Crystallographic and computational study of a network composed of [ZnCl4]2− anions and triply protonated 4′-functionalized terpyridine cations

Granifo, J.; Suárez, S.; Boubeta, F.; Baggio, R.

doi:10.1107/S2053229617016308

Crystallographic and computational study of a network composed of [ZnCl₄]²⁻ anions and triply protonated 4′-functionalized terpyridine cations

J. Granifo, S. Suárez, F. Boubeta and R. Baggio

We report herein the synthesis, crystallographic analysis and a study of the noncovalent interactions observed in the new 4′-substituted terpyridine-based derivative bis[4′-(isoquinolin-2-ium-4-yl)-2,2′:6′,2′′-terpyridine-1,1′′-diium] tris[tetrachloridozincate(II)] monohydrate, (C₂₄H₁₉N₄)₂[ZnCl₄]₃·H₂O or (ITPH₃)₂[ZnCl₄]₃·H₂O, where (ITPH₃)³⁺ is the triply protonated cation derived from 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine (ITP) [Granifo et al. (2016). Acta Cryst. C72, 932–938]. The (ITPH₃)³⁺ cation presents a number of interesting similarities and differences compared with its neutral ITP relative, mainly in the role fulfilled in the packing arrangement by the profuse set of D—H

A [D (donor) = C, N or O; A (acceptor) = O or Cl], π–π and anion

π noncovalent interactions present. We discuss these interactions in two different complementary ways, viz. using a point-to-point approach in the light of Bader's theory of Atoms In Molecules (AIM), analyzing the individual significance of each interaction, and in a more `global' analysis, making use of the Hirshfeld surfaces and the associated enrichment ratio (ER) approach, evaluating the surprisingly large co-operative effect of the superabundant weaker contacts.

Keywords: terpyridine; crystal structure; anion

π interactions; Hirshfeld surfaces; enrichment ratio; AIM analysis; computational chemistry.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229617016308/jx3001sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229617016308/jx3001Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229617016308/jx3001sup3.pdf A short introduction to Hirshfeld surface and enrichment ratio (ER) analysis, on one side, and to quantum-mechanical calculations and Atoms In Molecules (AIM) analysis on the other, plus some additional figures

CCDC reference: 1585155

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Bis[4'-(isoquinolin-2-ium-4-yl)-2,2':6',2'-terpyridine-1,1''-diium] tris[tetrachloridozincate(II)] monohydrate top

Crystal data top

(C₂₄H₁₉N₄)₂[ZnCl₄]₃·H₂O	Z = 2
M_r = 1366.39	F(000) = 1372
Triclinic, P1	D_x = 1.700 Mg m⁻³
a = 11.0485 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 16.0249 (8) Å	Cell parameters from 4044 reflections
c = 16.4318 (7) Å	θ = 3.5–28.4°
α = 100.824 (4)°	µ = 1.98 mm⁻¹
β = 103.574 (4)°	T = 150 K
γ = 102.737 (4)°	Prism, colourless
V = 2668.9 (2) Å³	0.30 × 0.25 × 0.20 mm

Data collection top

Rigaku Xcalibur Sapphire3 diffractometer	12387 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	9230 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ω scans	θ_max = 28.9°, θ_min = 3.3°
Absorption correction: multi-scan CrysAlisPro 1.171.38.41r (Rigaku Oxford Diffraction, 2015)	h = −14→13
T_min = 0.54, T_max = 0.70	k = −21→20
29335 measured reflections	l = −22→22

Refinement top

Refinement on F²	9 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0298P)² + 4.101P] where P = (F_o² + 2F_c²)/3
S = 0.93	(Δ/σ)_max = 0.001
12387 reflections	Δρ_max = 0.66 e Å⁻³
673 parameters	Δρ_min = −0.48 e Å⁻³

