Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046703/ez2098sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046703/ez2098Isup2.hkl |
CCDC reference: 667362
p-Toluenesulfonyl chloride (3.0 g, 15.7 mmol) and 4-methoxybenzyl alcohol (2.0 g, 14.7 mmol) were dissolved in dry pyridine (3.5 ml). The reaction was left for 5 days at room temperature with a CaCl2 tube fitted for protection against atmospheric moisture. The resulting solidified reaction mixture was washed with hexane. Recrystallization of the product from dichloromethane yielded 1-(4-methoxybenzyl)-pyridinium p-toluene-4-sulfonate (4.91 g, 90%) as colourless cuboid crystals; mp 128–131°; δH (300 MHz; CDCl3; Me4Si) 9.30 (2H, dd, J = 1.0 Hz and 8.0 Hz, H-36, H-32); 8.73 (2H, t, J = 8.0 Hz, H-35, H-33); 8.22 (1H, t, J = 8.0 Hz, H-34); 7.50 (2H, d, J = 9.0 Hz, H-25, H-23); 6.75 (2H, d, J = 9.0 Hz, H-26, H-22); 7.10 (2H, d, J = 8.0 Hz, H-15, H-13); 7.77 (2H, d, J = 8.0 Hz, H-16, H-12); 5.91 (2H, s, –CH2–, H-1); 3.74 (3H, s, Ar-OCH3, H-27); 2.34 (3H, s, Ar—CH3, H-17); δ13C{H} (75 MHz; CDCl3) 160.9 (C-24), 145.4 (C-32 and C-36), 144.2 (C-34), 142.6 (C-11'), 139.8 (C-14), 131.6(C-22 and C-26), 129.2 (C-13 and C-15), 128.6 (C-33 and C-35), 126.3 (C-12 and C-16), 125.7 (C-21), 115.1 (C-23 and C-25), 64.5 (–CH2–, C-1), 55.7 (Ar-OCH3, C-27), and 21.7 (Ar—CH3, C-17); m/z: (positive mode) 201.3 ([M+1]+, 10%), 200.3 (M+, 60%), 122.2 (24%), 121.2(100%); m/z (negative mode) 172.2 ([(M-1]-, 8%), 171.2 (M+, 100%).
The H atoms were positioned geometrically and refined using a riding model with fixed C—H distances of 0.93 Å (CH) [Uiso(H) = 1.2Ueq], 0.97 Å (CH2) [Uiso(H) = 1.2Ueq] and 0.96 Å (CH3) [Uiso(H) = 1.5Ueq] respectively.
The highest density peak is 0.32, located 0.78 Å from C11, and the deepest hole is -0.59, located at 0.56 Å from S.
Tosylation of p-methoxybenzylalcohol with tosylchloride in dry pyridine yielded N-(4-methoxybenzyl)-pyridinium toluene-4-sulfonate, (I), as a crystalline product in almost quantitative yield. This product exhibited not only NMR signals corresponding to the initially anticipated benzylic tosylate, but also peaks from a pyridine moiety, in a 1:1 ratio. Electro spray mass spectrometry showed a m/e = 200 base peak in positive mode corresponding to a N-(4-methoxybenzyl)-pyridinium cation and a m/e 171 base peak in negative mode corresponding to a toluene-4-sulfonic acid anion. The unexpected nature of this product and the reaction responsible for it prompted us to prove its structure unequivocally with crystallography. Benzylpyridinium derivatives are described as structurally and magnetically 1-D molecular solids. This is in part due to the cation being nonplanar. The stacking structure of benzylpyridinium molecules can be fine-tuned by varying substituents on the aromatic rings, creating a more conductive solid (Ren et al., 2002).
