Propane-1,3-diammonium dichromate(VI)

Trabelsi, S.; Marouani, H.; Al-Deyab, S.S.; Rzaigui, M.

doi:10.1107/S1600536812031042

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page m1056

https://doi.org/10.1107/S1600536812031042

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Propane-1,3-diammonium dichromate(VI)

Sonia Trabelsi,^a Houda Marouani,^a ^* Salem S. Al-Deyab ^b and Mohamed Rzaigui ^a

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and ^bPetrochemical Research Chair, College of Science, King Saud University, Riyadh, Saudi Arabia
^*Correspondence e-mail: houda_marouani@voila.fr

(Received 25 June 2012; accepted 7 July 2012; online 14 July 2012)

The title compound, (C₃H₁₂N₂)[Cr₂O₇], consists of a discrete dichromate anion with an eclipsed conformation and a propane-1,3-diammonium cation. Both kinds of ions have a mirror plane passing through the bridging O atom and the central methylene C atom of the Cr₂O₇²⁻ and C₃H₁₂N₂²⁺ moieties, respectively. Anions and cations are alternately stacked to form columns parallel to the b axis. Ions are linked by intra- and inter-column hydrogen bonds of types N—H⋯O and C—H⋯O, involving O atoms of the dichromate anions as acceptors, and ammonium or methylene groups as donors.

Related literature

For related structures, see: Akriche & Rzaigui (2009 ); Sieroń (2007 ); Khadhrani et al. (2006 ); Kallel et al. (1980 ); Pritchard et al. (1992 ). For a discussion on hydrogen bonding, see: Brown (1976 ); Blessing (1986 ). For background on Cr^VI species as industrial waste, see: Wani et al. (2007 ).

Experimental

Crystal data

(C₃H₁₂N₂)[Cr₂O₇]
M_r = 292.15
Orthorhombic, P n m a
a = 8.818 (2) Å
b = 13.764 (2) Å
c = 7.918 (2) Å
V = 961.1 (4) Å³
Z = 4
Ag Kα radiation
λ = 0.56083 Å
μ = 1.18 mm⁻¹
T = 293 K
0.30 × 0.15 × 0.10 mm

Data collection

Enraf–Nonius CAD4 diffractometer
4877 measured reflections
2430 independent reflections
1811 reflections with I > 2σ(I)
R_int = 0.020
2 standard reflections every 120 min intensity decay: 3%

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.096
S = 1.10
2430 reflections
69 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.89	2.12	2.9609 (19)	156
N1—H1B⋯O2ⁱⁱ	0.89	1.99	2.8168 (19)	154
N1—H1C⋯O4	0.89	2.17	2.955 (2)	147
N1—H1C⋯O2ⁱⁱⁱ	0.89	2.44	2.9844 (19)	120
C1—H1D⋯O3	0.97	2.51	3.405 (2)	153
C1—H1E⋯O2^iv	0.97	2.59	3.176 (2)	119
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) $[-x+{\script{3\over 2}}, -y, z-{\script{1\over 2}}]$ ; (iv) x, y, z-1.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812031042/bh2445sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031042/bh2445Isup2.hkl

checkCIF report

Comment top

Hexavalent chromium is a predominant waste product of several metal finishing, petroleum refining and steel industries (Wani et al., 2007). It exists as chromate in basic and neutral medium and as dichromate in acidic environment.

In presence of 1,3-diaminopropane in water, the chromic acid is condensed into dichromate to form the hybrid title compound, (C₃H₁₂N₂)Cr₂O₇. The observed molecular structure is depicted in Fig. 1. To counter-balance the electric charge of Cr₂O₇^2-, the used 1,3-diaminopropane has been doubly protonated. The title compound crystallizes in the orthorhombic Pnma space group, so that the dichromate anion and 1,3-diammoniumpropane should be symmetrical with respect to the symmetry plane (m). Owing of the passage of the latter through the bridging atoms O1 and C2 of Cr₂O₇ and C₃H₁₂N₂ respectively, the asymmetric unit is built by one independent CrO₄ group and the half of a 1,3-diammoniumpropane cation. The main geometrical features of Cr₂O₇^2- agree with those previously observed for this group in other compounds (Akriche & Rzaigui, 2009; Sieroń, 2007; Khadhrani et al., 2006).

The bond lengths and the angles within the cation are comparable with those observed in other 1,3-diammoniumpropane salts such as [C₃H₁₂N₂]ZnCl₄ (Kallel et al., 1980) and [C₃H₁₂N₂](ClO₄)₂ (Pritchard et al., 1992). In this structure, the cations and anions are alternately stacked to form columns parallel to the axis b (Fig. 2). The electrostatic interactions and H-bonds intra and inter columns keep up the three-dimensional network cohesion. The established weak H-bonds (Brown, 1976; Blessing, 1986) of types N—H···O and C—H···O involve oxygen atoms of the dichromate anions as acceptors, and the protonated nitrogen atoms and carbon atoms of 1,3-diammoniumpropane as donors.

