Supramolecular networks formation in crystals of 3-carboxybenzylphosphonic acid, its complexes and salts: From coordination bonds to weak intermolecular interactions

Article abstract of DOI:10.1039/c3ra44614j

3-Carboxybenzylphosphonic acid (H₃L) (1), three complexes [Ca(H₂L)₂(H₂O)₃]_n (2), [Ca(H₂L)₂(H₂O)₂]_n (3) and [Ca(H₂L)₂(H₂O)₄] bipy (4) and two polymorphs of the salt (bipyH₂)(H₂L)₂ (5, 6), were prepared and their structures were determined by single crystal X-ray diffraction analysis. Compounds 2 and 3 are polymeric species whereas 4 is a mononuclear complex. The calcium ion in 2, 3 and 4 is coordinated by monodeprotonated phosphonic groups (-PO₃H^-) and water molecules, the carboxylic group remains in the protonated form. The polymer chains or monomeric units are linked together by hydrogen bonds and ionic forces in the case of salts to afford three-dimensional layered supramolecular structures. Also the π...π stacking interactions in compounds 4, 5 and 6 contribute to the stabilization of the structures.

Full text of DOI:10.1039/c3ra44614j

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PAPER
Supramolecular networks formation in crystals of
3-carboxybenzylphosphonic acid, its complexes and
salts: from coordination bonds to weak intermolecular
interactions†
Cite this: RSC Adv., 2013, 3, 23119
a
a
b
ac
*
´
´
Danuta Dobrzynska, Joanna Kubiak, Jan Janczak and Jerzy Zon
3-Carboxybenzylphosphonic acid (H3L) (1), three complexes [Ca(H2L)2(H2O)3]n (2), [Ca(H2L)2(H2O)2]n (3)
and [Ca(H2L)2(H2O)4] bipy (4) and two polymorphs of the salt (bipyH2)(H2L)2 (5, 6), were prepared and
their structures were determined by single crystal X-ray diffraction analysis. Compounds 2 and 3 are
polymeric species whereas 4 is a mononuclear complex. The calcium ion in 2, 3 and 4 is coordinated by
monodeprotonated phosphonic groups (–PO3Hꢀ) and water molecules, the carboxylic group remains in
the protonated form. The polymer chains or monomeric units are linked together by hydrogen bonds
and ionic forces in the case of salts to afford three-dimensional layered supramolecular structures. Also
the p/p stacking interactions in compounds 4, 5 and 6 contribute to the stabilization of the structures.
Received 23rd August 2013
Accepted 26th September 2013
DOI: 10.1039/c3ra44614j
www.rsc.org/advances
inuence on exibility and directionality of this ligand. The
introduction of other functional groups into the phosphonate
Introduction
In the crystals of inorganic–organic hybrid materials the strong
coordination bonds formed between the metal ions and
bridging ligands lead to 1D, 2D or 3D frameworks,1,2 while in
crystals built from discrete units the formation of ordered
structure results from diverse intermolecular interactions.3 The
chemical and physical properties of the materials depend on
both molecular and supramolecular structures and allow a
plethora of applications: adsorption, separations, catalysis,
sensing and medical functions in drug storage and
delivery.1,3–12
Phosphonic acids are very efficient substrates in the eld of
crystal engineering13–17 and MOF chemistry17–27 because they
are good donors and acceptors in the hydrogen bond and
easily form the stable compounds with metal ions. Phosphonic
group is quasi tetrahedral, contains three oxygen donors and
can form two ionic forms (R-PO3Hꢀ and R-PO32ꢀ). For these
reasons the structures of metal phosphonates are strongly
dependent on the method of synthesis, e.g. pH and tempera-
ture of the solution, reagents molar ratios and are unpredict-
able.20,23,28 Also the organic core of phosphonate has an
ligand backbone further complicates the reaction with metal
ions. The study on the alkyl and aryl phosphonates containing
additionally carboxylic group illustrate the complexity of metal-
phosphonate chemistry as well as the limitations and advan-
tages of these compounds in MOF chemistry very well. The
solubility of phosphonates decreases as the valence state of the
metal increases. The divalent metal phosphonates can be
obtained as single crystals because they are moderately
soluble. The trivalent and tetravalent metal phosphonates very
oen precipitates as poorly crystalline materials. The impor-
tant advantage of poorly soluble metal phosphonates is great
thermal stability allowing for functionalization of this
materials.29,30
The number of nonporous31 and porous carboxy-
phosphonates32 have been obtained to date. In both categories of
these compounds the phosphonate groups always bind to metal
ion, whereas the carboxylic group can be ionized and coordinated
to metal ion or remains in the protonated form. Compare to high
abundance in nature and many biological function of calcium,
very oen involved with low soluble salts including phosphates,
the calcium carboxyphosphonates were not widely studied. Only
few examples of such compounds were reported, eight of them are
the coordination polymers whereas in the crystal of ninth
compound the discrete trinuclear units have been found.33–37
This paper deals with the synthesis and the crystal structure of
3-carboxybenzylophosphonic acid (alternative name: 3-phospho-
nomethylbenzoic acid), three calcium 3-carboxybenzyl-
phosphonates and two polymorphs of 4,40-bipyridinium
3-carboxybenzylophosphonate.
