2-[(1E)-[(Z)-2-({[(1Z)-[(E)-2-[(2-Hy­droxy­phen­yl)methyl­idene]hydrazin-1-yl­idene]({[(4-methyl­phen­yl)meth­yl]sulfan­yl})meth­yl]disulfan­yl}({[(4-methyl­phen­yl)meth­yl]sulfan­yl})methyl­idene)hydrazin-1-yl­idene]meth­yl]phenol: crystal structure, Hirshfeld surface analysis and computational study

Paulus, G.; Kwong, H.C.; Crouse, K.A.; Tiekink, E.R.T.

doi:10.1107/S2056989020008762

2-[(1E)-[(Z)-2-({[(1Z)-[(E)-2-[(2-Hydroxyphenyl)methylidene]hydrazin-1-ylidene]({[(4-methylphenyl)methyl]sulfanyl})methyl]disulfanyl}({[(4-methylphenyl)methyl]sulfanyl})methylidene)hydrazin-1-ylidene]methyl]phenol: crystal structure, Hirshfeld surface analysis and computational study

G. Paulus, H. C. Kwong, K. A. Crouse and E. R. T. Tiekink

The title hydrazine carbodithioate derivative is highly twisted as seen in the C—S—S—C torsion angle of 90.70 (8)°; the molecule is twofold symmetric. In the molecular packing, molecules are assembled into supramolecular layers in the ab plane by methylene-C—H

π(tolyl) interactions.

Keywords: crystal structure; Schiff base; hydrazine carbodithioate; hydrogen bonding; Hirshfeld surface analysis; DFT.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989020008762/hb7929sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989020008762/hb7929Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989020008762/hb7929Isup3.cml Supplementary material

CCDC reference: 2013050

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R factor = 0.038
wR factor = 0.102
Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.27 Report
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          2 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         32 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         14 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXT2014/4 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

2-[(1E)-[(Z)-2-({[(1Z)-[(E)-2-[(2-Hydroxyphenyl)methylidene]hydrazin-1-ylidene]({[(4-methylphenyl)methyl]sulfanyl})methyl]disulfanyl}({[(4-methylphenyl)methyl]sulfanyl})methylidene)hydrazin-1-ylidene]methyl]phenol top

Crystal data top

C₃₂H₃₀N₄O₂S₄	D_x = 1.371 Mg m⁻³
M_r = 630.84	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbcn	Cell parameters from 4566 reflections
a = 15.4653 (4) Å	θ = 3.4–71.1°
b = 7.9639 (2) Å	µ = 3.15 mm⁻¹
c = 24.8116 (7) Å	T = 100 K
V = 3055.90 (14) Å³	Plate, yellow
Z = 4	0.27 × 0.14 × 0.07 mm
F(000) = 1320

