Crystal structures of 3/4-pyrid­yl-based thio­semi­car­ba­zones and related Cu and Ni coordination compounds

In this investigation, the crystal structures of the thio-ligands 3-formyl­pyridine 4-phenyl­thio­semi­car­ba­zone (C₁₃H₁₂N₄S, 1) and 4-benzoyl­pyridine 4-ethyl­thio­semi­car­ba­zone (C₁₅H₁₆N₄S, 2), and of two new coordination compounds, chlorido­(3-formyl­pyridine 4-phenyl­thio­semi­car­ba­zone-κS)bis­(tri­phenyl­phos­phane-κP)copper(I) aceto­nitrile monosolvate, [CuCl(C₁₃H₁₂N₄S)(C₁₈H₁₅P)₂]·CH₃CN, 3, and bis­(3-formyl­pyridine 4-ethyl­thio­semicarbazonato-κ²N¹,S)nickel(II), [Ni(C₉H₁₁N₄S)₂], 4, are reported. In complex 3, the thio-ligand coordinates in a neutral form to the Cu atom through its S-donor atom, and in complex 4, the anionic thio-ligand chelates to the Ni atom through N- and S-donor atoms. The geometry of complex 3 is distorted tetra­hedral [bond angles 99.70 (5)–123.23 (5)°], with the P—Cu—P bond angle being the largest, while that of complex 4 is square planar, with trans-S—Ni—S and N—Ni—N bond angles of 180°.

Computing details

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2019); cell refinement: CrysAlis PRO (Rigaku OD, 2019); data reduction: CrysAlis PRO (Rigaku OD, 2019); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); 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).

(E)-N-Phenyl-2-(pyridin-3-ylmethylidene)hydrazine-1-carbothioamide (1)

Crystal data

C13H12N4S	F(000) = 536
Mr = 256.33	Dx = 1.378 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.2214 (2) Å	Cell parameters from 2191 reflections
b = 6.6059 (3) Å	θ = 3.1–31.7°
c = 25.9620 (9) Å	µ = 0.25 mm^−1
β = 94.233 (3)°	T = 173 K
V = 1235.10 (8) Å^3	Prism, colourless
Z = 4	0.44 × 0.34 × 0.14 mm

Data collection

Rigaku OD Eos Gemini diffractometer	4103 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3099 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 16.0416 pixels mm^-1	θmax = 32.8°, θmin = 2.8°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2019)	k = −9→9
Tmin = 0.758, Tmax = 1.000	l = −30→37
8496 measured 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)] = 0.049	w = 1/[σ^2(Fo^2) + (0.0631P)^2 + 0.2055P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.140	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.31 e Å^−3
4103 reflections	Δρmin = −0.36 e Å^−3
164 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0067 (19)
Primary atom site location: dual

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. The crystallographic data were measured using a Rigaku Oxford Diffraction Eos four-circle diffractometer for compounds 1-4, using graphite mono-chromated Mo-Kα (λ = 0.71073 Å) radiation. The crystal data were collected at 173 (2) K (Compounds 1-4), and processed with CrysAlisPro (data collection, data reduction and cell refinement). The structures were solved by the direct methods using the program OLEX2 1.3 refined by the full-matrix least-squares technique based on F² using SHELXL (Dolomanov et al., 2009; Sheldrick, G. M., 2015a). All the non-hydrogen atoms were refined anisotropically

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

	x	y	z	Uiso*/Ueq
S1	−0.20115 (5)	0.27705 (8)	0.39884 (2)	0.03922 (14)
N1	0.16815 (17)	0.31956 (18)	0.39061 (4)	0.0269 (3)
H1	0.277235	0.308804	0.407872	0.032*
N2	0.07158 (17)	0.26924 (18)	0.47051 (4)	0.0279 (3)
H2	−0.014759	0.256627	0.492511	0.033*
N3	0.25563 (16)	0.26605 (17)	0.48777 (4)	0.0252 (2)
N4	0.80532 (17)	0.21284 (19)	0.55000 (5)	0.0291 (3)
C1	0.0232 (2)	0.2920 (2)	0.41931 (5)	0.0255 (3)
C2	0.2879 (2)	0.2402 (2)	0.53643 (5)	0.0277 (3)
H2A	0.186938	0.230378	0.557781	0.033*
C3	0.47792 (19)	0.2255 (2)	0.55957 (5)	0.0246 (3)
C4	0.6305 (2)	0.2325 (2)	0.53022 (5)	0.0272 (3)
H4	0.609421	0.252361	0.494020	0.033*
C5	0.8321 (2)	0.1842 (2)	0.60113 (5)	0.0300 (3)
H5	0.955630	0.168090	0.615803	0.036*
C6	0.6894 (2)	0.1769 (2)	0.63343 (5)	0.0311 (3)
H6	0.714667	0.157619	0.669529	0.037*
C7	0.5095 (2)	0.1981 (2)	0.61263 (5)	0.0301 (3)
H7	0.408616	0.194029	0.634133	0.036*
C8	0.1765 (2)	0.3630 (2)	0.33743 (5)	0.0268 (3)
C9	0.0314 (2)	0.4507 (2)	0.30697 (5)	0.0313 (3)
H9	−0.084595	0.476670	0.320711	0.038*
C10	0.0594 (3)	0.4994 (2)	0.25630 (6)	0.0387 (4)
H10	−0.039371	0.558615	0.235259	0.046*
C11	0.2258 (3)	0.4646 (3)	0.23563 (6)	0.0454 (4)
H11	0.242214	0.500261	0.200817	0.054*
C12	0.3698 (3)	0.3768 (3)	0.26601 (6)	0.0442 (4)
H12	0.485723	0.352206	0.252109	0.053*
C13	0.3444 (2)	0.3251 (2)	0.31662 (6)	0.0339 (3)
H13	0.442705	0.263192	0.337261	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0233 (2)	0.0655 (3)	0.0283 (2)	−0.00102 (17)	−0.00201 (14)	−0.00361 (16)
N1	0.0239 (6)	0.0348 (6)	0.0218 (5)	0.0019 (5)	0.0002 (4)	0.0002 (4)
N2	0.0200 (5)	0.0406 (7)	0.0229 (5)	0.0009 (5)	0.0012 (4)	−0.0012 (4)
N3	0.0197 (5)	0.0319 (6)	0.0238 (5)	−0.0003 (4)	0.0007 (4)	−0.0011 (4)
N4	0.0221 (6)	0.0345 (6)	0.0307 (6)	−0.0005 (5)	0.0022 (5)	−0.0032 (5)
C1	0.0247 (6)	0.0277 (6)	0.0240 (6)	0.0028 (5)	0.0003 (5)	−0.0039 (5)
C2	0.0214 (6)	0.0394 (8)	0.0226 (6)	−0.0018 (6)	0.0034 (5)	0.0000 (5)
C3	0.0229 (6)	0.0290 (6)	0.0219 (6)	−0.0022 (5)	0.0013 (5)	0.0002 (4)
C4	0.0242 (6)	0.0347 (7)	0.0227 (6)	−0.0010 (5)	0.0024 (5)	−0.0014 (5)
C5	0.0255 (7)	0.0312 (7)	0.0324 (7)	0.0005 (5)	−0.0042 (5)	−0.0018 (5)
C6	0.0322 (7)	0.0358 (7)	0.0247 (6)	−0.0028 (6)	−0.0021 (5)	0.0042 (5)
C7	0.0279 (7)	0.0398 (8)	0.0229 (6)	−0.0047 (6)	0.0038 (5)	0.0035 (5)
C8	0.0334 (7)	0.0248 (6)	0.0218 (5)	−0.0005 (6)	0.0002 (5)	−0.0017 (4)
C9	0.0362 (8)	0.0287 (7)	0.0280 (6)	0.0021 (6)	−0.0039 (6)	−0.0006 (5)
C10	0.0545 (10)	0.0296 (7)	0.0304 (7)	0.0000 (7)	−0.0074 (7)	0.0034 (5)
C11	0.0700 (13)	0.0408 (9)	0.0261 (7)	−0.0009 (9)	0.0079 (7)	0.0058 (6)
C12	0.0512 (11)	0.0466 (10)	0.0369 (8)	0.0037 (8)	0.0177 (7)	0.0057 (7)
C13	0.0342 (8)	0.0374 (8)	0.0304 (7)	0.0016 (6)	0.0055 (6)	0.0047 (6)

Geometric parameters (Å, º)

