3,6,14,17-Tetramethoxy-22,23-diphenyl-1,10,12,21-tetraazahexacyclo[19.2.1.0.0.0.0]tetracosa-2(7),3,5,13(18),14,16-hexaene-11,24-di-thione.

The title compound, C(36)H(34)N(4)O(4)S(2), is a thio-glycoluril derivative, which bears two phenyl substituents on its convex face and two meth-oxy substituted o-xylylenes as sidewalls of the molecular clip. There is one half-mol-ecule in the asymmetric unit: a crystallographic twofold axis generates the complete molecule. The non-planar seven-membered rings adopt chair conformations, while the two five-membered rings exhibit envelope conformations and make a dihedral angle of 68.46 (12)°. The O atoms of the meth-oxy groups are coplanar with the six-membered o-xylylene sidewalls.

Related literature

For related structures, see: Broan et al. (1989 ▶); Cao et al. (2009 ▶); Wang et al. (2006 ▶); Wang & Xi (2009 ▶); Wu & Sun, (2009 ▶). For further synthetic details, see: Broan et al. (1989 ▶); Wu et al. (2002 ▶). The rigid concave shape of glycoluril makes it a versatile building block in supramolecular chemistry, see: Gao et al. (2009 ▶); Rowan et al. (1999 ▶); Hof et al. (2002 ▶); Kolbel & Menger (2001 ▶); Wu et al. (2002 ▶); Kang et al. (2004 ▶).

Experimental

Crystal data

C36H34N4O4S2

M = 650.79

Monoclinic,

a = 17.9993 (15) Å

b = 12.5069 (11) Å

c = 16.0934 (12) Å

β = 115.961 (3)°

V = 3257.3 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 298 K

0.23 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

13570 measured reflections

3546 independent reflections

2279 reflections with I > 2σ(I)

R int = 0.067

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.162

S = 0.98

3546 reflections

210 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681002204X/fl2304sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002204X/fl2304Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C36H34N4O4S2	F(000) = 1368
Mr = 650.79	Dx = 1.327 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2697 reflections
a = 17.9993 (15) Å	θ = 2.5–21.3°
b = 12.5069 (11) Å	µ = 0.21 mm−1
c = 16.0934 (12) Å	T = 298 K
β = 115.961 (3)°	Block, colorless
V = 3257.3 (5) Å3	0.23 × 0.20 × 0.10 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2279 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.067
graphite	θmax = 27.0°, θmin = 2.1°
phi and ω scans	h = −22→13
13570 measured reflections	k = −15→15
3546 independent reflections	l = −19→20

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.0878P)2] where P = (Fo2 + 2Fc2)/3
3546 reflections	(Δ/σ)max = 0.001
210 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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. 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.

