Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010400825X/na1654sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010400825X/na1654Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010400825X/na1654IIsup3.hkl |
CCDC references: 243600; 243601
For the preparation of (I), a mixture of 4'-phenyl-2,2',6',2''-terpyridine (0.3 g) and methyl-p-toluensulfonate (0.3 g, excess) was dissolved in toluene (5 ml) and refluxed for 12 h. The resulting oil was dissolved in acetonitrile (5 ml) and mixed with with a hot solution of NaClO4 (0.5 g) in acetonitrile (2 ml). The precipitate which formed was filtered off, washed with acetonitrile (2 ml) and ethanol (5 ml), and recrystallized twice from ethanol (yield 0.1 g; m.p. 571–573 K). Spectroscopic analysis: 1H NMR (300 MHz, DMSO-d6, δ, p.p.m.): 4.43 (s, 3H, NCH3), 7.58–7.70 (m, 5H, PyH, PhH), 8.01–804 (d, 2H, PhH), 8.14–8.20 (d, 1H, PyH), 8.25–8.28 (d, 1H, PyH), 8.51–8.60 (m,2H, PyH), 8.76–8.83 (m, 2H, PyH), 8.91–8.95 (d, 1H, PyH), 9.23–9.26 (d, 1H, PyH). For the preparation of (II), CH3I (0.5 g, excess) was added to a solution of 4'-(4-methoxyphenyl)-2,2':6',2''-terpyridine (0.3 g) in toluene (5 ml). After refluxing the reacting mixture for 8 h, the solvent was evaporated in vacuo and the solid product was recrystallized twice from methanol (yield 0.12 g; m.p. 478–481 K). Spectroscopic analysis: 1H NMR (300 MHz, DMSO-d6, δ, p.p.m.): 3.85 (s, 3H, OCH3), 4.42 (s, 3H, NCH3), 7.14–7.17 (d, 2H, PhH), 7.53–7.57 (m, 1H, PyH), 7.96–8.06 (m, 4H, PyH, PhH), 8.24–8.28 (m, 2H, PyH), 8.42–8.52 (m, 2H, PyH), 8.78–8.84 (m, 2H, PyH), 9.21–9.24 (d, 1H, PyH).
All H-atom positions of (I) and (II) were determined by difference Fourier syntheses and refined isotropically using restraints for a few atoms. Please provide brief details of restraints used.
For both compounds, data collection: SMART-NT (Bruker, 1999); cell refinement: SAINT-NT (Bruker, 1999); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: SHELXTL-NT (Sheldrick, 1999) for (I); SHELXTL-NT (Sheldrick, 1999) and CELLGRAF (Reck et al., 1996) for (II). For both compounds, software used to prepare material for publication: SHELXL97.
C22H19N32+·2ClO4− | F(000) = 1080 |
Mr = 524.30 | Dx = 1.502 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.015 (2) Å | Cell parameters from 134280 reflections |
b = 13.073 (4) Å | θ = 1.7–27.5° |
c = 29.501 (10) Å | µ = 0.34 mm−1 |
β = 91.441 (7)° | T = 293 K |
V = 2319.1 (13) Å3 | Needle, colourless |
Z = 4 | 0.55 × 0.15 × 0.12 mm |
Bruker SMART CCD area-detector diffractometer | 5216 independent reflections |
Radiation source: fine-focus sealed tube | 3175 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 27.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −7→7 |
Tmin = 0.831, Tmax = 0.961 | k = −16→14 |
13428 measured reflections | l = −38→33 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.174 | w = 1/[σ2(Fo2) + (0.108P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
5216 reflections | Δρmax = 0.51 e Å−3 |
393 parameters | Δρmin = −0.28 e Å−3 |
10 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0035 (11) |
C22H19N32+·2ClO4− | V = 2319.1 (13) Å3 |
Mr = 524.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.015 (2) Å | µ = 0.34 mm−1 |
b = 13.073 (4) Å | T = 293 K |
c = 29.501 (10) Å | 0.55 × 0.15 × 0.12 mm |
β = 91.441 (7)° |
Bruker SMART CCD area-detector diffractometer | 5216 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 3175 reflections with I > 2σ(I) |
Tmin = 0.831, Tmax = 0.961 | Rint = 0.039 |
13428 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 10 restraints |
wR(F2) = 0.174 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.51 e Å−3 |
5216 reflections | Δρmin = −0.28 e Å−3 |
393 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 | ||
N1 | 0.1439 (3) | 0.31305 (15) | 0.17264 (6) | 0.0467 (5) | |
