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

Kavitha, S.J.; Panchanatheswaran, K.; Low, J.N.; Ferguson, G.; Glidewell, C.

doi:10.1107/S0108270106005002

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 4| April 2006| Pages o165-o169

doi:10.1107/S0108270106005002

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

Savaridasson Jose Kavitha,^a Krishnaswamy Panchanatheswaran,^a John N. Low,^b George Ferguson ^c and Christopher Glidewell ^c ^*

^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 ), 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 its 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 protonated atom N11 and 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 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), 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 protonated atom O1 are systematically less than the other O—S—O angles (Table 3).

Regardless of the orientation of the cation, the components in (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 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 ) 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), 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, − $[{3\over 2}]$ + 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).

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). 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 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 takes the form of a rather complex sheet.

Figure 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
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
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
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. 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
A stereoview of part of the crystal structure of (II)

, 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
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
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
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.

Experimental

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) 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 of the solution to ambient temperature, slow evaporation of the solvent yielded crystals of (II) (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.

Compound (I)

Crystal data

C₁₀H₉N₂⁺·NCS⁻
M_r = 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
D_x = 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 )T_min = 0.898, T_max = 0.989
7990 measured reflections
2311 independent reflections
2145 reflections with I > 2σ(I)
R_int = 0.033
θ_max = 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(F_o²) + (0.0396P)² + 0.256P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), 968 Friedel pairs; χ = 0.57 (7)

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

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)

D—H⋯A	D—H	H⋯A	D⋯A	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)

Crystal data

C₁₀H₉N₂⁺·C₆H₂N₃O₇⁻
M_r = 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
D_x = 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)T_min = 0.975, T_max = 0.996
17473 measured reflections
3598 independent reflections
2432 reflections with I > 2σ(I)
R_int = 0.068
θ_max = 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(F_o²) + (0.0489P)² + 0.2955P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.35 e Å⁻³

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

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)

D—H⋯A	D—H	H⋯A	D⋯A	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)

Crystal data

C₁₀H₉N₂⁺·HSO₄⁻
M_r = 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
D_x = 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)T_min = 0.878, T_max = 0.981
19500 measured reflections
2373 independent reflections
2052 reflections with I > 2σ(I)
R_int = 0.043
θ_max = 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(F_o²) + (0.0285P)² + 2.1787P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.45 e Å⁻³

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

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)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4^iv	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⋯O4^v	0.95	2.44	3.389 (3)	173
C14—H14⋯O3^v	0.95	2.48	3.156 (3)	129
C15—H15⋯O3^vi	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), 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 P $[\overline{1}]$ 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 U_iso(H) values of 1.2U_eq(C,N) or 1.5U_eq(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).

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 ).

Supporting information

Crystal structure: contains datablocks global, I, II, III. DOI: 10.1107/S0108270106005002/sk1900sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270106005002/sk1900Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270106005002/sk1900IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270106005002/sk1900IIIsup4.hkl

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.

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

	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.
	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.
	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.
	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.
	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.
	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.
	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.
	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⁺·NCS⁻	F(000) = 448
M_r = 215.27	D_x = 1.364 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2311 reflections
a = 8.0954 (2) Å	θ = 3.6–27.5°
b = 11.7686 (6) Å	µ = 0.28 mm⁻¹
c = 11.0026 (6) Å	T = 120 K
V = 1048.23 (8) Å³	Plate, colourless
Z = 4	0.40 × 0.40 × 0.04 mm

Data collection top

Bruker KappaCCD diffractometer	2311 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2145 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
ϕ and ω scans	h = −10→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→15
T_min = 0.898, T_max = 0.989	l = −14→14
7990 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.0396P)² + 0.256P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2311 reflections	Δρ_max = 0.29 e Å⁻³
174 parameters	Δρ_min = −0.28 e Å⁻³
30 restraints	Absolute structure: Flack (1983), 968 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.57 (7)

