1-(Pyridin-4-yl)-4-thio­pyridine (PTP) in the crystalline state – pure PTP and a cocrystal and salt

The first in situ preparation and single-crystal structure identification of pure 1-(pyridin-4-yl)-4-thio­pyridine (PTP), C₁₀H₈N₂S, a simple and basic derivative of mercapto­pyridine, from a crystallization mixture is described. The same PTP was found in two multicomponent crystal forms with 3,5-di­nitro­benzoic acid as a classic two-component cocrystal, namely, 1-(pyridin-4-yl)-4-thio­pyridine–3,5-di­nitro­benzoic acid (1/1), C₇H₄N₂O₆·C₁₀H₈N₂S, and with 2-hy­droxy-3,5-di­nitro­benzoic acid as a salt formed via proton transfer from the hy­droxy group of the acid to the pyridyl N atom of PTP, namely, 4-(4-sul­fan­yl­­idene-1,4-di­hydro­pyridin-1-yl)pyridin-1-ium 1-carb­oxy-3,5-di­nitro­phe­nol­ate, C₁₀H₉N₂S⁺·C₇H₃N₂O₇⁻. The protonation energy of PTP is 944.64 kJ mol⁻¹, indicating slightly greater N-basicity compared to pyridine, a well characterized and very basic chemical reference. A variety of mol­ecular inter­actions can be observed in the three new crystal structures of PTP, which are all discussed in detail. Our findings confirm those of previous studies, indicating that PTP and 4-mercapto­pyridine may, under suitable conditions, be chemically converted to one another, and that this process can be stimulated by light (UV–Vis).

Computing details

1-(Pyridin-4-yl)pyridine-4-thiol–3,5-dinitrobenzoic acid (1/1) (II)

Crystal data

C7H4N2O6·C10H8N2S	F(000) = 824
Mr = 400.37	Dx = 1.526 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 12.02543 (19) Å	Cell parameters from 9752 reflections
b = 10.32242 (14) Å	θ = 3.7–76.3°
c = 14.3244 (2) Å	µ = 2.07 mm^−1
β = 101.4078 (15)°	T = 293 K
V = 1742.98 (5) Å^3	Irregular, dark yellow
Z = 4	0.18 × 0.10 × 0.05 mm

Data collection

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	2929 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	Rint = 0.023
Detector resolution: 10.0000 pixels mm^-1	θmax = 76.5°, θmin = 3.8°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	h = −15→13
Tmin = 0.880, Tmax = 1.000	k = −10→12
16749 measured reflections	l = −16→17
3424 independent reflections

Refinement

Refinement on F^2	6 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.129	w = 1/[σ^2(Fo^2) + (0.0693P)^2 + 0.3737P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3424 reflections	Δρmax = 0.57 e Å^−3
256 parameters	Δρmin = −0.30 e Å^−3

