A donor–acceptor compound, diaqua-1κO,2κO-[μ-11,23-dimethyl-3,7,15,19-tetraazatricyclo[19.3.1.19,13]hexacosa-1(25),2,7,9,11,13(26),14,19,21,23-decaene-25,26-diolato-1κ4N3,N7,O25,O26:2κ4N15,N19,O25,O26]dizinc(II) diperchlorate bis(8-methylquinoline) ethanol disolvate, [Zn2(C24H26N4O2)(H2O)2](ClO4)2·2C10H9N·2C2H6O, obtained by the reaction of a dinuclear zinc(II) complex of a Robson macrocycle (acceptor) and 8-methylquinoline (donor), lies about an inversion centre and the coordination about the unique Zn atom is a distorted square pyramid. The fifth coordination site is occupied by the water molecule, Zn—O = 2.016 (2) Å, and the average macrocyclic Zn—O and Zn—N distances are 2.059 (6) and 2.059 (3) Å, respectively.
Supporting information
CCDC reference: 156145
The dinuclear zinc(II) complex diperchlorate of a Robson macrocycle (0.732 g, 1 mmol), was prepared via a sodium template method as reported previously (Gou & Fenton, 1994), dissolved in 50 mL e thanol, then 8-methylquinoline (0.286 g, 2 mmol) was added. The mixture was refluxed for 1 h, then cooled to room temperature. The yellow precipitate was collected, washed with a small amount of ethanol and dried in vacuo. Yellow single crystals suitable for X-ray structure analysis were grown in an ethanol solution.
H atoms were introduced at calculated positions and refined using a riding model other than that of water molecule which was included in the refinement. The perchlorate ion and the ethanol solvent are disordered with major and minor components in ratio of 54:46 and 51:49, respectively.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
[Zn
2+]
2[µ-{11,23-dimethyl-3,7,15,19-tetraazatricyclo[19.3.1.1
9,13] hexacosa-1(25),2,7,9,11,13 (26),14,19,21,23-decaene-25,26-diolato-N
3, N
7,
O25,
O26:
N15,
N19,
O25,
O26}]
2− 2[ClO
4]
−, bis(8-methylquinoline), 2(C
2H
5OH)
top
Crystal data top
[Zn(C24H26N4O2)(OH2)2](ClO4)2·2C10H9N·2C2H6O | F(000) = 1192 |
Mr = 1146.70 | Dx = 1.459 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.8258 (2) Å | Cell parameters from 8192 reflections |
b = 15.1039 (1) Å | θ = 2.7–28.4° |
c = 14.7734 (2) Å | µ = 1.09 mm−1 |
β = 114.228 (1)° | T = 293 K |
V = 2609.82 (6) Å3 | Slab, light yellow |
Z = 2 | 0.44 × 0.34 × 0.28 mm |
Data collection top
Siemens SMART CCD area detector diffractometer | 6445 independent reflections |
Radiation source: fine-focus sealed tube | 4334 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 2.7° |
ω scans | h = −10→17 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −20→20 |
Tmin = 0.645, Tmax = 0.750 | l = −19→18 |
18483 measured reflections | |
Refinement top
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0548P)2] where P = (Fo2 + 2Fc2)/3 |
6445 reflections | (Δ/σ)max < 0.001 |
412 parameters | Δρmax = 0.57 e Å−3 |
124 restraints | Δρmin = −0.52 e Å−3 |
Crystal data top
[Zn(C24H26N4O2)(OH2)2](ClO4)2·2C10H9N·2C2H6O | V = 2609.82 (6) Å3 |
Mr = 1146.70 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.8258 (2) Å | µ = 1.09 mm−1 |