Related literature top

For related structures, see: Akriche & Rzaigui (2009); Sieroń (2007); Khadhrani et al. (2006); Kallel et al. (1980); Pritchard et al. (1992). For a discussion on hydrogen bonding, see: Brown (1976); Blessing (1986). For background on Cr^VI species as industrial waste, see: Wani et al. (2007).

Experimental top

Single crystals of the title compound were prepared at room temperature by dissolving CrO₃ (0.10 g, 1 mmol) and 1,3-diaminopropane (0.07 g, 1 mmol) in distilled water (20 ml). The resulting solution was stirred during 30 min. and then evaporated slowly at room temperature until the formation of orange prismatic single crystals.

Structure description top

For related structures, see: Akriche & Rzaigui (2009); Sieroń (2007); Khadhrani et al. (2006); Kallel et al. (1980); Pritchard et al. (1992). For a discussion on hydrogen bonding, see: Brown (1976); Blessing (1986). For background on Cr^VI species as industrial waste, see: Wani et al. (2007).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures top

	Fig. 1. An ORTEP view of the title compound with displacement ellipsoids at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Symmetry code: (i) x, y-1, z
	Fig. 2. Projection of the crystal structure along the c axis.

Propane-1,3-diammonium dichromate(VI) top

Crystal data top

(C₃H₁₂N₂)[Cr₂O₇]	F(000) = 592
M_r = 292.15	D_x = 2.019 Mg m⁻³
Orthorhombic, Pnma	Ag Kα radiation, λ = 0.56083 Å
Hall symbol: -P 2ac 2n	Cell parameters from 25 reflections
a = 8.818 (2) Å	θ = 9–11°
b = 13.764 (2) Å	µ = 1.18 mm⁻¹
c = 7.918 (2) Å	T = 293 K
V = 961.1 (4) Å³	Prism, orange
Z = 4	0.30 × 0.15 × 0.10 mm

Data collection top

Enraf–Nonius CAD4 diffractometer	R_int = 0.020
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.3°
Graphite monochromator	h = −14→3
non–profiled ω scans	k = −23→3
4877 measured reflections	l = −3→13
2430 independent reflections	2 standard reflections every 120 min
1811 reflections with I > 2σ(I)	intensity decay: 3%

Refinement top

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)] = 0.032	H-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0502P)² + 0.243P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2430 reflections	Δρ_max = 0.79 e Å⁻³
69 parameters	Δρ_min = −0.61 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.024 (2)
Primary atom site location: structure-invariant direct methods

Crystal data top

(C₃H₁₂N₂)[Cr₂O₇]	V = 961.1 (4) Å³
M_r = 292.15	Z = 4
Orthorhombic, Pnma	Ag Kα radiation, λ = 0.56083 Å
a = 8.818 (2) Å	µ = 1.18 mm⁻¹
b = 13.764 (2) Å	T = 293 K
c = 7.918 (2) Å	0.30 × 0.15 × 0.10 mm

Data collection top

Enraf–Nonius CAD4 diffractometer	R_int = 0.020
4877 measured reflections	2 standard reflections every 120 min
2430 independent reflections	intensity decay: 3%
1811 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.10	Δρ_max = 0.79 e Å⁻³
2430 reflections	Δρ_min = −0.61 e Å⁻³
69 parameters

