2,2′-[p-Phenyl­enebis(methyl­idene­aza­ne­di­yl)]dipyridinium bis­(hydrogensulfate) dihydrate

Gao, S.; Qi, X.-J.; Kong, L.-L.; Ng, S.W.

doi:10.1107/S1600536810047999

organic compounds

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Volume 66| Part 12| December 2010| Page o3300

https://doi.org/10.1107/S1600536810047999

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2,2′-[p-Phenylenebis(methylideneazanediyl)]dipyridinium bis(hydrogensulfate) dihydrate

Shan Gao,^a Xiao-Juan Qi,^a Li-Li Kong ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 15 November 2010; accepted 17 November 2010; online 27 November 2010)

The cation of the title salt, C₁₈H₂₀N₄²⁺·2HSO₄⁻·2H₂O, lies on a center of inversion with the mid-point directly in the middle of the p-phenylene ring. Within the hydrogensulfate ion, the S—O(H) bond is the longest of the S—O bonds. The dihedral angle between the central and terminal ring of the cation is 78.6 (2)°. In the crystal, the cation, anion and water molecule interact by O—H⋯O and N—H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

For the synthesis and structure of 1,4-bis(pyridine-2-aminomethyl)benzene, see: Zou et al. (2003 ).

Experimental

Crystal data

C₁₈H₂₀N₄²⁺·2HSO₄⁻·2H₂O
M_r = 522.55
Triclinic, $[P \overline 1]$
a = 7.1718 (5) Å
b = 9.3010 (7) Å
c = 9.5113 (5) Å
α = 97.648 (2)°
β = 92.340 (2)°
γ = 114.005 (2)°
V = 571.25 (7) Å³
Z = 1
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.25 × 0.21 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.930, T_max = 0.949
5648 measured reflections
2583 independent reflections
1624 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.143
S = 1.14
2583 reflections
169 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1wⁱ	0.84 (1)	1.75 (1)	2.592 (4)	178 (5)
O1w—H11⋯O2	0.84 (1)	1.93 (2)	2.749 (3)	164 (5)
O1w—H12⋯O4ⁱⁱ	0.84 (1)	1.98 (1)	2.813 (3)	174 (5)
N2—H2⋯O1	0.89 (1)	2.02 (2)	2.844 (3)	154 (3)
N1—H1⋯O4ⁱⁱⁱ	0.88 (1)	2.03 (1)	2.903 (3)	170 (3)
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) -x, -y+2, -z+2; (iii) x, y-1, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810047999/si2312sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047999/si2312Isup2.hkl

checkCIF report

Comment top

The synthesis complements other reports of the coordinating ability of 1,4-bis(2-pyridylaminomethyl)benzene, a relatively flexible N-donor ligand having aromatic as well as aliphatic donor sites. The structure of the neutral ligand has been reported (Zou et al., 2003). Protonation by a strong acid, sulfuric acid, occurs at both pyridyl nitrogen atoms to yield the hydrogensulfate salt, C₁₈H₂₀N₄²⁺ 2(HSO₄)^-.2H₂O (Scheme I, Fig. 1). The cation lies on a center-of-inversion with the mid-point directly in the middle of the p-phenylene ring. The hydrogensulfate anion bears a hydrogen atom, so that the S–O_H bond is the longest of the S–O bonds. The cation, anion and water molecule interact by O–H···O and N–H···O hydrogen bonds to generate a three-dimensional network (Table 1).

Related literature top

For the synthesis and structure of 1,4-bis(pyridine-2-aminomethyl)benzene, see: Zou et al. (2003).

Experimental top

1,4-Bis(2-pyridylaminomethyl)benzene (10 mmol, 2.90 g) was dissolved in methanol (50 ml). Strong sulfuric acid was added until the pH was 3. The solution was filtered; colorless crystals were isolated after several days.

Structure description top

For the synthesis and structure of 1,4-bis(pyridine-2-aminomethyl)benzene, see: Zou et al. (2003).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₈H₂₀N₄²⁺ 2(HSO₄)^-.2H₂O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The cation lies on a center-of-inversion.

