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In the title compound, C13H11N2+·C12H2Cl2N4.-, the N-methyl­phenazinium cations have a dimerized structure with an interplanar distance of 3.42 (9) Å without effective overlap between the dimers. On the other hand, the 2,5-di­chloro-7,7',8,8'-tetra­cyano­quinodimethanide radical anions form a one-dimensional columnar structure along the a axis. In the column, there are two different kinds of modes in the overlap of the mol­ecules: one mode has a slipped structure along a longer molecular axis of the mol­ecules, whose six-membered rings are shifted by 2.14 (8) Å, and in the other mode, the C(CN)2 groups are only overlapped with each other. The modes have interplanar distances of 3.11 (4) and 3.19 (2) Å, respectively.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008753/ob6044sup1.cif
Contains datablocks General, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008753/ob6044Isup2.hkl
Contains datablock I

CCDC reference: 170758

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.042
  • wR factor = 0.122
  • Data-to-parameter ratio = 16.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(7) - C(8) = 1.42 Ang. PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(8) - C(9) = 1.42 Ang. PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(10) - C(11) = 1.42 Ang. PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(11) - C(12) = 1.42 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
4 Alert Level C = Please check

Comment top

Much attention has been directed toward 7,7'8,8'-tetracyanoquinodimethanide radical anion (TCNQ.-) salts with alkali metal, ammonium, phosphonium and arsonium ions etc. for developing high electrical conducting organic materials (Hoekistra et al., 1972; Konno et al., 1974, 1977). For the TCNQ.- salts, the TCNQ.- molecules are usually dimerized and stacked one-dimensionally. As a result of such a structural feature, the room-temperature electrical conductivities were very low (< 10-2 S cm-1). Nevertheless, as an exception, an N-methylphenazinium salt of TCNQ.- (NMP+·TCNQ.-) exhibited very high room-temperature electrical conducting of 170 S cm-1 (Fritchie, 1966; Coleman et al., 1972; Kobayashi, 1975). In the crystals of NMP+·TCNQ.- at room temperature, the TCNQ.- molecules form a uniform and one-dimensional stacking. Although the temperature dependence of electrical conductivity is metallic at 200–300 K, a metal-to-insulator transition occurrs at around 200 K due to the preferential dimerization of TCNQ.- molecules (Epstein et al., 1972; Coleman et al., 1973). In order to maintain the metallic state down to low temperature and furthermore to achieve superconductivity, it is necessary to stabilize a uniform stacking structure of TCNQ.- molecules. A possible approach that dimerization of TCNQ.- molecules is suppressed is to introduce sterically bulky substitutents to TCNQ.- such as methyl groups and halogen atoms. In fact, for a tetramethylphosphonium (PMe4+) salt of 2,5-dimethyl-substituted TCNQ radical anion (Me2TCNQ.-) and a tetramethylarsonium (AsMe4+) salt of Cl2TCNQ.- the Me2TCNQ.- and Cl2TCNQ.- molecules form a uniform stacking structure at room temperature (Sugimoto et al., 1998; Ueda et al., 2001). In this paper, the structure of the title compound, NMP+·Cl2TCNQ.-, (I), has been determined.

The NMP+ molecule shows high planarity (Fig. 1). On the other hand, the dihedral angles between the six-membered ring and two C(CN)2 groups in the Cl2TCNQ.- molecule are 3.0 (3) and 5.7 (4)°, which are slightly larger than those in AsMe4+·Cl2TCNQ.- (Ueda et al., 2001). Two of C—CN bonds among four are slightly bent which may be due to avoid the short C—N···Cl non-bonded interaction. This may be also the driving force of the non-planar structure of the Cl2TCNQ.- molecule.