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.74573 (4)	0.87831 (3)	0.94630 (2)	0.01807 (10)
Cl11	0.79844 (8)	0.84870 (5)	1.07678 (5)	0.01833 (17)
Cl12	0.85218 (8)	1.01854 (5)	0.94663 (5)	0.01772 (17)
Cl13	0.52863 (8)	0.87294 (6)	0.90934 (5)	0.02331 (19)
Cl14	0.78516 (10)	0.78122 (6)	0.84490 (6)	0.0287 (2)
Zn2	0.28439 (4)	0.19736 (2)	0.56472 (2)	0.01446 (9)
Cl21	0.19816 (8)	0.24136 (5)	0.67270 (5)	0.01877 (18)
Cl22	0.17120 (8)	0.20948 (6)	0.43425 (5)	0.01898 (18)
Cl23	0.49308 (8)	0.28265 (5)	0.59620 (5)	0.01552 (17)
Cl24	0.28899 (8)	0.05541 (5)	0.55881 (5)	0.01903 (18)
Zn3	−0.04607 (4)	0.44630 (3)	0.25013 (2)	0.01746 (10)
Cl31	−0.00734 (9)	0.44474 (6)	0.12015 (5)	0.02125 (18)
Cl32	−0.26513 (8)	0.40361 (6)	0.23286 (5)	0.01881 (18)
Cl33	0.02092 (9)	0.33585 (6)	0.30103 (6)	0.0259 (2)
Cl34	0.05301 (9)	0.58200 (6)	0.33859 (5)	0.0258 (2)
N1A	0.4258 (3)	0.36566 (18)	0.98779 (17)	0.0160 (6)
H1NA	0.492 (2)	0.346 (2)	0.996 (2)	0.019*
N2A	0.5850 (3)	0.37384 (17)	0.88918 (17)	0.0147 (6)
N3A	0.7740 (3)	0.30000 (18)	0.93739 (18)	0.0169 (6)
H3NA	0.719 (3)	0.306 (2)	0.965 (2)	0.020*
N4A	0.6751 (3)	0.63017 (18)	0.64108 (18)	0.0173 (6)
H4NA	0.743 (2)	0.6668 (18)	0.641 (2)	0.021*
C1A	0.3542 (3)	0.3561 (2)	1.0424 (2)	0.0176 (7)
H1A	0.3761	0.3270	1.0852	0.021*
C2A	0.2488 (3)	0.3889 (2)	1.0359 (2)	0.0192 (7)
H2A	0.1982	0.3822	1.0734	0.023*
C3A	0.2198 (3)	0.4327 (2)	0.9712 (2)	0.0200 (7)
H3A	0.1499	0.4568	0.9659	0.024*
C4A	0.2948 (3)	0.4405 (2)	0.9148 (2)	0.0173 (7)
H4A	0.2743	0.4688	0.8711	0.021*
C5A	0.3999 (3)	0.4064 (2)	0.9234 (2)	0.0135 (7)
C6A	0.4916 (3)	0.4129 (2)	0.8702 (2)	0.0141 (7)
C7A	0.4803 (3)	0.4589 (2)	0.8062 (2)	0.0145 (7)
H7A	0.4131	0.4850	0.7945	0.017*
C8A	0.5708 (3)	0.4653 (2)	0.76012 (19)	0.0137 (7)
C9A	0.6699 (3)	0.4252 (2)	0.78013 (19)	0.0144 (7)
H9A	0.7325	0.4284	0.7508	0.017*
C10A	0.6733 (3)	0.3801 (2)	0.8450 (2)	0.0152 (7)
C11A	0.7741 (3)	0.3348 (2)	0.8686 (2)	0.0150 (7)
C12A	0.8665 (3)	0.3246 (2)	0.8263 (2)	0.0185 (7)
H12A	0.8705	0.3486	0.7793	0.022*
C13A	0.9534 (3)	0.2780 (2)	0.8550 (2)	0.0231 (8)
H13A	1.0149	0.2699	0.8264	0.028*
C14A	0.9491 (3)	0.2439 (2)	0.9252 (2)	0.0243 (8)
H14A	1.0068	0.2125	0.9442	0.029*
C15A	0.8587 (3)	0.2568 (2)	0.9667 (2)	0.0218 (8)
H15A	0.8560	0.2355	1.0153	0.026*
C16A	0.5655 (3)	0.5178 (2)	0.6940 (2)	0.0142 (7)
C17A	0.6759 (3)	0.5770 (2)	0.6971 (2)	0.0162 (7)
H17A	0.7530	0.5815	0.7378	0.019*
C18A	0.5681 (3)	0.6284 (2)	0.5834 (2)	0.0188 (7)
H18A	0.5712	0.6671	0.5478	0.023*
C19A	0.4502 (3)	0.5686 (2)	0.5757 (2)	0.0159 (7)
C20A	0.3357 (3)	0.5666 (2)	0.5144 (2)	0.0206 (8)
H20A	0.3377	0.6059	0.4794	0.025*
C21A	0.2218 (4)	0.5067 (2)	0.5066 (2)	0.0226 (8)
H21A	0.1457	0.5060	0.4671	0.027*
C22A	0.2196 (3)	0.4459 (2)	0.5583 (2)	0.0191 (7)
H22A	0.1420	0.4045	0.5517	0.023*
C23A	0.3293 (3)	0.4465 (2)	0.6180 (2)	0.0160 (7)
H23A	0.3261	0.4050	0.6506	0.019*
C24A	0.4473 (3)	0.5097 (2)	0.63051 (19)	0.0134 (7)
N1B	0.6444 (3)	0.07957 (18)	0.83412 (17)	0.0150 (6)
H1NB	0.706 (2)	0.056 (2)	0.845 (2)	0.018*
N2B	0.8062 (3)	0.06720 (17)	0.73738 (16)	0.0141 (6)
N3B	0.9733 (3)	−0.02531 (19)	0.78502 (18)	0.0177 (6)
H3NB	0.919 (3)	−0.015 (2)	0.811 (2)	0.021*
N4B	0.8957 (3)	0.25376 (19)	0.43406 (18)	0.0169 (6)
H4NB	0.9668 (19)	0.276 (2)	0.425 (2)	0.020*
C1B	0.5685 (3)	0.0794 (2)	0.8869 (2)	0.0171 (7)
H1B	0.5861	0.0558	0.9345	0.021*
C2B	0.4653 (3)	0.1139 (2)	0.8707 (2)	0.0195 (7)
H2B	0.4110	0.1127	0.9062	0.023*
C3B	0.4431 (3)	0.1505 (2)	0.8011 (2)	0.0183 (7)
H3B	0.3736	0.1746	0.7895	0.022*
C4B	0.5245 (3)	0.1513 (2)	0.7480 (2)	0.0164 (7)
H4B	0.5101	0.1765	0.7013	0.020*
C5B	0.6268 (3)	0.1145 (2)	0.76484 (19)	0.0141 (7)
C6B	0.7188 (3)	0.1097 (2)	0.71316 (19)	0.0132 (7)
C7B	0.7108 (3)	0.1476 (2)	0.6429 (2)	0.0139 (7)
H7B	0.6504	0.1789	0.6297	0.017*
C8B	0.7948 (3)	0.1378 (2)	0.5929 (2)	0.0138 (7)
C9B	0.8877 (3)	0.0947 (2)	0.6187 (2)	0.0154 (7)
H9B	0.9468	0.0881	0.5876	0.018*
C10B	0.8919 (3)	0.0613 (2)	0.6918 (2)	0.0135 (7)
C11B	0.9874 (3)	0.0131 (2)	0.7199 (2)	0.0140 (7)
C12B	1.0883 (3)	0.0055 (2)	0.6864 (2)	0.0174 (7)
H12B	1.1017	0.0325	0.6426	0.021*
C13B	1.1702 (3)	−0.0425 (2)	0.7182 (2)	0.0203 (8)
H13B	1.2380	−0.0484	0.6951	0.024*
C14B	1.1517 (4)	−0.0818 (2)	0.7839 (2)	0.0244 (8)
H14B	1.2062	−0.1143	0.8053	0.029*
C15B	1.0514 (3)	−0.0720 (2)	0.8171 (2)	0.0229 (8)
H15B	1.0375	−0.0976	0.8616	0.028*
C16B	0.7860 (3)	0.1736 (2)	0.5153 (2)	0.0133 (7)
C17B	0.8985 (3)	0.2176 (2)	0.5026 (2)	0.0163 (7)
H17B	0.9776	0.2227	0.5414	0.020*
C18B	0.7858 (3)	0.2519 (2)	0.3786 (2)	0.0182 (7)
H18B	0.7882	0.2809	0.3348	0.022*
C19B	0.6669 (3)	0.2071 (2)	0.3855 (2)	0.0147 (7)
C20B	0.5502 (3)	0.2018 (2)	0.3239 (2)	0.0190 (7)
H20B	0.5523	0.2306	0.2799	0.023*
C21B	0.4348 (3)	0.1546 (2)	0.3291 (2)	0.0201 (8)
H21B	0.3579	0.1520	0.2893	0.024*
C22B	0.4322 (3)	0.1101 (2)	0.3946 (2)	0.0189 (7)
H22B	0.3530	0.0775	0.3973	0.023*
C23B	0.5437 (3)	0.1133 (2)	0.4549 (2)	0.0152 (7)
H23B	0.5393	0.0820	0.4969	0.018*
C24B	0.6651 (3)	0.1637 (2)	0.45367 (19)	0.0123 (6)
O1W	0.6211 (2)	0.29045 (16)	1.04752 (15)	0.0204 (5)
H1WA	0.668 (3)	0.3251 (18)	1.0996 (11)	0.031*
H1WB	0.579 (3)	0.2402 (13)	1.057 (2)	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0231 (2)	0.0182 (2)	0.0170 (2)	0.00700 (17)	0.00999 (17)	0.00704 (16)
Cl11	0.0191 (4)	0.0225 (4)	0.0185 (4)	0.0096 (3)	0.0083 (3)	0.0091 (3)
