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A new compound in the Lys–HIO3–H2O system (where Lys = lysine), lysine–iodic acid (1/3), C6H14N2O2.3HIO3, has been discovered. Its crystals display nonlinear optical properties. They were investigated by X-ray analysis, IR spectroscopy and NQR methods. The parameters of the unit cell are a = 8.360 (2), b = 6.330 (1), c = 14.750 (3) Å, β = 92.86 (3)°, Dx = 2.87 Mg m−3, space group P21, Z = 2. The three iodate groups in the structure have different roles. Interaction of lysine and iodic acid results in a compound containing a doubly protonated lysine cation and two counterions, IO^-_3 and I2O5OH.

Supporting information

cif

Crystallographic Information File (CIF)
Contains datablock I

fcf

Structure factor file (CIF format)
Contains datablock I

CCDC reference: 132056

Computing details top

Data collection: CAD4; cell refinement: CAD4; data reduction: CAD4; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEP.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
α,ε–diaminocapronic acid·3HIO3 top
Crystal data top
C6H16N2O22+·HI2O6·IO3F(000) = 628
Mr = 673.92Dx = 2.87 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 8.360 (2) ÅCell parameters from 24 reflections
b = 6.330 (1) Åθ = 14–16°
c = 14.750 (3) ŵ = 6.07 mm1
β = 92.86 (3)°T = 293 K
V = 779.6 (3) Å3Plate, colourless
Z = 20.6 × 0.2 × 0.1 mm
Data collection top
Enraf-Nonius CAD4
diffractometer
2443 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.117
Graphite monochromatorθmax = 30.0°, θmin = 2.4°
ω–2θ scansh = 011
Absorption correction: empirical (using intensity measurements) via ψ scans
?
k = 08
Tmin = ?, Tmax = ?l = 2020
2601 measured reflections3 standard reflections every 3600 min
2452 independent reflections intensity decay: 10%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters not refined
R[F2 > 2σ(F2)] = 0.034Calculated w = 1/[σ2(Fo2) + (0.0765P)2 + 1.2606P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.092(Δ/σ)max = 0.210
S = 1.07Δρmax = 3.06 e Å3
2452 reflectionsΔρmin = 1.96 e Å3
200 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0100 (10)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.02 (5)
Crystal data top
C6H16N2O22+·HI2O6·IO3V = 779.6 (3) Å3
Mr = 673.92Z = 2
Monoclinic, P21Mo Kα radiation
a = 8.360 (2) ŵ = 6.07 mm1
b = 6.330 (1) ÅT = 293 K
c = 14.750 (3) Å0.6 × 0.2 × 0.1 mm
β = 92.86 (3)°
Data collection top
Enraf-Nonius CAD4
diffractometer
2443 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements) via ψ scans
?
Rint = 0.117
Tmin = ?, Tmax = ?3 standard reflections every 3600 min
2601 measured reflections intensity decay: 10%
2452 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters not refined
wR(F2) = 0.092(Δ/σ)max = 0.210
S = 1.07Δρmax = 3.06 e Å3
2452 reflectionsΔρmin = 1.96 e Å3
200 parametersAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
1 restraintAbsolute structure parameter: 0.02 (5)
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 on F2 for the reflections with F2 > σ(F2) or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 (Å2) top
xyzUiso*/Ueq
I10.72398 (4)0.38284 (7)0.87423 (3)0.01554 (13)
O110.6527 (8)0.1946 (11)0.7880 (4)0.0259 (12)
O120.6660 (8)0.6270 (11)0.8169 (4)0.0262 (12)
O130.9336 (5)0.3776 (14)0.8507 (4)0.0279 (13)
I20.22512 (4)0.35791 (7)0.93412 (3)0.01528 (13)
O210.1524 (7)0.1153 (11)0.9821 (5)0.0277 (12)
O220.1510 (7)0.5336 (13)1.0289 (4)0.0272 (14)
H22A0.0547 (7)0.5546 (13)1.0204 (4)0.041*
O230.4277 (6)0.3537 (11)0.9774 (4)0.0238 (11)
I30.43204 (5)0.08631 (7)0.81957 (2)0.01402 (13)
O310.2990 (7)0.1453 (10)0.8057 (4)0.0230 (11)
O320.4450 (7)0.1352 (12)0.7001 (3)0.0224 (11)
O330.2810 (7)0.2824 (10)0.8399 (4)0.0248 (12)
O10.5864 (7)0.4468 (14)0.5196 (4)0.032 (2)
O20.3679 (7)0.4472 (15)0.4265 (4)0.033 (2)
H2B0.4316 (7)0.4177 (15)0.3852 (4)0.080*
C10.4459 (9)0.4389 (14)0.5065 (4)0.0206 (13)
C20.3304 (8)0.4029 (15)0.5828 (4)0.0212 (13)
H2A0.2865 (8)0.2632 (15)0.5770 (4)0.080*
C30.1906 (9)0.5578 (15)0.5788 (5)0.0225 (14)
H3A0.1388 (9)0.5574 (15)0.5192 (5)0.080*
