Zinc and Cadmium Diphenate Coordination Polymers with Conformationally Flexible Dipyridylamide Ligands

Article abstract of DOI:10.1002/zaac.201700183

Zinc and cadmium diphenate (dip, biphenyl-2,2′-dicarboxylate) coordination polymers containing conformationally flexible dipyridylamide ligands show diverse chain and layer topologies as determined by single-crystal X-ray diffraction. [Cd(dipH)₂(bdin)]_n (1) [bdin = N,N′-(butane-1,3-diyl)diisonicotinamide] shows a simple 1D zigzag chain structure. {[Cd(dip)(pdin)(H₂O)]·1.25H₂O}_n (2) [pdin = N,N′-(propane-1,3-diyl)diisonicotinamide] shows bilayer slabs formed by interleaving of (4,4) rectangular grid layers. {[Zn₂(dip)₂(3-pna)₂]·3H₂O}_n (3) (3-pna = 3-pyridylnicotinamide) manifests a rare 4-connected 1D ribbon topology. {[Cd(dip)(4-ppbp)]·2H₂O}_n (4) [4-ppbp = propane-1,3-diylbis(piperidine-4,1-diyl)bis(pyridin-4-ylmethanone)] shows a 3,5-connected layer with (4²6)(4²6⁷8) 3,5L2 topology. {[Zn₄(dip)₄(H₂O)₂(4-ppbp)₂]·12H₂O}_n (5) exhibits 2D 3,6-connected layers with (4³)₂(4⁶6⁶8³) kgd topology featuring embedded R(8)A(2) classification 10-membered water clusters. Compounds 1, 4, and 5 undergo violet or blue-violet fluorescence upon ultraviolet irradiation. Thermal decomposition behavior of the new phases is also discussed.

Full text of DOI:10.1002/zaac.201700183

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201700183
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Zinc and Cadmium Diphenate Coordination Polymers with
Conformationally Flexible Dipyridylamide Ligands
Brianna L. Martinez[a] and Robert L. LaDuca*[a]
Abstract. Zinc and cadmium diphenate (dip, biphenyl-2,2Ј-dicarb-
oxylate) coordination polymers containing conformationally flexible
dipyridylamide ligands show diverse chain and layer topologies as de-
nected 1D ribbon topology. {[Cd(dip)(4-ppbp)]·2H2O}n (4) [4-ppbp =
propane-1,3-diylbis(piperidine-4,1-diyl)bis(pyridin-4-ylmethanone)]
shows a 3,5-connected layer with (426)(42678) 3,5L2 topology.
termined by single-crystal X-ray diffraction. [Cd(dipH)2(bdin)]n (1) {[Zn4(dip)4(H2O)2(4-ppbp)2]·12H2O}n (5) exhibits 2D 3,6-connected
[bdin = N,NЈ-(butane-1,3-diyl)diisonicotinamide] shows a simple 1D
layers with (43)2(466683) kgd topology featuring embedded R(8)A(2)
zigzag chain structure. {[Cd(dip)(pdin)(H2O)]·1.25H2O}n (2) [pdin = classification 10-membered water clusters. Compounds 1, 4, and 5
N,NЈ-(propane-1,3-diyl)diisonicotinamide] shows bilayer slabs formed undergo violet or blue-violet fluorescence upon ultraviolet irradiation.
by interleaving of (4,4) rectangular grid layers. {[Zn2(dip)2(3-pna)2]· Thermal decomposition behavior of the new phases is also discussed.
3H2O}n (3) (3-pna = 3-pyridylnicotinamide) manifests a rare 4-con-
different from those containing the ortho-dicarboxylate phthal-
ate ligand.[10,11] The dip ligand can show flexible conforma-
Introduction
tions about its central sp2(C)–sp2(C) σ bond in response to
specific supramolecular conditions during self-assembly,
which is not possible in monoaromatic ligands such as phthal-
ate. This flexibility has often generated helical subunits and
relatively uncommon topologies. For example, [Cu(dip)(bpy)]n
and [Cu(dip)(dpee)]n [dpee = 1,2-bis(4-pyridyl)ethylene] both
manifested a 4-connected non-diamondoid cds 658 topology,
constructed from [Cu(dip)]n helices linked by the tethering co-
ligands.[10a] Inclusion of the longer dpee ligand resulted in
twofold interpenetration, unlike the shorter rigid rod
One of the primary foci of inorganic chemistry basic re-
search in recent years has been the preparation, structural char-
acterization, and properties measurements of crystalline coor-
dination polymers containing divalent metal atoms. This genre
of solid-state materials has exhibited utility in hydrogen ad-
sorption,[1] molecular separations,[2] ion exchange,[3] hetero-
geneous catalysis for organic transformations,[4] and as sensors
for the detection of explosive compounds or substances of en-
vironmental concern.[5] The striking aesthetic appeal of the
underlying topologies of coordination polymers is also an un-
deniable impetus for continued investigation.[6] The most fre-
quent choices of ligand for the self-assembly of coordination
polymers have been aromatic dicarboxylates, as these can im-
bpy ligand, which afforded
a non-interpenetrated net.