The title compound, (I), crystallizes with anionic [p-Ts]- (p-Ts = p-toluenesulfonate) and cationic moieties [MeOBzPy]+ (MeOBzPy = 4-methoxy-benzylpyridinium) respectively. In the [MeOBzPy]+ cation packing of the pyridinium and 4-methoxybenzyl rings induces a slight distortion from ideal tetrahedral geometry at C1 (C21—C1—N angle of 111.25 (3)°). The methoxy moiety itself is almost in plane with the benzene ring as shown by the torsion angle of 178.23 (3)° through atoms C25—C24—O4—C27. In comparing the rotation of the pyridinium and 4-methoxyphenyl ring systems with respect to the plane formed by atoms C21–C1–N, dihedral angles of 77.6 (1)° and 73.7 (1)°, respectively, are observed. Other bond distances and angles for (I) fall well within the range of similar compounds reported to date [Cambridge Structural Database (CSD), Version 5.27, August 2006 update; Allen, 2002]. In this structure no significant π–π stacking is observed between the [MeOBzPy]+ moieties, as typically found in other similar compounds (Ren et al., 2002).
In the crystal packing, C1 of the [MeOBzPy]+ molecule acts as a hydrogen-bond donor, via H1B, to the sulfonate atom O1. Likewise, C32 acts as a donor, via H32, to atom O3, resulting in a intermolecular link and the preferred conformation of the sulfonate O-atoms (Fig. 1). The p-toluenesulfonate anions stack in a "tail to tail" fashion with an interplanar toluene–phenyl distance of 3.472 Å (Fig. 2).
For similar benzylpyridinium compounds, see: Ren et al., 2002. For reference bond-length data, see: Allen (2002).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).
C13H14NO+·C7H7O3S− | F(000) = 784 |
Mr = 371.44 | Dx = 1.377 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 9909 reflections |
a = 9.668 (5) Å | θ = 2.4–28.3° |
b = 20.096 (5) Å | µ = 0.21 mm−1 |
c = 9.852 (5) Å | T = 100 K |
β = 110.639 (5)° | Cuboid, colourless |
V = 1791.3 (14) Å3 | 0.4 × 0.2 × 0.1 mm |
Z = 4 |
Bruker X8 APEXII 4K KappaCCD diffractometer | 4447 independent reflections |
Radiation source: fine-focus sealed tube | 3789 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω and φ scans | θmax = 28.3°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −12→12 |
Tmin = 0.922, Tmax = 0.979 | k = −25→26 |
32879 measured reflections | l = −13→13 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0394P)2 + 0.9825P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.092 | (Δ/σ)max = 0.002 |
S = 1.06 | Δρmax = 0.32 e Å−3 |
4447 reflections | Δρmin = −0.59 e Å−3 |
237 parameters |
C13H14NO+·C7H7O3S− | V = 1791.3 (14) Å3 |
Mr = 371.44 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.668 (5) Å | µ = 0.21 mm−1 |
