organic compounds
A charge-transfer salt, 3,5-dimethyl-1-(4-nitrobenzyl)pyridinium 7,7,8,8-tetracyanoquinodimethane
aAnhui Key Laboratory of Functional Coordination Compounds, School of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246003, People's Republic of China
*Correspondence e-mail: liugx@live.com
In the title salt, C14H15N2O2+·C12H4N4−, the contains one cation and one anion. C—H⋯N and C—H⋯N and C—H⋯O hydrogen bonds and π–π stacking interactions (interplanar distance 3.845 Å) are found in the crystal structure.
Related literature
For general background, see: Madalan et al. (2002); Ren, Chen et al. (2002); Ren et al. (2003); Ren, Meng et al. (2002). For related literature, see: Liu et al. (2005); Wang et al. (2006).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808008258/cf2189sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808008258/cf2189Isup2.hkl
3,5-Dimethyl-1-(4-nitrobenzyl)pyridinium iodide was prepared by the direct combination of 1:1 molar equivalents of 3,5-dimethyl-1-(4-nitrobenzyl)pyridinium chloride and NaI in a warm solution in acetone at 313 K. A white precipitate was formed (NaCl), which was filtered off, and a white microcrystalline product was obtained by evaporating the filtrate. 1:2 Molar equivalents of 3,5-dimethyl-1-(4-nitrobenzyl)pyridinium iodide and TCNQ were mixed directly in a solution in methanol, and the mixture was refluxed for 12 h. The dark-green microcrystalline product which formed was filtered off, washed with MeOH and dried in vacuo. Single crystals of (I) suitable for structure analysis were obtained by diffusing diethyl ether into an acetonitrile solution of (I).
H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.
Data collection: SMART (Bruker, 2000); cell
SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C14H15N2O2+·C12H4N4− | Z = 2 |
Mr = 447.47 | F(000) = 466 |
Triclinic, P1 | Dx = 1.289 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.098 (2) Å | Cell parameters from 3033 reflections |
b = 9.137 (2) Å | θ = 2.3–27.9° |
c = 16.542 (4) Å | µ = 0.09 mm−1 |
α = 76.194 (3)° | T = 293 K |
β = 75.951 (3)° | Pillar, purple |
γ = 86.933 (3)° | 0.18 × 0.12 × 0.10 mm |
V = 1153.0 (5) Å3 |
Bruker SMART APEX CCD diffractometer | 3998 independent reflections |
Radiation source: sealed tube | 3255 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scans | θmax = 25.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −9→9 |
Tmin = 0.985, Tmax = 0.992 | k = −10→10 |
5765 measured reflections | l = −19→16 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0904P)2 + 0.1284P] where P = (Fo2 + 2Fc2)/3 |
3998 reflections | (Δ/σ)max < 0.001 |
309 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C14H15N2O2+·C12H4N4− | γ = 86.933 (3)° |
Mr = 447.47 | V = 1153.0 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.098 (2) Å | Mo Kα radiation |
b = 9.137 (2) Å | µ = 0.09 mm−1 |