b = 15.1039 (1) Å | T = 293 K |
c = 14.7734 (2) Å | 0.44 × 0.34 × 0.28 mm |
β = 114.228 (1)° | |
Data collection top
Siemens SMART CCD area detector diffractometer | 6445 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 4334 reflections with I > 2σ(I) |
Tmin = 0.645, Tmax = 0.750 | Rint = 0.066 |
18483 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 124 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.57 e Å−3 |
6445 reflections | Δρmin = −0.52 e Å−3 |
412 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Zn1 | 0.63271 (2) | −0.028475 (17) | 0.54039 (2) | 0.03520 (11) | |
O1 | 0.52767 (14) | 0.08100 (9) | 0.49760 (12) | 0.0380 (4) | |
N1 | 0.75237 (18) | 0.04122 (14) | 0.50914 (17) | 0.0431 (5) | |
N2 | 0.69007 (19) | −0.15173 (14) | 0.52408 (17) | 0.0459 (5) | |
C1 | 0.8041 (3) | −0.1624 (2) | 0.5229 (3) | 0.0752 (11) | |
H1A | 0.8400 | −0.2146 | 0.5614 | 0.090* | |
H1B | 0.7937 | −0.1734 | 0.4550 | 0.090* | |
C2 | 0.8828 (3) | −0.0870 (2) | 0.5616 (3) | 0.0771 (11) | |
H2A | 0.8908 | −0.0753 | 0.6287 | 0.092* | |
H2B | 0.9573 | −0.1053 | 0.5661 | 0.092* | |
C3 | 0.8532 (3) | −0.0036 (2) | 0.5065 (3) | 0.0653 (9) | |
H3A | 0.8390 | −0.0153 | 0.4378 | 0.078* | |
H3B | 0.9183 | 0.0361 | 0.5335 | 0.078* | |
C4 | 0.7534 (2) | 0.12564 (18) | 0.5041 (2) | 0.0449 (6) | |
H4 | 0.8186 | 0.1502 | 0.5015 | 0.054* | |
C5 | 0.6670 (2) | 0.18809 (16) | 0.50175 (18) | 0.0388 (6) | |
C6 | 0.6962 (2) | 0.27766 (17) | 0.5021 (2) | 0.0486 (7) | |
H6 | 0.7685 | 0.2914 | 0.5057 | 0.058* | |
C7 | 0.6232 (3) | 0.34623 (17) | 0.4973 (2) | 0.0511 (7) | |
C8 | 0.5158 (3) | 0.32255 (16) | 0.4897 (2) | 0.0492 (7) | |
H8 | 0.4645 | 0.3675 | 0.4857 | 0.059* | |
C9 | 0.4799 (2) | 0.23465 (14) | 0.48766 (17) | 0.0383 (6) | |
C10 | 0.5570 (2) | 0.16484 (14) | 0.49549 (16) | 0.0340 (5) | |
C11 | 0.6604 (3) | 0.44221 (19) | 0.5025 (3) | 0.0799 (11) | |
H11A | 0.5943 | 0.4792 | 0.4717 | 0.120* | |
H11B | 0.7096 | 0.4488 | 0.4684 | 0.120* | |
H11C | 0.7009 | 0.4593 | 0.5707 | 0.120* | |
C12 | 0.3655 (2) | 0.22325 (16) | 0.4818 (2) | 0.0453 (7) | |
H12 | 0.3269 | 0.2752 | 0.4824 | 0.054* | |
N3 | 0.7210 (2) | 0.34528 (14) | 0.25316 (16) | 0.0472 (6) | |
C13 | 0.8267 (3) | 0.3269 (2) | 0.2648 (2) | 0.0586 (8) | |
H13 | 0.8750 | 0.3739 | 0.2681 | 0.070* | |
C14 | 0.8702 (3) | 0.2410 (2) | 0.2723 (3) | 0.0673 (9) | |
H14 | 0.9456 | 0.2318 | 0.2817 | 0.081* | |
C15 | 0.8007 (3) | 0.1712 (2) | 0.2657 (2) | 0.0601 (8) | |
H15 | 0.8276 | 0.1136 | 0.2690 | 0.072* | |
C16 | 0.6877 (3) | 0.18699 (17) | 0.2539 (2) | 0.0484 (7) | |
C17 | 0.6112 (3) | 0.11731 (19) | 0.2470 (2) | 0.0596 (8) | |
H17 | 0.6347 | 0.0588 | 0.2492 | 0.072* | |
C18 | 0.5031 (3) | 0.1358 (2) | 0.2369 (3) | 0.0648 (9) | |
H18 | 0.4531 | 0.0897 | 0.2323 | 0.078* | |
C19 | 0.4661 (3) | 0.22402 (19) | 0.2334 (2) | 0.0564 (8) | |
H19 | 0.3923 | 0.2351 | 0.2277 | 0.068* | |
C20 | 0.5366 (3) | 0.29416 (17) | 0.23822 (19) | 0.0461 (6) | |
