Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008753/ob6044sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008753/ob6044Isup2.hkl |
CCDC reference: 170758
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).
H-atom positions were calculated at C—H distances of 0.95 Å and they were included in the final calculations but not refined.
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.
C13H11N2+·C12H2Cl2N4− | Dx = 1.450 Mg m−3 |
Mr = 468.32 | Mo Kα radiation, λ = 0.7107 Å |
Monoclinic, P21/c | Cell parameters from 15754 reflections |
a = 7.2978 (3) Å | θ = 2.9–27.5° |
b = 14.9895 (5) Å | µ = 0.33 mm−1 |
c = 19.6091 (6) Å | T = 296 K |
β = 91.042 (1)° | Prism, purple |
V = 2144.7 (1) Å3 | 0.50 × 0.35 × 0.10 mm |
Z = 4 |
Rigaku RAXIS-RAPID Imaging Plate diffractometer | 3415 reflections with I > 2σ(I) |
ω scans | Rint = 0.029 |
Absorption correction: multi-scan (PROCESS-AUTO; Rigaku Corporation, 1998) | θmax = 27.5° |
Tmin = 0.845, Tmax = 0.968 | h = 0→9 |
19531 measured reflections | k = 0→19 |
4866 independent reflections | l = −25→25 |
Refinement on F2 | H-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 = 1.32 | Δρmax = 0.20 e Å−3 |
4866 reflections | Δρmin = −0.19 e Å−3 |
298 parameters |
C13H11N2+·C12H2Cl2N4− | V = 2144.7 (1) Å3 |
Mr = 468.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.2978 (3) Å | µ = 0.33 mm−1 |
b = 14.9895 (5) Å | T = 296 K |
c = 19.6091 (6) Å | 0.50 × 0.35 × 0.10 mm |
β = 91.042 (1)° |
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 = 0.968 | Rint = 0.029 |
19531 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 298 parameters |
wR(F2) = 0.122 | H-atom parameters not refined |
S = 1.32 | Δρmax = 0.20 e Å−3 |
4866 reflections | Δρmin = −0.19 e Å−3 |
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). |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.88214 (8) | −0.14863 (3) | 0.33299 (3) | 0.0499 (2) | |
Cl2 | 0.85892 (9) | 0.20783 (3) | 0.49611 (3) | 0.0530 (2) | |
N1 | 1.0833 (4) | −0.0779 (2) | 0.1895 (1) | 0.0816 (8) | |
N2 | 1.1973 (3) | 0.1835 (1) | 0.2508 (1) | 0.0650 (7) | |
N3 | 0.5762 (3) | −0.1303 (1) | 0.58405 (9) | 0.0516 (5) | |
N4 | 0.6246 (3) | 0.1345 (1) | 0.6378 (1) | 0.0689 (7) | |
N5 | 0.6122 (3) | −0.0821 (1) | 0.12789 (9) | 0.0488 (5) | |
N6 | 0.7580 (3) | 0.0638 (1) | 0.05987 (10) | 0.0548 (6) | |
C1 | 0.8878 (3) | −0.0496 (1) | 0.37854 (9) | 0.0374 (5) | |
C2 | 0.9704 (3) | 0.0281 (1) | 0.35107 (9) | 0.0370 (5) | |
C3 | 0.9556 (3) | 0.1060 (1) | 0.39232 (10) | 0.0382 (5) | |
C4 | 0.8712 (3) | 0.1065 (1) | 0.45368 (10) | 0.0376 (5) | |
C5 | 0.7939 (3) | 0.0279 (1) | 0.48245 (9) | 0.0350 (5) | |
C6 | 0.8059 (3) | −0.0494 (1) | 0.44047 (10) | 0.0370 (5) | |
C7 | 1.0683 (3) | −0.0317 (2) | 0.2357 (1) | 0.0532 (7) | |
