The title compound is an ethanol-solvated salt, C
16H
38N
42+·2C
11H
7O
2-·2C
2H
6O, in which the cation lies across a centre of inversion in
P2
1/
c. The ions are linked by N-H
O hydrogen bonds [H
O = 1.70 and 2.30 Å, N
O = 2.624 (2) and 3.136 (2) Å, and N-H
O = 178 and 151°], and the ethanol molecule is linked to the anion by an O-H
O hydrogen bond [H
O = 1.90 Å, O
O = 2.728 (2) Å and O-H
O = 171°], to form a centrosymmetric five-component aggregate. C-H
O hydrogen bonds and aromatic
-
-stacking interactions are absent, but the aggregates are linked into sheets by a single C-H
(arene) hydrogen bond.
Supporting information
CCDC reference: 208026
Equimolar quantities of tet-a (Hay et al., 1975) and 2-naphthoic acid were separately dissolved in ethanol. The solutions were mixed and the mixture was set aside to crystallize, producing analytically pure (I). Analysis, found: C 69.9, H 8.9, N 8.1%; C42H64N4O6 requires: C 70.0, H 9.0, N 7.8%. Crystals of (I) suitable for single-crystal X-ray diffraction were selected directly from the analytical sample.
The space group P21/c was uniquely assigned from the systematic absences. H atoms were treated as riding, with O—H distances of 0.84 Å, N—H distances of 0.92 Å, and C—H distances of 0.95 (aromatic), 0.98 (CH3), 0.99 (CH2) or 1.00 Å (aliphatic CH).
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
Meso-5,5,7,12,12,14-hexamethyl-1,4-diaza-8,11-diazoniumcyclotetradecane bis(2-naphthoate) ethanol disolvate
top
Crystal data top
C16H38N42+·2C11H7O2−·2C2H6O | F(000) = 784 |
Mr = 720.97 | Dx = 1.185 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4606 reflections |
a = 10.9563 (4) Å | θ = 2.8–27.5° |
b = 10.9584 (5) Å | µ = 0.08 mm−1 |
c = 17.1665 (8) Å | T = 150 K |
β = 101.446 (2)° | Block, colourless |
V = 2020.08 (15) Å3 | 0.32 × 0.25 × 0.20 mm |
Z = 2 | |
Data collection top
Nonius KappaCCD diffractometer | 3130 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed X-ray tube | Rint = 0.075 |
Graphite monochromator | θmax = 27.5°, θmin = 2.8° |
ϕ scans, and ω scans with κ offsets | h = −14→13 |
17192 measured reflections | k = −14→14 |
4606 independent reflections | l = −22→22 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0539P)2 + 0.3194P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
4606 reflections | Δρmax = 0.16 e Å−3 |
241 parameters | Δρmin = −0.17 e Å−3 |
0 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: 0.014 (3) |
Crystal data top
C16H38N42+·2C11H7O2−·2C2H6O | V = 2020.08 (15) Å3 |
Mr = 720.97 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.9563 (4) Å | µ = 0.08 mm−1 |