C21 | 0.6505 (2) | 0.27590 (16) | 0.24855 (18) | 0.0400 (6) | |
C22 | 0.4940 (3) | 0.38725 (18) | 0.2328 (2) | 0.0569 (8) | |
H22A | 0.4191 | 0.3866 | 0.2328 | 0.085* | |
H22B | 0.4903 | 0.4147 | 0.1729 | 0.085* | |
H22C | 0.5452 | 0.4201 | 0.2891 | 0.085* | |
O7A | 0.1841 (12) | 0.1379 (12) | 0.1848 (12) | 0.109 (5) | 0.520 (15) |
H7A | 0.1690 | 0.1880 | 0.1969 | 0.163* | 0.520 (15) |
C23A | 0.1121 (12) | 0.1156 (8) | 0.0865 (10) | 0.130 (5) | 0.520 (15) |
H23A | 0.1374 | 0.0606 | 0.0681 | 0.156* | 0.520 (15) |
H23B | 0.1147 | 0.1617 | 0.0417 | 0.156* | 0.520 (15) |
C24A | −0.0064 (17) | 0.106 (2) | 0.078 (2) | 0.267 (15) | 0.520 (15) |
H24A | −0.0061 | 0.0723 | 0.1339 | 0.400* | 0.520 (15) |
H24B | −0.0509 | 0.0748 | 0.0180 | 0.400* | 0.520 (15) |
H24C | −0.0391 | 0.1629 | 0.0775 | 0.400* | 0.520 (15) |
O7B | 0.1421 (15) | 0.1294 (13) | 0.2055 (10) | 0.110 (5) | 0.480 (15) |
H7B | 0.1591 | 0.1805 | 0.1983 | 0.164* | 0.480 (15) |
C23B | 0.0458 (15) | 0.1073 (11) | 0.1297 (9) | 0.116 (6) | 0.480 (15) |
H23C | −0.0164 | 0.1235 | 0.1477 | 0.139* | 0.480 (15) |
H23D | 0.0450 | 0.0432 | 0.1248 | 0.139* | 0.480 (15) |
C24B | 0.0173 (12) | 0.1421 (10) | 0.0299 (8) | 0.113 (5) | 0.480 (15) |
H24D | 0.0201 | 0.2056 | 0.0322 | 0.170* | 0.480 (15) |
H24E | −0.0583 | 0.1233 | −0.0136 | 0.170* | 0.480 (15) |
H24F | 0.0713 | 0.1203 | 0.0056 | 0.170* | 0.480 (15) |
Cl1A | 0.1389 (5) | 0.3783 (4) | 0.2583 (5) | 0.085 (2) | 0.541 (10) |
O1A | 0.0392 (8) | 0.3641 (8) | 0.1694 (7) | 0.157 (5) | 0.541 (10) |
O2A | 0.1170 (11) | 0.3899 (7) | 0.3388 (8) | 0.142 (5) | 0.541 (10) |
O3A | 0.1932 (13) | 0.4478 (6) | 0.2393 (8) | 0.158 (6) | 0.541 (10) |
O4A | 0.2097 (8) | 0.3030 (5) | 0.2650 (7) | 0.163 (5) | 0.541 (10) |
Cl1B | 0.1383 (5) | 0.3785 (3) | 0.2555 (4) | 0.0503 (17) | 0.459 (10) |
O1B | 0.0842 (13) | 0.3207 (9) | 0.1836 (13) | 0.203 (8) | 0.459 (10) |
O2B | 0.2486 (7) | 0.4008 (9) | 0.2769 (11) | 0.158 (6) | 0.459 (10) |
O3B | 0.0739 (10) | 0.4548 (6) | 0.2335 (11) | 0.186 (7) | 0.459 (10) |
O4B | 0.1323 (13) | 0.3418 (13) | 0.3369 (11) | 0.241 (11) | 0.459 (10) |
O1W | 0.68803 (18) | −0.01673 (13) | 0.68876 (15) | 0.0493 (5) | |
H1W | 0.699 (3) | 0.034 (2) | 0.714 (3) | 0.094 (14)* | |
H2W | 0.736 (3) | −0.056 (2) | 0.728 (3) | 0.090 (13)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.02962 (17) | 0.03155 (15) | 0.04366 (17) | 0.00338 (11) | 0.01426 (12) | 0.00015 (12) |
O1 | 0.0340 (9) | 0.0271 (7) | 0.0516 (10) | 0.0014 (7) | 0.0164 (8) | 0.0019 (7) |
N1 | 0.0372 (12) | 0.0428 (12) | 0.0536 (13) | 0.0031 (9) | 0.0231 (10) | 0.0038 (10) |
N2 | 0.0370 (13) | 0.0395 (12) | 0.0624 (15) | 0.0070 (9) | 0.0217 (11) | −0.0011 (10) |
C1 | 0.055 (2) | 0.0552 (19) | 0.126 (3) | 0.0112 (15) | 0.048 (2) | −0.009 (2) |
C2 | 0.0426 (18) | 0.083 (2) | 0.111 (3) | 0.0205 (17) | 0.0372 (19) | 0.022 (2) |
C3 | 0.052 (2) | 0.0611 (18) | 0.099 (3) | 0.0083 (14) | 0.0473 (19) | 0.0099 (18) |
C4 | 0.0362 (15) | 0.0510 (15) | 0.0503 (16) | −0.0066 (11) | 0.0205 (12) | 0.0043 (12) |
