Structure and degree of charge transfer of two polymorphs of a 1:1 molecular complex: [2,2′-bis-1,3-dithiole][9-dicyanomethylene-4,5,7-trinitrofluorene-2-carboxylic acid methyl ester] (TTF-MeDC2TNF)

Salmerón-Valverde, A.; Bernès, S.; Robles-Martínez, J.G.

doi:10.1107/S0108768103011893

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Structure and degree of charge transfer of two polymorphs of a 1:1 molecular complex: [2,2′-bis-1,3-dithiole][9-dicyanomethylene-4,5,7-trinitrofluorene-2-carboxylic acid methyl ester] (TTF-MeDC2TNF)

A. Salmerón-Valverde, S. Bernès and J. G. Robles-Martínez

A new organic charge-transfer complex, C₁₈H₇N₅O₈·C₆H₄S₄, has been prepared using TTF (tetrathiafulvalene) as a donor (D) and MeDC2TNF (9-dicyanomethylene-4,5,7-trinitro-fluorene-2-carboxylic acid methyl ester) as an acceptor (A). Two monoclinic polymorphs of the 1:1 salt were crystallized and characterized by X-ray diffraction. Form α crystallizes in space group P2₁/n with Z′ = 1, while form β crystallizes in space group C2/c with Z′ = $1\over 2$ and the MeDC2TNF moiety disordered across a twofold axis. Both phases have mixed-stack crystal packings, which are characteristic of semiconducting one-dimensional organic complexes. However, the observed crystal packings are significantly different, with a single D

A interlayer separation of 3.452 Å for the disordered β polymorph and interlayer separations of 3.378 and 3.483 Å in the case of the ordered α form. These variations are reflected in the degree of charge transfer, δ, which was estimated on the basis of the b_2u stretching-mode frequency shift observed in the IR spectra for the cyano groups of the MeDC2TNF radical anion. The fact that the charge transfer is more efficient for α-(TTF-MeDC2TNF) than for β-(TTF-MeDC2TNF) (δ = 0.35 and 0.31, respectively) is consistent with the structural features observed for each crystalline form.

Keywords: polymorphism; charge-transfer complex; organic conductor; TTF.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768103011893/sn5000sup1.cif Contains datablocks cdc2tnf, cdc2tnfb, global
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768103011893/sn5000cdc2tnfsup2.hkl Contains datablock cdc2tnf
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768103011893/sn5000cdc2tnfbsup3.hkl Contains datablock cdc2tnfb

CCDC references: 219305; 219306

Computing details top

For both compounds, data collection: XSCANS 2.21 (Siemens, 1996); cell refinement: XSCANS 2.21 (Siemens, 1996); data reduction: XSCANS 2.21 (Siemens, 1996); program(s) used to solve structure: SHELXTL 5.10 (Sheldrick, 1998); program(s) used to refine structure: SHELX97 (Sheldrick, 1997); molecular graphics: SHELXTL 5.10 (Sheldrick, 1998); software used to prepare material for publication: SHELX97 (Sheldrick, 1997).

Figures top

(cdc2tnf) [2,2'-Bis-1,3-dithiole][9-dicyanomethylene-4,5,7- trinitro-fluorene-2-carboxylic acid methyl ester] top

Crystal data top

C₁₈H₇N₅O₈·C₆H₄S₄	F(000) = 1272
M_r = 625.62	D_x = 1.616 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 60 reflections
a = 6.7816 (17) Å	θ = 4.7–11.1°
b = 30.572 (4) Å	µ = 0.43 mm⁻¹
c = 12.4381 (13) Å	T = 296 K
β = 94.304 (11)°	Needle, dark brown
V = 2571.5 (8) Å³	0.70 × 0.16 × 0.08 mm
Z = 4

Data collection top

Bruker P4 diffractometer	θ_max = 25.0°, θ_min = 1.8°
Graphite monochromator	h = −8→1
2θ/ω scans	k = −1→36
5958 measured reflections	l = −14→14
4503 independent reflections	2 standard reflections every 48 reflections
3133 reflections with I > 2σ(I)	intensity decay: 1%
R_int = 0.041

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0585P)² + 5.5383P] where P = (F_o² + 2F_c²)/3
4503 reflections	(Δ/σ)_max = 0.001
370 parameters	Δρ_max = 0.66 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₈H₇N₅O₈·C₆H₄S₄	V = 2571.5 (8) Å³
M_r = 625.62	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7816 (17) Å	µ = 0.43 mm⁻¹
b = 30.572 (4) Å	T = 296 K
c = 12.4381 (13) Å	0.70 × 0.16 × 0.08 mm
β = 94.304 (11)°

