3,3′-Carbonyl­dipyridinium bis­(perchlorate)

Zhang, Y.; Li, A.; Wang, Z.; Wan, C.-Q.

doi:10.1107/S1600536812022817

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1896

doi:10.1107/S1600536812022817

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3,3′-Carbonyldipyridinium bis(perchlorate)

Ya Zhang,^a Ai-min Li,^a Zhi-wei Wang ^a and Chong-Qing Wan ^a ^*

^aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China
^*Correspondence e-mail: wanchqing@yahoo.com.cn

(Received 13 May 2012; accepted 18 May 2012; online 26 May 2012)

In the title molecular salt, C₁₁H₁₀N₂O²⁺·2ClO₄⁻, the complete cation is generated by crystallographic twofold symmetry. The dihedral angle between the pyridyl rings is 67.07 (7)°. The crystal structure features N—H⋯Cl hydrogen bonds, forming sheets in the ab plane.

Related literature

For the dipyridyl ketone dication, see: Crook & McElvain (1930 ); Favaro et al. (1990 ). For metal complexes of di-3-pyridyl ketone, see: Chen & Mak (2005 ); Chen et al. (2009 ).

Experimental

Crystal data

C₁₁H₁₀N₂O²⁺·2ClO₄⁻
M_r = 385.11
Orthorhombic, P 2₁ 2₁ 2
a = 8.5315 (3) Å
b = 15.1772 (6) Å
c = 5.6107 (2) Å
V = 726.50 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 296 K
0.40 × 0.30 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.835, T_max = 0.905
6343 measured reflections
1285 independent reflections
1235 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.073
S = 1.10
1285 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 503 Friedel pairs
Flack parameter: 0.10 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H7⋯O2	0.86	2.22	2.907 (3)	136
N1ⁱ—H7ⁱ⋯O4	0.86	2.34	2.967 (2)	130
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 and SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812022817/bt5923sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022817/bt5923Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812022817/bt5923Isup3.cml

checkCIF report

Comment top

Di-3-pyridyl ketone is an extraordinary ligand within the family of basic building blocks for construction of metal-organic complexes with intriguing architectures (Chen & Mak, 2005; Chen et al., 2009). However, the crystal structure of salts with the dipyridyl ketone dication is rarely reported until now. Several related literatures discussed the relationship between the acid-base properties of the dipyridyl ketone isomers and the positions of the nitrogen atoms on the rings, which were investigated by spectrophotometric measurements (Crook & McElvain, 1930; Favaro et al., 1990). In the present context, we report the structure of diprotonated di-3-pyridyl ketone perchlorate salt (Fig. 1). The two pyridyl rings exhibit a dihedral angle of 67.07 (7)°. The crystal structure is stabilized by N—H···(perchlorate) hydrogen bonds forming sheets in the ab plane.

Related literature top

For the dipyridyl ketone dication, see: Crook & McElvain (1930); Favaro et al. (1990). For metal complexes of di-3-pyridyl ketone, see: Chen & Mak (2005); Chen et al. (2009).

Experimental top

Di-3-pyridyl ketone was prepared following the literature procedure of Chen & Mak (2005). Copper(II) perchlorate (37 mg, 0.1 mmol) was heated with di-3-pyridyl ketone (18 mg, 0.1 mmol) in acetonitrile (5 ml) at 373 K for 24 h. After cooling to room temperature, the precipitate which had formed was filtrated off. Crystals of the title salt was deposited by slow evaporation of the filtrate, which can be viewed as the product of the perchloric acid from the copper(II) perchlorate and di-3-pyridyl ketone (yield 11.5 mg, 30% based on di-3-pyridyl ketone).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 and SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The atom-numbering scheme of the title salt; some H atoms have been omitted for clarity. Displacement ellipsoids are shown at the 30% probability level. [Symmetry code: (i) -x + 1, -y, z.]