Cl12	0.0170 (4)	0.0205 (4)	0.0189 (4)	0.0065 (3)	0.0055 (3)	0.0107 (3)
Cl13	0.0203 (5)	0.0270 (5)	0.0210 (4)	0.0024 (4)	0.0039 (3)	0.0097 (4)
Cl14	0.0468 (6)	0.0231 (5)	0.0232 (5)	0.0114 (4)	0.0210 (4)	0.0065 (4)
Zn2	0.0143 (2)	0.01442 (19)	0.01503 (19)	0.00396 (16)	0.00357 (15)	0.00529 (15)
Cl21	0.0193 (4)	0.0208 (4)	0.0195 (4)	0.0071 (3)	0.0087 (3)	0.0071 (3)
Cl22	0.0155 (4)	0.0244 (4)	0.0178 (4)	0.0057 (3)	0.0031 (3)	0.0090 (3)
Cl23	0.0146 (4)	0.0148 (4)	0.0168 (4)	0.0034 (3)	0.0032 (3)	0.0059 (3)
Cl24	0.0249 (5)	0.0134 (4)	0.0207 (4)	0.0052 (3)	0.0096 (3)	0.0053 (3)
Zn3	0.0154 (2)	0.0216 (2)	0.0173 (2)	0.00586 (17)	0.00472 (16)	0.00865 (17)
Cl31	0.0248 (5)	0.0227 (4)	0.0178 (4)	0.0059 (4)	0.0090 (3)	0.0060 (3)
Cl32	0.0161 (4)	0.0232 (4)	0.0187 (4)	0.0084 (3)	0.0049 (3)	0.0055 (3)
Cl33	0.0179 (5)	0.0341 (5)	0.0375 (5)	0.0120 (4)	0.0125 (4)	0.0256 (4)
Cl34	0.0297 (5)	0.0252 (5)	0.0189 (4)	0.0021 (4)	0.0060 (4)	0.0048 (4)
N1A	0.0152 (15)	0.0159 (14)	0.0166 (14)	0.0028 (12)	0.0056 (12)	0.0036 (12)
N2A	0.0129 (14)	0.0135 (14)	0.0176 (14)	0.0017 (11)	0.0055 (11)	0.0043 (11)
N3A	0.0154 (16)	0.0149 (14)	0.0200 (15)	0.0059 (12)	0.0039 (12)	0.0028 (12)
N4A	0.0167 (16)	0.0170 (15)	0.0213 (15)	0.0013 (12)	0.0110 (13)	0.0090 (12)
C1A	0.0207 (19)	0.0145 (17)	0.0153 (16)	−0.0010 (14)	0.0062 (14)	0.0039 (14)
C2A	0.0178 (18)	0.0184 (18)	0.0181 (17)	−0.0013 (14)	0.0078 (14)	0.0009 (14)
C3A	0.0165 (18)	0.0183 (18)	0.0246 (18)	0.0046 (15)	0.0074 (15)	0.0024 (15)
C4A	0.0148 (17)	0.0179 (17)	0.0200 (17)	0.0020 (14)	0.0072 (14)	0.0066 (14)
C5A	0.0131 (17)	0.0116 (16)	0.0138 (15)	0.0004 (13)	0.0027 (13)	0.0034 (13)
C6A	0.0133 (17)	0.0128 (16)	0.0143 (16)	0.0018 (13)	0.0044 (13)	0.0010 (13)
C7A	0.0128 (17)	0.0139 (16)	0.0157 (16)	0.0034 (13)	0.0022 (13)	0.0039 (13)
C8A	0.0165 (17)	0.0117 (15)	0.0108 (15)	0.0026 (13)	0.0029 (13)	0.0006 (13)
C9A	0.0125 (17)	0.0159 (16)	0.0117 (15)	0.0013 (13)	0.0023 (13)	0.0006 (13)
C10A	0.0140 (17)	0.0125 (16)	0.0144 (16)	0.0013 (13)	−0.0007 (13)	0.0010 (13)
C11A	0.0147 (17)	0.0101 (15)	0.0166 (16)	0.0002 (13)	0.0021 (13)	0.0017 (13)
C12A	0.0142 (17)	0.0164 (17)	0.0222 (18)	0.0017 (14)	0.0042 (14)	0.0032 (14)
C13A	0.0161 (18)	0.0146 (17)	0.034 (2)	0.0026 (14)	0.0048 (16)	−0.0006 (16)
C14A	0.0153 (18)	0.0150 (17)	0.040 (2)	0.0062 (15)	0.0020 (16)	0.0058 (16)
C15A	0.0208 (19)	0.0152 (17)	0.0275 (19)	0.0054 (15)	0.0019 (15)	0.0074 (15)
C16A	0.0183 (18)	0.0145 (16)	0.0124 (15)	0.0067 (14)	0.0080 (13)	0.0025 (13)
C17A	0.0163 (18)	0.0210 (18)	0.0139 (16)	0.0072 (14)	0.0060 (13)	0.0060 (14)
C18A	0.024 (2)	0.0209 (18)	0.0162 (17)	0.0097 (15)	0.0093 (15)	0.0077 (14)
C19A	0.0199 (18)	0.0161 (17)	0.0150 (16)	0.0079 (14)	0.0079 (14)	0.0046 (13)
C20A	0.024 (2)	0.0208 (18)	0.0193 (17)	0.0085 (16)	0.0065 (15)	0.0079 (15)
C21A	0.022 (2)	0.030 (2)	0.0147 (17)	0.0101 (16)	0.0020 (14)	0.0034 (15)
C22A	0.0174 (18)	0.0178 (17)	0.0172 (17)	0.0001 (14)	0.0031 (14)	0.0013 (14)
C23A	0.0193 (18)	0.0127 (16)	0.0148 (16)	0.0049 (14)	0.0044 (14)	0.0011 (13)
C24A	0.0162 (17)	0.0149 (16)	0.0074 (14)	0.0039 (13)	0.0046 (12)	−0.0018 (13)
N1B	0.0165 (15)	0.0167 (15)	0.0160 (14)	0.0083 (12)	0.0067 (12)	0.0066 (12)
N2B	0.0151 (15)	0.0131 (14)	0.0135 (13)	0.0037 (11)	0.0043 (11)	0.0018 (11)
N3B	0.0180 (16)	0.0228 (16)	0.0167 (15)	0.0078 (13)	0.0079 (12)	0.0091 (13)
N4B	0.0130 (15)	0.0207 (15)	0.0184 (14)	0.0022 (12)	0.0074 (12)	0.0076 (12)
C1B	0.0191 (18)	0.0204 (18)	0.0164 (16)	0.0061 (15)	0.0097 (14)	0.0090 (14)
C2B	0.0175 (18)	0.0237 (19)	0.0187 (17)	0.0054 (15)	0.0093 (14)	0.0041 (15)
C3B	0.0155 (18)	0.0223 (18)	0.0186 (17)	0.0080 (15)	0.0044 (14)	0.0061 (15)
C4B	0.0171 (18)	0.0192 (17)	0.0125 (16)	0.0044 (14)	0.0030 (13)	0.0053 (14)
C5B	0.0162 (17)	0.0149 (16)	0.0093 (15)	0.0017 (14)	0.0036 (13)	0.0016 (13)
C6B	0.0136 (17)	0.0131 (16)	0.0113 (15)	0.0017 (13)	0.0044 (13)	0.0007 (13)
C7B	0.0132 (17)	0.0138 (16)	0.0167 (16)	0.0048 (13)	0.0079 (13)	0.0029 (13)
C8B	0.0141 (17)	0.0129 (16)	0.0119 (15)	0.0013 (13)	0.0007 (13)	0.0041 (13)
C9B	0.0144 (17)	0.0164 (17)	0.0149 (16)	0.0013 (14)	0.0076 (13)	0.0019 (13)
C10B	0.0104 (16)	0.0134 (16)	0.0157 (16)	0.0031 (13)	0.0044 (13)	0.0012 (13)
C11B	0.0138 (17)	0.0128 (16)	0.0117 (15)	0.0005 (13)	0.0013 (13)	0.0011 (13)
C12B	0.0214 (19)	0.0167 (17)	0.0191 (17)	0.0071 (15)	0.0106 (14)	0.0084 (14)
C13B	0.0181 (19)	0.0216 (18)	0.0225 (18)	0.0086 (15)	0.0071 (15)	0.0037 (15)
C14B	0.025 (2)	0.026 (2)	0.027 (2)	0.0140 (17)	0.0067 (16)	0.0111 (16)
C15B	0.024 (2)	0.027 (2)	0.0242 (19)	0.0124 (16)	0.0076 (15)	0.0147 (16)
C16B	0.0170 (17)	0.0113 (15)	0.0128 (15)	0.0065 (13)	0.0055 (13)	0.0014 (13)
C17B	0.0151 (17)	0.0174 (17)	0.0157 (16)	0.0037 (14)	0.0031 (13)	0.0056 (14)
C18B	0.025 (2)	0.0153 (17)	0.0164 (17)	0.0064 (15)	0.0086 (15)	0.0063 (14)
C19B	0.0164 (18)	0.0140 (16)	0.0137 (16)	0.0040 (14)	0.0050 (13)	0.0028 (13)
C20B	0.024 (2)	0.0238 (19)	0.0136 (16)	0.0110 (16)	0.0061 (14)	0.0089 (14)
C21B	0.0171 (18)	0.0253 (19)	0.0145 (16)	0.0075 (15)	−0.0005 (14)	0.0013 (15)
C22B	0.0168 (18)	0.0196 (18)	0.0183 (17)	0.0024 (14)	0.0065 (14)	0.0015 (14)
C23B	0.0188 (18)	0.0146 (16)	0.0141 (16)	0.0075 (14)	0.0065 (14)	0.0025 (13)
C24B	0.0149 (17)	0.0105 (15)	0.0119 (15)	0.0049 (13)	0.0048 (13)	0.0005 (12)
O1W	0.0223 (14)	0.0228 (13)	0.0170 (12)	0.0058 (11)	0.0055 (10)	0.0080 (10)

