S-Benzyl­isothio­uronium nitrate

Hemalatha, P.; Veeravazhuthi, V.

doi:10.1107/S1600536808026512

organic compounds

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Volume 64| Part 9| September 2008| Page o1805

doi:10.1107/S1600536808026512

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S-Benzylisothiouronium nitrate

P. Hemalatha ^a and V. Veeravazhuthi ^b ^*

^aDepartment of Physics, PSG College of Technology, Coimbatore 641 004, TamilNadu, India, and ^bDepartment of Physics, PSG College of Arts and Science, Coimbatore 641 014, TamilNadu, India
^*Correspondence e-mail: vv_vazhuthi@rediffmail.com

(Received 25 July 2008; accepted 18 August 2008; online 23 August 2008)

In the crystal structure of the title compound, C₈H₁₁N₂S⁺·NO₃⁻, cations and anions are linked by intermolecular N—H⋯O hydrogen bonds, forming one-dimensional chains along [110].

Related literature

For related literature, see: Barker & Powell (1998 ); Boyd (1989 ); Hemalatha et al. (2006 ); Zaccaro et al. (1999 ); Zyss et al. (1984 ).

Experimental

Crystal data

C₈H₁₁N₂S⁺·NO₃⁻
M_r = 229.26
Monoclinic, P 2₁ /c
a = 5.8569 (4) Å
b = 7.5931 (5) Å
c = 23.9488 (16) Å
β = 93.304 (1)°
V = 1063.28 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 (2) K
0.25 × 0.21 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: none
11620 measured reflections
2492 independent reflections
2282 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.229
S = 1.00
2492 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 1.08 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.86	1.98	2.803 (4)	160
N1—H1B⋯O3ⁱ	0.86	2.23	3.009 (4)	151
N2—H2A⋯O1	0.86	2.21	3.040 (5)	164
N2—H2A⋯O2	0.86	2.56	3.240 (4)	136
N2—H2B⋯O1ⁱⁱ	0.86	2.12	2.913 (4)	152
Symmetry codes: (i) -x+2, -y, -z; (ii) -x+1, -y+1, -z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808026512/lh2669sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808026512/lh2669Isup2.hkl

checkCIF report

Comment top

Organic molecular materials have many potential applications in integrated optics, and one of the most attractive applications is diode laser frequency doublers (Boyd, 1989). In the last two decades, extensive research has shown that organic crystals can exhibit nonlinear optical [NLO] efficiencies higher than those of inorganic materials (Zyss et al., 1984 & Zaccaro et al., 1999). Organic nonlinear optical materials are often formed by weak Vander Waals and hydrogen bonds and hence posses high degree of delocalization. Organic materials are molecular materials that offer unique opportunities for fundamental research as well as for technological applications. The title compound (I) is potentially in the above category of materials, therefore we have undertaken its crystal structure determination.

The title molecule is shown in Fig. 1. The C—N, S—C bond lengths and C—S—C and N—C—N bond angles are comparable with the similar structure reported earlier (Barker & Powell, 1998). The bond angles for O1—N3—O3 is 128.7 (4); O1—N3—O2 is 116.7 (4); O3—N3—O2 is 114.6 (3), indicating slight deviations in the bond angle from the expected 120° in terms of the sp² hybridization. In the title crystal structure, C₈H₁₁N₂S, NO₃, cations and anions are linked by intermolecular N—H···O hydrogen bonds to form one-dimensional chains along [110] (Fig. 2).

Related literature top

For related literature, see: Barker & Powell (1998); Boyd (1989); Hemalatha et al. (2006); Zaccaro et al. (1999); Zyss et al. (1984).

Experimental top

S-benzylisothiouronium chloride (SBTC) was synthesized as reported earlier (Hemalatha et al., 2006). The solutions of SBTC (5 g m) and potassium nitrate (5 g m) were prepared in water separately. These solutions were mixed together, and then stirred for 1 hr at room temperature. The precipitate was filtered off and washed with triple distilled water and the product was recrystallized from 0.2 M nitric acid. Single crystals were grown by slow evaporation of a solution of the title compound in water.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. Part of the crystal structure of (I) showing hydrogen bonds as dashed lines.