Crystal data top

C₁₀H₉N₂⁺·NCS⁻	V = 1048.23 (8) Å³
M_r = 215.27	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 8.0954 (2) Å	µ = 0.28 mm⁻¹
b = 11.7686 (6) Å	T = 120 K
c = 11.0026 (6) Å	0.40 × 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)
T_min = 0.898, T_max = 0.989	R_int = 0.033
7990 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.077	Δρ_max = 0.29 e Å⁻³
S = 1.05	Δρ_min = −0.28 e Å⁻³
2311 reflections	Absolute structure: Flack (1983), 968 Friedel pairs
174 parameters	Absolute structure parameter: 0.57 (7)
30 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.97990 (4)	0.81858 (3)	0.22438 (6)	0.02287 (12)
C2	0.7788 (2)	0.81469 (12)	0.2406 (2)	0.0204 (4)
N3	0.63655 (19)	0.81096 (13)	0.25650 (18)	0.0324 (4)
N11	0.3605 (5)	0.8178 (3)	0.4079 (3)	0.0159 (6)	0.845 (2)
C12	0.2759 (3)	0.75006 (17)	0.4847 (2)	0.0141 (5)	0.845 (2)
C13	0.1612 (4)	0.8000 (3)	0.5632 (4)	0.0171 (6)	0.845 (2)
C14	0.1425 (8)	0.9171 (3)	0.5642 (5)	0.0173 (7)	0.845 (2)
C15	0.2387 (9)	0.9845 (3)	0.4884 (3)	0.0185 (8)	0.845 (2)
C16	0.3461 (11)	0.9316 (4)	0.4093 (7)	0.0179 (8)	0.845 (2)
N21	0.3800 (2)	0.59153 (15)	0.37469 (16)	0.0194 (4)	0.845 (2)
C22	0.3088 (3)	0.62650 (17)	0.47771 (17)	0.0149 (4)	0.845 (2)
C23	0.2646 (3)	0.55528 (17)	0.5728 (2)	0.0227 (4)	0.845 (2)
C24	0.2940 (3)	0.43905 (19)	0.5592 (2)	0.0287 (5)	0.845 (2)
C25	0.3639 (3)	0.4010 (2)	0.4524 (2)	0.0253 (5)	0.845 (2)
C26	0.4078 (3)	0.47899 (19)	0.3649 (2)	0.0239 (5)	0.845 (2)
N11A	0.139 (3)	0.8202 (17)	0.558 (2)	0.025*	0.155 (2)
C12A	0.222 (2)	0.7529 (11)	0.483 (2)	0.025*	0.155 (2)
C13A	0.354 (4)	0.805 (2)	0.423 (3)	0.025*	0.155 (2)
C14A	0.353 (8)	0.920 (3)	0.401 (5)	0.025*	0.155 (2)
C15A	0.244 (6)	0.985 (2)	0.467 (3)	0.025*	0.155 (2)
C16A	0.155 (6)	0.933 (2)	0.556 (4)	0.025*	0.155 (2)
N21A	0.1219 (13)	0.5881 (8)	0.5848 (10)	0.025*	0.155 (2)
C22A	0.1956 (18)	0.6284 (9)	0.4840 (10)	0.025*	0.155 (2)
C23A	0.2399 (16)	0.5581 (9)	0.3873 (11)	0.025*	0.155 (2)
C24A	0.2140 (16)	0.4412 (9)	0.3993 (11)	0.025*	0.155 (2)
C25A	0.1364 (16)	0.4002 (10)	0.5019 (11)	0.025*	0.155 (2)
C26A	0.0969 (16)	0.4775 (9)	0.5947 (11)	0.025*	0.155 (2)
H11	0.4278	0.7863	0.3548	0.019*	0.845 (2)
H13	0.0963	0.7539	0.6155	0.020*	0.845 (2)
H14	0.0638	0.9514	0.6168	0.021*	0.845 (2)
H15	0.2307	1.0650	0.4910	0.022*	0.845 (2)
H16	0.4106	0.9761	0.3551	0.022*	0.845 (2)
H23	0.2159	0.5846	0.6448	0.027*	0.845 (2)
H24	0.2664	0.3873	0.6223	0.034*	0.845 (2)
H25	0.3815	0.3221	0.4394	0.030*	0.845 (2)
H26	0.4608	0.4519	0.2935	0.029*	0.845 (2)
H11A	0.0700	0.7894	0.6099	0.030*	0.155 (2)
H13A	0.4451	0.7607	0.3974	0.030*	0.155 (2)
H14A	0.4248	0.9528	0.3419	0.030*	0.155 (2)
H15A	0.2313	1.0637	0.4516	0.030*	0.155 (2)
H16A	0.1047	0.9768	0.6182	0.030*	0.155 (2)
H23A	0.2864	0.5889	0.3152	0.030*	0.155 (2)
H24A	0.2495	0.3905	0.3374	0.030*	0.155 (2)
H25A	0.1105	0.3218	0.5097	0.030*	0.155 (2)
H26A	0.0501	0.4491	0.6678	0.030*	0.155 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0167 (2)	0.02194 (19)	0.0299 (2)	0.00122 (13)	0.0046 (2)	0.0016 (2)
C2	0.0222 (8)	0.0149 (7)	0.0241 (9)	0.0005 (5)	0.0010 (8)	−0.0002 (8)
N3	0.0197 (8)	0.0313 (9)	0.0462 (12)	0.0005 (6)	0.0020 (6)	−0.0020 (7)
N11	0.0196 (10)	0.0187 (14)	0.0095 (15)	0.0033 (8)	0.0029 (9)	0.0036 (9)
C12	0.0153 (13)	0.0149 (8)	0.0120 (8)	0.0002 (8)	0.0000 (12)	−0.0030 (8)
C13	0.0192 (14)	0.0176 (15)	0.0145 (10)	−0.0026 (10)	0.0024 (11)	−0.0012 (12)
C14	0.0155 (16)	0.0202 (18)	0.0164 (14)	0.0017 (13)	−0.0036 (10)	−0.0024 (14)
C15	0.0253 (11)	0.0148 (8)	0.015 (2)	0.0037 (10)	−0.0042 (18)	−0.0017 (11)
C16	0.0195 (16)	0.0163 (15)	0.0179 (18)	−0.0042 (16)	−0.0041 (11)	0.0028 (15)
N21	0.0222 (9)	0.0201 (9)	0.0157 (8)	0.0029 (6)	0.0000 (7)	−0.0012 (7)
C22	0.0163 (9)	0.0162 (9)	0.0121 (9)	0.0001 (6)	−0.0033 (7)	−0.0005 (7)
C23	0.0318 (11)	0.0199 (10)	0.0165 (9)	0.0017 (8)	0.0034 (9)	−0.0011 (8)
C24	0.0409 (14)	0.0203 (10)	0.0248 (12)	0.0015 (9)	0.0008 (10)	0.0057 (9)
C25	0.0320 (11)	0.0149 (10)	0.0290 (12)	0.0048 (8)	−0.0074 (9)	−0.0034 (8)
C26	0.0288 (12)	0.0225 (10)	0.0206 (11)	0.0073 (8)	−0.0023 (9)	−0.0058 (8)

