The role of π–π stacking and hydrogen-bonding inter­actions in the assembly of a series of isostructural group IIB coordination compounds

Hajiashrafi, T.; Zekriazadeh, R.; Flanagan, K.J.; Kia, F.; Bauzá, A.; Frontera, A.; Senge, M.O.

doi:10.1107/S2053229618018314

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 75| Part 2| February 2019| Pages 178-188

https://doi.org/10.1107/S2053229618018314

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The role of π–π stacking and hydrogen-bonding interactions in the assembly of a series of isostructural group IIB coordination compounds

Taraneh Hajiashrafi,^a ^* Roghayeh Zekriazadeh,^a Keith J. Flanagan,^b Farnoush Kia,^a Antonio Bauzá,^c Antonio Frontera ^c and Mathias O. Senge ^b ^*

^aDepartment of Chemistry, Faculty of Physics and Chemistry, Alzahra University, PO Box 1993891176, Tehran, Iran, ^bSchool of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Science Institute, Trinity College Dublin, The University of Dublin, 152–160 Pearse Street, Dublin 2, Ireland, and ^cDepartment of Chemistry, University of the Balearic Islands, Carretera de Valldemossa km 7.5, 07122 Palma de Mallorca, Illes Balears, Spain
^*Correspondence e-mail: t.hajiashrafi@alzahra.ac.ir, sengem@tcd.ie

Edited by A. L. Spek, Utrecht University, The Netherlands (Received 23 August 2018; accepted 24 December 2018; online 25 January 2019)

The supramolecular chemistry of coordination compounds has become an important research domain of modern inorganic chemistry. Herein, six isostructural group IIB coordination compounds containing a 2-{[(2-methoxyphenyl)imino]methyl}phenol ligand, namely dichloridobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)zinc(II), [ZnCl₂(C₂₈H₂₆N₂O₄)], 1, diiodidobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)zinc(II), [ZnI₂(C₂₈H₂₆N₂O₄)], 2, dibromidobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)cadmium(II), [CdBr₂(C₂₈H₂₆N₂O₄)], 3, diiodidobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)cadmium(II), [CdI₂(C₂₈H₂₆N₂O₄)], 4, dichloridobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)mercury(II), [HgCl₂(C₂₈H₂₆N₂O₄)], 5, and diiodidobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)mercury(II), [HgI₂(C₂₈H₂₆N₂O₄)], 6, were synthesized and characterized by X-ray crystallography and spectroscopic techniques. All six compounds exhibit an infinite one-dimensional ladder in the solid state governed by the formation of hydrogen-bonding and π–π stacking interactions. The crystal structures of these compounds were studied using geometrical and Hirshfeld surface analyses. They have also been studied using M06-2X/def2-TZVP calculations and Bader's theory of `atoms in molecules'. The energies associated with the interactions, including the contribution of the different forces, have been evaluated. In general, the π–π stacking interactions are stronger than those reported for conventional π–π complexes, which is attributed to the influence of the metal coordination, which is stronger for Zn than either Cd or Hg. The results reported herein might be useful for understanding the solid-state architecture of metal-containing materials that contain M^IIX₂ subunits and aromatic organic ligands.

Keywords: π-stacking; hydrogen bonding; noncolvalent interactions; metallosupramolecular assembly; crystal structure; coordination compound; group IIB.

CCDC references: 1861558; 1861557; 1861556; 1861555; 1861554; 1861553

1. Introduction

Over the last two decades, the supramolecular chemistry of metal-containing compounds has attracted intense attention, due not only to their fascinating structures (Holliday & Mirkin, 2001 ; Brammer, 2004 ), but also their potential applications in diverse fields such as medicine (McKinlay et al., 2010 ; Reedijk, 2009 ), ion and molecular recognition (Custelcean et al., 2012 ; Busschaert et al., 2015 ) and catalysis (Wang et al., 2013 ; Wiester et al., 2011 ).

The ultimate goal of supramolecular chemistry is to understand the inherent complexities of the association mechanisms of molecular and ionic building blocks organized through noncovalent intermolecular interactions with prescribed properties and functions (Lehn, 1995 ; Steed & Atwood, 2013 ). In the context of metallosupramolecular chemistry (Braga & Grepioni, 2000 ; Braga et al., 1998 ), hydrogen bonding (Reedijk, 2013 ; Azhdari Tehrani et al., 2016 ) and halogen bonding (Khavasi et al., 2015 ; Khavasi & Azhdari Tehrani, 2013 ; Li et al., 2016 ) have been widely used so far to drive the self-assembly of coordination compounds, because of their directionality and versatility (Politzer et al., 2010 ; Desiraju, 1998 ). However, there are some reports that provide evidence suggesting the crucial role of nondirectional intermolecular interactions, such as π–π stacking (Khavasi & Azizpoor Fard, 2010 ; Janiak, 2000 ; Khavasi & Sadegh, 2014 ; Semeniuc et al., 2010 ), for designing the supramolecular architecture of metal-containing species in the solid state. In this regard, supramolecular chemists and crystal engineers have explored and studied the use of noncovalent interactions as a key tool for constructing supramolecular architectures of metal-containing building units in the solid state in which X-ray crystallography could provide a detailed picture of the supramolecular structure (Desiraju, 2014 ; Blake et al., 1999 ; Đaković et al., 2018 ). These studies reveal an undeniable contribution of such noncovalent interactions to the organization and stabilization of the ultimate crystal structures. These studies also revealed that the ultimate supramolecular architecture of self-assembled metal-containing compounds could be affected by various factors, such as ligand and metal geometries (Khavasi et al., 2012 ; Hajiashrafi et al., 2013 ), counter-ions (Schottel et al., 2006 ; Zeng et al., 2010 ) and reaction conditions (Khavasi & Mohammad Sadegh, 2010 ; Mahata et al., 2009 ).

In continuation of our research aimed at understanding the role of noncovalent interactions in the fabrication and self-assembly of metal-containing building blocks (Hajiashrafi et al., 2013, 2016 ; Kielmann & Senge, 2018 ), a series of coordination compounds, namely [ZnL₂Cl₂] (1), [ZnL₂I₂] (2), [CdL₂Br₂] (3), [CdL₂I₂] (4), [HgL₂Cl₂] (5) and [HgL₂I₂] (6), where L is 2-{[(2-methoxyphenyl)azaniumylidene]methyl}phenolate, have been synthesized and characterized using X-ray crystallography and different spectroscopic techniques (see Scheme 1). Geometrical, Hirshfeld surface analysis and theoretical calculations reveal the importance of π–π stacking interactions, as well as hydrogen bonding, in governing the crystal packing of this series of isostructural metal-containing compounds.

2. Experimental

2.1. Materials and apparatus

Chemicals and reagents were purchased from commercial sources. 2-Hydroxybenzaldehyde, 2-methoxyaniline and anhydrous M^II halides, where M is Zn, Cd and Hg, were purchased from Sigma–Aldrich and Merck, and used as received. The Schiff base ligand 2-{[(2-methoxyphenyl)imino]methyl}phenol (L) was prepared according to a previously reported method (Song et al., 2013 ). The IR spectra were recorded on a Nicolet FT–IR 100 spectrometer in the range 500–4000 cm⁻¹ using the KBr disk technique. Elemental analyses (C, H and N) were performed using an ECS 4010 CHN-O made in Costech, Italy. Melting points were measured by an Electrothermal 9100 melting-point apparatus and corrected. The measurements were carried out using 10 mg of a powdered sample sealed in aluminium pans with a mechanical crimp.

2.2. Computational methods

The geometries of the complexes included in this study were computed at the M06-2X/def2-TZVP level of theory using the crystallographic coordinates within TURBOMOLE 7.0 (Ahlrichs et al., 1989 ). We have used the crystallographic coordinates instead of the optimized complexes because we are interested in estimating the binding energies of several assemblies as they stand in the crystal structure, instead of investigating the most favourable geometry for a given complex. The interaction energies were calculated with correction for the basis set superposition error (BSSE) by using the Boys–Bernardi counterpoise technique (Boys & Bernardi, 1970 ). The `atoms-in-molecules' (AIM) analysis of the electron density was performed at the same level of theory using the AIMAll program (Keith, 2013 ).

2.3. Synthesis and crystallization

The ligand 2-{[(2-methoxyphenyl)imino]methyl}phenol (L) was utilized previously for the preparation of a number of coordination compounds (Song et al., 2013; Gong et al., 2014 ; Reddy et al., 2003a ,b ; Li & Yuan, 2012 ). L was synthesized by reacting 2-hydroxybenzaldehyde (0.53 ml, 5 mmol) with 2-methoxyaniline (0.56 ml, 5 mmol) in ethanol. After stirring for 30 min at 323 K, the ligand precipitated from the reaction mixture as an orange powder which was filtered off, washed several times with cold ethanol and normal hexane, and then dried under vacuum.

The six coordination compounds [ZnL₂Cl₂] (1), [ZnL₂I₂] (2), [CdL₂Br₂] (3), [CdL₂I₂] (4), [HgL₂Cl₂] (5) and [HgL₂I₂] (6) were synthesized by combining a solution of MX₂ (0.1 mmol; M = Zn, Cd or Hg and X = Cl, Br or I) in methanol (5 ml) and a solution of L (0.2 mmol) in methanol (5 ml) with stirring. Each mixture was heated at 333 K for about 30 min. Reduction of the solvent volume resulted in the formation of a yellow-to-orange precipitate. The precipitate was filtered off, washed with methanol (3 × 2 ml) and then dried in vacuo. The solid was subsequently dissolved in boiling methanol, ethanol or acetonitrile (10 ml) and filtered. Upon slow evaporation of the filtrate at room temperature, crystals of complexes 1–6 suitable for X-ray crystallography were obtained (Hope, 1994 ; Senge, 2000 ). The coordination compounds were characterized using X-ray crystallography, FT–IR spectroscopy and elemental analysis.

2.3.1. Analytical data for L

M.p. 330 K. FT–IR (KBr, ν/cm⁻¹, selected bands): 3445 (w, broad), 1246 (s), 3061 (w), 1615 (s), 792 (s), 849 (m).

2.3.2. Analytical data for 1

Yield 52%. M.p. 505–507 K. FT–IR (KBr, ν/cm⁻¹, selected bands): 3679 (w), 3447 (w), 1637 (s), 1525 (m), 1382 (s), 1025 (m), 800 (m), 750 (m). Analysis calculated for C₂₈H₂₆Cl₂N₂O₄Zn (%): C 56.92, H 4.44, N 4.74; found: C 56.86, H 4.42, N 4.70.

2.3.3. Analytical data for 2

Yield 70%. M.p. 520–522 K. FT–IR (KBr, ν/cm⁻¹, selected bands): 3676 (w), 3447 (w), 1614 (s), 1542 (m), 1385 (s), 1019 (m), 805 (m), 754 (m). Analysis calculated for C₂₈H₂₆I₂N₂O₄Zn (%): C 43.47, H 3.39, N 3.62; found: C 43.36, H 3.42, N 3.58.

2.3.4. Analytical data for 3

Yield 54%. M.p. 543–545 K. FT–IR (KBr, ν/cm⁻¹, selected bands): 3674 (w), 3445 (m), 1620 (s), 1530 (m), 1484 (m), 1383 (s), 1020 (m), 794 (m), 753 (m). Analysis calculated for C₂₈H₂₆Br₂CdN₂O₄ (%): C 46.28, H 3.61, N 3.85; found: C 46.24, H 3.40, N 3.82.

2.3.5. Analytical data for 4

Yield 46%. M.p. 461–463 K. FT–IR (KBr, ν/cm⁻¹, selected bands): 3679 (w), 3447 (m), 1637 (s), 1520 (m), 1380 (m), 1025 (m), 796 (m), 741 (m). Analysis calculated for C₂₈H₂₆CdI₂N₂O₄ (%): C 40.98, H 3.19, N 3.41; found: C 40.88, H 3.12, N 3.44.

2.3.6. Analytical data for 5

Yield 65%. M.p. 438–440 K. FT–IR (KBr, ν/cm⁻¹, selected bands): 3675 (w), 3435 (m), 1622 (s), 1534 (m), 1378 (m), 1028 (m), 794 (m), 750 (m). Analysis calculated for C₂₈H₂₆Cl₂HgN₂O₄ (%): C 46.32, H 3.61, N 3.86; found: C 46.28, H 3.62, N 3.92.

2.3.7. Analytical data for 6

Yield 70%. M.p. 383–385 K. FT–IR (KBr, ν/cm⁻¹, selected bands): 3675 (w), 3446 (m), 1630 (s), 1523 (m), 1382 (m), 1018 (m), 796 (m), 738 (w). Analysis calculated for C₂₈H₂₆HgI₂N₂O₄ (%): C 37.00, H 2.88, N 3.08; found: C 36.94, H 2.80, N 3.10.

2.4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C- and N-bound H atoms were placed in their expected calculated positions and refined as riding, with N—H = 0.88 Å and C—H = 0.95–0.99 Å, and with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(N,C) otherwise. In the structure of 2, the C and N atoms were restrained to have similar isotropic displacement parameters. Atoms N1A, N1B and C14B were restrained to have close to isotropic displacement parameters. The structure was solved as a rotational twin rotated from the first domain by 179.8° about the reciprocal axis 0.002 1.000 0.001 and the real axis 0.434 1.000 0.197. The twin law to convert hkl from the first to this domain (SHELXL TWIN matrix) was −0.999 0.004 −0.001, 0.866 0.998 0.395, 0.007 0.003 −0.999. The structure of 3 was solved as a rotational twin rotated from the first domain by 179.7° about the reciprocal axis −0.003 −0.997 1.000 and the real axis 0.311 1.000 −0.257. The twin law to convert hkl from the first to this domain (SHELXL TWIN matrix) was −1.001 0.001 −0.004, 0.498 0.590 −0.407, −0.487 −1.593 −0.589. The structure of 5 was solved as a rotational twin rotated from the first domain by 179.9° about the reciprocal axis −0.001 1.000 −0.999 and the real axis 0.345 1.000 −0.274. The twin law to convert hkl from the first to this domain (SHELXL TWIN matrix) was −1.000 −0.001 0.001, 0.541 0.570 −0.431, −0.543 −1.570 −0.570. The structure of 6 was solved as a rotational twin rotated from the first domain by 149.8° about the reciprocal axis 1.000 0.235 0.787 and the real axis 1.000 0.533 0.319. The twin law to convert hkl from the first to this domain (SHELXL TWIN matrix) was 0.534 0.949 0.308, 0.116 −0.693 0.359, 1.269 −0.145 −0.569.

Table 1
Experimental details

	1	2	3
Crystal data
Chemical formula	[ZnCl₂(C₂₈H₂₆N₂O₄)]	[ZnI₂(C₂₈H₂₆N₂O₄)]	[CdBr₂(C₂₈H₂₆N₂O₄)]
M_r	590.78	773.68	726.73
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	100	100	100
a, b, c (Å)	9.1926 (2), 10.6101 (2), 14.8057 (3)	9.2709 (19), 10.020 (2), 16.248 (4)	9.2772 (3), 10.0935 (3), 16.1021 (5)
α, β, γ (°)	94.188 (1), 97.716 (1), 114.409 (1)	98.56 (4), 100.50 (4), 110.09 (3)	97.699 (2), 100.586 (2), 111.149 (2)
V (Å³)	1289.80 (5)	1356.7 (6)	1348.92 (8)
Z	2	2	2
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	1.20	3.22	3.81
Crystal size (mm)	0.26 × 0.12 × 0.11	0.14 × 0.07 × 0.03	0.27 × 0.13 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII area detector	Bruker APEXII area detector	Bruker APEXII area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )	Multi-scan (TWINABS; Bruker, 2012 )	Multi-scan (TWINABS; Bruker, 2012)
T_min, T_max	0.691, 0.747	0.612, 0.746	0.538, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	93163, 11965, 9331	7281, 7281, 4608	10130, 10130, 8342
R_int	0.053	0.116	0.020
(sin θ/λ)_max (Å⁻¹)	0.822	0.606	0.634

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.084, 1.02	0.067, 0.195, 0.99	0.040, 0.126, 1.03
No. of reflections	11965	7281	10130
No. of parameters	336	337	337
No. of restraints	0	174	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.77, −0.71	2.19, −1.18	1.04, −0.70

	4	5	6
Crystal data
Chemical formula	[CdI₂(C₂₈H₂₆N₂O₄)]	[HgCl₂(C₂₈H₂₆N₂O₄)]	[HgI₂(C₂₈H₂₆N₂O₄)]
M_r	820.71	726.00	908.90
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	100	100	100
a, b, c (Å)	9.3200 (3), 10.0498 (3), 16.6239 (5)	9.2456 (4), 10.1510 (4), 15.8499 (6)	9.2783 (14), 10.0060 (15), 16.695 (3)
α, β, γ (°)	99.140 (1), 100.528 (1), 109.332 (1)	96.5447 (15), 99.7441 (15), 112.6735 (14)	98.777 (1), 100.296 (1), 109.396 (1)
V (Å³)	1403.58 (8)	1326.25 (9)	1400.4 (4)
Z	2	2	2
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	3.01	6.04	7.74
Crystal size (mm)	0.40 × 0.26 × 0.14	0.17 × 0.14 × 0.08	0.38 × 0.19 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII area detector	Bruker APEXII area detector	Bruker APEXII area detector
Absorption correction	Numerical (SADABS; Bruker, 2016)	Multi-scan (TWINABS; Bruker, 2012)	Multi-scan (TWINABS; Bruker, 2012)
T_min, T_max	0.416, 0.667	0.630, 0.746	0.441, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	110757, 13807, 10917	22779, 22779, 21098	11185, 11185, 10132
R_int	0.055	0.012	0.071
(sin θ/λ)_max (Å⁻¹)	0.838	0.668	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.067, 1.03	0.022, 0.052, 1.03	0.032, 0.112, 1.08
No. of reflections	13807	22779	11185
No. of parameters	336	337	337
No. of restraints	0	0	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.04, −1.33	1.29, −0.60	1.48, −1.78
Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2015 ), SHELXT (Sheldrick, 2015b ), SHELXL2014 (Sheldrick, 2015a ) and OLEX2 (Dolomanov et al., 2009 ).

3. Results and discussion

3.1. Crystal structure analysis

X-ray crystallography revealed that compounds 1–6 are isostructural and crystallize in the triclinic space group P $[\overline{1}]$ (Fig. 1 and Table 1). The asymmetric units of these structures contain two L ligands, two halide ions and a metal ion of group IIB. Crystal structure analysis reveals that in compounds 1–6, the M^II ion is in a distorted trigonal pyramidal geometry, with four-coordinate geometry indices, τ₄ (Yang et al., 2007 ), of 0.83, 0.85, 0.83, 0.84, 0.75, and 0.77, respectively. Selected bond lengths and angles are listed in Table 2 and are in agreement with the values reported for similar compounds (Shkol'nikova et al., 1970 ; Gong et al., 2014). The trigonal pyramidal geometry around M^II is made up of two halide ions and two phenolate O atoms from two different L ligands. It should be noted that N-salicylideneanilines may exist in different tautomeric forms and the tautomeric isomerization reaction between the enol and keto forms is accompanied by intra- and intermolecular proton transfer (Dürr & Bouas-Laurent, 2003 ; Cohen & Schmidt, 1962 ; Cohen et al., 1964 ; Tsuchimoto et al., 2016 ). The Schiff base ligand L shows a self-isomerization induced by an intramolecular proton transfer from the hydroxy O to the imine N atom through an O—H⋯N hydrogen bond (Hoshino et al., 1988 ; Alarcón et al., 1999 ). Thus, the ligand is a zwitterion with the negative and positive charges located at atoms O1B and N1B, respectively (Charland et al., 1989 ; Redshaw et al., 2013 ; Tsuchimoto et al., 2016; Kargili et al., 2014 ). This is supported by the geometry of the ligand and the unambiguous location of the H atom attached to atom N1B. The ligand almost keeps it coplanarity upon coordination; the dihedral angles between the planes of the two aromatic rings of ligand L lie in the range 4.10–10.68° for compounds 1–6 (see supporting information), which is a consequence of intramolecular N—H⋯O hydrogen bonding. In this form, L can act as a monodentate ligand, where it is coordinated to the metal ion via the phenolate O atom. It should be noted that at basic pH, the L ligand may act as a tridentate ligand through the imine N, phenolate O and methoxy O atoms (Gong et al., 2014; Song et al., 2013; Reddy et al., 2003a).

Table 2
Selected bond lengths (Å) and angles (°) for compounds 1–6

Compound		1	2	3	4	5	6
Bond lengths	M1—X1	2.240 (4)	2.588 (3)	2.537 (1)	2.720 (1)	2.371 (1)	2.658 (1)
	M1—X2	2.243 (4)	2.568 (3)	2.545 (1)	2.710 (1)	2.369 (1)	2.654 (1)
	M1—O2A	1.985 (1)	1.990 (10)	2.216 (4)	2.231 (2)	2.259 (2)	2.387 (5)
	M1—O2B	1.983 (1)	1.990 (10)	2.225 (4)	2.216 (2)	2.356 (2)	2.378 (5)
Bond angles	X1—M1—X2	124.8 (2)	123.7 (1)	130.0 (1)	130.1 (1)	148.2 (1)	145.1 (1)
	O1A—M1—X1	103.9 (3)	104.0 (4)	104.4 (1)	103.7 (1)	98.3 (1)	102.0 (1)
	O1A—M1—X2	104.0 (3)	103.6 (4)	103.6 (1)	104.8 (1)	100.4 (1)	98.7 (1)
	O1B—M1—X1	105.5 (3)	106.2 (4)	104.8 (1)	102.9 (1)	98.8 (1)	98.6 (1)
	O1B—M1—X2	102.8 (3)	104.2 (4)	101.9 (1)	103.5 (1)	100.7 (1)	102.3 (1)
	O1A—M1—O1B	116.8 (4)	115.8 (5)	112.0 (2)	111.6 (1)	105.6 (1)	105.8 (2)

Figure 1
(a)–(f) The molecular structures of compounds 1–6, respectively, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

As shown in Fig. 2, the crystal packing of compounds 1–6 consists of mononuclear units which are connected in the crystallographic a direction through a combination of π–π stacking interactions involving the C=N group of the ligand and C—H⋯π interactions. These units are then linked to other units via C—H⋯X (X = Cl, Br and I) hydrogen-bonding interactions in the bc plane. The intermolecular contacts involved in the crystal packing of compounds 1–6 can be quantified via Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ; Mackenzie et al., 2017 ). The analysis shows that in compounds 1–6, the H⋯H interactions have the highest priority (the highest contribution to the Hirshfeld surface) and the C—H⋯π, M—X⋯H and π–π interactions have the next highest priorities, respectively. Also, it has been found that the probability of hydrogen-bonding M—X⋯H interactions involving metal-bound halogen increases for a given metal on going from a lighter to a heavier halogen atom. Selected contribution percentages are shown as a histogram in Fig. 3.

Figure 2
Representation of the self-assembly of compounds 1–6, showing the association of discrete units through π–π stacking interactions in the crystallographic a direction and C—H⋯X (X = Cl, Br and I) hydrogen bonding in the bc plane.

