Journal of Crystal Growth 213 (2000) 103}111

Growth and investigation of new non-linear optical crystals of

LAP family
A.M. Petrosyan , R.P. Sukiasyan , H.A. Karapetyan
, S.S. Terzyan
,
R.S. Feigelson*
Yerevan State University, Alex Manoogian St. 1, Yerevan 375049, Armenia

MSRC, NAS of Armenia, Azatutyan Ave., 26, Yerevan 375014, Armenia
Center for Material Research, Stanford University, 105 McCullough Building, Stanford, CA 94305-4045, USA
Received 18 November 1998; accepted 2 December 1999
Communicated by P.A. Morris Hotsenpiller

Abstract

The possibility of preparing new analogs of L-arginine phosphate monohydrate, (LAP), has been investigated. Single
crystals of the compound L-Arg ) HCOOH, which had earlier been obtained in powdered form, were successfully grown
during the course of this investigation. In addition, we have found that there is a class of compounds having the Arg ) 2Ax
composition, (where Ax is one of several inorganic or organic acids). Such compounds (Arg ) 2HIO , Arg ) 2HNO ,
 
Arg ) 2H PO , Arg ) 2HF, Arg ) 2HCl ) H O, and Arg ) 2HBr ) H O) have been synthesized and single crystals grown. The
   
crystals grown in this investigation were studied by IR and X-ray di!raction methods. The in#uence of the di!erent
amino acid groups on crystal symmetry and the in#uence of this symmetry on non-linear optical properties are
discussed.  2000 Elsevier Science B.V. All rights reserved.

PACS: 42.70.M; 61.66.H; 78.30

Keywords: Non-linear optical crystals; LAP-analogs

1. Introduction KDP, LAP can easily be grown from water solu-

The outstanding non-linear optical (NLO)
properties of L-arginine phosphate monohydrate
crystals, (LAP), chemical formula L-Arg ) H PO )
 
H O, (where Arg is NH C(NH)NH(CH )
  
CH(NH )COOH), were found by Chinese re-

searchers in 1983 [1]. Like the widely used crystal
* Corresponding author. Fax: #1-415-7233044.
E-mail address: feigel@popserver.standford.edu (R.S. Feigelson).
tion. It is, however, less hygroscopic than KDP
crystals and has a wide transparency range. Its
e!ective NLO coe$cient is three times greater, and
it has a much higher threshold power for optical
damage [2}4]. In addition, it is comparable to the
best NLO crystals now in use [5]. These properties
make it a strong candidate to replace KDP. It is,
therefore, very important that research to improve
both LAP's growth technology and properties (e.g.
by deuteration, which improves the transparency
range, and by other compositional modi"cations

0022-0248/00/$ - see front matter  2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 0 ) 0 0 0 1 1 - 7
104 A.M. Petrosyan et al. / Journal of Crystal Growth 213 (2000) 103}111
which can improve non-linear performance), be
undertaken [6}11].
The widest search for new compounds and crys-
tals of LAP analogs was carried out by Monaco
et al. [6]. They reacted arginine with equimolar
amounts of various acids and were successful in
crystallizing some new crystals. In some cases it was
not possible to get crystals because of the very high
solubility of the compounds or because they pre-
cipitated out as "ne non-crystalline powders (e.g.
Arg ) HIO and Arg ) HNO ). It was found that the
 
second-harmonic generation (SHG) signals coming
from crystals with a P2 symmetry were much

more intense than those from crystals with sym-
metry P2 2 2 . Their attempts to make arginine
  
monoarsenate Arg ) H AsO resulted in the un-
 
expected formation of arginine diarsenate
Arg ) 2H AsO .
 
In our attempts to prepare the acid iodate of
arginine, we obtained Arg ) 2HIO which, unlike

Arg ) HIO , crystallizes easily. However, deter-

mination of the crystal and molecular structure of
Arg ) 2HIO has shown that it does not contain an

HIO group [12]. Its formation is a consequence of
 
a peculiarity of the arginine structure (namely, due
to the existence of both amino and guanidyl
groups) and not the property of HIO to form

acid compounds. This realization and also the re-
sults of an analysis of the crystal structure of
Arg ) 2H AsO [13], has brought us to the con-
 
