metal-organic compounds
Dichloridobis(2-{1-[2-(1H-indol-3-yl)ethyliminio]ethyl}phenolate-κO)zinc(II)–2-{1-[2-(1H-indol-3-yl)ethyliminio]ethyl}phenolate (1/2)
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
In the mononuclear complex molecule of the title compond, [ZnCl2(C18H18N2O)2]·2C18H18N2O, the Zn atom, which lies on a twofold rotation axis, is coordinated by phenolate O atoms in a tetrahedral coordination geometry. The coordinated Schiff base uses its indole NH donor site to form a hydrogen bond to the negatively charged phenolate O atom of the uncoordinated zwitterionic Schiff base. There is an intramolecular N—H⋯O hydrogen bond in the coordinated and uncoordinated The indole NH site of the uncoordinated Schiff base does not engage in a hydrogen-bond interaction. The CH2—CH2 group in the uncoordinated Schiff base is disordered equally over two positions.
Related literature
For a related neutral Schiff base, see: Rodriguez et al. (1987). For a related but zwitterionic Schiff base, see: Ali et al. (2007). For zinc derivatives of such deprotonated see: Ali et al. (2008); Chen et al. (2007).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).
Supporting information
10.1107/S1600536808011161/sg2225sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011161/sg2225Isup2.hkl
The Schiff base was synthesized by condensing 2-(1H-indol-3-yl)ethylamine with 2-hydroxyacetophenone. The compound (0.50 g, 1.79 mmol) and zinc chloride (1.21 g, 0.89 mol) were heated in ethanol (10 ml) for an hour along with a small quantity (0.02 g) of sodium hydride. The compound was recrystallized from ethanol.
The ethylene linkage in the free Schiff base is disordered over two position; these were arbitrarily assigned 0.5 site occupancies; the temperature factors of the primed atoms were set to those of the unprimed atoms. The N3–C27 and N3–C27' were restrained to within 0.01 Å of each other; the four C–C bonds were restrained to 1.50±0.01 Å.
Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.98 Å) and were included in the
in the riding model approximation, with U(H) set to 1.2 to 1.5U(C). The amino H-atoms were located in a difference Fourier map, and were refined with an N–H distance restraint of 0.86±0.01 Å; their temperature factors were freely refined.Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).[ZnCl2(C18H18N2O)2]·2C18H18N2O | F(000) = 1312 |
Mr = 1249.65 | Dx = 1.325 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 8552 reflections |
a = 25.8073 (4) Å | θ = 2.4–23.8° |
b = 9.1754 (1) Å | µ = 0.54 mm−1 |
c = 14.3265 (2) Å | T = 295 K |
β = 112.566 (1)° | Irregular block, yellow |
V = 3132.67 (7) Å3 | 0.10 × 0.06 × 0.05 mm |
Z = 2 |
Bruker SMART APEXII diffractometer | 7190 independent reflections |
Radiation source: fine-focus sealed tube | 6008 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −33→32 |
Tmin = 0.866, Tmax = 0.974 | k = −11→11 |
36333 measured reflections | l = −18→18 |
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)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0481P)2 + 0.6205P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
