Two triclinic polymorphs of 2,3,5,6-tetrakis­(naphthalen-2-yl­sulfanyl­methyl)­pyrazine

The title compound, C₄₈H₃₆N₂S₄, can be crystallized as two polymorphic structures, (I) and (II), both of which are in the triclinic space group P and possess C_i symmetry. In the crystal structure of polymorph (I), the adjacent naphthalene moieties are orientated towards one another and are inclined to one another by 78.7 (1)°, resulting in weak C—H...π interactions. In polymorph (II), the adjacent substituents are orientated away from one another, enclosing the pyrazine N atoms. In this way, the S atom of one substituent sits below the plane of the naphthalene ring of the other substituent.

S1. Comment

Tetra-substituted pyrazine derivatives have been used for a number of years as ligands in coordination chemistry, and a review of the Cambridge Structural Database (Version 5.25 of November 2003; Allen, 2002), indicated the presence of more than 40 such complexes. The majority include mono- and binuclear coordination complexes, and some coordination polymers, involving the ligands 2,3,5,6-tetra(2-pyridyl)pyrazine and 2,3,5,6-pyrazinetetracarboxylic acid.

Two cases of polymorphs of tetra-substitued pyrazine derivaties are also known, namely 2,3,5,6-tetraphenylpyrazine (Bartnik et al., 1999) and 2,3,5,6-tetra(2-pyridyl)pyrazine (Bock et al., 1992; Greaves & Stoeckli-Evans, 1992). The title compound, L, which possesses four extended `arms', was synthesized in order to explore its coordination behaviour with first-row transition metals. Two polymorphic forms, (I) and (II), have been isolated. Both crystallize in space group P1 and possess C_i symmetry. Polymorph (I) was obtained by slow diffusion of methanol into a toluene solution of L. Polymorph (II) was obtained by slow evaporation of a 1:1 methanol/chloroform solution of L. In both cases, the crystals were colourless.

The molecular structures of the two polymorphs, (I) and (II), are shown in Figs. 1(a) and 2(a), respectively. The bond distances and angles are normal for such compounds, and selected geometric parameters are given in Tables 1 and 2. The molecular structures of (I) and (II) differ in the orientation of the naphthalen-2-ylsulfanyl moieties with respect to the plane of the pyrazine ring. This difference is reflected in the torsion angles about the C1—C3 and C2—C4 bonds, and S1—C3 and S2—C4 bonds, which are quite different in the two polymorphs (see Tables 1 and 2). It can be seen that opposite naphthalene moieties are parallel to one another by symmetry. The various dihedral angles formed by the naphthalene and pyrazine rings are given in Table 3.

In polymorph (I), adjacent napthalene ring planes are inclined to one another by 78.7 (1)°, resulting in a weak C—H···π interaction involving atom C12 and the centroid of the plane formed by atoms C17ⁱ–C22ⁱ [the C—H···centroid distance is 2.64 (3) Å]. This interaction? is illustrated in the CPK view of (I) (Fig. 1 b).

In polymorph (II), the adjacent substituents are orientated away from one another, enclosing the pyrazine N atoms. The plane of the naphthalene moiety defined by atoms C5–C14 is inclined to the plane of the second naphthalene moiety (C15–C24) by 57.0 (1)°. In this way, the S atom, S2, of one substituent sits below the plane of the naphthalene ring of the other substituent. This conformation is illustrated in the CPK view of (II) (Fig. 2 b). However, there are no short intramolecular interactions, as atom S2 is more than 3.7 Å from atom C12, for example.

In the crystal packing of (I) and (II), the molecules stack along the a axes, as shown in Figs. 3 and 4, respectively. There are no short intermolecular interactions between symmetry-related molecules in either structure.

S2. Experimental

In a 200 ml three-necked flask, NaOH (575 mg, 14.4 mmol, 4.4 equivalents) was dissolved in refluxing tetrahydrofuran (THF; 45 ml) and H₂O (5 ml). Naphthalene-2-thiol (2.188 g, 13.7 mmol, 4.1 equivalents), dissolved in THF (45 ml), was then added dropwise. The deprotonation of naphthalene-2-thiol occurred in 1 h. To this solution, a solution containing 2,3,5,6-tetrakis-bromomethylpyrazine (TBr; 1.515 g, 3.3 mmol, 1 equivalent) in THF (75 ml) was added dropwise. The reaction was then left to reflux for 29 h. The solvent was removed with a rotary evaporator, and a yellow powder (2.250 g) was obtained. The compound was purified on a chromatography column using CH₂Cl₂/toluene (10:3) as eluant (yield 42%). After evaporation of the solvent, a colourless powder was obtained. Crystals suitable for X-ray analysis of polymorph (I) were prepared by diffusion of an equal volume of methanol into a toluene solution containing the product. Suitable crystals of polymorph (II) were prepared by slow evaporation of a chloroform/methanol (1:1) mixture after heating for 1 h at refluxing temperature. ¹H NMR (CDCl₃, 400 MHz): δ 7.84 (m, 8H, H6,9), 7.76 (m, 8H, H7,11), 7.48 [dd, 4H, 3 J(12,11) = 9.4, 4 J(12,4) = 1.9 Hz, H12], 7.47 (s, 4H, H4), 7.39 [dd, 4H, 3 J(8,7) = 8.6 Hz, 4 J(8,6/9) = 1.9 Hz, H8], 4.49 (s, 8H, H2); ¹³C NMR (CDCl₃, 50 MHz): δ 149.59 (4 C, C1), 134.21 (4 C, C3), 133.88 (4 C, C5), 132.43 (4 C,C10), 129.13 (4 C, C11), 128.38 (12 C, C6,8,9), 127.91(4 C, C7), 127.38 (4 C, C12), 126.70 (4 C, C4), 37.25 (4 C, C2); ESI-MS: 769.09 [M⁺H]⁺; IR (KBr disc, cm⁻¹): 3049 (w), 2926 (w), 1622 (m), 1582 (m), 1500 (m), 1446 (m), 1402 (s), 1336 (w), 1269 (w), 1243 (w), 1199 (w), 1131 (m), 1077 (m) 1013 (w), 957 (w), 942 (w), 902 (w), 885 (w), 863 (w), 852 (s), 821 (s), 806 (s), 798 (s), 763 (w), 749 (s), 737 (s), 636 (w), 598 (w), 479 (s), 469 (s). Analysis calculated for C₄₈H₃₆N₂S₄: C 74.96, H 4.72, N 3.64%; found: C 74.90, H 4.93, N 3.41%.

