A donor–acceptor compound composed of a di­nuclear zinc(II) complex of a Robson macro­cycle with 8-methyl­quino­line

A donor–acceptor compound, di­aqua-1κO,2κO-[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-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.

S1. Comment

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).

S2. Experimental

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.

S3. Refinement

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.

Computing details

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).

Figures

Fig. 1. The structure of the D—A compound cation with the atom-numbering scheme. Displacement ellipsoids are shown at the 30% probability level.

[Zn²⁺]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-N³, N⁷,O²⁵,O²⁶:N¹⁵,N¹⁹,O²⁵,O²⁶}]²⁻ 2[ClO₄]⁻, bis(8-methylquinoline), 2(C₂H₅OH)

Crystal data

[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) Å^3	Slab, light yellow
Z = 2	0.44 × 0.34 × 0.28 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0548P)^2] where P = (Fo^2 + 2Fc^2)/3
6445 reflections	(Δ/σ)max < 0.001
412 parameters	Δρmax = 0.57 e Å^−3
124 restraints	Δρmin = −0.52 e Å^−3

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Zn1—O1	2.0615 (15)	C9—C12	1.445 (4)
Zn1—O1^i	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—C12^i	1.277 (3)	C20—C21	1.432 (4)
C12—N2^i	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—Zn1^i	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—O1^i	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—O1^i	89.12 (8)	C16—C17—H17	120.0
O1W—Zn1—O1	99.03 (8)	C17—C18—C19	120.7 (3)
O1^i—Zn1—O1	76.77 (6)	C17—C18—H18	119.6
O1—Zn1—N1	88.55 (7)	C19—C18—H18	119.6
O1^i—Zn1—N1	152.66 (8)	C20—C19—C18	121.5 (3)
C10—O1—Zn1^i	128.62 (14)	C20—C19—H19	119.3
C10—O1—Zn1	128.14 (14)	C18—C19—H19	119.3
Zn1^i—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)
C12^i—N2—C1	115.7 (2)	N3—C21—C20	118.9 (2)
C12^i—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)
N2^i—C12—C9	129.0 (2)	O2A—Cl1A—O4A	113.6 (8)
N2^i—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)
O1^i—Zn1—O1—C10	179.9 (2)	C7—C8—C9—C12	178.6 (3)
N1—Zn1—O1—C10	−23.4 (2)	Zn1^i—O1—C10—C9	15.4 (3)
O1W—Zn1—O1—Zn1^i	−99.65 (9)	Zn1—O1—C10—C9	−164.44 (16)
N2—Zn1—O1—Zn1^i	55.8 (2)	Zn1^i—O1—C10—C5	−165.11 (16)
O1^i—Zn1—O1—Zn1^i	0.0	Zn1—O1—C10—C5	15.1 (3)
N1—Zn1—O1—Zn1^i	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)
O1^i—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)
O1^i—Zn1—N1—C3	−112.4 (2)	C4—C5—C10—C9	−176.1 (2)
O1—Zn1—N1—C3	−169.2 (2)	C8—C9—C12—N2^i	177.7 (3)
O1W—Zn1—N2—C12^i	87.2 (2)	C10—C9—C12—N2^i	−5.0 (4)
O1^i—Zn1—N2—C12^i	−14.3 (2)	C21—N3—C13—C14	0.2 (4)
O1—Zn1—N2—C12^i	−67.8 (3)	N3—C13—C14—C15	1.2 (5)
N1—Zn1—N2—C12^i	−167.3 (2)	C13—C14—C15—C16	−1.5 (5)
O1W—Zn1—N2—C1	−90.1 (3)	C14—C15—C16—C17	−179.7 (3)
O1^i—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)
C12^i—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)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···N3^ii	0.84 (3)	1.90 (3)	2.731 (3)	172 (4)
O1W—H2W···O7A^i	0.88 (3)	1.78 (4)	2.648 (17)	171 (4)
C3—H3A···O3A^iii	0.97	2.54	3.508 (12)	177
C3—H3B···O1A^iv	0.97	2.48	3.348 (11)	149
C15—H15···O3A^iii	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.