Cocrystals of 2-(2,4,5,7-tetranitrofluoren-9-ylidene)propanedinitrile and 2,4,5,7-tetranitrofluoren-9-one with chlorobenzene

Crystallization of 2,4,5,7-tetra­nitro-9-(di­cyano­methyl­ene)­fluor­ene [DTeF; systematic name: 2-(2,4,5,7-tetra­nitro­fluorene-9-yl­idene)­propane­di­nitrile] and 2,4,5,7-tetra­nitrofluoren-9-one (TeNF) from chloro­benzene in the presence of π-donor compounds yielded the chloro­benzene solvate, C₁₆H₄N₆O₈·C₆H₅Cl, and the bis­(chloro­benzene) solvate, C₁₃H₄N₄O₉·2C₆H₅Cl, respectively. Both structures comprise mixed stacks of twisted fluorene moieties interspersed with nearly parallel chloro­benzene mol­ecules. Solvent-free crystals of DTeF and TeNF were obtained from pure chloro­benzene.

S1. Comment

2,4,5,7-Tetranitro-9-dicyanomethylenefluorene (DTeF) and 2,4,5,7-tetranitrofluoren-9-one (TeNF) are strong electron acceptors with potentially useful photoelectronic properties (Pravednikov et al., 1978). They readily form charge-transfer (CT) complexes with donor molecules (Brown et al., 1974; Grigg et al., 1978; Baldwin & Baughman, 1993; Shah & Baughman, 1994), particularly with tetrathiafulvalene (TTF) and its derivatives (Soriano-García et al., 1989; Perepichka et al., 1998, 2000; Bryce, Moore et al., 1999; Batsanov et al., 2001). CT complexes of DTeF and TeNF with bis(ethylenedioxy)tetrathiafulvalene (BEDO-TTF) have interesting electric properties: (TeNF)(BEDO-TTF) is a semiconductor, while (DTeF)(BEDO-TTF)₂ shows metallic conductivity (Horiuchi et al., 1996).

In search of new CT complexes, we attempted to co-crystallize DTeF with the π-donor compounds 4-iodo-4',5,5'-trimethyltetrathiafulvalene, (III) (John et al., 1998), or 8,9-bis(methylsulfanyl)acenaphtho[1,2-b][1,4]dithiine, (IV) (Bryce, Lay et al., 1999), and TeNF with N,N-dimethylaminoferrocene, (V), from chlorobenzene solutions. Unexpectedly, we obtained instead the chlorobenzene solvates, DTeF·PhCl, (I), and TeNF·2PhCl, (II), respectively. Even more surprisingly, crystallization of the same acceptor compounds from pure chlorobenzene gave only the previously known solvent-free phases of DTeF (Silverman et al., 1974) or TeNF (Chetkina et al., 1987; Baughman, 1987). Thus, the presence of compounds (III)-(V) in solution affects the composition of the growing crystal without these compounds themselves being incorporated into the structure. Although at present we have no evidence of how general this effect is, or of its possible mechanism, it certainly deserves attention. A plausible explanation (which, of course, requires much more experimental data to be proven) is that complexes between the electron donor (DTeF, TeNF) and acceptor [(III)-(V)] molecules exist in solution and, due to CT, are solvated more strongly than the isolated acceptor molecules. However, the CT complex itself is highly soluble and is not precipitated under these conditions. On cooling or on slow evaporation, the acceptor component of the CT complex starts to crystallize first, but due to the strong association between this component and the chlorobenzene solvent, desolvation does not occur and the mixed stack of acceptor molecules and solvent is formed. Obviously, this effect can not be observed if the CT complex has low solubility and crystallizes first. \sch

Complexes (I) and (II) do not exhibit CT bands in their UV-visible spectra and can be described as host–guest complexes of neutral molecules, in agreement with the structural data (see below). The DTeF molecule in (I) (Fig. 1) has essentially the same geometry as in the solvent-free phase studied at room temperature, apart from the usual systematic errors caused by thermal libration in the latter (i.e. a shortening of most bonds by 0.01–0.02 Å).

In (I), the longest bonds in the benzene rings are the fused ones, C10—C11 and C12—C13, while the opposing bonds C2—C3 and C6—C7 are the shortest [average 1.418 (2) versus 1.382 (2) Å)], as seen in Table 1. A similar relation was observed in pure TeNF [1.41 (1) versus 1.36 (1) Å], although the effect was somewhat exaggerated by thermal motion. Aromatic π delocalization is largely confined to the benzene rings. The C11—C12 bond linking the rings remains essentially single at 1.482 (2) Å, compared with the standard single C_arene—C_arene bond of 1.490 Å (Allen et al., 1987). The exocyclic C9═C14 bond of 1.357 (2) Å is longer than the standard double bond of 1.331 Å (Allen et al., 1987), due to π conjugation with the cyano groups, while the C9—C10 and C9—C13 bond distances [average 1.481 (2) Å] reveal the absence of conjugation between C9═C14 and the benzene rings. Note that the accumulation of negative charge on DTeF should result in the five-membered ring acquiring aromatic character.

The fluorene system of (I) has a twisted conformation, caused by steric crowding between the nitro groups in the 4- and 5-positions. These groups tilt out of the fluorene plane in opposite directions, dragging with them the adjacent parts of the fluorene moiety, especially atoms C4 and C5. Thus, atoms C1, C2, C7, C8, C9, C10, C12, C13, C14, C16 and N16 lie in one plane (plane A) to within ±0.03 Å. The deviations of other atoms from this plane are: C3 0.22, C4 0.32, C5 - 0.26, C6 - 1/5, C11 0.10, C15 - 0.11 and N15 - 0.21 Å. The torsion angles around the C4—N4 and C5—N5 bonds [22.6 (1) and 28.3 (1)°] are larger than those around the C2—N2 and C7—N7 bonds [15.1 (1) and 7.4 (1)°], and the C4—N4 and C5—N5 bonds are tilted out of the sp² planes of C4 and C5 by 4.4 (1) and 8.1 (1)°, respectively, which also reveals the steric strain.