clusion that the formation of Arg ) 2H AsO and
 
Arg ) 2HIO is the rule rather than the exception

[12].
The successful crystallization of Arg ) 2HNO ,

Arg ) 2H PO , Arg ) 2HF, Arg ) 2HCl ) H O, and
  
Arg ) 2HBr ) H O means that we have found an

entirely new class of arginine compounds with
composition Arg ) 2Ax, where Ax represents vari-
ous inorganic or organic acids.
2. Experimental procedure
The L-arginine amino acid used in the present
work was purchased from the Institute of Biotech-
nology (former Institute of Amino Acids, Yerevan).
Compounds were synthesized by interacting water
solutions of arginine and other acids in the desired
molar relationships and subsequently evaporating
them. IR spectra were recorded on a Specord 75IR
spectrophotometer using the nujol mull method
(powder mixed with oil). The X-ray data were col-
lected on an automatic di!ractometer ENRAF-
NONIUS CAD-4 (Mo K radiation, graphite
a
monochromator). The structures were solved by the
direct method and re"ned by the full-matrix least-
squares technique using the SHELXL-93 program
[14]. The SHG e!ect was measured in both powders
and crystals using a Nd : YAG Q-switched laser.
Crystals were grown by both the evaporation
and cooling methods. At this stage there was no
purpose in growing crystals of large sizes. It was
more important to "nd the simplest crystallization
conditions to produce small crystals suitable for
preliminary characterization. In the future, atten-
tion will be paid to the growth of larger, higher
quality crystals of the more promising materials.
3. Results and discussion
The arginine molecule (Arg) NH C(NH)NH
(CH ) CH(NH )COOH has two groups (guanidyl
 
and a-amino) which are able to be protonated. The
guanidyl group has more basicity and in an ar-
ginine dihydrate crystal [15], it is protonated
owing to its own carboxyl COOH group. In
Arg ) Ax-type salts, where Ax is HCl, HBr, H PO ,
 
the a-amino group is also protonated owing to the
hydrogen of the Ax acid. The carboxyl group re-
mains in an ionized state [16}20]. The C}O bond
lengths in the COO\ ionized groups are approxim-
ately equal to 2.5 As . The absorption band of the
COO\ ionized group in the IR spectrum is near
1600 cm\ (1575}1630 cm\). The deformation vi-
brations of the NH> and NH> groups [21] also
 
fall in this range.
In case of the Arg ) 2Ax-type salts, the COO\
group is also protonated to the carboxyl COOH
group. The C"O and C}OH bond length in
COOH group are 1.20}1.22 and 1.30}1.3 As , respec-
tively [22]. The COOH group is characterized by
the appearance of an absorption band near
1700 cm\ (1660}1750 cm\).
As pointed out above, Arg ) 2HIO can be cry-

stallized from aqueous solutions containing
 A.M. Petrosyan et al. / Journal of Crystal Growth 213 (2000) 103}111
arginine and iodic acid, in a ratio almost equal to
two. At Arg : HIO ratios of three or more, viscous

solutions formed. Based on preliminary estimates,
the solubility of Arg ) 2HIO increased from
 
14 g/100 g H O at 203C to 33 g/100 g H O at 503C.
 
Single crystals as large as 45;18;15 mm could
be grown using the temperature decreasing method
in the range of 40}153C. The habit of Arg ) 2HIO

crystals and their orientation axes were obtained by
means of optical goniometry (based on X-ray data),
and are shown in Fig. 1. It is interesting to note that
unlike LAP solutions, the appearance of microbes
during the growth of Arg ) 2HIO was not ob-
 
served. Probably, the iodine compounds act de-
structively on the growth of microbes. Some crystal
data for Arg ) 2HIO is presented in Table 1. The
 
IR and crystal structure data for Arg ) 2HIO were

presented in Ref. [12].
Fig. 1. The habit of L-Arg ) 2HIO crystals and their orientation

axes.
105
Another system, from which "ne powders were
obtained with a 1.1 composition, was Arg#
HNO #H O [6]. As we have stated previously,
 
the compound Arg ) 2HNO can be crystallized
from solutions containing Arg : HNO in ratios

from 2 to 10. The Arg ) 2HNO crystals belong to

the monoclinic system (Table 1). There is a narrow
absorption band near 815 cm\ (see Fig. 2) related
to the deformation vibration of the NO groups,

which is also found in the Arg ) HNO IR spectrum.

There is a strong absorption band near 1737 cm\
in the region of the COOH group absorption. This
band was absent from the spectrum of Arg ) HNO .
There was also an absorption band at 3450 cm\
(which is in the region of the O}H bond vibration).
Since Arg ) 2HNO crystals do not contain water
molecules, this band must be related to the stretch-
ing vibration of the O}H bond of the COOH
group.
A detailed description of the crystal structure of
Arg ) 2HNO and other crystals will be given else-

where because of the limited size of this paper. We
want to note that they con"rm the conclusions
deduced from the IR spectrum. The C"O and
C}OH bond lengths in the COOH group are
1.201(3) and 1.325(4) As , respectively. There is a net-
work of hydrogen bonds between the nitrate ions
and the hydrogen ions in the NH>, NH> and OH
 
groups. The stronger hydrogen bonds are in
NH>2ONO and OH2ONO with N2O
  
and O2O distances equal to 2.83 and 2.65 As ,
respectively. We have grown plate-shaped crystals
of Arg ) 2HNO in sizes up to 26;5;1 mm. The

wide range of crystallization conditions observed,
however, suggest that we should be able to "nd
more optimal processing parameters which will
allow the preparation of isometric crystals.
The Arg#H PO #H O system di!ers from
  
the two preceding ones because crystals with a
1 : 1 composition (i.e. LAP) also form. We were,
however, able to grow single crystals of the
Arg ) 2H PO composition by using solutions con-
 
taining an Arg : H PO ratio of more than two.
 
