Spacer length-controlled assembly of [CunIn]-based coordination polymers from CuI and bis(4-phenylpyrimidine-2-thio)alkane ligands

Article abstract of DOI:10.1039/c2ce06312c

Reactions of CuI with bis(4-phenylpyrimidine-2-thio)alkane ligands with different spacer lengths, [(phpy)(CH₂)_n(phpy)] (phpyH = 4-phenylpyrimidine-2-thiol; n = 1, bphpym; n = 2, bphpye; n = 3, bphpypr; n = 4, bphpyb; n = 5, bphpyp; n

Full text of DOI:10.1039/c2ce06312c

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PAPER
Spacer length-controlled assembly of [CunIn]-based coordination polymers
from CuI and bis(4-phenylpyrimidine-2-thio)alkane ligands†
a
a
a
a
a
Xiao-Juan Yang, Hong-Xi Li, Zhong-Lin Xu, Hai-Yan Li, Zhi-Gang Ren and Jian-Ping Lang
ab
*
*
Received 3rd October 2011, Accepted 1st December 2011
DOI: 10.1039/c2ce06312c
Reactions of CuI with bis(4-phenylpyrimidine-2-thio)alkane ligands with different spacer lengths,
[(phpy)(CH2)n(phpy)] (phpyH ¼ 4-phenylpyrimidine-2-thiol; n ¼ 1, bphpym; n ¼ 2, bphpye; n ¼ 3,
bphpypr; n ¼ 4, bphpyb; n ¼ 5, bphpyp; n ¼ 6, bphpyh), afforded a set of six [CunIn]-based coordination
polymers, [{Cu(m3-I)}2(phpym)]n (1), [{Cu(m3-I)}4(bphpye)]n (2), [{(MeCN)Cu3(m-I)2(m4-
I)}2(bphpypr)2]n (3), [{((MeCN)Cu)(m-I)}2(bphpyb)]n (4), [{Cu2(m-I)(m3-I)}2(bphpyp)2]n (5) and
[{((MeCN)Cu)(m3-I)}2{Cu(m-I)}2(bphpyh)2]n (6), respectively. Compounds 1–6 were characterized by
elemental analysis, IR and single-crystal X-ray crystallography. 1 and 2 consist of an unique 2D
network in which the 1D staircase [Cu2I2]n chains are linked by phpym or phpye ligands via the m-h1(N)-
h1(N) or m-h1(N),h1(S)-h1(N),h1(S) coordination modes, respectively. Complexes 3 and 5 consist of
double butterfly-shaped {(MeCN)Cu3(m-I)2(m4-I)}2 units or chair-like [Cu2(m-I)(m3-I)]2 units that are
linked to their neighboring ones by pairs of bphpypr or bphpyp bridges to form a 1D double chain. 4
contains a 1D zigzag chain assembled by dimeric [{(MeCN)Cu}(m-I)]2 cores and bphpyb ligands. In 6,
unique 1D tandem-rhomboid [Cu2I2]n chains are connected by dphpyh ligands to form a 2D staircase
network. In addition, the photoluminescent properties of 1–6 in the solid state at ambient temperature
were investigated.
assembly process, the 3D framework of copper(I) iodide is always
cleaved into various Cu/I structural motifs such as the [CuI]
monomeric unit,9 rhomboid [Cu2I2] dimeric unit,10 cubane-like or
chair-like [Cu4I4] tetrameric unit,10d,e,11 hexagonal prism-shaped
[Cu6I6] cluster unit,12 higher nuclear [CunIn] cluster unit
(n ¼ 8, 10),12c,13 split stair or zigzag [CuI]n chain,11c,14 ladder or
ribbon [Cu2I2]n chain,15 columnar chain,16 2D [CuI]n layer17 and
other [(CuxIy)xꢀy] cluster units or chains.12a,13b,18 The formation of
these structural variations is greatly affected by the nature of the
multitopic ligands along with the various synthetic conditions.
Among those ligands, N- or S-containing heterocyclic ligands such
as poly(pyridyl),8c,9c,10c,d,e,g,11a,g,12b,d,17 poly(pyrazolyl),10a poly(imi-
dazolyl),11h poly(triazolyl),11b,c poly(benzimidazolyl)9b or poly-
dentate thioether19 ligands have been extensively employed in the
assembly of the [CunIn]-based coordination polymers. The mixed
N,S-donor ligands such as bi(pyridylthio) ligands20 have also
attracted some attention because these ligands can coordinate Cu
(I) atoms with different coordination atoms. However, bi- or poly
(pyrimidylthio) ligands,21 which possess more coordination
modes, have been used less to construct [CunIn]-based coordina-
tion polymers. Recently, we have been interested in the syntheses,
structures and luminescent properties of [CunIn]-based coordina-
tion polymers using multitopic N-heterocyclic ligands.9b,10a,g It was
found that substituent groups on the N-heterocyclic rings and the
spacer lengths could impose great effects on the structures and
properties of the resulting products. For example, reactions of CuI
Introduction
In the past decades, inorganic–organic hybrid coordination poly-
mers have attracted much attention because of their intriguing
structural topologies and potential applications in catalysis, gas
storage or separation, luminescence, magnetism, and conduc-
tivity.1–4 For example, some preformed or in situ-generated tran-
sition metal clusters, especially those with unique physical
properties, could be used as building blocks for the construction of
cluster-based polymeric structures.5–7 The topological frameworks
of the resulting complexes are mainly determined by the geometry
of the metal clusters and the multitopic organic ligands. The
assembly of simple copper(I) halides like copper(I) iodide with
multitopic N-donor ligands often leads to the formation of various
[CunIn]-based coordination oligomers and polymers with rich
structural chemistry and photophysical properties.8 In such an
aKey Laboratory of Organic Synthesis of Jiangsu Province, College of
Chemistry, Chemical Engineering and Materials Science, Soochow
University, Suzhou, 215123, P. R. China. E-mail: jplang@suda.edu.cn;
lihx@suda.edu.cn; Fax: +86-512-65880089
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, P. R.