N2 | 0.2176 (5) | 0.33812 (18) | 0.25969 (8) | 0.0592 (6) | |
N3 | 0.3122 (4) | 0.45453 (17) | 0.10369 (7) | 0.0567 (6) | |
C1 | 0.0092 (4) | 0.25980 (18) | 0.19914 (8) | 0.0459 (6) | |
C2 | −0.1423 (4) | 0.18907 (19) | 0.18266 (8) | 0.0493 (6) | |
C3 | −0.1609 (4) | 0.17174 (18) | 0.13633 (8) | 0.0480 (6) | |
C4 | −0.0228 (4) | 0.22835 (19) | 0.10857 (8) | 0.0483 (6) | |
C5 | 0.1258 (4) | 0.29678 (18) | 0.12784 (8) | 0.0454 (6) | |
C6 | 0.0392 (5) | 0.28151 (17) | 0.24825 (8) | 0.0504 (6) | |
C7 | 0.2724 (7) | 0.3637 (2) | 0.30235 (10) | 0.0762 (9) | |
C8 | 0.1393 (8) | 0.3331 (3) | 0.33657 (11) | 0.0843 (11) | |
C9 | −0.0470 (8) | 0.2770 (2) | 0.32624 (10) | 0.0827 (11) | |
C10 | −0.0969 (6) | 0.2501 (2) | 0.28207 (9) | 0.0639 (8) | |
C11 | 0.2851 (4) | 0.35229 (19) | 0.09904 (8) | 0.0484 (6) | |
C12 | 0.4721 (6) | 0.5026 (3) | 0.07954 (11) | 0.0723 (9) | |
C13 | 0.5981 (6) | 0.4531 (3) | 0.05042 (11) | 0.0751 (9) | |
C14 | 0.5667 (5) | 0.3505 (3) | 0.04339 (10) | 0.0675 (8) | |
C15 | 0.4076 (5) | 0.2997 (2) | 0.06812 (9) | 0.0563 (7) | |
C16 | −0.3194 (4) | 0.09591 (18) | 0.11665 (9) | 0.0519 (6) | |
C17 | −0.5200 (5) | 0.0761 (2) | 0.13822 (11) | 0.0620 (7) | |
C18 | −0.6676 (6) | 0.0066 (3) | 0.11956 (15) | 0.0792 (10) | |
C19 | −0.6191 (7) | −0.0443 (3) | 0.08044 (16) | 0.0933 (13) | |
C20 | −0.4231 (8) | −0.0263 (3) | 0.05938 (14) | 0.0831 (11) | |
C21 | −0.2726 (6) | 0.0443 (2) | 0.07695 (10) | 0.0640 (8) | |
C22 | 0.1676 (7) | 0.5163 (2) | 0.13237 (13) | 0.0779 (10) | |
H2N | 0.295 (5) | 0.348 (2) | 0.2386 (11) | 0.071 (10)* | |
H2 | −0.227 (5) | 0.152 (2) | 0.2039 (9) | 0.065 (8)* | |
H4 | −0.037 (4) | 0.2175 (16) | 0.0772 (8) | 0.041 (6)* | |
H7 | 0.416 (5) | 0.401 (2) | 0.3057 (10) | 0.067 (8)* | |
H8 | 0.198 (6) | 0.350 (3) | 0.3655 (12) | 0.094 (11)* | |
H9 | −0.163 (5) | 0.261 (2) | 0.3473 (11) | 0.075 (9)* | |
H10 | −0.232 (5) | 0.219 (2) | 0.2742 (9) | 0.057 (8)* | |
H12 | 0.463 (5) | 0.572 (3) | 0.0848 (11) | 0.082 (10)* | |
H13 | 0.715 (7) | 0.478 (3) | 0.0309 (13) | 0.111 (12)* | |
H14 | 0.649 (5) | 0.3166 (19) | 0.0240 (9) | 0.056 (8)* | |
H15 | 0.383 (4) | 0.228 (2) | 0.0669 (8) | 0.052 (7)* | |
H17 | −0.565 (5) | 0.112 (2) | 0.1647 (10) | 0.071 (9)* | |
H18 | −0.805 (6) | −0.001 (2) | 0.1348 (11) | 0.079 (10)* | |
H19 | −0.724 (6) | −0.094 (2) | 0.0673 (10) | 0.083 (10)* | |
H20 | −0.384 (5) | −0.061 (2) | 0.0345 (9) | 0.066 (9)* | |
H21 | −0.132 (6) | 0.051 (2) | 0.0669 (10) | 0.076 (10)* | |
H221 | 0.229 (5) | 0.514 (3) | 0.1616 (7) | 0.151 (19)* | |
H222 | 0.165 (5) | 0.5817 (15) | 0.1182 (11) | 0.120 (14)* | |
H223 | 0.023 (3) | 0.483 (2) | 0.1299 (9) | 0.083 (10)* | |
Cl1 | 0.67194 (12) | 0.52574 (6) | 0.22201 (3) | 0.0676 (3) | |
O1 | 0.6044 (6) | 0.4251 (2) | 0.21433 (16) | 0.1516 (14) | |
O2 | 0.5139 (7) | 0.5747 (4) | 0.24582 (13) | 0.1776 (17) | |
O3 | 0.6842 (7) | 0.5761 (4) | 0.18081 (12) | 0.1889 (19) | |
O4 | 0.8807 (5) | 0.5251 (2) | 0.24329 (14) | 0.1423 (13) | |
Cl2 | 0.95011 (12) | 0.71573 (5) | 0.03513 (2) | 0.0596 (2) | |
O5 | 0.7447 (5) | 0.7140 (2) | 0.05727 (11) | 0.1207 (11) | |
O6 | 1.1291 (5) | 0.7245 (2) | 0.06693 (9) | 0.1188 (11) | |
O7 | 0.9708 (4) | 0.62420 (18) | 0.01018 (9) | 0.1031 (9) | |
O8 | 0.9621 (5) | 0.79993 (18) | 0.00478 (8) | 0.0963 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0525 (12) | 0.0492 (11) | 0.0385 (10) | −0.0045 (9) | 0.0025 (9) | 0.0038 (9) |
N2 | 0.0771 (17) | 0.0575 (14) | 0.0429 (13) | −0.0075 (12) | −0.0008 (12) | −0.0034 (11) |
N3 | 0.0649 (14) | 0.0568 (13) | 0.0486 (12) | −0.0096 (10) | 0.0078 (10) | 0.0115 (10) |
C1 | 0.0532 (14) | 0.0451 (13) | 0.0394 (12) | −0.0010 (11) | 0.0029 (10) | 0.0009 (10) |
C2 | 0.0557 (15) | 0.0517 (14) | 0.0407 (13) | −0.0062 (11) | 0.0064 (11) | 0.0046 (11) |
C3 | 0.0511 (14) | 0.0488 (13) | 0.0441 (13) | −0.0032 (11) | 0.0000 (10) | 0.0012 (11) |