b = 10.9584 (5) Å | T = 150 K |
c = 17.1665 (8) Å | 0.32 × 0.25 × 0.20 mm |
β = 101.446 (2)° | |
Data collection top
Nonius KappaCCD diffractometer | 3130 reflections with I > 2σ(I) |
17192 measured reflections | Rint = 0.075 |
4606 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.16 e Å−3 |
4606 reflections | Δρmin = −0.17 e Å−3 |
241 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.59018 (11) | 0.52392 (11) | 0.61507 (7) | 0.0312 (3) | |
C2 | 0.57058 (15) | 0.39781 (14) | 0.64207 (9) | 0.0356 (4) | |
C3 | 0.43695 (15) | 0.35860 (15) | 0.61481 (9) | 0.0370 (4) | |
N4 | 0.40393 (11) | 0.35695 (11) | 0.52786 (7) | 0.0325 (3) | |
C5 | 0.27070 (14) | 0.33163 (15) | 0.49161 (9) | 0.0361 (4) | |
C51 | 0.22189 (17) | 0.21533 (17) | 0.52546 (11) | 0.0480 (4) | |
C52 | 0.19147 (15) | 0.44189 (17) | 0.50605 (10) | 0.0439 (4) | |
C6 | 0.26297 (15) | 0.31186 (15) | 0.40202 (9) | 0.0368 (4) | |
C7 | 0.28454 (14) | 0.42168 (15) | 0.35181 (9) | 0.0348 (4) | |
C71 | 0.27610 (16) | 0.38570 (16) | 0.26513 (9) | 0.0429 (4) | |
O1 | 0.41503 (11) | 0.66378 (11) | 0.65109 (7) | 0.0457 (3) | |
O2 | 0.37126 (11) | 0.75854 (11) | 0.53397 (7) | 0.0440 (3) | |
C11 | 0.21341 (14) | 0.76163 (13) | 0.70018 (9) | 0.0320 (3) | |
C12 | 0.23857 (13) | 0.79095 (13) | 0.62741 (9) | 0.0310 (3) | |
C13 | 0.16199 (14) | 0.87711 (15) | 0.57892 (9) | 0.0365 (4) | |
C14 | 0.06376 (14) | 0.93073 (15) | 0.60461 (9) | 0.0385 (4) | |
C15 | −0.06156 (15) | 0.95855 (16) | 0.70949 (11) | 0.0430 (4) | |
C16 | −0.07952 (16) | 0.93351 (17) | 0.78424 (11) | 0.0466 (4) | |
C17 | −0.00250 (16) | 0.84944 (16) | 0.83312 (10) | 0.0432 (4) | |
C18 | 0.09168 (15) | 0.79137 (15) | 0.80623 (10) | 0.0376 (4) | |
C19 | 0.11366 (13) | 0.81656 (13) | 0.72887 (9) | 0.0319 (3) | |
C110 | 0.03700 (14) | 0.90262 (14) | 0.68001 (9) | 0.0348 (4) | |
C111 | 0.34968 (14) | 0.73366 (14) | 0.60124 (9) | 0.0340 (3) | |
O3 | 0.32676 (12) | 0.89822 (12) | 0.39975 (7) | 0.0528 (3) | |
C31 | 0.43030 (16) | 0.97600 (16) | 0.39884 (10) | 0.0444 (4) | |
C32 | 0.42512 (18) | 1.02307 (18) | 0.31655 (10) | 0.0500 (5) | |
H1A | 0.5300 | 0.5736 | 0.6287 | 0.037* | |
H1B | 0.5788 | 0.5237 | 0.5605 | 0.037* | |
H2A | 0.5928 | 0.3942 | 0.7008 | 0.043* | |
H2B | 0.6258 | 0.3409 | 0.6206 | 0.043* | |
H3A | 0.4252 | 0.2762 | 0.6357 | 0.044* | |
H3B | 0.3815 | 0.4157 | 0.6359 | 0.044* | |
H4 | 0.4522 | 0.2989 | 0.5097 | 0.039* | |
H51A | 0.2711 | 0.1450 | 0.5146 | 0.072* | |
H51B | 0.1344 | 0.2028 | 0.5004 | 0.072* | |
H51C | 0.2291 | 0.2242 | 0.5830 | 0.072* | |
