research communications
trans-2,5-dimethylpiperazine-1,4-diium tetrachloridocobaltate(II)
and Hirshfeld surface analysis ofaUniversité de Carthage, Faculté des Sciences de Bizerte, LR13ES08, Laboratoire de Chimie des Matériaux, 7021, Zarzouna Bizerte, Tunisia
*Correspondence e-mail: landolsimeriem@gmail.com
In the title molecular salt, (C6H16N2)[CoCl4], the complete dication is generated by crystallographic inversion symmetry and the piperazine ring adopts a chair conformation with the pendant methyl groups in equatorial orientations. The complete dianion is generated by crystallographic twofold symmetry. In the crystal, the (C6H16N2)2+ and [CoCl4]2− ions are linked by N—H⋯Cl and C—H⋯Cl hydrogen bonds, thereby forming a two-dimensional supramolecular network. The Hirshfeld surface analysis and fingerprint plots reveal that the largest contributions to the crystal stability come from H⋯Cl/Cl⋯H (68.4%) and H⋯H (27.4%) contacts.
CCDC reference: 1831453
1. Chemical context
Tetrachlorocobalt/copper (II) salts with organic cations, such as (C6H10N3)2[CoCl4] (Titi et al. 2020), [(CH3)2NH2]2[CoCl4] (Pietraszko et al. 2006) and (C7H7N2S)2[CuCl4] (Vishwakarma et al. 2017) have received attention due to their potential applications in the electronic, magnetic, optical and antimicrobial fields. In these materials, the negative charge on the inorganic complex ion is balanced by the organic groups, which usually act as structure-directing agents by the formation of N—H⋯Cl hydrogen bonds and significantly affect the structure and dimensionality of the supramolecular network.
As an extension of these studies, we now describe the synthesis, structure and Hirshfeld surface analysis of the title molecular salt, (I).
2. Structural commentary
The comprises half of a trans-2,5-dimethylpiperazine-1,4-dium cation and a half tetrachloridocobaltate anion (Fig. 1). The cation and anion are completed by crystallographic inversion and twofold symmetry, respectively. In the organic species, the N—C and C—C bond lengths vary from 1.490 (2) to 1.513 (2) Å and the angles C—C—C, N—C—C and C—N—C range from 109.15 (14) to 113.54 (15)°. These data are in agreement with those reported in other salts of the trans-2,5-dimethylpiperazine-1,4-diium cation (Gatfaoui et al., 2014; Ben Mleh et al., 2016). The Co2+ ion in (I) has a tetrahedral geometry, with Cl—Co—Cl angles ranging from 103.32 (2) to 116.57 (3)°. The average length of the Co—Cl bonds, 2.27 Å, is close to that observed in similar complexes (Tahenti et al., 2020; Zhang et al., 2005; Zeller et al., 2005).
of (I)3. Supramolecular features
In the crystal of (I), adjacent anions are interconnected by the cations via N—H⋯Cl hydrogen bonds and C—H⋯Cl interactions (Table 1) to form a layer built up from the organic and inorganic species, lying parallel to (101) (Fig. 2). The hydrogen bonds engage the chloride ions of the [CoCl4]2– tetrahedron, producing four types of graph-set motifs on the basis of Etter's notation (Etter et al., 1990; Bernstein et al., 1995). The isolated molecules can be described by the elementary graph-set descriptors Ead (n) (Daszkiewicz, 2012). The graph-set descriptor of the pattern can be easily obtained by the summation of elementary Ead (n) graph-sets of isolated ions and molecules. In the case of (I), the elementary graph-sets can be collected (Fig. 3) as follows:
|
E01 (1) + E20 (3) = R12 (4)
2E02 (3) + 2E10 (1) = R42 (8)
E02 (3) + E20 (5) = R22 (8)
2E10 (1) + 2E02 (4) = R42 (10).
4. Hirshfeld surface analysis
To further understand the different interactions and contacts in the crystal of (I), its Hirshfeld surface (HS) (McKinnon et al., 2004) was calculated. The dnorm surface (Fig. 4) and the associated two-dimensional fingerprint plots (see supporting information) were calculated using CrystalExplorer 3.1 (Wolff et al., 2013; Spackman & Jayatilaka, 2009). This figure shows the areas mapped in the range from −0.480 to 1.048 of the asymmetric ion-pair surrounded by neighboring ions where we can see some of the closest intermolecular contacts. The large dark-red spots on the HS indicate close contact interactions, which are primarily responsible for significant hydrogen-bond contacts. The fingerprint plots indicate that the most important interactions are H⋯Cl/Cl⋯H, which cover a HS range of 68.4% and appear as two shape-symmetric spikes in the two-dimensional fingerprint maps (where di ∼de ∼1.4 Å). It should be also noted that the the van der Waals radii of the hydrogen and chlorine atoms are 1.20 and 1.75 Å, respectively. The H⋯H contacts represent the second most abundant interactions with 27.4% of the total Hirshfeld surface, including a short H⋯H contact near 2.4 Å (where di ∼de ∼1.2 Å), represented by a cluster of points accumulated on the diagonal of the graph. Other contacts including Cl⋯Cl and Co⋯H/H⋯Co have negligible contributions (respectively 2.7% and 1.5%). It can be concluded that the Cl⋯H/H⋯Cl interactions dominate in the title compound.
