2,2′-[Anthracene-9,10-di­yldi(methyl­enethio)]dianiline

The title compound, C₂₈H₂₄N₂S₂, is a derivative of anthracenyl compounds which are extensively used in PET sensors. The mol­ecule of the title compound has inversion symmetry and forms two intra­molecular hydrogen bonds of the type N—H...S. In the crystal structure, the mol­ecules are linked by C—H...π hydrogen-bonding contacts with the benzenamines acting both as donor and acceptor units.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.043
• wR factor = 0.142
• Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT410_ALERT_2_C Short Intra H...H Contact  H4A    ..  H8B     ..       1.97 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1B    ...          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Anthracene derivatives have gained considerable interest in recent years because of its photophysical properties in PET sensors (Sclafani et al., 1996; Greiner et al.,2002;). These important class of products was used to design macrocyclic ligands (Quici et al., 2000; Tamayo et al., 2005). Recently, it was shown that sulfur containing macrocyclic ligands with strong binding capability for heavy metal ions display very attractive photophysical properties (Tamayo et al., 2006; Lee et al., 2006;).

The molecule of the title compound (Fig. 1) has inversion symmetry and forms two intramolecular hydrogen bonds of the type N—H···S. The inversion centre of the molecule is in the middle of the anthracene skeleton. Two Csp²===Csp² bonds, C1===C2 and C3===C4 clearly show local π systems with distances 1.354 (3) Å and 1.358 (3) Å, whereas the central ring of the anthracene skeleton has a delocalized π-system with distances in the range 1.400 (2) Å and 1.441 (2) Å. The Csp²—Csp³ bond for C7—C8, 1.514 (2) Å, represents a normal value. Atoms C9 - C14, N1 and S1 are coplanar. The bond angles of the anthracene half molecule vary between 117.54 (17)° and 121.94 (18)°, indicating that the anthracene rings exhibit distorted hexagonal configuration. In the crystal lattice the molecules are linked by C—H···π hydrogen bonding contacts with the benzenamines acting both as donor and acceptor units (Fig. 2 and Table 1).

Related literature

For related literature, see: Greiner & Maier (2002); Lee et al. (2006); Marciniak (2007); Miller et al. (1955); Quici et al. (2000); Sclafani et al. (1996); Tamayo et al. (2005, 2006).

S2. Experimental

The title compound was prepared according to the following procedure. To 2-aminobenzenethiol(1.02 g, 4.00 mol), dissolved in 25 mL of freshly distilled THF and cooled to 0 °C, the suspended solution of sodium hydride(0.44 g, 9.00 mol, 50%) in 25 mL THF was slowly added dropwise under nitrogen. Then the solution was slowly warmed up to RT and stirred for 30 min, and 9,10-bis(chloromethyl)anthracene (Miller et al., 1955) (1.10 g, 4.00 mol) in 25 ml of THF was added dropwise and stirred overnight. The solvent was removed in vacuum, the residue was taken up in water (50 ml), and the product was extracted three times with 30-ml portions of dichloromethane·The organic solvent was evaporated, and a brown oily material was obtained (1.67 g). Separation by flash chromatography (eluent, ethyl acetate: petroleum ether(60–90) =1:3), resulted in a yellow solid (1.37 g, 75.7%) m.p. 197–198°C. Single crystals suitable for X-ray diffraction were obtained by recrystallization from a mixture of dichloromethane and petroleum ether.

1H NMR (500 MHz, CDCl3): δ 4.40 (s, 4H, NH2), δ 4.94 (s, 4H, CH2), δ 6.63(t, 2H, benzene-H), δ 6.70(d, 2H, benzene-H), δ 7.12(t, 2H, benzene-H),δ 7.36(d, 2H, benzene-H), 7.47 (m, 4H, anthrance-H), 8.28 (m, 4H, anthrance-H); EI—MS: m/z (%) '453.17 (100) [M+1]'.

S3. Refinement

The H atoms on the C atoms were located in a difference Fourier map and refined as riding on their parent atoms with U_iso(H)=1.2 times U_eq(C) and with C—H distance of 0.93 and 0.97 Å. H atoms on N atoms were included in calculated positions, constrained to an ideal geometry with N—H distance of 0.86 Å and with U_iso(H)=1.2 times U_eq(N).

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2000).

