JOURNAL OF SOLID STATE CHEMISTRY 141, 343—351 (1998)
`ARTICLE NO. SC987933
`
`Crystal Structures and Thermal Behavior
`of Two New Organic Monophosphates
`Leila Baouab and Amor Jouini1
`Laboratoire de Chimie du Solide, De´ partement de Chimie, Faculte´ des Sciences, Universite´ du Centre, Monastir 5000, Tunisia
`
`Received July 29, 1997; in revised form June 8, 1998; accepted June 23, 1998
`
`· H2O
`· HPO22
`Two new organic monophosphates, C3H12N21
`4
`2
`(DAPHP) and C6H18N21
`
`· 2HPO24 · 4H2O (TMEDH2P), are
`3
`obtained by action of H3PO4 with respectively 1,2-diaminop-
`ropane and N,N,N@,N@-tetramethylethylenediamine. DAPHP is
`monoclinic, P21/n, with a 5 10.653(3) As , b 5 6.025(1) As , c 5
`13.159(2) As , b 5 92.37(2)°, Z 5 4, and qmeasd 5 1.48 g/cm3. Its
`atomic arrangement
`is described by infinite polyanions,
`(HPO4)2n2, organized in ribbons alternating with organic ca-
`
`n
`triclinic, with a 5 8.209(2) As , b 5
`tions. TMEDH2P is
`8.423(2) As ,
`c 5 8.709(2) As ,
`a 5 96.70(2)°,
`b 5 113.88(2)°,
`c 5 118.02(1)°, Z 5 1, and qmeasd 51.39 g/cm3. Its structure
`chains where organic cations are
`exhibits infinite (H2PO4)n2
`n
`anchored between adjacent polyanions. In both structures a net-
`work of strong hydrogen bonds connects the di§erent com-
`ponents in the building of the crystal. ( 1998 Academic Press
`
`I. INTRODUCTION
`
`The crystal chemistry of alkyl cations encapsulated be-
`4 ]n polyanions is
`4 ]n or [H2PO~
`tween chains of [HPO2~
`fascinating because it may lead to single crystals of polar
`materials. The various types of these polyanions, observed
`in many crystal structures, reveal the flexibility of the ag-
`gregation with respect to the chiral or achiral cations and
`the possible interaction of the small dipole moments of
`4 units with the dipole moments of the
`4 or H2PO~
`HPO2~
`organic moieties, which may induce acentricity in new ma-
`terials. The present work continues a series of investigations
`into the factors influencing the dimensions of phosphoric
`anion—organic cation interactions. In our previous papers
`(1—4), the e§ects of base modification and protonation in
`this new field of compounds including organic cations and
`phosphoric anions, linear P2O7, or cyclic PnO3n (n"3, 4, 6)
`have been mostly studied to inspect the influence of di§erent
`counteranions on the conformation and hydrogen-bonding
`properties of organic entities and water molecules in the
`solid state. In this context it may be appropriate to mention
`
`1To whom correspondence should be addressed.
`
`that the role of counteranions is rather e¶cient with small
`acentric ones such as (CuCl4)2~ (5),
`(HPO4)2~ (6), or
`(H2PO4)~ (7, 8). We report here the preparation and char-
`acterization of two new materials synthesized in the system
`org`—H3PO4—H2O as single crystals, where org` are 1,2-
`diammoniopropane [(C3H12N2)2`] and N,N,N@,N@-tetra-
`methylethylenediammonium [(C6H18N2)2`]. The
`two
`compound formulas C3H12N2(HPO4) ) H2O and C6H18N2
`respectively denoted
`(H2PO4)2 ) 4H2O are hereafter
`DAPHP and TMEDH2P.
`
`II. CRYSTAL CHEMISTRY
`1. Chemical Preparation
`
`Crystals of DAPHP and TMEDH2P are easily prepared
`by slow evaporation at room temperature of an aqueous
`solution of H3PO4 and the corresponding organic molecule
`in the stoichiometric ratio. Schematically the reactions are:
`H3PO4#CH3CH(NH2)CH2NH2
`P[CH3CH(NH3)CH2NH3]HPO4 ) H2O
`2H3PO4#(CH3)2N(CH2)2N(CH3)2
`P[(CH3)2NH(CH2)2NH(CH3)2](H2PO4)2 ) 4H2O
`After several weeks, the solutions lead to transparent thin
`single crystals of DAPHP and stout colorless monoclinic
`prisms of TMEDH2P. Their chemical syntheses are repro-
`ducible, and the crystals obtained in this way are pure
`and stable under normal conditions of temperature and
`humidity.
