Synthesis, structure, thermal and non-linear optical properties of L-argininium hydrogen selenite

L-Argininium hydrogen selenite (C₆H₁₅N₄O₂HSeO₃) is a new semiorganic compound of the hydrogen selenite family with non-linear optical properties. The crystal lattice is monoclinic with unit-cell parameters a = 22.493 (5), b = 5.1624 (13), c = 9.730 (4) Å, β = 95.68 (3)°, V = 1124.3 (6) ų, Z = 4, space group C2. Second-harmonic generation measurements performed on powder samples, using a Q-switched Nd:Yag laser (λ = 1064 nm), showed the second-harmonic power to be about twice that of urea. Differential scanning calorimetry measurements revealed the existence of a phase transition with onset at 289 K.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software (Enraf-Nonius, 1989); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

L-argininium hydrogenselenite

Crystal data

C6H15N4O2^+·HSeO3^−·0.1525(H2O)	F(000) = 622.1
Mr = 305.93	Dx = 1.807 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 22.493 (5) Å	Cell parameters from 25 reflections
b = 5.1624 (13) Å	θ = 5.5–15.4°
c = 9.730 (4) Å	µ = 3.36 mm^−1
β = 95.68 (3)°	T = 293 K
V = 1124.3 (6) Å^3	Block, light red
Z = 4	0.38 × 0.35 × 0.25 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	2542 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 30.0°, θmin = 3.6°
profile data from ω–2θ scans	h = −31→31
Absorption correction: ψ scan North et al. (1968). Acta Cryst A24, 351-359.	k = −6→7
Tmin = 0.251, Tmax = 0.432	l = −13→13
5336 measured reflections	3 standard reflections every 180 reflections
2674 independent reflections	intensity decay: 1.3%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.022	w = 1/[σ^2(Fo^2) + (0.045P)^2 + 0.2447P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.060	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.33 e Å^−3
2674 reflections	Δρmin = −0.51 e Å^−3
200 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0046 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.013 (8)