2,2'-[p-Phenylenebis(methylideneazanediyl)]dipyridinium bis(hydrogensulfate) dihydrate top

Crystal data top

C₁₈H₂₀N₄²⁺·2HSO₄⁻·2H₂O	Z = 1
M_r = 522.55	F(000) = 274
Triclinic, P1	D_x = 1.519 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1718 (5) Å	Cell parameters from 3948 reflections
b = 9.3010 (7) Å	θ = 3.1–27.4°
c = 9.5113 (5) Å	µ = 0.30 mm⁻¹
α = 97.648 (2)°	T = 293 K
β = 92.340 (2)°	Prism, colorless
γ = 114.005 (2)°	0.25 × 0.21 × 0.18 mm
V = 571.25 (7) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2583 independent reflections
Radiation source: fine-focus sealed tube	1624 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
ω scans	h = −9→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
T_min = 0.930, T_max = 0.949	l = −12→12
5648 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ²(F_o²) + (0.0586P)² + 0.3231P] where P = (F_o² + 2F_c²)/3
2583 reflections	(Δ/σ)_max = 0.001
169 parameters	Δρ_max = 0.48 e Å⁻³
5 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₁₈H₂₀N₄²⁺·2HSO₄⁻·2H₂O	γ = 114.005 (2)°
M_r = 522.55	V = 571.25 (7) Å³
Triclinic, P1	Z = 1
a = 7.1718 (5) Å	Mo Kα radiation
b = 9.3010 (7) Å	µ = 0.30 mm⁻¹
c = 9.5113 (5) Å	T = 293 K
α = 97.648 (2)°	0.25 × 0.21 × 0.18 mm
β = 92.340 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2583 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1624 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.949	R_int = 0.024
5648 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	5 restraints
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	Δρ_max = 0.48 e Å⁻³
2583 reflections	Δρ_min = −0.42 e Å⁻³
169 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.19334 (11)	0.92763 (8)	0.76081 (7)	0.0379 (2)
O1	0.1234 (3)	0.7575 (2)	0.7264 (2)	0.0508 (5)
O2	0.2506 (5)	0.9842 (3)	0.9097 (2)	0.0767 (8)
O3	0.3889 (4)	1.0040 (3)	0.6846 (3)	0.0627 (7)
H3	0.481 (5)	0.981 (5)	0.719 (4)	0.094*
O4	0.0542 (3)	0.9850 (3)	0.7002 (3)	0.0566 (6)
O1W	0.3282 (4)	1.0635 (4)	1.2016 (3)	0.0730 (8)
H11	0.286 (7)	1.023 (6)	1.1157 (19)	0.110*
H12	0.218 (4)	1.055 (6)	1.235 (5)	0.110*
N1	0.1175 (4)	0.3172 (3)	0.7485 (2)	0.0418 (6)
