Competition between chalcogen and halogen bonding assessed through isostructural species

The amino group of 2-amino-5-(4-halophen­yl)-1,3,4-chalcogena­diazole has been replaced with bromo/iodo substituents to obtain a library of four compositionally related com­pounds. These are 2-iodo-5-(4-iodo­phen­yl)-1,3,4-thia­di­azole, C₈H₄I₂N₂S, 2-bromo-5-(4-bromo­phen­yl)-1,3,4-selena­diazole, C₈H₄Br₂N₂Se, 2-bromo-5-(4-iodo­phen­yl)-1,3,4-selena­diazole, C₈H₄BrIN₂Se, and 2-bromo-5-(4-iodo­phen­yl)-1,3,4-thia­diazole, C₈H₄BrIN₂S. All were isostructural and contained bifurcated Ch...N (Ch is chalcogen) and X...X (X is halogen) inter­actions forming a zigzag packing motif. The noncovalent Ch...N inter­action between the chalcogen-bond donor and the best-acceptor N atom appeared preferentially instead of a possible halogen bond to the same N atom. Hirshfeld surface analysis and energy framework calculations showed that, collectively, a bifurcated chalcogen bond was stronger than halogen bonding and this is more structurally influential in this system.

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2020) for T1, T4; CrysAlis PRO 1.171.41.76a (Rigaku OD, 2020) for T2; CrysAlis PRO 1.171.40.84a (Rigaku OD, 2020) for T3. Cell refinement: CrysAlis PRO (Rigaku OD, 2020) for T1, T4; CrysAlis PRO 1.171.41.76a (Rigaku OD, 2020) for T2; CrysAlis PRO 1.171.40.84a (Rigaku OD, 2020) for T3. Data reduction: CrysAlis PRO (Rigaku OD, 2020) for T1, T4; CrysAlis PRO 1.171.41.76a (Rigaku OD, 2020) for T2; CrysAlis PRO 1.171.40.84a (Rigaku OD, 2020) for T3. Program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a) for T1; SHELXT (Sheldrick, 2015a) for T2, T3, T4. For all structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

2-Iodo-5-(4-iodophenyl)-1,3,4-thiadiazole (T1)

Crystal data

C8H4I2N2S	Dx = 2.608 Mg m^−3
Mr = 413.99	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 5508 reflections
a = 11.0392 (2) Å	θ = 3.8–69.0°
b = 8.1756 (2) Å	µ = 48.34 mm^−1
c = 23.3673 (4) Å	T = 293 K
V = 2108.95 (7) Å^3	Block, colourless
Z = 8	0.07 × 0.05 × 0.03 mm
F(000) = 1504