S1—C1	1.6704 (14)	C5—H5	0.9500
N1—C1	1.3412 (18)	C6—C7	1.377 (2)
N1—C8	1.4158 (16)	C6—H6	0.9500
N1—H1	0.8800	C7—H7	0.9500
N2—C1	1.3576 (17)	C8—C13	1.386 (2)
N2—N3	1.3711 (16)	C8—C9	1.3918 (19)
N2—H2	0.8800	C9—C10	1.383 (2)
N3—C2	1.2792 (16)	C9—H9	0.9500
N4—C4	1.3335 (18)	C10—C11	1.371 (3)
N4—C5	1.3408 (18)	C10—H10	0.9500
C2—C3	1.4601 (19)	C11—C12	1.385 (3)
C2—H2A	0.9500	C11—H11	0.9500
C3—C4	1.3862 (19)	C12—C13	1.383 (2)
C3—C7	1.3914 (17)	C12—H12	0.9500
C4—H4	0.9500	C13—H13	0.9500
C5—C6	1.376 (2)
C1—N1—C8	131.34 (12)	C5—C6—H6	120.5
C1—N1—H1	114.3	C7—C6—H6	120.5
C8—N1—H1	114.3	C6—C7—C3	118.83 (14)
C1—N2—N3	119.65 (12)	C6—C7—H7	120.6
C1—N2—H2	120.2	C3—C7—H7	120.6
N3—N2—H2	120.2	C13—C8—C9	119.82 (13)
C2—N3—N2	115.23 (12)	C13—C8—N1	116.44 (12)
C4—N4—C5	117.26 (13)	C9—C8—N1	123.63 (13)
N1—C1—N2	113.84 (12)	C10—C9—C8	118.71 (15)
N1—C1—S1	127.56 (10)	C10—C9—H9	120.6
N2—C1—S1	118.58 (11)	C8—C9—H9	120.6
N3—C2—C3	120.83 (13)	C11—C10—C9	121.78 (15)
N3—C2—H2A	119.6	C11—C10—H10	119.1
C3—C2—H2A	119.6	C9—C10—H10	119.1
C4—C3—C7	118.04 (13)	C10—C11—C12	119.35 (14)
C4—C3—C2	122.19 (12)	C10—C11—H11	120.3
C7—C3—C2	119.75 (13)	C12—C11—H11	120.3
N4—C4—C3	123.60 (12)	C13—C12—C11	119.87 (17)
N4—C4—H4	118.2	C13—C12—H12	120.1
C3—C4—H4	118.2	C11—C12—H12	120.1
N4—C5—C6	123.27 (13)	C12—C13—C8	120.46 (15)
N4—C5—H5	118.4	C12—C13—H13	119.8
C6—C5—H5	118.4	C8—C13—H13	119.8
C5—C6—C7	118.99 (13)
N1—C8—C9—C10	175.53 (13)	C4—N4—C5—C6	−0.8 (2)
N1—C8—C13—C12	−175.20 (14)	C4—C3—C7—C6	−0.7 (2)
N2—N3—C2—C3	177.47 (12)	C5—N4—C4—C3	0.2 (2)
N3—N2—C1—S1	175.25 (10)	C5—C6—C7—C3	0.2 (2)
N3—N2—C1—N1	−3.15 (18)	C7—C3—C4—N4	0.5 (2)
N3—C2—C3—C4	−2.0 (2)	C8—N1—C1—S1	7.0 (2)
N3—C2—C3—C7	179.75 (14)	C8—N1—C1—N2	−174.80 (13)
N4—C5—C6—C7	0.6 (2)	C8—C9—C10—C11	−0.4 (2)
C1—N1—C8—C9	22.1 (2)	C9—C8—C13—C12	1.0 (2)
C1—N1—C8—C13	−161.85 (14)	C9—C10—C11—C12	0.5 (3)
C1—N2—N3—C2	−178.72 (12)	C10—C11—C12—C13	0.1 (3)
C2—C3—C4—N4	−177.73 (13)	C11—C12—C13—C8	−0.9 (3)
C2—C3—C7—C6	177.58 (13)	C13—C8—C9—C10	−0.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N4^i	0.88	2.07	2.9461 (18)	174
C9—H9···S1	0.95	2.61	3.2275 (16)	123

Symmetry code: (i) x−1, y, z.

(E)-N-Ethyl-2-[phenyl(pyridin-4-yl)methylidene]hydrazine-1-carbothioamide (2)

Crystal data

C15H16N4S	Dx = 1.285 Mg m^−3
Mr = 284.38	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 10170 reflections
a = 15.8897 (3) Å	θ = 4.0–32.4°
b = 10.9845 (2) Å	µ = 0.22 mm^−1
c = 16.8393 (3) Å	T = 173 K
V = 2939.14 (9) Å^3	Prism, colourless
Z = 8	0.32 × 0.26 × 0.14 mm
F(000) = 1200

Data collection

Rigaku OD Gemini Eos diffractometer	5181 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	4133 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 16.0416 pixels mm^-1	θmax = 32.9°, θmin = 3.3°
ω scans	h = −23→22
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2019)	k = −16→16
Tmin = 0.875, Tmax = 1.000	l = −25→22
36150 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)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.110	w = 1/[σ^2(Fo^2) + (0.0522P)^2 + 0.706P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
5181 reflections	Δρmax = 0.35 e Å^−3
182 parameters	Δρmin = −0.27 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. The crystallographic data were measured using a Rigaku Oxford Diffraction Eos four-circle diffractometer for compounds 1-4, using graphite mono-chromated Mo-Kα (λ = 0.71073 Å) radiation. The crystal data were collected at 173 (2) K (Compounds 1-4), and processed with CrysAlisPro (data collection, data reduction and cell refinement). The structures were solved by the direct methods using the program OLEX2 1.3 refined by the full-matrix least-squares technique based on F² using SHELXL (Dolomanov et al., 2009; Sheldrick, G. M., 2015a). All the non-hydrogen atoms were refined anisotropically

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

	x	y	z	Uiso*/Ueq
S1	0.15876 (2)	0.77991 (3)	0.67701 (2)	0.03544 (9)
N1	0.32190 (6)	0.72393 (8)	0.66444 (6)	0.02645 (19)
H1	0.361902	0.683872	0.639466	0.032*
N2	0.23332 (6)	0.64807 (9)	0.56906 (6)	0.0288 (2)
H2	0.182345	0.637311	0.549863	0.035*
N3	0.30060 (6)	0.59710 (8)	0.53136 (6)	0.02595 (18)
N4	0.50794 (6)	0.37951 (10)	0.36409 (6)	0.0329 (2)
C1	0.24434 (7)	0.71581 (9)	0.63649 (6)	0.0245 (2)
C2	0.28598 (6)	0.52459 (9)	0.47264 (6)	0.02316 (19)
C3	0.36179 (6)	0.47578 (9)	0.43256 (6)	0.02238 (19)
C4	0.43464 (7)	0.54479 (10)	0.42607 (6)	0.0272 (2)
H4	0.435933	0.626335	0.444837	0.033*
C5	0.50532 (7)	0.49327 (11)	0.39193 (7)	0.0312 (2)
H5	0.554770	0.541505	0.388058	0.037*
C6	0.43704 (7)	0.31490 (11)	0.36882 (7)	0.0329 (2)
H6	0.437369	0.234220	0.348497	0.039*
C7	0.36292 (7)	0.35843 (10)	0.40161 (7)	0.0282 (2)
H7	0.313850	0.309069	0.402921	0.034*
C8	0.20158 (6)	0.48579 (9)	0.44413 (6)	0.02224 (19)
C9	0.17690 (7)	0.50928 (10)	0.36640 (7)	0.0281 (2)
H9	0.213599	0.551897	0.331600	0.034*
C10	0.09876 (8)	0.47061 (12)	0.33953 (8)	0.0356 (3)
H10	0.081909	0.487739	0.286565	0.043*
C11	0.04537 (8)	0.40736 (11)	0.38939 (9)	0.0372 (3)
H11	−0.007859	0.380379	0.370684	0.045*
C12	0.06965 (8)	0.38353 (11)	0.46643 (8)	0.0368 (3)
H12	0.032864	0.340268	0.500797	0.044*
C13	0.14732 (7)	0.42220 (10)	0.49415 (7)	0.0296 (2)
H13	0.163568	0.405321	0.547318	0.036*
C14	0.34520 (8)	0.79516 (10)	0.73407 (6)	0.0289 (2)
H14A	0.397390	0.761091	0.757239	0.035*
H14B	0.300134	0.788198	0.774412	0.035*
C15	0.35907 (10)	0.92783 (12)	0.71494 (8)	0.0392 (3)
H15A	0.404036	0.935383	0.675405	0.059*
H15B	0.375181	0.971505	0.763355	0.059*
H15C	0.307021	0.962791	0.693620	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.02965 (15)	0.03699 (17)	0.03968 (18)	0.00573 (11)	0.00703 (11)	−0.01253 (12)
N1	0.0285 (4)	0.0268 (4)	0.0240 (4)	0.0045 (3)	0.0016 (3)	−0.0071 (3)
N2	0.0244 (4)	0.0317 (5)	0.0302 (5)	0.0015 (3)	0.0021 (3)	−0.0113 (4)
N3	0.0260 (4)	0.0275 (4)	0.0244 (4)	0.0025 (3)	0.0026 (3)	−0.0062 (3)
N4	0.0270 (4)	0.0410 (5)	0.0308 (5)	0.0051 (4)	0.0016 (4)	−0.0080 (4)
C1	0.0293 (5)	0.0203 (4)	0.0238 (5)	0.0011 (4)	0.0046 (4)	−0.0019 (4)
C2	0.0248 (4)	0.0238 (4)	0.0208 (4)	0.0009 (3)	0.0005 (3)	−0.0020 (3)
C3	0.0237 (4)	0.0254 (5)	0.0180 (4)	0.0012 (3)	−0.0006 (3)	−0.0029 (3)
C4	0.0284 (5)	0.0279 (5)	0.0254 (5)	−0.0022 (4)	0.0013 (4)	−0.0048 (4)
C5	0.0257 (5)	0.0395 (6)	0.0284 (5)	−0.0030 (4)	0.0027 (4)	−0.0039 (5)
C6	0.0323 (5)	0.0305 (5)	0.0359 (6)	0.0050 (4)	0.0001 (5)	−0.0108 (5)
C7	0.0267 (5)	0.0267 (5)	0.0314 (5)	−0.0004 (4)	0.0001 (4)	−0.0059 (4)
C8	0.0242 (4)	0.0199 (4)	0.0226 (5)	0.0010 (3)	0.0023 (3)	−0.0028 (3)
C9	0.0304 (5)	0.0297 (5)	0.0243 (5)	−0.0028 (4)	−0.0012 (4)	0.0023 (4)
C10	0.0348 (6)	0.0350 (6)	0.0369 (6)	0.0020 (5)	−0.0117 (5)	−0.0024 (5)
C11	0.0251 (5)	0.0306 (5)	0.0559 (8)	−0.0010 (4)	−0.0022 (5)	−0.0123 (5)
C12	0.0328 (6)	0.0293 (5)	0.0483 (7)	−0.0076 (4)	0.0139 (5)	−0.0059 (5)
C13	0.0361 (6)	0.0273 (5)	0.0256 (5)	−0.0029 (4)	0.0068 (4)	−0.0005 (4)
C14	0.0369 (6)	0.0304 (5)	0.0194 (5)	0.0043 (4)	−0.0016 (4)	−0.0034 (4)
C15	0.0577 (8)	0.0353 (6)	0.0245 (5)	−0.0121 (6)	−0.0021 (5)	−0.0047 (5)