C4 | 0.0544 (15) | 0.0550 (15) | 0.0353 (12) | −0.0035 (11) | 0.0015 (11) | 0.0036 (11) |
C5 | 0.0480 (14) | 0.0495 (13) | 0.0389 (12) | −0.0023 (10) | 0.0043 (10) | 0.0053 (10) |
C6 | 0.0686 (17) | 0.0435 (13) | 0.0391 (13) | −0.0032 (12) | 0.0014 (12) | 0.0010 (10) |
C7 | 0.109 (3) | 0.0673 (19) | 0.0513 (18) | −0.0054 (19) | −0.0165 (18) | −0.0112 (15) |
C8 | 0.143 (3) | 0.066 (2) | 0.0437 (17) | −0.004 (2) | −0.0070 (19) | −0.0088 (15) |
C9 | 0.144 (4) | 0.0635 (19) | 0.0415 (16) | −0.010 (2) | 0.0199 (19) | 0.0013 (14) |
C10 | 0.091 (2) | 0.0540 (16) | 0.0473 (15) | −0.0114 (16) | 0.0145 (15) | −0.0035 (12) |
C11 | 0.0486 (14) | 0.0586 (15) | 0.0378 (12) | −0.0043 (11) | −0.0007 (10) | 0.0087 (11) |
C12 | 0.082 (2) | 0.069 (2) | 0.066 (2) | −0.0233 (17) | 0.0004 (17) | 0.0187 (16) |
C13 | 0.0605 (19) | 0.105 (3) | 0.0604 (18) | −0.0186 (18) | 0.0117 (15) | 0.0226 (18) |
C14 | 0.0576 (18) | 0.094 (2) | 0.0516 (16) | 0.0012 (16) | 0.0134 (14) | 0.0121 (16) |
C15 | 0.0558 (16) | 0.0668 (18) | 0.0466 (14) | −0.0005 (13) | 0.0063 (12) | 0.0086 (13) |
C16 | 0.0591 (16) | 0.0465 (13) | 0.0495 (14) | −0.0031 (11) | −0.0075 (12) | 0.0060 (11) |
C17 | 0.0603 (18) | 0.0560 (16) | 0.0691 (19) | −0.0069 (13) | −0.0068 (15) | 0.0134 (15) |
C18 | 0.067 (2) | 0.068 (2) | 0.102 (3) | −0.0184 (16) | −0.018 (2) | 0.017 (2) |
C19 | 0.092 (3) | 0.061 (2) | 0.124 (3) | −0.0198 (19) | −0.046 (3) | 0.004 (2) |
C20 | 0.106 (3) | 0.065 (2) | 0.076 (2) | −0.002 (2) | −0.033 (2) | −0.0138 (18) |
C21 | 0.074 (2) | 0.0617 (17) | 0.0556 (17) | −0.0004 (15) | −0.0131 (15) | −0.0013 (14) |
C22 | 0.102 (3) | 0.0539 (18) | 0.079 (2) | 0.0029 (18) | 0.020 (2) | 0.0049 (16) |
Cl1 | 0.0626 (5) | 0.0739 (5) | 0.0669 (5) | −0.0031 (3) | 0.0128 (4) | −0.0019 (4) |
O1 | 0.100 (2) | 0.099 (2) | 0.256 (4) | −0.0187 (17) | −0.014 (2) | −0.028 (2) |
O2 | 0.180 (4) | 0.215 (4) | 0.141 (3) | 0.105 (3) | 0.054 (3) | −0.025 (3) |
O3 | 0.172 (4) | 0.290 (5) | 0.105 (2) | −0.064 (4) | 0.013 (2) | 0.075 (3) |
O4 | 0.098 (2) | 0.108 (2) | 0.217 (4) | −0.0095 (16) | −0.070 (2) | 0.003 (2) |
Cl2 | 0.0695 (5) | 0.0628 (4) | 0.0471 (4) | −0.0130 (3) | 0.0150 (3) | −0.0056 (3) |
O5 | 0.111 (2) | 0.101 (2) | 0.154 (3) | −0.0188 (15) | 0.086 (2) | −0.0271 (17) |
O6 | 0.141 (3) | 0.124 (2) | 0.0897 (17) | −0.0425 (18) | −0.0433 (18) | 0.0259 (16) |
O7 | 0.1023 (19) | 0.0773 (15) | 0.132 (2) | −0.0199 (13) | 0.0509 (16) | −0.0384 (15) |
O8 | 0.132 (2) | 0.0891 (16) | 0.0675 (14) | −0.0121 (14) | 0.0048 (14) | 0.0202 (12) |
N1—C1 | 1.336 (3) | C13—C14 | 1.370 (5) |
N1—C5 | 1.340 (3) | C13—H13 | 0.98 (4) |
N2—C7 | 1.336 (4) | C14—C15 | 1.387 (4) |
N2—C6 | 1.340 (3) | C14—H14 | 0.89 (3) |
N2—H2N | 0.80 (3) | C15—H15 | 0.95 (3) |
N3—C11 | 1.353 (3) | C16—C21 | 1.387 (4) |
N3—C12 | 1.365 (4) | C16—C17 | 1.402 (4) |
N3—C22 | 1.470 (4) | C17—C18 | 1.376 (4) |
C1—C2 | 1.378 (3) | C17—H17 | 0.95 (3) |
C1—C6 | 1.483 (3) | C18—C19 | 1.370 (6) |
C2—C3 | 1.387 (3) | C18—H18 | 0.95 (3) |
C2—H2 | 0.95 (3) | C19—C20 | 1.366 (6) |
C3—C4 | 1.394 (3) | C19—H19 | 0.98 (3) |
C3—C16 | 1.484 (3) | C20—C21 | 1.385 (5) |
C4—C5 | 1.377 (4) | C20—H20 | 0.90 (2) |
C4—H4 | 0.94 (2) | C21—H21 | 0.90 (3) |
C5—C11 | 1.486 (3) | C22—H221 | 0.93 (2) |
C6—C10 | 1.370 (4) | C22—H222 | 0.95 (2) |
C7—C8 | 1.365 (5) | C22—H223 | 0.974 (19) |
C7—H7 | 0.99 (3) | Cl1—O2 | 1.357 (3) |
C8—C9 | 1.367 (6) | Cl1—O3 | 1.386 (3) |
C8—H8 | 0.94 (4) | Cl1—O4 | 1.390 (3) |
C9—C10 | 1.376 (4) | Cl1—O1 | 1.393 (3) |
C9—H9 | 0.97 (3) | Cl2—O7 | 1.412 (2) |
C10—H10 | 0.93 (3) | Cl2—O5 | 1.412 (3) |
C11—C15 | 1.372 (4) | Cl2—O6 | 1.415 (3) |
C12—C13 | 1.328 (5) | Cl2—O8 | 1.422 (2) |
C12—H12 | 0.92 (3) | ||
C1—N1—C5 | 117.31 (19) | C12—C13—H13 | 130 (2) |
C7—N2—C6 | 123.6 (3) | C14—C13—H13 | 110 (2) |
C7—N2—H2N | 124 (2) | C13—C14—C15 | 118.9 (3) |
