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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Simple hydrogen-bonded chains in 2,2′-bipyridinium thio­cyanate, hydrogen-bonded chains of rings in 2,2′-bipyridinium picrate and hydrogen-bonded sheets in 2,2′-bipyridinium hydrogensulfate

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aSchool of Chemistry, Bharathidasan University, Tiruchirappalli, Tamil Nadu 620 024, India, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 7 February 2006; accepted 10 February 2006; online 11 March 2006)

In 2,2′-bipyridinium thio­cyanate, C10H9N2+·NCS, the cations are disordered over two sets of sites with occupancies of 0.845 (2) and 0.155 (2). The ions are linked into simple chains by a combination of N—H⋯N and C—H⋯N hydrogen bonds, regardless of the orientation of the cation. In 2,2′-bipyridinium picrate, C10H9N2+·C6H2N3O7, the bond distances in the anion indicate a markedly non-classical electronic structure; the component ions are linked by a combination of six independent hydrogen bonds, viz. one of N—H⋯O type and five of C—H⋯O type, into a complex chain containing five distinct types of ring. The ions in 2,2′-bipyridinium hydrogensulfate, C10H9N2+·HSO4, are linked by a combination of five hydrogen bonds, viz. one each of O—H⋯O and N—H⋯O types, and three of C—H⋯O type, into complex sheets built from two one-dimensional substructures, each in the form of a complex chain of rings.

Comment

Two series of salts can be formed by 2,2′-bipyridine in which the cation is either monoprotonated, C10H9N2+ (Kavitha et al., 2005[Kavitha, S. J., Panchanatheswaran, K., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o473-o474.]), or diprotonated, C10H10N22+ (Nakatsu et al., 1972[Nakatsu, K., Yoshida, H., Matsui, M., Koda, S. & Ooi, S. (1972). Acta Cryst. A28, S24.]); the monocation can act as an acid, as a base or as a ligand. As part of a study of the coordination properties of this cation, we report here the mol­ecular and supramolecular structures of three related organic salts, viz. 2,2′-bipyridinium thio­cyanate, (I)[link], 2,2′-bipyridinium picrate, (II)[link], and 2,2′-bipyridinium hydrogensulfate, (III)[link] (Figs. 1[link]–3[link][link]), and we briefly compare the structure of the latter with that of its close analogue 2,2′-bipyridinium perchlorate, (IV) (Kavitha et al., 2005[Kavitha, S. J., Panchanatheswaran, K., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o473-o474.]).

[Scheme 1]

In (I)[link], the cation is disordered over two sets of sites, with refined occupancies 0.845 (2) and 0.155 (2) (Fig. 1[link]). Each orientation of the cation is nearly planar, but the N atoms are on opposite edges of the cation. Likewise, in each of (II)[link] and (III)[link], the cation has a nearly planar conformation, with the two N atoms on the same edge of the cation. In each compound, there is a short N—H⋯N contact within the cation, but the N—H⋯N angles are very small (Tables 2[link], 4[link] and 6[link]). The inter­nal angles at protonated atom N11 and unprotonated atom N21 (Tables 1[link], 3[link] and 5[link]) show very marked differences in the expected sense (Domenicano & Murray-Rust, 1979[Domenicano, A. & Murray-Rust, P. (1979). Tetrahedron Lett. pp. 2283-2386.]), with complementary differences in the inter­nal angles at atoms C12 and C22. The two exocyclic angles at each of C12 and C22 differ by ca 10°, always in the sense that the N—C—C angle is the smaller angle and the C—C—C angle is the larger angle (Tables 1[link], 3[link] and 5[link]).

In the anion of (II)[link], the nitro group at the 4-position is almost coplanar with the phenyl ring, but the nitro groups at the 2- and 6-positions are both twisted well out of the plane of the benzene ring, with dihedral angles between the nitro planes and the benzene plane of 46.3 (2) and 20.5 (2)°, respectively. The sense of these rotations is such that the anion retains approximate mirror symmetry. The bond distances within the ring indicate very marked deviation from regular hexa­gonal geometry, with the C31—C32 and C36—C31 bonds very much longer than the others, while the mean C—C distance for the C32—C33 and C35—C36 bonds is somewhat less than the mean distance for the C33—C34 and C34—C35 bonds. In addition, the C34—N34 bond is shorter than the C32—N32 and C36—N36 bonds, while the C31—O31 bond, which is a single bond in the classical representation of the anion (IIa)[link], is extremely short for such a single bond but is comparable to the mean value (1.222 Å; Allen et al. 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]) of C=O bonds in benzoquinones. These observations, taken all together, indicate that (IIa)[link] is an inappropriate representation of the picrate anion here, but that the quinonoid form (IIb)[link] and the penta­dienide form (IIc)[link] are both important contributors to the overall mol­ecular–electronic structure.

In the anion of (III)[link], the S—O(H) bond distance exceeds the other three S—O distances by more than 0.1 Å, while the O—S—O angles involving protonated atom O1 are systematically less than the other O—S—O angles (Table 3[link]).

Regardless of the orientation of the cation, the components in (I)[link] are linked by one N—H⋯N hydrogen bond and one C—H⋯N hydrogen bond (Table 2[link]), so forming a C12(6) chain running parallel to the [001] direction and generated by the c-glide plane at y = 0.25 (Fig. 4[link]). Two such chains run through each unit cell, but there are no direction-specific inter­actions between adjacent chains.

The component ions of (II)[link] are linked into rather complex chains of rings, which may alternatively be described as perforated ribbons, by a combination of one N—H⋯O hydrogen bond and no fewer than five C—H⋯O hydrogen bonds (Table 4[link]). Within the selected asymmetric unit (Fig. 2[link]), the ions are linked by the co-operative action of the N—H⋯O hydrogen bond and one of the C—H⋯O hydrogen bonds, generating a simple R22(7) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) motif in which the acceptors are the two O atoms of a single nitro group. Three C—H⋯O hydrogen bonds acting in concert link these ion-pair aggregates into chains of rings; atoms C13 and C23 in the cation at (x, y, z) both act as hydrogen-bond donors to atom O31 in the anion at (−1 + x, −1 + y, 1 + z), while atom C14 in the cation at (x, y, z) likewise acts as a donor to atom O21 in the anion at (−1 + x, −1 + y, 1 + z), so generating by translation a chain of rings running parallel to the [11[\overline{1}]] direction. The final C—H⋯O hydrogen bond links anti­parallel pairs of such chains to form the overall ribbon; atom C35 in the anion at (x, y, z) acts as a hydrogen-bond donor to atom O42 in the anion at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric R22(10) anion dimer centred at ([1\over2], [1\over2], [1\over2]). Propagation by translation and inversion of all these hydrogen bonds then generates a complex chain of rings along [11[\overline{1}]] containing a central strip of alternating edge-fused R22(10) and R64(22) rings, with the R22(10) rings centred at (n + [1\over2], n + [1\over2], −n + [1\over2]) (n = zero or integer) and the R64(22) rings centred at (n, n, −n) (n = zero or integer). This central array of centrosymmetric rings is flanked on each edge of the ribbon by strings of alternating single R22(7) rings, which lie within the asymmetric unit, and the edge-fused R21(7) and R22(8) rings, which are generated by translation. There are thus five distinct types of ring within this ribbon structure (Fig. 5[link]), but there are no direction-specific inter­actions between adjacent ribbons.

The components of (III)[link] are linked into complex sheets by a combination of O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds (Table 6[link]), but the formation of this sheet structure is readily analysed in terms of two one-dimensional substructures. The N—H⋯O hydrogen bond links the two components within the selected asymmetric unit (Fig. 3[link]), while the O—H⋯O hydrogen bond and three independent C—H⋯O hydrogen bonds link these ion-pair aggregates.

A very simple substructure is generated by the anions alone. Atom O1 in the anion at (x, y, z) acts as a hydrogen-bond donor to atom O4 in the anion at (x, 1 + y, z), so generating by translation a C(4) chain running parallel to the [010] direction (Fig. 6[link]). This [010] chain is reinforced by one of the C—H⋯O hydrogen bonds. Atom C15 in the cation at (x, y, z) acts as a hydrogen-bond donor to atom O3 in the anion at (1 − x, −[{3\over 2}] + y, [{1\over 2}]z), while atom C15 at (1 − x, −[{3\over 2}] + y, [{1\over 2}]z) in turn acts as a donor to atom O3 at (x, −3 + y, z), so producing a chain of edge-fused R66(24) rings generated by the 21 screw axis along ([1\over2], y, [1\over4]) (Fig. 7[link]).

A second one-dimensional substructure is generated by the concerted action of two C—H⋯O hydrogen bonds. Atoms C13 and C14 in the cation at (x, y, z) act as hydrogen-bond donors, respectively, to atoms O4 and O3, both in the anion at (x, [{1\over 2}]y, [{1\over 2}] + z). In combination with the N—H⋯O hydrogen bond within the asymmetric unit, these two C—H⋯O hydrogen bonds form a C22(8)C22(9)[R22(7)] chain of rings running parallel to the [001] direction and generated by the c-glide plane at y = 0.25 (Fig. 8[link]). The combination of the [010] and [001] substructures (Figs. 7[link] and 8[link]) generates a complex (100) sheet, but there are no direction-specific inter­actions between adjacent sheets.

