Crystal structure of 2-[bis(benzylsulfanyl)methyl]-6-methoxyphenol

The title compound is an example of an ortho-vanillin-based functionalized di­thio­ether, which could be useful as a potential chelating ligand or bridging ligand for coordination chemistry. Its crystal structure was determined at 100 K. Both weak intra­molecular O—H...O and inter­molecular O—H...S hydrogen bonding can be observed.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.034
• wR factor = 0.079
• Data-to-parameter ratio = 20.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9A      ..C20      .       2.86 Ang.

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details Found  in the CIF     Please Do !

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

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

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Computing details

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

2-[Bis(benzylsulfanyl)methyl]-6-methoxyphenol

Crystal data

C22H22O2S2	Dx = 1.309 Mg m^−3
Mr = 382.51	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9791 reflections
a = 7.7418 (8) Å	θ = 2.3–28.2°
b = 13.856 (3) Å	µ = 0.29 mm^−1
c = 36.197 (5) Å	T = 100 K
V = 3882.9 (10) Å^3	Block, colourless
Z = 8	0.49 × 0.42 × 0.25 mm
F(000) = 1616

Data collection

Bruker D8 VENTURE area detector diffractometer	5005 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	4510 reflections with I > 2σ(I)
HELIOS mirror optics monochromator	Rint = 0.033
Detector resolution: 10.4167 pixels mm^-1	θmax = 29.1°, θmin = 2.3°
ω and φ scans	h = −9→10
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −18→18
Tmin = 0.713, Tmax = 0.746	l = −49→45
107706 measured 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)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0287P)^2 + 2.6399P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.079	(Δ/σ)max = 0.003
S = 1.09	Δρmax = 0.34 e Å^−3
5005 reflections	Δρmin = −0.23 e Å^−3
241 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0017 (2)
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.