S3. Refinement

Crystals of both (I) and (II) diffracted weakly and the ratios of observed reflections to number of parameters were low (ca 7). It was only possible to access a maximum of ca 93% of the Ewald sphere in the triclinic system using the image-plate diffraction system if maximum atomic resolution was to be obtained, i.e. 0.81 Å. All H atoms were initially located in difference Fourier maps, and were subsequently included in the refinement in calculated positions and treated as riding atoms, using SHELXL97 (Sheldrick, 1997) default parameters. Polymorph (I) was measured at 153 K, and hence the C—H distances were 0.95–0.99 Å; polymorph (II) was measured at 293 K, and hence the C–H distances were 0.93–0.97 Å. In both cases, U_iso(H) values were taken to be equal to 1.2U_eq(C).

Computing details

For both compounds, data collection: EXPOSE (Stoe & Cie, 2000); cell refinement: CELL (Stoe & Cie, 2000); data reduction: INTEGRATE (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: PLATON (Spek, 1990) for (I); PLATON/PLUTON (Spek, 1990) for (II). For both compounds, software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. (a) A view of polymorph (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size. [Symmetry code: (a) 1 − x, 2 − y, 1 − z.] (b) A CPK view of polmorph (I).
	Fig. 2. (a) A view of polymorph (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size. [Symmetry code: (a) 1 − x, −y, −z.] (b) A CPK view of polmorph (II).
	Fig. 3. The molecular packing of polymorph (I), viewed along the a axis.
	Fig. 4. The molecular packing of polymorph (II), viewed along the a axis.

(I) 2,3,5,6-tetrakis(naphthalen-2-ylsulfanylmethyl)pyrazine

Crystal data

C48H36N2S4	Z = 1
Mr = 769.09	F(000) = 402
Triclinic, P1	Dx = 1.391 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.878 (1) Å	Cell parameters from 3169 reflections
b = 9.0432 (14) Å	θ = 2.4–25.9°
c = 15.613 (2) Å	µ = 0.30 mm^−1
α = 73.631 (17)°	T = 153 K
β = 82.265 (16)°	Rod, colourless
γ = 82.091 (18)°	0.45 × 0.20 × 0.10 mm
V = 918.2 (2) Å^3

