6)0.080 (3)
H22A0.79800.94170.44280.141 (14)*
H22B0.66830.98330.36330.141 (14)*
H22C0.87180.96480.35820.141 (14)*
O10.8755 (10)0.7889 (4)0.6141 (4)0.0754 (19)
C10.9995 (14)0.8517 (6)0.6025 (6)0.087 (3)
H1A0.96880.90070.62990.141 (14)*
H1B0.99200.86120.54090.141 (14)*
H1C1.12160.83560.62890.141 (14)*
H40.801 (11)0.721 (5)0.535 (5)0.081 (8)*
H10.803 (17)0.806 (8)0.636 (8)0.141 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0826 (15)0.0646 (12)0.0598 (11)0.0025 (11)0.0043 (10)0.0006 (10)
S10.0677 (12)0.0514 (10)0.0423 (9)0.0022 (9)0.0080 (8)0.0009 (8)
C20.046 (4)0.058 (4)0.040 (3)0.003 (3)0.016 (3)0.011 (3)
N30.061 (4)0.057 (4)0.042 (3)0.000 (3)0.005 (3)0.008 (3)
N40.065 (4)0.053 (3)0.039 (3)0.004 (3)0.008 (3)0.003 (3)
C50.047 (4)0.054 (4)0.054 (4)0.000 (3)0.012 (3)0.003 (3)
C60.049 (4)0.044 (4)0.052 (4)0.005 (3)0.008 (3)0.004 (3)
C70.094 (7)0.053 (5)0.047 (4)0.005 (4)0.007 (4)0.004 (3)
C80.068 (6)0.054 (5)0.061 (5)0.014 (4)0.003 (4)0.007 (4)
C90.047 (4)0.063 (5)0.041 (4)0.009 (4)0.009 (3)0.004 (3)
C100.116 (8)0.057 (5)0.037 (4)0.016 (5)0.013 (4)0.004 (3)
C110.119 (8)0.057 (5)0.044 (4)0.010 (5)0.008 (4)0.000 (4)
C120.050 (4)0.040 (4)0.051 (4)0.003 (3)0.018 (3)0.002 (3)
C130.060 (5)0.061 (5)0.055 (4)0.009 (4)0.013 (4)0.005 (4)
C140.066 (5)0.051 (4)0.072 (5)0.012 (4)0.023 (4)0.004 (4)
C150.078 (6)0.056 (5)0.066 (5)0.010 (4)0.026 (4)0.003 (4)
C160.085 (6)0.063 (5)0.053 (4)0.007 (5)0.015 (4)0.017 (4)
C170.073 (6)0.058 (5)0.046 (4)0.008 (4)0.009 (4)0.001 (3)
N180.076 (5)0.052 (4)0.043 (3)0.003 (3)0.006 (3)0.004 (3)
N190.061 (4)0.053 (4)0.057 (4)0.001 (3)0.012 (3)0.001 (3)
C200.051 (5)0.050 (4)0.069 (5)0.006 (3)0.020 (4)0.007 (4)
C210.083 (6)0.072 (6)0.062 (5)0.002 (5)0.003 (4)0.012 (4)
C220.094 (7)0.057 (5)0.089 (6)0.007 (5)0.019 (5)0.009 (4)
O10.106 (6)0.060 (3)0.060 (3)0.008 (3)0.018 (3)0.008 (3)
C10.091 (7)0.087 (7)0.079 (6)0.010 (6)0.005 (5)0.004 (5)
Geometric parameters (Å, º) top
S1—C51.724 (7)C14—C151.377 (11)
S1—C21.748 (7)C14—H140.93
C2—N31.287 (8)C15—C161.372 (11)
C2—C61.467 (9)C15—H150.93
N3—N41.361 (8)C16—C171.383 (10)
N4—C51.321 (9)C16—H160.93
N4—H41.02 (8)C17—H170.93
C5—N181.316 (9)N18—N191.386 (8)
C6—C111.374 (9)N18—H180.86
C6—C71.384 (10)N19—C201.283 (9)
C7—C81.367 (10)C20—C211.484 (10)
C7—H70.93C20—C221.504 (11)
C8—C91.392 (9)C21—H21A0.96
C8—H80.93C21—H21B0.96
C9—C101.381 (10)C21—H21C0.96
C9—C121.470 (10)C22—H22A0.96
C10—C111.354 (11)C22—H22B0.96
C10—H100.9300C22—H22C0.96
C11—H110.9300O1—C11.422 (11)
C12—C131.404 (9)O1—H10.75 (11)
C12—C171.404 (9)C1—H1A0.96
C13—C141.367 (10)C1—H1B0.96
C13—H130.93C1—H1C0.96
C5—S1—C287.6 (3)C15—C14—H14119.5
N3—C2—C6122.4 (6)C16—C15—C14118.5 (7)
N3—C2—S1114.8 (5)C16—C15—H15120.7
C6—C2—S1122.9 (5)C14—C15—H15120.7
C2—N3—N4110.5 (5)C15—C16—C17121.3 (7)
C5—N4—N3116.5 (6)C15—C16—H16119.4
C5—N4—H4127 (4)C17—C16—H16119.4
N3—N4—H4116 (4)C16—C17—C12121.0 (7)
N4—C5—N18124.9 (7)C16—C17—H17119.5
N4—C5—S1110.7 (5)C12—C17—H17119.5
N18—C5—S1124.4 (6)C5—N18—N19116.5 (6)
C11—C6—C7117.0 (7)C5—N18—H18121.8
C11—C6—C2121.0 (6)N19—N18—H18121.8
C7—C6—C2122.0 (6)C20—N19—N18116.8 (6)
C6—C7—C8121.2 (7)N19—C20—C21125.9 (7)
