In 1-[5-(biphenyl-2-yl)-1,3,4-thiadiazol-2-yl]methanaminium chloride, C
15H
14N
3S
+·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, C
17H
16N
4S, 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, C
17H
17N
4S
+·Cl
−·CH
3OH, 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
CCDC references: 278558; 278559; 278560
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.
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.
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.
(I) 1-[5-(biphenyl-2-yl)-1,3,4-thiadiazol-2-yl]methanaminium chloride
top
Crystal data top
C15H14N3S+·Cl− | Dx = 1.355 Mg m−3 |
Mr = 303.80 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 32 reflections |
a = 28.882 (6) Å | θ = 21–47° |
b = 9.198 (2) Å | µ = 3.52 mm−1 |
c = 5.605 (1) Å | T = 294 K |
V = 1489.0 (5) Å3 | Needle, colourless |
Z = 4 | 0.39 × 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 tube | Rint = 0.000 |
Ni filtered radiation monochromator | θmax = 65.0°, θmin = 3.1° |
ω?/2θ scan | h = 0→33 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.630, Tmax = 0.753 | l = 0→6 |
1515 measured reflections | 3 standard reflections every 100 reflections |
1515 independent reflections | intensity decay: 2.7% |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-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 = 1.04 | Δρmax = 0.26 e Å−3 |
1515 reflections | Δρmin = −0.23 e Å−3 |
185 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0016 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), number of Friedel pairs? |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.02 (5) |
Crystal data top
C15H14N3S+·Cl− | V = 1489.0 (5) Å3 |
Mr = 303.80 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 28.882 (6) Å | µ = 3.52 mm−1 |
b = 9.198 (2) Å | T = 294 K |
c = 5.605 (1) Å | 0.39 × 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 = 0.753 | 3 standard reflections every 100 reflections |
1515 measured reflections | intensity decay: 2.7% |
1515 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | H-atom parameters constrained |
wR(F2) = 0.124 | Δρmax = 0.26 e Å−3 |
S = 1.04 | Δρmin = −0.23 e Å−3 |
1515 reflections | Absolute structure: Flack (1983), number of Friedel pairs? |
185 parameters | Absolute 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 | x | y | z | Uiso*/Ueq | |
Cl1 | 0.81358 (6) | 0.13170 (18) | 0.6209 (3) | 0.0599 (5) | |
S2 | 0.66324 (6) | 0.20081 (18) | 0.8072 (3) | 0.0581 (5) | |
C3 | 0.65843 (19) | 0.3542 (6) | 0.6324 (12) | 0.0433 (14) | |
N4 | 0.68978 (18) | 0.4511 (5) | 0.6867 (11) | 0.0539 (15) | |
N5 | 0.71895 (18) | 0.4097 (6) | 0.8659 (12) | 0.0567 (15) | |
C6 | 0.7097 (2) | 0.2823 (7) | 0.9427 (12) | 0.0514 (17) | |
C7 | 0.6242 (2) | 0.3858 (6) | 0.4469 (12) | 0.0464 (16) | |
C8 | 0.5832 (2) | 0.3043 (7) | 0.4146 (11) | 0.0429 (15) | |
C9 | 0.5509 (2) | 0.3550 (8) | 0.2542 (13) | 0.063 (2) | |
H9 | 0.5234 | 0.3038 | 0.2361 | 0.082 (8)* | |
C10 | 0.5579 (3) | 0.4798 (8) | 0.1177 (17) | 0.082 (3) | |
H10 | 0.5351 | 0.5124 | 0.0134 | 0.082 (8)* | |
C11 | 0.5989 (3) | 0.5536 (8) | 0.1402 (17) | 0.080 (3) | |
H11 | 0.6048 | 0.6345 | 0.0455 | 0.082 (8)* | |
C12 | 0.6311 (3) | 0.5077 (7) | 0.3022 (14) | 0.065 (2) | |
H12 | 0.6585 | 0.5596 | 0.3168 | 0.082 (8)* | |
C13 | 0.5746 (2) | 0.1628 (7) | 0.5363 (12) | 0.0462 (17) | |
C14 | 0.5938 (2) | 0.0364 (8) | 0.4437 (16) | 0.065 (2) | |
H14 | 0.6123 | 0.0394 | 0.3081 | 0.082 (8)* | |
C15 | 0.5848 (3) | −0.0938 (8) | 0.5569 (19) | 0.078 (3) | |
H15 | 0.5973 | −0.1794 | 0.4965 | 0.082 (8)* | |
C16 | 0.5579 (3) | −0.0984 (10) | 0.756 (2) | 0.085 (3) | |
H16 | 0.5525 | −0.1868 | 0.8313 | 0.082 (8)* | |
C17 | 0.5387 (3) | 0.0255 (11) | 0.8447 (17) | 0.083 (3) | |
H17 | 0.5203 | 0.0224 | 0.9809 | 0.082 (8)* | |
C18 | 0.5468 (2) | 0.1547 (9) | 0.7305 (13) | 0.063 (2) | |
H18 | 0.5329 | 0.2389 | 0.7877 | 0.082 (8)* | |
C19 | 0.7355 (2) | 0.2148 (8) | 1.1481 (13) | 0.063 (2) | |
H19A | 0.7240 | 0.2539 | 1.2973 | 0.082 (8)* | |
H19B | 0.7305 | 0.1106 | 1.1487 | 0.082 (8)* | |
N20 | 0.78506 (17) | 0.2451 (5) | 1.1271 (10) | 0.0522 (14) | |
H20A | 0.7958 | 0.2068 | 0.9922 | 0.13 (2)* | |
H20B | 0.7999 | 0.2062 | 1.2506 | 0.13 (2)* | |
H20C | 0.7896 | 0.3408 | 1.1259 | 0.13 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0809 (11) | 0.0521 (9) | 0.0467 (10) | 0.0051 (9) | −0.0090 (9) | −0.0030 (9) |
S2 | 0.0618 (10) | 0.0495 (10) | 0.0629 (12) | −0.0139 (9) | −0.0161 (10) | 0.0158 (10) |
C3 | 0.040 (3) | 0.040 (3) | 0.050 (4) | 0.002 (3) | 0.002 (3) | 0.004 (3) |
N4 | 0.058 (3) | 0.045 (3) | 0.059 (4) | −0.011 (3) | −0.009 (3) | 0.013 (3) |
N5 | 0.059 (3) | 0.053 (3) | 0.058 (4) | −0.012 (3) | −0.011 (3) | 0.012 (3) |
C6 | 0.050 (4) | 0.049 (4) | 0.055 (4) | −0.011 (3) | 0.003 (3) | 0.017 (4) |