7190 reflections | Δρmax = 0.36 e Å−3 |
413 parameters | Δρmin = −0.30 e Å−3 |
10 restraints | Absolute structure: Flack (1983), 3669 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.000 (8) |
[ZnCl2(C18H18N2O)2]·2C18H18N2O | V = 3132.67 (7) Å3 |
Mr = 1249.65 | Z = 2 |
Monoclinic, C2 | Mo Kα radiation |
a = 25.8073 (4) Å | µ = 0.54 mm−1 |
b = 9.1754 (1) Å | T = 295 K |
c = 14.3265 (2) Å | 0.10 × 0.06 × 0.05 mm |
β = 112.566 (1)° |
Bruker SMART APEXII diffractometer | 7190 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 6008 reflections with I > 2σ(I) |
Tmin = 0.866, Tmax = 0.974 | Rint = 0.039 |
36333 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.091 | Δρmax = 0.36 e Å−3 |
S = 1.00 | Δρmin = −0.30 e Å−3 |
7190 reflections | Absolute structure: Flack (1983), 3669 Friedel pairs |
413 parameters | Absolute structure parameter: 0.000 (8) |
10 restraints |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.5000 | 0.50003 (3) | 0.0000 | 0.03995 (10) | |
Cl1 | 0.42528 (3) | 0.63088 (6) | −0.09253 (5) | 0.05459 (17) | |
O1 | 0.48035 (7) | 0.36059 (16) | 0.08739 (12) | 0.0449 (4) | |
O2 | 0.42302 (10) | 0.7684 (3) | 0.31515 (19) | 0.0846 (7) | |
N1 | 0.39707 (9) | 0.1849 (2) | 0.02989 (16) | 0.0455 (5) | |
H1N | 0.4136 (10) | 0.2679 (17) | 0.034 (2) | 0.055* | |
N2 | 0.34836 (9) | 0.5756 (2) | 0.16913 (19) | 0.0602 (6) | |
H2N | 0.3665 (11) | 0.646 (2) | 0.2068 (19) | 0.072* | |
N3 | 0.52785 (12) | 0.7793 (3) | 0.3958 (2) | 0.0850 (9) | |
H3N | 0.4975 (11) | 0.731 (4) | 0.388 (3) | 0.102* | |
N4 | 0.67920 (12) | 0.2805 (3) | 0.5240 (2) | 0.0729 (7) | |
H4N | 0.6967 (13) | 0.221 (3) | 0.5714 (19) | 0.087* | |
C1 | 0.51286 (10) | 0.2466 (2) | 0.12619 (16) | 0.0387 (5) | |
C2 | 0.57066 (11) | 0.2636 (3) | 0.18025 (18) | 0.0492 (6) | |
H2 | 0.5858 | 0.3570 | 0.1916 | 0.059* | |
C3 | 0.60560 (11) | 0.1461 (3) | 0.2170 (2) | 0.0541 (6) | |
H3 | 0.6438 | 0.1611 | 0.2525 | 0.065* | |
C4 | 0.58430 (10) | 0.0056 (4) | 0.20174 (17) | 0.0552 (6) | |
H4 | 0.6081 | −0.0740 | 0.2250 | 0.066* | |
C5 | 0.52764 (11) | −0.0147 (3) | 0.15191 (17) | 0.0499 (6) | |
H5 | 0.5134 | −0.1090 | 0.1424 | 0.060* | |
C6 | 0.49053 (10) | 0.1031 (2) | 0.11484 (16) | 0.0386 (5) | |
C7 | 0.43083 (10) | 0.0765 (3) | 0.06467 (18) | 0.0424 (6) | |
C8 | 0.40747 (13) | −0.0742 (3) | 0.0536 (2) | 0.0578 (7) | |
H8A | 0.3680 | −0.0695 | 0.0396 | 0.087* | |
H8B | 0.4262 | −0.1274 | 0.1151 | 0.087* | |
H8C | 0.4132 | −0.1226 | −0.0011 | 0.087* | |
C9 | 0.33622 (11) | 0.1796 (3) | −0.0260 (2) | 0.0558 (7) | |
H9A | 0.3186 | 0.1324 | 0.0148 | 0.067* | |
H9B | 0.3277 | 0.1231 | −0.0874 | 0.067* | |
C10 | 0.31327 (11) | 0.3332 (3) | −0.0526 (2) | 0.0588 (7) | |
H10A | 0.3338 | 0.3826 | −0.0877 | 0.071* | |
H10B | 0.2742 | 0.3278 | −0.0984 | 0.071* | |
C11 | 0.31755 (10) | 0.4211 (3) | 0.03838 (19) | 0.0480 (6) | |
C12 | 0.35561 (10) | 0.5266 (3) | 0.0851 (2) | 0.0553 (7) | |
H12 | 0.3828 | 0.5606 | 0.0629 | 0.066* | |
C13 | 0.28431 (9) | 0.4020 (2) | 0.09671 (18) | 0.0446 (5) | |