Although (III)[link] and (IV)[link] have similar compositions, they crystallize with very different unit cells in different space groups, viz. P21/c for (III)[link] and Pc for (IV) (Kavitha et al., 2005[Kavitha, S. J., Panchanatheswaran, K., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o473-o474.]). Despite this difference, they form a common substructural motif in the form of the C22(8)C22(9)[R22(7)] chain of rings (Fig. 6[link]), generated by the action of a glide plane in (III)[link] but by translation in (IV)[link]. There can be no anion-chain substructure in (IV)[link], but all four O atoms of the perchlorate anion act as acceptors in hydrogen bonds, and the overall supramolecular structure takes the form of a rather complex sheet.

[Figure 1]
Figure 1
The independent components of (I)[link], showing the cation disorder, the atom-labelling scheme and the two hydrogen bonds within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
The independent components of (II)[link], showing the atom-labelling scheme and the two hydrogen bonds within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3]
Figure 3
The independent components of (III)[link], showing the atom-labelling scheme and the hydrogen bond within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4]
Figure 4
Part of the crystal structure of (I)[link], showing the formation of a C12(6) chain along [001]. For the sake of clarity, only the major orientation of the cation is shown and H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ([{1\over 2}]x, y, [{1\over 2}] + z) and ([{1\over 2}]x, y, −[{1\over 2}] + z), respectively.
[Figure 5]
Figure 5
A stereoview of part of the crystal structure of (II)[link], showing the formation of a hydrogen-bonded [11[\overline{1}]] chain containing five different types of ring. For the sake of clarity, H atoms not involved in the hydrogen bonds shown have been omitted.
[Figure 6]
Figure 6
Part of the crystal structure of (III)[link], showing the formation of a hydrogen-bonded C(4) chain of anions along [010]. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, 1 + y, z) and (x, −1 + y, z), respectively.
[Figure 7]
Figure 7
A stereoview of part of the crystal structure of (III)[link], showing the formation of a hydrogen-bonded chain of edge-fused R66(24) rings along [010]. For the sake of clarity, H atoms not involved in the hydrogen bonds shown have been omitted.
[Figure 8]
Figure 8
A stereoview of part of the crystal structure of (III)[link], showing the formation of a hydrogen-bonded C22(8)C22(9)[R22(7)] chain of rings along [001]. For the sake of clarity, H atoms not involved in the hydrogen bonds shown have been omitted.

Experimental

For the synthesis of (I)[link], a solution in methanol (50 ml) of 2,2′-bi­pyridinium chloride (0.5 g) (itself prepared by the reaction between concentrated hydro­chloric acid and 2,2′-bipyridine in a 1:1 molar ratio in methanol) was added to ammonium thio­cyanate (0.23 g) and the resulting mixture was heated on a water bath for 30 min. The mixture was cooled to ambient temperature, and subsequent slow evaporation of the solvent gave crystals of (I)[link] (m.p. 401 K) suitable for single-crystal X-ray diffraction. For the synthesis of (II)[link], a solution of picric acid (0.44 g) in methanol (50 ml) was added to a solution of 2,2′-bipyridine (0.3 g) in methanol (50 ml); this mixture was then warmed on a water bath for 15 min. After cooling of the solution to ambient temperature, slow evaporation of the solvent yielded crystals of (II)[link] (m.p. 398 K) suitable for single-crystal X-ray diffraction. Compound (III)[link] (m.p. 418 K) was prepared in a similar manner using 0.5 g of 2,2′-bipyridine and 0.36 ml of concentrated sulfuric acid.

Compound (I)[link]

Crystal data
  • C10H9N2+·NCS

  • Mr = 215.27

  • Orthorhombic, P c a 21

  • a = 8.0954 (2) Å

  • b = 11.7686 (6) Å

  • c = 11.0026 (6) Å

  • V = 1048.23 (8) Å3

  • Z = 4

  • Dx = 1.364 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 2311 reflections

  • θ = 3.6–27.5°

  • μ = 0.28 mm−1

  • T = 120 (2) K

  • Plate, colourless

  • 0.40 × 0.40 × 0.04 mm

Data collection
  • Bruker KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.898, Tmax = 0.989

  • 7990 measured reflections

  • 2311 independent reflections

  • 2145 reflections with I > 2σ(I)

  • Rint = 0.033

  • θmax = 27.5°

  • h = −10 → 8

  • k = −12 → 15

  • l = −14 → 14

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.031

  • wR(F2) = 0.077

  • S = 1.05

  • 2311 reflections

  • 174 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0396P)2 + 0.256P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.29 e Å−3

  • Δρmin = −0.28 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 968 Friedel pairs; χ = 0.57 (7)

Table 1
Selected geometric parameters (Å, °) for (I)[link]

S1—C2 1.6383 (16)
C2—N3 1.166 (2)
C16—N11—C12 122.5 (3)
N11—C12—C13 118.4 (2)
N11—C12—C22 117.2 (2)
C13—C12—C22 124.4 (2)
N3—C2—S1 177.56 (19)
C26—N21—C22 116.25 (18)
N21—C22—C23 124.37 (19)
N21—C22—C12 115.08 (19)
C23—C22—C12 120.54 (19)
N11—C12—C22—N21 −18.9 (3)
N11A—C12A—C22A—N21A −19 (3)

Table 2
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N11—H11⋯N3 0.88 2.03 2.788 (4) 144
N11—H11⋯N21 0.88 2.33 2.693 (4) 104
N11A—H11A⋯N3i 0.88 2.34 3.12 (2) 148
N11A—H11A⋯N21A 0.88 2.42 2.75 (2) 103
C13—H13⋯N3i 0.95 2.53 3.217 (4) 129
C13A—H13A⋯N3 0.95 2.27 2.93 (3) 126
Symmetry code: (i) [-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}].

Compound (II)[link]

Crystal data
  • C10H9N2+·C6H2N3O7

  • Mr = 385.30

  • Triclinic, [P \overline 1]

  • a = 7.4139 (5) Å

  • b = 9.3768 (6) Å

  • c = 12.3694 (5) Å

  • α = 71.681 (3)°

  • β = 75.722 (3)°

  • γ = 77.391 (3)°

  • V = 781.79 (8) Å3

  • Z = 2

  • Dx = 1.637 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 3598 reflections

  • θ = 3.2–27.6°

  • μ = 0.13 mm−1

  • T = 120 (2) K

  • Lath, yellow

  • 0.12 × 0.09 × 0.03 mm

Data collection
  • Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.975, Tmax = 0.996

  • 17473 measured reflections

  • 3598 independent reflections

  • 2432 reflections with I > 2σ(I)

  • Rint = 0.068

  • θmax = 27.6°

  • h = −9 → 9

  • k = −12 → 12

  • l = −16 → 15

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.060

  • wR(F2) = 0.122

  • S = 1.04

  • 3598 reflections

  • 253 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0489P)2 + 0.2955P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.35 e Å−3

Table 3
Selected geometric parameters (Å, °) for (II)[link]

C31—C32 1.460 (3) 
C32—C33 1.359 (3)
C33—C34 1.401 (3)
C34—C35 1.376 (3)
C35—C36 1.376 (3)
C36—C31 1.452 (3)
C31—O31 1.243 (2)
C32—N32 1.454 (3)
C34—N34 1.436 (2)
C36—N36 1.454 (3)
C16—N11—C12 123.86 (18)
N11—C12—C13 117.78 (19)
N11—C12—C22 115.64 (17)
C13—C12—C22 126.53 (19)
C26—N21—C22 116.95 (18)
N21—C22—C23 123.67 (19)
N21—C22—C12 113.89 (18)
C23—C22—C12 122.40 (18)
N11—C12—C22—N21 −1.1 (3)
C31—C32—N32—O21 47.5 (3)
C33—C34—N34—O41 −1.8 (3)
C31—C36—N36—O61 158.46 (18)

Table 4
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N11—H11⋯N21 0.88 2.21 2.613 (3) 107
N11—H11⋯O42 0.88 2.55 3.204 (2) 131
C13—H13⋯O31ii 0.95 2.37 3.279 (2) 160
C14—H14⋯O21ii 0.95 2.38 3.028 (2) 125
C16—H16⋯O41 0.95 2.36 3.284 (3) 164
C23—H23⋯O31ii 0.95 2.42 3.325 (2) 159
C35—H35⋯O42iii 0.95 2.48 3.204 (3) 133
Symmetry codes: (ii) x-1, y-1, z+1; (iii) -x+1, -y+1, -z+1.