Data collection

Rigaku XtaLAB Synergy Custom diffractometer with a HyPix-Arc 150° detector	1942 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source	1753 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.024
Detector resolution: 10.0000 pixels mm^-1	θmax = 69.1°, θmin = 3.8°
ω scans	h = −11→13
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2020)	k = −8→9
Tmin = 0.209, Tmax = 0.522	l = −24→28
8336 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0388P)^2 + 4.6153P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
1942 reflections	Δρmax = 1.33 e Å^−3
118 parameters	Δρmin = −1.22 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
C1	0.6455 (4)	0.4015 (5)	0.40675 (18)	0.0196 (9)
C2	0.5284 (4)	0.4540 (6)	0.39544 (19)	0.0209 (9)
H2	0.465059	0.421230	0.419049	0.025*
C3	0.5054 (4)	0.5556 (5)	0.34887 (18)	0.0207 (9)
H3	0.427089	0.591795	0.341467	0.025*
C4	0.6006 (4)	0.6024 (5)	0.31353 (18)	0.0218 (9)
C5	0.7186 (4)	0.5514 (5)	0.32447 (19)	0.0245 (10)
H5	0.782009	0.584936	0.301019	0.029*
C6	0.7402 (4)	0.4498 (6)	0.37097 (18)	0.0219 (9)
H6	0.818500	0.413535	0.378344	0.026*
C7	0.6712 (4)	0.2974 (5)	0.45654 (18)	0.0205 (9)
N8	0.7801 (3)	0.2525 (4)	0.47101 (17)	0.0242 (9)
N9	0.7827 (3)	0.1583 (5)	0.52011 (16)	0.0243 (8)
C10	0.6745 (4)	0.1372 (5)	0.54045 (18)	0.0212 (9)
S11	0.55940 (10)	0.22850 (15)	0.50283 (5)	0.0246 (3)
I12	0.64084 (3)	0.00912 (3)	0.61590 (2)	0.02546 (12)
I13	0.56375 (3)	0.75148 (3)	0.24272 (2)	0.02576 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.021 (2)	0.018 (2)	0.020 (2)	0.0000 (17)	0.0006 (17)	−0.0003 (18)
C2	0.019 (2)	0.020 (2)	0.023 (2)	−0.0004 (18)	0.0016 (18)	−0.0021 (18)
C3	0.021 (2)	0.020 (2)	0.021 (2)	0.0020 (18)	0.0001 (18)	0.0002 (18)
C4	0.028 (2)	0.0163 (19)	0.021 (2)	0.0016 (18)	0.0005 (19)	−0.0001 (17)
C5	0.027 (2)	0.019 (2)	0.027 (2)	−0.0020 (19)	0.0067 (18)	−0.0058 (19)
C6	0.021 (2)	0.017 (2)	0.028 (2)	−0.0010 (18)	0.0026 (19)	−0.0052 (18)
C7	0.022 (2)	0.019 (2)	0.020 (2)	−0.0014 (18)	−0.0009 (18)	0.0002 (18)
N8	0.021 (2)	0.027 (2)	0.0241 (19)	0.0015 (16)	−0.0022 (15)	0.0023 (16)
N9	0.024 (2)	0.027 (2)	0.0223 (17)	0.0037 (17)	−0.0021 (16)	0.0015 (16)
C10	0.022 (2)	0.018 (2)	0.024 (2)	0.0003 (18)	−0.0040 (19)	−0.0023 (18)
S11	0.0187 (6)	0.0283 (6)	0.0267 (6)	0.0013 (4)	−0.0004 (4)	0.0053 (5)
I12	0.0279 (2)	0.02557 (18)	0.02293 (18)	0.00177 (11)	−0.00234 (11)	0.00194 (11)
I13	0.0349 (2)	0.02059 (18)	0.02173 (18)	−0.00176 (11)	−0.00195 (11)	0.00162 (11)

Geometric parameters (Å, º)

