⁷⁷Se and ¹²⁵Te solid-state NMR and X-ray diffraction structural study of chalco­gen-bonded 3,4-di­cyano-1,2,5-chalco­geno­diazole cocrystals

Three novel chalco­gen-bonded cocrystals featuring 3,4-di­cyano-1,2,5-seleno­diazole (C₄N₄Se) or 3,4-di­cyano-1,2,5-telluro­diazole (C₄N₄Te) as chalco­gen-bond donors and hydro­quinone (C₆H₆O₂), tetra­phenyl­phospho­nium chloride (C₂₄H₂₀P⁺·Cl⁻) or tetra­ethyl­phospho­nium chloride (C₈H₂₀P⁺·Cl⁻) as chalco­gen-bond acceptors have been prepared and characterized by single-crystal X-ray diffraction (XRD), powder X-ray diffraction and ⁷⁷Se/¹²⁵Te magic-angle spinning solid-state NMR spectroscopy. The single-crystal XRD results show that the chalco­geno­diazole mol­ecules inter­act with the electron donors through two σ-holes on each of the chalco­gen atoms, which results in highly directional and moderately strong chalco­gen bonds. Powder XRD confirms that the crystalline phases are preserved upon moderate grinding of the samples for solid-state NMR experiments. Measurement of ⁷⁷Se and ¹²⁵Te chemical shift tensors via magic-angle spinning solid-state NMR spectroscopy confirms the number of magnetically unique chalco­gen sites in each asymmetric unit and reveals the impact of chalco­gen-bond formation on the local electronic structure. These NMR data are further assessed in the context of analogous data for a wider range of crystalline chalco­gen-bonded systems.

Computing details

For all structures, data collection: APEX3 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b).

1,2,5-Tellurodiazole-3,4-dicarbonitrile tetraphenylphosphonium chloride (2c)

Crystal data

C4N4Te·C24H20P^+·Cl^−	F(000) = 1200
Mr = 606.50	Dx = 1.575 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 18.2538 (5) Å	Cell parameters from 9980 reflections
b = 7.3008 (2) Å	θ = 2.7–30.5°
c = 20.0497 (5) Å	µ = 1.36 mm^−1
β = 106.867 (2)°	T = 208 K
V = 2557.02 (12) Å^3	Needle, yellow
Z = 4	0.53 × 0.16 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	6408 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω and πhi scans	θmax = 30.6°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −26→26
Tmin = 0.665, Tmax = 0.746	k = −10→6
58500 measured reflections	l = −28→28
7883 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
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) = 0.061	w = 1/[σ^2(Fo^2) + (0.025P)^2 + 1.3443P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.003
7883 reflections	Δρmax = 0.73 e Å^−3
316 parameters	Δρmin = −0.49 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.