C7 | 0.050 (4) | 0.042 (3) | 0.047 (4) | 0.001 (3) | −0.006 (3) | 0.000 (3) |
C8 | 0.051 (4) | 0.044 (3) | 0.033 (4) | 0.008 (3) | −0.008 (3) | −0.003 (3) |
C9 | 0.065 (4) | 0.056 (4) | 0.069 (5) | 0.001 (4) | −0.012 (4) | −0.014 (4) |
C10 | 0.097 (6) | 0.062 (5) | 0.087 (6) | 0.016 (5) | −0.035 (6) | 0.019 (6) |
C11 | 0.118 (7) | 0.047 (4) | 0.076 (6) | 0.010 (5) | −0.033 (6) | 0.011 (5) |
C12 | 0.086 (5) | 0.045 (4) | 0.064 (5) | −0.009 (4) | −0.015 (5) | 0.004 (4) |
C13 | 0.039 (3) | 0.051 (4) | 0.048 (4) | −0.004 (3) | −0.011 (3) | −0.009 (3) |
C14 | 0.063 (5) | 0.052 (4) | 0.081 (6) | 0.013 (4) | −0.010 (4) | −0.002 (4) |
C15 | 0.077 (6) | 0.046 (5) | 0.112 (8) | 0.005 (4) | −0.012 (6) | −0.008 (5) |
C16 | 0.070 (6) | 0.071 (6) | 0.114 (8) | −0.027 (5) | −0.027 (6) | 0.036 (6) |
C17 | 0.066 (5) | 0.107 (7) | 0.075 (6) | −0.022 (5) | 0.011 (5) | 0.026 (6) |
C18 | 0.060 (4) | 0.071 (5) | 0.058 (5) | −0.005 (4) | 0.007 (4) | −0.002 (4) |
C19 | 0.062 (4) | 0.076 (5) | 0.050 (4) | −0.018 (4) | −0.013 (4) | 0.028 (4) |
N20 | 0.057 (3) | 0.050 (3) | 0.049 (3) | −0.006 (3) | −0.012 (3) | 0.002 (3) |
Geometric parameters (Å, º) top
S2—C6 | 1.715 (7) | C12—H12 | 0.93 |
S2—C3 | 1.723 (6) | C13—C18 | 1.355 (9) |
C3—N4 | 1.306 (7) | C13—C14 | 1.388 (9) |
C3—N4 | 1.306 (7) | C14—C15 | 1.380 (10) |
C3—C7 | 1.464 (8) | C14—H14 | 0.93 |
N4—N5 | 1.365 (7) | C15—C16 | 1.359 (12) |
N5—C6 | 1.276 (8) | C15—H15 | 0.93 |
N5—N4 | 1.365 (7) | C16—C17 | 1.362 (11) |
C6—C19 | 1.505 (9) | C16—H16 | 0.93 |
C7—C8 | 1.413 (8) | C17—C18 | 1.370 (10) |
C7—C12 | 1.399 (9) | C17—H17 | 0.93 |
C8—C9 | 1.377 (9) | C18—H18 | 0.93 |
C8—C13 | 1.490 (8) | C19—N20 | 1.462 (7) |
C9—C10 | 1.394 (10) | C19—H19A | 0.97 |
C9—H9 | 0.93 | C19—H19B | 0.97 |
C10—C11 | 1.372 (10) | N20—H20A | 0.89 |
C10—H10 | 0.93 | N20—H20B | 0.89 |
C11—C12 | 1.365 (10) | N20—H20C | 0.89 |
C11—H11 | 0.93 | | |
| | | |
C6—S2—C3 | 87.5 (3) | C18—C13—C14 | 119.4 (7) |
N4—C3—C7 | 119.9 (5) | C18—C13—C8 | 121.0 (6) |
N4—C3—C7 | 119.9 (5) | C14—C13—C8 | 119.6 (6) |
N4—C3—S2 | 111.7 (5) | C15—C14—C13 | 118.7 (8) |
N4—C3—S2 | 111.7 (5) | C15—C14—H14 | 120.7 |
C7—C3—S2 | 128.4 (5) | C13—C14—H14 | 120.7 |
C3—N4—N5 | 114.1 (5) | C14—C15—C16 | 120.8 (8) |
C6—N5—N4 | 112.0 (6) | C14—C15—H15 | 119.6 |
C6—N5—N4 | 112.0 (6) | C16—C15—H15 | 119.6 |
N5—C6—C19 | 122.2 (6) | C15—C16—C17 | 120.5 (8) |
N5—C6—S2 | 114.6 (5) | C15—C16—H16 | 119.8 |
C19—C6—S2 | 123.1 (5) | C17—C16—H16 | 119.8 |
C8—C7—C12 | 118.0 (6) | C18—C17—C16 | 119.0 (8) |
C8—C7—C3 | 123.5 (6) | C18—C17—H17 | 120.5 |
C12—C7—C3 | 118.4 (6) | C16—C17—H17 | 120.5 |
C9—C8—C7 | 118.1 (6) | C13—C18—C17 | 121.6 (8) |
C9—C8—C13 | 118.8 (6) | C13—C18—H18 | 119.2 |
C7—C8—C13 | 123.0 (5) | C17—C18—H18 | 119.2 |
C8—C9—C10 | 122.7 (7) | N20—C19—C6 | 110.2 (5) |
C8—C9—H9 | 118.7 | N20—C19—H19A | 109.6 |
C10—C9—H9 | 118.7 | C6—C19—H19A | 109.6 |
C11—C10—C9 | 118.8 (7) | N20—C19—H19B | 109.6 |
C11—C10—H10 | 120.6 | C6—C19—H19B | 109.6 |
C9—C10—H10 | 120.6 | H19A—C19—H19B | 108.1 |
C10—C11—C12 | 119.7 (7) | C19—N20—H20A | 109.5 |
C10—C11—H11 | 120.1 | C19—N20—H20B | 109.5 |
C12—C11—H11 | 120.1 | H20A—N20—H20B | 109.5 |
C11—C12—C7 | 122.5 (7) | C19—N20—H20C | 109.5 |
C11—C12—H12 | 118.8 | H20A—N20—H20C | 109.5 |
C7—C12—H12 | 118.8 | H20B—N20—H20C | 109.5 |
| | | |
C6—S2—C3—N4 | −0.8 (5) | C3—C7—C8—C9 | 172.0 (6) |
C6—S2—C3—N4 | −0.8 (5) | C12—C7—C8—C13 | 172.3 (6) |
C6—S2—C3—C7 | −179.0 (6) | C3—C7—C8—C13 | −11.3 (10) |
C7—C3—N4—N4 | 0.0 (5) | C7—C8—C9—C10 | 2.3 (10) |
S2—C3—N4—N4 | 0.0 (6) | C13—C8—C9—C10 | −174.5 (7) |
N4—C3—N4—N5 | 0 (100) | C8—C9—C10—C11 | 1.4 (12) |
C7—C3—N4—N5 | 178.6 (5) | C9—C10—C11—C12 | −3.0 (13) |
S2—C3—N4—N5 | 0.2 (7) | C10—C11—C12—C7 | 0.8 (12) |
N4—N4—N5—C6 | 0.0 (16) | C8—C7—C12—C11 | 2.9 (10) |
C3—N4—N5—C6 | 0.7 (8) | C3—C7—C12—C11 | −173.6 (7) |
C3—N4—N5—N4 | 0 (100) | C9—C8—C13—C18 | −81.9 (8) |
N4—N5—C6—C19 | −177.1 (6) | C7—C8—C13—C18 | 101.5 (7) |
N4—N5—C6—C19 | −177.1 (6) | C9—C8—C13—C14 | 95.4 (8) |
N4—N5—C6—S2 | −1.3 (8) | C7—C8—C13—C14 | −81.3 (8) |
N4—N5—C6—S2 | −1.3 (8) | C18—C13—C14—C15 | −1.7 (10) |
C3—S2—C6—N5 | 1.2 (6) | C8—C13—C14—C15 | −179.0 (7) |
C3—S2—C6—C19 | 176.9 (6) | C13—C14—C15—C16 | −0.2 (12) |
N4—C3—C7—C8 | −164.8 (6) | C14—C15—C16—C17 | 1.0 (13) |
N4—C3—C7—C8 | −164.8 (6) | C15—C16—C17—C18 | 0.2 (13) |
S2—C3—C7—C8 | 13.3 (9) | C14—C13—C18—C17 | 2.9 (10) |
N4—C3—C7—C12 | 11.6 (9) | C8—C13—C18—C17 | −179.8 (7) |
N4—C3—C7—C12 | 11.6 (9) | C16—C17—C18—C13 | −2.2 (12) |
S2—C3—C7—C12 | −170.3 (5) | N5—C6—C19—N20 | −42.0 (9) |
C12—C7—C8—C9 | −4.3 (9) | S2—C6—C19—N20 | 142.7 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N20—H20A···Cl1 | 0.89 | 2.25 | 3.134 (6) | 170 |
N20—H20B···Cl1i | 0.89 | 2.22 | 3.070 (6) | 160 |
N20—H20C···N4ii | 0.89 | 2.03 | 2.906 (7) | 167 |