[Zn(dip)(bpy)]n possessed a twofold interpenetrated network
with a rare uninodal 4-connected 4284 topology, construction
from the linkage of helical [Zn(dip)]n chains.[10b]
{[Cd6(dip)6(H2O)4(dpa)4]·5H2O}n (dpa = 4,4Ј-dipyridylamine)
features [Cd6(dip)6(H2O)4] arc-like hexanuclear clusters linked
together into 1D rods, that are further conjoined by dpa ligands
to form a very rare 5-connected 4466 nov 3D topology.[11]
part thermal stability and, occasionally, useful porosity.[7–9]
A
wide diversity of 1D chain, 2D layer, or 3D network structures,
and also multi-functional properties, can be obtained in these
systems by incorporating other neutral co-ligands. For
instance, the twofold interpenetrated 3D network
[Zn(bdc)(bpy)0.5] (bdc = 1,4-benzenedicarboxylate; bpy = bi-
pyridine) can act as a stationary phase for the gas chromato-
graphic size-dependent separation of n-pentane from
n-hexane.[8a] Employing the longer-spanning dipyridyl
ligand bis(4-pyridylmethyl)piperazine (bpmp) afforded
[Zn2Cl2(bdc)(bpmp)2]n, the first example of threaded-loop 1D
+ 1D Ǟ 1D interpenetration.[8b]
The ortho-diaromatic dicarboxylate ligand diphenate (dip,
Scheme 1) has afforded coordination polymers with topologies
* Dr. R. L. LaDuca
E-Mail: laduca@msu.edu
[a] Lyman Briggs College and Department of Chemistry
Michigan State University
Scheme 1. Ligands used in this study.
East Lansing, MI 48825 USA
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201700183 or from the au-
thor.
In this study we aimed to prepare cadmium and zinc diphen-
ate coordination polymers incorporating dipyridylamide li-
Z. Anorg. Allg. Chem. 0000, ᭿,0–0
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Journal of Inorganic and General Chemistry
ARTICLE
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acetone and drying in air. C44H36CdN4O10: calcd. C 59.17; H 4.06; N
gands that also possess a wide degree of conformational flexi-
6.27%; found C 59.55; H 4.49; N 6.27%. IR: ν˜ = 3445 (w, br), 2930
(w), 1623 (s), 1568 (w), 1542 (s), 1471 (w), 1435 (m), 1392 (s),
1281(m), 1028 (w), 1226 (w), 1152 (w), 1121 (w), 1068 (w), 982 (w),
893 (w), 848 (s), 810 (w), 745 (s), 708 (s), 682 (s), 647 (s), 618 (w),
609 (w) cm–1.
bility. The dipyridylamide ligands N,NЈ-(butane-1,3-diyl)diiso-
nicotinamide (bdin) and N,NЈ-(propane-1,3-diyl)diisonicotin-
amide (pdin) (Scheme 1) have both been seldom utilized in
the construction of coordination polymers. Series of copper
oxoanion or pseudohalide phases with bdin or pdin linkers
were prepared by Biradha,[12,13] and 1D or 2D copper isoph-
thalate coordination polymers containing bdin tethers were re-
ported by Lin et al.[14] The very long spanning dipyridylamide
ligand propane-1,3-diylbis(piperidine-4,1-diyl))bis(pyridin-4-
ylmethanone) (4-ppbp) (Scheme 1) has also been seldom
used in supramolecular or coordination polymer
chemistry. A very interesting topology was observed in
[Ni(tdc)(4-ppbp)2(H2O)]n, (tdc = 2,5-thiophenedicarboxylate),
which manifested a polycatenated system of 2D + 2D Ǟ 2D
parallel interpenetrated 2,6-connected looped layers.[15] While
less flexible, the dipyridylamide ligand 3-pyridylisonicotin-
amide (3-pna) (Scheme 1) can show syn, anti, or intermediate
twisted conformations of its pyridyl donor atoms.[16–17]
Preparation of {[Cd(dip)(pdin)(H2O)]·1.25H2O}n (2): Cd(NO3)2·
4H2O (114 mg, 0.37 mmol), diphenic acid (90 mg, 0.37 mmol), and
pdin (115 mg, 0.40 mmol) were mixed with deionized H2O (10 mL)
and 1 m NaOH (0.75 mL) in a 23 mL Teflon-lined acid digestion
bomb. The bomb was sealed and heated in an oven at 120 °C for 48
h. Afterwards it was removed from the oven and cooled under ambient
conditions to 25 °C. Straw-colored needles of 2 (155 mg, 62% yield
based on Cd) were isolated after washing with deionized water and
acetone and drying in air. C29H28.5CdN4O8.25: calcd. C 51.45; H 4.24;
N 8.28%; found C 51.66; H 4.33; N 7.75%. IR: ν˜ = 3298 (w, br),
2930 (w), 1607 (s), 1668 (w), 1540 (s), 1472 (w), 1435 (m), 1389 (s),
1282 (m), 1227 (w), 1152 (w), 1102 (w), 1069 (w), 1029 (w), 983 (w),
849 (s), 811 (w), 782 (w), 756 (s), 707 (m), 683 (s), 648 (m), 619 (w),
609 (w) cm–1.
In this contribution we report the synthesis and single-crys-
tal X-ray characterization of a structurally diverse group
of d10 metal coordination polymers [Cd(dipH)2(bdin)]n (1),
{[Cd(dip)(pdin)(H2O)]·1.25H2O}n (2), {[Zn2(dip)2(3-pna)2]·
Preparation of {[Zn2(dip)2(3-pna)2]·3H2O}n (3): Zn(NO3)2·6H2O
(110 mg, 0.37 mmol), diphenic acid (90 mg, 0.37 mmol), and 3-pna
(74 mg, 0.37 mmol) were mixed with deionized H2O (10 mL) and 1 m
NaOH (0.75 mL) in a 23 mL Teflon-lined acid digestion bomb. The
bomb was sealed and heated in an oven at 120 °C for 48 h. Afterwards
3H2O}n
(3),
{[Cd(dip)(4-ppbp)]·2H2O}n
(4),
and
{[Zn4(dip)4(H2O)2(4-ppbp)2]·12H2O}n (5). Thermal and fluo- it was removed from the oven and cooled under ambient conditions to
25 °C. Brown needles of 3 (84 mg, 42% yield based on Zn) were
isolated after washing with deionized water and acetone and drying in
air. C50H40N6O13Zn2: calcd. C 56.46; H 3.79; N 7.90%; found C
57.24; H 3.83; N 7.90%. IR: ν˜ 3353 (m, br), 2930 (w), 1606 (s), 1569
(w), 1541 (s), 1474 (w), 1434 (w), 1387 (m), 1353 (w), 1293 (w), 1196
(w), 1153 (w), 1122 (w), 1105 (w), 1069 (w), 1047 (w), 1030 (w),
1004 (w), 964 (w), 894 (w), 846 (m), 813 (m), 779 (w), 755 (w), 745
(w), 707 (w), 697 (w), 681 (w), 649 (w), 618 (w) cm–1.
rescent properties of 1–5 are also discussed herein.
