2-[(1E)-({[(Benzyl­sulfan­yl)methane­thio­yl]amino}­imino)­meth­yl]-6-meth­oxy­phenol: crystal structure and Hirshfeld surface analysis

Yusof, E.N.M.; Jotani, M.M.; Tiekink, E.R.T.; Ravoof, T.B.S.A.

doi:10.1107/S2056989016004291

2-[(1E)-({[(Benzylsulfanyl)methanethioyl]amino}imino)methyl]-6-methoxyphenol: crystal structure and Hirshfeld surface analysis

E. N. M. Yusof, M. M. Jotani, E. R. T. Tiekink and T. B. S. A. Ravoof

Two almost planar residues in the title thione are orientated perpendicularly [dihedral angle = 82.72 (5)°]; the conformation about the imine bond is E. In the crystal, centrosymmetric aggregates are formed via {

HNCS}₂ synthons which are linked into supramolecular layers by C—H

O interactions.

Keywords: crystal structure; hydrogen bonding; dithiocarbazate ester; Hirshfeld surface analysis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989016004291/hb7572sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989016004291/hb7572Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989016004291/hb7572Isup3.cml Supplementary material

CCDC reference: 1465209

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
R factor = 0.041
wR factor = 0.097
Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           3 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          5 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density           8 Note

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

2-[(1E)-({[(Benzylsulfanyl)methanethioyl]amino}imino)methyl]-6-methoxyphenol top

Crystal data top

C₁₆H₁₆N₂O₂S₂	F(000) = 1392
M_r = 332.43	D_x = 1.396 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.7896 (10) Å	Cell parameters from 2185 reflections
b = 4.6965 (2) Å	θ = 2–29°
c = 32.5217 (13) Å	µ = 0.35 mm⁻¹
β = 95.004 (4)°	T = 100 K
V = 3163.3 (2) Å³	Plate, light-yellow
Z = 8	0.25 × 0.15 × 0.07 mm

Data collection top

Agilent Xcalibur Eos Gemini diffractometer	3270 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2595 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 16.1952 pixels mm^-1	θ_max = 26.5°, θ_min = 2.4°
ω scans	h = −25→26
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −5→5
T_min = 0.87, T_max = 0.98	l = −27→40
6979 measured reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0382P)² + 1.7624P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.097	(Δ/σ)_max = 0.002
S = 1.06	Δρ_max = 0.33 e Å⁻³
3270 reflections	Δρ_min = −0.24 e Å⁻³
206 parameters

