2,3-Bis(thio­phen-2-yl)pyrazine­[2,3-f][1,10]phenanthroline

Zheng, C.-G.; Kong, J.; Zhang, P.; Dong, W.-X.

doi:10.1107/S160053681201522X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1443

doi:10.1107/S160053681201522X

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2,3-Bis(thiophen-2-yl)pyrazine[2,3-f][1,10]phenanthroline

Chang-Ge Zheng,^a ^* Jun Kong,^a Peng Zhang ^a and Wen-Xian Dong ^a

^aSchool of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi, Jiangsu Province 214122, People's Republic of China, and Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, 345 Lingling Road, Shanghai 200032, People's Republic of China
^*Correspondence e-mail: cgzheng@jiangnan.edu.cn

(Received 2 February 2012; accepted 6 April 2012; online 21 April 2012)

The molecule of the title compound, C₂₂H₁₂N₄S₂, shows no crystallographic symmetry. The thiophene rings form different dihedral angles [40.15 (9) and 15.43 (10)°] with the pyrazine ring. A strong π–π stacking interaction occurs between adjacent pyrazine[2,3-f][1,10]phenanthroline units with an interplanar distance of 3.4352 (16) Å.

Related literature

For the structure of 2,3-dithienylpyrazine[2,3-f]-1,10-phenanthroline, see: Chen & Li (2004 ). For the properties of 2,3-dithienylpyrazine[2,3-f]-1,10-phenanthroline, see: Armaroli et al. (1992 ); Aragoni et al. (2002 ); Bencini et al. (1999 ).

Experimental

Crystal data

C₂₂H₁₂N₄S₂
M_r = 396.48
Monoclinic, C 2/c
a = 27.016 (5) Å
b = 10.267 (2) Å
c = 13.835 (3) Å
β = 117.04 (3)°
V = 3418.1 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.763, T_max = 1.000
9577 measured reflections
3867 independent reflections
3057 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.130
S = 1.14
3867 reflections
253 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681201522X/aa2049sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201522X/aa2049Isup2.hkl

checkCIF report

Comment top

2,3-Dithienylpyrazine[2,3-f]-1,10-phenanthroline as a ligand is widely used as analytical probes, such as proton, ion sensors and organic light-emitting devices (Armaroli et al., 1992; Aragoni et al., 2002; Bencini et al., 1999; Chen & Li, 2004), due to its rigid structure and fluorescence property.

The molecule of the title compound, C₂₂H₁₂N₄S₂, is chemically symmetric but it shows no crystallographic symmetry. The dihedral angles between thiophene rings and pyrazine ring are 40.15 (9)° and 15.43 (10)°, respectively. The strong π-π stacking occurs in the crystal structure between parallel pyrazine[2,3-f]-1,10-phenanthroline molecules, the interplanar distance is 3.4352 (16) Å.

Related literature top

For the structure of 2,3-dithienylpyrazine[2,3-f]-1,10-phenanthroline, see: Chen & Li (2004). For the properties of 2,3-dithienylpyrazine[2,3-f]-1,10-phenanthroline, see: Armaroli et al. (1992); Aragoni et al. (2002); Bencini et al. (1999).

Experimental top

The title compound was synthesized by using 1,10-phenanthroline as the starting material according to the published route (Chen & Li, 2004). The single crystals were obtained by recrystallization from the mixture of methanol and methylene chloride at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.

2,3-Bis(thiophen-2-yl)pyrazine[2,3-f][1,10]phenanthroline top

Crystal data top

C₂₂H₁₂N₄S₂	F(000) = 1632
M_r = 396.48	D_x = 1.541 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7427 reflections
a = 27.016 (5) Å	θ = 3.0–27.5°
b = 10.267 (2) Å	µ = 0.33 mm⁻¹
c = 13.835 (3) Å	T = 293 K
β = 117.04 (3)°	Block, yellow
V = 3418.1 (15) Å³	0.30 × 0.30 × 0.10 mm
Z = 8

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3867 independent reflections
Radiation source: fine-focus sealed tube	3057 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
phi and ω scans	h = −34→34
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→11
T_min = 0.763, T_max = 1.000	l = −17→15
9577 measured reflections