Experimental Section
General Considerations: Metal nitrates and diphenic acid were com-
mercially obtained. The dipyridyl ligand propane-1,3-diylbis(piperid-
ine-4,1-diyl)bis(pyridin-4-ylmethanone) (4-ppbp) was synthesized ac-
cording to a modification the published procedure for the preparation
of bis(4-pyridylformyl)piperazine,[18] via condensation of trimethylbi-
piperidine and two molar equivalents of isonicotinoyl chloride hydro-
chloride in dry pyridine, followed by extraction with chloroform and
removal of volatiles in vacuo. The hydrate 4-ppbp·2H2O was formed
by recrystallizing the crude product from deionized water. The bdin
and pdin ligands were prepared similarly, utilizing 1,4-butanediamine
and 1,3-propanediamine, respectively, instead of trimethylbipiperidine
as the diamine component.[18] Condensation of 3-pyridylamine and
nicotinoyl chloride hydrochloride in dry pyridine was used to prepare
3-pyridylnicotinamide (3-pna), which was isolated via CH2Cl2 extrac-
tion and rotary evaporation.[19] Water was deionized above 3 MΩ·cm
with an in-house deionizing system. Elemental analysis was carried
out with a Perkin-Elmer 2400 Series II CHNS/O Analyzer. IR spectra
were recorded on powdered samples with a Perkin-Elmer Spectrum
One instrument. The luminescence spectra for 1–5 were obtained with
a Hitachi F-4500 Fluorescence Spectrometer on solid crystalline sam-
ples anchored to quartz microscope slides with Rexon Corporation
RX-22P ultraviolet-transparent epoxy adhesive.
Preparation of {[Cd(dip)(4-ppbp)]·2H2O}n (4): Cd(NO3)2·4H2O
(114 mg, 0.37 mmol), diphenic acid (90 mg, 0.37 mmol), and 4-ppbp
(152 mg, 0.37 mmol) were mixed with deionized H2O (10 mL) and
1 m NaOH (0.75 mL) in a 23 mL Teflon-lined acid digestion bomb.
The bomb was sealed and heated in an oven at 120 °C for 48 h. After-
wards it was removed from the oven and cooled under ambient condi-
tions to 25 °C. Straw-colored blocks of 4 (172 mg, 58% yield based
on Cd) were isolated after washing with deionized water and acetone
and drying in air. C39H44CdN4O8: calcd. C 57.89; H 5.48; N 6.92%;
found C 58.40; H 5.57; N 7.09%. IR: ν˜ = 3445 (w, br), 2930 (w),
1623 (s), 1541 (m), 1435 (m), 1384 (s), 1281 (s), 1222 (w), 1152 (w),
1120 (w), 1069 (w), 1028 (w), 1004 (w), 982 (w), 894 (w), 848 (s),
810 (w), 745 (s), 708 (s), 682 (s), 648 (s), 618 (w) cm–1.
Preparation of {[Zn4(dip)4(H2O)2(4-ppbp)2]·12H2O}n (5): Zn(NO3)2·
6H2O (110 mg, 0.37 mmol), diphenic acid (90 mg, 0.37 mmol), and 4-
ppbp (152 mg, 0.37 mmol) were mixed with deionized H2O (10 mL)
and 1 m NaOH (0.75 mL) in a 23 mL Teflon-lined acid digestion
bomb. The bomb was sealed and heated in an oven at 120 °C for 48
Preparation of [Cd(dipH)2(bdin)]n (1): Cd(NO3)2·4H2O (114 mg, h. Afterwards it was removed from the oven and cooled under ambient
0.37 mmol), diphenic acid (180 mg, 0.74 mmol), and bdin (112 mg, conditions to 25 °C. Colorless blocks of 5 (140 mg, 65% yield based
0.38 mmol) were mixed with deionized H2O (10 mL) and 1 m NaOH on Zn) were isolated after washing with deionized water and acetone
(0.75 mL) in a 23 mL Teflon-lined acid digestion bomb. The bomb
and drying in air. C53H62N4O17Zn2: calcd. C 54.98; H 5.40; N 4.84 ;
was sealed and heated in an oven at 120 °C for 48 h. Afterwards it found C 54.56; H 5.74; N 5.04%. IR: ν˜ = 3447 (w, br), 2921 (w),
was removed from the oven and cooled under ambient conditions to 1623 (s), 1541 (m), 1435 (m), 1384 (s), 1281 (m), 1221 (w), 1152 (w),
25 °C. Straw-colored needles of 1 (210 mg, 65% yield based on di-
1120 (w), 1069 (w), 1027 (w), 982 (w), 894 (w), 708 (s), 682 (s), 648
phenic acid) were isolated after washing with deionized water and (s), 609 (w) cm–1.
Z. Anorg. Allg. Chem. 0000, 0–0
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Journal of Inorganic and General Chemistry
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Table 1. Crystal and structure refinement data for 1–5.
