Packing polymorphism in the structure of trans-aqua­[N,N′-bis­(salicyl­idene)ethane-1,2-di­amine-κ4O,N,N′,O′]chlorido­manganese(III) monohydrate

Reyes Perea, J.A.; Bernès, S.; Quintero Téllez, M.G.

doi:10.1107/S2056989018015694

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Volume 74| Part 12| December 2018| Pages 1778-1782

https://doi.org/10.1107/S2056989018015694

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Packing polymorphism in the structure of trans-aqua[N,N′-bis(salicylidene)ethane-1,2-diamine-κ⁴O,N,N′,O′]chloridomanganese(III) monohydrate

Juan Alberto Reyes Perea,^a Sylvain Bernès ^b and Ma Guadalupe Quintero Téllez ^c ^*

^aFacultad de Ciencias Físico Matemáticas, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, ^bInstituto de Física, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, and ^cFacultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico
^*Correspondence e-mail: lupita_qt@hotmail.com

Edited by A. Van der Lee, Université de Montpellier II, France (Received 1 October 2018; accepted 6 November 2018; online 13 November 2018)

The crystal structure of the title complex (systematic name: trans-aquachlorido{2,2′[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato-κ⁴O,N,N′,O′}manganese(III) monohydrate), [Mn(C₁₆H₁₄N₂O₂)Cl(H₂O)]·H₂O has been reported previously in the space group P2₁/n [Panja et al. (2003 $[Panja, A., Shaikh, N., Ali, M., Vojt\?íšek, P. & Banerjee, P. (2003). Polyhedron, 22, 1191-1198.]$ ). Polyhedron, 22, 1191–1198]. We obtained the same hydrated complex through an alternative synthesis, and crystallized a new polymorph, in the space group P2₁. The molecular conformation of the complex is virtually unmodified, but the absence of the glide plane in the new polymorph halves the unit-cell parameter c, affording a non-centrosymmetric crystal structure with Z = 2, while the previously reported crystal is centrosymmetric with Z = 4. Both phases represent a case of packing polymorphism, similar to other dimorphic crystal structures retrieved from the Cambridge Structural Database.

Keywords: crystal structure; polymorphism; salen ligand; manganese; hydrate.

CCDC reference: 1877342

1. Chemical context

Schiff base organic compounds are widely employed ligands in modern coordination chemistry because they are easily accessible and display high versatility (Zarei et al., 2015 ). Within this field, the coordination chemistry of H₂salen [N,N′-bis(salicylidene)ethane-1,2-diamine] has been studied with virtually all transition metals. The chelating character of the dianionic ligand salen is known to stabilize not only M²⁺ cations, but also higher oxidation states, providing that ancillary anions such as Cl⁻ are present. In the case of manganese, this strategy may be used to stabilize Mn^III and Mn^IV oxidation states, generally in octahedral ligand fields. The resulting complexes are potentially of interest in various interdisciplinary fields such as structural chemistry, catalytic processes involving metalloproteins or enzymes (Sarkar et al., 2017 ), magnetochemistry (Blinov, 2017 ), and NLO materials. Regarding the sub-family of Mn^III–salen derivatives, they have been used mainly as models for biological systems involving this metal cation. For our part, we focus on salen-based materials, which can display non-linear optical response, for example with Co^III as the metal centre (Quintero-Téllez et al., 2016 ).

While extending our work to Mn^III, we prepared the title complex, for which a synthesis was previously reported (Panja et al., 2003 $[Panja, A., Shaikh, N., Ali, M., Vojt\?íšek, P. & Banerjee, P. (2003). Polyhedron, 22, 1191-1198.]$ ). These authors synthesized the complex using a Mn^III compound as starting material, namely [Mn(salen)OAc]·H₂O, which was reacted with MnCl₂·4H₂O in water. Crystallization at room temperature afforded brownish black microcrystals, and the authors characterized the complex in space group P2₁/n, with Z = 4. We obtained the same compound through a more straightforward synthetic route, using a one-pot reaction between salicylaldehyde, diethylenetriamine, and MnCl₂, in MeOH. In contrast to the previous synthesis, crystallization was carried out at low temperature (283 K) in methanol, affording brown crystals. The structure determination shows that this phase crystallizes in space group P2₁, with Z = 2.