Geometric parameters (Å, º)

S1—C1	1.6764 (10)	C7—H7	0.9500
N1—H1	0.8800	C8—C9	1.3907 (15)
N1—C1	1.3222 (14)	C8—C13	1.3931 (15)
N1—C14	1.4574 (14)	C9—H9	0.9500
N2—H2	0.8800	C9—C10	1.3881 (16)
N2—N3	1.3636 (12)	C10—H10	0.9500
N2—C1	1.3688 (14)	C10—C11	1.3811 (19)
N3—C2	1.2909 (13)	C11—H11	0.9500
N4—C5	1.3353 (15)	C11—C12	1.378 (2)
N4—C6	1.3339 (16)	C12—H12	0.9500
C2—C3	1.4812 (14)	C12—C13	1.3862 (17)
C2—C8	1.4867 (14)	C13—H13	0.9500
C3—C4	1.3881 (15)	C14—H14A	0.9900
C3—C7	1.3905 (14)	C14—H14B	0.9900
C4—H4	0.9500	C14—C15	1.5087 (17)
C4—C5	1.3827 (15)	C15—H15A	0.9800
C5—H5	0.9500	C15—H15B	0.9800
C6—H6	0.9500	C15—H15C	0.9800
C6—C7	1.3858 (15)
C1—N1—H1	118.0	C9—C8—C13	119.18 (10)
C1—N1—C14	124.01 (9)	C13—C8—C2	120.45 (10)
C14—N1—H1	118.0	C8—C9—H9	119.9
N3—N2—H2	119.7	C10—C9—C8	120.15 (11)
N3—N2—C1	120.60 (9)	C10—C9—H9	119.9
C1—N2—H2	119.7	C9—C10—H10	119.8
C2—N3—N2	117.96 (9)	C11—C10—C9	120.34 (12)
C6—N4—C5	116.78 (10)	C11—C10—H10	119.8
N1—C1—S1	125.65 (8)	C10—C11—H11	120.1
N1—C1—N2	116.82 (9)	C12—C11—C10	119.72 (11)
N2—C1—S1	117.53 (8)	C12—C11—H11	120.1
N3—C2—C3	115.21 (9)	C11—C12—H12	119.7
N3—C2—C8	125.92 (9)	C11—C12—C13	120.53 (11)
C3—C2—C8	118.86 (9)	C13—C12—H12	119.7
C4—C3—C2	121.09 (9)	C8—C13—H13	120.0
C4—C3—C7	117.77 (10)	C12—C13—C8	120.07 (11)
C7—C3—C2	121.12 (9)	C12—C13—H13	120.0
C3—C4—H4	120.4	N1—C14—H14A	109.1
C5—C4—C3	119.11 (10)	N1—C14—H14B	109.1
C5—C4—H4	120.4	N1—C14—C15	112.58 (9)
N4—C5—C4	123.67 (11)	H14A—C14—H14B	107.8
N4—C5—H5	118.2	C15—C14—H14A	109.1
C4—C5—H5	118.2	C15—C14—H14B	109.1
N4—C6—H6	118.0	C14—C15—H15A	109.5
N4—C6—C7	123.91 (10)	C14—C15—H15B	109.5
C7—C6—H6	118.0	C14—C15—H15C	109.5
C3—C7—H7	120.6	H15A—C15—H15B	109.5
C6—C7—C3	118.70 (10)	H15A—C15—H15C	109.5
C6—C7—H7	120.6	H15B—C15—H15C	109.5
C9—C8—C2	120.34 (9)
N2—N3—C2—C3	177.95 (9)	C3—C2—C8—C13	117.85 (11)
N2—N3—C2—C8	−3.27 (16)	C3—C4—C5—N4	0.22 (18)
N3—N2—C1—S1	177.57 (8)	C4—C3—C7—C6	2.41 (16)
N3—N2—C1—N1	−3.05 (15)	C5—N4—C6—C7	−1.06 (19)
N3—C2—C3—C4	−33.40 (15)	C6—N4—C5—C4	1.38 (18)
N3—C2—C3—C7	145.28 (11)	C7—C3—C4—C5	−2.12 (16)
N3—C2—C8—C9	121.10 (12)	C8—C2—C3—C4	147.73 (10)
N3—C2—C8—C13	−60.89 (15)	C8—C2—C3—C7	−33.59 (15)
N4—C6—C7—C3	−0.85 (19)	C8—C9—C10—C11	−0.76 (18)
C1—N1—C14—C15	−83.30 (14)	C9—C8—C13—C12	−0.24 (16)
C1—N2—N3—C2	173.43 (10)	C9—C10—C11—C12	0.56 (19)
C2—C3—C4—C5	176.60 (10)	C10—C11—C12—C13	−0.21 (18)
C2—C3—C7—C6	−176.32 (11)	C11—C12—C13—C8	0.06 (17)
C2—C8—C9—C10	178.63 (10)	C13—C8—C9—C10	0.59 (16)
C2—C8—C13—C12	−178.28 (10)	C14—N1—C1—S1	−2.61 (16)
C3—C2—C8—C9	−60.16 (13)	C14—N1—C1—N2	178.07 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4^i	0.88	2.18	2.9719 (13)	149

Symmetry code: (i) −x+1, −y+1, −z+1.

Chlorido[(E)-N-phenyl-2-(pyridin-3-ylmethylidene)hydrazine-1-carbothioamide-κS]bis(triphenylphosphane-κP)copper(I) acetonitrile monosolvate (3)

Crystal data

[CuCl(C13H12N4S)(C18H15P)2]·C2H3N	F(000) = 1912
Mr = 920.91	Dx = 1.359 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.7299 (9) Å	Cell parameters from 5023 reflections
b = 11.1592 (2) Å	θ = 3.7–31.3°
c = 21.6646 (7) Å	µ = 0.70 mm^−1
β = 96.296 (4)°	T = 173 K
V = 4500.8 (3) Å^3	Prism, colourless
Z = 4	0.44 × 0.36 × 0.28 mm

Data collection

Rigaku OD Gemini Eos diffractometer	14960 independent reflections
Radiation source: fine-focus sealed X-ray tube	8988 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm^-1	Rint = 0.058
ω scans	θmax = 32.9°, θmin = 3.4°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2019)	h = −28→20
Tmin = 0.765, Tmax = 1.000	k = −16→12
29820 measured reflections	l = −32→26

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)] = 0.115	H-atom parameters constrained
wR(F^2) = 0.232	w = 1/[σ^2(Fo^2) + 31.7681P] where P = (Fo^2 + 2Fc^2)/3
S = 1.17	(Δ/σ)max < 0.001
14960 reflections	Δρmax = 1.42 e Å^−3
582 parameters	Δρmin = −1.03 e Å^−3
210 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. The crystallographic data were measured using a Rigaku Oxford Diffraction Eos four-circle diffractometer for compounds 1-4, using graphite mono-chromated Mo-Kα (λ = 0.71073 Å) radiation. The crystal data were collected at 173 (2) K (Compounds 1-4), and processed with CrysAlisPro (data collection, data reduction and cell refinement). The structures were solved by the direct methods using the program OLEX2 1.3 refined by the full-matrix least-squares technique based on F² using SHELXL (Dolomanov et al., 2009; Sheldrick, G. M., 2015a). All the non-hydrogen atoms were refined anisotropically