Geometric parameters (Å, º) top

S1—C2	1.6383 (16)	C26—H26	0.95
C2—N3	1.166 (2)	N11A—C12A	1.323 (16)
N11—C16	1.345 (4)	N11A—C16A	1.328 (18)
N11—C12	1.348 (3)	N11A—H11A	0.88
N11—H11	0.88	C12A—C13A	1.397 (18)
C12—C13	1.398 (4)	C12A—C22A	1.481 (13)
C12—C22	1.480 (3)	C13A—C14A	1.371 (19)
C13—C14	1.387 (4)	C13A—H13A	0.95
C13—H13	0.95	C14A—C15A	1.380 (19)
C14—C15	1.390 (4)	C14A—H14A	0.95
C14—H14	0.95	C15A—C16A	1.362 (19)
C15—C16	1.378 (4)	C15A—H15A	0.95
C15—H15	0.95	C16A—H16A	0.95
C16—H16	0.95	N21A—C26A	1.322 (12)
N21—C22	1.337 (3)	N21A—C22A	1.346 (12)
N21—C26	1.348 (3)	C22A—C23A	1.395 (13)
C22—C23	1.387 (3)	C23A—C24A	1.398 (13)
C23—C24	1.396 (3)	C23A—H23A	0.95
C23—H23	0.95	C24A—C25A	1.379 (13)
C24—C25	1.379 (3)	C24A—H24A	0.95
C24—H24	0.95	C25A—C26A	1.404 (13)
C25—C26	1.377 (3)	C25A—H25A	0.95
C25—H25	0.95	C26A—H26A	0.95

C16—N11—C12	122.5 (3)	C12A—N11A—C16A	123 (2)
C16—N11—H11	118.7	C12A—N11A—H11A	118.7
C12—N11—H11	118.7	C16A—N11A—H11A	118.7
N11—C12—C13	118.4 (2)	N11A—C12A—C13A	114.6 (17)
N11—C12—C22	117.2 (2)	N11A—C12A—C22A	121.0 (15)
C13—C12—C22	124.4 (2)	C13A—C12A—C22A	123.4 (17)
N3—C2—S1	177.56 (19)	C14A—C13A—C12A	121 (2)
C14—C13—C12	119.7 (3)	C14A—C13A—H13A	119.4
C14—C13—H13	120.2	C12A—C13A—H13A	119.4
C12—C13—H13	120.2	C13A—C14A—C15A	117 (2)
C13—C14—C15	120.1 (4)	C13A—C14A—H14A	121.6
C13—C14—H14	120.0	C15A—C14A—H14A	121.6
C15—C14—H14	120.0	C16A—C15A—C14A	118 (2)
C16—C15—C14	118.4 (3)	C16A—C15A—H15A	121.0
C16—C15—H15	120.8	C14A—C15A—H15A	121.0
C14—C15—H15	120.8	N11A—C16A—C15A	121 (2)
N11—C16—C15	120.8 (4)	N11A—C16A—H16A	119.7
N11—C16—H16	119.6	C15A—C16A—H16A	119.7
C15—C16—H16	119.6	C26A—N21A—C22A	118.8 (10)
C26—N21—C22	116.25 (18)	N21A—C22A—C23A	122.3 (9)
N21—C22—C23	124.37 (19)	N21A—C22A—C12A	114.6 (11)
N21—C22—C12	115.08 (19)	C23A—C22A—C12A	123.1 (11)
C23—C22—C12	120.54 (19)	C22A—C23A—C24A	118.2 (10)
C22—C23—C24	117.9 (2)	C22A—C23A—H23A	120.9
C22—C23—H23	121.1	C24A—C23A—H23A	120.9
C24—C23—H23	121.1	C25A—C24A—C23A	119.4 (11)
C25—C24—C23	118.7 (2)	C25A—C24A—H24A	120.3
C25—C24—H24	120.7	C23A—C24A—H24A	120.3
C23—C24—H24	120.7	C24A—C25A—C26A	118.1 (11)
C26—C25—C24	119.0 (2)	C24A—C25A—H25A	120.9
C26—C25—H25	120.5	C26A—C25A—H25A	120.9
C24—C25—H25	120.5	N21A—C26A—C25A	122.9 (11)
N21—C26—C25	123.8 (2)	N21A—C26A—H26A	118.5
N21—C26—H26	118.1	C25A—C26A—H26A	118.5
C25—C26—H26	118.1

C16—N11—C12—C13	4.2 (8)	C16A—N11A—C12A—C13A	13 (5)
C16—N11—C12—C22	−177.2 (6)	C16A—N11A—C12A—C22A	−177 (3)
N11—C12—C13—C14	−2.9 (6)	N11A—C12A—C13A—C14A	−27 (6)
C22—C12—C13—C14	178.6 (4)	C22A—C12A—C13A—C14A	164 (4)
C12—C13—C14—C15	−0.7 (9)	C12A—C13A—C14A—C15A	17 (9)
C13—C14—C15—C16	3.0 (11)	C13A—C14A—C15A—C16A	5 (9)
C12—N11—C16—C15	−1.9 (13)	C12A—N11A—C16A—C15A	8 (7)
C14—C15—C16—N11	−1.8 (13)	C14A—C15A—C16A—N11A	−18 (8)
C26—N21—C22—C23	0.6 (3)	C26A—N21A—C22A—C23A	3 (2)
C26—N21—C22—C12	−178.54 (19)	C26A—N21A—C22A—C12A	−178.2 (13)
N11—C12—C22—N21	−18.9 (3)	N11A—C12A—C22A—N21A	−19 (3)
C13—C12—C22—N21	159.6 (2)	C13A—C12A—C22A—N21A	150 (3)
N11—C12—C22—C23	161.9 (3)	N11A—C12A—C22A—C23A	160 (2)
C13—C12—C22—C23	−19.6 (4)	C13A—C12A—C22A—C23A	−32 (3)
N21—C22—C23—C24	−1.1 (4)	N21A—C22A—C23A—C24A	−3 (2)
C12—C22—C23—C24	178.0 (2)	C12A—C22A—C23A—C24A	177.8 (14)
C22—C23—C24—C25	−0.5 (4)	C22A—C23A—C24A—C25A	4.2 (19)
C23—C24—C25—C26	2.4 (4)	C23A—C24A—C25A—C26A	−4.5 (19)
C22—N21—C26—C25	1.5 (3)	C22A—N21A—C26A—C25A	−3 (2)
C24—C25—C26—N21	−3.0 (4)	C24A—C25A—C26A—N21A	4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, y, z+1/2.