C6—N2—H2N | 112 (2) | C13—C14—H14 | 120.7 (17) |
C11—N3—C12 | 119.1 (3) | C15—C14—H14 | 120.3 (18) |
C11—N3—C22 | 122.0 (2) | C11—C15—C14 | 119.9 (3) |
C12—N3—C22 | 118.8 (3) | C11—C15—H15 | 115.8 (16) |
N1—C1—C2 | 123.3 (2) | C14—C15—H15 | 124.1 (16) |
N1—C1—C6 | 114.3 (2) | C21—C16—C17 | 119.3 (3) |
C2—C1—C6 | 122.4 (2) | C21—C16—C3 | 120.9 (3) |
C1—C2—C3 | 119.6 (2) | C17—C16—C3 | 119.9 (2) |
C1—C2—H2 | 118.1 (16) | C18—C17—C16 | 119.6 (3) |
C3—C2—H2 | 122.3 (16) | C18—C17—H17 | 117.0 (18) |
C2—C3—C4 | 117.3 (2) | C16—C17—H17 | 123.2 (18) |
C2—C3—C16 | 122.0 (2) | C19—C18—C17 | 120.6 (4) |
C4—C3—C16 | 120.8 (2) | C19—C18—H18 | 124 (2) |
C5—C4—C3 | 119.5 (2) | C17—C18—H18 | 116 (2) |
C5—C4—H4 | 123.3 (14) | C20—C19—C18 | 120.3 (3) |
C3—C4—H4 | 117.2 (14) | C20—C19—H19 | 119.2 (19) |
N1—C5—C4 | 123.1 (2) | C18—C19—H19 | 120.5 (19) |
N1—C5—C11 | 116.7 (2) | C19—C20—C21 | 120.5 (4) |
C4—C5—C11 | 120.1 (2) | C19—C20—H20 | 122 (2) |
N2—C6—C10 | 118.2 (2) | C21—C20—H20 | 118 (2) |
N2—C6—C1 | 115.4 (2) | C20—C21—C16 | 119.7 (4) |
C10—C6—C1 | 126.4 (3) | C20—C21—H21 | 123 (2) |
N2—C7—C8 | 119.2 (4) | C16—C21—H21 | 116 (2) |
N2—C7—H7 | 114.3 (17) | N3—C22—H221 | 107 (2) |
C8—C7—H7 | 126.4 (17) | N3—C22—H222 | 104.2 (18) |
C7—C8—C9 | 119.0 (3) | H221—C22—H222 | 116 (2) |
C7—C8—H8 | 113 (2) | N3—C22—H223 | 104.4 (16) |
C9—C8—H8 | 128 (2) | H221—C22—H223 | 113 (2) |
C8—C9—C10 | 120.4 (3) | H222—C22—H223 | 111 (2) |
C8—C9—H9 | 125.0 (19) | O2—Cl1—O3 | 106.5 (3) |
C10—C9—H9 | 114.1 (19) | O2—Cl1—O4 | 113.9 (3) |
C6—C10—C9 | 119.5 (3) | O3—Cl1—O4 | 109.4 (2) |
C6—C10—H10 | 118.7 (17) | O2—Cl1—O1 | 108.9 (3) |
C9—C10—H10 | 121.1 (17) | O3—Cl1—O1 | 109.1 (3) |
N3—C11—C15 | 119.8 (2) | O4—Cl1—O1 | 108.9 (2) |
N3—C11—C5 | 120.2 (2) | O7—Cl2—O5 | 108.51 (15) |
C15—C11—C5 | 120.0 (2) | O7—Cl2—O6 | 109.80 (19) |
C13—C12—N3 | 122.3 (3) | O5—Cl2—O6 | 110.8 (2) |
C13—C12—H12 | 129 (2) | O7—Cl2—O8 | 108.73 (16) |
N3—C12—H12 | 109 (2) | O5—Cl2—O8 | 111.23 (19) |
C12—C13—C14 | 119.8 (3) | O6—Cl2—O8 | 107.76 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1 | 0.80 (3) | 2.25 (3) | 2.942 (5) | 146 (3) |
N2—H2N···N1 | 0.80 (3) | 2.18 (3) | 2.616 (3) | 115 (3) |
C13—H13···O7 | 0.98 (4) | 2.53 (4) | 3.401 (4) | 148 (3) |
C2—H2···O2i | 0.95 (3) | 2.51 (3) | 3.452 (4) | 169 (2) |
C4—H4···O8ii | 0.94 (2) | 2.48 (2) | 3.393 (4) | 163.7 (19) |
C22—H222···O6iii | 0.95 (2) | 2.41 (2) | 3.341 (4) | 167 (3) |
C19—H19···O6iv | 0.98 (3) | 2.53 (3) | 3.400 (5) | 148 (2) |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x−2, y−1, z. |
C23H20N3O+·I− | F(000) = 960 |
Mr = 481.32 | Dx = 1.515 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.854 (4) Å | Cell parameters from 11870 reflections |
b = 13.448 (4) Å | θ = 2.2–27.5° |
c = 12.141 (4) Å | µ = 1.54 mm−1 |
β = 111.146 (5)° | T = 293 K |
V = 2109.7 (11) Å3 | Prism, colourless |
Z = 4 | 0.48 × 0.45 × 0.35 mm |
Bruker SMART CCD area-detector diffractometer | 4729 independent reflections |
Radiation source: fine-focus sealed tube | 4104 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −17→16 |
Tmin = 0.483, Tmax = 0.584 | k = −9→17 |
11870 measured reflections | l = −15→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.124 | w = 1/[σ2(Fo2) + (0.0696P)2 + 0.3488P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max = 0.001 |
4729 reflections | Δρmax = 0.77 e Å−3 |
334 parameters | Δρmin = −1.08 e Å−3 |
82 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0072 (8) |
C23H20N3O+·I− | V = 2109.7 (11) Å3 |
Mr = 481.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.854 (4) Å | µ = 1.54 mm−1 |
b = 13.448 (4) Å | T = 293 K |
c = 12.141 (4) Å | 0.48 × 0.45 × 0.35 mm |
β = 111.146 (5)° |
Bruker SMART CCD area-detector diffractometer | 4729 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 4104 reflections with I > 2σ(I) |
Tmin = 0.483, Tmax = 0.584 | Rint = 0.050 |