C1—C2	1.388 (6)	C5—H5	0.9300
C1—C6	1.395 (6)	C5—C6	1.389 (6)
C1—C7	1.469 (6)	C6—H6	0.9300
C2—H2	0.9300	C7—N8	1.302 (6)
C2—C3	1.392 (6)	C7—S11	1.735 (4)
C3—H3	0.9300	N8—N9	1.382 (5)
C3—C4	1.390 (6)	N9—C10	1.297 (6)
C4—C5	1.391 (6)	C10—S11	1.716 (4)
C4—I13	2.095 (4)	C10—I12	2.084 (4)
C2—C1—C6	119.7 (4)	C6—C5—H5	120.5
C2—C1—C7	120.6 (4)	C1—C6—H6	119.7
C6—C1—C7	119.6 (4)	C5—C6—C1	120.7 (4)
C1—C2—H2	119.9	C5—C6—H6	119.7
C1—C2—C3	120.2 (4)	C1—C7—S11	123.0 (3)
C3—C2—H2	119.9	N8—C7—C1	123.2 (4)
C2—C3—H3	120.3	N8—C7—S11	113.8 (3)
C4—C3—C2	119.4 (4)	C7—N8—N9	113.1 (4)
C4—C3—H3	120.3	C10—N9—N8	111.1 (3)
C3—C4—C5	121.1 (4)	N9—C10—S11	115.9 (3)
C3—C4—I13	118.8 (3)	N9—C10—I12	122.8 (3)
C5—C4—I13	120.1 (3)	S11—C10—I12	121.3 (2)
C4—C5—H5	120.5	C10—S11—C7	86.2 (2)
C6—C5—C4	118.9 (4)
C1—C2—C3—C4	0.7 (7)	C6—C1—C7—S11	−179.0 (3)
C1—C7—N8—N9	178.4 (4)	C7—C1—C2—C3	178.6 (4)
C1—C7—S11—C10	−178.5 (4)	C7—C1—C6—C5	−178.4 (4)
C2—C1—C6—C5	0.7 (7)	C7—N8—N9—C10	−0.1 (5)
C2—C1—C7—N8	−175.9 (4)	N8—C7—S11—C10	−0.4 (4)
C2—C1—C7—S11	1.9 (6)	N8—N9—C10—S11	−0.2 (5)
C2—C3—C4—C5	−1.0 (6)	N8—N9—C10—I12	−177.7 (3)
C2—C3—C4—I13	178.8 (3)	N9—C10—S11—C7	0.3 (4)
C3—C4—C5—C6	1.2 (6)	S11—C7—N8—N9	0.4 (5)
C4—C5—C6—C1	−1.0 (7)	I12—C10—S11—C7	177.9 (3)
C6—C1—C2—C3	−0.5 (7)	I13—C4—C5—C6	−178.6 (3)
C6—C1—C7—N8	3.2 (7)

2-Bromo-5-(4-bromophenyl)-1,3,4-selenadiazole (T2)

Crystal data

C8H4Br2N2Se	Dx = 2.407 Mg m^−3
Mr = 366.91	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 3007 reflections
a = 11.1945 (5) Å	θ = 3.5–74.7°
b = 7.1006 (3) Å	µ = 13.90 mm^−1
c = 25.4725 (9) Å	T = 100 K
V = 2024.74 (15) Å^3	Irregular, orange
Z = 8	0.02 × 0.02 × 0.02 mm
F(000) = 1360