China
† Electronic supplementary information (ESI) available. CCDC
reference numbers 819175–819180 for 1–6. For ESI and
crystallographic data in CIF or other electronic format see DOI:
10.1039/c2ce06312c
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135.2–135.7 ꢁC. Anal. Calcd for C21H16N4S2: C, 64.92; H, 4.15;
N, 14.42; found C, 65.09; H, 4.03; N, 14.68%. IR (KBr, cmꢀ1):
1560 (s), 1535 (s), 1494 (m), 1447 (w), 1417 (s), 1356 (m), 1337 (s),
1198 (m), 1075 (w), 834 (w), 787 (w), 756 (s), 695 (m), 625 (m). 1H
NMR (DMSO-d6, 400 MHz, ppm) d 8.76 (d, 2H, J ¼ 5.2 Hz,
pyrimidyl-H), 8.25–8.22 (m, 4H, Ph-H), 7.87 (d, 2H, J ¼ 5.2 Hz,
pyrimidyl-H), 7.61–7.54 (m, 6H, Ph-H), 5.11 (s, 2H, CH2). 13C
NMR (DMSO-d6, 100 MHz, ppm) d 170.9, 164.3, 159.9, 136.4,
132.6, 130.1, 128.1, 113.9, 33.2.
Scheme 1 Conformations of the flexible bis(4-phenylpyrimidine-2-thio)-
based ligands with different spacer lengths.
with bis(3,5-dimethylpyrazol-1-yl)methane (dmpzm), bis(4-
bromo-3,5-dimethylpyrazol-1-yl)methane (brdmpzm) or 1,4-bis
(3,5-dimethylpyrazol-1-yl)butane (dmpzb) gave rise to a dimeric
complex [(bzdmpzm)Cu(m-I)]2, a 1D scolopendra-like polymer
[CuI(brdmpzm)]n, and a 2D polymer [Cu2(m3-I)2(dmpzb)]n,
respectively.22 As an extension of our project, we prepared a set of
relatively bulk 4-phenylpyrimidine-2-thio-based ligands with
different alkyl (CH2)n spacers: [(phpy)(CH2)n(phpy)] (phpyH ¼ 4-
phenylpyrimidine-2-thiol; n ¼ 1, bphpym; n ¼ 2, bphpye; n ¼ 3,
bphpypr; n ¼ 4, bphpyb; n ¼ 5, bphpyp;n ¼ 6, bphpyh)(Scheme 1).
Reactionsof CuI with these ligandsafforded a family of six1D and
2D [CunIn]-based coordination polymers: [{Cu(m3-I)}2(phpym)]n
Preparation of bphpye. Ligand bphpye was prepared as
colorless crystals in a manner similar to that described for
bphpym, using 4-phenyl-pyrimidine-2-thiol (2.978 g, 15.84
mmol), KOH (0.952 g, 17 mmol) and BrCH2CH2Br (1.478 g,
7.87 mmol) as starting materials. Yield: 2.4677 g, 78%. Mp
145.4–146.8 ꢁC. Anal. Calcd for C22H18N4S2: C, 65.64; H, 4.51;
N, 13.92; found C, 65.38; H, 4.30; N, 13.76%. IR (KBr, cmꢀ1):
1655 (m), 1607 (w), 1557 (s), 1492 (m), 1448 (m), 1413 (s), 1350
(s), 1280 (w), 1195 (s), 1107 (w), 1072 (m), 1026 (w), 1000 (w), 924
(w), 826 (m), 783 (m), 755 (s), 686 (s), 624 (s), 501 (w), 467 (w),
421 (w). 1H NMR (CDCl3, 400 MHz, ppm): d 8.54 (d, 2H, J ¼ 5.2
Hz, pyrimidyl-H), 8.09–8.06 (m, 4H, Ph-H), 7.51–7.45 (m, 6H,
Ph-H), 7.37 (d, 2H, J ¼ 5.2 Hz, pyrimidyl-H), 3.70 (s, 4H, CH2).
13C NMR (CDCl3, 75 MHz, ppm): d 172.0, 164.4, 158.2, 136.5,
131.5, 129.1, 127.5, 112.5, 31.1. HRMS (EI) m/z: calcd for
C22H18N4S2 402.0973; found: 402.0970.