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
S4	−0.18075 (5)	0.76068 (6)	1.16443 (4)	0.0797 (2)
O27	0.38704 (12)	0.78919 (14)	0.62963 (10)	0.0670 (4)
H27	0.338438	0.778742	0.661812	0.101*
O28	0.30770 (12)	0.61331 (14)	0.55500 (10)	0.0712 (4)
O24	0.59808 (13)	0.55380 (16)	0.23806 (10)	0.0790 (4)
O23	0.45104 (15)	0.46540 (15)	0.27590 (11)	0.0805 (4)
O26	0.76296 (12)	0.93265 (15)	0.40816 (12)	0.0791 (4)
N23	0.52596 (14)	0.54626 (16)	0.28707 (10)	0.0595 (4)
N1	0.02194 (12)	0.76464 (14)	0.93288 (11)	0.0541 (4)
N25	0.69363 (13)	0.93001 (15)	0.46007 (13)	0.0618 (4)
N10	0.23877 (14)	0.77864 (18)	0.73753 (12)	0.0662 (4)
O25	0.69107 (15)	1.00916 (15)	0.52212 (13)	0.0872 (5)
C21	0.45872 (14)	0.71492 (15)	0.49861 (11)	0.0460 (4)
C23	0.52987 (14)	0.64090 (16)	0.36428 (11)	0.0480 (4)
C22	0.45469 (14)	0.62649 (15)	0.42532 (11)	0.0467 (4)
H22	0.402574	0.558852	0.417279	0.056*
C25	0.60987 (14)	0.82446 (16)	0.44697 (12)	0.0498 (4)
C24	0.60810 (14)	0.73922 (16)	0.37280 (12)	0.0501 (4)
H24	0.657359	0.747794	0.330639	0.060*
C26	0.53761 (14)	0.81491 (15)	0.51043 (12)	0.0493 (4)
H26	0.541617	0.874034	0.559978	0.059*
C27	0.37628 (15)	0.70071 (17)	0.56421 (12)	0.0509 (4)
C7	0.09216 (15)	0.76924 (17)	0.86333 (13)	0.0536 (4)
C2	−0.06605 (15)	0.84970 (17)	0.92952 (13)	0.0550 (4)
H2	−0.083419	0.907699	0.879058	0.066*
C8	0.12599 (16)	0.88665 (18)	0.83224 (13)	0.0582 (4)
H8	0.099736	0.964107	0.853042	0.070*
C3	−0.12840 (15)	0.85051 (18)	0.99904 (13)	0.0568 (4)
H3	−0.187702	0.909384	0.994966	0.068*
C4	−0.10562 (16)	0.76403 (18)	1.07774 (14)	0.0565 (4)
C5	−0.01376 (16)	0.6783 (2)	1.07658 (14)	0.0626 (5)
H5	0.005278	0.618358	1.125605	0.075*
C9	0.19935 (17)	0.8866 (2)	0.76983 (13)	0.0637 (5)
H9	0.222487	0.965731	0.749231	0.076*
C6	0.04677 (16)	0.68060 (19)	1.00712 (14)	0.0612 (5)
H6	0.107052	0.623338	1.009931	0.073*
C12	0.13072 (18)	0.65630 (19)	0.82888 (16)	0.0667 (5)
H12	0.107941	0.575792	0.847416	0.080*
C11	0.20394 (18)	0.6661 (2)	0.76622 (16)	0.0718 (6)
H11	0.230145	0.590282	0.742968	0.086*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S4	0.0822 (4)	0.0968 (4)	0.0703 (4)	−0.0152 (3)	0.0400 (3)	−0.0050 (3)
O27	0.0743 (9)	0.0749 (8)	0.0609 (8)	−0.0122 (7)	0.0356 (7)	−0.0173 (6)
O28	0.0777 (9)	0.0757 (9)	0.0686 (8)	−0.0241 (7)	0.0352 (7)	−0.0113 (7)
O24	0.0910 (10)	0.0955 (11)	0.0600 (8)	0.0210 (8)	0.0380 (8)	−0.0035 (7)
O23	0.0944 (11)	0.0780 (9)	0.0721 (9)	−0.0090 (8)	0.0241 (8)	−0.0282 (7)
O26	0.0674 (8)	0.0825 (10)	0.0921 (11)	−0.0126 (7)	0.0274 (8)	0.0218 (8)
N23	0.0694 (9)	0.0647 (9)	0.0458 (8)	0.0146 (8)	0.0150 (7)	−0.0031 (6)
N1	0.0531 (8)	0.0576 (8)	0.0548 (8)	0.0041 (6)	0.0188 (6)	0.0037 (6)
N25	0.0607 (9)	0.0546 (9)	0.0691 (10)	−0.0061 (7)	0.0107 (7)	0.0141 (8)
N10	0.0596 (9)	0.0894 (12)	0.0537 (9)	−0.0016 (8)	0.0211 (7)	−0.0100 (8)
O25	0.1003 (12)	0.0694 (9)	0.0923 (11)	−0.0240 (8)	0.0200 (9)	−0.0032 (8)
C21	0.0520 (8)	0.0473 (8)	0.0407 (8)	0.0017 (6)	0.0136 (7)	0.0036 (6)
C23	0.0536 (9)	0.0521 (8)	0.0394 (8)	0.0105 (7)	0.0118 (6)	0.0031 (6)
C22	0.0497 (8)	0.0482 (8)	0.0430 (8)	0.0011 (6)	0.0111 (6)	0.0028 (6)
C25	0.0509 (9)	0.0482 (8)	0.0508 (9)	0.0002 (7)	0.0116 (7)	0.0120 (7)
C24	0.0497 (9)	0.0572 (9)	0.0462 (9)	0.0080 (7)	0.0163 (7)	0.0123 (7)
C26	0.0582 (9)	0.0470 (8)	0.0437 (8)	0.0005 (7)	0.0125 (7)	0.0020 (6)
C27	0.0565 (9)	0.0545 (9)	0.0448 (8)	−0.0012 (7)	0.0172 (7)	0.0003 (7)
C7	0.0512 (9)	0.0628 (10)	0.0494 (9)	0.0013 (7)	0.0162 (7)	−0.0020 (7)
C2	0.0559 (9)	0.0558 (9)	0.0553 (10)	0.0048 (7)	0.0155 (8)	0.0011 (7)
C8	0.0646 (10)	0.0613 (10)	0.0527 (10)	−0.0021 (8)	0.0210 (8)	−0.0059 (8)
C3	0.0543 (9)	0.0571 (9)	0.0615 (10)	0.0010 (7)	0.0172 (8)	−0.0057 (8)
C4	0.0564 (10)	0.0615 (10)	0.0540 (10)	−0.0133 (8)	0.0166 (8)	−0.0072 (8)
C5	0.0593 (10)	0.0690 (11)	0.0605 (11)	−0.0018 (9)	0.0143 (8)	0.0132 (9)
C9	0.0674 (11)	0.0753 (12)	0.0523 (10)	−0.0087 (9)	0.0216 (8)	−0.0020 (9)
C6	0.0576 (10)	0.0636 (11)	0.0645 (11)	0.0070 (8)	0.0171 (8)	0.0113 (9)
C12	0.0695 (12)	0.0591 (10)	0.0762 (13)	0.0038 (9)	0.0260 (10)	−0.0026 (9)
C11	0.0700 (12)	0.0772 (13)	0.0735 (13)	0.0114 (10)	0.0270 (10)	−0.0127 (10)

