Bis(adamantan-1-aminium) tetra­chloridozincate(II) 18-crown-6 monohydrate clathrate

The structure of the title compound [systematic name: bis­(adamantan-1-aminium) tetra­chloridozincate(II)–1,4,7,10,13,16-hexa­oxacyclo­octa­decane–water (1/1/1)], (C₁₀H₁₈N)₂[ZnCl₄]·C₁₂H₂₄O₆·H₂O, consists of supra­molecular rotator–stator assemblies and ribbons of hydrogen bonds parallel to [010]. The assemblies are composed of one protonated adamantan-1-aminium cation and one crown ether mol­ecule (1,4,7,10,13,16-hexa­oxacyclo­octa­decane) to give an overall [(C₁₀H₁₈N)(18-crown-6)]⁺ cation. The –NH₃⁺ group of the cation nests in the crown and links to the crown-ether O atoms through N—H...O hydrogen bonds. The 18-crown-6 ring adopts a pseudo-C_3v conformation. The second adamantan-1-aminium forms part of ribbons of adamantan-1-aminium–water–tetra­chloridozincate units which are inter­connected by O—H...Cl, N—H...O and N—H...Cl hydrogen bonds via three different continuous rings with R₅⁴(12), R₄³(10) and R₃³(8) motifs.

S1. Comment

Crown ethers have attracted much attention due to their ability to form noncovalent and hydrogen-bonded complexes with ammonium cations, in both the solid state and solution (Fender et al., 2002; Rieger et al., 2005). Both the size of the crown ether and the nature of the ammonium cation (–NH₄⁺, RNH₃⁺ etc.) can influence the stoichiometry and stability of these host–guest adducts. Through the intermolecular interactions between the host molecules and guest species, it is easy to realise high selectivity in ionic or molecular recognition (Sato et al., 2007; Akutagawa et al., 2008). 18-Crown-6 and its derivatives exhibit the highest affinity with organic ammonium cations RNH₃⁺, with a 1:1 stoichiometry in most studies (Doxsee et al., 2000; Johnson et al., 2000; Buschmann et al., 2001). We now present the structure of the title compound, (I), containing an adduct of 18-crown-6 and an ammonium cation.

Compound (I) crystallizes in the space group Pbcn. The asymmetric unit contains two adamantan-1-aminium cations, one 18-crown-6 ether molecule, one [ZnCl₄]^2- anion, and one water molecule (Fig. 1). Only one of the two crystallographically independent adamantan-1-aminium cations joins the rotator–stator assembly with 18-crown-6, via a hydrogen-bonding interaction (Fig. 2). The –NH₃⁺ group of the cation interacts with the six crown ether O atoms through three short approximately linear N—H···O hydrogen bonds (Table 1) and three longer acute interactions [2.957 (4), 2.938 (4) and 2.958 (4) Å from N1 to atoms O1, O3 and O5, respectively].

The conformation of the crown-ether ring and the hydrogen-bond geometry in this assembly closely resemble those in related adducts of 18-crown-6 and primary alkylammonium salts (Henschel et al., 1997). The macrocycle adopts a conformation with approximate D_3d symmetry, with all C—C torsion angles being gauche and alternating in sign, and all C—O and O—C torsion angles being trans. The ether O atoms are nearly coplanar. O1, O3 and O5 are located below the mean O-atom plane [0.1798 (18), 0.1499 (18) and 0.1672 (19) Å, respectively] and O2, O4 and O6 are located above the plane [0.1635 (17), 0.1533 (18) and 0.1801 (18) Å, respectively]. The C—N bonds of the adamantan-1-aminium cation are almost perpendicular to the mean plane of the crown-ether O atoms. Atom N1 of the adamantan-1-aminium cation is 0.983 (3) Å out of the plane.

It is interesting that the second adamantan-1-aminium cation is not trapped by the 18-crown-6 ether. The reason may lie in the [ZnCl₄]^2- anions, which are relatively small {in contrast to the [Ni(dmit)₂]^- (dmit is 2-thioxo-1,3-dithiole-4,5-dithiolate; Akutagawa et al., 2002) and [PMo₁₂O₄₀]^4- (Akutagawa et al., 2006) anions} for embedding large and structurally diverse supramolecular cations in the crystal lattice.

The [ZnCl₄]^2- anions are present as counterions to the supramolecular [(C₁₀H₁₈N)(18-crown-6)]⁺ and isolated adamantan-1-aminium cations, and coordinate to both. The Zn^II centre adopts a tetrahedral coordination with four Cl^- ions, which has been observed in many crystal structures (Jin et al., 2005; Valkonen et al., 2006; Albrecht et al., 2003; Wickleder, 2001). Generally, the Zn—Cl bond lengths and Cl—Zn—Cl angles in a [ZnCl₄]^2- anion are not equal to one another (Wickleder, 2001; Albrecht et al. 2003) but vary with the environment around the Cl atoms. In (I), as Cl1, Cl3 and Cl4 are involved in stronger and more numerous N—H···Cl hydrogen bonds than Cl2, the Zn1—Cl2 bonds are obviously shorter than all the other Zn—Cl bonds. The [ZnCl₄]^2- anion shows typical Zn—Cl bond lengths [2.2354 (9)–2.3214 (10) Å] and the Cl—Zn—Cl angles range from 104.53 (4) to 115.96 (4)°. Owing to the obvious differences of the Zn—Cl distances and the Cl—Zn—Cl angles, the coordination geometry of the Zn atom could be regarded as a distorted tetrahedron.