Although we have no strong experimental evidences regarding the mechanism triggering the polymorphism for this complex, we believe that the temperature and the solvent of crystallization could be the key parameters. We report here the structure of the P2₁ polymorph, along with its characterization in solution by means of UV–Vis spectroscopy.

2. Structural commentary

The asymmetric unit of the P2₁ phase contains one [Mn(salen)(OH₂)Cl] neutral complex and one lattice water molecule, both in general positions (Fig. 1). As expected, the Mn^III centre displays a slightly distorted octahedral geometry, with the four donor sites of ligand salen in the equatorial plane (N1/N2/O1/O2). The metal deviates by only 0.056 Å from the equatorial plane, and axial sites are occupied by a water molecule (O3W) and the chloride ion (Cl) at normal distances. Deviations from an ideal octahedral geometry result from the bite angles of the chelating salen ligand.

Figure 1
The structure of the title solvate, with displacement ellipsoids for non-H atoms at the 50% probability level.

The relative position of the lattice water molecule and the complex molecule is very similar in both polymorphs: a fit between the asymmetric units of each phase, carried out using all non-H atoms in the complex, shows that the unique significant differences are for the phenol rings C1–C6 and C11–C16, which are rotated about their σ bonds C7—C6 and C10—C11, by ca 6.4 and 13.9°, respectively. However, such a limited change in the conformation of the complex is unlikely to promote the polymorphism. On the other hand, each phase gives a clearly different simulated powder diffraction pattern (Fig. 2).

Figure 2
Simulated powder diffraction patterns for the P2₁/n form of the title compound (Panja et al., 2003 $[Panja, A., Shaikh, N., Ali, M., Vojt\?íšek, P. & Banerjee, P. (2003). Polyhedron, 22, 1191-1198.]$ ; blue spectrum) and the P2₁ form (this work; red spectrum). A fit between the molecules constituting the asymmetric units in both phases is also displayed, using the same colour scheme (Macrae et al., 2008

The crystal structure reported by Panja et al. is based on a primitive monoclinic unit cell with parameters a = 6.6470 (2), b = 7.3330 (2), c = 33.8260 (10) Å and β = 95.1650 (17)°. The cell volume V is 1642.07 (8) Å³, corresponding to a P2₁/n structure with four formulas per unit cell. An obvious relation is observed with the parameters of our phase (Table 3): the cell symmetry is retained, with very similar a, b and β parameters, while the c parameter is almost exactly halved. The resulting cell volume is then V = 838.67 (10) Å³. Therefore, the unit-cell content is also halved to Z = 2, and a marginal difference of 2% for the calculated densities is observed between the two polymorphs. It is worth mentioning that after the data collection was completed, we checked the correctness of the short c parameter for the P2₁ polymorph, by re-building the reciprocal space: no extra diffraction spots with indices (h k l/2) for a potential supercell are observed in the 0kl and h0l layers. This can be quantitatively assessed by integrating the collected frames after doubling the c parameter: the statistics for intensities over the whole (hkl) pattern are then 〈I/σ(I)〉 = 4.70 if l is even (10251 reflections) and 〈I/σ(I)〉 = 0.16 if l is odd (10053 reflections). The previously reported P2₁/n polymorph gives much more balanced statistics, 〈I/σ(I)〉 = 84.74 for l = 2n and 〈I/σ(I)〉 = 85.67 for l = 2n + 1 [given that, apparently, original structure factors are not available anymore for this crystal, intensities F_o² and standard deviations σ(F_o²) were generated using the dedicated tool in PLATON (Spek, 2009 )]. These statistics support the correctness of the unit cells for both polymorphs.