1
2
3
4
5
Empirical formula
Formula weight
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
C44H36CdN4O10
893.16
monoclinic
C2/c
20.488(2)
7.8541(8)
24.255(3)
90
95.420(1)
90
3885.5(7)
4
1.527
0.629
0.37ϫ0.10ϫ0.04
0.8937
C29H28.5CdN4O8.25
677.46
orthorhombic
Pbca
17.5414(17)
9.2031(9)
35.638(3)
90
C50H40N6O13Zn2
1063.62
monoclinic
Cc
25.278(3)
19.459(3)
10.4575(14)
90
114.260(2)
90
4689.7(11)
4
C39H44CdN4O8
809.18
monoclinic
P21/n
20.145(6)
9.896(3)
20.549(6)
90
117.015(8)
90
C53H62N4O17Zn2
1157.80
triclinic
¯
P1
13.979(3)
14.190(3)
16.746(3)
64.951(2)
71.416(2)
61.134(2)
2608.0(9)
2
90
90
γ /°
V /Å3
5753.3(10)
8
1.564
0.817
0.31ϫ0.08ϫ0.04
0.8843
–21 Յ h Յ 21
–11 Յ k Յ 11
–42 Յ l Յ 42
43883
5273
0.1197
3649.5(18)
4
1.473
Z
D /g·cm–3
μ /mm–1
Crystal size /mm
Min./max. trans.
hkl ranges
1.506
1.097
1.474
0.997
0.657
0.36ϫ0.13ϫ0.08
0.9067
–30 Յ h Յ 30
–23 Յ k Յ 23
–12 Յ l Յ 12
18732
0.17ϫ0.07ϫ0.06 0.19ϫ0.16ϫ0.11
0.8678
–24 Յ h Յ 24
–11 Յ k Յ 11
–24 Յ l Յ 24
28433
–24 Յ h Յ 24
–9 Յ k Յ 9
–29 Յ l Յ 29
15318
3577
0.0526
–14 Յ h Յ 14
–11 Յ k Յ 11
–24 Յ l Յ 24
30975
9530
0.0322
Total reflections
Unique reflections
R(int)
8516
0.0406
6614
0.0862
Parameters
268
0.0505
0.0403
0.0951
397
0.0890
0.0443
0.1068
0.0877
1.253/–0.589
1.008
650
0.0615
0.0449
0.1103
0.1010
0.645/–0.282
1.025
475
0.0881
0.0445
0.1188
0.0989
0.914/–0.458
0.966
701
0.0594
0.0474
0.1425
0.1318
0.740/–0.800
1.056
a)
R1 (all data)
a)
R1 [I Ͼ 2σ(I)]
b)
wR2 (all data)
b)
wR2 [I Ͼ 2σ(I)]
0.0881
Max/min residual /e–·Å–3 1.225/–0.325
G.O.F.
1.086
2
2 2
2 2
a) R1 = Σ||Fo|–|Fc||/Σ|Fo|. b) wR2 = {Σ[w(Fo –Fc ) ]/Σ[wFo ] }1/2
.
X-ray Crystallography: Diffraction data for 1–5 were collected with
a Bruker-AXS SMART-CCD X-ray diffractometer using graphite-mo-
nochromated Mo-Kα radiation (λ = 0.71073 Å). The data were pro-
cessed via SAINT,[20] and subjected to Lorentz and polarization effect
and absorption corrections using SADABS.[21] The structures were
solved by direct methods with SHELXTL.[22] All non-hydrogen atoms
were refined anisotropically. Hydrogen atoms bound to carbon, nitro-
gen or oxygen were placed in calculated positions and refined iso-
tropically with a riding model. The crystal structure of 3 refined best
as an inversion twin in space group Cc, with poor refinements in the
ligand. Infrared spectra were consistent with the structural
components as ascertained by X-ray diffraction. Broadened,
weak bands at 3200–3500 cm–1 signify the O–H stretching
bands within the bound and unbound water molecules. Weaker,
high energy bands at 3000–3200 cm–1 are attributed to C–H
bond stretching modes in all cases. Asymmetric and symmetric
C–O stretching modes of the dicarboxylate ligands are indi-
cated by slightly broadened, strong bands at 1542 cm–1 and
1392 cm–1 (1), 1540 cm–1 and 1389 cm–1 (2), 1541 cm–1 and
centrosymmetric space group C2/c. Although the crystal of 2 diffracted 1387 cm–1 (3), 1541 cm–1 and 1384 cm–1 (4), and 1541 cm–1
and 1385 cm–1 (5). Sharp, medium intensity bands in the range
relatively weakly, resulting in a high R(int) value, the overall refine-
ment was wholly satisfactory. Crystallographic details for 1–5 are
given in Table 1.
of 1600 cm–1 to 1200 cm–1 are ascribed to stretching modes of
the pyridyl rings of the dipyridylamide ligands or the aromatic
rings of the diphenate ligands.[23] Features corresponding to
Crystallographic data (excluding structure factors) for the structures in
pyridyl and aryl ring puckering are observed in the region be-
tween 800 cm–1 and 600 cm–1. Sharp, moderate intensity bands
at 1623 cm–1 (1), 1607 cm–1 (2), 1606 cm–1 (3), 1623 cm–1 (4),
and 1623 cm–1 (5) indicate the carbonyl stretching modes
within the dipyridylamide ligands.
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-1552661, CCDC-1552662, CCDC-1552663, CCDC-
1552664, and CCDC-1552665 for 1–5 (Fax: +44-1223-336-033;
E-Mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
Supporting Information (see footnote on the first page of this article):
Additional molecular graphics, TGA traces, and hydrogen bonding in-
formation.