C14 | 0.23988 (10) | 0.3105 (3) | 0.0911 (2) | 0.0571 (7) | |
H14 | 0.2253 | 0.2449 | 0.0379 | 0.069* | |
C15 | 0.21779 (12) | 0.3177 (4) | 0.1644 (3) | 0.0705 (9) | |
H15 | 0.1883 | 0.2565 | 0.1604 | 0.085* | |
C16 | 0.23887 (14) | 0.4148 (4) | 0.2439 (3) | 0.0765 (10) | |
H16 | 0.2231 | 0.4177 | 0.2924 | 0.092* | |
C17 | 0.28259 (11) | 0.5073 (4) | 0.2531 (2) | 0.0671 (7) | |
H17 | 0.2967 | 0.5719 | 0.3070 | 0.081* | |
C18 | 0.30495 (9) | 0.5006 (3) | 0.17897 (18) | 0.0499 (5) | |
C19 | 0.42330 (12) | 0.9098 (3) | 0.31308 (19) | 0.0585 (7) | |
C20 | 0.37283 (12) | 0.9902 (5) | 0.2698 (2) | 0.0741 (9) | |
H20 | 0.3388 | 0.9407 | 0.2442 | 0.089* | |
C21 | 0.37302 (18) | 1.1387 (5) | 0.2649 (2) | 0.0867 (12) | |
H21 | 0.3391 | 1.1882 | 0.2358 | 0.104* | |
C22 | 0.4216 (2) | 1.2159 (5) | 0.3016 (3) | 0.0863 (12) | |
H22 | 0.4210 | 1.3170 | 0.2974 | 0.104* | |
C23 | 0.47149 (15) | 1.1436 (3) | 0.3450 (2) | 0.0668 (8) | |
H23 | 0.5047 | 1.1968 | 0.3701 | 0.080* | |
C24 | 0.47389 (10) | 0.9900 (4) | 0.35243 (16) | 0.0504 (6) | |
C25 | 0.52729 (12) | 0.9180 (4) | 0.3974 (2) | 0.0599 (7) | |
C26 | 0.58061 (12) | 1.0014 (6) | 0.4431 (2) | 0.0827 (9) | |
H26A | 0.6118 | 0.9377 | 0.4533 | 0.124* | |
H26B | 0.5834 | 1.0412 | 0.5069 | 0.124* | |
H26C | 0.5810 | 1.0793 | 0.3986 | 0.124* | |
C27 | 0.5727 (6) | 0.672 (2) | 0.4535 (10) | 0.089 (4) | 0.50 |
H27A | 0.6085 | 0.7217 | 0.4843 | 0.107* | 0.50 |
H27B | 0.5636 | 0.6270 | 0.5065 | 0.107* | 0.50 |
C28 | 0.5756 (7) | 0.560 (2) | 0.3803 (13) | 0.070 (3) | 0.50 |
H28A | 0.5819 | 0.6077 | 0.3251 | 0.084* | 0.50 |
H28B | 0.5401 | 0.5087 | 0.3524 | 0.084* | 0.50 |
C27' | 0.5826 (6) | 0.7006 (19) | 0.4208 (10) | 0.089 (4) | 0.50 |
H27C | 0.6029 | 0.7411 | 0.3822 | 0.107* | 0.50 |
H27D | 0.6057 | 0.7110 | 0.4921 | 0.107* | 0.50 |
C28' | 0.5698 (6) | 0.544 (2) | 0.3950 (14) | 0.070 (3) | 0.50 |
H28C | 0.5510 | 0.5343 | 0.3223 | 0.084* | 0.50 |
H28D | 0.5446 | 0.5093 | 0.4257 | 0.084* | 0.50 |
C29 | 0.62217 (12) | 0.4534 (3) | 0.4312 (2) | 0.0615 (7) | |
C30 | 0.63045 (14) | 0.3544 (4) | 0.5058 (2) | 0.0734 (9) | |
H30 | 0.6065 | 0.3392 | 0.5394 | 0.088* | |
C31 | 0.66965 (11) | 0.4438 (3) | 0.40353 (18) | 0.0511 (6) | |
C32 | 0.68572 (11) | 0.5145 (3) | 0.33287 (18) | 0.0600 (7) | |
H32 | 0.6629 | 0.5859 | 0.2911 | 0.072* | |
C33 | 0.73566 (13) | 0.4775 (4) | 0.3255 (2) | 0.0691 (8) | |
H33 | 0.7470 | 0.5266 | 0.2798 | 0.083* | |
C34 | 0.76939 (14) | 0.3683 (4) | 0.3852 (3) | 0.0743 (9) | |
H34 | 0.8028 | 0.3447 | 0.3782 | 0.089* | |
C35 | 0.75462 (13) | 0.2946 (3) | 0.4541 (2) | 0.0708 (9) | |
H35 | 0.7772 | 0.2211 | 0.4938 | 0.085* | |
C36 | 0.70474 (11) | 0.3333 (3) | 0.4627 (2) | 0.0547 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.04012 (19) | 0.02675 (16) | 0.0496 (2) | 0.000 | 0.01350 (16) | 0.000 |
Cl1 | 0.0518 (4) | 0.0378 (3) | 0.0632 (4) | 0.0119 (3) | 0.0098 (3) | 0.0003 (3) |
O1 | 0.0435 (9) | 0.0329 (7) | 0.0567 (10) | −0.0008 (7) | 0.0175 (8) | 0.0039 (7) |
O2 | 0.0729 (15) | 0.0688 (15) | 0.0839 (16) | −0.0066 (12) | −0.0012 (13) | −0.0150 (12) |