Geometric parameters (Å, º) top

Zn1—Cl14	2.2478 (9)	C21A—H21A	0.9300
Zn1—Cl11	2.2537 (9)	C22A—C23A	1.365 (5)
Zn1—Cl12	2.2935 (9)	C22A—H22A	0.9300
Zn1—Cl13	2.3098 (10)	C23A—C24A	1.408 (5)
Zn2—Cl24	2.2709 (9)	C23A—H23A	0.9300
Zn2—Cl21	2.2743 (9)	N1B—C1B	1.339 (4)
Zn2—Cl22	2.2809 (9)	N1B—C5B	1.353 (4)
Zn2—Cl23	2.2885 (9)	N1B—H1NB	0.848 (10)
Zn3—Cl34	2.2485 (10)	N2B—C6B	1.330 (4)
Zn3—Cl31	2.2713 (9)	N2B—C10B	1.347 (4)
Zn3—Cl33	2.2854 (9)	N3B—C15B	1.342 (4)
Zn3—Cl32	2.2981 (9)	N3B—C11B	1.353 (4)
N1A—C1A	1.337 (4)	N3B—H3NB	0.845 (10)
N1A—C5A	1.352 (4)	N4B—C18B	1.327 (4)
N1A—H1NA	0.851 (10)	N4B—C17B	1.358 (4)
N2A—C6A	1.327 (4)	N4B—H4NB	0.847 (10)
N2A—C10A	1.344 (4)	C1B—C2B	1.366 (5)
N3A—C15A	1.337 (4)	C1B—H1B	0.9300
N3A—C11A	1.351 (4)	C2B—C3B	1.377 (5)
N3A—H3NA	0.850 (10)	C2B—H2B	0.9300
N4A—C18A	1.321 (4)	C3B—C4B	1.392 (5)
N4A—C17A	1.367 (4)	C3B—H3B	0.9300
N4A—H4NA	0.846 (10)	C4B—C5B	1.382 (4)
C1A—C2A	1.370 (5)	C4B—H4B	0.9300
C1A—H1A	0.9300	C5B—C6B	1.475 (4)
C2A—C3A	1.394 (5)	C6B—C7B	1.396 (4)
C2A—H2A	0.9300	C7B—C8B	1.391 (4)
C3A—C4A	1.385 (5)	C7B—H7B	0.9300
C3A—H3A	0.9300	C8B—C9B	1.389 (4)
C4A—C5A	1.378 (4)	C8B—C16B	1.485 (4)
C4A—H4A	0.9300	C9B—C10B	1.399 (4)
C5A—C6A	1.485 (4)	C9B—H9B	0.9300
C6A—C7A	1.391 (4)	C10B—C11B	1.479 (4)
C7A—C8A	1.386 (4)	C11B—C12B	1.373 (4)
C7A—H7A	0.9300	C12B—C13B	1.386 (5)
C8A—C9A	1.393 (4)	C12B—H12B	0.9300
C8A—C16A	1.493 (4)	C13B—C14B	1.380 (5)
C9A—C10A	1.393 (4)	C13B—H13B	0.9300
C9A—H9A	0.9300	C14B—C15B	1.370 (5)
C10A—C11A	1.475 (4)	C14B—H14B	0.9300
C11A—C12A	1.385 (5)	C15B—H15B	0.9300
C12A—C13A	1.393 (5)	C16B—C17B	1.369 (5)
C12A—H12A	0.9300	C16B—C24B	1.431 (4)
C13A—C14A	1.372 (5)	C17B—H17B	0.9300
C13A—H13A	0.9300	C18B—C19B	1.393 (5)
C14A—C15A	1.364 (5)	C18B—H18B	0.9300
C14A—H14A	0.9300	C19B—C20B	1.414 (4)
C15A—H15A	0.9300	C19B—C24B	1.427 (4)
C16A—C17A	1.353 (5)	C20B—C21B	1.362 (5)
C16A—C24A	1.430 (4)	C20B—H20B	0.9300
C17A—H17A	0.9300	C21B—C22B	1.402 (5)
C18A—C19A	1.399 (5)	C21B—H21B	0.9300
C18A—H18A	0.9300	C22B—C23B	1.371 (5)
C19A—C20A	1.410 (5)	C22B—H22B	0.9300
C19A—C24A	1.422 (4)	C23B—C24B	1.411 (4)
C20A—C21A	1.367 (5)	C23B—H23B	0.9300
C20A—H20A	0.9300	O1W—H1WA	0.891 (10)
C21A—C22A	1.408 (5)	O1W—H1WB	0.893 (10)