C19—H19B···Cl1iii | 0.97 | 2.57 | 3.492 (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
C17H16N4S | Z = 4 |
Mr = 308.40 | F(000) = 648 |
Triclinic, P1 | Dx = 1.309 Mg m−3 |
a = 7.988 (2) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 14.150 (3) Å | Cell parameters from 32 reflections |
c = 14.545 (3) Å | θ = 27–53° |
α = 74.77 (3)° | µ = 1.84 mm−1 |
β = 89.60 (2)° | T = 294 K |
γ = 80.79 (2)° | Needle, colourless |
V = 1564.8 (7) Å3 | 0.33 × 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 tube | Rint = 0.073 |
Ni filtered radiation monochromator | θmax = 65.0°, θmin = 3.2° |
ω?/2θ scan | h = −9→0 |
Absorption correction: ψ scan (North et al., 1968) | k = −16→16 |
Tmin = 0.913, Tmax = 0.961 | l = −17→17 |
5739 measured reflections | 3 standard reflections every 100 reflections |
5322 independent reflections | intensity decay: 3.1% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.073 | H-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 reflections | Δρmax = 0.31 e Å−3 |
406 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0033 (3) |
Crystal data top
C17H16N4S | γ = 80.79 (2)° |
Mr = 308.40 | V = 1564.8 (7) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.988 (2) Å | Cu Kα radiation |
b = 14.150 (3) Å | µ = 1.84 mm−1 |
c = 14.545 (3) Å | T = 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 = 0.961 | 3 standard reflections every 100 reflections |
5739 measured reflections | intensity decay: 3.1% |
5322 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.073 | 0 restraints |
wR(F2) = 0.177 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.31 e Å−3 |
5322 reflections | Δρmin = −0.28 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
S1A | 0.70342 (15) | 0.53858 (8) | 0.54529 (7) | 0.0623 (3) | |
C2A | 0.7435 (5) | 0.4100 (3) | 0.5699 (3) | 0.0584 (10) | |
N3A | 0.6791 (5) | 0.3651 (3) | 0.6480 (2) | 0.0669 (10) | |
N4A | 0.5935 (5) | 0.4292 (3) | 0.6957 (2) | 0.0647 (10) | |
C5A | 0.5949 (5) | 0.5215 (3) | 0.6508 (3) | 0.0556 (10) | |
C6A | 0.8407 (5) | 0.3556 (3) | 0.5077 (3) | 0.0550 (10) | |
C7A | 0.9155 (6) | 0.2582 (3) | 0.5451 (3) | 0.0727 (13) | |
H7A | 0.9091 | 0.2290 | 0.6099 | 0.063 (4)* | |
C8A | 0.9998 (6) | 0.2033 (3) | 0.4883 (3) | 0.0720 (13) | |
H8A | 1.0499 | 0.1379 | 0.5157 | 0.063 (4)* | |
C9A | 1.0110 (5) | 0.2438 (3) | 0.3909 (3) | 0.0553 (10) | |
C10A | 0.9384 (5) | 0.3415 (3) | 0.3545 (3) | 0.0582 (10) | |
H10A | 0.9462 | 0.3710 | 0.2898 | 0.063 (4)* | |
C11A | 0.8537 (5) | 0.3975 (3) | 0.4111 (3) | 0.0577 (10) | |
H11A | 0.8057 | 0.4634 | 0.3841 | 0.063 (4)* | |
C12A | 1.0942 (5) | 0.1820 (3) | 0.3293 (3) | 0.0574 (10) | |
C13A | 1.1004 (7) | 0.0806 (3) | 0.3526 (4) | 0.0859 (16) | |
H13A | 1.0523 | 0.0492 | 0.4084 | 0.084 (5)* | |
C14A | 1.1772 (8) | 0.0249 (4) | 0.2942 (4) | 0.1014 (19) | |
H14A | 1.1793 | −0.0434 | 0.3111 | 0.084 (5)* | |
C15A | 1.2494 (7) | 0.0682 (4) | 0.2129 (4) | 0.0840 (15) | |
H15A | 1.3015 | 0.0297 | 0.1745 | 0.084 (5)* | |
C16A | 1.2453 (6) | 0.1683 (3) | 0.1874 (3) | 0.0717 (12) | |
H16A | 1.2937 | 0.1986 | 0.1313 | 0.084 (5)* | |
C17A | 1.1689 (6) | 0.2251 (3) | 0.2456 (3) | 0.0632 (11) | |
H17A | 1.1676 | 0.2933 | 0.2282 | 0.084 (5)* | |
N18A | 0.5265 (5) | 0.5999 (2) | 0.6847 (3) | 0.0645 (10) | |
H18A | 0.4916 | 0.5922 | 0.7418 | 0.128 (16)* | |
N19A | 0.5170 (5) | 0.6924 (2) | 0.6213 (2) | 0.0634 (9) | |
C20A | 0.4472 (6) | 0.7672 (3) | 0.6490 (3) | 0.0648 (11) | |
C21A | 0.3744 (6) | 0.7648 (3) | 0.7436 (3) | 0.0738 (13) | |
H21A | 0.2654 | 0.7441 | 0.7457 | 0.130 (6)* | |
H21B | 0.3619 | 0.8299 | 0.7538 | 0.130 (6)* | |
H21C | 0.4489 | 0.7189 | 0.7926 | 0.130 (6)* | |
C22A | 0.4402 (8) | 0.8661 (4) | 0.5793 (4) | 0.0968 (18) | |
H22A | 0.5085 | 0.8591 | 0.5261 | 0.130 (6)* | |
H22B | 0.4827 | 0.9106 | 0.6095 | 0.130 (6)* | |
H22C | 0.3249 | 0.8923 | 0.5572 | 0.130 (6)* | |
S1B | 0.31252 (14) | 0.42651 (7) | 1.03061 (7) | 0.0559 (3) | |
C2B | 0.2084 (5) | 0.5477 (3) | 0.9873 (3) | 0.0521 (9) | |
N3B | 0.2241 (5) | 0.5850 (3) | 0.8966 (2) | 0.0633 (9) | |
N4B | 0.3217 (4) | 0.5193 (2) | 0.8544 (2) | 0.0607 (9) | |
C5B | 0.3739 (5) | 0.4346 (3) | 0.9147 (3) | 0.0512 (9) | |
C6B | 0.1102 (5) | 0.6037 (3) | 1.0477 (3) | 0.0520 (9) | |
C7B | 0.0919 (5) | 0.5619 (3) | 1.1441 (3) | 0.0583 (10) | |
H7B | 0.1439 | 0.4970 | 1.1720 | 0.063 (4)* | |
C8B | −0.0028 (5) | 0.6155 (3) | 1.1994 (3) | 0.0582 (10) | |
H8B | −0.0148 | 0.5851 | 1.2635 | 0.063 (4)* | |
C9B | −0.0797 (5) | 0.7127 (3) | 1.1617 (3) | 0.0545 (10) | |
C10B | −0.0599 (6) | 0.7540 (3) | 1.0647 (3) | 0.0617 (11) | |
H10B | −0.1111 | 0.8191 | 1.0371 | 0.063 (4)* | |
C11B | 0.0333 (6) | 0.7015 (3) | 1.0083 (3) | 0.0628 (11) | |
H11B | 0.0447 | 0.7316 | 0.9441 | 0.063 (4)* | |
C12B | −0.1736 (5) | 0.7715 (3) | 1.2214 (3) | 0.0575 (10) | |
C13B | −0.2709 (6) | 0.7281 (3) | 1.2960 (3) | 0.0704 (12) | |