a
˙
´
Faculty of Chemistry, Wrocław University of Technology, Wybrzeze Wyspianskiego 27,
50-370 Wrocław, Poland
bInstitute of Low Temperature and Structure Research, Polish Academy of Sciences,
´
Okolna 2 Str., P. O. Box 1410, 50-950 Wrocław, Poland. E-mail: j.janczak@int.pan.
wroc.pl; Fax: +48 71 344 1029; Tel: +48 71 343 5021
cFaculty of Mechanical and Power Engineering, Wrocław University of Technology, 27
˙
´
Wybrzeze Wyspianskiego Street, 50-370 Wrocław, Poland
† Electronic supplementary information (ESI) available. CCDC reference numbers
945965–945970. See DOI: 10.1039/c3ra44614j
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product was recrystallized from hexane (25 cm3) to give a sticky
Experimental
1
ꢁ
white product III: 14.745 g (66%), mp 34–38 C. H NMR (300
MHz, CDCl3): d 3.92 (s, 3H, CH3OOC), 4.52 (s, 2H, BrCH2), 7.39–
7.48 (m, 1H, aromatic proton), 7.56–7.61 (m, 1H, aromatic
proton), 7.94–7.80 (m, 1H, aromatic proton) and 8.03–8.10 ppm
(m, 1H, aromatic proton).
In solution the 1H, 31P{1H}, 13C{1H} NMR spectra were recorded
at room temperature on Bruker Avance DRX300 instrument,
operating at 300.13, 121.50 and 75.46 MHz. Phosphorus decou-
pling was achieved by power gated decoupling using Waltz 16
sequence. Reference for H and 13C{1H} NMR was solvent lines
1
Diethyl 3-(carbomethoxy)benzylphosphonate (IV). Methyl 3-
(bromomethyl)benzoate (III, 1.2659 g, 0.005526 mole) and
triethylꢁphosphite (1.15 cm3, 0.06610 mole) were heated gradually
(chloroform: dH ¼ 7.26 ppm, triplet dC ¼ 77.00 ppm; dime-
thylsulfoxide: multiplet dH ¼ 2.49 ppm, multiplet dC ¼ 39.50
ppm). IR spectra were recorded in KBr pellets method (0.5 wt%
mass) using the Perkin Elmer FTIR-2000 spectrophotometer in
ꢁ
to 145 C and then kept at 145–150 C for 1 h. Flash chroma-
tography on silica gel using ethyl acetate as a eluent give pure
diethyl 3-(carbomethoxy)benzylphosphonate (IV): 1.1925 g, 75%,
Rf ¼ 0.203 (silica gel on TLC-PET foils with uorescent indicator
254 nm, eluent ethyl acetate, visualization by UV lamp). 1H NMR
(300 MHz, CDCl3): d 1.25 (t, JHH ¼ 7.0 Hz, 6H, CH3COP), 3.19 (d,
JHP ¼ 21.6 Hz, 2H, CH2P), 3.91 ppm (s, 3H, CH3OOC).
the spectral range 400–4000 cmꢀ1 with the resolution of 2 cmꢀ1
.
Synthesis of the ligand (3-carboxybenzylphosphonic acid,
H3L) (1)
3-Carboxybenzylphosphonic acid (1). Diethyl 3-(carboxy)-
benzylphosphonate (IV, 1.1925 g, 0.00416 mole), conc. hydro-
chloric acid (4 cm3) and water (4 cm3) were reuxed for 10 h. A
small amount of product was precipitated out during the
hydrolysis. The reaction mixture was le to crystallization at
room temperature. Crystalline 3-carbobenzylphosphonic acid (1)
was ltered and dried in air: 0.8275 g, 92%. Anal. calcd for
C8H9O5P: C, 44.46; H, 4.19; P, 14.33%. Found: C, 44.55; H, 4.17; P,
14.28%, mp 237–241 ꢁC. 1H NMR (300 MHz, DMSO-d6): d 3.01 (d,
JHP ¼ 21.4 Hz, 2H, CH2P), 4.2–6.7 (bs, 3.5H, PO3H2 and COOH),
7.31–7.48 (m, 2H, aromatic protons) and 7.70–7.85 ppm (m, 2H,
aromatic protons). 31P{1H} NMR (121 MHz, DMSO-d6): d 21.48
ppm (s). 13C{1H} NMR (75 MHz, DMSO-d6): d 35.54 (d, JCP ¼ 131.5
Hz, CH2P), 127.50 (d, JCP ¼ 2.6 Hz), 128.75 (d, JCP ¼ 2.1 Hz),
131.02, 131.10, 134.76 (d, JCP ¼ 6.0 Hz), 135.23 (d, JCP ¼ 8.6 Hz)
and 167.82 ppm. IR (KBr, cmꢀ1): nmax 2835, 1689, 1610, 1588,
1492, 1456, 1426, 1404, 1324, 1284, 1265, 1208, 1176, 1021, 963,
955, 935, 943, 826, 779, 772, 736, 691, 666, 603, 559, 518, 453, 433.