C8 | 1.0575 (3) | 0.0346 (1) | 0.28709 (10) | 0.0434 (6) | |
C9 | 1.1351 (3) | 0.1175 (2) | 0.2673 (1) | 0.0470 (6) | |
C10 | 0.6356 (3) | −0.0634 (1) | 0.56635 (10) | 0.0389 (5) | |
C11 | 0.7069 (3) | 0.0208 (1) | 0.54596 (10) | 0.0371 (5) | |
C12 | 0.6672 (3) | 0.0884 (1) | 0.5942 (1) | 0.0458 (6) | |
C13 | 0.5830 (4) | 0.0093 (2) | 0.2298 (1) | 0.0592 (7) | |
C14 | 0.6069 (4) | 0.0912 (2) | 0.2586 (1) | 0.0724 (9) | |
C15 | 0.6855 (4) | 0.1640 (2) | 0.2236 (2) | 0.0729 (9) | |
C16 | 0.7368 (4) | 0.1528 (2) | 0.1586 (1) | 0.0665 (8) | |
C17 | 0.7112 (3) | 0.0700 (2) | 0.1248 (1) | 0.0488 (6) | |
C18 | 0.6339 (3) | −0.0033 (1) | 0.1613 (1) | 0.0459 (6) | |
C19 | 0.6242 (4) | −0.1686 (2) | 0.0226 (1) | 0.0693 (9) | |
C20 | 0.6695 (5) | −0.1706 (2) | −0.0451 (2) | 0.083 (1) | |
C21 | 0.7450 (4) | −0.0960 (3) | −0.0773 (1) | 0.080 (1) | |
C22 | 0.7748 (4) | −0.0190 (2) | −0.0428 (1) | 0.0667 (8) | |
C23 | 0.7292 (3) | −0.0137 (2) | 0.0276 (1) | 0.0495 (6) | |
C24 | 0.6549 (3) | −0.0897 (2) | 0.0603 (1) | 0.0498 (6) | |
C25 | 0.5397 (5) | −0.1605 (2) | 0.1648 (1) | 0.0767 (9) | |
H1 | 0.7522 | −0.1040 | 0.4552 | 0.0802* | |
H2 | 1.0011 | 0.1624 | 0.3724 | 0.0802* | |
H3 | 0.5235 | −0.0436 | 0.2547 | 0.0802* | |
H4 | 0.5703 | 0.0921 | 0.3069 | 0.0802* | |
H5 | 0.7138 | 0.2234 | 0.2512 | 0.0802* | |
H6 | 0.7920 | 0.2068 | 0.1301 | 0.0802* | |
H7 | 0.5833 | −0.2276 | 0.0473 | 0.0802* | |
H8 | 0.6661 | −0.2274 | −0.0726 | 0.0802* | |
H9 | 0.7548 | −0.0958 | −0.1283 | 0.0802* | |
H10 | 0.8319 | 0.0397 | −0.0684 | 0.0802* | |
H11 | 0.6172 | −0.1758 | 0.2029 | 0.0917* | |
H12 | 0.4192 | −0.1487 | 0.1815 | 0.0917* | |
H13 | 0.5316 | −0.2115 | 0.1353 | 0.0917* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0683 (4) | 0.0389 (3) | 0.0428 (3) | −0.0057 (2) | 0.0100 (2) | −0.0078 (2) |
Cl2 | 0.0719 (4) | 0.0335 (3) | 0.0541 (3) | −0.0038 (3) | 0.0114 (3) | −0.0059 (2) |
N1 | 0.117 (2) | 0.077 (2) | 0.052 (1) | −0.009 (1) | 0.032 (1) | −0.010 (1) |
N2 | 0.078 (2) | 0.059 (1) | 0.059 (1) | −0.008 (1) | 0.010 (1) | 0.0174 (10) |
N3 | 0.059 (1) | 0.048 (1) | 0.049 (1) | −0.0065 (9) | 0.0089 (9) | 0.0056 (8) |
N4 | 0.078 (2) | 0.057 (1) | 0.072 (1) | −0.009 (1) | 0.032 (1) | −0.020 (1) |
N5 | 0.051 (1) | 0.046 (1) | 0.050 (1) | 0.0070 (8) | 0.0052 (9) | 0.0134 (8) |
N6 | 0.055 (1) | 0.058 (1) | 0.052 (1) | 0.0006 (9) | 0.0080 (9) | 0.0137 (9) |
C1 | 0.042 (1) | 0.0340 (10) | 0.0364 (10) | −0.0006 (8) | 0.0004 (8) | −0.0017 (8) |
C2 | 0.038 (1) | 0.0380 (10) | 0.0347 (9) | 0.0001 (8) | 0.0025 (8) | 0.0040 (8) |
C3 | 0.040 (1) | 0.0348 (10) | 0.0394 (10) | −0.0012 (8) | 0.0006 (8) | 0.0045 (8) |
C4 | 0.040 (1) | 0.0315 (9) | 0.041 (1) | 0.0004 (8) | 0.0009 (8) | −0.0015 (8) |
