The 1:1 charge-transfer complex dibenzo-tetra-thia-fulvalene-pyromellitic dianhydride (DBTTF-PMDA).

The title charge-transfer (CT) complex, C10H2O6·C14H8S4, composed of donor dibenzo-tetra-thia-fulvalene (DBTTF) and acceptor pyromellitic dianhydride (PMDA), forms a mixed stacking pattern along the [-110] direction. The constituent mol-ecules occupy crystallographic inversion centers. They are nearly parallel and lie ca.3.41 Å from each other. The crystals exhibit a high degree of donor/acceptor overlap [88.20 (4)%] in the long direction of the DBTTF and PMDA mol-ecules as compared with 51.27 (5)% in the shortest direction of the mol-ecules.

Related literature

General properties and potential applications of charge-transfer complexes in electronic devices are outlined by Goetz et al. (2014 ▶); Horiuchi et al. (2006 ▶); Tsutsumi et al. (2012 ▶); Kobayashi et al. (2012 ▶); Kagawa et al. (2010 ▶); Herbstein (2005 ▶); Ferraris et al. (1973 ▶); Kistenmacher et al. (1981 ▶); Takahashi et al. (2006 ▶); Wu et al. (2013 ▶). Related CT structures, containing the acceptor pyromellitic dianhydride (PMDA) include anthracene–PMDA (Robertson & Stezowski, 1978 ▶), phenanthrene–PMDA (Evans & Robinson, 1977 ▶), pyrene–PMDA (Herbstein & Snyman, 1969 ▶) and two polymorphs of bi­phenyl­ene–PMDA (Stezowski et al., 1986 ▶). Structure–property relationships in mol­ecular crystals have been described theoretically by Coropceanu et al. (2007 ▶) and experimentally by Mei et al. (2013 ▶), among others.

Experimental

Crystal data

C10H2O6·C14H8S4

M = 522.56

Triclinic,

a = 7.2292 (4) Å

b = 8.9572 (5) Å

c = 9.5224 (5) Å

α = 70.051 (1)°

β = 68.712 (1)°

γ = 70.136 (1)°

V = 523.39 (5) Å3

Z = 1

Mo Kα radiation

μ = 0.50 mm−1

T = 213 K

0.20 × 0.20 × 0.02 mm

Data collection

Bruker APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2012 ▶) T min = 0.703, T max = 0.746

10004 measured reflections

3023 independent reflections

2668 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.091

S = 1.07

3023 reflections

154 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.33 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2011 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXLS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814013324/pk2526sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013324/pk2526Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814013324/pk2526Isup3.cml

CCDC reference: 1007162

Additional supporting information: crystallographic information; 3D view; checkCIF report

C10H2O6·C14H8S4	Z = 1
Mr = 522.56	F(000) = 266
Triclinic, P1	Dx = 1.658 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2292 (4) Å	Cell parameters from 5268 reflections
b = 8.9572 (5) Å	θ = 3.5–31.3°
c = 9.5224 (5) Å	µ = 0.50 mm−1
α = 70.051 (1)°	T = 213 K
β = 68.712 (1)°	Plate, green-gold
γ = 70.136 (1)°	0.20 × 0.20 × 0.02 mm
V = 523.39 (5) Å3

Bruker APEX CCD diffractometer	3023 independent reflections
Radiation source: sealed x-ray tube	2668 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 30.0°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2012)	h = −10→10
Tmin = 0.703, Tmax = 0.746	k = −12→12
10004 measured reflections	l = −13→13

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H-atom parameters constrained
wR(F2) = 0.091	w = 1/[σ2(Fo2) + (0.0529P)2 + 0.115P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
3023 reflections	Δρmax = 0.30 e Å−3
154 parameters	Δρmin = −0.33 e Å−3
0 restraints

Experimental. Absorption correction: data were corrected for scaling and absorption effects using the multi-scan technique [SADABS (Sheldrick, 2012)]. The ratio of minimum to maximum apparent transmission was 0.942.