3,3'-Carbonyldipyridinium diperchlorate top

Crystal data top

C₁₁H₁₀N₂O²⁺·2ClO₄⁻	D_x = 1.760 Mg m⁻³
M_r = 385.11	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2	Cell parameters from 256 reflections
a = 8.5315 (3) Å	θ = 2.3–26.2°
b = 15.1772 (6) Å	µ = 0.50 mm⁻¹
c = 5.6107 (2) Å	T = 296 K
V = 726.50 (5) Å³	Block, colorless
Z = 2	0.40 × 0.30 × 0.20 mm
F(000) = 392

Data collection top

Bruker APEXII CCD area-detector diffractometer	1285 independent reflections
Radiation source: fine-focus sealed tube	1235 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
T_min = 0.835, T_max = 0.905	k = −18→16
6343 measured reflections	l = −6→6

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0315P)² + 0.4015P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.073	(Δ/σ)_max < 0.001
S = 1.10	Δρ_max = 0.34 e Å⁻³
1285 reflections	Δρ_min = −0.21 e Å⁻³
111 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.019 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 503 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.10 (10)

Crystal data top

C₁₁H₁₀N₂O²⁺·2ClO₄⁻	V = 726.50 (5) Å³
M_r = 385.11	Z = 2
Orthorhombic, P2₁2₁2	Mo Kα radiation
a = 8.5315 (3) Å	µ = 0.50 mm⁻¹
b = 15.1772 (6) Å	T = 296 K
c = 5.6107 (2) Å	0.40 × 0.30 × 0.20 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1285 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1235 reflections with I > 2σ(I)
T_min = 0.835, T_max = 0.905	R_int = 0.021
6343 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.073	Δρ_max = 0.34 e Å⁻³
S = 1.10	Δρ_min = −0.21 e Å⁻³
1285 reflections	Absolute structure: Flack (1983), 503 Friedel pairs
111 parameters	Absolute structure parameter: 0.10 (10)
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C1	0.1257 (3)	0.13417 (17)	0.4051 (5)	0.0416 (6)
H1	0.0408	0.1642	0.3402	0.050*
C2	0.1807 (3)	0.05924 (17)	0.2988 (4)	0.0372 (6)
H2	0.1340	0.0381	0.1604	0.045*
C3	0.3062 (3)	0.01520 (14)	0.3985 (4)	0.0317 (5)
H3	0.3449	−0.0357	0.3274	0.038*
C4	0.3745 (3)	0.04756 (14)	0.6063 (4)	0.0287 (5)
C5	0.3158 (3)	0.12400 (15)	0.7048 (4)	0.0334 (5)
H5	0.3609	0.1474	0.8419	0.040*
C6	0.5000	0.0000	0.7390 (6)	0.0308 (7)
N1	0.1948 (2)	0.16399 (13)	0.6032 (4)	0.0386 (5)
H7	0.1591	0.2113	0.6677	0.046*
O1	0.5000	0.0000	0.9548 (4)	0.0431 (6)
Cl1	0.30796 (6)	0.32979 (4)	1.13244 (10)	0.03518 (19)
O2	0.2552 (3)	0.31908 (15)	0.8930 (4)	0.0720 (7)
O3	0.1779 (3)	0.33349 (15)	1.2909 (4)	0.0647 (6)
O4	0.4064 (2)	0.25628 (13)	1.1946 (4)	0.0539 (6)
O5	0.3940 (3)	0.41004 (13)	1.1460 (5)	0.0622 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0318 (12)	0.0470 (14)	0.0461 (16)	0.0021 (11)	−0.0001 (12)	0.0095 (13)
C2	0.0350 (13)	0.0444 (14)	0.0323 (12)	−0.0082 (12)	−0.0038 (11)	0.0022 (10)
C3	0.0339 (11)	0.0321 (12)	0.0293 (11)	−0.0041 (10)	0.0037 (12)	−0.0010 (10)
C4	0.0293 (11)	0.0299 (11)	0.0269 (11)	−0.0019 (9)	0.0043 (11)	0.0025 (10)
C5	0.0348 (12)	0.0336 (12)	0.0319 (12)	−0.0013 (11)	0.0021 (11)	−0.0022 (9)
C6	0.0346 (18)	0.0289 (17)	0.0288 (18)	−0.0017 (15)	0.000	0.000
N1	0.0378 (10)	0.0327 (10)	0.0452 (12)	0.0081 (10)	0.0046 (10)	−0.0007 (10)
O1	0.0499 (15)	0.0537 (16)	0.0259 (13)	0.0073 (14)	0.000	0.000
Cl1	0.0335 (3)	0.0328 (3)	0.0393 (3)	−0.0005 (2)	0.0001 (3)	−0.0034 (3)
O2	0.0990 (17)	0.0660 (14)	0.0511 (12)	0.0026 (13)	−0.0214 (12)	−0.0129 (12)
O3	0.0620 (13)	0.0551 (12)	0.0770 (15)	0.0139 (12)	0.0314 (11)	0.0109 (12)
O4	0.0398 (10)	0.0402 (10)	0.0817 (16)	0.0070 (8)	−0.0062 (10)	−0.0008 (10)
O5	0.0604 (12)	0.0403 (11)	0.0858 (16)	−0.0138 (9)	−0.0075 (14)	0.0029 (12)