H1	0.112 (5)	0.220 (2)	0.740 (4)	0.063*
N2	0.2258 (4)	0.5652 (3)	0.8961 (2)	0.0388 (5)
H2	0.202 (5)	0.606 (4)	0.821 (2)	0.058*
C1	0.5953 (5)	0.6591 (3)	0.4870 (3)	0.0409 (7)
H1A	0.6588	0.7665	0.4787	0.049*
C2	0.4067 (5)	0.6003 (3)	0.5401 (3)	0.0417 (7)
H2A	0.3444	0.6687	0.5668	0.050*
C3	0.3092 (4)	0.4410 (3)	0.5541 (3)	0.0363 (6)
C4	0.1038 (5)	0.3747 (4)	0.6143 (3)	0.0432 (7)
H4A	0.0537	0.4573	0.6301	0.052*
H4B	0.0057	0.2875	0.5452	0.052*
C5	0.1854 (4)	0.4078 (3)	0.8764 (3)	0.0342 (6)
C6	0.2159 (4)	0.3435 (4)	0.9964 (3)	0.0407 (6)
H6	0.1907	0.2362	0.9874	0.049*
C7	0.2830 (5)	0.4399 (4)	1.1269 (3)	0.0492 (8)
H7	0.3020	0.3970	1.2064	0.059*
C8	0.3230 (5)	0.6011 (4)	1.1422 (3)	0.0502 (8)
H8	0.3689	0.6664	1.2308	0.060*
C9	0.2939 (4)	0.6600 (4)	1.0261 (3)	0.0453 (7)
H9	0.3206	0.7676	1.0345	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0398 (4)	0.0353 (4)	0.0421 (4)	0.0194 (3)	0.0045 (3)	0.0058 (3)
O1	0.0561 (13)	0.0329 (11)	0.0647 (14)	0.0198 (10)	0.0081 (10)	0.0079 (9)
O2	0.106 (2)	0.0816 (19)	0.0359 (13)	0.0403 (17)	−0.0082 (12)	−0.0100 (11)
O3	0.0481 (14)	0.0637 (16)	0.0861 (18)	0.0248 (12)	0.0202 (12)	0.0361 (13)
O4	0.0494 (13)	0.0527 (14)	0.0795 (16)	0.0314 (11)	0.0020 (11)	0.0175 (11)
O1W	0.0499 (15)	0.116 (2)	0.0588 (16)	0.0458 (16)	−0.0023 (12)	−0.0032 (15)
N1	0.0508 (15)	0.0357 (13)	0.0414 (13)	0.0204 (12)	0.0084 (10)	0.0059 (10)
N2	0.0420 (13)	0.0386 (14)	0.0403 (13)	0.0204 (11)	0.0020 (10)	0.0096 (10)
C1	0.0555 (18)	0.0352 (15)	0.0354 (15)	0.0226 (13)	0.0055 (12)	0.0047 (11)
C2	0.0557 (18)	0.0433 (17)	0.0371 (15)	0.0322 (15)	0.0059 (12)	0.0042 (12)
C3	0.0449 (16)	0.0423 (16)	0.0243 (13)	0.0220 (13)	0.0009 (10)	0.0025 (10)
C4	0.0469 (17)	0.0506 (18)	0.0346 (15)	0.0241 (14)	0.0008 (11)	0.0033 (12)
C5	0.0284 (13)	0.0360 (15)	0.0400 (15)	0.0138 (11)	0.0075 (10)	0.0096 (11)
C6	0.0418 (16)	0.0412 (16)	0.0472 (17)	0.0216 (13)	0.0103 (12)	0.0187 (12)
C7	0.0398 (16)	0.073 (2)	0.0443 (17)	0.0278 (15)	0.0096 (12)	0.0258 (15)
C8	0.0475 (18)	0.060 (2)	0.0428 (17)	0.0244 (16)	0.0010 (13)	0.0023 (14)
C9	0.0443 (17)	0.0401 (17)	0.0500 (17)	0.0184 (13)	0.0012 (13)	0.0009 (13)

