A sulfur coordination polymer with wide bandgap semiconductivity formed from zinc(II) and 5-methyl­sulfanyl-1,3,4-thia­diazole-2-thione

The sulfur coordination polymer catena-poly[zinc(II)-μ₂-bis[5-(methyl­sulfan­yl)-2-sulfanyl­idene-2,3-di­hydro-1,3,4-thia­diazol-3-ido-κ²N³:S]], [Zn(C₃H₃N₂S₃)₂]_n or [Zn₂MTT₄]_n, constructed from Zn²⁺ ions and 5-methyl­sulfanyl-1,3,4-thia­diazole-2-thione (HMTT), was synthesized successfully and structurally char­acterized. [Zn₂MTT₄]_n crystallizes in the tetra­gonal space group I (No. 82). Each MTT⁻ ligand (systematic name: 5-methyl­sulfanyl-2-sulfanyl­idene-2,3-di­hydro-1,3,4-thia­diazol-3-ide) coordinates to two different Zn^II ions, one via the thione group and the other via a ring N atom, with one Zn^II atom being in a tetra­hedral ZnS₄ and the other in a tetra­hedral ZnN₄ coordination environment. These tetra­hedral ZnS₄ and ZnN₄ units are alternately linked by the organic ligands, forming a one-dimensional chain structure along the c axis. The one-dimensional chains are further linked via C—H...N and C—H...S hydrogen bonds to form a three-dimensional network adopting an ABAB-style arrangement that lies along both the a and b axes. The three-dimensional Hirshfeld surface analysis and two-dimensional (2D) fingerprint plots confirm the major inter­actions as C—H...S hydrogen bonds with a total of 35.1%, while 7.4% are C—H...N hydrogen-bond inter­actions. [Zn₂MTT₄]_n possesses high thermal and chemical stability and a linear temperature dependence of the bandgap from room temperature to 270 °C. Further investigation revealed that the bandgap changes sharply in ammonia, but only fluctuates slightly in other solvents, indicating its promising application as a selective sensor.

Computing details

Data collection: APEX3 (Bruker, 2014); cell refinement: APEX3 (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

catena-Poly[zinc(II)-bis[µ₂-5-(methylsulfanyl)-2-sulfanylidene-2,3-dihydro-1,3,4-thiadiazol-3-ido-κ²N³:S]]

Crystal data

[Zn(C3H3N2S3)2]	Dx = 1.817 Mg m^−3
Mr = 391.96	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 3909 reflections
a = 18.1367 (12) Å	θ = 2.5–25.8°
c = 8.7103 (9) Å	µ = 2.57 mm^−1
V = 2865.2 (5) Å^3	T = 296 K
Z = 8	Block, colorless
F(000) = 1568	0.20 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer	2550 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.032
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θmax = 27.2°, θmin = 1.6°
Tmin = 0.624, Tmax = 0.746	h = −23→23
10994 measured reflections	k = −23→22
2908 independent reflections	l = −11→10

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.030	w = 1/[σ^2(Fo^2) + (0.0273P)^2 + 1.9481P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.064	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.31 e Å^−3
2908 reflections	Δρmin = −0.33 e Å^−3
155 parameters	Absolute structure: Refined as an inversion twin.
0 restraints	Absolute structure parameter: 0.32 (2)

Special details

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

Refinement. Refined as a 2-component inversion twin.