Figure 3
Relative contributions of the various noncovalent contacts to the Hirshfeld surface area in complexes 1–6.

3.2. Theoretical study

Six ML₂X₂ (M = Zn, Cd or Hg and X = Cl, Br or I) complexes have been synthesized and characterized by X-ray diffraction analysis (see Fig. 1). The ligand is monocoordinated to the metal centre and presents an extended π-system that comprises two phenyl rings and an imino group that connects both aromatic moieties.

The solid-state architecture of all six structures is governed by the formation of π-stacking interactions between the aromatic ligands. In particular, each ligand forms infinite one-dimensional (1D) ladders in the crystal packing, as detailed for compounds 1, 3 and 5 in Fig. 4 as representative systems.

Figure 4
Partial view of the X-ray crystal structures in compounds (a) 1 (Zn), (b) 3 (Cd) and (c) 5 (Hg).

We have focused the theoretical study on a comparison of the energetic features shown by the π-stacking and hydrogen-bonding interactions (depending on the type of metal) observed in the crystal packing of compounds 1–6 described above. In particular, we have analyzed the π–π and C—H⋯X noncovalent interactions that are crucial to understanding their solid-state architectures. First of all, in order to study the donor–acceptor ability of the ML₂X₂ complexes, we have computed the molecular electrostatic potential (MEP) surface of a model system (compound 1), which is shown in Fig. 5. As expected, the most negative electrostatic potential corresponds to the region of the Cl ligands (−75 kcal mol⁻¹). The MEP surface also reveals that the N—H group is totally inaccessible since it is involved in an intramolecular hydrogen bond with the O atom of the ligand. Consequently, the most positive part is located in the region of the exocyclic C—H group at the molecular plane, also influenced by the aromatic C—H groups (40 kcal mol⁻¹). Therefore, hydrogen-bonding interactions between these groups (C—H⋯X) should be electrostatically favoured. Furthermore, perpendicular to the molecular plane, we found that each aromatic ring presents negative MEP values (−17 and −8 kcal mol⁻¹); therefore, face-to-face π–π stacking interactions are not electrostatically favoured (electrostatic repulsion). Remarkably, the electrostatic potential over the π-system of the linker (C=N) is positive, thus explaining the large displacement observed in the antiparallel π-stacking interactions highlighted in Fig. 4 and further discussed below.

Figure 5
MEP surface of compound 1. The MEP values at selected points are given in kcal mol⁻¹.

In isostructural Zn compounds 1–3, we have computed the interaction energies of the self-assembled π-stacked dimers (shown in Fig. 6a) that are responsible for the formation of the 1D ladders shown in Fig. 3. The self-assembled dimers are stabilized by a combination of hydrogen bonds and π–π stacking interactions involving the C=N group of the ligand. The dimerization energies in 1 and 2 (ΔE1 = −33.0 kcal mol⁻¹ and ΔE2 = −31.4 kcal mol⁻¹, respectively) are very large due to the contribution of both hydrogen-bonding (red dashed lines in Fig. 6) and π–π interactions (blue dashed lines in Fig. 6), where the former involves the most positive (C—H groups, see Fig. 5) and the most negative (belts of the halide ligands) potential regions of the metal compound. In an effort to calculate the contribution of the different forces that govern the formation of the self-assembled dimers, we have computed additional theoretical models where the halide ligands that establish the hydrogen bonds have been replaced by hydride ligands (see Fig. 6b) and consequently the hydrogen-bonding interactions between the halide ligands and the C—H groups are not formed. As a result, the interaction energies are reduced to ΔE3 = −24.8 kcal mol⁻¹ and ΔE4 = −22.5 kcal mol⁻¹ in 1 and 2, respectively. Therefore, the contribution of both symmetrically equivalent hydrogen-bonding interactions can be roughly estimated by the difference (they are −8.2 and 8.9 kcal mol⁻¹ for 1 and 2, respectively) and it is similar in both compounds. Furthermore, we have used additional dimers where the ZnCl₂ group in 1 or the ZnI₂ group in 2 has been removed (see Fig. 6c) in order to evaluate the influence of the metal coordination on the interaction energy. The resulting interaction energies are almost identical for both complexes (ΔE5 = −14.0 kcal mol⁻¹ and ΔE6 = −14.1 kcal mol⁻¹ for 1 and 2, respectively) and reveal the strong influence of the metal coordination on the π–π stacking interaction. This is likely due to the stronger dipole–dipole interaction in the antiparallel arrangement of the assembly. It is also worthy to mention that the π–π interaction energy computed for these compounds is large compared to other π-stacking interactions (i.e. benzene dimer). This is due to the special arrangement of the two π-systems where the C=N bond is located over the aromatic ring (see the on-top representation in Fig. 6). This fact is in very good agreement with the MEP surface represented in Fig. 5 and explains the large interaction energy since two electrostatically enhanced π(CN)⋯π interactions are established.

Figure 6
(a) Interaction energies of the self-assembled π-stacked dimers observed in the solid state of compounds 1 and 2. (b)/(c) Interaction energies in several theoretical models of 1 and 2. (d) On-top representation of the π-stacking interaction. All distances are in Å.

In Cd compounds 3 and 4, the π-stacking binding mode is very similar to that described before for 1 and 2. As mentioned above, hydrogen-bonding and π–π interactions control the dimer formation (see Fig. 7a). The computed interaction energies of the self-assembled dimers are almost identical (ΔE7 = −30.9 kcal mol⁻¹ and ΔE8 = −29.9 kcal mol⁻¹ for 3 and 4, respectively), indicating that the halide (Br or I) has a minimal influence on the binding energy. Compared to 1 and 2, the interaction energies are less favourable, thus revealing a larger influence of the Zn ion on the binding energy of the assembly compared to Cd. Also, in both compounds, we have computed theoretical models where the Br or I ligands have been replaced by H atoms and consequently the hydrogen bonds are not formed (see Fig. 7b). As a result, the interaction energies are reduced to ΔE9 = −22.7 kcal mol⁻¹ and ΔE10 = −21.6 kcal mol⁻¹ in 3 and 4, respectively. Therefore, this contribution (both hydrogen bonds) can be roughly estimated by the difference (−8.2 and −8.3 kcal mol⁻¹ for 3 and 4, respectively). These values are very close to those found for compounds 1 and 2, thus indicating that the contribution of the hydrogen bonds is not influenced by the type of transition metal (Zn or Cd). Furthermore, we have used an additional dimer, where the CdBr₂ and CdI₂ groups have been removed. The interaction energies are further reduced to ΔE9 = −13.3 kcal mol⁻¹ and ΔE6 = −13.6 kcal mol⁻¹ for 3 and 4, respectively, which is in agreement with the Zn complexes, revealing a strong influence of the metal coordination on the strength of the π-stacking interaction.

Figure 7
(a) Interaction energies of the self-assembled π-stacked dimers observed in the solid state of compounds 3 and 4. (b)/(c) Interaction energies in several theoretical models of 3 and 4. All distances are in Å.

For Hg compounds 5 and 6, we have performed an equivalent study (see Fig. 8). The computed interaction energies of the self-assembled dimers are almost identical (ΔE13 = −28.3 kcal mol⁻¹ and ΔE14 = −25.1 kcal mol⁻¹ for 5 and 6, respectively), indicating that Hg has a smaller effect on the interaction energy than Cd and Zn. Also, in both Hg compounds, we have computed theoretical models where the Cl⁻ or I⁻ ligands have been replaced by H⁻ ligands and consequently the hydrogen bonds are not formed (see Fig. 8b). As a result, the interaction energies are reduced to ΔE15 = −19.9 kcal mol⁻¹ and ΔE16 = −17.5 kcal mol⁻¹ in 5 and 6, respectively. Therefore, this contribution (both hydrogen bonds) can be roughly estimated as −8.4 and −7.6 kcal mol⁻¹ for 5 and 6, respectively. These values are in agreement with those found for compounds 1–4, thus confirming that the interaction energy of the hydrogen bonds is not influenced by the type of transition metal (Zn/Cd/Hg). Furthermore, we have used an additional dimer, where the HgCl₂ and HgI₂ groups have been eliminated. Consequently, the interaction energies are further reduced to ΔE17 = −13.0 kcal mol⁻¹ and ΔE18 = −12.7 kcal mol⁻¹ for 5 and 6, respectively; which is in agreement to the rest of complexes commented on above and confirms the strong influence of the metal coordination on the strength of the π-stacking interaction.

Figure 8
(a) Interaction energies of the self-assembled π-stacked dimers observed in the solid state of compounds 5 and 6. (b)/(c) Interaction energies in several theoretical models of 5 and 6. All distances are in Å.

In order to provide additional evidence for the existence of the C—H⋯X hydrogen-bond and π–π stacking interactions, we have analyzed the self-assembled π-stacked dimer of compound 3 (as an exemplifying model) using Bader's theory of `atoms in molecules' (AIM) (Bader, 1991 ), which provides an unambiguous definition of chemical bonding. The AIM theory has been successfully used to characterize and understand a great variety of interactions, including those described herein. In Fig. 9 we show the AIM analysis of compound 3. It can be observed that the π–π interaction is characterized by the presence of three bond critical points that interconnect three C atoms of each aromatic ligand. The interaction is further characterized by several ring and cage critical points. Furthermore, the distribution of critical points reveals the existence of two symmetrically disposed sets of C—H⋯Br hydrogen-bonding interactions. Each one is characterized by a bond critical point and a bond path connecting one H atom of the C—H groups with the Br⁻ ligand, thus confirming the formation of the trifurcated hydrogen bonds. The value of the Laplacian at the bond critical points is positive, as is common in closed-shell interactions.

Figure 9
AIM analysis of the self-assembled dimers retrieved from the X-ray structure of compound 3. Bond, ring and cage critical points are represented by red, yellow and green spheres, respectively. The bond paths connecting bond critical points are also represented by dashed lines.

4. Conclusion

We herein reported the syntheses and structural characterization of six new metal complexes based on the 2-{[(2-methoxyphenyl)imino]methyl}phenol ligand. All compounds exhibited an infinite 1D ladder in the solid state governed by the formation of hydrogen-bonding and π–π stacking interactions in the solid state. The crystal structure of these compounds was studied using geometrical and Hirshfeld surface analyses. They have also been studied using M06-2X/def2-TZVP calculations and Bader's theory of `atoms in molecules'. The energies associated with the interactions, including the contribution of the different forces, have been evaluated. In general, the π–π stacking interactions are stronger than those reported for conventional π–π complexes, that is attributed to the influence of the metal coordination, which is stronger for Zn than for either Cd or Hg. The results reported herein might be useful for understanding the solid-state architecture of metal-containing materials that contain M^IIX₂ subunits and organic aromatic ligands.

Supporting information

CCDC references: 1861558; 1861557; 1861556; 1861555; 1861554; 1861553

Crystal structure: contains datablocks Compound_1, Compound_2, Compound_3, Compound_4, Compound_5, Compound_6, global. DOI: https://doi.org/10.1107/S2053229618018314/sk3704sup1.cif

Structure factors: contains datablock Compound_1. DOI: https://doi.org/10.1107/S2053229618018314/sk3704Compound_1sup2.hkl

Structure factors: contains datablock Compound_2. DOI: https://doi.org/10.1107/S2053229618018314/sk3704Compound_2sup3.hkl

Structure factors: contains datablock Compound_3. DOI: https://doi.org/10.1107/S2053229618018314/sk3704Compound_3sup4.hkl

Structure factors: contains datablock Compound_4. DOI: https://doi.org/10.1107/S2053229618018314/sk3704Compound_4sup5.hkl

Structure factors: contains datablock Compound_5. DOI: https://doi.org/10.1107/S2053229618018314/sk3704Compound_5sup6.hkl

Structure factors: contains datablock Compound_6. DOI: https://doi.org/10.1107/S2053229618018314/sk3704Compound_6sup7.hkl

Computing details top

For all structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015b); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015a); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Dichloridobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)zinc(II) (Compound_1) top

Crystal data top

[ZnCl₂(C₂₈H₂₆N₂O₄)]	Z = 2
M_r = 590.78	F(000) = 608
Triclinic, P1	D_x = 1.521 Mg m⁻³
a = 9.1926 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6101 (2) Å	Cell parameters from 9828 reflections
c = 14.8057 (3) Å	θ = 2.5–34.0°
α = 94.188 (1)°	µ = 1.20 mm⁻¹
β = 97.716 (1)°	T = 100 K
γ = 114.409 (1)°	Block, yellow
V = 1289.80 (5) Å³	0.26 × 0.12 × 0.11 mm

Data collection top

Bruker SMART APEXII area detector diffractometer	11965 independent reflections
Radiation source: standard sealed X-ray tube, Siemens, KFF Mo 2K -90 C	9331 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 7.9 pixels mm^-1	θ_max = 35.7°, θ_min = 2.1°
ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −17→17
T_min = 0.691, T_max = 0.747	l = −24→24
93163 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.037P)² + 0.6038P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
11965 reflections	Δρ_max = 0.77 e Å⁻³
336 parameters	Δρ_min = −0.71 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Zn1	0.78269 (2)	0.33923 (2)	0.71660 (2)	0.01225 (4)
Cl1	0.58971 (4)	0.39395 (3)	0.64597 (2)	0.01828 (6)
Cl2	1.05003 (4)	0.46074 (3)	0.72121 (2)	0.01983 (6)
O1A	0.75873 (12)	0.35079 (10)	0.84784 (6)	0.01486 (16)
O1B	0.73799 (11)	0.15246 (9)	0.65301 (6)	0.01458 (16)
O2B	1.01441 (12)	0.27418 (10)	0.49592 (7)	0.01827 (18)
O2A	0.63225 (13)	0.63174 (11)	0.84985 (7)	0.02096 (19)
N1B	0.78530 (13)	0.02994 (11)	0.50462 (7)	0.01276 (17)
H1B	0.8193	0.1044	0.5463	0.015*
N1A	0.73008 (13)	0.51596 (11)	0.97988 (8)	0.01443 (18)
H1A	0.7160	0.4892	0.9204	0.017*
C1B	0.60814 (15)	0.03742 (12)	0.65300 (8)	0.01257 (19)
C1A	0.81909 (14)	0.29733 (12)	0.91128 (8)	0.01229 (19)
C6A	0.83502 (15)	0.34584 (12)	1.00664 (8)	0.01243 (19)
C6B	0.56362 (15)	−0.08101 (12)	0.58464 (8)	0.01256 (19)
C7B	0.65395 (15)	−0.07798 (13)	0.51344 (8)	0.0135 (2)
H7B	0.6165	−0.1596	0.4695	0.016*
C2A	0.87012 (16)	0.19149 (13)	0.89030 (9)	0.0161 (2)
H2A	0.8635	0.1585	0.8278	0.019*
C2B	0.50596 (15)	0.02403 (13)	0.71897 (9)	0.0149 (2)
H2B	0.5319	0.1006	0.7653	0.018*
C7A	0.79231 (15)	0.45396 (13)	1.03586 (8)	0.0141 (2)
H7A	0.8099	0.4833	1.1001	0.017*
C5B	0.42209 (15)	−0.20542 (13)	0.58441 (9)	0.0150 (2)
H5B	0.3934	−0.2833	0.5386	0.018*
C9B	0.85462 (16)	−0.07663 (14)	0.37295 (9)	0.0168 (2)
H9B	0.7741	−0.1668	0.3771	0.020*
C5A	0.89772 (16)	0.28629 (14)	1.07591 (9)	0.0168 (2)
H5A	0.9085	0.3192	1.1390	0.020*
C10B	0.95009 (17)	−0.05883 (16)	0.30531 (9)	0.0210 (3)
H10B	0.9365	−0.1372	0.2639	0.025*
C13B	0.99865 (15)	0.17174 (14)	0.42983 (8)	0.0152 (2)
C8B	0.87793 (15)	0.03839 (13)	0.43438 (8)	0.0137 (2)
C3B	0.36930 (16)	−0.09889 (14)	0.71670 (9)	0.0159 (2)
H3B	0.3030	−0.1051	0.7617	0.019*
C9A	0.68435 (16)	0.66509 (15)	1.09870 (9)	0.0191 (2)
H9A	0.7179	0.6228	1.1467	0.023*
C4B	0.32585 (15)	−0.21493 (13)	0.64943 (9)	0.0157 (2)
H4B	0.2314	−0.2986	0.6489	0.019*
C8A	0.68327 (16)	0.62282 (13)	1.00706 (9)	0.0156 (2)
C12A	0.58437 (17)	0.79013 (15)	0.95712 (11)	0.0212 (3)
H12A	0.5507	0.8329	0.9095	0.025*
C12B	1.09137 (17)	0.18984 (16)	0.36023 (9)	0.0190 (2)
H12B	1.1710	0.2799	0.3551	0.023*
C4A	0.94279 (18)	0.18186 (15)	1.05275 (10)	0.0200 (2)
H4A	0.9826	0.1412	1.0994	0.024*
C11B	1.06531 (17)	0.07378 (17)	0.29848 (9)	0.0212 (3)
H11B	1.1275	0.0856	0.2508	0.025*
C13A	0.63154 (16)	0.68325 (14)	0.93594 (9)	0.0171 (2)
C14B	1.1425 (2)	0.41087 (15)	0.49745 (11)	0.0254 (3)
H14A	1.1247	0.4457	0.4394	0.038*
H14B	1.2472	0.4054	0.5051	0.038*
H14C	1.1428	0.4747	0.5489	0.038*
C3A	0.92945 (18)	0.13554 (14)	0.95946 (10)	0.0197 (2)
H3A	0.9620	0.0640	0.9435	0.024*
C11A	0.58748 (18)	0.83271 (16)	1.04881 (11)	0.0243 (3)
H11A	0.5563	0.9055	1.0636	0.029*
C14A	0.54557 (19)	0.66647 (16)	0.77481 (10)	0.0231 (3)
H14D	0.5446	0.6152	0.7167	0.035*
H14E	0.5994	0.7672	0.7726	0.035*
H14F	0.4337	0.6407	0.7839	0.035*
C10A	0.63522 (18)	0.77081 (16)	1.11873 (11)	0.0244 (3)
H10A	0.6347	0.8003	1.1808	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01434 (7)	0.01084 (6)	0.01021 (6)	0.00409 (5)	0.00255 (5)	0.00064 (4)
Cl1	0.02136 (14)	0.01873 (13)	0.01582 (13)	0.01077 (12)	0.00027 (10)	0.00101 (10)
Cl2	0.01624 (13)	0.02080 (14)	0.01455 (12)	0.00027 (11)	0.00358 (10)	0.00072 (10)
O1A	0.0187 (4)	0.0185 (4)	0.0116 (4)	0.0114 (3)	0.0037 (3)	0.0040 (3)
O1B	0.0136 (4)	0.0111 (4)	0.0169 (4)	0.0030 (3)	0.0049 (3)	−0.0005 (3)
O2B	0.0204 (5)	0.0149 (4)	0.0175 (4)	0.0043 (3)	0.0078 (3)	0.0018 (3)
O2A	0.0278 (5)	0.0268 (5)	0.0172 (4)	0.0195 (4)	0.0053 (4)	0.0057 (4)
N1B	0.0133 (4)	0.0133 (4)	0.0120 (4)	0.0061 (4)	0.0028 (3)	0.0009 (3)
N1A	0.0143 (5)	0.0150 (4)	0.0158 (4)	0.0079 (4)	0.0033 (4)	0.0015 (4)
C1B	0.0127 (5)	0.0121 (5)	0.0132 (5)	0.0058 (4)	0.0018 (4)	0.0015 (4)
C1A	0.0118 (5)	0.0129 (5)	0.0123 (5)	0.0052 (4)	0.0029 (4)	0.0020 (4)
C6A	0.0133 (5)	0.0133 (5)	0.0120 (5)	0.0068 (4)	0.0024 (4)	0.0021 (4)
C6B	0.0132 (5)	0.0108 (4)	0.0131 (5)	0.0048 (4)	0.0018 (4)	0.0010 (4)
C7B	0.0142 (5)	0.0130 (5)	0.0130 (5)	0.0060 (4)	0.0016 (4)	0.0012 (4)
C2A	0.0188 (6)	0.0161 (5)	0.0157 (5)	0.0101 (4)	0.0034 (4)	0.0001 (4)
C2B	0.0147 (5)	0.0153 (5)	0.0152 (5)	0.0068 (4)	0.0037 (4)	0.0008 (4)
C7A	0.0140 (5)	0.0144 (5)	0.0138 (5)	0.0060 (4)	0.0030 (4)	0.0007 (4)
C5B	0.0147 (5)	0.0122 (5)	0.0158 (5)	0.0041 (4)	0.0010 (4)	0.0021 (4)
C9B	0.0158 (5)	0.0206 (6)	0.0147 (5)	0.0096 (5)	0.0010 (4)	−0.0012 (4)
C5A	0.0198 (6)	0.0176 (5)	0.0136 (5)	0.0089 (5)	0.0016 (4)	0.0035 (4)
C10B	0.0192 (6)	0.0312 (7)	0.0146 (5)	0.0143 (5)	0.0016 (4)	−0.0030 (5)
C13B	0.0143 (5)	0.0192 (5)	0.0132 (5)	0.0082 (4)	0.0028 (4)	0.0029 (4)
C8B	0.0129 (5)	0.0187 (5)	0.0112 (5)	0.0085 (4)	0.0022 (4)	0.0020 (4)
C3B	0.0143 (5)	0.0183 (5)	0.0173 (5)	0.0080 (4)	0.0056 (4)	0.0056 (4)
C9A	0.0158 (6)	0.0238 (6)	0.0177 (6)	0.0104 (5)	0.0012 (4)	−0.0054 (5)
C4B	0.0134 (5)	0.0139 (5)	0.0188 (5)	0.0043 (4)	0.0029 (4)	0.0050 (4)
C8A	0.0139 (5)	0.0150 (5)	0.0185 (5)	0.0073 (4)	0.0026 (4)	−0.0005 (4)
C12A	0.0190 (6)	0.0178 (6)	0.0290 (7)	0.0099 (5)	0.0053 (5)	0.0019 (5)
C12B	0.0176 (6)	0.0262 (6)	0.0154 (5)	0.0103 (5)	0.0058 (4)	0.0064 (5)
C4A	0.0253 (7)	0.0199 (6)	0.0188 (6)	0.0141 (5)	0.0008 (5)	0.0057 (5)
C11B	0.0182 (6)	0.0344 (7)	0.0134 (5)	0.0137 (6)	0.0041 (4)	0.0020 (5)
C13A	0.0157 (5)	0.0161 (5)	0.0205 (6)	0.0075 (4)	0.0048 (4)	0.0018 (4)
C14B	0.0284 (7)	0.0163 (6)	0.0260 (7)	0.0018 (5)	0.0122 (6)	0.0035 (5)
C3A	0.0240 (6)	0.0175 (6)	0.0222 (6)	0.0137 (5)	0.0030 (5)	0.0025 (5)
C11A	0.0191 (6)	0.0202 (6)	0.0334 (8)	0.0105 (5)	0.0020 (5)	−0.0050 (5)
C14A	0.0273 (7)	0.0262 (7)	0.0217 (6)	0.0167 (6)	0.0044 (5)	0.0074 (5)
C10A	0.0199 (6)	0.0273 (7)	0.0247 (7)	0.0124 (6)	−0.0001 (5)	−0.0094 (5)

