2,4,5,7,9,10-Hexathia-1,3,6,8(1,4)-tetra­benzenacyclo­deca­phane

In the title macrocyclic mol­ecule, C₂₄H₁₆S₆, the S-S bond lengths are 2.0600 (11) and 2.0589 (12) Å. The crystal packing exhibits no classical inter­molecular inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.034
• wR factor = 0.089
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         S1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         S4

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.01
           From the CIF: _reflns_number_total               3815
           Count of symmetry unique reflns         2132
           Completeness (_total/calc)            178.94%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1683
           Fraction of Friedel pairs measured     0.789
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

In the title compound (Fig. 1), the S—S bond lengths are 2.0600 (11) Å [S2—S5] and 2.0589 (12) Å [S3—S6], which are consistent with the reported values (Ogawa et al., 1999). The intramolecular distances C2···C20 and C8···C18 are 4.418 (5) and 7.281 (7) Å, respectively.

Related literature

For S—S bond lengths, see: Ogawa et al. (1999).

S2. Experimental

To an ethanol (10 ml) solution of 4,4'-thiodibenzenethiol (1 mmol) was added an ethanol (5 ml) solution of iodine (2 mmol). The mixture was stirred for 4 h at room temperature, and a pale yellow solution was obtained and filtered. The filtrate was left undisturbed at room temperature for two weeks. Crystals of the title compound suitable for X-ray analysis were grown from an ethanol solution (yield 63%).

S3. Refinement

All H atoms were placed in geometrically idealized positions (C—H = 0.93 Å) and treated as riding on their parent atoms, with U_iso(H)=1.2U_eq(C).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and atomic numbering. H atoms have been omited for clarity.

2,4,5,7,9,10-Hexathia-1,3,6,8(1,4)-tetrabenzenacyclodecaphane

Crystal data

C24H16S6	F(000) = 1024
Mr = 496.73	Dx = 1.508 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 5516 reflections
a = 14.6300 (15) Å	θ = 2.8–28.2°
b = 25.025 (3) Å	µ = 0.64 mm^−1
c = 5.9754 (6) Å	T = 298 K
V = 2187.7 (4) Å^3	Block, colourless
Z = 4	0.33 × 0.11 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3815 independent reflections
Radiation source: fine-focus sealed tube	3452 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→12
Tmin = 0.818, Tmax = 0.951	k = −29→29
11286 measured reflections	l = −7→6