H13B | −0.2760 | 0.6608 | 1.3087 | 0.084 (5)* | |
C14B | −0.3594 (6) | 0.7833 (4) | 1.3513 (3) | 0.0786 (14) | |
H14B | −0.4233 | 0.7530 | 1.4007 | 0.084 (5)* | |
C15B | −0.3536 (7) | 0.8819 (4) | 1.3338 (4) | 0.0827 (15) | |
H15B | −0.4157 | 0.9195 | 1.3701 | 0.084 (5)* | |
C16B | −0.2550 (8) | 0.9261 (4) | 1.2619 (4) | 0.0876 (16) | |
H16B | −0.2473 | 0.9930 | 1.2513 | 0.084 (5)* | |
C17B | −0.1677 (7) | 0.8713 (3) | 1.2058 (3) | 0.0739 (13) | |
H17B | −0.1039 | 0.9023 | 1.1566 | 0.084 (5)* | |
N18B | 0.4722 (4) | 0.3567 (2) | 0.8927 (2) | 0.0612 (9) | |
H18B | 0.5054 | 0.3599 | 0.8358 | 0.128 (16)* | |
N19B | 0.5159 (5) | 0.2723 (2) | 0.9661 (2) | 0.0623 (9) | |
C20B | 0.6075 (6) | 0.1977 (3) | 0.9470 (3) | 0.0657 (11) | |
C21B | 0.6716 (6) | 0.1926 (3) | 0.8515 (3) | 0.0753 (13) | |
H21D | 0.5792 | 0.1895 | 0.8112 | 0.130 (6)* | |
H21E | 0.7560 | 0.1344 | 0.8587 | 0.130 (6)* | |
H21F | 0.7209 | 0.2506 | 0.8234 | 0.130 (6)* | |
C22B | 0.6555 (8) | 0.1076 (4) | 1.0282 (4) | 0.108 (2) | |
H22D | 0.6102 | 0.1206 | 1.0858 | 0.130 (6)* | |
H22E | 0.7769 | 0.0912 | 1.0352 | 0.130 (6)* | |
H22F | 0.6102 | 0.0530 | 1.0160 | 0.130 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1A | 0.0745 (8) | 0.0553 (6) | 0.0564 (6) | −0.0097 (5) | 0.0134 (5) | −0.0145 (5) |
C2A | 0.061 (3) | 0.061 (3) | 0.053 (2) | −0.008 (2) | 0.003 (2) | −0.015 (2) |
N3A | 0.081 (3) | 0.061 (2) | 0.054 (2) | −0.0020 (19) | 0.0140 (18) | −0.0135 (17) |
N4A | 0.082 (3) | 0.054 (2) | 0.056 (2) | −0.0035 (18) | 0.0178 (18) | −0.0159 (16) |
C5A | 0.062 (3) | 0.055 (2) | 0.052 (2) | −0.0063 (19) | 0.0080 (19) | −0.0200 (19) |
C6A | 0.059 (2) | 0.055 (2) | 0.052 (2) | −0.0056 (19) | 0.0017 (19) | −0.0180 (19) |
C7A | 0.102 (4) | 0.059 (3) | 0.045 (2) | 0.006 (2) | 0.009 (2) | −0.005 (2) |
C8A | 0.098 (4) | 0.049 (2) | 0.057 (3) | 0.010 (2) | −0.001 (2) | −0.007 (2) |
C9A | 0.056 (2) | 0.053 (2) | 0.054 (2) | −0.0066 (19) | 0.0028 (19) | −0.0110 (18) |
C10A | 0.072 (3) | 0.049 (2) | 0.051 (2) | −0.007 (2) | 0.012 (2) | −0.0088 (18) |
C11A | 0.065 (3) | 0.046 (2) | 0.057 (2) | −0.0042 (19) | 0.008 (2) | −0.0083 (18) |
C12A | 0.057 (2) | 0.059 (3) | 0.055 (2) | −0.001 (2) | 0.0021 (19) | −0.018 (2) |
C13A | 0.109 (4) | 0.058 (3) | 0.086 (3) | −0.010 (3) | 0.035 (3) | −0.012 (2) |
C14A | 0.133 (5) | 0.058 (3) | 0.121 (5) | −0.016 (3) | 0.045 (4) | −0.038 (3) |
C15A | 0.097 (4) | 0.075 (3) | 0.085 (4) | −0.005 (3) | 0.022 (3) | −0.036 (3) |
C16A | 0.079 (3) | 0.073 (3) | 0.063 (3) | −0.002 (2) | 0.013 (2) | −0.024 (2) |
C17A | 0.078 (3) | 0.050 (2) | 0.058 (2) | 0.001 (2) | 0.005 (2) | −0.0154 (19) |
N18A | 0.082 (3) | 0.049 (2) | 0.060 (2) | −0.0001 (17) | 0.0108 (19) | −0.0168 (16) |
N19A | 0.078 (2) | 0.0475 (19) | 0.064 (2) | −0.0066 (17) | 0.0111 (18) | −0.0157 (16) |
C20A | 0.075 (3) | 0.056 (2) | 0.063 (3) | −0.008 (2) | 0.006 (2) | −0.018 (2) |
C21A | 0.089 (3) | 0.067 (3) | 0.071 (3) | −0.007 (2) | 0.014 (3) | −0.031 (2) |
C22A | 0.142 (5) | 0.063 (3) | 0.079 (3) | −0.007 (3) | 0.028 (3) | −0.014 (3) |
S1B | 0.0650 (7) | 0.0478 (6) | 0.0520 (6) | −0.0033 (5) | 0.0084 (5) | −0.0116 (4) |
C2B | 0.056 (2) | 0.050 (2) | 0.051 (2) | −0.0085 (18) | 0.0030 (18) | −0.0142 (18) |
N3B | 0.070 (2) | 0.060 (2) | 0.057 (2) | −0.0016 (18) | 0.0088 (17) | −0.0176 (17) |
N4B | 0.067 (2) | 0.057 (2) | 0.0533 (19) | 0.0055 (17) | 0.0049 (17) | −0.0146 (16) |
C5B | 0.055 (2) | 0.043 (2) | 0.055 (2) | −0.0045 (17) | 0.0014 (18) | −0.0143 (17) |
C6B | 0.053 (2) | 0.054 (2) | 0.052 (2) | −0.0108 (18) | 0.0037 (18) | −0.0183 (18) |
C7B | 0.063 (3) | 0.048 (2) | 0.060 (3) | −0.0045 (19) | 0.005 (2) | −0.0130 (19) |
C8B | 0.070 (3) | 0.053 (2) | 0.050 (2) | −0.007 (2) | 0.011 (2) | −0.0114 (18) |
C9B | 0.055 (2) | 0.053 (2) | 0.056 (2) | −0.0099 (19) | 0.0049 (19) | −0.0164 (19) |
C10B | 0.075 (3) | 0.046 (2) | 0.056 (2) | 0.005 (2) | 0.002 (2) | −0.0079 (19) |
C11B | 0.075 (3) | 0.056 (2) | 0.053 (2) | −0.003 (2) | 0.002 (2) | −0.0114 (19) |
C12B | 0.063 (3) | 0.051 (2) | 0.054 (2) | 0.0043 (19) | 0.0009 (19) | −0.0142 (18) |
C13B | 0.084 (3) | 0.055 (3) | 0.074 (3) | −0.010 (2) | 0.018 (3) | −0.022 (2) |
C14B | 0.088 (4) | 0.074 (3) | 0.072 (3) | −0.001 (3) | 0.018 (3) | −0.023 (3) |
C15B | 0.094 (4) | 0.075 (3) | 0.074 (3) | 0.012 (3) | 0.015 (3) | −0.026 (3) |
C16B | 0.125 (5) | 0.050 (3) | 0.082 (3) | 0.005 (3) | 0.016 (3) | −0.020 (2) |
C17B | 0.101 (4) | 0.050 (2) | 0.063 (3) | −0.002 (2) | 0.017 (3) | −0.007 (2) |
N18B | 0.073 (2) | 0.053 (2) | 0.054 (2) | 0.0025 (17) | 0.0085 (17) | −0.0140 (16) |
N19B | 0.072 (2) | 0.052 (2) | 0.055 (2) | 0.0020 (17) | 0.0093 (17) | −0.0071 (16) |
C20B | 0.072 (3) | 0.052 (2) | 0.068 (3) | −0.003 (2) | 0.010 (2) | −0.010 (2) |
C21B | 0.082 (3) | 0.067 (3) | 0.075 (3) | 0.009 (2) | 0.007 (3) | −0.028 (2) |