Data collection top

Agilent Xcalibur, Eos, Gemini diffractometer	2933 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2637 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 16.1952 pixels mm^-1	θ_max = 71.3°, θ_min = 3.6°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlisPro; Agilent, 2012)	k = −7→9
T_min = 0.819, T_max = 1.000	l = −29→30
10206 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	Hydrogen site location: mixed
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0662P)² + 1.2702P] where P = (F_o² + 2F_c²)/3
2933 reflections	(Δ/σ)_max = 0.001
194 parameters	Δρ_max = 0.45 e Å⁻³
1 restraint	Δρ_min = −0.20 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.44788 (3)	0.20945 (5)	0.77532 (2)	0.02123 (14)
S2	0.41121 (3)	0.47744 (6)	0.69155 (2)	0.02165 (14)
O1	0.32052 (8)	0.08476 (16)	0.89877 (5)	0.0239 (3)
H1O	0.3312 (16)	0.141 (3)	0.8711 (7)	0.036*
N1	0.30058 (9)	0.38409 (19)	0.76780 (6)	0.0210 (3)
N2	0.28689 (10)	0.28083 (18)	0.81313 (6)	0.0200 (3)
C1	0.37582 (11)	0.3625 (2)	0.74728 (7)	0.0188 (3)
C2	0.20696 (11)	0.2752 (2)	0.82727 (7)	0.0208 (4)
H2	0.166079	0.339978	0.807651	0.025*
C3	0.17688 (11)	0.1739 (2)	0.87198 (7)	0.0202 (3)
C4	0.23359 (11)	0.0816 (2)	0.90530 (7)	0.0197 (3)
C5	0.19995 (12)	−0.0185 (2)	0.94637 (7)	0.0221 (4)
H5	0.237862	−0.080587	0.968950	0.027*
C6	0.11138 (13)	−0.0276 (2)	0.95434 (7)	0.0246 (4)
H6	0.089111	−0.097226	0.982149	0.029*
C7	0.05458 (11)	0.0638 (3)	0.92221 (7)	0.0259 (4)
H7	−0.006038	0.057531	0.928079	0.031*
C8	0.08769 (11)	0.1640 (2)	0.88161 (7)	0.0236 (4)
H8	0.049188	0.227355	0.859785	0.028*
C9	0.31721 (11)	0.6135 (2)	0.68128 (7)	0.0241 (4)
H9A	0.268116	0.547317	0.666962	0.029*
H9B	0.299350	0.664563	0.715912	0.029*
C10	0.34232 (11)	0.7481 (2)	0.64183 (7)	0.0206 (4)
C11	0.38760 (12)	0.8900 (2)	0.65887 (7)	0.0249 (4)
H11	0.402651	0.901799	0.695798	0.030*
C12	0.41082 (12)	1.0139 (2)	0.62245 (8)	0.0265 (4)
H12	0.441428	1.109823	0.634869	0.032*
C13	0.39015 (12)	1.0006 (2)	0.56792 (8)	0.0246 (4)
C14	0.34520 (12)	0.8595 (2)	0.55108 (7)	0.0252 (4)
H14	0.330262	0.848022	0.514124	0.030*
C15	0.32150 (12)	0.7340 (2)	0.58738 (7)	0.0234 (4)
H15	0.290918	0.638161	0.574895	0.028*
C16	0.41484 (14)	1.1379 (3)	0.52889 (9)	0.0370 (5)
H16A	0.408036	1.097062	0.491877	0.056*
H16B	0.475189	1.170350	0.534944	0.056*
H16C	0.377305	1.235519	0.534517	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0191 (2)	0.0229 (2)	0.0217 (2)	0.00008 (15)	0.00049 (14)	0.00357 (16)
S2	0.0204 (2)	0.0248 (2)	0.0197 (2)	0.00156 (16)	0.00321 (15)	0.00481 (16)
O1	0.0191 (6)	0.0272 (7)	0.0254 (6)	0.0013 (5)	0.0003 (5)	0.0051 (5)
N1	0.0216 (7)	0.0242 (7)	0.0173 (7)	−0.0009 (6)	−0.0002 (5)	0.0020 (6)
N2	0.0213 (7)	0.0223 (8)	0.0163 (7)	−0.0009 (6)	0.0004 (5)	0.0009 (5)
C1	0.0200 (8)	0.0198 (8)	0.0167 (8)	−0.0019 (6)	−0.0017 (6)	−0.0001 (6)
C2	0.0207 (8)	0.0227 (9)	0.0189 (8)	0.0017 (7)	−0.0024 (6)	−0.0021 (6)
C3	0.0224 (8)	0.0215 (8)	0.0168 (8)	−0.0005 (7)	0.0009 (6)	−0.0035 (7)
C4	0.0200 (8)	0.0199 (8)	0.0191 (8)	−0.0021 (7)	0.0011 (6)	−0.0045 (6)
C5	0.0266 (9)	0.0214 (9)	0.0182 (8)	−0.0001 (7)	−0.0008 (7)	−0.0015 (6)
C6	0.0299 (10)	0.0249 (9)	0.0189 (8)	−0.0053 (7)	0.0059 (7)	−0.0022 (7)
C7	0.0194 (9)	0.0343 (10)	0.0239 (9)	−0.0033 (7)	0.0029 (7)	−0.0041 (8)
C8	0.0204 (9)	0.0295 (9)	0.0211 (9)	0.0005 (7)	−0.0010 (6)	−0.0021 (7)
C9	0.0179 (8)	0.0283 (9)	0.0261 (9)	0.0034 (7)	0.0009 (7)	0.0069 (7)
C10	0.0170 (8)	0.0223 (8)	0.0226 (9)	0.0041 (6)	0.0009 (6)	0.0024 (7)
C11	0.0252 (9)	0.0282 (9)	0.0215 (9)	0.0031 (7)	−0.0033 (7)	−0.0024 (7)
C12	0.0234 (9)	0.0215 (9)	0.0347 (11)	−0.0020 (7)	−0.0059 (7)	−0.0020 (7)
C13	0.0205 (8)	0.0234 (9)	0.0299 (10)	0.0023 (7)	0.0004 (7)	0.0066 (7)
C14	0.0288 (9)	0.0275 (9)	0.0193 (8)	0.0027 (7)	−0.0031 (7)	0.0009 (7)
C15	0.0240 (9)	0.0208 (8)	0.0254 (9)	−0.0014 (7)	−0.0041 (7)	−0.0008 (7)
C16	0.0354 (11)	0.0336 (11)	0.0420 (12)	−0.0050 (9)	0.0003 (9)	0.0133 (9)