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

	x	y	z	Uiso*/Ueq
S1	0.61115 (4)	0.82824 (2)	0.63211 (2)	0.01667 (8)
S2	0.42202 (4)	0.68918 (2)	0.67748 (2)	0.01772 (8)
O1	1.02466 (13)	0.48649 (7)	0.70693 (3)	0.0234 (2)
O2	0.76523 (13)	0.52864 (7)	0.66212 (3)	0.0228 (2)
H2	0.826 (3)	0.4778 (15)	0.6649 (5)	0.043 (5)*
C1	0.62315 (15)	0.70907 (8)	0.65265 (3)	0.0146 (2)
H1	0.631957	0.660278	0.632378	0.017*
C2	0.77100 (15)	0.69329 (8)	0.67929 (3)	0.0147 (2)
C3	0.84314 (17)	0.76632 (9)	0.70092 (3)	0.0179 (2)
H3	0.799141	0.830165	0.699171	0.022*
C4	0.97814 (17)	0.74678 (10)	0.72490 (3)	0.0202 (3)
H4	1.025853	0.797416	0.739354	0.024*
C5	1.04472 (16)	0.65382 (9)	0.72807 (3)	0.0185 (2)
H5	1.137719	0.640764	0.744446	0.022*
C6	0.97346 (16)	0.58102 (9)	0.70704 (3)	0.0172 (2)
C7	0.83624 (16)	0.60032 (9)	0.68273 (3)	0.0157 (2)
C8	1.17946 (19)	0.46331 (11)	0.72664 (5)	0.0311 (3)
H8A	1.274327	0.503799	0.717632	0.047*
H8B	1.208119	0.395191	0.722705	0.047*
H8C	1.161929	0.475073	0.753070	0.047*
C9	0.81405 (17)	0.83571 (10)	0.60670 (4)	0.0222 (3)
H9A	0.828248	0.902523	0.597491	0.027*
H9B	0.910248	0.822557	0.623999	0.027*
C10	0.82841 (17)	0.76755 (10)	0.57454 (4)	0.0216 (3)
C11	0.7673 (2)	0.79298 (12)	0.53965 (4)	0.0294 (3)
H11	0.712651	0.853694	0.536144	0.035*
C12	0.7855 (2)	0.73040 (14)	0.51001 (4)	0.0354 (4)
H12	0.742688	0.748223	0.486385	0.043*
C13	0.8656 (2)	0.64242 (14)	0.51472 (4)	0.0367 (4)
H13	0.880248	0.600256	0.494264	0.044*
C14	0.9247 (2)	0.61563 (13)	0.54931 (5)	0.0360 (4)
H14	0.978548	0.554677	0.552712	0.043*
C15	0.90510 (18)	0.67790 (11)	0.57899 (4)	0.0275 (3)
H15	0.944821	0.658858	0.602728	0.033*
C16	0.26715 (16)	0.68531 (9)	0.63950 (3)	0.0188 (2)
H16A	0.150774	0.672722	0.649760	0.023*
H16B	0.264227	0.749436	0.627453	0.023*
C17	0.30595 (16)	0.61034 (9)	0.61075 (3)	0.0176 (2)
C18	0.25087 (18)	0.51529 (10)	0.61502 (4)	0.0231 (3)
H18	0.188646	0.497061	0.636537	0.028*
C19	0.2863 (2)	0.44732 (10)	0.58807 (4)	0.0274 (3)
H19	0.246189	0.382978	0.590983	0.033*
C20	0.37995 (19)	0.47228 (11)	0.55688 (4)	0.0264 (3)
H20	0.406356	0.424957	0.538749	0.032*
