Hirshfeld surface analysis of the 1,1′-(ethane-1,2-diyl)dipyridinium dication in two new salts: perchlorate and peroxo­di­sulfate

In the title salts, C₁₂H₁₄N₂²⁺·2ClO₄⁻, (I), and C₁₂H₁₄N₂²⁺·S₂O₈²⁻, (II), the dication is organized around an inversion centre located at the centre of the –CH₂CH₂– bridge and the two pyridine segments are anti with respect to one another. The peroxo­di­sulfate anion in (II) also exhibits inversion symmetry. Hirshfeld surface analysis shows closely similar Hirshfeld surface shapes for the dications in the two salts, reflecting similar inter­molecular contacts and similar conformations. The two-dimensional fingerprint plots (FPs) are quite asymmetric, due to the presence of more than one component (cation and anion). The most striking of the complementary features for each of the FPs of the dications is the broad green spike in the region d_e > d_i, without the presence of a cor­res­ponding spike in the region d_e < d_i, reflecting the absence of O...H contacts. Moreover, H...O inter­actions (51% in the dications of both salts) outnumber other contacts in both crystal structures.

S1. Introduction

Hirshfeld surface analysis is a very useful tool for the investigation of inter­molecular inter­actions in crystal structures, allowing easy comparison of inter­molecular contacts relative to van der Waals radii by a strategy based on a simple colouring scheme (Rohl et al., 2008; Tarahhomi et al., 2013). Such an analysis may be used in the case of symmetry-independent molecules within one structure, analogous structures, cation–anion compounds and polymorphs (Tarahhomi et al., 2013; Ling et al., 2010).

When comparing the crystal structures of cation–anion compounds with one identical component (cation or anion), Hirshfeld surfaces (HSs; Spackman & Byrom, 1997; Spackman & Jayatilaka, 2009; McKinnon et al., 2004) and fingerprint plots (FPs; Spackman & McKinnon, 2002; McKinnon et al., 2004) may be used for elucidating and comparing the inter­molecular inter­actions involved in the crystal packing.

In organic synthesis, some cation–anion compounds based on organic cations and oxidant anions can be employed to improve the selectivity, the mildness and, therefore, the effectiveness of the oxidant species, especially in the oxidation of complex and highly sensitive compounds (Bobbitt, 1998). There are some reported structures of such cation–anion compounds, for example, the 1,1'-(ethane-1,2-diyl)dipyridinium dication with dichromate(VI) (Gholizadeh et al., 2012) and iodate anions (Gholizadeh et al., 2011).

Here, we present the syntheses and crystal structures of two new salts of the 1,1'-(ethane-1,2-diyl)dipyridinium dication, namely the bis­(diperchlorate) salt, (I), and the hexaoxo-µ-peroxo-di­sulfate­(2-) (also known as peroxodi­sulfate) salt, (II). Furthermore, Hirshfeld surface analysis, using the CrystalExplorer software (Wolff et al., 2012), was used to investigate and compare the inter­molecular inter­actions, viz. the H···H, H···O, H···C and C···H contacts, in (I) and (II).

S2. Experimental

S2.1. Synthesis and crystallization

(C₁₄H₁₈N₂)Br₂ was prepared as described previously (Gholizadeh et al., 2011). The preparation of both (I) and (II) is identical, with the exception of the salts used for providing the counter-anions. To a solution of (C₁₄H₁₈N₂)Br₂ (10 mmol) in water (25 ml), an aqueous solution (25 ml) of KClO₄ (20 mmol) for (I), or a solution of K₂S₂O₈ (10 mmol) for (II), was added and the resulting solution stirred at room temperature. For both compounds, after 1 h, the precipitate was filtered off, washed with water and recrystallized from H₂O–di­methyl­formamide (1:1 v/v) at room temperature.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. For (I) and (II), all H atoms were placed in calculated positions, with C—H = 0.96 Å (aromatic and CH₂) and U_iso(H) = 1.2U_eq(C). The data-reduction program CrysAlis PRO (Agilent, 2010) discarded two low-angle reflections [001 for (I) and 100 for (II)]. They were recorded in positions close to the beam stop or the Lorentz area of the CCD detector.