Geometric parameters (Å, º)

S4—C4	1.6742 (19)	C25—C24	1.376 (2)
O27—C27	1.297 (2)	C25—C26	1.380 (2)
O27—H27	0.8200	C24—H24	0.9300
O28—C27	1.212 (2)	C26—H26	0.9300
O24—N23	1.221 (2)	C7—C8	1.380 (3)
O23—N23	1.215 (2)	C7—C12	1.381 (3)
O26—N25	1.222 (2)	C2—C3	1.360 (2)
N23—C23	1.469 (2)	C2—H2	0.9300
N1—C6	1.359 (2)	C8—C9	1.375 (2)
N1—C2	1.368 (2)	C8—H8	0.9300
N1—C7	1.429 (2)	C3—C4	1.422 (3)
N25—O25	1.212 (2)	C3—H3	0.9300
N25—C25	1.470 (2)	C4—C5	1.418 (3)
N10—C11	1.327 (3)	C5—C6	1.344 (3)
N10—C9	1.329 (3)	C5—H5	0.9300
C21—C22	1.385 (2)	C9—H9	0.9300
C21—C26	1.389 (2)	C6—H6	0.9300
C21—C27	1.502 (2)	C12—C11	1.380 (3)
C23—C24	1.373 (2)	C12—H12	0.9300
C23—C22	1.385 (2)	C11—H11	0.9300
C22—H22	0.9300
C27—O27—H27	109.5	O27—C27—C21	113.55 (14)
O23—N23—O24	124.07 (16)	C8—C7—C12	119.00 (17)
O23—N23—C23	117.92 (15)	C8—C7—N1	120.46 (15)
O24—N23—C23	118.01 (16)	C12—C7—N1	120.50 (16)
C6—N1—C2	119.06 (15)	C3—C2—N1	120.85 (17)
C6—N1—C7	119.88 (15)	C3—C2—H2	119.6
C2—N1—C7	120.92 (14)	N1—C2—H2	119.6
O25—N25—O26	123.39 (16)	C9—C8—C7	118.51 (17)
O25—N25—C25	118.48 (16)	C9—C8—H8	120.7
O26—N25—C25	118.13 (17)	C7—C8—H8	120.7
C11—N10—C9	118.00 (16)	C2—C3—C4	121.96 (17)
C22—C21—C26	120.19 (15)	C2—C3—H3	119.0
C22—C21—C27	118.78 (14)	C4—C3—H3	119.0
C26—C21—C27	121.03 (14)	C5—C4—C3	114.26 (16)
C24—C23—C22	123.02 (15)	C5—C4—S4	122.12 (15)
C24—C23—N23	118.54 (15)	C3—C4—S4	123.62 (15)
C22—C23—N23	118.44 (15)	C6—C5—C4	122.34 (18)
C23—C22—C21	118.60 (15)	C6—C5—H5	118.8
C23—C22—H22	120.7	C4—C5—H5	118.8
C21—C22—H22	120.7	N10—C9—C8	123.09 (18)
C24—C25—C26	123.19 (15)	N10—C9—H9	118.5
C24—C25—N25	118.53 (15)	C8—C9—H9	118.5
C26—C25—N25	118.27 (16)	C5—C6—N1	121.54 (17)
C23—C24—C25	116.54 (15)	C5—C6—H6	119.2
C23—C24—H24	121.7	N1—C6—H6	119.2
C25—C24—H24	121.7	C11—C12—C7	118.21 (19)
C25—C26—C21	118.46 (15)	C11—C12—H12	120.9
C25—C26—H26	120.8	C7—C12—H12	120.9
C21—C26—H26	120.8	N10—C11—C12	123.16 (18)
O28—C27—O27	124.86 (16)	N10—C11—H11	118.4
O28—C27—C21	121.59 (15)	C12—C11—H11	118.4
O23—N23—C23—C24	−174.69 (16)	C26—C21—C27—O27	0.3 (2)
O24—N23—C23—C24	5.2 (2)	C6—N1—C7—C8	−134.88 (19)
O23—N23—C23—C22	5.5 (2)	C2—N1—C7—C8	40.8 (2)
O24—N23—C23—C22	−174.54 (15)	C6—N1—C7—C12	42.7 (3)
C24—C23—C22—C21	−0.3 (2)	C2—N1—C7—C12	−141.69 (19)
N23—C23—C22—C21	179.51 (14)	C6—N1—C2—C3	−0.2 (3)
C26—C21—C22—C23	−0.6 (2)	C7—N1—C2—C3	−175.88 (16)
C27—C21—C22—C23	179.19 (14)	C12—C7—C8—C9	−1.7 (3)
O25—N25—C25—C24	176.01 (17)	N1—C7—C8—C9	175.92 (17)
O26—N25—C25—C24	−4.6 (2)	N1—C2—C3—C4	0.0 (3)
O25—N25—C25—C26	−4.7 (2)	C2—C3—C4—C5	−0.2 (3)
O26—N25—C25—C26	174.70 (15)	C2—C3—C4—S4	−179.47 (15)
C22—C23—C24—C25	0.7 (2)	C3—C4—C5—C6	0.7 (3)
N23—C23—C24—C25	−179.06 (14)	S4—C4—C5—C6	179.98 (16)
C26—C25—C24—C23	−0.4 (2)	C11—N10—C9—C8	1.0 (3)
N25—C25—C24—C23	178.89 (14)	C7—C8—C9—N10	0.4 (3)
C24—C25—C26—C21	−0.4 (2)	C4—C5—C6—N1	−1.0 (3)
N25—C25—C26—C21	−179.67 (15)	C2—N1—C6—C5	0.7 (3)
C22—C21—C26—C25	0.9 (2)	C7—N1—C6—C5	176.43 (18)
C27—C21—C26—C25	−178.87 (14)	C8—C7—C12—C11	1.5 (3)
C22—C21—C27—O28	0.8 (3)	N1—C7—C12—C11	−176.07 (18)
C26—C21—C27—O28	−179.43 (17)	C9—N10—C11—C12	−1.1 (3)
C22—C21—C27—O27	−179.48 (16)	C7—C12—C11—N10	−0.1 (3)