The data adsorption correction was carried out by multi-scan techniques using SADABS routine of APEX program (Bruker, 2014). The crystal structure was solved by Shelxt (Sheldrick, 2015a) subprogram using dual space algorithm and refined by full-matrix least-squares on F² using Shelxl (Sheldrick, 2015b) under the SHELXTL (Bruker, 2000) software package. All non-hydrogen atoms were refined anisotropically with displacement parameters during the final cycles.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn4	0.500000	0.500000	0.500000	0.0280 (3)
Zn3	0.500000	0.500000	1.000000	0.0317 (3)
S4	0.52520 (7)	0.39832 (7)	0.84020 (14)	0.0337 (3)
S5	0.36726 (8)	0.34550 (9)	0.80060 (16)	0.0483 (4)
S6	0.22995 (10)	0.35088 (14)	0.6101 (2)	0.0818 (7)
N4	0.4278 (2)	0.4347 (2)	0.6163 (4)	0.0288 (9)
N3	0.3570 (2)	0.4251 (2)	0.5583 (5)	0.0351 (10)
C4	0.4419 (3)	0.3974 (2)	0.7436 (6)	0.0308 (10)
C5	0.3197 (3)	0.3792 (3)	0.6432 (6)	0.0430 (13)
C6	0.2128 (4)	0.3882 (4)	0.4237 (9)	0.082 (2)
H6A	0.243705	0.363986	0.349855	0.123*
H6B	0.223365	0.440066	0.424045	0.123*
H6C	0.161965	0.380636	0.396955	0.123*
Zn2	1.000000	0.500000	0.750000	0.0275 (2)
Zn1	1.000000	0.500000	1.250000	0.0307 (3)
S1	0.95148 (8)	0.59642 (7)	1.10196 (16)	0.0368 (3)
S2	0.79737 (8)	0.53882 (9)	1.03997 (15)	0.0451 (4)
S3	0.70135 (8)	0.44608 (10)	0.83252 (18)	0.0513 (4)
N1	0.8472 (2)	0.4695 (2)	0.8064 (4)	0.0330 (10)
N2	0.9062 (2)	0.5067 (2)	0.8707 (5)	0.0311 (9)
C1	0.8903 (2)	0.5448 (2)	0.9943 (6)	0.0294 (10)
C2	0.7868 (3)	0.4817 (3)	0.8825 (6)	0.0350 (12)
C3	0.7250 (3)	0.4016 (4)	0.6546 (8)	0.0606 (18)
H3A	0.742644	0.437759	0.583021	0.091*
H3B	0.682097	0.377793	0.613151	0.091*
H3C	0.762732	0.365583	0.672783	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn4	0.0299 (4)	0.0299 (4)	0.0241 (6)	0.000	0.000	0.000
Zn3	0.0351 (4)	0.0351 (4)	0.0249 (6)	0.000	0.000	0.000
S4	0.0337 (7)	0.0364 (7)	0.0310 (7)	0.0030 (6)	−0.0034 (6)	−0.0030 (5)
S5	0.0457 (8)	0.0616 (10)	0.0377 (8)	−0.0195 (7)	−0.0040 (6)	0.0160 (7)
S6	0.0449 (10)	0.1328 (19)	0.0677 (12)	−0.0372 (11)	−0.0127 (9)	0.0203 (12)
N4	0.029 (2)	0.034 (2)	0.024 (2)	−0.0016 (18)	−0.0017 (17)	−0.0011 (18)
N3	0.033 (2)	0.044 (3)	0.028 (2)	0.0017 (19)	0.0014 (18)	−0.0020 (19)
C4	0.034 (3)	0.029 (2)	0.030 (3)	−0.0013 (19)	0.006 (2)	−0.005 (2)
C5	0.036 (3)	0.059 (3)	0.034 (3)	−0.008 (3)	−0.001 (2)	0.000 (3)
C6	0.051 (4)	0.098 (6)	0.098 (6)	0.008 (4)	−0.038 (4)	0.006 (5)
Zn2	0.0271 (3)	0.0271 (3)	0.0284 (6)	0.000	0.000	0.000
Zn1	0.0342 (4)	0.0342 (4)	0.0237 (6)	0.000	0.000	0.000
S1	0.0430 (8)	0.0327 (7)	0.0347 (7)	−0.0031 (6)	−0.0095 (6)	0.0020 (5)
S2	0.0305 (7)	0.0719 (10)	0.0329 (7)	0.0005 (7)	0.0046 (6)	−0.0105 (7)
S3	0.0309 (8)	0.0835 (12)	0.0396 (8)	−0.0152 (7)	−0.0043 (6)	0.0014 (8)
N1	0.027 (2)	0.042 (2)	0.030 (2)	−0.0039 (18)	−0.0022 (18)	0.0001 (18)
N2	0.029 (2)	0.036 (2)	0.029 (2)	−0.0003 (17)	−0.0004 (18)	−0.0008 (19)
C1	0.028 (2)	0.033 (3)	0.027 (2)	0.0001 (19)	−0.003 (2)	0.007 (2)
C2	0.031 (3)	0.045 (3)	0.029 (3)	−0.003 (2)	−0.006 (2)	0.004 (2)
C3	0.049 (4)	0.077 (5)	0.056 (4)	−0.006 (3)	−0.019 (3)	−0.015 (3)