N1 | 0.0477 (12) | 0.0389 (10) | 0.0508 (12) | −0.0063 (9) | 0.0199 (10) | −0.0071 (9) |
N2 | 0.0487 (12) | 0.0463 (12) | 0.0773 (16) | −0.0069 (10) | 0.0150 (12) | −0.0127 (11) |
N3 | 0.0659 (17) | 0.0699 (18) | 0.0893 (19) | 0.0228 (14) | −0.0037 (15) | −0.0205 (15) |
N4 | 0.0775 (18) | 0.0613 (15) | 0.0666 (17) | 0.0077 (14) | 0.0130 (14) | 0.0143 (13) |
C1 | 0.0482 (13) | 0.0333 (11) | 0.0359 (11) | −0.0014 (9) | 0.0176 (10) | 0.0008 (9) |
C2 | 0.0507 (14) | 0.0436 (12) | 0.0486 (13) | −0.0034 (11) | 0.0140 (11) | 0.0014 (11) |
C3 | 0.0478 (14) | 0.0616 (16) | 0.0481 (14) | 0.0046 (12) | 0.0132 (12) | 0.0063 (12) |
C4 | 0.0586 (14) | 0.0498 (13) | 0.0556 (13) | 0.0180 (16) | 0.0203 (11) | 0.0127 (15) |
C5 | 0.0703 (16) | 0.0344 (12) | 0.0517 (13) | 0.0056 (13) | 0.0310 (12) | 0.0038 (11) |
C6 | 0.0501 (13) | 0.0326 (10) | 0.0379 (11) | −0.0004 (10) | 0.0223 (10) | −0.0021 (9) |
C7 | 0.0588 (15) | 0.0348 (12) | 0.0398 (12) | −0.0054 (11) | 0.0257 (11) | −0.0087 (10) |
C8 | 0.0727 (19) | 0.0385 (13) | 0.0617 (16) | −0.0087 (13) | 0.0255 (15) | −0.0106 (12) |
C9 | 0.0436 (14) | 0.0582 (16) | 0.0607 (16) | −0.0075 (12) | 0.0145 (12) | −0.0154 (13) |
C10 | 0.0482 (15) | 0.0677 (17) | 0.0509 (15) | 0.0049 (13) | 0.0084 (12) | −0.0019 (13) |
C11 | 0.0375 (12) | 0.0447 (13) | 0.0550 (14) | 0.0059 (10) | 0.0101 (11) | 0.0052 (11) |
C12 | 0.0438 (13) | 0.0489 (17) | 0.0743 (17) | −0.0022 (11) | 0.0238 (12) | 0.0045 (13) |
C13 | 0.0348 (12) | 0.0366 (11) | 0.0531 (14) | 0.0066 (9) | 0.0066 (10) | 0.0057 (10) |
C14 | 0.0355 (13) | 0.0498 (14) | 0.0729 (18) | 0.0018 (11) | 0.0060 (13) | 0.0089 (13) |
C15 | 0.0380 (14) | 0.075 (2) | 0.095 (2) | 0.0076 (14) | 0.0222 (15) | 0.0353 (19) |
C16 | 0.0598 (19) | 0.102 (3) | 0.076 (2) | 0.0266 (19) | 0.0349 (17) | 0.031 (2) |
C17 | 0.0615 (16) | 0.0736 (18) | 0.0622 (15) | 0.0206 (19) | 0.0192 (13) | 0.0061 (18) |
C18 | 0.0412 (11) | 0.0427 (10) | 0.0610 (13) | 0.0091 (13) | 0.0144 (10) | 0.0040 (14) |
C19 | 0.0562 (16) | 0.0687 (18) | 0.0448 (14) | 0.0091 (14) | 0.0130 (13) | −0.0077 (13) |
C20 | 0.0525 (15) | 0.112 (3) | 0.0531 (15) | 0.023 (2) | 0.0152 (12) | 0.005 (2) |
C21 | 0.091 (3) | 0.113 (3) | 0.0546 (19) | 0.056 (3) | 0.0264 (19) | 0.016 (2) |
C22 | 0.125 (4) | 0.067 (2) | 0.071 (2) | 0.039 (2) | 0.043 (3) | 0.0180 (18) |
C23 | 0.085 (2) | 0.0625 (18) | 0.0589 (17) | 0.0018 (16) | 0.0335 (16) | −0.0014 (14) |
C24 | 0.0519 (13) | 0.0588 (14) | 0.0414 (11) | 0.0137 (15) | 0.0191 (10) | −0.0012 (13) |
C25 | 0.0546 (16) | 0.0717 (18) | 0.0478 (14) | 0.0089 (14) | 0.0134 (12) | −0.0180 (13) |
C26 | 0.0597 (17) | 0.117 (3) | 0.0654 (17) | −0.004 (2) | 0.0172 (14) | −0.019 (2) |
C27 | 0.092 (5) | 0.085 (7) | 0.060 (8) | 0.042 (6) | −0.005 (4) | −0.012 (5) |
C28 | 0.062 (3) | 0.076 (4) | 0.067 (5) | 0.018 (3) | 0.019 (2) | −0.008 (3) |
C27' | 0.092 (5) | 0.085 (7) | 0.060 (8) | 0.042 (6) | −0.005 (4) | −0.012 (5) |
C28' | 0.062 (3) | 0.076 (4) | 0.067 (5) | 0.018 (3) | 0.019 (2) | −0.008 (3) |
C29 | 0.0613 (17) | 0.0576 (16) | 0.0543 (15) | 0.0111 (13) | 0.0097 (13) | −0.0100 (12) |