H3B0.2342 (9)0.6963 (15)0.5896 (5)0.080*
C40.0650 (10)0.5108 (17)0.6487 (6)0.028 (2)
H4A0.0245 (10)0.3701 (17)0.6398 (6)0.080*
H4B0.1153 (10)0.5182 (17)0.7086 (6)0.080*
C50.0709 (10)0.6730 (17)0.6432 (6)0.030 (2)
H5A0.1017 (10)0.6940 (17)0.5803 (6)0.080*
H5B0.1608 (10)0.6127 (17)0.6719 (6)0.080*
C60.0343 (9)0.8843 (19)0.6861 (5)0.029 (2)
H6A0.0694 (9)0.9299 (19)0.6688 (5)0.080*
H6B0.1116 (9)0.9867 (19)0.6641 (5)0.080*
N70.0361 (8)0.8759 (15)0.7870 (4)0.0260 (14)
H7A0.0149 (8)1.0036 (15)0.8098 (4)0.039*
H7B0.0379 (8)0.7849 (15)0.8082 (4)0.039*
H7C0.1322 (8)0.8340 (15)0.8032 (4)0.039*
N80.4238 (8)0.4192 (13)0.6700 (4)0.0222 (12)
H8A0.5048 (8)0.3280 (13)0.6706 (4)0.033*
H8B0.3610 (8)0.3897 (13)0.7153 (4)0.033*
H8C0.4619 (8)0.5499 (13)0.6767 (4)0.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0147 (2)0.0116 (2)0.0204 (2)0.00019 (14)0.00143 (12)0.0000 (2)
O110.031 (3)0.022 (3)0.024 (3)0.006 (2)0.000 (2)0.004 (2)
O120.030 (3)0.019 (3)0.030 (3)0.005 (2)0.004 (2)0.007 (2)
O130.015 (2)0.043 (4)0.026 (2)0.003 (3)0.005 (2)0.005 (3)
I20.0142 (2)0.0118 (2)0.0201 (2)0.00007 (14)0.00309 (13)0.00182 (15)
O210.026 (3)0.020 (3)0.037 (3)0.005 (2)0.003 (2)0.011 (3)
O220.026 (3)0.032 (4)0.024 (3)0.003 (2)0.005 (2)0.013 (2)
O230.016 (2)0.022 (3)0.034 (3)0.000 (2)0.002 (2)0.005 (3)
I30.0192 (2)0.0082 (2)0.0149 (2)0.00035 (14)0.00294 (12)0.00005 (14)
O310.026 (3)0.018 (3)0.025 (3)0.007 (2)0.006 (2)0.001 (2)
O320.035 (3)0.018 (3)0.014 (2)0.006 (2)0.005 (2)0.002 (2)
O330.025 (3)0.012 (3)0.039 (3)0.006 (2)0.007 (2)0.007 (2)
O10.027 (3)0.043 (4)0.027 (3)0.004 (3)0.007 (2)0.003 (3)
O20.033 (3)0.049 (5)0.019 (2)0.006 (3)0.004 (2)0.001 (3)
C10.029 (3)0.017 (3)0.016 (3)0.002 (3)0.004 (2)0.001 (3)
C20.023 (3)0.020 (4)0.021 (3)0.001 (3)0.005 (2)0.005 (3)
C30.026 (3)0.021 (4)0.021 (3)0.001 (3)0.008 (2)0.002 (3)
C40.026 (3)0.025 (4)0.035 (4)0.006 (3)0.008 (3)0.003 (4)
C50.022 (3)0.031 (5)0.038 (4)0.000 (3)0.005 (3)0.007 (4)
C60.028 (3)0.033 (5)0.028 (3)0.005 (4)0.005 (2)0.004 (4)
N70.029 (3)0.025 (4)0.025 (3)0.001 (3)0.003 (2)0.006 (3)
N80.025 (3)0.018 (3)0.023 (3)0.003 (3)0.004 (2)0.002 (3)
Geometric parameters (Å, º) top
I1—O111.821 (6)I1—O21i2.740 (7)
I1—O121.816 (7)I1—O22ii2.805 (7)
I1—O131.804 (5)I1—O232.977 (5)
I2—O211.809 (7)I2—O13iii2.677 (5)
I2—O221.914 (6)I2—O312.429 (6)
I2—O231.780 (5)I2—O33iv2.720 (6)
I3—O311.845 (6)I3—O112.620 (7)
I3—O321.798 (5)I3—O12v2.670 (7)
I3—O331.806 (6)I3—O23ii3.184 (6)
O1—C11.182 (9)C1—O21.320 (9)
C2—C11.537 (10)C2—C31.524 (11)
C2—N81.474 (9)C3—C41.538 (11)
C5—C41.531 (13)C5—C61.50 (2)
N7—C61.491 (10)
O22···O21vi2.586 (8)O2···O32vii2.549 (8)
N8···O112.895 (10)N7···O33iv2.903 (10)
N8···O312.883 (9)N7···O12iii2.998 (10)
N8···O32iv2.859 (11)
O12—I1—O1199.3 (3)C3—C2—C1112.6 (7)
O13—I1—O1198.1 (3)N7—C6—C5112.1 (9)
O13—I1—O1299.5 (3)O23—I2—O21100.3 (3)
O23—I2—O3189.8 (2)O23—I2—O2294.8 (3)
O21—I2—O3186.5 (3)O21—I2—O2294.6 (4)
O22—I2—O31175.0 (2)O1—C1—O2126.0 (7)
O32—I3—O3397.0 (3)O1—C1—C2122.8 (7)
O32—I3—O3195.4 (3)O2—C1—C2111.1 (6)
O33—I3—O3198.1 (3)C4—C3—C2113.4 (7)
I3—O31—I2121.9 (3)C5—C4—C3111.4 (8)
N8—C2—C3111.2 (6)C6—C5—C4116.0 (7)
N8—C2—C1107.7 (6)
Symmetry codes: (i) x+1, y+1/2, z+2; (ii) x+1, y1/2, z+2; (iii) x1, y, z; (iv) x, y+1, z; (v) x, y1, z; (vi) x, y+1/2, z+2; (vii) x+1, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC6H16N2O22+·HI2O6·IO3
Mr673.92
Crystal system, space groupMonoclinic, P21
Temperature (K)293
a, b, c (Å)8.360 (2), 6.330 (1), 14.750 (3)
β (°) 92.86 (3)
V3)779.6 (3)
Z2
Radiation typeMo Kα
µ (mm1)6.07
Crystal size (mm)0.6 × 0.2 × 0.1
Data collection
DiffractometerEnraf-Nonius CAD4
diffractometer
Absorption correctionEmpirical (using intensity measurements) via ψ scans
No. of measured, independent and
observed [I > 2σ(I)] reflections
2601, 2452, 2443
Rint0.117
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.092, 1.07
No. of reflections2452
No. of parameters200
No. of restraints1
H-atom treatmentH-atom parameters not refined
(Δ/σ)max0.210
Δρmax, Δρmin (e Å3)3.06, 1.96
Absolute structureFlack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter0.02 (5)