Refinement top

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0537P)² + 1.3889P] where P = (F_o² + 2F_c²)/3
3867 reflections	(Δ/σ)_max < 0.001
253 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₂₂H₁₂N₄S₂	V = 3418.1 (15) Å³
M_r = 396.48	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 27.016 (5) Å	µ = 0.33 mm⁻¹
b = 10.267 (2) Å	T = 293 K
c = 13.835 (3) Å	0.30 × 0.30 × 0.10 mm
β = 117.04 (3)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3867 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3057 reflections with I > 2σ(I)
T_min = 0.763, T_max = 1.000	R_int = 0.039
9577 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.14	Δρ_max = 0.41 e Å⁻³
3867 reflections	Δρ_min = −0.45 e Å⁻³
253 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.20867 (3)	0.16082 (6)	0.37184 (6)	0.0384 (2)
S2	0.10144 (3)	−0.41137 (6)	0.25638 (6)	0.0385 (2)
C13	−0.00055 (10)	0.1677 (2)	0.12409 (19)	0.0261 (5)
C16	−0.04190 (9)	−0.0932 (2)	0.07706 (18)	0.0253 (5)
N4	−0.09519 (9)	0.2440 (2)	0.02141 (17)	0.0345 (5)
C11	0.03747 (9)	0.0587 (2)	0.16463 (18)	0.0245 (5)
C12	0.01743 (9)	−0.0683 (2)	0.14262 (18)	0.0245 (5)
N1	0.09256 (8)	0.08207 (19)	0.21974 (15)	0.0259 (4)
C9	0.10654 (9)	−0.1492 (2)	0.24045 (18)	0.0243 (5)
N2	0.05183 (8)	−0.17051 (19)	0.18208 (15)	0.0260 (4)
N3	−0.13437 (8)	−0.0055 (2)	−0.02387 (16)	0.0318 (5)
C15	−0.07901 (9)	0.0118 (2)	0.03844 (18)	0.0264 (5)
C14	−0.05811 (10)	0.1460 (2)	0.06220 (18)	0.0274 (5)
C10	0.12755 (9)	−0.0183 (2)	0.25369 (18)	0.0244 (5)
C18	−0.11870 (11)	−0.2366 (3)	−0.0142 (2)	0.0362 (6)
H18	−0.1337	−0.3196	−0.0343	0.043*
C19	−0.15243 (10)	−0.1264 (3)	−0.0490 (2)	0.0363 (6)
H19	−0.1902	−0.1389	−0.0929	0.044*
C2	0.18659 (10)	0.0169 (2)	0.30092 (19)	0.0267 (5)
C6	0.13841 (10)	−0.2672 (2)	0.28959 (18)	0.0260 (5)
C1	0.22833 (10)	−0.0375 (3)	0.28392 (19)	0.0307 (6)
H1	0.2246	−0.1151	0.2465	0.037*
C5	0.19175 (10)	−0.2883 (3)	0.36968 (19)	0.0312 (6)
H5	0.2183	−0.2229	0.3993	0.037*
C3	0.27773 (10)	0.0370 (3)	0.3294 (2)	0.0358 (6)
H3	0.3099	0.0135	0.3251	0.043*
C21	−0.01907 (11)	0.3958 (3)	0.0982 (2)	0.0426 (7)
H21	−0.0073	0.4821	0.1076	0.051*
C8	0.15717 (11)	−0.4972 (3)	0.3474 (2)	0.0394 (7)
H8	0.1568	−0.5866	0.3581	0.047*
C20	−0.07546 (11)	0.3638 (3)	0.0395 (2)	0.0390 (7)
H20	−0.1007	0.4319	0.0113	0.047*
C17	−0.06273 (10)	−0.2195 (3)	0.0506 (2)	0.0332 (6)
H17	−0.0391	−0.2909	0.0764	0.040*
C4	0.27329 (10)	0.1460 (3)	0.3795 (2)	0.0381 (7)
H4	0.3019	0.2056	0.4140	0.046*
C22	0.01805 (11)	0.2963 (2)	0.1410 (2)	0.0340 (6)
H22	0.0557	0.3143	0.1815	0.041*
C7	0.20172 (10)	−0.4207 (3)	0.4020 (2)	0.0344 (6)
H7	0.2355	−0.4514	0.4553	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0269 (3)	0.0271 (3)	0.0511 (4)	−0.0011 (3)	0.0089 (3)	−0.0050 (3)
S2	0.0289 (4)	0.0258 (3)	0.0491 (4)	−0.0013 (3)	0.0075 (3)	0.0031 (3)
C13	0.0225 (12)	0.0267 (13)	0.0261 (12)	0.0035 (10)	0.0085 (10)	0.0005 (10)
C16	0.0202 (11)	0.0317 (13)	0.0231 (11)	0.0009 (10)	0.0089 (9)	0.0029 (10)
N4	0.0266 (11)	0.0325 (12)	0.0386 (12)	0.0080 (9)	0.0096 (10)	0.0036 (10)
C11	0.0197 (11)	0.0297 (13)	0.0236 (12)	0.0034 (10)	0.0093 (9)	0.0021 (10)
C12	0.0225 (12)	0.0267 (12)	0.0242 (11)	0.0015 (10)	0.0105 (9)	0.0012 (10)
N1	0.0210 (10)	0.0258 (10)	0.0271 (10)	0.0020 (8)	0.0077 (8)	0.0001 (9)
C9	0.0223 (12)	0.0258 (12)	0.0238 (11)	0.0011 (9)	0.0096 (9)	0.0005 (10)
N2	0.0212 (10)	0.0274 (11)	0.0262 (10)	0.0008 (8)	0.0079 (8)	0.0010 (9)
N3	0.0218 (10)	0.0381 (12)	0.0305 (11)	−0.0004 (9)	0.0074 (9)	0.0013 (10)
C15	0.0211 (12)	0.0328 (13)	0.0243 (12)	0.0022 (10)	0.0092 (10)	0.0044 (10)
C14	0.0230 (12)	0.0335 (13)	0.0251 (12)	0.0046 (10)	0.0106 (10)	0.0016 (11)
C10	0.0210 (12)	0.0264 (12)	0.0233 (12)	0.0029 (10)	0.0077 (9)	0.0020 (10)
C18	0.0293 (14)	0.0332 (14)	0.0412 (15)	−0.0082 (11)	0.0117 (12)	−0.0007 (12)
C19	0.0182 (12)	0.0503 (17)	0.0353 (14)	−0.0029 (12)	0.0077 (10)	0.0054 (13)
C2	0.0237 (12)	0.0233 (12)	0.0279 (12)	−0.0011 (9)	0.0071 (10)	0.0027 (10)
C6	0.0221 (12)	0.0245 (12)	0.0284 (12)	0.0001 (9)	0.0089 (10)	−0.0002 (10)
C1	0.0243 (12)	0.0342 (14)	0.0315 (13)	0.0010 (11)	0.0108 (10)	0.0010 (11)
C5	0.0257 (13)	0.0311 (14)	0.0311 (13)	0.0022 (10)	0.0080 (10)	0.0045 (11)
C3	0.0226 (13)	0.0481 (17)	0.0348 (14)	0.0024 (12)	0.0113 (11)	0.0099 (13)
C21	0.0339 (15)	0.0288 (14)	0.0552 (18)	0.0039 (11)	0.0117 (13)	−0.0015 (13)
C8	0.0373 (15)	0.0282 (14)	0.0492 (17)	0.0078 (12)	0.0167 (13)	0.0104 (13)
C20	0.0330 (14)	0.0303 (14)	0.0443 (16)	0.0113 (12)	0.0094 (12)	0.0040 (12)
C17	0.0268 (13)	0.0314 (14)	0.0368 (14)	0.0008 (11)	0.0104 (11)	0.0034 (12)
C4	0.0225 (13)	0.0377 (15)	0.0418 (15)	−0.0073 (11)	0.0041 (11)	0.0071 (13)
C22	0.0247 (13)	0.0293 (13)	0.0417 (15)	0.0030 (10)	0.0097 (11)	−0.0014 (12)
C7	0.0265 (13)	0.0337 (14)	0.0363 (14)	0.0067 (11)	0.0083 (11)	0.0085 (12)