Data collection

Rigaku XtaLAB Synergy Custom diffractometer with a HyPix-Arc 150° detector	1965 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	1709 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.037
Detector resolution: 10.0000 pixels mm^-1	θmax = 74.8°, θmin = 3.5°
ω scans	h = −9→13
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2020)	k = −8→8
Tmin = 0.682, Tmax = 1.000	l = −29→30
6457 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 15.9376P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
1965 reflections	Δρmax = 1.95 e Å^−3
118 parameters	Δρmin = −1.46 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
C1	0.3302 (5)	0.3834 (8)	0.5943 (2)	0.0221 (12)
C2	0.4462 (6)	0.4100 (9)	0.6138 (2)	0.0281 (13)
H2	0.513177	0.382973	0.592141	0.034*
C3	0.4634 (7)	0.4753 (9)	0.6643 (3)	0.0350 (15)
H3	0.541775	0.495041	0.677551	0.042*
C4	0.3654 (7)	0.5113 (9)	0.6952 (2)	0.0329 (15)
C5	0.2498 (7)	0.4874 (8)	0.6768 (2)	0.0316 (14)
H5	0.183353	0.515334	0.698698	0.038*
C6	0.2326 (6)	0.4222 (8)	0.6263 (2)	0.0276 (13)
H6	0.153883	0.403931	0.613314	0.033*
C7	0.3101 (5)	0.3151 (8)	0.5401 (2)	0.0180 (11)
N8	0.2045 (4)	0.2908 (7)	0.52118 (18)	0.0227 (10)
N9	0.2012 (4)	0.2252 (7)	0.46988 (18)	0.0227 (10)
C10	0.3064 (5)	0.2028 (8)	0.4508 (2)	0.0211 (12)
Se11	0.43492 (5)	0.25540 (9)	0.49395 (2)	0.02259 (19)
Br12	0.32759 (6)	0.11997 (9)	0.38120 (2)	0.0301 (2)
Br13	0.39006 (10)	0.60799 (12)	0.76394 (3)	0.0541 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.033 (3)	0.017 (3)	0.016 (3)	0.000 (2)	−0.001 (2)	0.002 (2)
C2	0.036 (3)	0.030 (3)	0.018 (3)	−0.008 (3)	−0.002 (3)	0.009 (2)
C3	0.048 (4)	0.031 (3)	0.026 (3)	−0.007 (3)	−0.010 (3)	0.007 (3)
C4	0.059 (4)	0.026 (3)	0.014 (3)	−0.003 (3)	−0.002 (3)	0.004 (2)
C5	0.053 (4)	0.018 (3)	0.023 (3)	0.005 (3)	0.008 (3)	0.002 (3)
C6	0.034 (3)	0.020 (3)	0.028 (3)	0.004 (3)	0.000 (3)	0.002 (2)
C7	0.017 (3)	0.013 (2)	0.024 (3)	0.002 (2)	−0.001 (2)	0.002 (2)
N8	0.023 (2)	0.027 (3)	0.018 (2)	−0.002 (2)	0.0004 (19)	0.005 (2)
N9	0.024 (2)	0.024 (3)	0.020 (2)	−0.003 (2)	−0.0022 (19)	0.002 (2)
C10	0.026 (3)	0.017 (3)	0.020 (3)	−0.003 (2)	0.002 (2)	0.001 (2)
Se11	0.0167 (3)	0.0242 (3)	0.0269 (3)	−0.0007 (2)	0.0013 (2)	−0.0020 (2)
Br12	0.0405 (4)	0.0285 (3)	0.0213 (3)	−0.0041 (3)	0.0050 (3)	−0.0039 (3)
Br13	0.1013 (8)	0.0407 (4)	0.0205 (3)	−0.0056 (5)	−0.0081 (4)	−0.0012 (3)

Geometric parameters (Å, º)

C1—C2	1.403 (9)	C5—H5	0.9500
C1—C6	1.391 (9)	C5—C6	1.382 (8)
C1—C7	1.479 (8)	C6—H6	0.9500
C2—H2	0.9500	C7—N8	1.288 (7)
C2—C3	1.383 (9)	C7—Se11	1.876 (5)
C3—H3	0.9500	N8—N9	1.388 (7)
C3—C4	1.373 (10)	N9—C10	1.284 (7)
C4—C5	1.387 (10)	C10—Se11	1.849 (6)
C4—Br13	1.901 (6)	C10—Br12	1.882 (6)
C2—C1—C7	121.0 (5)	C6—C5—H5	120.5
C6—C1—C2	119.5 (5)	C1—C6—H6	119.9
C6—C1—C7	119.4 (5)	C5—C6—C1	120.2 (6)
C1—C2—H2	119.9	C5—C6—H6	119.9
C3—C2—C1	120.3 (6)	C1—C7—Se11	123.0 (4)
C3—C2—H2	119.9	N8—C7—C1	122.2 (5)
C2—C3—H3	120.5	N8—C7—Se11	114.7 (4)
C4—C3—C2	119.0 (6)	C7—N8—N9	115.0 (5)
C4—C3—H3	120.5	C10—N9—N8	112.0 (5)
C3—C4—C5	122.0 (6)	N9—C10—Se11	117.6 (4)
C3—C4—Br13	118.6 (5)	N9—C10—Br12	120.7 (4)
C5—C4—Br13	119.3 (5)	Se11—C10—Br12	121.7 (3)
C4—C5—H5	120.5	C10—Se11—C7	80.7 (2)
C6—C5—C4	119.0 (6)
C1—C2—C3—C4	0.8 (9)	C6—C1—C7—Se11	−179.2 (4)
C1—C7—N8—N9	−179.7 (5)	C7—C1—C2—C3	179.5 (5)
C1—C7—Se11—C10	−179.8 (5)	C7—C1—C6—C5	−179.6 (5)
C2—C1—C6—C5	0.3 (9)	C7—N8—N9—C10	−0.6 (7)
C2—C1—C7—N8	−179.5 (5)	N8—C7—Se11—C10	0.6 (4)
C2—C1—C7—Se11	1.0 (8)	N8—N9—C10—Se11	1.1 (6)
C2—C3—C4—C5	−1.2 (10)	N8—N9—C10—Br12	−178.7 (4)
C2—C3—C4—Br13	−178.2 (5)	N9—C10—Se11—C7	−1.0 (5)
C3—C4—C5—C6	1.2 (9)	Se11—C7—N8—N9	−0.2 (6)
C4—C5—C6—C1	−0.7 (9)	Br12—C10—Se11—C7	178.8 (4)
C6—C1—C2—C3	−0.3 (9)	Br13—C4—C5—C6	178.1 (4)
C6—C1—C7—N8	0.3 (8)