Structural Description of [Cd(dipH)2(bdin)]n (1)
The asymmetric unit of compound 1 consists of a cadmium
atom on a crystallographic twofold rotation axis, one singly
protonated dipH ligand, and half of a bdin ligand, whose cen-
tral C–C σ bond is sited over a crystallographic inversion cen-
ter. Operation of the rotation axis generates a {CdO4N2} coor-
Results and Discussion
Synthesis and Infrared Spectroscopy
Compounds 1–5 were prepared by hydrothermal reaction of dination octahedron (Figure 1a), with cis-disposed pyridyl ni-
a metal nitrate salt, diphenic acid, the requisite dipyridylamide trogen donor atoms belonging to two bdin ligands. A pair of
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chelating carboxylate groups from two dipH ligands occupies Structural Description of {[Cd(dip)(pdin)(H2O)]·1.25H2O}n
the remaining four coordination sites. Bond lengths and angles (2)
within the coordination sphere are listed in Table 2.
The asymmetric unit of compound 2 contains a divalent cad-
mium atom, a fully deprotonated dip ligand, a complete pdin
ligand, a bound water molecule and net one, and one quarter
water molecules of crystallization. The ligand donor set forms
a {CdO5N2} pentagonal bipyramidal coordination environment
(Figure 2a) with its axial positions taken up by pyridyl nitrogen
donor atoms from two pdin ligands. Chelating carboxylate
groups from two dip ligands and the aqua ligand comprise the
equatorial plane. Bond lengths and angles within the coordina-
tion sphere are listed in Table 3.
Table 3. Selected bond length /Å and angle /° data for 2.
Cd1–O1
2.441(3)
2.377(3)
2.425(4)
2.417(3)
2.287(3)
2.381(4)
2.391(4)
54.13(11)
88.25(12)
124.01(12)
107.41(13)
82.81(13)
131.87(11)
171.26(12)
O4#1–Cd1–O3#1 53.66(12)
Figure 1. (a) Coordination environment in 1. (b) [Cd(dipH)2(bdin)]n
coordination polymer chain in 1.
Cd1–O2
O7–Cd1–O1
O7–Cd1–O2
O7–Cd1–O3#1
O7–Cd1–O4#1
O7–Cd1–N1
O7–Cd1–N4#2
N1–Cd1–O1
N1–Cd1–O3#1
N1–Cd1–O4#1
N1–Cd1–N4#2
N4#2–Cd1–O1
91.47(12)
141.59(12)
130.15(12)
87.17(12)
80.84(13)
81.03(14)
82.54(12)
82.00(13)
105.73(13)
160.49(15)
90.78(13)
Cd1–O3#1
Cd1–O4#1
Cd1–O7
Table 2. Selected bond length /Å and angle /° data for 1.
Cd1–N1
Cd1–N4#2
Cd1–O3
2.326(2)
2.326(2)
2.312(2)
2.312(2)
2.316(3)
2.316(3)
129.00(12)
56.22(8)
98.81(8)
98.81(8)
O4–Cd1–O4#1
O4–Cd1–N1
124.21(13)
91.96(9)
O2–Cd1–O1
O2–Cd1–O3#1
O2–Cd1–O4#1
O2–Cd1–N1
O2–Cd1–N4#2
O3#1–Cd1–O1
O4#1–Cd1–O1
Cd1–O3#1
Cd1–O4
O4#1–Cd1–N1#1 91.96(9)
Cd1–O4#1
Cd1–N1
O4–Cd1–N1#1
O4#1–Cd1–N1
N1–Cd1–O3
131.46(9)
131.45(9)
129.44(9)
90.31(9)
90.31(9)
Cd1–N1#1
O3–Cd1–O3#1
O4–Cd1–O3
O4#1–Cd1–O3
O4–Cd1–O3#1
N4#2–Cd1–O3#1 115.51(14)
N4#2–Cd1–O4#1 80.48(13)
N1#1–Cd1–O3
N1–Cd1–O3#1
N1#1–Cd1–O3#1 129.44(9)
Symmetry transformations: #1 x, y–1, z; #2 x, –y+1/2, z+1/2
N1–Cd1–N1#1
83.83(13)
O4#1–Cd1–O3#1 56.22(8)
Bis(chelating) dip ligands construct [Cd(dip)(H2O)]n coordi-
nation polymer chains oriented parallel to the b crystal direc-
tion. The through-ligand Cd···Cd distance measures
Symmetry transformation: #1 –x+1, y, –z+3/2
Dipodal bdin ligands with an anti conformation of their cen- 9.203(1) Å, which denotes the b lattice parameter. In turn the
tral tetramethylene tethers connect neutral [Cd(dipH)2] coordi- chain motifs are pillared into [Cd(dip)(pdin)(H2O)]n (4,4) grid
nation fragments into zigzag [Cd(dipH)2(bdin)]n polymeric coordination polymer layers (Figure 2b). The tethering pdin li-
chain motifs oriented parallel to the c crystal direction (Fig- gands span a Cd···Cd distance of 17.820(2) Å, ca. 3 Å shorter
ure 1b). The Cd···Cd through-ligand distance measures than the distance spanned by the longer bdin ligands in poly-
20.459(2) Å. Hydrogen bonding donation between the amine mer 1. The central propylenediamine tether in the pdin ligands
group of the bdin ligands and the bound carboxylate oxygen is twisted in a gauche-anti conformation, with N–C–C–C tor-
toms of the dipH ligands (Table S1, Supporting Information) sion angles subtending 68.4 and 169.6°. The grid motif adopts
promotes formation of supramolecular layers of chain motifs nearly idealized rectangular apertures, with Cd···Cd···Cd angles
oriented parallel to the bc crystal planes. Adjacent supramolec- of 89.3 and 90.7°; through-space Cd···Cd distances across the
ular layers stack into the full crystal structure of 1 by means of rhomboid grid windows measure 19.956(2) and 20.157(2) Å.