The DTeF and chlorobenzene molecules in (I) form an infinite mixed stack (Fig. 3), wherein the planes of the benzene ring and the fluorene plane A are parallel to within 1°, with uniform interplanar separations of ca 3.36 Å. The Cl atom is situated over the centre of the five-membered fluorene ring and the resulting Cl···C distances range from 3.464 (3) to 3.623 (3) Å. The stacks pack in a herringbone motif, stabilized by interstack nonvalent interactions; Cl···O7(x, 1/2 - y, 1/2 + z) 3.077 (2) Å and O2···N5 (x, -1/2 - y, 1/2 + z) 2.912 (2) Å, cf. the standard van der Waals contacts Cl···O 3.33 and O···N 3.28 Å (Rowland & Taylor, 1996).

In structure (II) (Fig. 2), the bond geometry of the TeNF molecule is in good agreement with the results of the two independent room-temperature studies of pure TeNF (Chetkina et al., 1987; Baughman, 1987). The five-membered ring of TeNF displays even less π conjugation than in DTeF, with essentially single bonds at C11—C12 [1.502 (9) Å], and C9—C10 and C9—C13 [average 1.51 (1) Å]. The twist of the fluorene moiety is similar to that in DTeF: in (II), the average deviation of the 13 fluorene C atoms from their mean plane is 0.110 Å, and the maximum deviations are 0.17 (C4) and -0.22 Å (C5), compared with 0.115, 0.23 and -0.20 Å, respectively, in (I). Unlike DTeF, TeNF contains no extensive planar fragment. The torsion angles around the C2—N2, C4—N4, C5—N5 and C7—N7 bonds, 9.2 (2), 29.8 (2), 35.6 (2) and 3.1 (2)°, respectively, reflect steric crowding between the 4- and 5-nitro groups and the absence of strain elsewhere.

The structure of (II) also comprises infinite mixed stacks, parallel to the a axis, wherein TeNF molecules are interspersed with pairs of chlorobenzene molecules (Fig. 4). The latter are inclined by 17.2 (2) and 8.5 (1)° to the mean fluorene plane and by 17.6 (2)° to each other. Hence the interplanar separations are wider than in (II) [surely in (I)?] by ca 0.1 Å. Unlike (I), in (II) the molecular planes in adjacent stacks are nearly parallel. The interstack contacts Cl1···O9(x - 1, -1/2 - y, 1/2 + z) [3.198 (7) Å] and Cl2···O3 (1 - x, 1 - y, -z) [3.118 (8) Å] are shorter than the normal van der Waals contact of 3.33 Å (Rowland & Taylor, 1996).

Related literature

For related literature, see: Allen et al. (1987); Baldwin & Baughman (1993); Batsanov et al. (2001); Baughman (1987); Brown et al. (1974); Bryce, Lay, Chesney, Batsanov, Howard, Buser, Gerson & Merstetter (1999); Bryce, Moore, Batsanov, Howard, Robertson & Perepichka (1999); Chetkina et al. (1987); Grigg et al. (1978); Horiuchi et al. (1996); John et al. (1998); Perepichka et al. (1998, 2000); Pravednikov et al. (1978); Rowland & Taylor (1996); Shah & Baughman (1994); Silverman et al. (1974); Soriano-García, Toscano, Robles Martínez, Salmerón & Lezama (1989).

S2. Experimental

For the preparation of (I), DTeF (5.6 mg, 0.014 mmol) was dissolved in hot chlorobenzene (3.0 ml), compound (III) (10.4 mg, 0.028 mmol) was added and the solution was left to cool slowly to room temperature, affording fine yellow crystals of solvate (I). Repeating the procedure, scaled up fivefold, gave identical crystals. Analysis calculated for C₂₂H₉ClN₆O₈: C 50.74, H 1.74, Cl 6.81, N 16.14%; found: C 50.42, H 1.85, Cl 6.95, N 16.07%. In a different route, using an alternative π-donor compound, DTeF (7.0 mg, 0.017 mmol) was dissolved in hot chlorobenzene (7.0 ml), compound (IV) (5.9 mg, 0.018 mmol) was added, and the solution was allowed to cool to room temperature and left to evaporate slowly for several days, yielding crystals of (I). For the preparation of (II), TeNF (10.0 mg, 0.028 mmol) was dissolved in hot chlorobenzene (8.0 ml), compound (V) (20.0 mg, 0.082 mmol) was added and the solution was left at room temperature to evaporate slowly for two weeks, whereupon crystals of solvate (II) were formed, but only in small amounts and insufficient for elemental analysis. Control experiments were carried out as follows. DTeF (6.0 mg) was dissolved in hot chlorobenzene (2.5, 3.5 and 5.0 ml were used in three runs) and crystallized by slow evaporation. X-ray determination of the unit cell identified the crystals as solvent-free DTeF (Silverman et al., 1974). The same procedure was repeated with TeNF.

S3. Refinement

All H atoms in (I) were refined independently in an isotropic approximation [C—H bonds 0.94 (2) to 0.97 (2) Å]. In (II), the H atoms were treated as riding, with C—H = 0.95 Å and U_iso(H) fixed to 1.2U_eq of the parent C atom. The reflections from (II) were generally weak [average I/σ(I) ratio of 6.0] and surrounded with very anisotropic peaks of diffuse scattering, hence the high R_int, final R and S. Although the crystal faces were indexed, an absorption correction by numerical integration (T_max = 0.993, T_min = 0.847) resulted in no overall improvement.