Data collection

STOE image-plate diffraction system diffractometer	1735 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.055
Graphite monochromator	θmax = 25.9°, θmin = 2.4°
ϕ oscillation scans	h = −8→8
7208 measured reflections	k = −11→11
3332 independent reflections	l = −18→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H-atom parameters constrained
S = 1.00	w = [exp(3.00(sinθ/λ)^2)]/ [σ^2(Fo^2) + (0.0281P)^2] where P = (Fo^2 + 2Fc^2)/3
3332 reflections	(Δ/σ)max < 0.001
244 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. (I)n the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken (I)nto account (I)ndividually (I)n the estimation of e.s.d.'s (I)n distances, angles and torsion angles; correlations between e.s.d.'s (I)n cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s (I)s used for estimating e.s.d.'s (I)nvolving 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) (I)s used only for calculating R-factors(gt) etc. and (I)s 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
N1	0.3620 (3)	0.8960 (2)	0.54130 (14)	0.0307 (5)
S1	0.08272 (10)	0.78122 (8)	0.46604 (5)	0.0373 (2)
S2	0.68109 (12)	0.64792 (8)	0.68490 (5)	0.0428 (2)
C1	0.3564 (4)	0.9781 (3)	0.45529 (17)	0.0273 (6)
C2	0.5055 (4)	0.9179 (3)	0.58570 (17)	0.0286 (6)
C3	0.1956 (4)	0.9552 (3)	0.40560 (18)	0.0317 (6)
H3A	0.2512	0.9470	0.3451	0.038*
H3B	0.0945	1.0458	0.3985	0.038*
C4	0.5073 (4)	0.8199 (3)	0.68170 (17)	0.0344 (6)
H4A	0.3736	0.7894	0.7056	0.041*
H4B	0.5469	0.8801	0.7194	0.041*
C5	−0.0927 (4)	0.7800 (3)	0.39389 (19)	0.0320 (6)
C6	−0.2311 (4)	0.6698 (3)	0.42972 (19)	0.0369 (7)
H6	−0.2187	0.6005	0.4876	0.044*
C7	−0.3806 (4)	0.6610 (3)	0.3834 (2)	0.0390 (7)
H7	−0.4725	0.5873	0.4095	0.047*
C8	−0.4005 (4)	0.7621 (3)	0.29549 (19)	0.0339 (7)
C9	−0.5600 (4)	0.7636 (3)	0.2455 (2)	0.0426 (7)
H9	−0.6573	0.6940	0.2702	0.051*
C10	−0.5742 (4)	0.8638 (3)	0.1625 (2)	0.0443 (8)
H10	−0.6823	0.8650	0.1303	0.053*
C11	−0.4306 (4)	0.9643 (3)	0.1250 (2)	0.0431 (8)
H11	−0.4402	1.0319	0.0665	0.052*
C12	−0.2775 (4)	0.9676 (3)	0.17029 (19)	0.0380 (7)
H12	−0.1812	1.0372	0.1432	0.046*
C13	−0.2593 (4)	0.8680 (3)	0.25802 (18)	0.0321 (6)
C14	−0.1061 (4)	0.8753 (3)	0.30832 (19)	0.0342 (6)
H14	−0.0114	0.9468	0.2828	0.041*
C15	0.8451 (4)	0.6458 (3)	0.76307 (19)	0.0355 (7)
C16	0.8005 (4)	0.7110 (3)	0.83366 (18)	0.0366 (7)
H16	0.6731	0.7635	0.8426	0.044*
C17	0.9437 (4)	0.7004 (3)	0.89363 (18)	0.0337 (6)
C18	0.9043 (4)	0.7646 (3)	0.96732 (19)	0.0395 (7)
H18	0.7783	0.8182	0.9777	0.047*
C19	1.0448 (4)	0.7508 (3)	1.0244 (2)	0.0442 (8)