Geometric parameters (Å, º)

Zn4—N4	2.036 (4)	Zn2—N2	2.004 (4)
Zn4—N4^i	2.036 (4)	Zn2—N2^vi	2.004 (4)
Zn4—N4^ii	2.036 (4)	Zn2—N2^vii	2.004 (4)
Zn4—N4^iii	2.036 (4)	Zn2—N2^viii	2.004 (4)
Zn3—S4	2.3551 (13)	Zn1—S1	2.3442 (13)
Zn3—S4^iv	2.3552 (13)	Zn1—S1^ix	2.3442 (13)
Zn3—S4^v	2.3552 (13)	Zn1—S1^vii	2.3442 (13)
Zn3—S4^i	2.3552 (13)	Zn1—S1^x	2.3442 (13)
S4—C4	1.730 (5)	S1—C1	1.728 (5)
S5—C4	1.722 (5)	S2—C2	1.730 (5)
S5—C5	1.732 (5)	S2—C1	1.736 (5)
S6—C5	1.730 (5)	S3—C2	1.734 (5)
S6—C6	1.787 (8)	S3—C3	1.798 (6)
N4—C4	1.324 (7)	N1—C2	1.299 (6)
N4—N3	1.391 (5)	N1—N2	1.383 (5)
N3—C5	1.304 (6)	N2—C1	1.311 (6)
C6—H6A	0.9600	C3—H3A	0.9600
C6—H6B	0.9599	C3—H3B	0.9600
C6—H6C	0.9600	C3—H3C	0.9600
N4—Zn4—N4^i	120.3 (2)	N2—Zn2—N2^vi	105.99 (11)
N4—Zn4—N4^ii	104.35 (10)	N2—Zn2—N2^vii	116.7 (2)
N4^i—Zn4—N4^ii	104.35 (10)	N2^vi—Zn2—N2^vii	105.99 (11)
N4—Zn4—N4^iii	104.35 (10)	N2—Zn2—N2^viii	105.99 (11)
N4^i—Zn4—N4^iii	104.35 (10)	N2^vi—Zn2—N2^viii	116.7 (2)
N4^ii—Zn4—N4^iii	120.3 (2)	N2^vii—Zn2—N2^viii	105.99 (11)
S4—Zn3—S4^iv	110.44 (3)	S1—Zn1—S1^ix	107.61 (3)
S4—Zn3—S4^v	110.44 (3)	S1—Zn1—S1^vii	113.26 (7)
S4^iv—Zn3—S4^v	107.55 (6)	S1^ix—Zn1—S1^vii	107.61 (3)
S4—Zn3—S4^i	107.55 (6)	S1—Zn1—S1^x	107.61 (3)
S4^iv—Zn3—S4^i	110.44 (3)	S1^ix—Zn1—S1^x	113.26 (7)
S4^v—Zn3—S4^i	110.44 (3)	S1^vii—Zn1—S1^x	107.61 (3)
C4—S4—Zn3	97.21 (16)	C1—S1—Zn1	97.79 (16)
C4—S5—C5	88.3 (3)	C2—S2—C1	87.9 (2)
C5—S6—C6	101.7 (3)	C2—S3—C3	99.8 (3)
C4—N4—N3	114.7 (4)	C2—N1—N2	111.3 (4)
C4—N4—Zn4	126.2 (3)	C1—N2—N1	114.8 (4)
N3—N4—Zn4	119.1 (3)	C1—N2—Zn2	130.5 (3)
C5—N3—N4	110.7 (4)	N1—N2—Zn2	114.5 (3)
N4—C4—S5	111.7 (4)	N2—C1—S1	126.2 (4)
N4—C4—S4	124.8 (4)	N2—C1—S2	111.6 (4)