2-Bromo-5-(4-iodophenyl)-1,3,4-selenadiazole (T3)

Crystal data

C8H4BrIN2Se	Dx = 2.638 Mg m^−3
Mr = 413.90	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 7358 reflections
a = 11.1735 (4) Å	θ = 2.4–33.0°
b = 7.1222 (2) Å	µ = 10.36 mm^−1
c = 26.1875 (8) Å	T = 100 K
V = 2084.00 (11) Å^3	Plate, clear light yellow
Z = 8	0.3 × 0.1 × 0.06 mm
F(000) = 1504

Data collection

Rigaku XtaLAB Synergy Custom diffractometer with a HyPix-Arc 150° detector	2055 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	1815 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.035
Detector resolution: 10.0000 pixels mm^-1	θmax = 26.0°, θmin = 2.4°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2020)	k = −7→8
Tmin = 0.338, Tmax = 1.000	l = −32→32
12091 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.070	w = 1/[σ^2(Fo^2) + (0.030P)^2 + 10.0022P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2055 reflections	Δρmax = 2.00 e Å^−3
118 parameters	Δρmin = −1.01 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
C1	0.6730 (4)	0.6139 (6)	0.59069 (17)	0.0149 (9)
C2	0.5578 (4)	0.5876 (7)	0.61022 (17)	0.0196 (10)
H2	0.4902	0.6141	0.5894	0.023*
C3	0.5414 (5)	0.5230 (7)	0.65978 (18)	0.0226 (10)
H3	0.4630	0.5045	0.6729	0.027*
C4	0.6408 (5)	0.4859 (6)	0.68987 (16)	0.0195 (10)
C5	0.7557 (5)	0.5112 (6)	0.67115 (17)	0.0213 (10)
H5	0.8227	0.4847	0.6923	0.026*
C6	0.7731 (4)	0.5751 (6)	0.62163 (17)	0.0176 (10)
H6	0.8518	0.5925	0.6087	0.021*
C7	0.6914 (4)	0.6814 (6)	0.53853 (16)	0.0122 (9)
N8	0.7974 (3)	0.7053 (5)	0.51957 (14)	0.0171 (8)
N9	0.8006 (3)	0.7683 (5)	0.46942 (14)	0.0184 (8)
C10	0.6957 (4)	0.7927 (6)	0.45060 (17)	0.0151 (9)
Se11	0.56664 (4)	0.74266 (7)	0.49341 (2)	0.01587 (12)
Br12	0.67471 (4)	0.87353 (7)	0.38316 (2)	0.02129 (13)
I13	0.61637 (4)	0.38409 (5)	0.76407 (2)	0.03129 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.021 (2)	0.009 (2)	0.015 (2)	0.0004 (18)	0.0006 (17)	−0.0032 (17)
C2	0.024 (2)	0.020 (2)	0.015 (2)	−0.001 (2)	0.0017 (18)	−0.0052 (18)
C3	0.032 (3)	0.017 (2)	0.018 (2)	−0.005 (2)	0.0090 (19)	−0.005 (2)
C4	0.037 (3)	0.013 (2)	0.009 (2)	−0.003 (2)	0.0035 (18)	−0.0017 (18)
C5	0.032 (3)	0.014 (2)	0.018 (2)	0.002 (2)	−0.006 (2)	−0.006 (2)
C6	0.021 (2)	0.013 (2)	0.019 (2)	0.0007 (19)	−0.0012 (18)	−0.0013 (19)
C7	0.010 (2)	0.010 (2)	0.017 (2)	0.0010 (16)	−0.0019 (16)	−0.0065 (18)
N8	0.022 (2)	0.018 (2)	0.0111 (18)	−0.0010 (16)	−0.0003 (15)	−0.0007 (15)
N9	0.022 (2)	0.019 (2)	0.0140 (18)	−0.0021 (17)	0.0018 (15)	−0.0007 (16)
C10	0.021 (2)	0.012 (2)	0.012 (2)	−0.0014 (18)	−0.0026 (17)	−0.0018 (17)
Se11	0.0099 (2)	0.0196 (2)	0.0181 (2)	−0.00013 (18)	−0.00108 (16)	0.00323 (18)
Br12	0.0272 (3)	0.0214 (3)	0.0153 (2)	−0.0024 (2)	−0.00289 (17)	0.00333 (19)
I13	0.0553 (3)	0.0243 (2)	0.01430 (18)	−0.00140 (16)	0.00484 (14)	0.00152 (13)