(II) 2,2'-bipyridinium picrate top

Crystal data top

C₁₀H₉N₂⁺·C₆H₂N₃O₇⁻	Z = 2
M_r = 385.30	F(000) = 396
Triclinic, P1	D_x = 1.637 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4139 (5) Å	Cell parameters from 3598 reflections
b = 9.3768 (6) Å	θ = 3.2–27.6°
c = 12.3694 (5) Å	µ = 0.13 mm⁻¹
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 anode	2432 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.2°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
T_min = 0.975, T_max = 0.996	l = −16→15
17473 measured reflections

Refinement top

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0489P)² + 0.2955P] where P = (F_o² + 2F_c²)/3
3598 reflections	(Δ/σ)_max < 0.001
253 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₀H₉N₂⁺·C₆H₂N₃O₇⁻	γ = 77.391 (3)°
M_r = 385.30	V = 781.79 (8) Å³
Triclinic, P1	Z = 2
a = 7.4139 (5) Å	Mo Kα radiation
b = 9.3768 (6) Å	µ = 0.13 mm⁻¹
c = 12.3694 (5) Å	T = 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)
T_min = 0.975, T_max = 0.996	R_int = 0.068
17473 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.04	Δρ_max = 0.24 e Å⁻³
3598 reflections	Δρ_min = −0.35 e Å⁻³
253 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N11	0.4171 (2)	0.2553 (2)	0.86870 (14)	0.0218 (4)
C12	0.3315 (3)	0.1341 (2)	0.93360 (17)	0.0190 (5)
C13	0.2532 (3)	0.1275 (2)	1.04843 (17)	0.0207 (5)
C14	0.2549 (3)	0.2472 (2)	1.09054 (17)	0.0233 (5)
C15	0.3368 (3)	0.3724 (2)	1.01852 (17)	0.0233 (5)
C16	0.4215 (3)	0.3724 (3)	0.90728 (18)	0.0247 (5)
N21	0.4031 (2)	0.0635 (2)	0.75783 (14)	0.0236 (4)
C22	0.3247 (3)	0.0241 (2)	0.87156 (17)	0.0201 (5)
C23	0.2389 (3)	−0.1044 (2)	0.92588 (17)	0.0213 (5)
C24	0.2307 (3)	−0.1953 (3)	0.85863 (18)	0.0245 (5)
C25	0.3070 (3)	−0.1559 (3)	0.74172 (18)	0.0258 (5)
C26	0.3939 (3)	−0.0269 (3)	0.69570 (18)	0.0267 (5)
C31	1.0533 (3)	0.7446 (2)	0.30058 (17)	0.0194 (5)
O31	1.1755 (2)	0.78858 (17)	0.21397 (11)	0.0245 (4)
C32	1.0223 (3)	0.7930 (2)	0.40585 (16)	0.0198 (5)
N32	1.1307 (3)	0.9059 (2)	0.40382 (14)	0.0241 (4)
O21	1.1392 (2)	1.01949 (17)	0.32060 (12)	0.0310 (4)
O22	1.2054 (2)	0.88440 (19)	0.48734 (13)	0.0346 (4)
C33	0.9025 (3)	0.7397 (2)	0.50656 (17)	0.0203 (5)
C34	0.7940 (3)	0.6323 (2)	0.51074 (16)	0.0187 (5)
N34	0.6730 (2)	0.5704 (2)	0.61814 (14)	0.0216 (4)
O41	0.6728 (2)	0.61165 (17)	0.70434 (12)	0.0268 (4)
O42	0.5768 (2)	0.47558 (18)	0.62274 (12)	0.0284 (4)
C35	0.8116 (3)	0.5782 (2)	0.41669 (16)	0.0196 (5)
C36	0.9358 (3)	0.6318 (2)	0.31605 (16)	0.0189 (5)
N36	0.9535 (2)	0.5630 (2)	0.22294 (14)	0.0214 (4)
O61	0.8987 (2)	0.43891 (18)	0.24778 (12)	0.0294 (4)
O62	1.0201 (2)	0.63012 (18)	0.12300 (12)	0.0281 (4)
H11	0.4732	0.2571	0.7968	0.026*
H13	0.1986	0.0413	1.0980	0.025*
H14	0.1998	0.2439	1.1691	0.028*
H15	0.3339	0.4567	1.0463	0.028*
H16	0.4832	0.4550	0.8576	0.030*
H23	0.1874	−0.1293	1.0067	0.026*
H24	0.1729	−0.2842	0.8928	0.029*
H25	0.3002	−0.2155	0.6938	0.031*
H26	0.4497	−0.0018	0.6156	0.032*
H33	0.8926	0.7743	0.5725	0.024*
H35	0.7384	0.5044	0.4212	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N11	0.0189 (9)	0.0277 (11)	0.0174 (9)	−0.0068 (8)	0.0011 (7)	−0.0058 (8)
C12	0.0154 (10)	0.0199 (11)	0.0202 (10)	−0.0025 (9)	−0.0032 (8)	−0.0039 (9)
C13	0.0188 (11)	0.0213 (12)	0.0187 (10)	−0.0040 (9)	0.0000 (8)	−0.0032 (9)
C14	0.0228 (11)	0.0283 (13)	0.0173 (10)	−0.0051 (10)	0.0007 (9)	−0.0070 (9)
C15	0.0255 (12)	0.0217 (12)	0.0241 (11)	−0.0069 (9)	−0.0024 (9)	−0.0080 (9)
C16	0.0248 (12)	0.0246 (12)	0.0251 (12)	−0.0104 (10)	−0.0007 (9)	−0.0063 (10)
N21	0.0249 (10)	0.0273 (11)	0.0184 (9)	−0.0056 (8)	−0.0019 (7)	−0.0067 (8)
C22	0.0179 (11)	0.0229 (12)	0.0185 (11)	−0.0004 (9)	−0.0043 (9)	−0.0053 (9)
C23	0.0193 (11)	0.0238 (12)	0.0199 (11)	−0.0032 (9)	−0.0014 (8)	−0.0065 (9)
C24	0.0215 (11)	0.0245 (12)	0.0272 (12)	−0.0047 (10)	−0.0047 (9)	−0.0059 (10)
C25	0.0238 (12)	0.0299 (13)	0.0278 (12)	−0.0025 (10)	−0.0068 (9)	−0.0132 (10)
C26	0.0265 (12)	0.0334 (14)	0.0200 (11)	−0.0037 (10)	−0.0032 (9)	−0.0083 (10)
C31	0.0194 (11)	0.0197 (11)	0.0170 (10)	−0.0032 (9)	−0.0019 (9)	−0.0029 (9)
O31	0.0280 (8)	0.0271 (9)	0.0181 (7)	−0.0104 (7)	0.0019 (6)	−0.0066 (6)
C32	0.0208 (11)	0.0197 (11)	0.0178 (10)	−0.0061 (9)	−0.0019 (9)	−0.0031 (9)
N32	0.0264 (10)	0.0288 (11)	0.0173 (9)	−0.0113 (8)	0.0031 (8)	−0.0077 (8)
O21	0.0430 (10)	0.0252 (9)	0.0227 (8)	−0.0159 (8)	0.0007 (7)	−0.0020 (7)
O22	0.0433 (10)	0.0445 (11)	0.0219 (8)	−0.0217 (8)	−0.0084 (7)	−0.0056 (7)
C33	0.0210 (11)	0.0188 (11)	0.0187 (10)	−0.0014 (9)	−0.0017 (9)	−0.0045 (9)
C34	0.0170 (10)	0.0207 (11)	0.0159 (10)	−0.0046 (9)	−0.0004 (8)	−0.0026 (9)
N34	0.0185 (9)	0.0254 (10)	0.0183 (9)	−0.0040 (8)	−0.0019 (7)	−0.0033 (8)
O41	0.0309 (9)	0.0301 (9)	0.0185 (8)	−0.0108 (7)	0.0023 (6)	−0.0067 (7)
O42	0.0247 (8)	0.0361 (10)	0.0258 (8)	−0.0175 (7)	−0.0014 (6)	−0.0043 (7)
C35	0.0181 (11)	0.0177 (11)	0.0211 (11)	−0.0040 (9)	−0.0056 (9)	−0.0005 (9)
C36	0.0197 (11)	0.0203 (11)	0.0170 (10)	−0.0041 (9)	−0.0028 (8)	−0.0055 (9)
N36	0.0207 (9)	0.0236 (11)	0.0195 (9)	−0.0050 (8)	−0.0028 (7)	−0.0053 (8)
O61	0.0371 (9)	0.0268 (9)	0.0287 (9)	−0.0149 (8)	−0.0024 (7)	−0.0102 (7)
O62	0.0337 (9)	0.0337 (9)	0.0170 (8)	−0.0109 (7)	−0.0019 (7)	−0.0056 (7)

