In the tetramethylarsonium salt of 2,5-dichloro-7,7,8,8-tetracyanoquinodimethanide [systematic name: tetramethylarsonium 2,2'-(2,5-dichlorocyclohexa-2,5-diene-1,4-diylidene)bis(propanedinitrile)], C4H12As+·C12H2Cl2N4- or [As(CH3)4](C12H2Cl2N4), the cation lies disordered about a twofold axis and the radical ion lies about an inversion center forming a uniform [interplanar distance 3.35 (2) Å] and one-dimensional stacking without any slip. The electrical conductivity of the single crystal at room temperature was less than 10-9 S cm-1, and the temperature dependence of paramagnetic susceptibility obeyed a one-dimensional antiferromagnetic Heisenberg model with a spin-exchange integral of 83 K in the temperature range 1.8-320.0 K.
Supporting information
CCDC reference: 163902
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1985a); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985b); program(s) used to solve structure: SIR92; program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.
Crystal data top
C4H12As+·C12H2Cl2N4− | Dx = 1.350 Mg m−3 |
Mr = 408.14 | Mo Kα radiation, λ = 0.7107 Å |
Monoclinic, C2/c | Cell parameters from 24 reflections |
a = 11.046 (3) Å | θ = 12.9–14.8° |
b = 27.336 (4) Å | µ = 1.96 mm−1 |
c = 6.707 (6) Å | T = 296 K |
β = 97.45 (4)° | Prismatic, colorless |
V = 2007 (1) Å3 | 0.20 × 0.20 × 0.20 mm |
Z = 4 | |
Data collection top
Rigaku AFC-5R diffractometer | Rint = 0.011 |
ω–2θ scans | θmax = 27.5° |
Absorption correction: ψ scan (North et al., 1968) | h = 0→14 |
Tmin = 0.668, Tmax = 0.675 | k = 0→35 |
2434 measured reflections | l = −8→8 |
2323 independent reflections | 3 standard reflections every 200 reflections |
1157 reflections with F2 > 2σ(F2) | intensity decay: 10.0% |
Refinement top
Refinement on F | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.063 | w = 1/[σ2(Fo) + 0.00096|Fo|2] |
wR(F2) = 0.091 | (Δ/σ)max = 0.002 |
S = 1.95 | Δρmax = 0.78 e Å−3 |
1157 reflections | Δρmin = −0.28 e Å−3 |
114 parameters | |
Special details top
Refinement. Refinement using reflections with F2 > 2.0 σ(F2). The
weighted R-factor (wR), goodness of fit (S) and
R-factor (gt) are based on F, with F set to zero for
negative 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
As1 | 0 | 0.29698 (4) | 0.2500 | 0.0827 (4) | |
Cl1 | 0.2325 (2) | 0.06348 (8) | 0.5680 (4) | 0.1043 (9) | |
N1 | −0.2576 (10) | 0.1367 (3) | 0.434 (1) | 0.116 (3) | |
N2 | 0.1098 (9) | 0.1767 (2) | 0.543 (1) | 0.116 (3) | |
C1 | −0.158 (1) | 0.1221 (3) | 0.459 (1) | 0.083 (3) | |
C2 | −0.0376 (9) | 0.1040 (3) | 0.492 (1) | 0.073 (3) | |
C3 | 0.0513 (9) | 0.1431 (3) | 0.522 (1) | 0.083 (3) | |