Geometric parameters (Å, º) top

Zn1—Cl1	2.2404 (4)	C9B—C10B	1.3912 (19)
Zn1—Cl2	2.2427 (4)	C9B—C8B	1.3899 (18)
Zn1—O1A	1.9854 (9)	C5A—H5A	0.9500
Zn1—O1B	1.9832 (9)	C5A—C4A	1.3707 (19)
O1A—C1A	1.3076 (14)	C10B—H10B	0.9500
O1B—C1B	1.3078 (15)	C10B—C11B	1.389 (2)
O2B—C13B	1.3550 (16)	C13B—C8B	1.4050 (18)
O2B—C14B	1.4376 (17)	C13B—C12B	1.3981 (18)
O2A—C13A	1.3516 (16)	C3B—H3B	0.9500
O2A—C14A	1.4387 (17)	C3B—C4B	1.4053 (18)
N1B—H1B	0.8800	C9A—H9A	0.9500
N1B—C7B	1.3067 (16)	C9A—C8A	1.3949 (18)
N1B—C8B	1.4152 (16)	C9A—C10A	1.399 (2)
N1A—H1A	0.8800	C4B—H4B	0.9500
N1A—C7A	1.3077 (16)	C8A—C13A	1.4008 (19)
N1A—C8A	1.4197 (16)	C12A—H12A	0.9500
C1B—C6B	1.4314 (17)	C12A—C13A	1.4012 (19)
C1B—C2B	1.4187 (17)	C12A—C11A	1.392 (2)
C1A—C6A	1.4338 (17)	C12B—H12B	0.9500
C1A—C2A	1.4147 (17)	C12B—C11B	1.394 (2)
C6A—C7A	1.4151 (17)	C4A—H4A	0.9500
C6A—C5A	1.4213 (17)	C4A—C3A	1.404 (2)
C6B—C7B	1.4212 (17)	C11B—H11B	0.9500
C6B—C5B	1.4191 (17)	C14B—H14A	0.9800
C7B—H7B	0.9500	C14B—H14B	0.9800
C2A—H2A	0.9500	C14B—H14C	0.9800
C2A—C3A	1.3802 (19)	C3A—H3A	0.9500
C2B—H2B	0.9500	C11A—H11A	0.9500
C2B—C3B	1.3814 (18)	C11A—C10A	1.382 (2)
C7A—H7A	0.9500	C14A—H14D	0.9800
C5B—H5B	0.9500	C14A—H14E	0.9800
C5B—C4B	1.3742 (18)	C14A—H14F	0.9800
C9B—H9B	0.9500	C10A—H10A	0.9500

Cl1—Zn1—Cl2	124.837 (14)	O2B—C13B—C12B	125.28 (12)
O1A—Zn1—Cl1	103.90 (3)	C12B—C13B—C8B	119.56 (12)
O1A—Zn1—Cl2	104.04 (3)	C9B—C8B—N1B	123.25 (12)
O1B—Zn1—Cl1	105.46 (3)	C9B—C8B—C13B	120.69 (11)
O1B—Zn1—Cl2	102.79 (3)	C13B—C8B—N1B	116.05 (11)
O1B—Zn1—O1A	116.75 (4)	C2B—C3B—H3B	119.2
C1A—O1A—Zn1	125.54 (8)	C2B—C3B—C4B	121.66 (12)
C1B—O1B—Zn1	125.06 (8)	C4B—C3B—H3B	119.2
C13B—O2B—C14B	117.28 (11)	C8A—C9A—H9A	120.6
C13A—O2A—C14A	117.02 (11)	C8A—C9A—C10A	118.83 (14)
C7B—N1B—H1B	116.9	C10A—C9A—H9A	120.6
C7B—N1B—C8B	126.13 (11)	C5B—C4B—C3B	118.97 (12)
C8B—N1B—H1B	116.9	C5B—C4B—H4B	120.5
C7A—N1A—H1A	117.3	C3B—C4B—H4B	120.5
C7A—N1A—C8A	125.41 (11)	C9A—C8A—N1A	122.96 (12)
C8A—N1A—H1A	117.3	C9A—C8A—C13A	120.83 (12)
O1B—C1B—C6B	120.27 (11)	C13A—C8A—N1A	116.19 (11)
O1B—C1B—C2B	122.41 (11)	C13A—C12A—H12A	120.5
C2B—C1B—C6B	117.32 (11)	C11A—C12A—H12A	120.5
O1A—C1A—C6A	119.79 (11)	C11A—C12A—C13A	119.10 (14)
O1A—C1A—C2A	122.76 (11)	C13B—C12B—H12B	120.5
C2A—C1A—C6A	117.45 (11)	C11B—C12B—C13B	119.03 (13)
C7A—C6A—C1A	122.46 (11)	C11B—C12B—H12B	120.5
C7A—C6A—C5A	117.50 (11)	C5A—C4A—H4A	120.3
C5A—C6A—C1A	120.04 (11)	C5A—C4A—C3A	119.33 (12)
C7B—C6B—C1B	122.20 (11)	C3A—C4A—H4A	120.3
C5B—C6B—C1B	120.17 (11)	C10B—C11B—C12B	121.24 (13)
C5B—C6B—C7B	117.60 (11)	C10B—C11B—H11B	119.4
N1B—C7B—C6B	124.13 (11)	C12B—C11B—H11B	119.4
N1B—C7B—H7B	117.9	O2A—C13A—C8A	115.56 (11)
C6B—C7B—H7B	117.9	O2A—C13A—C12A	124.76 (13)
C1A—C2A—H2A	119.6	C8A—C13A—C12A	119.68 (13)
C3A—C2A—C1A	120.85 (12)	O2B—C14B—H14A	109.5
C3A—C2A—H2A	119.6	O2B—C14B—H14B	109.5
C1B—C2B—H2B	119.6	O2B—C14B—H14C	109.5
C3B—C2B—C1B	120.87 (12)	H14A—C14B—H14B	109.5
C3B—C2B—H2B	119.6	H14A—C14B—H14C	109.5
N1A—C7A—C6A	124.08 (11)	H14B—C14B—H14C	109.5
N1A—C7A—H7A	118.0	C2A—C3A—C4A	121.56 (12)
C6A—C7A—H7A	118.0	C2A—C3A—H3A	119.2
C6B—C5B—H5B	119.5	C4A—C3A—H3A	119.2
C4B—C5B—C6B	121.01 (12)	C12A—C11A—H11A	119.4
C4B—C5B—H5B	119.5	C10A—C11A—C12A	121.10 (13)
C10B—C9B—H9B	120.2	C10A—C11A—H11A	119.4
C8B—C9B—H9B	120.2	O2A—C14A—H14D	109.5
C8B—C9B—C10B	119.53 (13)	O2A—C14A—H14E	109.5
C6A—C5A—H5A	119.6	O2A—C14A—H14F	109.5
C4A—C5A—C6A	120.74 (12)	H14D—C14A—H14E	109.5
C4A—C5A—H5A	119.6	H14D—C14A—H14F	109.5
C9B—C10B—H10B	120.1	H14E—C14A—H14F	109.5
C11B—C10B—C9B	119.87 (13)	C9A—C10A—H10A	119.8
C11B—C10B—H10B	120.1	C11A—C10A—C9A	120.43 (14)
O2B—C13B—C8B	115.16 (11)	C11A—C10A—H10A	119.8

Zn1—O1A—C1A—C6A	161.78 (9)	C2B—C1B—C6B—C5B	0.11 (17)
Zn1—O1A—C1A—C2A	−18.43 (17)	C2B—C3B—C4B—C5B	0.01 (19)
Zn1—O1B—C1B—C6B	161.25 (9)	C7A—N1A—C8A—C9A	−6.4 (2)
Zn1—O1B—C1B—C2B	−18.45 (16)	C7A—N1A—C8A—C13A	174.92 (12)
O1A—C1A—C6A—C7A	−2.03 (18)	C7A—C6A—C5A—C4A	−179.52 (13)
O1A—C1A—C6A—C5A	178.83 (11)	C5B—C6B—C7B—N1B	179.18 (12)
O1A—C1A—C2A—C3A	−178.39 (13)	C9B—C10B—C11B—C12B	2.1 (2)
O1B—C1B—C6B—C7B	−1.78 (18)	C5A—C6A—C7A—N1A	−178.46 (12)
O1B—C1B—C6B—C5B	−179.60 (11)	C5A—C4A—C3A—C2A	−0.8 (2)
O1B—C1B—C2B—C3B	179.73 (12)	C10B—C9B—C8B—N1B	179.37 (12)
O2B—C13B—C8B—N1B	2.38 (16)	C10B—C9B—C8B—C13B	−1.12 (19)
O2B—C13B—C8B—C9B	−177.17 (11)	C13B—C12B—C11B—C10B	−0.4 (2)
O2B—C13B—C12B—C11B	177.94 (12)	C8B—N1B—C7B—C6B	−179.17 (11)
N1A—C8A—C13A—O2A	0.17 (17)	C8B—C9B—C10B—C11B	−1.3 (2)
N1A—C8A—C13A—C12A	−179.56 (12)	C8B—C13B—C12B—C11B	−2.06 (19)
C1B—C6B—C7B—N1B	1.32 (19)	C9A—C8A—C13A—O2A	−178.54 (12)
C1B—C6B—C5B—C4B	−0.20 (18)	C9A—C8A—C13A—C12A	1.7 (2)
C1B—C2B—C3B—C4B	−0.1 (2)	C8A—N1A—C7A—C6A	178.78 (12)
C1A—C6A—C7A—N1A	2.4 (2)	C8A—C9A—C10A—C11A	−0.4 (2)
C1A—C6A—C5A—C4A	−0.3 (2)	C12A—C11A—C10A—C9A	1.1 (2)
C1A—C2A—C3A—C4A	−0.5 (2)	C12B—C13B—C8B—N1B	−177.62 (11)
C6A—C1A—C2A—C3A	1.40 (19)	C12B—C13B—C8B—C9B	2.83 (19)
C6A—C5A—C4A—C3A	1.2 (2)	C13A—C12A—C11A—C10A	−0.4 (2)
C6B—C1B—C2B—C3B	0.03 (18)	C14B—O2B—C13B—C8B	176.51 (12)
C6B—C5B—C4B—C3B	0.14 (19)	C14B—O2B—C13B—C12B	−3.48 (19)
C7B—N1B—C8B—C9B	−10.54 (19)	C11A—C12A—C13A—O2A	179.28 (13)
C7B—N1B—C8B—C13B	169.93 (12)	C11A—C12A—C13A—C8A	−1.0 (2)
C7B—C6B—C5B—C4B	−178.11 (12)	C14A—O2A—C13A—C8A	165.83 (12)
C2A—C1A—C6A—C7A	178.17 (12)	C14A—O2A—C13A—C12A	−14.5 (2)
C2A—C1A—C6A—C5A	−0.96 (18)	C10A—C9A—C8A—N1A	−179.64 (13)
C2B—C1B—C6B—C7B	177.93 (11)	C10A—C9A—C8A—C13A	−1.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1B—H1B···O1B	0.88	1.96	2.6481 (14)	134
N1A—H1A···O1A	0.88	1.96	2.6424 (14)	134
C7B—H7B···Cl1ⁱ	0.95	2.70	3.6118 (13)	160
C7A—H7A···Cl2ⁱⁱ	0.95	2.69	3.5913 (13)	159
C14B—H14C···Cl2	0.98	2.79	3.5845 (16)	138
C14A—H14D···Cl1	0.98	2.71	3.5406 (16)	143

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

Diiodidobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)zinc(II) (Compound_2) top

Crystal data top

[ZnI₂(C₂₈H₂₆N₂O₄)]	Z = 2
M_r = 773.68	F(000) = 752
Triclinic, P1	D_x = 1.894 Mg m⁻³
a = 9.2709 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.020 (2) Å	Cell parameters from 4135 reflections
c = 16.248 (4) Å	θ = 4.4–51.3°
α = 98.56 (4)°	µ = 3.22 mm⁻¹
β = 100.50 (4)°	T = 100 K
γ = 110.09 (3)°	Plate, yellow
V = 1356.7 (6) Å³	0.14 × 0.07 × 0.03 mm

Data collection top

Bruker APEXII area detector diffractometer	7281 independent reflections
Radiation source: standard sealed X-ray tube, Siemens, KFF Mo 2K -90 C	4608 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.116
Detector resolution: 7.9 pixels mm^-1	θ_max = 25.5°, θ_min = 2.2°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (TWINABS; Bruker, 2012)	k = −12→12
T_min = 0.612, T_max = 0.746	l = −19→19
7281 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.067	H-atom parameters constrained
wR(F²) = 0.195	w = 1/[σ²(F_o²) + (0.1055P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max < 0.001
7281 reflections	Δρ_max = 2.19 e Å⁻³
337 parameters	Δρ_min = −1.18 e Å⁻³
174 restraints

Special details top

Refinement. The carbon and nitrogen atoms were fixed using the similarity restraint for Uij (SIMU). Atoms N1A, N1B, and C14B were fixed using the ISOR restraint. The structure was solved as a rotational twin rotated from first domain by 179.8 degrees about reciprocal axis 0.002 1.000 0.001 and real axis 0.434 1.000 0.197. Twin law to convert hkl from first to this domain (SHELXL TWIN matrix): -0.999 0.004 -0.001, 0.866 0.998 0.395, 0.007 0.003 -0.999.

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

	x	y	z	U_iso*/U_eq
C1A	0.334 (2)	0.3133 (16)	0.8865 (11)	0.0165 (17)
C1B	0.130 (2)	0.0695 (17)	0.6410 (10)	0.0129 (15)
C2A	0.396 (2)	0.2136 (16)	0.8566 (11)	0.0167 (17)
H2A	0.3964	0.1941	0.7976	0.020*
C2B	0.035 (2)	0.0640 (17)	0.7007 (10)	0.0131 (16)
H2B	0.0540	0.1491	0.7425	0.016*
C3A	0.457 (2)	0.1434 (17)	0.9096 (11)	0.0166 (17)
H3A	0.4988	0.0757	0.8867	0.020*
C3B	−0.086 (2)	−0.0684 (17)	0.6971 (10)	0.0129 (16)
H3B	−0.1476	−0.0722	0.7380	0.015*
C4A	0.461 (2)	0.1669 (17)	0.9945 (12)	0.0164 (17)
H4A	0.5043	0.1156	1.0299	0.020*
C4B	−0.120 (2)	−0.1964 (18)	0.6350 (10)	0.0125 (16)
H4B	−0.2036	−0.2844	0.6340	0.015*
C5A	0.402 (2)	0.2647 (16)	1.0300 (11)	0.0165 (17)
H5A	0.4031	0.2802	1.0893	0.020*
C5B	−0.030 (2)	−0.1933 (18)	0.5759 (10)	0.0126 (15)
H5B	−0.0511	−0.2793	0.5342	0.015*
C6A	0.339 (2)	0.3415 (16)	0.9766 (11)	0.0164 (16)
C6B	0.095 (2)	−0.0591 (17)	0.5779 (10)	0.0127 (15)
C7A	0.286 (2)	0.4453 (16)	1.0157 (12)	0.0165 (18)
H7A	0.2929	0.4567	1.0755	0.020*
C7B	0.179 (2)	−0.0640 (17)	0.5121 (10)	0.0127 (17)
H7B	0.1475	−0.1546	0.4723	0.015*
C8A	0.172 (2)	0.6273 (19)	1.0156 (12)	0.0191 (17)
C8B	0.373 (2)	0.0414 (18)	0.4378 (11)	0.0155 (17)
C9A	0.165 (2)	0.6426 (19)	1.1017 (11)	0.0191 (17)
H9A	0.1964	0.5837	1.1361	0.023*
C9B	0.347 (2)	−0.0865 (18)	0.3801 (11)	0.0156 (17)
H9B	0.2717	−0.1770	0.3831	0.019*
C10A	0.110 (2)	0.7469 (18)	1.1353 (12)	0.0195 (17)
H10A	0.0986	0.7564	1.1925	0.023*
C10B	0.430 (2)	−0.0809 (17)	0.3198 (11)	0.0158 (17)
H10B	0.4100	−0.1677	0.2791	0.019*
C11A	0.073 (2)	0.8366 (19)	1.0856 (11)	0.0193 (17)
H11A	0.0415	0.9105	1.1105	0.023*
C11B	0.544 (2)	0.0498 (17)	0.3160 (11)	0.0155 (17)
H11B	0.6030	0.0498	0.2740	0.019*
C12A	0.081 (2)	0.8227 (18)	1.0019 (12)	0.0193 (17)
H12A	0.0504	0.8825	0.9680	0.023*
C12B	0.573 (2)	0.1793 (17)	0.3719 (10)	0.0154 (17)
H12B	0.6483	0.2691	0.3679	0.018*
C13A	0.137 (2)	0.7151 (18)	0.9662 (11)	0.0193 (17)
C13B	0.489 (2)	0.1732 (17)	0.4339 (10)	0.0153 (17)
C14A	0.098 (3)	0.776 (2)	0.8298 (12)	0.037 (6)
H14A	0.1086	0.7446	0.7719	0.056*
H14B	0.1618	0.8807	0.8517	0.056*
H14C	−0.0139	0.7584	0.8274	0.056*
C14B	0.637 (2)	0.4251 (17)	0.5024 (11)	0.017 (4)
H14D	0.6157	0.4646	0.4518	0.026*
H14E	0.7343	0.4063	0.5057	0.026*
H14F	0.6489	0.4959	0.5544	0.026*
I1	0.06551 (14)	0.45980 (12)	0.65185 (7)	0.0183 (3)
I2	0.58382 (14)	0.53025 (12)	0.73369 (7)	0.0185 (3)
N1A	0.2297 (17)	0.5259 (14)	0.9761 (9)	0.015 (3)
H1A	0.2267	0.5179	0.9211	0.018*
N1B	0.2921 (16)	0.0437 (13)	0.5033 (8)	0.010 (3)
H1B	0.3227	0.1268	0.5411	0.012*
O1A	0.2721 (14)	0.3821 (12)	0.8366 (8)	0.017 (3)
O1B	0.2479 (14)	0.1894 (12)	0.6433 (7)	0.015 (3)
O2A	0.1519 (15)	0.6952 (12)	0.8862 (8)	0.021 (3)
O2B	0.5048 (13)	0.2897 (11)	0.4952 (7)	0.014 (3)
Zn1	0.2884 (3)	0.38214 (19)	0.71687 (14)	0.0131 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.021 (4)	0.006 (3)	0.021 (4)	0.002 (3)	0.008 (3)	0.004 (3)
C1B	0.011 (4)	0.015 (3)	0.013 (3)	0.006 (3)	0.001 (3)	0.001 (3)
C2A	0.021 (4)	0.006 (3)	0.022 (4)	0.002 (3)	0.008 (3)	0.004 (3)
C2B	0.011 (4)	0.015 (3)	0.013 (3)	0.006 (3)	0.001 (3)	0.001 (3)
C3A	0.021 (4)	0.006 (3)	0.022 (4)	0.002 (3)	0.008 (3)	0.005 (3)
C3B	0.011 (4)	0.015 (3)	0.012 (3)	0.006 (3)	0.002 (3)	0.001 (3)
C4A	0.021 (4)	0.006 (3)	0.022 (4)	0.002 (3)	0.009 (3)	0.004 (3)
C4B	0.011 (4)	0.014 (3)	0.012 (3)	0.006 (3)	0.002 (3)	0.002 (3)
C5A	0.021 (4)	0.006 (3)	0.021 (4)	0.002 (3)	0.009 (3)	0.004 (3)
C5B	0.011 (4)	0.014 (3)	0.012 (3)	0.006 (3)	0.002 (3)	0.001 (3)
C6A	0.021 (4)	0.006 (3)	0.021 (4)	0.002 (3)	0.009 (3)	0.005 (3)
C6B	0.011 (4)	0.014 (3)	0.013 (3)	0.006 (3)	0.001 (3)	0.001 (3)
C7A	0.021 (4)	0.007 (3)	0.021 (4)	0.002 (3)	0.008 (3)	0.005 (3)
C7B	0.011 (4)	0.014 (3)	0.013 (3)	0.006 (3)	0.001 (3)	0.001 (3)
C8A	0.011 (4)	0.023 (4)	0.022 (4)	0.010 (3)	0.002 (3)	−0.001 (3)
C8B	0.016 (4)	0.017 (3)	0.014 (4)	0.007 (3)	0.005 (3)	0.004 (3)
C9A	0.011 (4)	0.023 (4)	0.022 (4)	0.010 (3)	0.002 (3)	−0.002 (3)
C9B	0.016 (4)	0.017 (3)	0.014 (4)	0.006 (3)	0.005 (3)	0.004 (3)
C10A	0.012 (4)	0.024 (4)	0.023 (4)	0.010 (3)	0.002 (3)	−0.002 (3)
C10B	0.017 (4)	0.017 (3)	0.014 (4)	0.007 (3)	0.005 (3)	0.003 (3)
C11A	0.012 (4)	0.023 (4)	0.023 (4)	0.010 (3)	0.002 (3)	−0.002 (3)
C11B	0.016 (4)	0.017 (3)	0.014 (4)	0.007 (3)	0.005 (3)	0.004 (3)
C12A	0.012 (4)	0.023 (4)	0.023 (4)	0.010 (3)	0.002 (3)	−0.001 (3)
C12B	0.016 (4)	0.017 (3)	0.014 (4)	0.007 (3)	0.005 (3)	0.004 (3)
C13A	0.012 (4)	0.023 (4)	0.023 (4)	0.010 (3)	0.002 (3)	−0.001 (3)
C13B	0.016 (4)	0.017 (3)	0.013 (4)	0.007 (3)	0.005 (3)	0.004 (3)
C14A	0.063 (17)	0.032 (11)	0.027 (11)	0.026 (12)	0.016 (12)	0.009 (9)
C14B	0.018 (4)	0.016 (4)	0.018 (4)	0.007 (3)	0.005 (3)	0.002 (3)
I1	0.0170 (7)	0.0182 (6)	0.0184 (7)	0.0077 (5)	0.0005 (6)	0.0024 (5)
I2	0.0132 (7)	0.0233 (7)	0.0141 (6)	0.0012 (5)	0.0029 (5)	0.0044 (5)
N1A	0.015 (3)	0.014 (3)	0.015 (3)	0.0062 (17)	0.0030 (15)	0.0032 (14)
N1B	0.009 (3)	0.010 (3)	0.009 (3)	0.0029 (16)	0.0028 (14)	0.0020 (14)
O1A	0.011 (7)	0.013 (6)	0.027 (7)	0.008 (5)	0.000 (6)	0.002 (5)
O1B	0.010 (7)	0.013 (6)	0.016 (6)	0.003 (5)	0.002 (5)	−0.004 (5)
O2A	0.029 (8)	0.016 (6)	0.020 (7)	0.008 (6)	0.007 (6)	0.008 (5)
O2B	0.015 (7)	0.007 (5)	0.020 (6)	0.000 (5)	0.013 (6)	0.001 (5)
Zn1	0.0137 (10)	0.0132 (10)	0.0115 (9)	0.0043 (9)	0.0032 (7)	0.0021 (7)