C5 | 0.0397 (14) | 0.0367 (12) | 0.0377 (13) | −0.0030 (10) | 0.0136 (11) | 0.0031 (10) |
C6 | 0.0479 (17) | 0.0456 (15) | 0.0484 (15) | −0.0114 (12) | 0.0159 (13) | 0.0038 (12) |
C7 | 0.062 (2) | 0.0340 (13) | 0.0513 (16) | −0.0085 (12) | 0.0171 (14) | −0.0006 (12) |
C8 | 0.0622 (19) | 0.0293 (11) | 0.0511 (16) | 0.0064 (12) | 0.0182 (14) | 0.0010 (11) |
C9 | 0.0453 (15) | 0.0316 (11) | 0.0363 (13) | 0.0038 (10) | 0.0150 (11) | 0.0007 (10) |
C10 | 0.0382 (14) | 0.0301 (11) | 0.0295 (11) | −0.0001 (9) | 0.0096 (10) | 0.0007 (9) |
C11 | 0.097 (3) | 0.0360 (15) | 0.102 (3) | −0.0155 (16) | 0.036 (2) | −0.0012 (17) |
C12 | 0.0505 (17) | 0.0325 (13) | 0.0537 (16) | 0.0119 (11) | 0.0223 (13) | 0.0004 (11) |
N3 | 0.0480 (15) | 0.0436 (12) | 0.0443 (12) | −0.0030 (10) | 0.0132 (11) | 0.0045 (10) |
C13 | 0.0436 (18) | 0.0592 (18) | 0.0624 (19) | −0.0044 (14) | 0.0110 (14) | 0.0060 (15) |
C14 | 0.0446 (18) | 0.076 (2) | 0.076 (2) | 0.0107 (16) | 0.0191 (16) | 0.0120 (18) |
C15 | 0.059 (2) | 0.0530 (17) | 0.065 (2) | 0.0173 (15) | 0.0223 (16) | 0.0091 (15) |
C16 | 0.0610 (19) | 0.0422 (14) | 0.0402 (14) | 0.0020 (13) | 0.0190 (13) | 0.0055 (11) |
C17 | 0.080 (2) | 0.0378 (15) | 0.064 (2) | −0.0005 (14) | 0.0327 (17) | 0.0034 (13) |
C18 | 0.081 (3) | 0.0478 (17) | 0.078 (2) | −0.0162 (16) | 0.0450 (19) | −0.0010 (16) |
C19 | 0.0590 (19) | 0.0590 (18) | 0.0612 (19) | −0.0089 (14) | 0.0347 (15) | 0.0019 (15) |
C20 | 0.0544 (18) | 0.0446 (14) | 0.0423 (14) | −0.0009 (12) | 0.0230 (13) | 0.0019 (11) |
C21 | 0.0468 (16) | 0.0397 (13) | 0.0323 (12) | −0.0022 (11) | 0.0151 (11) | 0.0034 (10) |
C22 | 0.059 (2) | 0.0501 (16) | 0.067 (2) | 0.0053 (13) | 0.0317 (16) | 0.0056 (14) |
O7A | 0.093 (8) | 0.072 (5) | 0.112 (8) | 0.016 (5) | −0.009 (6) | 0.009 (5) |
C23A | 0.123 (11) | 0.138 (9) | 0.102 (9) | 0.003 (7) | 0.017 (8) | 0.042 (7) |
C24A | 0.24 (2) | 0.28 (3) | 0.27 (3) | 0.060 (19) | 0.087 (19) | −0.04 (2) |
O7B | 0.110 (10) | 0.089 (8) | 0.083 (6) | 0.033 (7) | −0.008 (6) | 0.005 (5) |
C23B | 0.117 (11) | 0.125 (9) | 0.077 (7) | 0.011 (8) | 0.012 (8) | 0.023 (7) |
C24B | 0.095 (9) | 0.152 (10) | 0.078 (7) | −0.012 (7) | 0.019 (6) | 0.025 (7) |
Cl1A | 0.063 (4) | 0.076 (4) | 0.098 (4) | 0.001 (3) | 0.013 (3) | 0.010 (3) |
O1A | 0.094 (6) | 0.210 (14) | 0.115 (6) | 0.029 (7) | −0.011 (5) | 0.005 (7) |
O2A | 0.207 (11) | 0.145 (8) | 0.143 (9) | −0.036 (7) | 0.141 (9) | −0.048 (7) |
O3A | 0.251 (16) | 0.091 (6) | 0.173 (9) | −0.088 (8) | 0.130 (11) | −0.010 (5) |
O4A | 0.151 (8) | 0.092 (5) | 0.197 (9) | 0.050 (5) | 0.022 (7) | −0.010 (5) |
Cl1B | 0.059 (4) | 0.041 (3) | 0.070 (3) | −0.003 (2) | 0.046 (3) | 0.012 (2) |
O1B | 0.181 (16) | 0.145 (10) | 0.284 (19) | −0.045 (9) | 0.096 (14) | −0.141 (12) |
O2B | 0.049 (5) | 0.208 (15) | 0.226 (13) | −0.025 (6) | 0.067 (6) | −0.016 (10) |
O3B | 0.141 (9) | 0.094 (7) | 0.267 (15) | 0.053 (6) | 0.027 (9) | 0.019 (8) |
O4B | 0.138 (9) | 0.34 (2) | 0.208 (14) | −0.019 (12) | 0.037 (9) | 0.226 (15) |