Geometric parameters (Å, º)

C1—C2	1.398 (7)	C5—H5	0.9500
C1—C6	1.408 (6)	C5—C6	1.388 (6)
C1—C7	1.462 (6)	C6—H6	0.9500
C2—H2	0.9500	C7—N8	1.295 (6)
C2—C3	1.389 (7)	C7—Se11	1.879 (4)
C3—H3	0.9500	N8—N9	1.388 (5)
C3—C4	1.387 (7)	N9—C10	1.284 (6)
C4—C5	1.386 (7)	C10—Se11	1.861 (5)
C4—I13	2.092 (4)	C10—Br12	1.872 (4)
C2—C1—C6	119.6 (4)	C6—C5—H5	119.9
C2—C1—C7	121.0 (4)	C1—C6—H6	120.3
C6—C1—C7	119.4 (4)	C5—C6—C1	119.4 (4)
C1—C2—H2	119.7	C5—C6—H6	120.3
C3—C2—C1	120.5 (5)	C1—C7—Se11	124.0 (3)
C3—C2—H2	119.7	N8—C7—C1	122.0 (4)
C2—C3—H3	120.4	N8—C7—Se11	114.0 (3)
C4—C3—C2	119.2 (5)	C7—N8—N9	115.4 (4)
C4—C3—H3	120.4	C10—N9—N8	112.5 (4)
C3—C4—I13	119.3 (3)	N9—C10—Se11	116.8 (3)
C5—C4—C3	121.1 (4)	N9—C10—Br12	121.2 (3)
C5—C4—I13	119.6 (4)	Se11—C10—Br12	122.0 (2)
C4—C5—H5	119.9	C10—Se11—C7	81.29 (19)
C4—C5—C6	120.2 (4)
C1—C2—C3—C4	0.4 (7)	C6—C1—C7—Se11	−178.9 (3)
C1—C7—N8—N9	179.4 (4)	C7—C1—C2—C3	179.8 (4)
C1—C7—Se11—C10	−179.4 (4)	C7—C1—C6—C5	180.0 (4)
C2—C1—C6—C5	0.0 (7)	C7—N8—N9—C10	0.3 (6)
C2—C1—C7—N8	−179.5 (4)	N8—C7—Se11—C10	1.1 (3)
C2—C1—C7—Se11	1.1 (6)	N8—N9—C10—Se11	0.7 (5)
C2—C3—C4—C5	−0.4 (7)	N8—N9—C10—Br12	−179.0 (3)
C2—C3—C4—I13	−178.9 (3)	N9—C10—Se11—C7	−1.0 (4)
C3—C4—C5—C6	0.2 (7)	Se11—C7—N8—N9	−1.1 (5)
C4—C5—C6—C1	0.0 (7)	Br12—C10—Se11—C7	178.7 (3)
C6—C1—C2—C3	−0.2 (7)	I13—C4—C5—C6	178.7 (3)
C6—C1—C7—N8	0.6 (6)