S-Benzylisothiouronium nitrate top

Crystal data top

C₈H₁₁N₂S⁺·NO₃⁻	F(000) = 480
M_r = 229.26	D_x = 1.432 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1296 reflections
a = 5.8569 (4) Å	θ = 1.7–28.0°
b = 7.5931 (5) Å	µ = 0.30 mm⁻¹
c = 23.9488 (16) Å	T = 293 K
β = 93.304 (1)°	Needle, colorless
V = 1063.28 (12) Å³	0.25 × 0.21 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEXCCD area-detector diffractometer	2282 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 28.0°, θ_min = 1.7°
ω scans	h = −7→7
11620 measured reflections	k = −10→9
2492 independent reflections	l = −31→30

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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.229	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1605P)² + 0.7215P], where P = (F_o² + 2F_c²)/3
2492 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 1.08 e Å⁻³
0 restraints	Δρ_min = −0.79 e Å⁻³

Crystal data top

C₈H₁₁N₂S⁺·NO₃⁻	V = 1063.28 (12) Å³
M_r = 229.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8569 (4) Å	µ = 0.30 mm⁻¹
b = 7.5931 (5) Å	T = 293 K
c = 23.9488 (16) Å	0.25 × 0.21 × 0.20 mm
β = 93.304 (1)°

Data collection top

Bruker SMART APEXCCD area-detector diffractometer	2282 reflections with I > 2σ(I)
11620 measured reflections	R_int = 0.021
2492 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	0 restraints
wR(F²) = 0.229	H-atom parameters constrained
S = 1.00	Δρ_max = 1.08 e Å⁻³
2492 reflections	Δρ_min = −0.79 e Å⁻³
136 parameters

Special details top

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
C1	0.4484 (5)	−0.0528 (3)	0.25594 (13)	0.0508 (6)
H1	0.5878	0.0053	0.2547	0.061*
C2	0.3462 (6)	−0.0682 (4)	0.30628 (13)	0.0593 (7)
H2	0.4173	−0.0216	0.3387	0.071*
C3	0.1385 (6)	−0.1527 (4)	0.30829 (13)	0.0604 (7)
H3	0.0683	−0.1617	0.3420	0.072*
C4	0.0359 (5)	−0.2230 (4)	0.26081 (14)	0.0582 (7)
H4	−0.1030	−0.2815	0.2626	0.070*
C5	0.1357 (4)	−0.2085 (3)	0.21013 (12)	0.0498 (6)
H5	0.0632	−0.2555	0.1779	0.060*
C6	0.3459 (4)	−0.1230 (3)	0.20739 (11)	0.0429 (5)
C7	0.4602 (5)	−0.1054 (4)	0.15294 (12)	0.0552 (7)
H7A	0.4431	−0.2135	0.1316	0.066*
H7B	0.6222	−0.0821	0.1600	0.066*
C8	0.5290 (4)	0.1362 (3)	0.06841 (10)	0.0436 (5)
N1	0.7023 (4)	0.0351 (3)	0.05812 (10)	0.0574 (6)
H1A	0.8017	0.0699	0.0355	0.069*
H1B	0.7168	−0.0662	0.0740	0.069*
N2	0.5046 (4)	0.2908 (3)	0.04458 (10)	0.0563 (6)
H2A	0.6031	0.3268	0.0219	0.068*
H2B	0.3900	0.3563	0.0516	0.068*
N3	0.9654 (5)	0.3266 (4)	−0.04824 (12)	0.0660 (7)
O1	0.7787 (6)	0.3965 (5)	−0.05407 (17)	0.1137 (13)
O2	1.0010 (6)	0.2296 (5)	−0.00529 (14)	0.0993 (10)
O3	1.1270 (5)	0.3341 (4)	−0.07925 (11)	0.0832 (8)
S1	0.32436 (11)	0.07656 (10)	0.11423 (3)	0.0538 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0463 (13)	0.0418 (12)	0.0640 (15)	−0.0041 (10)	0.0002 (11)	0.0033 (11)
C2	0.0728 (19)	0.0505 (15)	0.0540 (15)	−0.0015 (13)	−0.0025 (13)	−0.0016 (11)
C3	0.0714 (19)	0.0498 (15)	0.0619 (16)	0.0045 (13)	0.0204 (14)	0.0105 (12)
C4	0.0469 (14)	0.0474 (14)	0.0814 (19)	−0.0040 (10)	0.0136 (13)	0.0093 (13)
C5	0.0441 (12)	0.0435 (12)	0.0613 (14)	−0.0011 (10)	−0.0015 (11)	−0.0005 (11)
C6	0.0398 (11)	0.0346 (10)	0.0547 (13)	0.0050 (8)	0.0067 (9)	0.0049 (9)
C7	0.0588 (16)	0.0471 (13)	0.0612 (15)	0.0176 (11)	0.0168 (12)	0.0101 (11)
C8	0.0415 (12)	0.0452 (12)	0.0444 (11)	0.0058 (9)	0.0048 (9)	−0.0018 (9)
N1	0.0560 (14)	0.0561 (13)	0.0625 (13)	0.0195 (11)	0.0231 (11)	0.0085 (11)
N2	0.0581 (14)	0.0493 (12)	0.0632 (13)	0.0138 (10)	0.0174 (11)	0.0117 (10)
N3	0.0584 (14)	0.0686 (16)	0.0700 (16)	0.0209 (12)	−0.0037 (12)	−0.0270 (13)
O1	0.089 (2)	0.104 (2)	0.146 (3)	0.0491 (18)	−0.008 (2)	−0.031 (2)
O2	0.0851 (19)	0.126 (3)	0.0893 (18)	−0.0035 (19)	0.0280 (15)	0.0245 (19)
O3	0.0965 (19)	0.0875 (18)	0.0691 (14)	0.0096 (15)	0.0337 (13)	0.0199 (13)
S1	0.0424 (4)	0.0579 (5)	0.0624 (5)	0.0142 (2)	0.0143 (3)	0.0142 (3)