`
`2. Crystal Data and Structure Determination
`
`The Weissenberg and oscillation photographs taken with
`Cu(Ka1,2) radiation show that DAPHP and TMEDH2P
`crystallize in the triclinic and monoclinic systems. The unit
`cell dimensions of both salts were measured and refined
`using a set of high-angle reflections 14°(h(16° collected
`
`343
`
`0022-4596/98 $25.00
`Copyright ( 1998 by Academic Press
`All rights of reproduction in any form reserved.
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`344
`
`BAOUAB AND JOUINI
`
`TABLE 1
`Main Crystallographic Features, X-Ray Di§raction Data
`Collection Parameters, and Final Results for DAPHP
`
`TABLE 2
`Main Crystallographic Features, X-Ray Di§raction Data
`Collection Parameters, and Final Results for TMEDH2P
`
`I. Crystal data
`FW"190.14
`Formula: (C3H12N2)HPO4 ) H2O
`Space group: P21/n
`Crystal system: Monoclinic
`a"10.653(3) As , b"6.025(1) As
`»"843.9(3) As 3
`Z"4
`c"13.159(2) As , b"92.37(2)°
`o#!-#$/o.%!4$"1.497/1.48 g ) cm~3
`F(000)"408
`Linear absorption factor
`Morphology
`Crystal size
`
`k(MoKa)"0.311 mm~1
`Prism
`0.35]0.38]0.25 mm
`
`Temperature: 293 K
`Di§ractometer: Nonius CAD4
`Monochromator: graphite plate
`
`Variable scan speed
`h range:
`Background measuring time
`Measurement area: $h, k, l
`Number of scanned reflections:
`Number of unique reflections:
`Reference reflection (1)
`Intensity decay
`
`II. Intensity measurements
`Wavelength: MoKa (0.7107 As )
`Scan mode: u/2h
`Scan width: 0.61#0.87 tan h
`π.!9 per scan: 60 s
`2—25°
`π.!9/2
`h.!9"12, k.!9"7, l.!9"15
`1711
`1477 (R*/5"0.016)
`511 4 (every 2 h)
`0.73%
`
`I. Crystal data
`O FW"384.26
`) 4H
`2
`Space group: P11
`»"4496(1) As 3
`Z"1
`F(000)"206
`
`2
`
`PO
`)(H
`N
`Formula: (C
`H
`)
`2
`18
`6
`2
`4
`Crystal system: Triclinic
`a"8.209(2) As , b"8.423(2) As
`c"8.709(2) As , a"92.70(2)°
`b"113.88(2)°, c"118.02(1)°
`o#!-#$"1.422, o.%!4$"1.39 g ) cm~3
`Linear absorption factor
`Morphology
`Crystal size
`
`k(MoKa)"0.288mm~1
`Elongated triclinc prism
`0.12]0.13]0.21 mm
`
`Temperature: 293 K
`Di§ractometer: Nonius CAD4
`Monochromator: graphite plate
`
`Variable scan speed
`h range
`Background measuring time
`Measurement area: $h, $k, l
`Number of unique reflections:
`Reference reflection (1)
`Decay
`
`II. Intensity measurements
`Wavelength: MoKa (0.710 As )
`Scan mode: u/2h
`Scan width: 0.65#0.82 tan h
`π.!9 per scan: 60 s
`3—25°
`π.!9/2
`h.!9"8, k.!9"9, l.!9"16
`1701
`122 (every 2 h)
`2.1%
`
`Corrections
`
`III. Structure determination
`Lorentz and polarization corrections;
`no absorption correction
`SHELXS86 (9) (direct methods)
`SHELXL93 (10) on personal computer
`1297 (I'2pI)
`161
`1.073
`0.0040(4)
`0.088/0.029
`P"(F20#2F2#)/3
`9.17
`0.283 e As ~3
`0.000
`
`Structure determination
`Structure refinement
`Unique reflections included
`Refined parametersa
`S
`Secondary extinction coe¶cient
`R8/R
`w"1/[p2(F20)#(0.0587P)2#0.3705P]
`Number of reflections per parameter
`Final Fourier residual
`Largest shift/error
`
`aAll H-atom parameters refined; refinement on F. Atomic scattering factors from
`‘‘International Tables for X-ray Crystallogrpahy’’ (1992, Vol. C, Tables 4, 2, 6,
`8 and 6, 1, 1, 4).
