research communications
m-Xylylenediaminium sulfate: and Hirshfeld surface analysis
aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Université de Carthage, Tunisia, and bCentre de Diffractométrie X, UMR 6226 CNRS, Unité Sciences Chimiques de Rennes, Université de Rennes I, 263 Avenue du, Général Leclerc, 35042 Rennes, France
*Correspondence e-mail: afefguesmi2016@yahoo.fr
The 8H14N22+·SO42−, consists of infinite (100) sheets of alternating organic and inorganic entities The m-xylylenediaminium cations are linked to the sulfate anions by N—H⋯O and asymmetric bifurcated N—H⋯(O,O) hydrogen bonds, generating a three-dimensional network. A weak C—H⋯O interaction also occurs. The Hirshfeld surface analysis and the two-dimensional fingerprint maps indicate that the packing is dominated by H⋯O/O⋯H and H⋯H contacts.
of the title salt {systematic name: [1,3-phenylenebis(methylene)]bis(azanium) sulfate}, CKeywords: crystal structure; m-xylylenediaminium; sulfate; hydrogen bonding; Hirshfeld surface analysis; fingerprint maps.
CCDC reference: 1476189
1. Chemical context
m-Xylylenediaminum compounds have been intensively investigated due to their good antimicrobial activity against various antibacterial and antifungal species (Murugesan et al., 2015). Sequestration of carbon dioxide by m-xylylenediamine with formation of a crystalline adduct has been reported (Lee et al., 2013). In addition, polyamides of m-xylylenediamine possess dielectric properties (Murata et al., 1999). In this work, as part of our studies in this area, we report the synthesis, the structural investigation and the Hirshfeld surface analysis of a new organic sulfate salt, (C8H14N2)SO4, (I).
2. Structural commentary
The comprises one m-xylylenediaminium cation and one sulfate anion (Fig. 1). Both ammonium groups in the m-xylylenediaminium cation adopt a trans conformation with respect to the benzene ring. The same conformation has been observed in C8H14N22+·2Cl− (Cheng & Li, 2008), but in C8H14N22+·2NO3− (Gatfaoui et al., 2014) the cis conformation occurs. Thus, the cation conformation is modified when substituting sulfate or chloride anions by nitrates. Examination of the organic cations shows that the bond distances and angles show no significant differences from those in other compounds involving the same organic groups (Cheng & Li, 2008; Gatfaoui et al., 2014). The aromatic ring of the cation is essentially planar with an r.m.s. deviation of 0.0014 Å.
of (I)In the sulfate anion, the S—O bond lengths range from 1.4673 (12) to 1.4895 (11) Å. Their similar values confirm the absence of a proton in this anion. It is worth noting that the S—O4 distance is the longest because O4 accepts three hydrogen bonds, one of which is considered to be strong (Blessing, 1986; Brown, 1976). The average values of the S—O distances and O—S—O angles are 1.4799 Å and 109.46°, respectively. Similar geometrical features have also been observed in other crystal structures (Marouani et al., 2011a,b). The calculated average values of the distortion indices (Baur, 1974) corresponding to the different angles and distances in the SO4 tetrahedron [DI(SO) = 0.006, DI(OSO) = 0.008, and DI(OO) = 0.003] show a slight distortion of the OSO angles if compared to the SO and OO distances. Hence, the SO4 group can be considered as a rigid regular arrangement of oxygen atoms, with the sulfur atom slightly displaced from the centre of gravity.
3. Supramolecular features
The packing of the title salt is dominated by hydrogen bonding, as detailed in Table 1. Ten distinct hydrogen bonds of types N—H⋯O and C—H⋯O involve all of the oxygen atoms of the sulfate anions as acceptors, However, only two of the N—H⋯O hydrogen bonds are considered as strong according to the Blessing and Brown criteria (Blessing, 1986; Brown, 1976).
The packing for (I) generates rings with an R44(12) motif (Fig. 2) and the overall structure of the title compound consists of infinite sheets of organic and inorganic entities propagating parallel to (100). Each organic dication is connected to six different sulfate anions via N—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional supramolecular network (Fig. 3).
The inter-planar distance between nearby benzene rings in the π–π interactions (Janiak, 2000).
is in the vicinity of 4.63 Å, which is much longer than 3.80 Å, value required for the formation of4. Hirshfeld analysis
The three-dimensional Hirshfeld surfaces and two-dimensional fingerprint plots of (I) were prepared using CrystalExplorer (Wolff et al., 2012) and are shown in Fig. 4 and Fig. 5, respectively.