Computing details

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1995); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The asymmetric unit of (I), viewed as a parallel projection on the fluorene mean plane. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The asymmetric unit of (II), viewed as a parallel projection on the fluorene mean plane. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The crystal packing of (I), showing short intermolecular contacts.
	Fig. 4. The crystal packing of (II), showing short intermolecular contacts.

(I) 2-(2,4,5,7-tetranitrofluorene-9-ylidene)propanedinitrile chlorobenzene solvate

Crystal data

C16H4N6O8·C6H5Cl	F(000) = 1056
Mr = 520.80	Dx = 1.600 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.823 (2) Å	Cell parameters from 512 reflections
b = 8.360 (6) Å	θ = 12–20°
c = 17.461 (3) Å	µ = 0.24 mm^−1
β = 118.33 (1)°	T = 150 K
V = 2161.6 (16) Å^3	Prism, yellow
Z = 4	0.28 × 0.22 × 0.18 mm

Data collection

Siemens SMART 1K CCD area-detector diffractometer	4169 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 27.5°, θmin = 1.4°
Detector resolution: 8 pixels mm^-1	h = −21→20
ω scans	k = −10→10
22991 measured reflections	l = −22→22
4962 independent reflections

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)] = 0.038	Hydrogen site location: difference Fourier map
wR(F^2) = 0.092	All H-atom parameters refined
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0297P)^2 + 1.4795P] where P = (Fo^2 + 2Fc^2)/3
4962 reflections	(Δ/σ)max < 0.001
370 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.54 e Å^−3