C30 | 0.070 (2) | 0.075 (2) | 0.072 (2) | −0.0018 (17) | 0.0247 (17) | −0.0056 (17) |
C31 | 0.0500 (14) | 0.0413 (11) | 0.0441 (13) | 0.0061 (11) | −0.0018 (11) | −0.0081 (10) |
C32 | 0.0681 (16) | 0.0497 (14) | 0.0455 (12) | 0.0093 (15) | 0.0032 (11) | −0.0018 (13) |
C33 | 0.0711 (18) | 0.070 (2) | 0.0570 (15) | −0.0006 (16) | 0.0145 (14) | −0.0038 (15) |
C34 | 0.0569 (18) | 0.079 (2) | 0.076 (2) | 0.0046 (16) | 0.0129 (16) | −0.0055 (18) |
C35 | 0.0528 (17) | 0.0591 (17) | 0.079 (2) | 0.0162 (14) | 0.0013 (15) | 0.0040 (15) |
C36 | 0.0544 (16) | 0.0406 (14) | 0.0524 (15) | 0.0036 (12) | 0.0019 (12) | 0.0017 (11) |
Zn1—O1i | 1.987 (2) | C15—C16 | 1.383 (5) |
Zn1—O1 | 1.987 (2) | C15—H15 | 0.9300 |
Zn1—Cl1i | 2.2260 (6) | C16—C17 | 1.377 (5) |
Zn1—Cl1 | 2.2260 (6) | C16—H16 | 0.9300 |
O1—C1 | 1.323 (3) | C17—C18 | 1.391 (3) |
O2—C19 | 1.298 (4) | C17—H17 | 0.9300 |
N1—C7 | 1.290 (3) | C19—C24 | 1.414 (4) |
N1—C9 | 1.464 (3) | C19—C20 | 1.416 (4) |
N1—H1N | 0.86 (1) | C20—C21 | 1.365 (6) |
N2—C12 | 1.363 (4) | C20—H20 | 0.9300 |
N2—C18 | 1.367 (3) | C21—C22 | 1.358 (6) |
N2—H2N | 0.86 (1) | C21—H21 | 0.9300 |
N3—C25 | 1.273 (4) | C22—C23 | 1.367 (5) |
N3—C27 | 1.500 (7) | C22—H22 | 0.9300 |
N3—C27' | 1.502 (7) | C23—C24 | 1.413 (4) |
N3—H3N | 0.87 (1) | C23—H23 | 0.9300 |
N4—C30 | 1.364 (4) | C24—C25 | 1.438 (4) |
N4—C36 | 1.373 (4) | C25—C26 | 1.489 (5) |
N4—H4N | 0.86 (1) | C26—H26A | 0.9600 |
C1—C2 | 1.401 (3) | C26—H26B | 0.9600 |
C1—C6 | 1.421 (3) | C26—H26C | 0.9600 |
C2—C3 | 1.374 (4) | C27—C28 | 1.491 (9) |
C2—H2 | 0.9300 | C27—H27A | 0.9700 |
C3—C4 | 1.386 (4) | C27—H27B | 0.9700 |
C3—H3 | 0.9300 | C28—C29 | 1.506 (8) |
C4—C5 | 1.372 (3) | C28—H28A | 0.9700 |
C4—H4 | 0.9300 | C28—H28B | 0.9700 |
C5—C6 | 1.406 (3) | C27'—C28' | 1.485 (9) |
C5—H5 | 0.9300 | C27'—H27C | 0.9700 |
C6—C7 | 1.449 (3) | C27'—H27D | 0.9700 |
C7—C8 | 1.492 (3) | C28'—C29 | 1.502 (8) |
C8—H8A | 0.9600 | C28'—H28C | 0.9700 |
C8—H8B | 0.9600 | C28'—H28D | 0.9700 |
C8—H8C | 0.9600 | C29—C30 | 1.355 (4) |
C9—C10 | 1.520 (4) | C29—C31 | 1.428 (4) |
C9—H9A | 0.9700 | C30—H30 | 0.9300 |
C9—H9B | 0.9700 | C31—C32 | 1.392 (4) |
C10—C11 | 1.500 (4) | C31—C36 | 1.406 (3) |
C10—H10A | 0.9700 | C32—C33 | 1.375 (4) |
C10—H10B | 0.9700 | C32—H32 | 0.9300 |
C11—C12 | 1.358 (3) | C33—C34 | 1.386 (4) |
C11—C13 | 1.420 (4) | C33—H33 | 0.9300 |
C12—H12 | 0.9300 | C34—C35 | 1.365 (5) |
C13—C14 | 1.398 (3) | C34—H34 | 0.9300 |
C13—C18 | 1.418 (4) | C35—C36 | 1.386 (4) |
C14—C15 | 1.374 (4) | C35—H35 | 0.9300 |
C14—H14 | 0.9300 | ||
O1—Zn1—O1i | 99.84 (9) | N2—C18—C17 | 130.8 (3) |
O1—Zn1—Cl1 | 110.51 (5) | N2—C18—C13 | 107.3 (2) |
O1i—Zn1—Cl1i | 110.51 (5) | C17—C18—C13 | 122.0 (3) |
O1—Zn1—Cl1i | 110.14 (5) | O2—C19—C24 | 121.6 (3) |
O1i—Zn1—Cl1 | 110.14 (5) | O2—C19—C20 | 121.2 (3) |
Cl1—Zn1—Cl1i | 114.72 (3) | C24—C19—C20 | 117.2 (3) |
C1—O1—Zn1 | 120.01 (14) | C21—C20—C19 | 121.5 (4) |
C7—N1—C9 | 127.5 (2) | C21—C20—H20 | 119.3 |
C7—N1—H1N | 114 (2) | C19—C20—H20 | 119.3 |
C9—N1—H1N | 118 (2) | C20—C21—C22 | 121.4 (3) |
C12—N2—C18 | 108.7 (2) | C20—C21—H21 | 119.3 |