O1W | 0.0585 (13) | 0.0403 (11) | 0.0440 (11) | 0.0070 (9) | 0.0157 (9) | −0.0002 (9) |
Geometric parameters (Å, º) top
Zn1—O1 | 2.0615 (15) | C9—C12 | 1.445 (4) |
Zn1—O1i | 2.0562 (16) | C13—C14 | 1.398 (4) |
Zn1—O1W | 2.016 (2) | C14—C15 | 1.357 (5) |
Zn1—N1 | 2.064 (2) | C15—C16 | 1.407 (4) |
Zn1—N2 | 2.052 (2) | C16—C17 | 1.414 (4) |
O1—C10 | 1.325 (3) | C16—C21 | 1.417 (4) |
N1—C3 | 1.475 (4) | C17—C18 | 1.362 (4) |
N1—C4 | 1.278 (3) | C18—C19 | 1.408 (4) |
N2—C1 | 1.479 (4) | C19—C20 | 1.376 (4) |
N2—C12i | 1.277 (3) | C20—C21 | 1.432 (4) |
C12—N2i | 1.277 (3) | C20—C22 | 1.499 (4) |
N3—C13 | 1.325 (4) | O7A—C23A | 1.405 (16) |
N3—C21 | 1.367 (3) | C23A—C24A | 1.48 (2) |
O1—Zn1i | 2.0562 (16) | O7B—C23B | 1.325 (17) |
C1—C2 | 1.473 (5) | C23B—C24B | 1.464 (16) |
C2—C3 | 1.463 (4) | Cl1A—O2A | 1.340 (8) |
C4—C5 | 1.445 (4) | Cl1A—O3A | 1.351 (8) |
C5—C6 | 1.403 (3) | Cl1A—O1A | 1.424 (10) |
C5—C10 | 1.419 (3) | Cl1A—O4A | 1.434 (9) |
C6—C7 | 1.378 (4) | Cl1B—O1B | 1.329 (12) |
C7—C8 | 1.382 (4) | Cl1B—O4B | 1.355 (11) |
C7—C11 | 1.518 (4) | Cl1B—O2B | 1.360 (9) |
C8—C9 | 1.402 (3) | Cl1B—O3B | 1.377 (9) |
C8—H8 | 0.9300 | O1W—H1W | 0.84 (3) |
C9—C10 | 1.417 (3) | O1W—H2W | 0.88 (3) |
| | | |
O1W—Zn1—O1i | 101.37 (8) | C15—C16—C17 | 122.2 (3) |
O1W—Zn1—N1 | 103.66 (9) | C15—C16—C21 | 118.3 (3) |
O1W—Zn1—N2 | 102.96 (9) | C17—C16—C21 | 119.5 (3) |
N1—Zn1—N2 | 95.80 (9) | C18—C17—C16 | 120.1 (3) |
N2—Zn1—O1 | 155.84 (8) | C18—C17—H17 | 120.0 |
N2—Zn1—O1i | 89.12 (8) | C16—C17—H17 | 120.0 |
O1W—Zn1—O1 | 99.03 (8) | C17—C18—C19 | 120.7 (3) |
O1i—Zn1—O1 | 76.77 (6) | C17—C18—H18 | 119.6 |
O1—Zn1—N1 | 88.55 (7) | C19—C18—H18 | 119.6 |
O1i—Zn1—N1 | 152.66 (8) | C20—C19—C18 | 121.5 (3) |
C10—O1—Zn1i | 128.62 (14) | C20—C19—H19 | 119.3 |
C10—O1—Zn1 | 128.14 (14) | C18—C19—H19 | 119.3 |
Zn1i—O1—Zn1 | 103.23 (6) | C19—C20—C21 | 118.5 (3) |
C4—N1—C3 | 115.3 (2) | C19—C20—C22 | 120.1 (3) |
C4—N1—Zn1 | 123.26 (19) | C21—C20—C22 | 121.3 (2) |
C3—N1—Zn1 | 120.84 (18) | N3—C21—C16 | 121.5 (3) |
C12i—N2—C1 | 115.7 (2) | N3—C21—C20 | 118.9 (2) |
C12i—N2—Zn1 | 123.94 (18) | C16—C21—C20 | 119.6 (2) |
C1—N2—Zn1 | 120.31 (18) | C20—C22—H22A | 109.5 |
C2—C1—N2 | 115.8 (3) | C20—C22—H22B | 109.5 |
C2—C1—H1A | 108.3 | H22A—C22—H22B | 109.5 |
N2—C1—H1A | 108.3 | C20—C22—H22C | 109.5 |
C2—C1—H1B | 108.3 | H22A—C22—H22C | 109.5 |
N2—C1—H1B | 108.3 | H22B—C22—H22C | 109.5 |
H1A—C1—H1B | 107.4 | O7A—C23A—C24A | 108.9 (17) |
C3—C2—C1 | 118.0 (3) | O7A—C23A—H23A | 109.9 |
C3—C2—H2A | 107.8 | C24A—C23A—H23A | 109.9 |
C1—C2—H2A | 107.8 | O7A—C23A—H23B | 109.9 |
C3—C2—H2B | 107.8 | C24A—C23A—H23B | 109.9 |
C1—C2—H2B | 107.8 | H23A—C23A—H23B | 108.3 |
H2A—C2—H2B | 107.1 | C23A—C24A—H24A | 110.0 |
C2—C3—N1 | 114.2 (3) | C23A—C24A—H24B | 108.8 |
C2—C3—H3A | 108.7 | H24A—C24A—H24B | 109.5 |
N1—C3—H3A | 108.7 | C23A—C24A—H24C | 109.7 |
C2—C3—H3B | 108.7 | H24A—C24A—H24C | 109.5 |
N1—C3—H3B | 108.7 | H24B—C24A—H24C | 109.5 |