Refinement. none

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

	x	y	z	Uiso*/Ueq
Te1	0.76837 (2)	0.11309 (2)	0.40232 (2)	0.03137 (4)
Cl1	0.82995 (4)	−0.21490 (8)	0.44379 (4)	0.06429 (18)
P1	0.53900 (2)	0.50383 (6)	0.79116 (2)	0.02281 (8)
N1	0.63058 (15)	0.2746 (4)	0.59019 (11)	0.0706 (7)
N2	0.73064 (9)	0.0947 (2)	0.48627 (7)	0.0318 (3)
N3	0.71542 (9)	0.3628 (2)	0.38961 (8)	0.0342 (3)
N4	0.60955 (13)	0.6811 (3)	0.44978 (12)	0.0590 (5)
C1	0.65878 (13)	0.2594 (3)	0.54712 (10)	0.0442 (5)
C2	0.69348 (10)	0.2427 (3)	0.49107 (8)	0.0314 (4)
C3	0.68536 (10)	0.3871 (2)	0.43973 (9)	0.0313 (3)
C4	0.64358 (12)	0.5536 (3)	0.44507 (10)	0.0401 (4)
C5	0.51895 (9)	0.6486 (2)	0.71539 (8)	0.0253 (3)
C6	0.54541 (11)	0.6101 (3)	0.65862 (9)	0.0344 (4)
H6	0.574505	0.504130	0.658230	0.041*
C7	0.52839 (12)	0.7302 (3)	0.60231 (10)	0.0443 (5)
H7	0.546203	0.704917	0.563739	0.053*
C8	0.48569 (12)	0.8857 (3)	0.60252 (10)	0.0410 (4)
H8	0.475389	0.966937	0.564530	0.049*
C9	0.45806 (12)	0.9228 (3)	0.65808 (10)	0.0374 (4)
H9	0.428044	1.027677	0.657644	0.045*
C10	0.47469 (11)	0.8047 (3)	0.71477 (9)	0.0328 (4)
H10	0.456069	0.829996	0.752866	0.039*
C11	0.55642 (10)	0.6521 (2)	0.86513 (8)	0.0263 (3)
C12	0.61184 (10)	0.7894 (3)	0.87283 (9)	0.0318 (4)
H12	0.639206	0.801315	0.839924	0.038*
C13	0.62606 (11)	0.9071 (2)	0.92906 (10)	0.0347 (4)
H13	0.663091	0.999740	0.934505	0.042*
C14	0.58572 (12)	0.8883 (3)	0.97730 (9)	0.0373 (4)
H14	0.596101	0.967230	1.015969	0.045*
C15	0.53041 (12)	0.7550 (3)	0.96921 (9)	0.0361 (4)
H15	0.502905	0.744533	1.002063	0.043*
C16	0.51505 (10)	0.6361 (2)	0.91292 (8)	0.0294 (3)
H16	0.477067	0.545648	0.907234	0.035*
C17	0.45931 (9)	0.3566 (2)	0.78705 (8)	0.0239 (3)
C18	0.38917 (10)	0.3841 (2)	0.73768 (9)	0.0290 (3)
H18	0.382532	0.482650	0.706328	0.035*
C19	0.32895 (11)	0.2660 (3)	0.73467 (10)	0.0375 (4)
H19	0.281645	0.282794	0.700683	0.045*
C20	0.33854 (12)	0.1233 (3)	0.78173 (11)	0.0399 (4)
H20	0.297459	0.043856	0.779824	0.048*
C21	0.40827 (12)	0.0964 (3)	0.83176 (10)	0.0367 (4)
H21	0.414100	0.000098	0.863990	0.044*
C22	0.46904 (10)	0.2110 (2)	0.83420 (8)	0.0301 (3)
H22	0.516709	0.191474	0.867346	0.036*
C23	0.62056 (9)	0.3594 (2)	0.79919 (8)	0.0269 (3)
C24	0.68523 (10)	0.3713 (3)	0.85649 (10)	0.0370 (4)
H24	0.688031	0.458834	0.891513	0.044*
C25	0.74562 (12)	0.2515 (3)	0.86109 (13)	0.0516 (6)
H25	0.789755	0.258960	0.899437	0.062*
C26	0.74176 (14)	0.1230 (3)	0.81068 (15)	0.0553 (6)
H26	0.783276	0.043503	0.814499	0.066*
C27	0.67729 (14)	0.1092 (3)	0.75417 (13)	0.0482 (5)
H27	0.675016	0.020198	0.719743	0.058*
C28	0.61616 (11)	0.2258 (3)	0.74808 (10)	0.0348 (4)