`
`Corrections
`
`III. Structure determination
`Lorentz and polarization corrections;
`no absorption correction
`SPD (11)
`Micro-VAX 2000
`MULTAN (12)
`1308 (I'3pI)
`161
`0.615
`Unitary
`X"5.89]10~6
`10.56
`0.37 e ) As ~3
`0.049/0.045
`0.008
`
`Program used
`Computer
`Structure determination
`Unique reflections included
`Refined parametersa
`Esd
`Weigting scheme
`Secondary extinction
`Number of reflections per parameter
`Final Fourier residual
`R8/R
`Largest shift/error
`
`aAtomic scattering factors from ‘‘International Tables for X-ray Crystallo-
`graphy’’ (13).
`
`with an Enraf-Nonius CAD4 di§ractometer. The structural
`determinations show that the proper space groups are P21/n
`and P11 respectively for DAPHP and TMEDH2P. The aver-
`age density values, measured at room temperature with
`toluene as the pycnometric liquid, are in agreement with the
`calculated densities; formula units in the cells of both crys-
`tals are deduced from these values. The chemical crystal
`data, the parameters used for X-ray di§raction data collec-
`tion, and the strategy used for the crystal structure deter-
`minations and their results are listed in Tables 1 and 2.
`
`3. Thermal Behavior
`
`Setaram TG-DTA92 and DSC92 thermoanalyzers were
`used to perform thermal treatment on samples of DAPHP
`
`and TMEDH2P. The TG—DTA experiments were carried
`out with 7.49- and 18.72-mg samples in an open alumina
`crucible. The DSC analyses were carried out using weighed
`9-mg samples sealed in an aluminum DSC crucible. In both
`techniques, samples were heated in air at heating rates of
`3—5°C/min from room temperature to 400°C; an empty
`crucible was used as reference.
`
`III. STRUCTURE DESCRIPTION
`
`A large number of monophosphates of mineral or organic
`cations are presently well known. Their preparations in-
`volve the neutralization of H3PO4 with mineral carbonates
`or amines in water as solvent. Similarly, the atomic arrange-
`ments usually exhibit acidic monophosphate anions,
`
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`NEW ORGANIC MONOPHOSPHATES
`
`345
`
`4 , organized in infinite chains, ribbons, or
`4 or H2PO~
`HPO2~
`layers. The solvent molecules play an important role in the
`building of the anionic organization by forming polyanions
`or [H2PO4 ) H2O]n~n . Min-
`of formulas [HPO4 ) H2O]2n~n
`eral or organic cations via respectively their polyhedral
`surrounding or their H bonds originating from the amine
`donor groups, interconnect these anionic aggregations. We
`describe herein the crystal structures of both DAPHP and
`TMEDH2P. The acidic anion of the DAPHP arranged in
`ribbons is found to include one molecule of solvent, whereas
`that of the TMEDH2P, organized in chains, uses the solvent
`to assemble chains.
`
`1. DAPHP Structure Description
`The final atomic coordinates and the º equivalent tem-
`perature factors (isotropic for H atoms) are given in Table 3.
`Figure 1 displays the anionic structure located at z"1
`4 and
`viewed along the c direction. The polyanion resulting from
`4 and H2O through strong hydro-
`the aggregation of HPO2~
`gen bonds forms infinite inorganic ribbons of
`formula
`[HPO4H2O]2n~n
`parallel to the b axis. Organic cations, as
`
`TABLE 3
`Final Atomic Coordination and Ueq (Uiso for H Atoms)
`of DAPHP
`
`Atom
`
`P
`O(1)
`O(2)
`O(3)