b = 20.096 (5) Å | T = 100 K |
c = 9.852 (5) Å | 0.4 × 0.2 × 0.1 mm |
β = 110.639 (5)° |
Bruker X8 APEXII 4K KappaCCD diffractometer | 4447 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 3789 reflections with I > 2σ(I) |
Tmin = 0.922, Tmax = 0.979 | Rint = 0.043 |
32879 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.32 e Å−3 |
4447 reflections | Δρmin = −0.59 e Å−3 |
237 parameters |
Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD diffractometer using an exposure time of 20 s/frame. A total of 1896 frames were collected with a frame width of 0.5° covering up to θ = 28.3° with 100° completeness accomplished. |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.60595 (14) | 0.59526 (7) | 0.48918 (14) | 0.0132 (3) | |
H1A | 0.6495 | 0.5553 | 0.4661 | 0.016* | |
H1B | 0.5078 | 0.5841 | 0.4876 | 0.016* | |
C11 | 0.24154 (13) | 0.57692 (7) | 0.70133 (14) | 0.0109 (3) | |
C12 | 0.33487 (14) | 0.61530 (7) | 0.81413 (15) | 0.0127 (3) | |
H12 | 0.3693 | 0.6561 | 0.7947 | 0.015* | |
C13 | 0.37633 (14) | 0.59236 (7) | 0.95594 (15) | 0.0137 (3) | |
H13 | 0.4392 | 0.6181 | 1.0308 | 0.016* | |
C14 | 0.32567 (14) | 0.53154 (7) | 0.98852 (14) | 0.0131 (3) | |
C15 | 0.23085 (14) | 0.49412 (7) | 0.87397 (15) | 0.0138 (3) | |
H15 | 0.1953 | 0.4536 | 0.8934 | 0.017* | |
C16 | 0.18852 (14) | 0.51633 (7) | 0.73120 (14) | 0.0127 (3) | |
H16 | 0.1252 | 0.4908 | 0.6562 | 0.015* | |
C17 | 0.37284 (15) | 0.50757 (8) | 1.14311 (15) | 0.0174 (3) | |
H17A | 0.4769 | 0.515 | 1.1905 | 0.026* | |
H17B | 0.3522 | 0.4609 | 1.1442 | 0.026* | |
H17C | 0.3194 | 0.5315 | 1.1932 | 0.026* | |
C21 | 0.69908 (14) | 0.61896 (7) | 0.63891 (14) | 0.0116 (3) | |
C22 | 0.83990 (14) | 0.59323 (7) | 0.70717 (14) | 0.0131 (3) | |
H22 | 0.8782 | 0.5631 | 0.658 | 0.016* | |
C23 | 0.92469 (14) | 0.61195 (7) | 0.84837 (15) | 0.0134 (3) | |
H23 | 1.0187 | 0.5943 | 0.8935 | 0.016* | |
C24 | 0.86712 (14) | 0.65725 (7) | 0.92094 (14) | 0.0118 (3) | |
C25 | 0.72601 (14) | 0.68448 (7) | 0.85261 (14) | 0.0129 (3) | |
H25 | 0.6884 | 0.7153 | 0.901 | 0.015* | |
C26 | 0.64303 (14) | 0.66515 (7) | 0.71257 (14) | 0.0123 (3) | |
H26 | 0.5493 | 0.683 | 0.6671 | 0.015* | |
C27 | 1.08315 (15) | 0.65152 (8) | 1.13428 (15) | 0.0194 (3) | |
H27A | 1.0742 | 0.6042 | 1.1423 | 0.029* | |
H27B | 1.1233 | 0.6707 | 1.2295 | 0.029* | |
H27C | 1.1476 | 0.6609 | 1.0816 | 0.029* | |
C32 | 0.47083 (14) | 0.68464 (7) | 0.32476 (14) | 0.0122 (3) | |
H32 | 0.393 | 0.6777 | 0.3579 | 0.015* | |
C33 | 0.45966 (15) | 0.73291 (7) | 0.22225 (14) | 0.0145 (3) | |
H33 | 0.374 | 0.7582 | 0.1853 | 0.017* | |
