2-(Biphenyl-2-yl)-5-(1-methyl­hydrazino)-1,3,4-thia­diazole: a thia­diazole–hydrazine derivative with anticonvulsant properties

In the title compound, C₁₅H₁₄N₄S, the outer phenyl ring makes an angle of 101.4 (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 146.7 (2)°. In addition to weak N—H...N hydrogen bonds, creating a two-dimensional network parallel to the bc plane of the crystal structure, there is also one non-standard hydrogen-bond inter­action of the type C—H...N. Stereochemical comparison with the closely related compound 1-[5-(biphenyl-2-yl)-1,3,4-thia­diazol-2-yl]methanaminium chloride shows that the two compounds utilize the same mechanism for anticonvulsant activity.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.071
• wR factor = 0.136
• Data-to-parameter ratio = 11.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............      62.50 Deg.

Author Response: ...' see _exptl_special_details section'

Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.94
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C15
PLAT331_ALERT_2_B Small Average Phenyl C-C Dist.   C15    -C20           1.36 Ang.

Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           62.50
           From the CIF: _diffrn_reflns_theta_full          62.50
           From the CIF: _reflns_number_total               2259
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         2391
           Completeness (_total/calc)             94.48%
THETM01_ALERT_3_C  The value of sine(theta_max)/wavelength is less than 0.590
            Calculated sin(theta_max)/wavelength =    0.5753
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.94
PLAT023_ALERT_3_C Resolution (too) Low [sin(th)/Lambda < 0.6].....      62.50 Deg.
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         49 Perc.
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.83 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C15    -   C16     ..       5.65 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C16
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C17
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C19
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.03
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9

   1 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
  13 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   9 ALERT type 2 Indicator that the structure model may be wrong or deficient
   8 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: Picker Manual (Picker, 1967); cell refinement: Picker Manual; data reduction: DATRDN in The X-ray System (Stewart, 1976); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); 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.

2-(Biphenyl-2-yl)-5-(1-methylhydrazino)-1,3,4-thiadiazole

Crystal data

C15H14N4S	F(000) = 592
Mr = 282.36	Dx = 1.253 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 13.886 (3) Å	Cell parameters from 32 reflections
b = 9.898 (2) Å	θ = 19–38°
c = 10.896 (2) Å	µ = 1.88 mm^−1
β = 91.46 (2)°	T = 294 K
V = 1497.1 (5) Å^3	Needle, colorless
Z = 4	0.25 × 0.07 × 0.04 mm

Data collection

Picker FACS-1 four-circle diffractometer	1111 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Ni filtered radiation monochromator	θmax = 62.5°, θmin = 3.2°
θ/2θ scans	h = 0→15
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
Tmin = 0.851, Tmax = 0.926	l = −9→12
2259 measured reflections	3 standard reflections every 100 reflections
2259 independent reflections	intensity decay: 2.3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.071	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.136	w = 1/[σ^2(Fo^2) + (0.0477P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.89	(Δ/σ)max < 0.001
2259 reflections	Δρmax = 0.28 e Å^−3
193 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (3)

Special details

Experimental. Generally no observable reflections above θ = 60° due to poor quality of the crystal and high anisotropic temperature displacement parameters. A few visible reflections from the region θ = 60–65° have been identified on the Weissenberg photographs and duly collected.