Table 3
Experimental details

Crystal data
Chemical formula	[Mn(C₁₆H₁₄N₂O₂)Cl(H₂O)]·H₂O
M_r	392.71
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	6.7083 (4), 7.2414 (5), 17.2768 (13)
β (°)	92.153 (6)
V (Å³)	838.67 (10)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.97
Crystal size (mm)	0.30 × 0.30 × 0.15

Data collection
Diffractometer	Agilent Xcalibur Atlas Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.969, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10229, 4080, 3647
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.072, 1.06
No. of reflections	4080
No. of parameters	229
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.23
Absolute structure	Flack x determined using 1381 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.017 (12)
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

A comparison of unit cells shows that molecules related by the screw axis parallel to [010] remain in the same relative orientation (Fig. 3), including the water molecules. Each pair of molecules is inverted in the P2₁/n polymorph, while the lack of a glide plane in the new phase restrains the cell contents to this pair of molecules, which is extended in the crystal through lattice translations. The key point is then that the new phase crystallizes in a non-centrosymmetric space group, P2₁, while doubling the c parameter gives a centrosymmetric space group, P2₁/n. The presence or absence of an inversion centre affords two phases related by packing polymorphism (Brog et al., 2013 )

Figure 3
A comparison between the cell content for the P2₁/n and P2₁ forms (top and bottom, respectively). Dashed lines relate molecules with identical orientation in both crystals, and symmetry elements are displayed (top: screw axes, glide planes and inversion centres; bottom: screw axes).

The electronic spectrum of the title compound in DMSO shows one band at 264 nm assigned to the ligand π→π^* transition, and a broad band at 598 nm, which corresponds to d–d transitions (Fig. 4). The d–d band is satisfactorily fitted with two Gaussian functions (Fig. 4, inset; OriginLab Corp., 2017 ), and can be assigned to the ⁵E_g→⁵T_2g transition, consistent with the distorted octahedral ligand field observed for the metal centre in the solid state. If no conformational flexibility is possible for this complex, the polymorphism is then due to different packing structures, rather than geometric modifications.

Figure 4
UV–vis spectrum of the title polymorph dissolved in DMSO. The experimental spectrum (red line) is fitted with Gaussian functions for which maxima are indicated. The sum of these Gaussian functions affords the theoretical spectrum (dotted blue line). The visible range of the spectrum is displayed in the inset, using a scale allowing the d–d transitions to be assessed, fitted with two Gaussian functions, giving a maximum at λ = 598 nm.

3. Supramolecular features

The presence of both a coordinated and a lattice water molecules favours the formation of O—H⋯O hydrogen bonds in the crystal (Table 1). The coordinated molecule O3W serves as donor, forming bonds with the lattice water O4W and the chloride atom of a neighbouring complex in position (x, y − 1, z). The lattice molecule O4W serves both as donor and acceptor, forming bonds with the chloride and phenolate atom O2 of two symmetry-related complexes. The resulting supramolecular structure is a 3D framework based essentially on discrete chains extended to large ring motifs. The comparison between the Hirshfeld surfaces for the asymmetric units in the two phases (Fig. 5; Turner et al., 2017 ) is consistent with the observed crystal symmetries and provides some clues about the factor causing the packing polymorphism. For the P2₁/n phase, the inversion centre allows the formation of π–π contacts between symmetry-related C11–C16 benzene rings (symmetry code: 2 − x, −y, 1 − z). Such weak interactions are reflected in the red spots on the Hirshfeld surface, marked with arrows in Fig. 5. The main consequence of the absence of an inversion centre in the P2₁ crystal is the removal of these contacts (Fig. 5, bottom), in connection with the small rotation of 13.9° observed for this part of the Schiff base (see previous section and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3W—H31W⋯O4W	0.81 (5)	2.02 (5)	2.827 (4)	174 (5)
O3W—H32W⋯Clⁱ	0.80 (6)	2.45 (6)	3.249 (3)	173 (5)
O4W—H41W⋯O2ⁱⁱ	0.83 (6)	2.07 (6)	2.896 (4)	170 (5)
O4W—H42W⋯Clⁱⁱⁱ	0.81 (5)	2.41 (5)	3.228 (3)	178 (5)
Symmetry codes: (i) x, y-1, z; (ii) x-1, y, z; (iii) x-1, y-1, z.

Figure 5
Hirshfeld surfaces mapped over d_norm (−0.15 to 1.20 Å) for the P2₁/n polymorph reported in 2003 (Panja et al., 2003 $[Panja, A., Shaikh, N., Ali, M., Vojt\?íšek, P. & Banerjee, P. (2003). Polyhedron, 22, 1191-1198.]$ ; top) and the novel P2₁ polymorph (bottom). Arrows in the first case indicate regions where intermolecular distances are shorter than van der Waals contacts, because of π–π interactions.