Fig. 4 shows some crystals grown using the cooling
method over a 26 day period at growth rates of
1}1.4 mm/day. We had to add H O as in the case
 
of LAP [4] to inhibit microbe formation. The
Arg ) 2H PO crystals were more thermally stable
 
106 A.M. Petrosyan et al. / Journal of Crystal Growth 213 (2000) 103}111

Table 1
Crystal data of some crystals

Arg ) 2HIO Arg ) 2HNO Arg ) 2H PO Arg ) 2HBr ) H O Arg ) 2HCl ) H O Arg ) 2HF Arg ) HCOOH
     
a, As 6.9554 (14) 7.754(2) 7.000(1) 6.7998(14) 7.5280(15) 7.145(1) 7.702(2)
b, As 7.998(2) 7.286(1) 9.681(2) 7.2709(15) 7.5760(15) 8.258(2) 7.805(2)
c, As 25.038(5) 11.673(2) 21.756(4) 7.6650(15) 21.750(4) 17.782(4) 18.581(4)
a,3 90 90 90 68.77(3) 90 90 90
b,3 90 92.60(3) 90 82.87(3) 90 90 90
c,3 90 90 90 67.88(3) 90 90 90
V, As  1392.8 658.8 1473.3 327.21 1240.15 1049.2 1117.0
Z 4 2 4 1 4 4 4
D , g/cm 2.509 1.514 1.668 1.797 1.323 1.356 1.310

Space group P2 2 2 P2 P2 2 2 P1 P2 2 2 P2 2 2 P2 2 2
               

Fig. 2. Infrared spectrum of L-Arg ) 2HNO .



as they do not contain crystalline water. These
crystals, some of which were up to 3;7;31 mm
in size, had an LAP-like shape in spite of their
rhombic symmetry (Table 1). Similar crystals were
also grown by the evaporation method. In addition
to the absorption bands characteristic of the
H PO ion, which were also present in the
 
LAP spectrum [23,24], the IR spectrum of
Arg ) 2H PO (Fig. 3) consists of a band at
 
1715 cm\. This con"rms the existence of the
COOH group. From the X-ray di!raction data,
Arg ) 2H PO was found not to contain water mol-
 
ecules. Therefore, the high-frequency peak at
3433 cm\ may relate to the stretching vibration of
the O}H bond of the carboxyl group COOH. Our
attempts to obtain hydrated crystals by crystalliza-
tion at temperatures up to 03C failed. Bond leng-
ths in the dihydrogen phosphate ions in the
Arg ) 2H PO structure (Fig. 4) were close to the
 
appropriate bond lengths for LAP. Bond lengths of
 A.M. Petrosyan et al. / Journal of Crystal Growth 213 (2000) 103}111
Fig. 3. Infrared spectrum of L-Arg ) 2H PO .
Fig. 4. Photograph of typical Arg ) 2H PO crystals.
 
the C"O and C}OH bonds in the carboxyl group
(1.20(4) and 1.316(4) As , respectively), were close to
that of Arg ) 2HNO and Arg ) 2H AsO [11].
   
There is a hydrogen bond O}H2O with the oxy-
gen atom of one of the dihydrogen phosphate ions,
which is equal to 2.55 As .
The two other systems, Arg#HCl#H O and

Arg#HBr#H O form the hydrated crystals

Arg ) Ax ) H O and Arg ) 2Ax compounds. As in the

previous two cases there were absorption bands at
1733 and 1713 cm\, respectively, in the region of
the COOH group (Figs. 5 and 6). It shows that the
107
 
guanidyl and a-amino groups of arginine are proto-
nated owing to the two hydrogens in the HCl and
HBr molecules with the carboxyl group remaining
protonated. Since the stretching vibrations of the
O}H bonds in the COOH group fall into the same
region as the stretching vibrations of the OH bonds
in water molecules, and the deformation vibrations
of the water molecules fall into the region of the
deformation vibrations of NH> and NH> groups,
 
it is di$cult to determine with certainty the pres-
ence or absence of water molecules on the basis of
the IR spectra alone. A determination of the crystal
structure has shown that they contain molecular
water. We have grown single crystals of
Arg ) 2HCl ) H O in sizes up to 4;5;10 mm by
evaporation.
In the system Arg#HF#H O, in addition to

