4-Meth­oxy­benzyl­ammonium nitrate

Umarani, P.; Thiruvalluvar, A.; Ramachandra Raja, C.

doi:10.1107/S2414314617011142

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 8| August 2017| x171114

https://doi.org/10.1107/S2414314617011142

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4-Methoxybenzylammonium nitrate

P. Umarani,^a A. Thiruvalluvar ^b ^* and C. Ramachandra Raja ^a

^aDepartment of Physics, Government Arts College (Autonomous), Kumbakonam 612 002, Tamilnadu, India, and ^bPrincipal Government College for Women (Autonomous), Kumbakonam 612 001, Tamilnadu, India
^*Correspondence e-mail: thiruvalluvar.a@gmail.com

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 24 July 2017; accepted 27 July 2017; online 1 August 2017)

In the title salt, C₈H₁₂NO⁺·NO₃⁻, the 4-methoxybenzylammonium cation lies in the mirror plane m of space group Pnma and is thus planar by symmetry. The nitrate anion is also planar by symmetry, with an N O group in the mirror plane and one O atom in a general position. The dihedral angle between the benzene ring and the planar nitrate anion is constrained to be exactly 90°, because of the relative special positions for both ions. In the crystal, the cations are connected to the anions by C—H⋯O, C—H⋯N, N—H⋯N and N—H⋯O hydrogen bonds. Further, the crystal structure also features two C—H⋯π interactions involving the benzene ring of the cation, forming a three-dimensional network.

Keywords: crystal structure; salt; hydrogen bond; C—H⋯π interactions.

CCDC reference: 1565296

Structure description

Single crystals play an important role in non-linear optics. Non-linear optical materials have been of great interest among researchers in various applications such as laser frequency conversion, optical communication and optical data storage over the past few decades (Liu et al., 2015 ). Organic crystals possess greater non-linear susceptibility and fast response time, while inorganic crystals exhibit high mechanical and thermal properties (Vigneshwaran et al., 2017 ). Semi-organic crystals are expected to have the combined advantages of both organic and inorganic crystals. 4-Methoxybenzylamine based derivatives exhibit second order non-linear optical properties (Mahbouli Rhouma et al., 2016 ). These materials also possess antimicrobial activity (Joshi et al., 2014 ).

In the title salt, C₈H₁₂NO⁺·NO₃⁻ (Fig. 1), the 4-methoxybenzylammonium cation lies in the mirror m plane of space group Pnma (with some exceptions for H atoms bonded to tetrahedral sites: H1B, H1D and H8, which are in general positions). The cation is thus planar by symmetry. The nitrate anion is also planar, with atoms N2 and O3 placed in the mirror plane m. The dihedral angle between the benzene ring and the planar nitrate group is constrained to be exactly 90° by symmetry.

Figure 1
An ORTEP view of the title salt, with displacement ellipsoids drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dotted lines. [Symmetry codes: (i) x, $[{1\over 2}]$ − y, z; (ii) x, $[{3\over 2}]$ − y, z.]

In the crystal, analysis of potential hydrogen bonds shows that the cations are connected to the nitrate anions by C7—H7⋯O3, C1—H1C⋯N2, N1—H1A⋯N2, N1—H1A⋯O2, N1—H1A⋯O2, N1—H1B⋯N2, and N1—H1B⋯O2 hydrogen bonds (Fig. 2 and Table 1). Further, the crystal structure features two C1—H1D⋯π interactions involving the benzene (C2–C7) ring, leading to the formation of a three-dimensional network (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O3ⁱ	0.93	2.59	3.249 (2)	128
C1—H1C⋯N2ⁱⁱ	0.98 (3)	2.61 (3)	3.568 (3)	166 (3)
N1—H1A⋯N2ⁱⁱⁱ	0.92 (3)	2.59 (3)	3.452 (2)	157 (2)
N1—H1A⋯O2ⁱⁱⁱ	0.92 (3)	2.26 (3)	3.022 (2)	140 (2)
N1—H1A⋯O2^iv	0.92 (3)	2.26 (3)	3.022 (2)	140 (2)
N1—H1B⋯N2^v	0.96 (2)	2.67 (2)	3.5717 (8)	156.4 (18)
N1—H1B⋯O2^vi	0.96 (2)	1.94 (2)	2.9039 (16)	175.0 (19)
C1—H1D⋯Cg1^vii	0.978 (19)	2.65 (2)	3.4625 (5)	141.4 (14)
C1—H1D⋯Cg1^viii	0.978 (19)	2.65 (2)	3.4625 (5)	141.4 (14)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+1, -y+1, -z+1; (iii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) x, y-1, z; (vi) $[x, -y+{\script{1\over 2}}, z]$ ; (vii) $[x+{\script{3\over 2}}, -y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (viii) -x+1, -y, -z+1.