The crystal structure of the non-hydrated complex has been reported (Martínez et al., 2002 ), in space group P2₁, but the packing structure is then modified, since the array of hydrogen bonds is different.

4. Database survey

Retrieving cases of packing polymorphism by mining the Cambridge Structural Database is not a straightforward task, since no dedicated tools have been designed for such a search (CSD, version 5.39, updated May 2018; Groom et al., 2016 ). It is thus difficult to estimate whether or not this phenomenon is common. Restraining the search to the symmetry class 2/m, we however found some cases very similar to that observed for the title compound, with packing dimorphism in space groups P2₁/n and P2₁ (or any alternative settings for these groups), some of which are listed in Table 2. For each pair, the ratio between the unit-cell volumes for the P2₁/n and P2₁ phases is very close to 2, because of the loss of the glide plane and the halving of the cell parameter c. Very simple molecules are found, such as glycine (DOLBIR; Arul Asir Abraham et al., 2015 ) and also more complex molecules (YURVAI; van den Hende et al., 1995 ). Using simulated powder diffraction patterns in order to ensure that a pair of crystal structures forms a genuine case of packing dimorphism, false positive occurrences may also be detected. For example, the reported crystal structures for 4-cyano-4′-ethyl-bipbenyl, referenced KUSVID and KUSVID01 (space groups P2₁/c and P2₁, respectively; Haase et al., 1992 ) almost certainly represent the same crystal structure rather than two packing polymorphs resulting from a reversible distortive phase transition, as was reported.

Table 2
Examples of dimorphic crystal structures with packing polymorphism in the symmetry class 2/m

CSD references	Space groups	Volumes of unit cells (Å³)	Literature reference
CANDUR01, CANDUR02	P2₁/c, P2₁	1190, 610	Lutker & Matzger (2010 )
DOLBIR07, DOLBIR08	P2₁/n, P2₁	304, 155	Jiang et al. (2015 )
GEPSEA01, GEPSEA	P2₁/c, P2₁	1108, 554	Konno & Matsushita (2006 )
LIHGAM, LIHGAM01	P2₁/c, P2₁	1060, 502	Wang & Fu (2013 )
MIZHOT01, MIZHOT02	P2₁/c, P2₁	1472, 738	Sevinçek et al. (2011 ); Parveen et al. (2015 )
NORVEX, NORVEX01	P2₁/c, P2₁	1938, 966	Zhang et al. (2015 )
SOGUAN20, SOGUAN03	P2₁/c, P2₁	1026, 513	Alléaume et al. (1976 ); Eccles et al. (2011 )
YURVAI, YURVAI01	P2₁/c, P2₁	4798, 2285	van den Hende et al. (1995); Deacon et al. (2014 )

5. Synthesis and crystallization

Equimolar amounts (1 mmol) of MnCl₂ (0.125 g), salicylaldehyde (108 µl) and diethylenetriamine (106 µl) in MeOH (5 ml) were placed in a beaker and the mixture was kept under magnetic stirring for 30 minutes at room temperature. As the Schiff base ligand was formed in situ, the condensation reaction between the aldehyde and the amine afforded water, which participates as a reagent. The mixture was left at room temperature for one day, filtered, and then cooled to 283 K, affording brown single crystals of the title compound after eight days (51 mg, yield based on Mn: 17%). M.p. 447 K. IR (KBr pellet, cm⁻¹): 3436 (O—H), 1610 (C=N), 638 (Mn—O), 460 (Mn—N). The UV–Vis spectrum (Fig. 4) was measured in a DMSO solution (≃ 1.3×10⁻² mM) using a Cary 50 spectrophotometer (λ_max/∊, nm/10⁻³M⁻¹cm⁻¹): 264/114.5, 598/1.16.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms for water molecules O3W and O4W were found in a difference map, and freely refined. Other H atoms were refined as riding on their carrier atoms with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C).