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.051P)^2 + 0.7742P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
3815 reflections	Δρmax = 0.25 e Å^−3
272 parameters	Δρmin = −0.21 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (8)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
S1	0.04551 (7)	0.61284 (3)	−0.25432 (16)	0.0556 (3)
S2	0.19406 (5)	0.42222 (3)	0.33953 (16)	0.04216 (19)
S3	0.10998 (5)	0.81877 (3)	0.33467 (17)	0.0505 (2)
S4	0.42460 (7)	0.63478 (3)	0.83251 (19)	0.0586 (2)
S5	0.33401 (5)	0.42247 (3)	0.30183 (15)	0.0479 (2)
S6	0.24892 (6)	0.82644 (3)	0.29017 (17)	0.0495 (2)
C1	0.09121 (19)	0.56196 (11)	−0.0797 (5)	0.0373 (7)
C2	0.1331 (2)	0.57092 (12)	0.1244 (6)	0.0428 (8)
H2	0.1401	0.6057	0.1765	0.051*
C3	0.1646 (2)	0.52860 (11)	0.2518 (6)	0.0393 (7)
H3	0.1903	0.5349	0.3916	0.047*
C4	0.15771 (19)	0.47662 (11)	0.1706 (5)	0.0355 (7)
C5	0.1188 (2)	0.46789 (11)	−0.0373 (5)	0.0373 (7)
H5	0.1156	0.4333	−0.0940	0.045*
C6	0.08465 (19)	0.50999 (11)	−0.1612 (6)	0.0400 (6)
H6	0.0573	0.5036	−0.2992	0.048*
C7	0.0574 (2)	0.67187 (12)	−0.0927 (5)	0.0400 (7)
C8	0.0130 (2)	0.67842 (12)	0.1109 (6)	0.0441 (8)
H8	−0.0272	0.6523	0.1620	0.053*
C9	0.0283 (2)	0.72354 (12)	0.2371 (6)	0.0415 (7)
H9	0.0011	0.7270	0.3771	0.050*
C10	0.0843 (2)	0.76392 (12)	0.1554 (5)	0.0385 (7)
C11	0.1210 (2)	0.75951 (13)	−0.0562 (5)	0.0425 (7)
H11	0.1532	0.7880	−0.1178	0.051*
C12	0.11021 (19)	0.71307 (11)	−0.1764 (6)	0.0418 (7)
H12	0.1386	0.7094	−0.3148	0.050*
C13	0.4031 (2)	0.57457 (12)	0.6845 (6)	0.0404 (7)
C14	0.4422 (2)	0.56461 (12)	0.4793 (6)	0.0431 (8)
H14	0.4823	0.5893	0.4168	0.052*
C15	0.42192 (19)	0.51778 (11)	0.3656 (6)	0.0394 (7)
H15	0.4460	0.5119	0.2237	0.047*
C16	0.3658 (2)	0.47972 (11)	0.4632 (5)	0.0378 (7)
C17	0.3322 (2)	0.48796 (13)	0.6754 (6)	0.0451 (8)
H17	0.2985	0.4613	0.7457	0.054*
C18	0.3483 (2)	0.53591 (12)	0.7850 (6)	0.0436 (7)
H18	0.3226	0.5422	0.9249	0.052*
C19	0.3718 (2)	0.68490 (12)	0.6690 (6)	0.0392 (7)
C20	0.3303 (2)	0.67732 (12)	0.4636 (6)	0.0462 (8)
H20	0.3279	0.6433	0.4016	0.055*
C21	0.2923 (2)	0.72005 (11)	0.3493 (6)	0.0446 (7)
H21	0.2652	0.7145	0.2104	0.053*
C22	0.2943 (2)	0.77105 (11)	0.4405 (5)	0.0378 (7)
C23	0.3359 (2)	0.77856 (12)	0.6463 (6)	0.0414 (7)
H23	0.3380	0.8126	0.7088	0.050*
C24	0.37435 (19)	0.73607 (11)	0.7594 (6)	0.0410 (7)