Synthesis of [Ca(H2L)2(H2O)3]n (2). Synthesis of [Ca(H2L)2-
(H2O)3]n (2), the solution of 0.20 mmol (43.2 mg) of H3L in 5.0
cm3 of hot (70 ꢁC) water was mixed with 5.0 cm3 water solution
of 0.20 mmol (22.2 mg) of CaCl2 and le to stay in room
temperature; aer two months the colourless X-ray quality
crystals have been appeared. Anal. calcd for C16H22CaO13P2: C,
36.65; H, 4.23; P, 11.82%. Found: C, 36.20; H, 4.47; P, 11.85%. IR
(KBr, cmꢀ1) 3461, 3344, 3002, 2825, 2677, 2652, 1689, 1608,
1586, 1489, 1456, 1421, 1314, 1259, 1206, 1135, 1156, 1073,
1016, 931, 912, 880, 834, 779, 771, 740, 694, 666, 619, 525, 441.
Synthesis of [Ca(H2L)2(H2O)2]n (3). Synthesis of [Ca(H2L)2-
(H2O)2]n (3), the solution of 0.20 mmol (43.2 mg) of H3L and 20
Methyl 3-methylbenzoate (II). 3-Methylbenzoic acid (I,
14.4618 g, 0.1063 mole) and thionyl chloride (12 cm3, 0.1645
mole) were reuxed for 3 h under a protection from moisture.
Then, thionyl chloride was evaporated under atmospheric pres-
sure, nally under reduced pressure (at 50 mm Hg and temper-
ature of heating bath 70 ꢁC), to obtain crude the acid chloride as a
residue. At room temperature a mixture of methanol (30 cm3,
0.7406 mole) and methylene chloride (30 cm3) was added into the
residue and reaction mixture was reuxed for 1.5 h. Aer cooling
of the mixture, methylene chloride (50 cm3) was added, washed
with saturated solution of sodium hydrogen carbonate (2 ꢂ 25
cm3) and brine (2 ꢂ 25 cm3) and died over anhydrous magne-
sium sulphate. The solvent was evaporated to obtain crude
product II as an oil: 14.6190 g (92%) which is sufficiently pure to
use in the next reaction. 1H NMR (300 MHz, CDCl3): d 2.40 (s, 3H,
CH3), 3.91 (s, 3H, CH3OOC), 7.28–7.39 (m, 2H, aromatic protons)
and 7.81–7.87 ppm (m, 2H, aromatic protons) (Scheme 1).
Methyl 3-(bromomethyl)benzoate (III). Methyl 3-methyl-
benzoate (II, 14.6156 g, 0.0973 mole), dry carbon tetrachloride
(100 cm3), N-bromosuccimide (17.3127 g, 0.0973 mole) and
benzoyl peroxide (250 mg) were reuxed under a water
condenser for 2 h. Succimide was ltered off, washed with
carbon tetrachloride. The ltrate and washing were evaporated
to obtain crude product (23.1228 g, over 100%). The crude
3
ꢁ
mmol (32 mg) of pyrazine in 5.0 cm of hot (70 C) water was
mixed with 1.0 cm3 water solution of 0.20 mmol (22.2 mg) of
CaCl2 and le to stay in room temperature; aer few weeks the
X-ray quality crystals have been appeared. Anal. calcd for
C
16H20CaO12P2: C, 37.95; H 3.98; found: C, 38.15; H, 4.21%. IR
(KBr, cmꢀ1) 3495, 2821, 2680, 2561, 1690, 1609, 1587, 1489,
1456, 1424, 1314, 1295, 1257, 1157, 1124, 1072, 1124, 1073,
1019, 930, 881, 770, 694, 667, 619, 528, 437.
Synthesis of [Ca(H2L)2(H2O)4]$bipy (4) and bipy (H3L)2 (5).
Synthesis of [Ca(H2L)2(H2O)4]$bipy (4) and bipy (H3L)2 (5),
the solution of 0.20 mmol (43.2 mg) of H3L and 0.20 mmol
Scheme 1 Synthesis of 3-caboxybenzylphosphonic acid (1).