Figures

	Fig. 1. View of the title compound, with labelled atoms and displacement ellipsoids drawn at the 50% probability level. Atoms labelled with "a" are related by symmetry operator (1 - x, -y, -z). Intramolecular in-plane N—H···S contacts are indicated as dashed lines. H atoms are shown as small spheres of arbitrary size.
	Fig. 2. View of the b,c-projection of the unit cell, with translational symmetry of the molecules along the c-axis and the C—H···π contacts between adjacent molecules in a zigzag mode along the b and c axes.

2,2'-[Anthracene-9,10-diyldi(methylenethio)]dianiline

Crystal data

C28H24N2S2	F(000) = 476
Mr = 452.63	Dx = 1.365 Mg m^−3
Monoclinic, P21/c	Melting point: 197-198°C K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.0670 (8) Å	Cell parameters from 1747 reflections
b = 17.4159 (16) Å	θ = 2.3–29.4°
c = 7.1200 (6) Å	µ = 0.26 mm^−1
β = 101.620 (1)°	T = 295 K
V = 1101.28 (17) Å^3	Prism, yellow
Z = 2	0.26 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2746 independent reflections
Radiation source: fine-focus sealed tube	1747 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 29.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −12→11
Tmin = 0.937, Tmax = 0.972	k = −24→22
8318 measured reflections	l = −9→9

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0876P)^2] where P = (Fo^2 + 2Fc^2)/3
2746 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

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	0.27792 (6)	0.02595 (3)	0.41882 (7)	0.0557 (2)
N1	0.47587 (18)	0.14579 (11)	0.6551 (3)	0.0668 (5)
H1B	0.5395	0.1774	0.7196	0.080*
H1C	0.5050	0.1130	0.5799	0.080*
C1	0.2092 (2)	−0.06449 (12)	−0.0176 (3)	0.0553 (5)
H1A	0.1404	−0.0406	0.0440	0.066*
C2	0.1701 (2)	−0.13104 (14)	−0.1130 (3)	0.0628 (6)
H2A	0.0764	−0.1528	−0.1136	0.075*
C3	0.2707 (2)	−0.16739 (13)	−0.2114 (3)	0.0681 (6)
H3A	0.2423	−0.2126	−0.2785	0.082*
C4	0.4088 (2)	−0.13685 (12)	−0.2090 (3)	0.0591 (5)
H4A	0.4731	−0.1614	−0.2763	0.071*
C5	0.45849 (19)	−0.06799 (10)	−0.1060 (2)	0.0445 (4)
C6	0.35400 (19)	−0.02986 (10)	−0.0091 (2)	0.0430 (4)
C7	0.39599 (19)	0.03772 (10)	0.0944 (2)	0.0436 (4)
C8	0.2844 (2)	0.07694 (11)	0.1947 (3)	0.0482 (4)
H8A	0.1853	0.0769	0.1120	0.058*
H8B	0.3144	0.1299	0.2225	0.058*
C9	0.3273 (2)	0.14774 (11)	0.6723 (2)	0.0493 (4)
C10	0.2771 (3)	0.20063 (11)	0.7940 (3)	0.0571 (5)
H10A	0.3462	0.2332	0.8690	0.069*
C11	0.1291 (3)	0.20522 (12)	0.8044 (3)	0.0603 (5)
H11A	0.0989	0.2407	0.8867	0.072*
C12	0.0233 (2)	0.15810 (12)	0.6950 (3)	0.0596 (5)
H12A	−0.0778	0.1622	0.7016	0.072*
C13	0.0696 (2)	0.10473 (11)	0.5755 (3)	0.0507 (5)
H13A	−0.0011	0.0723	0.5029	0.061*
C14	0.2195 (2)	0.09871 (10)	0.5618 (2)	0.0448 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0736 (4)	0.0450 (3)	0.0583 (3)	0.0108 (2)	0.0366 (3)	0.0037 (2)
N1	0.0562 (11)	0.0756 (13)	0.0704 (12)	−0.0031 (8)	0.0171 (8)	0.0058 (10)
C1	0.0462 (10)	0.0667 (14)	0.0577 (12)	0.0027 (9)	0.0216 (9)	−0.0040 (10)
C2	0.0533 (11)	0.0732 (15)	0.0656 (13)	−0.0122 (10)	0.0206 (9)	−0.0097 (11)
C3	0.0717 (14)	0.0650 (14)	0.0721 (14)	−0.0140 (11)	0.0254 (11)	−0.0182 (11)
C4	0.0668 (13)	0.0552 (12)	0.0622 (12)	0.0013 (9)	0.0297 (10)	−0.0117 (10)
C5	0.0513 (10)	0.0458 (11)	0.0405 (9)	0.0058 (8)	0.0189 (8)	0.0035 (8)
C6	0.0453 (10)	0.0473 (11)	0.0398 (9)	0.0071 (7)	0.0170 (7)	0.0034 (8)
C7	0.0478 (10)	0.0457 (11)	0.0421 (9)	0.0096 (7)	0.0204 (7)	0.0047 (8)
C8	0.0527 (10)	0.0451 (11)	0.0531 (10)	0.0100 (8)	0.0254 (8)	0.0022 (8)
C9	0.0571 (11)	0.0498 (11)	0.0429 (9)	0.0026 (8)	0.0149 (8)	0.0098 (8)
C10	0.0822 (14)	0.0465 (11)	0.0427 (10)	−0.0026 (10)	0.0128 (9)	0.0014 (9)
C11	0.0913 (15)	0.0471 (12)	0.0500 (11)	0.0095 (10)	0.0320 (11)	−0.0004 (9)
C12	0.0661 (12)	0.0560 (13)	0.0673 (13)	0.0121 (10)	0.0386 (10)	0.0072 (10)
C13	0.0552 (11)	0.0489 (11)	0.0531 (11)	−0.0019 (8)	0.0227 (9)	−0.0002 (8)
C14	0.0562 (11)	0.0390 (10)	0.0448 (9)	0.0048 (7)	0.0233 (8)	0.0041 (7)