C4 | −0.0162 (8) | 0.0515 (2) | 0.4961 (10) | 0.064 (2) | |
C5 | 0.1002 (7) | 0.0286 (2) | 0.531 (1) | 0.065 (2) | |
C6 | −0.1156 (7) | 0.0199 (2) | 0.466 (1) | 0.064 (2) | |
C7 | −0.1269 (9) | 0.2608 (3) | 0.329 (2) | 0.108 (4) | |
C8 | −0.077 (2) | 0.3086 (9) | −0.054 (4) | 0.137 (10) | 0.50 |
C9 | 0.044 (2) | 0.3504 (9) | 0.378 (6) | 0.19 (2) | 0.50 |
H1 | −0.2088 | 0.0348 | 0.4483 | 0.0816* | |
H3 | −0.2089 | 0.2813 | 0.3118 | 0.1483* | |
H4 | −0.1393 | 0.2276 | 0.2357 | 0.1483* | |
H5 | −0.1034 | 0.2493 | 0.4840 | 0.1483* | |
H6 | −0.1779 | 0.3251 | −0.0401 | 0.2276* | 0.50 |
H7 | −0.0360 | 0.3285 | −0.1335 | 0.2276* | 0.50 |
H8 | −0.1090 | 0.2714 | −0.1179 | 0.2276* | 0.50 |
H9 | 0.0849 | 0.3445 | 0.5152 | 0.2208* | 0.50 |
H10 | 0.1252 | 0.3646 | 0.2827 | 0.2208* | 0.50 |
H11 | −0.0217 | 0.3770 | 0.3463 | 0.2208* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
As1 | 0.0597 (7) | 0.0475 (6) | 0.144 (1) | 0.0000 | 0.0233 (7) | 0.0000 |
Cl1 | 0.114 (2) | 0.063 (1) | 0.134 (2) | −0.015 (1) | 0.012 (2) | −0.002 (1) |
N1 | 0.142 (8) | 0.081 (5) | 0.126 (7) | 0.034 (5) | 0.017 (6) | 0.006 (5) |
N2 | 0.180 (9) | 0.049 (4) | 0.120 (7) | −0.023 (5) | 0.026 (6) | 0.003 (4) |
C1 | 0.129 (8) | 0.047 (4) | 0.075 (6) | 0.006 (5) | 0.021 (6) | −0.005 (4) |
C2 | 0.121 (7) | 0.048 (4) | 0.051 (5) | 0.008 (4) | 0.023 (5) | 0.004 (3) |
C3 | 0.134 (8) | 0.052 (4) | 0.065 (6) | 0.000 (5) | 0.023 (5) | 0.007 (4) |
C4 | 0.111 (6) | 0.044 (3) | 0.039 (4) | 0.006 (4) | 0.020 (4) | 0.000 (3) |
C5 | 0.096 (6) | 0.048 (4) | 0.053 (5) | −0.007 (4) | 0.011 (4) | 0.000 (3) |
C6 | 0.094 (5) | 0.043 (3) | 0.056 (5) | 0.002 (4) | 0.015 (4) | −0.003 (4) |
C7 | 0.108 (7) | 0.065 (5) | 0.164 (10) | −0.016 (5) | 0.068 (7) | −0.012 (6) |
C8 | 0.14 (2) | 0.13 (2) | 0.13 (2) | −0.04 (2) | −0.03 (2) | 0.06 (2) |
C9 | 0.14 (3) | 0.11 (2) | 0.33 (5) | −0.08 (2) | 0.10 (3) | −0.12 (2) |
Geometric parameters (Å, º) top
Cl1—C5 | 1.735 (8) | C2—C4 | 1.454 (9) |
N1—C1 | 1.16 (1) | C4—C5 | 1.42 (1) |
N2—C3 | 1.12 (1) | C4—C6 | 1.39 (1) |
C1—C2 | 1.41 (1) | C5—C6i | 1.336 (8) |
C2—C3 | 1.45 (1) | | |
| | | |
N1—C1—C2 | 179.4 (10) | C2—C4—C6 | 119.2 (8) |
C1—C2—C3 | 111.8 (7) | C5—C4—C6 | 115.5 (6) |
C1—C2—C4 | 119.8 (8) | Cl1—C5—C4 | 120.6 (5) |
C3—C2—C4 | 128.4 (8) | Cl1—C5—C6i | 116.1 (6) |
N2—C3—C2 | 172 (1) | C4—C5—C6i | 123.3 (7) |
C2—C4—C5 | 125.3 (7) | C4—C6—C5i | 121.2 (7) |
| | | |
Cl1—C5—C4—C2 | −1 (1) | C2—C4—C5—C6i | 179.6 (7) |
Cl1—C5—C4—C6 | 179.4 (5) | C2—C4—C6—C5i | −179.7 (7) |
Cl1—C5—C6i—C4i | −179.5 (5) | C3—C2—C4—C5 | 0 (1) |
C1—C2—C4—C5 | −179.0 (7) | C3—C2—C4—C6 | 179.1 (7) |
C1—C2—C4—C6 | 0 (1) | | |
Symmetry code: (i) −x, −y, −z+1. |