S3. Results and discussion

In the title bis­(diperchlorate), (I) (Fig. 1), and peroxodi­sulfate, (II) (Fig. 2), salts, the dications are organized around an inversion centre located at the centre of the –CH₂CH₂– bridge and the two pyridine segments are anti with respect to one another. The pyridinium rings are parallel in both cases, but the perpendicular distances between their planes are 1.486 (2) Å for (I) and 1.309 (4) Å for (II). This difference in the perpendicular distances of (I) and (II) is related to the difference in the angle between the plane of the pyridinium ring and the plane defined by atoms N2/C1/C1ⁱ/Nⁱ for (I) [symmetry code: (i) -x, -y + 1, -z] and N2/C1/C1ⁱⁱ/Nⁱⁱ for (II) [symmetry code: (ii) -x + 1, -y + 1, -z]. The angle between the planes of the rings of 83.76 (15)° in (I) is closer to 90° than that of 73.88 (14)° in (II), thus allowing for a larger separation of the pyridinium rings. The peroxodi­sulfate anion in (II) also exhibits inversion symmetry. The Cl atom in (I) and the S atom in (II) are in tetra­hedral environments. Selected bond lengths and angles for (I) and (II) are given in Tables 2 and 4, respectively. The crystal packing of both structures are stabilized by C—H···O hydrogen bonds (Tables 3 and 5).

For the dications of (I) and (II), the three-dimensional Hirshfeld surface (HS) maps are given in Fig. 3; contacts with distances equal to the sum of the van der Waals radii are shown in white, and contacts with distances shorter than or longer than the related sum values are shown in red (highlight contacts) or blue, respectively. Tables 3 and 5 list the short inter­molecular contacts with distances shorter than the sum of van der Waals radii, and these are identified with red spots on the HSs and labels as defined in Fig. 3. The shapes of the HSs of the dications in both structures are similar, reflecting similar inter­molecular contacts (Tables 3 and 5) and similar conformations.

In the crystal packing, the dication of (I) takes part in different inter­molecular contacts, viz. C—H···O (labels 1–6, 9 and 11 in Fig. 3), C···O (label 7), C···C (labels 10 and 12) and N···O (label 8), and the dication of (II) is involved in inter­molecular C—H···O inter­actions (all labels except 7) and N···O (label 7) contacts. In both structures, each dication participates in some similar C—H···O hydrogen bonds, labelled in Fig. 3 as 2, 3, 5, 6 and 9 (Tables 3 and 5). The dark-red spots are related to the shorter C—H···O hydrogen bonds for both structures, and also to the unique Csp₂···O inter­action for (I). The light-red spots on the HSs include other inter­molecular inter­actions (Fig. 3, and Tables 3 and 5).

Fig. 4 illustrates the analysis of the two-dimensional fingerprint plots (FPs) for the dications of (I) and (II). FPs are the two-dimensional representations of the information provided by visual inspection of the HSs, in which the distances of the nearest atoms outside, d_e, and inside, d_i, from the related HSs are plotted for evenly spaced points on the HSs. For a better identification of different H···X or X···H (X = H, O or C) contacts, the FP of each dication in (I) and (II) is decomposed into H···X-inter­actions-only fingerprints.

The two-dimensional fingerprint plots in Fig. 4 are quite asymmetric; this is expected, since inter­actions occur between two different species (cation and anion). In other words, the asymmetry about the plot diagonal is typical of structures that contain more than one component (molecule/ion) (Fabbiani et al., 2011).