4-(4-Sulfanylidene-1,4-dihydropyridin-1-yl)pyridin-1-ium; 1-carboxy-3,5-dinitrophenolate (III)

Crystal data

C10H9N2S^+·C7H3N2O7^−	Dx = 1.617 Mg m^−3
Mr = 416.37	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 9477 reflections
a = 6.7894 (1) Å	θ = 3.9–74.9°
b = 15.5750 (2) Å	µ = 2.18 mm^−1
c = 16.1749 (2) Å	T = 293 K
V = 1710.41 (4) Å^3	Needle, dark yellow
Z = 4	0.21 × 0.03 × 0.02 mm
F(000) = 856

Data collection

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	3077 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube	Rint = 0.029
Detector resolution: 10.0000 pixels mm^-1	θmax = 76.6°, θmin = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2022)	h = −7→8
Tmin = 0.773, Tmax = 1.000	k = −18→19
14886 measured reflections	l = −20→19
3266 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0398P)^2 + 0.189P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.071	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.15 e Å^−3
3266 reflections	Δρmin = −0.24 e Å^−3
273 parameters	Absolute structure: Flack (1983), refined as an inversion twin
6 restraints	Absolute structure parameter: 0.47 (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.

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

	x	y	z	Uiso*/Ueq
S4	0.90227 (14)	0.56171 (5)	0.29915 (4)	0.0634 (2)
O22	0.5753 (3)	0.83692 (10)	0.92264 (9)	0.0450 (4)
O28	0.5615 (3)	1.08631 (10)	0.99818 (11)	0.0516 (5)
O27	0.5107 (3)	0.99336 (12)	0.89758 (10)	0.0518 (5)
O25	0.6306 (3)	0.98242 (11)	1.27889 (10)	0.0542 (5)
O24	0.6755 (3)	0.67684 (11)	0.96630 (11)	0.0556 (5)
O26	0.7340 (3)	0.85430 (12)	1.30316 (11)	0.0563 (5)
O23	0.5822 (4)	0.64584 (11)	1.08964 (12)	0.0640 (6)
N25	0.6795 (3)	0.91095 (12)	1.25595 (11)	0.0401 (5)
N1	0.8591 (3)	0.66399 (11)	0.55851 (10)	0.0349 (4)
N23	0.6337 (3)	0.69753 (12)	1.03721 (12)	0.0421 (5)
N10	0.7232 (3)	0.75250 (12)	0.79342 (12)	0.0422 (5)
C26	0.6281 (3)	0.95626 (13)	1.11297 (13)	0.0361 (5)
H26	0.621225	1.012594	1.131807	0.043*
C24	0.6726 (3)	0.80617 (14)	1.14307 (14)	0.0369 (5)
H24	0.696769	0.762491	1.180936	0.044*
C21	0.6029 (3)	0.93891 (14)	1.03023 (13)	0.0351 (4)
C25	0.6636 (3)	0.89027 (15)	1.16829 (13)	0.0364 (5)
C22	0.6091 (3)	0.85245 (14)	0.99906 (13)	0.0342 (4)
C23	0.6449 (3)	0.78772 (13)	1.06021 (14)	0.0353 (5)
C8	0.7303 (4)	0.64001 (14)	0.69675 (14)	0.0402 (5)
H8	0.702500	0.583343	0.682885	0.048*
C27	0.5590 (3)	1.01281 (15)	0.97430 (14)	0.0390 (5)
C3	0.9178 (4)	0.54703 (14)	0.46717 (13)	0.0396 (5)
H3	0.946985	0.489141	0.460201	0.048*
C7	0.8164 (3)	0.69426 (13)	0.63954 (13)	0.0347 (5)
C6	0.8471 (4)	0.71806 (14)	0.49179 (14)	0.0393 (5)
H6	0.824907	0.776283	0.500490	0.047*
C5	0.8668 (4)	0.68858 (14)	0.41382 (14)	0.0421 (5)
H5	0.861888	0.727525	0.370278	0.050*