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.

	x	y	z	Uiso*/Ueq
S1	−0.06704 (4)	0.15387 (4)	0.15691 (4)	0.02936 (10)
S2	−0.31329 (5)	−0.02880 (4)	0.11851 (4)	0.03025 (10)
C1	−0.08003 (17)	0.02644 (15)	0.05769 (14)	0.0250 (2)
C2	−0.32321 (18)	0.17849 (14)	0.27098 (14)	0.0245 (2)
C3	−0.43823 (18)	0.09185 (14)	0.25298 (14)	0.0246 (2)
C4	−0.64247 (19)	0.10259 (16)	0.34069 (16)	0.0291 (3)
H4	−0.7200	0.0443	0.3290	0.035*
C5	−0.7294 (2)	0.20070 (17)	0.44543 (16)	0.0333 (3)
H5	−0.8672	0.2096	0.5042	0.040*
C6	−0.6146 (2)	0.28587 (17)	0.46427 (15)	0.0332 (3)
H6	−0.6754	0.3511	0.5362	0.040*
C7	−0.4108 (2)	0.27550 (16)	0.37773 (15)	0.0292 (3)
H7	−0.3334	0.3329	0.3909	0.035*
O1	0.08852 (14)	0.63648 (12)	0.27821 (12)	0.0338 (2)
O2	0.30802 (18)	0.75698 (14)	0.29107 (13)	0.0441 (3)
O3	−0.05194 (14)	0.48790 (13)	0.21480 (13)	0.0395 (2)
C8	0.2784 (2)	0.67350 (16)	0.23163 (15)	0.0301 (3)
C9	0.41355 (18)	0.59058 (14)	0.10654 (14)	0.0237 (2)
C10	0.30252 (17)	0.50435 (14)	0.08434 (14)	0.0237 (2)
C11	0.09415 (18)	0.53456 (16)	0.19353 (15)	0.0282 (2)
C12	0.61565 (17)	0.58997 (14)	0.02281 (14)	0.0252 (2)
H12	0.6905	0.6484	0.0375	0.030*

	U11	U22	U33	U12	U13	U23
S1	0.02281 (15)	0.03348 (17)	0.03676 (18)	−0.00701 (12)	−0.00525 (12)	−0.01796 (14)
S2	0.02316 (15)	0.03528 (18)	0.03745 (19)	−0.00885 (12)	−0.00331 (12)	−0.01913 (14)
C1	0.0214 (5)	0.0260 (5)	0.0281 (6)	−0.0048 (4)	−0.0051 (4)	−0.0102 (5)
C2	0.0249 (5)	0.0227 (5)	0.0237 (5)	−0.0048 (4)	−0.0055 (4)	−0.0057 (4)
C3	0.0234 (5)	0.0239 (5)	0.0246 (5)	−0.0043 (4)	−0.0059 (4)	−0.0062 (4)
C4	0.0249 (5)	0.0291 (6)	0.0303 (6)	−0.0072 (5)	−0.0050 (5)	−0.0060 (5)
C5	0.0282 (6)	0.0341 (7)	0.0274 (6)	−0.0061 (5)	0.0008 (5)	−0.0063 (5)
C6	0.0378 (7)	0.0298 (6)	0.0255 (6)	−0.0067 (5)	−0.0007 (5)	−0.0094 (5)
C7	0.0347 (6)	0.0266 (6)	0.0261 (6)	−0.0084 (5)	−0.0059 (5)	−0.0083 (5)
O1	0.0265 (4)	0.0378 (5)	0.0343 (5)	−0.0065 (4)	0.0015 (4)	−0.0179 (4)
O2	0.0466 (6)	0.0508 (6)	0.0436 (6)	−0.0154 (5)	−0.0036 (5)	−0.0288 (5)
O3	0.0246 (5)	0.0465 (6)	0.0462 (6)	−0.0133 (4)	−0.0009 (4)	−0.0153 (5)
C8	0.0295 (6)	0.0318 (6)	0.0280 (6)	−0.0075 (5)	−0.0028 (5)	−0.0119 (5)
C9	0.0242 (5)	0.0249 (5)	0.0228 (5)	−0.0061 (4)	−0.0051 (4)	−0.0082 (4)
C10	0.0204 (5)	0.0253 (5)	0.0239 (5)	−0.0065 (4)	−0.0048 (4)	−0.0050 (4)
C11	0.0234 (5)	0.0288 (6)	0.0287 (6)	−0.0054 (4)	−0.0031 (4)	−0.0084 (5)
C12	0.0239 (5)	0.0270 (6)	0.0274 (6)	−0.0082 (4)	−0.0065 (4)	−0.0086 (5)