Geometric parameters (Å, º) top

S1—C4	1.707 (3)	C18—C17	1.374 (3)
S1—C2	1.723 (2)	C18—C19	1.394 (4)
S2—C8	1.704 (3)	C18—H18	0.9300
S2—C6	1.727 (2)	C19—H19	0.9300
C13—C22	1.395 (3)	C2—C1	1.371 (3)
C13—C14	1.411 (3)	C6—C5	1.378 (3)
C13—C11	1.449 (3)	C1—C3	1.414 (3)
C16—C17	1.394 (3)	C1—H1	0.9300
C16—C15	1.402 (3)	C5—C7	1.418 (4)
C16—C12	1.462 (3)	C5—H5	0.9300
N4—C20	1.318 (3)	C3—C4	1.351 (4)
N4—C14	1.349 (3)	C3—H3	0.9300
C11—N1	1.350 (3)	C21—C22	1.364 (4)
C11—C12	1.391 (3)	C21—C20	1.401 (4)
C12—N2	1.343 (3)	C21—H21	0.9300
N1—C10	1.331 (3)	C8—C7	1.345 (4)
C9—N2	1.342 (3)	C8—H8	0.9300
C9—C10	1.437 (3)	C20—H20	0.9300
C9—C6	1.463 (3)	C17—H17	0.9300
N3—C19	1.321 (3)	C4—H4	0.9300
N3—C15	1.356 (3)	C22—H22	0.9300
C15—C14	1.468 (3)	C7—H7	0.9300
C10—C2	1.467 (3)

