The crystal structure, vibrational spectra, thermal behaviour and second harmonic generation of aminoguanidinium(1+) hydrogen l -tartrate monohydrate

Journal of Molecular Structure 832 (2007) 101–107 www.elsevier.com/locate/molstruc

The crystal structure, vibrational spectra, thermal behaviour and second harmonic generation of aminoguanidinium(1+) hydrogen L-tartrate monohydrate Zorka Macha´cˇkova´ a, Ivan Neˇmec a,*, Karel Teubner a, Petr Neˇmec b, Prˇemysl Vaneˇk c, Zdeneˇk Micˇka a a

Charles University in Prague, Faculty of Science, Department of Inorganic Chemistry, Hlavova 8, 128 40 Prague 2, Czech Republic b Charles University in Prague, Faculty of Mathematics and Physics, Department of Chemical Physics and Optics, Ke Karlovu 3, 121 16 Prague 2, Czech Republic c The Academy of Science of the Czech Republic, Institute of Physics, Na Slovance 2, 182 21 Prague 8, Czech Republic Received 20 May 2006; received in revised form 8 August 2006; accepted 8 August 2006 Available online 18 September 2006

Abstract Aminoguanidinium(1+) hydrogen L-tartrate monohydrate was prepared by crystallisation from aqueous solution and X-ray structur˚, al analysis was carried out. The substance crystallises in the orthorhombic system in space group P212121, a = 7.1380(2) A ˚ , c = 14.0790(6) A ˚ , V = 1001.94(7) A ˚ 3, Z = 4, R = 0.0271 for 2272 observed reflections. The crystal structure consists b = 9.9700(4) A of a 3D framework formed by hydrogen tartrate anions and water molecules with incorporated aminoguanidinium(1+) cations connected by a system of hydrogen bonds. The FTIR and FT Raman spectra of natural and N,O-deuterated compounds were measured and discussed at laboratory temperature. DSC measurements were carried out in the temperature range from 95 to 380 K. A weak anomaly was observed at a temperature of 268 K. Quantitative measurements of second harmonic generation of powdered aminoguanidinium(1+) hydrogen tartrate monohydrate at 800 nm were performed relative to KDP and a relative efficiency of 14% was observed.  2006 Elsevier B.V. All rights reserved. Keywords: Aminoguanidinium(1+) hydrogen L-tartrate monohydrate; Crystal structure; Vibrational spectra; Thermal behaviour; Second harmonic generation

1. Introduction At the present time, a many compounds based on the cations of guanidinium and its derivatives are the object of chemical research for their role in living organisms, molecular design and their interesting physical–chemical properties [1–5]. Attention is focused especially on the group of hydrogen-bonded solids that potentially exhibit non-linear optical properties. For example, compounds of guanidine with orthoarsenic and phosphorous acids [6], guanidinium L-hydrogen tartrate [7] and many other organic nitrogencontaining salts with L-tartaric acid [8] such as L-histidinium *

Corresponding author. Tel.: +420 221 951 255; fax: +420 221 951 253. E-mail address: [email protected] (I. Neˇmec).

0022-2860/$ - see front matter  2006 Elsevier B.V. All rights reserved. doi:10.1016/j.molstruc.2006.08.006

L-tartrate

hemihydrate [9], melaminium L-tartrate monohydrate [10], piperazinium(2+) bis-(hydrogen L-tartrate) [8] and L-lysinium L-tartrate [11] were studied as promising materials for second harmonic generation (SHG). Aminoguanidinium(1+) hydrogen L-tartrate monohydrate (L-AmgHT) has been prepared as a new member of the family of novel potential NLO materials based on chiral tartrate anionic building blocks [12]. In this type of materials organic cations (carrying the high optical polarizability) with hydrogen-bonding organic anions (providing thermal and structural stability) are combined [13]. Hydrogen bonding in these salts provides a notable energetic contribution to the total lattice energy [13] and contributes to the second-order NLO tensor coefficient (dijk) of the crystals [14,15].