Data collection top

Bruker P4 diffractometer	R_int = 0.041
5958 measured reflections	2 standard reflections every 48 reflections
4503 independent reflections	intensity decay: 1%
3133 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.169	H-atom parameters constrained
S = 1.06	Δρ_max = 0.66 e Å⁻³
4503 reflections	Δρ_min = −0.35 e Å⁻³
370 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
C1	0.2976 (7)	0.55190 (15)	0.2132 (3)	0.0367 (11)
H1A	0.3170	0.5423	0.2842	0.044*
C2	0.2778 (7)	0.52171 (14)	0.1290 (4)	0.0357 (11)
C3	0.2453 (7)	0.53659 (15)	0.0241 (4)	0.0409 (12)
H3A	0.2298	0.5165	−0.0321	0.049*
C4	0.2354 (7)	0.58046 (16)	0.0019 (3)	0.0387 (11)
C4A	0.2669 (6)	0.61197 (15)	0.0839 (3)	0.0317 (10)
C4B	0.2786 (7)	0.66021 (15)	0.0875 (3)	0.0333 (10)
C5	0.2852 (8)	0.69395 (16)	0.0124 (4)	0.0433 (12)
C6	0.2846 (8)	0.73740 (17)	0.0417 (4)	0.0474 (13)
H6A	0.2851	0.7593	−0.0101	0.057*
C7	0.2833 (8)	0.74778 (16)	0.1505 (4)	0.0444 (12)
C8	0.2890 (7)	0.71643 (14)	0.2293 (4)	0.0372 (11)
H8A	0.2938	0.7241	0.3018	0.045*
C8A	0.2875 (7)	0.67244 (14)	0.1973 (3)	0.0325 (10)
C9	0.2953 (7)	0.63326 (14)	0.2656 (3)	0.0316 (10)
C9A	0.2883 (7)	0.59582 (14)	0.1907 (3)	0.0317 (10)
C10	0.3050 (7)	0.63167 (15)	0.3760 (4)	0.0371 (11)
C11	0.3050 (8)	0.59168 (18)	0.4366 (4)	0.0437 (12)
N12	0.3027 (7)	0.56037 (16)	0.4868 (4)	0.0593 (13)
C13	0.3087 (9)	0.67029 (17)	0.4438 (4)	0.0509 (14)
N14	0.3088 (11)	0.69944 (19)	0.4987 (4)	0.095 (2)
C15	0.2863 (8)	0.47399 (16)	0.1481 (4)	0.0437 (12)
O16	0.2636 (8)	0.44730 (12)	0.0774 (3)	0.0776 (14)
O17	0.3190 (7)	0.46362 (11)	0.2507 (3)	0.0637 (11)
C18	0.3325 (13)	0.4170 (2)	0.2796 (5)	0.085 (2)
H18A	0.3564	0.4141	0.3563	0.128*
H18B	0.4392	0.4038	0.2448	0.128*
H18C	0.2107	0.4026	0.2565	0.128*
N19	0.1603 (8)	0.59223 (17)	−0.1088 (3)	0.0603 (13)
O20	0.0540 (6)	0.62625 (15)	−0.1203 (3)	0.0646 (11)
O21	0.1964 (8)	0.56729 (14)	−0.1819 (3)	0.0788 (14)
N22	0.3245 (9)	0.68566 (17)	−0.1014 (4)	0.0666 (15)
O23	0.4336 (7)	0.65394 (17)	−0.1197 (3)	0.0735 (13)
O24	0.2499 (9)	0.71146 (14)	−0.1688 (3)	0.0909 (17)
N25	0.2803 (8)	0.79436 (15)	0.1820 (4)	0.0630 (13)
O26	0.2897 (10)	0.82204 (14)	0.1126 (4)	0.1025 (19)
O27	0.2651 (8)	0.80272 (13)	0.2769 (4)	0.0840 (15)
S28	0.7867 (2)	0.54576 (4)	0.22884 (10)	0.0437 (3)
C29	0.7882 (8)	0.51976 (17)	0.3516 (5)	0.0536 (14)
H29A	0.7869	0.4894	0.3560	0.064*
C30	0.7911 (9)	0.5443 (2)	0.4401 (5)	0.0610 (16)
H30A	0.7902	0.5317	0.5082	0.073*
S31	0.7969 (2)	0.60078 (4)	0.42341 (9)	0.0473 (4)
C32	0.7880 (7)	0.59870 (16)	0.2825 (4)	0.0378 (11)
C33	0.7832 (7)	0.63553 (15)	0.2216 (3)	0.0346 (10)
S34	0.79314 (19)	0.68820 (4)	0.27898 (9)	0.0386 (3)
C35	0.7895 (7)	0.71523 (17)	0.1555 (4)	0.0430 (12)
H35A	0.7938	0.7456	0.1520	0.052*
C36	0.7806 (8)	0.69119 (17)	0.0670 (4)	0.0447 (12)
H36A	0.7800	0.7041	−0.0007	0.054*