S1—C1	1.7543 (13)	C6—H6	0.9400
S1—C2	1.7560 (12)	C7—H7	0.9400
S2—C3	1.7505 (13)	O1—C11	1.3923 (16)
S2—C1	1.7567 (12)	O1—C8	1.3993 (16)
C1—C1i	1.353 (2)	O2—C8	1.1878 (17)
C2—C7	1.3967 (17)	O3—C11	1.1907 (16)
C2—C3	1.3985 (17)	C8—C9	1.4800 (17)
C3—C4	1.3963 (16)	C9—C12	1.3864 (16)
C4—C5	1.3892 (19)	C9—C10	1.3933 (16)
C4—H4	0.9400	C10—C12ii	1.3839 (16)
C5—C6	1.391 (2)	C10—C11	1.4836 (16)
C5—H5	0.9400	C12—C10ii	1.3838 (16)
C6—C7	1.3913 (19)	C12—H12	0.9400
C1—S1—C2	95.38 (6)	C6—C7—C2	118.93 (13)
C3—S2—C1	95.34 (6)	C6—C7—H7	120.5
C1i—C1—S1	122.00 (13)	C2—C7—H7	120.5
C1i—C1—S2	122.26 (13)	C11—O1—C8	110.17 (10)
S1—C1—S2	115.74 (6)	O2—C8—O1	121.25 (13)
C7—C2—C3	120.37 (11)	O2—C8—C9	131.52 (13)
C7—C2—S1	123.12 (10)	O1—C8—C9	107.23 (11)
C3—C2—S1	116.50 (9)	C12—C9—C10	122.97 (11)
C4—C3—C2	120.30 (12)	C12—C9—C8	129.32 (11)
C4—C3—S2	122.83 (10)	C10—C9—C8	107.70 (10)
C2—C3—S2	116.88 (9)	C12ii—C10—C9	123.01 (10)
C5—C4—C3	119.04 (12)	C12ii—C10—C11	129.51 (11)
C5—C4—H4	120.5	C9—C10—C11	107.48 (11)
C3—C4—H4	120.5	O3—C11—O1	121.29 (12)
C4—C5—C6	120.69 (12)	O3—C11—C10	131.31 (13)
C4—C5—H5	119.7	O1—C11—C10	107.40 (10)
C6—C5—H5	119.7	C10ii—C12—C9	114.03 (10)
C5—C6—C7	120.66 (13)	C10ii—C12—H12	123.0
C5—C6—H6	119.7	C9—C12—H12	123.0
C7—C6—H6	119.7
C2—S1—C1—C1i	176.20 (15)	C11—O1—C8—O2	−178.78 (13)
C2—S1—C1—S2	−4.14 (8)	C11—O1—C8—C9	0.82 (14)
C3—S2—C1—C1i	−176.37 (15)	O2—C8—C9—C12	−0.6 (2)
C3—S2—C1—S1	3.97 (8)	O1—C8—C9—C12	179.86 (12)
C1—S1—C2—C7	−178.74 (11)	O2—C8—C9—C10	178.37 (15)
C1—S1—C2—C3	2.71 (10)	O1—C8—C9—C10	−1.17 (14)
C7—C2—C3—C4	0.54 (18)	C12—C9—C10—C12ii	0.2 (2)
S1—C2—C3—C4	179.13 (9)	C8—C9—C10—C12ii	−178.82 (11)
C7—C2—C3—S2	−179.00 (9)	C12—C9—C10—C11	−179.90 (11)
S1—C2—C3—S2	−0.41 (13)	C8—C9—C10—C11	1.05 (13)
C1—S2—C3—C4	178.35 (11)	C8—O1—C11—O3	179.96 (12)
C1—S2—C3—C2	−2.12 (10)	C8—O1—C11—C10	−0.18 (14)
C2—C3—C4—C5	0.16 (18)	C12ii—C10—C11—O3	−0.9 (2)
S2—C3—C4—C5	179.68 (10)	C9—C10—C11—O3	179.27 (14)
C3—C4—C5—C6	−0.7 (2)	C12ii—C10—C11—O1	179.29 (12)
C4—C5—C6—C7	0.5 (2)	C9—C10—C11—O1	−0.57 (13)
C5—C6—C7—C2	0.2 (2)	C10—C9—C12—C10ii	−0.21 (19)
C3—C2—C7—C6	−0.73 (18)	C8—C9—C12—C10ii	178.62 (12)
S1—C2—C7—C6	−179.23 (10)