Literature DB >> 21578895

2-Amino-3-methyl-pyridinium 2-amino-5-methyl-pyridinium sulfate monohydrate.

Jiang Gong, Gang Chen, Shi-Feng Ni, Yong-Yao Zhang, Hai-Bin Wang.

Abstract

The asymmetric unit of the title compound, 2C(6)H(9)N(2) (+)·SO(4) (2-)·H(2)O, contains two isomeric protonated amino-methyl-pyridine cations, a sulfate anion and a solvent water mol-ecule. The cations are in the iminium tautomeric form. In the crystal structure, inter-molecular O-H⋯O, N-H⋯O and weak C-H⋯O hydrogen bonds link the components into a three-dimensional network. Additional stabilization is provided by weak π-π stacking inter-actions, with centroid-centroid distances of 3.758 (2) and 3.774 (1) Å.

Entities: Chemical Disease Species

Year: 2009 PMID： 21578895 PMCID： PMC2972034 DOI： 10.1107/S1600536809049241

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For related structures, see: Nahringbauer & Kvick (1977 ▶); Espenbetov et al. (1985 ▶); Jin et al. (2000 ▶, 2001 ▶, 2005 ▶); Luque et al. (1997 ▶). For studies on the tautomeric forms of 2-aminopyridine systems, see: Inuzuka & Fujimoto (1986 ▶, 1990 ▶); Ishikawa et al. (2002 ▶).

Experimental

Crystal data

2C6H9N2 +·SO4 2−·H2O M = 332.39 Monoclinic, a = 8.4071 (7) Å b = 20.7654 (17) Å c = 9.3369 (8) Å β = 103.983 (1)° V = 1581.7 (2) Å3 Z = 4 Mo Kα radiation μ = 0.23 mm−1 T = 293 K 0.30 × 0.30 × 0.30 mm

Data collection

Bruker SMART APEX area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.908, T max = 0.923 8087 measured reflections 2780 independent reflections 2492 reflections with I > 2σ(I) R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.043 wR(F 2) = 0.129 S = 1.06 2780 reflections 207 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.37 e Å−3 Δρmin = −0.38 e Å−3 Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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: SHELXL97. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049241/lh2943sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049241/lh2943Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

2C₆H₉N₂⁺·SO₄²⁻·H₂O	Z = 4
M_r = 332.39	F(000) = 704.0
Monoclinic, P2₁/c	D_x = 1.396 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.4071 (7) Å	θ = 2.1–25.1°
b = 20.7654 (17) Å	µ = 0.23 mm⁻¹
c = 9.3369 (8) Å	T = 293 K
β = 103.983 (1)°	Prism, colorless
V = 1581.7 (2) Å³	0.30 × 0.30 × 0.30 mm

Bruker SMART APEX area-detector diffractometer	2780 independent reflections
Radiation source: fine-focus sealed tube	2492 reflections with I > 2σ(I)
graphite	R_int = 0.015
φ and ω scan	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→9
T_min = 0.908, T_max = 0.923	k = −24→23
8087 measured reflections	l = −11→10

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0672P)² + 1.0523P] where P = (F_o² + 2F_c²)/3
2780 reflections	(Δ/σ)_max = 0.001
207 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