11870 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 82 restraints |
wR(F2) = 0.124 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | Δρmax = 0.77 e Å−3 |
4729 reflections | Δρmin = −1.08 e Å−3 |
334 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 | ||
I1 | 0.544965 (16) | 0.714875 (16) | 0.084730 (19) | 0.06552 (13) | |
N1 | 0.83509 (16) | 0.10517 (16) | 0.44809 (18) | 0.0453 (4) | |
C1 | 0.92148 (18) | 0.12238 (17) | 0.5425 (2) | 0.0440 (5) | |
O1 | 0.8480 (2) | 0.0257 (2) | 1.14363 (18) | 0.0809 (7) | |
C2 | 0.92435 (19) | 0.11284 (19) | 0.6580 (2) | 0.0465 (5) | |
H2 | 0.989 (2) | 0.123 (2) | 0.723 (3) | 0.049 (7)* | |
N2 | 1.09247 (18) | 0.1904 (2) | 0.6072 (2) | 0.0584 (6) | |
C3 | 0.83606 (19) | 0.08379 (18) | 0.6791 (2) | 0.0445 (5) | |
N3 | 0.62810 (17) | 0.11599 (18) | 0.26728 (19) | 0.0509 (5) | |
C4 | 0.7459 (2) | 0.0689 (2) | 0.5808 (2) | 0.0472 (5) | |
H4 | 0.684 (3) | 0.052 (2) | 0.587 (3) | 0.052 (8)* | |
C5 | 0.74991 (18) | 0.08017 (18) | 0.4689 (2) | 0.0444 (5) | |
C6 | 1.01524 (19) | 0.15013 (18) | 0.5174 (2) | 0.0472 (5) | |
C7 | 1.1778 (3) | 0.2160 (3) | 0.5870 (4) | 0.0716 (9) | |
H7 | 1.229 (4) | 0.242 (3) | 0.657 (4) | 0.087 (12)* | |
C8 | 1.1894 (3) | 0.2040 (3) | 0.4806 (4) | 0.0730 (10) | |
H8 | 1.251 (2) | 0.223 (2) | 0.475 (3) | 0.063 (10)* | |
C9 | 1.1093 (3) | 0.1634 (2) | 0.3878 (4) | 0.0685 (8) | |
H9 | 1.112 (4) | 0.162 (3) | 0.310 (4) | 0.095 (13)* | |
C10 | 1.0208 (3) | 0.1356 (2) | 0.4066 (3) | 0.0573 (6) | |
H10 | 0.970 (3) | 0.107 (3) | 0.350 (3) | 0.071 (10)* | |
C11 | 0.65729 (19) | 0.05651 (19) | 0.3635 (2) | 0.0459 (5) | |
C12 | 0.5477 (2) | 0.0904 (3) | 0.1690 (3) | 0.0659 (8) | |
H12 | 0.532 (3) | 0.139 (3) | 0.117 (4) | 0.088 (12)* | |
C13 | 0.4959 (3) | 0.0033 (3) | 0.1632 (3) | 0.0749 (9) | |
H13 | 0.436 (4) | −0.014 (3) | 0.098 (4) | 0.092 (13)* | |
C14 | 0.5221 (3) | −0.0572 (3) | 0.2597 (3) | 0.0710 (8) | |
H14 | 0.489 (3) | −0.118 (3) | 0.263 (4) | 0.087 (12)* | |
C15 | 0.6025 (2) | −0.0298 (2) | 0.3606 (3) | 0.0568 (6) | |
H15 | 0.627 (3) | −0.067 (3) | 0.429 (3) | 0.067 (10)* | |
C16 | 0.8378 (2) | 0.06681 (19) | 0.8004 (2) | 0.0466 (5) | |
C17 | 0.9055 (3) | 0.1194 (2) | 0.8960 (3) | 0.0618 (7) | |
H17 | 0.949 (3) | 0.167 (3) | 0.885 (4) | 0.074 (11)* | |
C18 | 0.9066 (3) | 0.1046 (3) | 1.0086 (3) | 0.0706 (9) | |
H18 | 0.950 (3) | 0.135 (3) | 1.076 (4) | 0.079 (11)* | |
C19 | 0.8415 (3) | 0.0349 (2) | 1.0287 (2) | 0.0582 (6) | |
C20 | 0.7763 (2) | −0.0206 (2) | 0.9369 (2) | 0.0546 (6) | |
H20 | 0.739 (3) | −0.074 (3) | 0.947 (3) | 0.079 (11)* | |
C21 | 0.7747 (2) | −0.0038 (2) | 0.8226 (2) | 0.0522 (6) | |
H21 | 0.725 (2) | −0.045 (2) | 0.757 (3) | 0.058 (8)* | |
C22 | 0.6785 (3) | 0.2129 (2) | 0.2662 (4) | 0.0673 (9) | |
H223 | 0.639 (2) | 0.2531 (19) | 0.203 (2) | 0.060 (9)* | |
H222 | 0.685 (3) | 0.251 (2) | 0.335 (3) | 0.097 (14)* | |
H221 | 0.7442 (19) | 0.206 (2) | 0.265 (4) | 0.110 (19)* | |
C23 | 0.7822 (3) | −0.0437 (3) | 1.1689 (3) | 0.0711 (9) | |
H233 | 0.797 (3) | −0.037 (3) | 1.251 (4) | 0.080 (11)* | |
H232 | 0.709 (3) | −0.036 (3) | 1.121 (4) | 0.082 (12)* | |
H231 | 0.806 (3) | −0.115 (3) | 1.150 (4) | 0.081 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.06776 (18) | 0.07172 (18) | 0.06853 (19) | 0.00400 (8) | 0.03841 (13) | 0.00452 (8) |
N1 | 0.0461 (10) | 0.0461 (10) | 0.0463 (10) | 0.0024 (8) | 0.0198 (8) | 0.0028 (8) |
C1 | 0.0427 (11) | 0.0419 (12) | 0.0492 (12) | 0.0032 (9) | 0.0185 (10) | 0.0034 (9) |
O1 | 0.1092 (19) | 0.0934 (17) | 0.0409 (11) | −0.0192 (15) | 0.0281 (12) | −0.0018 (11) |
C2 | 0.0449 (12) | 0.0476 (12) | 0.0467 (13) | 0.0001 (10) | 0.0159 (10) | 0.0014 (10) |
N2 | 0.0467 (12) | 0.0659 (13) | 0.0619 (14) | −0.0040 (11) | 0.0189 (10) | 0.0077 (12) |
C3 | 0.0482 (12) | 0.0441 (11) | 0.0422 (11) | 0.0020 (9) | 0.0176 (9) | −0.0008 (9) |