As shown from the crystal structures viewed along a and b axes in Fig. 2, columns of the NMP+ and Cl2TCNQ.- molecules are alternatively arranged along b and c axes. The neighboring NMP+ molecules related by center of symmetry are dimerized with an interplanar distance of 3.42 (9) Å, which is comparable to a 'π-cloud thickness' (3.42 Å; Pauling, 1960). There is no overlap between the dimers, as is seen from the distance of 4.99 (2) Å between the centers of the pyrazine rings. On the other hand, the Cl2TCNQ.- molecules form a one-dimensional columnar structure along a axis. The columnar structure is not uniform, and there are two kinds of modes (A and B) in the overlap of Cl2TCNQ.- molecules (Fig. 3). In the A mode, the neighboring molecules slip along the longer molecular axis to each other, and the centers of six-membered rings are apart by 2.14 (8) Å. This stacking mode is very similar to that of TCNQ.- molecules in NMP+.TCNQ.-, in which the distance between the centers of six-membered rings is 2.09 (4) Å (Fritchie, 1966). While in the B mode, only the C(CN)2 groups of the neighboring molecules are overlapped with a large distance of 5.73 (1) Å between the centers of six-membered rings. The interplanar distances in the A and B modes are 3.11 (4) and 3.19 (2) Å, respectively, which are shorter than the 'π-cloud thickness.' As expected from such an irregular stacking of Cl2TCNQ.- molecules, the title compound (I) exhibits very low electrical conducting of 1 × 10-5 S cm-1 at room temperature.

Experimental top

Reaction of Cl2TCNQ (Wheland & Martin, 1975; 43.8 mg, 0.604 mmol) with LiI (66.0 mg, 0.4931 mmol) in 2 ml of CH3CN gave Li+ salt of Cl2TCNQ.- (36.0 mg, 53% yield), followed by the treatment with an equimolar amount of NMP+.CH3OSO3- (Khermann & Havas, 1913) in H2O to afford the title compound, (I). Crystals of (I) were obtained from a CH3CN/Et2O solution (m.p. > 573 K).

Refinement top

H-atom positions were calculated at C—H distances of 0.95 Å and they were included in the final calculations but not refined.

Computing details top

Data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with ellipsoids plotted at the 50% probability level.
[Figure 2] Fig. 2. The crystal structure of (I) viewed along the a (top) and b (bottom) axes.
[Figure 3] Fig. 3. Two kinds of overlap modes, A (top) and B (bottom), within the Cl2TCNQ.- column. The view direction is perpendicular to the molecular planes.
(I) top
Crystal data top
C13H11N2+·C12H2Cl2N4Dx = 1.450 Mg m3
Mr = 468.32Mo Kα radiation, λ = 0.7107 Å
Monoclinic, P21/cCell parameters from 15754 reflections
a = 7.2978 (3) Åθ = 2.9–27.5°
b = 14.9895 (5) ŵ = 0.33 mm1
c = 19.6091 (6) ÅT = 296 K
β = 91.042 (1)°Prism, purple
V = 2144.7 (1) Å30.50 × 0.35 × 0.10 mm
Z = 4
Data collection top
Rigaku RAXIS-RAPID Imaging Plate
diffractometer
3415 reflections with I > 2σ(I)
ω scansRint = 0.029
Absorption correction: multi-scan
(PROCESS-AUTO; Rigaku Corporation, 1998)
θmax = 27.5°
Tmin = 0.845, Tmax = 0.968h = 09
19531 measured reflectionsk = 019
4866 independent reflectionsl = 2525
Refinement top
Refinement on F2H-atom parameters not refined
R[F2 > 2σ(F2)] = 0.042 w = 1/[σ2(Fo2) + {0.05[Max(Fo2,0) + 2Fc2]/3}2]
wR(F2) = 0.122(Δ/σ)max = 0.005
S = 1.32Δρmax = 0.20 e Å3
4866 reflectionsΔρmin = 0.19 e Å3
298 parameters
Crystal data top
C13H11N2+·C12H2Cl2N4V = 2144.7 (1) Å3
Mr = 468.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.2978 (3) ŵ = 0.33 mm1
b = 14.9895 (5) ÅT = 296 K
c = 19.6091 (6) Å0.50 × 0.35 × 0.10 mm
β = 91.042 (1)°
Data collection top
Rigaku RAXIS-RAPID Imaging Plate
diffractometer
4866 independent reflections
Absorption correction: multi-scan
(PROCESS-AUTO; Rigaku Corporation, 1998)
3415 reflections with I > 2σ(I)
Tmin = 0.845, Tmax = 0.968Rint = 0.029
19531 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042298 parameters
wR(F2) = 0.122H-atom parameters not refined
S = 1.32Δρmax = 0.20 e Å3
4866 reflectionsΔρmin = 0.19 e Å3
Special details top