c = 16.542 (4) Å | T = 293 K |
α = 76.194 (3)° | 0.18 × 0.12 × 0.10 mm |
β = 75.951 (3)° |
Bruker SMART APEX CCD diffractometer | 3998 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 3255 reflections with I > 2σ(I) |
Tmin = 0.985, Tmax = 0.992 | Rint = 0.018 |
5765 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.15 e Å−3 |
3998 reflections | Δρmin = −0.20 e Å−3 |
309 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3034 (2) | −0.11674 (18) | 0.07248 (10) | 0.0532 (4) | |
C2 | 0.1837 (3) | −0.0094 (3) | 0.06055 (17) | 0.0920 (8) | |
H2 | 0.0998 | −0.0228 | 0.0332 | 0.110* | |
C3 | 0.1875 (3) | 0.1190 (3) | 0.08930 (16) | 0.0863 (7) | |
H3 | 0.1066 | 0.1934 | 0.0805 | 0.104* | |
C4 | 0.30938 (19) | 0.13943 (17) | 0.13103 (9) | 0.0464 (4) | |
C5 | 0.4274 (2) | 0.02782 (18) | 0.14337 (11) | 0.0557 (4) | |
H5 | 0.5097 | 0.0392 | 0.1721 | 0.067* | |
C6 | 0.4257 (2) | −0.10127 (18) | 0.11367 (11) | 0.0579 (4) | |
H6 | 0.5067 | −0.1761 | 0.1217 | 0.069* | |
C7 | 0.3015 (2) | 0.28325 (18) | 0.16136 (11) | 0.0513 (4) | |
H7A | 0.3025 | 0.3681 | 0.1131 | 0.062* | |
H7B | 0.1946 | 0.2855 | 0.2031 | 0.062* | |
C8 | 0.5758 (2) | 0.39025 (17) | 0.15325 (10) | 0.0506 (4) | |
H8 | 0.5780 | 0.4366 | 0.0964 | 0.061* | |
C9 | 0.7086 (2) | 0.41397 (18) | 0.18741 (10) | 0.0535 (4) | |
C10 | 0.6996 (2) | 0.34162 (18) | 0.27232 (11) | 0.0545 (4) | |
H10 | 0.7867 | 0.3563 | 0.2973 | 0.065* | |
C11 | 0.5642 (2) | 0.24809 (17) | 0.32079 (10) | 0.0502 (4) | |
C12 | 0.4356 (2) | 0.23031 (17) | 0.28237 (9) | 0.0481 (4) | |
H12 | 0.3430 | 0.1686 | 0.3134 | 0.058* | |
C13 | 0.8551 (3) | 0.5148 (3) | 0.13244 (14) | 0.0805 (6) | |
H13A | 0.8947 | 0.4865 | 0.0787 | 0.121* | |
H13B | 0.9460 | 0.5045 | 0.1613 | 0.121* | |
H13C | 0.8178 | 0.6177 | 0.1223 | 0.121* | |
C14 | 0.5536 (3) | 0.1662 (2) | 0.41234 (11) | 0.0665 (5) | |
H14A | 0.6636 | 0.1660 | 0.4245 | 0.100* | |
H14B | 0.5168 | 0.0643 | 0.4210 | 0.100* | |
H14C | 0.4735 | 0.2161 | 0.4499 | 0.100* | |
C15 | 0.8272 (2) | 0.8781 (2) | 0.25321 (12) | 0.0631 (5) | |
C16 | 0.9551 (2) | 1.0193 (2) | 0.32804 (11) | 0.0566 (4) | |
C17 | 0.8784 (2) | 0.88381 (18) | 0.32838 (10) | 0.0539 (4) | |
C18 | 0.8522 (2) | 0.76197 (17) | 0.40146 (10) | 0.0497 (4) | |
C19 | 0.9004 (2) | 0.77045 (17) | 0.47720 (10) | 0.0506 (4) | |
H19 | 0.9526 | 0.8578 | 0.4785 | 0.061* | |
C20 | 0.8724 (2) | 0.65455 (17) | 0.54774 (10) | 0.0502 (4) | |
H20 | 0.9058 | 0.6646 | 0.5961 | 0.060* | |
C21 | 0.7936 (2) | 0.51845 (17) | 0.54952 (10) | 0.0502 (4) | |
C22 | 0.7464 (2) | 0.50974 (18) | 0.47347 (11) | 0.0588 (4) | |
H22 | 0.6953 | 0.4221 | 0.4718 | 0.071* | |
C23 | 0.7742 (2) | 0.62636 (19) | 0.40311 (11) | 0.0581 (4) | |
H23 | 0.7409 | 0.6166 | 0.3547 | 0.070* | |
C24 | 0.7631 (2) | 0.39860 (18) | 0.62288 (10) | 0.0553 (4) | |
C25 | 0.7996 (2) | 0.41186 (19) | 0.70048 (11) | 0.0583 (4) | |
C26 | 0.6899 (3) | 0.2598 (2) | 0.62445 (11) | 0.0639 (5) | |