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.71690 (4)	0.52500 (6)	0.21090 (3)	0.02339 (14)
Cl1	0.79270 (10)	0.68562 (14)	0.18643 (7)	0.0410 (4)
S1	0.67380 (8)	0.56193 (12)	0.30881 (6)	0.0271 (3)
P1	0.62790 (7)	0.52908 (12)	0.13136 (6)	0.0205 (2)
P2	0.78630 (8)	0.35963 (12)	0.23579 (6)	0.0240 (3)
N1	0.7402 (3)	0.6646 (4)	0.4117 (2)	0.0296 (10)
H1	0.764148	0.726733	0.428185	0.036*
N2	0.7617 (3)	0.7449 (4)	0.3194 (2)	0.0284 (10)
H2	0.749725	0.755248	0.279296	0.034*
N3	0.8151 (3)	0.8149 (4)	0.3507 (2)	0.0279 (10)
C1	0.7284 (3)	0.6615 (5)	0.3503 (3)	0.0265 (11)
C2	0.8516 (3)	0.8758 (5)	0.3150 (3)	0.0288 (11)
H2A	0.838820	0.873621	0.271368	0.035*
C3	0.9127 (6)	0.9485 (14)	0.3407 (6)	0.0365 (13)	0.493 (14)
C4	0.9590 (7)	1.0015 (12)	0.3027 (5)	0.0374 (14)	0.493 (14)
H4A	0.949817	0.994547	0.258887	0.045*	0.493 (14)
C5	1.0187 (5)	1.0647 (10)	0.3290 (6)	0.0390 (14)	0.493 (14)
H5A	1.050346	1.100924	0.303076	0.047*	0.493 (14)
C6	1.0321 (4)	1.0749 (9)	0.3932 (6)	0.0401 (15)	0.493 (14)
H6A	1.072960	1.118101	0.411098	0.048*	0.493 (14)
N4	0.9859 (6)	1.0219 (10)	0.4311 (5)	0.0412 (14)	0.493 (14)
C7	0.9261 (6)	0.9587 (13)	0.4048 (6)	0.0384 (14)	0.493 (14)
H7A	0.894518	0.922523	0.430744	0.046*	0.493 (14)
C3A	0.9101 (5)	0.9525 (14)	0.3376 (6)	0.0365 (13)	0.507 (14)
C4A	0.9431 (6)	1.0030 (12)	0.2893 (5)	0.0380 (14)	0.507 (14)
H4AA	0.922932	0.991737	0.247567	0.046*	0.507 (14)
C5A	1.0055 (6)	1.0699 (9)	0.3022 (5)	0.0382 (15)	0.507 (14)
H5AA	1.028048	1.104434	0.269248	0.046*	0.507 (14)
C6A	1.0350 (4)	1.0864 (8)	0.3633 (6)	0.0402 (15)	0.507 (14)
H6AA	1.077690	1.132171	0.372150	0.048*	0.507 (14)
N4A	1.0021 (6)	1.0360 (9)	0.4116 (5)	0.0412 (14)	0.507 (14)
C7A	0.9396 (6)	0.9690 (12)	0.3987 (5)	0.0374 (13)	0.507 (14)
H7AA	0.917102	0.934516	0.431689	0.045*	0.507 (14)
C8	0.7180 (3)	0.5775 (5)	0.4538 (2)	0.0280 (11)
C9	0.6796 (4)	0.6151 (6)	0.5009 (3)	0.0384 (14)
H9	0.664983	0.696348	0.503020	0.046*
C10	0.6623 (4)	0.5332 (7)	0.5453 (3)	0.0497 (18)
H10	0.636659	0.558791	0.578416	0.060*
C11	0.6823 (4)	0.4146 (7)	0.5412 (3)	0.0470 (17)
H11	0.669798	0.358218	0.571082	0.056*
C12	0.7205 (4)	0.3787 (6)	0.4937 (3)	0.0434 (16)
H12	0.735060	0.297409	0.491442	0.052*
C13	0.7378 (3)	0.4592 (5)	0.4494 (3)	0.0331 (13)
H13	0.763185	0.433234	0.416153	0.040*
C14	0.5732 (3)	0.6644 (5)	0.1218 (3)	0.0277 (11)
C15	0.5559 (3)	0.7232 (5)	0.1751 (3)	0.0381 (14)
H15	0.576430	0.697151	0.214911	0.046*
C16	0.5091 (4)	0.8192 (6)	0.1701 (4)	0.0486 (18)
H16	0.498040	0.859062	0.206553	0.058*
C17	0.4782 (4)	0.8582 (6)	0.1127 (4)	0.0480 (18)
H17	0.444637	0.922298	0.109763	0.058*
C18	0.4967 (3)	0.8026 (5)	0.0598 (4)	0.0418 (16)
H18	0.477457	0.831025	0.020098	0.050*
C19	0.5434 (3)	0.7054 (5)	0.0642 (3)	0.0309 (12)
H19	0.554951	0.666766	0.027467	0.037*
C20	0.6616 (3)	0.5090 (4)	0.0557 (2)	0.0242 (10)
C21	0.7226 (3)	0.5723 (5)	0.0434 (3)	0.0301 (12)
H21	0.743377	0.629139	0.072705	0.036*
C22	0.7532 (4)	0.5531 (6)	−0.0111 (3)	0.0352 (13)
H22	0.795105	0.595938	−0.018812	0.042*
C23	0.7228 (3)	0.4718 (5)	−0.0541 (3)	0.0355 (13)
H23	0.743207	0.459917	−0.091824	0.043*
C24	0.6631 (4)	0.4080 (5)	−0.0425 (3)	0.0351 (14)
H24	0.642934	0.350748	−0.071888	0.042*
C25	0.6319 (3)	0.4270 (5)	0.0120 (2)	0.0298 (12)
H25	0.590073	0.383537	0.019444	0.036*
C26	0.5601 (3)	0.4115 (4)	0.1306 (2)	0.0230 (10)
C27	0.4877 (3)	0.4303 (5)	0.1150 (3)	0.0321 (12)
H27	0.470268	0.509178	0.106425	0.039*
C28	0.4403 (4)	0.3350 (6)	0.1117 (3)	0.0416 (15)
H28	0.390412	0.348529	0.100780	0.050*
C29	0.4653 (4)	0.2198 (6)	0.1242 (3)	0.0397 (15)
H29	0.432680	0.154303	0.121600	0.048*
C30	0.5371 (4)	0.2007 (5)	0.1402 (3)	0.0372 (14)
H30	0.554314	0.121706	0.148720	0.045*
C31	0.5842 (4)	0.2947 (5)	0.1441 (3)	0.0349 (13)
H31	0.633845	0.280515	0.156046	0.042*
C32	0.8491 (3)	0.3168 (5)	0.1823 (2)	0.0242 (10)
C33	0.8297 (3)	0.3322 (6)	0.1198 (3)	0.0355 (13)
H33	0.784439	0.367184	0.106176	0.043*
C34	0.8747 (4)	0.2977 (7)	0.0759 (3)	0.0461 (17)
H34	0.860584	0.310208	0.032898	0.055*
C35	0.9396 (4)	0.2456 (6)	0.0952 (3)	0.0405 (15)
H35	0.970445	0.221280	0.065564	0.049*
C36	0.9601 (3)	0.2285 (6)	0.1577 (3)	0.0376 (14)
H36	1.004894	0.191985	0.171243	0.045*
C37	0.9150 (3)	0.2648 (5)	0.2005 (3)	0.0309 (12)
H37	0.929720	0.253742	0.243499	0.037*
C38	0.8417 (3)	0.3764 (5)	0.3101 (2)	0.0267 (11)
C39	0.8581 (3)	0.2814 (5)	0.3511 (3)	0.0330 (13)
H39	0.840897	0.203060	0.340673	0.040*
C40	0.8998 (4)	0.3018 (6)	0.4075 (3)	0.0402 (15)
H40	0.911334	0.237049	0.435326	0.048*
C41	0.9242 (4)	0.4149 (7)	0.4230 (3)	0.0419 (15)
H41	0.952089	0.427933	0.461735	0.050*
C42	0.9088 (3)	0.5095 (6)	0.3833 (3)	0.0399 (15)
H42	0.925614	0.587703	0.394561	0.048*
C43	0.8684 (3)	0.4899 (5)	0.3262 (3)	0.0313 (12)
H43	0.858970	0.554705	0.297966	0.038*
C44	0.7381 (3)	0.2196 (5)	0.2465 (2)	0.0277 (11)
C45	0.6830 (4)	0.2211 (5)	0.2847 (3)	0.0348 (13)
H45	0.673094	0.292268	0.306207	0.042*
C46	0.6428 (4)	0.1198 (6)	0.2913 (3)	0.0411 (15)
H46	0.605456	0.122048	0.317565	0.049*
C47	0.6555 (4)	0.0160 (6)	0.2609 (3)	0.0405 (15)