Special details

Experimental. The data collection nominally covered a full sphere of reciprocal space by a combination of 5 sets of ω scans; each set at different ϕ and/or 2θ angles and each scan (10 s exposure) covered 0.3° in ω. The crystal to detector distance was 4.5 cm. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and comparing 263 duplicate reflections.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.23854 (11)	−0.19503 (19)	0.34253 (10)	0.0212 (3)
H1	0.1855 (13)	−0.230 (2)	0.3425 (12)	0.024 (5)*
C2	0.32228 (11)	−0.24500 (19)	0.40781 (10)	0.0221 (3)
C3	0.40327 (11)	−0.18737 (19)	0.41742 (10)	0.0219 (3)
H3	0.4602 (13)	−0.218 (2)	0.4659 (12)	0.024 (5)*
C4	0.40084 (10)	−0.07805 (18)	0.35642 (9)	0.0196 (3)
C5	0.34500 (10)	0.11195 (18)	0.16181 (10)	0.0182 (3)
C6	0.30495 (11)	0.20857 (18)	0.08858 (10)	0.0195 (3)
H6	0.3387 (12)	0.248 (2)	0.0629 (12)	0.023 (5)*
C7	0.21337 (11)	0.23966 (18)	0.05338 (9)	0.0202 (3)
C8	0.15945 (11)	0.17234 (19)	0.08505 (10)	0.0204 (3)
H8	0.0965 (13)	0.193 (2)	0.0568 (12)	0.023 (5)*
C9	0.16176 (10)	−0.01653 (18)	0.20435 (9)	0.0187 (3)
C10	0.23862 (10)	−0.09306 (18)	0.27946 (10)	0.0190 (3)
C11	0.32020 (10)	−0.03994 (17)	0.28250 (9)	0.0179 (3)
C12	0.29654 (10)	0.05363 (17)	0.20241 (9)	0.0174 (3)
C13	0.20180 (10)	0.07749 (18)	0.15932 (10)	0.0184 (3)
C14	0.07282 (11)	−0.03101 (19)	0.18105 (10)	0.0220 (3)
C15	0.03905 (11)	−0.1325 (2)	0.22607 (11)	0.0273 (4)
C16	0.00240 (11)	0.0503 (2)	0.10676 (11)	0.0240 (3)
N2	0.32456 (11)	−0.35946 (17)	0.47329 (9)	0.0282 (3)
N4	0.48503 (9)	0.01231 (17)	0.38111 (8)	0.0229 (3)
N5	0.43829 (9)	0.06086 (16)	0.18837 (8)	0.0196 (3)
N7	0.17001 (9)	0.34439 (17)	−0.02414 (8)	0.0244 (3)
N15	0.00956 (11)	−0.2142 (2)	0.25905 (11)	0.0405 (4)
N16	−0.05422 (10)	0.1107 (2)	0.04664 (10)	0.0330 (3)
O1	0.25449 (10)	−0.38247 (17)	0.47685 (9)	0.0404 (3)
O2	0.39689 (9)	−0.42598 (17)	0.51972 (9)	0.0421 (3)
O3	0.55675 (8)	−0.04650 (15)	0.43572 (8)	0.0301 (3)
O4	0.47786 (8)	0.14739 (14)	0.35047 (8)	0.0297 (3)
O5	0.46121 (8)	−0.07217 (14)	0.22242 (8)	0.0263 (3)
O6	0.48590 (7)	0.14971 (14)	0.17174 (7)	0.0256 (3)
O7	0.21897 (9)	0.41470 (16)	−0.04710 (8)	0.0321 (3)
O8	0.08731 (8)	0.35537 (18)	−0.06039 (8)	0.0380 (3)
Cl	0.24376 (4)	0.32680 (6)	0.33292 (3)	0.04034 (13)
C21	0.23139 (12)	0.4516 (2)	0.24742 (11)	0.0272 (4)
C22	0.30763 (12)	0.4980 (2)	0.24204 (11)	0.0272 (4)
H22	0.3672 (14)	0.463 (3)	0.2850 (13)	0.035 (5)*
C23	0.29692 (12)	0.5967 (2)	0.17370 (12)	0.0286 (4)
H23	0.3485 (14)	0.631 (3)	0.1685 (13)	0.037 (6)*
C24	0.21124 (13)	0.6465 (2)	0.11179 (12)	0.0297 (4)
H24	0.2054 (15)	0.714 (3)	0.0660 (15)	0.044 (6)*
C25	0.13567 (12)	0.5974 (2)	0.11843 (12)	0.0309 (4)
H25	0.0760 (15)	0.629 (3)	0.0760 (14)	0.039 (6)*
C26	0.14494 (12)	0.4998 (2)	0.18646 (12)	0.0302 (4)
H26	0.0942 (14)	0.468 (3)	0.1921 (13)	0.036 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0255 (8)	0.0198 (7)	0.0222 (7)	0.0001 (6)	0.0146 (7)	−0.0014 (6)
C2	0.0326 (9)	0.0182 (7)	0.0170 (7)	0.0019 (6)	0.0130 (7)	0.0000 (6)
C3	0.0262 (8)	0.0195 (7)	0.0171 (7)	0.0033 (6)	0.0079 (6)	−0.0021 (6)
C4	0.0208 (7)	0.0192 (7)	0.0182 (7)	0.0009 (6)	0.0088 (6)	−0.0037 (6)
C5	0.0183 (7)	0.0164 (7)	0.0198 (7)	−0.0004 (6)	0.0089 (6)	−0.0031 (6)
C6	0.0224 (8)	0.0180 (7)	0.0198 (7)	−0.0022 (6)	0.0114 (6)	−0.0014 (6)
C7	0.0248 (8)	0.0184 (7)	0.0154 (7)	0.0012 (6)	0.0079 (6)	0.0000 (6)
C8	0.0192 (8)	0.0203 (7)	0.0196 (7)	0.0010 (6)	0.0076 (6)	−0.0013 (6)
C9	0.0215 (8)	0.0165 (7)	0.0189 (7)	0.0017 (6)	0.0102 (6)	−0.0009 (6)
C10	0.0214 (7)	0.0171 (7)	0.0191 (7)	0.0021 (6)	0.0101 (6)	−0.0023 (6)
C11	0.0218 (8)	0.0152 (7)	0.0170 (7)	0.0023 (6)	0.0094 (6)	−0.0024 (5)
C12	0.0197 (7)	0.0151 (7)	0.0170 (7)	0.0001 (6)	0.0084 (6)	−0.0031 (5)
C13	0.0196 (7)	0.0171 (7)	0.0194 (7)	0.0008 (6)	0.0100 (6)	−0.0019 (6)
C14	0.0222 (8)	0.0239 (8)	0.0222 (7)	0.0008 (6)	0.0123 (6)	−0.0018 (6)
C15	0.0207 (8)	0.0341 (9)	0.0278 (8)	0.0016 (7)	0.0121 (7)	0.0012 (7)
C16	0.0200 (8)	0.0282 (8)	0.0273 (8)	−0.0002 (7)	0.0141 (7)	−0.0017 (7)
N2	0.0400 (9)	0.0235 (7)	0.0214 (7)	0.0015 (6)	0.0149 (6)	0.0022 (6)
N4	0.0219 (7)	0.0250 (7)	0.0193 (6)	−0.0006 (5)	0.0078 (5)	−0.0056 (5)
N5	0.0188 (6)	0.0211 (6)	0.0185 (6)	−0.0005 (5)	0.0086 (5)	−0.0026 (5)
N7	0.0272 (7)	0.0253 (7)	0.0193 (6)	0.0025 (6)	0.0098 (6)	0.0028 (5)
N15	0.0294 (8)	0.0530 (11)	0.0433 (9)	−0.0012 (8)	0.0208 (8)	0.0118 (8)
N16	0.0235 (7)	0.0416 (9)	0.0314 (8)	0.0052 (7)	0.0110 (6)	0.0041 (7)
O1	0.0506 (8)	0.0397 (8)	0.0462 (8)	0.0086 (7)	0.0355 (7)	0.0155 (6)
O2	0.0388 (8)	0.0428 (8)	0.0315 (7)	0.0016 (6)	0.0060 (6)	0.0177 (6)
O3	0.0196 (6)	0.0343 (7)	0.0264 (6)	0.0038 (5)	0.0028 (5)	−0.0046 (5)
O4	0.0301 (6)	0.0249 (6)	0.0291 (6)	−0.0057 (5)	0.0101 (5)	−0.0011 (5)
O5	0.0276 (6)	0.0224 (6)	0.0316 (6)	0.0072 (5)	0.0164 (5)	0.0056 (5)
O6	0.0207 (6)	0.0271 (6)	0.0299 (6)	−0.0045 (5)	0.0128 (5)	0.0006 (5)
O7	0.0359 (7)	0.0346 (7)	0.0297 (6)	0.0012 (6)	0.0188 (6)	0.0104 (5)
O8	0.0254 (7)	0.0503 (8)	0.0308 (7)	0.0065 (6)	0.0072 (5)	0.0146 (6)
Cl	0.0638 (3)	0.0312 (2)	0.0334 (2)	−0.0042 (2)	0.0291 (2)	−0.00185 (19)
C21	0.0376 (10)	0.0209 (8)	0.0265 (8)	−0.0018 (7)	0.0180 (7)	−0.0042 (6)
C22	0.0250 (9)	0.0242 (8)	0.0298 (9)	0.0002 (7)	0.0108 (7)	−0.0061 (7)
C23	0.0284 (9)	0.0263 (9)	0.0363 (9)	−0.0027 (7)	0.0197 (8)	−0.0041 (7)
C24	0.0352 (10)	0.0239 (8)	0.0309 (9)	0.0022 (7)	0.0165 (8)	−0.0012 (7)
C25	0.0249 (9)	0.0292 (9)	0.0353 (9)	0.0046 (7)	0.0116 (8)	−0.0049 (8)
C26	0.0286 (9)	0.0281 (9)	0.0399 (10)	−0.0043 (7)	0.0211 (8)	−0.0084 (8)