(1),
[{Cu(m3-I)}4(bphpye)]n
(2),
[{(MeCN)Cu3(m-I)2(m4-
I)}2(bphpypr)2]n (3), [{((MeCN)Cu)(m-I)}2(bphpyb)]n (4),
[{Cu2(m-I)(m3-I)}2(bphpyp)2]n (5) and [{((MeCN)Cu)(m3-I)}2{Cu
(m-I)}2(bphpyh)2]n (6), and their structures and photoluminescent
properties were investigated correspondingly, which are described
in this article.
Preparation of bphpypr. Ligand bphpypr was prepared as
colorless crystals in a manner similar to that described for
bphpym, using 4-phenyl-pyrimidine-2-thiol (2.531 g, 13.46
mmol), KOH (0.801 g, 14.3 mmol) and Br(CH2)3Br (1.312 g,
6.49 mmol) as starting materials. Yield: 1.892 g, 70%. Mp 67.9–
68.3 ꢁC. Anal. Calcd for C23H20N4S2: C, 66.32; H, 4.84; N,
13.45; found C, 66.56; H, 4.93; N, 13.21%. IR (KBr, cmꢀ1): 1558
(s), 1542 (m), 1494 (w), 1414 (m), 1345 (s), 1217 (w), 1196 (s),
1116 (w), 1079 (w), 823 (w), 786 (w), 754 (s), 690 (s), 621 (m). 1H
NMR (DMSO-d6, 400 MHz, ppm): d 8.66 (d, 2H, J ¼ 5.2 Hz,
pyrimidyl-H), 8.20–8.18 (m, 4H, Ph-H), 7.76 (d, 2H, J ¼ 5.2 Hz,
pyrimidyl-H), 7.56–7.53 (m, 6H, Ph-H), 3.43–3.40 (m, 4H,
CH2), 2.27–2.20 (m, 2H, CH2). 13C NMR (DMSO-d6, 75 MHz,
ppm): d 171.6, 163.7, 159.3, 136.2, 132.1, 129.7, 127.7, 113.2,
29.9, 29.6.
Experimental
Materials and methods
The ligand 4-phenylpyrimidine-2-thiol23 was prepared according
to the literature method. Other chemicals and reagents were
obtained from commercial sources and used as received. All
solvents were pre-dried over activated molecular sieves and
refluxed over the appropriate drying agents under argon. 1H and
13C NMR spectra were recorded at ambient temperature on
a Varian UNITYplus-300/400 spectrometer. H NMR and 13C
1
NMR chemical shifts were referenced to the solvent signal in
DMSO-d6 or CDCl3. Elemental analyses for C, H, N and S were
performed on a Carlo-Erbo CHNO-S microanalyzer. The IR
spectra (KBr disc) were recorded on a Nicolet MagNa-IR550
FT-IR spectrometer (4000–400 cmꢀ1). The uncorrected melting
points were measured on a Mel-Temo II apparatus. The emis-
sion/excitation spectra were measured on a Varian Cary Eclipse
fluorescence spectrophotometer equipped with a continuous
xenon lamp.
Preparation of bphpyb. Ligand bphpyb was prepared as
colorless crystals in a manner similar to that described for
bphpym, using 4-phenyl-pyrimidine-2-thiol (3.339 g, 17.76
mmol), KOH (0.952 g, 17 mmol) and Br(CH2)4Br (1.681 g, 7.82
mmol) as starting materials. Yield: 2.286 g, 68%. Mp 100.4–100.8
ꢁC. Anal. Calcd for C24H22N4S2: C, 66.94; H, 5.15; N, 13.01;
found C, 67.22; H, 5.46; N, 12.84%. IR (KBr, cmꢀ1): 1558 (s),
1541 (s), 1491 (w), 1458 (w), 1416 (s), 1342 (s), 1308 (w), 1275 (w),
1209 (m), 1175 (m), 1109 (w), 1067 (w), 1026 (w), 1001 (w), 827
(m), 786 (w), 753 (s), 711 (w), 686 (s), 628 (m), 545 (w), 512 (w),
462 (w), 412 (w). 1H NMR (DMSO-d6, 400 MHz, ppm): d 8.66 (d,
2H, J ¼ 4.8 Hz, pyrimidyl-H), 8.18–8.15 (m, 4H, Ph-H), 7.77 (d,
J ¼ 4.8 Hz, 2H, pyrimidyl-H), 7.57–7.50 (m, 6H, Ph-H), 3.26–
3.25 (m, 4H, CH2), 1.93–1.91 (m, 4H, CH2). 13C NMR (CDCl3,
100 MHz, ppm): d 172.5, 164.0, 157.9, 136.5, 131.3, 129.1, 127.3,
112.1, 30.7, 28.9.