Geometric parameters (Å, º) top

C1A—C2A	1.39 (2)	C8B—N1B	1.41 (2)
C1A—C6A	1.44 (2)	C9A—H9A	0.9500
C1A—O1A	1.31 (2)	C9A—C10A	1.39 (2)
C1B—C2B	1.42 (2)	C9B—H9B	0.9500
C1B—C6B	1.42 (2)	C9B—C10B	1.35 (2)
C1B—O1B	1.307 (19)	C10A—H10A	0.9500
C2A—H2A	0.9500	C10A—C11A	1.38 (2)
C2A—C3A	1.35 (2)	C10B—H10B	0.9500
C2B—H2B	0.9500	C10B—C11B	1.39 (2)
C2B—C3B	1.40 (2)	C11A—H11A	0.9500
C3A—H3A	0.9500	C11A—C12A	1.36 (2)
C3A—C4A	1.36 (2)	C11B—H11B	0.9500
C3B—H3B	0.9500	C11B—C12B	1.38 (2)
C3B—C4B	1.41 (2)	C12A—H12A	0.9500
C4A—H4A	0.9500	C12A—C13A	1.44 (2)
C4A—C5A	1.38 (2)	C12B—H12B	0.9500
C4B—H4B	0.9500	C12B—C13B	1.38 (2)
C4B—C5B	1.38 (2)	C13A—O2A	1.32 (2)
C5A—H5A	0.9500	C13B—O2B	1.362 (18)
C5A—C6A	1.42 (2)	C14A—H14A	0.9800
C5B—H5B	0.9500	C14A—H14B	0.9800
C5B—C6B	1.43 (2)	C14A—H14C	0.9800
C6A—C7A	1.41 (2)	C14A—O2A	1.44 (2)
C6B—C7B	1.44 (2)	C14B—H14D	0.9800
C7A—H7A	0.9500	C14B—H14E	0.9800
C7A—N1A	1.29 (2)	C14B—H14F	0.9800
C7B—H7B	0.9500	C14B—O2B	1.453 (18)
C7B—N1B	1.27 (2)	I1—Zn1	2.558 (3)
C8A—C9A	1.40 (2)	I2—Zn1	2.568 (3)
C8A—C13A	1.35 (2)	N1A—H1A	0.8800
C8A—N1A	1.43 (2)	N1B—H1B	0.8800
C8B—C9B	1.39 (2)	O1A—Zn1	1.979 (12)
C8B—C13B	1.41 (2)	O1B—Zn1	1.988 (11)

C2A—C1A—C6A	117.4 (16)	C10B—C9B—H9B	120.4
O1A—C1A—C2A	123.1 (16)	C9A—C10A—H10A	120.0
O1A—C1A—C6A	119.4 (15)	C11A—C10A—C9A	120.1 (17)
C2B—C1B—C6B	118.5 (15)	C11A—C10A—H10A	120.0
O1B—C1B—C2B	121.5 (15)	C9B—C10B—H10B	119.4
O1B—C1B—C6B	120.0 (14)	C9B—C10B—C11B	121.1 (16)
C1A—C2A—H2A	119.2	C11B—C10B—H10B	119.4
C3A—C2A—C1A	121.5 (17)	C10A—C11A—H11A	118.9
C3A—C2A—H2A	119.2	C12A—C11A—C10A	122.1 (17)
C1B—C2B—H2B	120.5	C12A—C11A—H11A	118.9
C3B—C2B—C1B	119.1 (15)	C10B—C11B—H11B	119.3
C3B—C2B—H2B	120.5	C12B—C11B—C10B	121.5 (16)
C2A—C3A—H3A	119.0	C12B—C11B—H11B	119.3
C2A—C3A—C4A	121.9 (17)	C11A—C12A—H12A	120.8
C4A—C3A—H3A	119.0	C11A—C12A—C13A	118.4 (16)
C2B—C3B—H3B	118.8	C13A—C12A—H12A	120.8
C2B—C3B—C4B	122.3 (16)	C11B—C12B—H12B	121.4
C4B—C3B—H3B	118.8	C11B—C12B—C13B	117.3 (15)
C3A—C4A—H4A	119.7	C13B—C12B—H12B	121.4
C3A—C4A—C5A	120.6 (17)	C8A—C13A—C12A	118.6 (16)
C5A—C4A—H4A	119.7	O2A—C13A—C8A	118.3 (15)
C3B—C4B—H4B	120.2	O2A—C13A—C12A	123.0 (16)
C5B—C4B—C3B	119.6 (16)	C12B—C13B—C8B	121.4 (15)
C5B—C4B—H4B	120.2	O2B—C13B—C8B	113.5 (14)
C4A—C5A—H5A	120.5	O2B—C13B—C12B	125.1 (14)
C4A—C5A—C6A	119.0 (16)	H14A—C14A—H14B	109.5
C6A—C5A—H5A	120.5	H14A—C14A—H14C	109.5
C4B—C5B—H5B	120.3	H14B—C14A—H14C	109.5
C4B—C5B—C6B	119.4 (15)	O2A—C14A—H14A	109.5
C6B—C5B—H5B	120.3	O2A—C14A—H14B	109.5
C5A—C6A—C1A	119.5 (15)	O2A—C14A—H14C	109.5
C7A—C6A—C1A	123.0 (16)	H14D—C14B—H14E	109.5
C7A—C6A—C5A	117.5 (16)	H14D—C14B—H14F	109.5
C1B—C6B—C5B	121.1 (15)	H14E—C14B—H14F	109.5
C1B—C6B—C7B	123.0 (15)	O2B—C14B—H14D	109.5
C5B—C6B—C7B	115.9 (15)	O2B—C14B—H14E	109.5
C6A—C7A—H7A	117.6	O2B—C14B—H14F	109.5
N1A—C7A—C6A	124.8 (17)	C7A—N1A—C8A	124.4 (15)
N1A—C7A—H7A	117.6	C7A—N1A—H1A	117.8
C6B—C7B—H7B	117.5	C8A—N1A—H1A	117.8
N1B—C7B—C6B	124.9 (16)	C7B—N1B—C8B	125.5 (14)
N1B—C7B—H7B	117.5	C7B—N1B—H1B	117.2
C9A—C8A—N1A	121.8 (15)	C8B—N1B—H1B	117.2
C13A—C8A—C9A	122.8 (16)	C1A—O1A—Zn1	124.5 (11)
C13A—C8A—N1A	115.1 (15)	C1B—O1B—Zn1	123.4 (10)
C9B—C8B—C13B	119.5 (15)	C13A—O2A—C14A	118.8 (13)
C9B—C8B—N1B	122.4 (14)	C13B—O2B—C14B	116.2 (12)
C13B—C8B—N1B	118.1 (15)	I1—Zn1—I2	123.65 (7)
C8A—C9A—H9A	121.1	O1A—Zn1—I1	104.0 (4)
C10A—C9A—C8A	117.8 (17)	O1A—Zn1—I2	103.6 (4)
C10A—C9A—H9A	121.1	O1A—Zn1—O1B	115.8 (4)
C8B—C9B—H9B	120.4	O1B—Zn1—I1	106.2 (4)
C10B—C9B—C8B	119.2 (16)	O1B—Zn1—I2	104.2 (3)

C1A—C2A—C3A—C4A	0 (3)	C9A—C8A—C13A—O2A	177.8 (17)
C1A—C6A—C7A—N1A	0 (3)	C9A—C8A—N1A—C7A	−3 (3)
C1B—C2B—C3B—C4B	−1 (2)	C9A—C10A—C11A—C12A	3 (3)
C1B—C6B—C7B—N1B	0 (3)	C9B—C8B—C13B—C12B	2 (3)
C2A—C1A—C6A—C5A	−2 (2)	C9B—C8B—C13B—O2B	−178.7 (15)
C2A—C1A—C6A—C7A	176.9 (16)	C9B—C8B—N1B—C7B	−7 (3)
C2A—C1A—O1A—Zn1	−11 (2)	C9B—C10B—C11B—C12B	−2 (3)
C2A—C3A—C4A—C5A	0 (3)	C10A—C11A—C12A—C13A	−3 (3)
C2B—C1B—C6B—C5B	−2 (2)	C10B—C11B—C12B—C13B	2 (3)
C2B—C1B—C6B—C7B	177.3 (16)	C11A—C12A—C13A—C8A	3 (3)
C2B—C1B—O1B—Zn1	−9 (2)	C11A—C12A—C13A—O2A	−178.6 (17)
C2B—C3B—C4B—C5B	1 (2)	C11B—C12B—C13B—C8B	−2 (3)
C3A—C4A—C5A—C6A	−1 (3)	C11B—C12B—C13B—O2B	178.6 (16)
C3B—C4B—C5B—C6B	−1 (2)	C12A—C13A—O2A—C14A	−5 (3)
C4A—C5A—C6A—C1A	2 (2)	C12B—C13B—O2B—C14B	−9 (2)
C4A—C5A—C6A—C7A	−177.2 (15)	C13A—C8A—C9A—C10A	4 (3)
C4B—C5B—C6B—C1B	2 (2)	C13A—C8A—N1A—C7A	171.6 (17)
C4B—C5B—C6B—C7B	−178.0 (15)	C13B—C8B—C9B—C10B	−2 (3)
C5A—C6A—C7A—N1A	178.4 (16)	C13B—C8B—N1B—C7B	175.7 (16)
C5B—C6B—C7B—N1B	179.6 (16)	N1A—C8A—C9A—C10A	178.3 (16)
C6A—C1A—C2A—C3A	1 (3)	N1A—C8A—C13A—C12A	−178.6 (16)
C6A—C1A—O1A—Zn1	169.1 (11)	N1A—C8A—C13A—O2A	3 (2)
C6A—C7A—N1A—C8A	177.8 (16)	N1B—C8B—C9B—C10B	−179.3 (16)
C6B—C1B—C2B—C3B	2 (2)	N1B—C8B—C13B—C12B	179.8 (16)
C6B—C1B—O1B—Zn1	170.6 (11)	N1B—C8B—C13B—O2B	−1 (2)
C6B—C7B—N1B—C8B	−178.3 (16)	O1A—C1A—C2A—C3A	−179.1 (16)
C8A—C9A—C10A—C11A	−4 (3)	O1A—C1A—C6A—C5A	178.3 (15)
C8A—C13A—O2A—C14A	172.8 (17)	O1A—C1A—C6A—C7A	−3 (3)
C8B—C9B—C10B—C11B	2 (3)	O1B—C1B—C2B—C3B	−177.9 (15)
C8B—C13B—O2B—C14B	171.9 (14)	O1B—C1B—C6B—C5B	177.7 (15)
C9A—C8A—C13A—C12A	−4 (3)	O1B—C1B—C6B—C7B	−3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2B—H2B···O1A	0.95	2.54	3.34 (2)	143
N1A—H1A···O1A	0.88	1.99	2.666 (18)	133
N1B—H1B···O1B	0.88	2.01	2.690 (16)	133

Dibromidobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)cadmium(II) (Compound_3) top

Crystal data top

[CdBr₂(C₂₈H₂₆N₂O₄)]	Z = 2
M_r = 726.73	F(000) = 716
Triclinic, P1	D_x = 1.789 Mg m⁻³
a = 9.2772 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0935 (3) Å	Cell parameters from 9888 reflections
c = 16.1021 (5) Å	θ = 4.4–53.3°
α = 97.699 (2)°	µ = 3.81 mm⁻¹
β = 100.586 (2)°	T = 100 K
γ = 111.149 (2)°	Fragment, orange
V = 1348.92 (8) Å³	0.27 × 0.13 × 0.10 mm

Data collection top

Bruker APEXII area detector diffractometer	10130 independent reflections
Radiation source: standard sealed X-ray tube, Siemens, KFF Mo 2K -90 C	8342 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 7.9 pixels mm^-1	θ_max = 26.8°, θ_min = 2.2°
ω and φ scans	h = −11→11
Absorption correction: multi-scan (TWINABS; Bruker, 2012)	k = −12→12
T_min = 0.538, T_max = 0.745	l = −20→20
10130 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0861P)² + 0.1296P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
10130 reflections	Δρ_max = 1.04 e Å⁻³
337 parameters	Δρ_min = −0.70 e Å⁻³
0 restraints

Special details top

Refinement. The structure was solved as a rotational twin. Rotated from first domain by 179.7 degrees about reciprocal axis -0.003 -0.997 1.000 and real axis 0.311 1.000 -0.257. Twin law to convert hkl from first to this domain (SHELXL TWIN matrix) -1.001 0.001 -0.004, 0.498 0.590 -0.407, -0.487 -1.593 -0.589.

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

	x	y	z	U_iso*/U_eq
Cd1	0.29206 (5)	0.39716 (4)	0.71100 (3)	0.01298 (12)
Br2	0.59152 (7)	0.53416 (7)	0.73453 (4)	0.02186 (16)
Br1	0.06225 (7)	0.45851 (6)	0.64168 (4)	0.01971 (15)
O1B	0.2700 (5)	0.3889 (4)	0.8457 (2)	0.0146 (8)
O1A	0.2436 (5)	0.1800 (4)	0.6336 (3)	0.0147 (8)
O2A	0.5041 (5)	0.2829 (4)	0.4950 (3)	0.0171 (8)
O2B	0.1460 (5)	0.6818 (4)	0.8836 (3)	0.0218 (9)
N1A	0.2869 (5)	0.0342 (5)	0.4984 (3)	0.0124 (9)
H1A	0.3168	0.1169	0.5359	0.015*
N1B	0.2287 (5)	0.5245 (5)	0.9842 (3)	0.0133 (9)
H1B	0.2207	0.5120	0.9281	0.016*
C13A	0.4882 (6)	0.1700 (6)	0.4328 (3)	0.0141 (11)
C13B	0.1329 (7)	0.7125 (6)	0.9656 (4)	0.0183 (12)
C6A	0.0867 (6)	−0.0710 (6)	0.5738 (3)	0.0139 (11)
C7B	0.2879 (7)	0.4445 (6)	1.0253 (4)	0.0156 (11)
H7B	0.2977	0.4569	1.0859	0.019*
C1B	0.3292 (7)	0.3179 (6)	0.8939 (3)	0.0131 (11)
C7A	0.1681 (6)	−0.0769 (6)	0.5082 (3)	0.0133 (11)
H7A	0.1344	−0.1673	0.4687	0.016*
C3A	−0.0890 (7)	−0.0731 (6)	0.6974 (4)	0.0172 (12)
H3A	−0.1492	−0.0739	0.7393	0.021*
C6B	0.3379 (6)	0.3411 (6)	0.9855 (3)	0.0144 (11)
C5A	−0.0396 (7)	−0.2009 (6)	0.5771 (4)	0.0152 (11)
H5A	−0.0644	−0.2882	0.5363	0.018*
C4B	0.4565 (7)	0.1660 (6)	1.0034 (4)	0.0195 (12)
H4B	0.4980	0.1138	1.0391	0.023*
C8B	0.1770 (7)	0.6279 (6)	1.0205 (4)	0.0164 (11)
C9B	0.1653 (7)	0.6496 (6)	1.1060 (4)	0.0182 (12)
H9B	0.1929	0.5919	1.1429	0.022*
C8A	0.3719 (6)	0.0354 (6)	0.4343 (3)	0.0146 (11)
C2A	0.0323 (7)	0.0545 (6)	0.6965 (4)	0.0156 (11)
H2A	0.0543	0.1403	0.7378	0.019*
C4A	−0.1254 (7)	−0.2027 (6)	0.6372 (4)	0.0172 (12)
H4A	−0.2091	−0.2904	0.6386	0.021*
C12B	0.0820 (8)	0.8187 (6)	0.9980 (4)	0.0224 (13)
H12B	0.0537	0.8771	0.9619	0.027*
C11A	0.5502 (7)	0.0530 (7)	0.3122 (4)	0.0208 (13)
H11A	0.6087	0.0586	0.2693	0.025*
C10A	0.4388 (7)	−0.0804 (6)	0.3155 (4)	0.0193 (12)
H10A	0.4241	−0.1658	0.2760	0.023*
C9A	0.3486 (7)	−0.0901 (6)	0.3759 (4)	0.0165 (11)
H9A	0.2714	−0.1817	0.3776	0.020*
C5B	0.4009 (7)	0.2633 (6)	1.0369 (4)	0.0178 (12)
H5B	0.4047	0.2792	1.0969	0.021*
C2B	0.3900 (6)	0.2169 (6)	0.8608 (4)	0.0146 (11)
H2B	0.3884	0.1993	0.8011	0.017*
C11B	0.0733 (8)	0.8379 (7)	1.0833 (4)	0.0256 (14)
H11B	0.0385	0.9102	1.1052	0.031*
C12A	0.5773 (7)	0.1788 (6)	0.3712 (3)	0.0173 (12)
H12A	0.6556	0.2696	0.3695	0.021*
C1A	0.1259 (6)	0.0609 (5)	0.6349 (3)	0.0123 (10)
C14B	0.0889 (8)	0.7543 (7)	0.8220 (4)	0.0242 (13)
H14A	0.1000	0.7187	0.7648	0.036*
H14B	0.1516	0.8595	0.8404	0.036*
H14C	−0.0238	0.7339	0.8189	0.036*
C3B	0.4512 (7)	0.1445 (6)	0.9144 (4)	0.0183 (12)
H3B	0.4912	0.0777	0.8906	0.022*
C14A	0.6346 (7)	0.4188 (6)	0.5035 (4)	0.0210 (12)
H14D	0.6140	0.4601	0.4531	0.032*
H14E	0.7334	0.4026	0.5071	0.032*
H14F	0.6456	0.4865	0.5563	0.032*
C10B	0.1136 (7)	0.7551 (7)	1.1377 (4)	0.0218 (13)
H10B	0.1061	0.7699	1.1960	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0152 (2)	0.0125 (2)	0.0107 (2)	0.00478 (16)	0.00380 (14)	0.00165 (14)
Br2	0.0161 (3)	0.0281 (3)	0.0152 (3)	0.0012 (3)	0.0051 (2)	0.0049 (2)
Br1	0.0196 (3)	0.0194 (3)	0.0196 (3)	0.0099 (2)	0.0008 (2)	0.0017 (2)
O1B	0.019 (2)	0.0186 (19)	0.0107 (19)	0.0105 (17)	0.0059 (16)	0.0051 (15)
O1A	0.015 (2)	0.0108 (18)	0.018 (2)	0.0044 (16)	0.0058 (16)	0.0015 (15)
O2A	0.016 (2)	0.0156 (19)	0.016 (2)	0.0007 (16)	0.0073 (17)	0.0018 (16)
O2B	0.030 (2)	0.025 (2)	0.016 (2)	0.0160 (19)	0.0051 (18)	0.0050 (17)
N1A	0.014 (2)	0.014 (2)	0.010 (2)	0.0072 (19)	0.0032 (19)	−0.0014 (18)
N1B	0.014 (2)	0.017 (2)	0.010 (2)	0.0059 (19)	0.0056 (18)	0.0033 (18)
C13A	0.012 (3)	0.017 (3)	0.011 (3)	0.007 (2)	−0.001 (2)	−0.001 (2)
C13B	0.017 (3)	0.021 (3)	0.014 (3)	0.007 (2)	0.002 (2)	−0.001 (2)
C6A	0.015 (3)	0.014 (3)	0.013 (3)	0.007 (2)	0.002 (2)	0.002 (2)
C7B	0.015 (3)	0.018 (3)	0.013 (3)	0.004 (2)	0.007 (2)	0.003 (2)
C1B	0.014 (3)	0.012 (2)	0.013 (3)	0.003 (2)	0.006 (2)	0.004 (2)
C7A	0.012 (3)	0.014 (3)	0.014 (3)	0.006 (2)	0.000 (2)	0.002 (2)
C3A	0.016 (3)	0.021 (3)	0.017 (3)	0.008 (2)	0.010 (2)	0.005 (2)
C6B	0.010 (3)	0.016 (3)	0.015 (3)	0.004 (2)	0.002 (2)	0.002 (2)
C5A	0.014 (3)	0.011 (3)	0.018 (3)	0.004 (2)	0.001 (2)	0.003 (2)
C4B	0.024 (3)	0.014 (3)	0.021 (3)	0.008 (2)	0.006 (3)	0.005 (2)
C8B	0.013 (3)	0.018 (3)	0.020 (3)	0.009 (2)	0.006 (2)	0.002 (2)
C9B	0.014 (3)	0.025 (3)	0.016 (3)	0.010 (2)	0.002 (2)	0.000 (2)
C8A	0.013 (3)	0.022 (3)	0.011 (3)	0.009 (2)	0.004 (2)	0.003 (2)
C2A	0.019 (3)	0.016 (3)	0.014 (3)	0.008 (2)	0.008 (2)	0.002 (2)
C4A	0.014 (3)	0.012 (3)	0.021 (3)	0.000 (2)	0.005 (2)	0.003 (2)
C12B	0.024 (3)	0.019 (3)	0.025 (3)	0.010 (3)	0.006 (3)	0.002 (3)
C11A	0.017 (3)	0.030 (3)	0.016 (3)	0.011 (3)	0.005 (2)	0.002 (3)
C10A	0.020 (3)	0.025 (3)	0.014 (3)	0.013 (3)	0.002 (2)	−0.002 (2)
C9A	0.016 (3)	0.018 (3)	0.017 (3)	0.007 (2)	0.006 (2)	0.001 (2)
C5B	0.022 (3)	0.018 (3)	0.012 (3)	0.006 (2)	0.004 (2)	0.004 (2)
C2B	0.013 (3)	0.018 (3)	0.012 (3)	0.006 (2)	0.004 (2)	0.000 (2)
C11B	0.024 (3)	0.023 (3)	0.033 (4)	0.017 (3)	0.007 (3)	−0.002 (3)
C12A	0.017 (3)	0.020 (3)	0.014 (3)	0.005 (2)	0.006 (2)	0.007 (2)
C1A	0.014 (3)	0.012 (2)	0.013 (3)	0.008 (2)	0.004 (2)	0.002 (2)
C14B	0.035 (4)	0.024 (3)	0.022 (3)	0.020 (3)	0.006 (3)	0.010 (3)
C3B	0.016 (3)	0.015 (3)	0.026 (3)	0.007 (2)	0.006 (3)	0.005 (2)
C14A	0.024 (3)	0.015 (3)	0.020 (3)	0.002 (2)	0.008 (3)	0.003 (2)
C10B	0.017 (3)	0.029 (3)	0.017 (3)	0.011 (3)	0.002 (2)	−0.005 (2)