H28	0.571945	0.215553	0.709940	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Te1	0.03376 (6)	0.02925 (7)	0.03059 (6)	0.00399 (5)	0.00851 (4)	0.00111 (5)
Cl1	0.0535 (3)	0.0394 (3)	0.1012 (5)	0.0189 (3)	0.0244 (3)	0.0182 (3)
P1	0.02465 (19)	0.0229 (2)	0.02068 (17)	0.00148 (15)	0.00630 (14)	−0.00144 (14)
N1	0.0948 (18)	0.0807 (17)	0.0481 (11)	0.0158 (14)	0.0395 (12)	0.0028 (11)
N2	0.0339 (7)	0.0317 (8)	0.0268 (6)	0.0013 (6)	0.0042 (6)	0.0045 (6)
N3	0.0409 (8)	0.0309 (8)	0.0291 (7)	0.0061 (7)	0.0076 (6)	0.0049 (6)
N4	0.0655 (13)	0.0429 (11)	0.0709 (14)	0.0170 (10)	0.0235 (11)	0.0014 (10)
C1	0.0554 (13)	0.0454 (12)	0.0329 (9)	0.0056 (10)	0.0145 (9)	0.0007 (8)
C2	0.0347 (9)	0.0339 (10)	0.0237 (7)	0.0006 (7)	0.0054 (6)	0.0000 (7)
C3	0.0344 (9)	0.0276 (9)	0.0284 (8)	0.0032 (7)	0.0037 (6)	−0.0005 (7)
C4	0.0451 (11)	0.0361 (10)	0.0374 (9)	0.0054 (9)	0.0094 (8)	−0.0004 (8)
C5	0.0265 (7)	0.0252 (8)	0.0233 (7)	−0.0005 (6)	0.0059 (6)	−0.0003 (6)
C6	0.0365 (9)	0.0395 (10)	0.0306 (8)	0.0059 (8)	0.0149 (7)	0.0030 (8)
C7	0.0471 (11)	0.0583 (14)	0.0317 (9)	0.0030 (10)	0.0181 (8)	0.0081 (9)
C8	0.0402 (10)	0.0441 (11)	0.0348 (9)	−0.0046 (9)	0.0048 (8)	0.0139 (8)
C9	0.0402 (10)	0.0267 (10)	0.0398 (9)	0.0026 (8)	0.0030 (8)	0.0043 (7)
C10	0.0398 (10)	0.0278 (9)	0.0318 (8)	0.0044 (8)	0.0121 (7)	−0.0011 (7)
C11	0.0307 (8)	0.0245 (8)	0.0222 (7)	0.0012 (6)	0.0054 (6)	−0.0021 (6)
C12	0.0348 (9)	0.0298 (9)	0.0303 (8)	−0.0027 (7)	0.0085 (7)	−0.0009 (7)
C13	0.0369 (9)	0.0248 (9)	0.0357 (9)	−0.0024 (7)	−0.0003 (7)	−0.0018 (7)
C14	0.0481 (11)	0.0296 (9)	0.0281 (8)	0.0054 (8)	0.0017 (7)	−0.0074 (7)
C15	0.0479 (11)	0.0353 (10)	0.0266 (8)	0.0048 (8)	0.0131 (7)	−0.0039 (7)
C16	0.0346 (9)	0.0273 (9)	0.0266 (7)	−0.0002 (7)	0.0093 (6)	−0.0023 (6)
C17	0.0271 (7)	0.0217 (8)	0.0234 (7)	0.0020 (6)	0.0083 (6)	−0.0021 (6)
C18	0.0294 (8)	0.0274 (8)	0.0278 (7)	0.0025 (7)	0.0046 (6)	−0.0023 (7)
C19	0.0281 (8)	0.0389 (11)	0.0440 (10)	−0.0021 (8)	0.0082 (7)	−0.0122 (8)
C20	0.0409 (10)	0.0350 (10)	0.0512 (11)	−0.0116 (8)	0.0250 (9)	−0.0152 (9)
C21	0.0548 (12)	0.0265 (9)	0.0358 (9)	−0.0017 (8)	0.0243 (8)	−0.0008 (7)
C22	0.0365 (9)	0.0286 (9)	0.0256 (7)	0.0045 (7)	0.0093 (7)	0.0015 (6)
C23	0.0246 (7)	0.0275 (9)	0.0290 (7)	0.0026 (6)	0.0082 (6)	0.0024 (6)
C24	0.0298 (9)	0.0398 (11)	0.0380 (9)	0.0006 (8)	0.0045 (7)	0.0053 (8)
C25	0.0282 (9)	0.0591 (15)	0.0628 (14)	0.0097 (10)	0.0056 (9)	0.0166 (12)
C26	0.0435 (12)	0.0514 (14)	0.0794 (17)	0.0227 (11)	0.0309 (12)	0.0203 (12)
C27	0.0575 (13)	0.0364 (11)	0.0617 (13)	0.0156 (10)	0.0348 (11)	0.0056 (10)
C28	0.0394 (10)	0.0322 (10)	0.0352 (9)	0.0060 (8)	0.0144 (7)	−0.0001 (7)