23120 | RSC Adv., 2013, 3, 23119–23127
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(31.2 mg) of 4,40-bipy in 5.0 cm3 of hot (70 ꢁC) water was mixed equipped with two-dimensional CCD area detector. Graphite
with 5.0 cm3 water solution of 0.20 mmol (22.2 mg) of CaCl2 and monochromatized Mo-Ka radiation (l ¼ 0.71073 A) and u-scan
˚
le to stay in room temperature; aer few weeks the colourless technique (Du ¼ 1ꢁ) were used for data collection. Data
(4) and pale yellow (5) X-ray quality crystals have been appeared. collection and reduction along with absorption correction were
The crystals of 4 and 5 were easily separated by hand. Anal. performed using CrysAlis soware package.38 The structures
calcd for: (4) C26H32CaN2O14P2: C, 44.70; H, 4.62; N, 4.01; found: were solved by direct methods using SHELXS-97 (ref. 39) that
C, 44.31; H, 4.28%. IR (KBr, cmꢀ1) 3473, 2413, 1943, 1698, 1626, revealed the positions of almost all non-hydrogen atoms. The
1605, 1589, 1492, 1407, 1327, 1305, 1286, 1254, 1201, 1129, remaining atoms were located from subsequent difference
1070, 1058, 1027, 1003, 939, 920, 805, 785, 694, 633, 614, 540, Fourier syntheses. The structure was rened using SHELXL-97
492, 463. Anal. calcd for (5) C26H26N2O10P2: C, 53.07; H, 4.45; N, (ref. 39) with the anisotropic thermal displacement parameters.
4.76; found: C, 52.77; H, 4.17%. IR (KBr, cmꢀ1) 3493, 3392, 3090, H atoms bonded to O and N atoms of were located from
2821, 1716, 1684, 1608, 1591, 1490, 1458, 1426, 1409, 1399, difference Fourier maps and were rened for the 1, 2, 5 and 6
1298, 1257, 1229, 1198, 1157, 1122, 1089, 1060, 1017, 933, 811, structures, whereas for structures 3 and 4 the H atoms bonded
770, 693, 657, 620, 540, 437.
to O were constrained. Visualisation of the structure was made
Synthesis of bipyH2 (H2L)2 (6). Synthesis of bipyH2 (H2L)2 (6), with the Diamond 3.0 program.40 Details of the data collection
the solution of 0.20 mmol (43.2 mg) of H3L and 0.20 mmol (31.2 parameters, crystallographic data and nal agreement param-
mg) of 4,40-bipy in 5,0 cm3 of hot (70 ꢁC) water was le to stay in eters are collected in Table 1.
room temperature; aer two weeks the colourless X-ray quality
crystals have been appeared. Anal. calcd for C26H26N2O10P2: C,
Results and discussion
Crystal structure of 3-carboxybenzylphosphonic acid (H3L) (1)
53.07; H, 4.45; N, 4.76; found: C, 53.27; H, 4.74%. IR (KBr, cmꢀ1
)
3433, 3100, 2403, 1924, 1673, 1638, 1604, 1590, 1498, 1430,
1409, 1394, 1308, 1294, 1220, 1204, 1156, 1122, 1001, 622, 918,
897, 830, 775, 751, 688, 613, 597, 540, 478, 437.
The molecular structure of 1 as an ORTEP drawing is shown in
Fig. 1, together with the atom numbering scheme. Selected
interatomic distances and angles as well as the details of
hydrogen bonding for compound 1 are given in Table 2. 3-
Carboxybenzylphosphonic acid crystallised in the monoclinic
space group P21/n. The crystal structure is dictated by the
X-ray single crystal measurements and crystal structure
analysis
Single crystal X-ray diffraction measurements of 1–6 were complex 3D system of strong hydrogen bonds (Table 2). The
carried out at 295 K on a four-circle KUMA KM4 diffractometer molecule of 1 is a triple donor and triple acceptor.
Table 1 Crystallographic data for compounds 1–6
Compound
1
2
3
4
5
6
Empirical formula
C8H9O5P
216.12
C16H22CaO13P2
524.36
C16H20CaO12P2
506.34
C26H32N2CaO14P2 C26H26N2O10P2
C13H13NO5P
294.21
Fw (g molꢀ1
)
698.56
588.43
Crystal system
Space group
Monoclinic
P21/n
5.4760 (11)
5.2150 (10)
33.117 (7)
Monoclinic
P2/c
16.6389 (22)
7.1141 (12)
9.1040 (17)
Triclinic
P1
Triclinic
P1
Monoclinic
P21/c
17.908 (4)
4.7119 (9)
17.201 (3)