Preparation of ligands (bphpym, bphpye, bphpypr, bphpyb,
bphpyp, bphpyh) and complexes 1–6
Preparation of bphpym. CH2I2 (2.665 g, 9.95 mmol) was added
gradually to a stirred solution of 4-phenyl-pyrimidine-2-thiol
(3.754 g, 19.97 mmol) and KOH (1.265 g, 22.6 mmol) in H2O
(25 mL). A large amount of precipitate was observed to form
within minutes. After stirring for 4 hours, the pale yellow
precipitate was filtered and further purified by recrystallization
from ethyl acetate and petroleum ether (boiling range 60–90 ꢁC)
to form colorless crystals of bphpym. Yield: 3.37 g, 87%. Mp
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Preparation of bphpyp. Ligand bphpyp was prepared as
CuI (29 mg, 0.15 mmol) as starting materials. Yield: 38 mg (74%
based on Cu). Mp 210.6–211.4 ꢁC. Anal. Calcd for
C25H23Cu3I3N5S2: C, 29.18; H, 2.25; N, 6.81; S, 6.23; found C,
29.32; H, 2.53; N, 6.46; S, 6.51%. IR (KBr, cmꢀ1): 2253 (m), 1633
(w), 1579 (s), 1531 (m), 1491 (w), 1410 (m), 1354 (s), 1202 (w),
1178 (m), 1113 (w), 1073 (w), 856 (w), 824 (w), 792 (w), 750 (m),
687 (w), 631 (w), 511 (w), 422 (w).
colorless crystals in a manner similar to that described for-
bphpym,
using
4-phenyl-pyrimidine-2-thiol
(2.521
g,
13.41 mmol), KOH (0.871 g, 15.55 mmol) and Br(CH2)5Br (1.279
g, 5.56 mmol) as starting materials. Yield: 1.755 g, 71%. Mp 85.8–
86.8 ꢁC. Anal. Calcd for C25H24N4S2: C, 67.53; H, 5.44; N, 12.60;
found C, 67.30; H, 5.79; N, 12.92%. IR (KBr, cmꢀ1): 1558 (s), 1542
(m), 1494 (w), 1457 (w), 1414 (m), 1351 (s), 1292 (w), 1201 (m),
1185 (m), 1121 (w), 1079 (w), 855 (w), 823 (w), 786 (w), 748 (s), 690
Preparation of [{((MeCN)Cu)(m-I)}2(bphpyb)]n (4). Yellow
crystals of 4 were isolated in a manner similar to that used for the
isolation of 1, using bphpyb (22 mg, 0.05 mmol) and CuI (19 mg,
0.1 mmol) as starting materials. Yield: 31 mg (70% based on Cu).
Mp 214.3–215.6 ꢁC. Anal. Calcd for C14H14CuIN3S: C, 37.63; H,
3.16; N, 9.40; S, 7.18; found C, 37.45; H, 3.31; N, 9.41; S, 7.42%.
IR (KBr, cmꢀ1): 2256 (m), 1558 (s), 1541 (m), 1491 (w), 1408 (m),
1350 (s), 1308 (w), 1283 (w), 1209 (m), 1167 (m), 1117 (w), 1076
(w), 1026 (w), 827 (m), 786 (w), 753 (s), 711 (w), 686 (m), 628 (m),
545 (w), 512 (w), 462 (w), 420 (w).
1
(s), 626 (m), 503 (w), 461 (w). H NMR (DMSO-d6, 400 MHz,
ppm): d 8.66 (d, 2H, J ¼ 5.6 Hz, pyrimidyl-H), 8.18–8.15 (m, 4H,
Ph-H), 7.74 (d, 2H, J ¼ 5.6 Hz, pyrimidyl-H), 7.57–7.50 (m, 6H,
Ph-H), 3.24–3.20 (t, 4H, CH2), 1.84–1.76 (m, 4H, CH2), 1.67–1.59
(m, 2H, CH2). 13C NMR (DMSO-d6, 100 MHz, ppm): d 172.2,
163.9, 159.6, 136.6, 132.4, 130.0, 127.9, 113.4, 30.9, 29.6, 28.6.
Preparation of bphpyh. Ligand bphpyh was prepared as color-
less crystals in a manner similar to that described for bphpym,
using 4-phenyl-pyrimidine-2-thiol (2.087 g, 11.11 mmol), KOH
(0.853 g, 15.23 mmol) and Br(CH2)6Br (1.151 g, 4.72 mmol) as
starting materials. Yield: 1.472 g, 68%. Mp 120.5–120.9 ꢁC. Anal.
Calcd for C26H26N4S2: C, 68.09; H, 5.71; N, 12.22; found C, 68.37;
H, 5.43; N, 12.17%. IR (KBr, cmꢀ1): 1558 (s), 1537 (s), 1489 (w),
1457 (w), 1420 (m), 1335 (s), 1308 (w), 1286 (w), 1094 (s), 1031
(w), 999 (w), 839 (m), 823 (m), 786 (w), 759 (s), 695 (s), 626 (s), 503
(w), 445 (w). 1H NMR (DMSO-d6, 400 MHz, ppm): d 8.66 (d, 2H,
J ¼ 4.6 Hz, pyrimidyl-H), 8.18–8.15 (m, 4H, Ph-H), 7.72 (d, J ¼ 4.6
Hz, 2H, pyrimidyl-H), 7.55–7.52 (m, 6H, Ph-H), 3.17–3.15 (m, 4H,
CH2), 1.73–1.71 (m, 4H, CH2), 1.47–1.44 (m, 4H, CH2). 13C NMR
(DMSO-d6, 100 MHz, ppm): d 172.3, 163.9, 159.4, 136.6, 132.3,
129.9, 127.9, 113.2, 31.0, 29.8, 28.9.