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

	x	y	z	U_iso*/U_eq
H5B	0.897 (4)	0.5692 (16)	0.975 (4)	0.072 (10)*
H5A	0.873 (4)	0.5243 (17)	1.060 (4)	0.076 (12)*
S1	0.13278 (6)	0.60692 (2)	0.79985 (6)	0.03698 (19)
O1	0.3104 (2)	0.60658 (8)	0.8712 (2)	0.0532 (5)
O2	0.0451 (2)	0.63253 (9)	0.9043 (2)	0.0589 (5)
O3	0.08256 (19)	0.53962 (8)	0.76110 (18)	0.0468 (4)
O4	0.1027 (3)	0.64557 (10)	0.6672 (2)	0.0701 (6)
O5	0.8248 (2)	0.55071 (10)	1.0044 (2)	0.0524 (5)
N1	0.4680 (2)	0.67850 (8)	1.09636 (19)	0.0366 (4)
H1	0.4085	0.6519	1.0356	0.044*
N2	0.2340 (2)	0.73695 (10)	1.0919 (2)	0.0537 (5)
H2A	0.1785	0.7101	1.0292	0.064*
H2B	0.1856	0.7691	1.1213	0.064*
N3	0.3036 (2)	0.47027 (10)	0.6431 (2)	0.0439 (5)
H3	0.2413	0.4940	0.6818	0.053*
N4	0.5202 (3)	0.50690 (11)	0.8229 (2)	0.0550 (6)
H4A	0.4523	0.5294	0.8577	0.066*
H4B	0.6232	0.5080	0.8647	0.066*
C1	0.3949 (3)	0.72881 (11)	1.1434 (2)	0.0383 (5)
C2	0.4942 (3)	0.77118 (11)	1.2445 (3)	0.0452 (5)
H2	0.4480	0.8064	1.2807	0.054*
C3	0.6580 (3)	0.76018 (12)	1.2886 (3)	0.0489 (6)
H3A	0.7229	0.7884	1.3552	0.059*
C4	0.7325 (3)	0.70730 (12)	1.2365 (3)	0.0443 (5)
C5	0.6321 (3)	0.66757 (11)	1.1403 (2)	0.0406 (5)
H5	0.6764	0.6320	1.1035	0.049*
C6	0.9147 (3)	0.69585 (16)	1.2847 (4)	0.0686 (8)
H6A	0.9644	0.7290	1.3526	0.103*
H6B	0.9607	0.6966	1.2001	0.103*
H6C	0.9350	0.6546	1.3322	0.103*
C7	0.4663 (3)	0.47068 (11)	0.7055 (2)	0.0409 (5)
C8	0.5701 (3)	0.43135 (11)	0.6419 (3)	0.0443 (5)
C9	0.4968 (4)	0.39642 (13)	0.5209 (3)	0.0584 (7)
H9	0.5618	0.3708	0.4764	0.070*
C10	0.3270 (4)	0.39747 (14)	0.4606 (3)	0.0668 (8)
H10	0.2803	0.3727	0.3783	0.080*
C11	0.2333 (3)	0.43492 (13)	0.5239 (3)	0.0553 (7)
H11	0.1205	0.4364	0.4856	0.066*
C12	0.7509 (3)	0.42992 (14)	0.7089 (3)	0.0584 (7)
H12A	0.7763	0.4577	0.7935	0.088*
H12B	0.8083	0.4444	0.6376	0.088*
H12C	0.7840	0.3867	0.7385	0.088*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0324 (3)	0.0332 (3)	0.0414 (3)	−0.0057 (2)	0.0014 (2)	0.0011 (2)
O1	0.0341 (9)	0.0525 (10)	0.0654 (11)	−0.0031 (7)	−0.0027 (8)	−0.0152 (8)
O2	0.0513 (11)	0.0522 (11)	0.0765 (12)	−0.0050 (8)	0.0215 (9)	−0.0146 (9)
O3	0.0433 (9)	0.0382 (9)	0.0543 (10)	−0.0094 (7)	0.0030 (7)	−0.0033 (7)
O4	0.0798 (14)	0.0605 (12)	0.0590 (12)	−0.0227 (10)	−0.0047 (10)	0.0196 (9)
O5	0.0385 (10)	0.0571 (11)	0.0607 (12)	−0.0011 (9)	0.0103 (9)	0.0047 (9)
N1	0.0374 (10)	0.0344 (9)	0.0361 (9)	−0.0005 (7)	0.0052 (7)	−0.0023 (7)
N2	0.0389 (11)	0.0536 (12)	0.0639 (14)	0.0080 (9)	0.0034 (10)	−0.0141 (10)
N3	0.0387 (10)	0.0449 (11)	0.0465 (11)	0.0045 (8)	0.0071 (8)	0.0032 (9)
N4	0.0383 (11)	0.0714 (15)	0.0506 (12)	0.0024 (10)	0.0018 (9)	−0.0153 (11)
C1	0.0404 (12)	0.0390 (12)	0.0347 (11)	0.0041 (9)	0.0077 (9)	0.0022 (9)
C2	0.0516 (14)	0.0408 (12)	0.0415 (12)	0.0046 (10)	0.0080 (10)	−0.0081 (10)
C3	0.0511 (14)	0.0475 (14)	0.0425 (13)	−0.0055 (11)	0.0003 (11)	−0.0078 (10)
C4	0.0385 (12)	0.0476 (13)	0.0444 (12)	−0.0003 (10)	0.0052 (10)	0.0027 (10)
C5	0.0401 (12)	0.0391 (12)	0.0429 (12)	0.0053 (9)	0.0108 (10)	0.0018 (9)
C6	0.0398 (14)	0.077 (2)	0.083 (2)	−0.0004 (13)	0.0031 (13)	−0.0047 (17)
C7	0.0430 (12)	0.0402 (12)	0.0375 (11)	−0.0011 (9)	0.0060 (9)	0.0052 (9)
C8	0.0453 (13)	0.0412 (12)	0.0459 (12)	0.0055 (10)	0.0101 (10)	0.0056 (10)
C9	0.0624 (17)	0.0525 (15)	0.0592 (16)	0.0093 (12)	0.0127 (13)	−0.0087 (12)
C10	0.0681 (19)	0.0652 (18)	0.0580 (17)	0.0031 (14)	−0.0028 (14)	−0.0178 (14)
C11	0.0488 (14)	0.0547 (15)	0.0529 (15)	−0.0019 (12)	−0.0061 (12)	−0.0008 (12)
C12	0.0462 (14)	0.0590 (16)	0.0687 (17)	0.0090 (12)	0.0116 (13)	0.0029 (13)