Geometric parameters (Å, º) top

Cd1—Br2	2.5445 (7)	C5A—C4A	1.361 (7)
Cd1—Br1	2.5374 (7)	C4B—H4B	0.9500
Cd1—O1B	2.225 (4)	C4B—C5B	1.360 (8)
Cd1—O1A	2.216 (4)	C4B—C3B	1.410 (8)
O1B—C1B	1.302 (6)	C8B—C9B	1.394 (8)
O1A—C1A	1.306 (6)	C9B—H9B	0.9500
O2A—C13A	1.358 (6)	C9B—C10B	1.392 (8)
O2A—C14A	1.434 (6)	C8A—C9A	1.394 (8)
O2B—C13B	1.354 (7)	C2A—H2A	0.9500
O2B—C14B	1.441 (6)	C2A—C1A	1.426 (7)
N1A—H1A	0.8800	C4A—H4A	0.9500
N1A—C7A	1.310 (7)	C12B—H12B	0.9500
N1A—C8A	1.409 (7)	C12B—C11B	1.383 (9)
N1B—H1B	0.8800	C11A—H11A	0.9500
N1B—C7B	1.312 (7)	C11A—C10A	1.385 (8)
N1B—C8B	1.400 (7)	C11A—C12A	1.391 (8)
C13A—C8A	1.403 (8)	C10A—H10A	0.9500
C13A—C12A	1.397 (7)	C10A—C9A	1.387 (8)
C13B—C8B	1.414 (8)	C9A—H9A	0.9500
C13B—C12B	1.397 (8)	C5B—H5B	0.9500
C6A—C7A	1.414 (7)	C2B—H2B	0.9500
C6A—C5A	1.423 (7)	C2B—C3B	1.374 (8)
C6A—C1A	1.429 (7)	C11B—H11B	0.9500
C7B—H7B	0.9500	C11B—C10B	1.381 (9)
C7B—C6B	1.413 (7)	C12A—H12A	0.9500
C1B—C6B	1.444 (7)	C14B—H14A	0.9800
C1B—C2B	1.422 (7)	C14B—H14B	0.9800
C7A—H7A	0.9500	C14B—H14C	0.9800
C3A—H3A	0.9500	C3B—H3B	0.9500
C3A—C2A	1.375 (8)	C14A—H14D	0.9800
C3A—C4A	1.409 (8)	C14A—H14E	0.9800
C6B—C5B	1.404 (8)	C14A—H14F	0.9800
C5A—H5A	0.9500	C10B—H10B	0.9500

Br1—Cd1—Br2	130.04 (2)	C9A—C8A—N1A	122.9 (5)
O1B—Cd1—Br2	101.88 (11)	C9A—C8A—C13A	120.1 (5)
O1B—Cd1—Br1	104.78 (10)	C3A—C2A—H2A	119.2
O1A—Cd1—Br2	103.56 (10)	C3A—C2A—C1A	121.5 (5)
O1A—Cd1—Br1	104.40 (10)	C1A—C2A—H2A	119.2
O1A—Cd1—O1B	111.99 (12)	C3A—C4A—H4A	120.3
C1B—O1B—Cd1	124.1 (3)	C5A—C4A—C3A	119.3 (5)
C1A—O1A—Cd1	123.5 (3)	C5A—C4A—H4A	120.3
C13A—O2A—C14A	116.8 (4)	C13B—C12B—H12B	120.4
C13B—O2B—C14B	117.8 (4)	C11B—C12B—C13B	119.2 (6)
C7A—N1A—H1A	116.5	C11B—C12B—H12B	120.4
C7A—N1A—C8A	127.0 (5)	C10A—C11A—H11A	119.6
C8A—N1A—H1A	116.5	C10A—C11A—C12A	120.8 (5)
C7B—N1B—H1B	116.7	C12A—C11A—H11A	119.6
C7B—N1B—C8B	126.6 (5)	C11A—C10A—H10A	119.8
C8B—N1B—H1B	116.7	C11A—C10A—C9A	120.5 (5)
O2A—C13A—C8A	114.6 (5)	C9A—C10A—H10A	119.8
O2A—C13A—C12A	125.5 (5)	C8A—C9A—H9A	120.3
C12A—C13A—C8A	119.9 (5)	C10A—C9A—C8A	119.5 (5)
O2B—C13B—C8B	114.9 (5)	C10A—C9A—H9A	120.3
O2B—C13B—C12B	125.3 (5)	C6B—C5B—H5B	119.0
C12B—C13B—C8B	119.8 (5)	C4B—C5B—C6B	122.0 (5)
C7A—C6A—C5A	118.1 (5)	C4B—C5B—H5B	119.0
C7A—C6A—C1A	121.9 (5)	C1B—C2B—H2B	119.7
C5A—C6A—C1A	119.9 (5)	C3B—C2B—C1B	120.5 (5)
N1B—C7B—H7B	117.8	C3B—C2B—H2B	119.7
N1B—C7B—C6B	124.4 (5)	C12B—C11B—H11B	119.0
C6B—C7B—H7B	117.8	C10B—C11B—C12B	122.0 (6)
O1B—C1B—C6B	120.5 (5)	C10B—C11B—H11B	119.0
O1B—C1B—C2B	122.7 (5)	C13A—C12A—H12A	120.4
C2B—C1B—C6B	116.8 (5)	C11A—C12A—C13A	119.2 (5)
N1A—C7A—C6A	124.3 (5)	C11A—C12A—H12A	120.4
N1A—C7A—H7A	117.8	O1A—C1A—C6A	120.4 (5)
C6A—C7A—H7A	117.8	O1A—C1A—C2A	122.8 (5)
C2A—C3A—H3A	119.5	C2A—C1A—C6A	116.8 (5)
C2A—C3A—C4A	121.0 (5)	O2B—C14B—H14A	109.5
C4A—C3A—H3A	119.5	O2B—C14B—H14B	109.5
C7B—C6B—C1B	121.0 (5)	O2B—C14B—H14C	109.5
C5B—C6B—C7B	118.9 (5)	H14A—C14B—H14B	109.5
C5B—C6B—C1B	120.1 (5)	H14A—C14B—H14C	109.5
C6A—C5A—H5A	119.3	H14B—C14B—H14C	109.5
C4A—C5A—C6A	121.4 (5)	C4B—C3B—H3B	118.9
C4A—C5A—H5A	119.3	C2B—C3B—C4B	122.2 (5)
C5B—C4B—H4B	120.8	C2B—C3B—H3B	118.9
C5B—C4B—C3B	118.4 (5)	O2A—C14A—H14D	109.5
C3B—C4B—H4B	120.8	O2A—C14A—H14E	109.5
N1B—C8B—C13B	116.8 (5)	O2A—C14A—H14F	109.5
C9B—C8B—N1B	123.8 (5)	H14D—C14A—H14E	109.5
C9B—C8B—C13B	119.3 (5)	H14D—C14A—H14F	109.5
C8B—C9B—H9B	119.7	H14E—C14A—H14F	109.5
C10B—C9B—C8B	120.6 (5)	C9B—C10B—H10B	120.4
C10B—C9B—H9B	119.7	C11B—C10B—C9B	119.1 (6)
C13A—C8A—N1A	116.9 (5)	C11B—C10B—H10B	120.4

Cd1—O1B—C1B—C6B	167.5 (4)	C3A—C2A—C1A—O1A	−178.7 (5)
Cd1—O1B—C1B—C2B	−11.5 (7)	C3A—C2A—C1A—C6A	0.6 (8)
Cd1—O1A—C1A—C6A	170.3 (4)	C6B—C1B—C2B—C3B	1.0 (8)
Cd1—O1A—C1A—C2A	−10.4 (7)	C5A—C6A—C7A—N1A	−179.5 (5)
O1B—C1B—C6B—C7B	−2.2 (8)	C5A—C6A—C1A—O1A	178.6 (5)
O1B—C1B—C6B—C5B	179.5 (5)	C5A—C6A—C1A—C2A	−0.7 (8)
O1B—C1B—C2B—C3B	−179.9 (5)	C8B—N1B—C7B—C6B	179.8 (5)
O2A—C13A—C8A—N1A	0.4 (7)	C8B—C13B—C12B—C11B	−1.0 (9)
O2A—C13A—C8A—C9A	−177.4 (5)	C8B—C9B—C10B—C11B	0.2 (9)
O2A—C13A—C12A—C11A	178.7 (5)	C8A—N1A—C7A—C6A	−179.6 (5)
O2B—C13B—C8B—N1B	0.2 (7)	C8A—C13A—C12A—C11A	−0.5 (8)
O2B—C13B—C8B—C9B	−179.0 (5)	C2A—C3A—C4A—C5A	−0.4 (9)
O2B—C13B—C12B—C11B	179.6 (6)	C4A—C3A—C2A—C1A	0.0 (9)
N1A—C8A—C9A—C10A	−179.0 (5)	C12B—C13B—C8B—N1B	−179.3 (5)
N1B—C7B—C6B—C1B	1.1 (9)	C12B—C13B—C8B—C9B	1.5 (8)
N1B—C7B—C6B—C5B	179.3 (5)	C12B—C11B—C10B—C9B	0.3 (9)
N1B—C8B—C9B—C10B	179.7 (5)	C11A—C10A—C9A—C8A	−0.7 (9)
C13A—C8A—C9A—C10A	−1.3 (8)	C10A—C11A—C12A—C13A	−1.4 (9)
C13B—C8B—C9B—C10B	−1.1 (9)	C5B—C4B—C3B—C2B	−0.9 (9)
C13B—C12B—C11B—C10B	0.0 (10)	C2B—C1B—C6B—C7B	176.9 (5)
C6A—C5A—C4A—C3A	0.2 (8)	C2B—C1B—C6B—C5B	−1.4 (8)
C7B—N1B—C8B—C13B	173.6 (5)	C12A—C13A—C8A—N1A	179.7 (5)
C7B—N1B—C8B—C9B	−7.2 (9)	C12A—C13A—C8A—C9A	1.9 (8)
C7B—C6B—C5B—C4B	−177.6 (5)	C12A—C11A—C10A—C9A	2.1 (9)
C1B—C6B—C5B—C4B	0.6 (9)	C1A—C6A—C7A—N1A	1.7 (8)
C1B—C2B—C3B—C4B	0.1 (9)	C1A—C6A—C5A—C4A	0.3 (8)
C7A—N1A—C8A—C13A	175.8 (5)	C14B—O2B—C13B—C8B	174.3 (5)
C7A—N1A—C8A—C9A	−6.4 (9)	C14B—O2B—C13B—C12B	−6.2 (8)
C7A—C6A—C5A—C4A	−178.6 (5)	C3B—C4B—C5B—C6B	0.5 (9)
C7A—C6A—C1A—O1A	−2.5 (8)	C14A—O2A—C13A—C8A	172.3 (5)
C7A—C6A—C1A—C2A	178.1 (5)	C14A—O2A—C13A—C12A	−7.0 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1A	0.88	1.94	2.638 (5)	135
N1B—H1B···O1B	0.88	1.93	2.621 (5)	135

Diiodidobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]\ methyl}phenolato-κO)cadmium(II) (Compound_4) top

Crystal data top

[CdI₂(C₂₈H₂₆N₂O₄)]	Z = 2
M_r = 820.71	F(000) = 788
Triclinic, P1	D_x = 1.942 Mg m⁻³
a = 9.3200 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0498 (3) Å	Cell parameters from 9951 reflections
c = 16.6239 (5) Å	θ = 2.3–35.6°
α = 99.140 (1)°	µ = 3.01 mm⁻¹
β = 100.528 (1)°	T = 100 K
γ = 109.332 (1)°	Block, yellow
V = 1403.58 (8) Å³	0.40 × 0.26 × 0.14 mm

Data collection top

Bruker SMART APEXII area detector diffractometer	13807 independent reflections
Radiation source: standard sealed X-ray tube, Siemens, KFF Mo 2K -90 C	10917 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
Detector resolution: 7.9 pixels mm^-1	θ_max = 36.6°, θ_min = 2.2°
ω and φ scans	h = −15→15
Absorption correction: numerical (SADABS; Bruker, 2016)	k = −16→16
T_min = 0.416, T_max = 0.667	l = −27→27
110757 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0166P)² + 3.1202P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.003
13807 reflections	Δρ_max = 1.04 e Å⁻³
336 parameters	Δρ_min = −1.33 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
I1	0.61219 (2)	0.54498 (2)	0.73702 (2)	0.02004 (3)
I2	0.05336 (2)	0.47473 (2)	0.64793 (2)	0.01951 (3)
Cd1	0.29815 (2)	0.40341 (2)	0.71415 (2)	0.01333 (3)
O1A	0.25028 (19)	0.18582 (17)	0.63597 (10)	0.0163 (3)
O1B	0.27608 (19)	0.39367 (18)	0.84469 (9)	0.0159 (3)
O2A	0.5029 (2)	0.28450 (17)	0.49378 (10)	0.0180 (3)
O2B	0.1482 (2)	0.6984 (2)	0.89037 (11)	0.0228 (3)
N1A	0.2908 (2)	0.03889 (19)	0.49969 (11)	0.0131 (3)
H1A	0.3210	0.1219	0.5369	0.016*
N1B	0.2263 (2)	0.5284 (2)	0.98053 (12)	0.0165 (3)
H1B	0.2193	0.5175	0.9262	0.020*
C1B	0.3350 (2)	0.3223 (2)	0.89094 (13)	0.0137 (3)
C6B	0.3388 (3)	0.3444 (2)	0.97888 (13)	0.0142 (3)
C3A	−0.0776 (3)	−0.0639 (2)	0.69293 (13)	0.0167 (4)
H3A	−0.1377	−0.0639	0.7334	0.020*
C1A	0.1349 (2)	0.0682 (2)	0.63543 (12)	0.0130 (3)
C2A	0.0430 (3)	0.0625 (2)	0.69497 (13)	0.0156 (4)
H2A	0.0649	0.1474	0.7371	0.019*
C7B	0.2850 (3)	0.4472 (2)	1.01879 (13)	0.0159 (4)
H7B	0.2922	0.4578	1.0774	0.019*
C2B	0.3980 (3)	0.2205 (2)	0.85860 (13)	0.0162 (4)
H2B	0.3978	0.2028	0.8007	0.019*
C6A	0.0955 (2)	−0.0632 (2)	0.57291 (12)	0.0129 (3)
C13A	0.4846 (3)	0.1676 (2)	0.43338 (13)	0.0146 (3)
C12A	0.5678 (3)	0.1712 (3)	0.37140 (14)	0.0181 (4)
H12A	0.6428	0.2604	0.3687	0.022*
C4B	0.4605 (3)	0.1683 (3)	0.99513 (15)	0.0194 (4)
H4B	0.5016	0.1155	1.0293	0.023*
C8A	0.3722 (2)	0.0350 (2)	0.43590 (13)	0.0140 (3)
C4A	−0.1135 (3)	−0.1924 (2)	0.63230 (14)	0.0181 (4)
H4A	−0.1955	−0.2790	0.6324	0.022*
C8B	0.1726 (3)	0.6332 (2)	1.01955 (14)	0.0174 (4)
C11A	0.5404 (3)	0.0439 (3)	0.31378 (14)	0.0195 (4)
H11A	0.5967	0.0467	0.2715	0.023*
C9B	0.1589 (3)	0.6470 (3)	1.10236 (14)	0.0196 (4)
H9B	0.1849	0.5850	1.1351	0.024*
C5B	0.4016 (3)	0.2664 (3)	1.02921 (14)	0.0186 (4)
H5B	0.4031	0.2818	1.0873	0.022*
C13B	0.1315 (3)	0.7227 (3)	0.97039 (14)	0.0195 (4)
C10A	0.4318 (3)	−0.0876 (3)	0.31701 (14)	0.0198 (4)
H10A	0.4154	−0.1741	0.2776	0.024*
C9A	0.3468 (3)	−0.0925 (2)	0.37816 (13)	0.0166 (4)
H9A	0.2722	−0.1822	0.3804	0.020*
C5A	−0.0285 (3)	−0.1913 (2)	0.57292 (13)	0.0165 (4)
H5A	−0.0532	−0.2776	0.5313	0.020*
C7A	0.1750 (2)	−0.0698 (2)	0.50829 (13)	0.0145 (3)
H7A	0.1416	−0.1598	0.4684	0.017*
C14A	0.6310 (3)	0.4168 (3)	0.49940 (15)	0.0205 (4)
H14A	0.6113	0.4513	0.4481	0.031*
H14B	0.7290	0.3987	0.5056	0.031*
H14C	0.6399	0.4906	0.5483	0.031*
C3B	0.4596 (3)	0.1470 (2)	0.90986 (14)	0.0180 (4)
H3B	0.5022	0.0805	0.8867	0.022*
C10B	0.1064 (3)	0.7531 (3)	1.13657 (16)	0.0249 (5)
H10B	0.0978	0.7643	1.1931	0.030*
C12B	0.0790 (3)	0.8278 (3)	1.00523 (17)	0.0250 (5)
H12B	0.0517	0.8893	0.9726	0.030*
C14B	0.1026 (4)	0.7842 (3)	0.83660 (17)	0.0271 (5)
H14D	0.1236	0.7587	0.7817	0.041*
H14E	0.1630	0.8874	0.8624	0.041*
H14F	−0.0098	0.7649	0.8291	0.041*
C11B	0.0670 (3)	0.8420 (3)	1.08820 (17)	0.0272 (5)
H11B	0.0313	0.9137	1.1119	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01512 (6)	0.02635 (7)	0.01340 (6)	0.00091 (5)	0.00337 (5)	0.00530 (5)
I2	0.01838 (7)	0.01849 (6)	0.01998 (6)	0.00879 (5)	0.00003 (5)	0.00123 (5)
Cd1	0.01452 (6)	0.01302 (6)	0.01137 (6)	0.00434 (5)	0.00314 (5)	0.00176 (4)
O1A	0.0159 (7)	0.0135 (6)	0.0174 (7)	0.0031 (5)	0.0065 (5)	0.0002 (5)
O1B	0.0183 (7)	0.0204 (7)	0.0127 (6)	0.0104 (6)	0.0054 (5)	0.0049 (5)
O2A	0.0198 (7)	0.0154 (7)	0.0171 (7)	0.0040 (6)	0.0080 (6)	0.0010 (5)
O2B	0.0323 (10)	0.0245 (8)	0.0160 (7)	0.0171 (8)	0.0047 (7)	0.0040 (6)
N1A	0.0129 (7)	0.0136 (7)	0.0133 (7)	0.0058 (6)	0.0045 (6)	0.0012 (6)
N1B	0.0166 (8)	0.0190 (8)	0.0156 (7)	0.0091 (7)	0.0049 (6)	0.0023 (6)
C1B	0.0132 (8)	0.0145 (8)	0.0130 (8)	0.0044 (7)	0.0043 (6)	0.0030 (6)
C6B	0.0161 (9)	0.0159 (8)	0.0117 (8)	0.0070 (7)	0.0046 (7)	0.0027 (6)
C3A	0.0154 (9)	0.0200 (9)	0.0154 (8)	0.0060 (8)	0.0064 (7)	0.0050 (7)
C1A	0.0119 (8)	0.0138 (8)	0.0128 (8)	0.0047 (7)	0.0027 (6)	0.0026 (6)
C2A	0.0154 (9)	0.0178 (9)	0.0145 (8)	0.0070 (7)	0.0057 (7)	0.0027 (7)
C7B	0.0174 (9)	0.0173 (9)	0.0138 (8)	0.0077 (7)	0.0046 (7)	0.0019 (7)
C2B	0.0176 (9)	0.0178 (9)	0.0130 (8)	0.0074 (7)	0.0044 (7)	0.0009 (7)
C6A	0.0124 (8)	0.0127 (8)	0.0131 (8)	0.0046 (6)	0.0030 (6)	0.0022 (6)
C13A	0.0151 (9)	0.0160 (9)	0.0128 (8)	0.0063 (7)	0.0033 (7)	0.0028 (7)
C12A	0.0188 (10)	0.0213 (10)	0.0166 (9)	0.0081 (8)	0.0075 (7)	0.0057 (7)
C4B	0.0254 (11)	0.0167 (9)	0.0185 (9)	0.0102 (8)	0.0059 (8)	0.0048 (7)
C8A	0.0131 (8)	0.0173 (9)	0.0119 (8)	0.0065 (7)	0.0036 (6)	0.0022 (6)
C4A	0.0181 (10)	0.0162 (9)	0.0186 (9)	0.0031 (8)	0.0061 (7)	0.0054 (7)
C8B	0.0155 (9)	0.0190 (9)	0.0173 (9)	0.0074 (8)	0.0042 (7)	0.0009 (7)
C11A	0.0192 (10)	0.0253 (11)	0.0157 (9)	0.0092 (9)	0.0072 (8)	0.0036 (8)
C9B	0.0164 (9)	0.0274 (11)	0.0152 (9)	0.0108 (8)	0.0039 (7)	−0.0006 (8)
C5B	0.0251 (11)	0.0189 (10)	0.0126 (8)	0.0102 (8)	0.0035 (7)	0.0032 (7)
C13B	0.0212 (10)	0.0206 (10)	0.0164 (9)	0.0094 (8)	0.0037 (8)	0.0008 (7)
C10A	0.0203 (10)	0.0234 (10)	0.0160 (9)	0.0094 (8)	0.0063 (8)	0.0001 (8)
C9A	0.0148 (9)	0.0174 (9)	0.0163 (9)	0.0061 (7)	0.0041 (7)	−0.0003 (7)
C5A	0.0182 (9)	0.0139 (8)	0.0155 (8)	0.0041 (7)	0.0046 (7)	0.0020 (7)
C7A	0.0147 (8)	0.0147 (8)	0.0134 (8)	0.0057 (7)	0.0030 (7)	0.0017 (6)
C14A	0.0188 (10)	0.0172 (9)	0.0190 (9)	−0.0003 (8)	0.0057 (8)	0.0004 (7)
C3B	0.0201 (10)	0.0153 (9)	0.0190 (9)	0.0093 (8)	0.0039 (8)	0.0008 (7)
C10B	0.0219 (11)	0.0342 (13)	0.0184 (10)	0.0142 (10)	0.0050 (8)	−0.0025 (9)
C12B	0.0284 (12)	0.0239 (11)	0.0252 (11)	0.0160 (10)	0.0053 (9)	0.0003 (9)
C14B	0.0340 (14)	0.0258 (12)	0.0226 (11)	0.0139 (11)	0.0030 (10)	0.0071 (9)
C11B	0.0278 (12)	0.0309 (13)	0.0236 (11)	0.0174 (11)	0.0040 (9)	−0.0028 (9)