H19	1.0159	0.7945	1.0739	0.053*
C20	1.2307 (4)	0.6724 (3)	1.0095 (2)	0.0474 (8)
H20	1.3282	0.6641	1.0488	0.057*
C21	1.2731 (4)	0.6084 (3)	0.9401 (2)	0.0443 (8)
H21	1.4002	0.5553	0.9313	0.053*
C22	1.1318 (4)	0.6188 (3)	0.87985 (19)	0.0361 (7)
C23	1.1687 (4)	0.5489 (3)	0.8085 (2)	0.0438 (8)
H23	1.2924	0.4908	0.8002	0.053*
C24	1.0309 (4)	0.5629 (3)	0.7514 (2)	0.0416 (7)
H24	1.0601	0.5163	0.7031	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0323 (12)	0.0324 (11)	0.0292 (12)	−0.0003 (9)	−0.0083 (10)	−0.0100 (10)
S1	0.0380 (4)	0.0390 (4)	0.0364 (4)	−0.0057 (3)	−0.0140 (3)	−0.0071 (3)
S2	0.0559 (5)	0.0353 (4)	0.0406 (5)	0.0031 (3)	−0.0196 (4)	−0.0126 (3)
C1	0.0282 (13)	0.0309 (13)	0.0260 (14)	0.0023 (11)	−0.0062 (12)	−0.0136 (11)
C2	0.0293 (13)	0.0335 (14)	0.0253 (14)	0.0041 (11)	−0.0083 (12)	−0.0125 (11)
C3	0.0304 (14)	0.0363 (14)	0.0308 (15)	−0.0020 (11)	−0.0104 (12)	−0.0101 (12)
C4	0.0367 (15)	0.0375 (14)	0.0291 (15)	−0.0043 (12)	−0.0074 (13)	−0.0069 (12)
C5	0.0299 (14)	0.0320 (14)	0.0369 (17)	−0.0005 (11)	−0.0059 (13)	−0.0137 (12)
C6	0.0388 (15)	0.0326 (14)	0.0399 (17)	−0.0037 (12)	−0.0052 (14)	−0.0099 (13)
C7	0.0325 (14)	0.0369 (15)	0.0520 (19)	−0.0066 (12)	−0.0034 (14)	−0.0182 (14)
C8	0.0315 (14)	0.0345 (15)	0.0420 (17)	0.0036 (12)	−0.0100 (13)	−0.0205 (13)
C9	0.0354 (15)	0.0435 (17)	0.058 (2)	−0.0043 (13)	−0.0088 (15)	−0.0259 (15)
C10	0.0438 (17)	0.0488 (17)	0.049 (2)	0.0044 (14)	−0.0211 (16)	−0.0240 (15)
C11	0.0454 (17)	0.0488 (18)	0.0417 (19)	0.0047 (14)	−0.0131 (15)	−0.0234 (14)
C12	0.0382 (16)	0.0413 (16)	0.0358 (17)	−0.0014 (12)	−0.0074 (14)	−0.0119 (13)
C13	0.0308 (14)	0.0338 (14)	0.0372 (17)	0.0012 (11)	−0.0075 (13)	−0.0185 (12)
C14	0.0279 (14)	0.0382 (15)	0.0382 (17)	−0.0048 (11)	−0.0046 (12)	−0.0118 (13)
C15	0.0411 (16)	0.0337 (15)	0.0307 (17)	−0.0010 (12)	−0.0066 (14)	−0.0068 (12)
C16	0.0376 (15)	0.0369 (15)	0.0339 (16)	0.0031 (12)	−0.0077 (13)	−0.0086 (13)
C17	0.0414 (16)	0.0292 (14)	0.0287 (15)	−0.0015 (12)	−0.0045 (13)	−0.0055 (12)
C18	0.0402 (16)	0.0417 (16)	0.0368 (17)	0.0010 (13)	−0.0072 (14)	−0.0118 (13)
C19	0.0534 (18)	0.0459 (17)	0.0373 (18)	−0.0051 (14)	−0.0132 (15)	−0.0136 (14)
C20	0.0517 (18)	0.0412 (16)	0.052 (2)	0.0044 (14)	−0.0266 (16)	−0.0107 (15)
C21	0.0402 (17)	0.0389 (16)	0.054 (2)	0.0044 (13)	−0.0161 (16)	−0.0120 (15)
C22	0.0398 (16)	0.0294 (14)	0.0364 (17)	0.0010 (12)	−0.0020 (14)	−0.0074 (13)
C23	0.0413 (17)	0.0429 (17)	0.0454 (19)	0.0066 (13)	−0.0068 (15)	−0.0131 (14)
C24	0.0447 (17)	0.0409 (16)	0.0371 (17)	0.0029 (13)	−0.0004 (14)	−0.0121 (13)