H52A | 0.1888 | 0.4469 | 0.5627 | 0.066* | |
H52B | 0.1067 | 0.4324 | 0.4750 | 0.066* | |
H52C | 0.2284 | 0.5167 | 0.4897 | 0.066* | |
H6A | 0.3246 | 0.2484 | 0.3956 | 0.044* | |
H6B | 0.1795 | 0.2784 | 0.3795 | 0.044* | |
H7 | 0.2191 | 0.4842 | 0.3547 | 0.042* | |
H71A | 0.2876 | 0.4582 | 0.2340 | 0.064* | |
H71B | 0.1941 | 0.3499 | 0.2443 | 0.064* | |
H71C | 0.3411 | 0.3258 | 0.2614 | 0.064* | |
H11 | 0.2641 | 0.7030 | 0.7323 | 0.038* | |
H13 | 0.1788 | 0.8979 | 0.5283 | 0.044* | |
H14 | 0.0128 | 0.9877 | 0.5712 | 0.046* | |
H15 | −0.1156 | 1.0140 | 0.6768 | 0.052* | |
H16 | −0.1447 | 0.9732 | 0.8035 | 0.056* | |
H17 | −0.0160 | 0.8329 | 0.8851 | 0.052* | |
H18 | 0.1426 | 0.7340 | 0.8393 | 0.045* | |
H3 | 0.3368 | 0.8616 | 0.4435 | 0.079* | |
H31A | 0.5087 | 0.9302 | 0.4168 | 0.053* | |
H31B | 0.4288 | 1.0452 | 0.4357 | 0.053* | |
H32A | 0.3463 | 1.0662 | 0.2984 | 0.075* | |
H32B | 0.4311 | 0.9546 | 0.2808 | 0.075* | |
H32C | 0.4947 | 1.0793 | 0.3166 | 0.075* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0325 (7) | 0.0346 (7) | 0.0276 (6) | 0.0034 (5) | 0.0087 (5) | 0.0004 (5) |
C2 | 0.0434 (9) | 0.0331 (8) | 0.0308 (8) | 0.0040 (7) | 0.0085 (6) | 0.0039 (6) |
C3 | 0.0445 (9) | 0.0376 (9) | 0.0317 (8) | −0.0017 (7) | 0.0141 (7) | 0.0026 (7) |
N4 | 0.0341 (7) | 0.0344 (7) | 0.0311 (6) | 0.0002 (5) | 0.0119 (5) | −0.0018 (5) |
C5 | 0.0334 (8) | 0.0382 (9) | 0.0390 (9) | −0.0030 (6) | 0.0127 (7) | 0.0007 (7) |
C51 | 0.0469 (10) | 0.0466 (10) | 0.0527 (11) | −0.0106 (8) | 0.0152 (8) | 0.0039 (8) |
C52 | 0.0399 (9) | 0.0511 (10) | 0.0443 (9) | 0.0053 (8) | 0.0169 (7) | 0.0001 (8) |
C6 | 0.0357 (8) | 0.0360 (8) | 0.0385 (9) | −0.0010 (6) | 0.0070 (7) | −0.0031 (7) |
C7 | 0.0314 (8) | 0.0383 (9) | 0.0343 (8) | 0.0030 (6) | 0.0059 (6) | −0.0020 (7) |
C71 | 0.0463 (10) | 0.0466 (10) | 0.0340 (8) | 0.0035 (8) | 0.0036 (7) | −0.0038 (7) |
O1 | 0.0469 (7) | 0.0525 (7) | 0.0414 (6) | 0.0206 (6) | 0.0177 (5) | 0.0117 (6) |
O2 | 0.0492 (7) | 0.0488 (7) | 0.0388 (6) | 0.0102 (5) | 0.0207 (5) | 0.0083 (5) |
C11 | 0.0318 (8) | 0.0282 (7) | 0.0360 (8) | 0.0019 (6) | 0.0069 (6) | 0.0010 (6) |
C12 | 0.0305 (8) | 0.0294 (8) | 0.0336 (8) | 0.0004 (6) | 0.0074 (6) | −0.0015 (6) |
C13 | 0.0391 (9) | 0.0384 (9) | 0.0324 (8) | 0.0031 (7) | 0.0079 (7) | 0.0017 (7) |
C14 | 0.0370 (8) | 0.0384 (9) | 0.0389 (9) | 0.0072 (7) | 0.0047 (7) | 0.0039 (7) |
C15 | 0.0368 (9) | 0.0424 (9) | 0.0507 (10) | 0.0091 (7) | 0.0106 (7) | 0.0021 (8) |
C16 | 0.0395 (9) | 0.0513 (10) | 0.0539 (11) | 0.0066 (8) | 0.0206 (8) | −0.0022 (9) |