Geometric parameters (Å, º)

C1—C2	1.391 (2)	C14—C15	1.444 (2)
C1—C10	1.393 (2)	C14—C16	1.446 (2)
C1—H1	0.940 (19)	C15—N15	1.147 (2)
C2—C3	1.378 (2)	C16—N16	1.147 (2)
C2—N2	1.477 (2)	N2—O1	1.225 (2)
C3—C4	1.389 (2)	N2—O2	1.229 (2)
C3—H3	0.964 (19)	N4—O4	1.231 (2)
C4—N4	1.478 (2)	N4—O3	1.2307 (17)
C4—C11	1.395 (2)	N5—O6	1.2241 (17)
C5—C6	1.387 (2)	N5—O5	1.2334 (19)
C5—C12	1.398 (2)	N7—O7	1.2240 (18)
C5—N5	1.4730 (19)	N7—O8	1.2284 (18)
C6—C7	1.386 (2)	Cl—C21	1.7508 (18)
C6—H6	0.935 (19)	C21—C22	1.385 (2)
C7—N7	1.481 (2)	C21—C26	1.394 (3)
C7—C8	1.386 (2)	C22—C23	1.390 (3)
C8—C13	1.393 (2)	C22—H22	0.97 (2)
C8—H8	0.949 (19)	C23—C24	1.393 (3)
C9—C10	1.480 (2)	C23—H23	0.96 (2)
C9—C13	1.481 (2)	C24—C25	1.392 (3)
C9—C14	1.357 (2)	C24—H24	0.94 (2)
C10—C11	1.419 (2)	C25—C26	1.387 (3)
C11—C12	1.482 (2)	C25—H25	0.96 (2)
C12—C13	1.417 (2)	C26—H26	0.94 (2)
C2—C1—C10	116.82 (15)	C8—C13—C9	129.48 (14)
C2—C1—H1	119.9 (11)	C12—C13—C9	108.89 (13)
C10—C1—H1	123.3 (11)	C9—C14—C15	123.50 (15)
C3—C2—C1	123.58 (15)	C9—C14—C16	123.00 (15)
C3—C2—N2	118.10 (14)	C15—C14—C16	113.47 (14)
C1—C2—N2	118.24 (15)	N15—C15—C14	177.56 (19)
C2—C3—C4	117.97 (15)	N16—C16—C14	178.05 (19)
C2—C3—H3	121.7 (11)	O1—N2—O2	124.80 (15)
C4—C3—H3	120.3 (11)	O1—N2—C2	117.96 (14)
C3—C4—N4	115.93 (14)	O2—N2—C2	117.24 (15)
C11—C4—N4	122.00 (14)	O4—N4—O3	124.14 (14)
C3—C4—C11	121.43 (15)	O4—N4—C4	117.36 (13)
C6—C5—N5	115.98 (13)	O3—N4—C4	118.25 (14)
C12—C5—N5	122.00 (13)	O6—N5—O5	124.85 (13)
C6—C5—C12	121.71 (14)	O6—N5—C5	117.94 (13)
C7—C6—C5	118.01 (14)	O5—N5—C5	117.12 (13)
C7—C6—H6	121.5 (11)	O7—N7—O8	124.68 (14)
C5—C6—H6	120.5 (11)	O7—N7—C7	117.85 (13)
C6—C7—C8	123.18 (14)	O8—N7—C7	117.46 (14)
C6—C7—N7	118.55 (14)	C22—C21—C26	122.09 (16)
C8—C7—N7	118.22 (14)	C22—C21—Cl	119.06 (14)
C7—C8—C13	117.39 (14)	C26—C21—Cl	118.85 (14)
C7—C8—H8	119.9 (11)	C21—C22—C23	118.53 (16)
C13—C8—H8	122.7 (11)	C21—C22—H22	120.9 (12)
C14—C9—C10	127.04 (14)	C23—C22—H22	120.6 (12)
C14—C9—C13	127.07 (14)	C22—C23—C24	120.55 (17)
C10—C9—C13	105.88 (13)	C22—C23—H23	120.3 (13)
C1—C10—C11	121.70 (14)	C24—C23—H23	119.2 (13)
C1—C10—C9	129.54 (14)	C25—C24—C23	119.78 (17)
C11—C10—C9	108.69 (13)	C25—C24—H24	120.9 (13)
C4—C11—C10	117.50 (14)	C23—C24—H24	119.3 (13)
C4—C11—C12	134.53 (14)	C26—C25—C24	120.58 (17)
C10—C11—C12	107.93 (13)	C26—C25—H25	118.4 (13)
C5—C12—C13	117.48 (13)	C24—C25—H25	121.1 (13)
C5—C12—C11	134.62 (14)	C25—C26—C21	118.47 (17)
C13—C12—C11	107.82 (13)	C25—C26—H26	121.1 (13)
C8—C13—C12	121.59 (14)	C21—C26—H26	120.4 (13)