Computer programs: CAD4, SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), ORTEP.

Selected geometric parameters (Å, º) top
I1—O111.821 (6)I1—O21i2.740 (7)
I1—O121.816 (7)I1—O22ii2.805 (7)
I1—O131.804 (5)I1—O232.977 (5)
I2—O211.809 (7)I2—O13iii2.677 (5)
I2—O221.914 (6)I2—O312.429 (6)
I2—O231.780 (5)I2—O33iv2.720 (6)
I3—O311.845 (6)I3—O112.620 (7)
I3—O321.798 (5)I3—O12v2.670 (7)
I3—O331.806 (6)I3—O23ii3.184 (6)
O1—C11.182 (9)C1—O21.320 (9)
C2—C11.537 (10)C2—C31.524 (11)
C2—N81.474 (9)C3—C41.538 (11)
C5—C41.531 (13)C5—C61.50 (2)
N7—C61.491 (10)
O22···O21vi2.586 (8)O2···O32vii2.549 (8)
N8···O112.895 (10)N7···O33iv2.903 (10)
N8···O312.883 (9)N7···O12iii2.998 (10)
N8···O32iv2.859 (11)
O12—I1—O1199.3 (3)O23—I2—O21100.3 (3)
O13—I1—O1198.1 (3)O23—I2—O2294.8 (3)
O13—I1—O1299.5 (3)O21—I2—O2294.6 (4)
O32—I3—O3397.0 (3)O1—C1—O2126.0 (7)
O32—I3—O3195.4 (3)O1—C1—C2122.8 (7)
O33—I3—O3198.1 (3)O2—C1—C2111.1 (6)
N8—C2—C3111.2 (6)C4—C3—C2113.4 (7)
N8—C2—C1107.7 (6)C5—C4—C3111.4 (8)
C3—C2—C1112.6 (7)C6—C5—C4116.0 (7)
N7—C6—C5112.1 (9)
Symmetry codes: (i) x+1, y+1/2, z+2; (ii) x+1, y1/2, z+2; (iii) x1, y, z; (iv) x, y+1, z; (v) x, y1, z; (vi) x, y+1/2, z+2; (vii) x+1, y+1/2, z+1.
 
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