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.29751 (10)	0.10959 (11)	0.65738 (10)	0.0663 (5)
C2	0.3943 (3)	0.1980 (4)	0.7163 (4)	0.0554 (12)
N3	0.4067 (3)	0.3187 (4)	0.6690 (3)	0.0672 (11)
N4	0.3356 (3)	0.3456 (4)	0.5818 (3)	0.0659 (11)
C5	0.2746 (3)	0.2488 (4)	0.5631 (4)	0.0546 (12)
N6	0.4544 (3)	0.1436 (4)	0.8035 (3)	0.0712 (12)
N7	0.4229 (4)	0.0191 (4)	0.8514 (4)	0.0691 (13)
C8	0.5231 (4)	0.2243 (6)	0.8746 (5)	0.0957 (19)
H8A	0.5403	0.3028	0.8283	0.143 (15)*
H8B	0.5798	0.1716	0.8925	0.143 (15)*
H8C	0.4947	0.2518	0.9500	0.143 (15)*
C9	0.1910 (4)	0.2645 (4)	0.4771 (4)	0.0654 (14)
C10	0.1511 (4)	0.1594 (5)	0.4071 (4)	0.0695 (14)
C11	0.0748 (4)	0.1868 (6)	0.3240 (5)	0.100 (2)
H11	0.0471	0.1168	0.2783	0.123 (7)*
C12	0.0408 (5)	0.3162 (7)	0.3097 (6)	0.125 (3)
H12	−0.0080	0.3339	0.2519	0.123 (7)*
C13	0.0781 (5)	0.4192 (6)	0.3795 (6)	0.123 (2)
H13	0.0527	0.5058	0.3716	0.123 (7)*
C14	0.1534 (4)	0.3947 (5)	0.4618 (5)	0.0907 (17)
H14	0.1795	0.4656	0.5076	0.123 (7)*
C15	0.1850 (4)	0.0177 (5)	0.4161 (5)	0.0659 (14)
C16	0.2673 (6)	−0.0234 (8)	0.3623 (6)	0.126 (3)
H16	0.3051	0.0392	0.3218	0.123 (7)*
C17	0.2961 (7)	−0.1603 (10)	0.3672 (7)	0.154 (4)
H17	0.3505	−0.1886	0.3264	0.123 (7)*
C18	0.2457 (7)	−0.2468 (8)	0.4293 (9)	0.141 (3)
H18	0.2657	−0.3363	0.4344	0.123 (7)*
C19	0.1665 (6)	−0.2092 (7)	0.4852 (9)	0.147 (4)
H19	0.1305	−0.2724	0.5274	0.123 (7)*
C20	0.1374 (4)	−0.0762 (6)	0.4807 (6)	0.107 (2)
H20	0.0833	−0.0503	0.5235	0.123 (7)*
H71	0.396 (5)	0.029 (7)	0.934 (6)	0.15 (3)*
H72	0.477 (5)	−0.033 (7)	0.854 (5)	0.13 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0930 (10)	0.0403 (6)	0.0643 (8)	−0.0036 (7)	−0.0231 (6)	0.0088 (6)
C2	0.061 (3)	0.048 (3)	0.057 (3)	0.004 (2)	−0.010 (2)	−0.001 (2)
N3	0.085 (3)	0.052 (2)	0.065 (3)	−0.014 (2)	−0.008 (2)	0.000 (2)
N4	0.093 (3)	0.048 (2)	0.055 (2)	−0.010 (2)	−0.017 (2)	0.0016 (18)
C5	0.076 (3)	0.042 (3)	0.045 (3)	0.002 (2)	−0.006 (3)	0.003 (2)
N6	0.089 (3)	0.061 (3)	0.063 (3)	−0.002 (2)	−0.024 (2)	0.000 (2)
N7	0.095 (4)	0.051 (3)	0.060 (3)	0.008 (2)	−0.018 (3)	0.005 (2)
C8	0.114 (5)	0.101 (4)	0.071 (4)	−0.023 (4)	−0.023 (4)	0.006 (3)
C9	0.088 (4)	0.039 (3)	0.068 (3)	−0.005 (2)	−0.015 (3)	0.008 (2)
C10	0.098 (4)	0.048 (3)	0.062 (3)	−0.004 (3)	−0.017 (3)	0.012 (2)
C11	0.120 (5)	0.067 (4)	0.109 (5)	−0.009 (4)	−0.058 (4)	0.008 (3)
C12	0.136 (6)	0.083 (4)	0.153 (6)	−0.005 (4)	−0.081 (5)	0.031 (4)
C13	0.139 (6)	0.067 (4)	0.160 (6)	0.005 (4)	−0.062 (5)	0.021 (4)
C14	0.111 (5)	0.049 (3)	0.111 (4)	0.007 (3)	−0.030 (4)	0.006 (3)
C15	0.073 (4)	0.059 (3)	0.066 (3)	−0.013 (3)	−0.010 (3)	−0.002 (3)
C16	0.178 (8)	0.102 (6)	0.099 (5)	0.007 (5)	0.045 (5)	0.022 (4)
C17	0.205 (10)	0.128 (7)	0.131 (7)	0.063 (7)	0.073 (6)	−0.013 (6)
C18	0.162 (9)	0.060 (4)	0.200 (10)	0.018 (6)	−0.019 (8)	−0.015 (5)
C19	0.112 (6)	0.062 (5)	0.268 (11)	−0.007 (4)	0.011 (7)	0.042 (5)
C20	0.082 (5)	0.065 (4)	0.174 (6)	−0.002 (3)	0.008 (4)	0.018 (4)