N3 | 0.0479 (10) | 0.0583 (13) | 0.0478 (11) | 0.0068 (9) | 0.0187 (9) | 0.0039 (9) |
C4 | 0.0438 (12) | 0.0540 (13) | 0.0462 (12) | −0.0015 (10) | 0.0190 (10) | 0.0000 (10) |
C5 | 0.0452 (11) | 0.0439 (12) | 0.0441 (12) | 0.0013 (9) | 0.0163 (9) | −0.0011 (9) |
C6 | 0.0464 (12) | 0.0417 (11) | 0.0572 (14) | 0.0057 (9) | 0.0230 (11) | 0.0073 (10) |
C7 | 0.0514 (16) | 0.077 (2) | 0.086 (2) | −0.0085 (14) | 0.0249 (17) | 0.0138 (17) |
C8 | 0.0576 (17) | 0.0689 (19) | 0.108 (3) | 0.0064 (14) | 0.0482 (19) | 0.0190 (17) |
C9 | 0.077 (2) | 0.0615 (18) | 0.088 (2) | 0.0104 (15) | 0.0539 (18) | 0.0085 (16) |
C10 | 0.0608 (15) | 0.0551 (15) | 0.0637 (16) | 0.0030 (13) | 0.0316 (14) | −0.0003 (13) |
C11 | 0.0455 (12) | 0.0520 (12) | 0.0430 (11) | 0.0025 (10) | 0.0192 (10) | −0.0010 (10) |
C12 | 0.0548 (15) | 0.088 (2) | 0.0501 (15) | 0.0102 (15) | 0.0134 (12) | 0.0054 (15) |
C13 | 0.0539 (16) | 0.104 (3) | 0.0584 (18) | −0.0058 (17) | 0.0099 (14) | −0.0160 (18) |
C14 | 0.0589 (16) | 0.077 (2) | 0.076 (2) | −0.0158 (15) | 0.0229 (15) | −0.0147 (16) |
C15 | 0.0545 (14) | 0.0595 (16) | 0.0571 (16) | −0.0061 (12) | 0.0210 (12) | −0.0036 (13) |
C16 | 0.0503 (12) | 0.0482 (12) | 0.0429 (12) | 0.0010 (10) | 0.0186 (10) | −0.0001 (10) |
C17 | 0.080 (2) | 0.0560 (15) | 0.0488 (14) | −0.0183 (14) | 0.0219 (13) | −0.0038 (12) |
C18 | 0.093 (2) | 0.0683 (18) | 0.0448 (15) | −0.0246 (17) | 0.0178 (15) | −0.0086 (13) |
C19 | 0.0726 (17) | 0.0622 (16) | 0.0411 (13) | 0.0000 (13) | 0.0222 (12) | 0.0013 (11) |
C20 | 0.0571 (14) | 0.0631 (16) | 0.0483 (14) | −0.0075 (13) | 0.0246 (12) | −0.0005 (12) |
C21 | 0.0523 (13) | 0.0627 (15) | 0.0429 (12) | −0.0084 (12) | 0.0189 (11) | −0.0059 (11) |
C22 | 0.0652 (19) | 0.0637 (19) | 0.069 (2) | 0.0034 (13) | 0.0192 (16) | 0.0214 (15) |
C23 | 0.081 (2) | 0.091 (2) | 0.0518 (16) | 0.0102 (19) | 0.0377 (16) | 0.0117 (16) |
N1—C5 | 1.336 (3) | C10—H10 | 0.87 (4) |
N1—C1 | 1.345 (3) | C11—C15 | 1.380 (4) |
C1—C2 | 1.395 (4) | C12—C13 | 1.362 (6) |
C1—C6 | 1.485 (3) | C12—H12 | 0.88 (5) |
O1—C19 | 1.370 (3) | C13—C14 | 1.363 (6) |
O1—C23 | 1.413 (4) | C13—H13 | 0.94 (4) |
C2—C3 | 1.393 (4) | C14—C15 | 1.375 (4) |
C2—H2 | 0.96 (3) | C14—H14 | 0.95 (4) |
N2—C6 | 1.335 (4) | C15—H15 | 0.92 (4) |
N2—C7 | 1.337 (4) | C16—C21 | 1.381 (4) |
C3—C4 | 1.396 (4) | C16—C17 | 1.394 (4) |
C3—C16 | 1.482 (3) | C17—C18 | 1.375 (4) |
N3—C12 | 1.351 (4) | C17—H17 | 0.92 (3) |
N3—C11 | 1.352 (3) | C18—C19 | 1.383 (4) |
N3—C22 | 1.481 (4) | C18—H18 | 0.92 (4) |
C4—C5 | 1.388 (3) | C19—C20 | 1.375 (4) |
C4—H4 | 0.91 (3) | C20—C21 | 1.398 (4) |
C5—C11 | 1.483 (3) | C20—H20 | 0.91 (4) |
C6—C10 | 1.389 (4) | C21—H21 | 1.01 (3) |
C7—C8 | 1.368 (6) | C22—H223 | 0.94 (2) |
C7—H7 | 0.96 (5) | C22—H222 | 0.96 (2) |
C8—C9 | 1.377 (6) | C22—H221 | 0.92 (2) |
C8—H8 | 0.92 (2) | C23—H233 | 0.95 (4) |
C9—C10 | 1.378 (4) | C23—H232 | 0.97 (4) |
C9—H9 | 0.95 (5) | C23—H231 | 1.07 (4) |
C5—N1—C1 | 117.2 (2) | C13—C12—H12 | 128 (3) |
N1—C1—C2 | 122.3 (2) | C12—C13—C14 | 119.7 (3) |
N1—C1—C6 | 116.4 (2) | C12—C13—H13 | 123 (3) |
C2—C1—C6 | 121.3 (2) | C14—C13—H13 | 117 (3) |
C19—O1—C23 | 118.0 (3) | C13—C14—C15 | 119.0 (3) |
C3—C2—C1 | 120.2 (2) | C13—C14—H14 | 125 (3) |
C3—C2—H2 | 120.5 (18) | C15—C14—H14 | 116 (3) |
C1—C2—H2 | 119.3 (18) | C14—C15—C11 | 120.6 (3) |
C6—N2—C7 | 117.2 (3) | C14—C15—H15 | 125 (2) |
C2—C3—C4 | 117.2 (2) | C11—C15—H15 | 115 (2) |
C2—C3—C16 | 121.7 (2) | C21—C16—C17 | 118.0 (2) |
C4—C3—C16 | 121.1 (2) | C21—C16—C3 | 121.0 (2) |
C12—N3—C11 | 120.5 (3) | C17—C16—C3 | 120.9 (2) |
C12—N3—C22 | 117.2 (3) | C18—C17—C16 | 121.1 (3) |
C11—N3—C22 | 122.2 (2) | C18—C17—H17 | 118 (3) |
C5—C4—C3 | 118.8 (2) | C16—C17—H17 | 121 (3) |
C5—C4—H4 | 118 (2) | C17—C18—C19 | 120.0 (3) |
C3—C4—H4 | 123 (2) | C17—C18—H18 | 126 (3) |
N1—C5—C4 | 124.2 (2) | C19—C18—H18 | 114 (2) |