C34 | 0.57662 (15) | 0.74365 (7) | 0.17419 (15) | 0.0164 (3) | |
H34 | 0.5701 | 0.776 | 0.1048 | 0.02* | |
C35 | 0.70346 (15) | 0.70537 (8) | 0.23123 (15) | 0.0174 (3) | |
H35 | 0.7832 | 0.7121 | 0.2009 | 0.021* | |
C36 | 0.71029 (14) | 0.65740 (7) | 0.33293 (15) | 0.0148 (3) | |
H36 | 0.7951 | 0.6316 | 0.3715 | 0.018* | |
N | 0.59458 (11) | 0.64748 (6) | 0.37720 (12) | 0.0108 (2) | |
O1 | 0.24697 (11) | 0.55275 (5) | 0.44539 (11) | 0.0182 (2) | |
O2 | 0.03159 (10) | 0.60938 (5) | 0.46323 (11) | 0.0174 (2) | |
O3 | 0.26504 (10) | 0.66785 (5) | 0.52365 (10) | 0.0145 (2) | |
O4 | 0.94071 (10) | 0.67943 (5) | 1.05911 (10) | 0.0161 (2) | |
S | 0.19217 (3) | 0.603727 (16) | 0.51832 (3) | 0.01009 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0142 (6) | 0.0113 (7) | 0.0119 (6) | −0.0007 (5) | 0.0018 (5) | 0.0025 (5) |
C11 | 0.0092 (5) | 0.0124 (7) | 0.0117 (6) | 0.0022 (5) | 0.0042 (5) | 0.0011 (5) |
C12 | 0.0128 (6) | 0.0109 (6) | 0.0151 (6) | −0.0008 (5) | 0.0057 (5) | 0.0000 (5) |
C13 | 0.0135 (6) | 0.0150 (7) | 0.0121 (6) | −0.0011 (5) | 0.0039 (5) | −0.0025 (5) |
C14 | 0.0132 (6) | 0.0144 (7) | 0.0130 (6) | 0.0035 (5) | 0.0063 (5) | 0.0020 (5) |
C15 | 0.0141 (6) | 0.0111 (7) | 0.0176 (7) | −0.0003 (5) | 0.0073 (5) | 0.0019 (5) |
C16 | 0.0112 (5) | 0.0123 (7) | 0.0140 (6) | −0.0004 (5) | 0.0037 (5) | −0.0015 (5) |
C17 | 0.0198 (6) | 0.0185 (7) | 0.0146 (7) | 0.0014 (6) | 0.0070 (5) | 0.0028 (6) |
C21 | 0.0122 (6) | 0.0113 (6) | 0.0103 (6) | −0.0018 (5) | 0.0028 (5) | 0.0020 (5) |
C22 | 0.0138 (6) | 0.0124 (7) | 0.0130 (6) | 0.0015 (5) | 0.0045 (5) | −0.0004 (5) |
C23 | 0.0107 (5) | 0.0150 (7) | 0.0130 (6) | 0.0028 (5) | 0.0023 (5) | 0.0018 (5) |
C24 | 0.0121 (6) | 0.0136 (7) | 0.0095 (6) | −0.0009 (5) | 0.0035 (5) | 0.0014 (5) |
C25 | 0.0138 (6) | 0.0137 (7) | 0.0129 (6) | 0.0013 (5) | 0.0068 (5) | 0.0007 (5) |
C26 | 0.0098 (5) | 0.0134 (7) | 0.0131 (6) | 0.0006 (5) | 0.0034 (5) | 0.0028 (5) |
C27 | 0.0139 (6) | 0.0265 (8) | 0.0138 (7) | 0.0028 (6) | −0.0001 (5) | −0.0015 (6) |
C32 | 0.0101 (5) | 0.0151 (7) | 0.0118 (6) | 0.0006 (5) | 0.0045 (5) | −0.0021 (5) |
C33 | 0.0161 (6) | 0.0126 (7) | 0.0139 (6) | 0.0032 (5) | 0.0042 (5) | −0.0007 (5) |
C34 | 0.0234 (7) | 0.0127 (7) | 0.0141 (6) | −0.0045 (5) | 0.0077 (5) | −0.0011 (5) |
C35 | 0.0152 (6) | 0.0224 (8) | 0.0175 (7) | −0.0060 (5) | 0.0092 (5) | −0.0049 (6) |
C36 | 0.0092 (5) | 0.0181 (7) | 0.0165 (7) | −0.0001 (5) | 0.0039 (5) | −0.0038 (5) |
N | 0.0105 (5) | 0.0115 (6) | 0.0097 (5) | −0.0004 (4) | 0.0027 (4) | −0.0014 (4) |
O1 | 0.0246 (5) | 0.0158 (5) | 0.0153 (5) | 0.0057 (4) | 0.0084 (4) | −0.0011 (4) |