C22B | 0.146 (6) | 0.066 (3) | 0.090 (4) | 0.018 (3) | 0.031 (4) | −0.004 (3) |
Geometric parameters (Å, º) top
S1A—C2A | 1.736 (4) | C22A—H22C | 0.96 |
S1A—C5A | 1.737 (4) | S1B—C5B | 1.732 (4) |
C2A—N3A | 1.295 (5) | S1B—C2B | 1.735 (4) |
C2A—C6A | 1.477 (5) | C2B—N3B | 1.300 (5) |
N3A—N4A | 1.377 (5) | C2B—C6B | 1.474 (5) |
N4A—C5A | 1.299 (5) | N3B—N4B | 1.381 (4) |
N4A—N3A | 1.377 (5) | N4B—C5B | 1.294 (5) |
C5A—N4A | 1.299 (5) | C5B—N18B | 1.356 (5) |
C5A—N18A | 1.365 (5) | C6B—C7B | 1.387 (5) |
C6A—C7A | 1.379 (5) | C6B—C11B | 1.393 (5) |
C6A—C11A | 1.384 (5) | C7B—C8B | 1.386 (5) |
C7A—C8A | 1.379 (6) | C7B—H7B | 0.93 |
C7A—H7A | 0.930 | C8B—C9B | 1.382 (5) |
C8A—C9A | 1.390 (5) | C8B—H8B | 0.93 |
C8A—H8A | 0.93 | C9B—C10B | 1.396 (5) |
C9A—C10A | 1.375 (5) | C9B—C12B | 1.476 (5) |
C9A—C12A | 1.492 (5) | C10B—C11B | 1.383 (5) |
C10A—C11A | 1.388 (5) | C10B—H10B | 0.93 |
C10A—H10A | 0.93 | C11B—H11B | 0.93 |
C11A—H11A | 0.93 | C12B—C17B | 1.379 (6) |
C12A—C13A | 1.377 (6) | C12B—C13B | 1.396 (6) |
C12A—C17A | 1.387 (5) | C13B—C14B | 1.379 (6) |
C13A—C14A | 1.381 (7) | C13B—H13B | 0.93 |
C13A—H13A | 0.93 | C14B—C15B | 1.359 (6) |
C14A—C15A | 1.353 (7) | C14B—H14B | 0.93 |
C14A—H14A | 0.93 | C15B—C16B | 1.381 (7) |
C15A—C16A | 1.363 (6) | C15B—H15B | 0.93 |
C15A—H15A | 0.93 | C16B—C17B | 1.380 (6) |
C16A—C17A | 1.388 (6) | C16B—H16B | 0.93 |
C16A—H16A | 0.93 | C17B—H17B | 0.93 |
C17A—H17A | 0.93 | N18B—N19B | 1.374 (4) |
N18A—N19A | 1.379 (4) | N18B—H18B | 0.86 |
N18A—H18A | 0.86 | N19B—C20B | 1.277 (5) |
N19A—C20A | 1.276 (5) | C20B—C21B | 1.491 (6) |
C20A—C21A | 1.484 (6) | C20B—C22B | 1.493 (6) |
C20A—C22A | 1.490 (6) | C21B—H21D | 0.96 |
C21A—H21A | 0.96 | C21B—H21E | 0.96 |
C21A—H21B | 0.96 | C21B—H21F | 0.96 |
C21A—H21C | 0.96 | C22B—H22D | 0.96 |
C22A—H22A | 0.96 | C22B—H22E | 0.96 |
C22A—H22B | 0.96 | C22B—H22F | 0.96 |
| | | |
C2A—S1A—C5A | 86.24 (19) | C5B—S1B—C2B | 86.22 (18) |
N3A—C2A—C6A | 122.4 (4) | N3B—C2B—C6B | 122.7 (4) |
N3A—C2A—S1A | 114.0 (3) | N3B—C2B—S1B | 114.1 (3) |
C6A—C2A—S1A | 123.6 (3) | C6B—C2B—S1B | 123.2 (3) |
C2A—N3A—N4A | 113.3 (3) | C2B—N3B—N4B | 112.7 (3) |
C5A—N4A—N3A | 111.9 (3) | C5B—N4B—N3B | 112.0 (3) |
C5A—N4A—N3A | 111.9 (3) | N4B—C5B—N18B | 124.5 (4) |
N4A—C5A—N18A | 123.9 (4) | N4B—C5B—S1B | 114.9 (3) |
N4A—C5A—S1A | 114.6 (3) | N18B—C5B—S1B | 120.6 (3) |
N18A—C5A—S1A | 121.4 (3) | C7B—C6B—C11B | 118.2 (4) |
C7A—C6A—C11A | 118.1 (4) | C7B—C6B—C2B | 121.9 (4) |
C7A—C6A—C2A | 119.6 (4) | C11B—C6B—C2B | 119.9 (4) |
C11A—C6A—C2A | 122.3 (4) | C6B—C7B—C8B | 121.0 (4) |
C6A—C7A—C8A | 121.3 (4) | C6B—C7B—H7B | 119.5 |
C6A—C7A—H7A | 119.3 | C8B—C7B—H7B | 119.5 |
C8A—C7A—H7A | 119.3 | C9B—C8B—C7B | 121.7 (4) |
C7A—C8A—C9A | 121.2 (4) | C9B—C8B—H8B | 119.1 |
C7A—C8A—H8A | 119.4 | C7B—C8B—H8B | 119.1 |
C9A—C8A—H8A | 119.4 | C8B—C9B—C10B | 116.7 (4) |
C10A—C9A—C8A | 117.0 (4) | C8B—C9B—C12B | 121.8 (4) |
C10A—C9A—C12A | 122.3 (4) | C10B—C9B—C12B | 121.4 (4) |
C8A—C9A—C12A | 120.7 (4) | C11B—C10B—C9B | 122.3 (4) |
C9A—C10A—C11A | 122.2 (4) | C11B—C10B—H10B | 118.8 |
C9A—C10A—H10A | 118.9 | C9B—C10B—H10B | 118.8 |
C11A—C10A—H10A | 118.9 | C10B—C11B—C6B | 120.0 (4) |
C6A—C11A—C10A | 120.1 (4) | C10B—C11B—H11B | 120.0 |
C6A—C11A—H11A | 119.9 | C6B—C11B—H11B | 120.0 |
C10A—C11A—H11A | 119.9 | C17B—C12B—C13B | 117.5 (4) |
C13A—C12A—C17A | 117.3 (4) | C17B—C12B—C9B | 121.1 (4) |
C13A—C12A—C9A | 121.9 (4) | C13B—C12B—C9B | 121.3 (4) |
C17A—C12A—C9A | 120.8 (4) | C14B—C13B—C12B | 121.2 (4) |
C12A—C13A—C14A | 120.9 (5) | C14B—C13B—H13B | 119.4 |
C12A—C13A—H13A | 119.6 | C12B—C13B—H13B | 119.4 |
C14A—C13A—H13A | 119.6 | C15B—C14B—C13B | 120.3 (5) |
C15A—C14A—C13A | 121.1 (5) | C15B—C14B—H14B | 119.9 |
C15A—C14A—H14A | 119.5 | C13B—C14B—H14B | 119.9 |
C13A—C14A—H14A | 119.5 | C14B—C15B—C16B | 119.6 (5) |
C14A—C15A—C16A | 119.7 (5) | C14B—C15B—H15B | 120.2 |
C14A—C15A—H15A | 120.2 | C16B—C15B—H15B | 120.2 |
C16A—C15A—H15A | 120.2 | C17B—C16B—C15B | 120.3 (5) |
C15A—C16A—C17A | 119.8 (4) | C17B—C16B—H16B | 119.9 |
C15A—C16A—H16A | 120.1 | C15B—C16B—H16B | 119.9 |
C17A—C16A—H16A | 120.1 | C12B—C17B—C16B | 121.1 (5) |
C16A—C17A—C12A | 121.2 (4) | C12B—C17B—H17B | 119.5 |
C16A—C17A—H17A | 119.4 | C16B—C17B—H17B | 119.5 |
C12A—C17A—H17A | 119.4 | C5B—N18B—N19B | 116.6 (3) |
C5A—N18A—N19A | 115.6 (3) | C5B—N18B—H18B | 121.7 |
C5A—N18A—H18A | 122.2 | N19B—N18B—H18B | 121.7 |
N19A—N18A—H18A | 122.2 | C20B—N19B—N18B | 117.7 (3) |
C20A—N19A—N18A | 117.5 (4) | N19B—C20B—C21B | 126.1 (4) |
N19A—C20A—C21A | 126.2 (4) | N19B—C20B—C22B | 116.6 (4) |
N19A—C20A—C22A | 116.2 (4) | C21B—C20B—C22B | 117.2 (4) |
C21A—C20A—C22A | 117.6 (4) | C20B—C21B—H21D | 109.5 |
C20A—C21A—H21A | 109.5 | C20B—C21B—H21E | 109.5 |
C20A—C21A—H21B | 109.5 | H21D—C21B—H21E | 109.5 |