Supporting information

CCDC reference: 1877342

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018015694/vn2136sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018015694/vn2136Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

trans-Aquachlorido{2,2'[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato-κ⁴O,N,N',O'}manganese(III) monohydrate top

Crystal data top

[Mn(C₁₆H₁₄N₂O₂)Cl(H₂O)]·H₂O	D_x = 1.555 Mg m⁻³
M_r = 392.71	Melting point: 447 K
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.7083 (4) Å	Cell parameters from 4867 reflections
b = 7.2414 (5) Å	θ = 3.7–27.5°
c = 17.2768 (13) Å	µ = 0.97 mm⁻¹
β = 92.153 (6)°	T = 298 K
V = 838.67 (10) Å³	Plate, brown
Z = 2	0.30 × 0.30 × 0.15 mm
F(000) = 404

Data collection top

Agilent Xcalibur Atlas Gemini diffractometer	4080 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3647 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 29.7°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	h = −9→9
T_min = 0.969, T_max = 1.000	k = −9→10
10229 measured reflections	l = −23→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0269P)² + 0.0549P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
4080 reflections	Δρ_max = 0.40 e Å⁻³
229 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1381 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.017 (12)

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

	x	y	z	U_iso*/U_eq
Mn	0.09362 (6)	0.52766 (6)	0.76613 (3)	0.02725 (13)
Cl	0.21462 (13)	0.86787 (12)	0.78160 (7)	0.0449 (3)
O1	0.2621 (3)	0.4339 (3)	0.84472 (14)	0.0314 (5)
O2	0.2725 (3)	0.4682 (3)	0.68703 (14)	0.0319 (6)
O3W	−0.0502 (4)	0.2359 (4)	0.7460 (2)	0.0468 (8)
H31W	−0.167 (8)	0.208 (7)	0.741 (3)	0.070*
H32W	0.022 (8)	0.150 (8)	0.757 (3)	0.070*
O4W	−0.4622 (4)	0.1624 (5)	0.7235 (2)	0.0489 (8)
H41W	−0.541 (8)	0.251 (8)	0.719 (3)	0.073*
H42W	−0.544 (7)	0.087 (7)	0.737 (3)	0.073*
N1	−0.1165 (4)	0.5785 (4)	0.84081 (18)	0.0295 (7)
N2	−0.1111 (4)	0.6231 (4)	0.69079 (18)	0.0314 (7)
C1	0.2606 (5)	0.4706 (4)	0.9199 (2)	0.0276 (7)
C2	0.4299 (5)	0.4261 (5)	0.9660 (2)	0.0338 (8)
H21	0.539320	0.372846	0.943141	0.041*
C3	0.4374 (6)	0.4598 (5)	1.0446 (2)	0.0415 (9)
H31	0.552417	0.431406	1.073893	0.050*
C4	0.2745 (6)	0.5358 (6)	1.0804 (2)	0.0460 (9)
H41	0.280228	0.559014	1.133357	0.055*
C5	0.1057 (6)	0.5760 (5)	1.0368 (2)	0.0404 (10)
H51	−0.004513	0.623686	1.061044	0.048*
C6	0.0944 (5)	0.5471 (5)	0.95632 (19)	0.0316 (8)
C7	−0.0886 (5)	0.5890 (4)	0.9141 (2)	0.0324 (8)
H71	−0.195999	0.627022	0.942692	0.039*
C8	−0.3150 (5)	0.6098 (5)	0.8028 (2)	0.0380 (9)