Geometric parameters (Å, º)

Te1—N2	1.9994 (15)	C13—C14	1.382 (3)
Te1—N3	2.0448 (15)	C13—H13	0.9400
Te1—Cl1	2.6734 (6)	C14—C15	1.378 (3)
P1—C11	1.7887 (16)	C14—H14	0.9400
P1—C17	1.7911 (17)	C15—C16	1.386 (2)
P1—C23	1.7932 (17)	C15—H15	0.9400
P1—C5	1.7991 (16)	C16—H16	0.9400
N1—C1	1.132 (3)	C17—C18	1.387 (2)
N2—C2	1.295 (2)	C17—C22	1.399 (2)
N3—C3	1.289 (2)	C18—C19	1.384 (3)
N4—C4	1.138 (3)	C18—H18	0.9400
C1—C2	1.446 (3)	C19—C20	1.382 (3)
C2—C3	1.451 (2)	C19—H19	0.9400
C3—C4	1.455 (3)	C20—C21	1.387 (3)
C5—C6	1.388 (2)	C20—H20	0.9400
C5—C10	1.395 (2)	C21—C22	1.379 (3)
C6—C7	1.391 (3)	C21—H21	0.9400
C6—H6	0.9400	C22—H22	0.9400
C7—C8	1.378 (3)	C23—C24	1.391 (2)
C7—H7	0.9400	C23—C28	1.400 (2)
C8—C9	1.377 (3)	C24—C25	1.389 (3)
C8—H8	0.9400	C24—H24	0.9400
C9—C10	1.388 (3)	C25—C26	1.366 (4)
C9—H9	0.9400	C25—H25	0.9400
C10—H10	0.9400	C26—C27	1.380 (4)
C11—C16	1.386 (2)	C26—H26	0.9400
C11—C12	1.400 (2)	C27—C28	1.380 (3)
C12—C13	1.381 (3)	C27—H27	0.9400
C12—H12	0.9400	C28—H28	0.9400
N2—Te1—N3	84.21 (6)	C15—C14—C13	120.57 (17)
N2—Te1—Cl1	83.93 (5)	C15—C14—H14	119.7
N3—Te1—Cl1	168.08 (5)	C13—C14—H14	119.7
C11—P1—C17	110.37 (8)	C14—C15—C16	120.43 (17)
C11—P1—C23	109.77 (8)	C14—C15—H15	119.8
C17—P1—C23	107.06 (8)	C16—C15—H15	119.8
C11—P1—C5	106.75 (8)	C11—C16—C15	119.18 (17)
C17—P1—C5	110.50 (7)	C11—C16—H16	120.4
C23—P1—C5	112.42 (8)	C15—C16—H16	120.4
C2—N2—Te1	108.80 (11)	C18—C17—C22	120.13 (16)
C3—N3—Te1	108.54 (12)	C18—C17—P1	121.02 (13)
N1—C1—C2	178.7 (3)	C22—C17—P1	118.85 (13)
N2—C2—C1	119.02 (17)	C19—C18—C17	119.86 (17)
N2—C2—C3	120.12 (16)	C19—C18—H18	120.1
C1—C2—C3	120.84 (17)	C17—C18—H18	120.1
N3—C3—C2	118.32 (16)	C20—C19—C18	119.86 (18)
N3—C3—C4	121.52 (17)	C20—C19—H19	120.1
C2—C3—C4	120.16 (16)	C18—C19—H19	120.1
N4—C4—C3	178.2 (2)	C19—C20—C21	120.54 (18)
C6—C5—C10	119.77 (16)	C19—C20—H20	119.7
C6—C5—P1	122.66 (13)	C21—C20—H20	119.7
C10—C5—P1	117.57 (12)	C22—C21—C20	119.99 (18)
C5—C6—C7	119.28 (18)	C22—C21—H21	120.0
C5—C6—H6	120.4	C20—C21—H21	120.0
C7—C6—H6	120.4	C21—C22—C17	119.59 (17)
C8—C7—C6	120.66 (18)	C21—C22—H22	120.2
C8—C7—H7	119.7	C17—C22—H22	120.2
C6—C7—H7	119.7	C24—C23—C28	120.18 (17)
C9—C8—C7	120.32 (18)	C24—C23—P1	121.41 (14)
C9—C8—H8	119.8	C28—C23—P1	118.31 (13)
C7—C8—H8	119.8	C25—C24—C23	118.9 (2)
C8—C9—C10	119.74 (18)	C25—C24—H24	120.6