Figure 2
The crystal structure of the title salt, viewed along the b axis, showing the formation of hydrogen bonding. Dashed lines indicate hydrogen bonds and H atoms not involved in hydrogen bonds have been omitted.

The crystal structure of 4-methylbenzylammonium nitrate, closely related to the title compound, has been reported in space group P2₁/c (Gatfaoui et al., 2013 ): in that case, both the cation and anion are placed in general positions, and the N atom of the 4-methylbenzylammonium cation is displaced by 1.366 (2) Å from the mean plane of the other atoms.

Synthesis and crystallization

4-Methoxybenzylammonium nitrate crystals were synthesized by mixing 4-methoxybenzylamine (2 mmol, 0.274 g), dilute nitric acid (2 ml, 1 mol) and nickel nitrate (1 mmol, 0.291 g) in doubly distilled water. This solution was stirred continuously for about 3 h using a magnetic stirrer and then allowed to evaporate slowly at room temperature. Colourless crystals of the title compound suitable for single-crystal X-ray analysis were obtained after two weeks.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₁₂NO⁺·NO₃⁻
M_r	200.20
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	296
a, b, c (Å)	15.8203 (17), 6.8156 (7), 8.7275 (8)
V (Å³)	941.04 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.696, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	18099, 1663, 1126
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.740

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.131, 1.06
No. of reflections	1663
No. of parameters	101
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2004), SIR92 (Altomare et al., 1993 ), SHELXL2017 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2015 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1565296

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617011142/bh4027sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617011142/bh4027Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617011142/bh4027Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617011142/bh4027Isup4.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: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2015); software used to prepare material for publication: publCIF (Westrip, 2010).

4-Methoxybenzylammonium nitrate top

Crystal data top

C₈H₁₂NO⁺·NO₃⁻	D_x = 1.413 Mg m⁻³
M_r = 200.20	Melting point: 375 K
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
a = 15.8203 (17) Å	Cell parameters from 4546 reflections
b = 6.8156 (7) Å	θ = 2.6–29.6°
c = 8.7275 (8) Å	µ = 0.11 mm⁻¹
V = 941.04 (16) Å³	T = 296 K
Z = 4	Block, colourless
F(000) = 424	0.25 × 0.20 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1126 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
ω and φ scan	θ_max = 31.7°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −23→23
T_min = 0.696, T_max = 0.746	k = −9→9
18099 measured reflections	l = −12→12
1663 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.131	w = 1/[σ²(F_o²) + (0.0547P)² + 0.2894P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1663 reflections	Δρ_max = 0.30 e Å⁻³
101 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL2017 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.021 (3)
Primary atom site location: structure-invariant direct methods

Special details top

Refinement. The N-bound H atoms, CH₂ H atoms and CH₃ H atoms were located in a difference Fourier map and refined freely; N1—H1A = 0.92 (3) and N1—H1B = 0.96 (2) Å, C8—H8 = 0.971 (18), C1—H1C = 0.98 (3) and C1—H1D = 0.978 (19) Å. The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å (aromatic); U_iso(H) = 1.2U_eq(C).