the compound Arg ) HF, crystals of which were the
most promising among the crystals obtained by
Ref. [6], we discovered a new compound from
solutions with a ratio of Arg : HF of more than 1 : 2.
The IR spectra of these crystals di!ered from that of
Arg ) HF. However, the IR spectrum (Fig. 7) did not
contain a band with a frequency of more than
108 A.M. Petrosyan et al. / Journal of Crystal Growth 213 (2000) 103}111
Fig. 5. Infrared spectrum of L-Arg ) 2HCl ) H O.
1700 cm\, which is characteristic for COOH
groups in crystals having the Arg ) 2Ax composition.
A determination of the crystal structure allowed us
to explain the reason for this peculiarity. Guanidyl
and a-amino groups of arginine are protonated due
to the ionization of a carboxyl group and a proton
from one of the HF groups. The other proton par-
ticipates in the creation of an (F2H2F)\ anion
with an almost symmetric hydrogen bond. A strong
similarity exists between the crystal data of
Arg ) 2HF and Arg ) HCOOH (see Table 1).
Another system besides Arg#HIO #H O
 
and Arg#HNO #H O, which was found to
 
form "ne non-crystallizing powders of the Arg ) Ax
composition [6], was Arg#HCOOH#H O.

Like the two previous cases we also tried to obtain
crystals with the Arg ) 2Ax composition. From solu-
tions containing an Arg : HCOOH ratio in the
range 2}5, we obtained crystals which gave rather
strong SHG signals. The IR spectrum from these
crystals (Fig. 8) did not contain an absorption band
with a frequency higher than 1700 cm\ which is
characteristic of the COOH group and crystals
with the Arg ) 2Ax composition. Nevertheless, on

basis of the absorption band at 1690 cm\ we can
only conjecture about the formation of crystals
with a 1.2 composition. A determination of the
crystal structure by X-ray di!raction analysis, how-
ever, showed that the true composition of these
crystals was Arg ) HCOOH. Moreover, it was found
that the white non-crystalline precipitate formed
from solution with an Arg : HCOOH ratio equal to
one, can be recrystallized by using seed crystals of
Arg ) HCOOH obtained from more acidic solu-
tions. There is an ionized COO\ group in the
arginine molecule in Arg ) HCOOH crystals and
the guanidyl and a-amino groups are protonated.
The C}O bond distances in COO\ are 1.244(3) and
1.256(3) As . However, the C}O bond lengths in the
formate ion, HCOO\, are essentially shorter:
1.221(3) and 1.231(3) As , which can explain the exist-
ence of the band near 1690 cm\. Crystal data on
arginine formate are presented in Table 1. These
crystals had rhombic symmetry which apparently
di!ers from a monoclinic modi"cation reported by
Suresh et al. [25] who used di!erent preparative
procedures. Single crystals of Arg ) HCOOH up to
3;5;7 mm have been grown in this study.
A.M. Petrosyan et al. / Journal of Crystal Growth 213 (2000) 103}111 109

Fig. 6. Infrared spectrum of L-Arg ) 2HBr ) H O.



Fig. 7. Infrared spectrum of L-Arg ) 2HF.

110 A.M. Petrosyan et al. / Journal of Crystal Growth 213 (2000) 103}111

Fig. 8. Infrared spectrum of L-Arg ) HCOOH.

We were not able to obtain crystals of the composi- covery of Arg ) 2H AsO , Arg ) 2H PO , Arg )
   
tion Arg ) 2Ax for HClO . The known 1.1 compound 2HIO , Arg ) 2HNO , Arg ) 2HF, Arg ) 2HCl ) H O
   
is the only one which formed from Arg#2HClO and Arg ) 2HBr ) H O indicate that a class of ma-
 
solutions. At Arg#3HClO and higher ratios a vis- terials of this type does exist, and some may be

cous non-crystallizing solution is formed. promising for non-linear optic applications.
To guarantee the creation of enantiomorphic
and hence acentric crystals, it is necessary to use
optically active amino acids. Crystals of com- Acknowledgements
pounds with arginine, lysine, citrulline, etc. seem to
be promising. Among the ten most popular space We thank Dr. E.S. Abovyan for his assistance.
groups just P2 2 2 (11.6%), P2 (6.7%) and P1
    The research described in this publication was
(1.0%) are enantiomorphic [26]. The P2 and P1
 made possible in part by Award No. ACH-009-98
space groups have some advantages in that they of the National Foundation of Science and Ad-
allow the maximal contribution of the molecular vanced Technology and No. AB2-958 of the US
non-linearity to the macroscopic crystal non-lin- Civilian R&D Foundation for the Independent
earity (38%) compared with 19% for the P2 2 2
   States of the Former Soviet Union (CRDF).
structure [26]. In addition, the P2 and P1 space

groups allow non-critical phase-matching, while in
case of P2 2 2 this is impossible [26,27].
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