Refinement. Refinement using reflections with F2 > -10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.88214 (8)0.14863 (3)0.33299 (3)0.0499 (2)
Cl20.85892 (9)0.20783 (3)0.49611 (3)0.0530 (2)
N11.0833 (4)0.0779 (2)0.1895 (1)0.0816 (8)
N21.1973 (3)0.1835 (1)0.2508 (1)0.0650 (7)
N30.5762 (3)0.1303 (1)0.58405 (9)0.0516 (5)
N40.6246 (3)0.1345 (1)0.6378 (1)0.0689 (7)
N50.6122 (3)0.0821 (1)0.12789 (9)0.0488 (5)
N60.7580 (3)0.0638 (1)0.05987 (10)0.0548 (6)
C10.8878 (3)0.0496 (1)0.37854 (9)0.0374 (5)
C20.9704 (3)0.0281 (1)0.35107 (9)0.0370 (5)
C30.9556 (3)0.1060 (1)0.39232 (10)0.0382 (5)
C40.8712 (3)0.1065 (1)0.45368 (10)0.0376 (5)
C50.7939 (3)0.0279 (1)0.48245 (9)0.0350 (5)
C60.8059 (3)0.0494 (1)0.44047 (10)0.0370 (5)
C71.0683 (3)0.0317 (2)0.2357 (1)0.0532 (7)
C81.0575 (3)0.0346 (1)0.28709 (10)0.0434 (6)
C91.1351 (3)0.1175 (2)0.2673 (1)0.0470 (6)
C100.6356 (3)0.0634 (1)0.56635 (10)0.0389 (5)
C110.7069 (3)0.0208 (1)0.54596 (10)0.0371 (5)
C120.6672 (3)0.0884 (1)0.5942 (1)0.0458 (6)
C130.5830 (4)0.0093 (2)0.2298 (1)0.0592 (7)
C140.6069 (4)0.0912 (2)0.2586 (1)0.0724 (9)
C150.6855 (4)0.1640 (2)0.2236 (2)0.0729 (9)
C160.7368 (4)0.1528 (2)0.1586 (1)0.0665 (8)
C170.7112 (3)0.0700 (2)0.1248 (1)0.0488 (6)
C180.6339 (3)0.0033 (1)0.1613 (1)0.0459 (6)
C190.6242 (4)0.1686 (2)0.0226 (1)0.0693 (9)
C200.6695 (5)0.1706 (2)0.0451 (2)0.083 (1)
C210.7450 (4)0.0960 (3)0.0773 (1)0.080 (1)
C220.7748 (4)0.0190 (2)0.0428 (1)0.0667 (8)
C230.7292 (3)0.0137 (2)0.0276 (1)0.0495 (6)
C240.6549 (3)0.0897 (2)0.0603 (1)0.0498 (6)
C250.5397 (5)0.1605 (2)0.1648 (1)0.0767 (9)
H10.75220.10400.45520.0802*
H21.00110.16240.37240.0802*
H30.52350.04360.25470.0802*
H40.57030.09210.30690.0802*
H50.71380.22340.25120.0802*
H60.79200.20680.13010.0802*
H70.58330.22760.04730.0802*
H80.66610.22740.07260.0802*
H90.75480.09580.12830.0802*
H100.83190.03970.06840.0802*
H110.61720.17580.20290.0917*
H120.41920.14870.18150.0917*
H130.53160.21150.13530.0917*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0683 (4)0.0389 (3)0.0428 (3)0.0057 (2)0.0100 (2)0.0078 (2)
Cl20.0719 (4)0.0335 (3)0.0541 (3)0.0038 (3)0.0114 (3)0.0059 (2)
N10.117 (2)0.077 (2)0.052 (1)0.009 (1)0.032 (1)0.010 (1)
N20.078 (2)0.059 (1)0.059 (1)0.008 (1)0.010 (1)0.0174 (10)
N30.059 (1)0.048 (1)0.049 (1)0.0065 (9)0.0089 (9)0.0056 (8)
N40.078 (2)0.057 (1)0.072 (1)0.009 (1)0.032 (1)0.020 (1)
N50.051 (1)0.046 (1)0.050 (1)0.0070 (8)0.0052 (9)0.0134 (8)
N60.055 (1)0.058 (1)0.052 (1)0.0006 (9)0.0080 (9)0.0137 (9)
C10.042 (1)0.0340 (10)0.0364 (10)0.0006 (8)0.0004 (8)0.0017 (8)
C20.038 (1)0.0380 (10)0.0347 (9)0.0001 (8)0.0025 (8)0.0040 (8)
C30.040 (1)0.0348 (10)0.0394 (10)0.0012 (8)0.0006 (8)0.0045 (8)
C40.040 (1)0.0315 (9)0.041 (1)0.0004 (8)0.0009 (8)0.0015 (8)
C50.0336 (10)0.0353 (10)0.0361 (9)0.0003 (8)0.0001 (8)0.0023 (8)
C60.039 (1)0.0332 (9)0.0390 (10)0.0032 (8)0.0013 (8)0.0019 (8)
C70.062 (1)0.056 (1)0.042 (1)0.002 (1)0.012 (1)0.004 (1)
C80.047 (1)0.047 (1)0.036 (1)0.0010 (10)0.0041 (9)0.0057 (9)
C90.052 (1)0.052 (1)0.037 (1)0.004 (1)0.0055 (10)0.0078 (9)