`O(4)
`O(W)
`N(1)
`N(2)
`C(1)
`C(2)
`C(3)
`H(O1)
`H(1W)
`H(2W)
`H(1N1)
`H(2N1)
`H(3N1)
`H(1N2)
`H(2N2)
`H(3N2)
`H(1C1)
`H(2C1)
`H(C2)
`H(1C3)
`H(2C3)
`H(3C3)
`
`x(p)
`
`y(p)
`
`z(p)
`
`0.2986(1)
`0.1435(1)
`0.4988(1)
`0.1935(1)
`0.2730(3)
`0.4974(1)
`0.2918(1)
`0.0030(2)
`0.3811(1)
`0.3085(1)
`0.0057(2)
`0.6180(1)
`0.3828(1)
`0.3178(2)
`0.4948(1)
`0.1866(1)
`0.6320(3)
`0.6392(1)
`0.1388(1)
`0.1162(3)
`0.2099(2)
`0.1482(1) !0.1623(3) !0.0516(1)
`0.2620(2)
`0.1408(3)
`0.0363(1)
`0.2759(2) !0.0769(3) !0.0199(1)
`0.3494(2) !0.2523(3)
`0.0391(2)
`0.535(2)
`0.382(5)
`0.197(2)
`0.628(3)
`0.738(5)
`0.216(2)
`0.720(3)
`0.609(5)
`0.193(2)
`0.268(2)
`0.075(4)
`0.183(2)
`0.147(2)
`0.028(4)
`0.136(2)
`0.176(2)
`0.253(4)
`0.160(2)
`0.101(2) !0.194(4)
`0.005(2)
`0.106(2) !0.057(4) !0.082(2)
`0.149(2) !0.280(5) !0.092(2)
`0.345(2)
`0.205(4)
`0.048(1)
`0.238(4) !0.001(1)
`0.211(2)
`0.314(2) !0.041(3) !0.080(1)
`0.302(2) !0.299(4)
`0.094(2)
`0.428(2) !0.195(4)
`0.065(2)
`0.363(3) !0.381(5)
`0.001(2)
`
`º%2(As 2)
`
`0.0183(2)
`0.0327(4)
`0.0293(3)
`0.0317(4)
`0.0279(3)
`0.0380(4)
`0.0249(4)
`0.0245(4)
`0.0266(4)
`0.0249(4)
`0.0341(5)
`0.039(7)*
`0.055(9)*
`0.057(8)*
`0.036(6)*
`0.031(6)*
`0.040(6)*
`0.048(7)*
`0.031(5)*
`0.048(7)*
`0.030(5)*
`0.031(5)*
`0.019(4)*
`0.053(7)*
`0.051(7)*
`0.063(8)*
`
`Note. Starred atoms were refined isotropically. Esds are given in paren-
`3 +i +jºija*i a*j aiaj.
`theses. º%2"1
`
`FIG. 1. Projection along the c direction of the [HPO4]H2O ribbon in
`DAPHP. The PO4 groups are given with a polyhedral representation.
`Large circles represent oxygen water molecules, and small circles indicate
`hydrogen atoms. Hydrogen bonds are denoted by full and dotted lines.
`
`shown in Fig. 2 giving the atomic arrangement, are anchor-
`ed onto the anionic ribbons through hydrogen contacts.
`The detailed geometry of HPO2~
`(Table 4) shows that the
`4
`P—O bonds are significantly shorter [1.512(1)—1.528(1) As ]
`
`FIG. 2. Projection along the b direction of the DAPHP atomic ar-
`rangement. In this figure and Figs. 3 and 4, the circles represent oxygen
`water molecules (large dark-gray circles), nitrogen atoms (large light-gray
`circles), carbon atoms (small black circles), and hydrogen atoms (small
`white circles). Hydrogen bonds are denoted by full and dotted lines.
`
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`

`346
`
`BAOUAB AND JOUINI
`
`TABLE 4
`Main Interatomic Distances (As ) and Bond Angles (Deg)
`in DAPHP
`
`P
`
`O(1)
`O(2)
`O(3)
`O(4)
`
`O(1)
`
`O(2)
`
`O(3)
`
`O(4)
`
`tetrahedron
`PO
`4
`108.76(8)
`104.25(7)
`1.587(1)
`112.78(8)
`1.512(1)
`2.447(2)
`1.518(1)
`2.524(2)
`2.525(2)
`2.514(2)
`2.525(2)
`2.507(2)
`P—P"5.575(1) P—O(1)—H(O1)"113(2)
`
`107.11(8)
`112.29(7)
`111.20(7)
`1.528(1)
`
`N(1)—H(1N1)
`N(1)—H(2N1)
`N(1)—H(3N1)
`N(2)—H(1N2)
`N(2)—H(2N2)
`N(2)—H(3N2)
`N(1)—C(1)
`C(1)—C(2)
`C(2)—N(2)
`C(2)—C(3)
`
`1,2-Diammoniopropane cation
`H(1N1)—N(1)—H(2N1)
`0.86(2)
`H(1N1)—N(1)—H(3N1)
`0.86(2)
`H(2N1)—N(1)—H(3N1)
`0.95(3)
`H(1N2)—N(2)—H(2N2)
`0.94(3)
`H(1N2)—N(2)—H(3N2)
`0.87(3)
`H(2N2)—N(2)—H(3N2)
`0.88(3)
`N(1)—C(1)—C(2)
`1.487(2)
`N(2)—C(2)—C(1)
`1.516(3)
`N(2)—C(2)—C(3)
`1.497(2)
`C(3)—C(2)—C(1)
`1.511(3)
`
`113(2)
`109(2)
`104(2)
`103(2)
`109(2)
`109(2)
`113.8(1)
`109.1(1)
`110.4(1)
`114.4(2)
`
`Note. Esds are given in parentheses.