It has been reported that Cl atoms coordinating to metal atom centres are good hydrogen-bond acceptors (Aullon et al., 1998). In this structure, only one of the four Cl atoms (Cl2) of [ZnCl₄]^2- fails to engage in hydrogen-bonding interactions (Table 1). The O—H···Cl, N—H···O and N—H···Cl hydrogen bonds between discrete tetrahedral tetrachlorozincate(II) anions, isolated adamantylammonium cations and solvent water molecules result in a noteworthy one-dimensional ribbon-like structure along the b axis (Fig. 3). This ribbon motif (Fig. 3) is the dominant hydrogen-bonding motif (Hulme et al., 2006) in the structure of (I). This structure propagates via two types of rings: one of level four [R₄³(10)], and one of level three [R₃³(8)]. The R₄³(10) ring includes four hydrogen bonds, viz. N2—H2D···Cl4, N2—H2E···Cl1, O1W—H1WA···Cl4 and O1W—H1WB···Cl3. The second-order motif involves three hydrogen bonds, viz. N2—H2D···Cl4, N2—H2F···O1W and O1W—H1WB···Cl3. The discrete adamantan-1-aminium–crown ether units are located on both sides of the ribbon, forming possible C—H···Cl hydrogen bonds which would link all the units into a two-dimensional network.

This study is also part of our systematic investigation of dielectric, ferroelectric and phase-transition materials (Ye et al., 2009; Zhang et al., 2009), including organic compounds, metal–organic coordination compounds and organic–inorganic hybrids. The measurement of the dielectric constant of (I) as a function of temperature showed that the permittivity is basically temperature-independent (dielectric constant of 6–7) below room temperature. Such a dielectric response suggests that this compound might not undergo a distinct structural phase transition in the lower temperature range. Similarly, in the range from room temperature to near its melting point (m.p. > 470 K), the dielectric constant increases smoothly as a function of temperature, and no dielectric anomaly was observed (dielectric constant 7–17).

Related literature

For related literature, see: Akutagawa et al. (2002, 2006, 2008); Albrecht et al. (2003); Aullon et al. (1998); Buschmann et al. (2001); Doxsee et al. (2000); Fender et al. (2002); Henschel et al. (1997); Hulme & Tocher (2006); Jin et al. (2005); Johnson et al. (2000); Rieger & Muclring (2005); Sato et al. (2007); Valkonen et al. (2006); Wickleder (2001); Ye et al. (2009); Zhang et al. (2009).

S2. Experimental

Adamantylammonium chloride (2 mmol, 0.375 g) and 18-crown-6 (2 mmol, 0.528 g) were dissolved in methanol (40 ml). Zinc(II) dichloride (2 mmol, 0.272 g) was added to the solution, followed by concentrated hydrochloric acid (5 ml). Single crystals of (I) suitable for X-ray diffraction analysis were obtained via slow evaporation of the methanol solution at room temperature after two weeks. The crystals were colourless, of prismatic habitus and of an average size of about 0.2 × 0.3 × 0.4 mm.

Dielectric studies (capacitance and dielectric-loss measurements) were performed on powder samples which had been pressed into tablets, on the surfaces of which conducting carbon glue was deposited. An automatic impedance TongHui2828 Analyzer was used. In the measured temperature range (80–430 K), the title structure showed no dielectric anomaly.

S3. Refinement

All C-bound H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å, and allowed to ride on the parent C atoms, with U_iso(H) = 1.2U_eq(C).

All the N- and O-bound H atoms were discernible in the difference electron-density map. The positions of the N-bound H atoms were refined using a riding model, with N—H = 0.89 Å and U_iso(H) = 1.5U_eq(N). The coordinates of the water H atoms were refined with the restraint O—H = 0.84 (2) Å, and with U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The interactions between an adamantylammonium cation and a crown ether molecule in (I). Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen-bonding interactions have been omitted.
	Fig. 3. A ribbon motif of the hydrogen-bonded adamantylammonium–water–tetrachloridozincate units. The graph-set notation for the three types of hydrogen-bonding patterns is R5^4(12), R4^3(10) and R3^3(8). Only selected H atoms are shown. Dashed lines indicate hydrogen-bonding interactions.

Bis(adamantan-1-aminium) tetrachloridozincate(II)–1,4,7,10,13,16-hexaoxacyclooctadecane–water (1/1/1)