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This work, which is part of our project focused on preparation and study of novel materials with NLO properties, based on the salts of organic nitrogen-containing bases with tartaric acid, deals with the preparation, determination of the crystal structure, study of the vibrational spectra, the thermal behaviour and the efficiency of second harmonic generation of aminoguanidinium(1+) hydrogen L-tartrate monohydrate. 2. Experimental Crystals of L-AmgHT were prepared by slow spontaneous evaporation of the aqueous solution obtained by dissolving of aminoguanidine hydrogen carbonate (98.5%, Aldrich) in an L-tartaric acid solution (99%, Fluka, 2 mol dm3) in an equimolar ratio at laboratory temperature. The colourless crystals obtained were collected under vacuum on an S4 frit, washed with ethanol and dried in a desiccator over KOH. The results of elemental analysis (25.2% C, 5.6% H and 22.8% N) agree with the theoretical content (24.80% C, 5.83% H and 23.13% N). The N,O-deuterated compound was prepared by repeated recrystallisation of natural L-AmgHT from D2O (99%) in a desiccator over KOH. The infrared spectra of nujol and fluorolube mulls were recorded on a Nicolet Magna 760 FTIR spectrometer with 2 cm1 resolution and Happ-Genzel apodization in the 400–4000 cm1 region. The Raman spectra of polycrystalline samples were measured using a Nicolet Magna 760 FTIR spectrometer equipped with Nicolet Nexus FT Raman module. The measurements were carried out in the range of 100 to 3700 cm1 (Happ-Genzel apodization, 2 cm1 resolution, 1064 nm Nd:YVO4 laser excitation, 590 mW power at the sample). The spectra were processed using the OMNIC program [16]. The DSC measurements were carried out on Perkin-Elmer Pyris Diamond DSC and DSC 7 instruments in the temperature range from 95 to 380 K (heating rate of 10 K min1, nitrogen atmosphere-flow rate of 20 ml min1). The sample (about 10 mg) was enclosed in a small aluminium capsule. X-ray data collection was carried out on a NoniusKappa CCD diffractometer (Mo Ka radiation, graphite monochromator). The phase problem was solved by direct methods (SIR-92 [17]) and the non-hydrogen atoms were refined anisotropically, using the full-matrix least-squares procedure and the SHELX-97 program [18]. The positions of hydrogen atoms bound to non-carbon atoms were found from the difference Fourier map and their displacement factors were refined isotropically; the hydrogen atoms bound to carbon atoms were fixed in the theoretical positions. The basic crystallographic data, measurement and refinement details of L-AmgHT are summarised in Table 1. Crystallographic data (excluding structural factors) have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication CCDC 252737. A copy of the data can be obtained free of charge on applica-

tion to CCDC, 12 Union Road, Cambridge CB21 EZ, UK (fax: +44 1223 336 033; e-mail: [email protected]). The UV-VIS-NIR spectrum of aqueous solution (quartz cells) was recorded in the 190–1100 nm range using Unicam UV 300 spectrometer. The measurements of SHG at 800 nm were performed with 90 fs laser pulses generated at 82 MHz repetition rate by a Ti:sapphire laser (Tsunami, Spectra Physics). For quantitative determination of the SHG efficiency, the intensity of the back scattered laser light at 400 nm generated in the sample was measured by a grating spectrograph with diode array (InstaSpec II, Oriel) and the signal was compared with that generated in KDP (i.e., KH2PO4). The experiment was performed using powdered samples (75–150 lm particle size) loaded into 5 mm glass cells with the aid of vibrator and the measurements were repeated on different areas of the same sample (the results were averaged). This experimental procedure minimises the signal fluctuations induced by sample packing. 3. Results and discussion 3.1. The crystal structure The crystal structure of L-AmgHT is formed by aminoguanidinium(1+) cations, hydrogen L-tartrate anions and molecules of water connected by a system of hydrogen bonds. The atom numbering can be seen in Fig. 1 (PLATON software [19]). The selected bond lengths and angles are presented in Table 2. Hydrogen tartrate anions and molecules of water form a 3D framework (see Fig. 2) via O–H  O hydrogen bonds ˚ (see Table 3). The with the lengths of 2.588(1)–3.188(1) A ˚ ) connects strongest H-bond (O6–H6  O1vii 2.588(1) A protonised carboxylic group with the carboxylate group of another anion. Existence of this hydrogen bond is ˚) reflected in elongation of the C2–O1 bond (1.280(2) A ˚ ). The influence compared to the C2–O2 bond (1.236(2) A of different participation of hydroxyl groups in the H-bond network is also apparent in the slight elongation of the C3– ˚ ) bond compared to the C4–O4 bond O3 (1.422(2) A ˚ ). The O3 oxygen atom acts as an acceptor of (1.411(2) A medium O  H–O and weak O  H–N hydrogen bonds compared to atom O4, which is an acceptor of two weak O  H–N bonds (see Table 3). Non-hydrogen atoms in the aminoguanidinium(1+) cations form an almost ideal plane with deviations of atoms ˚ . The lengths of the C– from the plane of less than 0.01 A ˚ . The cations N bonds vary from 1.320(2) to 1.335(2) A are located in the centre of the anion framework cavities and are interconnected with the framework by N–H  O hydrogen bonds (see Fig. 3) with lengths of 2.842(2)– ˚ . The intramolecular hydrogen bond of the N– 3.246(2) A ˚ ) belongs H  N type (N4  N1 distance equal to 2.682(2) A to interesting bifurcated H-bond involving atoms N4, N1, O6 and H4A (see Table 3).