H3A—C3—H3B | 107.6 | C23B—O7B—H7B | 109.5 |
N1—C4—C5 | 128.8 (2) | O7B—C23B—C24B | 121.4 (15) |
N1—C4—H4 | 115.6 | O7B—C23B—H24A | 124.6 |
C5—C4—H4 | 115.6 | C24B—C23B—H24A | 114.0 |
C6—C5—C10 | 119.7 (2) | O7B—C23B—H24C | 125.8 |
C6—C5—C4 | 115.3 (2) | C24B—C23B—H24C | 52.2 |
C10—C5—C4 | 124.9 (2) | H24A—C23B—H24C | 87.5 |
C7—C6—C5 | 123.3 (3) | O7B—C23B—H23C | 107.0 |
C7—C6—H6 | 118.3 | C24B—C23B—H23C | 107.0 |
C5—C6—H6 | 118.3 | H24A—C23B—H23C | 52.8 |
C6—C7—C8 | 116.3 (2) | H24C—C23B—H23C | 55.6 |
C6—C7—C11 | 121.5 (3) | O7B—C23B—H23D | 107.0 |
C8—C7—C11 | 122.2 (3) | C24B—C23B—H23D | 107.0 |
C7—C8—C9 | 123.7 (3) | H24A—C23B—H23D | 54.3 |
C7—C8—H8 | 118.2 | H24C—C23B—H23D | 126.9 |
C9—C8—H8 | 118.2 | H23C—C23B—H23D | 106.7 |
C8—C9—C10 | 119.4 (3) | C23B—C24B—H24B | 74.5 |
C8—C9—C12 | 115.5 (2) | C23B—C24B—H24C | 58.8 |
C10—C9—C12 | 125.0 (2) | H24B—C24B—H24C | 76.0 |
O1—C10—C9 | 121.2 (2) | C23B—C24B—H24D | 109.5 |
O1—C10—C5 | 121.3 (2) | C23B—C24B—H24E | 109.5 |
C9—C10—C5 | 117.6 (2) | H24D—C24B—H24E | 109.5 |
C7—C11—H11A | 109.5 | C23B—C24B—H24F | 109.5 |
C7—C11—H11B | 109.5 | H24D—C24B—H24F | 109.5 |
H11A—C11—H11B | 109.5 | H24E—C24B—H24F | 109.5 |
C7—C11—H11C | 109.5 | O2A—Cl1A—O3A | 113.4 (8) |
H11A—C11—H11C | 109.5 | O2A—Cl1A—O1A | 113.7 (8) |
H11B—C11—H11C | 109.5 | O3A—Cl1A—O1A | 105.6 (8) |
N2i—C12—C9 | 129.0 (2) | O2A—Cl1A—O4A | 113.6 (8) |
N2i—C12—H12 | 115.5 | O3A—Cl1A—O4A | 105.3 (8) |
C9—C12—H12 | 115.5 | O1A—Cl1A—O4A | 104.4 (7) |
C13—N3—C21 | 117.8 (2) | O1B—Cl1B—O4B | 103.9 (11) |
N3—C13—C14 | 123.9 (3) | O1B—Cl1B—O2B | 120.0 (9) |
N3—C13—H13 | 118.0 | O4B—Cl1B—O2B | 109.1 (9) |
C14—C13—H13 | 118.0 | O1B—Cl1B—O3B | 107.2 (9) |
C15—C14—C13 | 119.1 (3) | O4B—Cl1B—O3B | 107.8 (10) |
C15—C14—H14 | 120.5 | O2B—Cl1B—O3B | 108.3 (7) |
C13—C14—H14 | 120.5 | Zn1—O1W—H1W | 119 (3) |
C14—C15—C16 | 119.3 (3) | Zn1—O1W—H2W | 120 (3) |
C14—C15—H15 | 120.3 | H1W—O1W—H2W | 113 (4) |
C16—C15—H15 | 120.3 | | |
| | | |
O1W—Zn1—O1—C10 | 80.2 (2) | C11—C7—C8—C9 | −178.1 (3) |
N2—Zn1—O1—C10 | −124.4 (2) | C7—C8—C9—C10 | 1.2 (4) |
O1i—Zn1—O1—C10 | 179.9 (2) | C7—C8—C9—C12 | 178.6 (3) |
N1—Zn1—O1—C10 | −23.4 (2) | Zn1i—O1—C10—C9 | 15.4 (3) |
O1W—Zn1—O1—Zn1i | −99.65 (9) | Zn1—O1—C10—C9 | −164.44 (16) |
N2—Zn1—O1—Zn1i | 55.8 (2) | Zn1i—O1—C10—C5 | −165.11 (16) |
O1i—Zn1—O1—Zn1i | 0.0 | Zn1—O1—C10—C5 | 15.1 (3) |
N1—Zn1—O1—Zn1i | 156.75 (9) | C8—C9—C10—O1 | 177.4 (2) |
O1W—Zn1—N1—C4 | −78.6 (2) | C12—C9—C10—O1 | 0.3 (4) |
N2—Zn1—N1—C4 | 176.5 (2) | C8—C9—C10—C5 | −2.1 (3) |
O1i—Zn1—N1—C4 | 77.2 (3) | C12—C9—C10—C5 | −179.2 (2) |
O1—Zn1—N1—C4 | 20.4 (2) | C6—C5—C10—O1 | −178.2 (2) |
O1W—Zn1—N1—C3 | 91.9 (2) | C4—C5—C10—O1 | 4.4 (4) |
N2—Zn1—N1—C3 | −13.0 (2) | C6—C5—C10—C9 | 1.3 (3) |
O1i—Zn1—N1—C3 | −112.4 (2) | C4—C5—C10—C9 | −176.1 (2) |
O1—Zn1—N1—C3 | −169.2 (2) | C8—C9—C12—N2i | 177.7 (3) |
O1W—Zn1—N2—C12i | 87.2 (2) | C10—C9—C12—N2i | −5.0 (4) |
O1i—Zn1—N2—C12i | −14.3 (2) | C21—N3—C13—C14 | 0.2 (4) |