The O⋯H/H⋯O contacts, which are attributed to N—H⋯O and C—H⋯O hydrogen-bonding interactions, appear as two sharp symmetric spikes in the two-dimensional fingerprint maps with a prominent long spike at de + di = 1.8 Å. They have the most significant contribution to the total Hirshfeld surfaces (51.4%). The H⋯H contacts appear in the middle of the scattered points in the two-dimensional fingerprint maps with a single broad peak at de = di = 1 Å and a percentage contribution of 32.1%. The 15.9% contribution from the C⋯H/H⋯C contacts to the Hirshfeld surface, generally slightly favoured in a sample of CH aromatic molecules, results in a symmetric pair of wings, Fig. 5c. The O⋯O contacts, which represent only 0.2% of the Hirshfeld surface, Fig. 5d, are extremely impoverished in the crystal (enrichment ratio EOO = 0.03) (Jelsch et al. 2014), as the oxygen atoms bound to sulfur and the SO4 group as a whole are electronegative, therefore the O⋯O contacts are electrostatically repulsive.
5. Synthesis and crystallization
Equimolar solutions of m-xylylenediamine dissolved in methanol and aqueous sulfuric acid were mixed together and stirred for about 1 h. Crystals of (I) were formed as the solvent evaporated over a few days at room temperature: these were filtered off, dried and repeatedly recrystallized as colourless prisms to enhance the purity of the product.
6. Refinement
Crystal data, data collection and structure . H atoms bonded to N atoms were located from a difference map and were allowed to refine. The rest of the H atoms were treated as riding, with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene) with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 2
|
Supporting information
CCDC reference: 1476189
https://doi.org/10.1107/S2056989016006940/hb7579sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016006940/hb7579Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989016006940/hb7579Isup3.cml
Data collection: SAINT (Bruker, 2014) and XPREP (Sheldrick, 2015); cell
APEX2 (Bruker, 2014) and SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014) and XPREP (Sheldrick, 2015); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).C8H14N22+·SO42− | F(000) = 496 |
Mr = 234.27 | Dx = 1.534 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.841 (1) Å | Cell parameters from 9927 reflections |
b = 6.0989 (5) Å | θ = 3.7–27.5° |
c = 15.9642 (9) Å | µ = 0.32 mm−1 |
β = 125.791 (4)° | T = 150 K |
V = 1014.15 (13) Å3 | Prism, colourless |
Z = 4 | 0.56 × 0.44 × 0.30 mm |
APEXII, Bruker-AXS diffractometer | 2293 independent reflections |
Radiation source: fine-focus sealed tube | 2131 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
CCD rotation images, thin slices scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −16→16 |
Tmin = 0.735, Tmax = 0.910 | k = −7→7 |
10992 measured reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0639P)2 + 0.4545P] where P = (Fo2 + 2Fc2)/3 |