Crystal data

(C10H18N)2[ZnCl4]·C12H24O6·H2O	F(000) = 3376
Mr = 794.03	Dx = 1.363 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 16230 reflections
a = 26.9702 (12) Å	θ = 2.5–27.5°
b = 11.4912 (7) Å	µ = 0.96 mm^−1
c = 24.9646 (18) Å	T = 293 K
V = 7737.0 (8) Å^3	Prism, colourless
Z = 8	0.40 × 0.30 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer	7595 independent reflections
Radiation source: fine-focus sealed tube	6098 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.094
Detector resolution: 28.5714 pixels mm^-1	θmax = 26.0°, θmin = 2.5°
CCD profile fitting scans	h = −33→33
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
Tmin = 0.716, Tmax = 0.826	l = −30→30
72972 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0495P)^2 + 10.437P] where P = (Fo^2 + 2Fc^2)/3
7595 reflections	(Δ/σ)max = 0.011
439 parameters	Δρmax = 0.87 e Å^−3
9 restraints	Δρmin = −0.46 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
O1	0.01397 (9)	0.9551 (2)	0.32499 (10)	0.0215 (6)
O2	−0.04104 (9)	0.74527 (19)	0.33211 (9)	0.0170 (5)
O3	0.01826 (9)	0.5450 (2)	0.32173 (10)	0.0211 (6)
O4	0.12103 (9)	0.5388 (2)	0.34175 (10)	0.0234 (6)
O5	0.16665 (9)	0.7566 (2)	0.33494 (11)	0.0235 (6)
O6	0.11567 (9)	0.9724 (2)	0.34748 (10)	0.0226 (6)
C1	0.08890 (14)	1.0634 (3)	0.32143 (16)	0.0259 (9)
H1A	0.0902	1.0523	0.2829	0.031*
H1B	0.1040	1.1378	0.3297	0.031*
C2	0.03598 (14)	1.0632 (3)	0.33970 (15)	0.0220 (8)
H2A	0.0345	1.0732	0.3782	0.026*
H2B	0.0181	1.1270	0.3231	0.026*
C3	−0.03863 (13)	0.9530 (3)	0.33264 (15)	0.0207 (8)
H3A	−0.0534	1.0225	0.3174	0.025*
H3B	−0.0463	0.9510	0.3706	0.025*
C4	−0.05914 (13)	0.8473 (3)	0.30571 (14)	0.0204 (8)
H4A	−0.0951	0.8488	0.3071	0.024*
H4B	−0.0492	0.8464	0.2684	0.024*
C5	−0.05830 (13)	0.6416 (3)	0.30644 (15)	0.0201 (8)
H5A	−0.0502	0.6440	0.2686	0.024*
H5B	−0.0940	0.6359	0.3099	0.024*
C6	−0.03415 (13)	0.5381 (3)	0.33204 (15)	0.0213 (8)
H6A	−0.0403	0.5383	0.3703	0.026*
H6B	−0.0476	0.4669	0.3171	0.026*
C7	0.04329 (14)	0.4389 (3)	0.33304 (15)	0.0229 (8)
H7A	0.0268	0.3749	0.3151	0.027*
H7B	0.0427	0.4240	0.3713	0.027*
C8	0.09578 (14)	0.4481 (3)	0.31395 (15)	0.0234 (8)
H8A	0.1127	0.3747	0.3199	0.028*
H8B	0.0961	0.4640	0.2758	0.028*
C9	0.17039 (14)	0.5525 (3)	0.32144 (17)	0.0277 (9)
H9A	0.1694	0.5644	0.2830	0.033*
H9B	0.1896	0.4829	0.3286	0.033*
C10	0.19394 (14)	0.6552 (3)	0.34806 (18)	0.0300 (9)
H10A	0.1942	0.6441	0.3866	0.036*
H10B	0.2280	0.6633	0.3360	0.036*
C11	0.19128 (14)	0.8623 (3)	0.34754 (18)	0.0300 (9)
H11A	0.2248	0.8603	0.3336	0.036*
H11B	0.1931	0.8715	0.3861	0.036*
C12	0.16392 (15)	0.9623 (3)	0.32375 (18)	0.0324 (10)
H12A	0.1824	1.0335	0.3297	0.039*
H12B	0.1606	0.9509	0.2854	0.039*
N1	0.06286 (11)	0.7499 (3)	0.37307 (12)	0.0159 (6)
C45	0.01869 (13)	0.8261 (3)	0.45260 (14)	0.0206 (8)
H45A	−0.0125	0.7985	0.4381	0.025*
H45B	0.0240	0.9051	0.4401	0.025*
C46	0.06108 (12)	0.7478 (3)	0.43363 (13)	0.0144 (7)
C47	0.05219 (15)	0.6227 (3)	0.45224 (14)	0.0236 (8)
H47A	0.0786	0.5727	0.4393	0.028*