	x	y	z	Uiso*/Ueq
S1	0.11451 (4)	0.22118 (5)	0.14339 (5)	0.0528 (3)
N1	0.09215 (11)	0.31734 (13)	0.27979 (13)	0.0335 (5)
N2	−0.00738 (11)	0.34780 (13)	0.14082 (13)	0.0325 (4)
C13	0.07957 (13)	0.50126 (16)	0.32973 (15)	0.0343 (5)
C9	0.16813 (14)	0.27755 (17)	0.35521 (17)	0.0388 (6)
H9A	0.1970	0.3371	0.3949	0.047*
H9B	0.2036	0.2489	0.3294	0.047*
C12	0.03855 (13)	0.39284 (16)	0.29759 (15)	0.0306 (5)
C10	0.06573 (14)	0.29489 (16)	0.18917 (16)	0.0326 (5)
O2	0.06197 (14)	0.16264 (16)	0.57355 (15)	0.0713 (6)
O1	0.24132 (13)	0.08009 (14)	0.37734 (15)	0.0683 (6)
C1	0.15415 (14)	0.19204 (17)	0.41322 (17)	0.0393 (6)
C2	0.10798 (15)	0.21274 (17)	0.46227 (17)	0.0406 (6)
C6	0.19350 (16)	0.09225 (18)	0.42349 (19)	0.0477 (7)
C18	0.13789 (15)	0.53676 (19)	0.30210 (19)	0.0497 (7)
H18	0.1560	0.4916	0.2688	0.060*
C11	−0.06462 (15)	0.31850 (18)	0.04628 (16)	0.0392 (6)
H11A	−0.0343	0.3157	0.0092	0.047*
H11B	−0.1060	0.3742	0.0209	0.047*
C3	0.10368 (17)	0.1344 (2)	0.52320 (19)	0.0512 (7)
C14	0.05429 (16)	0.56979 (18)	0.37978 (18)	0.0463 (7)
H14	0.0150	0.5469	0.3988	0.056*
C4	0.14195 (17)	0.0364 (2)	0.5309 (2)	0.0578 (8)
H4	0.1379	−0.0156	0.5701	0.069*
C17	0.16966 (18)	0.6394 (2)	0.3237 (2)	0.0655 (9)
H17	0.2086	0.6631	0.3045	0.079*
C5	0.18588 (18)	0.0156 (2)	0.4811 (2)	0.0564 (8)
H5	0.2108	−0.0508	0.4863	0.068*
C15	0.0865 (2)	0.6717 (2)	0.4019 (2)	0.0638 (9)
H15	0.0693	0.7170	0.4360	0.077*
C16	0.1438 (2)	0.7055 (2)	0.3733 (2)	0.0731 (10)
H16	0.1654	0.7742	0.3878	0.088*
C7	0.2729 (2)	−0.0224 (2)	0.3750 (3)	0.0859 (11)
H7A	0.2924	−0.0550	0.4348	0.129*
H7B	0.3178	−0.0162	0.3583	0.129*
H7C	0.2301	−0.0658	0.3302	0.129*
C8	0.0599 (2)	0.0907 (3)	0.6401 (2)	0.0865 (11)
H8A	0.0241	0.0319	0.6094	0.130*
H8B	0.0396	0.1269	0.6787	0.130*
H8C	0.1146	0.0643	0.6775	0.130*

	U11	U22	U33	U12	U13	U23
S1	0.0520 (5)	0.0520 (4)	0.0612 (5)	0.0130 (3)	0.0311 (4)	−0.0081 (3)
N1	0.0300 (11)	0.0293 (9)	0.0435 (12)	0.0043 (7)	0.0181 (9)	0.0014 (8)
N2	0.0341 (11)	0.0273 (9)	0.0390 (11)	0.0020 (8)	0.0189 (9)	−0.0016 (8)
C13	0.0316 (13)	0.0300 (11)	0.0397 (13)	−0.0029 (9)	0.0141 (10)	0.0006 (9)
C9	0.0268 (13)	0.0385 (13)	0.0466 (14)	0.0035 (10)	0.0118 (11)	0.0042 (10)
C12	0.0317 (12)	0.0264 (10)	0.0391 (12)	0.0013 (9)	0.0205 (10)	0.0006 (9)
C10	0.0327 (13)	0.0270 (11)	0.0395 (14)	−0.0012 (9)	0.0170 (11)	0.0011 (9)
O2	0.0922 (16)	0.0662 (13)	0.0746 (14)	0.0174 (11)	0.0543 (13)	0.0311 (11)
O1	0.0756 (15)	0.0481 (11)	0.0968 (17)	0.0248 (10)	0.0521 (13)	0.0162 (10)
C1	0.0328 (14)	0.0343 (12)	0.0433 (14)	0.0000 (10)	0.0097 (11)	0.0030 (10)
C2	0.0390 (14)	0.0331 (12)	0.0430 (14)	−0.0015 (10)	0.0118 (12)	0.0037 (10)
C6	0.0452 (16)	0.0364 (13)	0.0582 (17)	0.0053 (11)	0.0197 (13)	0.0014 (11)
C18	0.0428 (16)	0.0428 (14)	0.0692 (19)	−0.0048 (11)	0.0300 (14)	0.0017 (12)
C11	0.0397 (14)	0.0408 (13)	0.0357 (13)	0.0020 (10)	0.0153 (11)	−0.0017 (10)
C3	0.0549 (18)	0.0474 (15)	0.0536 (17)	−0.0009 (13)	0.0259 (14)	0.0083 (12)
C14	0.0582 (17)	0.0334 (13)	0.0518 (16)	−0.0035 (11)	0.0284 (14)	−0.0037 (11)
C4	0.063 (2)	0.0437 (15)	0.0596 (18)	0.0013 (13)	0.0207 (16)	0.0190 (13)
C17	0.0486 (18)	0.0531 (17)	0.091 (2)	−0.0183 (14)	0.0267 (17)	0.0117 (16)
C5	0.065 (2)	0.0345 (14)	0.0639 (19)	0.0073 (12)	0.0226 (16)	0.0073 (13)
C15	0.090 (2)	0.0359 (14)	0.0624 (19)	−0.0065 (15)	0.0304 (17)	−0.0115 (13)
C16	0.084 (3)	0.0387 (16)	0.080 (2)	−0.0232 (16)	0.021 (2)	−0.0042 (15)
C7	0.112 (3)	0.055 (2)	0.113 (3)	0.0199 (19)	0.070 (3)	−0.0035 (18)
C8	0.099 (3)	0.095 (3)	0.076 (2)	0.009 (2)	0.048 (2)	0.036 (2)