H21A—C21A—H21B | 109.5 | C20B—C21B—H21F | 109.5 |
C20A—C21A—H21C | 109.5 | H21D—C21B—H21F | 109.5 |
H21A—C21A—H21C | 109.5 | H21E—C21B—H21F | 109.5 |
H21B—C21A—H21C | 109.5 | C20B—C22B—H22D | 109.5 |
C20A—C22A—H22A | 109.5 | C20B—C22B—H22E | 109.5 |
C20A—C22A—H22B | 109.5 | H22D—C22B—H22E | 109.5 |
H22A—C22A—H22B | 109.5 | C20B—C22B—H22F | 109.5 |
C20A—C22A—H22C | 109.5 | H22D—C22B—H22F | 109.5 |
H22A—C22A—H22C | 109.5 | H22E—C22B—H22F | 109.5 |
H22B—C22A—H22C | 109.5 | | |
| | | |
C5A—S1A—C2A—N3A | 0.3 (4) | C5B—S1B—C2B—N3B | −0.3 (3) |
C5A—S1A—C2A—C6A | 179.7 (4) | C5B—S1B—C2B—C6B | 179.5 (4) |
C6A—C2A—N3A—N4A | 179.9 (4) | C6B—C2B—N3B—N4B | 180.0 (4) |
S1A—C2A—N3A—N4A | −0.7 (5) | S1B—C2B—N3B—N4B | −0.2 (5) |
C2A—N3A—N4A—C5A | 0.7 (6) | C2B—N3B—N4B—C5B | 0.9 (5) |
N3A—N4A—C5A—N18A | −176.7 (4) | N3B—N4B—C5B—N18B | −179.8 (4) |
N3A—N4A—C5A—S1A | −0.4 (5) | N3B—N4B—C5B—S1B | −1.2 (5) |
C2A—S1A—C5A—N4A | 0.0 (4) | C2B—S1B—C5B—N4B | 0.8 (3) |
C2A—S1A—C5A—N18A | 176.5 (4) | C2B—S1B—C5B—N18B | 179.6 (4) |
N3A—C2A—C6A—C7A | −22.5 (7) | N3B—C2B—C6B—C7B | 178.6 (4) |
S1A—C2A—C6A—C7A | 158.1 (4) | S1B—C2B—C6B—C7B | −1.2 (6) |
N3A—C2A—C6A—C11A | 154.6 (4) | N3B—C2B—C6B—C11B | −1.7 (6) |
S1A—C2A—C6A—C11A | −24.7 (6) | S1B—C2B—C6B—C11B | 178.5 (3) |
C11A—C6A—C7A—C8A | −0.7 (7) | C11B—C6B—C7B—C8B | 1.1 (6) |
C2A—C6A—C7A—C8A | 176.6 (5) | C2B—C6B—C7B—C8B | −179.2 (4) |
C6A—C7A—C8A—C9A | −0.6 (8) | C6B—C7B—C8B—C9B | −1.3 (7) |
C7A—C8A—C9A—C10A | 1.6 (7) | C7B—C8B—C9B—C10B | 1.0 (6) |
C7A—C8A—C9A—C12A | −176.6 (5) | C7B—C8B—C9B—C12B | −177.0 (4) |
C8A—C9A—C10A—C11A | −1.4 (7) | C8B—C9B—C10B—C11B | −0.7 (7) |
C12A—C9A—C10A—C11A | 176.7 (4) | C12B—C9B—C10B—C11B | 177.3 (4) |
C7A—C6A—C11A—C10A | 0.8 (6) | C9B—C10B—C11B—C6B | 0.5 (7) |
C2A—C6A—C11A—C10A | −176.3 (4) | C7B—C6B—C11B—C10B | −0.8 (6) |
C9A—C10A—C11A—C6A | 0.2 (7) | C2B—C6B—C11B—C10B | 179.6 (4) |
C10A—C9A—C12A—C13A | −151.2 (5) | C8B—C9B—C12B—C17B | 143.0 (4) |
C8A—C9A—C12A—C13A | 26.9 (7) | C10B—C9B—C12B—C17B | −34.9 (6) |
C10A—C9A—C12A—C17A | 28.8 (6) | C8B—C9B—C12B—C13B | −36.7 (6) |
C8A—C9A—C12A—C17A | −153.1 (4) | C10B—C9B—C12B—C13B | 145.4 (4) |
C17A—C12A—C13A—C14A | −0.4 (8) | C17B—C12B—C13B—C14B | 0.8 (7) |
C9A—C12A—C13A—C14A | 179.6 (5) | C9B—C12B—C13B—C14B | −179.5 (4) |
C12A—C13A—C14A—C15A | 0.4 (10) | C12B—C13B—C14B—C15B | 0.1 (8) |
C13A—C14A—C15A—C16A | −0.5 (10) | C13B—C14B—C15B—C16B | −1.7 (8) |
C14A—C15A—C16A—C17A | 0.7 (8) | C14B—C15B—C16B—C17B | 2.4 (8) |
C15A—C16A—C17A—C12A | −0.7 (7) | C13B—C12B—C17B—C16B | 0.0 (7) |
C13A—C12A—C17A—C16A | 0.6 (7) | C9B—C12B—C17B—C16B | −179.7 (5) |
C9A—C12A—C17A—C16A | −179.5 (4) | C15B—C16B—C17B—C12B | −1.6 (8) |
N4A—C5A—N18A—N19A | −170.6 (4) | N4B—C5B—N18B—N19B | 179.9 (4) |
S1A—C5A—N18A—N19A | 13.3 (5) | S1B—C5B—N18B—N19B | 1.3 (5) |
C5A—N18A—N19A—C20A | 177.1 (4) | C5B—N18B—N19B—C20B | 179.5 (4) |
N18A—N19A—C20A—C21A | 0.0 (7) | N18B—N19B—C20B—C21B | −0.4 (7) |
N18A—N19A—C20A—C22A | 179.5 (4) | N18B—N19B—C20B—C22B | 179.1 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N18A—H18A···N4B | 0.86 | 2.26 | 3.022 (5) | 147 |
N18B—H18B···N4A | 0.86 | 2.18 | 2.990 (5) | 157 |
C21B—H21F···N3A | 0.96 | 2.63 | 3.312 (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−·CH4O | F(000) = 792 |
Mr = 376.90 | Dx = 1.339 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 7.472 (3) Å | Cell parameters from 32 reflections |
b = 16.437 (4) Å | θ = 18–41° |
c = 15.532 (2) Å | µ = 2.96 mm−1 |
β = 101.41 (2)° | T = 294 K |
V = 1869.9 (9) Å3 | Needle, colourless |
Z = 4 | 0.21 × 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 tube | Rint = 0.000 |
Ni filtered radiation monochromator | θmax = 65.1°, θmin = 4.0° |
θ/2θ scan | h = 0→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −19→0 |
Tmin = 0.835, Tmax = 0.912 | l = −18→17 |
3167 measured reflections | 3 standard reflections every 100 reflections |
3167 independent reflections | intensity decay: 1.8% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.092 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.264 | H 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 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
Crystal data top
C17H17N4S+·Cl−·CH4O | V = 1869.9 (9) Å3 |
Mr = 376.90 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 7.472 (3) Å | µ = 2.96 mm−1 |
b = 16.437 (4) Å | T = 294 K |
c = 15.532 (2) Å | 0.21 × 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 = 0.912 | 3 standard reflections every 100 reflections |
3167 measured reflections | intensity decay: 1.8% |
3167 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.092 | 0 restraints |
wR(F2) = 0.264 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.89 | Δρmax = 0.28 e Å−3 |
3167 reflections | Δρmin = −0.29 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Cl | 0.5415 (3) | 0.64738 (12) | 0.18004 (13) | 0.0703 (7) | |