C8—C9—H9	120.1	C23—C24—H24	120.6
C10—C9—H9	120.1	C26—C25—C24	120.9 (2)
C9—C10—C5	120.21 (17)	C26—C25—H25	119.5
C9—C10—H10	119.9	C24—C25—H25	119.5
C5—C10—H10	119.9	C25—C26—C27	120.4 (2)
C16—C11—C12	120.36 (15)	C25—C26—H26	119.8
C16—C11—P1	121.35 (13)	C27—C26—H26	119.8
C12—C11—P1	118.27 (13)	C26—C27—C28	120.1 (2)
C13—C12—C11	119.60 (17)	C26—C27—H27	119.9
C13—C12—H12	120.2	C28—C27—H27	119.9
C11—C12—H12	120.2	C27—C28—C23	119.45 (19)
C12—C13—C14	119.84 (18)	C27—C28—H28	120.3
C12—C13—H13	120.1	C23—C28—H28	120.3
C14—C13—H13	120.1
Te1—N2—C2—C1	178.40 (15)	C13—C14—C15—C16	0.8 (3)
Te1—N2—C2—C3	0.0 (2)	C12—C11—C16—C15	−1.4 (3)
Te1—N3—C3—C2	−0.7 (2)	P1—C11—C16—C15	−179.64 (14)
Te1—N3—C3—C4	179.86 (15)	C14—C15—C16—C11	0.5 (3)
N2—C2—C3—N3	0.5 (3)	C11—P1—C17—C18	106.65 (14)
C1—C2—C3—N3	−177.89 (18)	C23—P1—C17—C18	−133.92 (14)
N2—C2—C3—C4	179.99 (17)	C5—P1—C17—C18	−11.18 (16)
C1—C2—C3—C4	1.6 (3)	C11—P1—C17—C22	−74.06 (14)
C11—P1—C5—C6	140.98 (15)	C23—P1—C17—C22	45.37 (14)
C17—P1—C5—C6	−98.98 (16)	C5—P1—C17—C22	168.10 (12)
C23—P1—C5—C6	20.56 (18)	C22—C17—C18—C19	−0.6 (2)
C11—P1—C5—C10	−39.24 (16)	P1—C17—C18—C19	178.63 (13)
C17—P1—C5—C10	80.79 (15)	C17—C18—C19—C20	1.2 (3)
C23—P1—C5—C10	−159.66 (14)	C18—C19—C20—C21	−0.5 (3)
C10—C5—C6—C7	1.1 (3)	C19—C20—C21—C22	−0.9 (3)
P1—C5—C6—C7	−179.11 (16)	C20—C21—C22—C17	1.5 (3)
C5—C6—C7—C8	−0.1 (3)	C18—C17—C22—C21	−0.7 (2)
C6—C7—C8—C9	−1.2 (3)	P1—C17—C22—C21	179.99 (13)
C7—C8—C9—C10	1.3 (3)	C11—P1—C23—C24	−0.02 (17)
C8—C9—C10—C5	−0.3 (3)	C17—P1—C23—C24	−119.83 (15)
C6—C5—C10—C9	−1.0 (3)	C5—P1—C23—C24	118.64 (15)
P1—C5—C10—C9	179.26 (15)	C11—P1—C23—C28	176.35 (14)
C17—P1—C11—C16	4.56 (17)	C17—P1—C23—C28	56.53 (15)
C23—P1—C11—C16	−113.21 (15)	C5—P1—C23—C28	−64.99 (16)
C5—P1—C11—C16	124.68 (14)	C28—C23—C24—C25	1.5 (3)
C17—P1—C11—C12	−173.73 (13)	P1—C23—C24—C25	177.76 (16)
C23—P1—C11—C12	68.50 (15)	C23—C24—C25—C26	−0.5 (3)
C5—P1—C11—C12	−53.61 (15)	C24—C25—C26—C27	−0.3 (4)
C16—C11—C12—C13	1.1 (3)	C25—C26—C27—C28	0.2 (4)
P1—C11—C12—C13	179.39 (14)	C26—C27—C28—C23	0.8 (3)
C11—C12—C13—C14	0.2 (3)	C24—C23—C28—C27	−1.6 (3)
C12—C13—C14—C15	−1.1 (3)	P1—C23—C28—C27	−178.06 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1	0.94	2.55	3.397 (3)	149
C18—H18···N3^i	0.94	2.48	3.278 (2)	142
C24—H24···N2^ii	0.94	2.66	3.485 (2)	147