S37	0.7699 (2)	0.63441 (4)	0.08083 (9)	0.0412 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.048 (3)	0.035 (3)	0.026 (2)	0.000 (2)	−0.002 (2)	0.0002 (19)
C2	0.042 (3)	0.029 (2)	0.037 (3)	0.000 (2)	0.004 (2)	−0.0026 (19)
C3	0.054 (3)	0.036 (3)	0.032 (3)	−0.006 (2)	0.003 (2)	−0.011 (2)
C4	0.055 (3)	0.042 (3)	0.019 (2)	0.000 (2)	0.001 (2)	−0.0034 (19)
C4A	0.031 (2)	0.036 (3)	0.028 (2)	0.000 (2)	0.0017 (18)	−0.0009 (19)
C4B	0.037 (3)	0.034 (2)	0.028 (2)	0.001 (2)	−0.0010 (19)	−0.0002 (19)
C5	0.060 (3)	0.037 (3)	0.033 (3)	−0.005 (2)	0.000 (2)	0.004 (2)
C6	0.061 (3)	0.040 (3)	0.040 (3)	0.000 (2)	−0.003 (2)	0.012 (2)
C7	0.047 (3)	0.030 (3)	0.055 (3)	−0.003 (2)	−0.003 (2)	−0.003 (2)
C8	0.047 (3)	0.032 (3)	0.033 (2)	0.001 (2)	0.005 (2)	−0.007 (2)
C8A	0.035 (2)	0.033 (2)	0.029 (2)	0.0006 (19)	−0.0002 (19)	0.0017 (18)
C9	0.037 (3)	0.033 (2)	0.025 (2)	−0.001 (2)	0.0015 (19)	−0.0019 (18)
C9A	0.038 (3)	0.034 (3)	0.023 (2)	0.001 (2)	0.0015 (18)	−0.0026 (18)
C10	0.047 (3)	0.037 (3)	0.027 (2)	0.001 (2)	−0.001 (2)	−0.0075 (19)
C11	0.054 (3)	0.050 (3)	0.027 (2)	−0.002 (2)	0.002 (2)	−0.004 (2)
N12	0.077 (3)	0.058 (3)	0.043 (3)	−0.003 (3)	0.004 (2)	0.015 (2)
C13	0.084 (4)	0.043 (3)	0.025 (2)	0.004 (3)	0.003 (2)	−0.005 (2)
N14	0.178 (7)	0.063 (4)	0.042 (3)	−0.009 (4)	0.005 (3)	−0.023 (3)
C15	0.060 (3)	0.033 (3)	0.038 (3)	−0.001 (2)	0.002 (2)	−0.005 (2)
O16	0.150 (4)	0.035 (2)	0.046 (2)	−0.009 (2)	−0.005 (2)	−0.0126 (18)
O17	0.115 (3)	0.035 (2)	0.040 (2)	0.000 (2)	−0.007 (2)	0.0005 (16)
C18	0.144 (7)	0.046 (4)	0.064 (4)	−0.006 (4)	−0.007 (4)	0.002 (3)
N19	0.092 (4)	0.057 (3)	0.030 (2)	−0.005 (3)	−0.004 (2)	−0.002 (2)
O20	0.072 (3)	0.083 (3)	0.037 (2)	−0.006 (2)	−0.0092 (19)	0.011 (2)
O21	0.141 (4)	0.068 (3)	0.0272 (19)	0.004 (3)	0.003 (2)	−0.0154 (19)
N22	0.113 (5)	0.051 (3)	0.036 (3)	−0.012 (3)	0.008 (3)	0.004 (2)
O23	0.088 (3)	0.097 (4)	0.038 (2)	−0.006 (3)	0.018 (2)	−0.008 (2)
O24	0.175 (5)	0.057 (3)	0.038 (2)	−0.001 (3)	−0.010 (3)	0.023 (2)
N25	0.076 (4)	0.037 (3)	0.075 (4)	0.001 (2)	0.000 (3)	−0.003 (3)
O26	0.189 (6)	0.036 (2)	0.080 (3)	−0.006 (3)	−0.006 (3)	0.015 (2)
O27	0.129 (4)	0.043 (2)	0.082 (3)	0.007 (3)	0.017 (3)	−0.016 (2)
S28	0.0540 (8)	0.0377 (7)	0.0397 (7)	−0.0009 (6)	0.0049 (6)	−0.0042 (5)
C29	0.069 (4)	0.036 (3)	0.057 (4)	0.000 (3)	0.009 (3)	0.010 (3)
C30	0.078 (4)	0.059 (4)	0.045 (3)	0.005 (3)	−0.003 (3)	0.019 (3)
S31	0.0636 (9)	0.0484 (8)	0.0295 (6)	0.0016 (6)	0.0009 (6)	0.0008 (5)
C32	0.040 (3)	0.043 (3)	0.030 (2)	0.001 (2)	0.002 (2)	−0.004 (2)
C33	0.038 (3)	0.039 (3)	0.026 (2)	−0.002 (2)	0.0008 (19)	−0.0054 (19)
S34	0.0495 (7)	0.0373 (7)	0.0290 (6)	−0.0028 (5)	0.0026 (5)	−0.0040 (5)
C35	0.053 (3)	0.040 (3)	0.036 (3)	−0.002 (2)	0.002 (2)	0.007 (2)
C36	0.054 (3)	0.045 (3)	0.035 (3)	−0.005 (2)	0.002 (2)	0.012 (2)
S37	0.0529 (8)	0.0437 (7)	0.0269 (6)	−0.0005 (6)	0.0024 (5)	−0.0054 (5)