Geometric parameters (Å, º) top

N11—C16	1.338 (3)	C25—H25	0.95
N11—C12	1.352 (3)	C26—H26	0.95
N11—H11	0.88	C31—C32	1.460 (3)
C12—C13	1.383 (3)	C32—C33	1.359 (3)
C12—C22	1.481 (3)	C33—C34	1.401 (3)
C13—C14	1.381 (3)	C34—C35	1.376 (3)
C13—H13	0.95	C35—C36	1.376 (3)
C14—C15	1.388 (3)	C36—C31	1.452 (3)
C14—H14	0.95	C31—O31	1.243 (2)
C15—C16	1.364 (3)	C32—N32	1.454 (3)
C15—H15	0.95	C34—N34	1.436 (2)
C16—H16	0.95	C36—N36	1.454 (3)
N21—C26	1.332 (3)	N32—O21	1.227 (2)
N21—C22	1.348 (3)	N32—O22	1.231 (2)
C22—C23	1.387 (3)	C33—H33	0.95
C23—C24	1.384 (3)	N34—O42	1.236 (2)
C23—H23	0.95	N34—O41	1.243 (2)
C24—C25	1.378 (3)	C35—H35	0.95
C24—H24	0.95	N36—O62	1.230 (2)
C25—C26	1.389 (3)	N36—O61	1.238 (2)

C16—N11—C12	123.86 (18)	N21—C26—C25	123.5 (2)
C16—N11—H11	118.1	N21—C26—H26	118.2
C12—N11—H11	118.1	C25—C26—H26	118.2
N11—C12—C13	117.78 (19)	O31—C31—C36	126.16 (19)
N11—C12—C22	115.64 (17)	O31—C31—C32	122.66 (18)
C13—C12—C22	126.53 (19)	C36—C31—C32	110.99 (17)
C14—C13—C12	119.54 (19)	C33—C32—N32	116.99 (18)
C14—C13—H13	120.2	C33—C32—C31	125.55 (19)
C12—C13—H13	120.2	N32—C32—C31	117.45 (16)
C13—C14—C15	120.25 (19)	O21—N32—O22	123.35 (18)
C13—C14—H14	119.9	O21—N32—C32	118.46 (17)
C15—C14—H14	119.9	O22—N32—C32	118.15 (16)
C16—C15—C14	119.0 (2)	C32—C33—C34	118.35 (19)
C16—C15—H15	120.5	C32—C33—H33	120.8
C14—C15—H15	120.5	C34—C33—H33	120.8
N11—C16—C15	119.44 (19)	C35—C34—C33	121.16 (18)
N11—C16—H16	120.3	C35—C34—N34	119.88 (18)
C15—C16—H16	120.3	C33—C34—N34	118.80 (18)
C26—N21—C22	116.95 (18)	O42—N34—O41	122.30 (16)
N21—C22—C23	123.67 (19)	O42—N34—C34	119.29 (17)
N21—C22—C12	113.89 (18)	O41—N34—C34	118.38 (17)
C23—C22—C12	122.40 (18)	C36—C35—C34	119.63 (19)
C24—C23—C22	117.86 (19)	C36—C35—H35	120.2
C24—C23—H23	121.1	C34—C35—H35	120.2
C22—C23—H23	121.1	C35—C36—C31	124.29 (18)
C25—C24—C23	119.5 (2)	C35—C36—N36	116.21 (18)
C25—C24—H24	120.2	C31—C36—N36	119.43 (17)
C23—C24—H24	120.2	O62—N36—O61	122.54 (17)
C24—C25—C26	118.4 (2)	O62—N36—C36	119.23 (17)
C24—C25—H25	120.8	O61—N36—C36	118.22 (16)
C26—C25—H25	120.8