N1 | 0.3014 (2) | −0.25176 (18) | 0.03913 (9) | 0.0650 (4) | |
N2 | 0.44324 (16) | 0.30155 (13) | 0.20044 (8) | 0.0456 (3) | |
N3 | 0.7848 (3) | 0.8728 (2) | 0.19242 (12) | 0.0903 (6) | |
N4 | 1.0142 (2) | 1.12948 (19) | 0.33055 (11) | 0.0752 (5) | |
N5 | 0.8270 (3) | 0.4254 (2) | 0.76315 (10) | 0.0802 (5) | |
N6 | 0.6314 (3) | 0.1475 (2) | 0.62508 (12) | 0.0907 (6) | |
O1 | 0.1827 (2) | −0.2699 (2) | 0.00906 (11) | 0.0984 (5) | |
O2 | 0.4200 (2) | −0.33952 (15) | 0.04148 (8) | 0.0797 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0619 (10) | 0.0509 (9) | 0.0478 (9) | −0.0093 (7) | −0.0113 (7) | −0.0133 (7) |
C2 | 0.0824 (14) | 0.1014 (16) | 0.134 (2) | 0.0240 (12) | −0.0685 (14) | −0.0698 (15) |
C3 | 0.0792 (14) | 0.0869 (14) | 0.1301 (19) | 0.0341 (11) | −0.0692 (14) | −0.0587 (14) |
C4 | 0.0492 (8) | 0.0473 (8) | 0.0439 (8) | −0.0011 (6) | −0.0155 (6) | −0.0082 (6) |
C5 | 0.0644 (10) | 0.0535 (9) | 0.0587 (10) | 0.0069 (7) | −0.0338 (8) | −0.0135 (7) |
C6 | 0.0739 (11) | 0.0473 (9) | 0.0563 (10) | 0.0070 (8) | −0.0274 (8) | −0.0089 (7) |
C7 | 0.0539 (9) | 0.0485 (8) | 0.0569 (9) | 0.0028 (7) | −0.0238 (7) | −0.0125 (7) |
C8 | 0.0615 (10) | 0.0445 (8) | 0.0447 (8) | −0.0022 (7) | −0.0143 (7) | −0.0058 (6) |
C9 | 0.0573 (10) | 0.0478 (8) | 0.0572 (9) | −0.0040 (7) | −0.0146 (8) | −0.0135 (7) |
C10 | 0.0587 (10) | 0.0546 (9) | 0.0595 (10) | 0.0006 (7) | −0.0241 (8) | −0.0207 (7) |
C11 | 0.0617 (10) | 0.0477 (8) | 0.0453 (8) | 0.0049 (7) | −0.0169 (7) | −0.0156 (7) |
C12 | 0.0552 (9) | 0.0449 (8) | 0.0443 (8) | −0.0021 (6) | −0.0115 (7) | −0.0107 (6) |
C13 | 0.0729 (13) | 0.0809 (14) | 0.0830 (14) | −0.0252 (11) | −0.0143 (11) | −0.0090 (11) |
C14 | 0.0828 (13) | 0.0734 (12) | 0.0456 (9) | −0.0002 (9) | −0.0220 (9) | −0.0113 (8) |
C15 | 0.0654 (11) | 0.0626 (11) | 0.0613 (11) | 0.0035 (8) | −0.0258 (9) | −0.0042 (8) |
C16 | 0.0548 (10) | 0.0537 (10) | 0.0570 (10) | 0.0021 (8) | −0.0132 (8) | −0.0051 (7) |
C17 | 0.0556 (9) | 0.0501 (9) | 0.0559 (9) | 0.0043 (7) | −0.0179 (7) | −0.0083 (7) |
C18 | 0.0522 (9) | 0.0460 (8) | 0.0529 (9) | 0.0062 (7) | −0.0153 (7) | −0.0140 (7) |
C19 | 0.0545 (9) | 0.0458 (8) | 0.0553 (9) | 0.0005 (7) | −0.0146 (7) | −0.0176 (7) |
C20 | 0.0570 (9) | 0.0498 (8) | 0.0484 (9) | 0.0045 (7) | −0.0149 (7) | −0.0186 (7) |
C21 | 0.0578 (9) | 0.0460 (8) | 0.0496 (9) | 0.0056 (7) | −0.0141 (7) | −0.0161 (7) |
C22 | 0.0759 (11) | 0.0463 (9) | 0.0603 (10) | −0.0065 (8) | −0.0261 (8) | −0.0129 (7) |
C23 | 0.0762 (11) | 0.0518 (9) | 0.0544 (9) | 0.0000 (8) | −0.0294 (8) | −0.0137 (7) |
C24 | 0.0677 (10) | 0.0481 (9) | 0.0509 (9) | 0.0010 (7) | −0.0141 (8) | −0.0130 (7) |
C25 | 0.0734 (11) | 0.0492 (9) | 0.0490 (10) | 0.0027 (8) | −0.0104 (8) | −0.0097 (7) |
C26 | 0.0795 (12) | 0.0543 (10) | 0.0566 (10) | −0.0027 (9) | −0.0187 (9) | −0.0071 (8) |
N1 | 0.0819 (11) | 0.0605 (9) | 0.0519 (8) | −0.0165 (8) | −0.0075 (7) | −0.0163 (7) |