(II) 2,4,5,7-tetranitrofluoren-9-one bis(chlorobenzene) solvate

Crystal data

C13H4N4O9·2C6H5Cl	Dx = 1.589 Mg m^−3
Mr = 585.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 266 reflections
a = 6.984 (1) Å	θ = 10–18°
b = 15.088 (2) Å	µ = 0.33 mm^−1
c = 23.217 (2) Å	T = 150 K
V = 2446.5 (5) Å^3	Needle, pale yellow
Z = 4	0.52 × 0.03 × 0.02 mm
F(000) = 1192

Data collection

Siemens SMART 1K CCD area-detector diffractometer	2896 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.138
Graphite monochromator	θmax = 25.0°, θmin = 1.6°
Detector resolution: 8 pixels mm^-1	h = −8→8
ω scans	k = −17→14
14660 measured reflections	l = −27→27
4312 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)] = 0.076	H-atom parameters constrained
wR(F^2) = 0.150	w = 1/[σ^2(Fo^2) + (0.0001P)^2 + 6.6293P] where P = (Fo^2 + 2Fc^2)/3
S = 1.26	(Δ/σ)max < 0.001
4312 reflections	Δρmax = 0.38 e Å^−3
361 parameters	Δρmin = −0.39 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (14)

Special details

Experimental. The data collection nominally covered over a hemisphere of reciprocal space, by a combination of 4 sets of ω scans; each set at different ϕ and/or 2θ angles and each scan (30 s exposure) covered 0.3° in ω. The crystal to detector distance was 4.5 cm. Crystal decay was monitored by repeating 50 initial frames at the end of data collection and comparing 92 duplicate reflections.