Compound (III)[link]

Crystal data
  • C10H9N2+·HSO4

  • Mr = 254.26

  • Monoclinic, P 21 /c

  • a = 12.8274 (4) Å

  • b = 4.4774 (2) Å

  • c = 18.2844 (5) Å

  • β = 100.568 (2)°

  • V = 1032.32 (6) Å3

  • Z = 4

  • Dx = 1.636 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 2373 reflections

  • θ = 3.6–27.5°

  • μ = 0.32 mm−1

  • T = 120 (2) K

  • Plate, pink

  • 0.42 × 0.16 × 0.06 mm

Data collection
  • Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.878, Tmax = 0.981

  • 19500 measured reflections

  • 2373 independent reflections

  • 2052 reflections with I > 2σ(I)

  • Rint = 0.043

  • θmax = 27.5°

  • h = −16 → 16

  • k = −5 → 5

  • l = −23 → 23

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.122

  • S = 1.26

  • 2373 reflections

  • 154 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0285P)2 + 2.1787P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.39 e Å−3

  • Δρmin = −0.45 e Å−3

Table 5
Selected geometric parameters (Å, °) for (III)[link]

S1—O1 1.5699 (19)
S1—O2 1.4526 (19)
S1—O4 1.4672 (19)
C16—N11—C12 123.5 (2)
N11—C12—C13 118.0 (2)
N11—C12—C22 115.8 (2)
C13—C12—C22 126.2 (2)
O1—S1—O2 105.72 (11)
O1—S1—O3 106.92 (11)
O1—S1—O4 105.05 (11)
C26—N21—C22 117.7 (2)
N21—C22—C23 123.3 (2)
N21—C22—C12 114.4 (2)
C23—C22—C12 122.2 (2)
O2—S1—O3 113.97 (11)
O2—S1—O4 111.05 (11)
O3—S1—O4 113.33 (11)
N11—C12—C22—N21 5.3 (3) 

Table 6
Hydrogen-bond geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯O4iv 0.94 1.70 2.640 (3) 173
N11—H11⋯O2 0.88 1.98 2.752 (3) 146
N11—H11⋯N21 0.88 2.23 2.625 (3) 107
C13—H13⋯O4v 0.95 2.44 3.389 (3) 173
C14—H14⋯O3v 0.95 2.48 3.156 (3) 129
C15—H15⋯O3vi 0.95 2.52 3.433 (3) 161
Symmetry codes: (iv) x, y+1, z; (v) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (vi) [-x+1, y-{\script{3\over 2}}, -z+{\script{1\over 2}}].

For (I)[link], the systematic absences permitted Pca21 or Pcam (= Pbcm, No. 57) as possible space groups; Pca21 was selected and confirmed by the structure analysis. Crystals of (II)[link] are triclinic; the space group P[\overline{1}] was selected and confirmed by the subsequent structure analysis. For (III)[link], the space group P21/c was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms with C—H distances of 0.95 Å, N—H distances of 0.88 Å and an O—H distance of 0.94 Å, and with Uiso(H) values of 1.2Ueq(C,N) or 1.5Ueq(O). For (I)[link], the refined occupancies of the major and minor orientations of the cation were 0.845 (2) and 0.155 (2), respectively; in addition, the crystals of (I)[link] were found to exhibit inversion twinning with twin fractions 0.57 (7) and 0.43 (7).

For all compounds, data collection: COLLECT (Hooft, 1999[Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

Two series of salts can be formed by 2,2'-bipyridine in which the cation is either monoprotonated, C10H9N2+ (Kavitha et al., 2005), or diprotonated, C10H10N22+ (Nakatsu et al., 1972); the monocation can act as an acid, as a base or as a ligand. As part of a study of the coordination properties of this cation, we report here the molecular and supramolecular structures of three related organic salts, viz. 2,2'-bipyridinium thiocyanate, (I), 2,2'-bipyridinium picrate, (II), and 2,2'-bipyridinium hydrogensulfate, (III) (Figs. 1–3), and we briefly compare the structure of the latter with that of it close analogue 2,2'-bipyridinium perchlorate, (IV) (Kavitha et al., 2005).

In (I), the cation is disordered over two sets of sites, with refined occupancies 0.845 (2) and 0.155 (2) (Fig. 1). Each orientation of the cation is nearly planar, but the N atoms are on opposite edges of the cation. Likewise, in each of (II) and (III), the cation has a nearly planar conformation with the two N atoms on the same edge of the cation. In each compound, there is a short N—H···N contact within the cation, but the N—H···N angles are very small (Tables 2, 4 and 6). The internal angles at the protonated atom N11 and the unprotonated atom N21 (Tables 1, 3 and 5) show very marked differences in the expected sense (Domenicano & Murray-Rust, 1979), with complementary differences in the internal angles at atoms C12 and C22. The two exocyclic angles at each of C12 and C22 differ by ca 10°, always in the sense that the N—C—C angle is the smaller angle and the C—C—C angle is the larger angle (Tables 1, 3 and 5).

In the anion of (II), the nitro group at the 4-position is almost coplanar with the phenyl ring, but the nitro groups at the 2- and 6-positions are both twisted well out of the plane of the phenyl ring with dihedral angles between the nitro planes and the phenyl plane of 46.3 (2) and 20.5 (2)°, respectively. The sense of these rotations is such that the anion retains approximate mirror symmetry. The bond distances within the ring indicate very marked deviation from regular hexagonal geometry, with the C31—C32 and C36—C31 bonds very much longer than the others, while the mean C—C distance for the C32—C33 and C35—C36 bonds is somewhat less than the mean distance for the C33—C34 and C34—C35 bonds. In addition, the C34—N34 bond is shorter than the C32—N32 and C36—N36 bonds, while the C31—O31 bond, which is a single bond in the classical representation of the anion (IIa), is extremely short for such a single bond, but is comparable to the mean value (1.222 Å; Allen et al. 1987) of C=O bonds in benzoquinones. These observations, taken all together, indicate that (IIa) is an inappropriate representation of the picrate anion here, but that the quinonoid form (IIb) and the pentadienide form (IIc) are both important contributors to the overall molecular–electronic structure.

In the anion of (III), the S—O(H) bond distance exceeds the other three S—O distances by more than 0.1 Å, while the O—S—O angles involving the protonated atom O1 are systematically less than the remaining O—S—O angles (Table 3).

Regardless of the orientation of the cation, the components in compound (I) are linked by one N—H···N hydrogen bond and one C—H···N hydrogen bond (Table 2), so forming a C12(6) chain running parallel to the [001] direction and generated by the c-glide plane at y = 0.25 (Fig. 4). Two such chains run through each unit cell but there are no direction-specific interactions between adjacent chains.

The component ions of (II) are linked into rather complex chains of rings, which may alternatively be described as perforated ribbons, by a combination of one N—H···O hydrogen bond and no fewer than five C—H···O hydrogen bonds (Table 4). Within the selected asymmetric unit (Fig. 2), the ions are linked by the cooperative action of the N—H···O hydrogen bond and one of the C—H···O hydrogen bonds, to generate a simple R22(7) (Bernstein et al., 1995) motif in which the acceptors are the two O atoms of a single nitro group. Three C—H···O hydrogen bonds acting in concert link these ion-pair aggregates into chains of rings; atoms C13 and C23 in the cation at (x, y, z) both act as hydrogen-bond donors to atom O31 in the anion at (−1 + x, −1 + y, 1 + z), while atom C14 in the cation at (x, y, z) likewise acts as a donor to atom O21 in the anion at (−1 + x, −1 + y, 1 + z), so generating by translation a chain of rings running parallel to the [111] direction. The final C—H···O hydrogen bond links antiparallel pairs of such chains to form the overall ribbon; atom C35 in the anion at (x, y, z) acts as a hydrogen-bond donor to atom O42 in the anion at (1 − x, 1 − y, 1 − z), so forming a centrosymmetric R22(10) anion dimer centred at (1/2, 1/2, 1/2). Propagation by translation and inversion of all these hydrogen bonds then generates a complex chain of rings along [111] containing a central strip of alternating edge-fused R22(10) and R46(22) rings, with the R22(10) rings centred at (n + 1/2, n + 1/2,-n + 1/2) (n = zero or integer), and the R46(22) rings centred at (n, n,-n) (n = zero or integer). This central array of centrosymmetric rings is flanked on each edge of the ribbon by strings of alternating single R22(7) rings, which lie within the asymmetric unit, and the edge-fused R12(7) and R22(8) rings, which are generated by translation. There are thus five distinct types of ring within this ribbon structure (Fig. 5), but there are no direction-specific interactions between adjacent ribbons.

The components of (III) are linked into complex sheets by a combination of O—H···O, N—H···O and C—H···O hydrogen bonds (Table 6), but the formation of this sheet structure is readily analysed in terms of two one-dimensional substructures. The N—H···O hydrogen bond links the two components within the selected asymmetric unit (Fig. 3), while the O—H···O hydrogen bond and three independent C—H···O hydrogen bonds link these ion-pair aggregates.

A very simple substructure is generated by the anions alone. Atom O1 in the anion at (x, y, z) acts as a hydrogen-bond donor to atom O4 in the anion at (x, 1 + y, z), so generating by translation a C(4) chain running parallel to the [010] direction (Fig. 6). This [010] chain is reinforced by one of the C—H···O hydrogen bonds. Atom C15 in the cation at (x, y, z) acts as a hydrogen-bond donor to atom O3 in the anion at (1 − x, −3/2 + y, 1/2 − z), while atom C15 at (1 − x, −3/2 + y, 1/2 − z) in turn acts as a donor to atom O3 at (x, −3 + y, z), so producing a chain of edge-fused R66(24) rings generated by the 21 screw axis along (1/2, y, 1/4) (Fig. 7).