C17 | 0.0424 (9) | 0.0467 (10) | 0.0446 (9) | −0.0014 (8) | 0.0187 (8) | −0.0007 (8) |
C18 | 0.0373 (8) | 0.0374 (9) | 0.0397 (9) | −0.0010 (7) | 0.0117 (7) | 0.0028 (7) |
C19 | 0.0294 (7) | 0.0299 (7) | 0.0373 (8) | −0.0020 (6) | 0.0086 (6) | −0.0010 (6) |
C110 | 0.0311 (8) | 0.0339 (8) | 0.0398 (8) | 0.0004 (6) | 0.0079 (6) | −0.0029 (7) |
C111 | 0.0351 (8) | 0.0317 (8) | 0.0366 (8) | 0.0012 (6) | 0.0103 (7) | −0.0016 (7) |
O3 | 0.0558 (8) | 0.0567 (8) | 0.0439 (7) | −0.0062 (6) | 0.0052 (6) | 0.0125 (6) |
C31 | 0.0484 (10) | 0.0435 (10) | 0.0400 (9) | 0.0004 (8) | 0.0058 (7) | −0.0043 (8) |
C32 | 0.0579 (11) | 0.0538 (11) | 0.0409 (9) | −0.0116 (9) | 0.0165 (8) | −0.0085 (8) |
Geometric parameters (Å, º) top
N1—C2 | 1.487 (2) | O1—C111 | 1.2602 (19) |
N1—C7i | 1.501 (2) | O2—C111 | 1.2538 (18) |
N1—H1A | 0.92 | C11—C12 | 1.370 (2) |
N1—H1B | 0.92 | C11—C19 | 1.419 (2) |
C2—C3 | 1.508 (2) | C11—H11 | 0.95 |
C2—H2A | 0.99 | C12—C13 | 1.418 (2) |
C2—H2B | 0.99 | C12—C111 | 1.515 (2) |
N4—C3 | 1.465 (2) | C13—C14 | 1.373 (2) |
C3—H3A | 0.99 | C13—H13 | 0.95 |
C3—H3B | 0.99 | C14—C110 | 1.417 (2) |
N4—C5 | 1.495 (2) | C14—H14 | 0.95 |
N4—H4 | 0.92 | C15—C16 | 1.364 (2) |
C5—C52 | 1.536 (2) | C15—C110 | 1.419 (2) |
C5—C6 | 1.539 (2) | C15—H15 | 0.95 |
C5—C51 | 1.540 (2) | C16—C17 | 1.409 (2) |
C51—H51A | 0.98 | C16—H16 | 0.95 |
C51—H51B | 0.98 | C17—C18 | 1.368 (2) |
C51—H51C | 0.98 | C17—H17 | 0.95 |
C52—H52A | 0.98 | C18—C19 | 1.423 (2) |
C52—H52B | 0.98 | C18—H18 | 0.95 |
C52—H52C | 0.98 | C19—C110 | 1.421 (2) |
C6—C7 | 1.526 (2) | O3—C31 | 1.421 (2) |
C6—H6A | 0.99 | O3—H3 | 0.84 |
C6—H6B | 0.99 | C31—C32 | 1.494 (2) |
C7—C71 | 1.524 (2) | C31—H31A | 0.99 |
C7—H7 | 1.00 | C31—H31B | 0.99 |
C71—H71A | 0.98 | C32—H32A | 0.98 |
C71—H71B | 0.98 | C32—H32B | 0.98 |
C71—H71C | 0.98 | C32—H32C | 0.98 |
| | | |
C2—N1—C7i | 115.40 (12) | C7—C71—H71B | 109.5 |
C2—N1—H1A | 108.4 | H71A—C71—H71B | 109.5 |
C7i—N1—H1A | 108.4 | C7—C71—H71C | 109.5 |
C2—N1—H1B | 108.4 | H71A—C71—H71C | 109.5 |
C7i—N1—H1B | 108.4 | H71B—C71—H71C | 109.5 |
H1A—N1—H1B | 107.5 | C12—C11—C19 | 121.69 (14) |
N1—C2—C3 | 111.07 (13) | C12—C11—H11 | 119.2 |
N1—C2—H2A | 109.4 | C19—C11—H11 | 119.2 |
C3—C2—H2A | 109.4 | C11—C12—C13 | 119.26 (13) |
N1—C2—H2B | 109.4 | C11—C12—C111 | 119.48 (13) |
C3—C2—H2B | 109.4 | C13—C12—C111 | 121.23 (13) |
H2A—C2—H2B | 108.0 | C14—C13—C12 | 120.43 (14) |
N4—C3—C2 | 110.36 (12) | C14—C13—H13 | 119.8 |
N4—C3—H3A | 109.6 | C12—C13—H13 | 119.8 |
C2—C3—H3A | 109.6 | C13—C14—C110 | 121.18 (15) |
N4—C3—H3B | 109.6 | C13—C14—H14 | 119.4 |
C2—C3—H3B | 109.6 | C110—C14—H14 | 119.4 |
