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Packing trans-aqua[N,N′-bis(salicylidene)ethane-1,2-diamine-κ4O,N,N′,O′]chloridomanganese(III) monohydrate
in the structure ofaFacultad 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
The 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 P21/n [Panja et al. (2003). Polyhedron, 22, 1191–1198]. We obtained the same hydrated complex through an alternative synthesis, and crystallized a new polymorph, in the 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 with Z = 2, while the previously reported crystal is centrosymmetric with Z = 4. Both phases represent a case of packing 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 MnIII and MnIV 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 MnIII–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 CoIII as the metal centre (Quintero-Téllez et al., 2016
).
While extending our work to MnIII, we prepared the title complex, for which a synthesis was previously reported (Panja et al., 2003). These authors synthesized the complex using a MnIII 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 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 shows that this phase crystallizes in P21, with Z = 2.
Although we have no strong experimental evidences regarding the mechanism triggering the P21 polymorph, along with its characterization in solution by means of UV–Vis spectroscopy.
for this complex, we believe that the temperature and the solvent of crystallization could be the key parameters. We report here the structure of the2. Structural commentary
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 MnIII 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 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 ![]() ![]() |
The et al. is based on a primitive monoclinic 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 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 no extra diffraction spots with indices (h k l/2) for a potential 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 Fo2 and standard deviations σ(Fo2) were generated using the dedicated tool in PLATON (Spek, 2009
)]. These statistics support the correctness of the unit cells for both polymorphs.
|
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 P21, while doubling the c parameter gives a centrosymmetric P21/n. The presence or absence of an inversion centre affords two phases related by packing (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 5Eg→5T2g transition, consistent with the distorted octahedral observed for the metal centre in the solid state. If no conformational flexibility is possible for this complex, the 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 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
).
|
![]() | Figure 5 Hirshfeld surfaces mapped over dnorm (−0.15 to 1.20 Å) for the P21/n polymorph reported in 2003 (Panja et al., 2003 ![]() |
The et al., 2002), in P21, but the packing structure is then modified, since the array of hydrogen bonds is different.
4. Database survey
Retrieving cases of packing 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 rather than two packing polymorphs resulting from a reversible distortive as was reported.
|
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 (λmax/∊, nm/10−3M−1cm−1): 264/114.5, 598/1.16.
6. Refinement
Crystal data, data collection and structure . 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 Uiso(H) = 1.2Ueq(C).
Supporting information
CCDC reference: 1877342
https://doi.org/10.1107/S2056989018015694/vn2136sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018015694/vn2136Isup2.hkl
Data collection: CrysAlis PRO (Agilent, 2013); cell
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).[Mn(C16H14N2O2)Cl(H2O)]·H2O | Dx = 1.555 Mg m−3 |
Mr = 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 |
Agilent Xcalibur Atlas Gemini diffractometer | 4080 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3647 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 29.7°, θmin = 3.0° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | h = −9→9 |
Tmin = 0.969, Tmax = 1.000 | k = −9→10 |
10229 measured reflections | l = −23→21 |
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(Fo2) + (0.0269P)2 + 0.0549P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
4080 reflections | Δρmax = 0.40 e Å−3 |
229 parameters | Δρmin = −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) |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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. |
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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