C–H···π interactions between dip ligands in neighboring chains Pairs of [Cd(dip)(pdin)(H2O)]n layers aggregate into supra-
(Figure S1, Supporting Information).
molecular slabs by means of hydrogen bonding donation
Figure 2. (a) Coordination environment in 2. (b) Rectangular grid {[Cd(dip)(pdin)(H2O)]n coordination polymer layer in 2.
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Figure 3. Supramolecular slab consisting of a pair of hydrogen-bonded {[Cd(dip)(pdin)(H2O)]n coordination polymer layers in 2.
(Table S1) from the aqua ligands to ligated dip carboxylate
The bis(monodentate) dip ligands connect Zn1 and Zn2
oxygen atoms (Figure 3). Hydrogen bonding pathways involv- atoms into [Zn2(dip)2]n coordination polymer chains situated
ing the pdin carbonyl oxygen atoms, water molecules of along the c crystal direction, with Zn1···Zn2 distances of
crystallization, and ligated dip carboxylate oxygen atoms serve 5.68(1) Å. Within the chain motif, Zn1 atoms are connected to
to anchor the slabs in an ABAB pattern to form the full crystal other Zn1 atoms by twisted 3-pna ligands that span a Zn1···Zn1
structure of 2 (Figure S2, Supporting Information).
distance of 10.458(1) Å. Similarly, the Zn2 atoms are con-
nected to others Zn2 atoms. As a result the chain motif in 3
has a stoichiometry of [Zn2(dip)2(3-pna)2]n and each zinc atom
is 4-connected (Figure 4b).
Structural Description of {[Zn2(dip)2(3-pna)2]·3H2O}n (3)
The asymmetric unit of compound 3 contains two crystallo-
graphically distinct divalent zinc atoms (Zn1, Zn2), two crys-
tallographically distinct dip and 3-pna ligand sets, two full oc-
cupancy water molecules of crystallization, and two half occu-
pancy water molecules of crystallization. Both zinc atoms are
coordinated in a {ZnN2O2} tetrahedral fashion, with mono-
dentate carboxylate oxygen atom donors from two dip ligands
and pyridyl nitrogen donor atoms from two 3-pna ligands (Fig-
ure 4a) Bond lengths and angles of compound 3 are listed in
Table 4.
Discrete three-water molecule chains with D(3) classifica-
tion,[24] with disordered terminal oxygen atoms connect neigh-
boring [Zn2(dip)2(3-pna)2]n chains into the full crystal struc-
ture of 3 (Figure S3, Supporting Information) Hydrogen bond-
ing between unligated dip carboxylate oxygen atoms, water
molecules of crystallization, and 3-pna carbonyl oxygen atoms
plays the predominant supramolecular aggregation role (Table
S1).
Structural Description of {[Cd(dip)(4-ppbp)]·2H2O}n (4)
The asymmetric unit of compound 4 contains a divalent cad-
mium atom, a fully deprotonated dip ligand, a full 4-ppbp li-
gand, and two water molecules of crystallization. The cad-
mium atom displays a distorted {CdN2O4} octahedral coordi-
nation environment (Figure 5a), with pyridyl nitrogen donor
atoms from two 4-ppbp ligands in the nominal axial positions.
Monodentate oxygen atom donors from each carboxylate ter-
minus of a single dip ligand fill two of the cis coordination
sites in the nominal equatorial plane; the other two cis coordi-
nation sites are taken up by monodentate oxygen atom donors
from two other dip ligands. Bond lengths and angles within
the coordination environment of 4 are listed in Table 5.
Figure 4. (a) Coordination environments in 3. (b) 4-Connected
{[Zn2(dip)2(3-pna)2]·3H2O}n coordination polymer ribbon in 3.
Table 4. Selected bond length /Å and angle /° data for 3.
Zn1–O5
Zn1–O6
1.953(5)
1.957(5)
2.055(5)
2.044(6)
1.957(5)
1.949(5)
2.058(5)
2.041(6)
94.1(2)
O5–Zn1–N6#1
O6–Zn1–N4
107.7(2)
107.0(2)
120.1(2)
106.2(2)
Zn1–N4
O6–Zn1–N6#1
N6#1–Zn1–N4
Zn1–N6#1
Zn2–O2#1
Zn2–O8
O2#1–Zn2–N1#2 106.8(2)
O2#1–Zn2–N3
O8–Zn2–O2#1
O8–Zn2–N1#2
O8–Zn2–N3
120.1(2)
93.9(2)
123.0(2)
107.7(2)
106.2(2)
Zn2–N1#2
Zn2–N3
O5–Zn1–O6
O5–Zn1–N4
122.5(2)
N3–Zn2–N1#2
Figure 5. Coordination environment in 4. (b) [Cd(dip)]n chain submo-
tif in 4, showing exotridentate dip ligands.
Symmetry transformations: #1 x, y, z+1; #2 x, y, z–1.
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Table 5. Selected bond length /Å and angle /° data for 4.
Structural Description of {[Zn4(dip)4(H2O)2(4-ppbp)2]·
12H2O}n (5)
Cd1–O1
2.297(3)
2.317(3)
2.309(3)
2.309(3)
2.352(4)
2.345(4)
86.71(11)
95.77(11)
173.25(10)
87.17(12)
96.30(12)
O2#1–Cd1–N1
79.11(11)
Cd1–O2#1
O2#1–Cd1–N4#3 92.32(12)
The asymmetric unit of compound 5 contains two crystallo-
graphically distinct divalent zinc atoms (Zn1, Zn2), two dip
ligands, one complete 4-ppbp ligand, one bound water mol-
ecule, and six water molecules of crystallization. The Zn1
atoms display a {ZnNO3} tetrahedral coordination environ-
ment with a pyridyl nitrogen donor atom from a 4-ppbp ligand
and monodentate oxygen atom donors from two dip ligands.