Geometric parameters (Å, º)

S1—C14	1.7720 (17)	C6—C7	1.400 (2)
S1—C8	1.8375 (18)	C7—C5^i	1.408 (2)
N1—C9	1.377 (2)	C7—C8	1.514 (2)
N1—H1B	0.86	C8—H8A	0.97
N1—H1C	0.86	C8—H8B	0.97
C1—C2	1.354 (3)	C9—C10	1.402 (3)
C1—C6	1.435 (3)	C9—C14	1.412 (3)
C1—H1A	0.93	C10—C11	1.361 (3)
C2—C3	1.407 (3)	C10—H10A	0.93
C2—H2A	0.93	C11—C12	1.378 (3)
C3—C4	1.358 (3)	C11—H11A	0.93
C3—H3A	0.93	C12—C13	1.381 (3)
C4—C5	1.430 (3)	C12—H12A	0.93
C4—H4A	0.93	C13—C14	1.386 (2)
C5—C7^i	1.408 (2)	C13—H13A	0.93
C5—C6	1.441 (2)
C14—S1—C8	102.65 (8)	C7—C8—S1	109.45 (12)
C9—N1—H1B	120.0	C7—C8—H8A	109.8
C9—N1—H1C	120.0	S1—C8—H8A	109.8
H1B—N1—H1C	120.0	C7—C8—H8B	109.8
C2—C1—C6	121.73 (17)	S1—C8—H8B	109.8
C2—C1—H1A	119.1	H8A—C8—H8B	108.2
C6—C1—H1A	119.1	N1—C9—C10	121.08 (18)
C1—C2—C3	120.28 (19)	N1—C9—C14	121.02 (17)
C1—C2—H2A	119.9	C10—C9—C14	117.85 (17)
C3—C2—H2A	119.9	C11—C10—C9	121.26 (19)
C4—C3—C2	120.4 (2)	C11—C10—H10A	119.4
C4—C3—H3A	119.8	C9—C10—H10A	119.4
C2—C3—H3A	119.8	C10—C11—C12	121.04 (18)
C3—C4—C5	121.94 (18)	C10—C11—H11A	119.5
C3—C4—H4A	119.0	C12—C11—H11A	119.5
C5—C4—H4A	119.0	C11—C12—C13	119.04 (18)
C7^i—C5—C4	122.58 (16)	C11—C12—H12A	120.5
C7^i—C5—C6	119.87 (16)	C13—C12—H12A	120.5
C4—C5—C6	117.54 (17)	C12—C13—C14	121.22 (19)
C7—C6—C1	121.67 (16)	C12—C13—H13A	119.4
C7—C6—C5	120.26 (16)	C14—C13—H13A	119.4
C1—C6—C5	118.04 (17)	C13—C14—C9	119.58 (16)
C6—C7—C5^i	119.86 (15)	C13—C14—S1	120.35 (14)
C6—C7—C8	119.41 (16)	C9—C14—S1	119.94 (13)
C5^i—C7—C8	120.73 (17)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···S1	0.86	2.63	3.032 (2)	110
C11—H11A···Cg3^ii	0.93	2.80	3.628 (2)	149

Symmetry code: (ii) x, −y−1/2, z−1/2.