N2 | 0.0523 (7) | 0.0422 (6) | 0.0459 (7) | 0.0010 (5) | −0.0171 (6) | −0.0121 (5) |
N3 | 0.0981 (14) | 0.1037 (14) | 0.0760 (12) | 0.0055 (11) | −0.0442 (11) | −0.0116 (10) |
N4 | 0.0802 (11) | 0.0611 (10) | 0.0811 (11) | −0.0123 (8) | −0.0199 (9) | −0.0071 (8) |
N5 | 0.1159 (15) | 0.0736 (11) | 0.0536 (9) | 0.0017 (10) | −0.0239 (9) | −0.0160 (8) |
N6 | 0.1217 (16) | 0.0631 (11) | 0.0885 (13) | −0.0249 (10) | −0.0333 (11) | −0.0059 (9) |
O1 | 0.0935 (11) | 0.1097 (12) | 0.1151 (13) | −0.0195 (9) | −0.0270 (9) | −0.0635 (10) |
O2 | 0.1179 (12) | 0.0539 (7) | 0.0688 (8) | 0.0086 (8) | −0.0227 (8) | −0.0187 (6) |
C1—C2 | 1.356 (3) | C13—H13B | 0.960 |
C1—C6 | 1.362 (2) | C13—H13C | 0.960 |
C1—N1 | 1.469 (2) | C14—H14A | 0.960 |
C2—C3 | 1.372 (3) | C14—H14B | 0.960 |
C2—H2 | 0.930 | C14—H14C | 0.960 |
C3—C4 | 1.377 (2) | C15—N3 | 1.151 (2) |
C3—H3 | 0.930 | C15—C17 | 1.416 (2) |
C4—C5 | 1.373 (2) | C16—N4 | 1.151 (2) |
C4—C7 | 1.508 (2) | C16—C17 | 1.413 (2) |
C5—C6 | 1.384 (2) | C17—C18 | 1.416 (2) |
C5—H5 | 0.930 | C18—C23 | 1.412 (2) |
C6—H6 | 0.930 | C18—C19 | 1.419 (2) |
C7—N2 | 1.4818 (19) | C19—C20 | 1.357 (2) |
C7—H7A | 0.970 | C19—H19 | 0.930 |
C7—H7B | 0.970 | C20—C21 | 1.419 (2) |
C8—N2 | 1.343 (2) | C20—H20 | 0.930 |
C8—C9 | 1.379 (2) | C21—C24 | 1.408 (2) |
C8—H8 | 0.930 | C21—C22 | 1.421 (2) |
C9—C10 | 1.388 (2) | C22—C23 | 1.359 (2) |
C9—C13 | 1.509 (2) | C22—H22 | 0.930 |
C10—C11 | 1.386 (2) | C23—H23 | 0.930 |
C10—H10 | 0.930 | C24—C25 | 1.418 (2) |
C11—C12 | 1.379 (2) | C24—C26 | 1.420 (3) |
C11—C14 | 1.505 (2) | C25—N5 | 1.147 (2) |
C12—N2 | 1.3442 (19) | C26—N6 | 1.150 (2) |
C12—H12 | 0.930 | N1—O1 | 1.220 (2) |
C13—H13A | 0.960 | N1—O2 | 1.220 (2) |
C2—C1—C6 | 121.58 (16) | H13A—C13—H13C | 109.5 |
C2—C1—N1 | 118.90 (16) | H13B—C13—H13C | 109.5 |
C6—C1—N1 | 119.51 (16) | C11—C14—H14A | 109.5 |
C1—C2—C3 | 119.27 (16) | C11—C14—H14B | 109.5 |
C1—C2—H2 | 120.4 | H14A—C14—H14B | 109.5 |
C3—C2—H2 | 120.4 | C11—C14—H14C | 109.5 |
C2—C3—C4 | 121.06 (17) | H14A—C14—H14C | 109.5 |
C2—C3—H3 | 119.5 | H14B—C14—H14C | 109.5 |
C4—C3—H3 | 119.5 | N3—C15—C17 | 179.6 (2) |
C5—C4—C3 | 118.37 (15) | N4—C16—C17 | 177.63 (19) |
C5—C4—C7 | 124.51 (13) | C16—C17—C15 | 116.70 (15) |
C3—C4—C7 | 117.11 (14) | C16—C17—C18 | 120.87 (14) |
C4—C5—C6 | 120.97 (14) | C15—C17—C18 | 122.42 (15) |
C4—C5—H5 | 119.5 | C23—C18—C17 | 121.56 (14) |
C6—C5—H5 | 119.5 | C23—C18—C19 | 116.56 (14) |
C1—C6—C5 | 118.74 (15) | C17—C18—C19 | 121.88 (14) |
C1—C6—H6 | 120.6 | C20—C19—C18 | 121.80 (14) |
C5—C6—H6 | 120.6 | C20—C19—H19 | 119.1 |
N2—C7—C4 | 113.85 (12) | C18—C19—H19 | 119.1 |
N2—C7—H7A | 108.8 | C19—C20—C21 | 121.66 (14) |
C4—C7—H7A | 108.8 | C19—C20—H20 | 119.2 |
N2—C7—H7B | 108.8 | C21—C20—H20 | 119.2 |
C4—C7—H7B | 108.8 | C24—C21—C20 | 121.76 (14) |
H7A—C7—H7B | 107.7 | C24—C21—C22 | 121.76 (14) |
N2—C8—C9 | 121.24 (14) | C20—C21—C22 | 116.48 (14) |
