Growth, morphology, structure and character­ization of L-histidinium dihydrogen arsenate orthoarsenic acid single crystal

L-Histidinium dihydrogen arsenate orthoarsenic acid (LHAS) crystals were grown by the slow evaporation method. Single-crystal X-ray diffraction confirms monoclinic structure. The growth rates of various planes of LHAS crystals were estimated by morphological study. Hirshfeld surface and fingerprint plots were analyzed to investigate the intermolecular interactions at 0.002 a.u. present in the crystal structure. The functional groups and phase behavior of the compound are studied by FTIR spectroscopy and differential scanning calorimetry (DSC). A ferroelectric to paraelectric phase transition at 307 K was observed in dielectric studies. The piezoelectric charge coefficients of the grown crystal were found to be 2 pC/N. The values of coercive field (E_c), remnant polarization (P_r) and spontaneous polarization (P_s) in the hysteresis loop are found to be 5.236 kV cm⁻¹, 0.654 µC cm⁻² and 2.841 µC cm⁻², respectively. Piezoelectricity and ferroelectricity are reported for the first time in LHAS crystals. The mechanical strength was confirmed from microhardness study and void volume. Due to the low value of the dielectric constant, and good piezoelectric and ferroelectric properties, LHAS crystals can be used in microelectronics, sensors and advanced electronic devices.

Computing details

Program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013).

(I)

Crystal data

C6H10N3O2·AsH3O4·AsH2O4	F(000) = 436
Mr = 439.05	Dx = 2.123 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 9.2196 (6) Å	Cell parameters from 2792 reflections
b = 8.9077 (6) Å	θ = 3.3–29.1°
c = 8.8300 (6) Å	µ = 4.92 mm^−1
β = 108.690 (7)°	T = 303 K
V = 686.93 (8) Å^3	Prism
Z = 2	0.5 × 0.25 × 0.25 mm

Data collection

Xcalibur, Sapphire3 diffractometer	2706 reflections with I > 2σ(I)
ω scans	Rint = 0.062
Absorption correction: multi-scan CrysAlisPro Agilent Technologies	θmax = 30.0°, θmin = 3.3°
Tmin = 0.238, Tmax = 0.292	h = −11→11
5060 measured reflections	k = −12→11
3979 independent reflections	l = −10→12