A second one-dimensional substructure is generated by the concerted action of two C—H···O hydrogen bonds. Atoms C13 and C14 in the cation at (x, y, z) act as hydrogen-bond donors, respectively, to atoms O4 and O3, both in the anion at (x, 1/2 − y, 1/2 + z). In combination with the N—H···O hydrogen bond within the asymmetric unit, these two C—H···O hydrogen bonds form a C22(8)C22(9)[R22(7)] chain of rings running parallel to the [001] direction and generated by the c-glide pane at y = 0.25 (Fig. 8). The combination of the [010] and [001] substructures (Figs. 7 and 8) generates a complex (100) sheet, but there are no direction-specific interactions between adjacent sheets.

Although (III) and (IV) have very similar compositions, they crystallize with very different unit cells in different space groups, viz. P21/c for (III) and Pc for (IV) (Kavitha et al., 2005). Despite this difference, they form a common substructural motif in the form of the C22(8)C22(9)[R22(7)] chain of rings (Fig. 6), generated by the action of a glide plane in (III), but by translation in (IV). There can be no anion-chain substructure in (IV), but all four O atoms of the perchlorate anion act as acceptors in hydrogen bonds, and the overall supramolecular structure in (IV) takes the form of a rather complex sheet.

Experimental top

For the synthesis of (I) a solution in methanol (50 ml) of 2,2'-bipyridinium chloride (0.5 g) (itself prepared by the reaction between concentrated hydrochloric acid and 2,2'-bipyridine in a 1:1 molar ratio in methanol solution) was added to ammonium thiocyanate (0.23 g) and the resulting mixture was heated on a water bath for 30 min. The mixture was cooled to ambient temperature and subsequent slow evaporation of the solvent gave crystals of (I) (m.p. 401 K) suitable for single-crystal X-ray diffraction. For the synthesis of (II), a solution of picric acid (0.44 g) in methanol (50 ml) was added to a solution of 2,2'-bipyridine (0.3 g) in methanol (50 ml); this mixture was then warmed on a water bath for 15 min. After cooling the solution to ambient temperature, slow evaporation of the solvent yielded crystals of (I) (m.p. 398 K) suitable for single-crystal X-ray diffraction. Compound (III) (m.p. 418 K) was prepared in a similar manner using 0.5 g of 2,2'-bipyridine and 0.36 ml of concentrated sulfuric acid.

Refinement top

For (I), the systematic absences permitted Pca21 or Pcam (= Pbcm, No. 57) as possible space groups; Pca21 was selected, and confirmed by the structure analysis. Crystals of (II) are triclinic; the space group P1 was selected, and confirmed by the subsequent structure analysis. For (III), the space group P21/c was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms with C—H distances of 0.95 Å, N—H distances of 0.88 Å and an O—H distance of 0.94 Å, and with Uiso(H) values of 1.2Ueq(C,N) or 1.5Ueq(O). For (I), the refined occupancies of the major and minor orientations of the cation were 0.845 (2) and 0.155 (2), respectively; in addition, the crystals of (I) were found to exhibit inversion twinning with twin fractions 0.57 (7) and 0.43 (7).