In FPs of cation–anion compounds, the contact regions between the HSs of the two species (cation and anion) in the asymmetric unit are visible, and it is possible to identify complementary regions in the FPs, where one component (cation) acts as an H-atom donor (d_e > d_i) and the other as an acceptor (d_e < d_i). The most striking of these complementary features is the broad green spike in the region d_e > d_i on each of the full plots, resulting from the H···O contacts; similar spikes are not visible in the region d_e < d_i, due to the absence of O···H contacts. Moreover, the FPs in Fig. 4 clearly show the similarities, as well as the minor differences, between the distributions of inter­actions of the dications in (I) and (II).

Fig. 5 shows the relative contributions of the H···H, H···O, H···C and C···H contacts to the HS areas for the respective dications. By comparing the results in Fig. 5, it is seen that the H···O inter­actions outnumber the other contacts in the crystal structures (versus 0% area for the O···H inter­actions). Moreover, the percentages of the areas in Fig. 5 reveal that there are minor differences in the distribution of H···H and C···H inter­actions for the dications of (I) and (II).

Related literature

For related literature, see: Agilent (2010); Bobbitt (1998); Fabbiani et al. (2011); Gholizadeh et al. (2011, 2012); Ling et al. (2010); McKinnon et al. (2004); Rohl et al. (2008); Spackman & Byrom (1997); Spackman & Jayatilaka (2009); Spackman & McKinnon (2002); Tarahhomi et al. (2013); Wolff et al. (2012).

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2006), enCIFer (Allen, et al., 2004) and PLATON (Spek, 2009).

Figures

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry-related atoms are generated by a crystallographic inversion centre. [Symmetry code: (i) -x, -y + 1, -z.]

Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry-related atoms are generated by a crystallographic inversion centre. [Symmetry codes: (i) -x + 1, -y, -z; (ii) -x + 1, -y + 1, -z.]

Fig. 3. Views of the Hirshfeld surfaces (HSs) in two orientations for the dications of (I) and (II) (HSs mapped with d_norm). The labels on the HSs are as follows. For (I), (1) C3—H1C3···O2; (2) C7—H1C7···O2ⁱ; (3) C1—H2C1···O2ⁱ; (4) C3—H1C3···O3; (5) C4—H1C4···O3ⁱⁱ; (6) C1—H1C1···O2ⁱⁱⁱ; (7) C3···O4^iv; (8) N2···O4^iv; (9) C1—H1C1···O4^iv; (10) C5···C5^v; (11) C5—H1C5···O3^vi; (12) C5···C4^vi. For (II), (1) C1—H2C1···O1ⁱ; (2) C7—H1C7···O4ⁱ; (3) C3—H1C3···O2; (4) C3—H1C3···O1ⁱⁱ; (5) C7—H1C7···O4ⁱⁱⁱ; (6) C1—H1C1···O2; (7) N2···O2^iv; (8) C5—H1C5···O1^v; (9) C5—H1C5···O3^vi; (10) C4—H1C4···O3^vi. The symmetry codes are as in Tables 3 and 5.

Fig. 4. Full fingerprint plots (FPs) for the dications of (I) and (II), and FPs resolved into H···H, H···O, H···C and C···H close contacts. The first two rows are related to the dication of (I), and the third and fourth rows are related to the dication of (II).

Fig. 5. Relative contributions to the Hirshfeld surface areas for the various intermolecular contacts (H···H, H···O, H···C and C···H) in the dications of (I) (dark-blue columns) and (II) (light-blue columns). The N···O and C···O contacts (with negligible percentage of contact contributions) are not considered.