N1—C5—C11 | 116.0 (2) | O1—C19—C20 | 124.0 (3) |
C4—C5—C11 | 119.6 (2) | O1—C19—C18 | 115.7 (3) |
N2—C6—C10 | 122.6 (3) | C20—C19—C18 | 120.3 (3) |
N2—C6—C1 | 116.0 (2) | C19—C20—C21 | 119.2 (3) |
C10—C6—C1 | 121.4 (2) | C19—C20—H20 | 124 (3) |
N2—C7—C8 | 123.8 (4) | C21—C20—H20 | 117 (3) |
N2—C7—H7 | 111 (3) | C16—C21—C20 | 121.3 (2) |
C8—C7—H7 | 126 (3) | C16—C21—H21 | 121.3 (18) |
C7—C8—C9 | 119.0 (3) | C20—C21—H21 | 117.4 (18) |
C7—C8—H8 | 117 (2) | N3—C22—H223 | 112.3 (18) |
C9—C8—H8 | 124 (2) | N3—C22—H222 | 111 (2) |
C8—C9—C10 | 118.4 (3) | H223—C22—H222 | 105 (2) |
C8—C9—H9 | 121 (3) | N3—C22—H221 | 113 (2) |
C10—C9—H9 | 120 (3) | H223—C22—H221 | 109 (2) |
C9—C10—C6 | 119.1 (3) | H222—C22—H221 | 107 (2) |
C9—C10—H10 | 120 (3) | O1—C23—H233 | 105 (2) |
C6—C10—H10 | 121 (3) | O1—C23—H232 | 115 (3) |
N3—C11—C15 | 119.0 (2) | H233—C23—H232 | 114 (4) |
N3—C11—C5 | 121.0 (2) | O1—C23—H231 | 106 (2) |
C15—C11—C5 | 120.0 (2) | H233—C23—H231 | 110 (3) |
N3—C12—C13 | 121.1 (3) | H232—C23—H231 | 107 (3) |
N3—C12—H12 | 111 (3) | ||
C5—N1—C1—C2 | 1.4 (4) | N1—C5—C11—N3 | −46.6 (3) |
C5—N1—C1—C6 | −179.9 (2) | C4—C5—C11—N3 | 137.7 (2) |
N1—C1—C2—C3 | 0.5 (4) | N1—C5—C11—C15 | 130.2 (3) |
C6—C1—C2—C3 | −178.1 (2) | C4—C5—C11—C15 | −45.5 (3) |
C1—C2—C3—C4 | −2.4 (4) | C11—N3—C12—C13 | −1.8 (4) |
C1—C2—C3—C16 | 176.2 (2) | C22—N3—C12—C13 | −179.0 (3) |
C2—C3—C4—C5 | 2.3 (4) | N3—C12—C13—C14 | 3.2 (5) |
C16—C3—C4—C5 | −176.3 (2) | C12—C13—C14—C15 | −1.6 (6) |
C1—N1—C5—C4 | −1.5 (4) | C13—C14—C15—C11 | −1.2 (5) |
C1—N1—C5—C11 | −176.9 (2) | N3—C11—C15—C14 | 2.6 (4) |
C3—C4—C5—N1 | −0.4 (4) | C5—C11—C15—C14 | −174.2 (3) |
C3—C4—C5—C11 | 174.9 (2) | C2—C3—C16—C21 | −147.8 (3) |
C7—N2—C6—C10 | −0.7 (4) | C4—C3—C16—C21 | 30.6 (4) |
C7—N2—C6—C1 | 180.0 (3) | C2—C3—C16—C17 | 30.1 (4) |
N1—C1—C6—N2 | 164.2 (2) | C4—C3—C16—C17 | −151.5 (3) |
C2—C1—C6—N2 | −17.2 (3) | C21—C16—C17—C18 | −2.7 (5) |
N1—C1—C6—C10 | −15.2 (3) | C3—C16—C17—C18 | 179.4 (3) |
C2—C1—C6—C10 | 163.5 (3) | C16—C17—C18—C19 | 1.5 (6) |
C6—N2—C7—C8 | 0.6 (5) | C23—O1—C19—C20 | −1.4 (5) |
N2—C7—C8—C9 | 0.0 (5) | C23—O1—C19—C18 | 179.3 (3) |
C7—C8—C9—C10 | −0.6 (5) | C17—C18—C19—O1 | −179.8 (3) |
C8—C9—C10—C6 | 0.5 (5) | C17—C18—C19—C20 | 0.8 (6) |
N2—C6—C10—C9 | 0.2 (4) | O1—C19—C20—C21 | 178.9 (3) |
C1—C6—C10—C9 | 179.5 (3) | C18—C19—C20—C21 | −1.7 (5) |
C12—N3—C11—C15 | −1.1 (4) | C17—C16—C21—C20 | 1.7 (4) |
C22—N3—C11—C15 | 175.9 (3) | C3—C16—C21—C20 | 179.6 (3) |
C12—N3—C11—C5 | 175.7 (2) | C19—C20—C21—C16 | 0.5 (5) |
C22—N3—C11—C5 | −7.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N2 | 0.96 (3) | 2.51 (3) | 2.816 (4) | 98 (2) |
C10—H10···N1 | 0.87 (4) | 2.55 (4) | 2.824 (4) | 99 (3) |
C22—H221···N1 | 0.92 (2) | 2.52 (4) | 2.868 (4) | 103 (3) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C22H19N32+·2ClO4− | C23H20N3O+·I− |
Mr | 524.30 | 481.32 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 6.015 (2), 13.073 (4), 29.501 (10) | 13.854 (4), 13.448 (4), 12.141 (4) |
β (°) | 91.441 (7) | 111.146 (5) |
V (Å3) | 2319.1 (13) | 2109.7 (11) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.34 | 1.54 |
Crystal size (mm) | 0.55 × 0.15 × 0.12 | 0.48 × 0.45 × 0.35 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.831, 0.961 | 0.483, 0.584 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13428, 5216, 3175 | 11870, 4729, 4104 |
Rint | 0.039 | 0.050 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.174, 0.99 | 0.038, 0.124, 1.16 |
No. of reflections | 5216 | 4729 |
No. of parameters | 393 | 334 |
No. of restraints | 10 | 82 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.51, −0.28 | 0.77, −1.08 |
Computer programs: SMART-NT (Bruker, 1999), SAINT-NT (Bruker, 1999), SAINT-NT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-NT (Sheldrick, 1999) and CELLGRAF (Reck et al., 1996), SHELXL97.
