7
6
K. Latham et al. / Journal of Molecular Structure 987 (2011) 74–85
1H NMR d (CDCl
32, 124.6 ppm.
): 8.30, 8.05 ppm. 13C NMR d (CDCl
3
3
): 150, 147,
2
phonic acid: guanidinium carbonate. Effervescence of CO was
1
observed, and a precipitate of guanidinium 3-nitrobenzenephosph-
onate formed which was recrystallised from hot 1:1 water: etha-
nol. Colourless needles began to form after 5 min which were
2.3. Synthesis of guanidinium benzene-oxy acid complexes
recovered in 65% yield. ESI–MS Calc. for [C
Found: 338 [MꢀH]. FTIR (KBr): 3454, 3350 and 3153 (
PO–H), 1674 (dN–H), 1585, 1518 ( NOasym), 1354 ( NOsym),
085 and 967 ( P–O), 802, 775, 681, 551 cm
8
H
18
N
7
O
6
P]: 339 [M].
The general equation for the synthesis of the guanidinium sul-
phonate materials was:
tN–H,
t
1
t
t
ꢀ1
t
(tO–P–O).
þ
ꢀ
þ
2ꢀ
þ
SO Þ þ Hþ
1ꢀ
G Cl =ðG Þ ðCO Þ þ C
6
H
5
SO
3
H ! ðG ÞðC
6 5
H
2
3
3
ꢀ
þ Cl =H
2
O; CO
2
2.3.6. Guanidinium 4-nitrobenzenephosphonate nonahydrate,
þ
2ꢀ
½
CðNH
2
Þ ꢂ ꢁ[4-NO
2
–C
6 5
H PO
3
]
ꢁ9H
2
O (7)
3
2
þ
þ
This compound was prepared following the same method as for
G
¼ guanidinium cation ¼ CðNH Þ
2
3
the 3-nitrobenzenephosphonate but using 4-nitrobenzenephos-
phonic acid. Pale-yellow needles formed which were recovered
in 68% yield. The crude product was recrystallised from hot water,
with the addition of hot ethanol and 2 drops of acetone, to produce
X-ray quality crystals over 2 days (7). ESI–MS Calc. for [C H N O
+
ꢀ
6 5 3
H SO ] (1)
2
.3.1. Guanidinium benzenesulphonate, [C(NH
(
2 3
) ] ꢁ[C
1) was synthesized according to the method of Ward et al. [4].
Colourless crystals formed after 4 weeks in 29% yield. ESI–MS Calc.
for [C
S]: 217 [M]. Found: 216 [MꢀH]. FTIR (KBr): 3340
and 3192 ( N–H), 2850, 2580, 1678 (dN–H), 1580, 1518, 1400,
180, 1130 and 1025 ( S–O), 967, 930, 725, 681, 551, 520,
80 cm . Elemental analysis, Found: C 38.81; H 4.93; N 19.21; S
4.55%. Calc. for [C ]: C 38.70; H 5.10; N 19.34; S 14.76%.
8
22
7 12
7
11
H N
3
O
3
P]: 481 [M]. Found: 480 [MꢀH], 465 [M–O]. FTIR (KBr): 3123 and
3050 and 3035 ( N–H, PO–H), 2840 (broad – H O), 2230, 2105,
1970, 1820, 1705 (dN–H), 1610, 1530, 1518 (
1354 ( NOsym), 1180/1130/1025/967 ( P–O), 775, 681, 551 and
t
t
t
2
1
4
1
t
tNOasym), 1400,
ꢀ1
t
t
ꢀ1
H
7 11
1
S N
3
O
3
520 cm
(tO–P–O).
2
.3.2. Guanidinium 3-nitrobenzenesulphonate,
2.3.7. Guanidinium benzenearsonate dihydrate,
+
ꢀ
þ
2ꢀ
3
[C(NH
2
)
3
] ꢁ[3-NO
2
–C
6
H
5
SO
3
]
(4)
½CðNH
2
Þ ꢂ ꢁ[C
6
H
5
AsO
]
ꢁ2H
2
O (3)
3
2
(
4) was synthesized according to the method of Ward et al. [6].
Equimolar amounts of guanidinium carbonate and benzenear-
sonic acid were dissolved in separate vials, each containing 2 mL
of mixed solvent (1:1 ratio water: ethanol), and the clear colourless
Light-tan block-like crystals began to form after 5 min and were
recovered in 56% yield. ESI–MS Calc. for [C S]: 262 [M].