4.1. Synthesis and crystallization
A 1:1 mixture of trans-2,5-dimethylpiperazine and cobalt(II) chloride hexahydrate was dissolved in a solution of concentrated hydrochloric acid and the resulting solution was magnetically stirred for 1 h. After two weeks of evaporation, dark-blue prismatic crystals of (I) had formed, which were recovered by filtration and dried in air.
5. Refinement
Crystal data, data collection and structure . The N-bound and C-bound hydrogen atoms were positioned geometrically and treated as riding atoms: N—H = 0.86 Å, C—H = 0.96 Å with Uiso(H) = 1.2Ueq(N,C).
details are summarized in Table 2Supporting information
CCDC reference: 1831453
https://doi.org/10.1107/S2056989021002954/hb7971sup1.cif
contains datablock I. DOI:Two-dimensional fingerprint plots. DOI: https://doi.org/10.1107/S2056989021002954/hb7971sup3.pdf
Data collection: CrysAlis PRO (Agilent, 2014); cell
CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006) and ORTEP-III (Burnett & Johnson, 1996).C6H16N22+·Cl4Co2− | F(000) = 644 |
Mr = 316.94 | Dx = 1.655 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6431 (3) Å | Cell parameters from 2258 reflections |
b = 11.9347 (6) Å | θ = 4.1–29.0° |
c = 14.0058 (7) Å | µ = 2.15 mm−1 |
β = 95.519 (4)° | T = 293 K |
V = 1271.66 (10) Å3 | Prism, blue |
Z = 4 | 0.15 × 0.10 × 0.08 mm |
Agilent SuperNova, Single source at offset, Eos diffractometer | 1370 reflections with I > 2σ(I) |
Detector resolution: 16.0233 pixels mm-1 | Rint = 0.029 |
ω scans | θmax = 29.1°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlisPro; Agilent 2014) | h = −10→9 |
Tmin = 0.816, Tmax = 1.000 | k = −15→15 |
4627 measured reflections | l = −18→13 |
1546 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0365P)2 + 0.515P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.027 |
1546 reflections | Δρmax = 0.27 e Å−3 |
60 parameters | Δρmin = −0.59 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.500000 | 0.52995 (3) | 0.750000 | 0.02694 (13) | |
Cl1 | 0.74705 (6) | 0.42227 (4) | 0.77647 (3) | 0.03237 (14) | |
Cl2 | 0.54849 (7) | 0.62944 (5) | 0.61790 (4) | 0.04332 (16) | |
N1 | 0.9250 (2) | 0.51194 (13) | 0.58839 (11) | 0.0276 (3) | |
H1A | 1.015221 | 0.493869 | 0.630538 | 0.033* | |
H1B | 0.833857 | 0.527625 | 0.621121 | 0.033* | |
C1 | 0.8798 (2) | 0.41357 (16) | 0.52524 (14) | 0.0290 (4) | |
H1C | 0.774246 | 0.429831 | 0.483440 | 0.035* | |
H1D | 0.856092 | 0.349324 | 0.564406 | 0.035* | |
C2 | 1.0282 (2) | 0.38575 (15) | 0.46508 (13) | 0.0272 (4) | |
H2 | 1.130901 | 0.361989 | 0.507561 | 0.033* | |
C3 | 0.9775 (3) | 0.29268 (17) | 0.39440 (16) | 0.0404 (5) | |
H3A | 0.947344 | 0.226813 | 0.428597 | 0.061* | |
H3B | 0.878228 | 0.315843 | 0.351734 | 0.061* | |
H3C | 1.074621 | 0.276353 | 0.358031 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.02007 (18) | 0.0374 (2) | 0.0236 (2) | 0.000 | 0.00304 (14) | 0.000 |
Cl1 | 0.0239 (2) | 0.0401 (3) | 0.0327 (3) | 0.00345 (18) | 0.00040 (18) | 0.00462 (18) |
Cl2 | 0.0334 (3) | 0.0564 (3) | 0.0408 (3) | 0.0047 (2) | 0.0073 (2) | 0.0198 (2) |
N1 | 0.0252 (7) | 0.0368 (8) | 0.0217 (8) | −0.0012 (6) | 0.0072 (6) | 0.0004 (6) |
C1 | 0.0262 (9) | 0.0337 (10) | 0.0279 (10) | −0.0075 (7) | 0.0065 (7) | −0.0013 (7) |
C2 | 0.0253 (8) | 0.0307 (9) | 0.0255 (9) | 0.0012 (7) | 0.0023 (7) | 0.0026 (7) |