S5—C4—S4	123.5 (3)	S1—C1—S2	122.2 (3)
N3—C5—S6	125.7 (4)	N1—C2—S2	114.4 (4)
N3—C5—S5	114.6 (4)	N1—C2—S3	124.2 (4)
S6—C5—S5	119.7 (3)	S2—C2—S3	121.4 (3)
S6—C6—H6A	109.5	S3—C3—H3A	109.5
S6—C6—H6B	109.5	S3—C3—H3B	109.5
H6A—C6—H6B	109.5	H3A—C3—H3B	109.5
S6—C6—H6C	109.5	S3—C3—H3C	109.5
H6A—C6—H6C	109.5	H3A—C3—H3C	109.5
H6B—C6—H6C	109.5	H3B—C3—H3C	109.5
C4—N4—N3—C5	−1.1 (6)	C2—N1—N2—C1	1.1 (6)
Zn4—N4—N3—C5	177.0 (3)	C2—N1—N2—Zn2	−174.1 (3)
N3—N4—C4—S5	0.9 (5)	N1—N2—C1—S1	179.5 (3)
Zn4—N4—C4—S5	−177.2 (2)	Zn2—N2—C1—S1	−6.2 (7)
N3—N4—C4—S4	179.6 (3)	N1—N2—C1—S2	−1.2 (5)
Zn4—N4—C4—S4	1.5 (6)	Zn2—N2—C1—S2	173.1 (3)
C5—S5—C4—N4	−0.3 (4)	Zn1—S1—C1—N2	−82.5 (4)
C5—S5—C4—S4	−179.0 (4)	Zn1—S1—C1—S2	98.2 (3)
Zn3—S4—C4—N4	89.0 (4)	C2—S2—C1—N2	0.7 (4)
Zn3—S4—C4—S5	−92.5 (3)	C2—S2—C1—S1	−179.9 (3)
N4—N3—C5—S6	−179.0 (4)	N2—N1—C2—S2	−0.6 (5)
N4—N3—C5—S5	0.9 (6)	N2—N1—C2—S3	178.3 (3)
C6—S6—C5—N3	8.9 (6)	C1—S2—C2—N1	−0.1 (4)
C6—S6—C5—S5	−170.9 (4)	C1—S2—C2—S3	−179.0 (3)
C4—S5—C5—N3	−0.4 (4)	C3—S3—C2—N1	−4.7 (5)
C4—S5—C5—S6	179.5 (4)	C3—S3—C2—S2	174.1 (3)

Symmetry codes: (i) −x+1, −y+1, z; (ii) −y+1, x, −z+1; (iii) y, −x+1, −z+1; (iv) −y+1, x, −z+2; (v) y, −x+1, −z+2; (vi) −y+3/2, x−1/2, −z+3/2; (vii) −x+2, −y+1, z; (viii) y+1/2, −x+3/2, −z+3/2; (ix) y+1/2, −x+3/2, −z+5/2; (x) −y+3/2, x−1/2, −z+5/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3C···S6^xi	0.96	3.02	3.887 (7)	151
C3—H3B···N3^ii	0.96	2.48	3.392 (7)	158
C6—H6B···S1^xii	0.96	3.04	3.599 (7)	119
C6—H6B···S1^xii	0.96	3.04	3.599 (7)	119
C3—H3B···N3^ii	0.96	2.48	3.392 (7)	158
C3—H3C···S6^xi	0.96	3.02	3.887 (7)	151

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