(I) 1,1'-(Ethane-1,2-diyl)dipyridinium bis(perchlorate)

Crystal data

C12H14N2^2+·2ClO4^−	Z = 1
Mr = 385.15	F(000) = 198
Triclinic, P1	Dx = 1.655 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 6.0687 (3) Å	Cell parameters from 4357 reflections
b = 6.7263 (4) Å	θ = 3.1–29.3°
c = 9.8005 (3) Å	µ = 0.47 mm^−1
α = 97.858 (4)°	T = 120 K
β = 95.503 (4)°	Prism, colourless
γ = 100.655 (4)°	0.57 × 0.31 × 0.17 mm
V = 386.44 (3) Å^3

Data collection

Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector	1904 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1717 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 10.3784 pixels mm^-1	θmax = 29.3°, θmin = 3.1°
ω scans	h = −8→7
Absorption correction: analytical (CrysAlis PRO; Agilent, 2010)	k = −8→9
Tmin = 0.88, Tmax = 0.946	l = −12→13
6178 measured reflections

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.030	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0016I^2)
wR(F^2) = 0.104	(Δ/σ)max = 0.010
S = 1.79	Δρmax = 0.29 e Å^−3
1904 reflections	Δρmin = −0.33 e Å^−3
110 parameters	Extinction correction: B–C type 1 Gaussian isotropic (Becker & Coppens, 1974) Becker, P. J. & Coppens, P. (1974). Acta Cryst. A30, 129–147.
0 restraints	Extinction coefficient: 1600 (400)
28 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.51205 (6)	0.20569 (6)	0.21529 (3)	0.01404 (14)
O1	0.75374 (18)	0.23345 (19)	0.24274 (12)	0.0210 (4)
O2	0.45627 (19)	0.32895 (18)	0.11147 (11)	0.0195 (4)
O3	0.4230 (2)	0.2722 (2)	0.34055 (12)	0.0296 (5)
O4	0.4163 (2)	−0.0060 (2)	0.16526 (14)	0.0328 (5)
N2	0.0120 (2)	0.66514 (19)	0.17194 (12)	0.0120 (4)
C6	−0.2013 (3)	0.7874 (2)	0.34153 (16)	0.0170 (5)
C4	0.1380 (3)	0.6737 (2)	0.40854 (15)	0.0163 (5)
C5	−0.0477 (3)	0.7514 (2)	0.44444 (15)	0.0167 (5)
C1	0.0473 (2)	0.6135 (2)	0.02463 (14)	0.0141 (5)
C3	0.1645 (3)	0.6299 (2)	0.27022 (15)	0.0145 (5)
C7	−0.1676 (3)	0.7436 (2)	0.20407 (15)	0.0148 (5)
H1C6	−0.330164	0.842353	0.365405	0.0204*
H1C4	0.247221	0.650526	0.479091	0.0195*
H1C5	−0.070031	0.780266	0.540231	0.0201*
H1C1	0.206125	0.642718	0.016718	0.017*
H2C1	−0.02975	0.692644	−0.030912	0.017*
H1C3	0.291729	0.574231	0.243952	0.0174*
H1C7	−0.272253	0.769263	0.13189	0.0178*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0130 (2)	0.0157 (2)	0.0137 (2)	0.00278 (15)	0.00156 (14)	0.00366 (14)
O1	0.0123 (6)	0.0268 (7)	0.0249 (6)	0.0045 (5)	−0.0001 (4)	0.0082 (5)
O2	0.0218 (6)	0.0236 (7)	0.0160 (6)	0.0092 (5)	0.0022 (4)	0.0071 (5)
O3	0.0281 (7)	0.0511 (9)	0.0160 (6)	0.0188 (6)	0.0093 (5)	0.0087 (6)
O4	0.0323 (8)	0.0164 (7)	0.0439 (8)	−0.0064 (6)	−0.0035 (6)	0.0053 (6)
N2	0.0138 (6)	0.0111 (6)	0.0099 (6)	−0.0003 (5)	0.0017 (4)	0.0009 (5)
C6	0.0177 (8)	0.0154 (8)	0.0189 (8)	0.0049 (6)	0.0063 (6)	0.0012 (6)
C4	0.0195 (8)	0.0145 (8)	0.0129 (7)	0.0004 (6)	−0.0026 (6)	0.0026 (6)
C5	0.0223 (9)	0.0137 (8)	0.0122 (7)	−0.0007 (6)	0.0036 (6)	0.0000 (6)
C1	0.0168 (8)	0.0149 (8)	0.0098 (7)	0.0009 (6)	0.0033 (5)	0.0010 (6)
C3	0.0135 (8)	0.0132 (7)	0.0165 (7)	0.0024 (6)	0.0015 (6)	0.0027 (6)
C7	0.0132 (8)	0.0150 (8)	0.0156 (8)	0.0026 (6)	−0.0003 (5)	0.0017 (6)