C2	0.8984 (4)	0.57848 (13)	0.54426 (13)	0.0377 (5)
H2	0.911822	0.541518	0.589063	0.045*
C12	0.8565 (4)	0.77920 (15)	0.66141 (14)	0.0430 (6)
H12	0.915389	0.816604	0.624032	0.052*
C9	0.6863 (4)	0.67040 (16)	0.77384 (13)	0.0424 (5)
H9	0.630504	0.633961	0.812912	0.051*
C4	0.8948 (4)	0.59998 (15)	0.39585 (13)	0.0408 (5)
C11	0.8067 (4)	0.80615 (14)	0.73959 (15)	0.0456 (6)
H11	0.831519	0.862603	0.755144	0.055*
H27	0.527 (5)	0.934 (2)	0.8921 (19)	0.069 (10)*
H10	0.685 (4)	0.7748 (17)	0.8420 (17)	0.043 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S4	0.1034 (6)	0.0541 (4)	0.0328 (3)	−0.0124 (4)	0.0070 (3)	−0.0095 (3)
O22	0.0645 (11)	0.0392 (8)	0.0313 (7)	0.0105 (8)	0.0005 (8)	−0.0049 (7)
O28	0.0738 (13)	0.0299 (8)	0.0510 (9)	0.0007 (8)	−0.0052 (9)	0.0024 (7)
O27	0.0813 (13)	0.0394 (10)	0.0348 (9)	0.0126 (9)	−0.0043 (8)	0.0040 (7)
O25	0.0798 (13)	0.0436 (9)	0.0392 (9)	−0.0008 (9)	0.0025 (9)	−0.0069 (7)
O24	0.0839 (14)	0.0393 (9)	0.0436 (9)	0.0102 (9)	0.0031 (9)	−0.0102 (8)
O26	0.0794 (13)	0.0522 (10)	0.0374 (8)	−0.0004 (10)	−0.0110 (9)	0.0095 (8)
O23	0.1020 (17)	0.0323 (8)	0.0577 (11)	−0.0079 (10)	0.0131 (12)	0.0038 (8)
N25	0.0489 (11)	0.0386 (10)	0.0329 (9)	−0.0072 (9)	−0.0014 (9)	0.0018 (8)
N1	0.0455 (10)	0.0303 (9)	0.0288 (8)	0.0013 (8)	0.0013 (8)	−0.0012 (7)
N23	0.0490 (11)	0.0317 (9)	0.0456 (11)	0.0025 (8)	0.0010 (9)	−0.0024 (8)
N10	0.0512 (12)	0.0440 (11)	0.0314 (10)	0.0082 (9)	0.0002 (9)	−0.0097 (9)
C26	0.0442 (12)	0.0286 (10)	0.0357 (10)	−0.0016 (9)	−0.0005 (9)	−0.0015 (8)
C24	0.0400 (12)	0.0336 (11)	0.0372 (11)	0.0000 (9)	−0.0009 (9)	0.0045 (9)
C21	0.0401 (11)	0.0315 (10)	0.0337 (10)	0.0010 (10)	0.0013 (9)	0.0013 (9)
C25	0.0425 (12)	0.0367 (11)	0.0301 (10)	−0.0037 (10)	−0.0002 (9)	0.0006 (9)
C22	0.0365 (10)	0.0335 (10)	0.0326 (9)	0.0010 (9)	0.0036 (9)	−0.0038 (8)
C23	0.0376 (11)	0.0296 (10)	0.0386 (11)	0.0040 (9)	0.0024 (9)	−0.0031 (9)
C8	0.0512 (13)	0.0348 (11)	0.0347 (11)	−0.0039 (10)	0.0015 (10)	−0.0046 (9)
C27	0.0444 (12)	0.0366 (11)	0.0360 (11)	0.0013 (10)	0.0017 (10)	0.0030 (10)
C3	0.0514 (13)	0.0300 (10)	0.0375 (10)	0.0026 (10)	0.0049 (10)	−0.0029 (9)
C7	0.0411 (12)	0.0321 (10)	0.0309 (10)	0.0040 (9)	−0.0004 (9)	−0.0057 (8)
C6	0.0500 (13)	0.0285 (10)	0.0393 (11)	−0.0012 (10)	0.0020 (10)	0.0020 (9)
C5	0.0555 (15)	0.0368 (11)	0.0339 (10)	−0.0008 (10)	0.0031 (10)	0.0063 (9)
C2	0.0492 (12)	0.0295 (10)	0.0343 (10)	0.0046 (9)	0.0035 (10)	0.0012 (8)
C12	0.0570 (15)	0.0332 (11)	0.0387 (11)	0.0004 (11)	0.0010 (11)	−0.0029 (9)
C9	0.0502 (13)	0.0441 (12)	0.0329 (10)	−0.0033 (11)	0.0023 (10)	−0.0029 (10)
C4	0.0480 (13)	0.0417 (12)	0.0327 (10)	−0.0062 (10)	0.0049 (10)	−0.0016 (9)
C11	0.0637 (15)	0.0322 (11)	0.0409 (12)	0.0052 (11)	−0.0037 (12)	−0.0085 (10)