Geometric parameters (Å, º) top

S1—C1	1.7921 (17)	C7—H7	0.9500
S1—S1ⁱ	2.0439 (8)	C8—H8	0.9500
S2—C1	1.7463 (17)	C9—C10	1.503 (2)
S2—C9	1.8308 (18)	C9—H9A	0.9900
O1—C4	1.354 (2)	C9—H9B	0.9900
O1—H1O	0.839 (10)	C10—C15	1.393 (2)
N1—C1	1.282 (2)	C10—C11	1.395 (3)
N1—N2	1.409 (2)	C11—C12	1.385 (3)
N2—C2	1.286 (2)	C11—H11	0.9500
C2—C3	1.448 (2)	C12—C13	1.394 (3)
C2—H2	0.9500	C12—H12	0.9500
C3—C8	1.402 (2)	C13—C14	1.386 (3)
C3—C4	1.412 (2)	C13—C16	1.510 (3)
C4—C5	1.394 (2)	C14—C15	1.394 (3)
C5—C6	1.386 (3)	C14—H14	0.9500
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.392 (3)	C16—H16A	0.9800
C6—H6	0.9500	C16—H16B	0.9800
C7—C8	1.383 (3)	C16—H16C	0.9800

C1—S1—S1ⁱ	104.58 (6)	C10—C9—H9A	110.1
C1—S2—C9	99.87 (8)	S2—C9—H9A	110.1
C4—O1—H1O	107.7 (17)	C10—C9—H9B	110.1
C1—N1—N2	112.04 (14)	S2—C9—H9B	110.1
C2—N2—N1	112.49 (14)	H9A—C9—H9B	108.4
N1—C1—S2	121.92 (13)	C15—C10—C11	118.36 (16)
N1—C1—S1	120.10 (13)	C15—C10—C9	120.95 (16)
S2—C1—S1	117.98 (10)	C11—C10—C9	120.68 (16)
N2—C2—C3	122.48 (16)	C12—C11—C10	120.62 (17)
N2—C2—H2	118.8	C12—C11—H11	119.7
C3—C2—H2	118.8	C10—C11—H11	119.7
C8—C3—C4	118.81 (16)	C11—C12—C13	121.29 (17)
C8—C3—C2	118.54 (16)	C11—C12—H12	119.4
C4—C3—C2	122.63 (16)	C13—C12—H12	119.4
O1—C4—C5	117.93 (16)	C14—C13—C12	117.98 (17)
O1—C4—C3	122.47 (15)	C14—C13—C16	121.39 (18)
C5—C4—C3	119.59 (16)	C12—C13—C16	120.62 (18)
C6—C5—C4	120.20 (17)	C13—C14—C15	121.21 (17)
C6—C5—H5	119.9	C13—C14—H14	119.4
C4—C5—H5	119.9	C15—C14—H14	119.4
C5—C6—C7	120.98 (17)	C10—C15—C14	120.53 (17)
C5—C6—H6	119.5	C10—C15—H15	119.7
C7—C6—H6	119.5	C14—C15—H15	119.7
C8—C7—C6	119.01 (17)	C13—C16—H16A	109.5
C8—C7—H7	120.5	C13—C16—H16B	109.5
C6—C7—H7	120.5	H16A—C16—H16B	109.5
C7—C8—C3	121.39 (17)	C13—C16—H16C	109.5
C7—C8—H8	119.3	H16A—C16—H16C	109.5
C3—C8—H8	119.3	H16B—C16—H16C	109.5
C10—C9—S2	107.91 (12)