Geometric parameters (Å, º) top

C1—C9A	1.372 (6)	N19—O20	1.268 (6)
C1—C2	1.395 (6)	N22—O24	1.232 (6)
C2—C3	1.384 (6)	N22—O23	1.251 (7)
C2—C15	1.479 (7)	N25—O26	1.213 (6)
C3—C4	1.370 (7)	N25—O27	1.220 (6)
C4—C4A	1.407 (6)	S28—C29	1.721 (5)
C4—N19	1.476 (6)	S28—C32	1.750 (5)
C4A—C9A	1.415 (6)	C29—C30	1.330 (8)
C4A—C4B	1.478 (6)	C30—S31	1.740 (6)
C4B—C5	1.395 (6)	S31—C32	1.751 (5)
C4B—C8A	1.413 (6)	C32—C33	1.356 (6)
C5—C6	1.378 (7)	C33—S37	1.747 (4)
C5—N22	1.481 (7)	C33—S34	1.760 (4)
C6—C7	1.390 (7)	S34—C35	1.743 (5)
C7—C8	1.370 (7)	C35—C36	1.321 (7)
C7—N25	1.478 (7)	C36—S37	1.746 (5)
C8—C8A	1.403 (6)	C1—H1A	0.9300
C8A—C9	1.467 (6)	C3—H3A	0.9300
C9—C10	1.371 (6)	C6—H6A	0.9300
C9—C9A	1.474 (6)	C8—H8A	0.9300
C10—C11	1.436 (7)	C18—H18A	0.9600
C10—C13	1.451 (7)	C18—H18B	0.9600
C11—N12	1.144 (6)	C18—H18C	0.9600
C13—N14	1.122 (7)	C29—H29A	0.9300
C15—O16	1.201 (6)	C30—H30A	0.9300
C15—O17	1.318 (6)	C35—H35A	0.9300
O17—C18	1.471 (7)	C36—H36A	0.9300
N19—O21	1.225 (6)

C9A—C1—C2	119.6 (4)	O24—N22—O23	126.2 (5)
C3—C2—C1	119.3 (4)	O24—N22—C5	116.5 (5)
C3—C2—C15	118.5 (4)	O23—N22—C5	117.3 (5)
C1—C2—C15	122.1 (4)	O26—N25—O27	123.7 (5)
C4—C3—C2	120.9 (4)	O26—N25—C7	118.7 (5)
C3—C4—C4A	121.4 (4)	O27—N25—C7	117.6 (5)
C3—C4—N19	115.8 (4)	C29—S28—C32	95.1 (2)
C4A—C4—N19	122.1 (4)	C30—C29—S28	118.2 (4)
C4—C4A—C9A	116.2 (4)	C29—C30—S31	117.4 (4)
C4—C4A—C4B	135.2 (4)	C30—S31—C32	94.8 (3)
C9A—C4A—C4B	108.6 (4)	C33—C32—S28	123.8 (3)
C5—C4B—C8A	116.8 (4)	C33—C32—S31	121.8 (4)
C5—C4B—C4A	136.2 (4)	S28—C32—S31	114.5 (3)
C8A—C4B—C4A	107.0 (4)	C32—C33—S37	122.7 (3)
C6—C5—C4B	122.3 (4)	C32—C33—S34	122.3 (3)
C6—C5—N22	115.0 (4)	S37—C33—S34	114.9 (3)
C4B—C5—N22	122.0 (4)	C35—S34—C33	94.5 (2)
C5—C6—C7	118.6 (4)	C36—C35—S34	117.8 (4)
C8—C7—C6	122.4 (4)	C35—C36—S37	118.1 (4)
C8—C7—N25	119.0 (5)	C36—S37—C33	94.6 (2)
C6—C7—N25	118.6 (5)	C9A—C1—H1A	120.2
C7—C8—C8A	117.9 (4)	C2—C1—H1A	120.2
C8—C8A—C4B	121.8 (4)	C4—C3—H3A	119.5
C8—C8A—C9	128.2 (4)	C2—C3—H3A	119.5
C4B—C8A—C9	109.9 (4)	C5—C6—H6A	120.7
C10—C9—C8A	127.3 (4)	C7—C6—H6A	120.7
C10—C9—C9A	127.0 (4)	C7—C8—H8A	121.0
C8A—C9—C9A	105.7 (3)	C8A—C8—H8A	121.0
C1—C9A—C4A	122.2 (4)	O17—C18—H18A	109.5
C1—C9A—C9	129.2 (4)	O17—C18—H18B	109.5
C4A—C9A—C9	108.6 (4)	H18A—C18—H18B	109.5
C9—C10—C11	123.7 (4)	O17—C18—H18C	109.5
C9—C10—C13	123.5 (4)	H18A—C18—H18C	109.5
C11—C10—C13	112.8 (4)	H18B—C18—H18C	109.5
N12—C11—C10	178.3 (5)	C30—C29—H29A	120.9
N14—C13—C10	177.9 (6)	S28—C29—H29A	120.9
O16—C15—O17	123.3 (5)	C29—C30—H30A	121.3
O16—C15—C2	123.4 (5)	S31—C30—H30A	121.3
O17—C15—C2	113.2 (4)	C36—C35—H35A	121.1
C15—O17—C18	118.2 (4)	S34—C35—H35A	121.1
O21—N19—O20	124.8 (5)	C35—C36—H36A	121.0
O21—N19—C4	117.8 (5)	S37—C36—H36A	121.0
O20—N19—C4	117.3 (4)