Geometric parameters (Å, º)

S4—C4	1.675 (2)	C24—C23	1.384 (3)
O22—C22	1.280 (3)	C24—H24	0.9300
O28—C27	1.208 (3)	C21—C22	1.438 (3)
O27—C27	1.319 (3)	C21—C27	1.494 (3)
O27—H27	0.93 (3)	C22—C23	1.433 (3)
O25—N25	1.219 (3)	C8—C9	1.367 (3)
O24—N23	1.225 (3)	C8—C7	1.383 (3)
O26—N25	1.224 (2)	C8—H8	0.9300
O23—N23	1.220 (3)	C3—C2	1.346 (3)
N25—C25	1.458 (3)	C3—C4	1.427 (3)
N1—C6	1.371 (3)	C3—H3	0.9300
N1—C2	1.378 (3)	C7—C12	1.396 (3)
N1—C7	1.423 (3)	C6—C5	1.349 (3)
N23—C23	1.455 (3)	C6—H6	0.9300
N10—C11	1.333 (3)	C5—C4	1.423 (3)
N10—C9	1.341 (3)	C5—H5	0.9300
N10—H10	0.90 (3)	C2—H2	0.9300
C26—C21	1.376 (3)	C12—C11	1.375 (3)
C26—C25	1.384 (3)	C12—H12	0.9300
C26—H26	0.9300	C9—H9	0.9300
C24—C25	1.373 (3)	C11—H11	0.9300
C27—O27—H27	107 (2)	C9—C8—H8	120.3
O25—N25—O26	123.39 (19)	C7—C8—H8	120.3
O25—N25—C25	118.52 (19)	O28—C27—O27	121.5 (2)
O26—N25—C25	118.02 (19)	O28—C27—C21	122.3 (2)
C6—N1—C2	118.26 (17)	O27—C27—C21	116.26 (19)
C6—N1—C7	120.63 (17)	C2—C3—C4	121.9 (2)
C2—N1—C7	120.92 (17)	C2—C3—H3	119.1
O23—N23—O24	122.9 (2)	C4—C3—H3	119.1
O23—N23—C23	118.31 (19)	C8—C7—C12	119.5 (2)
O24—N23—C23	118.77 (19)	C8—C7—N1	120.02 (19)
C11—N10—C9	121.5 (2)	C12—C7—N1	120.5 (2)
C11—N10—H10	116.8 (17)	C5—C6—N1	121.4 (2)
C9—N10—H10	121.5 (17)	C5—C6—H6	119.3
C21—C26—C25	120.3 (2)	N1—C6—H6	119.3
C21—C26—H26	119.8	C6—C5—C4	122.3 (2)
C25—C26—H26	119.8	C6—C5—H5	118.9
C25—C24—C23	118.7 (2)	C4—C5—H5	118.9
C25—C24—H24	120.7	C3—C2—N1	121.7 (2)
C23—C24—H24	120.7	C3—C2—H2	119.1
C26—C21—C22	121.41 (19)	N1—C2—H2	119.1
C26—C21—C27	117.55 (19)	C11—C12—C7	118.3 (2)
C22—C21—C27	120.98 (19)	C11—C12—H12	120.8
C24—C25—C26	121.6 (2)	C7—C12—H12	120.8
C24—C25—N25	119.75 (19)	N10—C9—C8	120.3 (2)
C26—C25—N25	118.5 (2)	N10—C9—H9	119.8
O22—C22—C23	124.32 (19)	C8—C9—H9	119.8
O22—C22—C21	120.67 (19)	C5—C4—C3	114.21 (19)
C23—C22—C21	114.94 (19)	C5—C4—S4	122.69 (18)
C24—C23—C22	123.06 (19)	C3—C4—S4	123.10 (18)
C24—C23—N23	117.07 (19)	N10—C11—C12	120.9 (2)
C22—C23—N23	119.60 (19)	N10—C11—H11	119.5
C9—C8—C7	119.4 (2)	C12—C11—H11	119.5
C25—C26—C21—C22	1.1 (3)	C22—C21—C27—O28	−176.7 (2)
C25—C26—C21—C27	178.2 (2)	C26—C21—C27—O27	−171.6 (2)
C23—C24—C25—C26	−0.1 (3)	C22—C21—C27—O27	5.5 (3)
C23—C24—C25—N25	176.0 (2)	C9—C8—C7—C12	−0.2 (4)
C21—C26—C25—C24	−0.8 (4)	C9—C8—C7—N1	−178.7 (2)
C21—C26—C25—N25	−176.9 (2)	C6—N1—C7—C8	146.6 (2)
O25—N25—C25—C24	−164.8 (2)	C2—N1—C7—C8	−28.3 (3)
O26—N25—C25—C24	12.3 (3)	C6—N1—C7—C12	−31.9 (3)
O25—N25—C25—C26	11.4 (3)	C2—N1—C7—C12	153.2 (2)
O26—N25—C25—C26	−171.5 (2)	C2—N1—C6—C5	2.1 (3)
C26—C21—C22—O22	176.4 (2)	C7—N1—C6—C5	−173.0 (2)
C27—C21—C22—O22	−0.6 (3)	N1—C6—C5—C4	2.0 (4)
C26—C21—C22—C23	−0.6 (3)	C4—C3—C2—N1	−1.3 (4)
C27—C21—C22—C23	−177.6 (2)	C6—N1—C2—C3	−2.4 (4)
C25—C24—C23—C22	0.6 (3)	C7—N1—C2—C3	172.6 (2)
C25—C24—C23—N23	−173.4 (2)	C8—C7—C12—C11	−0.6 (4)
O22—C22—C23—C24	−177.1 (2)	N1—C7—C12—C11	177.9 (2)
C21—C22—C23—C24	−0.3 (3)	C11—N10—C9—C8	−1.3 (4)
O22—C22—C23—N23	−3.2 (3)	C7—C8—C9—N10	1.1 (4)
C21—C22—C23—N23	173.6 (2)	C6—C5—C4—C3	−5.4 (4)
O23—N23—C23—C24	24.6 (3)	C6—C5—C4—S4	175.2 (2)
O24—N23—C23—C24	−155.7 (2)	C2—C3—C4—C5	5.0 (4)
O23—N23—C23—C22	−149.7 (2)	C2—C3—C4—S4	−175.6 (2)
O24—N23—C23—C22	30.1 (3)	C9—N10—C11—C12	0.6 (4)
C26—C21—C27—O28	6.2 (3)	C7—C12—C11—N10	0.4 (4)