H47	0.627631	−0.053610	0.266407	0.049*
C48	0.7092 (4)	0.0133 (5)	0.2219 (3)	0.0413 (15)
H48	0.717861	−0.057963	0.199903	0.050*
C49	0.7504 (3)	0.1142 (5)	0.2149 (3)	0.0330 (13)
H49	0.787457	0.111607	0.188264	0.040*
N1S	0.8869 (4)	0.7128 (6)	0.5053 (3)	0.065 (2)
C1S	0.8788 (4)	0.6517 (6)	0.5452 (4)	0.0466 (17)
C2S	0.8666 (5)	0.5746 (7)	0.5967 (4)	0.066 (2)
H2SA	0.837170	0.506040	0.581316	0.099*
H2SB	0.841615	0.619654	0.626651	0.099*
H2SC	0.912814	0.545934	0.616930	0.099*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0272 (3)	0.0209 (3)	0.0220 (3)	−0.0003 (3)	0.0021 (2)	−0.0026 (2)
Cl1	0.0592 (11)	0.0368 (8)	0.0293 (7)	−0.0206 (7)	0.0147 (7)	−0.0064 (6)
S1	0.0272 (7)	0.0299 (7)	0.0246 (6)	−0.0035 (5)	0.0047 (5)	−0.0049 (5)
P1	0.0231 (6)	0.0185 (6)	0.0200 (6)	−0.0005 (5)	0.0032 (5)	−0.0019 (5)
P2	0.0279 (7)	0.0204 (6)	0.0238 (6)	0.0017 (5)	0.0040 (5)	−0.0022 (5)
N1	0.048 (3)	0.025 (2)	0.017 (2)	−0.007 (2)	0.0063 (19)	−0.0027 (16)
N2	0.037 (3)	0.024 (2)	0.023 (2)	−0.007 (2)	0.0013 (19)	−0.0026 (17)
N3	0.033 (3)	0.021 (2)	0.030 (2)	−0.0047 (19)	0.0029 (19)	−0.0027 (18)
C1	0.030 (3)	0.023 (2)	0.028 (3)	0.001 (2)	0.009 (2)	0.001 (2)
C2	0.033 (3)	0.024 (3)	0.029 (3)	−0.002 (2)	0.002 (2)	0.000 (2)
C3	0.034 (3)	0.025 (2)	0.050 (3)	−0.007 (2)	0.005 (2)	0.001 (2)
C4	0.034 (3)	0.028 (3)	0.050 (3)	−0.008 (2)	0.005 (2)	0.000 (3)
C5	0.035 (3)	0.029 (2)	0.053 (4)	−0.011 (2)	0.005 (3)	0.001 (3)
C6	0.036 (3)	0.032 (3)	0.053 (4)	−0.013 (2)	0.007 (3)	0.001 (3)
N4	0.037 (3)	0.033 (3)	0.054 (3)	−0.013 (2)	0.007 (3)	0.002 (3)
C7	0.035 (3)	0.030 (3)	0.051 (3)	−0.009 (2)	0.005 (2)	0.000 (3)
C3A	0.034 (3)	0.025 (2)	0.050 (3)	−0.007 (2)	0.005 (2)	0.001 (2)
C4A	0.035 (3)	0.029 (2)	0.051 (3)	−0.009 (2)	0.005 (2)	0.000 (3)
C5A	0.034 (3)	0.030 (3)	0.051 (4)	−0.011 (2)	0.004 (3)	0.001 (3)
C6A	0.036 (3)	0.032 (3)	0.053 (4)	−0.011 (2)	0.003 (3)	0.001 (3)
N4A	0.037 (3)	0.032 (3)	0.054 (3)	−0.012 (2)	0.004 (2)	0.000 (3)
C7A	0.034 (3)	0.028 (3)	0.051 (3)	−0.010 (2)	0.005 (2)	0.001 (3)
C8	0.038 (3)	0.028 (3)	0.019 (2)	−0.006 (2)	0.005 (2)	0.002 (2)
C9	0.046 (4)	0.039 (3)	0.032 (3)	0.012 (3)	0.012 (3)	0.004 (3)
C10	0.056 (4)	0.065 (5)	0.031 (3)	0.011 (4)	0.019 (3)	0.012 (3)
C11	0.048 (4)	0.053 (4)	0.041 (4)	−0.002 (3)	0.008 (3)	0.020 (3)
C12	0.051 (4)	0.031 (3)	0.048 (4)	−0.007 (3)	0.002 (3)	0.007 (3)
C13	0.038 (3)	0.028 (3)	0.034 (3)	−0.002 (2)	0.007 (2)	−0.003 (2)
C14	0.023 (3)	0.022 (2)	0.038 (3)	−0.002 (2)	0.004 (2)	−0.005 (2)
C15	0.036 (3)	0.032 (3)	0.046 (4)	0.006 (3)	0.002 (3)	−0.008 (3)
C16	0.046 (4)	0.036 (4)	0.064 (5)	0.004 (3)	0.009 (4)	−0.019 (3)
C17	0.042 (4)	0.023 (3)	0.077 (5)	0.003 (3)	0.000 (4)	−0.004 (3)
C18	0.030 (3)	0.028 (3)	0.066 (5)	0.003 (3)	−0.004 (3)	0.010 (3)
C19	0.029 (3)	0.023 (3)	0.039 (3)	−0.001 (2)	0.001 (2)	0.006 (2)
C20	0.026 (3)	0.021 (2)	0.025 (2)	0.004 (2)	0.0017 (19)	0.0028 (19)
C21	0.036 (3)	0.028 (3)	0.026 (3)	−0.002 (2)	0.005 (2)	0.002 (2)
C22	0.041 (3)	0.038 (3)	0.027 (3)	−0.003 (3)	0.008 (2)	0.004 (2)
C23	0.045 (4)	0.035 (3)	0.027 (3)	0.012 (3)	0.007 (2)	0.006 (2)
C24	0.054 (4)	0.030 (3)	0.022 (3)	0.001 (3)	0.005 (2)	−0.004 (2)
C25	0.036 (3)	0.029 (3)	0.024 (3)	0.000 (2)	0.002 (2)	−0.005 (2)
C26	0.027 (3)	0.022 (2)	0.021 (2)	−0.005 (2)	0.0049 (19)	−0.0003 (18)
C27	0.026 (3)	0.025 (3)	0.046 (3)	−0.001 (2)	0.007 (2)	−0.001 (2)
C28	0.028 (3)	0.040 (4)	0.058 (4)	−0.004 (3)	0.009 (3)	0.001 (3)
C29	0.041 (4)	0.033 (3)	0.046 (4)	−0.014 (3)	0.008 (3)	0.002 (3)
C30	0.049 (4)	0.021 (3)	0.040 (3)	−0.005 (3)	0.000 (3)	0.006 (2)
C31	0.036 (3)	0.028 (3)	0.038 (3)	0.002 (2)	−0.004 (3)	0.005 (2)
C32	0.026 (3)	0.022 (2)	0.025 (2)	0.000 (2)	0.001 (2)	−0.0036 (19)
C33	0.029 (3)	0.044 (3)	0.033 (3)	0.008 (3)	0.004 (2)	0.002 (3)
C34	0.046 (4)	0.062 (5)	0.032 (3)	0.007 (4)	0.010 (3)	−0.002 (3)
C35	0.042 (4)	0.042 (4)	0.041 (4)	0.003 (3)	0.017 (3)	−0.009 (3)
C36	0.027 (3)	0.039 (3)	0.047 (4)	0.010 (3)	0.007 (3)	−0.006 (3)
C37	0.028 (3)	0.034 (3)	0.031 (3)	0.005 (2)	0.003 (2)	−0.001 (2)
C38	0.033 (3)	0.028 (3)	0.019 (2)	0.002 (2)	0.003 (2)	0.0005 (19)
C39	0.039 (3)	0.030 (3)	0.030 (3)	0.008 (3)	0.005 (2)	−0.001 (2)
C40	0.042 (4)	0.049 (4)	0.030 (3)	0.014 (3)	0.002 (3)	0.007 (3)
C41	0.033 (3)	0.059 (4)	0.032 (3)	−0.005 (3)	−0.001 (3)	0.001 (3)
C42	0.030 (3)	0.054 (4)	0.034 (3)	−0.015 (3)	−0.003 (2)	−0.004 (3)
C43	0.022 (3)	0.035 (3)	0.037 (3)	−0.006 (2)	0.002 (2)	0.006 (2)
C44	0.031 (3)	0.026 (3)	0.025 (3)	0.004 (2)	0.001 (2)	0.002 (2)
C45	0.045 (4)	0.031 (3)	0.029 (3)	−0.003 (3)	0.008 (3)	−0.004 (2)
C46	0.043 (4)	0.050 (4)	0.031 (3)	−0.008 (3)	0.004 (3)	0.005 (3)
C47	0.046 (4)	0.034 (3)	0.039 (3)	−0.010 (3)	−0.006 (3)	0.011 (3)
C48	0.049 (4)	0.025 (3)	0.048 (4)	−0.001 (3)	−0.005 (3)	−0.002 (3)
C49	0.039 (3)	0.027 (3)	0.033 (3)	0.003 (2)	0.003 (2)	−0.005 (2)
N1S	0.083 (6)	0.058 (4)	0.050 (4)	−0.004 (4)	−0.007 (4)	0.002 (3)
C1S	0.046 (4)	0.039 (4)	0.054 (4)	0.003 (3)	0.002 (3)	−0.010 (3)
C2S	0.085 (7)	0.047 (4)	0.067 (6)	0.017 (4)	0.017 (5)	0.010 (4)