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	0.22247 (2)	0.46299 (12)	0.61684 (2)	0.02185 (15)
S2	0.17478 (3)	0.80851 (12)	0.54164 (2)	0.02258 (15)
O1	0.35672 (7)	−0.0373 (3)	0.63252 (4)	0.0239 (3)
H1O	0.3342 (10)	0.086 (4)	0.6194 (7)	0.036*
O2	0.43677 (8)	−0.4115 (3)	0.66547 (5)	0.0305 (4)
N1	0.27458 (8)	0.4630 (4)	0.54712 (5)	0.0203 (4)
H1N	0.2819 (10)	0.519 (5)	0.5223 (4)	0.024*
N2	0.31479 (8)	0.2682 (4)	0.56753 (5)	0.0194 (4)
C1	0.22604 (9)	0.5777 (4)	0.56594 (6)	0.0179 (4)
C2	0.15287 (10)	0.6579 (5)	0.63209 (6)	0.0237 (5)
H2A	0.1579	0.8639	0.6268	0.028*
H2B	0.1130	0.5907	0.6161	0.028*
C3	0.14873 (10)	0.6059 (5)	0.67741 (6)	0.0223 (5)
C4	0.18779 (13)	0.7499 (6)	0.70649 (8)	0.0395 (6)
H4	0.2181	0.8838	0.6979	0.047*
C5	0.18365 (13)	0.7029 (6)	0.74845 (8)	0.0432 (7)
H5	0.2108	0.8059	0.7682	0.052*
C6	0.14056 (12)	0.5086 (5)	0.76139 (7)	0.0356 (6)
H6	0.1381	0.4735	0.7900	0.043*
C7	0.10141 (14)	0.3670 (7)	0.73262 (8)	0.0502 (8)
H7	0.0708	0.2346	0.7413	0.060*
C8	0.10538 (13)	0.4127 (6)	0.69076 (8)	0.0404 (7)
H8	0.0779	0.3096	0.6712	0.048*
C9	0.35930 (10)	0.1553 (4)	0.54759 (6)	0.0192 (4)
H9	0.3635	0.2118	0.5199	0.023*
C10	0.40308 (9)	−0.0564 (4)	0.56664 (6)	0.0188 (4)
C11	0.40002 (9)	−0.1423 (4)	0.60766 (6)	0.0191 (4)
C12	0.44376 (10)	−0.3469 (5)	0.62508 (7)	0.0236 (5)
C13	0.48986 (10)	−0.4610 (5)	0.60167 (7)	0.0282 (5)
H13	0.5196	−0.5984	0.6134	0.034*
C14	0.49292 (11)	−0.3747 (5)	0.56070 (7)	0.0286 (5)
H14	0.5246	−0.4541	0.5448	0.034*
C15	0.45042 (10)	−0.1762 (5)	0.54345 (7)	0.0239 (5)
H15	0.4529	−0.1189	0.5156	0.029*
C16	0.47583 (12)	−0.6366 (5)	0.68359 (8)	0.0346 (6)
H16A	0.4679	−0.8109	0.6674	0.052*
H16B	0.4649	−0.6693	0.7119	0.052*
H16C	0.5215	−0.5840	0.6839	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0221 (3)	0.0271 (3)	0.0169 (3)	0.0071 (2)	0.0051 (2)	0.0040 (2)
S2	0.0225 (3)	0.0273 (3)	0.0180 (3)	0.0075 (2)	0.0024 (2)	0.0047 (2)
O1	0.0258 (8)	0.0281 (9)	0.0183 (7)	0.0072 (7)	0.0044 (6)	0.0034 (7)
O2	0.0399 (9)	0.0269 (9)	0.0238 (8)	0.0075 (7)	−0.0035 (7)	0.0064 (7)
N1	0.0206 (9)	0.0253 (10)	0.0154 (8)	0.0044 (8)	0.0040 (7)	0.0058 (8)
N2	0.0180 (8)	0.0208 (9)	0.0194 (9)	0.0039 (7)	0.0024 (7)	0.0026 (8)
C1	0.0181 (10)	0.0179 (10)	0.0176 (10)	−0.0018 (8)	0.0016 (8)	0.0000 (9)
C2	0.0239 (11)	0.0257 (12)	0.0222 (11)	0.0080 (9)	0.0061 (9)	0.0038 (10)
C3	0.0234 (11)	0.0231 (12)	0.0212 (11)	0.0093 (9)	0.0059 (9)	0.0005 (9)
C4	0.0430 (15)	0.0457 (16)	0.0293 (13)	−0.0093 (13)	0.0010 (12)	0.0040 (12)
C5	0.0523 (17)	0.0504 (17)	0.0258 (13)	−0.0002 (14)	−0.0034 (12)	−0.0029 (13)
C6	0.0411 (14)	0.0470 (16)	0.0200 (11)	0.0152 (12)	0.0103 (11)	0.0032 (12)
C7	0.0549 (18)	0.066 (2)	0.0310 (14)	−0.0188 (16)	0.0104 (13)	0.0078 (14)
C8	0.0493 (16)	0.0480 (16)	0.0244 (12)	−0.0172 (13)	0.0063 (12)	−0.0001 (12)
C9	0.0225 (10)	0.0203 (11)	0.0150 (10)	−0.0017 (9)	0.0028 (9)	0.0010 (9)
C10	0.0184 (10)	0.0170 (10)	0.0210 (10)	−0.0013 (9)	0.0015 (8)	−0.0030 (9)
C11	0.0185 (10)	0.0189 (11)	0.0197 (10)	−0.0013 (8)	0.0004 (9)	−0.0039 (9)
C12	0.0264 (11)	0.0194 (11)	0.0239 (11)	−0.0004 (9)	−0.0046 (9)	−0.0011 (9)
C13	0.0239 (11)	0.0238 (12)	0.0355 (13)	0.0068 (10)	−0.0067 (10)	−0.0046 (11)
C14	0.0228 (11)	0.0301 (13)	0.0331 (13)	0.0063 (10)	0.0035 (10)	−0.0077 (11)
C15	0.0223 (11)	0.0269 (12)	0.0228 (11)	0.0012 (9)	0.0041 (9)	−0.0030 (10)
C16	0.0411 (14)	0.0237 (13)	0.0363 (14)	−0.0008 (11)	−0.0129 (12)	0.0070 (11)

Geometric parameters (Å, º) top

S1—C1	1.749 (2)	C6—C7	1.359 (4)
S1—C2	1.817 (2)	C6—H6	0.9500
S2—C1	1.670 (2)	C7—C8	1.388 (3)
O1—C11	1.354 (2)	C7—H7	0.9500
O1—H1O	0.836 (10)	C8—H8	0.9500
O2—C12	1.368 (3)	C9—C10	1.450 (3)
O2—C16	1.429 (3)	C9—H9	0.9500
N1—C1	1.338 (2)	C10—C11	1.401 (3)
N1—N2	1.371 (2)	C10—C15	1.408 (3)
N1—H1N	0.874 (9)	C11—C12	1.408 (3)
N2—C9	1.290 (2)	C12—C13	1.383 (3)
C2—C3	1.504 (3)	C13—C14	1.400 (3)
C2—H2A	0.9900	C13—H13	0.9500
C2—H2B	0.9900	C14—C15	1.370 (3)
C3—C4	1.370 (3)	C14—H14	0.9500
C3—C8	1.376 (3)	C15—H15	0.9500
C4—C5	1.392 (3)	C16—H16A	0.9800
C4—H4	0.9500	C16—H16B	0.9800
C5—C6	1.370 (4)	C16—H16C	0.9800
C5—H5	0.9500