S1 | 0.6729 (3) | 0.56449 (11) | 0.38191 (11) | 0.0542 (5) | |
C2 | 0.7528 (9) | 0.5380 (4) | 0.4918 (4) | 0.0470 (16) | |
N3 | 0.8075 (8) | 0.5983 (4) | 0.5431 (3) | 0.0539 (15) | |
N4 | 0.7871 (9) | 0.6695 (4) | 0.4975 (4) | 0.0525 (15) | |
C5 | 0.7188 (10) | 0.6644 (4) | 0.4125 (5) | 0.0518 (18) | |
C6 | 0.7569 (10) | 0.4538 (4) | 0.5235 (4) | 0.0488 (17) | |
C7 | 0.7003 (12) | 0.3892 (5) | 0.4675 (5) | 0.065 (2) | |
H7 | 0.6595 | 0.3991 | 0.4079 | 0.081 (8)* | |
C8 | 0.7034 (11) | 0.3112 (5) | 0.4983 (5) | 0.062 (2) | |
H8 | 0.6635 | 0.2694 | 0.4588 | 0.081 (8)* | |
C9 | 0.7640 (9) | 0.2920 (5) | 0.5866 (4) | 0.0506 (18) | |
C10 | 0.8208 (13) | 0.3581 (5) | 0.6400 (5) | 0.074 (3) | |
H10 | 0.8627 | 0.3487 | 0.6996 | 0.081 (8)* | |
C11 | 0.8192 (13) | 0.4357 (5) | 0.6106 (5) | 0.077 (3) | |
H11 | 0.8609 | 0.4773 | 0.6500 | 0.081 (8)* | |
C12 | 0.7693 (9) | 0.2083 (4) | 0.6203 (4) | 0.0457 (16) | |
C13 | 0.6887 (11) | 0.1425 (5) | 0.5695 (5) | 0.0584 (19) | |
H13 | 0.6289 | 0.1519 | 0.5119 | 0.081 (8)* | |
C14 | 0.6954 (11) | 0.0650 (5) | 0.6019 (5) | 0.062 (2) | |
H14 | 0.6422 | 0.0228 | 0.5658 | 0.081 (8)* | |
C15 | 0.7799 (11) | 0.0485 (5) | 0.6872 (5) | 0.065 (2) | |
H15 | 0.7831 | −0.0042 | 0.7092 | 0.081 (8)* | |
C16 | 0.8590 (12) | 0.1116 (5) | 0.7390 (5) | 0.067 (2) | |
H16 | 0.9138 | 0.1015 | 0.7971 | 0.081 (8)* | |
C17 | 0.8590 (11) | 0.1899 (5) | 0.7064 (5) | 0.060 (2) | |
H17 | 0.9193 | 0.2309 | 0.7419 | 0.081 (8)* | |
N18 | 0.6907 (9) | 0.7266 (4) | 0.3581 (4) | 0.0580 (16) | |
H18 | 0.6447 | 0.7204 | 0.3032 | 0.081 (8)* | |
N19 | 0.7393 (8) | 0.8025 (4) | 0.3940 (4) | 0.0571 (16) | |
C20 | 0.7119 (10) | 0.8634 (4) | 0.3414 (5) | 0.0559 (19) | |
C21 | 0.6321 (12) | 0.8598 (5) | 0.2461 (5) | 0.074 (2) | |
H21A | 0.7180 | 0.8351 | 0.2156 | 0.141 (14)* | |
H21B | 0.6048 | 0.9139 | 0.2241 | 0.141 (14)* | |
H21C | 0.5220 | 0.8282 | 0.2369 | 0.141 (14)* | |
C22 | 0.7675 (13) | 0.9458 (5) | 0.3799 (6) | 0.080 (3) | |
H22A | 0.7980 | 0.9417 | 0.4428 | 0.141 (14)* | |
H22B | 0.6683 | 0.9833 | 0.3633 | 0.141 (14)* | |
H22C | 0.8718 | 0.9648 | 0.3582 | 0.141 (14)* | |
O1 | 0.8755 (10) | 0.7889 (4) | 0.6141 (4) | 0.0754 (19) | |
C1 | 0.9995 (14) | 0.8517 (6) | 0.6025 (6) | 0.087 (3) | |
H1A | 0.9688 | 0.9007 | 0.6299 | 0.141 (14)* | |
H1B | 0.9920 | 0.8612 | 0.5409 | 0.141 (14)* | |
H1C | 1.1216 | 0.8356 | 0.6289 | 0.141 (14)* | |
H4 | 0.801 (11) | 0.721 (5) | 0.535 (5) | 0.081 (8)* | |
H1 | 0.803 (17) | 0.806 (8) | 0.636 (8) | 0.141 (14)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0826 (15) | 0.0646 (12) | 0.0598 (11) | −0.0025 (11) | 0.0043 (10) | −0.0006 (10) |
S1 | 0.0677 (12) | 0.0514 (10) | 0.0423 (9) | −0.0022 (9) | 0.0080 (8) | 0.0009 (8) |
C2 | 0.046 (4) | 0.058 (4) | 0.040 (3) | −0.003 (3) | 0.016 (3) | −0.011 (3) |
N3 | 0.061 (4) | 0.057 (4) | 0.042 (3) | 0.000 (3) | 0.005 (3) | 0.008 (3) |
N4 | 0.065 (4) | 0.053 (3) | 0.039 (3) | −0.004 (3) | 0.008 (3) | −0.003 (3) |
C5 | 0.047 (4) | 0.054 (4) | 0.054 (4) | 0.000 (3) | 0.012 (3) | −0.003 (3) |
C6 | 0.049 (4) | 0.044 (4) | 0.052 (4) | 0.005 (3) | 0.008 (3) | 0.004 (3) |
C7 | 0.094 (7) | 0.053 (5) | 0.047 (4) | −0.005 (4) | 0.007 (4) | −0.004 (3) |
C8 | 0.068 (6) | 0.054 (5) | 0.061 (5) | −0.014 (4) | 0.003 (4) | −0.007 (4) |
C9 | 0.047 (4) | 0.063 (5) | 0.041 (4) | −0.009 (4) | 0.009 (3) | 0.004 (3) |
C10 | 0.116 (8) | 0.057 (5) | 0.037 (4) | −0.016 (5) | −0.013 (4) | 0.004 (3) |
C11 | 0.119 (8) | 0.057 (5) | 0.044 (4) | −0.010 (5) | −0.008 (4) | 0.000 (4) |
C12 | 0.050 (4) | 0.040 (4) | 0.051 (4) | 0.003 (3) | 0.018 (3) | −0.002 (3) |
C13 | 0.060 (5) | 0.061 (5) | 0.055 (4) | −0.009 (4) | 0.013 (4) | −0.005 (4) |
C14 | 0.066 (5) | 0.051 (4) | 0.072 (5) | −0.012 (4) | 0.023 (4) | −0.004 (4) |
C15 | 0.078 (6) | 0.056 (5) | 0.066 (5) | 0.010 (4) | 0.026 (4) | 0.003 (4) |
C16 | 0.085 (6) | 0.063 (5) | 0.053 (4) | 0.007 (5) | 0.015 (4) | 0.017 (4) |
C17 | 0.073 (6) | 0.058 (5) | 0.046 (4) | −0.008 (4) | 0.009 (4) | −0.001 (3) |
N18 | 0.076 (5) | 0.052 (4) | 0.043 (3) | −0.003 (3) | 0.006 (3) | 0.004 (3) |
N19 | 0.061 (4) | 0.053 (4) | 0.057 (4) | −0.001 (3) | 0.012 (3) | −0.001 (3) |
C20 | 0.051 (5) | 0.050 (4) | 0.069 (5) | 0.006 (3) | 0.020 (4) | 0.007 (4) |
C21 | 0.083 (6) | 0.072 (6) | 0.062 (5) | −0.002 (5) | 0.003 (4) | 0.012 (4) |
C22 | 0.094 (7) | 0.057 (5) | 0.089 (6) | 0.007 (5) | 0.019 (5) | 0.009 (4) |
O1 | 0.106 (6) | 0.060 (3) | 0.060 (3) | −0.008 (3) | 0.018 (3) | −0.008 (3) |
C1 | 0.091 (7) | 0.087 (7) | 0.079 (6) | −0.010 (6) | 0.005 (5) | 0.004 (5) |
Geometric parameters (Å, º) top
S1—C5 | 1.724 (7) | C14—C15 | 1.377 (11) |
S1—C2 | 1.748 (7) | C14—H14 | 0.93 |
C2—N3 | 1.287 (8) | C15—C16 | 1.372 (11) |
C2—C6 | 1.467 (9) | C15—H15 | 0.93 |
N3—N4 | 1.361 (8) | C16—C17 | 1.383 (10) |