S1—C10	1.652 (2)	C6—C5	1.381 (4)
N1—C10	1.351 (3)	C18—C17	1.386 (4)
N1—C9	1.462 (3)	C18—H18	0.9300
N1—C12	1.465 (3)	C11—C2i	1.511 (3)
N2—C10	1.371 (3)	C11—H11A	0.9700
N2—C12i	1.450 (3)	C11—H11B	0.9700
N2—C11	1.462 (3)	C3—C4	1.384 (4)
C13—C18	1.381 (3)	C14—C15	1.381 (3)
C13—C14	1.382 (3)	C14—H14	0.9300
C13—C12	1.522 (3)	C4—C5	1.375 (4)
C9—C1	1.511 (3)	C4—H4	0.9300
C9—H9A	0.9700	C17—C16	1.364 (4)
C9—H9B	0.9700	C17—H17	0.9300
C12—N2i	1.450 (3)	C5—H5	0.9300
C12—C12i	1.553 (4)	C15—C16	1.369 (4)
O2—C3	1.370 (3)	C15—H15	0.9300
O2—C8	1.412 (3)	C16—H16	0.9300
O1—C6	1.369 (3)	C7—H7A	0.9600
O1—C7	1.410 (3)	C7—H7B	0.9600
C1—C2	1.398 (3)	C7—H7C	0.9600
C1—C6	1.409 (3)	C8—H8A	0.9600
C2—C3	1.412 (3)	C8—H8B	0.9600
C2—C11i	1.511 (3)	C8—H8C	0.9600
C10—N1—C9	125.79 (19)	N2—C11—H11A	108.6
C10—N1—C12	113.23 (17)	C2i—C11—H11A	108.6
C9—N1—C12	120.91 (18)	N2—C11—H11B	108.6
C10—N2—C12i	111.24 (18)	C2i—C11—H11B	108.6
C10—N2—C11	122.26 (18)	H11A—C11—H11B	107.6
C12i—N2—C11	120.09 (18)	O2—C3—C4	123.7 (2)
C18—C13—C14	118.6 (2)	O2—C3—C2	116.3 (2)
C18—C13—C12	120.1 (2)	C4—C3—C2	120.0 (3)
C14—C13—C12	121.1 (2)	C15—C14—C13	121.0 (3)
N1—C9—C1	113.92 (19)	C15—C14—H14	119.5
N1—C9—H9A	108.8	C13—C14—H14	119.5
C1—C9—H9A	108.8	C5—C4—C3	120.4 (2)
N1—C9—H9B	108.8	C5—C4—H4	119.8
C1—C9—H9B	108.8	C3—C4—H4	119.8
H9A—C9—H9B	107.7	C16—C17—C18	120.0 (3)
N2i—C12—N1	111.61 (16)	C16—C17—H17	120.0
N2i—C12—C13	112.90 (18)	C18—C17—H17	120.0
N1—C12—C13	112.20 (18)	C4—C5—C6	120.8 (2)
N2i—C12—C12i	103.2 (2)	C4—C5—H5	119.6
N1—C12—C12i	100.82 (17)	C6—C5—H5	119.6
C13—C12—C12i	115.23 (12)	C16—C15—C14	119.4 (3)
N1—C10—N2	108.02 (18)	C16—C15—H15	120.3
N1—C10—S1	126.35 (17)	C14—C15—H15	120.3
N2—C10—S1	125.57 (17)	C17—C16—C15	120.7 (3)
C3—O2—C8	119.2 (2)	C17—C16—H16	119.7
C6—O1—C7	118.2 (2)	C15—C16—H16	119.7
C2—C1—C6	119.4 (2)	O1—C7—H7A	109.5
C2—C1—C9	121.2 (2)	O1—C7—H7B	109.5
C6—C1—C9	119.2 (2)	H7A—C7—H7B	109.5
C1—C2—C3	119.4 (2)	O1—C7—H7C	109.5