C3 | 0.0450 (11) | 0.0375 (11) | 0.0394 (12) | −0.0026 (9) | 0.0074 (10) | −0.0076 (9) |
Co1—Cl2i | 2.2588 (5) | C1—C2 | 1.513 (2) |
Co1—Cl2 | 2.2588 (5) | C1—H1C | 0.9700 |
Co1—Cl1 | 2.2846 (5) | C1—H1D | 0.9700 |
Co1—Cl1i | 2.2847 (5) | C2—C3 | 1.513 (3) |
N1—C1 | 1.490 (2) | C2—H2 | 0.9800 |
N1—C2ii | 1.494 (2) | C3—H3A | 0.9600 |
N1—H1A | 0.8900 | C3—H3B | 0.9600 |
N1—H1B | 0.8900 | C3—H3C | 0.9600 |
Cl2i—Co1—Cl2 | 116.57 (3) | N1—C1—H1D | 109.4 |
Cl2i—Co1—Cl1 | 111.157 (19) | C2—C1—H1D | 109.4 |
Cl2—Co1—Cl1 | 103.324 (18) | H1C—C1—H1D | 108.0 |
Cl2i—Co1—Cl1i | 103.325 (18) | N1ii—C2—C1 | 109.15 (14) |
Cl2—Co1—Cl1i | 111.155 (19) | N1ii—C2—C3 | 109.31 (16) |
Cl1—Co1—Cl1i | 111.54 (3) | C1—C2—C3 | 111.50 (16) |
C1—N1—C2ii | 113.54 (15) | N1ii—C2—H2 | 108.9 |
C1—N1—H1A | 108.9 | C1—C2—H2 | 108.9 |
C2ii—N1—H1A | 108.9 | C3—C2—H2 | 108.9 |
C1—N1—H1B | 108.9 | C2—C3—H3A | 109.5 |
C2ii—N1—H1B | 108.9 | C2—C3—H3B | 109.5 |
H1A—N1—H1B | 107.7 | H3A—C3—H3B | 109.5 |
N1—C1—C2 | 111.10 (14) | C2—C3—H3C | 109.5 |
N1—C1—H1C | 109.4 | H3A—C3—H3C | 109.5 |
C2—C1—H1C | 109.4 | H3B—C3—H3C | 109.5 |
C2ii—N1—C1—C2 | 56.5 (2) | N1—C1—C2—C3 | −174.91 (16) |
N1—C1—C2—N1ii | −54.0 (2) |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1iii | 0.89 | 2.30 | 3.1777 (2) | 171 |
N1—H1B···Cl1 | 0.89 | 2.65 | 3.2594 (2) | 126 |
N1—H1B···Cl2 | 0.89 | 2.49 | 3.2631 (2) | 145 |
C1—H1C···Cl2iv | 0.97 | 2.82 | 3.7065 (2) | 153 |
Symmetry codes: (iii) −x+2, y, −z+3/2; (iv) −x+1, −y+1, −z+1. |
Acknowledgements
We would like thank Professor Shu Hua Zhang from Guilin University of Technology for collecting the XRD data.
References
Agilent (2014). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England. Google Scholar
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Ben Mleh, C., Roisnel, T. & Marouani, H. (2016). Acta Cryst. E72, 593–596. CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Daszkiewicz, M. (2012). Struct. Chem. 23, 307–313. Web of Science CSD CrossRef CAS Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef ICSD CAS Web of Science IUCr Journals Google Scholar
Gatfaoui, S., Roisnel, T., Dhaouadi, H. & Marouani, H. (2014). Acta Cryst. E70, o725. CSD CrossRef IUCr Journals Google Scholar
McKinnon, J. J., Spackman, M. A. & Mitchell, A. S. (2004). Acta Cryst. B60, 627–668. Web of Science CrossRef CAS IUCr Journals Google Scholar
Pietraszko, A., Kirpichnikova, L. F., Sheleg, A. U. & Yachkovsky, A. Ya. (2006). Crystallogr. Rep. 51, 34–36. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Tahenti, M., Gatfaoui, S., Issaoui, N., Roisnel, T. & Marouani, H. (2020). J. Mol. Struct. 1207, 1–5. CSD CrossRef Google Scholar
Titi, A., Warad, I., Tillard, M., Touzani, R., Messali, M., El Kodadi, M., Eddike, D. & Zarrouk, A. (2020). J. Mol. Struct. 1217, 128422. CSD CrossRef Google Scholar
Vishwakarma, A. K., Kumari, R., Ghalsasi, P. S. & Arulsamy, N. (2017). J. Mol. Struct. 1141, 93–98. CSD CrossRef CAS Google Scholar
Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2013). Crystal Explorer. University of Western Australia. Google Scholar
Zeller, A., Herdtweck, E. & Strassner, T. (2005). Acta Cryst. C61, m46–m47. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Zhang, H., Fang, L. & Yuan, R. (2005). Acta Cryst. E61, m677–m678. Web of Science CSD CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.