Cl14—Zn1—Cl11	111.40 (4)	C23A—C22A—H22A	119.4
Cl14—Zn1—Cl12	108.56 (4)	C21A—C22A—H22A	119.4
Cl11—Zn1—Cl12	113.15 (3)	C22A—C23A—C24A	120.5 (3)
Cl14—Zn1—Cl13	110.21 (4)	C22A—C23A—H23A	119.8
Cl11—Zn1—Cl13	108.22 (3)	C24A—C23A—H23A	119.8
Cl12—Zn1—Cl13	105.10 (3)	C23A—C24A—C19A	118.1 (3)
Cl24—Zn2—Cl21	107.85 (3)	C23A—C24A—C16A	124.3 (3)
Cl24—Zn2—Cl22	110.83 (3)	C19A—C24A—C16A	117.6 (3)
Cl21—Zn2—Cl22	112.43 (3)	C1B—N1B—C5B	123.4 (3)
Cl24—Zn2—Cl23	108.03 (3)	C1B—N1B—H1NB	118 (2)
Cl21—Zn2—Cl23	109.70 (3)	C5B—N1B—H1NB	119 (2)
Cl22—Zn2—Cl23	107.91 (3)	C6B—N2B—C10B	117.8 (3)
Cl34—Zn3—Cl31	108.35 (4)	C15B—N3B—C11B	123.2 (3)
Cl34—Zn3—Cl33	113.83 (4)	C15B—N3B—H3NB	118 (2)
Cl31—Zn3—Cl33	108.80 (4)	C11B—N3B—H3NB	119 (2)
Cl34—Zn3—Cl32	113.05 (4)	C18B—N4B—C17B	122.5 (3)
Cl31—Zn3—Cl32	110.43 (3)	C18B—N4B—H4NB	119 (2)
Cl33—Zn3—Cl32	102.23 (3)	C17B—N4B—H4NB	119 (2)
C1A—N1A—C5A	123.4 (3)	N1B—C1B—C2B	120.0 (3)
C1A—N1A—H1NA	116 (2)	N1B—C1B—H1B	120.0
C5A—N1A—H1NA	120 (2)	C2B—C1B—H1B	120.0
C6A—N2A—C10A	118.2 (3)	C1B—C2B—C3B	119.0 (3)
C15A—N3A—C11A	123.4 (3)	C1B—C2B—H2B	120.5
C15A—N3A—H3NA	117 (2)	C3B—C2B—H2B	120.5
C11A—N3A—H3NA	119 (2)	C2B—C3B—C4B	120.0 (3)
C18A—N4A—C17A	122.5 (3)	C2B—C3B—H3B	120.0
C18A—N4A—H4NA	115 (2)	C4B—C3B—H3B	120.0
C17A—N4A—H4NA	123 (2)	C5B—C4B—C3B	119.9 (3)
N1A—C1A—C2A	120.6 (3)	C5B—C4B—H4B	120.1
N1A—C1A—H1A	119.7	C3B—C4B—H4B	120.1
C2A—C1A—H1A	119.7	N1B—C5B—C4B	117.7 (3)
C1A—C2A—C3A	117.9 (3)	N1B—C5B—C6B	116.9 (3)
C1A—C2A—H2A	121.0	C4B—C5B—C6B	125.3 (3)
C3A—C2A—H2A	121.0	N2B—C6B—C7B	123.5 (3)
C4A—C3A—C2A	120.1 (3)	N2B—C6B—C5B	116.0 (3)
C4A—C3A—H3A	119.9	C7B—C6B—C5B	120.5 (3)
C2A—C3A—H3A	119.9	C8B—C7B—C6B	118.9 (3)
C5A—C4A—C3A	120.1 (3)	C8B—C7B—H7B	120.6
C5A—C4A—H4A	119.9	C6B—C7B—H7B	120.6
C3A—C4A—H4A	119.9	C9B—C8B—C7B	117.9 (3)
N1A—C5A—C4A	117.8 (3)	C9B—C8B—C16B	121.4 (3)
N1A—C5A—C6A	116.1 (3)	C7B—C8B—C16B	120.7 (3)
C4A—C5A—C6A	126.0 (3)	C8B—C9B—C10B	119.5 (3)
N2A—C6A—C7A	122.9 (3)	C8B—C9B—H9B	120.2
N2A—C6A—C5A	115.7 (3)	C10B—C9B—H9B	120.2
C7A—C6A—C5A	121.3 (3)	N2B—C10B—C9B	122.3 (3)
C8A—C7A—C6A	119.1 (3)	N2B—C10B—C11B	116.6 (3)
C8A—C7A—H7A	120.4	C9B—C10B—C11B	121.1 (3)
C6A—C7A—H7A	120.4	N3B—C11B—C12B	118.3 (3)
C7A—C8A—C9A	118.3 (3)	N3B—C11B—C10B	116.2 (3)
C7A—C8A—C16A	120.5 (3)	C12B—C11B—C10B	125.5 (3)
C9A—C8A—C16A	121.1 (3)	C11B—C12B—C13B	119.6 (3)
C8A—C9A—C10A	118.7 (3)	C11B—C12B—H12B	120.2
C8A—C9A—H9A	120.7	C13B—C12B—H12B	120.2
C10A—C9A—H9A	120.7	C14B—C13B—C12B	120.4 (3)
N2A—C10A—C9A	122.7 (3)	C14B—C13B—H13B	119.8
N2A—C10A—C11A	115.6 (3)	C12B—C13B—H13B	119.8
C9A—C10A—C11A	121.7 (3)	C15B—C14B—C13B	118.7 (3)
N3A—C11A—C12A	118.1 (3)	C15B—C14B—H14B	120.6
N3A—C11A—C10A	116.2 (3)	C13B—C14B—H14B	120.6
C12A—C11A—C10A	125.8 (3)	N3B—C15B—C14B	119.7 (3)
C11A—C12A—C13A	119.0 (3)	N3B—C15B—H15B	120.2
C11A—C12A—H12A	120.5	C14B—C15B—H15B	120.2
C13A—C12A—H12A	120.5	C17B—C16B—C24B	119.1 (3)
C14A—C13A—C12A	120.5 (3)	C17B—C16B—C8B	118.4 (3)
C14A—C13A—H13A	119.7	C24B—C16B—C8B	122.5 (3)
C12A—C13A—H13A	119.7	N4B—C17B—C16B	120.7 (3)
C15A—C14A—C13A	119.0 (3)	N4B—C17B—H17B	119.6
C15A—C14A—H14A	120.5	C16B—C17B—H17B	119.6
C13A—C14A—H14A	120.5	N4B—C18B—C19B	120.6 (3)
N3A—C15A—C14A	120.0 (3)	N4B—C18B—H18B	119.7
N3A—C15A—H15A	120.0	C19B—C18B—H18B	119.7
C14A—C15A—H15A	120.0	C18B—C19B—C20B	120.4 (3)
C17A—C16A—C24A	119.7 (3)	C18B—C19B—C24B	118.9 (3)
C17A—C16A—C8A	118.2 (3)	C20B—C19B—C24B	120.6 (3)
C24A—C16A—C8A	122.0 (3)	C21B—C20B—C19B	120.0 (3)
C16A—C17A—N4A	120.6 (3)	C21B—C20B—H20B	120.0
C16A—C17A—H17A	119.7	C19B—C20B—H20B	120.0
N4A—C17A—H17A	119.7	C20B—C21B—C22B	119.8 (3)
N4A—C18A—C19A	120.3 (3)	C20B—C21B—H21B	120.1
N4A—C18A—H18A	119.8	C22B—C21B—H21B	120.1
C19A—C18A—H18A	119.8	C23B—C22B—C21B	121.6 (3)
C18A—C19A—C20A	120.5 (3)	C23B—C22B—H22B	119.2
C18A—C19A—C24A	119.1 (3)	C21B—C22B—H22B	119.2
C20A—C19A—C24A	120.4 (3)	C22B—C23B—C24B	120.5 (3)
C21A—C20A—C19A	119.8 (3)	C22B—C23B—H23B	119.7
C21A—C20A—H20A	120.1	C24B—C23B—H23B	119.7
C19A—C20A—H20A	120.1	C23B—C24B—C19B	117.4 (3)
C20A—C21A—C22A	120.0 (3)	C23B—C24B—C16B	124.7 (3)
C20A—C21A—H21A	120.0	C19B—C24B—C16B	117.9 (3)
C22A—C21A—H21A	120.0	H1WA—O1W—H1WB	106 (2)
C23A—C22A—C21A	121.2 (3)