Special details

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 F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Se	0.254283 (7)	0.43142 (4)	0.820758 (17)	0.02440 (6)
O1	0.19805 (7)	0.4981 (3)	0.93394 (19)	0.0325 (4)
H1	0.1930 (15)	0.368 (7)	0.994 (4)	0.049*
O2	0.31249 (7)	0.5803 (4)	0.90397 (19)	0.0338 (4)
O3	0.23183 (9)	0.6274 (4)	0.69211 (18)	0.0384 (4)
O4	−0.02420 (6)	0.9673 (4)	0.83458 (15)	0.0263 (3)
O5	0.00933 (7)	1.3706 (3)	0.8188 (2)	0.0386 (4)
N1	0.11753 (8)	0.4397 (6)	0.22936 (18)	0.0317 (3)
H1A	0.1403 (14)	0.329 (7)	0.201 (3)	0.038*
H1B	0.0840 (13)	0.419 (9)	0.204 (3)	0.038*
N2	0.18979 (9)	0.5082 (4)	0.4092 (2)	0.0315 (4)
H2A	0.2026 (14)	0.553 (6)	0.488 (4)	0.038*
H2B	0.2143 (13)	0.400 (7)	0.379 (3)	0.038*
N3	0.10228 (10)	0.7480 (5)	0.3893 (2)	0.0363 (5)
H3	0.0760 (14)	0.801 (7)	0.332 (3)	0.044*
N4	0.08233 (9)	0.7831 (4)	0.9401 (2)	0.0251 (4)
H4A	0.0612 (14)	0.683 (6)	0.893 (4)	0.038*
H4B	0.0732 (14)	0.779 (7)	1.022 (4)	0.038*
H4C	0.1199 (15)	0.727 (7)	0.948 (4)	0.038*
C1	0.13695 (9)	0.5645 (4)	0.3450 (2)	0.0246 (4)
C2	0.11910 (10)	0.9241 (7)	0.5024 (2)	0.0333 (4)
H2C	0.1053 (14)	1.105 (7)	0.478 (3)	0.040*
H2D	0.1584 (14)	0.925 (8)	0.522 (3)	0.040*
C3	0.09064 (11)	0.8611 (5)	0.6328 (2)	0.0302 (5)
H3A	0.0935 (14)	0.683 (6)	0.659 (3)	0.036*
H3B	0.0498 (14)	0.874 (6)	0.605 (3)	0.036*
C4	0.11496 (10)	1.0435 (4)	0.7473 (2)	0.0263 (4)
H4D	0.1546 (14)	1.014 (5)	0.773 (3)	0.032*
H4E	0.1112 (13)	1.219 (6)	0.704 (3)	0.032*
C5	0.08085 (9)	1.0432 (4)	0.8742 (2)	0.0209 (4)
H5	0.1007 (13)	1.148 (6)	0.945 (3)	0.025*
C6	0.01594 (9)	1.1330 (4)	0.8404 (2)	0.0217 (4)
O6	0.0000	0.306 (2)	0.5000	0.064 (4)	0.305 (11)
H6	0.0026	0.3233	0.5872	0.096*	0.305 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Se	0.02395 (9)	0.02489 (9)	0.02400 (9)	−0.00007 (9)	0.00059 (6)	−0.00208 (9)
O1	0.0258 (7)	0.0334 (10)	0.0397 (9)	0.0023 (5)	0.0094 (6)	0.0046 (6)
O2	0.0218 (7)	0.0448 (9)	0.0337 (9)	−0.0050 (7)	−0.0024 (6)	0.0017 (7)
O3	0.0395 (9)	0.0462 (10)	0.0274 (8)	−0.0027 (8)	−0.0067 (7)	0.0076 (7)
O4	0.0214 (6)	0.0282 (9)	0.0288 (6)	−0.0033 (6)	−0.0010 (5)	0.0034 (6)
O5	0.0286 (8)	0.0225 (8)	0.0624 (12)	0.0019 (5)	−0.0069 (8)	0.0028 (7)
N1	0.0260 (7)	0.0414 (9)	0.0274 (8)	0.0007 (13)	0.0007 (6)	−0.0080 (13)
N2	0.0282 (9)	0.0360 (11)	0.0291 (9)	0.0022 (7)	−0.0033 (7)	−0.0039 (7)
N3	0.0332 (10)	0.0503 (12)	0.0246 (10)	0.0119 (9)	−0.0015 (8)	−0.0050 (9)
N4	0.0234 (9)	0.0253 (8)	0.0259 (9)	0.0040 (7)	−0.0013 (7)	0.0030 (7)
C1	0.0255 (9)	0.0285 (10)	0.0203 (9)	−0.0038 (8)	0.0053 (7)	0.0023 (8)
C2	0.0425 (11)	0.0323 (10)	0.0262 (9)	0.0058 (14)	0.0084 (8)	−0.0011 (13)
C3	0.0355 (11)	0.0303 (11)	0.0258 (10)	−0.0058 (8)	0.0081 (8)	−0.0040 (7)
C4	0.0257 (9)	0.0256 (9)	0.0283 (10)	−0.0024 (8)	0.0067 (8)	−0.0032 (8)
C5	0.0186 (8)	0.0209 (8)	0.0227 (9)	−0.0008 (7)	−0.0008 (7)	−0.0025 (7)
C6	0.0206 (8)	0.0229 (9)	0.0209 (8)	0.0019 (7)	−0.0015 (7)	−0.0013 (7)
O6	0.088 (10)	0.053 (7)	0.048 (7)	0.000	−0.007 (6)	0.000

Geometric parameters (Å, º)

