Bis(2-amino-3-nitro­pyridinium) dichromate(VI)

Akriche, S.; Rzaigui, M.

doi:10.1107/S1600536808043018

metal-organic compounds

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Volume 65| Part 1| January 2009| Page m123

doi:10.1107/S1600536808043018

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Bis(2-amino-3-nitropyridinium) dichromate(VI)

Samah Akriche ^a ^* and Mohamed Rzaigui ^a

^aLaboratoire de chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia
^*Correspondence e-mail: samah.akriche@fsb.rnu.tn

(Received 12 December 2008; accepted 17 December 2008; online 20 December 2008)

The title compound, (C₅H₆N₃O₂)₂[Cr₂O₇], consists of 2-amino-3-nitropyridinium cations and discrete dichromate anions linked together by N—H⋯O and C—H⋯O hydrogen bonds, forming thick layers parallel to (101). Layer cohesion is ensured by N—H⋯O hydrogen bonding in addition to electrostatic and van der Waals interactions, forming a three-dimensional framework. The dichromate anion is located on a twofold axis that passes through its bridging O atom.

Related literature

For related structures, see: Akriche & Rzaigui (2000 ); Khadhrani et al. (2006 ); Nicoud et al. (1997 ); Panunto et al. (1987 ); Sieroń (2007 ); Le Fur et al. (1998 ). For a discussion of hydrogen bonding, see: Desiraju (1989 , 1995 ).

Experimental

Crystal data

(C₅H₆N₃O₂)₂[Cr₂O₇]
M_r = 496.26
Monoclinic, C 2/c
a = 14.799 (2) Å
b = 7.464 (3) Å
c = 17.870 (5) Å
β = 116.71 (4)°
V = 1763.3 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.31 mm⁻¹
T = 298 K
0.25 × 0.23 × 0.19 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: none
3444 measured reflections
2123 independent reflections
1562 reflections with I > 2σ(I)
R_int = 0.021
2 standard reflections frequency: 120 min intensity decay: 3%

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.106
S = 1.04
2123 reflections
132 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	1.87	2.707 (3)	165
N2—H2A⋯O4	0.86	2.17	2.974 (4)	155
N2—H2B⋯O6	0.86	2.06	2.654 (4)	125
N2—H2B⋯O6ⁱ	0.86	2.59	3.061 (4)	116
C3—H3⋯O4ⁱⁱ	0.93	2.58	3.494 (4)	167
C4—H4⋯O3ⁱⁱⁱ	0.93	2.50	3.337 (4)	150
C5—H5⋯O2^iv	0.93	2.34	3.232 (4)	160
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-32 for Windows (Farrugia, 1998 ); DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808043018/dn2417sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043018/dn2417Isup2.hkl

checkCIF report

Comment top

A new engineering strategy using organic-inorganic hybrid materials have appeared over the past years. The challenge was to combine the advantages of organic crystals and those of the inorganic materials. As a part of our study of crystal packing in amino-nitro "push-pull" system, a new organic-inorganic salt, bis (2-amino-3-nitropyridinium) dichromate (I) have been synthesized.

The dichromate anion has a binary internal symmetry since its bridging oxygen atom is located on a twofold axis, and so is built by only one independent (CrO₄) group. This later with one independent (2-NH₂-3-NO₂C₅H₃NH)₊ cation constitute the asymmetric unit of (I) (Fig. 1).

As expected, the main geometrical features of anion agree with those previously observed for this group in other coumpounds (Sieroń, 2007; Khadhrani et al.,2006). The bond lengths and the angles within the cation are comparable with those observed for 2-amino-3-nitropyridinium dihydrogenphosphate (Akriche et al.,2000), 2-amino-3-nitropyridinium hydrogensulfate(Le Fur et al., 1998) and 2-amino-3-nitropyridinium chloride (Nicoud et al.,1997).

The dichromate and organic entities manifest different interactions (electrostatic, H-bonds, Van Der Waals) to keep up the three-dimensionel network cohesion (Fig. 2). The main links are from the N—H···O bonds (Table 1) with H···O bond lengths falling in the range from 1.87–2.59 Å.

Long C—H···O contacts occur between cations and cation-anion moities with C···O bond lengths ranging from 3.494 (4)–3.232 (4)Å (Desiraju, 1989; Desiraju, 1995).

It's worth noticing the intracation contact N2—H2B···O6 (see Table 1 for symmetry code) which is always present in nitroaniline in which nitro and amino groups are ortho to one another, as clearly shown in a study of hydrogen patterns of nitroaniline derivatives (Panunto et al., 1987). This situation precludes the rotation of the nitro group with respect to pyridinium ring. The angle between the planes of the NO₂group and the heterocycle is 7.98° for cation, indicating a coplanar geometry.

Related literature top

For related structures, see: Akriche & Rzaigui (2000); Khadhrani et al. (2006); Nicoud et al. (1997); Panunto et al. (1987); Sieroń (2007); Le Fur, Masse & Nicoud (1998). For a discussion of hydrogen bonding, see: Desiraju (1989, 1995).

Experimental top

0.004 mol of 2-amino-3-nitropyridine was dissolved in 20 ml of pure acetic acid. 5 ml solution containing 0.004 mol of CrO₃ was added drop by drop under stirring at 333 K. The obtained solution is slowly evaporated at the ambiant temperature. After some days, Brown single crystals of the title compound are formed in the reactionnel midle.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-32 for Windows (Farrugia, 1998); DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures top

	Fig. 1. An ORTEP view of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are represented as dashed lines. [Symmetry code: (i) -x+1, y, -z+1/2]
	Fig. 2. Projection of (I) along the b axis.

Bis(2-amino-3-nitropyridinium) dichromate(VI) top

Crystal data top

(C₅H₆N₃O₂)₂[Cr₂O₇]	F(000) = 1000
M_r = 496.26	D_x = 1.869 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 14.799 (2) Å	θ = 9–11°
b = 7.464 (3) Å	µ = 1.31 mm⁻¹
c = 17.870 (5) Å	T = 298 K
β = 116.71 (4)°	Diamond-shaped, brown
V = 1763.3 (11) Å³	0.25 × 0.23 × 0.19 mm
Z = 4

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.021
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.6°
Graphite monochromator	h = −19→19
non–profiled ω scans	k = 0→9
3444 measured reflections	l = −10→23
2123 independent reflections	2 standard reflections every 120 min
1562 reflections with I > 2σ(I)	intensity decay: 3%

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0546P)² + 0.8978P] where P = (F_o² + 2F_c²)/3
2123 reflections	(Δ/σ)_max = 0.002
132 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

(C₅H₆N₃O₂)₂[Cr₂O₇]	V = 1763.3 (11) Å³
M_r = 496.26	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.799 (2) Å	µ = 1.31 mm⁻¹
b = 7.464 (3) Å	T = 298 K
c = 17.870 (5) Å	0.25 × 0.23 × 0.19 mm
β = 116.71 (4)°

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.021
3444 measured reflections	2 standard reflections every 120 min
2123 independent reflections	intensity decay: 3%
1562 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.04	Δρ_max = 0.44 e Å⁻³
2123 reflections	Δρ_min = −0.37 e Å⁻³
132 parameters

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 > 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.

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

	x	y	z	U_iso*/U_eq
Cr1	0.51253 (3)	0.65455 (6)	0.34930 (3)	0.03488 (15)
O1	0.5000	0.5931 (6)	0.2500	0.0760 (11)
O2	0.63121 (14)	0.6372 (3)	0.41598 (13)	0.0434 (5)
O3	0.4736 (2)	0.8522 (3)	0.35084 (18)	0.0672 (7)
O4	0.44934 (17)	0.5121 (3)	0.37400 (14)	0.0544 (6)
O5	0.7372 (2)	−0.1246 (3)	0.67939 (16)	0.0607 (7)
O6	0.6258 (2)	−0.0987 (3)	0.55077 (17)	0.0687 (7)
N1	0.70398 (18)	0.4291 (3)	0.55486 (16)	0.0416 (6)
H1	0.6730	0.5020	0.5139	0.050*
N2	0.58479 (19)	0.2213 (4)	0.47828 (16)	0.0544 (7)
H2A	0.5568	0.3004	0.4397	0.065*
H2B	0.5594	0.1155	0.4719	0.065*
N3	0.69260 (19)	−0.0377 (3)	0.61537 (17)	0.0425 (6)
C1	0.6667 (2)	0.2622 (4)	0.54739 (17)	0.0351 (6)
C2	0.72292 (19)	0.1482 (3)	0.61610 (16)	0.0317 (5)
C3	0.8061 (2)	0.2088 (4)	0.68474 (18)	0.0402 (6)
H3	0.8409	0.1320	0.7296	0.048*
C4	0.8388 (2)	0.3827 (4)	0.6881 (2)	0.0499 (8)
H4	0.8953	0.4252	0.7345	0.060*
C5	0.7856 (2)	0.4899 (4)	0.6213 (2)	0.0494 (8)
H5	0.8063	0.6077	0.6218	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr1	0.0320 (2)	0.0429 (3)	0.0274 (2)	0.0004 (2)	0.01125 (17)	0.00519 (19)
O1	0.073 (2)	0.122 (3)	0.0321 (17)	0.000	0.0232 (17)	0.000
O2	0.0357 (9)	0.0461 (11)	0.0406 (11)	−0.0011 (9)	0.0101 (9)	0.0065 (9)
O3	0.0642 (15)	0.0518 (14)	0.0762 (18)	0.0208 (12)	0.0233 (14)	0.0154 (12)
O4	0.0483 (12)	0.0604 (14)	0.0583 (13)	−0.0093 (11)	0.0272 (11)	0.0052 (11)
O5	0.0850 (18)	0.0428 (13)	0.0624 (15)	0.0050 (12)	0.0402 (15)	0.0172 (11)
O6	0.0712 (16)	0.0492 (13)	0.0703 (17)	−0.0253 (12)	0.0182 (14)	−0.0142 (12)
N1	0.0445 (13)	0.0357 (12)	0.0502 (15)	0.0080 (11)	0.0263 (12)	0.0123 (11)
N2	0.0428 (14)	0.0691 (18)	0.0389 (14)	−0.0034 (13)	0.0072 (12)	0.0105 (13)
N3	0.0505 (14)	0.0339 (12)	0.0511 (15)	−0.0035 (11)	0.0298 (12)	−0.0016 (12)
C1	0.0334 (12)	0.0418 (15)	0.0339 (14)	0.0036 (12)	0.0186 (11)	0.0044 (12)
C2	0.0343 (12)	0.0304 (12)	0.0323 (13)	0.0013 (11)	0.0168 (11)	0.0004 (11)
C3	0.0407 (14)	0.0429 (15)	0.0327 (14)	0.0044 (12)	0.0128 (12)	0.0036 (12)
C4	0.0453 (16)	0.0486 (18)	0.0464 (17)	−0.0110 (14)	0.0122 (14)	−0.0121 (14)
C5	0.0550 (18)	0.0321 (15)	0.068 (2)	−0.0080 (13)	0.0342 (17)	−0.0074 (14)