Geometric parameters (Å, º) top

I1—Cd1	2.7202 (2)	C12A—H12A	0.9500
I2—Cd1	2.7104 (2)	C12A—C11A	1.387 (3)
Cd1—O1A	2.2157 (15)	C4B—H4B	0.9500
Cd1—O1B	2.2312 (15)	C4B—C5B	1.374 (3)
O1A—C1A	1.306 (3)	C4B—C3B	1.397 (3)
O1B—C1B	1.299 (3)	C8A—C9A	1.395 (3)
O2A—C13A	1.359 (3)	C4A—H4A	0.9500
O2A—C14A	1.439 (3)	C4A—C5A	1.373 (3)
O2B—C13B	1.361 (3)	C8B—C9B	1.395 (3)
O2B—C14B	1.440 (3)	C8B—C13B	1.404 (3)
N1A—H1A	0.8800	C11A—H11A	0.9500
N1A—C8A	1.415 (3)	C11A—C10A	1.389 (3)
N1A—C7A	1.306 (3)	C9B—H9B	0.9500
N1B—H1B	0.8800	C9B—C10B	1.398 (3)
N1B—C7B	1.305 (3)	C5B—H5B	0.9500
N1B—C8B	1.426 (3)	C13B—C12B	1.393 (3)
C1B—C6B	1.435 (3)	C10A—H10A	0.9500
C1B—C2B	1.421 (3)	C10A—C9A	1.395 (3)
C6B—C7B	1.416 (3)	C9A—H9A	0.9500
C6B—C5B	1.411 (3)	C5A—H5A	0.9500
C3A—H3A	0.9500	C7A—H7A	0.9500
C3A—C2A	1.380 (3)	C14A—H14A	0.9800
C3A—C4A	1.405 (3)	C14A—H14B	0.9800
C1A—C2A	1.418 (3)	C14A—H14C	0.9800
C1A—C6A	1.436 (3)	C3B—H3B	0.9500
C2A—H2A	0.9500	C10B—H10B	0.9500
C7B—H7B	0.9500	C10B—C11B	1.385 (4)
C2B—H2B	0.9500	C12B—H12B	0.9500
C2B—C3B	1.379 (3)	C12B—C11B	1.393 (4)
C6A—C5A	1.418 (3)	C14B—H14D	0.9800
C6A—C7A	1.417 (3)	C14B—H14E	0.9800
C13A—C12A	1.396 (3)	C14B—H14F	0.9800
C13A—C8A	1.409 (3)	C11B—H11B	0.9500

I2—Cd1—I1	130.043 (8)	C5A—C4A—C3A	119.2 (2)
O1A—Cd1—I1	103.73 (4)	C5A—C4A—H4A	120.4
O1A—Cd1—I2	104.76 (4)	C9B—C8B—N1B	122.4 (2)
O1A—Cd1—O1B	111.56 (6)	C9B—C8B—C13B	120.6 (2)
O1B—Cd1—I1	102.91 (4)	C13B—C8B—N1B	116.9 (2)
O1B—Cd1—I2	103.54 (4)	C12A—C11A—H11A	119.5
C1A—O1A—Cd1	124.04 (13)	C12A—C11A—C10A	121.0 (2)
C1B—O1B—Cd1	125.04 (13)	C10A—C11A—H11A	119.5
C13A—O2A—C14A	116.36 (17)	C8B—C9B—H9B	120.4
C13B—O2B—C14B	117.4 (2)	C8B—C9B—C10B	119.2 (2)
C8A—N1A—H1A	117.1	C10B—C9B—H9B	120.4
C7A—N1A—H1A	117.1	C6B—C5B—H5B	119.6
C7A—N1A—C8A	125.77 (18)	C4B—C5B—C6B	120.7 (2)
C7B—N1B—H1B	117.3	C4B—C5B—H5B	119.6
C7B—N1B—C8B	125.34 (19)	O2B—C13B—C8B	115.4 (2)
C8B—N1B—H1B	117.3	O2B—C13B—C12B	125.1 (2)
O1B—C1B—C6B	120.25 (19)	C12B—C13B—C8B	119.6 (2)
O1B—C1B—C2B	122.92 (19)	C11A—C10A—H10A	120.0
C2B—C1B—C6B	116.83 (19)	C11A—C10A—C9A	120.0 (2)
C7B—C6B—C1B	121.86 (19)	C9A—C10A—H10A	120.0
C5B—C6B—C1B	120.45 (19)	C8A—C9A—C10A	119.6 (2)
C5B—C6B—C7B	117.66 (19)	C8A—C9A—H9A	120.2
C2A—C3A—H3A	119.3	C10A—C9A—H9A	120.2
C2A—C3A—C4A	121.4 (2)	C6A—C5A—H5A	119.6
C4A—C3A—H3A	119.3	C4A—C5A—C6A	120.9 (2)
O1A—C1A—C2A	122.80 (19)	C4A—C5A—H5A	119.6
O1A—C1A—C6A	120.39 (18)	N1A—C7A—C6A	124.70 (19)
C2A—C1A—C6A	116.81 (19)	N1A—C7A—H7A	117.7
C3A—C2A—C1A	121.3 (2)	C6A—C7A—H7A	117.7
C3A—C2A—H2A	119.3	O2A—C14A—H14A	109.5
C1A—C2A—H2A	119.3	O2A—C14A—H14B	109.5
N1B—C7B—C6B	124.4 (2)	O2A—C14A—H14C	109.5
N1B—C7B—H7B	117.8	H14A—C14A—H14B	109.5
C6B—C7B—H7B	117.8	H14A—C14A—H14C	109.5
C1B—C2B—H2B	119.5	H14B—C14A—H14C	109.5
C3B—C2B—C1B	121.10 (19)	C2B—C3B—C4B	121.4 (2)
C3B—C2B—H2B	119.5	C2B—C3B—H3B	119.3
C5A—C6A—C1A	120.41 (18)	C4B—C3B—H3B	119.3
C7A—C6A—C1A	122.09 (19)	C9B—C10B—H10B	119.9
C7A—C6A—C5A	117.49 (18)	C11B—C10B—C9B	120.1 (2)
O2A—C13A—C12A	125.0 (2)	C11B—C10B—H10B	119.9
O2A—C13A—C8A	115.48 (18)	C13B—C12B—H12B	120.2
C12A—C13A—C8A	119.57 (19)	C11B—C12B—C13B	119.6 (2)
C13A—C12A—H12A	120.2	C11B—C12B—H12B	120.2
C11A—C12A—C13A	119.6 (2)	O2B—C14B—H14D	109.5
C11A—C12A—H12A	120.2	O2B—C14B—H14E	109.5
C5B—C4B—H4B	120.2	O2B—C14B—H14F	109.5
C5B—C4B—C3B	119.5 (2)	H14D—C14B—H14E	109.5
C3B—C4B—H4B	120.2	H14D—C14B—H14F	109.5
C13A—C8A—N1A	116.80 (18)	H14E—C14B—H14F	109.5
C9A—C8A—N1A	122.9 (2)	C10B—C11B—C12B	120.9 (2)
C9A—C8A—C13A	120.26 (19)	C10B—C11B—H11B	119.6
C3A—C4A—H4A	120.4	C12B—C11B—H11B	119.6

Cd1—O1A—C1A—C2A	−10.7 (3)	C2B—C1B—C6B—C7B	177.5 (2)
Cd1—O1A—C1A—C6A	169.28 (14)	C2B—C1B—C6B—C5B	−0.5 (3)
Cd1—O1B—C1B—C6B	168.58 (15)	C6A—C1A—C2A—C3A	0.4 (3)
Cd1—O1B—C1B—C2B	−11.4 (3)	C13A—C12A—C11A—C10A	−0.4 (4)
O1A—C1A—C2A—C3A	−179.6 (2)	C13A—C8A—C9A—C10A	−1.0 (3)
O1A—C1A—C6A—C5A	179.2 (2)	C12A—C13A—C8A—N1A	−179.4 (2)
O1A—C1A—C6A—C7A	−2.2 (3)	C12A—C13A—C8A—C9A	1.5 (3)
O1B—C1B—C6B—C7B	−2.5 (3)	C12A—C11A—C10A—C9A	0.9 (4)
O1B—C1B—C6B—C5B	179.5 (2)	C8A—N1A—C7A—C6A	179.9 (2)
O1B—C1B—C2B—C3B	180.0 (2)	C8A—C13A—C12A—C11A	−0.9 (3)
O2A—C13A—C12A—C11A	179.0 (2)	C4A—C3A—C2A—C1A	0.6 (3)
O2A—C13A—C8A—N1A	0.7 (3)	C8B—N1B—C7B—C6B	−179.5 (2)
O2A—C13A—C8A—C9A	−178.4 (2)	C8B—C9B—C10B—C11B	0.7 (4)
O2B—C13B—C12B—C11B	−180.0 (3)	C8B—C13B—C12B—C11B	−0.5 (4)
N1A—C8A—C9A—C10A	−180.0 (2)	C11A—C10A—C9A—C8A	−0.2 (4)
N1B—C8B—C9B—C10B	179.5 (2)	C9B—C8B—C13B—O2B	−179.4 (2)
N1B—C8B—C13B—O2B	−0.1 (3)	C9B—C8B—C13B—C12B	1.1 (4)
N1B—C8B—C13B—C12B	−179.6 (2)	C9B—C10B—C11B—C12B	−0.1 (4)
C1B—C6B—C7B—N1B	1.0 (4)	C5B—C6B—C7B—N1B	179.0 (2)
C1B—C6B—C5B—C4B	0.2 (4)	C5B—C4B—C3B—C2B	−1.2 (4)
C1B—C2B—C3B—C4B	0.8 (4)	C13B—C8B—C9B—C10B	−1.2 (4)
C6B—C1B—C2B—C3B	0.0 (3)	C13B—C12B—C11B—C10B	0.0 (4)
C3A—C4A—C5A—C6A	0.9 (3)	C5A—C6A—C7A—N1A	179.7 (2)
C1A—C6A—C5A—C4A	0.2 (3)	C7A—N1A—C8A—C13A	174.5 (2)
C1A—C6A—C7A—N1A	1.2 (3)	C7A—N1A—C8A—C9A	−6.4 (3)
C2A—C3A—C4A—C5A	−1.2 (4)	C7A—C6A—C5A—C4A	−178.4 (2)
C2A—C1A—C6A—C5A	−0.8 (3)	C14A—O2A—C13A—C12A	−7.9 (3)
C2A—C1A—C6A—C7A	177.7 (2)	C14A—O2A—C13A—C8A	172.1 (2)
C7B—N1B—C8B—C9B	−8.5 (4)	C3B—C4B—C5B—C6B	0.6 (4)
C7B—N1B—C8B—C13B	172.3 (2)	C14B—O2B—C13B—C8B	178.0 (2)
C7B—C6B—C5B—C4B	−177.9 (2)	C14B—O2B—C13B—C12B	−2.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1A	0.88	1.98	2.660 (2)	134
N1B—H1B···O1B	0.88	1.96	2.641 (2)	134
C7B—H7B···I1ⁱ	0.95	3.06	3.979 (2)	164

Symmetry code: (i) −x+1, −y+1, −z+2.

Dichloridobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)mercury(II) (Compound_5) top

Crystal data top

[HgCl₂(C₂₈H₂₆N₂O₄)]	Z = 2
M_r = 726.00	F(000) = 708
Triclinic, P1	D_x = 1.818 Mg m⁻³
a = 9.2456 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1510 (4) Å	Cell parameters from 9113 reflections
c = 15.8499 (6) Å	θ = 2.2–28.3°
α = 96.5447 (15)°	µ = 6.04 mm⁻¹
β = 99.7441 (15)°	T = 100 K
γ = 112.6735 (14)°	Block, yellow
V = 1326.25 (9) Å³	0.17 × 0.14 × 0.08 mm

Data collection top

Bruker APEXII area detector diffractometer	22779 independent reflections
Radiation source: standard sealed X-ray tube, Siemens, KFF Mo 2K -90 C	21098 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
Detector resolution: 7.9 pixels mm^-1	θ_max = 28.4°, θ_min = 2.2°
ω and φ scans	h = −12→12
Absorption correction: multi-scan (TWINABS; Bruker, 2012)	k = −13→13
T_min = 0.630, T_max = 0.746	l = −21→21
22779 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.052	w = 1/[σ²(F_o²) + (0.0276P)² + 0.8324P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
22779 reflections	Δρ_max = 1.29 e Å⁻³
337 parameters	Δρ_min = −0.60 e Å⁻³
0 restraints

Special details top

Refinement. The structure was solved as a rotational twin. Rotated from first domain by 179.9 degrees about reciprocal axis -0.001 1.000 -0.999 and real axis 0.345 1.000 -0.274. Twin law to convert hkl from first to this domain (SHELXL TWIN matrix): -1.000 -0.001 0.001 0.541 0.570 -0.431 -0.543 -1.570 -0.570.

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

	x	y	z	U_iso*/U_eq
Hg1	0.30358 (2)	0.41553 (2)	0.70492 (2)	0.01398 (4)
Cl2	0.06386 (10)	0.43743 (9)	0.64325 (5)	0.02133 (17)
Cl1	0.58885 (10)	0.51131 (10)	0.73464 (5)	0.02286 (18)
O2A	0.5129 (3)	0.2848 (2)	0.49846 (15)	0.0175 (5)
O1B	0.2698 (3)	0.3921 (2)	0.84731 (14)	0.0150 (4)
O1A	0.2471 (3)	0.1792 (2)	0.63192 (14)	0.0147 (4)
O2B	0.1477 (3)	0.6740 (3)	0.87712 (15)	0.0214 (5)
N1A	0.2871 (3)	0.0338 (3)	0.49857 (16)	0.0123 (5)
H1A	0.3172	0.1153	0.5364	0.015*
N1B	0.2302 (3)	0.5248 (3)	0.98489 (17)	0.0135 (5)
H1B	0.2219	0.5096	0.9281	0.016*
C6A	0.0819 (4)	−0.0724 (3)	0.57465 (19)	0.0119 (6)
C8A	0.3768 (3)	0.0384 (3)	0.43409 (19)	0.0130 (6)
C2A	0.0318 (4)	0.0563 (3)	0.69823 (19)	0.0146 (6)
H2A	0.0564	0.1423	0.7392	0.018*
C7A	0.1641 (4)	−0.0786 (3)	0.50788 (19)	0.0126 (6)
H7A	0.1287	−0.1683	0.4681	0.015*
C9A	0.3520 (4)	−0.0831 (4)	0.3737 (2)	0.0161 (6)
H9A	0.2712	−0.1757	0.3741	0.019*
C1A	0.1262 (3)	0.0614 (3)	0.63542 (19)	0.0122 (6)
C13A	0.4973 (4)	0.1755 (3)	0.43428 (19)	0.0140 (6)
C12A	0.5898 (4)	0.1900 (4)	0.3723 (2)	0.0175 (6)
H12A	0.6704	0.2823	0.3713	0.021*
C6B	0.3353 (4)	0.3439 (3)	0.98874 (19)	0.0128 (6)
C4A	−0.1357 (4)	−0.2007 (3)	0.6417 (2)	0.0158 (6)
H4A	−0.2226	−0.2875	0.6448	0.019*
C5A	−0.0490 (4)	−0.2005 (3)	0.5798 (2)	0.0148 (6)
H5A	−0.0771	−0.2881	0.5394	0.018*
C2B	0.3820 (4)	0.2177 (3)	0.8629 (2)	0.0153 (6)
H2B	0.3789	0.1999	0.8023	0.018*
C10A	0.4462 (4)	−0.0686 (4)	0.3128 (2)	0.0195 (7)
H10A	0.4308	−0.1516	0.2719	0.023*
C7B	0.2878 (4)	0.4476 (3)	1.0288 (2)	0.0150 (6)
H7B	0.2982	0.4616	1.0902	0.018*
C11A	0.5626 (4)	0.0670 (4)	0.3116 (2)	0.0199 (7)
H11A	0.6247	0.0763	0.2688	0.024*
C1B	0.3269 (3)	0.3208 (3)	0.89657 (19)	0.0126 (6)
C3A	−0.0941 (4)	−0.0702 (4)	0.7008 (2)	0.0150 (6)
H3A	−0.1548	−0.0699	0.7435	0.018*
C8B	0.1798 (4)	0.6305 (3)	1.0193 (2)	0.0156 (6)
C9B	0.1697 (4)	0.6556 (4)	1.1058 (2)	0.0194 (7)
H9B	0.1983	0.6011	1.1452	0.023*
C3B	0.4400 (4)	0.1430 (4)	0.9168 (2)	0.0186 (7)
H3B	0.4768	0.0752	0.8925	0.022*
C5B	0.3953 (4)	0.2647 (3)	1.0420 (2)	0.0174 (6)
H5B	0.4005	0.2810	1.1029	0.021*
C13B	0.1358 (4)	0.7097 (4)	0.9603 (2)	0.0176 (6)
C4B	0.4460 (4)	0.1646 (4)	1.0069 (2)	0.0204 (7)
H4B	0.4846	0.1108	1.0428	0.024*
C10B	0.1178 (4)	0.7604 (4)	1.1341 (2)	0.0246 (8)
H10B	0.1101	0.7776	1.1930	0.029*
C14A	0.6461 (4)	0.4226 (4)	0.5090 (2)	0.0246 (8)
H14A	0.6325	0.4646	0.4570	0.037*
H14B	0.7465	0.4090	0.5165	0.037*
H14C	0.6505	0.4885	0.5605	0.037*
C12B	0.0854 (4)	0.8158 (4)	0.9899 (2)	0.0228 (7)
H12B	0.0568	0.8710	0.9510	0.027*
C11B	0.0772 (4)	0.8402 (4)	1.0765 (3)	0.0254 (8)
H11B	0.0432	0.9128	1.0966	0.030*
C14B	0.0805 (5)	0.7343 (4)	0.8123 (2)	0.0246 (7)
H14D	0.0861	0.6931	0.7546	0.037*
H14E	0.1414	0.8403	0.8245	0.037*
H14F	−0.0323	0.7110	0.8134	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.01692 (6)	0.01312 (6)	0.01094 (6)	0.00545 (5)	0.00344 (4)	0.00119 (4)
Cl2	0.0208 (4)	0.0204 (4)	0.0215 (4)	0.0104 (3)	0.0002 (3)	−0.0001 (3)
Cl1	0.0166 (4)	0.0301 (4)	0.0151 (4)	0.0023 (3)	0.0043 (3)	0.0045 (3)
O2A	0.0194 (12)	0.0133 (11)	0.0176 (11)	0.0030 (9)	0.0098 (9)	−0.0001 (9)
O1B	0.0189 (11)	0.0184 (11)	0.0122 (10)	0.0115 (9)	0.0051 (8)	0.0041 (8)
O1A	0.0141 (10)	0.0109 (10)	0.0167 (11)	0.0028 (8)	0.0056 (8)	−0.0009 (8)
O2B	0.0288 (13)	0.0255 (13)	0.0175 (12)	0.0180 (11)	0.0066 (10)	0.0067 (10)
N1A	0.0127 (12)	0.0130 (12)	0.0108 (12)	0.0058 (10)	0.0030 (9)	−0.0007 (9)
N1B	0.0153 (12)	0.0159 (13)	0.0112 (12)	0.0085 (10)	0.0043 (10)	0.0006 (10)
C6A	0.0123 (14)	0.0123 (14)	0.0111 (13)	0.0053 (11)	0.0025 (11)	0.0015 (11)
C8A	0.0107 (13)	0.0192 (15)	0.0110 (13)	0.0080 (12)	0.0034 (11)	0.0028 (11)
C2A	0.0149 (14)	0.0160 (15)	0.0126 (14)	0.0065 (12)	0.0037 (11)	0.0004 (11)
C7A	0.0140 (14)	0.0118 (14)	0.0117 (13)	0.0062 (11)	0.0016 (11)	0.0001 (11)
C9A	0.0129 (14)	0.0191 (15)	0.0148 (14)	0.0066 (12)	0.0021 (11)	−0.0004 (12)
C1A	0.0116 (13)	0.0135 (14)	0.0121 (13)	0.0060 (11)	0.0020 (11)	0.0025 (11)
C13A	0.0142 (14)	0.0169 (15)	0.0121 (14)	0.0083 (12)	0.0022 (11)	0.0013 (11)
C12A	0.0153 (15)	0.0217 (16)	0.0173 (15)	0.0082 (13)	0.0061 (12)	0.0051 (12)
C6B	0.0116 (13)	0.0147 (14)	0.0131 (14)	0.0056 (11)	0.0048 (11)	0.0038 (11)
C4A	0.0138 (14)	0.0146 (15)	0.0170 (15)	0.0034 (12)	0.0042 (12)	0.0043 (12)
C5A	0.0142 (14)	0.0118 (14)	0.0155 (15)	0.0035 (12)	0.0021 (12)	0.0004 (11)
C2B	0.0167 (15)	0.0161 (15)	0.0131 (14)	0.0068 (12)	0.0052 (12)	0.0008 (11)
C10A	0.0192 (16)	0.0261 (17)	0.0136 (15)	0.0118 (14)	0.0034 (12)	−0.0027 (13)
C7B	0.0146 (14)	0.0182 (15)	0.0106 (13)	0.0055 (12)	0.0032 (11)	0.0010 (11)
C11A	0.0186 (16)	0.0299 (19)	0.0145 (15)	0.0130 (14)	0.0063 (12)	0.0029 (13)
C1B	0.0110 (13)	0.0127 (14)	0.0134 (14)	0.0041 (11)	0.0035 (11)	0.0020 (11)
C3A	0.0152 (15)	0.0194 (16)	0.0124 (14)	0.0081 (13)	0.0046 (12)	0.0045 (12)
C8B	0.0133 (14)	0.0163 (15)	0.0172 (15)	0.0075 (12)	0.0032 (12)	−0.0011 (12)
C9B	0.0155 (15)	0.0248 (17)	0.0165 (15)	0.0098 (13)	0.0018 (12)	−0.0033 (13)
C3B	0.0209 (16)	0.0155 (15)	0.0212 (17)	0.0100 (13)	0.0051 (13)	0.0016 (13)
C5B	0.0194 (16)	0.0177 (15)	0.0138 (15)	0.0061 (13)	0.0036 (12)	0.0043 (12)
C13B	0.0144 (15)	0.0178 (16)	0.0204 (16)	0.0070 (13)	0.0045 (12)	0.0012 (12)
C4B	0.0248 (17)	0.0180 (16)	0.0218 (16)	0.0120 (14)	0.0037 (13)	0.0085 (13)
C10B	0.0193 (17)	0.0309 (19)	0.0206 (17)	0.0121 (15)	0.0022 (13)	−0.0087 (14)
C14A	0.0262 (18)	0.0151 (16)	0.0260 (18)	−0.0002 (14)	0.0126 (15)	0.0010 (13)
C12B	0.0191 (17)	0.0186 (17)	0.0302 (19)	0.0097 (14)	0.0031 (14)	0.0003 (14)
C11B	0.0204 (17)	0.0234 (18)	0.0296 (19)	0.0108 (15)	0.0028 (14)	−0.0073 (15)
C14B	0.0303 (19)	0.0247 (18)	0.0235 (18)	0.0152 (15)	0.0054 (14)	0.0105 (14)