C16—N11—C12—C13	−3.7 (3)	C33—C32—N32—O21	−133.5 (2)
C16—N11—C12—C22	173.81 (18)	C31—C32—N32—O21	47.5 (3)
N11—C12—C13—C14	3.8 (3)	C33—C32—N32—O22	44.6 (3)
C22—C12—C13—C14	−173.40 (19)	C31—C32—N32—O22	−134.4 (2)
C12—C13—C14—C15	−0.8 (3)	N32—C32—C33—C34	179.09 (18)
C13—C14—C15—C16	−2.5 (3)	C31—C32—C33—C34	−2.0 (3)
C12—N11—C16—C15	0.4 (3)	C32—C33—C34—C35	1.9 (3)
C14—C15—C16—N11	2.8 (3)	C32—C33—C34—N34	177.35 (18)
C26—N21—C22—C23	0.8 (3)	C35—C34—N34—O42	−4.5 (3)
C26—N21—C22—C12	−176.93 (18)	C33—C34—N34—O42	−179.97 (18)
N11—C12—C22—N21	−1.1 (3)	C35—C34—N34—O41	173.68 (18)
C13—C12—C22—N21	176.17 (19)	C33—C34—N34—O41	−1.8 (3)
N11—C12—C22—C23	−178.91 (18)	C33—C34—C35—C36	−0.9 (3)
C13—C12—C22—C23	−1.6 (3)	N34—C34—C35—C36	−176.31 (18)
N21—C22—C23—C24	−1.2 (3)	C34—C35—C36—C31	−0.1 (3)
C12—C22—C23—C24	176.33 (19)	C34—C35—C36—N36	176.78 (18)
C22—C23—C24—C25	0.0 (3)	O31—C31—C36—C35	175.1 (2)
C23—C24—C25—C26	1.4 (3)	C32—C31—C36—C35	0.1 (3)
C22—N21—C26—C25	0.8 (3)	O31—C31—C36—N36	−1.7 (3)
C24—C25—C26—N21	−1.9 (3)	C32—C31—C36—N36	−176.68 (17)
O31—C31—C32—C33	−174.2 (2)	C35—C36—N36—O62	160.79 (18)
C36—C31—C32—C33	1.0 (3)	C31—C36—N36—O62	−22.2 (3)
O31—C31—C32—N32	4.7 (3)	C35—C36—N36—O61	−18.6 (3)
C36—C31—C32—N32	179.89 (17)	C31—C36—N36—O61	158.46 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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···O31ⁱ	0.95	2.37	3.279 (2)	160
C14—H14···O21ⁱ	0.95	2.38	3.028 (2)	125
C16—H16···O41	0.95	2.36	3.284 (3)	164
C23—H23···O31ⁱ	0.95	2.42	3.325 (2)	159
C35—H35···O42ⁱⁱ	0.95	2.48	3.204 (3)	133

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

(III) 2,2'-bipyridinium hydrogensulfate top

Crystal data top

C₁₀H₉N₂⁺·HO₄S⁻	F(000) = 528
M_r = 254.26	D_x = 1.636 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2373 reflections
a = 12.8274 (4) Å	θ = 3.6–27.5°
b = 4.4774 (2) Å	µ = 0.32 mm⁻¹
c = 18.2844 (5) Å	T = 120 K
β = 100.568 (2)°	Plate, pink
V = 1032.32 (6) Å³	0.42 × 0.16 × 0.06 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2373 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2052 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
ϕ and ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −5→5
T_min = 0.878, T_max = 0.981	l = −23→23
19500 measured reflections