Geometric parameters (Å, º)

Cl1—O1	1.4381 (12)	C4—C5	1.382 (2)
Cl1—O2	1.4510 (13)	C4—C3	1.379 (2)
Cl1—O3	1.4374 (13)	C4—H1C4	0.96
Cl1—O4	1.4332 (13)	C5—H1C5	0.96
N2—C1	1.4835 (18)	C1—C1^i	1.5211 (19)
N2—C3	1.347 (2)	C1—H1C1	0.96
N2—C7	1.341 (2)	C1—H2C1	0.96
C6—C5	1.383 (2)	C3—H1C3	0.96
C6—C7	1.382 (2)	C7—H1C7	0.96
C6—H1C6	0.96
O1—Cl1—O2	109.06 (7)	C6—C5—C4	119.62 (14)
O1—Cl1—O3	109.45 (7)	C6—C5—H1C5	120.19
O1—Cl1—O4	109.70 (8)	C4—C5—H1C5	120.19
O2—Cl1—O3	108.85 (8)	N2—C1—C1^i	108.98 (12)
O2—Cl1—O4	109.68 (7)	N2—C1—H1C1	109.47
O3—Cl1—O4	110.09 (8)	N2—C1—H2C1	109.47
C1—N2—C3	117.85 (13)	C1^i—C1—H1C1	109.47
C1—N2—C7	120.22 (12)	C1^i—C1—H2C1	109.47
C3—N2—C7	121.93 (13)	H1C1—C1—H2C1	109.95
C5—C6—C7	119.46 (16)	N2—C3—C4	120.04 (15)
C5—C6—H1C6	120.27	N2—C3—H1C3	119.98
C7—C6—H1C6	120.27	C4—C3—H1C3	119.98
C5—C4—C3	119.21 (15)	N2—C7—C6	119.73 (14)
C5—C4—H1C4	120.4	N2—C7—H1C7	120.14
C3—C4—H1C4	120.4	C6—C7—H1C7	120.14
C3—N2—C1—C1^i	83.48 (15)	C4—C3—N2—C1	−179.44 (13)
C7—N2—C1—C1^i	−96.28 (15)	C6—C7—N2—C1	178.73 (13)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H1C3···O2	0.96	2.38	3.263 (2)	152
C7—H1C7···O2^i	0.96	2.48	3.3322 (18)	148
C1—H2C1···O2^i	0.96	2.60	3.326 (2)	132
C3—H1C3···O3	0.96	2.58	3.220 (2)	125
C4—H1C4···O3^ii	0.96	2.47	3.3792 (19)	159
C1—H1C1···O2^iii	0.96	2.50	3.3888 (19)	155
C3···O4^iv			3.000 (2)
N2···O4^iv			2.997 (2)
C1—H1C1···O4^iv	0.96	2.63	3.129 (2)	113
C5···C5^v			3.297 (2)
C5—H1C5···O3^vi	0.96	2.53	3.245 (2)	132
C5···C4^vi			3.354 (2)

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

(II) 1,1'-(Ethane-1,2-diyl)dipyridinium hexaoxo-µ-peroxo-disulfate(2-)