O2 | 0.0093 (4) | 0.0252 (6) | 0.0158 (5) | 0.0009 (4) | 0.0019 (4) | 0.0039 (4) |
O3 | 0.0160 (4) | 0.0141 (5) | 0.0137 (5) | −0.0020 (4) | 0.0055 (4) | 0.0016 (4) |
O4 | 0.0137 (4) | 0.0223 (6) | 0.0099 (5) | 0.0032 (4) | 0.0011 (4) | −0.0027 (4) |
S | 0.00905 (14) | 0.01113 (17) | 0.00985 (15) | 0.00089 (11) | 0.00302 (11) | 0.00019 (12) |
C1—N | 1.4983 (17) | C23—H23 | 0.93 |
C1—C21 | 1.5091 (19) | C24—O4 | 1.3693 (17) |
C1—H1A | 0.97 | C24—C25 | 1.4022 (18) |
C1—H1B | 0.97 | C25—C26 | 1.3849 (19) |
C11—C12 | 1.3918 (19) | C25—H25 | 0.93 |
C11—C16 | 1.3921 (19) | C26—H26 | 0.93 |
C11—S | 1.7783 (16) | C27—O4 | 1.4285 (17) |
C12—C13 | 1.389 (2) | C27—H27A | 0.96 |
C12—H12 | 0.93 | C27—H27B | 0.96 |
C13—C14 | 1.3954 (19) | C27—H27C | 0.96 |
C13—H13 | 0.93 | C32—N | 1.3492 (17) |
C14—C15 | 1.397 (2) | C32—C33 | 1.377 (2) |
C14—C17 | 1.507 (2) | C32—H32 | 0.93 |
C15—C16 | 1.393 (2) | C33—C34 | 1.3881 (19) |
C15—H15 | 0.93 | C33—H33 | 0.93 |
C16—H16 | 0.93 | C34—C35 | 1.388 (2) |
C17—H17A | 0.96 | C34—H34 | 0.93 |
C17—H17B | 0.96 | C35—C36 | 1.375 (2) |
C17—H17C | 0.96 | C35—H35 | 0.93 |
C21—C22 | 1.3884 (19) | C36—N | 1.3511 (17) |
C21—C26 | 1.3996 (19) | C36—H36 | 0.93 |
C22—C23 | 1.3945 (19) | O1—S | 1.4542 (11) |
C22—H22 | 0.93 | O2—S | 1.4573 (12) |
C23—C24 | 1.3895 (19) | O3—S | 1.4606 (11) |
N—C1—C21 | 111.25 (11) | O4—C24—C25 | 115.27 (12) |
N—C1—H1A | 109.4 | C23—C24—C25 | 120.47 (12) |
C21—C1—H1A | 109.4 | C26—C25—C24 | 119.52 (12) |
N—C1—H1B | 109.4 | C26—C25—H25 | 120.2 |
C21—C1—H1B | 109.4 | C24—C25—H25 | 120.2 |
H1A—C1—H1B | 108 | C25—C26—C21 | 120.55 (12) |
C12—C11—C16 | 119.96 (12) | C25—C26—H26 | 119.7 |
C12—C11—S | 120.55 (11) | C21—C26—H26 | 119.7 |
C16—C11—S | 119.48 (10) | O4—C27—H27A | 109.5 |
C13—C12—C11 | 119.67 (13) | O4—C27—H27B | 109.5 |
C13—C12—H12 | 120.2 | H27A—C27—H27B | 109.5 |
C11—C12—H12 | 120.2 | O4—C27—H27C | 109.5 |
C12—C13—C14 | 121.44 (13) | H27A—C27—H27C | 109.5 |
C12—C13—H13 | 119.3 | H27B—C27—H27C | 109.5 |
C14—C13—H13 | 119.3 | N—C32—C33 | 120.03 (12) |
C13—C14—C15 | 118.00 (12) | N—C32—H32 | 120 |
C13—C14—C17 | 120.45 (12) | C33—C32—H32 | 120 |
C15—C14—C17 | 121.55 (13) | C32—C33—C34 | 119.81 (13) |
C16—C15—C14 | 121.27 (13) | C32—C33—H33 | 120.1 |
C16—C15—H15 | 119.4 | C34—C33—H33 | 120.1 |
C14—C15—H15 | 119.4 | C35—C34—C33 | 119.04 (13) |
C11—C16—C15 | 119.66 (12) | C35—C34—H34 | 120.5 |
C11—C16—H16 | 120.2 | C33—C34—H34 | 120.5 |
C15—C16—H16 | 120.2 | C36—C35—C34 | 119.49 (13) |
C14—C17—H17A | 109.5 | C36—C35—H35 | 120.3 |
C14—C17—H17B | 109.5 | C34—C35—H35 | 120.3 |
H17A—C17—H17B | 109.5 | N—C36—C35 | 120.41 (13) |
C14—C17—H17C | 109.5 | N—C36—H36 | 119.8 |