N2—C8—H8 | 119.4 | C23—C22—C21 | 121.60 (15) |
C9—C8—H8 | 119.4 | C23—C22—H22 | 119.2 |
C8—C9—C10 | 117.15 (15) | C21—C22—H22 | 119.2 |
C8—C9—C13 | 119.71 (16) | C22—C23—C18 | 121.90 (15) |
C10—C9—C13 | 123.14 (16) | C22—C23—H23 | 119.1 |
C11—C10—C9 | 121.71 (14) | C18—C23—H23 | 119.1 |
C11—C10—H10 | 119.1 | C21—C24—C25 | 121.48 (14) |
C9—C10—H10 | 119.1 | C21—C24—C26 | 122.28 (14) |
C12—C11—C10 | 117.85 (14) | C25—C24—C26 | 116.22 (15) |
C12—C11—C14 | 119.55 (15) | N5—C25—C24 | 178.50 (19) |
C10—C11—C14 | 122.60 (15) | N6—C26—C24 | 179.5 (2) |
N2—C12—C11 | 120.51 (14) | O1—N1—O2 | 122.89 (16) |
N2—C12—H12 | 119.7 | O1—N1—C1 | 118.57 (17) |
C11—C12—H12 | 119.7 | O2—N1—C1 | 118.52 (15) |
C9—C13—H13A | 109.5 | C8—N2—C12 | 121.53 (13) |
C9—C13—H13B | 109.5 | C8—N2—C7 | 119.09 (12) |
H13A—C13—H13B | 109.5 | C12—N2—C7 | 119.38 (13) |
C9—C13—H13C | 109.5 | ||
C6—C1—C2—C3 | 1.1 (4) | C23—C18—C19—C20 | −0.3 (2) |
N1—C1—C2—C3 | −178.1 (2) | C17—C18—C19—C20 | 178.78 (15) |
C1—C2—C3—C4 | −0.9 (4) | C18—C19—C20—C21 | 0.1 (2) |
C2—C3—C4—C5 | −0.1 (3) | C19—C20—C21—C24 | −179.44 (15) |
C2—C3—C4—C7 | −179.1 (2) | C19—C20—C21—C22 | 0.3 (2) |
C3—C4—C5—C6 | 0.9 (3) | C24—C21—C22—C23 | 179.20 (16) |
C7—C4—C5—C6 | 179.83 (16) | C20—C21—C22—C23 | −0.6 (3) |
C2—C1—C6—C5 | −0.4 (3) | C21—C22—C23—C18 | 0.4 (3) |
N1—C1—C6—C5 | 178.90 (15) | C17—C18—C23—C22 | −179.01 (16) |
C4—C5—C6—C1 | −0.7 (3) | C19—C18—C23—C22 | 0.0 (3) |
C5—C4—C7—N2 | 4.9 (2) | C20—C21—C24—C25 | 4.2 (3) |
C3—C4—C7—N2 | −176.16 (17) | C22—C21—C24—C25 | −175.56 (16) |
N2—C8—C9—C10 | 0.3 (2) | C20—C21—C24—C26 | −177.65 (16) |
N2—C8—C9—C13 | −179.80 (16) | C22—C21—C24—C26 | 2.6 (3) |
C8—C9—C10—C11 | 0.7 (2) | C2—C1—N1—O1 | −6.9 (3) |
C13—C9—C10—C11 | −179.16 (17) | C6—C1—N1—O1 | 173.77 (16) |
C9—C10—C11—C12 | −1.0 (2) | C2—C1—N1—O2 | 171.89 (19) |
C9—C10—C11—C14 | 178.76 (15) | C6—C1—N1—O2 | −7.4 (2) |
C10—C11—C12—N2 | 0.2 (2) | C9—C8—N2—C12 | −1.1 (2) |
C14—C11—C12—N2 | −179.49 (14) | C9—C8—N2—C7 | 178.29 (13) |
C16—C17—C18—C23 | 179.39 (16) | C11—C12—N2—C8 | 0.8 (2) |
C15—C17—C18—C23 | 0.5 (3) | C11—C12—N2—C7 | −178.60 (13) |
C16—C17—C18—C19 | 0.4 (2) | C4—C7—N2—C8 | 99.78 (16) |
C15—C17—C18—C19 | −178.44 (16) | C4—C7—N2—C12 | −80.84 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···N2 | 0.93 | 2.56 | 2.895 (2) | 102 |
C7—H7B···N4i | 0.97 | 2.43 | 3.245 (3) | 141 |
C8—H8···O2ii | 0.93 | 2.46 | 3.119 (2) | 128 |
Symmetry codes: (i) x−1, y−1, z; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C14H15N2O2+·C12H4N4− |
Mr | 447.47 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.098 (2), 9.137 (2), 16.542 (4) |
α, β, γ (°) | 76.194 (3), 75.951 (3), 86.933 (3) |
V (Å3) | 1153.0 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.18 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.985, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5765, 3998, 3255 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.144, 1.00 |