`
`than the P—OH bond [1.587(1) As ]. The H2O bonds, which
`maintain the cohesion of the ribbons, are characterized by
`relatively short distances, from 1.83(3) to 2.03(3) As . Since the
`O2O distances in this hydrogen scheme [2.642(2)—2.779(2) As ]
`are of the same order of magnitude as in the HPO4 acidic
`tetrahedron [2.447(2)—2.525(2) As ], the [HPO4H2O]2n~n
`rib-
`bons should be considered as a polyanion. The short P—P
`distance observed in the ribbon is 5.575(1) As .
`With regard to the organic arrangement, the main fea-
`tures of which are reported in Table 4, each cation is
`anchored onto both adjacent anionic ribbons by N—H2O
`hydrogen bonds. This interaction contributes to the cohe-
`sion of the structure. All the D (donor)—H2A (acceptor)
`hydrogen bonds are listed in Table 5 with an upper limit of
`
`TABLE 5
`Bond Lengths (As ) and Angles (Deg) in the Hydrogen-Bonding
`Scheme of DAPHP
`
`N(O)—H H2O N(O)2O N(O)—H2O
`
`N(1)—H(1N1)2O(2)
`N(1)—H(2N1)2O(4)
`N(1)—H(3N1)2O(2)
`N(2)—H(1N2)2O(4)
`N(2)—H(2N2)2O(4)
`N(2)—H(3N2)2O(3)
`O(W)—H(1W)2O(3)
`O(W)—H(2W)2O(3)
`O(1)—H(O1)2O(W)
`
`0.86(2)
`0.86(2)
`0.95(3)
`0.94(3)
`0.87(3)
`0.88(3)
`0.76(3)
`0.88(3)
`0.77(3)
`
`1.89(2)
`1.98(2)
`1.75(3)
`1.83(3)
`1.90(3)
`1.91(3)
`2.03(3)
`1.83(3)
`1.88(3)
`
`2.747(2)
`2.831(2)
`2.698(2)
`2.748(2)
`2.759(2)
`2.779(2)
`2.779(2)
`2.695(2)
`2.642(2)
`
`Note. Esds are given in parenthesis.
`
`173(2)
`175(2)
`176(2)
`166(2)
`166(2)
`168(2)
`172(3)
`168(3)
`171(3)
`
`for the H2A distances and a lower limit of
`2.03(3) As
`166(2)° for the D—H2A bond angles (4, 14—18). Thus, this
`atomic arrangement exhibits three types of hydrogen bonds:
`(i) O(W)—H2O, including two relatively short contacts
`with H2O of 1.83(3) and 2.03(3) As , (ii) O(P)—H2O, in-
`volving one short contact with H2O of 1.88(3) As , and (iii)
`N—H2O, including six short distances with H2O values
`in the range 1.75(3)—1.98(2) As . The first two types ensure the
`cohesion between PO4 tetrahedra to build the ribbons, and
`the last one links parallel ribbons.
`
`2. TMEDH2P Structure Description
`Table 6 presents the atomic coordinates and the º equiv-
`alent temperature factors (isotropic for H atoms). The struc-
`ture can be described as being built up by chains of H2PO~
`4
`spreading with planes y"(2n#1)/2 or z"
`anions
`(2n#1)/2 and alternating with planes y"0 or z"0 con-
`taining the organic groups with water molecules. In the two
`configurations, the chains are parallel to the a direction.
`Figure 3 gives a projection in the (b, c) plane showing
`columns of anions and cations running along the a axis.