A bound water molecule rounds out the coordination sphere.
The Zn2 atoms in contrast display a {ZnNO4} square-pyrami-
dal coordination environment (τ = 0.014, with τ = 0 for ideal-
ized square pyramidal arrangement and τ = 1 for idealized
trigonal bipyramidal environment).[28] Its apical position is
taken up by a pyridyl nitrogen donor atom from a 4-ppbp li-
gand and the basal plane is comprised of carboxylate oxygen
atom donors from four different dip ligands. Bond lengths and
angles within the disparate coordination environments in 5 are
listed in Table 6, whereas a thermal ellipsoid depiction is
shown in Figure 7a. Consistent with the well-known trend of
shorter bond lengths for a lower coordination number, the bond
lengths at Zn1 average 1.97 Å, whereas the bond lengths at
Zn2 average 2.05 Å.
Cd1–O3
O3–Cd1–O2#1
O3–Cd1–N1
O3–Cd1–N4#3
177.32(10)
101.98(11)
86.42(12)
Cd1–O4#2
Cd1–N1
Cd1–N4#3
O4#2–Cd1–O2#1 87.92(11)
O1–Cd1–O2#1
O1–Cd1–O3
O1–Cd1–O4#2
O1–Cd1–N1
O1–Cd1–N4#3
O4#2–Cd1–O3
O4#2–Cd1–N1
89.53(11)
95.83(12)
O4#2–Cd1–N4#3 79.83(12)
N4#3–Cd1–N1
170.58(13)
Symmetry transformations: #1 –x, –y+1, –z+1; #2 –x, –y+2,
–z+1; #3 x–1, y+1, z.
In contrast to the bis(chelating) dip binding mode in 2 and
the bis(monodentate) dip binding mode in 3, the dip ligands in
4 adopt an exotridentate μ3-κ4-O:OЈ, OЈЈ: OЈЈЈ binding mode.
These dip ligands link cadmium atoms into [Cd(dip)]n chain
submotifs that are oriented parallel to the b crystal direction
(Figure 5b). The bridging carboxylate groups of the dip ligands
construct a chain of spiro-fused anti-syn {Cd2(OCO)2} eight-
membered rings with Cd···Cd distances of 4.966(3) and
5.091(3) Å.
Parallel [Cd(dip)]n chain submotifs are pillared into
[Cd(dip)(4-ppbp)]n coordination polymer layers situated paral-
lel to the ab crystal planes in 4 (Figure 6a) by 4-ppbp ligands
with a gauche-anti conformation of their central aliphatic
tethers (C–C–C–C torsion angles = 90.7°, 154.9°). The Cd···Cd
distance through the full span of the 4-ppbp ligands measures
22.444(6) Å. The underlying layer topology can be simplified
by treating the exotridentate dip ligands as 3-connected nodes,
the Cd atoms as 5-connected nodes, and the 4-ppbp ligands as
simple linkers. Analysis with TOPOS software[25] reveals the
presence of (426)(42678) 3,5L2 network topology (Figure 6b),
seen previously in [Zn(isophthalate)(3-pna)]n and other exam-
ples.[16,26,27] Adjacent parallel [Cd(dip)(4-ppbp)]n coordination
polymer layers stack in an ABAB pattern along the c crystal
Table 6. Selected bond length /Å and angle /° data for 5.
Zn1–O2
1.927(2)
1.957(2)
1.953(2)
2.049(3)
2.041(2)
2.016(2)
2.087(2)
2.066(2)
2.039(3)
109.08(10)
111.90(10)
102.72(11)
106.30(10)
O6–Zn1–O5
125.45(9)
98.15(10)
Zn1–O5
O6–Zn1–N4#1
Zn1–O6
O3#2–Zn2–O8#3 91.94(9)
O3#2–Zn2–O9#4 89.06(9)
Zn1–N4#1
Zn2–O3#2
Zn2–O4
O4–Zn2–O3#2
O4–Zn2–O8#3
O4–Zn2–O9#4
O4–Zn2–N1
159.48(9)
86.25(9)
Zn2–O8#3
Zn2–O9#4
Zn2–N1
85.41(10)
104.85(10)
O9#4–Zn2–O8#3 158.65(9)
O2–Zn1–O5
O2–Zn1–O6
O2–Zn1–N4#1
O5–Zn1–N4#1
N1–Zn2–O3#2
N1–Zn2–O8#3
N1–Zn2–O9#4
95.53(10)
101.93(10)
99.20(10)
direction (Figure S4, Supporting Information), mediated by Symmetry transformations: #1 –x+1, –y+1, –z+1; #2 –x, –y,
–z+2; #3 –x+1, –y, –z+2; #4 x–1, y, z.
hydrogen bonding patterns involving the carbonyl groups of
the 4-ppbp ligands, pairs of water molecules of crystallization,
and ligated dip carboxylate oxygen atoms (Table S1).
Figure 6. (a) [Cd(dip)(4-ppbp)]n layer motif in 4. (b) Schematic repre-
sentation of the (426)(42678) 3,5L2 topology of the layer in 4. The
larger and smaller spheres represent the Cd atoms and the diphenate Figure 7. Distinct coordination environments in 5. (b) [Zn4(dip)4]n
ligand nodes, respectively.
chain submotif in 5.