N1—C1 | 1.336 (3) | N3—C12 | 1.365 (4) |
N1—C5 | 1.340 (3) | N3—C22 | 1.470 (4) |
N2—C7 | 1.336 (4) | C1—C6 | 1.483 (3) |
N2—C6 | 1.340 (3) | C3—C16 | 1.484 (3) |
N3—C11 | 1.353 (3) | C5—C11 | 1.486 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O1 | 0.80 (3) | 2.25 (3) | 2.942 (5) | 146 (3) |
N2—H2N···N1 | 0.80 (3) | 2.18 (3) | 2.616 (3) | 115 (3) |
C13—H13···O7 | 0.98 (4) | 2.53 (4) | 3.401 (4) | 148 (3) |
C2—H2···O2i | 0.95 (3) | 2.51 (3) | 3.452 (4) | 169 (2) |
C4—H4···O8ii | 0.94 (2) | 2.48 (2) | 3.393 (4) | 163.7 (19) |
C22—H222···O6iii | 0.95 (2) | 2.41 (2) | 3.341 (4) | 167 (3) |
C19—H19···O6iv | 0.98 (3) | 2.53 (3) | 3.400 (5) | 148 (2) |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x−2, y−1, z. |
N1—C5 | 1.336 (3) | N2—C7 | 1.337 (4) |
N1—C1 | 1.345 (3) | C3—C16 | 1.482 (3) |
C1—C6 | 1.485 (3) | N3—C12 | 1.351 (4) |
O1—C19 | 1.370 (3) | N3—C11 | 1.352 (3) |
O1—C23 | 1.413 (4) | N3—C22 | 1.481 (4) |
N2—C6 | 1.335 (4) | C5—C11 | 1.483 (3) |
C19—O1—C23 | 118.0 (3) | C12—N3—C11 | 120.5 (3) |
C6—N2—C7 | 117.2 (3) | C12—N3—C22 | 117.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···N2 | 0.96 (3) | 2.51 (3) | 2.816 (4) | 98 (2) |
C10—H10···N1 | 0.87 (4) | 2.55 (4) | 2.824 (4) | 99 (3) |
C22—H221···N1 | 0.92 (2) | 2.52 (4) | 2.868 (4) | 103 (3) |
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Substituted terpyridines, which are common planar tridentate ligands for the complexation of a broad variety of heavy and transition metal ions, are frequently used as building blocks for supramolecular assemblies and composite fluorescent sensors (Cargill Thompson, 1997; Lainé et al., 2002; Goodall et al., 2002; Mutai et al., 2001). Terpyridines can be also exploited for the construction of bifunctional fluorescent reporters, enabling the simultaneous and cooperative spectroscopic recognition of two different analytes, thereby meeting the increasing interest in advanced sensory devices responding to two or more chemical inputs. A straightforward approach to such bifunctional molecules signalling protons and metal ions involves 4'-aryl-substituted 2,2':6',2''-terpyridines equipped with different donor substituents (Li et al., 2004). The stepwise and unexpectedly strong protonation-induced spectroscopic effects observed for these molecules led us synthesize the alkylated compounds, (I) and (II), as model systems for the corresponding protonated ligands. \sch
The molecular structures of (I) and (II) are shown in Figs. 1 and 2, respectively. While the molecule of (II) carries only a single positive charge, protonation of the N atom in pyridine ring 2 gives rise to a second positive charge in the molecule of (I). The H atom at N2 in (I) was found in a difference Fourier map. Its existence also follows from the C6—N2—C7 bond angle of 123.6 (3)°. The bond angles at the non-protonated pyridine N atoms are significantly smaller than 120°, e.g. C1—N1—C5 117.3 (2)° in (I), and C1—N1—C5 117.2 (2)° and C6—N2—C7 117.2 (3)° in (II). In the crystal structure of (I), there are two perchlorate anions, one of which is connected to the molecular cation by an intermolecular N2—H···O1 hydogen bond (Table 2). Furthermore, the protonated atom N2 acts as a donor for an intramolecular N2—H···N1 hydrogen bond. Despite the connection of one perchlorate anion to the cation, both anions show a high degree of rotational disorder, as indicated by the displacement ellipsoids (Fig. 1).
The molecular conformations of (I) and (II) can be described by the dihedral angles between the pyridine rings. These angles are very similar for (I) and (II), as shown by following values. The dihedral angle between rings 1 and 2 is 11.3 (2)° in (I) and 16.5 (1)° in (II), that between rings 1 and 3 is 49.6 (1)° in (I) and 46.8 (1)° in (II), and that between rings 1 and 4 is 30.6 (1)° in (I) and 30.7 (1)° in (II). However, while in (I) the atoms N1 and N2 are in cis positions, in (II) a trans position is observed. This different orientation of pyridine ring 2 is indicated by the N1—C1—C6—N2 torsion angle, which is −10.0 (3)° in (I) and 164.2 (2)° in (II).
π–π electron interactions between pyridine rings of neighbouring molecules are of special interest for the explanation of spectroscopic properties. These interactions are defined by the distance between the ring centroids (DC), the perpendicular distance of the centroid of one ring from the plane of the other (DP?), and the interplanar angle. Surprisingly, only weak π–π electron interactions were observed in the crystal structure of (II). These interactions between two symmetry-related molecules form dimers, as depicted in Fig. 3. The parameters are as follows: for rings N1/C1—C5 and N2/C7—C11(2 − x, −y, 1 − z), and for rings N2/C7—C11 and N1/C1—C5(2 − x, −y, 1 − z), DC = 3.896 (2) Å, DP = 3.493 and 3.835 Å, and the interplanar angle = 16.52°.