Preparation of [{Cu2(m-I)(m3-I)}2(bphpyp)2]n (5). Yellow crys-
tals of 5 were obtained in a manner similar to that used for the
isolation of 1, using bphpyp (23 mg, 0.05 mmol) and CuI (19 mg,
0.1 mmol) as starting materials. Yield: 28 mg (68% based on Cu).
Mp 164.7–165.9 ꢁC. Anal. Calcd for C25H24Cu2I2N4S2: C, 36.37;
H, 2.93; N, 6.79; S, 7.77; found C, 36.65; H, 2.77; N, 6.57; S,
7.81%. IR (KBr, cmꢀ1): 1574 (s), 1533 (m), 1491 (w), 1450 (w),
1416 (m), 1350 (s), 1283 (w), 1200 (w), 1175 (m), 1117 (w), 1067
(w), 993 (w), 827 (w), 794 (w), 753 (m), 694 (w), 628 (m), 512 (w),
420 (w).
Preparation of [{((MeCN)Cu)(m3-I)}2{Cu(m-I)}2(bphpyh)2]n (6).
Yellow crystals of 6 were obtained in a manner similar to that
used for the isolation of 1, using bphpyh (23 mg, 0.05 mmol) and
CuI (38 mg, 0.2 mmol) as starting materials. Yield: 46 mg (71%
based on Cu). Mp 247.3–248.9 ꢁC. Anal. Calcd for
C15H16Cu2I2N3S: C, 27.66; H, 2.48; N, 6.45; S, 4.92; found C,
27.49; H, 2.72; N, 6.44; S, 4.76%. IR (KBr, cmꢀ1): 2249 (m), 1634
(w), 1563 (s), 1537 (s), 1494 (w), 1452 (w), 1409 (m), 1361 (m),
1313 (w), 1260 (w), 1201 (w), 1175 (m), 1111 (w), 1074 (w), 1020
(w), 850 (w), 823 (w), 786 (m), 754 (m), 706 (w), 690 (m), 631 (m),
503 (w), 467 (w), 418 (w).
Preparation of [{Cu(m3-I)}2(phpym)]n (1). To the CuI (19 mg,
0.1 mmol) solution in acetonitrile (3 mL) was added the solution
of bphpym (19 mg, 0.05 mmol) in CHCl3 (3 mL). The mixture
was stirred at room temperature for 3 h and then filtered. Et2O
(30 mL) was layered onto the filtrate to produce yellow crystals
of 1 in 2 days, which were collected by filtration, washed with
Et2O and dried in air. Yield: 17 mg (45% based on Cu). Mp
215.2–215.8 ꢁC. Anal. Calcd for C21H15Cu2I2N4S2: C, 32.82; H,
1.97; N, 7.29; S, 8.35; found C, 32.69; H, 1.78; N, 7.53; S, 8.17%.
IR (KBr, cmꢀ1): 1571 (s), 1532 (s), 1491 (w), 1446 (w), 1408 (s),
1359 (s), 1309 (w), 1198 (w), 1175 (w), 1000 (w), 842 (m), 786 (m),
750 (s), 694 (m), 624 (m).
X-Ray crystallographic study
All measurements were made on a Rigaku Mercury CCD X-ray
diffractometer (3 kV, sealed tube) by using graphite mono-
Preparation of [{Cu(m3-I)}4(bphpye)]n (2). Yellow crystals of 2
were isolated in a manner similar to that used for the isolation of
1, using bphpye (20 mg, 0.05 mmol) and CuI (38 mg, 0.2 mmol)
as starting materials. Yield: 38 mg (65% based on Cu). Mp 233.6–
234.1 ꢁC. Anal. Calcd for C11H9Cu2I2N2S: C, 22.69; H, 1.56; N,
4.81; S, 5.51; found C, 22.45; H, 1.86; N, 4.54; S, 5.66%. IR (KBr,
cmꢀ1): 3090 (w), 3036 (w), 1649 (w), 1568 (s), 1488 (w), 1450 (w),
1413 (m), 1397 (w), 1354 (s), 1306 (w), 1279 (w), 1199 (m), 1178
(m), 1113 (w), 1076 (w), 995 (w), 824 (w), 776 (m), 749 (m), 711
(w), 679 (m), 631 (w).
ꢀ
chromated Mo-Ka (l ¼ 0.71073 A). Single crystals of 1–6 were
obtained directly from the above preparations. Single crystals of
1–6 were mounted on glass fibers with grease and cooled in
a liquid nitrogen stream at 223 K. Diffraction data were collected
at u mode with a detector distance of 35 mm to the crystals. The
collected data were reduced by using the program CrystalClear
(Rigaku and MSC, Ver. 1.3, 2001) and an absorption correction
(multi-scan) was applied. The reflection data were also corrected
for Lorentz and polarization effects.