C12—N2—H2N | 125 (2) | C22—C21—H21 | 119.3 |
C18—N2—H2N | 126 (2) | C21—C22—C23 | 119.5 (4) |
C25—N3—C27 | 130.9 (9) | C21—C22—H22 | 120.3 |
C25—N3—C27' | 119.5 (9) | C23—C22—H22 | 120.3 |
C27—N3—C27' | 25.6 (9) | C22—C23—C24 | 121.6 (3) |
C25—N3—H3N | 120 (3) | C22—C23—H23 | 119.2 |
C27—N3—H3N | 102 (3) | C24—C23—H23 | 119.2 |
C27'—N3—H3N | 121 (3) | C19—C24—C23 | 118.8 (3) |
C30—N4—C36 | 109.6 (3) | C19—C24—C25 | 121.3 (3) |
C30—N4—H4N | 130 (2) | C23—C24—C25 | 119.9 (3) |
C36—N4—H4N | 120 (2) | N3—C25—C24 | 117.8 (3) |
O1—C1—C2 | 120.9 (2) | N3—C25—C26 | 120.5 (3) |
O1—C1—C6 | 121.4 (2) | C24—C25—C26 | 121.7 (3) |
C2—C1—C6 | 117.8 (2) | C25—C26—H26A | 109.5 |
C3—C2—C1 | 121.8 (2) | C25—C26—H26B | 109.5 |
C3—C2—H2 | 119.1 | H26A—C26—H26B | 109.5 |
C1—C2—H2 | 119.1 | C25—C26—H26C | 109.5 |
C2—C3—C4 | 120.5 (2) | H26A—C26—H26C | 109.5 |
C2—C3—H3 | 119.8 | H26B—C26—H26C | 109.5 |
C4—C3—H3 | 119.8 | C28—C27—N3 | 107.4 (8) |
C5—C4—C3 | 119.2 (3) | C28—C27—H27A | 110.2 |
C5—C4—H4 | 120.4 | N3—C27—H27A | 110.2 |
C3—C4—H4 | 120.4 | C28—C27—H27B | 110.2 |
C4—C5—C6 | 121.9 (3) | N3—C27—H27B | 110.2 |
C4—C5—H5 | 119.1 | H27A—C27—H27B | 108.5 |
C6—C5—H5 | 119.1 | C27—C28—C29 | 110.8 (10) |
C5—C6—C1 | 118.8 (2) | C27—C28—H28A | 109.5 |
C5—C6—C7 | 119.9 (2) | C29—C28—H28A | 109.5 |
C1—C6—C7 | 121.3 (2) | C27—C28—H28B | 109.5 |
N1—C7—C6 | 119.6 (2) | C29—C28—H28B | 109.5 |
N1—C7—C8 | 119.2 (2) | H28A—C28—H28B | 108.1 |
C6—C7—C8 | 121.2 (2) | C28'—C27'—N3 | 107.8 (10) |
C7—C8—H8A | 109.5 | C28'—C27'—H27C | 110.2 |
C7—C8—H8B | 109.5 | N3—C27'—H27C | 110.2 |
H8A—C8—H8B | 109.5 | C28'—C27'—H27D | 110.2 |
C7—C8—H8C | 109.5 | N3—C27'—H27D | 110.2 |
H8A—C8—H8C | 109.5 | H27C—C27'—H27D | 108.5 |
H8B—C8—H8C | 109.5 | C27'—C28'—C29 | 111.4 (11) |
N1—C9—C10 | 109.8 (2) | C27'—C28'—H28C | 109.3 |
N1—C9—H9A | 109.7 | C29—C28'—H28C | 109.3 |
C10—C9—H9A | 109.7 | C27'—C28'—H28D | 109.3 |
N1—C9—H9B | 109.7 | C29—C28'—H28D | 109.3 |
C10—C9—H9B | 109.7 | H28C—C28'—H28D | 108.0 |
H9A—C9—H9B | 108.2 | C30—C29—C31 | 106.5 (3) |
C11—C10—C9 | 112.9 (2) | C30—C29—C28 | 132.3 (8) |
C11—C10—H10A | 109.0 | C31—C29—C28 | 121.1 (8) |
C9—C10—H10A | 109.0 | C30—C29—C28' | 119.6 (8) |
C11—C10—H10B | 109.0 | C31—C29—C28' | 133.9 (8) |
C9—C10—H10B | 109.0 | C28—C29—C28' | 12.8 (15) |
H10A—C10—H10B | 107.8 | C29—C30—N4 | 109.8 (3) |
C12—C11—C13 | 106.5 (2) | C29—C30—H30 | 125.1 |
C12—C11—C10 | 127.6 (3) | N4—C30—H30 | 125.1 |
C13—C11—C10 | 125.8 (2) | C32—C31—C36 | 118.1 (3) |
C11—C12—N2 | 110.6 (2) | C32—C31—C29 | 134.4 (2) |
C11—C12—H12 | 124.7 | C36—C31—C29 | 107.5 (3) |
N2—C12—H12 | 124.7 | C33—C32—C31 | 119.4 (3) |
C14—C13—C18 | 118.0 (2) | C33—C32—H32 | 120.3 |
C14—C13—C11 | 135.1 (2) | C31—C32—H32 | 120.3 |
C18—C13—C11 | 106.9 (2) | C32—C33—C34 | 121.1 (3) |
C15—C14—C13 | 119.9 (3) | C32—C33—H33 | 119.5 |
C15—C14—H14 | 120.0 | C34—C33—H33 | 119.5 |
C13—C14—H14 | 120.0 | C35—C34—C33 | 121.3 (3) |
C14—C15—C16 | 120.8 (3) | C35—C34—H34 | 119.3 |
C14—C15—H15 | 119.6 | C33—C34—H34 | 119.3 |
C16—C15—H15 | 119.6 | C34—C35—C36 | 117.6 (3) |
C17—C16—C15 | 121.6 (3) | C34—C35—H35 | 121.2 |