Refinement top

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.26	w = 1/[σ²(F_o²) + (0.0285P)² + 2.1787P] where P = (F_o² + 2F_c²)/3
2373 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₁₀H₉N₂⁺·HO₄S⁻	V = 1032.32 (6) Å³
M_r = 254.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.8274 (4) Å	µ = 0.32 mm⁻¹
b = 4.4774 (2) Å	T = 120 K
c = 18.2844 (5) Å	0.42 × 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)
T_min = 0.878, T_max = 0.981	R_int = 0.043
19500 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.26	Δρ_max = 0.39 e Å⁻³
2373 reflections	Δρ_min = −0.45 e Å⁻³
154 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N11	0.33239 (17)	0.2531 (5)	0.32521 (11)	0.0151 (4)
C12	0.28089 (19)	0.2546 (6)	0.38388 (13)	0.0144 (5)
C13	0.3176 (2)	0.0668 (6)	0.44311 (14)	0.0168 (5)
C14	0.4037 (2)	−0.1188 (6)	0.44003 (14)	0.0182 (5)
C15	0.4546 (2)	−0.1106 (6)	0.37940 (14)	0.0184 (5)
C16	0.4165 (2)	0.0815 (6)	0.32194 (14)	0.0177 (5)
N21	0.16619 (17)	0.6042 (5)	0.31266 (12)	0.0172 (5)
C22	0.19049 (19)	0.4625 (6)	0.37810 (14)	0.0154 (5)
C23	0.1372 (2)	0.5108 (6)	0.43683 (15)	0.0200 (6)
C24	0.0539 (2)	0.7108 (7)	0.42632 (16)	0.0239 (6)
C25	0.0270 (2)	0.8579 (6)	0.35880 (16)	0.0224 (6)
C26	0.0862 (2)	0.8002 (6)	0.30398 (15)	0.0203 (6)
S1	0.28324 (5)	0.72539 (14)	0.13661 (3)	0.01370 (17)
O1	0.20959 (16)	0.9688 (4)	0.16231 (11)	0.0238 (5)
O2	0.34670 (14)	0.6073 (4)	0.20444 (10)	0.0196 (4)
O3	0.34452 (15)	0.8727 (4)	0.08819 (10)	0.0194 (4)
O4	0.21062 (15)	0.4977 (4)	0.09861 (10)	0.0189 (4)
H11	0.3090	0.3717	0.2874	0.018*
H13	0.2844	0.0646	0.4855	0.020*
H14	0.4278	−0.2525	0.4799	0.022*
H15	0.5143	−0.2343	0.3776	0.022*
H16	0.4501	0.0919	0.2798	0.021*
H23	0.1576	0.4091	0.4828	0.024*
H24	0.0153	0.7472	0.4651	0.029*
H25	−0.0304	0.9950	0.3503	0.027*
H26	0.0690	0.9047	0.2581	0.024*
H1	0.2159	1.1593	0.1414	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N11	0.0174 (10)	0.0152 (10)	0.0127 (9)	−0.0022 (9)	0.0030 (8)	0.0003 (8)
C12	0.0154 (11)	0.0145 (12)	0.0138 (11)	−0.0042 (10)	0.0040 (9)	−0.0027 (10)
C13	0.0169 (12)	0.0189 (13)	0.0147 (11)	−0.0050 (10)	0.0029 (9)	−0.0008 (10)
C14	0.0193 (13)	0.0157 (12)	0.0174 (12)	−0.0044 (10)	−0.0021 (10)	0.0013 (10)
C15	0.0155 (12)	0.0164 (13)	0.0227 (13)	−0.0026 (10)	0.0019 (10)	−0.0024 (10)
C16	0.0169 (12)	0.0189 (13)	0.0177 (12)	−0.0037 (10)	0.0044 (10)	−0.0034 (10)
N21	0.0167 (10)	0.0169 (11)	0.0183 (10)	−0.0018 (9)	0.0038 (8)	−0.0021 (9)
C22	0.0142 (12)	0.0147 (12)	0.0176 (12)	−0.0047 (10)	0.0037 (9)	−0.0026 (10)
C23	0.0231 (13)	0.0199 (13)	0.0183 (12)	−0.0045 (11)	0.0070 (10)	−0.0013 (11)
C24	0.0245 (14)	0.0211 (14)	0.0298 (15)	−0.0046 (11)	0.0145 (12)	−0.0060 (12)
C25	0.0167 (12)	0.0182 (13)	0.0327 (15)	−0.0009 (11)	0.0060 (11)	−0.0024 (12)
C26	0.0181 (12)	0.0196 (13)	0.0223 (13)	−0.0003 (11)	0.0016 (10)	−0.0011 (11)
S1	0.0152 (3)	0.0126 (3)	0.0144 (3)	0.0000 (2)	0.0056 (2)	0.0005 (2)
O1	0.0309 (11)	0.0125 (9)	0.0340 (11)	0.0046 (8)	0.0217 (9)	0.0033 (8)
O2	0.0184 (9)	0.0243 (10)	0.0160 (9)	−0.0001 (8)	0.0032 (7)	0.0022 (8)
O3	0.0221 (9)	0.0188 (9)	0.0202 (9)	−0.0023 (8)	0.0110 (7)	0.0029 (8)
O4	0.0217 (9)	0.0144 (9)	0.0198 (9)	−0.0032 (8)	0.0013 (7)	0.0001 (7)

Geometric parameters (Å, º) top

N11—C16	1.335 (3)	C22—C23	1.391 (3)
N11—C12	1.359 (3)	C23—C24	1.381 (4)
N11—H11	0.88	C23—H23	0.95
C12—C13	1.384 (4)	C24—C25	1.386 (4)
C12—C22	1.476 (4)	C24—H24	0.95
C13—C14	1.391 (4)	C25—C26	1.387 (4)
C13—H13	0.95	C25—H25	0.95
C14—C15	1.387 (4)	C26—H26	0.95
C14—H14	0.95	S1—O1	1.5699 (19)
C15—C16	1.376 (4)	S1—O2	1.4526 (19)
C15—H15	0.95	S1—O3	1.4464 (18)
C16—H16	0.95	S1—O4	1.4672 (19)
N21—C26	1.338 (3)	O1—H1	0.94
N21—C22	1.340 (3)

C16—N11—C12	123.5 (2)	C26—N21—C22	117.7 (2)
C16—N11—H11	118.3	N21—C22—C23	123.3 (2)
C12—N11—H11	118.3	N21—C22—C12	114.4 (2)
N11—C12—C13	118.0 (2)	C23—C22—C12	122.2 (2)
N11—C12—C22	115.8 (2)	C24—C23—C22	118.1 (3)
C13—C12—C22	126.2 (2)	C24—C23—H23	121.0
O1—S1—O2	105.72 (11)	C22—C23—H23	121.0
O1—S1—O3	106.92 (11)	C23—C24—C25	119.5 (3)
O1—S1—O4	105.05 (11)	C23—C24—H24	120.3
C12—C13—C14	119.4 (2)	C25—C24—H24	120.3
C12—C13—H13	120.3	C24—C25—C26	118.4 (3)
C14—C13—H13	120.3	C24—C25—H25	120.8
C15—C14—C13	120.7 (2)	C26—C25—H25	120.8
C15—C14—H14	119.7	N21—C26—C25	123.1 (3)
C13—C14—H14	119.7	N21—C26—H26	118.5
C16—C15—C14	118.2 (2)	C25—C26—H26	118.5
C16—C15—H15	120.9	O2—S1—O3	113.97 (11)
C14—C15—H15	120.9	O2—S1—O4	111.05 (11)
N11—C16—C15	120.2 (2)	O3—S1—O4	113.33 (11)
N11—C16—H16	119.9	S1—O1—H1	113.9
C15—C16—H16	119.9