1-(Pyridin-4-yl)pyridine-4-thiol (I)

Crystal data

C10H8N2S	F(000) = 788.815
Mr = 188.26	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 19758 reflections
a = 10.2407 (1) Å	θ = 4.3–75.8°
b = 13.1096 (1) Å	T = 293 K
c = 13.3608 (1) Å	Irregular, dark yellow
V = 1793.71 (3) Å^3	0.24 × 0.12 × 0.04 mm
Z = 8

Data collection

Rigaku XtaLAB Synergy Dualflex diffractometer with a HyPix detector	1771 reflections with I ≥ 2σ(I)
Mirror monochromator	Rint = 0.021
Detector resolution: 10.0000 pixels mm^-1	θmax = 76.7°, θmin = 6.4°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2023)	h = −10→12
Tmin = 0.835, Tmax = 1.000	k = −16→15
30686 measured reflections	l = −16→15
1860 independent reflections

Refinement

Refinement on F^2	7 restraints
Least-squares matrix: full	14 constraints
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0583P)^2 + 0.3252P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = −0.0004
1860 reflections	Δρmax = 0.21 e Å^−3
123 parameters	Δρmin = −0.20 e Å^−3

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

	x	y	z	Uiso*/Ueq
S4	0.10294 (3)	0.24581 (2)	0.38637 (3)	0.05356 (16)
N1	0.49752 (10)	0.39800 (7)	0.37360 (7)	0.0403 (3)
N10	0.86190 (13)	0.54926 (10)	0.35533 (11)	0.0609 (3)
C5	0.36975 (17)	0.24670 (9)	0.37695 (10)	0.0459 (3)
H5	0.36706 (17)	0.17580 (9)	0.37615 (10)	0.0551 (4)*
C3	0.26715 (12)	0.40963 (9)	0.38938 (9)	0.0454 (3)
H3	0.19357 (12)	0.45058 (9)	0.39649 (9)	0.0544 (4)*
C6	0.48718 (12)	0.29426 (9)	0.37100 (9)	0.0447 (3)
H6	0.56254 (12)	0.25515 (9)	0.36501 (9)	0.0537 (3)*
C4	0.25124 (12)	0.30173 (9)	0.38432 (8)	0.0410 (3)
C7	0.62203 (13)	0.44766 (10)	0.36569 (9)	0.0419 (3)
C2	0.38552 (12)	0.45404 (9)	0.38416 (9)	0.0447 (3)
H2	0.39137 (12)	0.52473 (9)	0.38783 (9)	0.0537 (4)*
C8	0.63032 (12)	0.54499 (9)	0.32552 (11)	0.0497 (3)
H8	0.55663 (12)	0.57796 (9)	0.30087 (11)	0.0596 (4)*
C12	0.73502 (13)	0.40137 (11)	0.39944 (11)	0.0518 (3)
H12	0.73304 (13)	0.33604 (11)	0.42652 (11)	0.0621 (4)*
C9	0.75121 (14)	0.59143 (11)	0.32322 (12)	0.0572 (4)
C11	0.85143 (14)	0.45488 (12)	0.39189 (12)	0.0605 (4)
H11	0.92727 (14)	0.42285 (12)	0.41377 (12)	0.0726 (5)*
H9	0.7594 (16)	0.6595 (13)	0.2961 (14)	0.078 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S4	0.0395 (2)	0.0444 (2)	0.0768 (3)	−0.00491 (11)	0.00097 (13)	−0.00091 (13)
