Benzene-1,2-diaminium bis­(hydrogen phospho­nate)

Zahid, M.; Akilan, R.; Ganesh, T.; Kumar, R.M.; Chakkaravarthi, G.

doi:10.1107/S2414314616015911

organic compounds

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ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161591

https://doi.org/10.1107/S2414314616015911

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Benzene-1,2-diaminium bis(hydrogen phosphonate)

Md. Zahid,^a R. Akilan,^b T. Ganesh,^a ^* R. Mohan Kumar ^a and G. Chakkaravarthi ^c ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bDepartment of Physics, Aksheyaa College of Engineering, Kancheepuram 603 314, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: ntganesh@yahoo.co.in, chakkaravarthi_2005@yahoo.com

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 5 October 2016; accepted 8 October 2016; online 14 October 2016)

The asymmetric unit of the title molecular salt, C₆H₁₀N₂²⁺·2H₂PO₃⁻, contains half of a benzene-1,2-diaminium cation and a phosphite anion, the complete cation being generated by a crystallographic mirror plane. In the crystal, N—H⋯O hydrogen bonds generate R₂²(9) and R₂²(8) ring motifs and O—H⋯O hydrogen bonds generate an R₂²(8) ring motif. Overall, these generate a three-dimensional framework. The crystal structure also features π–π interactions [centroid-to-centroid distance = 3.8642 (7) Å].

Keywords: crystal structure; molecular salt; hydrogen bonding.

CCDC reference: 1508896

Structure description

Inorganic-organic hybrid compounds provide a class of materials with interesting potential technological applications (Dai et al., 2002 ). We report herein the synthesis and the crystal structure of the title molecular salt (Fig. 1). The salt contains half of a benzene-1,2-diaminium cation and a phosphite anion in the asymmetric unit, the complete cation being generated by a crystallographic mirror plane. The cation is protonated at the amine N atoms and the anion is deprotonated at a hydroxyl O atom. Bond lengths are comparable with those found in related structures (Idrissi et al., 2002 ; Soudani et al., 2013 ).

Figure 1
The molecular structure of the title molecular salt, with atom labelling and 30% probability displacement ellipsoids. [Symmetry code: (a) 1 − x, y, $[{3\over 2}]$ − z.]

In the crystal, classical N—H⋯O and O—H⋯O hydrogen bonds (Table 1, Fig. 2) which link the adjacent ions into an infinite three dimensional framework. The N1—H1A⋯O1 and N1—H1C⋯O3 hydrogen bonds generate an R₂²(9) ring motif while an R₂²(8) ring motif is generated by N1—H1C⋯O3 and N1—H1B⋯O3 hydrogen bonds and the O2—H2A⋯O1 hydrogen bonds generate an R₂²(8) ring motif (Table 1, Fig. 3). The crystal structure also features π–π interactions [Cg1⋯Cg1ⁱ, Cg1⋯Cg1ⁱⁱ, Cg1⋯Cg1ⁱⁱⁱ and Cg1⋯Cg1^iv with equal distances of 3.8642 (7) Å; Cg1 is the centroid of the C1/C2/C3/C1a/C2a/C3a ring; symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 1 − x, 1 − y, 2 − z; (iii) x, 1 − y, − $[{1\over 2}]$ + z; (iv) x, 1 − y, $[{1\over 2}]$ + z].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.88 (2)	1.85 (2)	2.7217 (14)	171 (2)
N1—H1B⋯O3ⁱⁱ	0.87 (1)	1.87 (1)	2.7220 (13)	165 (1)
N1—H1C⋯O3ⁱⁱⁱ	0.86 (2)	1.87 (2)	2.7193 (14)	169 (1)
O2—H2A⋯O1^iv	0.81 (2)	1.80 (2)	2.5959 (14)	166 (2)
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x, -y+1, -z+1.

Figure 2
The crystal packing of the title molecular salt viewed along the c axis. The hydrogen bonds are shown as dashed lines. H atoms not involving in hydrogen bonding have been omitted for clarity.

Figure 3
A partial view of the crystal packing showing different ring motifs.

Synthesis and crystallization

o-Phenlyenediamine (0.5 g) and phosphorous acid (1.6 g) were dissolved in 10 ml of Millipore water and allowed to evaporate slowly at room temperature. Good quality crystals suitable for X-ray intensity data collection were collected after a period of one week.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₁₀N₂²⁺·2H₂PO₃⁻
M_r	272.13
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	13.6564 (6), 12.3755 (4), 7.7281 (3)
β (°)	117.586 (1)
V (Å³)	1157.61 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.39
Crystal size (mm)	0.26 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.699, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	8958, 2065, 1822
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.766

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.092, 1.07
No. of reflections	2065
No. of parameters	93
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.28
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1508896

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616015911/vm4016sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616015911/vm4016Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616015911/vm4016Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015) and PLATON (Spek, 2009).

Benzene-1,2-diaminium bis(hydrogen phosphonate) top

Crystal data top

C₆H₁₀N₂²⁺·2H₂PO₃⁻	F(000) = 568
M_r = 272.13	D_x = 1.561 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.6564 (6) Å	Cell parameters from 4562 reflections
b = 12.3755 (4) Å	θ = 2.9–32.4°
c = 7.7281 (3) Å	µ = 0.39 mm⁻¹
β = 117.586 (1)°	T = 295 K
V = 1157.61 (8) Å³	Block, colourless
Z = 4	0.26 × 0.24 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1822 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.021
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 33.0°, θ_min = 2.4°
T_min = 0.699, T_max = 0.747	h = −18→20
8958 measured reflections	k = −18→18
2065 independent reflections	l = −11→11

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.0546P)² + 0.3312P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.092	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.35 e Å⁻³
2065 reflections	Δρ_min = −0.28 e Å⁻³
93 parameters	Extinction correction: SHELXL2016 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
4 restraints	Extinction coefficient: 0.0168 (18)

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.