C5A—N1A—C1A—C2A	−0.7 (5)	C5B—N1B—C1B—C2B	1.6 (5)
N1A—C1A—C2A—C3A	−0.4 (5)	N1B—C1B—C2B—C3B	−1.6 (5)
C1A—C2A—C3A—C4A	1.3 (5)	C1B—C2B—C3B—C4B	0.5 (5)
C2A—C3A—C4A—C5A	−1.2 (5)	C2B—C3B—C4B—C5B	0.7 (5)
C1A—N1A—C5A—C4A	0.8 (5)	C1B—N1B—C5B—C4B	−0.4 (5)
C1A—N1A—C5A—C6A	178.6 (3)	C1B—N1B—C5B—C6B	179.9 (3)
C3A—C4A—C5A—N1A	0.1 (5)	C3B—C4B—C5B—N1B	−0.7 (5)
C3A—C4A—C5A—C6A	−177.4 (3)	C3B—C4B—C5B—C6B	179.0 (3)
C10A—N2A—C6A—C7A	0.8 (5)	C10B—N2B—C6B—C7B	0.5 (5)
C10A—N2A—C6A—C5A	−177.8 (3)	C10B—N2B—C6B—C5B	179.9 (3)
N1A—C5A—C6A—N2A	3.3 (4)	N1B—C5B—C6B—N2B	3.4 (4)
C4A—C5A—C6A—N2A	−179.1 (3)	C4B—C5B—C6B—N2B	−176.3 (3)
N1A—C5A—C6A—C7A	−175.3 (3)	N1B—C5B—C6B—C7B	−177.2 (3)
C4A—C5A—C6A—C7A	2.3 (5)	C4B—C5B—C6B—C7B	3.1 (5)
N2A—C6A—C7A—C8A	−0.5 (5)	N2B—C6B—C7B—C8B	2.7 (5)
C5A—C6A—C7A—C8A	178.0 (3)	C5B—C6B—C7B—C8B	−176.6 (3)
C6A—C7A—C8A—C9A	−0.1 (5)	C6B—C7B—C8B—C9B	−3.6 (5)
C6A—C7A—C8A—C16A	−177.0 (3)	C6B—C7B—C8B—C16B	177.4 (3)
C7A—C8A—C9A—C10A	0.4 (4)	C7B—C8B—C9B—C10B	1.5 (5)
C16A—C8A—C9A—C10A	177.3 (3)	C16B—C8B—C9B—C10B	−179.5 (3)
C6A—N2A—C10A—C9A	−0.5 (5)	C6B—N2B—C10B—C9B	−2.8 (5)
C6A—N2A—C10A—C11A	−179.5 (3)	C6B—N2B—C10B—C11B	−179.6 (3)
C8A—C9A—C10A—N2A	−0.1 (5)	C8B—C9B—C10B—N2B	1.8 (5)
C8A—C9A—C10A—C11A	178.9 (3)	C8B—C9B—C10B—C11B	178.5 (3)
C15A—N3A—C11A—C12A	0.3 (5)	C15B—N3B—C11B—C12B	−1.5 (5)
C15A—N3A—C11A—C10A	179.8 (3)	C15B—N3B—C11B—C10B	179.3 (3)
N2A—C10A—C11A—N3A	−6.5 (4)	N2B—C10B—C11B—N3B	4.3 (4)
C9A—C10A—C11A—N3A	174.5 (3)	C9B—C10B—C11B—N3B	−172.5 (3)
N2A—C10A—C11A—C12A	173.0 (3)	N2B—C10B—C11B—C12B	−174.8 (3)
C9A—C10A—C11A—C12A	−6.0 (5)	C9B—C10B—C11B—C12B	8.4 (5)
N3A—C11A—C12A—C13A	1.1 (5)	N3B—C11B—C12B—C13B	1.6 (5)
C10A—C11A—C12A—C13A	−178.3 (3)	C10B—C11B—C12B—C13B	−179.3 (3)
C11A—C12A—C13A—C14A	−1.1 (5)	C11B—C12B—C13B—C14B	−0.8 (5)
C12A—C13A—C14A—C15A	−0.3 (5)	C12B—C13B—C14B—C15B	−0.2 (5)
C11A—N3A—C15A—C14A	−1.8 (5)	C11B—N3B—C15B—C14B	0.5 (5)
C13A—C14A—C15A—N3A	1.8 (5)	C13B—C14B—C15B—N3B	0.4 (5)
C7A—C8A—C16A—C17A	130.7 (3)	C9B—C8B—C16B—C17B	−42.9 (4)
C9A—C8A—C16A—C17A	−46.1 (4)	C7B—C8B—C16B—C17B	136.1 (3)
C7A—C8A—C16A—C24A	−46.8 (4)	C9B—C8B—C16B—C24B	136.9 (3)
C9A—C8A—C16A—C24A	136.4 (3)	C7B—C8B—C16B—C24B	−44.1 (4)
C24A—C16A—C17A—N4A	1.1 (5)	C18B—N4B—C17B—C16B	2.9 (5)
C8A—C16A—C17A—N4A	−176.5 (3)	C24B—C16B—C17B—N4B	2.0 (5)
C18A—N4A—C17A—C16A	1.8 (5)	C8B—C16B—C17B—N4B	−178.2 (3)
C17A—N4A—C18A—C19A	−2.2 (5)	C17B—N4B—C18B—C19B	−4.2 (5)
N4A—C18A—C19A—C20A	179.9 (3)	N4B—C18B—C19B—C20B	−177.1 (3)
N4A—C18A—C19A—C24A	−0.2 (5)	N4B—C18B—C19B—C24B	0.6 (5)
C18A—C19A—C20A—C21A	178.7 (3)	C18B—C19B—C20B—C21B	177.2 (3)
C24A—C19A—C20A—C21A	−1.1 (5)	C24B—C19B—C20B—C21B	−0.4 (5)
C19A—C20A—C21A—C22A	−1.4 (5)	C19B—C20B—C21B—C22B	−1.1 (5)
C20A—C21A—C22A—C23A	1.3 (5)	C20B—C21B—C22B—C23B	0.6 (5)
C21A—C22A—C23A—C24A	1.4 (5)	C21B—C22B—C23B—C24B	1.4 (5)
C22A—C23A—C24A—C19A	−3.8 (5)	C22B—C23B—C24B—C19B	−2.8 (4)
C22A—C23A—C24A—C16A	177.2 (3)	C22B—C23B—C24B—C16B	177.8 (3)
C18A—C19A—C24A—C23A	−176.1 (3)	C18B—C19B—C24B—C23B	−175.3 (3)
C20A—C19A—C24A—C23A	3.7 (5)	C20B—C19B—C24B—C23B	2.3 (5)
C18A—C19A—C24A—C16A	2.9 (4)	C18B—C19B—C24B—C16B	4.1 (4)
C20A—C19A—C24A—C16A	−177.2 (3)	C20B—C19B—C24B—C16B	−178.3 (3)
C17A—C16A—C24A—C23A	175.7 (3)	C17B—C16B—C24B—C23B	174.0 (3)
C8A—C16A—C24A—C23A	−6.9 (5)	C8B—C16B—C24B—C23B	−5.8 (5)
C17A—C16A—C24A—C19A	−3.3 (4)	C17B—C16B—C24B—C19B	−5.4 (4)
C8A—C16A—C24A—C19A	174.1 (3)	C8B—C16B—C24B—C19B	174.8 (3)