C17—C16—H16 | 119.2 | C36—C35—H35 | 121.2 |
C15—C16—H16 | 119.2 | N4—C36—C35 | 131.0 (3) |
C16—C17—C18 | 117.7 (3) | N4—C36—C31 | 106.5 (2) |
C16—C17—H17 | 121.2 | C35—C36—C31 | 122.5 (3) |
C18—C17—H17 | 121.2 | ||
O1i—Zn1—O1—C1 | 44.94 (13) | C21—C22—C23—C24 | 0.1 (5) |
Cl1i—Zn1—O1—C1 | −71.31 (16) | O2—C19—C24—C23 | 178.0 (3) |
Cl1—Zn1—O1—C1 | 160.91 (14) | C20—C19—C24—C23 | −1.1 (4) |
Zn1—O1—C1—C2 | 52.2 (3) | O2—C19—C24—C25 | −0.6 (4) |
Zn1—O1—C1—C6 | −127.91 (18) | C20—C19—C24—C25 | −179.7 (2) |
O1—C1—C2—C3 | −176.8 (2) | C22—C23—C24—C19 | 0.6 (4) |
C6—C1—C2—C3 | 3.3 (4) | C22—C23—C24—C25 | 179.2 (3) |
C1—C2—C3—C4 | −0.2 (4) | C27—N3—C25—C24 | −165.0 (6) |
C2—C3—C4—C5 | −1.9 (4) | C27'—N3—C25—C24 | 166.8 (6) |
C3—C4—C5—C6 | 0.7 (4) | C27—N3—C25—C26 | 15.9 (8) |
C4—C5—C6—C1 | 2.4 (3) | C27'—N3—C25—C26 | −12.3 (7) |
C4—C5—C6—C7 | −178.6 (2) | C19—C24—C25—N3 | 3.7 (4) |
O1—C1—C6—C5 | 175.8 (2) | C23—C24—C25—N3 | −174.9 (3) |
C2—C1—C6—C5 | −4.3 (3) | C19—C24—C25—C26 | −177.3 (2) |
O1—C1—C6—C7 | −3.1 (3) | C23—C24—C25—C26 | 4.2 (4) |
C2—C1—C6—C7 | 176.7 (2) | C25—N3—C27—C28 | −135.0 (9) |
C9—N1—C7—C6 | 177.4 (2) | C27'—N3—C27—C28 | −63 (3) |
C9—N1—C7—C8 | −3.4 (4) | N3—C27—C28—C29 | 176.6 (14) |
C5—C6—C7—N1 | −179.3 (2) | C25—N3—C27'—C28' | −169.8 (9) |
C1—C6—C7—N1 | −0.3 (3) | C27—N3—C27'—C28' | 66 (4) |
C5—C6—C7—C8 | 1.5 (4) | N3—C27'—C28'—C29 | −171.8 (10) |
C1—C6—C7—C8 | −179.5 (2) | C27—C28—C29—C30 | 64.7 (16) |
C7—N1—C9—C10 | −179.8 (2) | C27—C28—C29—C31 | −114.6 (11) |
N1—C9—C10—C11 | −67.5 (3) | C27—C28—C29—C28' | 69 (7) |
C9—C10—C11—C12 | 102.8 (3) | C27'—C28'—C29—C30 | 113.1 (11) |
C9—C10—C11—C13 | −72.5 (3) | C27'—C28'—C29—C31 | −67.4 (16) |
C13—C11—C12—N2 | −0.2 (3) | C27'—C28'—C29—C28 | −64 (7) |
C10—C11—C12—N2 | −176.2 (2) | C31—C29—C30—N4 | −2.0 (3) |
C18—N2—C12—C11 | 0.5 (3) | C28—C29—C30—N4 | 178.6 (12) |
C12—C11—C13—C14 | −178.4 (3) | C28'—C29—C30—N4 | 177.6 (10) |
C10—C11—C13—C14 | −2.3 (4) | C36—N4—C30—C29 | 1.6 (4) |
C12—C11—C13—C18 | −0.1 (3) | C30—C29—C31—C32 | 179.5 (3) |
C10—C11—C13—C18 | 176.0 (2) | C28—C29—C31—C32 | −1.0 (11) |
C18—C13—C14—C15 | −0.3 (3) | C28'—C29—C31—C32 | 0.0 (13) |
C11—C13—C14—C15 | 177.8 (3) | C30—C29—C31—C36 | 1.6 (3) |
C13—C14—C15—C16 | 0.1 (4) | C28—C29—C31—C36 | −178.9 (10) |
C14—C15—C16—C17 | −0.2 (4) | C28'—C29—C31—C36 | −177.9 (12) |
C15—C16—C17—C18 | 0.3 (4) | C36—C31—C32—C33 | −2.0 (4) |
C12—N2—C18—C17 | 177.8 (3) | C29—C31—C32—C33 | −179.8 (3) |
C12—N2—C18—C13 | −0.5 (3) | C31—C32—C33—C34 | 1.9 (4) |
C16—C17—C18—N2 | −178.6 (3) | C32—C33—C34—C35 | −0.7 (5) |
C16—C17—C18—C13 | −0.5 (4) | C33—C34—C35—C36 | −0.3 (5) |
C14—C13—C18—N2 | 179.0 (2) | C30—N4—C36—C35 | 179.4 (3) |
C11—C13—C18—N2 | 0.4 (3) | C30—N4—C36—C31 | −0.6 (3) |
C14—C13—C18—C17 | 0.5 (4) | C34—C35—C36—N4 | −179.9 (3) |
C11—C13—C18—C17 | −178.1 (2) | C34—C35—C36—C31 | 0.1 (4) |
O2—C19—C20—C21 | −178.1 (3) | C32—C31—C36—N4 | −179.0 (2) |
C24—C19—C20—C21 | 0.9 (4) | C29—C31—C36—N4 | −0.6 (3) |
C19—C20—C21—C22 | −0.2 (5) | C32—C31—C36—C35 | 1.1 (4) |
C20—C21—C22—C23 | −0.3 (5) | C29—C31—C36—C35 | 179.4 (3) |