2-Bromo-5-(4-iodophenyl)-1,3,4-thiadiazole (T4)

Crystal data

C8H4BrIN2S	Dx = 2.401 Mg m^−3
Mr = 367.00	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 5134 reflections
a = 10.9919 (2) Å	θ = 3.3–70.6°
b = 6.9945 (1) Å	µ = 30.95 mm^−1
c = 26.4076 (4) Å	T = 293 K
V = 2030.29 (6) Å^3	Plate, colourless
Z = 8	0.05 × 0.04 × 0.01 mm
F(000) = 1360

Data collection

Rigaku XtaLAB Synergy Custom diffractometer with a HyPix-Arc 150° detector	1920 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source	1802 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.025
Detector resolution: 10.0000 pixels mm^-1	θmax = 70.7°, θmin = 3.4°
ω scans	h = −13→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2020)	k = −8→7
Tmin = 0.373, Tmax = 1.000	l = −27→31
7258 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.021	H-atom parameters constrained
wR(F^2) = 0.052	w = 1/[σ^2(Fo^2) + (0.0219P)^2 + 2.6464P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
1920 reflections	Δρmax = 0.57 e Å^−3
118 parameters	Δρmin = −0.67 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
C1	0.6729 (3)	0.3732 (4)	0.40837 (11)	0.0202 (6)
C2	0.5551 (3)	0.4009 (4)	0.38896 (11)	0.0228 (7)
H2	0.487684	0.378054	0.409375	0.027*
C3	0.5392 (3)	0.4619 (5)	0.33964 (11)	0.0252 (7)
H3	0.461242	0.482985	0.327092	0.030*
C4	0.6391 (3)	0.4915 (5)	0.30907 (11)	0.0245 (7)
C5	0.7571 (3)	0.4651 (5)	0.32710 (11)	0.0232 (6)
H5	0.823891	0.487009	0.306263	0.028*
C6	0.7730 (3)	0.4053 (4)	0.37681 (12)	0.0217 (6)
H6	0.851192	0.386382	0.389268	0.026*
C7	0.6931 (3)	0.3097 (5)	0.46055 (11)	0.0205 (6)
N8	0.8022 (2)	0.2851 (4)	0.47936 (9)	0.0229 (6)
N9	0.8006 (2)	0.2255 (4)	0.52908 (9)	0.0236 (6)
C10	0.6900 (3)	0.2081 (5)	0.54533 (11)	0.0225 (6)
S11	0.57681 (6)	0.25939 (12)	0.50282 (3)	0.02332 (17)
Br12	0.65699 (3)	0.13399 (5)	0.61220 (2)	0.02781 (10)
I13	0.61471 (2)	0.58780 (3)	0.23455 (2)	0.03153 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0209 (14)	0.0211 (16)	0.0184 (15)	0.0008 (12)	0.0000 (12)	−0.0028 (11)
C2	0.0190 (15)	0.0291 (18)	0.0204 (15)	0.0019 (12)	−0.0010 (12)	−0.0040 (12)
C3	0.0244 (15)	0.0303 (18)	0.0211 (14)	0.0021 (14)	−0.0046 (13)	−0.0044 (13)
C4	0.0322 (16)	0.0261 (17)	0.0152 (14)	0.0011 (14)	−0.0025 (12)	−0.0021 (13)
C5	0.0246 (14)	0.0259 (17)	0.0192 (14)	0.0008 (13)	0.0030 (12)	−0.0013 (13)
C6	0.0202 (14)	0.0236 (16)	0.0214 (15)	−0.0017 (12)	−0.0003 (12)	−0.0004 (12)
C7	0.0158 (13)	0.0244 (16)	0.0214 (14)	0.0011 (13)	0.0022 (11)	−0.0026 (12)
N8	0.0170 (12)	0.0342 (15)	0.0175 (12)	0.0005 (12)	0.0000 (9)	−0.0004 (11)
N9	0.0201 (12)	0.0331 (15)	0.0176 (12)	0.0025 (12)	−0.0008 (10)	−0.0007 (11)
C10	0.0221 (14)	0.0267 (16)	0.0185 (14)	0.0021 (13)	−0.0008 (12)	0.0010 (12)
S11	0.0155 (3)	0.0343 (4)	0.0201 (3)	0.0007 (3)	0.0012 (3)	0.0040 (3)
Br12	0.02913 (18)	0.0356 (2)	0.01864 (17)	0.00341 (15)	0.00365 (13)	0.00393 (13)
I13	0.04468 (15)	0.03386 (14)	0.01605 (12)	0.00057 (10)	−0.00390 (8)	0.00102 (8)