2293 reflections | (Δ/σ)max = 0.001 |
160 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.61 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
S | −0.43829 (3) | −0.22666 (6) | −0.83072 (3) | 0.01170 (15) | |
O1 | −0.57682 (10) | −0.1916 (2) | −0.88190 (9) | 0.0190 (3) | |
O2 | −0.36751 (12) | −0.22945 (19) | −0.71797 (9) | 0.0236 (3) | |
O3 | −0.38903 (10) | −0.04803 (18) | −0.86220 (9) | 0.0187 (3) | |
O4 | −0.41947 (10) | −0.43848 (17) | −0.86666 (8) | 0.0155 (2) | |
N1 | 0.29551 (12) | −0.2271 (2) | −0.79401 (10) | 0.0131 (3) | |
C1 | 0.16854 (14) | −0.1870 (4) | −0.89148 (12) | 0.0256 (4) | |
H1A | 0.1423 | −0.3180 | −0.9338 | 0.031* | |
H1B | 0.1768 | −0.0699 | −0.9284 | 0.031* | |
C2 | 0.06392 (13) | −0.1263 (3) | −0.87945 (11) | 0.0158 (3) | |
C3 | 0.06536 (13) | 0.0745 (3) | −0.83697 (10) | 0.0161 (3) | |
H3 | 0.1357 | 0.1674 | −0.8089 | 0.019* | |
C4 | −0.03879 (13) | 0.1353 (2) | −0.83668 (11) | 0.0147 (3) | |
H4 | −0.0374 | 0.2689 | −0.8080 | 0.018* | |
C5 | −0.14527 (12) | −0.0016 (2) | −0.87887 (10) | 0.0125 (3) | |
H5 | −0.2147 | 0.0417 | −0.8789 | 0.015* | |
C6 | −0.14779 (13) | −0.2033 (2) | −0.92106 (11) | 0.0114 (3) | |
C7 | −0.04235 (14) | −0.2636 (2) | −0.92037 (12) | 0.0150 (3) | |
H7 | −0.0430 | −0.3985 | −0.9478 | 0.018* | |
C8 | −0.25953 (13) | −0.3597 (2) | −0.96596 (12) | 0.0160 (3) | |
H8A | −0.2567 | −0.4632 | −1.0107 | 0.019* | |
H8B | −0.2511 | −0.4421 | −0.9103 | 0.019* | |
N2 | −0.38513 (12) | −0.2467 (2) | −1.02553 (12) | 0.0175 (3) | |
H1N1 | 0.3194 (19) | −0.114 (4) | −0.7518 (16) | 0.020 (5)* | |
H2N1 | 0.350 (2) | −0.234 (3) | −0.8120 (18) | 0.027 (6)* | |
H3N1 | 0.299 (2) | −0.352 (4) | −0.7644 (17) | 0.029 (6)* | |
H1N2 | −0.445 (2) | −0.340 (4) | −1.0567 (16) | 0.021 (5)* | |
H2N2 | −0.387 (2) | −0.161 (5) | −1.064 (2) | 0.039 (7)* | |
H3N2 | −0.399 (3) | −0.172 (5) | −0.977 (2) | 0.059 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S | 0.0084 (2) | 0.0123 (2) | 0.0163 (2) | −0.00019 (11) | 0.00831 (17) | −0.00144 (11) |
O1 | 0.0099 (5) | 0.0250 (6) | 0.0266 (6) | 0.0029 (4) | 0.0133 (5) | 0.0046 (5) |
O2 | 0.0256 (6) | 0.0229 (6) | 0.0167 (6) | 0.0027 (5) | 0.0092 (5) | −0.0022 (4) |
O3 | 0.0199 (5) | 0.0146 (5) | 0.0308 (6) | −0.0049 (4) | 0.0201 (5) | −0.0037 (4) |
O4 | 0.0148 (5) | 0.0134 (5) | 0.0212 (5) | −0.0007 (4) | 0.0122 (4) | −0.0036 (4) |
N1 | 0.0098 (6) | 0.0150 (6) | 0.0167 (6) | 0.0016 (4) | 0.0091 (5) | 0.0017 (5) |
C1 | 0.0064 (6) | 0.0557 (12) | 0.0145 (7) | −0.0006 (7) | 0.0061 (6) | −0.0075 (7) |
C2 | 0.0066 (6) | 0.0296 (8) | 0.0114 (6) | −0.0004 (5) | 0.0054 (5) | −0.0016 (6) |
C3 | 0.0081 (6) | 0.0241 (8) | 0.0137 (6) | −0.0050 (5) | 0.0050 (5) | −0.0007 (5) |
C4 | 0.0129 (6) | 0.0159 (7) | 0.0138 (6) | −0.0015 (5) | 0.0070 (5) | −0.0016 (5) |
C5 | 0.0092 (6) | 0.0168 (7) | 0.0130 (6) | 0.0012 (5) | 0.0074 (5) | 0.0004 (5) |