Geometric parameters (Å, º)

N1—C1	1.342 (3)	C10—H10	0.9500
N1—C2	1.345 (3)	C11—C12	1.353 (4)
S1—C5	1.761 (2)	C11—H11	0.9500
S1—C3	1.809 (3)	C12—C13	1.422 (4)
S2—C15	1.764 (3)	C12—H12	0.9500
S2—C4	1.820 (3)	C13—C14	1.415 (3)
C1—C2^i	1.392 (4)	C14—H14	0.9500
C1—C3	1.501 (3)	C15—C16	1.371 (4)
C2—C1^i	1.392 (4)	C15—C24	1.407 (4)
C2—C4	1.512 (3)	C16—C17	1.424 (4)
C3—H3A	0.9900	C16—H16	0.9500
C3—H3B	0.9900	C17—C18	1.408 (4)
C4—H4A	0.9900	C17—C22	1.420 (4)
C4—H4B	0.9900	C18—C19	1.371 (4)
C5—C14	1.378 (4)	C18—H18	0.9500
C5—C6	1.420 (4)	C19—C20	1.398 (4)
C6—C7	1.357 (4)	C19—H19	0.9500
C6—H6	0.9500	C20—C21	1.348 (4)
C7—C8	1.431 (4)	C20—H20	0.9500
C7—H7	0.9500	C21—C22	1.417 (4)
C8—C13	1.411 (4)	C21—H21	0.9500
C8—C9	1.426 (4)	C22—C23	1.408 (4)
C9—C10	1.362 (4)	C23—C24	1.356 (4)
C9—H9	0.9500	C23—H23	0.9500
C10—C11	1.391 (4)	C24—H24	0.9500
C1—N1—C2	117.5 (2)	C10—C11—H11	119.4
C5—S1—C3	101.12 (12)	C11—C12—C13	120.7 (3)
C15—S2—C4	105.59 (13)	C11—C12—H12	119.7
N1—C1—C2^i	120.8 (2)	C13—C12—H12	119.7
N1—C1—C3	117.8 (2)	C8—C13—C14	119.9 (2)
C2^i—C1—C3	121.5 (2)	C8—C13—C12	118.5 (2)
N1—C2—C1^i	121.7 (2)	C14—C13—C12	121.5 (3)
N1—C2—C4	115.2 (2)	C5—C14—C13	120.8 (3)
C1^i—C2—C4	123.0 (2)	C5—C14—H14	119.6
C1—C3—S1	110.34 (17)	C13—C14—H14	119.6
C1—C3—H3A	109.6	C16—C15—C24	120.0 (2)
S1—C3—H3A	109.6	C16—C15—S2	125.2 (2)
C1—C3—H3B	109.6	C24—C15—S2	114.8 (2)
S1—C3—H3B	109.6	C15—C16—C17	120.5 (3)
H3A—C3—H3B	108.1	C15—C16—H16	119.8
C2—C4—S2	108.9 (2)	C17—C16—H16	119.8
C2—C4—H4A	109.9	C18—C17—C22	118.8 (2)
S2—C4—H4A	109.9	C18—C17—C16	122.5 (3)
C2—C4—H4B	109.9	C22—C17—C16	118.7 (3)
S2—C4—H4B	109.9	C19—C18—C17	121.0 (3)
H4A—C4—H4B	108.3	C19—C18—H18	119.5
C14—C5—C6	118.8 (2)	C17—C18—H18	119.5
C14—C5—S1	126.0 (2)	C18—C19—C20	119.9 (3)
C6—C5—S1	115.2 (2)	C18—C19—H19	120.1
C7—C6—C5	121.6 (3)	C20—C19—H19	120.1
C7—C6—H6	119.2	C21—C20—C19	120.7 (3)
C5—C6—H6	119.2	C21—C20—H20	119.6
C6—C7—C8	120.3 (3)	C19—C20—H20	119.6
C6—C7—H7	119.8	C20—C21—C22	121.3 (3)
C8—C7—H7	119.8	C20—C21—H21	119.3
C13—C8—C9	118.7 (3)	C22—C21—H21	119.3
C13—C8—C7	118.4 (2)	C23—C22—C21	122.8 (3)
C9—C8—C7	122.9 (3)	C23—C22—C17	118.8 (2)
C10—C9—C8	120.7 (3)	C21—C22—C17	118.3 (3)
C10—C9—H9	119.7	C24—C23—C22	121.2 (3)
C8—C9—H9	119.7	C24—C23—H23	119.4
C9—C10—C11	120.1 (2)	C22—C23—H23	119.4
C9—C10—H10	119.9	C23—C24—C15	120.6 (3)
C11—C10—H10	119.9	C23—C24—H24	119.7
C12—C11—C10	121.2 (3)	C15—C24—H24	119.7