C9A—C1—C2—C3	−1.2 (7)	C8A—C9—C10—C11	177.6 (5)
C9A—C1—C2—C15	−180.0 (5)	C9A—C9—C10—C11	−1.7 (8)
C1—C2—C3—C4	1.0 (7)	C8A—C9—C10—C13	0.2 (8)
C15—C2—C3—C4	179.8 (5)	C9A—C9—C10—C13	−179.1 (5)
C2—C3—C4—C4A	3.0 (8)	C9—C10—C11—N12	−15E1 (2)
C2—C3—C4—N19	−167.9 (5)	C13—C10—C11—N12	3E1 (2)
C3—C4—C4A—C9A	−6.4 (7)	C9—C10—C13—N14	152 (19)
N19—C4—C4A—C9A	163.9 (4)	C11—C10—C13—N14	−25 (19)
C3—C4—C4A—C4B	175.8 (5)	C3—C2—C15—O16	−1.1 (8)
N19—C4—C4A—C4B	−13.9 (8)	C1—C2—C15—O16	177.6 (5)
C4—C4A—C4B—C5	−8.7 (10)	C3—C2—C15—O17	179.7 (5)
C9A—C4A—C4B—C5	173.3 (5)	C1—C2—C15—O17	−1.6 (7)
C4—C4A—C4B—C8A	172.3 (5)	O16—C15—O17—C18	1.4 (9)
C9A—C4A—C4B—C8A	−5.6 (5)	C2—C15—O17—C18	−179.4 (5)
C8A—C4B—C5—C6	−5.0 (7)	C3—C4—N19—O21	−32.5 (7)
C4A—C4B—C5—C6	176.1 (5)	C4A—C4—N19—O21	156.6 (5)
C8A—C4B—C5—N22	165.3 (5)	C3—C4—N19—O20	143.7 (5)
C4A—C4B—C5—N22	−13.6 (9)	C4A—C4—N19—O20	−27.1 (7)
C4B—C5—C6—C7	1.9 (8)	C6—C5—N22—O24	−38.5 (8)
N22—C5—C6—C7	−169.0 (5)	C4B—C5—N22—O24	150.5 (5)
C5—C6—C7—C8	2.2 (8)	C6—C5—N22—O23	139.9 (5)
C5—C6—C7—N25	−179.3 (5)	C4B—C5—N22—O23	−31.1 (8)
C6—C7—C8—C8A	−2.8 (8)	C8—C7—N25—O26	174.7 (6)
N25—C7—C8—C8A	178.7 (4)	C6—C7—N25—O26	−3.9 (8)
C7—C8—C8A—C4B	−0.5 (7)	C8—C7—N25—O27	−6.4 (8)
C7—C8—C8A—C9	179.1 (5)	C6—C7—N25—O27	175.0 (5)
C5—C4B—C8A—C8	4.3 (7)	C32—S28—C29—C30	−0.5 (5)
C4A—C4B—C8A—C8	−176.5 (4)	S28—C29—C30—S31	−0.9 (7)
C5—C4B—C8A—C9	−175.4 (4)	C29—C30—S31—C32	1.8 (5)
C4A—C4B—C8A—C9	3.8 (5)	C29—S28—C32—C33	−178.5 (5)
C8—C8A—C9—C10	0.3 (8)	C29—S28—C32—S31	1.7 (3)
C4B—C8A—C9—C10	179.9 (5)	C30—S31—C32—C33	178.2 (4)
C8—C8A—C9—C9A	179.7 (5)	C30—S31—C32—S28	−2.1 (3)
C4B—C8A—C9—C9A	−0.6 (5)	S28—C32—C33—S37	1.4 (6)
C2—C1—C9A—C4A	−2.6 (7)	S31—C32—C33—S37	−178.8 (3)
C2—C1—C9A—C9	176.7 (4)	S28—C32—C33—S34	−177.8 (3)
C4—C4A—C9A—C1	6.2 (7)	S31—C32—C33—S34	2.0 (6)
C4B—C4A—C9A—C1	−175.4 (4)	C32—C33—S34—C35	178.0 (4)
C4—C4A—C9A—C9	−173.1 (4)	S37—C33—S34—C35	−1.3 (3)
C4B—C4A—C9A—C9	5.3 (5)	C33—S34—C35—C36	0.3 (5)
C10—C9—C9A—C1	−2.8 (8)	S34—C35—C36—S37	0.8 (6)
C8A—C9—C9A—C1	177.8 (5)	C35—C36—S37—C33	−1.4 (5)
C10—C9—C9A—C4A	176.5 (5)	C32—C33—S37—C36	−177.7 (4)
C8A—C9—C9A—C4A	−2.9 (5)	S34—C33—S37—C36	1.6 (3)

(cdc2tnfb) [2,2'-Bis-1,3-dithiole][9-dicyanomethylene-4,5,7- trinitro-fluorene-2-carboxylic acid methyl ester] top

Crystal data top

C₁₈H₇N₅O₈·C₆H₄S₄	F(000) = 1272
M_r = 625.62	D_x = 1.607 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 70 reflections
a = 15.2489 (14) Å	θ = 4.3–11.9°
b = 12.692 (1) Å	µ = 0.43 mm⁻¹
c = 13.7950 (13) Å	T = 296 K
β = 104.350 (7)°	Block, dark brown
V = 2586.6 (4) Å³	0.40 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker P4 diffractometer	R_int = 0.020
Graphite monochromator	θ_max = 25.0°, θ_min = 2.1°
2θ/ω scans	h = −18→6
Absorption correction: ψ scan XSCANS 2.21 (Siemens, 1996)	k = −15→1
T_min = 0.890, T_max = 0.926	l = −16→16
3590 measured reflections	2 standard reflections every 48 reflections
2274 independent reflections	intensity decay: 1%
1768 reflections with I > 2σ(I)