Geometric parameters (Å, º)

C1—C2	1.407 (4)	C5—H5	0.9300
C1—C6	1.398 (4)	C5—C6	1.388 (4)
C1—C7	1.465 (4)	C6—H6	0.9300
C2—H2	0.9300	C7—N8	1.309 (4)
C2—C3	1.382 (4)	C7—S11	1.733 (3)
C3—H3	0.9300	N8—N9	1.378 (3)
C3—C4	1.379 (4)	N9—C10	1.295 (4)
C4—C5	1.394 (4)	C10—S11	1.714 (3)
C4—I13	2.097 (3)	C10—Br12	1.876 (3)
C2—C1—C7	121.6 (3)	C6—C5—H5	120.7
C6—C1—C2	119.0 (3)	C1—C6—H6	119.6
C6—C1—C7	119.4 (3)	C5—C6—C1	120.9 (3)
C1—C2—H2	119.9	C5—C6—H6	119.6
C3—C2—C1	120.2 (3)	C1—C7—S11	123.8 (2)
C3—C2—H2	119.9	N8—C7—C1	122.4 (3)
C2—C3—H3	120.1	N8—C7—S11	113.9 (2)
C4—C3—C2	119.8 (3)	C7—N8—N9	113.0 (2)
C4—C3—H3	120.1	C10—N9—N8	110.8 (2)
C3—C4—C5	121.4 (3)	N9—C10—S11	116.4 (2)
C3—C4—I13	119.7 (2)	N9—C10—Br12	121.3 (2)
C5—C4—I13	118.8 (2)	S11—C10—Br12	122.26 (17)
C4—C5—H5	120.7	C10—S11—C7	85.92 (14)
C6—C5—C4	118.7 (3)
C1—C2—C3—C4	1.5 (5)	C6—C1—C7—S11	−178.3 (2)
C1—C7—N8—N9	179.9 (3)	C7—C1—C2—C3	179.6 (3)
C1—C7—S11—C10	−179.7 (3)	C7—C1—C6—C5	179.8 (3)
C2—C1—C6—C5	0.5 (5)	C7—N8—N9—C10	0.0 (4)
C2—C1—C7—N8	−179.3 (3)	N8—C7—S11—C10	0.6 (3)
C2—C1—C7—S11	1.0 (4)	N8—N9—C10—S11	0.5 (4)
C2—C3—C4—C5	−1.4 (5)	N8—N9—C10—Br12	−178.7 (2)
C2—C3—C4—I13	−179.2 (2)	N9—C10—S11—C7	−0.6 (3)
C3—C4—C5—C6	0.8 (5)	S11—C7—N8—N9	−0.5 (4)
C4—C5—C6—C1	−0.4 (5)	Br12—C10—S11—C7	178.6 (2)
C6—C1—C2—C3	−1.0 (5)	I13—C4—C5—C6	178.6 (2)
C6—C1—C7—N8	1.3 (5)