Computing details top

For all compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The independent components of (I), showing the cation disorder, the atom-labelling scheme and the two hydrogen bonds within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The independent components of (II), showing the atom-labelling scheme and the two hydrogen bonds within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. The independent components of (III), showing the atom-labelling scheme and the hydrogen bond within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation of a C12(6) chain along [001]. For the sake of clarity, only the major orientation of the cation is shown and H atoms not involved in the motif shown have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 − x, y, 1/2 + z) and (1/2 − x, y, −1/2 + z), respectively.
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded [111] chain containing five different types of ring. For the sake of clarity, H atoms not involved in the hydrogen bonds shown have been omitted.
[Figure 6] Fig. 6. Part of the crystal structure of (III), showing the formation of a hydrogen-bonded C(4) chain of anions along [010]. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, 1 + y, z) and (x, −1 + y, z), respectively.
[Figure 7] Fig. 7. A stereoview of part of the crystal structure of (III), showing the formation of a hydrogen-bonded chain of edge-fused R66(24) rings along [010]. For the sake of clarity, H atoms not involved in the hydrogen bonds shown have been omitted.
[Figure 8] Fig. 8. A stereoview of part of the crystal structure of (III), showing the formation of a hydrogen-bonded C22(8) C22(9)[R22(7)] chain of rings along [001]. For the sake of clarity, H atoms not involved in the hydrogen bonds shown have been omitted.
(I) 2,2'-bipyridinium thiocyanate top
Crystal data top
C10H9N2+·NCSF(000) = 448
Mr = 215.27Dx = 1.364 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 2311 reflections
a = 8.0954 (2) Åθ = 3.6–27.5°
b = 11.7686 (6) ŵ = 0.28 mm1
c = 11.0026 (6) ÅT = 120 K
V = 1048.23 (8) Å3Plate, colourless
Z = 40.40 × 0.40 × 0.04 mm
Data collection top
Bruker KappaCCD
diffractometer
2311 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2145 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.6°
ϕ and ω scansh = 108
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1215
Tmin = 0.898, Tmax = 0.989l = 1414
7990 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.077 w = 1/[σ2(Fo2) + (0.0396P)2 + 0.256P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2311 reflectionsΔρmax = 0.29 e Å3
174 parametersΔρmin = 0.28 e Å3
30 restraintsAbsolute structure: Flack (1983), 968 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.57 (7)
Crystal data top
C10H9N2+·NCSV = 1048.23 (8) Å3
Mr = 215.27Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 8.0954 (2) ŵ = 0.28 mm1
b = 11.7686 (6) ÅT = 120 K
c = 11.0026 (6) Å0.40 × 0.40 × 0.04 mm
Data collection top
Bruker KappaCCD
diffractometer
2311 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2145 reflections with I > 2σ(I)
Tmin = 0.898, Tmax = 0.989Rint = 0.033
7990 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.077Δρmax = 0.29 e Å3
S = 1.05Δρmin = 0.28 e Å3
2311 reflectionsAbsolute structure: Flack (1983), 968 Friedel pairs
174 parametersAbsolute structure parameter: 0.57 (7)
30 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.97990 (4)0.81858 (3)0.22438 (6)0.02287 (12)
C20.7788 (2)0.81469 (12)0.2406 (2)0.0204 (4)
N30.63655 (19)0.81096 (13)0.25650 (18)0.0324 (4)
N110.3605 (5)0.8178 (3)0.4079 (3)0.0159 (6)0.845 (2)
C120.2759 (3)0.75006 (17)0.4847 (2)0.0141 (5)0.845 (2)
C130.1612 (4)0.8000 (3)0.5632 (4)0.0171 (6)0.845 (2)
C140.1425 (8)0.9171 (3)0.5642 (5)0.0173 (7)0.845 (2)
C150.2387 (9)0.9845 (3)0.4884 (3)0.0185 (8)0.845 (2)
C160.3461 (11)0.9316 (4)0.4093 (7)0.0179 (8)0.845 (2)
N210.3800 (2)0.59153 (15)0.37469 (16)0.0194 (4)0.845 (2)
C220.3088 (3)0.62650 (17)0.47771 (17)0.0149 (4)0.845 (2)
C230.2646 (3)0.55528 (17)0.5728 (2)0.0227 (4)0.845 (2)
C240.2940 (3)0.43905 (19)0.5592 (2)0.0287 (5)0.845 (2)
C250.3639 (3)0.4010 (2)0.4524 (2)0.0253 (5)0.845 (2)
C260.4078 (3)0.47899 (19)0.3649 (2)0.0239 (5)0.845 (2)
N11A0.139 (3)0.8202 (17)0.558 (2)0.025*0.155 (2)
C12A0.222 (2)0.7529 (11)0.483 (2)0.025*0.155 (2)
C13A0.354 (4)0.805 (2)0.423 (3)0.025*0.155 (2)
C14A0.353 (8)0.920 (3)0.401 (5)0.025*0.155 (2)
C15A0.244 (6)0.985 (2)0.467 (3)0.025*0.155 (2)
C16A0.155 (6)0.933 (2)0.556 (4)0.025*0.155 (2)
N21A0.1219 (13)0.5881 (8)0.5848 (10)0.025*0.155 (2)
C22A0.1956 (18)0.6284 (9)0.4840 (10)0.025*0.155 (2)
C23A0.2399 (16)0.5581 (9)0.3873 (11)0.025*0.155 (2)
C24A0.2140 (16)0.4412 (9)0.3993 (11)0.025*0.155 (2)
C25A0.1364 (16)0.4002 (10)0.5019 (11)0.025*0.155 (2)
C26A0.0969 (16)0.4775 (9)0.5947 (11)0.025*0.155 (2)
H110.42780.78630.35480.019*0.845 (2)
H130.09630.75390.61550.020*0.845 (2)
H140.06380.95140.61680.021*0.845 (2)
H150.23071.06500.49100.022*0.845 (2)
H160.41060.97610.35510.022*0.845 (2)
H230.21590.58460.64480.027*0.845 (2)
H240.26640.38730.62230.034*0.845 (2)
H250.38150.32210.43940.030*0.845 (2)
H260.46080.45190.29350.029*0.845 (2)
H11A0.07000.78940.60990.030*0.155 (2)
H13A0.44510.76070.39740.030*0.155 (2)
H14A0.42480.95280.34190.030*0.155 (2)
H15A0.23131.06370.45160.030*0.155 (2)
H16A0.10470.97680.61820.030*0.155 (2)
H23A0.28640.58890.31520.030*0.155 (2)
H24A0.24950.39050.33740.030*0.155 (2)
H25A0.11050.32180.50970.030*0.155 (2)
H26A0.05010.44910.66780.030*0.155 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0167 (2)0.02194 (19)0.0299 (2)0.00122 (13)0.0046 (2)0.0016 (2)
C20.0222 (8)0.0149 (7)0.0241 (9)0.0005 (5)0.0010 (8)0.0002 (8)
N30.0197 (8)0.0313 (9)0.0462 (12)0.0005 (6)0.0020 (6)0.0020 (7)
N110.0196 (10)0.0187 (14)0.0095 (15)0.0033 (8)0.0029 (9)0.0036 (9)
C120.0153 (13)0.0149 (8)0.0120 (8)0.0002 (8)0.0000 (12)0.0030 (8)
C130.0192 (14)0.0176 (15)0.0145 (10)0.0026 (10)0.0024 (11)0.0012 (12)
C140.0155 (16)0.0202 (18)0.0164 (14)0.0017 (13)0.0036 (10)0.0024 (14)
C150.0253 (11)0.0148 (8)0.015 (2)0.0037 (10)0.0042 (18)0.0017 (11)
C160.0195 (16)0.0163 (15)0.0179 (18)0.0042 (16)0.0041 (11)0.0028 (15)
N210.0222 (9)0.0201 (9)0.0157 (8)0.0029 (6)0.0000 (7)0.0012 (7)
C220.0163 (9)0.0162 (9)0.0121 (9)0.0001 (6)0.0033 (7)0.0005 (7)
C230.0318 (11)0.0199 (10)0.0165 (9)0.0017 (8)0.0034 (9)0.0011 (8)
C240.0409 (14)0.0203 (10)0.0248 (12)0.0015 (9)0.0008 (10)0.0057 (9)
C250.0320 (11)0.0149 (10)0.0290 (12)0.0048 (8)0.0074 (9)0.0034 (8)
C260.0288 (12)0.0225 (10)0.0206 (11)0.0073 (8)0.0023 (9)0.0058 (8)
Geometric parameters (Å, º) top
S1—C21.6383 (16)C26—H260.95
C2—N31.166 (2)N11A—C12A1.323 (16)
N11—C161.345 (4)N11A—C16A1.328 (18)
N11—C121.348 (3)N11A—H11A0.88
N11—H110.88C12A—C13A1.397 (18)
C12—C131.398 (4)C12A—C22A1.481 (13)
C12—C221.480 (3)C13A—C14A1.371 (19)
C13—C141.387 (4)C13A—H13A0.95
C13—H130.95C14A—C15A1.380 (19)
C14—C151.390 (4)C14A—H14A0.95
C14—H140.95C15A—C16A1.362 (19)
C15—C161.378 (4)C15A—H15A0.95
C15—H150.95C16A—H16A0.95
C16—H160.95N21A—C26A1.322 (12)
N21—C221.337 (3)N21A—C22A1.346 (12)
N21—C261.348 (3)C22A—C23A1.395 (13)
C22—C231.387 (3)C23A—C24A1.398 (13)
C23—C241.396 (3)C23A—H23A0.95
C23—H230.95C24A—C25A1.379 (13)
C24—C251.379 (3)C24A—H24A0.95
C24—H240.95C25A—C26A1.404 (13)
C25—C261.377 (3)C25A—H25A0.95
C25—H250.95C26A—H26A0.95
C16—N11—C12122.5 (3)C12A—N11A—C16A123 (2)
C16—N11—H11118.7C12A—N11A—H11A118.7
C12—N11—H11118.7C16A—N11A—H11A118.7
N11—C12—C13118.4 (2)N11A—C12A—C13A114.6 (17)
N11—C12—C22117.2 (2)N11A—C12A—C22A121.0 (15)
C13—C12—C22124.4 (2)C13A—C12A—C22A123.4 (17)
N3—C2—S1177.56 (19)C14A—C13A—C12A121 (2)
C14—C13—C12119.7 (3)C14A—C13A—H13A119.4
C14—C13—H13120.2C12A—C13A—H13A119.4
C12—C13—H13120.2C13A—C14A—C15A117 (2)
C13—C14—C15120.1 (4)C13A—C14A—H14A121.6
C13—C14—H14120.0C15A—C14A—H14A121.6
C15—C14—H14120.0C16A—C15A—C14A118 (2)
C16—C15—C14118.4 (3)C16A—C15A—H15A121.0
C16—C15—H15120.8C14A—C15A—H15A121.0
C14—C15—H15120.8N11A—C16A—C15A121 (2)
N11—C16—C15120.8 (4)N11A—C16A—H16A119.7
N11—C16—H16119.6C15A—C16A—H16A119.7
C15—C16—H16119.6C26A—N21A—C22A118.8 (10)
C26—N21—C22116.25 (18)N21A—C22A—C23A122.3 (9)
N21—C22—C23124.37 (19)N21A—C22A—C12A114.6 (11)
N21—C22—C12115.08 (19)C23A—C22A—C12A123.1 (11)
C23—C22—C12120.54 (19)C22A—C23A—C24A118.2 (10)
C22—C23—C24117.9 (2)C22A—C23A—H23A120.9
C22—C23—H23121.1C24A—C23A—H23A120.9
C24—C23—H23121.1C25A—C24A—C23A119.4 (11)
C25—C24—C23118.7 (2)C25A—C24A—H24A120.3
C25—C24—H24120.7C23A—C24A—H24A120.3
C23—C24—H24120.7C24A—C25A—C26A118.1 (11)