`
`TABLE 6
`Final Atomic Co-ordination of Ueq (Uiso for H Atoms)
`of TMEDH2P
`
`Atom
`
`P
`O(1)
`O(2)
`O(3)
`O(4)
`O(W1)
`OW2)
`N
`C(1)
`C(2)
`C(3)
`H(O1)
`H(O2)
`H(N)
`H(1W1)
`H(2W1)
`H(1W2)
`H(2W2)
`H(1C1)
`H(2C1)
`H(3C1)
`H(1C2)
`H(2C2)
`H(3C2)
`H(1C3)
`H(2C3)
`
`x(p)
`
`y(p)
`
`z(p)
`
`0.2063(1)
`0.1174(3)
`0.4317(3)
`0.7681(3)
`0.9372(3)
`0.0494(3)
`0.0610(3)
`0.3993(4)
`0.5277(6)
`0.6424(6)
`0.5063(5)
`0.932(5)
`0.540(6)
`0.286(4)
`0.021(5)
`0.046(5)
`0.945(5)
`0.028(5)
`0.543(5)
`0.330(7)
`0.474(6)
`0.730(6)
`0.504(5)
`0.279(6)
`0.348(5)
`0.586(6)
`
`0.4320(1)
`0.5229(3)
`0.6026(4)
`0.7005(3)
`0.6616(3)
`0.8226(4)
`0.1066(3)
`0.8167(4)
`0.9239(6)
`0.3800(5)
`0.0924(5)
`0.428(5)
`0.641(5)
`0.809(4)
`0.843(4)
`0.215(5)
`0.820(5)
`0.000(5)
`0.159(5)
`0.058(7)
`0.976(6)
`0.453(6)
`0.363(5)
`0.559(6)
`0.062(5)
`0.094(5)
`
`0.4821(1)
`0.3540(3)
`0.6476(4)
`0.6237(3)
`0.4462(3)
`0.0045(5)
`0.7501(3)
`0.1035(4)
`0.3017(6)
`0.9369(6)
`0.0033(5)
`0.616(5)
`0.633(6)
`0.075(4)
`0.063(5)
`0.100(5)
`0.322(5)
`0.307(5)
`0.638(5)
`0.646(7)
`0.676(6)
`0.064(6)
`0.886(5)
`0.118(7)
`0.946(5)
`0.133(6)
`
`º%2(As 2)
`
`0.0256(2)
`0.0461(6)
`0.0513(8)
`0.0334(6)
`0.0388(6)
`0.0438(7)
`0.0399(7)
`0.0316(7)
`0.053(1)
`0.049(1)
`0.047(1)
`0.02(1)*
`0.04(1)*
`0.01(1)*
`0.01(1)*
`0.04(1)*
`0.03(1)*
`0.02(1)*
`0.02(1)*
`0.07(2)*
`0.04(1)*
`0.05(1)*
`0.03(1)*
`0.06(1)*
`0.03(1)*
`0.05(1)*
`
`Note. Starred atoms were refined isotropically. Esds are given paren-
`3 +i +jºija*i a*j aiaj.
`theses. º%2"1
`
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`NEW ORGANIC MONOPHOSPHATES
`
`347
`
`FIG. 3. Projection along the a direction of the TMEDH2P atomic
`arrangement showing the H2PO4 columns linked by H bonds from water
`molecules and organic cations. Hydrogen bonds are denoted by full and
`dotted lines.
`
`Displayed in the (a, c) plane, as shown in Fig. 4, the H2PO4
`groups, running in a parallel direction with the a axis, are
`connected by strong hydrogen bonds since the H2O con-
`tacts maintaining the cohesion in the chain have short
`distances, 1.73(5) and 1.77(5) As . It is worth noting that the
`O2O distances involved in the hydrogen bonds [2.561(5)
`and 2.590(4) As ] are of the same order of magnitude as the
`O2O distances in the H2PO4 tetrahedron [2.455(3)—
`2.512(4) As ]. This and the short P2P distance of 4.416(1) As
`allow us to consider the [H2PO4]n~n
`subnetwork as a poly-
`4 anion is given
`anion. The detailed geometry of the H2PO~
`in Table 7. Water molecules located in planes as the organic
`cations are assembled in pairs linked to N atoms via O(W1)
`is, O(W1)—H(1W1)
`by strong hydrogen bonds,
`that
`2O(W2) [H2O, 2.07(5) As ; O2O, 2.742(5) As ] on one
`side, and N—H2O(W1)
`[H2O, 1.85(4) As ; N2O,
`2.670(4) As ] on the other side. All the other H atoms of the
`water molecules are involved in H bonds with the non-
`protonated oxygen atoms of adjacent [H2PO4]n~n polyan-
`ions. As observed in the DAPHP structure, the P—O bonds,
`shorter than the P—OH bonds, are in accordance with data
`relative to the protonated oxoanions (19). The geometrical
`features of the organic cation, given in Table 7, are similar to
`those observed in the organic diphosphate C6H18N2 )
`H2P2O7 ) 2H2O (20) containing the same organic molecule.
`
`FIG. 4. Projection along the b direction of the TMEDH2P atomic
`arrangement giving the (H2PO4)n chains located at y"(2n#1)/2 planes.
`Hydrogen bonds are denoted by full and dotted lines.