H82	−0.396791	0.684398	0.835810	0.046*
H81	−0.382002	0.492807	0.793394	0.046*
C9	−0.2848 (5)	0.7073 (5)	0.7279 (2)	0.0410 (10)
H91	−0.403077	0.695316	0.694177	0.049*
H92	−0.260526	0.837639	0.737189	0.049*
C10	−0.0941 (5)	0.6321 (5)	0.6175 (2)	0.0374 (9)
H101	−0.202462	0.678747	0.588561	0.045*
C11	0.0782 (5)	0.5765 (5)	0.5754 (2)	0.0362 (9)
C12	0.0738 (6)	0.6076 (5)	0.4951 (2)	0.0480 (10)
H121	−0.040128	0.658706	0.471451	0.058*
C13	0.2312 (7)	0.5651 (6)	0.4508 (2)	0.0548 (12)
H131	0.225258	0.587309	0.397749	0.066*
C14	0.4005 (6)	0.4880 (6)	0.4864 (2)	0.0511 (11)
H141	0.509161	0.459366	0.456736	0.061*
C15	0.4104 (5)	0.4534 (5)	0.5645 (2)	0.0381 (9)
H151	0.524048	0.398346	0.586650	0.046*
C16	0.2515 (5)	0.4998 (5)	0.61183 (19)	0.0315 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn	0.0191 (2)	0.0312 (3)	0.0315 (3)	0.0036 (2)	0.00186 (16)	−0.0002 (2)
Cl	0.0318 (5)	0.0302 (4)	0.0722 (8)	−0.0033 (4)	−0.0032 (4)	0.0006 (4)
O1	0.0250 (12)	0.0383 (13)	0.0308 (14)	0.0071 (10)	0.0006 (10)	−0.0004 (11)
O2	0.0249 (11)	0.0394 (14)	0.0316 (14)	0.0052 (10)	0.0028 (10)	0.0005 (10)
O3W	0.0326 (15)	0.0306 (15)	0.077 (2)	−0.0012 (12)	−0.0035 (15)	0.0004 (14)
O4W	0.0321 (15)	0.0432 (18)	0.072 (2)	0.0047 (13)	0.0084 (14)	0.0092 (15)
N1	0.0179 (13)	0.0290 (16)	0.0417 (19)	0.0024 (10)	0.0022 (12)	−0.0047 (12)
N2	0.0235 (14)	0.0311 (15)	0.0395 (19)	0.0014 (12)	−0.0023 (12)	0.0014 (13)
C1	0.0287 (16)	0.0230 (16)	0.0312 (19)	−0.0042 (13)	0.0027 (14)	0.0035 (13)
C2	0.0294 (18)	0.0333 (19)	0.039 (2)	0.0001 (14)	0.0017 (15)	0.0076 (16)
C3	0.046 (2)	0.040 (2)	0.039 (2)	−0.0069 (17)	−0.0072 (17)	0.0110 (17)
C4	0.067 (2)	0.041 (2)	0.0303 (19)	−0.002 (2)	0.0007 (17)	0.000 (2)
C5	0.050 (2)	0.033 (2)	0.039 (2)	−0.0002 (16)	0.0134 (18)	−0.0011 (15)
C6	0.0311 (16)	0.0283 (18)	0.0356 (19)	−0.0006 (16)	0.0053 (13)	0.0000 (16)
C7	0.0286 (18)	0.0255 (17)	0.044 (2)	−0.0008 (13)	0.0123 (16)	−0.0028 (15)
C8	0.0200 (17)	0.040 (2)	0.054 (3)	0.0034 (15)	0.0047 (16)	−0.0066 (18)
C9	0.0238 (18)	0.038 (2)	0.060 (3)	0.0101 (15)	−0.0049 (17)	−0.0045 (19)
C10	0.0328 (19)	0.0297 (19)	0.049 (3)	−0.0010 (15)	−0.0099 (16)	0.0050 (17)
C11	0.041 (2)	0.031 (2)	0.035 (2)	−0.0024 (15)	−0.0034 (16)	0.0028 (14)
C12	0.062 (3)	0.041 (2)	0.039 (2)	−0.004 (2)	−0.011 (2)	0.0094 (18)
C13	0.085 (3)	0.051 (3)	0.028 (2)	−0.013 (2)	0.003 (2)	0.0035 (18)
C14	0.063 (3)	0.050 (3)	0.042 (2)	−0.011 (2)	0.018 (2)	−0.007 (2)
C15	0.0373 (19)	0.040 (2)	0.037 (2)	−0.0049 (16)	0.0063 (16)	−0.0037 (16)
C16	0.0356 (17)	0.0282 (19)	0.0310 (19)	−0.0063 (16)	0.0034 (14)	0.0001 (16)