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

1,2,5-Tellurodiazole-3,4-dicarbonitrile tetraethylphosphonium chloride (2b)

Crystal data

C4N4Te·C8H20P^+·Cl^−	Z = 2
Mr = 414.34	F(000) = 408
Triclinic, P1	Dx = 1.593 Mg m^−3
a = 6.9500 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5921 (15) Å	Cell parameters from 9536 reflections
c = 13.604 (2) Å	θ = 2.2–30.5°
α = 102.427 (2)°	µ = 1.96 mm^−1
β = 101.890 (2)°	T = 213 K
γ = 91.876 (2)°	Plate, yellow
V = 863.8 (2) Å^3	0.72 × 0.35 × 0.31 mm

Data collection

Bruker APEXII CCD diffractometer	5740 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω and πhi scans	θmax = 32.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −10→10
Tmin = 0.617, Tmax = 0.746	k = −14→14
20481 measured reflections	l = −20→19
5948 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0118P)^2 + 3.3734P] where P = (Fo^2 + 2Fc^2)/3
S = 1.17	(Δ/σ)max < 0.001
5948 reflections	Δρmax = 2.00 e Å^−3
179 parameters	Δρmin = −1.44 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.

Refinement. none

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

	x	y	z	Uiso*/Ueq
Te1	0.09776 (3)	0.78751 (2)	0.14068 (2)	0.02687 (6)
Cl1	0.000000	0.500000	0.000000	0.0513 (4)
Cl2	0.000000	0.000000	0.000000	0.0631 (5)
P1	0.69352 (14)	0.30361 (10)	0.21843 (7)	0.03072 (17)
N1	0.1463 (5)	0.9557 (3)	0.2638 (2)	0.0342 (6)
N2	0.1952 (5)	0.6719 (3)	0.2462 (2)	0.0330 (6)
N3	0.2738 (9)	1.0727 (6)	0.5311 (4)	0.0741 (15)
N4	0.3786 (10)	0.6562 (6)	0.4970 (4)	0.0762 (16)
C1	0.2461 (7)	1.0040 (5)	0.4494 (3)	0.0464 (9)
C2	0.2101 (6)	0.9088 (4)	0.3469 (3)	0.0340 (7)
C3	0.2396 (6)	0.7571 (4)	0.3366 (3)	0.0345 (7)
C4	0.3174 (8)	0.7015 (5)	0.4266 (3)	0.0485 (10)
C5	0.6400 (7)	0.2837 (5)	0.0812 (3)	0.0447 (9)
H5A	0.720150	0.357762	0.064619	0.054*
H5AB	0.679124	0.190432	0.049338	0.054*
C6	0.4254 (10)	0.2944 (9)	0.0344 (5)	0.082 (2)
H6A	0.411122	0.298234	−0.037344	0.124*
H6B	0.380116	0.380466	0.071717	0.124*
H6C	0.347336	0.211203	0.038953	0.124*
C7	0.6058 (7)	0.4660 (4)	0.2809 (3)	0.0395 (8)
H7A	0.462620	0.462406	0.255927	0.047*
H7AB	0.631621	0.471097	0.355242	0.047*
C8	0.6992 (9)	0.6007 (5)	0.2632 (5)	0.0590 (13)
H8A	0.666860	0.599915	0.190263	0.089*
H8B	0.841292	0.604662	0.286730	0.089*
H8C	0.649334	0.683947	0.301423	0.089*
C9	0.9574 (6)	0.3056 (5)	0.2575 (4)	0.0480 (10)
H9A	0.999429	0.215866	0.221420	0.058*
H9AB	1.017988	0.384155	0.235725	0.058*
C10	1.0346 (10)	0.3230 (8)	0.3728 (5)	0.083 (2)
H10A	0.996669	0.236863	0.393035	0.125*
H10B	0.979175	0.404187	0.409943	0.125*
H10C	1.177311	0.338997	0.389062	0.125*
C11	0.5701 (7)	0.1561 (4)	0.2504 (4)	0.0439 (9)
H11A	0.599751	0.168791	0.325510	0.053*
H11B	0.427286	0.158849	0.227469	0.053*
C12	0.6282 (8)	0.0105 (5)	0.2025 (5)	0.0608 (14)
H12A	0.610193	0.000174	0.128577	0.091*
H12B	0.546162	−0.063657	0.216209	0.091*
H12C	0.765531	0.001795	0.232005	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Te1	0.03133 (11)	0.02183 (9)	0.02766 (10)	0.00372 (7)	0.00701 (7)	0.00531 (7)
Cl1	0.0608 (9)	0.0270 (6)	0.0644 (10)	0.0003 (6)	0.0212 (8)	0.0000 (6)
Cl2	0.0891 (13)	0.0414 (8)	0.0815 (12)	0.0247 (8)	0.0449 (11)	0.0347 (8)
P1	0.0322 (4)	0.0283 (4)	0.0333 (4)	0.0051 (3)	0.0112 (3)	0.0064 (3)
N1	0.0407 (16)	0.0250 (13)	0.0358 (15)	0.0058 (11)	0.0087 (12)	0.0035 (11)
N2	0.0414 (16)	0.0273 (13)	0.0323 (14)	0.0066 (11)	0.0086 (12)	0.0099 (11)
N3	0.100 (4)	0.067 (3)	0.041 (2)	0.019 (3)	0.004 (2)	−0.008 (2)
N4	0.125 (5)	0.065 (3)	0.043 (2)	0.029 (3)	0.016 (3)	0.024 (2)
C1	0.052 (2)	0.041 (2)	0.039 (2)	0.0064 (18)	0.0028 (18)	0.0009 (16)
C2	0.0368 (17)	0.0307 (16)	0.0314 (16)	0.0035 (13)	0.0066 (13)	0.0010 (13)
C3	0.0404 (18)	0.0329 (16)	0.0318 (16)	0.0064 (14)	0.0099 (14)	0.0087 (13)
C4	0.065 (3)	0.051 (2)	0.0308 (18)	0.009 (2)	0.0108 (18)	0.0107 (17)
C5	0.048 (2)	0.053 (2)	0.0363 (19)	0.0048 (19)	0.0132 (17)	0.0127 (17)
C6	0.076 (4)	0.098 (5)	0.057 (3)	0.018 (4)	−0.021 (3)	0.014 (3)
C7	0.050 (2)	0.0304 (16)	0.044 (2)	0.0082 (15)	0.0221 (17)	0.0083 (15)
C8	0.066 (3)	0.032 (2)	0.088 (4)	0.006 (2)	0.038 (3)	0.012 (2)
C9	0.0339 (19)	0.037 (2)	0.068 (3)	0.0059 (15)	0.0054 (19)	0.0054 (19)
C10	0.066 (4)	0.077 (4)	0.081 (4)	0.017 (3)	−0.024 (3)	0.001 (3)
C11	0.052 (2)	0.0333 (18)	0.054 (2)	0.0032 (16)	0.025 (2)	0.0120 (17)
C12	0.055 (3)	0.031 (2)	0.099 (4)	0.0029 (18)	0.032 (3)	0.007 (2)

Geometric parameters (Å, º)