`
`tetramethylethylenediam-
`In this compound, atoms of
`monium were found in general positions, whereas those in
`the TMEDH2P are located around the (1
`2 0 0) inversion
`center of the triclinic cell. The N—C and C—C distances and
`the C—N—C and C—C—N angles are similar and lie within
`the ranges 1.475(5)—1.503(6) As and 106.8(4)—117.1(2)°, re-
`spectively. The main geometric features of the hydrogen-
`bonding scheme are described in Table 8. This structure
`includes seven potential hydrogen bond donors (one N—H
`and six O—H) and four O or OH acceptors. Among the
`acceptor atoms, O(W1) and O(W2) are single acceptors,
`whereas O(3) and O(4) atoms are respectively threefold and
`twofold acceptors.
`
`IV. THERMAL BEHAVIOR
`
`Thermal decomposition of DAPHP occurs in four stages
`between 100 and 400°C, corresponding to the successive
`losses of water and ammonia molecules (Fig. 5). The first
`
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`348
`
`BAOUAB AND JOUINI
`
`TABLE 7
`Main Interatomic Distances (As ) and Bond Angles (Deg)
`in TMEDH2P
`
`TABLE 8
`Bond Lengths (As ) and Angles (Deg) in the Hydrogen-Bonding
`Scheme of TMEDH2P
`
`P
`
`O(1)
`
`O(2)
`
`O(3)
`
`O(4)
`
`(N,O)—H
`
`H2O (N,O)2O (N,O)—H2O
`
`tetrahedron
`PO
`4
`109.8(2)
`106.8(2)
`107.1(2)
`1.557(3)
`O(1)
`107.0(2)
`110.1(2)
`1.558(2)
`2.505(3)
`O(2)
`115.8(2)
`1.507(3)
`2.512(4)
`2.460(4)
`O(3)
`1.495(3)
`2.543(4)
`2.455(3)
`2.498(4)
`O(4)
`P—P"4.416(1) P—O(1)—H(O1)"116(3) P—O(2)—H(O2)"115(2)
`
`N(1)—H(N)2O(W1)
`O(W1)—H(1W1)2O(W2)
`O(W1)—H(2W1)2O(3)
`O(W2)—H(1W2)2O(4)
`O(W2)—H(2W2)2O(3)
`O(2)—H(O2)2O(3)
`O(1)—H(O1)2O(4)
`
`0.83(4)
`0.67(5)
`0.81(4)
`0.93(5)
`0.76(3)
`0.86(5)
`0.79(5)
`
`1.85(4)
`2.07(5)
`2.06(4)
`1.81(4)
`2.10(3)
`1.73(5)
`1.77(5)
`
`2.670(2)
`2.742(5)
`2.857(3)
`2.735(4)
`2.817(3)
`2.590(4)
`2.498(4)
`
`172(4)
`176(5)
`167(5)
`176(3)
`160(4)
`172(5)
`175(3)
`
`N—C(1)
`N—C(2)
`N—C(3)
`C(3)—C(3)
`
`N,N,N@,N@-tetramethylenediammonium cation
`C(1)—N—C(2)
`1.475(5)
`C(1)—N—C(3)
`1.488(6)
`C(2)—N—C(3)
`1.496(6)
`N—C(3)—C(3)
`1.503(6)
`
`109.7(3)
`117.1(2)
`106.8(4)
`110.7(4)
`
`Note. Esds are given in parentheses.
`
`process starts at 100°C and is complete at 202°C. It corres-
`ponds to the loss of the only water molecule of the formula
`(weight loss, calculated 9.47%, experimental 9.29%), leading
`to a white microcrystalline powder. The second stage, from
`202 to 250°C, is attributed to the further beginning of
`degradation and melting of the compound. Indeed, an addi-
`tional treatment in a separate carbolite furnace, with a run
`heating of 5°C/min, leads to a very viscous yellow liquid
`which does not crystallize when cooled at room temper-
`
`Note. Esds are given in parentheses.
`
`the sample is polymerized and an
`ature. Apparently,
`amorphous phase, as confirmed by XRD, is formed. The TG
`curve shows, after the elimination of H2O, a rather vigorous
`and continuous weight loss corresponding to the evolution
`of ammonia from the structure, probably in many steps. The
`DTA curve exhibits large endotherms at 142, 221, 229, and
`329°C and a set of endotherms from 365 to 400°C in accord-
`ance with the elimination of the water and ammonia mol-
`ecules. It should be noted that the thermal decomposition
`ends up in a bad smell, escaping from the resulting black
`product.
`Figure 6 showing the DSC thermogram registered from
`room temperature to 250°C, reveals the same thermal be-
`havior as DAPHP, in accordance with what is observed in
`
`FIG. 5. TG—DTA analysis of DAPHP.
`
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`NEW ORGANIC MONOPHOSPHATES
`
`349
`
`FIG. 6. DSC curve of DAPHP.