C6 | 0.0063 (6) | 0.0161 (7) | 0.0122 (6) | −0.0003 (5) | 0.0056 (5) | 0.0004 (5) |
C7 | 0.0088 (6) | 0.0209 (7) | 0.0151 (7) | 0.0006 (5) | 0.0069 (6) | −0.0044 (5) |
C8 | 0.0079 (6) | 0.0138 (7) | 0.0247 (7) | −0.0008 (5) | 0.0087 (6) | −0.0035 (6) |
N2 | 0.0066 (6) | 0.0187 (7) | 0.0211 (7) | −0.0022 (5) | 0.0047 (5) | 0.0051 (5) |
S—O2 | 1.4673 (12) | C3—H3 | 0.9300 |
S—O1 | 1.4756 (10) | C4—C5 | 1.3941 (19) |
S—O3 | 1.4871 (11) | C4—H4 | 0.9300 |
S—O4 | 1.4895 (11) | C5—C6 | 1.393 (2) |
N1—C1 | 1.4738 (19) | C5—H5 | 0.9300 |
N1—H1N1 | 0.88 (2) | C6—C7 | 1.3971 (19) |
N1—H2N1 | 0.90 (3) | C6—C8 | 1.5100 (19) |
N1—H3N1 | 0.88 (3) | C7—H7 | 0.9300 |
C1—C2 | 1.510 (2) | C8—N2 | 1.4787 (18) |
C1—H1A | 0.9700 | C8—H8A | 0.9700 |
C1—H1B | 0.9700 | C8—H8B | 0.9700 |
C2—C3 | 1.395 (2) | N2—H1N2 | 0.84 (2) |
C2—C7 | 1.395 (2) | N2—H2N2 | 0.80 (3) |
C3—C4 | 1.391 (2) | N2—H3N2 | 1.00 (3) |
O2—S—O1 | 111.24 (7) | C3—C4—C5 | 120.81 (14) |
O2—S—O3 | 110.02 (7) | C3—C4—H4 | 119.6 |
O1—S—O3 | 108.67 (7) | C5—C4—H4 | 119.6 |
O2—S—O4 | 109.80 (6) | C6—C5—C4 | 120.08 (13) |
O1—S—O4 | 109.08 (7) | C6—C5—H5 | 120.0 |
O3—S—O4 | 107.96 (6) | C4—C5—H5 | 120.0 |
C1—N1—H1N1 | 110.6 (13) | C5—C6—C7 | 118.71 (13) |
C1—N1—H2N1 | 104.9 (15) | C5—C6—C8 | 122.29 (12) |
H1N1—N1—H2N1 | 107.1 (19) | C7—C6—C8 | 119.00 (13) |
C1—N1—H3N1 | 112.8 (15) | C2—C7—C6 | 121.56 (14) |
H1N1—N1—H3N1 | 112 (2) | C2—C7—H7 | 119.2 |
H2N1—N1—H3N1 | 109 (2) | C6—C7—H7 | 119.2 |
N1—C1—C2 | 115.06 (13) | N2—C8—C6 | 112.76 (12) |
N1—C1—H1A | 108.5 | N2—C8—H8A | 109.0 |
C2—C1—H1A | 108.5 | C6—C8—H8A | 109.0 |
N1—C1—H1B | 108.5 | N2—C8—H8B | 109.0 |
C2—C1—H1B | 108.5 | C6—C8—H8B | 109.0 |
H1A—C1—H1B | 107.5 | H8A—C8—H8B | 107.8 |
C3—C2—C7 | 119.07 (13) | C8—N2—H1N2 | 109.8 (15) |
C3—C2—C1 | 121.14 (14) | C8—N2—H2N2 | 108.8 (18) |
C7—C2—C1 | 119.50 (15) | H1N2—N2—H2N2 | 112 (2) |
C4—C3—C2 | 119.76 (13) | C8—N2—H3N2 | 109.3 (18) |
C4—C3—H3 | 120.1 | H1N2—N2—H3N2 | 105 (2) |
C2—C3—H3 | 120.1 | H2N2—N2—H3N2 | 112 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···O4i | 0.88 (2) | 1.88 (2) | 2.7271 (17) | 160.1 (19) |
N1—H1N1···O2i | 0.88 (2) | 2.54 (2) | 3.1461 (18) | 126.1 (16) |
N1—H2N1···O1ii | 0.90 (3) | 1.85 (3) | 2.7191 (17) | 162 (2) |
N1—H3N1···O3iii | 0.88 (3) | 2.03 (2) | 2.8264 (17) | 150 (2) |
N1—H3N1···O2iii | 0.88 (3) | 2.54 (2) | 3.1733 (18) | 129.4 (18) |
N2—H1N2···O4iv | 0.84 (2) | 1.97 (2) | 2.8096 (17) | 177 (2) |
N2—H2N2···O1v | 0.80 (3) | 2.26 (3) | 2.9537 (18) | 145 (2) |
N2—H3N2···O3 | 1.00 (3) | 1.92 (3) | 2.9021 (19) | 168 (3) |
N2—H3N2···O4 | 1.00 (3) | 2.52 (3) | 3.0502 (18) | 113 (2) |
C5—H5···O3 | 0.93 | 2.47 | 3.3050 (17) | 150 |
Symmetry codes: (i) −x, y+1/2, −z−3/2; (ii) x+1, y, z; (iii) −x, y−1/2, −z−3/2; (iv) −x−1, −y−1, −z−2; (v) −x−1, −y, −z−2. |
Acknowledgements
This work was supported by the Tunisian Ministry of Higher Education Scientific Research.
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