C26—C25—C24119.0 (2)C24A—C25A—H25A120.9
C26—C25—H25120.5C26A—C25A—H25A120.9
C24—C25—H25120.5N21A—C26A—C25A122.9 (11)
N21—C26—C25123.8 (2)N21A—C26A—H26A118.5
N21—C26—H26118.1C25A—C26A—H26A118.5
C25—C26—H26118.1
C16—N11—C12—C134.2 (8)C16A—N11A—C12A—C13A13 (5)
C16—N11—C12—C22177.2 (6)C16A—N11A—C12A—C22A177 (3)
N11—C12—C13—C142.9 (6)N11A—C12A—C13A—C14A27 (6)
C22—C12—C13—C14178.6 (4)C22A—C12A—C13A—C14A164 (4)
C12—C13—C14—C150.7 (9)C12A—C13A—C14A—C15A17 (9)
C13—C14—C15—C163.0 (11)C13A—C14A—C15A—C16A5 (9)
C12—N11—C16—C151.9 (13)C12A—N11A—C16A—C15A8 (7)
C14—C15—C16—N111.8 (13)C14A—C15A—C16A—N11A18 (8)
C26—N21—C22—C230.6 (3)C26A—N21A—C22A—C23A3 (2)
C26—N21—C22—C12178.54 (19)C26A—N21A—C22A—C12A178.2 (13)
N11—C12—C22—N2118.9 (3)N11A—C12A—C22A—N21A19 (3)
C13—C12—C22—N21159.6 (2)C13A—C12A—C22A—N21A150 (3)
N11—C12—C22—C23161.9 (3)N11A—C12A—C22A—C23A160 (2)
C13—C12—C22—C2319.6 (4)C13A—C12A—C22A—C23A32 (3)
N21—C22—C23—C241.1 (4)N21A—C22A—C23A—C24A3 (2)
C12—C22—C23—C24178.0 (2)C12A—C22A—C23A—C24A177.8 (14)
C22—C23—C24—C250.5 (4)C22A—C23A—C24A—C25A4.2 (19)
C23—C24—C25—C262.4 (4)C23A—C24A—C25A—C26A4.5 (19)
C22—N21—C26—C251.5 (3)C22A—N21A—C26A—C25A3 (2)
C24—C25—C26—N213.0 (4)C24A—C25A—C26A—N21A4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···N30.882.032.788 (4)144
N11—H11···N210.882.332.693 (4)104
N11A—H11A···N3i0.882.343.12 (2)148
N11A—H11A···N21A0.882.422.75 (2)103
C13—H13···N3i0.952.533.217 (4)129
C13A—H13A···N30.952.272.93 (3)126
Symmetry code: (i) x+1/2, y, z+1/2.
(II) 2,2'-bipyridinium picrate top
Crystal data top
C10H9N2+·C6H2N3O7Z = 2
Mr = 385.30F(000) = 396
Triclinic, P1Dx = 1.637 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4139 (5) ÅCell parameters from 3598 reflections
b = 9.3768 (6) Åθ = 3.2–27.6°
c = 12.3694 (5) ŵ = 0.13 mm1
α = 71.681 (3)°T = 120 K
β = 75.722 (3)°Lath, yellow
γ = 77.391 (3)°0.12 × 0.09 × 0.03 mm
V = 781.79 (8) Å3
Data collection top
Nonius KappaCCD
diffractometer
3598 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2432 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.068
Detector resolution: 9.091 pixels mm-1θmax = 27.6°, θmin = 3.2°
ϕ and ω scansh = 99
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1212
Tmin = 0.975, Tmax = 0.996l = 1615
17473 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0489P)2 + 0.2955P]
where P = (Fo2 + 2Fc2)/3
3598 reflections(Δ/σ)max < 0.001
253 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
C10H9N2+·C6H2N3O7γ = 77.391 (3)°
Mr = 385.30V = 781.79 (8) Å3
Triclinic, P1Z = 2
a = 7.4139 (5) ÅMo Kα radiation
b = 9.3768 (6) ŵ = 0.13 mm1
c = 12.3694 (5) ÅT = 120 K
α = 71.681 (3)°0.12 × 0.09 × 0.03 mm
β = 75.722 (3)°
Data collection top
Nonius KappaCCD
diffractometer
3598 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2432 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.996Rint = 0.068
17473 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.122H-atom parameters constrained
S = 1.04Δρmax = 0.24 e Å3
3598 reflectionsΔρmin = 0.35 e Å3
253 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.4171 (2)0.2553 (2)0.86870 (14)0.0218 (4)
C120.3315 (3)0.1341 (2)0.93360 (17)0.0190 (5)
C130.2532 (3)0.1275 (2)1.04843 (17)0.0207 (5)
C140.2549 (3)0.2472 (2)1.09054 (17)0.0233 (5)
C150.3368 (3)0.3724 (2)1.01852 (17)0.0233 (5)
C160.4215 (3)0.3724 (3)0.90728 (18)0.0247 (5)
N210.4031 (2)0.0635 (2)0.75783 (14)0.0236 (4)
C220.3247 (3)0.0241 (2)0.87156 (17)0.0201 (5)
C230.2389 (3)0.1044 (2)0.92588 (17)0.0213 (5)
C240.2307 (3)0.1953 (3)0.85863 (18)0.0245 (5)
C250.3070 (3)0.1559 (3)0.74172 (18)0.0258 (5)
C260.3939 (3)0.0269 (3)0.69570 (18)0.0267 (5)
C311.0533 (3)0.7446 (2)0.30058 (17)0.0194 (5)
O311.1755 (2)0.78858 (17)0.21397 (11)0.0245 (4)
C321.0223 (3)0.7930 (2)0.40585 (16)0.0198 (5)
N321.1307 (3)0.9059 (2)0.40382 (14)0.0241 (4)
O211.1392 (2)1.01949 (17)0.32060 (12)0.0310 (4)
O221.2054 (2)0.88440 (19)0.48734 (13)0.0346 (4)
C330.9025 (3)0.7397 (2)0.50656 (17)0.0203 (5)
C340.7940 (3)0.6323 (2)0.51074 (16)0.0187 (5)
N340.6730 (2)0.5704 (2)0.61814 (14)0.0216 (4)
O410.6728 (2)0.61165 (17)0.70434 (12)0.0268 (4)
O420.5768 (2)0.47558 (18)0.62274 (12)0.0284 (4)
C350.8116 (3)0.5782 (2)0.41669 (16)0.0196 (5)
C360.9358 (3)0.6318 (2)0.31605 (16)0.0189 (5)
N360.9535 (2)0.5630 (2)0.22294 (14)0.0214 (4)
O610.8987 (2)0.43891 (18)0.24778 (12)0.0294 (4)
O621.0201 (2)0.63012 (18)0.12300 (12)0.0281 (4)
H110.47320.25710.79680.026*
H130.19860.04131.09800.025*
H140.19980.24391.16910.028*
H150.33390.45671.04630.028*
H160.48320.45500.85760.030*
H230.18740.12931.00670.026*
H240.17290.28420.89280.029*
H250.30020.21550.69380.031*
H260.44970.00180.61560.032*
H330.89260.77430.57250.024*
H350.73840.50440.42120.023*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0189 (9)0.0277 (11)0.0174 (9)0.0068 (8)0.0011 (7)0.0058 (8)
C120.0154 (10)0.0199 (11)0.0202 (10)0.0025 (9)0.0032 (8)0.0039 (9)
C130.0188 (11)0.0213 (12)0.0187 (10)0.0040 (9)0.0000 (8)0.0032 (9)
C140.0228 (11)0.0283 (13)0.0173 (10)0.0051 (10)0.0007 (9)0.0070 (9)
C150.0255 (12)0.0217 (12)0.0241 (11)0.0069 (9)0.0024 (9)0.0080 (9)
C160.0248 (12)0.0246 (12)0.0251 (12)0.0104 (10)0.0007 (9)0.0063 (10)
N210.0249 (10)0.0273 (11)0.0184 (9)0.0056 (8)0.0019 (7)0.0067 (8)
C220.0179 (11)0.0229 (12)0.0185 (11)0.0004 (9)0.0043 (9)0.0053 (9)
C230.0193 (11)0.0238 (12)0.0199 (11)0.0032 (9)0.0014 (8)0.0065 (9)
C240.0215 (11)0.0245 (12)0.0272 (12)0.0047 (10)0.0047 (9)0.0059 (10)
C250.0238 (12)0.0299 (13)0.0278 (12)0.0025 (10)0.0068 (9)0.0132 (10)
C260.0265 (12)0.0334 (14)0.0200 (11)0.0037 (10)0.0032 (9)0.0083 (10)
C310.0194 (11)0.0197 (11)0.0170 (10)0.0032 (9)0.0019 (9)0.0029 (9)
O310.0280 (8)0.0271 (9)0.0181 (7)0.0104 (7)0.0019 (6)0.0066 (6)
C320.0208 (11)0.0197 (11)0.0178 (10)0.0061 (9)0.0019 (9)0.0031 (9)
N320.0264 (10)0.0288 (11)0.0173 (9)0.0113 (8)0.0031 (8)0.0077 (8)
O210.0430 (10)0.0252 (9)0.0227 (8)0.0159 (8)0.0007 (7)0.0020 (7)
O220.0433 (10)0.0445 (11)0.0219 (8)0.0217 (8)0.0084 (7)0.0056 (7)
C330.0210 (11)0.0188 (11)0.0187 (10)0.0014 (9)0.0017 (9)0.0045 (9)
C340.0170 (10)0.0207 (11)0.0159 (10)0.0046 (9)0.0004 (8)0.0026 (9)
N340.0185 (9)0.0254 (10)0.0183 (9)0.0040 (8)0.0019 (7)0.0033 (8)
O410.0309 (9)0.0301 (9)0.0185 (8)0.0108 (7)0.0023 (6)0.0067 (7)
O420.0247 (8)0.0361 (10)0.0258 (8)0.0175 (7)0.0014 (6)0.0043 (7)
C350.0181 (11)0.0177 (11)0.0211 (11)0.0040 (9)0.0056 (9)0.0005 (9)
C360.0197 (11)0.0203 (11)0.0170 (10)0.0041 (9)0.0028 (8)0.0055 (9)
N360.0207 (9)0.0236 (11)0.0195 (9)0.0050 (8)0.0028 (7)0.0053 (8)
O610.0371 (9)0.0268 (9)0.0287 (9)0.0149 (8)0.0024 (7)0.0102 (7)
O620.0337 (9)0.0337 (9)0.0170 (8)0.0109 (7)0.0019 (7)0.0056 (7)
Geometric parameters (Å, º) top
N11—C161.338 (3)C25—H250.95
N11—C121.352 (3)C26—H260.95
N11—H110.88C31—C321.460 (3)
C12—C131.383 (3)C32—C331.359 (3)
C12—C221.481 (3)C33—C341.401 (3)
C13—C141.381 (3)C34—C351.376 (3)
C13—H130.95C35—C361.376 (3)
C14—C151.388 (3)C36—C311.452 (3)
C14—H140.95C31—O311.243 (2)
C15—C161.364 (3)C32—N321.454 (3)
C15—H150.95C34—N341.436 (2)
C16—H160.95C36—N361.454 (3)
N21—C261.332 (3)N32—O211.227 (2)
N21—C221.348 (3)N32—O221.231 (2)
C22—C231.387 (3)C33—H330.95
C23—C241.384 (3)N34—O421.236 (2)
C23—H230.95N34—O411.243 (2)
C24—C251.378 (3)C35—H350.95
C24—H240.95N36—O621.230 (2)
C25—C261.389 (3)N36—O611.238 (2)
C16—N11—C12123.86 (18)N21—C26—C25123.5 (2)
C16—N11—H11118.1N21—C26—H26118.2
C12—N11—H11118.1C25—C26—H26118.2
N11—C12—C13117.78 (19)O31—C31—C36126.16 (19)
N11—C12—C22115.64 (17)O31—C31—C32122.66 (18)
C13—C12—C22126.53 (19)C36—C31—C32110.99 (17)
C14—C13—C12119.54 (19)C33—C32—N32116.99 (18)
C14—C13—H13120.2C33—C32—C31125.55 (19)
C12—C13—H13120.2N32—C32—C31117.45 (16)
C13—C14—C15120.25 (19)O21—N32—O22123.35 (18)
C13—C14—H14119.9O21—N32—C32118.46 (17)
C15—C14—H14119.9O22—N32—C32118.15 (16)
C16—C15—C14119.0 (2)C32—C33—C34118.35 (19)
C16—C15—H15120.5C32—C33—H33120.8
C14—C15—H15120.5C34—C33—H33120.8
N11—C16—C15119.44 (19)C35—C34—C33121.16 (18)
N11—C16—H16120.3C35—C34—N34119.88 (18)
C15—C16—H16120.3C33—C34—N34118.80 (18)
C26—N21—C22116.95 (18)O42—N34—O41122.30 (16)
N21—C22—C23123.67 (19)O42—N34—C34119.29 (17)
N21—C22—C12113.89 (18)O41—N34—C34118.38 (17)
C23—C22—C12122.40 (18)C36—C35—C34119.63 (19)
C24—C23—C22117.86 (19)C36—C35—H35120.2
C24—C23—H23121.1C34—C35—H35120.2
C22—C23—H23121.1C35—C36—C31124.29 (18)
C25—C24—C23119.5 (2)C35—C36—N36116.21 (18)
C25—C24—H24120.2C31—C36—N36119.43 (17)
C23—C24—H24120.2O62—N36—O61122.54 (17)
C24—C25—C26118.4 (2)O62—N36—C36119.23 (17)
C24—C25—H25120.8O61—N36—C36118.22 (16)
C26—C25—H25120.8