Z. Macha´cˇkova´ et al. / Journal of Molecular Structure 832 (2007) 101–107 Table 1 Basic crystallographic data, data collection and refinement parameters of L-AmgHT Empirical formula Formula weight Temperature Wavelength Crystal system Space group Unit-cell dimensions

Volume Z, Calculated density Absorption coefficient F (000) Crystal size Theta range for data collection Range of h, k and l

C5H14N4O7 242.20 g mol1 150(2) K ˚ 0.71073 A Orthorhombic P212121 ˚ a = 7.1380(2) A ˚ b = 9.9700(4) A ˚ c = 14.0790(6) A ˚3 V = 1001.94(7) A

4, 1.606 g cm3 0.149 mm1 512 0.325 · 0.525 · 0.625 mm 2.50 to 27.49 9 fi 9, 12 fi 12, 18 fi 18 Reflection collected/unique (Rint) 2272/2201 (0.020) Refinement method Full-matrix least-squares on F2 Data/restrains/parameters 2272/0/193 Goodness-of-fit on F2 1.118 Final R indices [I > 2r(I)] R1 = 0.0259, wR2 = 0.0708 R indices (all data) R1 = 0.0271, wR2 = 0.0716 ˚ 3 Largest diffraction max. and min. 0.209 and 0.210 e A No. and H range of unit-cell 2272, 1–27.5 determination Scan technique x scan to fill Ewald sphere P P Function minimised ½ ðwðF 2o  F 2c ÞÞ2 = ðwðF 2o ÞÞ2 1=2 Weighting scheme w ¼ ½r2 ðF 2 Þ þ ð0:0346P Þ2 þ 0:2487P 1

103

Table 2 ˚ ) and angles () for L-AmgHT Selected bond lengths (A Bond

Value

Angle

Value

N(1)–N(2) N(2)–C(1) N(3)–C(1) N(4)–C(1) C(2)–O(2) C(2)–O(1) C(2)–C(3) C(3)–O(3) C(3)–C(4) C(4)–O(4) C(4)–C(5) C(5)–O(5) C(5)–O(6)

1.414(2) 1.325(2) 1.335(2) 1.320(2) 1.236(2) 1.280(2) 1.537(2) 1.422(2) 1.531(2) 1.411(1) 1.532(2) 1.204(2) 1.329(2)

O(5)–C(5)–O(6) O(5)–C(5)–C(4) C(1)–N(2)–N(1) N(4)–C(1)–N(2) N(4)–C(1)–N(3) N(2)–C(1)–N(3) O(2)–C(2)–O(1) O(2)–C(2)–C(3) O(1)–C(2)–C(3) O(3)–C(3)—C(4) O(3)–C(3)–C(2) C(4)–C(3)–C(2) O(4)–C(4)–C(3) O(4)–C(4)–C(5) C(3)–C(4)–C(5) O(6)–C(5)–C(4)

125.2(1) 123.8(1) 118.9(1) 120.6(1) 120.5(1) 118.9(1) 126.1(1) 119.0(1) 114.9(1) 109.7(1) 110.3(1) 111.2(1) 107.6(1) 111.1(1) 108.1(1) 110.9(1)

o

P ¼ ðF 2o þ 2F 2c Þ=3

Fig. 2. Three-dimensional framework of hydrogen tartrate anions and molecules of water (projection to yz plane). Dashed lines indicate hydrogen bonds.