Geometric parameters (Å, º) top

Cr1—O3	1.588 (2)	N2—H2A	0.8600
Cr1—O4	1.603 (2)	N2—H2B	0.8600
Cr1—O2	1.625 (2)	N3—C2	1.457 (3)
Cr1—O1	1.7601 (14)	C1—C2	1.416 (4)
O1—Cr1ⁱ	1.7601 (14)	C2—C3	1.366 (4)
O5—N3	1.219 (3)	C3—C4	1.377 (4)
O6—N3	1.221 (4)	C3—H3	0.9300
N1—C5	1.336 (4)	C4—C5	1.356 (5)
N1—C1	1.344 (4)	C4—H4	0.9300
N1—H1	0.8600	C5—H5	0.9300
N2—C1	1.320 (4)

O3—Cr1—O4	110.50 (14)	N2—C1—N1	118.1 (3)
O3—Cr1—O2	110.01 (13)	N2—C1—C2	127.3 (3)
O4—Cr1—O2	108.49 (11)	N1—C1—C2	114.6 (2)
O3—Cr1—O1	112.62 (17)	C3—C2—C1	121.3 (3)
O4—Cr1—O1	107.14 (15)	C3—C2—N3	118.2 (2)
O2—Cr1—O1	107.93 (9)	C1—C2—N3	120.4 (2)
Cr1ⁱ—O1—Cr1	149.8 (3)	C2—C3—C4	120.5 (3)
C5—N1—C1	124.7 (3)	C2—C3—H3	119.7
C5—N1—H1	117.7	C4—C3—H3	119.7
C1—N1—H1	117.7	C5—C4—C3	117.7 (3)
C1—N2—H2A	120.0	C5—C4—H4	121.2
C1—N2—H2B	120.0	C3—C4—H4	121.2
H2A—N2—H2B	120.0	N1—C5—C4	121.1 (3)
O5—N3—O6	123.8 (3)	N1—C5—H5	119.4
O5—N3—C2	117.6 (3)	C4—C5—H5	119.4
O6—N3—C2	118.6 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.87	2.707 (3)	165
N2—H2A···O4	0.86	2.17	2.974 (4)	155
N2—H2B···O6	0.86	2.06	2.654 (4)	125
N2—H2B···O6ⁱⁱ	0.86	2.59	3.061 (4)	116
C3—H3···O4ⁱⁱⁱ	0.93	2.58	3.494 (4)	167
C4—H4···O3^iv	0.93	2.50	3.337 (4)	150
C5—H5···O2^v	0.93	2.34	3.232 (4)	160

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

Experimental details

Crystal data
Chemical formula	(C₅H₆N₃O₂)₂[Cr₂O₇]
M_r	496.26
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	14.799 (2), 7.464 (3), 17.870 (5)
β (°)	116.71 (4)
V (Å³)	1763.3 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.31
Crystal size (mm)	0.25 × 0.23 × 0.19

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3444, 2123, 1562
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.106, 1.04
No. of reflections	2123
No. of parameters	132
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.37

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-32 for Windows (Farrugia, 1998); DIAMOND (Brandenburg & Putz, 2005), WinGX publication routines (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.87	2.707 (3)	164.6
N2—H2A···O4	0.86	2.17	2.974 (4)	154.7
N2—H2B···O6	0.86	2.06	2.654 (4)	125.1
N2—H2B···O6ⁱ	0.86	2.59	3.061 (4)	115.8
C3—H3···O4ⁱⁱ	0.93	2.58	3.494 (4)	166.5
C4—H4···O3ⁱⁱⁱ	0.93	2.50	3.337 (4)	149.6
C5—H5···O2^iv	0.93	2.34	3.232 (4)	159.5

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

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doi:10.1107/S1600536808043018

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