C4—S1—C2	92.22 (13)	C1—C2—C10	129.5 (2)
C8—S2—C6	92.10 (13)	C1—C2—S1	110.35 (18)
C22—C13—C14	117.7 (2)	C10—C2—S1	119.32 (18)
C22—C13—C11	121.9 (2)	C5—C6—C9	133.1 (2)
C14—C13—C11	120.3 (2)	C5—C6—S2	110.26 (19)
C17—C16—C15	118.8 (2)	C9—C6—S2	116.07 (17)
C17—C16—C12	121.6 (2)	C2—C1—C3	112.8 (2)
C15—C16—C12	119.6 (2)	C2—C1—H1	123.6
C20—N4—C14	117.2 (2)	C3—C1—H1	123.6
N1—C11—C12	120.7 (2)	C6—C5—C7	112.5 (2)
N1—C11—C13	119.1 (2)	C6—C5—H5	123.7
C12—C11—C13	120.2 (2)	C7—C5—H5	123.7
N2—C12—C11	121.0 (2)	C4—C3—C1	113.0 (2)
N2—C12—C16	118.4 (2)	C4—C3—H3	123.5
C11—C12—C16	120.5 (2)	C1—C3—H3	123.5
C10—N1—C11	119.0 (2)	C22—C21—C20	117.9 (3)
N2—C9—C10	119.5 (2)	C22—C21—H21	121.1
N2—C9—C6	113.5 (2)	C20—C21—H21	121.1
C10—C9—C6	126.9 (2)	C7—C8—S2	112.2 (2)
C9—N2—C12	119.1 (2)	C7—C8—H8	123.9
C19—N3—C15	117.3 (2)	S2—C8—H8	123.9
N3—C15—C16	122.1 (2)	N4—C20—C21	124.6 (2)
N3—C15—C14	117.8 (2)	N4—C20—H20	117.7
C16—C15—C14	120.0 (2)	C21—C20—H20	117.7
N4—C14—C13	122.7 (2)	C18—C17—C16	118.9 (2)
N4—C14—C15	118.0 (2)	C18—C17—H17	120.5
C13—C14—C15	119.3 (2)	C16—C17—H17	120.5
N1—C10—C9	120.2 (2)	C3—C4—S1	111.7 (2)
N1—C10—C2	114.8 (2)	C3—C4—H4	124.2
C9—C10—C2	125.0 (2)	S1—C4—H4	124.2
C17—C18—C19	118.3 (2)	C21—C22—C13	119.9 (2)
C17—C18—H18	120.9	C21—C22—H22	120.0
C19—C18—H18	120.9	C13—C22—H22	120.0
N3—C19—C18	124.5 (2)	C8—C7—C5	112.9 (2)
N3—C19—H19	117.7	C8—C7—H7	123.5
C18—C19—H19	117.7	C5—C7—H7	123.5

Experimental details

Crystal data
Chemical formula	C₂₂H₁₂N₄S₂
M_r	396.48
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	27.016 (5), 10.267 (2), 13.835 (3)
β (°)	117.04 (3)
V (Å³)	3418.1 (15)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.30 × 0.30 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.763, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9577, 3867, 3057
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.130, 1.14
No. of reflections	3867
No. of parameters	253
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.45

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

The authors are grateful for financial support from the Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.

References

Aragoni, M. C., Arca, M., Demartin, F., Devillanova, F. A., Isaia, F., Garau, A., Lippolis, V., Jalali, F., Papke, U., Shamsipur, M., Tei, L., Yari, A. & Verani, G. (2002). Inorg. Chem. 41, 6623–6632. Web of Science CSD CrossRef PubMed CAS Google Scholar
Armaroli, N., Cola, L. D., Balzani, V., Sauvage, J. P., Buchecker, C. O. D. & Kern, J. M. (1992). J. Chem. Soc. Faraday Trans. 88, 553–556. CrossRef CAS Web of Science Google Scholar
Bencini, A., Bernardo, M. A., Bianchi, A., Fusi, V., Giorgi, C., Pina, F. & Valtancoli, B. (1999). Eur. J. Inorg. Chem. pp. 1911–1918. CrossRef Google Scholar
Bruker (2005). APEX2 and SAINT. Bruker Axs Inc., Madison, Wisconsin, USA. Google Scholar
Chen, J. P. & Li, X. C. C. (2004). US Patent 6713781 B1. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar