Literature DB >> 21583764

Bis(4-amino-pyridinium) tetra-chlorido-cobaltate(II).

Samuel Robinson Jebas, A Sinthiya, B Ravindran Durai Nayagam, Dieter Schollmeyer, S Alfred Cecil Raj.

Abstract

In the title compound, (C(5)H(7)N(2))(2)[CoCl(4)], the cobalt(II) ion is coordinated by four chloride ions in a slightly distorted tetra-hedral geometry. The crystal packing is stabilized by inter-molecular N-H⋯Cl hydrogen bonding, forming a three-dimensional network. The crystal was a non-merohedral twin emulating tetra-gonal symmetry, but being in fact ortho-rhom-bic.

Entities: Chemical Disease Species

Year: 2009 PMID： 21583764 PMCID： PMC2977578 DOI： 10.1107/S1600536809013270

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

Related literature

For the biological activity of 4-aminopyridine, see: Judge & Bever (2006 ▶); Schwid et al. (1997 ▶); Strupp et al. (2004 ▶). For related structures, see: Anderson et al. (2005 ▶); Chao & Schempp (1977 ▶); Jebas et al. (2006 ▶); Zhang et al. (2005 ▶). For bond-length data, see: Anderson et al. (2005 ▶).

Experimental

Crystal data

(C5H7N2)2[CoCl4] M = 390.98 Orthorhombic, a = 15.0051 (12) Å b = 14.9751 (12) Å c = 7.1723 (6) Å V = 1611.6 (2) Å3 Z = 4 Mo Kα radiation μ = 1.72 mm−1 T = 173 K 0.25 × 0.22 × 0.17 mm

Data collection

Bruker APEXII SMART CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.650, T max = 0.746 45299 measured reflections 3884 independent reflections 3802 reflections with I > 2σ(I) R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.021 wR(F 2) = 0.052 S = 1.02 3884 reflections 173 parameters H-atom parameters constrained Δρmax = 0.25 e Å−3 Δρmin = −0.13 e Å−3 Absolute structure: Flack (1983 ▶), 1654 Friedel pairs Flack parameter: −0.12 (2) Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 ▶). Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013270/bt2925sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013270/bt2925Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C₅H₇N₂)₂[CoCl₄]	F(000) = 788
M_r = 390.98	D_x = 1.611 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9192 reflections
a = 15.0051 (12) Å	θ = 2.7–27.8°
b = 14.9751 (12) Å	µ = 1.72 mm⁻¹
c = 7.1723 (6) Å	T = 173 K
V = 1611.6 (2) Å³	Block, blue
Z = 4	0.25 × 0.22 × 0.17 mm

Bruker APEXII SMART CCD diffractometer	3884 independent reflections
Radiation source: sealed Tube	3802 reflections with I > 2σ(I)
graphite	R_int = 0.035
CCD scan	θ_max = 28.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −19→19
T_min = 0.650, T_max = 0.746	k = −19→19
45299 measured reflections	l = −9→9

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)] = 0.021	H-atom parameters constrained
wR(F²) = 0.052	w = 1/[σ²(F_o²) + (0.0281P)² + 0.361P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3884 reflections	Δρ_max = 0.25 e Å⁻³
173 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1654 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.12 (2)

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. Structure was refined as tetragonal twin with basf=0.34063