Geometric parameters (Å, º) top

Hg1—Cl2	2.3693 (8)	C4A—H4A	0.9500
Hg1—Cl1	2.3709 (8)	C4A—C5A	1.369 (4)
Hg1—O1B	2.356 (2)	C4A—C3A	1.407 (4)
Hg1—O1A	2.359 (2)	C5A—H5A	0.9500
O2A—C13A	1.363 (4)	C2B—H2B	0.9500
O2A—C14A	1.432 (4)	C2B—C1B	1.421 (4)
O1B—C1B	1.302 (4)	C2B—C3B	1.377 (4)
O1A—C1A	1.299 (4)	C10A—H10A	0.9500
O2B—C13B	1.361 (4)	C10A—C11A	1.387 (5)
O2B—C14B	1.427 (4)	C7B—H7B	0.9500
N1A—H1A	0.8800	C11A—H11A	0.9500
N1A—C8A	1.415 (4)	C3A—H3A	0.9500
N1A—C7A	1.308 (4)	C8B—C9B	1.391 (4)
N1B—H1B	0.8800	C8B—C13B	1.406 (5)
N1B—C7B	1.305 (4)	C9B—H9B	0.9500
N1B—C8B	1.416 (4)	C9B—C10B	1.387 (5)
C6A—C7A	1.413 (4)	C3B—H3B	0.9500
C6A—C1A	1.442 (4)	C3B—C4B	1.409 (5)
C6A—C5A	1.417 (4)	C5B—H5B	0.9500
C8A—C9A	1.389 (4)	C5B—C4B	1.374 (5)
C8A—C13A	1.407 (4)	C13B—C12B	1.394 (4)
C2A—H2A	0.9500	C4B—H4B	0.9500
C2A—C1A	1.424 (4)	C10B—H10B	0.9500
C2A—C3A	1.372 (4)	C10B—C11B	1.385 (6)
C7A—H7A	0.9500	C14A—H14A	0.9800
C9A—H9A	0.9500	C14A—H14B	0.9800
C9A—C10A	1.389 (4)	C14A—H14C	0.9800
C13A—C12A	1.393 (4)	C12B—H12B	0.9500
C12A—H12A	0.9500	C12B—C11B	1.386 (5)
C12A—C11A	1.397 (5)	C11B—H11B	0.9500
C6B—C7B	1.415 (4)	C14B—H14D	0.9800
C6B—C1B	1.437 (4)	C14B—H14E	0.9800
C6B—C5B	1.417 (4)	C14B—H14F	0.9800

Cl2—Hg1—Cl1	148.23 (3)	C11A—C10A—C9A	120.1 (3)
O1B—Hg1—Cl2	100.65 (6)	C11A—C10A—H10A	119.9
O1B—Hg1—Cl1	98.78 (6)	N1B—C7B—C6B	122.7 (3)
O1B—Hg1—O1A	105.56 (7)	N1B—C7B—H7B	118.6
O1A—Hg1—Cl2	100.40 (6)	C6B—C7B—H7B	118.6
O1A—Hg1—Cl1	98.27 (6)	C12A—C11A—H11A	119.5
C13A—O2A—C14A	117.3 (3)	C10A—C11A—C12A	120.9 (3)
C1B—O1B—Hg1	125.42 (19)	C10A—C11A—H11A	119.5
C1A—O1A—Hg1	124.97 (19)	O1B—C1B—C6B	120.3 (3)
C13B—O2B—C14B	117.0 (3)	O1B—C1B—C2B	122.5 (3)
C8A—N1A—H1A	116.5	C2B—C1B—C6B	117.1 (3)
C7A—N1A—H1A	116.5	C2A—C3A—C4A	121.7 (3)
C7A—N1A—C8A	126.9 (3)	C2A—C3A—H3A	119.2
C7B—N1B—H1B	116.7	C4A—C3A—H3A	119.2
C7B—N1B—C8B	126.6 (3)	C9B—C8B—N1B	123.3 (3)
C8B—N1B—H1B	116.7	C9B—C8B—C13B	120.3 (3)
C7A—C6A—C1A	121.4 (3)	C13B—C8B—N1B	116.3 (3)
C7A—C6A—C5A	118.5 (3)	C8B—C9B—H9B	120.2
C5A—C6A—C1A	120.1 (3)	C10B—C9B—C8B	119.7 (3)
C9A—C8A—N1A	123.5 (3)	C10B—C9B—H9B	120.2
C9A—C8A—C13A	120.4 (3)	C2B—C3B—H3B	119.1
C13A—C8A—N1A	116.1 (3)	C2B—C3B—C4B	121.7 (3)
C1A—C2A—H2A	119.3	C4B—C3B—H3B	119.1
C3A—C2A—H2A	119.3	C6B—C5B—H5B	119.5
C3A—C2A—C1A	121.3 (3)	C4B—C5B—C6B	120.9 (3)
N1A—C7A—C6A	122.8 (3)	C4B—C5B—H5B	119.5
N1A—C7A—H7A	118.6	O2B—C13B—C8B	115.2 (3)
C6A—C7A—H7A	118.6	O2B—C13B—C12B	125.5 (3)
C8A—C9A—H9A	120.2	C12B—C13B—C8B	119.3 (3)
C10A—C9A—C8A	119.6 (3)	C3B—C4B—H4B	120.5
C10A—C9A—H9A	120.2	C5B—C4B—C3B	119.0 (3)
O1A—C1A—C6A	120.6 (3)	C5B—C4B—H4B	120.5
O1A—C1A—C2A	122.8 (3)	C9B—C10B—H10B	120.0
C2A—C1A—C6A	116.7 (3)	C11B—C10B—C9B	120.0 (3)
O2A—C13A—C8A	114.7 (3)	C11B—C10B—H10B	120.0
O2A—C13A—C12A	125.5 (3)	O2A—C14A—H14A	109.5
C12A—C13A—C8A	119.8 (3)	O2A—C14A—H14B	109.5
C13A—C12A—H12A	120.4	O2A—C14A—H14C	109.5
C13A—C12A—C11A	119.1 (3)	H14A—C14A—H14B	109.5
C11A—C12A—H12A	120.4	H14A—C14A—H14C	109.5
C7B—C6B—C1B	121.3 (3)	H14B—C14A—H14C	109.5
C7B—C6B—C5B	118.4 (3)	C13B—C12B—H12B	120.2
C5B—C6B—C1B	120.3 (3)	C11B—C12B—C13B	119.6 (3)
C5A—C4A—H4A	120.5	C11B—C12B—H12B	120.2
C5A—C4A—C3A	119.0 (3)	C10B—C11B—C12B	121.0 (3)
C3A—C4A—H4A	120.5	C10B—C11B—H11B	119.5
C6A—C5A—H5A	119.4	C12B—C11B—H11B	119.5
C4A—C5A—C6A	121.3 (3)	O2B—C14B—H14D	109.5
C4A—C5A—H5A	119.4	O2B—C14B—H14E	109.5
C1B—C2B—H2B	119.5	O2B—C14B—H14F	109.5
C3B—C2B—H2B	119.5	H14D—C14B—H14E	109.5
C3B—C2B—C1B	120.9 (3)	H14D—C14B—H14F	109.5
C9A—C10A—H10A	119.9	H14E—C14B—H14F	109.5

Hg1—O1B—C1B—C6B	164.0 (2)	C5A—C6A—C1A—C2A	−0.5 (4)
Hg1—O1B—C1B—C2B	−16.4 (4)	C5A—C4A—C3A—C2A	−0.6 (5)
Hg1—O1A—C1A—C6A	166.7 (2)	C2B—C3B—C4B—C5B	−1.1 (5)
Hg1—O1A—C1A—C2A	−13.6 (4)	C7B—N1B—C8B—C9B	−7.0 (5)
O2A—C13A—C12A—C11A	178.4 (3)	C7B—N1B—C8B—C13B	174.3 (3)
O2B—C13B—C12B—C11B	179.3 (3)	C7B—C6B—C1B—O1B	−2.3 (4)
N1A—C8A—C9A—C10A	−179.8 (3)	C7B—C6B—C1B—C2B	178.0 (3)
N1A—C8A—C13A—O2A	1.4 (4)	C7B—C6B—C5B—C4B	−178.8 (3)
N1A—C8A—C13A—C12A	−179.2 (3)	C1B—C6B—C7B—N1B	1.9 (5)
N1B—C8B—C9B—C10B	−179.4 (3)	C1B—C6B—C5B—C4B	−0.1 (5)
N1B—C8B—C13B—O2B	−0.1 (4)	C1B—C2B—C3B—C4B	0.5 (5)
N1B—C8B—C13B—C12B	−179.8 (3)	C3A—C2A—C1A—O1A	−179.3 (3)
C8A—N1A—C7A—C6A	−179.9 (3)	C3A—C2A—C1A—C6A	0.5 (4)
C8A—C9A—C10A—C11A	−0.9 (5)	C3A—C4A—C5A—C6A	0.5 (5)
C8A—C13A—C12A—C11A	−0.9 (5)	C8B—N1B—C7B—C6B	180.0 (3)
C7A—N1A—C8A—C9A	−4.8 (5)	C8B—C9B—C10B—C11B	−0.4 (5)
C7A—N1A—C8A—C13A	175.9 (3)	C8B—C13B—C12B—C11B	−0.9 (5)
C7A—C6A—C1A—O1A	−2.3 (4)	C9B—C8B—C13B—O2B	−178.8 (3)
C7A—C6A—C1A—C2A	178.0 (3)	C9B—C8B—C13B—C12B	1.4 (5)
C7A—C6A—C5A—C4A	−178.5 (3)	C9B—C10B—C11B—C12B	0.9 (6)
C9A—C8A—C13A—O2A	−177.9 (3)	C3B—C2B—C1B—O1B	−179.3 (3)
C9A—C8A—C13A—C12A	1.5 (5)	C3B—C2B—C1B—C6B	0.4 (4)
C9A—C10A—C11A—C12A	1.4 (5)	C5B—C6B—C7B—N1B	−179.5 (3)
C1A—C6A—C7A—N1A	2.1 (5)	C5B—C6B—C1B—O1B	179.1 (3)
C1A—C6A—C5A—C4A	0.0 (5)	C5B—C6B—C1B—C2B	−0.5 (4)
C1A—C2A—C3A—C4A	0.1 (5)	C13B—C8B—C9B—C10B	−0.8 (5)
C13A—C8A—C9A—C10A	−0.6 (5)	C13B—C12B—C11B—C10B	−0.2 (5)
C13A—C12A—C11A—C10A	−0.5 (5)	C14A—O2A—C13A—C8A	172.4 (3)
C6B—C5B—C4B—C3B	1.0 (5)	C14A—O2A—C13A—C12A	−6.9 (5)
C5A—C6A—C7A—N1A	−179.4 (3)	C14B—O2B—C13B—C8B	170.3 (3)
C5A—C6A—C1A—O1A	179.2 (3)	C14B—O2B—C13B—C12B	−9.9 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1A	0.88	1.89	2.599 (3)	137
N1B—H1B···O1B	0.88	1.87	2.585 (3)	137
C7A—H7A···Cl2ⁱ	0.95	2.80	3.719 (3)	163
C7B—H7B···Cl1ⁱⁱ	0.95	2.74	3.656 (3)	163

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

Diiodidobis(2-{(E)-[(2-methoxyphenyl)azaniumylidene]methyl}phenolato-κO)mercury(II) (Compound_6) top

Crystal data top

[HgI₂(C₂₈H₂₆N₂O₄)]	Z = 2
M_r = 908.90	F(000) = 852
Triclinic, P1	D_x = 2.155 Mg m⁻³
a = 9.2783 (14) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0060 (15) Å	Cell parameters from 9897 reflections
c = 16.695 (3) Å	θ = 4.4–54.9°
α = 98.777 (1)°	µ = 7.74 mm⁻¹
β = 100.296 (1)°	T = 100 K
γ = 109.396 (1)°	Block, orange
V = 1400.4 (4) Å³	0.38 × 0.19 × 0.13 mm

Data collection top

Bruker APEXII area detector diffractometer	11185 independent reflections
Radiation source: standard sealed X-ray tube, Siemens, KFF Mo 2K -90 C	10132 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
Detector resolution: 7.9 pixels mm^-1	θ_max = 27.5°, θ_min = 2.2°
ω and φ scans	h = −12→12
Absorption correction: multi-scan (TWINABS; Bruker, 2012)	k = −12→12
T_min = 0.441, T_max = 0.746	l = −21→21
11185 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0782P)² + 0.6965P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
11185 reflections	Δρ_max = 1.48 e Å⁻³
337 parameters	Δρ_min = −1.78 e Å⁻³
0 restraints

Special details top

Refinement. The structure was solved as a rotational twin. Rotated from first domain by 149.8 degrees about reciprocal axis 1.000 0.235 0.787 and real axis 1.000 0.533 0.319. Twin law to convert hkl from first to this domain (SHELXL TWIN matrix) 0.534 0.949 0.308, 0.116 -0.693 0.359, 1.269 -0.145 -0.569.

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

	x	y	z	U_iso*/U_eq
C1A	0.6673 (8)	0.6731 (7)	0.1093 (4)	0.0127 (13)
C1B	0.8585 (8)	0.9260 (7)	0.3661 (4)	0.0125 (13)
C2A	0.6036 (9)	0.7737 (8)	0.1421 (4)	0.0174 (14)
H2A	0.6028	0.7890	0.1996	0.021*
C2B	0.9490 (8)	0.9298 (8)	0.3052 (4)	0.0149 (13)
H2B	0.9249	0.8450	0.2630	0.018*
C3A	0.5431 (8)	0.8495 (8)	0.0928 (4)	0.0169 (15)
H3A	0.5022	0.9168	0.1171	0.020*
C3B	1.0718 (8)	1.0564 (8)	0.3071 (4)	0.0152 (14)
H3B	1.1330	1.0555	0.2672	0.018*
C4A	0.5396 (9)	0.8304 (8)	0.0060 (5)	0.0190 (16)
H4A	0.4963	0.8832	−0.0274	0.023*
C4B	1.1086 (9)	1.1864 (8)	0.3666 (5)	0.0171 (16)
H4B	1.1906	1.2730	0.3654	0.020*
C5A	0.5999 (9)	0.7349 (8)	−0.0278 (4)	0.0180 (15)
H5A	0.5998	0.7224	−0.0854	0.022*
C5B	1.0261 (8)	1.1863 (7)	0.4251 (4)	0.0142 (14)
H5B	1.0525	1.2735	0.4659	0.017*
C6A	0.6634 (8)	0.6528 (8)	0.0212 (4)	0.0143 (14)
C6B	0.9001 (8)	1.0591 (7)	0.4277 (4)	0.0135 (13)
C7A	0.7163 (8)	0.5513 (7)	−0.0189 (4)	0.0134 (13)
H7A	0.7096	0.5419	−0.0770	0.016*
C7B	0.8215 (8)	1.0664 (7)	0.4921 (4)	0.0124 (13)
H7B	0.8552	1.1565	0.5315	0.015*
C8A	0.8298 (8)	0.3650 (8)	−0.0185 (4)	0.0156 (14)
C8B	0.6225 (8)	0.9598 (8)	0.5647 (4)	0.0129 (13)
C9A	0.8442 (8)	0.3500 (8)	−0.1012 (4)	0.0165 (14)
H9A	0.8185	0.4122	−0.1340	0.020*
C9B	0.6492 (8)	1.0855 (8)	0.6224 (4)	0.0165 (14)
H9B	0.7256	1.1750	0.6203	0.020*
C10A	0.8962 (9)	0.2439 (9)	−0.1351 (5)	0.0247 (17)
H10A	0.9060	0.2333	−0.1912	0.030*
C10B	0.5643 (9)	1.0816 (8)	0.6839 (4)	0.0179 (15)
H10B	0.5808	1.1681	0.7230	0.022*
C11A	0.9336 (10)	0.1536 (9)	−0.0865 (5)	0.0259 (18)
H11A	0.9694	0.0815	−0.1099	0.031*
C11B	0.4558 (9)	0.9494 (8)	0.6866 (4)	0.0179 (15)
H11B	0.4002	0.9453	0.7293	0.022*
C12A	0.9197 (9)	0.1665 (9)	−0.0045 (5)	0.0225 (16)
H12A	0.9452	0.1034	0.0278	0.027*
C12B	0.4262 (9)	0.8216 (8)	0.6279 (5)	0.0183 (15)
H12B	0.3498	0.7323	0.6303	0.022*
C13A	0.8680 (8)	0.2727 (8)	0.0302 (5)	0.0156 (14)
C13B	0.5088 (8)	0.8260 (8)	0.5663 (4)	0.0150 (14)
C14A	0.8940 (10)	0.2095 (8)	0.1624 (5)	0.0227 (17)
H14A	0.8269	0.1069	0.1389	0.034*
H14B	0.8797	0.2400	0.2182	0.034*
H14C	1.0046	0.2219	0.1667	0.034*
C14B	0.3629 (9)	0.5751 (8)	0.5007 (5)	0.0227 (16)
H14D	0.2643	0.5922	0.4983	0.034*
H14E	0.3874	0.5375	0.5502	0.034*
H14F	0.3513	0.5040	0.4503	0.034*
Hg1	0.69274 (3)	0.57222 (3)	0.28950 (2)	0.01351 (9)
I1	0.38080 (6)	0.46487 (6)	0.26379 (3)	0.01957 (13)
I2	0.95749 (6)	0.53212 (5)	0.34679 (3)	0.01950 (13)
N1A	0.7749 (7)	0.4679 (6)	0.0195 (4)	0.0150 (12)
H1A	0.7800	0.4773	0.0734	0.018*
N1B	0.7048 (7)	0.9565 (6)	0.5009 (4)	0.0136 (11)
H1B	0.6748	0.8735	0.4641	0.016*
O1A	0.7251 (6)	0.5993 (5)	0.1535 (3)	0.0156 (10)
O1B	0.7437 (6)	0.8100 (5)	0.3671 (3)	0.0162 (10)
O2A	0.8515 (7)	0.2962 (6)	0.1094 (3)	0.0223 (12)
O2B	0.4891 (6)	0.7101 (5)	0.5057 (3)	0.0186 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.008 (3)	0.012 (3)	0.018 (3)	0.004 (3)	0.002 (3)	0.004 (3)
C1B	0.012 (3)	0.012 (3)	0.017 (3)	0.006 (3)	0.005 (3)	0.007 (3)
C2A	0.019 (4)	0.018 (3)	0.016 (3)	0.009 (3)	0.005 (3)	0.000 (3)
C2B	0.017 (3)	0.017 (3)	0.014 (3)	0.010 (3)	0.006 (3)	0.003 (3)
C3A	0.015 (3)	0.012 (3)	0.018 (3)	0.005 (3)	−0.001 (3)	−0.007 (3)
C3B	0.012 (3)	0.022 (4)	0.013 (3)	0.007 (3)	0.005 (3)	0.005 (3)
C4A	0.017 (4)	0.012 (3)	0.022 (4)	0.003 (3)	0.000 (3)	0.001 (3)
C4B	0.019 (4)	0.017 (4)	0.021 (4)	0.008 (3)	0.012 (3)	0.012 (3)
C5A	0.024 (4)	0.016 (3)	0.014 (3)	0.007 (3)	0.006 (3)	0.004 (3)
C5B	0.017 (3)	0.010 (3)	0.011 (3)	0.003 (3)	0.001 (3)	0.000 (3)
C6A	0.016 (3)	0.014 (3)	0.013 (3)	0.006 (3)	0.001 (3)	0.005 (3)
C6B	0.015 (3)	0.012 (3)	0.010 (3)	0.004 (3)	−0.002 (3)	0.001 (2)
C7A	0.013 (3)	0.013 (3)	0.013 (3)	0.001 (3)	0.006 (3)	0.002 (3)
C7B	0.009 (3)	0.009 (3)	0.015 (3)	0.001 (3)	−0.001 (3)	0.001 (3)
C8A	0.018 (4)	0.016 (3)	0.014 (3)	0.008 (3)	0.005 (3)	0.000 (3)
C8B	0.011 (3)	0.015 (3)	0.015 (3)	0.007 (3)	0.005 (3)	0.004 (3)
C9A	0.010 (3)	0.023 (4)	0.015 (3)	0.006 (3)	0.001 (3)	0.003 (3)
C9B	0.014 (3)	0.019 (4)	0.015 (3)	0.005 (3)	0.004 (3)	0.002 (3)
C10A	0.014 (4)	0.035 (5)	0.017 (4)	0.009 (3)	−0.003 (3)	−0.009 (3)
C10B	0.017 (4)	0.019 (4)	0.017 (3)	0.010 (3)	0.003 (3)	−0.004 (3)
C11A	0.026 (4)	0.025 (4)	0.028 (4)	0.019 (4)	0.001 (3)	−0.003 (3)
C11B	0.016 (4)	0.021 (4)	0.017 (3)	0.008 (3)	0.004 (3)	0.003 (3)
C12A	0.023 (4)	0.022 (4)	0.024 (4)	0.013 (3)	0.002 (3)	0.002 (3)
C12B	0.016 (4)	0.028 (4)	0.014 (3)	0.009 (3)	0.007 (3)	0.008 (3)
C13A	0.013 (3)	0.014 (3)	0.023 (4)	0.011 (3)	0.002 (3)	0.003 (3)
C13B	0.016 (3)	0.018 (3)	0.010 (3)	0.008 (3)	0.000 (3)	0.001 (3)
C14A	0.030 (4)	0.022 (4)	0.020 (4)	0.014 (3)	0.002 (3)	0.009 (3)
C14B	0.024 (4)	0.016 (4)	0.023 (4)	0.000 (3)	0.008 (3)	0.003 (3)
Hg1	0.01544 (14)	0.01255 (14)	0.01221 (14)	0.00467 (11)	0.00395 (9)	0.00241 (10)
I1	0.0150 (2)	0.0260 (3)	0.0142 (2)	0.0019 (2)	0.00385 (18)	0.0070 (2)
I2	0.0182 (3)	0.0166 (2)	0.0215 (3)	0.0077 (2)	0.00010 (19)	0.00114 (19)
N1A	0.017 (3)	0.013 (3)	0.016 (3)	0.007 (3)	0.005 (2)	0.004 (2)
N1B	0.016 (3)	0.013 (3)	0.013 (3)	0.009 (2)	0.004 (2)	−0.002 (2)
O1A	0.019 (3)	0.017 (3)	0.015 (2)	0.010 (2)	0.006 (2)	0.004 (2)
O1B	0.017 (3)	0.011 (2)	0.021 (3)	0.005 (2)	0.010 (2)	0.002 (2)
O2A	0.032 (3)	0.023 (3)	0.017 (3)	0.015 (2)	0.007 (2)	0.009 (2)
O2B	0.021 (3)	0.016 (2)	0.017 (3)	0.004 (2)	0.008 (2)	0.001 (2)