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. Excluding Friedel equivalents: 2485 independent reflections, 1780 observed.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7506 (11)	0.2251 (5)	0.3300 (3)	0.0258 (18)
H1	0.7288	0.1649	0.3397	0.031*
C2	0.7577 (10)	0.2529 (5)	0.2732 (3)	0.0215 (16)
C3	0.7972 (11)	0.3404 (4)	0.2578 (3)	0.0242 (17)
H3	0.8044	0.3572	0.2184	0.029*
C4	0.8250 (10)	0.4025 (5)	0.3019 (3)	0.0224 (17)
C5	0.8149 (10)	0.5156 (5)	0.4324 (3)	0.0201 (16)
C6	0.8476 (10)	0.5404 (5)	0.4892 (3)	0.0238 (17)
H6	0.8509	0.6011	0.5000	0.029*
C7	0.8718 (10)	0.4752 (5)	0.5301 (3)	0.0233 (18)
C8	0.8553 (10)	0.3858 (5)	0.5172 (3)	0.0251 (18)
H8	0.8629	0.3416	0.5462	0.030*
C9	0.7924 (12)	0.2740 (5)	0.4362 (3)	0.0268 (19)
C10	0.7765 (10)	0.2879 (5)	0.3715 (3)	0.0206 (16)
C11	0.8039 (10)	0.3789 (4)	0.3598 (3)	0.0175 (16)
C12	0.8165 (10)	0.4269 (5)	0.4164 (3)	0.0190 (16)
C13	0.8273 (10)	0.3647 (5)	0.4606 (3)	0.0206 (17)
O1	0.6679 (8)	0.1145 (3)	0.2402 (2)	0.0342 (14)
O2	0.7580 (9)	0.2121 (4)	0.1769 (2)	0.0402 (15)
O3	0.8291 (9)	0.5189 (3)	0.2371 (2)	0.0440 (16)
O4	1.0009 (8)	0.5295 (3)	0.3156 (2)	0.0338 (14)
O5	0.6383 (7)	0.5686 (3)	0.3554 (2)	0.0260 (12)
O6	0.8301 (8)	0.6611 (3)	0.3997 (2)	0.0348 (13)
O7	0.9267 (8)	0.5818 (4)	0.6005 (2)	0.0393 (15)
O8	0.9506 (8)	0.4433 (4)	0.6251 (2)	0.0357 (14)
O9	0.7786 (9)	0.2042 (3)	0.4615 (2)	0.0376 (15)
N2	0.7257 (9)	0.1883 (4)	0.2263 (3)	0.0269 (15)
N4	0.8889 (9)	0.4909 (4)	0.2837 (3)	0.0276 (15)
N5	0.7576 (9)	0.5869 (4)	0.3922 (2)	0.0237 (15)
N7	0.9196 (9)	0.5024 (5)	0.5893 (3)	0.0293 (15)
Cl1	0.2935 (3)	0.32668 (13)	0.40230 (7)	0.0308 (5)
C15	0.2965 (10)	0.3233 (5)	0.3260 (3)	0.0222 (16)
C16	0.2576 (10)	0.2436 (4)	0.2996 (3)	0.0219 (17)
H16	0.2327	0.1918	0.3216	0.026*
C17	0.2578 (10)	0.2407 (5)	0.2393 (3)	0.0243 (18)
H17	0.2286	0.1870	0.2199	0.029*
C18	0.2992 (11)	0.3166 (5)	0.2081 (3)	0.0297 (18)
H18	0.3005	0.3137	0.1672	0.036*
C19	0.3393 (11)	0.3962 (5)	0.2353 (3)	0.0270 (18)
H19	0.3695	0.4476	0.2135	0.032*
C20	0.3359 (11)	0.3995 (5)	0.2962 (3)	0.0283 (19)
H20	0.3600	0.4535	0.3159	0.034*
Cl2	0.4537 (3)	0.49893 (17)	0.62038 (9)	0.0469 (6)
C21	0.4234 (12)	0.5614 (6)	0.5570 (3)	0.034 (2)
C22	0.3507 (11)	0.5185 (6)	0.5092 (4)	0.038 (2)
H22	0.3180	0.4575	0.5107	0.046*
C23	0.3284 (12)	0.5672 (6)	0.4586 (4)	0.044 (2)
H23	0.2761	0.5396	0.4253	0.053*
C24	0.3838 (12)	0.6560 (6)	0.4575 (3)	0.041 (2)
H24	0.3687	0.6895	0.4232	0.049*
C25	0.4591 (12)	0.6956 (5)	0.5061 (3)	0.037 (2)
H25	0.4966	0.7560	0.5048	0.044*
C26	0.4817 (12)	0.6483 (6)	0.5567 (3)	0.038 (2)
H26	0.5347	0.6752	0.5901	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.026 (5)	0.026 (4)	0.025 (4)	0.008 (4)	0.002 (3)	0.001 (3)
C2	0.018 (4)	0.025 (4)	0.022 (4)	0.004 (3)	−0.004 (3)	−0.004 (3)
C3	0.028 (4)	0.024 (4)	0.020 (4)	0.003 (4)	0.000 (3)	−0.006 (3)
C4	0.019 (4)	0.028 (4)	0.020 (4)	0.000 (3)	−0.003 (3)	−0.002 (3)
C5	0.014 (4)	0.023 (4)	0.023 (4)	−0.004 (3)	0.001 (3)	0.003 (3)
C6	0.020 (4)	0.025 (4)	0.027 (4)	−0.001 (3)	0.004 (3)	−0.002 (3)
C7	0.023 (4)	0.033 (5)	0.014 (4)	0.000 (3)	−0.006 (3)	−0.002 (3)
C8	0.023 (4)	0.025 (4)	0.027 (4)	0.003 (3)	0.002 (4)	0.012 (4)
C9	0.028 (5)	0.021 (4)	0.032 (4)	0.003 (4)	0.001 (4)	−0.005 (4)
C10	0.019 (4)	0.024 (4)	0.019 (4)	0.000 (3)	−0.003 (3)	−0.006 (3)
C11	0.014 (4)	0.024 (4)	0.015 (3)	0.005 (3)	−0.001 (3)	0.001 (3)
C12	0.016 (4)	0.027 (4)	0.015 (4)	−0.004 (3)	−0.002 (3)	0.001 (3)
C13	0.016 (4)	0.024 (4)	0.022 (4)	0.004 (3)	−0.002 (3)	−0.002 (3)
O1	0.042 (4)	0.019 (3)	0.041 (3)	−0.004 (3)	0.003 (3)	−0.011 (3)
O2	0.054 (4)	0.045 (3)	0.022 (3)	0.007 (3)	−0.003 (3)	−0.011 (3)
O3	0.080 (5)	0.033 (3)	0.019 (3)	0.007 (3)	0.007 (3)	0.007 (3)
O4	0.032 (3)	0.029 (3)	0.040 (3)	−0.007 (3)	0.011 (3)	−0.009 (3)
O5	0.029 (3)	0.028 (3)	0.021 (3)	0.005 (2)	−0.003 (2)	0.000 (2)
O6	0.049 (4)	0.022 (3)	0.033 (3)	−0.003 (3)	0.003 (3)	−0.001 (3)
O7	0.056 (4)	0.033 (4)	0.029 (3)	−0.003 (3)	−0.014 (3)	−0.010 (3)
O8	0.041 (4)	0.043 (4)	0.023 (3)	0.002 (3)	−0.010 (3)	0.002 (3)
O9	0.064 (4)	0.023 (3)	0.027 (3)	−0.005 (3)	−0.002 (3)	0.003 (2)
N2	0.019 (4)	0.034 (4)	0.027 (4)	0.010 (3)	−0.006 (3)	−0.012 (3)
N4	0.032 (4)	0.019 (4)	0.032 (4)	−0.001 (3)	0.013 (3)	−0.006 (3)
N5	0.029 (4)	0.020 (4)	0.023 (3)	0.000 (3)	0.008 (3)	−0.002 (3)
N7	0.026 (4)	0.035 (4)	0.027 (4)	−0.001 (3)	−0.005 (3)	−0.006 (4)
Cl1	0.0340 (12)	0.0398 (11)	0.0187 (9)	0.0041 (9)	0.0005 (9)	−0.0012 (9)
C15	0.014 (4)	0.035 (4)	0.017 (3)	0.011 (4)	−0.004 (3)	0.004 (3)
C16	0.027 (5)	0.013 (4)	0.025 (4)	0.004 (3)	−0.003 (3)	0.003 (3)
C17	0.018 (4)	0.023 (4)	0.032 (4)	0.006 (3)	−0.003 (3)	−0.001 (4)
C18	0.025 (4)	0.038 (5)	0.027 (4)	−0.003 (4)	−0.002 (3)	0.001 (4)
C19	0.020 (4)	0.035 (5)	0.026 (4)	0.000 (4)	0.000 (3)	0.005 (4)
C20	0.025 (5)	0.026 (4)	0.033 (4)	0.003 (4)	−0.004 (4)	−0.004 (4)
Cl2	0.0472 (14)	0.0548 (15)	0.0386 (12)	0.0015 (12)	0.0068 (11)	0.0098 (12)
C21	0.027 (5)	0.045 (6)	0.029 (5)	0.007 (4)	0.009 (4)	−0.002 (4)
C22	0.025 (5)	0.045 (6)	0.043 (5)	0.001 (4)	0.008 (4)	−0.003 (5)
C23	0.025 (5)	0.063 (7)	0.043 (5)	0.007 (5)	−0.002 (4)	−0.030 (5)
C24	0.032 (5)	0.063 (7)	0.026 (5)	0.017 (5)	0.006 (4)	−0.001 (5)
C25	0.040 (5)	0.033 (5)	0.037 (5)	0.016 (4)	−0.001 (4)	−0.008 (4)
C26	0.040 (6)	0.044 (6)	0.032 (5)	0.009 (5)	−0.003 (4)	−0.010 (4)