Geometric parameters (Å, º)

Cu1—P1	2.2627 (14)	C19—H19	0.9500
Cu1—P2	2.2874 (15)	C20—C25	1.388 (7)
Cu1—Cl1	2.3820 (16)	C20—C21	1.393 (8)
Cu1—S1	2.3869 (15)	C21—C22	1.384 (8)
S1—C1	1.700 (6)	C21—H21	0.9500
P1—C14	1.824 (6)	C22—C23	1.378 (9)
P1—C26	1.825 (5)	C22—H22	0.9500
P1—C20	1.833 (5)	C23—C24	1.371 (9)
P2—C32	1.805 (5)	C23—H23	0.9500
P2—C38	1.826 (5)	C24—C25	1.390 (8)
P2—C44	1.831 (6)	C24—H24	0.9500
N1—C1	1.324 (7)	C25—H25	0.9500
N1—C8	1.425 (7)	C26—C27	1.378 (8)
N1—H1	0.8800	C26—C31	1.400 (8)
N2—C1	1.340 (7)	C27—C28	1.383 (8)
N2—N3	1.386 (6)	C27—H27	0.9500
N2—H2	0.8800	C28—C29	1.384 (9)
N3—C2	1.283 (7)	C28—H28	0.9500
C2—C3A	1.434 (9)	C29—C30	1.369 (9)
C2—C3	1.462 (9)	C29—H29	0.9500
C2—H2A	0.9500	C30—C31	1.367 (8)
C3—C4	1.3900	C30—H30	0.9500
C3—C7	1.3900	C31—H31	0.9500
C4—C5	1.3900	C32—C33	1.374 (8)
C4—H4A	0.9500	C32—C37	1.382 (7)
C5—C6	1.3900	C33—C34	1.393 (8)
C5—H5A	0.9500	C33—H33	0.9500
C6—N4	1.3900	C34—C35	1.370 (9)
C6—H6A	0.9500	C34—H34	0.9500
N4—C7	1.3900	C35—C36	1.380 (9)
C7—H7A	0.9500	C35—H35	0.9500
C3A—C4A	1.3900	C36—C37	1.380 (8)
C3A—C7A	1.3900	C36—H36	0.9500
C4A—C5A	1.3900	C37—H37	0.9500
C4A—H4AA	0.9500	C38—C43	1.392 (8)
C5A—C6A	1.3900	C38—C39	1.397 (8)
C5A—H5AA	0.9500	C39—C40	1.395 (8)
C6A—N4A	1.3900	C39—H39	0.9500
C6A—H6AA	0.9500	C40—C41	1.372 (10)
N4A—C7A	1.3900	C40—H40	0.9500
C7A—H7AA	0.9500	C41—C42	1.373 (9)
C8—C9	1.377 (8)	C41—H41	0.9500
C8—C13	1.378 (8)	C42—C43	1.396 (8)
C9—C10	1.391 (9)	C42—H42	0.9500
C9—H9	0.9500	C43—H43	0.9500
C10—C11	1.380 (10)	C44—C49	1.393 (8)
C10—H10	0.9500	C44—C45	1.393 (8)
C11—C12	1.376 (10)	C45—C46	1.373 (9)
C11—H11	0.9500	C45—H45	0.9500
C12—C13	1.380 (8)	C46—C47	1.367 (9)
C12—H12	0.9500	C46—H46	0.9500
C13—H13	0.9500	C47—C48	1.384 (9)
C14—C19	1.389 (8)	C47—H47	0.9500
C14—C15	1.396 (8)	C48—C49	1.383 (9)
C15—C16	1.381 (9)	C48—H48	0.9500
C15—H15	0.9500	C49—H49	0.9500
C16—C17	1.382 (10)	N1S—C1S	1.125 (10)
C16—H16	0.9500	C1S—C2S	1.445 (11)
C17—C18	1.381 (10)	C2S—H2SA	0.9800
C17—H17	0.9500	C2S—H2SB	0.9800
C18—C19	1.389 (8)	C2S—H2SC	0.9800
C18—H18	0.9500
P1—Cu1—P2	123.23 (5)	C18—C19—H19	119.8
P1—Cu1—Cl1	102.86 (6)	C14—C19—H19	119.8
P2—Cu1—Cl1	108.81 (6)	C25—C20—C21	118.6 (5)
P1—Cu1—S1	112.37 (5)	C25—C20—P1	122.6 (4)
P2—Cu1—S1	99.70 (5)	C21—C20—P1	118.6 (4)
Cl1—Cu1—S1	109.62 (5)	C22—C21—C20	120.6 (5)
C1—S1—Cu1	109.90 (19)	C22—C21—H21	119.7
C14—P1—C26	102.3 (2)	C20—C21—H21	119.7
C14—P1—C20	104.1 (2)	C23—C22—C21	120.0 (6)
C26—P1—C20	102.2 (2)	C23—C22—H22	120.0
C14—P1—Cu1	117.43 (19)	C21—C22—H22	120.0
C26—P1—Cu1	116.47 (17)	C24—C23—C22	120.2 (6)
C20—P1—Cu1	112.41 (18)	C24—C23—H23	119.9
C32—P2—C38	104.2 (3)	C22—C23—H23	119.9
C32—P2—C44	102.7 (2)	C23—C24—C25	120.2 (6)
C38—P2—C44	102.5 (2)	C23—C24—H24	119.9
C32—P2—Cu1	117.12 (18)	C25—C24—H24	119.9
C38—P2—Cu1	112.22 (18)	C20—C25—C24	120.4 (6)
C44—P2—Cu1	116.29 (19)	C20—C25—H25	119.8
C1—N1—C8	126.6 (5)	C24—C25—H25	119.8
C1—N1—H1	116.7	C27—C26—C31	118.7 (5)
C8—N1—H1	116.7	C27—C26—P1	123.9 (4)
C1—N2—N3	119.7 (5)	C31—C26—P1	117.4 (4)
C1—N2—H2	120.1	C26—C27—C28	120.3 (6)
N3—N2—H2	120.1	C26—C27—H27	119.8
C2—N3—N2	114.0 (5)	C28—C27—H27	119.8
N1—C1—N2	116.7 (5)	C27—C28—C29	120.2 (6)
N1—C1—S1	124.9 (4)	C27—C28—H28	119.9
N2—C1—S1	118.4 (4)	C29—C28—H28	119.9
N3—C2—C3A	123.3 (7)	C30—C29—C28	119.7 (6)
N3—C2—C3	120.8 (7)	C30—C29—H29	120.1
N3—C2—H2A	119.6	C28—C29—H29	120.1
C3—C2—H2A	119.6	C31—C30—C29	120.4 (6)
C4—C3—C7	120.0	C31—C30—H30	119.8
C4—C3—C2	121.6 (9)	C29—C30—H30	119.8
C7—C3—C2	118.3 (9)	C30—C31—C26	120.7 (6)
C5—C4—C3	120.0	C30—C31—H31	119.7
C5—C4—H4A	120.0	C26—C31—H31	119.7
C3—C4—H4A	120.0	C33—C32—C37	117.8 (5)
C4—C5—C6	120.0	C33—C32—P2	118.6 (4)
C4—C5—H5A	120.0	C37—C32—P2	123.6 (4)
C6—C5—H5A	120.0	C32—C33—C34	121.6 (6)
N4—C6—C5	120.0	C32—C33—H33	119.2
N4—C6—H6A	120.0	C34—C33—H33	119.2
C5—C6—H6A	120.0	C35—C34—C33	119.4 (6)
C7—N4—C6	120.0	C35—C34—H34	120.3
N4—C7—C3	120.0	C33—C34—H34	120.3
N4—C7—H7A	120.0	C34—C35—C36	120.1 (6)
C3—C7—H7A	120.0	C34—C35—H35	120.0
C4A—C3A—C7A	120.0	C36—C35—H35	120.0
C4A—C3A—C2	111.8 (9)	C35—C36—C37	119.6 (6)
C7A—C3A—C2	127.8 (9)	C35—C36—H36	120.2
C5A—C4A—C3A	120.0	C37—C36—H36	120.2
C5A—C4A—H4AA	120.0	C36—C37—C32	121.6 (6)
C3A—C4A—H4AA	120.0	C36—C37—H37	119.2
C4A—C5A—C6A	120.0	C32—C37—H37	119.2
C4A—C5A—H5AA	120.0	C43—C38—C39	119.0 (5)
C6A—C5A—H5AA	120.0	C43—C38—P2	117.9 (4)
C5A—C6A—N4A	120.0	C39—C38—P2	123.2 (4)
C5A—C6A—H6AA	120.0	C40—C39—C38	119.8 (6)
N4A—C6A—H6AA	120.0	C40—C39—H39	120.1
C6A—N4A—C7A	120.0	C38—C39—H39	120.1
N4A—C7A—C3A	120.0	C41—C40—C39	120.3 (6)
N4A—C7A—H7AA	120.0	C41—C40—H40	119.9
C3A—C7A—H7AA	120.0	C39—C40—H40	119.9
C9—C8—C13	120.6 (5)	C40—C41—C42	120.9 (6)
C9—C8—N1	118.6 (5)	C40—C41—H41	119.5