Relevant dihedral angles (°) between pyridine rings in (II) top

<Cg–Cg>	(IIA)	(IIB)
<Cg2–Cg1>	4.6 (2)	3.1 (2)
<Cg2–Cg3>	6.6 (2)	6.6 (2)
<Cg2–Cg4>	46.7 (2)	42.2 (2)
<Cg2–Cg5>	47.7 (2)	44.7 (2)
<Cg4–Cg5>	2.5 (2)	1.6 (2)

Hydrogen-bond geometry in (II) top

Code	D—H···A	D—H	H···A	D···A	D—H···A	100r(r) (a.u.)	10Ñ²r(r) (a.u.)
#1	(N1A—H1NA)···O1W	0.85 (1)	1.95 (2)	2.769 (4)	161 (3)	2.59	0.66
#2	(N3A—H3NA)···O1W	0.85 (1)	1.95 (2)	2.753 (4)	158 (3)	2.64	1.08
#3	(C14A—H14A)ⁱ···Cl11	0.93	2.62	3.440 (4)	148	1.15	0.38
#4	(C2B—H2B)ⁱⁱ···Cl11	0.93	2.59	3.370 (4)	142	1.22	0.42
#5	(N1B—H1NB)ⁱⁱⁱ···Cl12	0.85 (1)	2.30 (2)	3.053 (3)	148 (3)	2.09	0.72
#6	(N3B—H3NB)ⁱⁱⁱ···Cl12	0.85 (1)	2.51 (2)	3.274 (3)	151 (3)	1.35	0.45
#7	(C1B—H1B)ⁱⁱⁱ···Cl13	0.93	2.79	3.342 (3)	119	0.83	0.24
#8	(C2B—H2B)ⁱⁱ···Cl13	0.93	2.90	3.564 (3)	130	0.80	0.22
#9	(O1W—H1WB)ⁱⁱ···Cl13	0.89 (1)	2.18 (1)	3.071 (3)	173 (3)	2.71	0.66
#10	(C1A—H1A)ⁱⁱ···Cl14	0.93	2.80	3.467 (3)	129	0.87	0.25
#11	(C15B—H15B)ⁱⁱⁱ···Cl14	0.93	2.94	3.518 (4)	121	0.89	0.24
#12	(C3B—H3B)···Cl21	0.93	2.93	3.756 (3)	150	0.90	0.25
#13	(C17B—H17B)^iv···Cl21	0.93	2.77	3.690 (3)	173	0.84	0.25
#14	(N4A—H4NA)^v···Cl22	0.85 (1)	2.64 (2)	3.358 (3)	143 (3)	0.98	0.35
#15	(C18A—H18A)^v···Cl22	0.93	3.00	3.536 (4)	118	0.64	0.22
#16	(N4B—H4NB)^iv···Cl22	0.85 (1)	2.69 (3)	3.273 (3)	127 (3)	0.96	0.34
#17	(C18A—H18A)^v···Cl23	0.93	2.63	3.503 (3)	156	1.08	0.35
#18	(C20A—H20A)^v···Cl23	0.93	2.95	3.737 (4)	144	0.94	0.30
#19	(C4B—H4B)···Cl23	0.93	2.65	3.559 (3)	167	1.05	0.40
#20	(C7B—H7B)···Cl23	0.93	2.69	3.620 (3)	175	0.97	0.35
#21	(C4B—H4B)···Cl24	0.93	2.96	3.382 (3)	110	0.82	0.27
#22	(C12B—H12B)^iv···Cl24	0.93	2.74	3.461 (3)	135	0.94	0.30
#23	(C2A—H2A)^vi···Cl31	0.93	2.88	3.636 (4)	140	0.83	0.24
#24	(C3A—H3A)^viii···Cl31	0.93	2.80	3.620 (4)	147	0.84	0.25
#25	(O1W—H1WA)^vii···Cl32	0.89 (1)	2.17 (1)	3.044 (2)	166 (3)	2.65	0.62
#26	(C4A—H4A)^viii···Cl32	0.93	2.90	3.808 (3)	165	0.83	0.25
#27	(C7A—H7A)^viii···Cl32	0.93	2.70	3.612 (3)	166	0.85	0.26
#28	(C18B—H18B)^iv···Cl32	0.93	2.88	3.757 (3)	158	0.66	0.19
#29	(N4A—H4NA)^v···Cl33	0.85 (1)	2.57 (3)	3.159 (3)	127 (3)	1.24	0.47
#30	(C17A—H17A)^v···Cl33	0.93	2.83	3.324 (3)	114	0.93	0.33
#31	(N4B—H4NB)^iv···Cl33	0.85 (1)	2.55 (3)	3.181 (3)	133 (3)	1.23	0.47
#32	(C18B—H18B)^iv···Cl33	0.93	2.75	3.292 (4)	118	1.02	0.37
#33	(C12A—H12A)^v···Cl34	0.93	2.62	3.526 (4)	165	0.59	0.17

To facilitate the packing description, these interactions have been described with the acceptor at the `reference site', the symmetry operations being applied to the X—H donor (X = O, N or C).

Symmetry codes on the donor groups: (i) -x+2, -y+1, -z+2; (ii) -x+1, -y+1, -z+2; (iii) x, y+1, z; (iv) x-1, y, z; (v) -x+1, -y+1, -z+1; (vi) x, y, z-1; (vii) x-1, y, z-1; (viii) -x, -y+1, -z+1.