`
`the first two regions of the TG—DTA curves. Indeed, the
`second shouldered endothermic e§ect corresponds to both
`evolution of ammonia and melting of the anhydrous com-
`pound. This combined e§ect was recently observed in the
`organic cyclohexaphosphate [C6H18N3]2P6O18 ) 6H2O (4).
`The first endothermic peak, occurring in the temperature
`range 124—159°C (Fig. 6), corresponds to the dehydration
`with *H"42.98 kJ/mol. The overall *H of the elimination
`of ammonia and fusion, occurring in the region 208—239°C,
`is 57.72 kJ/mol.
`Figure 7 shows both TG and DTA thermograms of
`TMEDH2P from room temperature to 300°C. The weight
`loss is divided into three areas, 53—106, 106—176, and
`176—210°C, and the total weight loss is found to be 18.86%,
`close to the calculated value, 18.75%. The TG weight loss
`(13.82%) in the first two ranges, due to the elimination of
`is close to the calculated value
`three H2O molecules,
`(14.06%) and related to the first large endotherm and the set
`of endothermic peaks as shown in the DTA curve. The last
`water molecule of the structure is evolved in the third
`temperature area,
`since the experimental weight
`loss
`(5.44%) is close to the calculated value (5.45%). Thus, all
`endotherms are considered to result from the evolution of
`the water from the structure. Tested by IR and XRD, the
`resulting, still white, powder exhibits infrared bands charac-
`teristic of the monophosphate anion and a well-crystallized
`anhydrous compound. The di§erential calorimetric study,
`displayed in Fig. 8, shows a large shouldered endotherm in
`the range 50—80°C, followed by a set of endotherms from 80
`
`to 170°C assigned to the dehydration of three molecules of
`water, in accordance with the TG—DTA study. The overall
`*H of this dehydration is found to be 115.44 kJ/mol. The
`endothermic peak at 187°C corresponds to the elimination
`of
`the last water molecule from the structure with
`*H"20.47 kJ/mol. The exotherm at 197°C is probably due
`to the enhanced partial pressure of water vapor. All en-
`dothermic peaks are shifted to a low temperature by a de-
`crease in the run heating from 5°C/min (TG—DTA) to
`3°C/min (DSC).
`On the other hand, the baselines, as shown in the DTA
`curves (Figs. 5 and 7), are gently sloping up, and their slopes
`may change with temperature. Such premonitory phe-
`nomena may be associated with an increase of atomic
`motions—in the sample in particular, the increase of dis-
`order—as the decomposition is approached. This decompo-
`sition, with ammonia evolution by the pyrolysis,
`is
`confirmed as follows: An eßuent dry nitrogen is introduced
`continuously into 30 cm3 of 0.01 mol/l sulfuric acid at
`50 cm3/min. The gas is passed into the acid for a further
`30 min after the TG—DTA furnace has reached the required
`temperature to absorb any ammonia remaining in the
`sealed device. The ammonia absorbed in the solution is
`determined by means of a back-titration technique, using
`a 0.02 mol/l sodium hydroxide solution and a pH meter.
`Thus,
`the
`thermal decomposition of DAPHP and
`TMDH2P can be described by, first, the elimination of
`water molecules and then the evolution of ammonia when
`the temperature of pyrolysis is reached.
`
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`

`350
`
`BAOUAB AND JOUINI
`
`FIG. 7. TG—DTA analysis of TMEDH2P.
`
`V. CONCLUSION
`
`DAPHP and TMEDH2P exhibit two kinds of polyanion
`organizations, infinite ribbons and chains. Organic cations
`
`connect them through two types of hydrogen-bonding net-
`works. Strong hydrogen bonds of type O—H2O built the
`polyanions, which are themselves interconnected with the
`organic groups through the second type of hydrogen bonds,
`
`FIG. 8. DSC curve of TMEDH2P.
`
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`

`NEW ORGANIC MONOPHOSPHATES
`
`351
`
`namely, N—H2O originating from the N—H donors. The
`thermal behavior studies, summarized by elimination of the
`water molecules and the evolution of ammonia when the
`temperature of pyrolysis is reached, specify the stability of
`the DAPHP and TMDH2P compounds. The only di§er-
`ence between these two compounds is the melting of
`DAPHP before pyrolysis whereas the TMEDH2P degrades
`without melting.
`
`ACKNOWLEDGMENTS
`
`The authors express their most grateful thanks to Dr. T. Jouini, De´ parte-
`ment de Chimie, Faculte´ des Sciences de Tunis, Tunisia, for the X-ray data
`collection.
`
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`
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`13.
`
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