C12—C11—H11	119.4
C2—N1—C1—C2^i	−0.2 (4)	C11—C12—C13—C14	−176.6 (3)
C2—N1—C1—C3	−179.5 (2)	C6—C5—C14—C13	2.4 (4)
C1—N1—C2—C1^i	0.2 (4)	S1—C5—C14—C13	−177.3 (2)
C1—N1—C2—C4	−178.7 (2)	C8—C13—C14—C5	0.0 (4)
N1—C1—C3—S1	−15.3 (3)	C12—C13—C14—C5	178.7 (3)
C2^i—C1—C3—S1	165.4 (2)	C4—S2—C15—C16	27.0 (3)
C5—S1—C3—C1	−178.9 (2)	C4—S2—C15—C24	−156.2 (2)
N1—C2—C4—S2	95.7 (2)	C24—C15—C16—C17	2.4 (4)
C1^i—C2—C4—S2	−83.2 (3)	S2—C15—C16—C17	179.1 (2)
C15—S2—C4—C2	125.36 (19)	C15—C16—C17—C18	−179.6 (3)
C3—S1—C5—C14	9.8 (3)	C15—C16—C17—C22	−1.2 (4)
C3—S1—C5—C6	−169.9 (2)	C22—C17—C18—C19	0.8 (4)
C14—C5—C6—C7	−3.0 (4)	C16—C17—C18—C19	179.3 (3)
S1—C5—C6—C7	176.7 (2)	C17—C18—C19—C20	0.2 (4)
C5—C6—C7—C8	1.1 (4)	C18—C19—C20—C21	−0.7 (5)
C6—C7—C8—C13	1.3 (4)	C19—C20—C21—C22	0.2 (5)
C6—C7—C8—C9	−176.7 (3)	C20—C21—C22—C23	−177.8 (3)
C13—C8—C9—C10	1.0 (4)	C20—C21—C22—C17	0.8 (4)
C7—C8—C9—C10	179.0 (3)	C18—C17—C22—C23	177.3 (3)
C8—C9—C10—C11	1.1 (5)	C16—C17—C22—C23	−1.2 (4)
C9—C10—C11—C12	−1.6 (5)	C18—C17—C22—C21	−1.3 (4)
C10—C11—C12—C13	−0.1 (4)	C16—C17—C22—C21	−179.8 (3)
C9—C8—C13—C14	176.3 (3)	C21—C22—C23—C24	−179.1 (3)
C7—C8—C13—C14	−1.8 (4)	C17—C22—C23—C24	2.3 (4)
C9—C8—C13—C12	−2.5 (4)	C22—C23—C24—C15	−1.2 (5)
C7—C8—C13—C12	179.4 (3)	C16—C15—C24—C23	−1.2 (4)
C11—C12—C13—C8	2.1 (4)	S2—C15—C24—C23	−178.3 (2)

Symmetry code: (i) −x+1, −y+2, −z+1.

(II) 2,3,5,6-tetrakis(naphthalen-2-ylsulfanylmethyl)pyrazine

Crystal data

C48H36N2S4	Z = 1
Mr = 769.09	F(000) = 402
Triclinic, P1	Dx = 1.303 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7641 (11) Å	Cell parameters from 2628 reflections
b = 9.7771 (19) Å	θ = 2.2–26.0°
c = 18.006 (4) Å	µ = 0.28 mm^−1
α = 75.40 (2)°	T = 293 K
β = 87.87 (2)°	Plate, colourless
γ = 86.66 (2)°	0.50 × 0.30 × 0.03 mm
V = 980.1 (3) Å^3

Data collection

STOE image-plate diffraction system diffractometer	1467 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.062
Graphite monochromator	θmax = 26.0°, θmin = 2.2°
Detector resolution: 0.81Å pixels mm^-1	h = −7→7
ϕ oscillation scans	k = −11→12
7633 measured reflections	l = −22→22
3545 independent reflections

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) = 0.086	w = [exp(4.00(sinθ/λ)^2)]/ [σ^2(Fo^2) + (0.0241P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3545 reflections	Δρmax = 0.15 e Å^−3
245 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0125 (14)