S1—O4	1.4460 (19)	C2—H2	0.9300
S1—O2	1.4577 (19)	C3—C4	1.408 (3)
S1—O3	1.4792 (16)	C3—H3A	0.9300
S1—O1	1.4808 (17)	C4—C5	1.354 (3)
O5—H5B	0.82 (4)	C4—C6	1.508 (3)
O5—H5A	0.79 (4)	C5—H5	0.9300
N1—C1	1.339 (3)	C6—H6A	0.9600
N1—C5	1.360 (3)	C6—H6B	0.9600
N1—H1	0.8600	C6—H6C	0.9600
N2—C1	1.333 (3)	C7—C8	1.426 (3)
N2—H2A	0.8600	C8—C9	1.358 (4)
N2—H2B	0.8600	C8—C12	1.498 (3)
N3—C11	1.345 (3)	C9—C10	1.402 (4)
N3—C7	1.351 (3)	C9—H9	0.9300
N3—H3	0.8600	C10—C11	1.341 (4)
N4—C7	1.316 (3)	C10—H10	0.9300
N4—H4A	0.8600	C11—H11	0.9300
N4—H4B	0.8600	C12—H12A	0.9600
C1—C2	1.407 (3)	C12—H12B	0.9600
C2—C3	1.358 (3)	C12—H12C	0.9600

O4—S1—O2	111.00 (13)	C4—C5—N1	121.5 (2)
O4—S1—O3	109.53 (11)	C4—C5—H5	119.2
O2—S1—O3	110.35 (10)	N1—C5—H5	119.2
O4—S1—O1	109.70 (12)	C4—C6—H6A	109.5
O2—S1—O1	108.56 (11)	C4—C6—H6B	109.5
O3—S1—O1	107.63 (9)	H6A—C6—H6B	109.5
H5B—O5—H5A	104 (3)	C4—C6—H6C	109.5
C1—N1—C5	122.93 (19)	H6A—C6—H6C	109.5
C1—N1—H1	118.5	H6B—C6—H6C	109.5
C5—N1—H1	118.5	N4—C7—N3	118.1 (2)
C1—N2—H2A	120.0	N4—C7—C8	123.5 (2)
C1—N2—H2B	120.0	N3—C7—C8	118.3 (2)
H2A—N2—H2B	120.0	C9—C8—C7	116.9 (2)
C11—N3—C7	123.8 (2)	C9—C8—C12	123.2 (2)
C11—N3—H3	118.1	C7—C8—C12	119.9 (2)
C7—N3—H3	118.1	C8—C9—C10	122.6 (3)
C7—N4—H4A	120.0	C8—C9—H9	118.7
C7—N4—H4B	120.0	C10—C9—H9	118.7
H4A—N4—H4B	120.0	C11—C10—C9	118.8 (3)
N2—C1—N1	119.1 (2)	C11—C10—H10	120.6
N2—C1—C2	123.3 (2)	C9—C10—H10	120.6
N1—C1—C2	117.6 (2)	C10—C11—N3	119.6 (2)
C3—C2—C1	119.5 (2)	C10—C11—H11	120.2
C3—C2—H2	120.3	N3—C11—H11	120.2
C1—C2—H2	120.3	C8—C12—H12A	109.5
C2—C3—C4	122.0 (2)	C8—C12—H12B	109.5
C2—C3—H3A	119.0	H12A—C12—H12B	109.5
C4—C3—H3A	119.0	C8—C12—H12C	109.5
C5—C4—C3	116.5 (2)	H12A—C12—H12C	109.5
C5—C4—C6	121.9 (2)	H12B—C12—H12C	109.5
C3—C4—C6	121.6 (2)