	x	y	z	U_iso*/U_eq
Co1	0.49922 (2)	0.24481 (2)	0.37955 (6)	0.02580 (7)
Cl1	0.45208 (4)	0.12712 (5)	0.20160 (11)	0.03485 (16)
Cl2	0.59477 (5)	0.18722 (5)	0.59594 (11)	0.03872 (17)
Cl3	0.38406 (6)	0.30281 (5)	0.54058 (11)	0.04194 (19)
Cl4	0.56931 (5)	0.33990 (5)	0.18373 (14)	0.04232 (17)
C1	0.19394 (17)	0.06484 (18)	0.2826 (4)	0.0289 (5)
C2	0.2459 (2)	−0.0132 (2)	0.2552 (4)	0.0337 (6)
H2	0.3091	−0.0095	0.2540	0.040*
C3	0.2050 (2)	−0.0935 (2)	0.2307 (4)	0.0379 (7)
H3	0.2400	−0.1455	0.2116	0.045*
N4	0.11624 (18)	−0.10010 (17)	0.2331 (3)	0.0413 (6)
H4	0.0873	−0.1508	0.2248	0.050*
C5	0.0644 (2)	−0.0280 (2)	0.2604 (4)	0.0403 (7)
H5	0.0015	−0.0348	0.2631	0.048*
C6	0.10048 (18)	0.0545 (2)	0.2843 (4)	0.0342 (6)
H6	0.0630	0.1049	0.3021	0.041*
N7	0.23233 (15)	0.14446 (15)	0.3030 (4)	0.0382 (5)
H7A	0.2002	0.1883	0.3330	0.057*
H7B	0.2909	0.1553	0.2895	0.057*
C8	0.32310 (18)	0.44022 (18)	0.0283 (4)	0.0289 (5)
C9	0.3084 (2)	0.34727 (18)	0.0205 (4)	0.0326 (6)
H9	0.3562	0.3066	0.0389	0.039*
C10	0.2245 (2)	0.3171 (2)	−0.0139 (4)	0.0398 (7)
H10	0.2142	0.2546	−0.0204	0.048*
N11	0.15584 (17)	0.37337 (19)	−0.0389 (3)	0.0418 (6)
H11	0.1000	0.3568	−0.0377	0.050*
C12	0.1679 (2)	0.4632 (2)	−0.0254 (4)	0.0382 (7)
H12	0.1183	0.5021	−0.0385	0.046*
C13	0.24960 (17)	0.4974 (3)	0.0064 (4)	0.0331 (6)
H13	0.2575	0.5602	0.0140	0.040*
N14	0.40431 (15)	0.47315 (16)	0.0593 (3)	0.0375 (5)
H14A	0.4522	0.4383	0.0767	0.056*
H14B	0.4130	0.5288	0.0656	0.056*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02267 (19)	0.0223 (2)	0.03247 (13)	0.00081 (16)	−0.00149 (13)	−0.00034 (12)
Cl1	0.0261 (3)	0.0370 (4)	0.0415 (4)	−0.0058 (2)	0.0005 (3)	−0.0129 (3)
Cl2	0.0389 (4)	0.0279 (3)	0.0493 (4)	0.0002 (2)	−0.0190 (3)	0.0004 (3)
Cl3	0.0407 (4)	0.0315 (4)	0.0536 (4)	0.0119 (3)	0.0134 (3)	0.0012 (3)
Cl4	0.0296 (3)	0.0346 (4)	0.0628 (4)	−0.0003 (3)	0.0073 (3)	0.0151 (3)
C1	0.0278 (13)	0.0327 (14)	0.0263 (13)	0.0030 (10)	−0.0015 (11)	0.0023 (11)
C2	0.0296 (15)	0.0333 (15)	0.0383 (15)	0.0032 (11)	0.0010 (11)	0.0018 (13)
C3	0.0486 (17)	0.0302 (14)	0.0349 (15)	0.0031 (12)	−0.0027 (13)	−0.0019 (11)
N4	0.0536 (15)	0.0364 (13)	0.0338 (12)	−0.0155 (11)	−0.0055 (11)	0.0029 (10)
C5	0.0334 (16)	0.0515 (17)	0.0359 (15)	−0.0080 (13)	−0.0017 (12)	0.0069 (12)
C6	0.0289 (14)	0.0408 (16)	0.0329 (14)	0.0033 (11)	−0.0021 (12)	0.0026 (12)
N7	0.0303 (11)	0.0273 (12)	0.0570 (15)	0.0018 (8)	0.0002 (11)	0.0017 (11)
C8	0.0279 (13)	0.0328 (13)	0.0261 (12)	0.0014 (10)	0.0004 (11)	0.0015 (11)
C9	0.0403 (15)	0.0260 (13)	0.0317 (13)	0.0018 (11)	0.0001 (12)	0.0001 (11)
C10	0.0500 (17)	0.0372 (17)	0.0321 (14)	−0.0146 (14)	0.0024 (13)	−0.0031 (12)
N11	0.0305 (12)	0.0627 (17)	0.0322 (11)	−0.0136 (12)	−0.0010 (10)	−0.0001 (12)
C12	0.0342 (15)	0.0499 (18)	0.0304 (14)	0.0011 (12)	0.0018 (12)	0.0038 (13)
C13	0.0307 (14)	0.0327 (16)	0.0357 (14)	0.0041 (10)	0.0040 (13)	0.0027 (11)
N14	0.0279 (11)	0.0295 (11)	0.0550 (15)	−0.0007 (8)	−0.0018 (11)	−0.0008 (10)

Co1—Cl3	2.2527 (8)	N7—H7A	0.8422
Co1—Cl4	2.2597 (8)	N7—H7B	0.8984
Co1—Cl2	2.2822 (8)	C8—N14	1.333 (3)
Co1—Cl1	2.2880 (8)	C8—C13	1.405 (4)
C1—N7	1.332 (3)	C8—C9	1.410 (4)
C1—C6	1.411 (4)	C9—C10	1.360 (4)
C1—C2	1.419 (4)	C9—H9	0.9500
C2—C3	1.361 (4)	C10—N11	1.344 (4)
C2—H2	0.9500	C10—H10	0.9500
C3—N4	1.335 (4)	N11—C12	1.360 (4)
C3—H3	0.9500	N11—H11	0.8737
N4—C5	1.345 (4)	C12—C13	1.348 (4)
N4—H4	0.8772	C12—H12	0.9500
C5—C6	1.359 (4)	C13—H13	0.9500
C5—H5	0.9500	N14—H14A	0.8967
C6—H6	0.9500	N14—H14B	0.8440