Geometric parameters (Å, º)

C1—C10	1.363 (9)	O5—N5	1.225 (7)
C1—C2	1.386 (9)	O6—N5	1.242 (7)
C1—H1	0.9495	O7—N7	1.228 (8)
C2—C3	1.395 (9)	O8—N7	1.238 (8)
C2—N2	1.478 (8)	Cl1—C15	1.772 (6)
C3—C4	1.401 (9)	C15—C20	1.370 (10)
C3—H3	0.9498	C15—C16	1.377 (9)
C4—C11	1.400 (9)	C16—C17	1.401 (9)
C4—N4	1.469 (9)	C16—H16	0.9496
C5—C12	1.389 (9)	C17—C18	1.385 (9)
C5—C6	1.392 (9)	C17—H17	0.9497
C5—N5	1.478 (8)	C18—C19	1.387 (10)
C6—C7	1.377 (9)	C18—H18	0.9499
C6—H6	0.9495	C19—C20	1.414 (10)
C7—C8	1.386 (10)	C19—H19	0.9497
C7—N7	1.473 (9)	C20—H20	0.9496
C8—C13	1.367 (10)	Cl2—C21	1.761 (8)
C8—H8	0.9497	C21—C26	1.372 (11)
C9—O9	1.209 (8)	C21—C22	1.382 (11)
C9—C13	1.500 (10)	C22—C23	1.394 (11)
C9—C10	1.521 (9)	C22—H22	0.9496
C10—C11	1.412 (9)	C23—C24	1.395 (12)
C11—C12	1.502 (9)	C23—H23	0.9499
C12—C13	1.393 (9)	C24—C25	1.379 (11)
O1—N2	1.228 (8)	C24—H24	0.9498
O2—N2	1.223 (7)	C25—C26	1.385 (11)
O3—N4	1.233 (7)	C25—H25	0.9494
O4—N4	1.224 (7)	C26—H26	0.9500
C10—C1—C2	117.3 (7)	O3—N4—C4	117.4 (6)
C10—C1—H1	121.3	O5—N5—O6	125.3 (6)
C2—C1—H1	121.5	O5—N5—C5	117.4 (6)
C1—C2—C3	122.5 (7)	O6—N5—C5	117.2 (6)
C1—C2—N2	119.8 (6)	O7—N7—O8	123.6 (6)
C3—C2—N2	117.8 (6)	O7—N7—C7	118.6 (6)
C2—C3—C4	118.2 (6)	O8—N7—C7	117.8 (6)
C2—C3—H3	120.6	C20—C15—C16	123.2 (6)
C4—C3—H3	121.2	C20—C15—Cl1	118.9 (6)
C11—C4—C3	121.2 (6)	C16—C15—Cl1	117.9 (5)
C11—C4—N4	122.7 (6)	C15—C16—C17	118.1 (6)
C3—C4—N4	116.0 (6)	C15—C16—H16	121.0
C12—C5—C6	120.8 (6)	C17—C16—H16	120.9
C12—C5—N5	122.3 (6)	C18—C17—C16	119.9 (7)
C6—C5—N5	116.6 (6)	C18—C17—H17	120.2
C7—C6—C5	118.8 (6)	C16—C17—H17	119.9
C7—C6—H6	120.4	C17—C18—C19	121.3 (7)
C5—C6—H6	120.8	C17—C18—H18	119.1
C6—C7—C8	122.5 (7)	C19—C18—H18	119.6
C6—C7—N7	118.1 (6)	C18—C19—C20	118.9 (7)
C8—C7—N7	119.4 (7)	C18—C19—H19	120.6
C13—C8—C7	116.5 (7)	C20—C19—H19	120.5
C13—C8—H8	121.8	C15—C20—C19	118.6 (7)
C7—C8—H8	121.7	C15—C20—H20	120.8
O9—C9—C13	128.6 (7)	C19—C20—H20	120.6
O9—C9—C10	126.4 (7)	C26—C21—C22	123.6 (8)
C13—C9—C10	105.0 (6)	C26—C21—Cl2	118.6 (6)
C1—C10—C11	123.9 (6)	C22—C21—Cl2	117.7 (7)
C1—C10—C9	127.7 (7)	C21—C22—C23	118.1 (8)
C11—C10—C9	108.3 (6)	C21—C22—H22	120.8
C4—C11—C10	116.5 (6)	C23—C22—H22	121.1
C4—C11—C12	135.3 (6)	C22—C23—C24	119.3 (8)
C10—C11—C12	108.0 (6)	C22—C23—H23	119.8
C5—C12—C13	116.9 (6)	C24—C23—H23	120.9
C5—C12—C11	134.3 (6)	C25—C24—C23	120.5 (8)
C13—C12—C11	108.7 (6)	C25—C24—H24	119.8
C8—C13—C12	124.0 (7)	C23—C24—H24	119.7
C8—C13—C9	126.8 (7)	C24—C25—C26	120.9 (8)
C12—C13—C9	109.2 (6)	C24—C25—H25	119.7
O2—N2—O1	125.1 (6)	C26—C25—H25	119.3
O2—N2—C2	117.9 (6)	C21—C26—C25	117.5 (8)
O1—N2—C2	117.0 (6)	C21—C26—H26	121.3
O4—N4—O3	125.7 (7)	C25—C26—H26	121.2
O4—N4—C4	116.9 (6)