Geometric parameters (Å, º) top

C1—C2	1.381 (4)	C7—H7A	0.9700
C1—C6	1.384 (4)	C7—H7B	0.9700
C1—H1	0.9300	C8—N1	1.307 (3)
C2—C3	1.379 (5)	C8—N2	1.309 (3)
C2—H2	0.9300	C8—S1	1.731 (3)
C3—C4	1.364 (5)	N1—H1A	0.8600
C3—H3	0.9300	N1—H1B	0.8600
C4—C5	1.382 (4)	N2—H2A	0.8600
C4—H4	0.9300	N2—H2B	0.8600
C5—C6	1.396 (3)	N3—O1	1.217 (4)
C5—H5	0.9300	N3—O3	1.237 (4)
C6—C7	1.506 (4)	N3—O2	1.273 (4)
C7—S1	1.821 (3)

C2—C1—C6	120.8 (3)	C6—C7—H7A	110.2
C2—C1—H1	119.6	S1—C7—H7A	110.2
C6—C1—H1	119.6	C6—C7—H7B	110.2
C1—C2—C3	119.8 (3)	S1—C7—H7B	110.2
C1—C2—H2	120.1	H7A—C7—H7B	108.5
C3—C2—H2	120.1	N1—C8—N2	120.7 (2)
C4—C3—C2	120.0 (3)	N1—C8—S1	122.6 (2)
C4—C3—H3	120.0	N2—C8—S1	116.66 (19)
C2—C3—H3	120.0	C8—N1—H1A	120.0
C3—C4—C5	120.8 (3)	C8—N1—H1B	120.0
C3—C4—H4	119.6	H1A—N1—H1B	120.0
C5—C4—H4	119.6	C8—N2—H2A	120.0
C4—C5—C6	119.8 (3)	C8—N2—H2B	120.0
C4—C5—H5	120.1	H2A—N2—H2B	120.0
C6—C5—H5	120.1	O1—N3—O3	128.7 (4)
C1—C6—C5	118.7 (2)	O1—N3—O2	116.7 (4)
C1—C6—C7	120.0 (2)	O3—N3—O2	114.6 (3)
C5—C6—C7	121.3 (3)	C8—S1—C7	102.89 (12)
C6—C7—S1	107.78 (17)

C6—C1—C2—C3	−0.7 (4)	C4—C5—C6—C7	179.7 (2)
C1—C2—C3—C4	0.9 (5)	C1—C6—C7—S1	−99.7 (3)
C2—C3—C4—C5	−1.0 (5)	C5—C6—C7—S1	79.9 (3)
C3—C4—C5—C6	0.9 (4)	N1—C8—S1—C7	15.6 (3)
C2—C1—C6—C5	0.6 (4)	N2—C8—S1—C7	−163.5 (2)
C2—C1—C6—C7	−179.8 (2)	C6—C7—S1—C8	158.3 (2)
C4—C5—C6—C1	−0.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	1.98	2.803 (4)	160
N1—H1B···O3ⁱ	0.86	2.23	3.009 (4)	151
N2—H2A···O1	0.86	2.21	3.040 (5)	164
N2—H2A···O2	0.86	2.56	3.240 (4)	136
N2—H2B···O1ⁱⁱ	0.86	2.12	2.913 (4)	152

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

Experimental details

Crystal data
Chemical formula	C₈H₁₁N₂S⁺·NO₃⁻
M_r	229.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.8569 (4), 7.5931 (5), 23.9488 (16)
β (°)	93.304 (1)
V (Å³)	1063.28 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.25 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART APEXCCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11620, 2492, 2282
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.229, 1.00
No. of reflections	2492
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.08, −0.79

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PARST (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	1.98	2.803 (4)	160.0
N1—H1B···O3ⁱ	0.86	2.23	3.009 (4)	150.5
N2—H2A···O1	0.86	2.21	3.040 (5)	163.7
N2—H2A···O2	0.86	2.56	3.240 (4)	136.2
N2—H2B···O1ⁱⁱ	0.86	2.12	2.913 (4)	152.4

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

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1805

doi:10.1107/S1600536808026512

Open

access