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

	x	y	z	U_iso*/U_eq
C1	0.45170 (15)	0.250000	0.6753 (2)	0.0419 (5)
C2	0.47135 (11)	0.250000	0.4038 (2)	0.0305 (4)
C3	0.55852 (11)	0.250000	0.4177 (2)	0.0341 (4)
H3	0.583441	0.250000	0.514185	0.041*
C4	0.60883 (11)	0.250000	0.2864 (2)	0.0334 (4)
H4	0.667343	0.250000	0.296668	0.040*
C5	0.57361 (11)	0.250000	0.14141 (19)	0.0291 (4)
C6	0.48549 (11)	0.250000	0.1299 (2)	0.0353 (4)
H6	0.460461	0.250000	0.033433	0.042*
C7	0.43498 (11)	0.250000	0.2584 (2)	0.0373 (4)
H7	0.376470	0.250000	0.248118	0.045*
C8	0.62382 (12)	0.250000	−0.0055 (2)	0.0388 (4)
N1	0.71654 (11)	0.250000	0.0170 (2)	0.0377 (4)
N2	0.74586 (10)	0.750000	0.12747 (17)	0.0354 (4)
O1	0.41614 (8)	0.250000	0.52492 (15)	0.0414 (4)
O2	0.76246 (8)	0.59369 (17)	0.19519 (14)	0.0569 (4)
O3	0.71238 (11)	0.750000	0.00086 (18)	0.0616 (5)
H1A	0.7431 (17)	0.250000	−0.076 (4)	0.059 (7)*
H1B	0.7340 (13)	0.134 (3)	0.071 (3)	0.077 (6)*
H1C	0.404 (2)	0.250000	0.747 (4)	0.077 (9)*
H1D	0.4873 (11)	0.135 (3)	0.692 (2)	0.058 (5)*
H8	0.6126 (11)	0.135 (3)	−0.067 (2)	0.061 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0487 (12)	0.0453 (12)	0.0317 (9)	0.000	0.0074 (8)	0.000
C2	0.0310 (8)	0.0295 (8)	0.0312 (8)	0.000	0.0025 (6)	0.000
C3	0.0326 (9)	0.0433 (10)	0.0264 (8)	0.000	−0.0036 (7)	0.000
C4	0.0255 (8)	0.0442 (10)	0.0306 (8)	0.000	−0.0017 (6)	0.000
C5	0.0291 (8)	0.0301 (8)	0.0280 (8)	0.000	−0.0007 (6)	0.000
C6	0.0338 (9)	0.0435 (10)	0.0287 (8)	0.000	−0.0067 (7)	0.000
C7	0.0257 (8)	0.0485 (11)	0.0377 (9)	0.000	−0.0045 (7)	0.000
C8	0.0352 (9)	0.0529 (13)	0.0284 (8)	0.000	−0.0003 (7)	0.000
N1	0.0357 (8)	0.0455 (10)	0.0319 (8)	0.000	0.0053 (6)	0.000
N2	0.0278 (7)	0.0464 (9)	0.0319 (7)	0.000	0.0016 (6)	0.000
O1	0.0337 (7)	0.0559 (9)	0.0347 (7)	0.000	0.0057 (5)	0.000
O2	0.0783 (8)	0.0383 (6)	0.0541 (7)	−0.0045 (5)	−0.0173 (6)	0.0043 (5)
O3	0.0567 (10)	0.0924 (14)	0.0357 (8)	0.000	−0.0140 (7)	0.000

Geometric parameters (Å, º) top

C1—O1	1.428 (2)	C5—C8	1.508 (2)
C1—H1C	0.98 (3)	C6—C7	1.377 (3)
C1—H1D	0.978 (19)	C6—H6	0.9300
C1—H1Dⁱ	0.978 (19)	C7—H7	0.9300
C2—O1	1.371 (2)	C8—N1	1.480 (3)
C2—C3	1.384 (2)	C8—H8	0.971 (18)
C2—C7	1.393 (2)	C8—H8ⁱ	0.971 (18)
C3—C4	1.395 (2)	N1—H1A	0.92 (3)
C3—H3	0.9300	N1—H1B	0.96 (2)
C4—C5	1.383 (2)	N2—O3	1.225 (2)
C4—H4	0.9300	N2—O2ⁱⁱ	1.2463 (14)
C5—C6	1.398 (2)	N2—O2	1.2463 (14)