C5 | 0.0336 (10) | 0.0353 (10) | 0.0361 (9) | 0.0003 (8) | −0.0001 (8) | 0.0023 (8) |
C6 | 0.039 (1) | 0.0332 (9) | 0.0390 (10) | −0.0032 (8) | 0.0013 (8) | 0.0019 (8) |
C7 | 0.062 (1) | 0.056 (1) | 0.042 (1) | −0.002 (1) | 0.012 (1) | 0.004 (1) |
C8 | 0.047 (1) | 0.047 (1) | 0.036 (1) | 0.0010 (10) | 0.0041 (9) | 0.0057 (9) |
C9 | 0.052 (1) | 0.052 (1) | 0.037 (1) | 0.004 (1) | 0.0055 (10) | 0.0078 (9) |
C10 | 0.039 (1) | 0.044 (1) | 0.0337 (9) | 0.0016 (9) | 0.0040 (8) | 0.0005 (8) |
C11 | 0.036 (1) | 0.0376 (10) | 0.0377 (10) | −0.0012 (8) | 0.0023 (8) | 0.0004 (8) |
C12 | 0.045 (1) | 0.045 (1) | 0.048 (1) | −0.0053 (10) | 0.0099 (10) | −0.0017 (10) |
C13 | 0.055 (1) | 0.078 (2) | 0.045 (1) | 0.011 (1) | 0.007 (1) | 0.008 (1) |
C14 | 0.064 (2) | 0.106 (2) | 0.048 (1) | 0.029 (2) | 0.004 (1) | −0.006 (1) |
C15 | 0.077 (2) | 0.071 (2) | 0.071 (2) | 0.017 (2) | −0.007 (1) | −0.013 (1) |
C16 | 0.073 (2) | 0.055 (1) | 0.072 (2) | 0.007 (1) | 0.000 (1) | 0.002 (1) |
C17 | 0.046 (1) | 0.050 (1) | 0.050 (1) | 0.008 (1) | 0.0028 (10) | 0.0087 (10) |
C18 | 0.042 (1) | 0.052 (1) | 0.044 (1) | 0.0113 (10) | 0.0036 (9) | 0.0089 (9) |
C19 | 0.083 (2) | 0.051 (1) | 0.073 (2) | 0.014 (1) | −0.003 (1) | −0.001 (1) |
C20 | 0.102 (2) | 0.083 (2) | 0.065 (2) | 0.034 (2) | −0.008 (2) | −0.017 (2) |
C21 | 0.079 (2) | 0.112 (3) | 0.048 (1) | 0.025 (2) | 0.005 (1) | −0.006 (2) |
C22 | 0.056 (2) | 0.096 (2) | 0.048 (1) | 0.008 (1) | 0.008 (1) | 0.010 (1) |
C23 | 0.044 (1) | 0.060 (1) | 0.045 (1) | 0.008 (1) | 0.0050 (10) | 0.008 (1) |
C24 | 0.049 (1) | 0.051 (1) | 0.049 (1) | 0.014 (1) | 0.004 (1) | 0.0077 (10) |
C25 | 0.104 (2) | 0.056 (2) | 0.071 (2) | −0.004 (2) | 0.016 (2) | 0.023 (1) |
Cl1—C1 | 1.732 (2) | C11—C12 | 1.420 (3) |
Cl2—C4 | 1.734 (2) | C13—C14 | 1.361 (4) |
N1—C7 | 1.149 (3) | C13—C18 | 1.413 (3) |
N2—C9 | 1.139 (3) | C13—H3 | 1.031 |
N3—C10 | 1.148 (3) | C14—C15 | 1.417 (4) |
N4—C12 | 1.146 (3) | C14—H4 | 0.989 |
N5—C18 | 1.357 (3) | C15—C16 | 1.345 (4) |
N5—C24 | 1.371 (3) | C15—H5 | 1.061 |
N5—C25 | 1.483 (3) | C16—C17 | 1.417 (4) |
N6—C17 | 1.328 (3) | C16—H6 | 1.067 |
N6—C23 | 1.337 (3) | C17—C18 | 1.433 (3) |
C1—C2 | 1.422 (3) | C19—C20 | 1.374 (4) |
C1—C6 | 1.363 (3) | C19—C24 | 1.410 (4) |
C2—C3 | 1.426 (3) | C19—H7 | 1.054 |
C2—C8 | 1.420 (3) | C20—C21 | 1.403 (5) |
C3—C4 | 1.362 (3) | C20—H8 | 1.008 |
C3—H2 | 0.990 | C21—C22 | 1.354 (5) |
C4—C5 | 1.427 (3) | C21—H9 | 1.004 |
C5—C6 | 1.425 (3) | C22—C23 | 1.428 (3) |
C5—C11 | 1.412 (3) | C22—H10 | 1.098 |
C6—H1 | 0.954 | C23—C24 | 1.421 (3) |
C7—C8 | 1.418 (3) | C25—H11 | 0.958 |
C8—C9 | 1.421 (3) | C25—H12 | 0.960 |
C10—C11 | 1.426 (3) | C25—H13 | 0.960 |
C18—N5—C24 | 120.8 (2) | C15—C14—H4 | 125.0 |
C18—N5—C25 | 119.6 (2) | C14—C15—C16 | 119.1 (3) |
C24—N5—C25 | 119.6 (2) | C14—C15—H5 | 118.3 |