Geometric parameters (Å, º) top

Mn—O1	1.862 (2)	C4—H41	0.9300
Mn—O2	1.901 (2)	C5—C6	1.405 (5)
Mn—N1	1.981 (3)	C5—H51	0.9300
Mn—N2	1.981 (3)	C6—C7	1.436 (5)
Mn—O3W	2.343 (3)	C7—H71	0.9300
Mn—Cl	2.6045 (10)	C8—C9	1.496 (5)
O1—C1	1.326 (4)	C8—H82	0.9700
O2—C16	1.322 (4)	C8—H81	0.9700
O3W—H31W	0.81 (5)	C9—H91	0.9700
O3W—H32W	0.80 (6)	C9—H92	0.9700
O4W—H41W	0.83 (6)	C10—C11	1.446 (5)
O4W—H42W	0.81 (5)	C10—H101	0.9300
N1—C7	1.276 (5)	C11—C12	1.405 (5)
N1—C8	1.480 (4)	C11—C16	1.414 (5)
N2—C10	1.277 (5)	C12—C13	1.362 (6)
N2—C9	1.482 (4)	C12—H121	0.9300
C1—C2	1.400 (5)	C13—C14	1.388 (6)
C1—C6	1.414 (4)	C13—H131	0.9300
C2—C3	1.379 (5)	C14—C15	1.372 (5)
C2—H21	0.9300	C14—H141	0.9300
C3—C4	1.389 (5)	C15—C16	1.408 (4)
C3—H31	0.9300	C15—H151	0.9300
C4—C5	1.368 (5)

O1—Mn—O2	93.41 (10)	C6—C5—H51	119.1
O1—Mn—N1	91.15 (11)	C5—C6—C1	119.0 (3)
O2—Mn—N1	173.66 (11)	C5—C6—C7	119.0 (3)
O1—Mn—N2	173.37 (11)	C1—C6—C7	122.0 (3)
O2—Mn—N2	92.71 (11)	N1—C7—C6	125.6 (3)
N1—Mn—N2	82.56 (12)	N1—C7—H71	117.2
O1—Mn—O3W	90.85 (11)	C6—C7—H71	117.2
O2—Mn—O3W	87.51 (11)	N1—C8—C9	107.9 (3)
N1—Mn—O3W	88.01 (11)	N1—C8—H82	110.1
N2—Mn—O3W	86.87 (11)	C9—C8—H82	110.1
O1—Mn—Cl	95.26 (8)	N1—C8—H81	110.1
O2—Mn—Cl	94.89 (7)	C9—C8—H81	110.1
N1—Mn—Cl	89.08 (8)	H82—C8—H81	108.4
N2—Mn—Cl	86.75 (9)	N2—C9—C8	108.3 (3)
O3W—Mn—Cl	173.28 (8)	N2—C9—H91	110.0
C1—O1—Mn	127.9 (2)	C8—C9—H91	110.0
C16—O2—Mn	128.4 (2)	N2—C9—H92	110.0
Mn—O3W—H31W	129 (4)	C8—C9—H92	110.0
Mn—O3W—H32W	115 (4)	H91—C9—H92	108.4
H31W—O3W—H32W	114 (5)	N2—C10—C11	125.9 (3)
H41W—O4W—H42W	96 (4)	N2—C10—H101	117.0
C7—N1—C8	121.8 (3)	C11—C10—H101	117.0
C7—N1—Mn	125.2 (2)	C12—C11—C16	119.3 (3)
C8—N1—Mn	113.0 (2)	C12—C11—C10	117.7 (3)
C10—N2—C9	120.5 (3)	C16—C11—C10	123.0 (3)
C10—N2—Mn	125.7 (2)	C13—C12—C11	122.1 (4)
C9—N2—Mn	113.4 (2)	C13—C12—H121	119.0
O1—C1—C2	118.3 (3)	C11—C12—H121	119.0
O1—C1—C6	123.3 (3)	C12—C13—C14	118.7 (4)
C2—C1—C6	118.3 (3)	C12—C13—H131	120.6
C3—C2—C1	121.2 (3)	C14—C13—H131	120.6
C3—C2—H21	119.4	C15—C14—C13	121.2 (4)
C1—C2—H21	119.4	C15—C14—H141	119.4
C2—C3—C4	120.6 (3)	C13—C14—H141	119.4
C2—C3—H31	119.7	C14—C15—C16	121.2 (4)
C4—C3—H31	119.7	C14—C15—H151	119.4
C5—C4—C3	119.2 (3)	C16—C15—H151	119.4
C5—C4—H41	120.4	O2—C16—C15	118.3 (3)
C3—C4—H41	120.4	O2—C16—C11	124.1 (3)
C4—C5—C6	121.7 (3)	C15—C16—C11	117.6 (3)
C4—C5—H51	119.1