C16—N11—C12—C133.7 (3)C33—C32—N32—O21133.5 (2)
C16—N11—C12—C22173.81 (18)C31—C32—N32—O2147.5 (3)
N11—C12—C13—C143.8 (3)C33—C32—N32—O2244.6 (3)
C22—C12—C13—C14173.40 (19)C31—C32—N32—O22134.4 (2)
C12—C13—C14—C150.8 (3)N32—C32—C33—C34179.09 (18)
C13—C14—C15—C162.5 (3)C31—C32—C33—C342.0 (3)
C12—N11—C16—C150.4 (3)C32—C33—C34—C351.9 (3)
C14—C15—C16—N112.8 (3)C32—C33—C34—N34177.35 (18)
C26—N21—C22—C230.8 (3)C35—C34—N34—O424.5 (3)
C26—N21—C22—C12176.93 (18)C33—C34—N34—O42179.97 (18)
N11—C12—C22—N211.1 (3)C35—C34—N34—O41173.68 (18)
C13—C12—C22—N21176.17 (19)C33—C34—N34—O411.8 (3)
N11—C12—C22—C23178.91 (18)C33—C34—C35—C360.9 (3)
C13—C12—C22—C231.6 (3)N34—C34—C35—C36176.31 (18)
N21—C22—C23—C241.2 (3)C34—C35—C36—C310.1 (3)
C12—C22—C23—C24176.33 (19)C34—C35—C36—N36176.78 (18)
C22—C23—C24—C250.0 (3)O31—C31—C36—C35175.1 (2)
C23—C24—C25—C261.4 (3)C32—C31—C36—C350.1 (3)
C22—N21—C26—C250.8 (3)O31—C31—C36—N361.7 (3)
C24—C25—C26—N211.9 (3)C32—C31—C36—N36176.68 (17)
O31—C31—C32—C33174.2 (2)C35—C36—N36—O62160.79 (18)
C36—C31—C32—C331.0 (3)C31—C36—N36—O6222.2 (3)
O31—C31—C32—N324.7 (3)C35—C36—N36—O6118.6 (3)
C36—C31—C32—N32179.89 (17)C31—C36—N36—O61158.46 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···N210.882.212.613 (3)107
N11—H11···O420.882.553.204 (2)131
C13—H13···O31i0.952.373.279 (2)160
C14—H14···O21i0.952.383.028 (2)125
C16—H16···O410.952.363.284 (3)164
C23—H23···O31i0.952.423.325 (2)159
C35—H35···O42ii0.952.483.204 (3)133
Symmetry codes: (i) x1, y1, z+1; (ii) x+1, y+1, z+1.
(III) 2,2'-bipyridinium hydrogensulfate top
Crystal data top
C10H9N2+·HO4SF(000) = 528
Mr = 254.26Dx = 1.636 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2373 reflections
a = 12.8274 (4) Åθ = 3.6–27.5°
b = 4.4774 (2) ŵ = 0.32 mm1
c = 18.2844 (5) ÅT = 120 K
β = 100.568 (2)°Plate, pink
V = 1032.32 (6) Å30.42 × 0.16 × 0.06 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
2373 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2052 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.6°
ϕ and ω scansh = 1616
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 55
Tmin = 0.878, Tmax = 0.981l = 2323
19500 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.26 w = 1/[σ2(Fo2) + (0.0285P)2 + 2.1787P]
where P = (Fo2 + 2Fc2)/3
2373 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.45 e Å3
Crystal data top
C10H9N2+·HO4SV = 1032.32 (6) Å3
Mr = 254.26Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.8274 (4) ŵ = 0.32 mm1
b = 4.4774 (2) ÅT = 120 K
c = 18.2844 (5) Å0.42 × 0.16 × 0.06 mm
β = 100.568 (2)°
Data collection top
Nonius KappaCCD
diffractometer
2373 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2052 reflections with I > 2σ(I)
Tmin = 0.878, Tmax = 0.981Rint = 0.043
19500 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.122H-atom parameters constrained
S = 1.26Δρmax = 0.39 e Å3
2373 reflectionsΔρmin = 0.45 e Å3
154 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.33239 (17)0.2531 (5)0.32521 (11)0.0151 (4)
C120.28089 (19)0.2546 (6)0.38388 (13)0.0144 (5)
C130.3176 (2)0.0668 (6)0.44311 (14)0.0168 (5)
C140.4037 (2)0.1188 (6)0.44003 (14)0.0182 (5)
C150.4546 (2)0.1106 (6)0.37940 (14)0.0184 (5)
C160.4165 (2)0.0815 (6)0.32194 (14)0.0177 (5)
N210.16619 (17)0.6042 (5)0.31266 (12)0.0172 (5)
C220.19049 (19)0.4625 (6)0.37810 (14)0.0154 (5)
C230.1372 (2)0.5108 (6)0.43683 (15)0.0200 (6)
C240.0539 (2)0.7108 (7)0.42632 (16)0.0239 (6)
C250.0270 (2)0.8579 (6)0.35880 (16)0.0224 (6)
C260.0862 (2)0.8002 (6)0.30398 (15)0.0203 (6)
S10.28324 (5)0.72539 (14)0.13661 (3)0.01370 (17)
O10.20959 (16)0.9688 (4)0.16231 (11)0.0238 (5)
O20.34670 (14)0.6073 (4)0.20444 (10)0.0196 (4)
O30.34452 (15)0.8727 (4)0.08819 (10)0.0194 (4)
O40.21062 (15)0.4977 (4)0.09861 (10)0.0189 (4)
H110.30900.37170.28740.018*
H130.28440.06460.48550.020*
H140.42780.25250.47990.022*
H150.51430.23430.37760.022*
H160.45010.09190.27980.021*
H230.15760.40910.48280.024*
H240.01530.74720.46510.029*
H250.03040.99500.35030.027*
H260.06900.90470.25810.024*
H10.21591.15930.14140.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0174 (10)0.0152 (10)0.0127 (9)0.0022 (9)0.0030 (8)0.0003 (8)
C120.0154 (11)0.0145 (12)0.0138 (11)0.0042 (10)0.0040 (9)0.0027 (10)
C130.0169 (12)0.0189 (13)0.0147 (11)0.0050 (10)0.0029 (9)0.0008 (10)
C140.0193 (13)0.0157 (12)0.0174 (12)0.0044 (10)0.0021 (10)0.0013 (10)
C150.0155 (12)0.0164 (13)0.0227 (13)0.0026 (10)0.0019 (10)0.0024 (10)
C160.0169 (12)0.0189 (13)0.0177 (12)0.0037 (10)0.0044 (10)0.0034 (10)
N210.0167 (10)0.0169 (11)0.0183 (10)0.0018 (9)0.0038 (8)0.0021 (9)
C220.0142 (12)0.0147 (12)0.0176 (12)0.0047 (10)0.0037 (9)0.0026 (10)
C230.0231 (13)0.0199 (13)0.0183 (12)0.0045 (11)0.0070 (10)0.0013 (11)
C240.0245 (14)0.0211 (14)0.0298 (15)0.0046 (11)0.0145 (12)0.0060 (12)
C250.0167 (12)0.0182 (13)0.0327 (15)0.0009 (11)0.0060 (11)0.0024 (12)
C260.0181 (12)0.0196 (13)0.0223 (13)0.0003 (11)0.0016 (10)0.0011 (11)
S10.0152 (3)0.0126 (3)0.0144 (3)0.0000 (2)0.0056 (2)0.0005 (2)
O10.0309 (11)0.0125 (9)0.0340 (11)0.0046 (8)0.0217 (9)0.0033 (8)
O20.0184 (9)0.0243 (10)0.0160 (9)0.0001 (8)0.0032 (7)0.0022 (8)
O30.0221 (9)0.0188 (9)0.0202 (9)0.0023 (8)0.0110 (7)0.0029 (8)
O40.0217 (9)0.0144 (9)0.0198 (9)0.0032 (8)0.0013 (7)0.0001 (7)
Geometric parameters (Å, º) top
N11—C161.335 (3)C22—C231.391 (3)
N11—C121.359 (3)C23—C241.381 (4)
N11—H110.88C23—H230.95
C12—C131.384 (4)C24—C251.386 (4)
C12—C221.476 (4)C24—H240.95
C13—C141.391 (4)C25—C261.387 (4)
C13—H130.95C25—H250.95
C14—C151.387 (4)C26—H260.95
C14—H140.95S1—O11.5699 (19)
C15—C161.376 (4)S1—O21.4526 (19)
C15—H150.95S1—O31.4464 (18)
C16—H160.95S1—O41.4672 (19)
N21—C261.338 (3)O1—H10.94
N21—C221.340 (3)
C16—N11—C12123.5 (2)C26—N21—C22117.7 (2)
C16—N11—H11118.3N21—C22—C23123.3 (2)
C12—N11—H11118.3N21—C22—C12114.4 (2)
N11—C12—C13118.0 (2)C23—C22—C12122.2 (2)
N11—C12—C22115.8 (2)C24—C23—C22118.1 (3)
C13—C12—C22126.2 (2)C24—C23—H23121.0
O1—S1—O2105.72 (11)C22—C23—H23121.0
O1—S1—O3106.92 (11)C23—C24—C25119.5 (3)
O1—S1—O4105.05 (11)C23—C24—H24120.3
C12—C13—C14119.4 (2)C25—C24—H24120.3
C12—C13—H13120.3C24—C25—C26118.4 (3)
C14—C13—H13120.3C24—C25—H25120.8
C15—C14—C13120.7 (2)C26—C25—H25120.8
C15—C14—H14119.7N21—C26—C25123.1 (3)
C13—C14—H14119.7N21—C26—H26118.5
C16—C15—C14118.2 (2)C25—C26—H26118.5
C16—C15—H15120.9O2—S1—O3113.97 (11)
C14—C15—H15120.9O2—S1—O4111.05 (11)
N11—C16—C15120.2 (2)O3—S1—O4113.33 (11)
N11—C16—H16119.9S1—O1—H1113.9
C15—C16—H16119.9
C16—N11—C12—C130.3 (4)N11—C12—C22—N215.3 (3)
C16—N11—C12—C22179.1 (2)C13—C12—C22—N21175.4 (2)
N11—C12—C13—C141.2 (4)N11—C12—C22—C23173.3 (2)
C22—C12—C13—C14179.5 (2)C13—C12—C22—C236.0 (4)
C12—C13—C14—C151.9 (4)N21—C22—C23—C241.3 (4)
C13—C14—C15—C161.2 (4)C12—C22—C23—C24179.7 (2)
C12—N11—C16—C151.0 (4)C22—C23—C24—C250.8 (4)
C14—C15—C16—N110.2 (4)C23—C24—C25—C260.6 (4)
C26—N21—C22—C230.4 (4)C22—N21—C26—C251.1 (4)
C26—N21—C22—C12178.9 (2)C24—C25—C26—N211.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4i0.941.702.640 (3)173
N11—H11···O20.881.982.752 (3)146
N11—H11···N210.882.232.625 (3)107
C13—H13···O4ii0.952.443.389 (3)173
C14—H14···O3ii0.952.483.156 (3)129
C15—H15···O3iii0.952.523.433 (3)161
Symmetry codes: (i) x, y+1, z; (ii) x, y+1/2, z+1/2; (iii) x+1, y3/2, z+1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC10H9N2+·NCSC10H9N2+·C6H2N3O7C10H9N2+·HO4S
Mr215.27385.30254.26
Crystal system, space groupOrthorhombic, Pca21Triclinic, P1Monoclinic, P21/c
Temperature (K)120120120
a, b, c (Å)8.0954 (2), 11.7686 (6), 11.0026 (6)7.4139 (5), 9.3768 (6), 12.3694 (5)12.8274 (4), 4.4774 (2), 18.2844 (5)
α, β, γ (°)90, 90, 9071.681 (3), 75.722 (3), 77.391 (3)90, 100.568 (2), 90
V3)1048.23 (8)781.79 (8)1032.32 (6)
Z424
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.280.130.32
Crystal size (mm)0.40 × 0.40 × 0.040.12 × 0.09 × 0.030.42 × 0.16 × 0.06
Data collection
DiffractometerBruker KappaCCD
diffractometer
Nonius KappaCCD
diffractometer
Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.898, 0.9890.975, 0.9960.878, 0.981
No. of measured, independent and
observed [I > 2σ(I)] reflections
7990, 2311, 2145 17473, 3598, 2432 19500, 2373, 2052
Rint0.0330.0680.043
(sin θ/λ)max1)0.6490.6510.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.077, 1.05 0.060, 0.122, 1.04 0.044, 0.122, 1.26
No. of reflections231135982373
No. of parameters174253154
No. of restraints3000
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.280.24, 0.350.39, 0.45
Absolute structureFlack (1983), 968 Friedel pairs??
Absolute structure parameter0.57 (7)??

Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) for (I) top
S1—C21.6383 (16)C2—N31.166 (2)
C16—N11—C12122.5 (3)C26—N21—C22116.25 (18)
N11—C12—C13118.4 (2)N21—C22—C23124.37 (19)
N11—C12—C22117.2 (2)N21—C22—C12115.08 (19)
C13—C12—C22124.4 (2)C23—C22—C12120.54 (19)
N3—C2—S1177.56 (19)
N11—C12—C22—N2118.9 (3)N11A—C12A—C22A—N21A19 (3)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N11—H11···N30.882.032.788 (4)144
N11—H11···N210.882.332.693 (4)104
N11A—H11A···N3i0.882.343.12 (2)148
N11A—H11A···N21A0.882.422.75 (2)103
C13—H13···N3i0.952.533.217 (4)129
C13A—H13A···N30.952.272.93 (3)126
Symmetry code: (i) x+1/2, y, z+1/2.
Selected geometric parameters (Å, º) for (II) top
C31—C321.460 (3)C36—C311.452 (3)
C32—C331.359 (3)C31—O311.243 (2)
C33—C341.401 (3)C32—N321.454 (3)
C34—C351.376 (3)C34—N341.436 (2)
C35—C361.376 (3)C36—N361.454 (3)
C16—N11—C12123.86 (18)C26—N21—C22116.95 (18)
N11—C12—C13117.78 (19)N21—C22—C23123.67 (19)
N11—C12—C22115.64 (17)N21—C22—C12113.89 (18)
C13—C12—C22126.53 (19)C23—C22—C12122.40 (18)
N11—C12—C22—N211.1 (3)C33—C34—N34—O411.8 (3)
C31—C32—N32—O2147.5 (3)C31—C36—N36—O61158.46 (18)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N11—H11···N210.882.212.613 (3)107
N11—H11···O420.882.553.204 (2)131
C13—H13···O31i0.952.373.279 (2)160
C14—H14···O21i0.952.383.028 (2)125
C16—H16···O410.952.363.284 (3)164
C23—H23···O31i0.952.423.325 (2)159
C35—H35···O42ii0.952.483.204 (3)133
Symmetry codes: (i) x1, y1, z+1; (ii) x+1, y+1, z+1.
Selected geometric parameters (Å, º) for (III) top
S1—O11.5699 (19)S1—O41.4672 (19)
S1—O21.4526 (19)
C16—N11—C12123.5 (2)C26—N21—C22117.7 (2)
N11—C12—C13118.0 (2)N21—C22—C23123.3 (2)
N11—C12—C22115.8 (2)N21—C22—C12114.4 (2)
C13—C12—C22126.2 (2)C23—C22—C12122.2 (2)
O1—S1—O2105.72 (11)O2—S1—O3113.97 (11)
O1—S1—O3106.92 (11)O2—S1—O4111.05 (11)
O1—S1—O4105.05 (11)O3—S1—O4113.33 (11)
N11—C12—C22—N215.3 (3)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4i0.941.702.640 (3)173
N11—H11···O20.881.982.752 (3)146
N11—H11···N210.882.232.625 (3)107
C13—H13···O4ii0.952.443.389 (3)173
C14—H14···O3ii0.952.483.156 (3)129
C15—H15···O3iii0.952.523.433 (3)161
Symmetry codes: (i) x, y+1, z; (ii) x, y+1/2, z+1/2; (iii) x+1, y3/2, z+1/2.
 

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England. The authors thank the staff for all their help and advice.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationBernstein, 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
First citationDomenicano, A. & Murray-Rust, P. (1979). Tetrahedron Lett. pp. 2283–2386.  CrossRef Google Scholar
First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationHooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationKavitha, S. J., Panchanatheswaran, K., Low, J. N. & Glidewell, C. (2005). Acta Cryst. C61, o473–o474.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationMcArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.  Google Scholar
First citationNakatsu, K., Yoshida, H., Matsui, M., Koda, S. & Ooi, S. (1972). Acta Cryst. A28, S24.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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