H47B	0.0210	0.5943	0.4380	0.028*
C48	0.11047 (13)	0.7926 (3)	0.45525 (14)	0.0208 (8)
H48A	0.1162	0.8713	0.4428	0.025*
H48B	0.1373	0.7437	0.4425	0.025*
C49	0.09984 (16)	0.6659 (3)	0.53586 (16)	0.0304 (9)
H49A	0.1267	0.6164	0.5237	0.036*
H49B	0.0991	0.6636	0.5747	0.036*
C50	0.10870 (14)	0.7904 (3)	0.51700 (15)	0.0242 (8)
H50A	0.1403	0.8188	0.5314	0.029*
C51	0.05087 (16)	0.6210 (3)	0.51374 (15)	0.0286 (9)
H51A	0.0454	0.5412	0.5262	0.034*
C52	0.06640 (14)	0.8686 (3)	0.53647 (15)	0.0252 (8)
H52A	0.0719	0.9478	0.5245	0.030*
H52B	0.0654	0.8686	0.5753	0.030*
C53	0.00837 (15)	0.6991 (3)	0.53328 (15)	0.0279 (9)
H53A	−0.0229	0.6706	0.5193	0.033*
H53B	0.0068	0.6973	0.5721	0.033*
C54	0.01700 (14)	0.8238 (3)	0.51428 (14)	0.0229 (8)
H54A	−0.0101	0.8736	0.5269	0.027*
N2	0.28509 (13)	0.1901 (3)	0.12694 (15)	0.0268 (7)
C35	0.27675 (16)	0.2430 (3)	−0.04315 (17)	0.0332 (10)
H35A	0.2863	0.2619	−0.0796	0.040*
H35B	0.2423	0.2189	−0.0434	0.040*
C36	0.30930 (16)	0.1437 (3)	−0.02189 (17)	0.0327 (10)
H36A	0.3053	0.0751	−0.0449	0.039*
C37	0.36369 (16)	0.1823 (4)	−0.02240 (18)	0.0346 (10)
H37A	0.3738	0.2006	−0.0587	0.042*
H37B	0.3846	0.1198	−0.0093	0.042*
C38	0.36985 (15)	0.2902 (4)	0.01342 (18)	0.0338 (10)
H38A	0.4046	0.3154	0.0130	0.041*
C39	0.33667 (16)	0.3889 (3)	−0.00756 (17)	0.0341 (10)
H39A	0.3404	0.4570	0.0150	0.041*
H39B	0.3466	0.4098	−0.0436	0.041*
C40	0.28288 (16)	0.3497 (3)	−0.00755 (16)	0.0298 (9)
H40A	0.2619	0.4128	−0.0211	0.036*
C41	0.29381 (15)	0.1133 (3)	0.03515 (16)	0.0287 (9)
H41A	0.3141	0.0501	0.0486	0.034*
H41B	0.2595	0.0884	0.0356	0.034*
C42	0.35450 (14)	0.2596 (3)	0.07097 (17)	0.0283 (9)
H42A	0.3753	0.1974	0.0846	0.034*
H42B	0.3585	0.3269	0.0940	0.034*
C43	0.30025 (13)	0.2209 (3)	0.07056 (16)	0.0214 (8)
C44	0.26747 (14)	0.3198 (3)	0.05008 (15)	0.0265 (9)
H44A	0.2713	0.3876	0.0729	0.032*
H44B	0.2329	0.2962	0.0509	0.032*
Zn1	0.151271 (15)	0.26010 (3)	0.193239 (16)	0.01715 (12)
Cl1	0.16918 (4)	0.43733 (8)	0.15504 (4)	0.0302 (2)
Cl2	0.07045 (3)	0.24824 (7)	0.21232 (4)	0.02010 (19)
Cl3	0.20360 (3)	0.24701 (8)	0.26389 (4)	0.0278 (2)
Cl4	0.17186 (3)	0.10892 (8)	0.13571 (4)	0.0247 (2)
O1W	0.29515 (11)	0.3741 (3)	0.19759 (12)	0.0368 (7)
H1WA	0.3011 (15)	0.442 (2)	0.1855 (17)	0.044*
H1WB	0.2671 (10)	0.373 (4)	0.2132 (17)	0.044*
H2F	0.2905 (19)	0.255 (3)	0.1474 (18)	0.055*
H2E	0.3040 (16)	0.131 (3)	0.1377 (19)	0.055*
H2D	0.2532 (11)	0.175 (4)	0.1285 (19)	0.055*
H1F	0.0717 (18)	0.818 (3)	0.3620 (19)	0.055*
H1E	0.0328 (12)	0.731 (4)	0.3592 (19)	0.055*
H1D	0.0856 (15)	0.704 (4)	0.3584 (19)	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0212 (14)	0.0147 (12)	0.0284 (14)	−0.0018 (10)	−0.0019 (11)	−0.0020 (11)
O2	0.0196 (12)	0.0137 (12)	0.0177 (12)	−0.0005 (10)	−0.0023 (10)	−0.0013 (10)
O3	0.0199 (13)	0.0143 (12)	0.0291 (14)	−0.0017 (10)	0.0019 (11)	−0.0011 (11)
O4	0.0215 (14)	0.0173 (13)	0.0314 (15)	−0.0018 (10)	0.0051 (11)	−0.0084 (11)
O5	0.0191 (13)	0.0159 (12)	0.0354 (16)	−0.0008 (10)	0.0024 (11)	−0.0013 (11)