O2—Mn—O1—C1	160.2 (2)	Mn—N1—C8—C9	−34.8 (3)
N1—Mn—O1—C1	−24.2 (2)	C10—N2—C9—C8	155.3 (3)
O3W—Mn—O1—C1	−112.2 (2)	Mn—N2—C9—C8	−31.2 (4)
Cl—Mn—O1—C1	65.0 (2)	N1—C8—C9—N2	41.5 (4)
Mn—O1—C1—C2	−163.0 (2)	C9—N2—C10—C11	171.8 (3)
Mn—O1—C1—C6	18.9 (4)	Mn—N2—C10—C11	−0.7 (5)
O1—C1—C2—C3	−179.7 (3)	N2—C10—C11—C12	−176.2 (3)
C6—C1—C2—C3	−1.5 (5)	N2—C10—C11—C16	1.4 (6)
C1—C2—C3—C4	1.3 (5)	C16—C11—C12—C13	0.4 (6)
C2—C3—C4—C5	0.4 (6)	C10—C11—C12—C13	178.0 (4)
C3—C4—C5—C6	−1.8 (6)	C11—C12—C13—C14	0.3 (6)
C4—C5—C6—C1	1.5 (5)	C12—C13—C14—C15	0.5 (6)
C4—C5—C6—C7	178.8 (4)	C13—C14—C15—C16	−1.9 (6)
O1—C1—C6—C5	178.2 (3)	Mn—O2—C16—C15	176.1 (2)
C2—C1—C6—C5	0.2 (5)	Mn—O2—C16—C11	−4.3 (5)
O1—C1—C6—C7	0.9 (5)	C14—C15—C16—O2	−177.9 (3)
C2—C1—C6—C7	−177.1 (3)	C14—C15—C16—C11	2.5 (5)
C8—N1—C7—C6	175.0 (3)	C12—C11—C16—O2	178.7 (3)
Mn—N1—C7—C6	−6.9 (5)	C10—C11—C16—O2	1.2 (5)
C5—C6—C7—N1	176.2 (3)	C12—C11—C16—C15	−1.7 (5)
C1—C6—C7—N1	−6.5 (5)	C10—C11—C16—C15	−179.2 (3)
C7—N1—C8—C9	143.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H31W···O4W	0.81 (5)	2.02 (5)	2.827 (4)	174 (5)
O3W—H32W···Clⁱ	0.80 (6)	2.45 (6)	3.249 (3)	173 (5)
O4W—H41W···O2ⁱⁱ	0.83 (6)	2.07 (6)	2.896 (4)	170 (5)
O4W—H42W···Clⁱⁱⁱ	0.81 (5)	2.41 (5)	3.228 (3)	178 (5)
C8—H81···O1ⁱⁱ	0.97	2.61	3.217 (4)	121

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

Examples of dimorphic crystal structures with packing polymorphism in the symmetry class 2/m top

CSD references	Space groups	Volumes of unit cells (Å³)	Literature reference
CANDUR01, CANDUR02	P2₁/c, P2₁	1190, 610	Lutker & Matzger (2010)
DOLBIR07, DOLBIR08	P2₁/n, P2₁	304, 155	Jiang et al. (2015)
GEPSEA01, GEPSEA	P2₁/c, P2₁	1108, 554	Konno & Matsushita (2006)
LIHGAM, LIHGAM01	P2₁/c, P2₁	1060, 502	Wang & Fu (2013)
MIZHOT01, MIZHOT02	P2₁/c, P2₁	1472, 738	Sevinçek et al. (2011); Parveen et al. (2015)
NORVEX, NORVEX01	P2₁/c, P2₁	1938, 966	Zhang et al. (2015)
SOGUAN20, SOGUAN03	P2₁/c, P2₁	1026, 513	Alléaume et al. (1976); Eccles et al. (2011)
YURVAI, YURVAI01	P2₁/c, P2₁	4798, 2285	van den Hende et al. (1995); Deacon et al. (2014)

Acknowledgements

The authors thank Dr Angel Mendoza, IC-UAP (Puebla, Mexico) for X-ray measurements.

Funding information

The present work was partially supported by the Vicerrectroría de Investigación y Estudios de Posgrado from BUAP, Projects QUTM-NAT17-I and QUTM-NAT18-I.

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