Symmetry code: (i) −x+1, y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1n···O1 | 0.86 (1) | 1.81 (2) | 2.557 (3) | 144 (3) |
N2—H2n···O2 | 0.86 (1) | 2.01 (1) | 2.851 (3) | 164 (3) |
N3—H3n···O2 | 0.87 (1) | 1.83 (3) | 2.503 (4) | 133 (4) |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C18H18N2O)2]·2C18H18N2O |
Mr | 1249.65 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 295 |
a, b, c (Å) | 25.8073 (4), 9.1754 (1), 14.3265 (2) |
β (°) | 112.566 (1) |
V (Å3) | 3132.67 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.54 |
Crystal size (mm) | 0.10 × 0.06 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.866, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36333, 7190, 6008 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.091, 1.00 |
No. of reflections | 7190 |
No. of parameters | 413 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.30 |
Absolute structure | Flack (1983), 3669 Friedel pairs |
Absolute structure parameter | 0.000 (8) |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).
Zn1—O1 | 1.987 (2) | Zn1—Cl1 | 2.2260 (6) |
O1—Zn1—O1i | 99.84 (9) | O1—Zn1—Cl1i | 110.14 (5) |
O1—Zn1—Cl1 | 110.51 (5) | Cl1—Zn1—Cl1i | 114.72 (3) |
Symmetry code: (i) −x+1, y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1n···O1 | 0.86 (1) | 1.81 (2) | 2.557 (3) | 144 (3) |
N2—H2n···O2 | 0.86 (1) | 2.01 (1) | 2.851 (3) | 164 (3) |
N3—H3n···O2 | 0.87 (1) | 1.83 (3) | 2.503 (4) | 133 (4) |
Acknowledgements
We thank the Science Fund (12–02-03–2031) for supporting this study, and the University of Malaya for the purchase of the diffractometer.
References
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The reaction of zinc acetate with 2-[2-(1H-indol-3-yl)ethyliminomethy]phenol, a neutral Schiff base (Rodriguez et al., 1987) furnishes the expected zinc complex with the deprotonated ligand in which the deprotonated ligand N,O-chelates to the metal center (Chen et al., 2007). Similarly, the reaction of zinc acetate with the 4-methyl substituted Schiff base (the methyl substituent is para to the negatively-charged phenoxy group) affords the corresponding tetrahdral zinc compound; the structure of the Schiff base itself is not known.
On the other hand, the 4-methyl substituted Schiff base of 2-[2-(1H-indol-3-yl)ethylimino-1-ethy]phenol exists in the zwitterionic form; the presence of methyl group on the imino –C=N– double-bond probably induces charge separation (Ali et al., 2007). 2-[2-(1H-Indol-3-yl)ethylimino-1-ethy]phenol in the title cocrystal is a zwitterionic species; it coordinates to zinc chloride, so that the coordination geometry at the metal center is an Cl2O2Zn tetraheron. The compound crystallizes as a cocrystal (Scheme I, Fig. 1). Both the coordinated and free zwitterionis have an intramolecular N···O hydrogen bond. The coordinated Schiff base uses its N–Hindolyl donor site to form a hydrogen bond to the negatively-charged phenolato-O atom of the free Schiff base. The N–Hindolyl site of the free Schiff base does not engage in a hydrogen-bonding interaction.