Monoclinic
C2/c
22.995 (5)
11.763 (2)
9.2980 (19)
ꢀ
ꢀ
˚
a (A)
16.6389 (22)
5.7684 (12)
16.702 (3)
92.08 (1)
90.42 (1)
93.12 (2)
510.95 (18)
1
4.9848 (9)
6.5942 (11)
22.857 (5)
85.39 (1)
84.54 (1)
85.06 (1)
743.2 (3)
1
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
g (ꢁ)
94.12 (1)
95.46 (1)
115.94 (1)
96.14 (1)
3
˚
V (A )
943.3 (3)
4
1.522/1.52
0.284
112
1072.8 (4)
2
1.623/1.62
0.509
1305.2 (4)
2
1.497/1.49
0.230
2500.6 (9)
8
1.563/1.56
0.240
Z
Dcalc/Dobs (g cmꢀ3
)
1.646/1.64
0.528
262
1.561/1.56
0.393
364
m (mmꢀ1
F(000)
)
544
612
1224
Crystal size (mm)
Wavelength, l (A)
0.28 ꢂ 0.26 ꢂ 0.12 0.36 ꢂ 0.24 ꢂ 0.14 0.25 ꢂ 0.24 ꢂ 0.11 0.29 ꢂ 0.24 ꢂ 0.18 0.29 ꢂ 0.24 ꢂ 0.18 0.35 ꢂ 0.21 ꢂ 0.19
˚
Mo Ka, 0.71073
295 (2)
Mo Ka, 0.71073
295 (2)
Mo Ka, 0.71073
295 (2)
Mo Ka, 0.71073
295 (2)
Mo Ka, 0.71073
295 (2)
Mo Ka, 0.71073
295 (2)
Temperature (K)
q range(ꢁ)
3.70–28.91
0.9261/0.9692
11944
2.86–28.42
0.8411/0.9353
13864
3.54–28.11
0.8804/0.9312
6897
2.69–28.22
0.9061/0.9422
9903
2.69–28.55
0.8952/0.9333
16768
2.87–29.04
0.9208/0.9558
16883
Tmin/Tmax
Refs collected
Res unique
Res observed
Rint
2479
2682
2473
3646
3293
3221
1791
1604
1749
1929
1926
2597
0.0259
0.0772
0.0253
0.0519
0.0857
0.0211
R[F2 > 2s(F2)]
0.0334
0.0392
0.0299
0.0795
0.0495
0.0318
wR (F2 all reections) 0.0771
0.0689
0.0622
0.1689
0.0589
0.0913
Goodness-of-t, Sꢀ3
1.002
+0.261, ꢀ0.296
1.001
+0.297, ꢀ0.288
1.001
+0.318, ꢀ0.256
1.009
+0.698, ꢀ0.398
1.001
+0.264, ꢀ0.278
1.001
+0.290, ꢀ0.354
˚
Drmax, Drmin (e A
)
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Fig. 1 The molecular structure of 3-carboxybenzylphosphonic acid (1) with the
atom numbering scheme, plotted with 50% probability of displacement ellipsoid.
ꢁ
˚
Table 2 Selected bond length (A), angles ( ) and hydrogen bond geometry for
a
ꢁ
˚
Fig. 3 The molecular structure of compound 2 with the atom-numbering
compound 1 (A,
)
scheme, plotted with 50% probability of displacement ellipsoids.
P1–O1
P1–O3
C8–O5
C1–C7
O1–P1–O2
O1–P1–C7
C2–C1–C7
O5–C8–C3
O2–P1–C7
C6–C1–C7
C2–C3–C8
1.4938 (10)
1.5470 (11)
1.2566 (17)
1.5132 (19)
112.36 (6)
110.97 (6)
121.06 (13)
119.11 (13)
108.71 (7)
120.19 (13)
120.36 (13)
P1–O2
P1–C7
C8–O4
C2–C3
O2–P1–O3
O3–P1–C7
O5–C8–O4
O1–P1–O3
C1–C7–P1
C5–C3–C8
O4–C8–C3
1.5457 (11)
1.7884 (14)
1.2681 (18)
1.3922 (19)
105.35 (6)
105.49 (7)
122.91 (14)
113.54 (6)
113.69 (10)
119.97 (13)
117.98 (13)
details of hydrogen bonding for compound 2 are given in
Table 2. The molecule is located on the c2 axis passing by
calcium ion and O7 oxygen atom. The calcium ion is seven co-
ordinated with four phosphonate oxygen atoms from four
neighbour ligands and three water molecules. The geometry of
CaO7 polyhedron can be described as a distorted pentagonal
bipyramid, the Ca, O3ii, O3iii O6, O6i, and O7 atoms dene the
equatorial plane whereas O2 and O2i atoms occupy the apical
positions. Each phosphonate group acts as a bridging ligand
connecting the calcium ions in the m2 (O2,O3) mode. The zigzag
chain of coordination polymer is parallel to the c crystallo-
graphic axis (Fig. 4a). The complex system of hydrogen bonds
(Table 3) between coordinated phosphonate groups and water
D–H/A
D–H
H/A
D/A
D–H/A
O2–H2O/O1i
O3–H3O/O1ii
0.88 (2)
0.85 (2)
0.96 (2)
1.68 (2)
1.75 (2)
1.67 (2)
2.556 (2)
2.601 (2)
2.629 (2)
175.4 (18)
179.1 (18)
176 (2)
O4–H4O/O5iii
a
Symmetry codes: (i) ꢀx ꢀ 1/2, y + 1/2, ꢀz + 1/2; (ii) ꢀx + 1/2, y + 1/2, ꢀz +
1/2; (iii) ꢀx + 1, ꢀy + 1, ꢀz.
The molecular units are mutually located in the head-to-
head relation according to both phosphonic and carboxylic
groups. Each phosphonic group interacts with four phosphonic
groups coming from the neighbour molecules of acid, Fig. 2.