O6	0.0217 (14)	0.0154 (13)	0.0308 (15)	0.0019 (10)	0.0034 (11)	0.0062 (11)
C1	0.030 (2)	0.0163 (18)	0.031 (2)	−0.0036 (16)	−0.0061 (17)	0.0077 (16)
C2	0.028 (2)	0.0095 (16)	0.028 (2)	−0.0002 (15)	−0.0063 (16)	0.0022 (15)
C3	0.0223 (19)	0.0150 (17)	0.025 (2)	0.0039 (15)	−0.0008 (15)	0.0018 (15)
C4	0.0198 (19)	0.0227 (19)	0.0187 (18)	0.0027 (15)	−0.0028 (15)	0.0030 (15)
C5	0.0189 (19)	0.0180 (18)	0.0233 (19)	−0.0020 (14)	−0.0039 (15)	−0.0030 (15)
C6	0.022 (2)	0.0163 (17)	0.025 (2)	−0.0039 (15)	−0.0018 (15)	−0.0033 (15)
C7	0.030 (2)	0.0109 (17)	0.028 (2)	−0.0002 (15)	−0.0002 (16)	0.0000 (15)
C8	0.028 (2)	0.0156 (17)	0.027 (2)	0.0029 (15)	−0.0051 (16)	−0.0047 (15)
C9	0.020 (2)	0.024 (2)	0.038 (2)	0.0040 (16)	0.0046 (17)	−0.0071 (17)
C10	0.021 (2)	0.022 (2)	0.047 (3)	0.0009 (16)	0.0048 (18)	0.0003 (18)
C11	0.021 (2)	0.026 (2)	0.043 (3)	−0.0064 (16)	0.0084 (18)	−0.0004 (18)
C12	0.029 (2)	0.024 (2)	0.044 (3)	−0.0060 (17)	0.0118 (19)	0.0036 (19)
N1	0.0168 (15)	0.0161 (15)	0.0148 (15)	−0.0019 (12)	0.0008 (12)	−0.0001 (13)
C45	0.0178 (19)	0.0228 (19)	0.0213 (19)	0.0041 (15)	0.0006 (15)	−0.0023 (15)
C46	0.0188 (17)	0.0120 (16)	0.0124 (16)	−0.0009 (13)	0.0008 (13)	0.0010 (13)
C47	0.037 (2)	0.0128 (17)	0.021 (2)	−0.0064 (16)	0.0005 (16)	0.0019 (15)
C48	0.0198 (19)	0.0206 (18)	0.022 (2)	−0.0020 (15)	0.0006 (15)	−0.0042 (15)
C49	0.044 (3)	0.028 (2)	0.019 (2)	0.0145 (19)	−0.0055 (18)	0.0006 (17)
C50	0.021 (2)	0.029 (2)	0.022 (2)	−0.0023 (16)	−0.0020 (16)	−0.0015 (16)
C51	0.047 (3)	0.0167 (18)	0.022 (2)	−0.0078 (18)	−0.0006 (18)	0.0058 (16)
C52	0.034 (2)	0.0200 (19)	0.022 (2)	−0.0022 (16)	0.0011 (17)	−0.0054 (16)
C53	0.031 (2)	0.035 (2)	0.0177 (19)	−0.0114 (18)	0.0055 (16)	0.0043 (17)
C54	0.022 (2)	0.028 (2)	0.0185 (19)	0.0047 (16)	−0.0003 (15)	−0.0057 (16)
N2	0.0230 (18)	0.0206 (17)	0.037 (2)	0.0016 (14)	−0.0014 (15)	0.0033 (15)
C35	0.033 (2)	0.038 (2)	0.029 (2)	−0.0022 (19)	−0.0033 (18)	0.0013 (19)
C36	0.045 (3)	0.020 (2)	0.033 (2)	−0.0031 (18)	0.0008 (19)	−0.0063 (17)
C37	0.036 (2)	0.028 (2)	0.040 (3)	0.0069 (19)	0.008 (2)	−0.0004 (19)
C38	0.021 (2)	0.037 (2)	0.043 (3)	−0.0079 (18)	0.0041 (18)	0.001 (2)
C39	0.044 (3)	0.021 (2)	0.037 (2)	−0.0045 (19)	0.007 (2)	0.0031 (18)
C40	0.037 (2)	0.0208 (19)	0.032 (2)	0.0061 (17)	−0.0045 (18)	0.0029 (17)
C41	0.030 (2)	0.0157 (18)	0.040 (2)	−0.0017 (16)	0.0013 (18)	−0.0005 (17)
C42	0.019 (2)	0.030 (2)	0.035 (2)	0.0001 (17)	−0.0038 (16)	0.0023 (18)
C43	0.0163 (18)	0.0176 (18)	0.030 (2)	0.0016 (14)	−0.0003 (15)	0.0040 (15)
C44	0.025 (2)	0.0198 (19)	0.034 (2)	0.0035 (16)	−0.0010 (17)	−0.0010 (17)
Zn1	0.0169 (2)	0.0144 (2)	0.0201 (2)	−0.00041 (16)	−0.00345 (16)	0.00073 (17)
Cl1	0.0322 (5)	0.0212 (5)	0.0372 (5)	−0.0078 (4)	−0.0038 (4)	0.0102 (4)
Cl2	0.0177 (4)	0.0126 (4)	0.0300 (5)	−0.0007 (3)	−0.0016 (3)	0.0002 (4)
Cl3	0.0265 (5)	0.0293 (5)	0.0277 (5)	−0.0027 (4)	−0.0123 (4)	0.0048 (4)
Cl4	0.0268 (5)	0.0203 (4)	0.0270 (5)	0.0022 (4)	−0.0021 (4)	−0.0046 (4)
O1W	0.0364 (18)	0.0383 (18)	0.0357 (18)	−0.0118 (14)	0.0037 (14)	−0.0017 (14)