Fig. 1. Atom numbering scheme in asymmetric unit of L-AmgHT.

3.2. Vibrational spectra The number of normal modes of the crystalline L-AmgHT was determined by extended nuclear site group analysis [20]. Crystals of L-AmgHT belong in the P212121 ðD42 Þ space group with 30 atoms per asymmetric unit (Z = 4). All the atoms occupy fourfold positions a(C1).

Three types of species present in the unit-cell, aminoguanidinium(1+) cation, hydrogen L-tartrate anion and molecule of water, occupying fourfold positions a(C1), were considered in more detailed calculations of the internal and external modes. The results are the representations 18 A (RA) + 17 B1 (IR, RA) + 17 B2 (IR, RA) + 17 B3 (IR, RA) for external modes (excluding B1 + B2 + B3 acoustic modes) and 72 A (RA) + 72 B1 (IR, RA) + 72 B2 (IR, RA) + 72 B3 (IR, RA) for internal modes. However, expected level of factor group splitting has not been recorded. This observation could be explained by small inter-ion interaction in the unit-cell and also in terms of the fact that all the measurements were carried out on polycrystalline samples. The vibrational spectra of L-AmgHT are depicted in Fig. 4. The wavenumbers of the observed maxima and their intensities are given in Table 4. The assignment of the bands of the aminoguanidinium(1+) cation (see Table 4) is based on ab initio calculations

D–H  A i

N1–H1A  O4 N1–H1B  O5ii N2–H2A  O7iii N3–H3A  O1iv N3–H3B  O3 N3–H3B  O4 N4–H4A  N1 N4–H4A  O6v N4–H4B  O4 N4–H4B  O5 N4–H4B  O2vi O3–H3H  O7 O4–H4H  O3vi O4–H4H  O2vi O6–H6H  O1vii O7–H1W  O2vii O7–H2W  O1viii

d(D–H)

d(H  A)

d(D  A)

<(DHA)

0.92(2) 0.89(2) 0.76(2) 0.83(2) 0.81(2) 0.81(2) 0.80(2) 0.80(2) 0.81(2) 0.81(2) 0.81(2) 0.88(3) 0.88(3) 0.88(3) 0.91(3) 0.92(3) 0.81(2)

2.38(2) 2.35(2) 2.08(2) 2.27(2) 2.37(2) 2.60(2) 2.28(2) 2.38(2) 2.36(2) 2.49(2) 2.62(2) 1.79(3) 1.91(2) 2.53(2) 1.69(3) 1.78(3) 1.98(2)

3.236(2) 3.105(2) 2.842(2) 3.085(2) 3.070(2) 3.246(2) 2.682(2) 3.133(2) 3.002(2) 3.195(2) 3.142(2) 2.650(1) 2.742(1) 3.188(1) 2.588(1) 2.701(1) 2.762(2)

156(2) 143(2) 171(2) 168(2) 145(2) 138(2) 111(2) 157(2) 136(2) 145(2) 123(2) 166(2) 155(2) 132(2) 170(3) 176(2) 164(2)

Note. Equivalent positions: (i) x + 1/2,y + 3/2,z + 1; (ii) x  1/2,y + 3/ 2,z + 1; (iii) x + 3/2, y + 1,z + 1/2; (iv) x + 1,y  1/2,z + 1/2; (v) x + 3/2,y + 2,z + 1/2; (vi) x + 1,y + 1/2,z + 1/2; (vii) x + 1,y,z; (viii) x + 1/2,y + 3/2,z. Abbreviations: A, acceptor; D, donor.