C13—C8—N1	120.6 (5)	C42—C41—H41	119.5
C8—C9—C10	119.5 (6)	C41—C42—C43	119.4 (6)
C8—C9—H9	120.2	C41—C42—H42	120.3
C10—C9—H9	120.2	C43—C42—H42	120.3
C11—C10—C9	120.0 (6)	C38—C43—C42	120.6 (6)
C11—C10—H10	120.0	C38—C43—H43	119.7
C9—C10—H10	120.0	C42—C43—H43	119.7
C12—C11—C10	119.6 (6)	C49—C44—C45	118.3 (5)
C12—C11—H11	120.2	C49—C44—P2	123.3 (4)
C10—C11—H11	120.2	C45—C44—P2	118.2 (4)
C11—C12—C13	120.8 (6)	C46—C45—C44	120.2 (6)
C11—C12—H12	119.6	C46—C45—H45	119.9
C13—C12—H12	119.6	C44—C45—H45	119.9
C8—C13—C12	119.3 (6)	C47—C46—C45	121.5 (6)
C8—C13—H13	120.3	C47—C46—H46	119.3
C12—C13—H13	120.3	C45—C46—H46	119.3
C19—C14—C15	118.8 (5)	C46—C47—C48	119.2 (6)
C19—C14—P1	122.7 (4)	C46—C47—H47	120.4
C15—C14—P1	118.3 (5)	C48—C47—H47	120.4
C16—C15—C14	120.1 (6)	C49—C48—C47	120.1 (6)
C16—C15—H15	120.0	C49—C48—H48	119.9
C14—C15—H15	120.0	C47—C48—H48	119.9
C15—C16—C17	121.0 (7)	C48—C49—C44	120.7 (6)
C15—C16—H16	119.5	C48—C49—H49	119.7
C17—C16—H16	119.5	C44—C49—H49	119.7
C18—C17—C16	119.1 (6)	N1S—C1S—C2S	178.5 (9)
C18—C17—H17	120.5	C1S—C2S—H2SA	109.5
C16—C17—H17	120.5	C1S—C2S—H2SB	109.5
C17—C18—C19	120.5 (7)	H2SA—C2S—H2SB	109.5
C17—C18—H18	119.8	C1S—C2S—H2SC	109.5
C19—C18—H18	119.7	H2SA—C2S—H2SC	109.5
C18—C19—C14	120.4 (6)	H2SB—C2S—H2SC	109.5
C1—N2—N3—C2	168.1 (5)	C21—C22—C23—C24	−1.3 (9)
C8—N1—C1—N2	−171.9 (5)	C22—C23—C24—C25	1.5 (9)
C8—N1—C1—S1	9.2 (9)	C21—C20—C25—C24	0.6 (8)
N3—N2—C1—N1	11.2 (8)	P1—C20—C25—C24	−174.7 (4)
N3—N2—C1—S1	−169.8 (4)	C23—C24—C25—C20	−1.1 (9)
Cu1—S1—C1—N1	−149.9 (4)	C14—P1—C26—C27	10.1 (5)
Cu1—S1—C1—N2	31.2 (5)	C20—P1—C26—C27	−97.5 (5)
N2—N3—C2—C3A	−178.9 (9)	Cu1—P1—C26—C27	139.5 (4)
N2—N3—C2—C3	−176.3 (9)	C14—P1—C26—C31	−173.0 (4)
N3—C2—C3—C4	170.8 (7)	C20—P1—C26—C31	79.4 (5)
N3—C2—C3—C7	−5.8 (12)	Cu1—P1—C26—C31	−43.5 (5)
C7—C3—C4—C5	0.0	C31—C26—C27—C28	−1.1 (9)
C2—C3—C4—C5	−176.6 (14)	P1—C26—C27—C28	175.8 (5)
C3—C4—C5—C6	0.0	C26—C27—C28—C29	0.1 (10)
C4—C5—C6—N4	0.0	C27—C28—C29—C30	0.4 (10)
C5—C6—N4—C7	0.0	C28—C29—C30—C31	0.1 (10)
C6—N4—C7—C3	0.0	C29—C30—C31—C26	−1.2 (10)
C4—C3—C7—N4	0.0	C27—C26—C31—C30	1.7 (9)
C2—C3—C7—N4	176.7 (13)	P1—C26—C31—C30	−175.4 (5)
N3—C2—C3A—C4A	176.7 (6)	C38—P2—C32—C33	−160.4 (5)
N3—C2—C3A—C7A	4.1 (15)	C44—P2—C32—C33	93.0 (5)
C7A—C3A—C4A—C5A	0.0	Cu1—P2—C32—C33	−35.8 (5)
C2—C3A—C4A—C5A	−173.3 (12)	C38—P2—C32—C37	22.2 (5)
C3A—C4A—C5A—C6A	0.0	C44—P2—C32—C37	−84.4 (5)
C4A—C5A—C6A—N4A	0.0	Cu1—P2—C32—C37	146.8 (4)
C5A—C6A—N4A—C7A	0.0	C37—C32—C33—C34	−0.5 (9)
C6A—N4A—C7A—C3A	0.0	P2—C32—C33—C34	−178.0 (5)
C4A—C3A—C7A—N4A	0.0	C32—C33—C34—C35	0.9 (11)
C2—C3A—C7A—N4A	172.1 (14)	C33—C34—C35—C36	−0.5 (11)
C1—N1—C8—C9	−126.9 (6)	C34—C35—C36—C37	−0.4 (10)
C1—N1—C8—C13	56.4 (9)	C35—C36—C37—C32	0.8 (10)
C13—C8—C9—C10	1.7 (10)	C33—C32—C37—C36	−0.4 (9)
N1—C8—C9—C10	−175.0 (6)	P2—C32—C37—C36	177.0 (5)
C8—C9—C10—C11	−1.4 (11)	C32—P2—C38—C43	93.0 (5)
C9—C10—C11—C12	1.1 (12)	C44—P2—C38—C43	−160.2 (5)
C10—C11—C12—C13	−1.2 (11)	Cu1—P2—C38—C43	−34.7 (5)
C9—C8—C13—C12	−1.8 (9)	C32—P2—C38—C39	−87.2 (5)
N1—C8—C13—C12	174.9 (6)	C44—P2—C38—C39	19.6 (6)
C11—C12—C13—C8	1.6 (10)	Cu1—P2—C38—C39	145.1 (4)
C26—P1—C14—C19	−83.3 (5)	C43—C38—C39—C40	0.9 (9)
C20—P1—C14—C19	22.9 (5)	P2—C38—C39—C40	−178.9 (5)
Cu1—P1—C14—C19	147.9 (4)	C38—C39—C40—C41	0.6 (10)
C26—P1—C14—C15	91.4 (5)	C39—C40—C41—C42	−0.7 (10)
C20—P1—C14—C15	−162.5 (5)	C40—C41—C42—C43	−0.6 (10)
Cu1—P1—C14—C15	−37.5 (5)	C39—C38—C43—C42	−2.2 (9)
C19—C14—C15—C16	1.0 (9)	P2—C38—C43—C42	177.6 (5)
P1—C14—C15—C16	−173.9 (5)	C41—C42—C43—C38	2.0 (9)
C14—C15—C16—C17	0.5 (11)	C32—P2—C44—C49	−3.0 (5)
C15—C16—C17—C18	−2.4 (11)	C38—P2—C44—C49	−111.0 (5)
C16—C17—C18—C19	2.8 (10)	Cu1—P2—C44—C49	126.2 (5)
C17—C18—C19—C14	−1.4 (9)	C32—P2—C44—C45	−178.3 (5)
C15—C14—C19—C18	−0.6 (9)	C38—P2—C44—C45	73.8 (5)
P1—C14—C19—C18	174.1 (5)	Cu1—P2—C44—C45	−49.0 (5)
C14—P1—C20—C25	−101.2 (5)	C49—C44—C45—C46	0.9 (9)
C26—P1—C20—C25	5.0 (5)	P2—C44—C45—C46	176.4 (5)
Cu1—P1—C20—C25	130.6 (4)	C44—C45—C46—C47	−0.2 (10)
C14—P1—C20—C21	83.5 (5)	C45—C46—C47—C48	−0.9 (10)
C26—P1—C20—C21	−170.3 (4)	C46—C47—C48—C49	1.2 (10)
Cu1—P1—C20—C21	−44.6 (5)	C47—C48—C49—C44	−0.4 (10)
C25—C20—C21—C22	−0.4 (8)	C45—C44—C49—C48	−0.6 (9)
P1—C20—C21—C22	175.0 (5)	P2—C44—C49—C48	−175.9 (5)
C20—C21—C22—C23	0.8 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N1S	0.88	2.69	3.275 (9)	125
N2—H2···Cl1	0.88	2.38	3.072 (5)	136
C2—H2A···Cl1	0.95	2.86	3.579 (6)	133
C6—H6A···N1S^i	0.95	2.67	3.467 (11)	142
C6A—H6AA···Cl1^ii	0.95	2.92	3.683 (9)	138
C15—H15···S1	0.95	2.99	3.886 (7)	158
C21—H21···Cl1	0.95	2.61	3.469 (6)	150
C43—H43···Cl1	0.95	2.98	3.873 (6)	158
C45—H45···S1	0.95	3.01	3.846 (6)	148
C2S—H2SB···Cl1^iii	0.98	2.74	3.667 (9)	158