Geometric parameters (Å, º)

O1—C2	1.425 (4)	C48—C50	1.542 (5)
O1—C3	1.432 (4)	C48—H48A	0.9700
O2—C5	1.430 (4)	C48—H48B	0.9700
O2—C4	1.431 (4)	C49—C51	1.521 (6)
O3—C7	1.422 (4)	C49—C50	1.526 (5)
O3—C6	1.439 (4)	C49—H49A	0.9700
O4—C8	1.426 (4)	C49—H49B	0.9700
O4—C9	1.433 (4)	C50—C52	1.531 (5)
O5—C10	1.417 (4)	C50—H50A	0.9800
O5—C11	1.419 (4)	C51—C53	1.535 (6)
O6—C1	1.428 (4)	C51—H51A	0.9800
O6—C12	1.435 (4)	C52—C54	1.532 (5)
C1—C2	1.499 (5)	C52—H52A	0.9700
C1—H1A	0.9700	C52—H52B	0.9700
C1—H1B	0.9700	C53—C54	1.527 (5)
C2—H2A	0.9700	C53—H53A	0.9700
C2—H2B	0.9700	C53—H53B	0.9700
C3—C4	1.495 (5)	C54—H54A	0.9800
C3—H3A	0.9700	N2—C43	1.508 (5)
C3—H3B	0.9700	N2—H2F	0.91 (3)
C4—H4A	0.9700	N2—H2E	0.89 (3)
C4—H4B	0.9700	N2—H2D	0.88 (3)
C5—C6	1.499 (5)	C35—C40	1.523 (5)
C5—H5A	0.9700	C35—C36	1.535 (6)
C5—H5B	0.9700	C35—H35A	0.9700
C6—H6A	0.9700	C35—H35B	0.9700
C6—H6B	0.9700	C36—C41	1.524 (6)
C7—C8	1.497 (5)	C36—C37	1.533 (6)
C7—H7A	0.9700	C36—H36A	0.9800
C7—H7B	0.9700	C37—C38	1.537 (6)
C8—H8A	0.9700	C37—H37A	0.9700
C8—H8B	0.9700	C37—H37B	0.9700
C9—C10	1.495 (5)	C38—C42	1.536 (6)
C9—H9A	0.9700	C38—C39	1.537 (6)
C9—H9B	0.9700	C38—H38A	0.9800
C10—H10A	0.9700	C39—C40	1.519 (6)
C10—H10B	0.9700	C39—H39A	0.9700
C11—C12	1.489 (6)	C39—H39B	0.9700
C11—H11A	0.9700	C40—C44	1.536 (5)
C11—H11B	0.9700	C40—H40A	0.9800
C12—H12A	0.9700	C41—C43	1.529 (5)
C12—H12B	0.9700	C41—H41A	0.9700
N1—C46	1.513 (4)	C41—H41B	0.9700
N1—H1F	0.87 (3)	C42—C43	1.529 (5)
N1—H1E	0.91 (3)	C42—H42A	0.9700
N1—H1D	0.89 (3)	C42—H42B	0.9700
C45—C46	1.530 (5)	C43—C44	1.528 (5)
C45—C54	1.541 (5)	C44—H44A	0.9700
C45—H45A	0.9700	C44—H44B	0.9700
C45—H45B	0.9700	Zn1—Cl2	2.2354 (9)
C46—C48	1.527 (5)	Zn1—Cl3	2.2639 (10)
C46—C47	1.529 (4)	Zn1—Cl1	2.3001 (10)
C47—C51	1.536 (5)	Zn1—Cl4	2.3214 (10)
C47—H47A	0.9700	O1W—H1WA	0.857 (18)
C47—H47B	0.9700	O1W—H1WB	0.851 (18)
C2—O1—C3	113.1 (3)	C51—C49—H49A	109.7
C5—O2—C4	111.4 (3)	C50—C49—H49A	109.7
C7—O3—C6	112.6 (3)	C51—C49—H49B	109.7
C8—O4—C9	110.6 (3)	C50—C49—H49B	109.7
C10—O5—C11	114.2 (3)	H49A—C49—H49B	108.2
C1—O6—C12	109.3 (3)	C49—C50—C52	109.6 (3)
O6—C1—C2	110.0 (3)	C49—C50—C48	109.2 (3)
O6—C1—H1A	109.7	C52—C50—C48	109.3 (3)
C2—C1—H1A	109.7	C49—C50—H50A	109.6
O6—C1—H1B	109.7	C52—C50—H50A	109.6
C2—C1—H1B	109.7	C48—C50—H50A	109.6
H1A—C1—H1B	108.2	C49—C51—C53	109.5 (3)
O1—C2—C1	108.6 (3)	C49—C51—C47	109.8 (3)
O1—C2—H2A	110.0	C53—C51—C47	109.1 (3)
C1—C2—H2A	110.0	C49—C51—H51A	109.5
O1—C2—H2B	110.0	C53—C51—H51A	109.5
C1—C2—H2B	110.0	C47—C51—H51A	109.5
H2A—C2—H2B	108.3	C50—C52—C54	109.6 (3)
O1—C3—C4	108.7 (3)	C50—C52—H52A	109.7
O1—C3—H3A	110.0	C54—C52—H52A	109.7
C4—C3—H3A	110.0	C50—C52—H52B	109.7
O1—C3—H3B	110.0	C54—C52—H52B	109.7
C4—C3—H3B	110.0	H52A—C52—H52B	108.2
H3A—C3—H3B	108.3	C54—C53—C51	109.6 (3)
O2—C4—C3	109.4 (3)	C54—C53—H53A	109.7