No. of reflections | 3998 |
No. of parameters | 309 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.20 |
Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···N2 | 0.93 | 2.56 | 2.895 (2) | 102 |
C7—H7B···N4i | 0.97 | 2.43 | 3.245 (3) | 141 |
C8—H8···O2ii | 0.93 | 2.46 | 3.119 (2) | 128 |
Symmetry codes: (i) x−1, y−1, z; (ii) x, y+1, z. |
Acknowledgements
This work was supported by the National Natural Science Foundation of China (project Nos. 20371002 and 20771006) and the Natural Science Foundation of the Education Committee of Anhui Province, China (project No. KJ2008B004).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Recently, using benzylpyridinium derivatives ([RBzPy]+ where R represents a substituent group) with flexible molecular configuration as a counter-cation to control the arrangement of anions [M(mnt)2]- (M = Ni, Pd, Pt), a series of ion-pair compounds that show segregated columnar stacks of cations and anions has been prepared (Madalan et al., 2002; Ren, Chen et al., 2002; Ren et al., 2003; Ren, Meng et al., 2002). The radical of TCNQ also shows a planar arrangement and extended electronic structures that are similar to the [M(mnt)2]- ion, and has been extensively used to build molecular solids with low-dimensional conductivity and magnetic features, in which the electronic transport and magnetically coupled interactions can be achieved through π–π interactions between radicals along the direction of the radical stack column (Liu et al., 2005; Wang et al., 2006). This character of the TCNQ- ion prompted us to extend our research to a series of [RBzPy][TCNQ] compounds in order to gain more insight into the relationship between the intermolecular cooperation interactions and the magnetic properties of the compounds with low-dimensional structural features. In this paper, we report the crystal structure of the title compound.
The asymmetric unit contains one (C14H15N2O2)+ cation and one [C8H4(CN)4]- anion (Fig. 1). It stacks as completely segregated columns of TCNQ anions/molecules and 3,5-dimethyl-1-(4-nitrobenzyl)pyridinium cations, as illustrated by the projection along the crystallographic a axis in Fig. 2. The cation and anion columns are linked by hydrogen-bonding interactions. Within an anionic column, a strongly bound [(TCNQ)2]2- unit is formed, and adjacent units are displaced relative to each other along the direction of the shorter molecular axis of TCNQ. The benzene rings are parallel to each other. In a TCNQ column, the mean interplanar separations within two different overlapping pairs are 5.745 Å inter-dimer and 3.845 Å intra-dimer, respectively, indicating weak π–π stacking interactions. The (C14H15N2O2)+ cation has a Λ-shaped conformation, and the dihedral angles formed by the C4/C7/N2 plane with the benzene and pyridinium rings are 4.12 (11) and 80.45 (12)°, respectively.