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0359P)² + 3.2371P] where P = (F_o² + 2F_c²)/3
2274 reflections	(Δ/σ)_max < 0.001
218 parameters	Δρ_max = 0.25 e Å⁻³
7 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₈H₇N₅O₈·C₆H₄S₄	V = 2586.6 (4) Å³
M_r = 625.62	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.2489 (14) Å	µ = 0.43 mm⁻¹
b = 12.692 (1) Å	T = 296 K
c = 13.7950 (13) Å	0.40 × 0.20 × 0.18 mm
β = 104.350 (7)°

Data collection top

Bruker P4 diffractometer	1768 reflections with I > 2σ(I)
Absorption correction: ψ scan XSCANS 2.21 (Siemens, 1996)	R_int = 0.020
T_min = 0.890, T_max = 0.926	2 standard reflections every 48 reflections
3590 measured reflections	intensity decay: 1%
2274 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	7 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.05	Δρ_max = 0.25 e Å⁻³
2274 reflections	Δρ_min = −0.26 e Å⁻³
218 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.33426 (18)	0.4681 (2)	0.66201 (19)	0.0366 (6)
H1A	0.3174	0.5382	0.6499	0.044*
C2	0.27175 (18)	0.3887 (2)	0.6318 (2)	0.0421 (7)
C3	0.29481 (19)	0.2842 (2)	0.6552 (2)	0.0444 (7)
H3A	0.2514	0.2315	0.6376	0.053*
C4	0.38232 (19)	0.2593 (2)	0.70446 (19)	0.0375 (6)
C5	0.45035 (17)	0.3354 (2)	0.72824 (18)	0.0321 (6)
C6	0.42279 (16)	0.4420 (2)	0.71072 (17)	0.0298 (6)
C7	0.5000	0.5113 (3)	0.7500	0.0307 (8)
C8	0.5000	0.6200 (3)	0.7500	0.0356 (9)
C9	0.4190 (2)	0.6819 (2)	0.7201 (2)	0.0439 (7)
N10	0.3560 (2)	0.7330 (2)	0.6981 (2)	0.0689 (8)
N11	0.1810 (9)	0.4095 (10)	0.5688 (18)	0.048 (5)	0.50
O12	0.1321 (11)	0.3341 (15)	0.5386 (15)	0.076 (4)	0.50
O13	0.1638 (13)	0.5072 (15)	0.5662 (18)	0.078 (6)	0.50
C14	0.1751 (11)	0.4175 (18)	0.583 (2)	0.074 (9)	0.50
O15	0.1159 (13)	0.3513 (16)	0.5616 (19)	0.114 (7)	0.50
O16	0.1603 (10)	0.5098 (11)	0.5415 (16)	0.045 (2)	0.50
C17	0.0699 (5)	0.5295 (7)	0.4845 (6)	0.086 (3)	0.50
H17A	0.0616	0.6038	0.4727	0.129*	0.50
H17B	0.0278	0.5048	0.5208	0.129*	0.50
H17C	0.0595	0.4932	0.4216	0.129*	0.50
N18	0.39646 (18)	0.1501 (2)	0.7409 (2)	0.0510 (7)
O19	0.35021 (18)	0.08123 (18)	0.6914 (2)	0.0835 (8)
O20	0.45130 (16)	0.13580 (17)	0.82109 (17)	0.0601 (6)
S21	0.46610 (5)	0.66761 (6)	0.48993 (6)	0.0444 (2)
C22	0.3510 (2)	0.6833 (3)	0.4384 (2)	0.0505 (8)
H22A	0.3249	0.7499	0.4312	0.061*
C23	0.3010 (2)	0.5978 (3)	0.4095 (2)	0.0491 (8)
H23A	0.2392	0.6026	0.3804	0.059*
S24	0.35557 (5)	0.47723 (6)	0.42836 (5)	0.0405 (2)
C25	0.46282 (17)	0.5302 (2)	0.48226 (18)	0.0330 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0321 (15)	0.0393 (15)	0.0386 (14)	0.0020 (14)	0.0090 (12)	−0.0007 (12)
C2	0.0282 (15)	0.0562 (19)	0.0409 (15)	−0.0015 (14)	0.0065 (12)	0.0004 (14)
C3	0.0342 (16)	0.0536 (19)	0.0438 (16)	−0.0168 (14)	0.0068 (13)	−0.0052 (14)
C4	0.0399 (16)	0.0352 (15)	0.0382 (14)	−0.0075 (13)	0.0113 (12)	−0.0023 (12)
C5	0.0315 (14)	0.0349 (15)	0.0298 (13)	−0.0011 (12)	0.0074 (11)	−0.0012 (11)
C6	0.0258 (14)	0.0340 (14)	0.0299 (12)	−0.0005 (11)	0.0076 (11)	−0.0012 (11)
C7	0.0257 (19)	0.036 (2)	0.0306 (17)	0.000	0.0067 (15)	0.000
C8	0.037 (2)	0.032 (2)	0.039 (2)	0.000	0.0110 (17)	0.000
C9	0.0474 (19)	0.0347 (16)	0.0485 (17)	0.0031 (15)	0.0101 (14)	−0.0008 (13)
N10	0.064 (2)	0.0557 (18)	0.084 (2)	0.0246 (17)	0.0127 (16)	0.0071 (16)
N11	0.040 (8)	0.051 (7)	0.054 (8)	0.007 (5)	0.016 (5)	0.003 (4)
O12	0.032 (7)	0.071 (5)	0.107 (6)	−0.019 (6)	−0.019 (5)	−0.014 (4)
O13	0.044 (6)	0.112 (9)	0.067 (12)	0.023 (6)	−0.005 (5)	0.002 (7)
C14	0.017 (7)	0.15 (2)	0.053 (9)	−0.006 (10)	−0.003 (7)	0.011 (10)
O15	0.033 (6)	0.105 (12)	0.187 (18)	−0.009 (6)	−0.003 (7)	0.049 (10)
O16	0.027 (4)	0.053 (5)	0.045 (7)	0.001 (3)	−0.010 (3)	0.001 (3)
C17	0.054 (4)	0.101 (6)	0.084 (5)	0.021 (5)	−0.016 (4)	−0.037 (5)
N18	0.0488 (16)	0.0401 (15)	0.0642 (17)	−0.0090 (13)	0.0145 (14)	−0.0027 (13)
O19	0.0759 (18)	0.0430 (14)	0.118 (2)	−0.0217 (13)	−0.0014 (16)	−0.0135 (14)
O20	0.0711 (16)	0.0480 (13)	0.0597 (14)	−0.0025 (12)	0.0136 (13)	0.0122 (11)
S21	0.0432 (4)	0.0358 (4)	0.0533 (4)	−0.0010 (3)	0.0106 (3)	0.0002 (3)
C22	0.0489 (19)	0.0477 (19)	0.0571 (18)	0.0130 (16)	0.0170 (15)	0.0101 (15)
C23	0.0367 (17)	0.059 (2)	0.0506 (17)	0.0066 (16)	0.0095 (14)	0.0114 (15)
S24	0.0325 (4)	0.0463 (4)	0.0406 (4)	−0.0047 (3)	0.0052 (3)	0.0022 (3)
C25	0.0298 (13)	0.0364 (15)	0.0329 (13)	−0.0022 (11)	0.0081 (11)	0.0019 (11)