C21	0.43459 (18)	0.56639 (12)	0.55233 (4)	0.0269 (3)
H21	0.498143	0.584070	0.530921	0.032*
C22	0.39681 (17)	0.63509 (10)	0.57896 (4)	0.0223 (3)
H22	0.433413	0.699893	0.575465	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01657 (15)	0.01393 (14)	0.01952 (15)	−0.00028 (11)	−0.00002 (11)	0.00077 (10)
S2	0.01469 (15)	0.02377 (16)	0.01471 (14)	−0.00302 (11)	−0.00020 (11)	0.00089 (11)
O1	0.0226 (5)	0.0196 (4)	0.0279 (5)	0.0043 (4)	−0.0075 (4)	0.0010 (4)
O2	0.0254 (5)	0.0145 (4)	0.0285 (5)	0.0022 (4)	−0.0092 (4)	−0.0048 (4)
C1	0.0133 (5)	0.0145 (5)	0.0159 (5)	−0.0009 (4)	−0.0003 (4)	0.0000 (4)
C2	0.0129 (5)	0.0164 (5)	0.0147 (5)	−0.0011 (4)	0.0002 (4)	−0.0002 (4)
C3	0.0184 (6)	0.0174 (6)	0.0180 (6)	−0.0009 (5)	−0.0005 (5)	−0.0022 (4)
C4	0.0207 (6)	0.0231 (6)	0.0169 (6)	−0.0049 (5)	−0.0014 (5)	−0.0035 (5)
C5	0.0147 (6)	0.0266 (6)	0.0141 (5)	−0.0014 (5)	−0.0013 (4)	0.0017 (5)
C6	0.0166 (6)	0.0193 (6)	0.0158 (5)	0.0013 (5)	0.0007 (4)	0.0022 (4)
C7	0.0146 (6)	0.0172 (5)	0.0154 (5)	−0.0018 (4)	0.0003 (4)	−0.0012 (4)
C8	0.0235 (7)	0.0270 (7)	0.0428 (9)	0.0027 (6)	−0.0105 (6)	0.0110 (6)
C9	0.0189 (6)	0.0261 (6)	0.0217 (6)	−0.0069 (5)	0.0026 (5)	0.0003 (5)
C10	0.0148 (6)	0.0315 (7)	0.0186 (6)	−0.0065 (5)	0.0025 (5)	−0.0010 (5)
C11	0.0307 (8)	0.0356 (8)	0.0221 (6)	−0.0084 (6)	−0.0008 (6)	0.0060 (6)
C12	0.0323 (8)	0.0572 (10)	0.0168 (6)	−0.0122 (8)	−0.0003 (6)	0.0013 (6)
C13	0.0223 (7)	0.0615 (11)	0.0264 (7)	−0.0047 (7)	0.0033 (6)	−0.0175 (7)
C14	0.0210 (7)	0.0494 (10)	0.0376 (8)	0.0090 (7)	−0.0038 (6)	−0.0153 (7)
C15	0.0167 (6)	0.0423 (8)	0.0236 (7)	0.0046 (6)	−0.0036 (5)	−0.0051 (6)
C16	0.0131 (6)	0.0258 (6)	0.0175 (6)	−0.0020 (5)	−0.0024 (5)	0.0022 (5)
C17	0.0121 (5)	0.0250 (6)	0.0157 (5)	−0.0019 (5)	−0.0037 (4)	0.0027 (5)
C18	0.0216 (6)	0.0254 (6)	0.0222 (6)	−0.0030 (5)	−0.0006 (5)	0.0061 (5)
C19	0.0304 (8)	0.0213 (6)	0.0306 (7)	−0.0009 (6)	−0.0054 (6)	0.0034 (5)
C20	0.0227 (7)	0.0319 (7)	0.0247 (7)	0.0049 (6)	−0.0067 (5)	−0.0060 (6)
C21	0.0219 (7)	0.0411 (8)	0.0177 (6)	−0.0061 (6)	0.0007 (5)	−0.0017 (6)
C22	0.0205 (6)	0.0282 (7)	0.0182 (6)	−0.0083 (5)	−0.0017 (5)	0.0022 (5)