O2—C4—H4A	109.8	C51—C53—H53A	109.7
C3—C4—H4A	109.8	C54—C53—H53B	109.7
O2—C4—H4B	109.8	C51—C53—H53B	109.7
C3—C4—H4B	109.8	H53A—C53—H53B	108.2
H4A—C4—H4B	108.2	C53—C54—C52	109.6 (3)
O2—C5—C6	109.2 (3)	C53—C54—C45	109.3 (3)
O2—C5—H5A	109.8	C52—C54—C45	109.3 (3)
C6—C5—H5A	109.8	C53—C54—H54A	109.5
O2—C5—H5B	109.8	C52—C54—H54A	109.5
C6—C5—H5B	109.8	C45—C54—H54A	109.5
H5A—C5—H5B	108.3	C43—N2—H2F	107 (3)
O3—C6—C5	107.9 (3)	C43—N2—H2E	108 (3)
O3—C6—H6A	110.1	H2F—N2—H2E	111 (4)
C5—C6—H6A	110.1	C43—N2—H2D	111 (3)
O3—C6—H6B	110.1	H2F—N2—H2D	107 (4)
C5—C6—H6B	110.1	H2E—N2—H2D	113 (4)
H6A—C6—H6B	108.4	C40—C35—C36	109.6 (3)
O3—C7—C8	109.0 (3)	C40—C35—H35A	109.8
O3—C7—H7A	109.9	C36—C35—H35A	109.8
C8—C7—H7A	109.9	C40—C35—H35B	109.8
O3—C7—H7B	109.9	C36—C35—H35B	109.8
C8—C7—H7B	109.9	H35A—C35—H35B	108.2
H7A—C7—H7B	108.3	C41—C36—C37	109.7 (3)
O4—C8—C7	110.4 (3)	C41—C36—C35	109.7 (3)
O4—C8—H8A	109.6	C37—C36—C35	109.2 (3)
C7—C8—H8A	109.6	C41—C36—H36A	109.4
O4—C8—H8B	109.6	C37—C36—H36A	109.4
C7—C8—H8B	109.6	C35—C36—H36A	109.4
H8A—C8—H8B	108.1	C36—C37—C38	109.4 (3)
O4—C9—C10	108.9 (3)	C36—C37—H37A	109.8
O4—C9—H9A	109.9	C38—C37—H37A	109.8
C10—C9—H9A	109.9	C36—C37—H37B	109.8
O4—C9—H9B	109.9	C38—C37—H37B	109.8
C10—C9—H9B	109.9	H37A—C37—H37B	108.2
H9A—C9—H9B	108.3	C42—C38—C39	109.3 (3)
O5—C10—C9	109.0 (3)	C42—C38—C37	109.3 (3)
O5—C10—H10A	109.9	C39—C38—C37	109.5 (4)
C9—C10—H10A	109.9	C42—C38—H38A	109.6
O5—C10—H10B	109.9	C39—C38—H38A	109.6
C9—C10—H10B	109.9	C37—C38—H38A	109.6
H10A—C10—H10B	108.3	C40—C39—C38	109.7 (3)
O5—C11—C12	109.9 (3)	C40—C39—H39A	109.7
O5—C11—H11A	109.7	C38—C39—H39A	109.7
C12—C11—H11A	109.7	C40—C39—H39B	109.7
O5—C11—H11B	109.7	C38—C39—H39B	109.7
C12—C11—H11B	109.7	H39A—C39—H39B	108.2
H11A—C11—H11B	108.2	C39—C40—C35	110.0 (3)
O6—C12—C11	110.3 (3)	C39—C40—C44	108.9 (3)
O6—C12—H12A	109.6	C35—C40—C44	109.7 (3)
C11—C12—H12A	109.6	C39—C40—H40A	109.4
O6—C12—H12B	109.6	C35—C40—H40A	109.4
C11—C12—H12B	109.6	C44—C40—H40A	109.4
H12A—C12—H12B	108.1	C36—C41—C43	108.9 (3)
C46—N1—H1F	110 (3)	C36—C41—H41A	109.9
C46—N1—H1E	110 (3)	C43—C41—H41A	109.9
H1F—N1—H1E	110 (4)	C36—C41—H41B	109.9
C46—N1—H1D	115 (3)	C43—C41—H41B	109.9
H1F—N1—H1D	103 (4)	H41A—C41—H41B	108.3
H1E—N1—H1D	108 (4)	C43—C42—C38	108.6 (3)
C46—C45—C54	108.7 (3)	C43—C42—H42A	110.0
C46—C45—H45A	109.9	C38—C42—H42A	110.0
C54—C45—H45A	109.9	C43—C42—H42B	110.0
C46—C45—H45B	109.9	C38—C42—H42B	110.0
C54—C45—H45B	109.9	H42A—C42—H42B	108.4
H45A—C45—H45B	108.3	N2—C43—C44	109.2 (3)
N1—C46—C48	108.7 (3)	N2—C43—C42	108.7 (3)
N1—C46—C47	108.9 (3)	C44—C43—C42	109.8 (3)
C48—C46—C47	110.3 (3)	N2—C43—C41	108.6 (3)
N1—C46—C45	108.9 (3)	C44—C43—C41	110.0 (3)
C48—C46—C45	110.1 (3)	C42—C43—C41	110.3 (3)
C47—C46—C45	110.0 (3)	C43—C44—C40	108.8 (3)
C46—C47—C51	108.6 (3)	C43—C44—H44A	109.9