Geometric parameters (Å, º) top

C1—C2	1.379 (4)	N11—O12	1.222 (13)
C1—C6	1.391 (4)	N11—O13	1.266 (17)
C1—H1A	0.9300	C14—O15	1.214 (16)
C2—C3	1.389 (4)	C14—O16	1.301 (17)
C2—N11	1.464 (12)	O16—C17	1.431 (15)
C2—C14	1.505 (14)	C17—H17A	0.9600
C3—C4	1.376 (4)	C17—H17B	0.9600
C3—H3A	0.9300	C17—H17C	0.9600
C4—C5	1.396 (4)	N18—O19	1.220 (3)
C4—N18	1.471 (4)	N18—O20	1.224 (3)
C5—C6	1.419 (4)	S21—C22	1.734 (3)
C5—C5ⁱ	1.484 (5)	S21—C25	1.747 (3)
C6—C7	1.462 (3)	C22—C23	1.329 (4)
C7—C8	1.379 (5)	C22—H22A	0.9300
C7—C6ⁱ	1.462 (3)	C23—S24	1.731 (3)
C8—C9ⁱ	1.436 (4)	C23—H23A	0.9300
C8—C9	1.436 (4)	S24—C25	1.754 (3)
C9—N10	1.137 (4)	C25—C25ⁱⁱ	1.356 (5)

C2—C1—C6	119.2 (3)	O12—N11—O13	130.7 (16)
C2—C1—H1A	120.4	O12—N11—C2	117.9 (13)
C6—C1—H1A	120.4	O13—N11—C2	110.7 (12)
C1—C2—C3	120.8 (3)	O15—C14—O16	118.5 (18)
C1—C2—N11	121.9 (5)	O15—C14—C2	121.8 (18)
C3—C2—N11	117.2 (5)	O16—C14—C2	117.3 (15)
C1—C2—C14	119.0 (9)	C14—O16—C17	116.0 (12)
C3—C2—C14	119.9 (9)	O16—C17—H17A	109.5
N11—C2—C14	10 (2)	O16—C17—H17B	109.5
C4—C3—C2	119.5 (3)	H17A—C17—H17B	109.5
C4—C3—H3A	120.2	O16—C17—H17C	109.5
C2—C3—H3A	120.2	H17A—C17—H17C	109.5
C3—C4—C5	122.0 (3)	H17B—C17—H17C	109.5
C3—C4—N18	115.3 (2)	O19—N18—O20	124.8 (3)
C5—C4—N18	122.3 (2)	O19—N18—C4	117.9 (3)
C4—C5—C6	116.6 (2)	O20—N18—C4	117.2 (2)
C4—C5—C5ⁱ	135.98 (16)	C22—S21—C25	94.51 (14)
C6—C5—C5ⁱ	107.36 (14)	C23—C22—S21	118.5 (2)
C1—C6—C5	121.4 (2)	C23—C22—H22A	120.8
C1—C6—C7	129.2 (3)	S21—C22—H22A	120.8
C5—C6—C7	109.5 (2)	C22—C23—S24	117.3 (2)
C8—C7—C6	127.01 (15)	C22—C23—H23A	121.4
C8—C7—C6ⁱ	127.01 (15)	S24—C23—H23A	121.4
C6—C7—C6ⁱ	106.0 (3)	C23—S24—C25	95.03 (14)
C7—C8—C9ⁱ	123.21 (17)	C25ⁱⁱ—C25—S21	122.3 (3)
C7—C8—C9	123.21 (17)	C25ⁱⁱ—C25—S24	123.0 (3)
C9ⁱ—C8—C9	113.6 (3)	S21—C25—S24	114.72 (15)
N10—C9—C8	178.2 (3)