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

	x	y	z	U_iso*/U_eq
Cr	0.58026 (3)	0.131997 (16)	0.65346 (3)	0.01952 (8)
O2	0.59121 (13)	0.05330 (8)	0.80635 (15)	0.0271 (2)
O4	0.72115 (14)	0.11753 (9)	0.52532 (16)	0.0324 (3)
O3	0.42366 (14)	0.11686 (10)	0.55239 (19)	0.0388 (3)
O1	0.5853 (2)	0.2500	0.7434 (2)	0.0322 (4)
N1	0.66136 (15)	0.07105 (9)	0.16706 (17)	0.0263 (2)
H1A	0.7277	0.0716	0.0824	0.039*
H1B	0.6016	0.0192	0.1578	0.039*
H1C	0.7109	0.0687	0.2649	0.039*
C2	0.6661 (2)	0.2500	0.1633 (3)	0.0237 (3)
H2A	0.7327	0.2500	0.0658	0.028*
H2B	0.7285	0.2500	0.2642	0.028*
C1	0.56785 (16)	0.16037 (11)	0.16067 (19)	0.0231 (2)
H1D	0.4995	0.1615	0.2567	0.028*
H1E	0.5070	0.1601	0.0586	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cr	0.02104 (11)	0.01893 (11)	0.01860 (11)	−0.00012 (7)	−0.00096 (8)	0.00048 (7)
O2	0.0335 (5)	0.0232 (4)	0.0245 (4)	−0.0013 (4)	−0.0003 (4)	0.0043 (4)
O4	0.0308 (6)	0.0386 (6)	0.0277 (5)	0.0028 (4)	0.0079 (5)	0.0010 (5)
O3	0.0285 (6)	0.0481 (7)	0.0398 (7)	−0.0008 (5)	−0.0122 (5)	−0.0022 (6)
O1	0.0481 (10)	0.0202 (6)	0.0282 (7)	0.000	0.0002 (7)	0.000
N1	0.0279 (6)	0.0220 (5)	0.0289 (6)	0.0000 (5)	0.0022 (5)	0.0018 (5)
C2	0.0207 (8)	0.0216 (7)	0.0287 (9)	0.000	0.0028 (7)	0.000
C1	0.0206 (6)	0.0235 (6)	0.0252 (6)	−0.0010 (4)	−0.0002 (5)	−0.0005 (5)

Geometric parameters (Å, º) top

Cr—O3	1.6096 (13)	N1—H1C	0.8900
Cr—O4	1.6165 (13)	C2—C1	1.5077 (19)
Cr—O2	1.6274 (12)	C2—C1ⁱ	1.5077 (19)
Cr—O1	1.7740 (8)	C2—H2A	0.9700
O1—Crⁱ	1.7740 (8)	C2—H2B	0.9700
N1—C1	1.481 (2)	C1—H1D	0.9700
N1—H1A	0.8900	C1—H1E	0.9700
N1—H1B	0.8900

O3—Cr—O4	109.35 (8)	C1—C2—C1ⁱ	109.83 (17)
O3—Cr—O2	109.55 (7)	C1—C2—H2A	109.7
O4—Cr—O2	109.84 (6)	C1ⁱ—C2—H2A	109.7
O3—Cr—O1	109.85 (8)	C1—C2—H2B	109.7
O4—Cr—O1	110.21 (8)	C1ⁱ—C2—H2B	109.7
O2—Cr—O1	108.02 (7)	H2A—C2—H2B	108.2
Cr—O1—Crⁱ	132.57 (11)	N1—C1—C2	111.03 (13)
C1—N1—H1A	109.5	N1—C1—H1D	109.4
C1—N1—H1B	109.5	C2—C1—H1D	109.4
H1A—N1—H1B	109.5	N1—C1—H1E	109.4
C1—N1—H1C	109.5	C2—C1—H1E	109.4
H1A—N1—H1C	109.5	H1D—C1—H1E	108.0
H1B—N1—H1C	109.5

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱ	0.89	2.51	2.9326 (19)	110
N1—H1A···O3ⁱⁱⁱ	0.89	2.12	2.9609 (19)	156
N1—H1B···O2^iv	0.89	1.99	2.8168 (19)	154
N1—H1C···O4	0.89	2.17	2.955 (2)	147
N1—H1C···O2^v	0.89	2.44	2.9844 (19)	120
C1—H1D···O3	0.97	2.51	3.405 (2)	153
C1—H1E···O2ⁱⁱ	0.97	2.59	3.176 (2)	119

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

Experimental details

Crystal data
Chemical formula	(C₃H₁₂N₂)[Cr₂O₇]
M_r	292.15
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	8.818 (2), 13.764 (2), 7.918 (2)
V (Å³)	961.1 (4)
Z	4
Radiation type	Ag Kα, λ = 0.56083 Å
µ (mm⁻¹)	1.18
Crystal size (mm)	0.30 × 0.15 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD4
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4877, 2430, 1811
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.836

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.096, 1.10
No. of reflections	2430
No. of parameters	69
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.61

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and 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—H1A···O3ⁱ	0.89	2.12	2.9609 (19)	156.3
N1—H1B···O2ⁱⁱ	0.89	1.99	2.8168 (19)	153.5
N1—H1C···O4	0.89	2.17	2.955 (2)	146.7
N1—H1C···O2ⁱⁱⁱ	0.89	2.44	2.9844 (19)	119.5
C1—H1D···O3	0.97	2.51	3.405 (2)	153.1
C1—H1E···O2^iv	0.97	2.59	3.176 (2)	119.1

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

Acknowledgements

This work was supported by the Tunisian Ministry of H.E.Sc.R. The authors are also grateful to the Deanship of Scientific Research at King Saud University for funding the paper through the Research Group Project No. RGP-VPP-089.

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