N4—C5 | 1.321 (9) | C16—H16 | 0.93 |
N4—H4 | 1.02 (8) | C17—H17 | 0.93 |
C5—N18 | 1.316 (9) | N18—N19 | 1.386 (8) |
C6—C11 | 1.374 (9) | N18—H18 | 0.86 |
C6—C7 | 1.384 (10) | N19—C20 | 1.283 (9) |
C7—C8 | 1.367 (10) | C20—C21 | 1.484 (10) |
C7—H7 | 0.93 | C20—C22 | 1.504 (11) |
C8—C9 | 1.392 (9) | C21—H21A | 0.96 |
C8—H8 | 0.93 | C21—H21B | 0.96 |
C9—C10 | 1.381 (10) | C21—H21C | 0.96 |
C9—C12 | 1.470 (10) | C22—H22A | 0.96 |
C10—C11 | 1.354 (11) | C22—H22B | 0.96 |
C10—H10 | 0.9300 | C22—H22C | 0.96 |
C11—H11 | 0.9300 | O1—C1 | 1.422 (11) |
C12—C13 | 1.404 (9) | O1—H1 | 0.75 (11) |
C12—C17 | 1.404 (9) | C1—H1A | 0.96 |
C13—C14 | 1.367 (10) | C1—H1B | 0.96 |
C13—H13 | 0.93 | C1—H1C | 0.96 |
| | | |
C5—S1—C2 | 87.6 (3) | C15—C14—H14 | 119.5 |
N3—C2—C6 | 122.4 (6) | C16—C15—C14 | 118.5 (7) |
N3—C2—S1 | 114.8 (5) | C16—C15—H15 | 120.7 |
C6—C2—S1 | 122.9 (5) | C14—C15—H15 | 120.7 |
C2—N3—N4 | 110.5 (5) | C15—C16—C17 | 121.3 (7) |
C5—N4—N3 | 116.5 (6) | C15—C16—H16 | 119.4 |
C5—N4—H4 | 127 (4) | C17—C16—H16 | 119.4 |
N3—N4—H4 | 116 (4) | C16—C17—C12 | 121.0 (7) |
N4—C5—N18 | 124.9 (7) | C16—C17—H17 | 119.5 |
N4—C5—S1 | 110.7 (5) | C12—C17—H17 | 119.5 |
N18—C5—S1 | 124.4 (6) | C5—N18—N19 | 116.5 (6) |
C11—C6—C7 | 117.0 (7) | C5—N18—H18 | 121.8 |
C11—C6—C2 | 121.0 (6) | N19—N18—H18 | 121.8 |
C7—C6—C2 | 122.0 (6) | C20—N19—N18 | 116.8 (6) |
C6—C7—C8 | 121.2 (7) | N19—C20—C21 | 125.9 (7) |
C6—C7—H7 | 119.4 | N19—C20—C22 | 116.9 (7) |
C8—C7—H7 | 119.4 | C21—C20—C22 | 117.2 (7) |
C9—C8—C7 | 122.5 (7) | C20—C21—H21A | 109.5 |
C9—C8—H8 | 118.8 | C20—C21—H21B | 109.5 |
C7—C8—H8 | 118.8 | H21A—C21—H21B | 109.5 |
C8—C9—C10 | 114.5 (7) | C20—C21—H21C | 109.5 |
C8—C9—C12 | 123.0 (7) | H21A—C21—H21C | 109.5 |
C10—C9—C12 | 122.5 (6) | H21B—C21—H21C | 109.5 |
C11—C10—C9 | 123.9 (7) | C20—C22—H22A | 109.5 |
C11—C10—H10 | 118.1 | C20—C22—H22B | 109.5 |
C9—C10—H10 | 118.1 | H22A—C22—H22B | 109.5 |
C6—C11—C10 | 121.0 (7) | C20—C22—H22C | 109.5 |
C6—C11—H11 | 119.5 | H22A—C22—H22C | 109.5 |
C10—C11—H11 | 119.5 | H22B—C22—H22C | 109.5 |
C13—C12—C17 | 116.1 (6) | C1—O1—H1 | 110 (10) |
C13—C12—C9 | 122.8 (6) | O1—C1—H1A | 109.5 |
C17—C12—C9 | 121.1 (6) | O1—C1—H1B | 109.5 |
C14—C13—C12 | 122.0 (7) | H1A—C1—H1B | 109.5 |
C14—C13—H13 | 119.0 | O1—C1—H1C | 109.5 |
C12—C13—H13 | 119.0 | H1A—C1—H1C | 109.5 |
C13—C14—C15 | 120.9 (7) | H1B—C1—H1C | 109.5 |
C13—C14—H14 | 119.5 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cli | 0.75 (13) | 2.32 (13) | 3.064 (8) | 169 (13) |
N4—H4···O1 | 1.02 (8) | 1.67 (8) | 2.664 (9) | 163 (7) |
N18—H18···Cl | 0.86 | 2.26 | 3.061 (7) | 155 |
Symmetry code: (i) x, −y+3/2, z+1/2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C15H14N3S+·Cl− | C17H16N4S | C17H17N4S+·Cl−·CH4O |
Mr | 303.80 | 308.40 | 376.90 |
Crystal system, space group | Orthorhombic, P212121 | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 294 | 294 | 294 |
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, 90 | 74.77 (3), 89.60 (2), 80.79 (2) | 90, 101.41 (2), 90 |
V (Å3) | 1489.0 (5) | 1564.8 (7) | 1869.9 (9) |
Z | 4 | 4 | 4 |
Radiation type | Cu Kα | Cu Kα | Cu Kα |
µ (mm−1) | 3.52 | 1.84 | 2.96 |
Crystal size (mm) | 0.39 × 0.12 × 0.08 | 0.33 × 0.04 × 0.02 | 0.21 × 0.05 × 0.03 |
|
Data collection |
Diffractometer | PICKER FACS-1 four-circle diffractometer | PICKER FACS-1 four-circle diffractometer | PICKER FACS-1 four-circle diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.630, 0.753 | 0.913, 0.961 | 0.835, 0.912 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1515, 1515, 1138 | 5739, 5322, 3511 | 3167, 3167, 1725 |
Rint | 0.000 | 0.073 | 0.000 |
(sin θ/λ)max (Å−1) | 0.588 | 0.588 | 0.588 |
|
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 reflections | 1515 | 5322 | 3167 |
No. of parameters | 185 | 406 | 237 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.23 | 0.31, −0.28 | 0.28, −0.29 |
Absolute structure | Flack (1983), number of Friedel pairs? | ? | ? |
Absolute structure parameter | 0.02 (5) | ? | ? |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N20—H20A···Cl1 | 0.89 | 2.25 | 3.134 (6) | 170 |
N20—H20B···Cl1i | 0.89 | 2.22 | 3.070 (6) | 160 |
N20—H20C···N4ii | 0.89 | 2.03 | 2.906 (7) | 167 |
C19—H19B···Cl1iii | 0.97 | 2.57 | 3.492 (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···A | D—H | H···A | D···A | D—H···A |
N18A—H18A···N4B | 0.86 | 2.26 | 3.022 (5) | 147 |
N18B—H18B···N4A | 0.86 | 2.18 | 2.990 (5) | 157 |
C21B—H21F···N3A | 0.96 | 2.63 | 3.312 (6) | 129 |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cli | 0.75 (13) | 2.32 (13) | 3.064 (8) | 169 (13) |
N4—H4···O1 | 1.02 (8) | 1.67 (8) | 2.664 (9) | 163 (7) |
N18—H18···Cl | 0.86 | 2.2607 | 3.061 (7) | 155 |
Symmetry code: (i) x, −y+3/2, z+1/2. |
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.