C6—C1—C2—C3	4.1 (4)	C9ⁱ—C8—C9—N10	−31 (11)
C6—C1—C2—N11	−171.7 (12)	C1—C2—N11—O12	174.2 (17)
C6—C1—C2—C14	177.2 (17)	C3—C2—N11—O12	−2 (3)
C1—C2—C3—C4	−3.4 (4)	C14—C2—N11—O12	−110 (8)
N11—C2—C3—C4	172.6 (12)	C1—C2—N11—O13	−14 (2)
C14—C2—C3—C4	−176.4 (17)	C3—C2—N11—O13	169.8 (15)
C2—C3—C4—C5	−2.9 (4)	C14—C2—N11—O13	62 (7)
C2—C3—C4—N18	170.0 (3)	C1—C2—C14—O15	−175 (3)
C3—C4—C5—C6	7.8 (4)	C3—C2—C14—O15	−2 (4)
N18—C4—C5—C6	−164.5 (2)	N11—C2—C14—O15	75 (7)
C3—C4—C5—C5ⁱ	−174.0 (3)	C1—C2—C14—O16	23 (3)
N18—C4—C5—C5ⁱ	13.6 (5)	C3—C2—C14—O16	−163.8 (19)
C2—C1—C6—C5	1.2 (4)	N11—C2—C14—O16	−87 (8)
C2—C1—C6—C7	−179.5 (2)	O15—C14—O16—C17	9 (4)
C4—C5—C6—C1	−7.0 (4)	C2—C14—O16—C17	172 (2)
C5ⁱ—C5—C6—C1	174.4 (2)	C3—C4—N18—O19	33.4 (4)
C4—C5—C6—C7	173.57 (19)	C5—C4—N18—O19	−153.8 (3)
C5ⁱ—C5—C6—C7	−5.1 (3)	C3—C4—N18—O20	−143.6 (3)
C1—C6—C7—C8	2.6 (3)	C5—C4—N18—O20	29.3 (4)
C5—C6—C7—C8	−177.98 (13)	C25—S21—C22—C23	−1.6 (3)
C1—C6—C7—C6ⁱ	−177.4 (3)	S21—C22—C23—S24	1.2 (4)
C5—C6—C7—C6ⁱ	2.02 (13)	C22—C23—S24—C25	−0.1 (3)
C6—C7—C8—C9ⁱ	−172.74 (18)	C22—S21—C25—C25ⁱⁱ	−177.0 (3)
C6ⁱ—C7—C8—C9ⁱ	7.26 (18)	C22—S21—C25—S24	1.40 (17)
C6—C7—C8—C9	7.26 (18)	C23—S24—C25—C25ⁱⁱ	177.4 (3)
C6ⁱ—C7—C8—C9	−172.74 (18)	C23—S24—C25—S21	−0.93 (17)
C7—C8—C9—N10	149 (11)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+1.

Experimental details

	(cdc2tnf)	(cdc2tnfb)
Crystal data
Chemical formula	C₁₈H₇N₅O₈·C₆H₄S₄	C₁₈H₇N₅O₈·C₆H₄S₄
M_r	625.62	625.62
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, C2/c
Temperature (K)	296	296
a, b, c (Å)	6.7816 (17), 30.572 (4), 12.4381 (13)	15.2489 (14), 12.692 (1), 13.7950 (13)
β (°)	94.304 (11)	104.350 (7)
V (Å³)	2571.5 (8)	2586.6 (4)
Z	4	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.43	0.43
Crystal size (mm)	0.70 × 0.16 × 0.08	0.40 × 0.20 × 0.18

Data collection
Diffractometer	Bruker P4 diffractometer	Bruker P4 diffractometer
Absorption correction	–	ψ scan XSCANS 2.21 (Siemens, 1996)
T_min, T_max	–	0.890, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	5958, 4503, 3133	3590, 2274, 1768
R_int	0.041	0.020
(sin θ/λ)_max (Å⁻¹)	0.595	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.169, 1.06	0.041, 0.098, 1.05
No. of reflections	4503	2274
No. of parameters	370	218
No. of restraints	0	7
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.35	0.25, −0.26

Computer programs: XSCANS 2.21 (Siemens, 1996), SHELXTL 5.10 (Sheldrick, 1998), SHELX97 (Sheldrick, 1997).

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