Geometric parameters (Å, º) top

S1—O2	1.425 (2)	C1—H1A	0.9300
S1—O1	1.437 (2)	C2—C3	1.385 (4)
S1—O4	1.443 (2)	C2—H2A	0.9300
S1—O3	1.551 (2)	C3—C1ⁱ	1.390 (4)
O3—H3	0.84 (1)	C3—C4	1.517 (4)
O1W—H11	0.84 (1)	C4—H4A	0.9700
O1W—H12	0.84 (1)	C4—H4B	0.9700
N1—C5	1.331 (4)	C5—C6	1.406 (4)
N1—C4	1.462 (4)	C6—C7	1.371 (4)
N1—H1	0.88 (1)	C6—H6	0.9300
N2—C5	1.356 (3)	C7—C8	1.394 (5)
N2—C9	1.362 (4)	C7—H7	0.9300
N2—H2	0.89 (1)	C8—C9	1.341 (4)
C1—C2	1.382 (4)	C8—H8	0.9300
C1—C3ⁱ	1.390 (4)	C9—H9	0.9300

O2—S1—O1	112.24 (15)	C1ⁱ—C3—C4	119.7 (3)
O2—S1—O4	113.33 (16)	N1—C4—C3	112.3 (2)
O1—S1—O4	113.05 (14)	N1—C4—H4A	109.1
O2—S1—O3	107.05 (17)	C3—C4—H4A	109.1
O1—S1—O3	107.22 (14)	N1—C4—H4B	109.1
O4—S1—O3	103.15 (13)	C3—C4—H4B	109.1
S1—O3—H3	109 (3)	H4A—C4—H4B	107.9
H11—O1W—H12	101 (5)	N1—C5—N2	121.3 (2)
C5—N1—C4	125.7 (2)	N1—C5—C6	121.2 (3)
C5—N1—H1	117 (2)	N2—C5—C6	117.5 (2)
C4—N1—H1	115 (2)	C7—C6—C5	119.6 (3)
C5—N2—C9	122.4 (2)	C7—C6—H6	120.2
C5—N2—H2	118 (2)	C5—C6—H6	120.2
C9—N2—H2	120 (2)	C6—C7—C8	121.0 (3)
C2—C1—C3ⁱ	120.5 (3)	C6—C7—H7	119.5
C2—C1—H1A	119.7	C8—C7—H7	119.5
C3ⁱ—C1—H1A	119.7	C9—C8—C7	118.4 (3)
C1—C2—C3	120.9 (3)	C9—C8—H8	120.8
C1—C2—H2A	119.6	C7—C8—H8	120.8
C3—C2—H2A	119.6	C8—C9—N2	121.2 (3)
C2—C3—C1ⁱ	118.6 (3)	C8—C9—H9	119.4
C2—C3—C4	121.7 (3)	N2—C9—H9	119.4

C3ⁱ—C1—C2—C3	0.3 (5)	C9—N2—C5—N1	179.5 (3)
C1—C2—C3—C1ⁱ	−0.3 (4)	C9—N2—C5—C6	0.2 (4)
C1—C2—C3—C4	179.0 (2)	N1—C5—C6—C7	−179.0 (3)
C5—N1—C4—C3	80.0 (3)	N2—C5—C6—C7	0.3 (4)
C2—C3—C4—N1	−115.8 (3)	C5—C6—C7—C8	−0.5 (4)
C1ⁱ—C3—C4—N1	63.5 (3)	C6—C7—C8—C9	0.2 (5)
C4—N1—C5—N2	8.5 (4)	C7—C8—C9—N2	0.3 (5)
C4—N1—C5—C6	−172.2 (3)	C5—N2—C9—C8	−0.5 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1wⁱⁱ	0.84 (1)	1.75 (1)	2.592 (4)	178 (5)
O1w—H11···O2	0.84 (1)	1.93 (2)	2.749 (3)	164 (5)
O1w—H12···O4ⁱⁱⁱ	0.84 (1)	1.98 (1)	2.813 (3)	174 (5)
N2—H2···O1	0.89 (1)	2.02 (2)	2.844 (3)	154 (3)
N1—H1···O4^iv	0.88 (1)	2.03 (1)	2.903 (3)	170 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₈H₂₀N₄²⁺·2HSO₄⁻·2H₂O
M_r	522.55
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.1718 (5), 9.3010 (7), 9.5113 (5)
α, β, γ (°)	97.648 (2), 92.340 (2), 114.005 (2)
V (Å³)	571.25 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.25 × 0.21 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.930, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	5648, 2583, 1624
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.143, 1.14
No. of reflections	2583
No. of parameters	169
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.42

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1wⁱ	0.84 (1)	1.75 (1)	2.592 (4)	178 (5)
O1w—H11···O2	0.84 (1)	1.93 (2)	2.749 (3)	164 (5)
O1w—H12···O4ⁱⁱ	0.84 (1)	1.98 (1)	2.813 (3)	174 (5)
N2—H2···O1	0.89 (1)	2.02 (2)	2.844 (3)	154 (3)
N1—H1···O4ⁱⁱⁱ	0.88 (1)	2.03 (1)	2.903 (3)	170 (3)

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

Acknowledgements

We thank the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Innovation Team of the Education Bureau of Heilongjiang Province (No. 2010 t d03), Heilongjiang Education Department (No. 11531274), Heilongjiang University and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zou, R.-Y., Xu, F.-B., Li, Q.-S., Song, H.-B., Lv, H. & Zhang, Z.-Z. (2003). Acta Cryst. E59, o1312–o1313. Web of Science CSD CrossRef IUCr Journals Google Scholar

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

2,2′-[p-Phenyl­enebis(methyl­­idene­aza­ne­di­yl)]dipyridinium bis­­(hydrogensulfate) dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2,2′-[p-Phenylenebis(methylideneazanediyl)]dipyridinium bis(hydrogensulfate) dihydrate