The crystal structures of 1–6 were solved by direct methods24
and refined by full matrix least-squares on F2.25 All non-hydrogen
atoms were refined anisotropically. All non-hydrogen atoms were
Preparation of [{(MeCN)Cu3(m-I)2(m4-I)}2(bphpypr)2]n (3).
Yellow crystals of 3 were obtained in a manner similar to that
used for the isolation of 1, using bphpypr (21 mg, 0.05 mmol) and
ꢀ
placed in geometrically idealized positions (C–H ¼ 0.98 A for
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Table 1 Summary of crystallographic data for 1–6
1
2
3
4
5
6
Empirical formula
Formula mass
Crystal system
Space group
C21H15Cu2I2N4S2 C11H9Cu2I2N2S
C25H23Cu3I3N5S2 C14H14CuIN3S
1028.97
Triclinic
C25H24Cu2I2N4S2
825.52
Triclinic
C15H16Cu2I2N3S
651.28
Triclinic
P1
0.45 ꢂ 0.25 ꢂ 0.15
768.41
Monoclinic
C2
582.17
Triclinic
ꢁ
P1
446.80
Triclinic
ꢁ
P1
ꢁ
P1
ꢁ
ꢁ
P1
Crystal dimension
/mm3
0.40 ꢂ 0.30 ꢂ 0.20 0.60 ꢂ 0.20 ꢂ 0.10 0.60 ꢂ 0.45 ꢂ 0.20 0.40 ꢂ 0.20 ꢂ 0.20 0.20 ꢂ 0.20 ꢂ 0.10
ꢀ
a/A
19.885(4)
4.2080(8)
13.807(3)
7.6628(15)
8.3550(17)
11.668(2)
95.20(3)
102.55(3)
93.44(3)
723.7(2)
2
10.357(2)
11.510(2)
13.130(3)
93.44(3)
102.57(3)
97.87(3)
1506.8(6)
2
7.7834(16)
9.768(2)
11.779(2)
110.16(3)
91.73(3)
109.35(3)
782.5(4)
2
10.868(2)
13.951(3)
19.474(4)
86.82(3)
88.76(3)
76.72(3)
2869.1(11)
2
1.911
1592
3.801
26 110
9.889(2)
10.169(2)
10.898(2)
91.87(3)
95.71(3)
116.91(3)
968.7(4)
2
2.233
614
5.491
8767
ꢀ
b/A
ꢀ
c/A
a/ꢁ
b/ꢁ
g/ꢁ
V/A
Z
100.83(3)
3
ꢀ
1134.7(4)
2
Dcalc/g cmꢀ3
F(000)
m/mmꢀ1
2.249
730
2.671
538
2.268
972
1.896
434
4.797
6924
7.330
6248
5.335
11 164
3.494
7422
Total no. of reflns
No. of unique reflns
No. of observed reflns 1865 (I > 2.00s(I)) 2514 (I > 2.00s(I)) 4728 (I > 2.00s(I)) 2827 (I > 2.00s(I)) 10 081 (I > 2.00s(I)) 3355 (I > 2.00s(I))
1872 (Rint ¼ 0.0313) 3246 (Rint ¼ 0.0377) 5126 (Rint ¼ 0.0611) 3509 (Rint ¼ 0.0400) 12 921 (Rint ¼ 0.0495) 4346 (Rint ¼ 0.0278)
No. of variables
Transmission factor
118
163
344
183
631
209
0.1899–0.3871
0.0560
0.1272
0.996
1.376, ꢀ1.429
0.1963–0.4777
0.0309
0.0734
1.026
0.824, ꢀ1.504
0.0720–0.3450
0.0483
0.1305
1.082
1.594, ꢀ2.046
0.3354–0.5417
0.0306
0.0702
0.4839–0.6824
0.0648
0.1107
1.151
1.351, ꢀ1.070
0.2124–0.4361
0.0331
0.0749
0.945
1.402, ꢀ1.142
a
R1
wR2
b
GOFc
1.017
0.769, ꢀ0.971
ꢀ3
ꢀ
Residual peaks (e A
)
a
c
R1 ¼ SkFo| ꢀ |Fck/S|Fo|. b wR2 ¼ {Sw(Fo ꢀ Fc )2/Sw(Fo2)2}1/2
.
GOF ¼ {Sw((Fo ꢀ Fc )2)/(n ꢀ p)}1/2, where n ¼ number of reflections and p ¼ total
2
2
2
2
number of parameters refined.