H3A—C3—H3B | 108.1 | C16—C15—C110 | 120.70 (16) |
C3—N4—C5 | 116.74 (11) | C16—C15—H15 | 119.7 |
C3—N4—H4 | 108.1 | C110—C15—H15 | 119.7 |
C5—N4—H4 | 108.1 | C15—C16—C17 | 120.71 (15) |
N4—C5—C52 | 108.86 (13) | C15—C16—H16 | 119.6 |
N4—C5—C6 | 107.32 (12) | C17—C16—H16 | 119.6 |
C52—C5—C6 | 110.56 (13) | C18—C17—C16 | 120.40 (16) |
N4—C5—C51 | 112.34 (13) | C18—C17—H17 | 119.8 |
C52—C5—C51 | 109.90 (13) | C16—C17—H17 | 119.8 |
C6—C5—C51 | 107.84 (13) | C17—C18—C19 | 120.22 (15) |
C5—C51—H51A | 109.5 | C17—C18—H18 | 119.9 |
C5—C51—H51B | 109.5 | C19—C18—H18 | 119.9 |
H51A—C51—H51B | 109.5 | C11—C19—C110 | 118.85 (14) |
C5—C51—H51C | 109.5 | C11—C19—C18 | 121.76 (14) |
H51A—C51—H51C | 109.5 | C110—C19—C18 | 119.34 (14) |
H51B—C51—H51C | 109.5 | C14—C110—C15 | 122.81 (15) |
C5—C52—H52A | 109.5 | C14—C110—C19 | 118.59 (13) |
C5—C52—H52B | 109.5 | C15—C110—C19 | 118.59 (14) |
H52A—C52—H52B | 109.5 | O2—C111—O1 | 124.89 (14) |
C5—C52—H52C | 109.5 | O2—C111—C12 | 119.51 (14) |
H52A—C52—H52C | 109.5 | O1—C111—C12 | 115.60 (13) |
H52B—C52—H52C | 109.5 | C31—O3—H3 | 109.5 |
C7—C6—C5 | 118.01 (13) | O3—C31—C32 | 109.68 (14) |
C7—C6—H6A | 107.8 | O3—C31—H31A | 109.7 |
C5—C6—H6A | 107.8 | C32—C31—H31A | 109.7 |
C7—C6—H6B | 107.8 | O3—C31—H31B | 109.7 |
C5—C6—H6B | 107.8 | C32—C31—H31B | 109.7 |
H6A—C6—H6B | 107.1 | H31A—C31—H31B | 108.2 |
N1i—C7—C71 | 110.27 (12) | C31—C32—H32A | 109.5 |
N1i—C7—C6 | 109.38 (12) | C31—C32—H32B | 109.5 |
C71—C7—C6 | 111.17 (13) | H32A—C32—H32B | 109.5 |
N1i—C7—H7 | 108.7 | C31—C32—H32C | 109.5 |
C71—C7—H7 | 108.7 | H32A—C32—H32C | 109.5 |
C6—C7—H7 | 108.7 | H32B—C32—H32C | 109.5 |
C7—C71—H71A | 109.5 | | |
| | | |
N1—C2—C3—N4 | 62.09 (16) | C15—C16—C17—C18 | −0.1 (3) |
C2—C3—N4—C5 | −174.22 (13) | C16—C17—C18—C19 | 0.8 (3) |
C3—N4—C5—C6 | −170.12 (13) | C12—C11—C19—C110 | 1.1 (2) |
N4—C5—C6—C7 | −69.22 (17) | C12—C11—C19—C18 | −176.40 (14) |
C5—C6—C7—N1i | 56.87 (17) | C17—C18—C19—C11 | 177.53 (15) |
C6—C7—N1i—C2i | −163.05 (12) | C17—C18—C19—C110 | 0.1 (2) |
C7i—N1—C2—C3 | 172.03 (12) | C13—C14—C110—C15 | 178.26 (16) |
C3—N4—C5—C52 | 70.19 (16) | C13—C14—C110—C19 | −0.4 (2) |
C3—N4—C5—C51 | −51.76 (18) | C16—C15—C110—C14 | −176.37 (16) |
C52—C5—C6—C7 | 49.37 (18) | C16—C15—C110—C19 | 2.3 (3) |
C51—C5—C6—C7 | 169.54 (14) | C11—C19—C110—C14 | −0.4 (2) |
C5—C6—C7—C71 | 178.87 (13) | C18—C19—C110—C14 | 177.16 (14) |
C19—C11—C12—C13 | −0.9 (2) | C11—C19—C110—C15 | −179.13 (14) |
C19—C11—C12—C111 | 177.33 (14) | C18—C19—C110—C15 | −1.6 (2) |
C11—C12—C13—C14 | 0.1 (2) | C11—C12—C111—O2 | 178.54 (14) |