Fig. 3. Incorporation of aminoguanidinium(1+) cation in cavity formed by hydrogen tartrate anions and molecules of water (projection to yz plane). Dashed lines indicate hydrogen bonds.

of vibrational spectra (HF/6-31G(d), precomputed vibrational scaling factor 0.899 [21]) using Gaussian 98W [22] and the GaussViewW 2.1 [23] program package. Details of these calculations will be published in a later paper concerning aminoguanidine compounds with nitric acid [24]. The assignment of hydrogen tartrate vibrational manifestations was performed according to previous spectroscopic studies of compounds of L-tartaric acid [11,25,26]. The spectra of

Raman intensity

Table 3 ˚ ) and angles () for L-AmgHT Hydrogen bond lengths (A

% Transmittance

Z. Macha´cˇkova´ et al. / Journal of Molecular Structure 832 (2007) 101–107

104

FTIR

FT Raman

4000

3500

3000

2500

2000

1500

1000

500

0

Wavenumber [cm-1]

Fig. 4. FTIR (compiled from nujol and fluorolube mulls) and FT Raman spectra of L-AmgHT.

the N,O-deuterated compound were measured to confirm the proposed interpretation (see Fig. 5 and Table 5). The strong broad structured band in the 3600 to 2200 cm1 region in the IR spectrum and medium bands located in the Raman spectrum in the 3450 to 3000 cm1 region correspond to the stretching vibrations of the NH and OH groups participating in the hydrogen bonds of the N–H  N, N–H  O or O–H  O types. As expected, these bands are shifted to the 2650–2100 cm1 region in the spectra of the deuterated sample. The vibrational manifestations of out-of-plane O–H(  O) and N–H(  O) bending modes, which are sensitive to deuteration, are present in the 910 to 820 cm1 region. Bands observed at 2946 and 2915 cm1 in the Raman spectrum (2945 cm1 in the IR spectrum) correspond to the C–H stretching vibrations of hydrogen tartrate anions. The strong band of the stretching C@O vibration located in the IR spectrum at 1732 cm1 (1733 cm1 Raman) is associated with the presence of a protonised carboxylic group in the structure. Strong to medium intensity bands originating from the antisymmetric stretching vibration of the carboxylate group (mixed with cation vibrations) were observed at 1620 and 1590 cm1 (shoulder) in the IR spectrum and at 1576 cm1 in the Raman spectrum, while those of the symmetric stretching vibration were recorded at 1446 and 1425 cm1 in both spectra. For the assignment of the other vibrational bands of hydrogen tartrate anions, see Table 4. The presence of aminoganidinium(1+) cations in the crystal structure is manifested in strong to medium intensity bands (sensitive to deuteration) in the IR spectrum at 1682, 1668, 1643, 1620, 1590 (shoulder) and 1533 cm1 (Raman 1681, 1666, 1657, 1638, 1574 and 1533 cm1), which can be assigned to the dNH2, mCN and dCNH vibrations. The influence of the rocking and wagging vibrations of the NH2 group in the cation vibrational bands (mostly mixed) at 1306, 1246, 1205, 1072, 991, 613, 495 and 480 cm1 in the IR spectrum (Raman 1307, 1239, 1219, 1076, 990, 613, 492, 480 and 340 cm1) is reflected in their sensitivity to deuteration.

Z. Macha´cˇkova´ et al. / Journal of Molecular Structure 832 (2007) 101–107

105

Table 4 FTIR and FT Raman spectra (cm1) of L-AmgHT FTIR

FT Raman (intensity)

Assignment

3440 3352 3327 3150 3090 2972 2945

s s s sb sb m m

3440 (3) 3352 (22) 3300 (18)

mN–H(  O), mN–H(  N) mO–H(  O), mN–H(  O), mN–H(  N)

2946 (28) 2915 (11)

mC–H

2875 2727 2500 2445 1960 1920 1885 1732

m m wb wb wb wb wb s

Computed aminoguanidinium(1+) frequencies HF/6-31G(d) Wavenumber

1682 s 1668 s 1643 1620 1590 1533 1446 1425 1360 1306

s s sh m m sh m s

1246 1205 1128 1072

s s s s

1001 m 991 m

1733 (24)

mC@O

1681 1666 1657 1638

(18) (15) (15) (8)

dNH2, mCN, dCNH dNH2, mCN, dCNH, dH2O dNH2, mCN, dCNH

1574 1533 1446 1425 1365 1307 1268 1239 1219 1136 1076

(7) (13) (9) (9) (18) (16) (10) (18) (18) (10) (20)

990 967 906 892

(34) (100) (17) (57)