ꢀ
methyl groups, C–H ¼ 0.99 Afor methylene groupsorC–H ¼ 0.95
the heterocyclic of the pyrimidyl ring. The singlets or multiplets
at d ¼ 5.11 ppm (bphpym), 3.70 ppm (bphpye), 3.43–3.40 and
2.27–2.20 (bphpypr), 3.26–3.25 and 1.93–1.91 (bphpyb), 3.24–
3.20, 1.84–1.76 and 1.67–1.59 (bphpyp), and 3.17–3.15, 1.73–1.71
and 1.47–1.44 (bphpyh) were assignable to the two protons of the
methyl groups of bridges in the [(phpy)(CH2)n(phpy)] ligands. As
shown in Scheme 2, reactions of CuI with bphpym in a 2 : 1
molar ratio in MeCN/CHCl3 afforded yellow crystals of a 2D
polymer [(CuI)2(bphpym)]n (1) in 45% yield. However, a 1 : 1 or
1 : 2 reaction mixture of CuI and bphpym could not give rise to
the corresponding 1 : 1 or 1 : 2 product. Compound 1 was the
only product isolated in a crystalline form regardless of the CuI/
bphpym molar ratios. The analogous reactions of CuI with
bphpye, bphpypr, bphpyb, bphpyp, or bphpyh gave rise to 2–6 in
higher yields. As discussed later in this paper, the 3D framework
of the bulk CuI has been cleaved into various [CunIn] motifs such
as rhomboid dinuclear [Cu(m-I)]2 units in 4, chair-like tetranu-
clear [Cu4(m-I)2(m3-I)2] units in 5, unique double butterfly-shaped
hexanuclear [Cu3(m-I)2(m4-I)]2 units in 3, staircase [Cu2I2]n chains
in 1 and 2, and uncommon rhomboid tandem [Cu2I2]n chains in
6. These resulting units are further interconnected via phpym,
phpye, phpypr, phpyb, phpyp or phpyh to form different [CunIn]-
based topological structures of 1–6. In 1–6, these ligands showed
three coordination modes: m-h1(N)-h1(N) (1 and 4), m-h1(N),
h1(S)-h1(N) (2 and 6) and m-h1(N),h1(S)-h1(N),h1(S) (3 and 5).
Thus, we assumed that the above six ligands [(phpy)
(CH2)n(phpy)] (n ¼ 1–6) with different spacer lengths, and
various coordination modes, might play an important role in the
formation of 1–6 (Scheme 2). Compounds 1–6 are relatively air-
and moisture-stable, and insoluble in common organic solvents
ꢀ
A for phenyl groups) and constrained to ride on their parent
atoms with Uiso(H) ¼ 1.2Ueq(C), or 1.5 Ueq(C) for methyl groups.
All the calculations were performed on a Dell workstation using
the CrystalStructure crystallographic software package (Rigaku
and MSC, Ver. 3.60, 2004). The crystal of 1 is a racemic twin and
the ratio of the racemate is 51 : 49. In the case of 3, the largest
residual electron density (1.594 e Aꢀ3) in the final Fourier map is
ꢀ
close to the I(1) atom (0.917 A). A summary of the important
ꢀ
crystallographic information for 1–6 is provided in Table 1. The
selected bond distances and angles of 1–3 are listed in Table 2 and
the selected bond distances and angles of 4–6 are listed in Table 3.
Results and discussion
Synthesis
Treatment of 4-phenyl-pyrimidine-2-thiol with KOH and CH2I2
in water followed by a standard workup afforded bphpym in 87%
yield. Other ligands (bphpye, bphpypr, bphpyb, bphpyp and
bphpyh) were prepared by analogous reactions of 4-phenyl-
pyrimidine-2-thiol with the corresponding dibromoalkane Br
(CH2)nBr (n ¼ 2, 3, 4, 5, 6) in high yields. These ligands are stable
toward air and moisture, and freely soluble in common organic