C1—N1—N2—C2	−166.57 (15)	C5—C6—C7—C8	0.4 (3)
N2—N1—C1—S2	−178.60 (11)	C6—C7—C8—C3	0.6 (3)
N2—N1—C1—S1	2.0 (2)	C4—C3—C8—C7	−1.2 (3)
C9—S2—C1—N1	2.05 (17)	C2—C3—C8—C7	177.24 (16)
C9—S2—C1—S1	−178.53 (10)	C1—S2—C9—C10	168.30 (13)
S1ⁱ—S1—C1—N1	174.92 (13)	S2—C9—C10—C15	97.92 (17)
S1ⁱ—S1—C1—S2	−4.51 (11)	S2—C9—C10—C11	−81.68 (18)
N1—N2—C2—C3	178.45 (15)	C15—C10—C11—C12	0.3 (3)
N2—C2—C3—C8	−174.53 (17)	C9—C10—C11—C12	179.90 (16)
N2—C2—C3—C4	3.8 (3)	C10—C11—C12—C13	−0.3 (3)
C8—C3—C4—O1	−179.81 (15)	C11—C12—C13—C14	0.2 (3)
C2—C3—C4—O1	1.8 (3)	C11—C12—C13—C16	179.13 (18)
C8—C3—C4—C5	0.8 (3)	C12—C13—C14—C15	−0.2 (3)
C2—C3—C4—C5	−177.54 (16)	C16—C13—C14—C15	−179.12 (18)
O1—C4—C5—C6	−179.26 (15)	C11—C10—C15—C14	−0.3 (3)
C3—C4—C5—C6	0.2 (3)	C9—C10—C15—C14	−179.90 (16)
C4—C5—C6—C7	−0.8 (3)	C13—C14—C15—C10	0.3 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the (C10–C15) ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2	0.84 (2)	1.94 (2)	2.6877 (19)	148 (2)
C9—H9A···Cg1ⁱⁱ	0.99	2.93	3.9075 (18)	169

Symmetry code: (ii) x, −y−1, z−1/2.

A summary of short interatomic contacts (Å) for (I)^a top

Contact	Distance	Symmetry operation
C2···O1	3.07	1/2 - x, 1/2 + y, z
C2···C4	3.25	1/2 - x, 1/2 + y+, z
C12—H12···S1	2.82	1 - x, 1 + y+1, 3/2 - z
C9—H9B···N1	2.59	1/2 - x, 1/2 + y, z
C8—H8···C11	2.74	-1/2 + x, -1/2 + y, 3/2 - z
H6···H14	2.39	1/2 - x, 1/2 - y, 1/2 + z

Note: (a) The interatomic distances are calculated in Crystal Explorer 17 (Turner et al., 2017) with the X—H bond lengths adjusted to their neutron values.

The percentage contributions of interatomic contacts to the Hirshfeld surface for (I) top

Contact	Percentage contribution
H···H	43.9
H···C/C···H	25.5
H···S/S···H	13.6
H···O/O···H	5.7
N···C/C···N	3.6
H···N/N···H	3.4
O···C/C···O	1.7
C···C	1.2
S···C/C···S	1.0
N···N	0.4

A summary of interaction energies (kJ mol^-1) calculated for (I) top

Contact	R (Å)	E_ele	E_pol	E_dis	E_rep	E_tot
Intra-layer region
C9—H9A···Cg1ⁱ +
C2···O1ⁱⁱ +
C2···C4ⁱⁱ +
C9—H9B···N1ⁱⁱ +
C8—H8···C11ⁱⁱⁱ	8.70	-19.7	-3.5	-98.9	71.0	-65.7
C12—H12···S1^iv	7.96	-11.1	-1.9	-43.0	33.7	-29.7
H6···H16B^v	14.23	-0.6	-0.2	-6.7	3.0	-4.8
Inter-layer region
H5···H14^vi	12.44	-10.3	-2.1	-28.1	20.0	-24.6
H16A···H16B ^vii	15.29	-1.5	-0.4	-11.8	3.5	-10.0
H6···H14^viii	14.93	-3.4	-0.5	-13.6	10.2	-9.5
H6···H16C^ix	15.43	-1.8	-0.4	-10.9	6.2	-7.8
H6···H7^x	21.02	-1.2	-0.2	-7.8	5.4	-4.9

Notes: Symmetry operations: (i) -x + 1/2, y - 1/2, z; (ii) -x + 1/2, y + 1/2, z; (iii) x - 1/2, y - 1/2, -z + 3/2; (iv) -x + 1, y + 1, -z + 3/2; (v) x - 1/2, y - 3/2, -z + 3/2; (vi) x, -y + 1, z + 1/2; (vii) x, -y + 2, z + 1/2; (viii) -x + 1/2, -y + 1/2, z + 1/2; (ix) x + 1/2, -y + 3/2, -z + 1; (x) -x, -y, -z + 2

A comparison of key geometric parameters (Å, °) in structures related to (I) top

Compound	Symmetry	S—S	C—S—S—C	Refcode	Ref.
(I)	2	2.0439 (8)	90.70 (8)	–	This work
(II)	–	2.0386 (7)	88.73 (9)	MUYRIJ	Madanhire et al. (2015)
(III)	2	2.0443 (7)	104.67 (8)	DIBYOF01	Yekke-ghasemi et al. (2018)
(IV)	–	2.0373 (4)	91.54 (6)	LAGLUD	Islam et al. (2016)
(V)	2	2.0504 (7)	96.2 (1)	CUHHET	How et al. (2009)

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