C5—N1—C1—N2	178.2 (2)	C11—N3—C7—C8	−0.1 (3)
C5—N1—C1—C2	−0.9 (3)	N4—C7—C8—C9	179.8 (2)
N2—C1—C2—C3	−178.4 (2)	N3—C7—C8—C9	0.6 (3)
N1—C1—C2—C3	0.7 (3)	N4—C7—C8—C12	−0.1 (4)
C1—C2—C3—C4	−0.1 (4)	N3—C7—C8—C12	−179.3 (2)
C2—C3—C4—C5	−0.3 (4)	C7—C8—C9—C10	−0.9 (4)
C2—C3—C4—C6	179.3 (2)	C12—C8—C9—C10	179.0 (3)
C3—C4—C5—N1	0.2 (3)	C8—C9—C10—C11	0.7 (5)
C6—C4—C5—N1	−179.5 (2)	C9—C10—C11—N3	−0.1 (4)
C1—N1—C5—C4	0.4 (3)	C7—N3—C11—C10	−0.1 (4)
C11—N3—C7—N4	−179.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.82	2.657 (2)	164
N2—H2A···O2	0.86	2.14	2.991 (3)	170
N3—H3···O3	0.86	1.93	2.781 (3)	173
N4—H4A···O1	0.86	2.02	2.826 (3)	156
N4—H4B···O5	0.86	2.07	2.857 (3)	152
C5—H5···O5	0.93	2.41	3.334 (3)	171
O5—H5B···O2ⁱ	0.82 (3)	2.03 (3)	2.833 (3)	167 (3)
O5—H5A···O3ⁱⁱ	0.80 (2)	2.10 (4)	2.845 (3)	157 (3)
C2—H2···O1ⁱⁱⁱ	0.93	2.41	3.334 (3)	176
N2—H2B···O4ⁱⁱⁱ	0.86	1.99	2.835 (3)	168
C11—H11···O3^iv	0.93	2.56	3.317 (3)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	1.82	2.657 (2)	164
N2—H2A⋯O2	0.86	2.14	2.991 (3)	170
N3—H3⋯O3	0.86	1.93	2.781 (3)	173
N4—H4A⋯O1	0.86	2.02	2.826 (3)	156
N4—H4B⋯O5	0.86	2.07	2.857 (3)	152
C5—H5⋯O5	0.93	2.41	3.334 (3)	171
O5—H5B⋯O2ⁱ	0.82 (3)	2.03 (3)	2.833 (3)	167 (3)
O5—H5A⋯O3ⁱⁱ	0.80 (2)	2.10 (4)	2.845 (3)	157 (3)
C2—H2⋯O1ⁱⁱⁱ	0.93	2.41	3.334 (3)	176
N2—H2B⋯O4ⁱⁱⁱ	0.86	1.99	2.835 (3)	168
C11—H11⋯O3^iv	0.93	2.56	3.317 (3)	138

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

2 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Bis(2-amino-6-methylpyridinium) tetrachlorozincate(II).

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Journal: Acta Crystallogr C Date: 2004-12-18 Impact factor: 1.172

2 in total