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.144P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.069	(Δ/σ)max = 0.005
wR(F^2) = 0.203	Δρmax = 0.24 e Å^−3
S = 1.12	Δρmin = −0.50 e Å^−3
2819 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
191 parameters	Extinction coefficient: 0.32 (3)
1 restraint	Absolute structure: Flack x determined using 1009 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons and Flack (2004), Acta Cryst. A60, s61).
Hydrogen site location: inferred from neighbouring sites	Absolute structure parameter: −0.04 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O8	0.6583 (10)	0.1581 (13)	0.6293 (11)	0.030 (2)
H8	0.6968	0.2287	0.5964	0.039*
O7	0.4163 (13)	0.3328 (13)	0.6255 (12)	0.036 (3)
H7	0.3231	0.3424	0.5998	0.054*
O4	0.8156 (10)	0.3251 (13)	0.5050 (11)	0.0281 (19)
O5	0.3931 (10)	0.1644 (14)	0.3653 (9)	0.0254 (19)
O6	0.4048 (12)	0.0218 (14)	0.6397 (11)	0.034 (3)
H6	0.3112	0.0195	0.6147	0.051*
O2	1.0800 (13)	0.1467 (15)	0.5549 (18)	0.055 (4)
H11	1.1124	0.1430	0.6018	0.082*
O3	1.0292 (13)	0.3048 (17)	0.7882 (12)	0.042 (3)
H10	0.9905	0.2984	0.8393	0.064*
O1	1.1233 (11)	0.4477 (12)	0.5655 (11)	0.027 (2)
C2	0.9725 (15)	0.1868 (16)	1.1331 (13)	0.023 (3)
H2	0.9704	0.0826	1.1273	0.028*
C1	0.8464 (14)	0.2798 (12)	1.0775 (12)	0.016 (2)
N2	0.9071 (12)	0.4246 (12)	1.1183 (11)	0.020 (2)
H2A	0.8542	0.5061	1.0999	0.023*
N1	1.1042 (15)	0.2744 (14)	1.1996 (13)	0.028 (3)
H1	1.1964	0.2418	1.2390	0.033*
C5	0.6757 (14)	0.2520 (13)	0.9951 (12)	0.017 (2)
H5A	0.6645	0.1543	0.9441	0.021*
H5B	0.6391	0.3261	0.9110	0.021*
C4	0.5691 (14)	0.2565 (12)	1.0996 (11)	0.016 (2)
H4	0.5868	0.3505	1.1605	0.019*
C3	1.0599 (16)	0.4175 (17)	1.1905 (14)	0.026 (3)
H3	1.1241	0.4993	1.2279	0.031*
O9	0.3260 (12)	0.3582 (10)	0.9401 (11)	0.028 (2)
H9	0.2355	0.3389	0.8941	0.042*
O10	0.3326 (13)	0.1158 (11)	1.0025 (13)	0.033 (2)
N3	0.6140 (12)	0.1309 (12)	1.2111 (11)	0.024 (2)
H3A	0.6874	0.0725	1.2084	0.023*
H3B	0.5670	0.1152	1.2794	0.023*
C6	0.3938 (15)	0.2416 (15)	1.0061 (14)	0.019 (2)
As1	0.45832 (13)	0.17047 (11)	0.55164 (11)	0.0172 (4)
As2	1.00811 (13)	0.31294 (13)	0.60006 (13)	0.0189 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O8	0.011 (4)	0.045 (5)	0.030 (4)	−0.003 (4)	0.002 (3)	−0.014 (4)
O7	0.023 (6)	0.050 (7)	0.032 (5)	−0.006 (5)	0.005 (4)	−0.016 (5)
O4	0.012 (4)	0.045 (5)	0.027 (4)	−0.006 (4)	−0.006 (3)	0.011 (4)
O5	0.012 (4)	0.054 (5)	0.007 (3)	0.004 (5)	−0.000 (3)	0.000 (4)
O6	0.017 (6)	0.058 (6)	0.022 (4)	−0.004 (5)	−0.002 (4)	0.015 (4)
O2	0.015 (6)	0.047 (7)	0.097 (11)	0.003 (5)	−0.001 (6)	−0.032 (7)
O3	0.018 (5)	0.085 (8)	0.019 (4)	−0.016 (6)	−0.002 (4)	0.019 (5)
O1	0.008 (5)	0.039 (5)	0.029 (5)	−0.008 (4)	−0.001 (4)	0.009 (4)
C2	0.010 (6)	0.040 (7)	0.016 (4)	−0.002 (6)	−0.001 (4)	−0.001 (5)
C1	0.010 (6)	0.025 (5)	0.009 (4)	−0.003 (4)	−0.002 (4)	0.003 (3)
N2	0.006 (5)	0.030 (5)	0.020 (4)	0.003 (4)	−0.001 (4)	0.000 (4)
N1	0.015 (6)	0.045 (7)	0.020 (5)	0.013 (5)	0.001 (4)	0.000 (4)
C5	0.012 (6)	0.028 (5)	0.009 (4)	0.000 (5)	0.000 (4)	−0.002 (4)
C4	0.016 (7)	0.022 (5)	0.005 (4)	0.003 (5)	−0.003 (4)	0.000 (3)
C3	0.012 (7)	0.042 (7)	0.019 (5)	−0.004 (6)	−0.004 (4)	−0.002 (5)
O9	0.013 (5)	0.033 (4)	0.027 (5)	0.002 (4)	−0.008 (4)	0.009 (3)
O10	0.021 (6)	0.032 (5)	0.035 (5)	−0.007 (4)	−0.008 (4)	0.008 (4)
N3	0.012 (5)	0.036 (6)	0.019 (4)	0.011 (4)	−0.001 (3)	0.000 (3)
C6	0.009 (6)	0.035 (6)	0.014 (5)	0.003 (5)	0.005 (4)	−0.002 (4)
As1	0.0079 (7)	0.0316 (7)	0.0097 (5)	0.0003 (5)	−0.0005 (4)	0.0018 (4)
As2	0.0069 (7)	0.0251 (6)	0.0203 (6)	−0.0008 (5)	−0.0018 (5)	0.0026 (4)

Geometric parameters (Å, º)

O8—As1	1.753 (8)	C1—N2	1.407 (15)
O7—As1	1.682 (11)	C1—C5	1.528 (16)
O4—As2	1.706 (9)	N2—C3	1.349 (17)
O5—As1	1.561 (7)	N1—C3	1.33 (2)
O6—As1	1.687 (11)	C5—C4	1.549 (16)
O2—As2	1.720 (12)	C4—N3	1.460 (14)
O3—As2	1.611 (9)	C4—C6	1.567 (17)
O1—As2	1.694 (9)	O9—C6	1.255 (16)
C2—C1	1.383 (17)	O10—C6	1.251 (17)
C2—N1	1.404 (17)
C1—C2—N1	109.4 (12)	O9—C6—C4	116.8 (11)
C2—C1—N2	103.8 (10)	O5—As1—O7	112.3 (6)
C2—C1—C5	133.8 (10)	O5—As1—O6	112.8 (6)
N2—C1—C5	122.4 (10)	O7—As1—O6	111.0 (5)
C3—N2—C1	110.3 (11)	O5—As1—O8	114.3 (4)
C3—N1—C2	107.4 (12)	O7—As1—O8	104.3 (6)
C1—C5—C4	117.7 (8)	O6—As1—O8	101.3 (5)
N3—C4—C5	106.5 (10)	O3—As2—O1	110.0 (6)
N3—C4—C6	108.2 (10)	O3—As2—O4	105.8 (5)
C5—C4—C6	115.3 (9)	O1—As2—O4	118.7 (5)
N1—C3—N2	109.1 (12)	O3—As2—O2	105.8 (8)
O10—C6—O9	125.2 (13)	O1—As2—O2	104.9 (6)
O10—C6—C4	118.0 (11)	O4—As2—O2	111.0 (6)