Geometric parameters (Å, º) top

C1—N1	1.337 (3)	C5—N1	1.327 (3)
C1—C2	1.368 (4)	C5—H5	0.9300
C1—H1	0.9300	C6—O1	1.210 (4)
C2—C3	1.381 (4)	C6—C4ⁱ	1.491 (3)
C2—H2	0.9300	N1—H7	0.8600
C3—C4	1.393 (3)	Cl1—O3	1.423 (2)
C3—H3	0.9300	Cl1—O5	1.4242 (19)
C4—C5	1.379 (3)	Cl1—O2	1.426 (2)
C4—C6	1.491 (3)	Cl1—O4	1.439 (2)

N1—C1—C2	119.5 (2)	C4—C5—H5	120.2
N1—C1—H1	120.2	O1—C6—C4	119.97 (14)
C2—C1—H1	120.2	O1—C6—C4ⁱ	119.97 (14)
C1—C2—C3	119.5 (2)	C4—C6—C4ⁱ	120.1 (3)
C1—C2—H2	120.3	C5—N1—C1	123.1 (2)
C3—C2—H2	120.3	C5—N1—H7	118.5
C2—C3—C4	119.5 (2)	C1—N1—H7	118.5
C2—C3—H3	120.2	O3—Cl1—O5	109.56 (14)
C4—C3—H3	120.2	O3—Cl1—O2	110.31 (16)
C5—C4—C3	118.7 (2)	O5—Cl1—O2	108.08 (15)
C5—C4—C6	117.9 (2)	O3—Cl1—O4	109.53 (13)
C3—C4—C6	123.2 (2)	O5—Cl1—O4	110.44 (12)
N1—C5—C4	119.7 (2)	O2—Cl1—O4	108.90 (14)
N1—C5—H5	120.2

N1—C1—C2—C3	0.4 (4)	C5—C4—C6—O1	34.0 (2)
C1—C2—C3—C4	0.2 (3)	C3—C4—C6—O1	−141.03 (17)
C2—C3—C4—C5	−1.0 (3)	C5—C4—C6—C4ⁱ	−146.0 (2)
C2—C3—C4—C6	174.0 (2)	C3—C4—C6—C4ⁱ	38.97 (17)
C3—C4—C5—N1	1.2 (3)	C4—C5—N1—C1	−0.6 (4)
C6—C4—C5—N1	−174.1 (2)	C2—C1—N1—C5	−0.2 (4)

Symmetry code: (i) −x+1, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H7···O2	0.86	2.22	2.907 (3)	136
N1ⁱⁱ—H7ⁱⁱ···O4	0.86	2.34	2.967 (2)	130

Symmetry code: (ii) x+1/2, −y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₂O²⁺·2ClO₄⁻
M_r	385.11
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	296
a, b, c (Å)	8.5315 (3), 15.1772 (6), 5.6107 (2)
V (Å³)	726.50 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.835, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	6343, 1285, 1235
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.073, 1.10
No. of reflections	1285
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.21
Absolute structure	Flack (1983), 503 Friedel pairs
Absolute structure parameter	0.10 (10)

Computer programs: APEX2 (Bruker, 2007), APEX2 and SAINT (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H7···O2	0.86	2.22	2.907 (3)	136.3
N1ⁱ—H7ⁱ···O4	0.86	2.34	2.967 (2)	129.8

Symmetry code: (i) x+1/2, −y+1/2, −z+2.

Acknowledgements

We thank the State Key Laboratory of Structural Chemistry of China (Reference No. 20110001) and the Beijing Natural Science Foundation (grant No. 2022011) for financial support.

References

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