Crystal data

C12H14N2^2+·S2O8^2^−	F(000) = 392
Mr = 378.4	Dx = 1.625 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ycb	Cell parameters from 3143 reflections
a = 8.2189 (5) Å	θ = 3.0–29.3°
b = 9.6676 (6) Å	µ = 0.39 mm^−1
c = 9.8361 (4) Å	T = 120 K
β = 98.359 (4)°	Prism, colourless
V = 773.24 (7) Å^3	0.76 × 0.63 × 0.54 mm
Z = 2

Data collection

Agilent Xcalibur Gemini Ultra diffractometer with Atlas detector	1848 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1687 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.017
Detector resolution: 10.3784 pixels mm^-1	θmax = 29.3°, θmin = 3.0°
ω scans	h = −11→11
Absorption correction: analytical (CrysAlis PRO; Agilent, 2010)	k = −10→13
Tmin = 0.801, Tmax = 0.845	l = −13→12
5426 measured reflections

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.028	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0016I^2)
wR(F^2) = 0.092	(Δ/σ)max = 0.007
S = 1.71	Δρmax = 0.31 e Å^−3
1848 reflections	Δρmin = −0.27 e Å^−3
110 parameters	Extinction correction: B–C type 1 Gaussian isotropic (Becker & Coppens, 1974)
0 restraints	Extinction coefficient: 34400 (1600)
28 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.33725 (4)	0.11885 (3)	0.07649 (3)	0.01224 (12)
O1	0.27332 (12)	0.18207 (11)	−0.05252 (9)	0.0201 (3)
O2	0.46015 (11)	0.20123 (10)	0.15908 (9)	0.0176 (3)
O3	0.21787 (12)	0.05361 (11)	0.14885 (10)	0.0211 (3)
O4	0.43319 (11)	−0.02305 (10)	0.03799 (9)	0.0182 (3)
N2	0.33808 (12)	0.56967 (12)	0.09676 (10)	0.0121 (3)
C6	0.10858 (16)	0.71905 (15)	0.05622 (13)	0.0203 (4)
C5	0.03187 (17)	0.64228 (15)	0.14892 (14)	0.0195 (4)
C7	0.26360 (16)	0.68040 (14)	0.03245 (13)	0.0170 (4)
C4	0.11152 (17)	0.52957 (15)	0.21390 (13)	0.0183 (4)
C3	0.26629 (15)	0.49407 (15)	0.18680 (12)	0.0147 (3)
C1	0.50530 (15)	0.53315 (13)	0.07117 (12)	0.0136 (3)
H1C6	0.054444	0.797422	0.00978	0.0243*
H1C5	−0.075686	0.667742	0.167356	0.0234*
H1C7	0.318515	0.732784	−0.030259	0.0204*
H1C4	0.059549	0.476065	0.277688	0.022*
H1C3	0.322568	0.415913	0.231844	0.0176*
H1C1	0.553291	0.468653	0.139716	0.0163*
H2C1	0.571429	0.615268	0.074414	0.0163*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0108 (2)	0.0126 (2)	0.0138 (2)	0.00277 (11)	0.00332 (13)	−0.00073 (11)
O1	0.0194 (5)	0.0226 (6)	0.0173 (5)	0.0064 (4)	−0.0012 (4)	0.0022 (4)
O2	0.0179 (5)	0.0183 (5)	0.0162 (4)	−0.0024 (4)	0.0010 (4)	−0.0024 (4)
O3	0.0161 (5)	0.0244 (6)	0.0252 (5)	−0.0010 (4)	0.0114 (4)	−0.0018 (4)
O4	0.0165 (5)	0.0113 (5)	0.0306 (5)	0.0007 (4)	0.0160 (4)	0.0013 (4)
N2	0.0104 (5)	0.0136 (6)	0.0127 (5)	−0.0004 (4)	0.0029 (4)	−0.0021 (4)
C6	0.0180 (7)	0.0177 (7)	0.0258 (7)	0.0058 (6)	0.0058 (5)	0.0064 (6)
C5	0.0140 (6)	0.0234 (8)	0.0224 (7)	0.0037 (5)	0.0068 (5)	0.0023 (6)
C7	0.0179 (6)	0.0145 (7)	0.0198 (6)	0.0005 (5)	0.0064 (5)	0.0029 (5)
C4	0.0173 (6)	0.0214 (7)	0.0179 (6)	0.0006 (6)	0.0080 (5)	0.0036 (5)
C3	0.0149 (6)	0.0160 (6)	0.0131 (5)	0.0021 (5)	0.0021 (4)	0.0017 (5)
C1	0.0096 (5)	0.0171 (7)	0.0141 (5)	0.0012 (5)	0.0021 (4)	−0.0026 (5)