Geometric parameters (Å, º)

S1—C1	1.8132 (12)	C10—C11	1.3940 (19)
S1—C9	1.8232 (14)	C10—C15	1.386 (2)
S2—C1	1.8189 (12)	C11—H11	0.9500
S2—C16	1.8250 (13)	C11—C12	1.387 (2)
O1—C6	1.3685 (15)	C12—H12	0.9500
O1—C8	1.4312 (17)	C12—C13	1.378 (3)
O2—H2	0.85 (2)	C13—H13	0.9500
O2—C7	1.3584 (15)	C13—C14	1.383 (2)
C1—H1	1.0000	C14—H14	0.9500
C1—C2	1.5126 (16)	C14—C15	1.386 (2)
C2—C3	1.3960 (17)	C15—H15	0.9500
C2—C7	1.3893 (17)	C16—H16A	0.9900
C3—H3	0.9500	C16—H16B	0.9900
C3—C4	1.3854 (18)	C16—C17	1.5007 (18)
C4—H4	0.9500	C17—C18	1.3929 (18)
C4—C5	1.3920 (19)	C17—C22	1.3917 (17)
C5—H5	0.9500	C18—H18	0.9500
C5—C6	1.3789 (18)	C18—C19	1.383 (2)
C6—C7	1.4051 (17)	C19—H19	0.9500
C8—H8A	0.9800	C19—C20	1.385 (2)
C8—H8B	0.9800	C20—H20	0.9500
C8—H8C	0.9800	C20—C21	1.381 (2)
C9—H9A	0.9900	C21—H21	0.9500
C9—H9B	0.9900	C21—C22	1.386 (2)
C9—C10	1.5031 (19)	C22—H22	0.9500
C1—S1—C9	102.38 (6)	C15—C10—C9	120.31 (12)
C1—S2—C16	101.22 (6)	C15—C10—C11	118.51 (13)
C6—O1—C8	117.12 (11)	C10—C11—H11	119.7
C7—O2—H2	108.5 (14)	C12—C11—C10	120.54 (15)
S1—C1—S2	107.26 (6)	C12—C11—H11	119.7
S1—C1—H1	108.6	C11—C12—H12	119.9
S2—C1—H1	108.6	C13—C12—C11	120.22 (14)
C2—C1—S1	115.59 (8)	C13—C12—H12	119.9
C2—C1—S2	108.11 (8)	C12—C13—H13	120.1
C2—C1—H1	108.6	C12—C13—C14	119.86 (15)
C3—C2—C1	123.74 (11)	C14—C13—H13	120.1
C7—C2—C1	117.80 (10)	C13—C14—H14	120.1
C7—C2—C3	118.45 (11)	C13—C14—C15	119.88 (16)
C2—C3—H3	119.6	C15—C14—H14	120.1
C4—C3—C2	120.77 (12)	C10—C15—H15	119.5
C4—C3—H3	119.6	C14—C15—C10	120.96 (14)
C3—C4—H4	119.6	C14—C15—H15	119.5
C3—C4—C5	120.79 (12)	S2—C16—H16A	108.7
C5—C4—H4	119.6	S2—C16—H16B	108.7
C4—C5—H5	120.6	H16A—C16—H16B	107.6
C6—C5—C4	118.90 (12)	C17—C16—S2	114.28 (9)
C6—C5—H5	120.6	C17—C16—H16A	108.7
O1—C6—C5	125.87 (12)	C17—C16—H16B	108.7
O1—C6—C7	113.53 (11)	C18—C17—C16	121.08 (11)
C5—C6—C7	120.59 (12)	C22—C17—C16	120.27 (12)
O2—C7—C2	118.79 (11)	C22—C17—C18	118.65 (12)
O2—C7—C6	120.71 (11)	C17—C18—H18	119.8
C2—C7—C6	120.50 (11)	C19—C18—C17	120.31 (13)
O1—C8—H8A	109.5	C19—C18—H18	119.8
O1—C8—H8B	109.5	C18—C19—H19	119.7
O1—C8—H8C	109.5	C18—C19—C20	120.56 (13)
H8A—C8—H8B	109.5	C20—C19—H19	119.7
H8A—C8—H8C	109.5	C19—C20—H20	120.2
H8B—C8—H8C	109.5	C21—C20—C19	119.55 (13)
S1—C9—H9A	108.6	C21—C20—H20	120.2
S1—C9—H9B	108.6	C20—C21—H21	120.0
H9A—C9—H9B	107.6	C20—C21—C22	120.06 (13)
C10—C9—S1	114.75 (9)	C22—C21—H21	120.0
C10—C9—H9A	108.6	C17—C22—H22	119.6
C10—C9—H9B	108.6	C21—C22—C17	120.83 (13)
C11—C10—C9	121.18 (13)	C21—C22—H22	119.6
S1—C1—C2—C3	30.00 (15)	C7—C2—C3—C4	0.84 (18)
S1—C1—C2—C7	−151.09 (9)	C8—O1—C6—C5	−8.60 (19)
S1—C9—C10—C11	87.20 (15)	C8—O1—C6—C7	170.97 (12)
S1—C9—C10—C15	−93.52 (14)	C9—S1—C1—S2	−177.44 (6)
S2—C1—C2—C3	−90.18 (13)	C9—S1—C1—C2	61.92 (10)
S2—C1—C2—C7	88.73 (12)	C9—C10—C11—C12	178.27 (13)
S2—C16—C17—C18	85.08 (14)	C9—C10—C15—C14	−177.74 (14)
S2—C16—C17—C22	−95.56 (13)	C10—C11—C12—C13	−0.4 (2)
O1—C6—C7—O2	0.73 (17)	C11—C10—C15—C14	1.6 (2)
O1—C6—C7—C2	−179.12 (11)	C11—C12—C13—C14	1.4 (2)
C1—S1—C9—C10	66.89 (11)	C12—C13—C14—C15	−0.8 (2)
C1—S2—C16—C17	56.83 (10)	C13—C14—C15—C10	−0.6 (2)
C1—C2—C3—C4	179.74 (11)	C15—C10—C11—C12	−1.0 (2)
C1—C2—C7—O2	0.19 (17)	C16—S2—C1—S1	66.50 (7)
C1—C2—C7—C6	−179.95 (11)	C16—S2—C1—C2	−168.23 (8)
C2—C3—C4—C5	−0.18 (19)	C16—C17—C18—C19	179.38 (12)
C3—C2—C7—O2	179.17 (11)	C16—C17—C22—C21	179.52 (12)
C3—C2—C7—C6	−0.98 (18)	C17—C18—C19—C20	1.3 (2)
C3—C4—C5—C6	−0.34 (19)	C18—C17—C22—C21	−1.1 (2)
C4—C5—C6—O1	179.74 (12)	C18—C19—C20—C21	−1.5 (2)
C4—C5—C6—C7	0.19 (19)	C19—C20—C21—C22	0.4 (2)
C5—C6—C7—O2	−179.67 (11)	C20—C21—C22—C17	0.9 (2)
C5—C6—C7—C2	0.48 (19)	C22—C17—C18—C19	0.0 (2)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···S1^i	0.85 (2)	2.44 (2)	3.1315 (13)	139.0 (17)
O2—H2···O1	0.85 (2)	2.17 (2)	2.6469 (16)	115.4 (16)
C9—H9A···C20^ii	0.99	2.86	3.528 (2)	125
C5—H5···Cg1^iii	0.95	2.84	3.7487 (15)	160
C16—H16A···Cg1^iv	0.99	2.71	3.6316 (15)	154

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