The carboxylic groups form the common carboxylic dimer
motif, thereby completing the number of hydrogen bonds to six
(Fig. 2).
Crystal structure of [Ca(H2L)2(H2O)3]n (2)
The molecular unit of 2 with the labelling scheme is shown in
Fig. 3. Selected interatomic distances and angles as well as the
Fig.
2
The pattern of the hydrogen bonds in the crystal of 3-carboxy-
Fig. 4 (a) The polymer chain propagating along the c axis, (b) packing in the
crystal of compound 2.
benzylphosphonic acid (1). Symmetry code as in Table 2.
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ꢁ
ꢁ
)
˚
˚
Table 3 Selected bond length (A), angles ( ) and hydrogen bond geometry (A,
for compound 2a
Ca–O2
2.3597 (14)
2.4057 (17)
2.5021 (14)
2.3597 (14)
1.5014 (14)
1.257 (3)
Ca–O6i
2.4057 (17)
2.453 (2)
2.5021 (14)
1.5744 (14)
1.5109 (13)
1.265 (3)
Ca–O6
Ca–O7
Ca–O3ii
Ca–O3iii
Ca–O2i
P1–O1
P1–O3
C8–O5
P1–O2
C8–O4
O2–Ca–O2i
O2–Ca–O6
O2–Ca–O7
O2–Ca–O3ii
O6–Ca–O3ii
O2–Ca–O3iii
O6–Ca–O3iii
173.61 (7)
101.03 (5)
93.19 (3)
82.43 (4)
73.38 (5)
O2–Ca–O6i
O6i–Ca–O6
O6–Ca–O7
O2i–Ca–O3ii
O7–Ca–O3ii
O2i–Ca–O3iii
O3ii–Ca–O3iii
81.38 (5)
136.52 (8)
68.26 (4)
92.67 (5)
139.76 (3)
82.43 (4)
92.67 (5)
148.39 (5)
80.48 (7)
Fig. 6 Coordination polymer and packing in the crystal of 3.
D–H/A
D–H
H/A
D/A
D–H/A
O1–H1O1/O3ii
O5–H1O5/O4iv
O6–H1O6/O2v
O6–H2O6/O1ii
O7–H1O7/O2vi
O7–H1O7/O3vi
0.80 (2)
0.81 (3)
0.88 (3)
0.77 (2)
0.76 (2)
0.76 (2)
1.77 (2)
1.80 (3)
1.97 (3)
2.07 (2)
2.41 (3)
2.57 (3)
2.574 (2)
2.606 (2)
2.824 (2)
2.819 (2)
3.095 (2)
3.191 (3)
179 (3)
172 (3)
164 (2)
163 (3)
150 (3)
139 (3)
a
Symmetry codes: (i) ꢀx + 1, y, ꢀz + 1/2; (ii) x, ꢀy, z ꢀ 1/2; (iii) ꢀx + 1, ꢀy,
ꢀz + 1; (iv) ꢀx, ꢀy, ꢀz; (v) x, ꢀy + 1, z ꢀ 1/2; (vi) ꢀx + 1, ꢀy + 1, ꢀz + 1.
Fig. 7 The molecular structure of compound 4 with the atom-numbering
scheme, plotted with 50% probability of displacement ellipsoids.
molecules joins the chains into the wide layer parallel to the
crystallographic bc plane. The carboxylic groups located outside
the layer interact with the adjacent layers through the strong
hydrogen bonds of the carboxylic dimer type (R822), forming the
3D structure, Fig. 4b. The shortest distances between the
˚
˚
calcium ions equal 5.891 A in chain and 5.667 A between
neighbour chains.
Crystal structure of [Ca(H2L)2(H2O)2]n (3)
Fig. 5 The molecular structure of compound 3 with the atom-numbering
The molecular unit of 3 with the labelling scheme is shown in
Fig. 5. Selected interatomic distances and angles as well as the
details of hydrogen bonding for compound 3 are given in Table 4.
The calcium ion is positioned on the centre of symmetry. Six
oxygen atoms from four phosphonate ligands and two water
molecules are co-ordinated to calcium affording the slightly
deformed octahedral geometry. The phosphonate ion acts as a
bridging ligand (m2-O1,O2) connecting the metal centres sepa-
scheme, plotted with 50% probability of displacement ellipsoids.