Geometric parameters (Å, º)

S1—O1	1.4374 (10)	C5—C4	1.379 (2)
S1—O2	1.4408 (9)	C5—H1C5	0.96
S1—O3	1.4388 (11)	C7—H1C7	0.96
O4—O4^i	1.4839 (13)	C4—C3	1.3805 (19)
N2—C7	1.3447 (17)	C4—H1C4	0.96
N2—C3	1.3485 (17)	C3—H1C3	0.96
N2—C1	1.4757 (16)	C1—C1^ii	1.5308 (16)
C6—C5	1.395 (2)	C1—H1C1	0.96
C6—C7	1.3800 (19)	C1—H2C1	0.96
C6—H1C6	0.96
O1—S1—O2	113.52 (6)	C6—C7—H1C7	119.86
O1—S1—O3	115.79 (6)	C5—C4—C3	119.70 (13)
O2—S1—O3	115.85 (6)	C5—C4—H1C4	120.15
C7—N2—C3	121.85 (11)	C3—C4—H1C4	120.15
C7—N2—C1	118.80 (11)	N2—C3—C4	119.70 (12)
C3—N2—C1	119.32 (11)	N2—C3—H1C3	120.15
C5—C6—C7	118.86 (13)	C4—C3—H1C3	120.15
C5—C6—H1C6	120.57	N2—C1—C1^ii	109.00 (9)
C7—C6—H1C6	120.57	N2—C1—H1C1	109.47
C6—C5—C4	119.60 (13)	N2—C1—H2C1	109.47
C6—C5—H1C5	120.2	C1^ii—C1—H1C1	109.47
C4—C5—H1C5	120.2	C1^ii—C1—H2C1	109.47
N2—C7—C6	120.28 (13)	H1C1—C1—H2C1	109.94
N2—C7—H1C7	119.86
C3—N2—C1—C1^ii	107.08 (12)	O1—S1—O4—O4^i	61.05 (8)
C7—N2—C1—C1^ii	−74.94 (14)	O2—S1—O4—O4^i	−59.71 (8)
C4—C3—N2—C1	178.41 (12)	O3—S1—O4—O4^i	−179.30 (7)
C6—C7—N2—C1	−178.69 (12)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H2C1···O1^ii	0.96	2.36	3.3198 (17)	173
C7—H1C7···O2^ii	0.96	2.45	3.3552 (17)	158
C3—H1C3···O2	0.96	2.52	3.279 (2)	136
C3—H1C3···O1^iii	0.96	2.41	3.0715 (16)	126
C7—H1C7···O4^iv	0.96	2.59	3.185 (2)	120
C1—H1C1···O2	0.96	2.71	3.358 (2)	125
N2···O2^v			2.996 (1)
C5—H1C5···O1^vi	0.96	2.34	3.063 (2)	131
C5—H1C5···O3^vii	0.96	2.54	3.177 (2)	124
C4—H1C4···O3^vii	0.96	2.60	3.204 (2)	121

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x, −y+1/2, z+1/2; (iv) x, y+1, z; (v) −x+1, y+1/2, −z+1/2; (vi) −x, −y+1, −z; (vii) −x, y+1/2, −z+1/2.