Te1—N2	2.020 (3)	C7—C8	1.514 (6)
Te1—N1	2.023 (3)	C7—H7A	0.9800
P1—C5	1.793 (4)	C7—H7AB	0.9800
P1—C7	1.796 (4)	C8—H8A	0.9700
P1—C9	1.800 (4)	C8—H8B	0.9700
P1—C11	1.807 (4)	C8—H8C	0.9700
N1—C2	1.305 (5)	C9—C10	1.520 (8)
N2—C3	1.293 (5)	C9—H9A	0.9800
N3—C1	1.138 (6)	C9—H9AB	0.9800
N4—C4	1.145 (6)	C10—H10A	0.9700
C1—C2	1.460 (5)	C10—H10B	0.9700
C2—C3	1.457 (5)	C10—H10C	0.9700
C3—C4	1.450 (6)	C11—C12	1.514 (6)
C5—C6	1.512 (7)	C11—H11A	0.9800
C5—H5A	0.9800	C11—H11B	0.9800
C5—H5AB	0.9800	C12—H12A	0.9700
C6—H6A	0.9700	C12—H12B	0.9700
C6—H6B	0.9700	C12—H12C	0.9700
C6—H6C	0.9700
N2—Te1—N1	84.57 (13)	P1—C7—H7AB	108.8
C5—P1—C7	110.9 (2)	H7A—C7—H7AB	107.6
C5—P1—C9	106.0 (2)	C7—C8—H8A	109.5
C7—P1—C9	111.1 (2)	C7—C8—H8B	109.5
C5—P1—C11	109.7 (2)	H8A—C8—H8B	109.5
C7—P1—C11	107.54 (19)	C7—C8—H8C	109.5
C9—P1—C11	111.5 (2)	H8A—C8—H8C	109.5
C2—N1—Te1	108.5 (2)	H8B—C8—H8C	109.5
C3—N2—Te1	108.7 (2)	C10—C9—P1	114.5 (4)
N3—C1—C2	176.8 (6)	C10—C9—H9A	108.6
N1—C2—C3	118.8 (3)	P1—C9—H9A	108.6
N1—C2—C1	121.4 (4)	C10—C9—H9AB	108.6
C3—C2—C1	119.7 (4)	P1—C9—H9AB	108.6
N2—C3—C4	120.0 (4)	H9A—C9—H9AB	107.6
N2—C3—C2	119.4 (3)	C9—C10—H10A	109.5
C4—C3—C2	120.6 (4)	C9—C10—H10B	109.5
N4—C4—C3	179.3 (5)	H10A—C10—H10B	109.5
C6—C5—P1	114.1 (4)	C9—C10—H10C	109.5
C6—C5—H5A	108.7	H10A—C10—H10C	109.5
P1—C5—H5A	108.7	H10B—C10—H10C	109.5
C6—C5—H5AB	108.7	C12—C11—P1	113.9 (3)
P1—C5—H5AB	108.7	C12—C11—H11A	108.8
H5A—C5—H5AB	107.6	P1—C11—H11A	108.8
C5—C6—H6A	109.5	C12—C11—H11B	108.8
C5—C6—H6B	109.5	P1—C11—H11B	108.8
H6A—C6—H6B	109.5	H11A—C11—H11B	107.7
C5—C6—H6C	109.5	C11—C12—H12A	109.5
H6A—C6—H6C	109.5	C11—C12—H12B	109.5
H6B—C6—H6C	109.5	H12A—C12—H12B	109.5
C8—C7—P1	114.0 (3)	C11—C12—H12C	109.5
C8—C7—H7A	108.8	H12A—C12—H12C	109.5
P1—C7—H7A	108.8	H12B—C12—H12C	109.5
C8—C7—H7AB	108.8
Te1—N1—C2—C3	2.1 (4)	C11—P1—C5—C6	65.2 (5)
Te1—N1—C2—C1	−175.9 (3)	C5—P1—C7—C8	−61.2 (4)
Te1—N2—C3—C4	−178.8 (3)	C9—P1—C7—C8	56.5 (5)
Te1—N2—C3—C2	1.4 (4)	C11—P1—C7—C8	178.8 (4)
N1—C2—C3—N2	−2.6 (6)	C5—P1—C9—C10	179.5 (4)
C1—C2—C3—N2	175.5 (4)	C7—P1—C9—C10	58.9 (5)
N1—C2—C3—C4	177.7 (4)	C11—P1—C9—C10	−61.1 (5)
C1—C2—C3—C4	−4.3 (6)	C5—P1—C11—C12	59.0 (5)
C7—P1—C5—C6	−53.5 (5)	C7—P1—C11—C12	179.7 (4)
C9—P1—C5—C6	−174.3 (4)	C9—P1—C11—C12	−58.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···Cl1^i	0.98	2.73	3.684 (5)	164
C7—H7AB···N4^ii	0.98	2.58	3.451 (6)	148
C11—H11A···N4^ii	0.98	2.60	3.460 (7)	147

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

1,2,5-Selenodiazole-3,4-dicarbonitrile–hydroquinone (1/1) (1a)

Crystal data

2C4N4Se·C6H6O2	F(000) = 460
Mr = 476.19	Dx = 1.872 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.2634 (16) Å	Cell parameters from 5992 reflections
b = 7.4089 (19) Å	θ = 3.0–37.6°
c = 18.320 (5) Å	µ = 4.41 mm^−1
β = 96.420 (5)°	T = 203 K
V = 844.8 (4) Å^3	Plate, orange
Z = 2	0.55 × 0.49 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer	3289 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
ω and πhi scans	θmax = 38.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −10→10
Tmin = 0.478, Tmax = 0.747	k = −12→12
17649 measured reflections	l = −31→31
4607 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0302P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.073	(Δ/σ)max = 0.001
S = 1.00	Δρmax = 0.63 e Å^−3
4607 reflections	Δρmin = −0.55 e Å^−3
120 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0216 (11)
Primary atom site location: structure-invariant direct methods