C1—C2—C11i	121.4 (2)	H7A—C7—H7C	109.5
C3—C2—C11i	119.2 (2)	H7B—C7—H7C	109.5
O1—C6—C5	123.9 (2)	O2—C8—H8A	109.5
O1—C6—C1	116.0 (2)	O2—C8—H8B	109.5
C5—C6—C1	120.0 (3)	H8A—C8—H8B	109.5
C13—C18—C17	120.3 (3)	O2—C8—H8C	109.5
C13—C18—H18	119.8	H8A—C8—H8C	109.5
C17—C18—H18	119.8	H8B—C8—H8C	109.5
N2—C11—C2i	114.50 (19)
C10—N1—C9—C1	−106.3 (3)	C7—O1—C6—C5	11.7 (4)
C12—N1—C9—C1	77.1 (3)	C7—O1—C6—C1	−171.6 (3)
C10—N1—C12—N2i	122.1 (2)	C2—C1—C6—O1	−176.5 (2)
C9—N1—C12—N2i	−60.9 (2)	C9—C1—C6—O1	−1.2 (3)
C10—N1—C12—C13	−110.1 (2)	C2—C1—C6—C5	0.4 (4)
C9—N1—C12—C13	66.9 (2)	C9—C1—C6—C5	175.7 (2)
C10—N1—C12—C12i	13.1 (2)	C14—C13—C18—C17	−0.5 (4)
C9—N1—C12—C12i	−169.92 (18)	C12—C13—C18—C17	173.8 (2)
C18—C13—C12—N2i	155.7 (2)	C10—N2—C11—C2i	70.0 (3)
C14—C13—C12—N2i	−30.1 (3)	C12i—N2—C11—C2i	−79.4 (2)
C18—C13—C12—N1	28.6 (3)	C8—O2—C3—C4	2.6 (4)
C14—C13—C12—N1	−157.3 (2)	C8—O2—C3—C2	−175.9 (3)
C18—C13—C12—C12i	−86.0 (3)	C1—C2—C3—O2	175.8 (2)
C14—C13—C12—C12i	88.1 (3)	C11i—C2—C3—O2	−2.3 (4)
C9—N1—C10—N2	−179.57 (19)	C1—C2—C3—C4	−2.8 (4)
C12—N1—C10—N2	−2.7 (2)	C11i—C2—C3—C4	179.0 (2)
C9—N1—C10—S1	−2.1 (3)	C18—C13—C14—C15	0.0 (4)
C12—N1—C10—S1	174.75 (16)	C12—C13—C14—C15	−174.3 (2)
C12i—N2—C10—N1	−10.2 (2)	O2—C3—C4—C5	−177.0 (3)
C11—N2—C10—N1	−162.05 (19)	C2—C3—C4—C5	1.5 (4)
C12i—N2—C10—S1	172.29 (15)	C13—C18—C17—C16	0.6 (4)
C11—N2—C10—S1	20.5 (3)	C3—C4—C5—C6	0.8 (4)
N1—C9—C1—C2	−61.3 (3)	O1—C6—C5—C4	174.9 (2)
N1—C9—C1—C6	123.5 (2)	C1—C6—C5—C4	−1.8 (4)
C6—C1—C2—C3	1.8 (4)	C13—C14—C15—C16	0.5 (4)
C9—C1—C2—C3	−173.4 (2)	C18—C17—C16—C15	−0.2 (5)
C6—C1—C2—C11i	180.0 (2)	C14—C15—C16—C17	−0.4 (5)
C9—C1—C2—C11i	4.8 (3)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···Cg1ii	0.97	2.70	3.540	145
C11—H11A···O2ii	0.97	2.26	2.757 (3)	111
C14—H14···N2ii	0.93	2.56	2.879 (3)	101
C18—H18···N1	0.93	2.51	2.842 (3)	102
C9—H9B···S1	0.97	2.73	3.189 (3)	110
C9—H9B···O1	0.97	2.25	2.748 (3)	111