1695 1682 1660

51/100 96/45 21/9

dNH2, mCN dNH2, mCN, dCNH

masCOO, dNH2, mCN, dCNH

1609

25/9

dNH2, mCN, dCNH

dNH2, mCN, dCNH msCOO msCOO, dCNH, mCN dCOH qNH2 ? dCNH, mNN, qNH2, dCH

1546

3/9

1429

9/9

dCNH, mCN

1311

0/36

qNH2

1202

6/36

dCNH, mNN, qNH2

1070 1055

0/0 2/36

qNH2, mCN

968 933

9/91 23/45

msCN3, xNH2, qNH2 xNH2

724

9/0

dsCN3, sNH2

633 602

7/9 1/18

dNCN, dCNN, cNH2, qNH2

520

36/27

cCNH, sNH2

473 468 379

100/9 0/18 3/0

cCNH, xNH2, dNCN

325 315

1/0 19/0

dNCN, dCNN xNH2, cCNH

219

1/0

cCNH, sNH2

158

1/0

cCNN, cNCN

mC–O mC–O, qNH2, mCN

677 s

681 (10)

dCOO, sNH2, dsCN3

613 592 538 495 480

613 599 543 492 480

dNCN, dCNN, cNH2, qNH2 dCOO cCNH, sNH2 cCNH, xNH2, dNCN dNCN, cCNH, xNH2

w m m m s

mN–H

?

831 (16) 780 (57)

w w w m m

Assignment

mO–H(  O)

mCC mCC, xNH2, qNH2 msCN3, xNH2, qNH2 cO–H(  O), xNH2 mCC cO–H(  O), cN–H(  O) dCOO, cO–H(  O), cN–H(  O) dCOO

908 889 879 831 781

Intensity (IR/RA)

3540–3367a

(24) (19) (9) (33) (24)

374 (15) 340 (19)

xCOO, sCC, sNH2 xNH2, cCNH, dNCN, dCNN

320 (10) 256 (10)

xCOO, sCC, xNH2, cCNH xCOO, sCC

197 (34) 173 (34) 145 (83)

sCOO cCNN, cNCN External mode

sNH2

Note. Abbreviations: s, strong; m, medium; w, weak; b, broad; sh, shoulder; m, stretching; d, deformation or in-plane bending; c, out-of-plane bending; q, rocking; x, wagging; s, torsion; s, symmetric; as, antisymmetric. a Formation of hydrogen bonds, which strongly affects positions and intensities of the bands, was not considered in calculations.

Z. Macha´cˇkova´ et al. / Journal of Molecular Structure 832 (2007) 101–107

Raman intensity

% Transmittance

106

Table 5 FTIR and FT Raman spectra (cm1) of N,O-deuterated L-AmgHT

FTIR

FT Raman

4000

3500

3000

2500

2000

1500

1000

500

0

Wavenumber [cm-1]

Fig. 5. FTIR (compiled from nujol and fluorolube mulls) and FT Raman spectra of N,O-deuterated L-AmgHT.

The most intense band in the Raman spectrum at 967 cm1 is very characteristic for the aminoguanidinium(1+) moiety, and can be assigned to the mixed vibrations ms CN3, xNH2 and qNH2. This band is also very sensitive to N,O-deuteration of the sample. The Raman band at 145 cm1 can be assigned to external mode of the L-AmgHT crystals.

FTIR

FT Raman (intensity)

Assignment

3404 w, 3367 m

3367 (5)

3326 m 3180 mb, 3050 wb

3324 (9)

2947 2914 2890 2594 2576 2507

2947 (92) 2914 (61)

residual mN–H(  O), mN–H(  N) 2 · mC@O residual mN–H(  O), mO–H(  O) mC–H

w w wb, 2725 w, 2667 w s s s

2474 s 2436 s 2407 s s sh, 2035 w w, 1903 w s s s

3.3. Thermal behaviour Crystals of L-AmgHT are stable in the air up to a temperature of 388 K, when they begin to melt. DSC measurements were carried out from a temperature of 95 K up to 380 K. Only a weak endothermic effect was observed (onset 268 K, DH = 49 J mol1) on heating the sample. The effect was shifted to lower temperatures (onset 247 K, DH = 34 J mol1) in the subsequent cooling run. The nature of this effect is unclear because subsequent crystal structure determinations at 293 and 150 K did not show any change in the structure. However, the existence of an isostructural phase transition cannot be excluded.