O1—C1—H1C	106.1 (18)	C7—C6—H6	119.3
O1—C1—H1D	111.3 (11)	C5—C6—H6	119.3
H1C—C1—H1D	110.5 (14)	C6—C7—C2	120.15 (16)
O1—C1—H1Dⁱ	111.3 (11)	C6—C7—H7	119.9
H1C—C1—H1Dⁱ	110.5 (14)	C2—C7—H7	119.9
H1D—C1—H1Dⁱ	107 (2)	N1—C8—C5	114.15 (15)
O1—C2—C3	124.53 (15)	N1—C8—H8	104.8 (10)
O1—C2—C7	116.05 (15)	C5—C8—H8	112.1 (11)
C3—C2—C7	119.43 (16)	N1—C8—H8ⁱ	104.8 (10)
C2—C3—C4	119.76 (16)	C5—C8—H8ⁱ	112.1 (11)
C2—C3—H3	120.1	H8—C8—H8ⁱ	108 (2)
C4—C3—H3	120.1	C8—N1—H1A	109.6 (17)
C5—C4—C3	121.44 (15)	C8—N1—H1B	110.5 (12)
C5—C4—H4	119.3	H1A—N1—H1B	107.8 (15)
C3—C4—H4	119.3	O3—N2—O2ⁱⁱ	121.25 (8)
C4—C5—C6	117.90 (15)	O3—N2—O2	121.25 (8)
C4—C5—C8	124.46 (15)	O2ⁱⁱ—N2—O2	117.48 (16)
C6—C5—C8	117.64 (15)	C2—O1—C1	117.24 (14)
C7—C6—C5	121.32 (16)

O1—C2—C3—C4	180.000 (1)	C5—C6—C7—C2	0.000 (1)
C7—C2—C3—C4	0.000 (1)	O1—C2—C7—C6	180.000 (1)
C2—C3—C4—C5	0.000 (1)	C3—C2—C7—C6	0.000 (1)
C3—C4—C5—C6	0.000 (1)	C4—C5—C8—N1	0.0
C3—C4—C5—C8	180.000 (1)	C6—C5—C8—N1	180.0
C4—C5—C6—C7	0.000 (1)	C3—C2—O1—C1	0.000 (1)
C8—C5—C6—C7	180.000 (1)	C7—C2—O1—C1	180.000 (1)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C2–C7 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O3ⁱⁱⁱ	0.93	2.59	3.249 (2)	128
C1—H1C···N2^iv	0.98 (3)	2.61 (3)	3.568 (3)	166 (3)
N1—H1A···N2^v	0.92 (3)	2.59 (3)	3.452 (2)	157 (2)
N1—H1A···O2^v	0.92 (3)	2.26 (3)	3.022 (2)	140 (2)
N1—H1A···O2^vi	0.92 (3)	2.26 (3)	3.022 (2)	140 (2)
N1—H1B···N2^vii	0.96 (2)	2.67 (2)	3.5717 (8)	156.4 (18)
N1—H1B···O2ⁱ	0.96 (2)	1.94 (2)	2.9039 (16)	175.0 (19)
C1—H1D···Cg1^viii	0.978 (19)	2.65 (2)	3.4625 (5)	141.4 (14)
C1—H1D···Cg1^ix	0.978 (19)	2.65 (2)	3.4625 (5)	141.4 (14)

Symmetry codes: (i) x, −y+1/2, z; (iii) −x+1, −y+1, −z; (iv) −x+1, −y+1, −z+1; (v) −x+3/2, −y+1, z−1/2; (vi) −x+3/2, y−1/2, z−1/2; (vii) x, y−1, z; (viii) x+3/2, −y−1/2, −z+3/2; (ix) −x+1, −y, −z+1.

Acknowledgements

The authors are thankful to the Sophisticated Analytical Instrument Facility (SAIF), IITM, Chennai 600 036, Tamilnadu, India for the single-crystal X-ray diffraction data.

Funding information

Funding for this research was provided by: Council of Scientific and Industrial Research (CSIR), New Delhi, India (grant No. 03(1301)13/EMR II to CR).

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