O1—Zn1—N2—C12i | −67.8 (3) | N3—C13—C14—C15 | 1.2 (5) |
N1—Zn1—N2—C12i | −167.3 (2) | C13—C14—C15—C16 | −1.5 (5) |
O1W—Zn1—N2—C1 | −90.1 (3) | C14—C15—C16—C17 | −179.7 (3) |
O1i—Zn1—N2—C1 | 168.5 (2) | C14—C15—C16—C21 | 0.5 (4) |
O1—Zn1—N2—C1 | 114.9 (3) | C15—C16—C17—C18 | 179.1 (3) |
N1—Zn1—N2—C1 | 15.4 (3) | C21—C16—C17—C18 | −1.1 (4) |
C12i—N2—C1—C2 | −160.8 (3) | C16—C17—C18—C19 | −0.1 (5) |
Zn1—N2—C1—C2 | 16.7 (4) | C17—C18—C19—C20 | 1.1 (5) |
N2—C1—C2—C3 | −66.0 (5) | C18—C19—C20—C21 | −1.0 (4) |
C1—C2—C3—N1 | 68.4 (5) | C18—C19—C20—C22 | 179.1 (3) |
C4—N1—C3—C2 | 149.5 (3) | C13—N3—C21—C16 | −1.3 (4) |
Zn1—N1—C3—C2 | −21.7 (4) | C13—N3—C21—C20 | 178.6 (2) |
C3—N1—C4—C5 | 177.9 (3) | C15—C16—C21—N3 | 1.0 (4) |
Zn1—N1—C4—C5 | −11.2 (4) | C17—C16—C21—N3 | −178.8 (3) |
N1—C4—C5—C6 | 176.3 (3) | C15—C16—C21—C20 | −178.9 (2) |
N1—C4—C5—C10 | −6.2 (4) | C17—C16—C21—C20 | 1.3 (4) |
C10—C5—C6—C7 | 0.5 (4) | C19—C20—C21—N3 | 179.9 (2) |
C4—C5—C6—C7 | 178.1 (3) | C22—C20—C21—N3 | −0.2 (4) |
C5—C6—C7—C8 | −1.4 (4) | C19—C20—C21—C16 | −0.2 (4) |
C5—C6—C7—C11 | 177.2 (3) | C22—C20—C21—C16 | 179.7 (2) |
C6—C7—C8—C9 | 0.6 (4) | | |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···N3ii | 0.84 (3) | 1.90 (3) | 2.731 (3) | 172 (4) |
O1W—H2W···O7Ai | 0.88 (3) | 1.78 (4) | 2.648 (17) | 171 (4) |
C3—H3A···O3Aiii | 0.97 | 2.54 | 3.508 (12) | 177 |
C3—H3B···O1Aiv | 0.97 | 2.48 | 3.348 (11) | 149 |
C15—H15···O3Aiii | 0.93 | 2.52 | 3.377 (10) | 154 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x+1, −y+1/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Zn(C24H26N4O2)(OH2)2](ClO4)2·2C10H9N·2C2H6O |
Mr | 1146.70 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 12.8258 (2), 15.1039 (1), 14.7734 (2) |
β (°) | 114.228 (1) |
V (Å3) | 2609.82 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.09 |
Crystal size (mm) | 0.44 × 0.34 × 0.28 |
|
Data collection |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.645, 0.750 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18483, 6445, 4334 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.667 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.115, 0.94 |
No. of reflections | 6445 |
No. of parameters | 412 |
No. of restraints | 124 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.52 |
Selected geometric parameters (Å, º) topZn1—O1 | 2.0615 (15) | N1—C4 | 1.278 (3) |
Zn1—O1i | 2.0562 (16) | N2—C1 | 1.479 (4) |
Zn1—O1W | 2.016 (2) | N2—C12i | 1.277 (3) |
Zn1—N1 | 2.064 (2) | C12—N2i | 1.277 (3) |
Zn1—N2 | 2.052 (2) | N3—C13 | 1.325 (4) |
O1—C10 | 1.325 (3) | N3—C21 | 1.367 (3) |
N1—C3 | 1.475 (4) | | |
| | | |
O1W—Zn1—O1i | 101.37 (8) | O1W—Zn1—O1 | 99.03 (8) |
O1W—Zn1—N1 | 103.66 (9) | O1i—Zn1—O1 | 76.77 (6) |
O1W—Zn1—N2 | 102.96 (9) | O1—Zn1—N1 | 88.55 (7) |
N1—Zn1—N2 | 95.80 (9) | O1i—Zn1—N1 | 152.66 (8) |
N2—Zn1—O1 | 155.84 (8) | C10—O1—Zn1i | 128.62 (14) |
N2—Zn1—O1i | 89.12 (8) | | |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···N3ii | 0.84 (3) | 1.90 (3) | 2.731 (3) | 172 (4) |