H24	0.4022	0.7417	0.8973	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0788 (6)	0.0384 (4)	0.0496 (5)	0.0030 (4)	−0.0241 (5)	0.0010 (4)
S2	0.0472 (4)	0.0278 (3)	0.0515 (5)	−0.0022 (3)	−0.0025 (4)	0.0039 (4)
S3	0.0544 (4)	0.0424 (4)	0.0547 (5)	0.0143 (3)	−0.0033 (5)	−0.0102 (4)
S4	0.0803 (6)	0.0408 (4)	0.0545 (5)	0.0112 (4)	−0.0296 (5)	−0.0075 (5)
S5	0.0467 (4)	0.0367 (4)	0.0603 (6)	0.0083 (3)	−0.0029 (4)	−0.0104 (4)
S6	0.0575 (5)	0.0309 (4)	0.0602 (6)	−0.0033 (3)	−0.0076 (4)	0.0049 (4)
C1	0.0365 (15)	0.0324 (15)	0.0430 (19)	0.0011 (12)	−0.0013 (13)	0.0013 (13)
C2	0.0506 (19)	0.0294 (15)	0.048 (2)	0.0001 (13)	−0.0111 (16)	−0.0056 (14)
C3	0.0466 (16)	0.0314 (15)	0.0399 (18)	0.0009 (12)	−0.0067 (15)	−0.0029 (13)
C4	0.0340 (15)	0.0303 (15)	0.0423 (18)	0.0009 (12)	0.0043 (14)	0.0008 (13)
C5	0.0396 (16)	0.0292 (15)	0.0431 (18)	−0.0018 (12)	0.0027 (14)	−0.0050 (13)
C6	0.0436 (15)	0.0404 (15)	0.0361 (16)	−0.0034 (12)	−0.0025 (15)	−0.0047 (16)
C7	0.0420 (16)	0.0339 (15)	0.0442 (19)	0.0049 (12)	−0.0109 (14)	0.0035 (13)
C8	0.0432 (18)	0.0398 (18)	0.049 (2)	−0.0031 (14)	0.0014 (15)	0.0115 (15)
C9	0.0381 (15)	0.0490 (18)	0.0374 (17)	0.0071 (13)	0.0047 (14)	0.0066 (15)
C10	0.0391 (16)	0.0332 (15)	0.0431 (19)	0.0098 (13)	−0.0050 (14)	0.0022 (14)
C11	0.0466 (18)	0.0396 (17)	0.0414 (18)	−0.0044 (13)	0.0014 (15)	0.0039 (14)
C12	0.0454 (15)	0.0447 (16)	0.0353 (17)	0.0023 (12)	0.0015 (16)	0.0020 (15)
C13	0.0436 (17)	0.0351 (16)	0.0425 (18)	0.0078 (13)	−0.0116 (14)	−0.0011 (14)
C14	0.0453 (17)	0.0351 (16)	0.049 (2)	0.0006 (13)	0.0002 (15)	0.0065 (15)
C15	0.0399 (15)	0.0384 (15)	0.0398 (18)	0.0071 (12)	0.0025 (14)	0.0014 (15)
C16	0.0365 (16)	0.0359 (16)	0.0411 (18)	0.0043 (12)	−0.0040 (14)	0.0018 (14)
C17	0.0402 (18)	0.049 (2)	0.046 (2)	−0.0048 (14)	0.0010 (15)	0.0024 (16)
C18	0.0414 (15)	0.0526 (18)	0.0368 (18)	0.0068 (13)	−0.0003 (14)	−0.0012 (16)
C19	0.0378 (16)	0.0340 (15)	0.0458 (19)	0.0053 (13)	−0.0046 (14)	−0.0050 (14)
C20	0.058 (2)	0.0341 (16)	0.046 (2)	0.0079 (14)	−0.0123 (16)	−0.0108 (15)
C21	0.0536 (17)	0.0387 (15)	0.0413 (17)	0.0072 (13)	−0.0118 (17)	−0.0070 (16)
C22	0.0383 (16)	0.0288 (14)	0.0464 (18)	0.0001 (12)	0.0010 (14)	−0.0018 (13)
C23	0.0432 (17)	0.0324 (16)	0.049 (2)	−0.0024 (13)	0.0013 (15)	−0.0109 (14)
C24	0.0420 (16)	0.0383 (16)	0.0428 (18)	−0.0012 (12)	−0.0057 (15)	−0.0081 (14)