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

Bis[(Z)-N-ethyl-2-(pyridin-3-ylmethylidene)hydrazine-1-carbothioamidato-κ²N¹,S]nickel(II) (4)

Crystal data

[Cu(C9H11N4S)2]	F(000) = 492
Mr = 473.26	Dx = 1.542 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.6398 (6) Å	Cell parameters from 2040 reflections
b = 14.3930 (8) Å	θ = 3.6–32.8°
c = 9.7339 (7) Å	µ = 1.18 mm^−1
β = 107.823 (8)°	T = 173 K
V = 1018.97 (13) Å^3	Irregular, black
Z = 2	0.44 × 0.26 × 0.14 mm

Data collection

Rigaku OD Gemini Eos diffractometer	3361 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2679 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 16.0416 pixels mm^-1	θmax = 32.8°, θmin = 3.6°
ω scans	h = −10→5
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2019)	k = −21→17
Tmin = 0.714, Tmax = 1.000	l = −13→14
6410 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)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0373P)^2 + 0.2595P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3361 reflections	Δρmax = 0.51 e Å^−3
134 parameters	Δρmin = −0.45 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. The crystallographic data were measured using a Rigaku Oxford Diffraction Eos four-circle diffractometer for compounds 1-4, using graphite mono-chromated Mo-Kα (λ = 0.71073 Å) radiation. The crystal data were collected at 173 (2) K (Compounds 1-4), and processed with CrysAlisPro (data collection, data reduction and cell refinement). The structures were solved by the direct methods using the program OLEX2 1.3 refined by the full-matrix least-squares technique based on F² using SHELXL (Dolomanov et al., 2009; Sheldrick, G. M., 2015a). All the non-hydrogen atoms were refined anisotropically

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

	x	y	z	Uiso*/Ueq
Ni1	0.500000	0.500000	0.500000	0.01959 (10)
S1	0.28068 (7)	0.41744 (3)	0.53468 (6)	0.03300 (14)
N1	0.2833 (2)	0.23263 (10)	0.52257 (18)	0.0252 (3)
H1	0.193263	0.236274	0.561124	0.030*
N2	0.4954 (2)	0.30337 (10)	0.43840 (17)	0.0225 (3)
N3	0.5682 (2)	0.38802 (10)	0.41885 (16)	0.0208 (3)
N4	0.9864 (2)	0.26032 (12)	0.17375 (18)	0.0282 (4)
C1	0.3608 (2)	0.31063 (12)	0.4955 (2)	0.0221 (4)
C2	0.6913 (2)	0.38364 (12)	0.3506 (2)	0.0227 (4)
H2	0.738495	0.441960	0.332841	0.027*
C3	0.7673 (2)	0.30355 (12)	0.29762 (19)	0.0205 (3)
C4	0.7246 (3)	0.20950 (13)	0.3076 (2)	0.0255 (4)
H4	0.635248	0.191448	0.352097	0.031*
C5	0.8150 (3)	0.14384 (13)	0.2516 (2)	0.0277 (4)
H5	0.789450	0.079704	0.258356	0.033*
C6	0.9421 (3)	0.17112 (14)	0.1859 (2)	0.0280 (4)
H6	1.001571	0.124567	0.147229	0.034*
C7	0.8998 (3)	0.32339 (13)	0.2288 (2)	0.0255 (4)
H7	0.929893	0.386806	0.220990	0.031*
C8	0.3433 (3)	0.14187 (12)	0.4902 (2)	0.0268 (4)
H8A	0.477915	0.136086	0.535078	0.032*
H8B	0.316050	0.135112	0.384461	0.032*
C9	0.2471 (3)	0.06604 (14)	0.5463 (2)	0.0355 (5)
H9A	0.114611	0.069119	0.496757	0.053*
H9B	0.269954	0.074333	0.650256	0.053*
H9C	0.294265	0.005398	0.528385	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02144 (17)	0.01572 (15)	0.02694 (18)	−0.00262 (11)	0.01529 (13)	−0.00140 (12)
S1	0.0346 (3)	0.0185 (2)	0.0599 (4)	−0.00595 (18)	0.0352 (3)	−0.0067 (2)
N1	0.0275 (8)	0.0184 (7)	0.0377 (9)	−0.0048 (6)	0.0218 (7)	−0.0036 (6)
N2	0.0241 (8)	0.0168 (7)	0.0321 (8)	−0.0051 (6)	0.0166 (6)	−0.0023 (6)
N3	0.0230 (7)	0.0180 (7)	0.0259 (8)	−0.0015 (5)	0.0139 (6)	−0.0002 (6)
N4	0.0258 (8)	0.0329 (9)	0.0322 (9)	0.0023 (7)	0.0182 (7)	−0.0008 (7)
C1	0.0223 (8)	0.0193 (8)	0.0282 (9)	−0.0041 (6)	0.0129 (7)	−0.0023 (7)
C2	0.0239 (9)	0.0208 (8)	0.0284 (9)	−0.0016 (7)	0.0155 (7)	−0.0007 (7)
C3	0.0211 (8)	0.0209 (8)	0.0221 (8)	−0.0007 (6)	0.0106 (7)	−0.0024 (7)
C4	0.0282 (9)	0.0229 (9)	0.0313 (10)	−0.0022 (7)	0.0176 (8)	−0.0028 (8)
C5	0.0312 (10)	0.0219 (9)	0.0337 (11)	0.0012 (7)	0.0153 (8)	−0.0021 (8)
C6	0.0255 (9)	0.0314 (10)	0.0308 (10)	0.0042 (8)	0.0142 (8)	−0.0049 (8)
C7	0.0245 (9)	0.0256 (9)	0.0312 (10)	−0.0009 (7)	0.0157 (8)	−0.0001 (8)
C8	0.0287 (10)	0.0188 (8)	0.0363 (11)	−0.0026 (7)	0.0150 (8)	−0.0022 (8)
C9	0.0390 (12)	0.0212 (9)	0.0489 (13)	−0.0055 (8)	0.0174 (10)	0.0019 (9)

Geometric parameters (Å, º)

Ni1—S1	2.1633 (5)	C3—C4	1.403 (2)
Ni1—S1^i	2.1633 (5)	C3—C7	1.404 (2)
Ni1—N3^i	1.9352 (14)	C4—H4	0.9500
Ni1—N3	1.9352 (14)	C4—C5	1.378 (3)
S1—C1	1.7397 (18)	C5—H5	0.9500
N1—H1	0.8800	C5—C6	1.372 (3)
N1—C1	1.333 (2)	C6—H6	0.9500
N1—C8	1.451 (2)	C7—H7	0.9500
N2—N3	1.3767 (19)	C8—H8A	0.9900
N2—C1	1.314 (2)	C8—H8B	0.9900
N3—C2	1.309 (2)	C8—C9	1.509 (3)
N4—C6	1.342 (3)	C9—H9A	0.9800
N4—C7	1.329 (2)	C9—H9B	0.9800
C2—H2	0.9500	C9—H9C	0.9800
C2—C3	1.454 (2)
S1—Ni1—S1^i	180.00 (2)	C3—C4—H4	120.7
N3^i—Ni1—S1	94.33 (4)	C5—C4—C3	118.65 (17)
N3—Ni1—S1^i	94.33 (4)	C5—C4—H4	120.7
N3—Ni1—S1	85.67 (4)	C4—C5—H5	120.0
N3^i—Ni1—S1^i	85.67 (4)	C6—C5—C4	119.97 (18)
N3^i—Ni1—N3	180.0	C6—C5—H5	120.0
C1—S1—Ni1	96.31 (6)	N4—C6—C5	123.26 (18)
C1—N1—H1	119.1	N4—C6—H6	118.4
C1—N1—C8	121.75 (15)	C5—C6—H6	118.4
C8—N1—H1	119.1	N4—C7—C3	125.05 (17)
C1—N2—N3	112.94 (15)	N4—C7—H7	117.5
N2—N3—Ni1	120.66 (11)	C3—C7—H7	117.5
C2—N3—Ni1	124.93 (12)	N1—C8—H8A	109.5
C2—N3—N2	114.28 (15)	N1—C8—H8B	109.5
C7—N4—C6	116.57 (16)	N1—C8—C9	110.55 (16)
N1—C1—S1	119.57 (13)	H8A—C8—H8B	108.1
N2—C1—S1	122.44 (13)	C9—C8—H8A	109.5
N2—C1—N1	117.98 (16)	C9—C8—H8B	109.5
N3—C2—H2	114.9	C8—C9—H9A	109.5
N3—C2—C3	130.17 (17)	C8—C9—H9B	109.5
C3—C2—H2	114.9	C8—C9—H9C	109.5
C4—C3—C2	127.89 (16)	H9A—C9—H9B	109.5
C4—C3—C7	116.50 (16)	H9A—C9—H9C	109.5
C7—C3—C2	115.61 (16)	H9B—C9—H9C	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4^ii	0.88	2.18	3.060 (2)	175
C2—H2···S1^i	0.95	2.43	3.0568 (18)	124

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