C46—C47—H47A	110.0	C40—C44—H44A	109.9
C51—C47—H47A	110.0	C43—C44—H44B	109.9
C46—C47—H47B	110.0	C40—C44—H44B	109.9
C51—C47—H47B	110.0	H44A—C44—H44B	108.3
H47A—C47—H47B	108.3	Cl2—Zn1—Cl3	115.96 (4)
C46—C48—C50	108.7 (3)	Cl2—Zn1—Cl1	110.31 (4)
C46—C48—H48A	109.9	Cl3—Zn1—Cl1	104.53 (4)
C50—C48—H48A	109.9	Cl2—Zn1—Cl4	108.63 (4)
C46—C48—H48B	109.9	Cl3—Zn1—Cl4	106.45 (4)
C50—C48—H48B	109.9	Cl1—Zn1—Cl4	110.85 (4)
H48A—C48—H48B	108.3	H1WA—O1W—H1WB	110 (3)
C51—C49—C50	110.0 (3)
C12—O6—C1—C2	171.3 (3)	C48—C50—C52—C54	60.3 (4)
C3—O1—C2—C1	−170.3 (3)	C49—C51—C53—C54	59.5 (4)
O6—C1—C2—O1	−61.9 (4)	C47—C51—C53—C54	−60.6 (4)
C2—O1—C3—C4	168.3 (3)	C51—C53—C54—C52	−59.5 (4)
C5—O2—C4—C3	−177.9 (3)	C51—C53—C54—C45	60.3 (4)
O1—C3—C4—O2	65.6 (4)	C50—C52—C54—C53	59.4 (4)
C4—O2—C5—C6	174.2 (3)	C50—C52—C54—C45	−60.3 (4)
C7—O3—C6—C5	−166.2 (3)	C46—C45—C54—C53	−59.9 (4)
O2—C5—C6—O3	−64.6 (4)	C46—C45—C54—C52	60.1 (4)
C6—O3—C7—C8	172.0 (3)	C40—C35—C36—C41	60.0 (4)
C9—O4—C8—C7	−176.6 (3)	C40—C35—C36—C37	−60.2 (4)
O3—C7—C8—O4	62.0 (4)	C41—C36—C37—C38	−60.2 (4)
C8—O4—C9—C10	174.9 (3)	C35—C36—C37—C38	60.0 (4)
C11—O5—C10—C9	−166.5 (3)	C36—C37—C38—C42	60.3 (4)
O4—C9—C10—O5	−62.3 (4)	C36—C37—C38—C39	−59.5 (4)
C10—O5—C11—C12	170.1 (3)	C42—C38—C39—C40	−60.5 (4)
C1—O6—C12—C11	−175.9 (3)	C37—C38—C39—C40	59.2 (4)
O5—C11—C12—O6	64.4 (4)	C38—C39—C40—C35	−59.6 (4)
C54—C45—C46—N1	−180.0 (3)	C38—C39—C40—C44	60.7 (4)
C54—C45—C46—C48	−60.9 (4)	C36—C35—C40—C39	60.2 (4)
C54—C45—C46—C47	60.8 (4)	C36—C35—C40—C44	−59.6 (4)
N1—C46—C47—C51	179.5 (3)	C37—C36—C41—C43	59.9 (4)
C48—C46—C47—C51	60.4 (4)	C35—C36—C41—C43	−60.0 (4)
C45—C46—C47—C51	−61.2 (4)	C39—C38—C42—C43	59.8 (4)
N1—C46—C48—C50	−180.0 (3)	C37—C38—C42—C43	−60.1 (4)
C47—C46—C48—C50	−60.7 (4)	C38—C42—C43—N2	179.7 (3)
C45—C46—C48—C50	60.8 (4)	C38—C42—C43—C44	−60.8 (4)
C51—C49—C50—C52	59.6 (4)	C38—C42—C43—C41	60.7 (4)
C51—C49—C50—C48	−60.1 (4)	C36—C41—C43—N2	−179.8 (3)
C46—C48—C50—C49	59.8 (4)	C36—C41—C43—C44	60.7 (4)
C46—C48—C50—C52	−60.0 (4)	C36—C41—C43—C42	−60.6 (4)
C50—C49—C51—C53	−59.6 (4)	N2—C43—C44—C40	−179.5 (3)
C50—C49—C51—C47	60.2 (4)	C42—C43—C44—C40	61.3 (4)
C46—C47—C51—C49	−59.5 (4)	C41—C43—C44—C40	−60.3 (4)
C46—C47—C51—C53	60.5 (4)	C39—C40—C44—C43	−60.8 (4)
C49—C50—C52—C54	−59.3 (4)	C35—C40—C44—C43	59.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···Cl3	0.85 (2)	2.57 (2)	3.312 (3)	146 (4)
N2—H2F···O1W	0.91 (3)	1.86 (3)	2.767 (5)	171 (5)
N2—H2D···Cl4	0.88 (3)	2.33 (3)	3.201 (4)	172 (5)
N1—H1E···O2	0.91 (3)	2.11 (3)	2.983 (4)	161 (4)
N1—H1D···O4	0.89 (3)	2.16 (3)	2.993 (4)	155 (5)
N1—H1F···O6	0.87 (3)	2.16 (3)	2.996 (4)	161 (5)
O1W—H1WA···Cl4^i	0.86 (2)	2.39 (2)	3.234 (3)	167 (4)
N2—H2E···Cl1^ii	0.89 (3)	2.38 (3)	3.233 (3)	160 (4)

Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) −x+1/2, y−1/2, z.