C111—C12—C13—C14 | −178.13 (15) | C13—C12—C111—O2 | −3.3 (2) |
C12—C13—C14—C110 | 0.6 (2) | C11—C12—C111—O1 | −2.1 (2) |
C110—C15—C16—C17 | −1.5 (3) | C13—C12—C111—O1 | 176.06 (14) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···N4i | 0.92 | 2.04 | 2.791 (2) | 138 |
N1—H1A···O1 | 0.92 | 1.70 | 2.624 (2) | 178 |
N4—H4···O2i | 0.92 | 2.30 | 3.136 (2) | 151 |
O3—H3···O2 | 0.84 | 1.90 | 2.728 (2) | 171 |
C7—H7···Cg2ii | 1.00 | 2.94 | 3.785 (2) | 143 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z−1/2. |
Experimental details
Crystal data |
Chemical formula | C16H38N42+·2C11H7O2−·2C2H6O |
Mr | 720.97 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 10.9563 (4), 10.9584 (5), 17.1665 (8) |
β (°) | 101.446 (2) |
V (Å3) | 2020.08 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.32 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17192, 4606, 3130 |
Rint | 0.075 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.130, 1.02 |
No. of reflections | 4606 |
No. of parameters | 241 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.17 |
Selected geometric parameters (Å, º) topN1—C2 | 1.487 (2) | N4—C3 | 1.465 (2) |
N1—C7i | 1.501 (2) | N4—C5 | 1.495 (2) |
| | | |
N1—C2—C3—N4 | 62.09 (16) | C5—C6—C7—N1i | 56.87 (17) |
C2—C3—N4—C5 | −174.22 (13) | C6—C7—N1i—C2i | −163.05 (12) |
C3—N4—C5—C6 | −170.12 (13) | C7i—N1—C2—C3 | 172.03 (12) |
N4—C5—C6—C7 | −69.22 (17) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···N4i | 0.92 | 2.04 | 2.791 (2) | 138 |
N1—H1A···O1 | 0.92 | 1.70 | 2.624 (2) | 178 |
N4—H4···O2i | 0.92 | 2.30 | 3.136 (2) | 151 |
O3—H3···O2 | 0.84 | 1.90 | 2.728 (2) | 171 |
C7—H7···Cg2ii | 1.00 | 2.94 | 3.785 (2) | 143 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z−1/2. |
The nickel(II) complex [(RCOO)2Ni(cyclam)], where RCOO− represents 2-naphthoate, C10H7COO−, and cyclam is 1,4,8,11-tetraazacyclotetradecane, C10H24N4, is centrosymmetric, with naphthoate ligands occupying mutually trans sites in an octahedral NiN4O2 chromophore (Zakaria et al., 2002). An unexpected feature of this structure is the complete absence of aromatic π···π stacking interactions between the naphthalene rings in adjacent complexes, even though the closest approach between these rings is across a centre of inversion, so that the rings involved are strictly parallel. While the shortest interplanar spacing between such rings is only 3.122 (2) Å, the corresponding distance between the ring centroids is 5.260 (2) Å, with a corresponding centroid offset of 4.233 (2) Å, so that there is no ring overlap whatsoever.