1333 s 1290 s 1255 m 1225 m 1207 m 1171 w 1150 sh 1134 s 1107 m 1088 m 1051 m 1003 m 964 w

3.4. Second harmonic generation

930 w 893 w 868 w 798 764 675 654

w m w m

600 w 553 w

4. Conclusions 473 w

The title compound, aminoguanidinium(1+) hydrogen monohydrate, was prepared and its crystal structure was solved by X-ray structural analysis. The crystal structure consists of a 3D framework formed by hydrogen tartrate anions and water molecules (via O–H  O hydrogen bonds) with incorporated aminoguanidini-

L-tartrate

2480 2474 2459 2441

residual mO–H(  O) mN–D(  O), mN–D(  N) mO–D(  O), mN–D(  O), mN–D(  N)

(39) (40) (48) (100)

2380 (34) 2335 2170 1975 1730 1630 1589

1460 w 1400 s

According to the acentric orthorhombic space group (P212121) of L-AmgHT and the fact that the material is optically transparent down to 300 nm (see Fig. 6), quantitative measurements of the SHG efficiency were carried out at 800 nm. The relative efficiency of powdered LAmgHT was observed as equal to 14% compared to KDP.

2593 (23) 2573 (22) 2506 (61)

mO–D(  O) 1729 (36) 1602 (19) 1505 (10) 1396 1379 1332 1288 1256 1226 1204 1173

(21) (16) (28) (23) (9) (25) (12) (12)

1138 1104 1079 1054 1010 959 946 930 893 870 825 798 764

(16) (4) (10) (6) (9) (19) (17) (35) (49) (33) (12) (19) (25)

652 (8) 590 576 564 543 472 420 366 329 306 252 191 176 144

(20) (14) (15) (10) (16) (12) (11) (9) (14) (11) (37) (35) (42)

mC@O masCOO, mCN mCN msCOO, mCN dND2 dND2, dCND mNN, dCH mNN, dCH, dND2, dCND mNN, dCH dND2, dCND mC–O dND2, dCND mC–O, mCN dCOD, qND2 mCC, qND2 msCN3, qND2 qND2 mCC dCND, qND2 dCOO, dCND, qND2 qND2, dCOO dCOO dCOO, dsCN3 dCOO, dsCN3, cO–D(  O), cN–D(  O) dCOO sND2

dNCN cCND, sND2 xCOO, sCC cCND, xND2 xCOO, sCC, cCND, xND2 xCOO, sCC sCOO External modes

Z. Macha´cˇkova´ et al. / Journal of Molecular Structure 832 (2007) 101–107 100 90 80

% Transmittance

70 60 50 40 30 20 10 0 200

300

400

500

600

700

800

900

1000

1100

Wavenumber [nm]

Fig. 6. UV-VIS-NIR spectrum of L-AmgHT aqueous solution.

um(1+) cations connected by a system of N–H  O hydrogen bonds. The FTIR and FT Raman spectra of polycrystalline substance were measured and interpreted. The thermal behaviour of the compound was studied by the DSC method in the temperature range of 95–380 K. Despite the existence of a weak anomaly at 268 K, no change in the crystal structure was observed. Measurements of the SHG efficiency of the powdered sample (14% efficiency compared to KDP) together with thermal stability (melting at 388 K) and optical transparency of the material evince that L-AmgHT is a quite promising novel second harmonic generator. Acknowledgements This work was financially supported by the Grant Agency of Charles University in Prague (Grant No. 337/2005/BCh) and the Ministry of Education, Youth and Sports of the Czech Republic (Grant No. 1902/2004). References [1] P.S. Pereira Silva, J.A. Paixa˜o, A. Matos Beja, M.R. Silva, L.A. da Veiga, Acta Crystallogr. C 55 (1999) 1096. [2] J.A. Paixa˜o, P.S. Pereira Silva, A. Matos Beja, M.R. Silva, E.deM. Gomes, M. Belsey, Acta Crystallogr. C 55 (1999) 1287. [3] M. Drozd, J. Baran, A. Pietraszko, Spectrochim. Acta A61 (2005) 2775.

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