H17A—C17—H17C | 109.5 | C35—C36—H36 | 119.8 |
H17B—C17—H17C | 109.5 | C32—N—C36 | 121.20 (12) |
C22—C21—C26 | 119.25 (12) | C32—N—C1 | 119.65 (11) |
C22—C21—C1 | 120.08 (12) | C36—N—C1 | 119.13 (11) |
C26—C21—C1 | 120.63 (12) | C24—O4—C27 | 117.11 (11) |
C21—C22—C23 | 120.93 (13) | O1—S—O2 | 113.37 (6) |
C21—C22—H22 | 119.5 | O1—S—O3 | 112.59 (6) |
C23—C22—H22 | 119.5 | O2—S—O3 | 112.43 (6) |
C24—C23—C22 | 119.26 (12) | O1—S—C11 | 105.86 (7) |
C24—C23—H23 | 120.4 | O2—S—C11 | 105.74 (6) |
C22—C23—H23 | 120.4 | O3—S—C11 | 106.09 (6) |
O4—C24—C23 | 124.25 (12) | ||
C16—C11—C12—C13 | 0.95 (19) | C22—C21—C26—C25 | −0.8 (2) |
S—C11—C12—C13 | −177.72 (10) | C1—C21—C26—C25 | 176.94 (12) |
C11—C12—C13—C14 | −0.4 (2) | N—C32—C33—C34 | −0.7 (2) |
C12—C13—C14—C15 | −0.28 (19) | C32—C33—C34—C35 | −0.2 (2) |
C12—C13—C14—C17 | 179.68 (12) | C33—C34—C35—C36 | 0.5 (2) |
C13—C14—C15—C16 | 0.43 (19) | C34—C35—C36—N | 0.0 (2) |
C17—C14—C15—C16 | −179.53 (12) | C33—C32—N—C36 | 1.2 (2) |
C12—C11—C16—C15 | −0.80 (19) | C33—C32—N—C1 | 179.75 (12) |
S—C11—C16—C15 | 177.88 (10) | C35—C36—N—C32 | −0.9 (2) |
C14—C15—C16—C11 | 0.11 (19) | C35—C36—N—C1 | −179.44 (12) |
N—C1—C21—C22 | −107.37 (14) | C21—C1—N—C32 | −101.63 (14) |
N—C1—C21—C26 | 74.91 (15) | C21—C1—N—C36 | 76.93 (15) |
C26—C21—C22—C23 | 1.1 (2) | C23—C24—O4—C27 | −2.85 (19) |
C1—C21—C22—C23 | −176.69 (12) | C25—C24—O4—C27 | 178.23 (12) |
C21—C22—C23—C24 | −0.3 (2) | C12—C11—S—O1 | 118.83 (11) |
C22—C23—C24—O4 | −179.58 (12) | C16—C11—S—O1 | −59.85 (12) |
C22—C23—C24—C25 | −0.7 (2) | C12—C11—S—O2 | −120.61 (11) |
O4—C24—C25—C26 | 179.93 (12) | C16—C11—S—O2 | 60.72 (12) |
C23—C24—C25—C26 | 1.0 (2) | C12—C11—S—O3 | −1.01 (12) |
C24—C25—C26—C21 | −0.2 (2) | C16—C11—S—O3 | −179.68 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O1 | 0.97 | 2.49 | 3.450 (2) | 172 |
C32—H32···O3 | 0.93 | 2.38 | 3.265 (2) | 159 |
Experimental details
Crystal data | |
Chemical formula | C13H14NO+·C7H7O3S− |
Mr | 371.44 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 9.668 (5), 20.096 (5), 9.852 (5) |
β (°) | 110.639 (5) |
V (Å3) | 1791.3 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.4 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Bruker X8 APEXII 4K KappaCCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.922, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32879, 4447, 3789 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.092, 1.06 |
No. of reflections | 4447 |
No. of parameters | 237 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.59 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004) and XPREP (Bruker, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O1 | 0.97 | 2.49 | 3.450 (2) | 171.7 |