N1	0.0360 (5)	0.0355 (5)	0.0493 (5)	0.0004 (4)	0.0017 (4)	−0.0002 (4)
N10	0.0448 (6)	0.0634 (7)	0.0743 (8)	−0.0108 (6)	0.0037 (6)	0.0011 (6)
C5	0.0447 (7)	0.0326 (6)	0.0604 (8)	0.0019 (4)	−0.0017 (5)	−0.0022 (5)
C3	0.0393 (6)	0.0362 (6)	0.0605 (7)	0.0051 (5)	0.0050 (5)	−0.0005 (5)
C6	0.0402 (6)	0.0343 (6)	0.0597 (7)	0.0051 (5)	0.0002 (5)	−0.0023 (5)
C4	0.0413 (6)	0.0378 (6)	0.0439 (6)	−0.0006 (5)	0.0000 (4)	0.0001 (4)
C7	0.0370 (6)	0.0412 (6)	0.0474 (6)	−0.0009 (5)	0.0041 (4)	−0.0028 (5)
C2	0.0432 (7)	0.0317 (6)	0.0593 (7)	0.0037 (4)	0.0054 (5)	−0.0010 (4)
C8	0.0434 (6)	0.0452 (7)	0.0604 (8)	−0.0021 (5)	−0.0002 (6)	0.0060 (5)
C12	0.0416 (7)	0.0476 (7)	0.0661 (8)	0.0012 (5)	0.0007 (6)	0.0041 (6)
C9	0.0513 (7)	0.0512 (7)	0.0690 (9)	−0.0107 (6)	0.0017 (6)	0.0069 (6)
C11	0.0384 (7)	0.0642 (9)	0.0788 (10)	0.0019 (6)	−0.0009 (6)	0.0014 (7)

Geometric parameters (Å, º)

S4—C4	1.6867 (12)	C3—C2	1.3465 (18)
N1—C6	1.3646 (15)	C6—H6	0.9300
N1—C7	1.4356 (16)	C7—C8	1.3867 (18)
N1—C2	1.3694 (15)	C7—C12	1.3823 (19)
N10—C9	1.3321 (19)	C2—H2	0.9300
N10—C11	1.335 (2)	C8—H8	0.9300
C5—H5	0.9300	C8—C9	1.3800 (18)
C5—C6	1.357 (2)	C12—H12	0.9300
C5—C4	1.415 (2)	C12—C11	1.387 (2)
C3—H3	0.9300	C9—H9	0.967 (17)
C3—C4	1.4255 (17)	C11—H11	0.9300
C7—N1—C6	121.27 (10)	C12—C7—N1	121.36 (11)
C2—N1—C6	118.18 (10)	C12—C7—C8	118.62 (12)
C2—N1—C7	120.55 (10)	C3—C2—N1	121.83 (11)
C11—N10—C9	115.74 (13)	H2—C2—N1	119.08 (7)
C6—C5—H5	119.00 (7)	H2—C2—C3	119.08 (7)
C4—C5—H5	119.00 (7)	H8—C8—C7	121.00 (8)
C4—C5—C6	121.99 (11)	C9—C8—C7	118.00 (12)
C4—C3—H3	119.02 (7)	C9—C8—H8	121.00 (8)
C2—C3—H3	119.02 (7)	H12—C12—C7	120.86 (8)
C2—C3—C4	121.96 (11)	C11—C12—C7	118.28 (13)
C5—C6—N1	121.69 (11)	C11—C12—H12	120.86 (9)
H6—C6—N1	119.16 (7)	C8—C9—N10	124.97 (13)
H6—C6—C5	119.16 (7)	H9—C9—N10	115.5 (10)
C5—C4—S4	123.48 (10)	H9—C9—C8	119.6 (10)
C3—C4—S4	122.24 (9)	C12—C11—N10	124.38 (14)
C3—C4—C5	114.28 (11)	H11—C11—N10	117.81 (9)
C8—C7—N1	120.01 (11)	H11—C11—C12	117.81 (9)
S4—C4—C5—C6	177.01 (10)	N1—C2—C3—C4	0.06 (14)
S4—C4—C3—C2	−177.61 (10)	N10—C9—C8—C7	1.14 (19)
N1—C6—C5—C4	1.17 (14)	N10—C11—C12—C7	1.00 (19)
N1—C7—C8—C9	177.34 (12)	C5—C4—C3—C2	2.05 (12)
N1—C7—C12—C11	−178.30 (13)