O1W—H2W···O7Ai | 0.88 (3) | 1.78 (4) | 2.648 (17) | 171 (4) |
C3—H3A···O3Aiii | 0.97 | 2.54 | 3.508 (12) | 177 |
C3—H3B···O1Aiv | 0.97 | 2.48 | 3.348 (11) | 149 |
C15—H15···O3Aiii | 0.93 | 2.52 | 3.377 (10) | 154 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x+1, −y+1/2, z+1/2. |
Since the synthesis of crown ethers and the discovery of their complexing properties towards alkali metal cations in 1967 (Pedersen, 1967), host–guest chemistry has developed rapidly and now includes ancillary fields of study such as supermolecular chemistry, biomimetic chemistry and materials science (Lehn, 1995). The self-assembly process driven by noncovalent interactions such as hydrogen bonding, π-π stacking, electrostatic and van der Waals forces, hydrophobic and hydrophilic interactions is now universally recognized to be crucial in the proliferation of all biological organisms (Stang & Olenyuk, 1997). A variety of receptor molecules have been devised, and various anion binding strategies have been exploited which yield a plethora of novel structures of possible biological and chemical significance (Hawthorne & Zheng, 1997; Fyfe & Stoddart, 1997). Here we choose a dinuclear zinc(II) complex of a Robson macrocycle as a host and 8-methylquinoline as a guest to form a donor-acceptor compound, (I), in order to study the interactions between the two kinds of molecules. \sch
The asymmetric unit contains half a molecule with the Zn atom lying near the inversion centre. The coordination geometry around each metal may be considered to be a distorted square pyramid whose base plane is composed of O1, O1i, symmetry operator (i) 1 − x, −y, 1 − z, N1 and N2. These crystal data about the macrocyclic zinc complex are similar to that of a reported dinuclear zinc(II) complex of a Robson macrocycle diperchlorate (Adams et al., 1995). The water molecule (O1W) occupies the fifth coordinating site of Zn [Zn1—O1W = 2.015 (2) Å]. The crystal structure of the title complex contains two parallel planes: the macrocyclic plane and 8-methylquinoline plane. In the macrocyclic plane, there are two five-coordinate zinc(II) metals derived from four donors (two phenolic O atoms and two imine N atoms) on the macrocyclic framework with the water molecule out of the plane.
The six-membered ring, Zn1, N1, O1, C4, C5 and C10, adopts an envelope conformation. The 8-methylquinoline ring is planar and is essentially coplanar to the macrocyclic plane making an dihedral angle of 2.19 (5)°. The two Zn atoms are 3.228 (1) Å apart. The water molecule is involved in intermolecular O—H···N and O—H···O hydrogen bonds with the methylquinoline ring and solvent ethanol (Table 2). The perchlorate ion, highly disordered, connects the methylquinoline ring to the anion to form a two-dimensional network. An intra- and intermolecular C—H···π interaction is observed between the methylquinoline ring and centroid of the planar four-membered ring (Zn1, O1, Zn1i, O1i).