Special details

Geometry. All e.s.d.'s (except the e.s.d. (I)n the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken (I)nto account (I)ndividually (I)n the estimation of e.s.d.'s (I)n distances, angles and torsion angles; correlations between e.s.d.'s (I)n cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s (I)s used for estimating e.s.d.'s (I)nvolving 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) (I)s used only for calculating R-factors(gt) etc. and (I)s 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
N1	0.6922 (5)	−0.0392 (2)	−0.04072 (13)	0.0495 (7)
S1	0.4067 (2)	−0.33094 (9)	−0.07442 (5)	0.0697 (3)
S2	0.67603 (16)	0.26801 (8)	−0.17826 (4)	0.0524 (3)
C1	0.5474 (6)	−0.1353 (3)	−0.00134 (15)	0.0454 (8)
C2	0.6474 (6)	0.0962 (3)	−0.03917 (16)	0.0457 (8)
C3	0.6003 (7)	−0.2845 (3)	−0.00787 (17)	0.0601 (9)
H3B	0.5832	−0.3495	0.0423	0.072*
H3A	0.7600	−0.2940	−0.0255	0.072*
C4	0.8107 (6)	0.2007 (3)	−0.08628 (15)	0.0523 (8)
H4B	0.9614	0.1547	−0.0923	0.063*
H4A	0.8313	0.2769	−0.0619	0.063*
C5	0.4713 (6)	−0.1988 (3)	−0.15920 (17)	0.0505 (8)
C6	0.6834 (7)	−0.2099 (3)	−0.19910 (18)	0.0584 (9)
H6A	0.7879	−0.2860	−0.1807	0.070*
C7	0.7374 (6)	−0.1107 (3)	−0.26437 (18)	0.0547 (9)
H7A	0.8790	−0.1189	−0.2897	0.066*
C8	0.5803 (6)	0.0044 (3)	−0.29375 (16)	0.0464 (8)
C9	0.6313 (6)	0.1109 (4)	−0.36094 (17)	0.0612 (9)
H9A	0.7718	0.1047	−0.3873	0.073*
C10	0.4782 (8)	0.2214 (4)	−0.3873 (2)	0.0713 (11)
H10A	0.5137	0.2904	−0.4316	0.086*
C11	0.2651 (8)	0.2322 (4)	−0.3477 (2)	0.0704 (11)
H11A	0.1614	0.3089	−0.3658	0.085*
C12	0.2100 (6)	0.1319 (3)	−0.28353 (18)	0.0585 (9)
H12A	0.0674	0.1399	−0.2587	0.070*
C13	0.3651 (6)	0.0158 (3)	−0.25384 (16)	0.0452 (8)
C14	0.3162 (6)	−0.0894 (3)	−0.18596 (17)	0.0508 (8)
H14A	0.1760	−0.0833	−0.1594	0.061*
C15	0.8540 (5)	0.4048 (3)	−0.22703 (15)	0.0412 (7)
C16	0.7849 (5)	0.4810 (3)	−0.29849 (15)	0.0429 (7)
H16A	0.6485	0.4596	−0.3182	0.052*
C17	0.9175 (6)	0.5910 (3)	−0.34236 (15)	0.0442 (8)
C18	0.8492 (6)	0.6727 (4)	−0.41597 (17)	0.0609 (10)
H18A	0.7150	0.6521	−0.4373	0.073*
C19	0.9779 (7)	0.7805 (4)	−0.45554 (18)	0.0695 (11)
H19A	0.9292	0.8341	−0.5033	0.083*
C20	1.1829 (7)	0.8121 (4)	−0.42539 (19)	0.0661 (10)
H20A	1.2701	0.8857	−0.4533	0.079*
C21	1.2550 (6)	0.7355 (3)	−0.35556 (17)	0.0520 (8)
H21A	1.3915	0.7573	−0.3361	0.062*
C22	1.1257 (5)	0.6234 (3)	−0.31201 (15)	0.0417 (7)
C23	1.1921 (6)	0.5427 (3)	−0.23896 (16)	0.0463 (8)
H23A	1.3286	0.5619	−0.2184	0.056*
C24	1.0613 (6)	0.4372 (3)	−0.19773 (16)	0.0459 (8)
H24A	1.1093	0.3858	−0.1495	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.062 (2)	0.0371 (14)	0.0481 (15)	−0.0059 (14)	−0.0088 (13)	−0.0067 (11)
S1	0.1101 (10)	0.0429 (5)	0.0595 (6)	−0.0251 (5)	−0.0053 (5)	−0.0138 (4)
S2	0.0533 (6)	0.0529 (5)	0.0475 (5)	−0.0158 (4)	−0.0055 (4)	−0.0027 (4)
C1	0.064 (2)	0.0300 (14)	0.0405 (16)	−0.0061 (16)	−0.0147 (15)	−0.0033 (12)
C2	0.059 (2)	0.0364 (16)	0.0408 (16)	−0.0082 (16)	−0.0122 (15)	−0.0064 (13)
C3	0.087 (3)	0.0334 (16)	0.0594 (19)	−0.0035 (16)	−0.0102 (17)	−0.0089 (13)
C4	0.062 (2)	0.0412 (16)	0.0485 (17)	−0.0114 (16)	−0.0065 (15)	0.0010 (13)
C5	0.062 (3)	0.0403 (17)	0.0542 (19)	−0.0069 (17)	−0.0049 (17)	−0.0191 (14)
C6	0.063 (3)	0.0490 (19)	0.066 (2)	0.0086 (18)	−0.0101 (19)	−0.0209 (17)
C7	0.043 (2)	0.061 (2)	0.064 (2)	0.0047 (18)	−0.0008 (17)	−0.0248 (17)
C8	0.047 (2)	0.0503 (18)	0.0475 (18)	−0.0031 (17)	−0.0058 (16)	−0.0214 (14)
C9	0.062 (3)	0.072 (2)	0.0490 (19)	−0.011 (2)	0.0041 (17)	−0.0137 (17)
C10	0.089 (3)	0.065 (2)	0.055 (2)	−0.014 (2)	−0.013 (2)	−0.0032 (18)
C11	0.080 (3)	0.053 (2)	0.077 (3)	0.007 (2)	−0.020 (2)	−0.0126 (19)
C12	0.053 (2)	0.057 (2)	0.070 (2)	0.0028 (19)	−0.0038 (18)	−0.0246 (18)
C13	0.042 (2)	0.0439 (17)	0.0535 (18)	−0.0047 (16)	−0.0059 (16)	−0.0188 (14)
C14	0.050 (2)	0.0490 (18)	0.0594 (19)	−0.0094 (17)	0.0027 (16)	−0.0226 (15)
C15	0.039 (2)	0.0389 (15)	0.0460 (17)	−0.0044 (14)	0.0010 (14)	−0.0107 (13)
C16	0.039 (2)	0.0496 (17)	0.0407 (16)	−0.0067 (15)	−0.0041 (13)	−0.0099 (13)
C17	0.044 (2)	0.0452 (17)	0.0415 (17)	−0.0025 (15)	0.0037 (14)	−0.0077 (13)
C18	0.057 (2)	0.076 (2)	0.0431 (18)	−0.007 (2)	−0.0040 (16)	0.0000 (16)
C19	0.070 (3)	0.076 (2)	0.049 (2)	−0.004 (2)	0.0065 (18)	0.0098 (18)
C20	0.067 (3)	0.060 (2)	0.061 (2)	−0.013 (2)	0.0154 (19)	0.0014 (17)
C21	0.044 (2)	0.0522 (18)	0.060 (2)	−0.0111 (17)	0.0082 (16)	−0.0144 (16)
C22	0.039 (2)	0.0393 (16)	0.0468 (17)	−0.0022 (15)	0.0067 (14)	−0.0126 (13)
C23	0.040 (2)	0.0470 (17)	0.0532 (18)	−0.0046 (16)	−0.0066 (14)	−0.0142 (14)
C24	0.045 (2)	0.0478 (17)	0.0430 (16)	−0.0017 (16)	−0.0066 (14)	−0.0075 (13)