Cl3—Co1—Cl4	115.64 (3)	C1—N7—H7A	118.5
Cl3—Co1—Cl2	106.20 (4)	C1—N7—H7B	124.9
Cl4—Co1—Cl2	111.62 (3)	H7A—N7—H7B	116.6
Cl3—Co1—Cl1	110.24 (3)	N14—C8—C13	120.7 (3)
Cl4—Co1—Cl1	106.41 (4)	N14—C8—C9	121.0 (2)
Cl2—Co1—Cl1	106.41 (3)	C13—C8—C9	118.3 (3)
N7—C1—C6	121.8 (2)	C10—C9—C8	118.7 (3)
N7—C1—C2	121.0 (3)	C10—C9—H9	120.7
C6—C1—C2	117.2 (3)	C8—C9—H9	120.7
C3—C2—C1	119.8 (3)	N11—C10—C9	121.7 (3)
C3—C2—H2	120.1	N11—C10—H10	119.1
C1—C2—H2	120.1	C9—C10—H10	119.1
N4—C3—C2	121.0 (3)	C10—N11—C12	120.6 (3)
N4—C3—H3	119.5	C10—N11—H11	123.8
C2—C3—H3	119.5	C12—N11—H11	114.0
C3—N4—C5	121.2 (3)	C13—C12—N11	120.6 (3)
C3—N4—H4	123.8	C13—C12—H12	119.7
C5—N4—H4	114.8	N11—C12—H12	119.7
N4—C5—C6	121.2 (3)	C12—C13—C8	120.1 (3)
N4—C5—H5	119.4	C12—C13—H13	120.0
C6—C5—H5	119.4	C8—C13—H13	120.0
C5—C6—C1	119.6 (3)	C8—N14—H14A	122.7
C5—C6—H6	120.2	C8—N14—H14B	121.0
C1—C6—H6	120.2	H14A—N14—H14B	116.3

N7—C1—C2—C3	−178.6 (3)	N14—C8—C9—C10	−179.2 (3)
C6—C1—C2—C3	0.5 (4)	C13—C8—C9—C10	2.2 (4)
C1—C2—C3—N4	−0.4 (4)	C8—C9—C10—N11	−0.5 (4)
C2—C3—N4—C5	−0.2 (5)	C9—C10—N11—C12	−1.8 (4)
C3—N4—C5—C6	0.8 (4)	C10—N11—C12—C13	2.5 (5)
N4—C5—C6—C1	−0.7 (4)	N11—C12—C13—C8	−0.8 (4)
N7—C1—C6—C5	179.1 (3)	N14—C8—C13—C12	179.8 (3)
C2—C1—C6—C5	0.0 (4)	C9—C8—C13—C12	−1.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···Cl2ⁱ	0.88	2.94	3.563 (3)	130
N4—H4···Cl3ⁱ	0.88	2.67	3.335 (3)	134
N7—H7A···Cl2ⁱⁱ	0.84	2.50	3.338 (2)	175
N7—H7B···Cl1	0.90	2.53	3.387 (2)	158
N11—H11···Cl1ⁱⁱⁱ	0.87	2.52	3.272 (3)	144
N14—H14B···Cl2^iv	0.84	2.64	3.394 (3)	149
N14—H14A···Cl4	0.90	2.42	3.303 (2)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯Cl2ⁱ	0.88	2.94	3.563 (3)	130
N4—H4⋯Cl3ⁱ	0.88	2.67	3.335 (3)	134
N7—H7A⋯Cl2ⁱⁱ	0.84	2.50	3.338 (2)	175
N7—H7B⋯Cl1	0.90	2.53	3.387 (2)	158
N11—H11⋯Cl1ⁱⁱⁱ	0.87	2.52	3.272 (3)	144
N14—H14B⋯Cl2^iv	0.84	2.64	3.394 (3)	149
N14—H14A⋯Cl4	0.90	2.42	3.303 (2)	169

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

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1. A short history of SHELX.

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Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Quantitative assessment of sustained-release 4-aminopyridine for symptomatic treatment of multiple sclerosis.

Authors: S R Schwid; M D Petrie; M P McDermott; D S Tierney; D H Mason; A D Goodman
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3. Treatment of episodic ataxia type 2 with the potassium channel blocker 4-aminopyridine.

Authors: M Strupp; R Kalla; M Dichgans; T Freilinger; S Glasauer; T Brandt
Journal: Neurology Date: 2004-05-11 Impact factor: 9.910

Review 4. Potassium channel blockers in multiple sclerosis: neuronal Kv channels and effects of symptomatic treatment.

Authors: Susan I V Judge; Christopher T Bever
Journal: Pharmacol Ther Date: 2006-02-09 Impact factor: 12.310

5. Structure validation in chemical crystallography.

Authors: Anthony L Spek
Journal: Acta Crystallogr D Biol Crystallogr Date: 2009-01-20