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

	x	y	z	U_iso*/U_eq
C1	0.44886 (8)	0.40189 (8)	0.66686 (14)	0.02418 (18)
C2	0.39713 (9)	0.49869 (9)	0.58591 (17)	0.0325 (2)
H2	0.328163	0.498858	0.476438	0.039*
C3	0.44871 (12)	0.59530 (9)	0.6689 (2)	0.0408 (3)
H3	0.414075	0.660483	0.615223	0.049*
N1	0.39441 (7)	0.30090 (7)	0.57724 (13)	0.02768 (18)
O1	0.00568 (7)	0.64051 (7)	0.50188 (13)	0.0394 (2)
O2	0.15544 (8)	0.49792 (7)	0.63278 (16)	0.0452 (2)
O3	0.20193 (7)	0.68978 (7)	0.73819 (12)	0.0366 (2)
P1	0.12641 (2)	0.61846 (2)	0.57358 (4)	0.02759 (10)
H1	0.1469 (14)	0.6272 (12)	0.429 (2)	0.040 (4)*
H1A	0.4365 (11)	0.2541 (11)	0.558 (2)	0.039 (4)*
H1B	0.3384 (9)	0.3133 (11)	0.4632 (14)	0.031 (3)*
H1C	0.3696 (12)	0.2700 (12)	0.649 (2)	0.040 (4)*
H2A	0.1013 (12)	0.4605 (15)	0.573 (3)	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0213 (4)	0.0239 (4)	0.0272 (4)	0.0007 (3)	0.0111 (3)	0.0009 (3)
C2	0.0324 (5)	0.0294 (5)	0.0371 (5)	0.0081 (4)	0.0172 (4)	0.0080 (4)
C3	0.0518 (7)	0.0244 (5)	0.0538 (7)	0.0067 (4)	0.0308 (6)	0.0068 (5)
N1	0.0201 (4)	0.0267 (4)	0.0277 (4)	−0.0007 (3)	0.0039 (3)	0.0014 (3)
O1	0.0259 (4)	0.0282 (4)	0.0485 (5)	0.0018 (3)	0.0041 (3)	−0.0065 (3)
O2	0.0287 (4)	0.0268 (4)	0.0617 (6)	0.0019 (3)	0.0053 (4)	0.0001 (4)
O3	0.0281 (4)	0.0352 (4)	0.0350 (4)	−0.0029 (3)	0.0048 (3)	−0.0104 (3)
P1	0.02555 (15)	0.02557 (15)	0.02480 (14)	−0.00026 (8)	0.00585 (10)	−0.00370 (8)

Geometric parameters (Å, º) top

C1—C2	1.3843 (13)	N1—H1B	0.872 (9)
C1—C1ⁱ	1.3928 (19)	N1—H1C	0.861 (9)
C1—N1	1.4552 (12)	O1—P1	1.5012 (9)
C2—C3	1.3852 (17)	O2—P1	1.5569 (9)
C2—H2	0.9300	O2—H2A	0.811 (9)
C3—C3ⁱ	1.381 (3)	O3—P1	1.4987 (8)
C3—H3	0.9300	P1—H1	1.276 (16)
N1—H1A	0.876 (9)

C2—C1—C1ⁱ	120.05 (6)	H1A—N1—H1B	106.3 (14)
C2—C1—N1	119.13 (9)	C1—N1—H1C	110.0 (11)
C1ⁱ—C1—N1	120.81 (5)	H1A—N1—H1C	107.5 (15)
C1—C2—C3	119.61 (11)	H1B—N1—H1C	107.8 (14)
C1—C2—H2	120.2	P1—O2—H2A	109.8 (15)
C3—C2—H2	120.2	O3—P1—O1	114.38 (5)
C3ⁱ—C3—C2	120.32 (7)	O3—P1—O2	109.47 (5)
C3ⁱ—C3—H3	119.8	O1—P1—O2	111.67 (5)
C2—C3—H3	119.8	O3—P1—H1	110.5 (7)
C1—N1—H1A	114.7 (10)	O1—P1—H1	108.1 (8)
C1—N1—H1B	110.2 (9)	O2—P1—H1	102.1 (7)

C1ⁱ—C1—C2—C3	1.30 (18)	C1—C2—C3—C3ⁱ	0.2 (2)
N1—C1—C2—C3	−179.38 (10)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱⁱ	0.88 (2)	1.85 (2)	2.7217 (14)	171 (2)
N1—H1B···O3ⁱⁱⁱ	0.87 (1)	1.87 (1)	2.7220 (13)	165 (1)
N1—H1C···O3^iv	0.86 (2)	1.87 (2)	2.7193 (14)	169 (1)
O2—H2A···O1^v	0.81 (2)	1.80 (2)	2.5959 (14)	166 (2)

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

Acknowledgements

The authors acknowledge the SAIF, IIT, Madras, for the data collection.

References

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