Geometric parameters (Å, º)

N1—C1	1.339 (4)	C10—H10A	0.9300
N1—C2	1.341 (4)	C11—C12	1.355 (5)
S1—C5	1.777 (3)	C11—H11A	0.9300
S1—C3	1.822 (3)	C12—C13	1.409 (4)
S2—C15	1.765 (3)	C12—H12A	0.9300
S2—C4	1.807 (3)	C13—C14	1.416 (4)
C1—C2^i	1.403 (4)	C14—H14A	0.9300
C1—C3	1.506 (4)	C15—C16	1.375 (3)
C2—C1^i	1.403 (4)	C15—C24	1.408 (4)
C2—C4	1.506 (4)	C16—C17	1.410 (4)
C3—H3B	0.9700	C16—H16A	0.9300
C3—H3A	0.9700	C17—C18	1.421 (4)
C4—H4B	0.9700	C17—C22	1.421 (4)
C4—H4A	0.9700	C18—C19	1.357 (5)
C5—C14	1.355 (4)	C18—H18A	0.9300
C5—C6	1.408 (5)	C19—C20	1.401 (5)
C6—C7	1.361 (4)	C19—H19A	0.9300
C6—H6A	0.9300	C20—C21	1.357 (4)
C7—C8	1.408 (4)	C20—H20A	0.9300
C7—H7A	0.9300	C21—C22	1.411 (4)
C8—C9	1.417 (4)	C21—H21A	0.9300
C8—C13	1.423 (4)	C22—C23	1.407 (4)
C9—C10	1.354 (5)	C23—C24	1.359 (4)
C9—H9A	0.9300	C23—H23A	0.9300
C10—C11	1.409 (5)	C24—H24A	0.9300
C1—N1—C2	117.7 (3)	C10—C11—H11A	119.7
C5—S1—C3	100.06 (15)	C11—C12—C13	121.1 (3)
C15—S2—C4	104.07 (14)	C11—C12—H12A	119.4
N1—C1—C2^i	121.5 (3)	C13—C12—H12A	119.4
N1—C1—C3	115.4 (3)	C12—C13—C14	122.8 (3)
C2^i—C1—C3	123.0 (3)	C12—C13—C8	118.4 (3)
N1—C2—C1^i	120.8 (3)	C14—C13—C8	118.8 (3)
N1—C2—C4	115.7 (3)	C5—C14—C13	120.8 (3)
C1^i—C2—C4	123.4 (3)	C5—C14—H14A	119.6
C1—C3—S1	111.3 (2)	C13—C14—H14A	119.6
C1—C3—H3B	109.4	C16—C15—C24	119.2 (3)
S1—C3—H3B	109.4	C16—C15—S2	116.9 (2)
C1—C3—H3A	109.4	C24—C15—S2	123.9 (2)
S1—C3—H3A	109.4	C15—C16—C17	121.0 (3)
H3B—C3—H3A	108.0	C15—C16—H16A	119.5
C2—C4—S2	105.7 (2)	C17—C16—H16A	119.5
C2—C4—H4B	110.6	C16—C17—C18	122.4 (3)
S2—C4—H4B	110.6	C16—C17—C22	119.3 (2)
C2—C4—H4A	110.6	C18—C17—C22	118.3 (3)
S2—C4—H4A	110.6	C19—C18—C17	120.7 (3)
H4B—C4—H4A	108.7	C19—C18—H18A	119.7
C14—C5—C6	120.2 (3)	C17—C18—H18A	119.7
C14—C5—S1	120.3 (3)	C18—C19—C20	120.8 (3)
C6—C5—S1	119.4 (2)	C18—C19—H19A	119.6
C7—C6—C5	120.8 (3)	C20—C19—H19A	119.6
C7—C6—H6A	119.6	C21—C20—C19	120.2 (3)
C5—C6—H6A	119.6	C21—C20—H20A	119.9
C6—C7—C8	120.5 (3)	C19—C20—H20A	119.9
C6—C7—H7A	119.8	C20—C21—C22	121.0 (3)
C8—C7—H7A	119.8	C20—C21—H21A	119.5
C7—C8—C9	122.2 (3)	C22—C21—H21A	119.5
C7—C8—C13	118.9 (3)	C23—C22—C21	122.8 (3)
C9—C8—C13	118.9 (3)	C23—C22—C17	118.1 (3)
C10—C9—C8	120.9 (3)	C21—C22—C17	119.0 (3)
C10—C9—H9A	119.6	C24—C23—C22	121.5 (3)
C8—C9—H9A	119.6	C24—C23—H23A	119.3
C9—C10—C11	120.1 (3)	C22—C23—H23A	119.3
C9—C10—H10A	120.0	C23—C24—C15	120.9 (3)
C11—C10—H10A	120.0	C23—C24—H24A	119.6
C12—C11—C10	120.6 (3)	C15—C24—H24A	119.6
C12—C11—H11A	119.7
C2—N1—C1—C2^i	1.2 (5)	C9—C8—C13—C14	−178.9 (3)
C2—N1—C1—C3	177.5 (2)	C6—C5—C14—C13	−0.5 (4)
C1—N1—C2—C1^i	−1.2 (5)	S1—C5—C14—C13	−179.4 (2)
C1—N1—C2—C4	−178.2 (2)	C12—C13—C14—C5	−179.5 (3)
N1—C1—C3—S1	−101.8 (3)	C8—C13—C14—C5	0.2 (4)
C2^i—C1—C3—S1	74.5 (3)	C4—S2—C15—C16	−176.8 (2)
C5—S1—C3—C1	58.9 (3)	C4—S2—C15—C24	4.6 (3)
N1—C2—C4—S2	93.8 (3)	C24—C15—C16—C17	−0.4 (4)
C1^i—C2—C4—S2	−83.2 (3)	S2—C15—C16—C17	−179.1 (2)
C15—S2—C4—C2	173.1 (2)	C15—C16—C17—C18	−179.2 (3)
C3—S1—C5—C14	−107.1 (3)	C15—C16—C17—C22	−0.1 (4)
C3—S1—C5—C6	73.9 (3)	C16—C17—C18—C19	178.0 (3)
C14—C5—C6—C7	0.8 (5)	C22—C17—C18—C19	−1.1 (5)
S1—C5—C6—C7	179.7 (3)	C17—C18—C19—C20	1.2 (6)
C5—C6—C7—C8	−0.8 (5)	C18—C19—C20—C21	−0.5 (6)
C6—C7—C8—C9	179.2 (3)	C19—C20—C21—C22	−0.1 (5)
C6—C7—C8—C13	0.4 (4)	C20—C21—C22—C23	−179.1 (3)
C7—C8—C9—C10	−179.1 (3)	C20—C21—C22—C17	0.1 (4)
C13—C8—C9—C10	−0.3 (5)	C16—C17—C22—C23	0.5 (4)
C8—C9—C10—C11	0.3 (5)	C18—C17—C22—C23	179.7 (3)
C9—C10—C11—C12	−0.7 (6)	C16—C17—C22—C21	−178.7 (3)
C10—C11—C12—C13	1.2 (5)	C18—C17—C22—C21	0.5 (4)
C11—C12—C13—C14	178.5 (3)	C21—C22—C23—C24	178.6 (3)
C11—C12—C13—C8	−1.2 (4)	C17—C22—C23—C24	−0.6 (4)
C7—C8—C13—C12	179.6 (3)	C22—C23—C24—C15	0.2 (5)
C9—C8—C13—C12	0.8 (4)	C16—C15—C24—C23	0.3 (4)
C7—C8—C13—C14	−0.1 (4)	S2—C15—C24—C23	178.9 (2)

Symmetry code: (i) −x+1, −y, −z.