Se—O3	1.6493 (18)	N4—H4A	0.81 (3)
Se—O2	1.6585 (17)	N4—H4B	0.84 (3)
Se—O1	1.7908 (18)	N4—H4C	0.89 (3)
O1—H1	0.90 (4)	C2—C3	1.512 (3)
O4—C6	1.241 (3)	C2—H2C	1.01 (4)
O5—C6	1.251 (3)	C2—H2D	0.89 (3)
N1—C1	1.333 (3)	C3—C4	1.519 (3)
N1—H1A	0.83 (3)	C3—H3A	0.95 (3)
N1—H1B	0.78 (3)	C3—H3B	0.93 (3)
N2—C1	1.319 (3)	C4—C5	1.517 (3)
N2—H2A	0.83 (4)	C4—H4D	0.91 (3)
N2—H2B	0.86 (3)	C4—H4E	1.00 (3)
N3—C1	1.326 (3)	C5—C6	1.536 (3)
N3—C2	1.448 (4)	C5—H5	0.95 (3)
N3—H3	0.82 (3)	O6—H6	0.8496
N4—C5	1.486 (3)
O3—Se—O2	104.71 (10)	N3—C2—H2D	110 (2)
O3—Se—O1	99.61 (10)	C3—C2—H2D	108.2 (19)
O2—Se—O1	100.50 (9)	H2C—C2—H2D	109 (3)
Se—O1—H1	113 (2)	C2—C3—C4	109.3 (2)
C1—N1—H1A	117 (2)	C2—C3—H3A	114 (2)
C1—N1—H1B	124 (3)	C4—C3—H3A	113.2 (19)
H1A—N1—H1B	114 (4)	C2—C3—H3B	103.1 (19)
C1—N2—H2A	126 (2)	C4—C3—H3B	116 (2)
C1—N2—H2B	124.1 (19)	H3A—C3—H3B	100 (3)
H2A—N2—H2B	109 (3)	C5—C4—C3	114.97 (18)
C1—N3—C2	125.3 (2)	C5—C4—H4D	109.8 (19)
C1—N3—H3	115 (2)	C3—C4—H4D	111.3 (19)
C2—N3—H3	115 (3)	C5—C4—H4E	108.4 (18)
C5—N4—H4A	110 (2)	C3—C4—H4E	104.1 (18)
C5—N4—H4B	116 (2)	H4D—C4—H4E	108 (3)
H4A—N4—H4B	110 (3)	N4—C5—C4	111.12 (18)
C5—N4—H4C	108 (2)	N4—C5—C6	110.19 (17)
H4A—N4—H4C	110 (3)	C4—C5—C6	111.85 (18)
H4B—N4—H4C	103 (3)	N4—C5—H5	102.3 (18)
N2—C1—N3	122.3 (2)	C4—C5—H5	110.4 (18)
N2—C1—N1	119.9 (2)	C6—C5—H5	110.6 (18)
N3—C1—N1	117.8 (2)	O4—C6—O5	126.5 (2)
N3—C2—C3	113.7 (3)	O4—C6—C5	118.26 (18)
N3—C2—H2C	110.4 (19)	O5—C6—C5	115.24 (18)
C3—C2—H2C	104.8 (18)
C2—N3—C1—N2	6.2 (4)	C3—C4—C5—C6	−62.2 (2)
C2—N3—C1—N1	−172.0 (3)	N4—C5—C6—O4	−19.1 (3)
C1—N3—C2—C3	−105.4 (3)	C4—C5—C6—O4	105.0 (2)
N3—C2—C3—C4	175.6 (2)	N4—C5—C6—O5	162.2 (2)
C2—C3—C4—C5	167.1 (2)	C4—C5—C6—O5	−73.7 (2)
C3—C4—C5—N4	61.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.90 (4)	1.80 (4)	2.696 (3)	172 (3)
N1—H1A···O2^ii	0.83 (3)	2.01 (3)	2.830 (3)	169 (3)
N1—H1B···O5^iii	0.78 (3)	2.10 (3)	2.868 (3)	167 (3)
N2—H2A···O3	0.83 (4)	2.06 (4)	2.887 (3)	174 (3)
N2—H2B···O3^ii	0.86 (3)	2.02 (3)	2.879 (3)	176 (3)
N3—H3···O4^iv	0.82 (3)	2.08 (3)	2.890 (3)	168 (3)
N4—H4A···O5^v	0.81 (3)	2.08 (3)	2.871 (3)	165 (3)
N4—H4B···O4^vi	0.84 (3)	2.10 (3)	2.827 (3)	144 (3)
N4—H4C···O1	0.89 (3)	2.13 (3)	2.996 (3)	163 (3)
O6—H6···O5^v	0.85	2.26	3.106 (3)	180

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