ꢁ
˚
Table 4 Selected bond length (A), angles ( ) and hydrogen bond geometry for
compound 3a
Ca–O1
Ca–O6
P1–O1
P1–O3
2.3236 (12)
2.3741 (14)
1.5008 (11)
1.5958 (12)
1.266 (2)
94.34 (4)
89.59 (5)
90.35 (5)
Ca–O2ii
Caiv–O2
P1–O2
2.3300 (12)
2.3300 (12)
1.5104 (11)
˚
rated by 5.768 A. The carboxylic groups are not co-ordinated. The
1D co-ordination chains extending along the crystallographic b
axis are connected by system of medium hydrogen bonds into the
layer parallel to ab crystallographic plane (Fig. 6). The shortest
distance between calcium ions coming from neighbour chain
C8–O4
C8–O5
1.260 (2)
85.66 (4)
90.41 (5)
89.59 (5)
O1–Ca–O2ii
O1–Ca–O6i
O2ii–Ca–O6
O1–Ca–O2iii
O1–Ca–O6
O1i–Ca–O6
˚
equals 5.315 A. The layers are connected by the very strong
hydrogen bonds (R822) between carboxylic groups.
D–H/A
D–H
H/A
D/A
D–H/A
O3–H13/O2v
O4–H14/O5vi
O6–H16/O3vii
O6–H26/O1viii
0.82 (1)
0.82 (2)
0.82 (1)
0.82 (1)
1.90 (1)
1.83 (2)
2.03 (1)
2.05 (1)
2.705 (2)
2.643 (2)
2.829 (2)
2.861 (2)
171 (2)
173 (2)
167 (2)
170 (2)
Crystal structure of [Ca(H2L)2(H2O)4] bipy (4)
The molecular unit of 4 with the labelling scheme is shown in
Fig. 7. Selected interatomic distances and angles as well as the
details of hydrogen bonding for compound 4 are given in Table 5.
In the crystal of 4 the discrete molecules of [Ca(H2L)2(H2O)4] and
4,4,-bipyridine are found. In the complex molecule the calcium
a
Symmetry codes: (i) ꢀx + 1, ꢀy + 1, ꢀz + 1; (ii) x, y + 1, z; (iii) ꢀx + 1, ꢀy,
ꢀz + 1; (iv) x, y ꢀ 1, z; (v) ꢀx + 2, ꢀy, ꢀz + 1; (vi) ꢀx + 3, ꢀy, ꢀz; (vii) x ꢀ 1,
y + 1, z; (viii) x ꢀ 1, y, z.
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ꢁ
Selected bond length (A), angles (ꢁ) and hydrogen bonds for
˚
˚
Table 5 Selected bond length (A), angles ( ) and hydrogen bond geometry for
compound 4a
Table
6
compounds 5 and 6a
Ca–O1
P1–O1
P1–O3
C8–O5
2.335 (2)
1.490 (3)
1.580 (3)
1.226 (5)
91.51 (10)
93.44 (10)
86.56 (10)
Ca–O1W
P1–O2
C8–O4
O2W–Ca–O1
O2W–Ca–O1Wi
O1i–Ca–O1Wi
O2W–Ca–O1W
2.368 (3)
1.503 (3)
1.306 (5)
88.49 (10)
94.09 (10)
86.56 (10)
85.91 (10)
5
6
P1–O1
P1–O2
P1–O3
C8–O4
C8–O5
1.5056 (15)
1.5071 (15)
1.5617 (17)
1.185 (3)
1.4915 (10)
1.5186 (10)
1.5819 (10)
1.2118 (16)
1.3191 (17)
O2W–Ca–O1i
O1–Ca–O1Wi
O1–Ca–O1W
1.314 (3)
D–H/A
D–H
H/A
D/A
D–H/A
D–H/A
D–H
H/A
D/A
D–H/A
O1W–H1W1/O1ii
O1W–H1W2/O2iii
O2W–H2W1/O3iv
O2W–H2W2/O2v
O3–H3/O2ii
0.96
0.95
0.97
0.96
0.82
0.82
1.93
2.00
2.00
2.02
1.95
1.83
2.844 (4)
2.906 (4)
2.925 (4)
2.679 (4)
2.676 (3)
2.626 (4)
159
159
158
124
147
164
For 5
O3–H3O/O1i
N1–H1N/O2i
O5–H5O/O1ii
0.87 (2)
1.17 (2)
0.90 (3)
1.64 (2)
1.35 (2)
1.70 (3)
2.508 (2)
2.515 (2)
2.593 (2)
173 (3)
176 (2)
169 (3)
For 6
O4–H4O/N14
N1–H1N/O2
O3–H3O/O2i
O5–H5O/O1ii
0.92 (2)
0.83 (2)
0.88 (2)
1.74 (2)
1.85 (2)
1.65 (2)
2.657 (2)
2.672 (2)
2.536 (2)
175 (2)
177 (2)
176 (2)
a
Symmetry codes: (i) ꢀx, ꢀy, ꢀz; (ii) x + 1, y, z; (iii) x + 1, y ꢀ 1, z; (iv) x, y
ꢀ 1, z; (v) ꢀx ꢀ 1, ꢀy, ꢀz.
a
Symmetry codes for 5: (i) x, y ꢀ 1, z; (ii) x, ꢀy + 3/2, z ꢀ 1/2. For 6: (i) x,
ꢀy, z + 1/2; (ii) ꢀx + 1/2, ꢀy ꢀ 1/2, ꢀz + 2.
ion is six co-ordinated to two monodentate phosphonate ligands
and four water molecules.