Found: 261 [MꢀH], 232 [M–NO]. FTIR (KBr): 3305 and 3210 ( N–
H), 2950, 1638 (dN–H), 1610, 1570, 1540 ( NOasym), 1370 ( NOsym),
S–O), 987, 950, 800, 775,
7
10 4 5
H N O
t
2
solutions combined. Effervescence of CO was observed, and a
clear, colourless solution formed, which, after sealing and standing
for 2 weeks resulted in colourless block crystals forming in 23%
t
t
1
7
230, 1200, 1150 and 1090 and 1025 (t
ꢀ1
40, 671, 610, 551, 520 cm
.
yield. ESI–MS Calc. for [C
8
H
21
N
6
O
5
As]: 356 [M]. Found: 355
O, N–H, AsO–
[
MꢀH]. FTIR (KBr): 3350 and 3140 (v. broad – H
2
t
t
2
.3.3. Guanidinium 4-nitrobenzenesulphonate,
H), 1760, 1670 (dN–H, and H
1041/993/967 (
2
O), 1585, 1463, 1377, 1254, 1165/
+
ꢀ
ꢀ1
[C(NH
2 3
)
] ꢁ[4-NO
2 6
–C H
5
SO
3
] (6)
tAs–O), 835, 775, 661, 521 cm
(tO–As–O). Ele-
(
6) was synthesized according to the method of Ward et al. [6].
mental analysis, Found: C 28.94; H 5.63; N 26.41; As 23.19%. Calc.
for [C ] (dehydrated (3)): C 30.01; H 5.35; N 26.25; As
23.40%.
Light-tan block-like crystals began to form after 5 min and were
recovered in 71% yield. ESI–MS Calc. for [C S]: 262 [M].
Found: 261 [MꢀH], 232 [M–NO]. FTIR (KBr): 3408 and 3219 ( N–
H), 1670 (dN–H), 1527 ( NOasym), 1351 ( NOsym), 1195, 1126 and
035 (
S–O), 855, 748, 670, 610, 580, 480 cmꢀ1.
The general equation for the synthesis of the guanidinium phos-
phonate and arsonate materials was:
8 1 6 3
H17As N O
7 10 4 5
H N O
t
t
t
2.4. Characterization techniques
1
t
All products were analysed by FTIR, electrospray mass spec-
trometry (ESIꢀMS), powder X-ray diffraction, and single crystal
XRD. Elemental analysis (C, H, N, P, S and As) was performed by
the Campbell Microanalytical Laboratory, University of Otago,
New Zealand. FTIR spectra were obtained on a Varian FTIR Spec-
trometer One using KBr discs. The discs were prepared by grinding
the sample (1–2 mg) and IR-grade KBr (100 mg), into a homoge-
neous powder using a mortar and pestle. The powder was then
placed in a die press (Specac 13 mm), and compacted under vac-
uum for approximately 5 min using 8 tonne of pressure. The spec-
tra were collected using the following conditions: scan range
þ
2ꢀ
þ
2ꢀ
ðG Þ2ðCO ÞþC
6
H
5
DO
3
H
2
! ðG Þ ðC
6
H
5
DO ÞꢁxH
2
OþH
2
OþCO
2
3
2
3
þ
þ
G
¼ guanidinium cation ¼ CðNH
2
Þ ; D ¼ P; As
3
2
.3.4. Guanidinium benzenephosphonate dihydrate,
+
3
2ꢀ
[
C(NH
2) was prepared according to Weakley [13]. X-ray quality sin-
gle crystals were produced within 24 h in 31% yield. ESI–MS Calc.
for [C
P]: 312 [M]. Found: 311 [MꢀH]. FTIR (KBr): 3270/
175/3080 (broad – H O, N–H, PO–H), 2820, 1677 (H O, and
dN–H), 1585, 1413, 1120/1085/1034/978 ( P–O), 783, 711, 692,
O–P–O). Elemental analysis, Found: C 34.67;
H 6.71; N 30.52; P 11.16%. Calc. for [C ] (dehydrated
2
)
]
2 6
ꢁ[C H
5
PO
3
]
2
ꢁ2H O (2)
(
ꢀ1
4000–400 cm ; number of scans 8; single beam; resolution:
ꢀ
1
1
13
H
8 21
N
6
O
5
4 cm . H and C NMR spectra for the 4-nitrobenzenephosphonic
acid were obtained on a Bruker AVANCE 300 MHz spectrometer.
Samples were prepared by dissolving approximately 20 mg in deu-
3
2
t
t
2
t
ꢀ
1
5
81/525/508 cm
(t
terated water (D O) and placed into a 5 mm diameter glass NMR
2
H
8 17
P
1
N
6
O
3
tube. ESI mass spectra were obtained on a Micromass Platform II
(2)): C 34.78; H 6.20; N 30.42; P 11.21%.
mass spectrometer equipped with a LC-10AD Shimadzu solvent
3 2
delivery component (50% CH CN/H O at a flow rate of 0.1 mL/
2
.3.5. Guanidinium 3-nitrobenzenephosphonate hydrate,
min) in both the positive and negative ionisation modes, using
cone voltages of 20–30 V. Powder diffractograms were recorded
on a Bruker D8 ADVANCE powder diffractometer in h–h continuous
3
þ
2ꢀ
3
[CðNH
2
Þ
ꢂ ꢁ[3-NO
2
–C
6 5
H PO
]
ꢁH O (5)
2
2
Guanidinium carbonate and 3-nitrobenzenephosphonic acid
were dissolved in separate vials, each containing 2 mL of mixed
solvent (1:1 ratio water:ethanol). The clear colourless solutions
were then combined to give a 1:1 mol ratio of 3-nitrobenzenephos-
mode using Cu Ka radiation (k = 1.5406 Å) fitted with a graphite
monochromator and a scintillation counter detector. Scan range
2h = 3–60°, count rate = 2 s/step, and step size = 0.02°.