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Both crystallographically distinct types of dip ligands in 5 loss of 4.3% consistent with elimination of one molar equiva-
show a μ3-κ3-O:OЈ:OЈЈ binding mode, binding to one Zn1 lent of CO2 (calcd. 4.1%). A 3.0% mass loss between 25 and
atom and two Zn2 atoms. Sets of four syn-syn bridging dip 100 °C for compound 4 denotes elimination of the water mol-
carboxylate groups connect Zn2 atoms into [Zn2(OCO)4] pad- ecules of crystallization. The predicted value of 4.5% for loss
dlewheel dimer units with a Zn2···Zn2 distance of 2.949(4) Å. of two molar equivalents of water indicates that some dehy-
These alternate with pairs of Zn1 atoms, bound by the mono- dration occurred on long-term storage (Ͼ60 d). Combustion of
dentate dip carboxylate end groups; the Zn1···Zn1 through- organic ligands occurred above 290 °C. Dehydration of com-
space distance is 6.182(3) Å. The chain motif therefore possess pound 5 occurred between 270 and 300 °C, with a mass loss
a stoichiometry of {[Zn4(dip)4(H2O)2]n (Figure 7b). These of 8.8% corresponding well with elimination of six molar
chains are pillared into a [Zn4(dip)4(H2O)2(4-ppbp)2]n coordi- equivalents of water (calcd. 9.3%). The dense packing of the
nation polymer layer by dipodal 4-ppbp ligands (Figure 8a), coordination polymer layers in 5 rendered the water clusters
which span a Zn···Zn distance of 18.88(2) Å. As in 4, the 4- somewhat difficult to remove. Combustion of the organic li-
ppbp ligands exhibit a gauche-anti central aliphatic tether (tor- gands occurred above 300 °C. TGA traces for 1–5 are shown
sion angles = 72.8, 179.9°). The topology of the layer was in Figures S6–S10 (Supporting Information).
invoked by treating the [Zn2(OCO)4] paddlewheel dimers as
6-connected nodes linking through dip and 4-ppbp ligands to
six other Zn1 atoms, and considering the Zn1 atoms as 3-con-
Luminescent Properties
nected nodes linking to three [Zn2(OCO)4] paddlewheel di-
mers. Analysis with TOPOS revealed a 3,6-connected binodal
net with an uncommon (43)2(466683) kgd topology (Figure 8b),
Excitation of a solid state sample of 1 with ultraviolet light
of wavelength 253 nm resulted in modest violet visible light
emission, with a maximum emission wavelength of 417 nm.
Compounds 2 and 3 underwent poor emission under ultraviolet
irradiation at 350 nm and 380 nm, respectively. When irradi-
ated with ultraviolet light of wavelength 320 nm, compound 4
exhibited violet light emission with a maximum at 394 nm and
a profile tailing into the visible region. Compound 5 mani-
fested strong blue-violet light emission at a maximum wave-
length of 432 nm upon excitation with 350 nm ultraviolet radi-
ation. The emission profiles for 1–5 are shown in Figure 9.
Electronic transitions within the aromatic molecular orbitals of
diphenate and dipyridylamide ligands are the probable origin
of the emissive behavior, as MLCT or LMCT behavior at
closed-shell configuration cadmium or zinc ions is rather un-
likely.[31]
seen previously in [Mn(3-cptpy)2]n [3-Hcptpy
= 4-(4-
carboxyphenyl)-3,2Ј:6Ј,3ЈЈ-terpyridine][29] and {[Co(5-(pyr-
idin-4-yl)isophthalate)(H2O)]·H2O}n.[30] Adjacent layers inter-
digitate and stack in a direct AAA pattern along the b crystal
direction (Figure S5, Supporting Information). Ten-membered
water molecule clusters with a R(8)A(2) classification[24] are
embedded in the interlamellar regions held to the coordination
polymer lattice by hydrogen bonding to carbonyl groups of the
4-ppbp ligands and to unligated dip carboxylate oxygen atoms
(Table S1).
Figure 8. (a) [Zn4(dip)4(4-ppbp)2]n layer motif in 5. (b) Schematic
representation of the (43)2(466683) kgd topology of the layer in 5.
Thermal Properties
Thermogravimetric analysis was undertaken in order to in-
vestigate the desolvation and decomposition behavior of 1–5.
Compound 1 underwent elimination of CO2 from the unligated
dip carboxylate groups between 150 and 290 °C, as evidenced
by a mass loss of 9.0% (9.9% calcd. for two molar equivalents
of CO2). Above 290 °C, the organic ligands are combusted.
Compound 2 underwent dehydration between 50 and 260 °C,
with a mass loss of 5.7% matching well with the predicted
value of 6.0% for elimination of 2.25 molar equivalents of
water. Above 260 °C, the organic ligands are combusted. Com-
pound 3 underwent dehydration between 25 and 50 °C, with a
mass loss of 6.3% corresponding roughly to the predicted
value of 5.1% for three molar equivalents of water. Possible
Figure 9. Emission profiles of solid-state samples of 1–5. Excitation
wavelengths are as follows: 253 nm (1), 350 nm (2), 380 nm (3),
320 nm (4), 350 nm (5).
Conclusions
Cadmium and zinc diphenate coordination polymers with
decarboxylation occurred between 50 and 100 °C, with a mass dipyridylamide neutral coligands manifest a variety of 1D
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ments in coordination environment resulting in different top-
ologies including the 3,5L2 net in the cadmium derivative 4
and an uncommon kgd net in the zinc derivative 5. A rare
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Acknowledgements
Funding for the work was provided by Lyman Briggs College and the
Honors College of Michigan State University. We thank Dr. Rui Huang
for elemental analysis.
Keywords: Hydrothermal synthesis; Cadmium; Zinc; Coordi-
nation polymer; Crystal structure
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Published Online: ᭿
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B. L. Martinez, R. L. LaDuca* ......................................... 1–9
Zinc and Cadmium Diphenate Coordination Polymers with
Conformationally Flexible Dipyridylamide Ligands
Z. Anorg. Allg. Chem. 0000, 0–0
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