C16—N11—C12—C13	−0.3 (4)	N11—C12—C22—N21	5.3 (3)
C16—N11—C12—C22	179.1 (2)	C13—C12—C22—N21	−175.4 (2)
N11—C12—C13—C14	−1.2 (4)	N11—C12—C22—C23	−173.3 (2)
C22—C12—C13—C14	179.5 (2)	C13—C12—C22—C23	6.0 (4)
C12—C13—C14—C15	1.9 (4)	N21—C22—C23—C24	1.3 (4)
C13—C14—C15—C16	−1.2 (4)	C12—C22—C23—C24	179.7 (2)
C12—N11—C16—C15	1.0 (4)	C22—C23—C24—C25	−0.8 (4)
C14—C15—C16—N11	−0.2 (4)	C23—C24—C25—C26	−0.6 (4)
C26—N21—C22—C23	−0.4 (4)	C22—N21—C26—C25	−1.1 (4)
C26—N21—C22—C12	−178.9 (2)	C24—C25—C26—N21	1.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	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···O4ⁱⁱ	0.95	2.44	3.389 (3)	173
C14—H14···O3ⁱⁱ	0.95	2.48	3.156 (3)	129
C15—H15···O3ⁱⁱⁱ	0.95	2.52	3.433 (3)	161

Symmetry codes: (i) x, y+1, z; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−3/2, −z+1/2.

Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₁₀H₉N₂⁺·NCS⁻	C₁₀H₉N₂⁺·C₆H₂N₃O₇⁻	C₁₀H₉N₂⁺·HO₄S⁻
M_r	215.27	385.30	254.26
Crystal system, space group	Orthorhombic, Pca2₁	Triclinic, P1	Monoclinic, P2₁/c
Temperature (K)	120	120	120
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, 90	71.681 (3), 75.722 (3), 77.391 (3)	90, 100.568 (2), 90
V (Å³)	1048.23 (8)	781.79 (8)	1032.32 (6)
Z	4	2	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.28	0.13	0.32
Crystal size (mm)	0.40 × 0.40 × 0.04	0.12 × 0.09 × 0.03	0.42 × 0.16 × 0.06

Data collection
Diffractometer	Bruker KappaCCD diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.898, 0.989	0.975, 0.996	0.878, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	7990, 2311, 2145	17473, 3598, 2432	19500, 2373, 2052
R_int	0.033	0.068	0.043
(sin θ/λ)_max (Å⁻¹)	0.649	0.651	0.651

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 reflections	2311	3598	2373
No. of parameters	174	253	154
No. of restraints	30	0	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.28	0.24, −0.35	0.39, −0.45
Absolute structure	Flack (1983), 968 Friedel pairs	?	?
Absolute structure parameter	0.57 (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—C2	1.6383 (16)	C2—N3	1.166 (2)

C16—N11—C12	122.5 (3)	C26—N21—C22	116.25 (18)
N11—C12—C13	118.4 (2)	N21—C22—C23	124.37 (19)
N11—C12—C22	117.2 (2)	N21—C22—C12	115.08 (19)
C13—C12—C22	124.4 (2)	C23—C22—C12	120.54 (19)
N3—C2—S1	177.56 (19)

N11—C12—C22—N21	−18.9 (3)	N11A—C12A—C22A—N21A	−19 (3)

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	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+1/2, y, z+1/2.

Selected geometric parameters (Å, º) for (II) top

C31—C32	1.460 (3)	C36—C31	1.452 (3)
C32—C33	1.359 (3)	C31—O31	1.243 (2)
C33—C34	1.401 (3)	C32—N32	1.454 (3)
C34—C35	1.376 (3)	C34—N34	1.436 (2)
C35—C36	1.376 (3)	C36—N36	1.454 (3)

C16—N11—C12	123.86 (18)	C26—N21—C22	116.95 (18)
N11—C12—C13	117.78 (19)	N21—C22—C23	123.67 (19)
N11—C12—C22	115.64 (17)	N21—C22—C12	113.89 (18)
C13—C12—C22	126.53 (19)	C23—C22—C12	122.40 (18)

N11—C12—C22—N21	−1.1 (3)	C33—C34—N34—O41	−1.8 (3)
C31—C32—N32—O21	47.5 (3)	C31—C36—N36—O61	158.46 (18)

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	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···O31ⁱ	0.95	2.37	3.279 (2)	160
C14—H14···O21ⁱ	0.95	2.38	3.028 (2)	125
C16—H16···O41	0.95	2.36	3.284 (3)	164
C23—H23···O31ⁱ	0.95	2.42	3.325 (2)	159
C35—H35···O42ⁱⁱ	0.95	2.48	3.204 (3)	133

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

Selected geometric parameters (Å, º) for (III) top

S1—O1	1.5699 (19)	S1—O4	1.4672 (19)
S1—O2	1.4526 (19)

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

N11—C12—C22—N21	5.3 (3)

Hydrogen-bond geometry (Å, º) for (III) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	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···O4ⁱⁱ	0.95	2.44	3.389 (3)	173
C14—H14···O3ⁱⁱ	0.95	2.48	3.156 (3)	129
C15—H15···O3ⁱⁱⁱ	0.95	2.52	3.433 (3)	161

Symmetry codes: (i) x, y+1, z; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y−3/2, −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

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. CrossRef Web of Science Google Scholar
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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. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
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ISSN: 2053-2296

Volume 62| Part 4| April 2006| Pages o165-o169

doi:10.1107/S0108270106005002

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Comment

Experimental

Compound (I)

Crystal data

Data collection

Refinement

Compound (II)

Crystal data

Data collection

Refinement

Compound (III)

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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