C1—S1—C2	101.75 (10)	C3—C8—C7	120.5 (2)
C11—O1—H1O	108.6 (16)	C3—C8—H8	119.7
C12—O2—C16	117.13 (17)	C7—C8—H8	119.7
C1—N1—N2	119.96 (16)	N2—C9—C10	121.21 (18)
C1—N1—H1N	120.0 (15)	N2—C9—H9	119.4
N2—N1—H1N	120.0 (15)	C10—C9—H9	119.4
C9—N2—N1	117.70 (17)	C11—C10—C15	119.1 (2)
N1—C1—S2	121.37 (15)	C11—C10—C9	121.72 (18)
N1—C1—S1	113.89 (15)	C15—C10—C9	119.15 (18)
S2—C1—S1	124.74 (11)	O1—C11—C10	123.47 (19)
C3—C2—S1	107.49 (14)	O1—C11—C12	116.60 (18)
C3—C2—H2A	110.2	C10—C11—C12	119.92 (18)
S1—C2—H2A	110.2	O2—C12—C13	125.4 (2)
C3—C2—H2B	110.2	O2—C12—C11	114.77 (18)
S1—C2—H2B	110.2	C13—C12—C11	119.8 (2)
H2A—C2—H2B	108.5	C12—C13—C14	120.2 (2)
C4—C3—C8	118.2 (2)	C12—C13—H13	119.9
C4—C3—C2	121.0 (2)	C14—C13—H13	119.9
C8—C3—C2	120.8 (2)	C15—C14—C13	120.4 (2)
C3—C4—C5	121.0 (2)	C15—C14—H14	119.8
C3—C4—H4	119.5	C13—C14—H14	119.8
C5—C4—H4	119.5	C14—C15—C10	120.6 (2)
C6—C5—C4	120.3 (3)	C14—C15—H15	119.7
C6—C5—H5	119.8	C10—C15—H15	119.7
C4—C5—H5	119.8	O2—C16—H16A	109.5
C7—C6—C5	118.8 (2)	O2—C16—H16B	109.5
C7—C6—H6	120.6	H16A—C16—H16B	109.5
C5—C6—H6	120.6	O2—C16—H16C	109.5
C6—C7—C8	121.1 (3)	H16A—C16—H16C	109.5
C6—C7—H7	119.4	H16B—C16—H16C	109.5
C8—C7—H7	119.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N2	0.84 (2)	1.90 (2)	2.639 (2)	146 (2)
N1—H1N···S2ⁱ	0.88 (2)	2.47 (2)	3.3351 (18)	168 (2)
C6—H6···O1ⁱⁱ	0.95	2.51	3.453 (3)	170

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

Major percentage contribution of the different intermolecular interactions to the Hirshfeld surface of the title compound top

Contact	%
H···H	43.4
O···H/H···O	10.3
S···H/H···S	14.4
C···H/H···C	21.3
N···H/H···N	0.8
C···C	2.5
S···S	0.4
C···N/N···C	2.9
S···O/O···S	1.4
S···N/N···S	1.4
C···S/S···C	0.9

Additional short interatomic contacts (Å) for the title compound top

Interaction	distance	symmetry operation
H8···H16C	2.25	-1/2 + x, 1/2 + y, z
C6···H16B	2.86	1/2 - x, 3/2 + y, 3/2 - z
O1···H16A	2.70	x, 1 + y, z
C11···H16A	2.78	x, 1 + y, z
C12···H16A	2.89	x, 1 + y, z

Enrichment ratios (ER) for the title compound. top

Interaction	ER
H···H	0.97
O···H/H···O	1.28
S···H/H···S	1.14
C···C	1.09
C···H/H···C	1.05
S···O/O···S	1.24
S···S	0.45
C···S/S···C	0.31

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2-[(1E)-({[(Benzyl­sulfan­yl)methane­thio­yl]amino}­imino)­meth­yl]-6-meth­oxy­phenol: crystal structure and Hirshfeld surface analysis

Supporting information

Key indicators

checkCIF/PLATON results

2-[(1E)-({[(Benzylsulfanyl)methanethioyl]amino}imino)methyl]-6-methoxyphenol: crystal structure and Hirshfeld surface analysis