C17—N6—C23 | 118.3 (2) | C16—C15—H5 | 122.3 |
Cl1—C1—C2 | 120.9 (1) | C15—C16—C17 | 121.0 (2) |
Cl1—C1—C6 | 117.0 (1) | C15—C16—H6 | 121.1 |
C2—C1—C6 | 122.1 (2) | C17—C16—H6 | 117.9 |
C1—C2—C3 | 114.8 (2) | N6—C17—C16 | 118.4 (2) |
C1—C2—C8 | 126.2 (2) | N6—C17—C18 | 122.3 (2) |
C3—C2—C8 | 119.0 (2) | C16—C17—C18 | 119.3 (2) |
C2—C3—C4 | 123.1 (2) | N5—C18—C13 | 123.0 (2) |
C2—C3—H2 | 116.5 | N5—C18—C17 | 118.0 (2) |
C4—C3—H2 | 120.3 | C13—C18—C17 | 119.0 (2) |
Cl2—C4—C3 | 117.2 (1) | C20—C19—C24 | 119.1 (3) |
Cl2—C4—C5 | 120.6 (1) | C20—C19—H7 | 120.1 |
C3—C4—C5 | 122.2 (2) | C24—C19—H7 | 120.4 |
C4—C5—C6 | 114.5 (2) | C19—C20—C21 | 121.4 (3) |
C4—C5—C11 | 126.7 (2) | C19—C20—H8 | 122.1 |
C6—C5—C11 | 118.8 (2) | C21—C20—H8 | 116.0 |
C1—C6—C5 | 123.3 (2) | C20—C21—C22 | 121.0 (3) |
C1—C6—H1 | 117.1 | C20—C21—H9 | 119.2 |
C5—C6—H1 | 119.6 | C22—C21—H9 | 118.8 |
N1—C7—C8 | 172.5 (3) | C21—C22—C23 | 119.5 (3) |
C2—C8—C7 | 127.7 (2) | C21—C22—H10 | 120.9 |
C2—C8—C9 | 119.2 (2) | C23—C22—H10 | 119.6 |
C7—C8—C9 | 113.0 (2) | N6—C23—C22 | 118.0 (2) |
N2—C9—C8 | 179.3 (2) | N6—C23—C24 | 122.7 (2) |
N3—C10—C11 | 178.4 (2) | C22—C23—C24 | 119.3 (2) |
C5—C11—C10 | 119.1 (2) | N5—C24—C19 | 122.7 (2) |
C5—C11—C12 | 129.3 (2) | N5—C24—C23 | 117.7 (2) |
C10—C11—C12 | 111.4 (2) | C19—C24—C23 | 119.6 (2) |
N4—C12—C11 | 171.2 (2) | N5—C25—H11 | 111.1 |
C14—C13—C18 | 118.8 (2) | N5—C25—H12 | 110.9 |
C14—C13—H3 | 123.2 | N5—C25—H13 | 110.9 |
C18—C13—H3 | 117.9 | H11—C25—H12 | 108.0 |
C13—C14—C15 | 122.9 (2) | H11—C25—H13 | 108.0 |
C13—C14—H4 | 112.0 | H12—C25—H13 | 107.8 |
Experimental details
Crystal data | |
Chemical formula | C13H11N2+·C12H2Cl2N4− |
Mr | 468.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 7.2978 (3), 14.9895 (5), 19.6091 (6) |
β (°) | 91.042 (1) |
V (Å3) | 2144.7 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.50 × 0.35 × 0.10 |
Data collection | |
Diffractometer | Rigaku RAXIS-RAPID Imaging Plate diffractometer |
Absorption correction | Multi-scan (PROCESS-AUTO; Rigaku Corporation, 1998) |
Tmin, Tmax | 0.845, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19531, 4866, 3415 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.122, 1.32 |
No. of reflections | 4866 |
No. of parameters | 298 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.20, −0.19 |
Computer programs: PROCESS-AUTO (Rigaku Corporation, 1998), PROCESS-AUTO, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), TEXSAN.
Cl1—C1 | 1.732 (2) | Cl2—C4 | 1.734 (2) |
Cl1—C1—C2 | 120.9 (1) | N1—C7—C8 | 172.5 (3) |
Cl1—C1—C6 | 117.0 (1) | N2—C9—C8 | 179.3 (2) |
Cl2—C4—C3 | 117.2 (1) | N3—C10—C11 | 178.4 (2) |
Cl2—C4—C5 | 120.6 (1) | N4—C12—C11 | 171.2 (2) |
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.