C32—H32···O3 | 0.93 | 2.38 | 3.265 (2) | 159 |
Tosylation of p-methoxybenzylalcohol with tosylchloride in dry pyridine yielded N-(4-methoxybenzyl)-pyridinium toluene-4-sulfonate, (I), as a crystalline product in almost quantitative yield. This product exhibited not only NMR signals corresponding to the initially anticipated benzylic tosylate, but also peaks from a pyridine moiety, in a 1:1 ratio. Electro spray mass spectrometry showed a m/e = 200 base peak in positive mode corresponding to a N-(4-methoxybenzyl)-pyridinium cation and a m/e 171 base peak in negative mode corresponding to a toluene-4-sulfonic acid anion. The unexpected nature of this product and the reaction responsible for it prompted us to prove its structure unequivocally with crystallography. Benzylpyridinium derivatives are described as structurally and magnetically 1-D molecular solids. This is in part due to the cation being nonplanar. The stacking structure of benzylpyridinium molecules can be fine-tuned by varying substituents on the aromatic rings, creating a more conductive solid (Ren et al., 2002).
The title compound, (I), crystallizes with anionic [p-Ts]- (p-Ts = p-toluenesulfonate) and cationic moieties [MeOBzPy]+ (MeOBzPy = 4-methoxy-benzylpyridinium) respectively. In the [MeOBzPy]+ cation packing of the pyridinium and 4-methoxybenzyl rings induces a slight distortion from ideal tetrahedral geometry at C1 (C21—C1—N angle of 111.25 (3)°). The methoxy moiety itself is almost in plane with the benzene ring as shown by the torsion angle of 178.23 (3)° through atoms C25—C24—O4—C27. In comparing the rotation of the pyridinium and 4-methoxyphenyl ring systems with respect to the plane formed by atoms C21–C1–N, dihedral angles of 77.6 (1)° and 73.7 (1)°, respectively, are observed. Other bond distances and angles for (I) fall well within the range of similar compounds reported to date [Cambridge Structural Database (CSD), Version 5.27, August 2006 update; Allen, 2002]. In this structure no significant π–π stacking is observed between the [MeOBzPy]+ moieties, as typically found in other similar compounds (Ren et al., 2002).
In the crystal packing, C1 of the [MeOBzPy]+ molecule acts as a hydrogen-bond donor, via H1B, to the sulfonate atom O1. Likewise, C32 acts as a donor, via H32, to atom O3, resulting in a intermolecular link and the preferred conformation of the sulfonate O-atoms (Fig. 1). The p-toluenesulfonate anions stack in a "tail to tail" fashion with an interplanar toluene–phenyl distance of 3.472 Å (Fig. 2).