Intrigued by this feature, we have now studied a related 2-naphthoic acid derivative, the title ethanol-solvated adduct, (I), formed between this acid and tet-a (meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane), C16H36N4. The constitution of (I) (Fig. 1) is that of a salt, C16H38N42+·2C10H7COO−·2C2H5OH, in which the fully ordered cation lies across a centre of inversion, chosen for the sake of convenience as that at (1/2, 1/2, 1/2), while the anion and the ethanol molecule lie in general positions. \sch
The cation adopts the usual and characteristic trans-III configuration (Barefield et al., 1986), with four methyl groups in equatorial sites and two in axial sites, and with paired intra-cation N—H···N hydrogen bonds generating an R22(10) motif (Bernstein et al., 1995). There is almost perfect staggering about all of the C—C and C—N bonds in the cation (Table 1), and there are four axial N—H bonds available for intermolecular hydrogen-bond formation, two on each face of the disk-like cation. The C—N bond lengths in the cation (Table 1) are consistent with the site of N-protonation, while the C—C distances in the anion exhibit the marked bond fixation typical of the naphthalene ring system.
Within the selected asymmetric unit, atoms N1 at (x, y, z) and N4 at (1 − x, 1 − y, 1 − z), both part of the cation centred at (1/2, 1/2, 1/2), act as hydrogen-bond donors to, respectively, carboxylate atoms O1 and O2 in the anion at (x, y, z), forming an R33(8) motif, while ethanol atom O3 also acts as a donor towards O2 (Fig. 1). In this manner, a centrosymmetric five-component aggregate is formed, which accommodates all of the hard (Desiraju & Steiner, 1999) hydrogen-bond donors. Similar R33(8) motifs involving [(tet-a)H2]2+ cations and aromatic carboxylate anions have been observed in salts with terephthalate (Lough et al., 2000), 5-hydroxyisophthalate (Burchell et al., 2000) and 5-nitroisophthalate (MacLean et al., 2002), although not in the analogous salts formed by 3- and 4-hydroxybenzoate or 3,5-dihydroxybenzoate anions (Gregson et al., 2000).
For the closest approach of naphthalene rings in adjacent aggregates in (I), the centroid separation is 5.493 (2) Å. Whereas in [(C10H7COO)2Ni(cyclam)], the nearest-neighbour naphthoate units are related by inversion, in (I) they are related by a twofold screw axis, and the naphthalene rings involved are almost orthogonal (Fig. 2), with a dihedral angle of 84.5 (3)° between the ring planes, so that aromatic π···π stacking interactions are absent. However, the aggregates are linked into sheets by a single C—H···π(arene) hydrogen bond (Table 2). The metrical systematics of C—H···π(arene) hydrogen bonds have been studied by Braga et al. (1998) using neutron diffraction results extracted from the Cambridge Structural Database (CSD, Version?; Allen, 2002). The most frequently observed H···Cg distances (Cg represents the centroid of the arene ring) lie in the range 2.9–3.0 Å, while the mean values of the C—H ···Cg angle and the C···Cg distances were found to be 142 (2)° and 3.69 (2) Å, respectively. The values found here for (I) are thus fairly typical for interactions of this type.
Atom C7 in the cation is adjacent to a protonated ring N atom, and hence the axial C7—H7 bond can be expected to be moderately acidic for an aliphatic C—H bond. Atom C7 at (x, y, z), which lies in the cation centred at (1/2, 1/2, 1/2) acts as hydrogen-bond donor to the unsubstituted C15—C110 aryl ring of the anion at (x, 3/2 − y, z − 1/2), which forms part of the aggregate centred at (1/2, 1, 0), while atom C7 at (1 − x, 1 − y, 1 − z) in the same (1/2, 1/2, 1/2) aggregate acts as a donor to the naphthoate anion at (1 − x, y − 1/2, 3/2 − z), which is part of the aggregate centred at (1/2, 0, 1). The two naphthoate anions in the (1/2, 1/2, 1/2) aggregate likewise act as acceptors from atoms C7 in the aggregates centred at (1/2, 0, 0) and (1/2, 1, 1) and in this manner the five-component aggregates are linked into a (100) sheet (Fig. 3).
Table 2. Hydrogen-bond parameters (Å, °) for (I). Cg is the centroid of the C15—C110 ring in the anion.