The CaO6 polyhedron can be described as a deformed octa-
6 crystallised in monoclinic P21/c and C2/c space group,
respectively. Crystals of 5 and 6 are built of the ionic species:
4,40-bypirydinium cations and monodeprotonated 3-carboxy-
benzylphopsphonic acid (Fig. 9). The carboxylic groups in both
compounds are protonated.
The crystal structure in 5 and 6 is generated by very strong
intermolecular hydrogen bonds between phosphonate group
and bipyridinium ion as well as carboxylic group (Table 6). The
˚
hedron, the medium value of Ca–O bond equals 2.341(3) A, the
carboxylic groups do not coordinate. The layered 3D structure of
the crystal of 4 is very similar to those found for 2 and 3.
Due to the complex network of hydrogen bonds, between the
ligands coordinated to calcium ion, the molecules of
[Ca(H2L)2(H2O)4] form the closely packed layer (Fig. 8) parallel to
the ab crystallographic plane. The shortest distances between the
˚
˚
calcium ions in the layer equal 4.955 A and 6.985 A. The layers
made of the [Ca(H2L)2(H2O)4] are separated by 4,40-bipyridine
molecules which form the very strong hydrogen bonds with
carboxylic groups (Fig. 8, Table 5). The 4,40-bipyridine molecules
form the stacks in which the Cg–Cg distance, for molecules related
˚
˚
very short N/O distances, equal 2.515(2) A and 2.6566(15) A, for
5 and 6 respectively, are the good evidence that N–H/O
˚
by the 1 ꢀ x, 1 ꢀ y, 1 ꢀ z symmetry operation, equals 3.608 A.
Crystal structure of (4,40-bipyH2) (H2L)2 (5) and (6)
The compounds 5 and 6 in the solid state, as shown from the
X-ray single crystal analysis are the same. The polymorphs 5 and
Fig. 9 The molecular structure of compound 5 (a) and 6 (b) with the atom
Fig. 8 Packing in the crystal of 4.
numbering scheme, plotted with 50% probability of displacement ellipsoids.
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hydrogen bridges between bipyridinium cation and phospho- C2–C1–C7–P1 in 6 equals 113.4ꢁ. The pyridinium rings in
nate ion are among the strongest ones.41,42 The proton is located bipyridinium ions are coplanar in both polymorphs. The
at the nitrogen atom in both isomorphs, the N–H distance in 5 structures of 5 and 6 are stabilized by offset stacking interac-
˚
˚
equals 1.17(2) A and in 6 is equal only 0.923(18) A. The C–N–C tions between bipyridine ring systems (Fig. 9 and 10).
angles are characteristic for protonated bipyridinium ions
(Table 6) and are signicantly greater than that found in 4,4,-
bipyridine molecule in 4 to equal 114.9(4). The data on similar
Conclusions
interaction between phosphonate ion and double protonated In the present contribution we describe synthesis and the
4,40-bipyridine are scarce, only three examples have been found: structural study of 3-carboxybenzylphosphonic acid (1), three
ethane-1,2-diphosphonic acid-4,40-bipyridine–water (1/1/2).41,42 calcium 3-carboxybenzylphosphonates (2, 3, 4) and two poly-
1-Amino-phenylethane-1,10-diphosphonic acid-4,40-bipyridine43 morphs 4,4-bipyridinium 3-carboxybenzylphosphonates (5, 6).
and 1,3,5-benzenetriphosphonic acid-4,40-bipyridine–water Compounds 2 and 3 are co-ordination polymers, the crystal of 4
(1/13).44
is built of discrete units of mononuclear complexes. In 2, 3 and
Several differences in the structures of 5 and 6 are observed 4 the monodeprotonated phosphonate ions and water mole-
on the molecular and intermolecular level. The P–O bond cules coordinates to calcium ions. The uncoordinated carbox-
length in the hydrophosphonate groups shows signicant ylate groups, phosphonate groups and water molecules bear
differences, Table 6. Also the positions of PO3Hꢀ and COOH hydrogen bonding donor/acceptor functions what allow the
groups in relation to the benzene ring are not the same in 5 and formation of complex systems of hydrogen bonds. The inor-
6, the C1–C2–C1–P1 angle in 5 equals 118.4ꢁ whereas the angle ganic parts (coordination polyhedral) of the complexes are
collected in thin layers that are isolated by wide layers of
benzene rings and carboxylate groups. In 2 and 3 carboxylate
form very strong “carboxylate dimer motifs”. In 4, the organic
layer is widened by incorporation of 4,40-bipyridine between
terminal carboxylate groups via strong hydrogen bond of the
O–H/N type. The very strong hydrogen bond networks in the
crystals of acid (1) and 4,40-bipyridinium phosphonates (5, 6)
afford the 3D complicated supramolecular structure.
Acknowledgements
D. D., J. K. and J. Z. are grateful for nancial support from the
Department of Chemistry, Wrocław University of Technology,
Wrocław.
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