C100.039 (1)0.044 (1)0.0337 (9)0.0016 (9)0.0040 (8)0.0005 (8)
C110.036 (1)0.0376 (10)0.0377 (10)0.0012 (8)0.0023 (8)0.0004 (8)
C120.045 (1)0.045 (1)0.048 (1)0.0053 (10)0.0099 (10)0.0017 (10)
C130.055 (1)0.078 (2)0.045 (1)0.011 (1)0.007 (1)0.008 (1)
C140.064 (2)0.106 (2)0.048 (1)0.029 (2)0.004 (1)0.006 (1)
C150.077 (2)0.071 (2)0.071 (2)0.017 (2)0.007 (1)0.013 (1)
C160.073 (2)0.055 (1)0.072 (2)0.007 (1)0.000 (1)0.002 (1)
C170.046 (1)0.050 (1)0.050 (1)0.008 (1)0.0028 (10)0.0087 (10)
C180.042 (1)0.052 (1)0.044 (1)0.0113 (10)0.0036 (9)0.0089 (9)
C190.083 (2)0.051 (1)0.073 (2)0.014 (1)0.003 (1)0.001 (1)
C200.102 (2)0.083 (2)0.065 (2)0.034 (2)0.008 (2)0.017 (2)
C210.079 (2)0.112 (3)0.048 (1)0.025 (2)0.005 (1)0.006 (2)
C220.056 (2)0.096 (2)0.048 (1)0.008 (1)0.008 (1)0.010 (1)
C230.044 (1)0.060 (1)0.045 (1)0.008 (1)0.0050 (10)0.008 (1)
C240.049 (1)0.051 (1)0.049 (1)0.014 (1)0.004 (1)0.0077 (10)
C250.104 (2)0.056 (2)0.071 (2)0.004 (2)0.016 (2)0.023 (1)
Geometric parameters (Å, º) top
Cl1—C11.732 (2)C11—C121.420 (3)
Cl2—C41.734 (2)C13—C141.361 (4)
N1—C71.149 (3)C13—C181.413 (3)
N2—C91.139 (3)C13—H31.031
N3—C101.148 (3)C14—C151.417 (4)
N4—C121.146 (3)C14—H40.989
N5—C181.357 (3)C15—C161.345 (4)
N5—C241.371 (3)C15—H51.061
N5—C251.483 (3)C16—C171.417 (4)
N6—C171.328 (3)C16—H61.067
N6—C231.337 (3)C17—C181.433 (3)
C1—C21.422 (3)C19—C201.374 (4)
C1—C61.363 (3)C19—C241.410 (4)
C2—C31.426 (3)C19—H71.054
C2—C81.420 (3)C20—C211.403 (5)
C3—C41.362 (3)C20—H81.008
C3—H20.990C21—C221.354 (5)
C4—C51.427 (3)C21—H91.004
C5—C61.425 (3)C22—C231.428 (3)
C5—C111.412 (3)C22—H101.098
C6—H10.954C23—C241.421 (3)
C7—C81.418 (3)C25—H110.958
C8—C91.421 (3)C25—H120.960
C10—C111.426 (3)C25—H130.960
C18—N5—C24120.8 (2)C15—C14—H4125.0
C18—N5—C25119.6 (2)C14—C15—C16119.1 (3)
C24—N5—C25119.6 (2)C14—C15—H5118.3
C17—N6—C23118.3 (2)C16—C15—H5122.3
Cl1—C1—C2120.9 (1)C15—C16—C17121.0 (2)
Cl1—C1—C6117.0 (1)C15—C16—H6121.1
C2—C1—C6122.1 (2)C17—C16—H6117.9
C1—C2—C3114.8 (2)N6—C17—C16118.4 (2)
C1—C2—C8126.2 (2)N6—C17—C18122.3 (2)
C3—C2—C8119.0 (2)C16—C17—C18119.3 (2)
C2—C3—C4123.1 (2)N5—C18—C13123.0 (2)
C2—C3—H2116.5N5—C18—C17118.0 (2)
C4—C3—H2120.3C13—C18—C17119.0 (2)
Cl2—C4—C3117.2 (1)C20—C19—C24119.1 (3)
Cl2—C4—C5120.6 (1)C20—C19—H7120.1
C3—C4—C5122.2 (2)C24—C19—H7120.4
C4—C5—C6114.5 (2)C19—C20—C21121.4 (3)
C4—C5—C11126.7 (2)C19—C20—H8122.1
C6—C5—C11118.8 (2)C21—C20—H8116.0
C1—C6—C5123.3 (2)C20—C21—C22121.0 (3)
C1—C6—H1117.1C20—C21—H9119.2
C5—C6—H1119.6C22—C21—H9118.8
N1—C7—C8172.5 (3)C21—C22—C23119.5 (3)
C2—C8—C7127.7 (2)C21—C22—H10120.9
C2—C8—C9119.2 (2)C23—C22—H10119.6
C7—C8—C9113.0 (2)N6—C23—C22118.0 (2)
N2—C9—C8179.3 (2)N6—C23—C24122.7 (2)
N3—C10—C11178.4 (2)C22—C23—C24119.3 (2)
C5—C11—C10119.1 (2)N5—C24—C19122.7 (2)
C5—C11—C12129.3 (2)N5—C24—C23117.7 (2)
C10—C11—C12111.4 (2)C19—C24—C23119.6 (2)
N4—C12—C11171.2 (2)N5—C25—H11111.1
C14—C13—C18118.8 (2)N5—C25—H12110.9
C14—C13—H3123.2N5—C25—H13110.9
C18—C13—H3117.9H11—C25—H12108.0
C13—C14—C15122.9 (2)H11—C25—H13108.0
C13—C14—H4112.0H12—C25—H13107.8