Geometric parameters (Å, º)

S1—C2	1.715 (4)	C11—C12	1.373 (8)
S1—C5	1.743 (4)	C11—H11	0.9300
C2—N3	1.314 (5)	C12—C13	1.366 (8)
C2—N6	1.361 (5)	C12—H12	0.9300
N3—N4	1.378 (5)	C13—C14	1.382 (7)
N4—C5	1.292 (5)	C13—H13	0.9300
C5—C9	1.482 (6)	C14—H14	0.9300
N6—N7	1.412 (5)	C15—C20	1.349 (7)
N6—C8	1.453 (6)	C15—C16	1.360 (8)
N7—H71	0.99 (6)	C16—C17	1.413 (10)
N7—H72	0.91 (6)	C16—H16	0.9300
C8—H8A	0.9600	C17—C18	1.306 (10)
C8—H8B	0.9600	C17—H17	0.9300
C8—H8C	0.9600	C18—C19	1.324 (11)
C9—C14	1.399 (6)	C18—H18	0.9300
C9—C10	1.396 (6)	C19—C20	1.377 (8)
C10—C11	1.402 (6)	C19—H19	0.9300
C10—C15	1.482 (7)	C20—H20	0.9300
C2—S1—C5	86.9 (2)	C12—C11—H11	119.8
N3—C2—N6	123.4 (4)	C13—C12—C11	120.6 (5)
N3—C2—S1	115.2 (3)	C13—C12—H12	119.7
N6—C2—S1	121.4 (3)	C11—C12—H12	119.7
C2—N3—N4	110.3 (3)	C12—C13—C14	120.0 (5)
C5—N4—N3	114.9 (3)	C12—C13—H13	120.0
N4—C5—C9	121.5 (4)	C14—C13—H13	120.0
N4—C5—S1	112.6 (3)	C13—C14—C9	120.9 (5)
C9—C5—S1	125.7 (3)	C13—C14—H14	119.6
C2—N6—N7	114.4 (4)	C9—C14—H14	119.6
C2—N6—C8	122.5 (4)	C20—C15—C16	116.5 (6)
N7—N6—C8	119.2 (4)	C20—C15—C10	121.8 (6)
N6—N7—H71	112 (4)	C16—C15—C10	121.7 (6)
N6—N7—H72	104 (4)	C17—C16—C15	120.7 (7)
H71—N7—H72	111 (5)	C17—C16—H16	119.7
N6—C8—H8A	109.5	C15—C16—H16	119.7
N6—C8—H8B	109.5	C18—C17—C16	119.6 (8)
H8A—C8—H8B	109.5	C18—C17—H17	120.2
N6—C8—H8C	109.5	C16—C17—H17	120.2
H8A—C8—H8C	109.5	C17—C18—C19	121.1 (8)
H8B—C8—H8C	109.5	C17—C18—H18	119.5
C14—C9—C10	118.7 (4)	C19—C18—H18	119.5
C14—C9—C5	117.1 (4)	C18—C19—C20	119.9 (8)
C10—C9—C5	124.1 (4)	C18—C19—H19	120.0
C11—C10—C9	119.4 (4)	C20—C19—H19	120.0
C11—C10—C15	117.3 (4)	C15—C20—C19	122.0 (7)
C9—C10—C15	123.2 (4)	C15—C20—H20	119.0
C10—C11—C12	120.4 (5)	C19—C20—H20	119.0
C10—C11—H11	119.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H71···N4^i	0.99 (6)	2.21 (7)	3.118 (7)	151 (5)
N7—H72···N3^ii	0.91 (6)	2.20 (7)	3.100 (7)	169 (5)
C16—H16···N3^iii	0.93	2.62	3.534 (8)	168

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x, −y+1/2, z−1/2.