Geometric parameters (Å, º)

S1—C7	1.773 (3)	C9—H9	0.9300
S1—C1	1.777 (3)	C10—C11	1.379 (5)
S2—C4	1.776 (3)	C11—C12	1.376 (4)
S2—S5	2.0600 (11)	C11—H11	0.9300
S3—C10	1.781 (3)	C12—H12	0.9300
S3—S6	2.0589 (12)	C13—C14	1.376 (5)
S4—C19	1.768 (3)	C13—C18	1.393 (4)
S4—C13	1.775 (3)	C14—C15	1.387 (4)
S5—C16	1.789 (3)	C14—H14	0.9300
S6—C22	1.780 (3)	C15—C16	1.386 (4)
C1—C2	1.383 (4)	C15—H15	0.9300
C1—C6	1.392 (4)	C16—C17	1.376 (5)
C2—C3	1.383 (4)	C17—C18	1.387 (4)
C2—H2	0.9300	C17—H17	0.9300
C3—C4	1.392 (4)	C18—H18	0.9300
C3—H3	0.9300	C19—C20	1.382 (4)
C4—C5	1.384 (4)	C19—C24	1.390 (4)
C5—C6	1.381 (4)	C20—C21	1.386 (4)
C5—H5	0.9300	C20—H20	0.9300
C6—H6	0.9300	C21—C22	1.388 (4)
C7—C12	1.383 (4)	C21—H21	0.9300
C7—C8	1.389 (5)	C22—C23	1.385 (5)
C8—C9	1.376 (5)	C23—C24	1.380 (4)
C8—H8	0.9300	C23—H23	0.9300
C9—C10	1.390 (4)	C24—H24	0.9300
C7—S1—C1	103.91 (14)	C11—C12—C7	120.4 (3)
C4—S2—S5	103.48 (10)	C11—C12—H12	119.8
C10—S3—S6	101.69 (11)	C7—C12—H12	119.8
C19—S4—C13	104.44 (15)	C14—C13—C18	119.9 (3)
C16—S5—S2	101.66 (10)	C14—C13—S4	121.6 (3)
C22—S6—S3	103.33 (11)	C18—C13—S4	118.5 (3)
C2—C1—C6	119.4 (3)	C13—C14—C15	120.0 (3)
C2—C1—S1	124.6 (2)	C13—C14—H14	120.0
C6—C1—S1	116.0 (2)	C15—C14—H14	120.0
C3—C2—C1	120.6 (3)	C16—C15—C14	120.1 (3)
C3—C2—H2	119.7	C16—C15—H15	119.9
C1—C2—H2	119.7	C14—C15—H15	119.9
C2—C3—C4	120.0 (3)	C17—C16—C15	119.8 (3)
C2—C3—H3	120.0	C17—C16—S5	121.6 (2)
C4—C3—H3	120.0	C15—C16—S5	118.5 (3)
C5—C4—C3	119.3 (3)	C16—C17—C18	120.3 (3)
C5—C4—S2	120.8 (2)	C16—C17—H17	119.9
C3—C4—S2	119.8 (2)	C18—C17—H17	119.9
C6—C5—C4	120.6 (3)	C17—C18—C13	119.7 (3)
C6—C5—H5	119.7	C17—C18—H18	120.2
C4—C5—H5	119.7	C13—C18—H18	120.2
C5—C6—C1	120.0 (3)	C20—C19—C24	118.9 (3)
C5—C6—H6	120.0	C20—C19—S4	125.8 (2)
C1—C6—H6	120.0	C24—C19—S4	115.3 (2)
C12—C7—C8	119.4 (3)	C19—C20—C21	120.5 (3)
C12—C7—S1	118.6 (3)	C19—C20—H20	119.7
C8—C7—S1	122.0 (2)	C21—C20—H20	119.7
C9—C8—C7	120.0 (3)	C20—C21—C22	120.5 (3)
C9—C8—H8	120.0	C20—C21—H21	119.8
C7—C8—H8	120.0	C22—C21—H21	119.8
C8—C9—C10	120.0 (3)	C23—C22—C21	118.9 (3)
C8—C9—H9	120.0	C23—C22—S6	120.4 (2)
C10—C9—H9	120.0	C21—C22—S6	120.6 (2)
C11—C10—C9	119.6 (3)	C24—C23—C22	120.6 (3)
C11—C10—S3	122.1 (2)	C24—C23—H23	119.7
C9—C10—S3	118.3 (2)	C22—C23—H23	119.7
C12—C11—C10	120.1 (3)	C23—C24—C19	120.6 (3)
C12—C11—H11	119.9	C23—C24—H24	119.7
C10—C11—H11	119.9	C19—C24—H24	119.7
C4—S2—S5—C16	73.11 (15)	S1—C7—C12—C11	180.0 (2)
C10—S3—S6—C22	−73.89 (15)	C19—S4—C13—C14	67.7 (3)
C7—S1—C1—C2	−5.4 (3)	C19—S4—C13—C18	−115.1 (3)
C7—S1—C1—C6	175.8 (2)	C18—C13—C14—C15	4.6 (5)
C6—C1—C2—C3	−2.9 (5)	S4—C13—C14—C15	−178.2 (2)
S1—C1—C2—C3	178.3 (3)	C13—C14—C15—C16	−3.2 (4)
C1—C2—C3—C4	2.7 (5)	C14—C15—C16—C17	−1.6 (4)
C2—C3—C4—C5	−0.3 (4)	C14—C15—C16—S5	175.0 (2)
C2—C3—C4—S2	−177.5 (2)	S2—S5—C16—C17	47.7 (3)
S5—S2—C4—C5	103.3 (2)	S2—S5—C16—C15	−128.9 (2)
S5—S2—C4—C3	−79.6 (2)	C15—C16—C17—C18	5.0 (5)
C3—C4—C5—C6	−1.8 (4)	S5—C16—C17—C18	−171.5 (2)
S2—C4—C5—C6	175.3 (2)	C16—C17—C18—C13	−3.7 (5)
C4—C5—C6—C1	1.6 (4)	C14—C13—C18—C17	−1.2 (5)
C2—C1—C6—C5	0.8 (4)	S4—C13—C18—C17	−178.4 (2)
S1—C1—C6—C5	179.7 (2)	C13—S4—C19—C20	−4.6 (3)
C1—S1—C7—C12	119.6 (2)	C13—S4—C19—C24	176.0 (2)
C1—S1—C7—C8	−62.4 (3)	C24—C19—C20—C21	0.3 (5)
C12—C7—C8—C9	−5.9 (5)	S4—C19—C20—C21	−179.0 (3)
S1—C7—C8—C9	176.2 (2)	C19—C20—C21—C22	−0.8 (5)
C7—C8—C9—C10	3.5 (5)	C20—C21—C22—C23	0.8 (5)
C8—C9—C10—C11	2.8 (4)	C20—C21—C22—S6	177.9 (3)
C8—C9—C10—S3	−174.6 (2)	S3—S6—C22—C23	−104.9 (2)
S6—S3—C10—C11	−43.3 (3)	S3—S6—C22—C21	78.0 (3)
S6—S3—C10—C9	134.0 (2)	C21—C22—C23—C24	−0.4 (5)
C9—C10—C11—C12	−6.7 (5)	S6—C22—C23—C24	−177.5 (2)
S3—C10—C11—C12	170.6 (2)	C22—C23—C24—C19	−0.1 (5)
C10—C11—C12—C7	4.3 (5)	C20—C19—C24—C23	0.1 (5)
C8—C7—C12—C11	2.0 (5)	S4—C19—C24—C23	179.5 (2)