Experimental details

Crystal data
Chemical formulaC13H11N2+·C12H2Cl2N4
Mr468.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)7.2978 (3), 14.9895 (5), 19.6091 (6)
β (°) 91.042 (1)
V3)2144.7 (1)
Z4
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.50 × 0.35 × 0.10
Data collection
DiffractometerRigaku RAXIS-RAPID Imaging Plate
diffractometer
Absorption correctionMulti-scan
(PROCESS-AUTO; Rigaku Corporation, 1998)
Tmin, Tmax0.845, 0.968
No. of measured, independent and
observed [I > 2σ(I)] reflections
19531, 4866, 3415
Rint0.029
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.122, 1.32
No. of reflections4866
No. of parameters298
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.20, 0.19

Computer programs: PROCESS-AUTO (Rigaku Corporation, 1998), PROCESS-AUTO, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), TEXSAN.

Selected geometric parameters (Å, º) top
Cl1—C11.732 (2)Cl2—C41.734 (2)
Cl1—C1—C2120.9 (1)N1—C7—C8172.5 (3)
Cl1—C1—C6117.0 (1)N2—C9—C8179.3 (2)
Cl2—C4—C3117.2 (1)N3—C10—C11178.4 (2)
Cl2—C4—C5120.6 (1)N4—C12—C11171.2 (2)
 

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