C6—C7—H7119.4N19—C20—C22116.9 (7)
C8—C7—H7119.4C21—C20—C22117.2 (7)
C9—C8—C7122.5 (7)C20—C21—H21A109.5
C9—C8—H8118.8C20—C21—H21B109.5
C7—C8—H8118.8H21A—C21—H21B109.5
C8—C9—C10114.5 (7)C20—C21—H21C109.5
C8—C9—C12123.0 (7)H21A—C21—H21C109.5
C10—C9—C12122.5 (6)H21B—C21—H21C109.5
C11—C10—C9123.9 (7)C20—C22—H22A109.5
C11—C10—H10118.1C20—C22—H22B109.5
C9—C10—H10118.1H22A—C22—H22B109.5
C6—C11—C10121.0 (7)C20—C22—H22C109.5
C6—C11—H11119.5H22A—C22—H22C109.5
C10—C11—H11119.5H22B—C22—H22C109.5
C13—C12—C17116.1 (6)C1—O1—H1110 (10)
C13—C12—C9122.8 (6)O1—C1—H1A109.5
C17—C12—C9121.1 (6)O1—C1—H1B109.5
C14—C13—C12122.0 (7)H1A—C1—H1B109.5
C14—C13—H13119.0O1—C1—H1C109.5
C12—C13—H13119.0H1A—C1—H1C109.5
C13—C14—C15120.9 (7)H1B—C1—H1C109.5
C13—C14—H14119.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cli0.75 (13)2.32 (13)3.064 (8)169 (13)
N4—H4···O11.02 (8)1.67 (8)2.664 (9)163 (7)
N18—H18···Cl0.862.263.061 (7)155
Symmetry code: (i) x, y+3/2, z+1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC15H14N3S+·ClC17H16N4SC17H17N4S+·Cl·CH4O
Mr303.80308.40376.90
Crystal system, space groupOrthorhombic, P212121Triclinic, P1Monoclinic, P21/c
Temperature (K)294294294
a, b, c (Å)28.882 (6), 9.198 (2), 5.605 (1)7.988 (2), 14.150 (3), 14.545 (3)7.472 (3), 16.437 (4), 15.532 (2)
α, β, γ (°)90, 90, 9074.77 (3), 89.60 (2), 80.79 (2)90, 101.41 (2), 90
V3)1489.0 (5)1564.8 (7)1869.9 (9)
Z444
Radiation typeCu KαCu KαCu Kα
µ (mm1)3.521.842.96
Crystal size (mm)0.39 × 0.12 × 0.080.33 × 0.04 × 0.020.21 × 0.05 × 0.03
Data collection
DiffractometerPICKER FACS-1 four-circle
diffractometer
PICKER FACS-1 four-circle
diffractometer
PICKER FACS-1 four-circle
diffractometer
Absorption correctionψ scan
(North et al., 1968)
ψ scan
(North et al., 1968)
ψ scan
(North et al., 1968)
Tmin, Tmax0.630, 0.7530.913, 0.9610.835, 0.912
No. of measured, independent and
observed [I > 2σ(I)] reflections
1515, 1515, 1138 5739, 5322, 3511 3167, 3167, 1725
Rint0.0000.0730.000
(sin θ/λ)max1)0.5880.5880.588
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.124, 1.04 0.073, 0.177, 1.03 0.092, 0.264, 0.89
No. of reflections151553223167
No. of parameters185406237
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.26, 0.230.31, 0.280.28, 0.29
Absolute structureFlack (1983), number of Friedel pairs???
Absolute structure parameter0.02 (5)??

Computer programs: Picker Operating Manual (Picker, 1967), Picker Operating Manual, DATRDN The X-ray System (Stewart, 1976), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N20—H20A···Cl10.892.253.134 (6)170
N20—H20B···Cl1i0.892.223.070 (6)160
N20—H20C···N4ii0.892.032.906 (7)167
C19—H19B···Cl1iii0.972.573.492 (7)159
Symmetry codes: (i) x, y, z+1; (ii) x+3/2, y+1, z+1/2; (iii) x+3/2, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N18A—H18A···N4B0.862.263.022 (5)147
N18B—H18B···N4A0.862.182.990 (5)157
C21B—H21F···N3A0.962.633.312 (6)129
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cli0.75 (13)2.32 (13)3.064 (8)169 (13)
N4—H4···O11.02 (8)1.67 (8)2.664 (9)163 (7)
N18—H18···Cl0.862.26073.061 (7)155
Symmetry code: (i) x, y+3/2, z+1/2.
 

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