π–π contacts in (II) top

Interaction code	Cg···Cg	ccd (Å)	da (°)	sa (°)	ipd (Å)	100r(r) (a.u.)	10Ñ²r(r) (a.u.)
#34	Cg1A···Cg2Aⁱⁱ	3.6718 (18)	4.28 (15)	24 (2)	3.35 (5)	0.58	0.17
#35	Cg4A···Cg5Aⁱ	3.8686 (19)	2.74 (15)	24.8 (15)	3.50 (4)	0.52	0.16
#36	Cg3A···Cg1B	3.7397 (19)	3.96 (15)	28 (1)	3.30 (3)	0.55	0.16

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

Ring Codes as in Fig. 1

Notes: ccd is the centre-to-centre distance; da is the dihedral angle between rings; sa is the slippage angle; ipd is the interplanar distance, or (mean) distance from one plane to the neighbouring centroid. For details, see Janiak (2000).

Anion···π (to Cg2 and Cg5) and anion···π⁺ (to Cg1 and Cg3) interactions in (II) top

Code	Zn—Cl···Cg	Cl···Cg (Å)	d (Å)	α (°)	β (°)	hⁿ	100r(r) (a.u.)	10Ñ²r(r) (a.u.)
#37	Zn1—Cl11···Cg3B^v	3.449	3.358	15.10	82.3	h⁴	0.93	0.29
#38	Zn1—Cl11···Cg1Aⁱⁱ	3.746	3.324	28.65	97.1	h³	0.95	0.31
#39	Zn2—Cl22···Cg3B^ix	3.741	3.739	11.01	79.8	h²	0.43	0.12
#40	Zn2—Cl23···Cg2A	3.764	3.292	33.82	98.9	h²	0.94	0.29
#41	Zn2—Cl23···Cg5B	3.843	3.461	27.01	95.3	h³	0.67	0.20
#42	Zn2—Cl24···Cg2B^ix	3.838	3.275	37.42	104.5	h²	0.97	0.28
#43	Zn3—Cl31···Cg3Aⁱ	3.776	3.427	32.24	94.4	h²	0.86	0.23
#44	Zn3—Cl32···Cg5A^iv	3.650	3.410	21.52	88.7	h³	0.83	0.22

Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+1, -z+2; (iv) -x, -y+1, -z+1; (v) -x+2, -y+1, -z+2; (ix) -x+1, -y, -z+1.

Notes: d is the Cl···X distance (Å), where X is the atom in the ring which lays nearest the Cl anion; α is the angle subtended by the Cl–Cg vector to the ring normal (°); β is the angle subtended by the X–Cg and X–Cl vectors (°). (β < 90° = the anion projects within the ring; 90° < β = anion projects outside the ring; and n (in hⁿ) is the number of interacting atoms

Nota Bene: according to standard requirements for anion···p interactions (Gamez, 2014; Giese et al., 2015; Bauza et al., 2016), β should be < 100°. However, see interaction #42, ranked by AIM as the strongest among the anion···p interactions.

Hirshfeld contact surfaces and enrichment ratios (ERs) for (ITPH₃)₂[ZnCl₄]₃·H₂O, computed around the two (ITPH₃)³⁺ cations (A and B), the three [ZnCl₄]^2- anions and the water molecule.
The second column corresponds to `interior' atoms. top

	C	N	O	Cl	Zn	H_C	H_N	H_OH
Actual contacts (merged) (%)
C	10.01
N	2.94	0.00
O	0.16	0.02	0.00
Cl	18.62	1.44	0.00	2.02
Zn	1.54	0.00	0.00	0.31	0.00
H_C	7.74	0.62	0.25	34.66	4.49	2.40
H_N	0.92	0.00	1.62	5.03	0.15	0.76	0.00
H_OH	0.35	0.00	0.00	2.86	0.20	0.67	0.21	0.00

Surface interior (%)	27.32	2.71	0.99	32.20	3.19	27.18	4.30	2.10
Surface exterior (%)	24.98	2.30	1.05	34.76	3.51	26.81	4.38	2.20

Enrichment ratios (merged)
C	1.47
N	2.25	0.00
O	0.30	0.45	0.00
Cl	1.06	0.85	0.00	0.18
Zn	0.88	0.00	0.00	0.14	0.00
H_C	0.55	0.46	0.45	1.92	2.48	0.33
H_N	0.41	0.00	18.19	1.73	0.50	0.32	0.00
H_OH	0.31	0.00	0.00	1.99	1.42	0.58	1.14	0.00

Hirshfeld contact surfaces and enrichment ratios for ITP.
The second column corresponds to `interior' atoms. top

	C	N	H_C
Actual contacts (merged) (%)
C	21.45
N	7.05	0.25
H_C	35.69	10.40	25.16

Surface interior (%)	44.42	9.11	46.47
Surface exterior (%)	41.22	8.84	49.94

Enrichment ratios (merged)
C	1.17
N	0.92	0.31
H_C	0.86	1.20	1.08

Hirshfeld contact surfaces (%) for the [ZnCl₄]^2-···X contacts top

	C	N	O	Cl	Zn	H_C	H_N	H_OH
Zn1 interior surface	0.00	0.00	0.00	90.99	9.01	0.00	0.00	0.00
Zn1 exterior surface	20.61	3.11	0.00	8.13	1.37	51.37	9.80	5.61
Zn2 interior surface	0.00	0.00	0.00	91.34	8.66	0.00	0.00	0.00
Zn2 exterior surface	37.11	0.79	0.00	4.81	0.00	51.61	5.68	0.00
Zn3 interior surface	0.00	0.00	0.00	89.97	10.03	0.00	0.00	0.00
Zn3 exterior surface	22.90	1.14	0.00	6.93	0.00	55.46	6.32	7.26

Hirshfeld contact surfaces (%) for Cl···X contacts involving each of the 12 independent Cl^- anions. top

	C	N	O	Cl	Zn	H_C	H_N	H_OH
Cl11	24.89	6.97	0.00	2.77	27.77	36.10	1.50	0.00
Cl12	8.67	0.37	0.00	0.00	31.15	37.13	22.69	0.00
Cl13	23.29	0.01	0.00	0.37	25.10	32.97	0.00	18.26
Cl14	13.18	3.25	0.00	8.92	27.65	42.52	4.48	0.00
Cl21	21.00	0.00	0.00	8.42	25.32	45.26	0.00	0.00
Cl22	26.63	2.52	0.00	7.21	30.31	13.41	19.90	0.00
Cl23	28.99	0.00	0.00	0.40	26.04	44.57	0.00	0.00
Cl24	33.14	0.00	0.00	0.00	29.17	37.69	0.00	0.00
Cl31	22.20	3.64	0.00	0.00	32.27	38.72	1.86	1.30
Cl32	15.09	0.00	0.00	0.13	28.09	38.87	0.00	17.81
Cl33	13.80	0.00	0.00	13.48	33.78	18.94	20.00	0.00
Cl34	14.09	0.40	0.00	6.50	31.91	47.11	0.00	0.00

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