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. none

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

	x	y	z	Uiso*/Ueq
Se1	0.72849 (2)	0.36938 (2)	0.97332 (2)	0.02089 (5)
O1	0.38261 (18)	0.32324 (16)	0.54309 (6)	0.0253 (2)
H1	0.410146	0.326207	0.588459	0.038*
N1	0.9199 (2)	0.48058 (17)	0.92321 (6)	0.0212 (2)
N2	1.0510 (3)	0.6182 (2)	0.75384 (9)	0.0459 (5)
N3	0.5560 (2)	0.31610 (19)	0.89180 (7)	0.0250 (3)
N4	0.4783 (3)	0.3335 (3)	0.70232 (9)	0.0428 (4)
C1	0.9651 (3)	0.5513 (2)	0.79843 (8)	0.0289 (3)
C2	0.8484 (2)	0.47000 (19)	0.85316 (7)	0.0203 (3)
C3	0.6477 (2)	0.3788 (2)	0.83607 (8)	0.0217 (3)
C4	0.5494 (3)	0.3530 (2)	0.76190 (9)	0.0293 (3)
C5	0.1915 (2)	0.41095 (19)	0.52294 (8)	0.0189 (2)
C6	0.1351 (2)	0.44688 (19)	0.44862 (7)	0.0198 (3)
H6	0.226185	0.410757	0.413872	0.024*
C7	−0.0553 (2)	0.53587 (19)	0.42603 (7)	0.0204 (3)
H7	−0.092749	0.560488	0.375902	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Se1	0.02157 (8)	0.02412 (8)	0.01721 (7)	−0.00006 (6)	0.00320 (5)	0.00112 (5)
O1	0.0211 (5)	0.0326 (6)	0.0213 (5)	0.0056 (4)	−0.0022 (4)	−0.0012 (4)
N1	0.0215 (6)	0.0228 (6)	0.0195 (5)	−0.0017 (5)	0.0027 (4)	−0.0020 (4)
N2	0.0533 (11)	0.0546 (11)	0.0321 (8)	−0.0183 (9)	0.0149 (8)	−0.0007 (7)
N3	0.0206 (6)	0.0314 (6)	0.0226 (6)	−0.0034 (5)	0.0011 (5)	0.0019 (5)
N4	0.0370 (9)	0.0612 (11)	0.0279 (7)	0.0035 (8)	−0.0064 (7)	−0.0023 (7)
C1	0.0309 (8)	0.0328 (8)	0.0237 (7)	−0.0070 (7)	0.0064 (6)	−0.0021 (6)
C2	0.0212 (6)	0.0216 (6)	0.0185 (6)	0.0000 (5)	0.0044 (5)	−0.0003 (5)
C3	0.0196 (6)	0.0259 (7)	0.0191 (6)	0.0011 (6)	0.0000 (5)	0.0002 (5)
C4	0.0249 (8)	0.0369 (9)	0.0251 (7)	0.0006 (7)	−0.0010 (6)	0.0020 (6)
C5	0.0177 (6)	0.0183 (6)	0.0200 (6)	−0.0004 (5)	−0.0003 (5)	−0.0010 (5)
C6	0.0197 (6)	0.0229 (7)	0.0170 (6)	−0.0008 (5)	0.0034 (5)	−0.0025 (5)
C7	0.0231 (7)	0.0224 (6)	0.0154 (6)	−0.0001 (5)	0.0006 (5)	−0.0013 (5)

Geometric parameters (Å, º)

Se1—N3	1.7869 (13)	C1—C2	1.437 (2)
Se1—N1	1.7901 (13)	C2—C3	1.431 (2)
O1—C5	1.3760 (19)	C3—C4	1.440 (2)
O1—H1	0.8300	C5—C7^i	1.391 (2)
N1—C2	1.3134 (18)	C5—C6	1.3934 (19)
N2—C1	1.141 (2)	C6—C7	1.385 (2)
N3—C3	1.311 (2)	C6—H6	0.9400
N4—C4	1.141 (2)	C7—H7	0.9400
N3—Se1—N1	92.87 (6)	N4—C4—C3	177.64 (19)
C5—O1—H1	109.5	O1—C5—C7^i	122.27 (13)
C2—N1—Se1	107.40 (10)	O1—C5—C6	118.04 (13)
C3—N3—Se1	107.20 (10)	C7^i—C5—C6	119.68 (13)
N2—C1—C2	177.6 (2)	C7—C6—C5	119.90 (13)
N1—C2—C3	115.92 (13)	C7—C6—H6	120.0
N1—C2—C1	120.83 (14)	C5—C6—H6	120.0
C3—C2—C1	123.23 (13)	C6—C7—C5^i	120.42 (12)
N3—C3—C2	116.60 (13)	C6—C7—H7	119.8
N3—C3—C4	120.63 (14)	C5^i—C7—H7	119.8
C2—C3—C4	122.77 (14)
N3—Se1—N1—C2	−0.58 (11)	C1—C2—C3—N3	−177.88 (15)
N1—Se1—N3—C3	0.71 (11)	N1—C2—C3—C4	−178.91 (14)
Se1—N1—C2—C3	0.32 (16)	C1—C2—C3—C4	3.0 (2)
Se1—N1—C2—C1	178.50 (12)	O1—C5—C6—C7	−179.61 (13)
Se1—N3—C3—C2	−0.67 (17)	C7^i—C5—C6—C7	0.3 (2)
Se1—N3—C3—C4	178.50 (12)	C5—C6—C7—C5^i	−0.3 (2)
N1—C2—C3—N3	0.2 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N4	0.83	2.08	2.913 (2)	180