Geometric parameters (Å, º) top

C1A—C2A	1.417 (10)	C8B—N1B	1.418 (9)
C1A—C6A	1.446 (9)	C9A—H9A	0.9500
C1A—O1A	1.290 (8)	C9A—C10A	1.391 (11)
C1B—C2B	1.427 (9)	C9B—H9B	0.9500
C1B—C6B	1.442 (9)	C9B—C10B	1.398 (10)
C1B—O1B	1.294 (8)	C10A—H10A	0.9500
C2A—H2A	0.9500	C10A—C11A	1.388 (12)
C2A—C3A	1.370 (10)	C10B—H10B	0.9500
C2B—H2B	0.9500	C10B—C11B	1.384 (10)
C2B—C3B	1.385 (10)	C11A—H11A	0.9500
C3A—H3A	0.9500	C11A—C12A	1.390 (12)
C3A—C4A	1.426 (11)	C11B—H11B	0.9500
C3B—H3B	0.9500	C11B—C12B	1.400 (11)
C3B—C4B	1.409 (11)	C12A—H12A	0.9500
C4A—H4A	0.9500	C12A—C13A	1.395 (10)
C4A—C5A	1.359 (11)	C12B—H12B	0.9500
C4B—H4B	0.9500	C12B—C13B	1.386 (10)
C4B—C5B	1.343 (10)	C13A—O2A	1.352 (9)
C5A—H5A	0.9500	C13B—O2B	1.355 (8)
C5A—C6A	1.430 (9)	C14A—H14A	0.9800
C5B—H5B	0.9500	C14A—H14B	0.9800
C5B—C6B	1.427 (9)	C14A—H14C	0.9800
C6A—C7A	1.401 (10)	C14A—O2A	1.424 (8)
C6B—C7B	1.408 (10)	C14B—H14D	0.9800
C7A—H7A	0.9500	C14B—H14E	0.9800
C7A—N1A	1.320 (9)	C14B—H14F	0.9800
C7B—H7B	0.9500	C14B—O2B	1.443 (8)
C7B—N1B	1.312 (9)	Hg1—I1	2.6580 (7)
C8A—C9A	1.400 (10)	Hg1—I2	2.6536 (7)
C8A—C13A	1.408 (10)	Hg1—O1A	2.387 (5)
C8A—N1A	1.410 (9)	Hg1—O1B	2.378 (5)
C8B—C9B	1.382 (10)	N1A—H1A	0.8800
C8B—C13B	1.411 (10)	N1B—H1B	0.8800

C2A—C1A—C6A	116.8 (6)	C10B—C9B—H9B	119.8
O1A—C1A—C2A	123.4 (6)	C9A—C10A—H10A	120.2
O1A—C1A—C6A	119.8 (6)	C11A—C10A—C9A	119.5 (7)
C2B—C1B—C6B	116.9 (6)	C11A—C10A—H10A	120.2
O1B—C1B—C2B	122.7 (6)	C9B—C10B—H10B	120.6
O1B—C1B—C6B	120.5 (6)	C11B—C10B—C9B	118.7 (7)
C1A—C2A—H2A	119.3	C11B—C10B—H10B	120.6
C3A—C2A—C1A	121.5 (7)	C10A—C11A—H11A	119.3
C3A—C2A—H2A	119.3	C10A—C11A—C12A	121.4 (7)
C1B—C2B—H2B	119.7	C12A—C11A—H11A	119.3
C3B—C2B—C1B	120.5 (7)	C10B—C11B—H11B	119.3
C3B—C2B—H2B	119.7	C10B—C11B—C12B	121.5 (7)
C2A—C3A—H3A	119.1	C12B—C11B—H11B	119.3
C2A—C3A—C4A	121.9 (7)	C11A—C12A—H12A	120.2
C4A—C3A—H3A	119.1	C11A—C12A—C13A	119.5 (7)
C2B—C3B—H3B	119.1	C13A—C12A—H12A	120.2
C2B—C3B—C4B	121.8 (7)	C11B—C12B—H12B	120.1
C4B—C3B—H3B	119.1	C13B—C12B—C11B	119.7 (7)
C3A—C4A—H4A	120.8	C13B—C12B—H12B	120.1
C5A—C4A—C3A	118.4 (7)	C12A—C13A—C8A	119.6 (7)
C5A—C4A—H4A	120.8	O2A—C13A—C8A	115.7 (6)
C3B—C4B—H4B	120.5	O2A—C13A—C12A	124.7 (7)
C5B—C4B—C3B	119.1 (7)	C12B—C13B—C8B	118.9 (7)
C5B—C4B—H4B	120.5	O2B—C13B—C8B	116.1 (6)
C4A—C5A—H5A	119.2	O2B—C13B—C12B	125.0 (7)
C4A—C5A—C6A	121.6 (7)	H14A—C14A—H14B	109.5
C6A—C5A—H5A	119.2	H14A—C14A—H14C	109.5
C4B—C5B—H5B	119.0	H14B—C14A—H14C	109.5
C4B—C5B—C6B	122.0 (7)	O2A—C14A—H14A	109.5
C6B—C5B—H5B	119.0	O2A—C14A—H14B	109.5
C5A—C6A—C1A	119.8 (6)	O2A—C14A—H14C	109.5
C7A—C6A—C1A	121.8 (6)	H14D—C14B—H14E	109.5
C7A—C6A—C5A	118.4 (6)	H14D—C14B—H14F	109.5
C5B—C6B—C1B	119.7 (6)	H14E—C14B—H14F	109.5
C7B—C6B—C1B	121.6 (6)	O2B—C14B—H14D	109.5
C7B—C6B—C5B	118.7 (6)	O2B—C14B—H14E	109.5
C6A—C7A—H7A	118.1	O2B—C14B—H14F	109.5
N1A—C7A—C6A	123.8 (6)	I2—Hg1—I1	145.097 (18)
N1A—C7A—H7A	118.1	O1A—Hg1—I1	102.05 (12)
C6B—C7B—H7B	118.0	O1A—Hg1—I2	98.69 (12)
N1B—C7B—C6B	124.1 (6)	O1B—Hg1—I1	98.64 (12)
N1B—C7B—H7B	118.0	O1B—Hg1—I2	102.36 (13)
C9A—C8A—C13A	120.0 (7)	O1B—Hg1—O1A	105.74 (16)
C9A—C8A—N1A	123.2 (6)	C7A—N1A—C8A	125.4 (6)
C13A—C8A—N1A	116.8 (6)	C7A—N1A—H1A	117.3
C9B—C8B—C13B	120.7 (6)	C8A—N1A—H1A	117.3
C9B—C8B—N1B	123.1 (6)	C7B—N1B—C8B	125.7 (6)
C13B—C8B—N1B	116.2 (6)	C7B—N1B—H1B	117.2
C8A—C9A—H9A	120.0	C8B—N1B—H1B	117.2
C10A—C9A—C8A	120.0 (7)	C1A—O1A—Hg1	125.7 (4)
C10A—C9A—H9A	120.0	C1B—O1B—Hg1	124.7 (4)
C8B—C9B—H9B	119.8	C13A—O2A—C14A	118.1 (6)
C8B—C9B—C10B	120.4 (7)	C13B—O2B—C14B	117.2 (6)

C1A—C2A—C3A—C4A	0.6 (11)	C9A—C8A—C13A—O2A	179.5 (6)
C1A—C6A—C7A—N1A	−0.8 (11)	C9A—C8A—N1A—C7A	7.1 (11)
C1B—C2B—C3B—C4B	−2.3 (10)	C9A—C10A—C11A—C12A	0.2 (12)
C1B—C6B—C7B—N1B	−1.2 (10)	C9B—C8B—C13B—C12B	−1.3 (10)
C2A—C1A—C6A—C5A	1.2 (10)	C9B—C8B—C13B—O2B	178.4 (6)
C2A—C1A—C6A—C7A	−177.0 (6)	C9B—C8B—N1B—C7B	5.1 (10)
C2A—C1A—O1A—Hg1	13.7 (9)	C9B—C10B—C11B—C12B	−2.1 (11)
C2A—C3A—C4A—C5A	−0.6 (11)	C10A—C11A—C12A—C13A	−0.4 (12)
C2B—C1B—C6B—C5B	0.4 (9)	C10B—C11B—C12B—C13B	1.2 (11)
C2B—C1B—C6B—C7B	−178.1 (6)	C11A—C12A—C13A—C8A	0.3 (11)
C2B—C1B—O1B—Hg1	13.4 (9)	C11A—C12A—C13A—O2A	−179.3 (7)
C2B—C3B—C4B—C5B	2.6 (11)	C11B—C12B—C13B—C8B	0.5 (10)
C3A—C4A—C5A—C6A	1.0 (11)	C11B—C12B—C13B—O2B	−179.2 (7)
C3B—C4B—C5B—C6B	−1.4 (11)	C12A—C13A—O2A—C14A	1.9 (11)
C4A—C5A—C6A—C1A	−1.3 (11)	C12B—C13B—O2B—C14B	5.8 (10)
C4A—C5A—C6A—C7A	176.9 (7)	C13A—C8A—C9A—C10A	0.0 (11)
C4B—C5B—C6B—C1B	−0.1 (10)	C13A—C8A—N1A—C7A	−171.6 (7)
C4B—C5B—C6B—C7B	178.5 (7)	C13B—C8B—C9B—C10B	0.4 (11)
C5A—C6A—C7A—N1A	−179.0 (7)	C13B—C8B—N1B—C7B	−175.2 (6)
C5B—C6B—C7B—N1B	−179.7 (6)	N1A—C8A—C9A—C10A	−178.6 (7)
C6A—C1A—C2A—C3A	−0.8 (10)	N1A—C8A—C13A—C12A	178.6 (7)
C6A—C1A—O1A—Hg1	−165.2 (5)	N1A—C8A—C13A—O2A	−1.8 (9)
C6A—C7A—N1A—C8A	−179.7 (6)	N1B—C8B—C9B—C10B	−179.9 (6)
C6B—C1B—C2B—C3B	0.8 (10)	N1B—C8B—C13B—C12B	179.0 (6)
C6B—C1B—O1B—Hg1	−166.9 (5)	N1B—C8B—C13B—O2B	−1.3 (9)
C6B—C7B—N1B—C8B	−179.7 (6)	O1A—C1A—C2A—C3A	−179.8 (7)
C8A—C9A—C10A—C11A	−0.1 (11)	O1A—C1A—C6A—C5A	−179.8 (6)
C8A—C13A—O2A—C14A	−177.7 (6)	O1A—C1A—C6A—C7A	2.1 (10)
C8B—C9B—C10B—C11B	1.3 (11)	O1B—C1B—C2B—C3B	−179.4 (6)
C8B—C13B—O2B—C14B	−174.0 (6)	O1B—C1B—C6B—C5B	−179.4 (6)
C9A—C8A—C13A—C12A	−0.1 (10)	O1B—C1B—C6B—C7B	2.1 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1A	0.88	1.92	2.611 (8)	134
N1B—H1B···O1B	0.88	1.94	2.629 (7)	134

Selected bond lengths (Å) and angles (°) for compounds 1–6 top

Compound		1	2	3	4	5	6
Bond length	M1—X1	2.240 (4)	2.588 (3)	2.537 (1)	2.720 (1)	2.371 (1)	2.658 (1)
	M1—X2	2.243 (4)	2.568 (3)	2.545 (1)	2.710 (1)	2.369 (1)	2.654 (1)
	M1—O2A	1.985 (1)	1.990 (10)	2.216 (4)	2.231 (2)	2.259 (2)	2.387 (5)
	M1—O2B	1.983 (1)	1.990 (10)	2.225 (4)	2.216 (2)	2.356 (2)	2.378 (5)
Bond angles	X1—M1—X2	124.8 (2)	123.7 (1)	130.0 (1)	130.1 (1)	148.2 (1)	145.1 (1)
	O1A—M1—X1	103.9 (3)	104.0 (4)	104.4 (1)	103.7 (1)	98.3 (1)	102.0 (1)
	O1A—M1—X2	104.0 (3)	103.6 (4)	103.6 (1)	104.8 (1)	100.4 (1)	98.7 (1)
	O1B—M1—X1	105.5 (3)	106.2 (4)	104.8 (1)	102.9 (1)	98.8 (1)	98.6 (1)
	O1B—M1—X2	102.8 (3)	104.2 (4)	101.9 (1)	103.5 (1)	100.7 (1)	102.3 (1)
	O1A—M1—O1B	116.8 (4)	115.8 (5)	112.0 (2)	111.6 (1)	105.6 (1)	105.8 (2)

Relative contributions (%) of various noncovalent contacts to the Hirshfeld surface area in complexes 1–6 top

Compound	H···H	C···H	M—X···H	O···H	C···C	N···C
1	46.2	20.2	15.7	6.0	7.9	3.0
2	43.4	20.4	18.7	6.3	7.1	2.8
3	42.9	20.2	18.2	6.8	7.1	2.8
4	43.5	20.1	19.2	6.8	6.9	2.8
5	43.5	20.5	16.5	6.7	7.2	2.9
6	41.3	20.2	18.3	6.9	6.9	2.8

Dihedral angles (°) between the two least-squares planes of the aromatic rings of ligand L top

Plane A consists of atoms C1–C6 and plane B consists of atoms C8–C13.

Structure	Ligand A	Ligand B
1	4.34	10.68
2	8.76	5.17
3	4.10	7.07
4	5.86	8.20
5	3.62	5.23
6	8.83	5.31

Acknowledgements

The authors gratefully acknowledge financial support from the Research Council of Alzahra University, and the Centre de Tecnologies de la Informació (CTI) at the UIB for computational facilities.

Funding information

Funding for this research was provided by: Research Council of Alzahra University; Science Foundation Ireland (SFI grant No. IvP 13/IA/1894); MINECO/AEI of Spain (project No. CTQ2017-85821-R, FEDER funds, to AF and AB).

References

Ahlrichs, R., Bär, M., Häser, M., Horn, H. & Kölmel, C. (1989). Chem. Phys. Lett. 162, 165–169. CrossRef CAS Web of Science Google Scholar
Alarcón, S., Pagani, D., Bacigalupo, J. & Olivieri, A. (1999). J. Mol. Struct. 475, 233–240. Google Scholar
Azhdari Tehrani, A., Abedi, S. & Morsali, A. (2016). Cryst. Growth Des. 17, 255–261. CrossRef Google Scholar
Bader, R. F. (1991). Chem. Rev. 91, 893–928. CrossRef CAS Google Scholar
Blake, A. J., Champness, N. R., Hubberstey, P., Li, W.-S., Withersby, M. A. & Schröder, M. (1999). Coord. Chem. Rev. 183, 117–138. Web of Science CrossRef CAS Google Scholar
Boys, S. F. & Bernardi, F. D. (1970). Mol. Phys. 19, 553–566. CrossRef CAS Google Scholar
Braga, D. & Grepioni, F. (2000). Acc. Chem. Res. 33, 601–608. Web of Science CrossRef PubMed CAS Google Scholar
Braga, D., Grepioni, F. & Desiraju, G. R. (1998). Chem. Rev. 98, 1375–1406. Web of Science CrossRef PubMed CAS Google Scholar
Brammer, L. (2004). Chem. Soc. Rev. 33, 476–489. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2012). TWINABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2015). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2016). APEX3 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Busschaert, N., Caltagirone, C., Van Rossom, W. & Gale, P. A. (2015). Chem. Rev. 115, 8038–8155. CrossRef CAS Google Scholar
Charland, J., Gabe, E., Khoo, L. & Smith, F. (1989). Polyhedron, 8, 1897–1901. CrossRef CAS Google Scholar
Cohen, M. & Schmidt, G. (1962). J. Phys. Chem. 66, 2442–2446. CrossRef CAS Google Scholar
Cohen, M., Schmidt, G. & Flavian, S. (1964). J. Chem. Soc. pp. 2041–2051. CrossRef Google Scholar
Custelcean, R., Bonnesen, P. V., Duncan, N. C., Zhang, X., Watson, L. A., Van Berkel, G., Parson, W. B. & Hay, B. P. (2012). J. Am. Chem. Soc. 134, 8525–8534. CrossRef CAS Google Scholar
Đaković, M., Soldin, Ž., Kukovec, B.-M., Kodrin, I., Aakeröy, C. B., Baus, N. & Rinkovec, T. (2018). IUCrJ, 5, 13–21. CrossRef IUCr Journals Google Scholar
Desiraju, G. (1998). Chem. Commun. pp. 891–892. Google Scholar
Desiraju, G. R. (2014). Angew. Chem. Int. Ed. 53, 604–605. CrossRef CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Dürr, H. & Bouas-Laurent, H. (2003). In Photochromism: Molecules and Systems. Amsterdam: Elsevier. Google Scholar
Gong, D., Wang, B., Jia, X. & Zhang, X. (2014). Dalton Trans. 43, 4169–4178. CrossRef CAS Google Scholar
Hajiashrafi, T., Kharat, A. N., Love, J. A. & Patrick, B. O. (2013). Polyhedron, 60, 30–38. CrossRef CAS Google Scholar
Hajiashrafi, T., Ziarani, G. M., Kubicki, M., Fadaei, F. T. & Schenk, K. J. (2016). Polyhedron, 119, 260–266. CrossRef CAS Google Scholar
Holliday, B. J. & Mirkin, C. A. (2001). Angew. Chem. Int. Ed. 40, 2022–2043. CrossRef CAS Google Scholar
Hope, H. (1994). Prog. Inorg. Chem. 41, 1–19. CrossRef CAS Web of Science Google Scholar
Hoshino, N., Inabe, T., Mitani, T. & Maruyama, Y. (1988). Bull. Chem. Soc. Jpn, 61, 4207–4214. CrossRef CAS Web of Science Google Scholar
Janiak, C. (2000). J. Chem. Soc. Dalton Trans. pp. 3885–3896. Web of Science CrossRef Google Scholar
Kargili, H., Alpaslan, G., Macit, M., Erdönmez, A. & Büyükgüngör, O. (2014). Opt. Spectrosc. 116, 179–186. CrossRef CAS Google Scholar
Keith, T. A. (2013). AIMAll. Version 13.05.06. TK Gristmill Software, Overland Park, KS, USA. Google Scholar
Khavasi, H. R. & Azhdari Tehrani, A. (2013). Inorg. Chem. 52, 2891–2905. CrossRef CAS PubMed Google Scholar
Khavasi, H. R. & Azizpoor Fard, M. (2010). Cryst. Growth Des. 10, 1892–1896. CrossRef CAS Google Scholar
Khavasi, H. R., Barforoush, M. M. & Fard, M. A. (2012). CrystEngComm, 14, 7236–7244. CrossRef CAS Google Scholar
Khavasi, H. R. & Mohammad Sadegh, B. M. (2010). Inorg. Chem. 49, 5356–5358. CrossRef CAS Google Scholar
Khavasi, H. R., Norouzi, F. & Azhdari Tehrani, A. (2015). Cryst. Growth Des. 15, 2579–2583. CrossRef CAS Google Scholar
Khavasi, H. R. & Sadegh, B. M. M. (2014). Dalton Trans. 43, 5564–5573. CrossRef CAS Google Scholar
Kielmann, M. & Senge, M. O. (2018). Angew. Chem. Int. Ed. 58, 418–441. CrossRef Google Scholar
Lehn, J.-M. (1995). In Supramolecular Chemistry. Weinheim: VCH. Google Scholar
Li, B., Zang, S.-Q., Wang, L.-Y. & Mak, T. C. (2016). Coord. Chem. Rev. 308, 1–21. CrossRef CAS Google Scholar
Li, L. & Yuan, F. (2012). Synth. React. Inorg. Met.-Org. Nano-Met. Chem. 42, 994–998. Web of Science CrossRef CAS Google Scholar
Mackenzie, C. F., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). IUCrJ, 4, 575–587. Web of Science CrossRef CAS PubMed IUCr Journals Google Scholar
Mahata, P., Prabu, M. & Natarajan, S. (2009). Cryst. Growth Des. 9, 3683–3691. Web of Science CrossRef CAS Google Scholar
McKinlay, A. C., Morris, R. E., Horcajada, P., Férey, G., Gref, R., Couvreur, P. & Serre, C. (2010). Angew. Chem. Int. Ed. 49, 6260–6266. Web of Science CrossRef CAS Google Scholar
Politzer, P., Murray, J. S. & Clark, T. (2010). Phys. Chem. Chem. Phys. 12, 7748–7757. Web of Science CrossRef CAS PubMed Google Scholar
Reddy, P. A., Nethaji, M. & Chakravarty, A. R. (2003a). Eur. J. Inorg. Chem. pp. 2318–2324. CrossRef Google Scholar
Reddy, P. A., Nethaji, M. & Chakravarty, A. R. (2003b). Inorg. Chem. Commun. 6, 698–701. CrossRef CAS Google Scholar
Redshaw, C., Walton, M., Clowes, L., Hughes, D. L., Fuller, A. M., Chao, Y., Walton, A., Sumerin, V., Elo, P. & Soshnikov, I. (2013). Chem. Eur. J. 19, 8884–8899. CrossRef CAS Google Scholar
Reedijk, J. (2009). Eur. J. Inorg. Chem. pp. 1303–1312. Web of Science CrossRef Google Scholar
Reedijk, J. (2013). Chem. Soc. Rev. 42, 1776–1783. CrossRef CAS Google Scholar
Schottel, B. L., Chifotides, H. T., Shatruk, M., Chouai, A., Pérez, L. M., Bacsa, J. & Dunbar, K. R. (2006). J. Am. Chem. Soc. 128, 5895–5912. Web of Science CrossRef PubMed CAS Google Scholar
Semeniuc, R. F., Reamer, T. J. & Smith, M. D. (2010). New J. Chem. 34, 439–452. CrossRef CAS Google Scholar
Senge, M. O. (2000). Z. Naturforsch. Teil B, 55, 336–344. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shkol'nikova, L., Obodovskaya, A. & Shugam, E. (1970). J. Struct. Chem. 11, 47–53. Google Scholar
Song, X., Wang, Z., Zhao, J. & Hor, T. A. (2013). Chem. Commun. 49, 4992–4994. CrossRef CAS Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Steed, J. W. & Atwood, J. L. (2013). In Supramolecular Chemistry. London: John Wiley & Sons. Google Scholar
Tsuchimoto, M., Yoshida, N., Sugimoto, A., Teramoto, N. & Nakajima, K. (2016). J. Mol. Struct. 1105, 152–158. CrossRef CAS Google Scholar
Wang, Z. J., Clary, K. N., Bergman, R. G., Raymond, K. N. & Toste, F. D. (2013). Nat. Chem. 5, 100–103. CrossRef CAS Google Scholar
Wiester, M. J., Ulmann, P. A. & Mirkin, C. A. (2011). Angew. Chem. Int. Ed. 50, 114–137. CrossRef CAS Google Scholar
Yang, L., Powell, D. R. & Houser, R. P. (2007). Dalton Trans. pp. 955–964. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zeng, F., Ni, J., Wang, Q., Ding, Y., Ng, S. W., Zhu, W. & Xie, Y. (2010). Cryst. Growth Des. 10, 1611–1622. Web of Science CrossRef CAS Google Scholar

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STRUCTURAL
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ISSN: 2053-2296

Volume 75| Part 2| February 2019| Pages 178-188

https://doi.org/10.1107/S2053229618018314

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research papers\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

The role of π–π stacking and hydrogen-bonding inter­actions in the assembly of a series of isostructural group IIB coordination compounds

1. Introduction

2. Experimental

2.1. Materials and apparatus

2.2. Computational methods

2.3. Synthesis and crystallization

2.3.1. Analytical data for L

2.3.2. Analytical data for 1

2.3.3. Analytical data for 2

2.3.4. Analytical data for 3

2.3.5. Analytical data for 4

2.3.6. Analytical data for 5

2.3.7. Analytical data for 6

2.4. Refinement

3. Results and discussion

3.1. Crystal structure analysis

3.2. Theoretical study

4. Conclusion

Supporting information

Acknowledgements

Funding information

References

research papers

The role of π–π stacking and hydrogen-bonding interactions in the assembly of a series of isostructural group IIB coordination compounds