1
solvents (MeCN, CH2Cl2, and DMF). The H NMR spectra of
ligands [(phpy)(CH2)n(phpy)] showed two doublets at d ¼ 8.76
ppm and 7.87 ppm (bphpym), 8.54 ppm and 7.37 ppm (bphpye),
8.66 ppm and 7.76 ppm (bphpypr), 8.66 ppm and 7.77 ppm
(bphpyb), 8.66 ppm and 7.74 ppm (bphpyp), and 8.86 ppm and
7.72 ppm (bphpyh), which were assignable to the two protons of
1644 | CrystEngComm, 2012, 14, 1641–1652
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a
a
ꢁ
ꢁ
ꢀ
Table 2 Selected bond lengths (A) and angles ( ) for 1–3
ꢀ
Table 3 Selected bond lengths (A) and angles ( ) for 4–6
Compound 1
Cu(1)–I(1)
Cu(1)–I(1A)
Cu(1)/Cu(1A)
N(1)–Cu(1)–I(1)
I(1)–Cu(1)–I(1A)
I(1)–Cu(1)–I(1B)
Compound 2
Compound 4
Cu(1)–N(3)
Cu(1)–I(1)
Cu(1)/Cu(1A)
N(3)–Cu(1)–N(2)
N(2)–Cu(1)–I(1)
N(2)–Cu(1)–I(1A)
Compound 5
2.5788(17)
2.692(3)
2.907(2)
122.1(2)
113.55(11)
112.93(11)
Cu(1)–N(1)
Cu(1)–I(1B)
2.091(5)
2.711(3)
2.043(3)
2.6386(9)
2.6851(11)
101.73(12)
109.05(10)
110.80(10)
Cu(1)–N(2)
Cu(1)–I(1A)
2.077(3)
2.6642(11)
N(1)–Cu(1)–I(1A)
N(1)–Cu(1)–I(1B)
I(1A)–Cu(1)–I(1B)
109.4(2)
93.1(3)
102.30(6)
N(3)–Cu(1)–I(1)
N(3)–Cu(1)–I(1A)
I(1)–Cu(1)–I(1A)
111.18(10)
103.44(11)
119.16(3)
Cu(1)–S(1)
Cu(1)–I(2B)
Cu(2)–N(2A)
Cu(2)–I(2B)
Cu(1)/Cu(2)
Cu(2)/Cu(2A)
S(1)–Cu(1)–I(1)
I(1)–Cu(1)–I(2B)
I(1)–Cu(1)–I(2)
N(2A)–Cu(2)–I(1)
I(1)–Cu(2)–I(2B)
I(1)–Cu(2)–I(1A)
Compound 3
Cu(1)–N(5)
Cu(1)–I(1)
Cu(2)–S(2B)
Cu(2)–I(2)
Cu(3)–N(4B)
Cu(3)–I(2A)
Cu(1)/Cu(2)
Cu(3)/Cu(3A)
N(5)–Cu(1)–N(2)
N(2)–Cu(1)–I(1)
N(2)–Cu(1)–I(2)
S(2B)–Cu(2)–I(1)
I(1)–Cu(2)–I(2)
I(1)–Cu(2)–I(3A)
N(4B)–Cu(3)–I(3)
I(3)–Cu(3)–I(2A)
I(3)–Cu(3)–I(2)
2.3520(18)
2.6684(11)
2.046(4)
Cu(1)–I(1)
Cu(1)–I(2)
Cu(2)–I(1)
Cu(2)–I(1A)
Cu(1)/Cu(1B)
Cu(1)/Cu(1A)
S(1)–Cu(1)–I(2B)
S(1)–Cu(1)–I(2)
I(2B)–Cu(1)–I(2)
N(2A)–Cu(2)–I(2B)
N(2A)–Cu(2)–I(1A)
I(2B)–Cu(2)–I(1A)
2.5918(11)
2.6744(13)
2.6253(12)
2.7234(13)
2.6388(16)
3.3470(16)
99.74(6)
103.18(5)
120.81(4)
108.19(14)
107.57(15)
102.14(4)
Cu(1)–N(2)
Cu(1)–I(2)
Cu(2)–N(4B)
Cu(2)–I(1)
Cu(3)–N(6)
Cu(3)–I(3)
Cu(4)–N(8E)
Cu(4)–I(3)
Cu(1)/Cu(2)
Cu(3)/Cu(3D)
N(2)–Cu(1)–S(2C)
S(2C)–Cu(1)–I(2)
N(2)–Cu(1)–I(1)
I(1)–Cu(2)–I(2C)
N(4B)–Cu(2)–I(1)
N(4B)–Cu(2)–I(2A)
N(6)–Cu(3)–I(3D)
I(3D)–Cu(3)–I(3)
I(3D)–Cu(3)–I(4)
N(8E)–Cu(4)–S(3)
S(3)–Cu(4)–I(3)
S(3)–Cu(4)–I(4D)
Compound 6
Cu(1)–N(3)
Cu(1)–I(1)
Cu(2)–S(1A)
Cu(2)–I(1)
Cu(1)/Cu(1A)
N(3)–Cu(1)–N(1)
N(1)–Cu(1)–I(1)
N(1)–Cu(1)–I(1A)
S(1A)–Cu(2)–I(2)
I(2)–Cu(2)–I(1)
I(2)–Cu(2)–I(2B)
2.047(6)
2.6088(11)
2.065(6)
2.6805(12)
2.077(6)
2.6863(13)
2.037(6)
2.6065(14)
2.8346(17)
2.906(2)
117.44(16)
112.12(6)
104.31(15)
104.33(4)
106.22(16)
99.46(19)
120.97(16)
113.58(4)
103.61(4)
115.22(16)
109.79(6)
106.66(6)
Cu(1)–S(2C)
Cu(1)–I(1)
Cu(2)–I(2)
Cu(2)–I(2A)
Cu(3)–I(3D)
Cu(3)–I(4)
Cu(4)–S(3)
Cu(4)–I(4D)
Cu(2) /Cu(2A)
Cu(3) /Cu(4D)
N(2)–Cu(1)–I(2)
I(2)–Cu(1)–I(1)
S(2C)–Cu(1)–I(1)
N(4B)–Cu(2)–I(2)
I(2)–Cu(2)–I(1)
I(2)–Cu(2)–I(2A)
N(6)–Cu(3)–I(3)
N(6)–Cu(3)–I(4)
I(3)–Cu(3)–I(4)
N(8E)–Cu(4)–I(3)
N(8E)–Cu(4)–I(4D)
I(3)–Cu(4)–I(4D)
2.323(2)
2.6675(10)
2.6374(11)
2.7097(12)
2.6177(13)
2.7185(14)
2.3375(19)
2.6888(13)
2.8998(19)
2.9895(16)
110.73(15)
111.36(4)
100.00(6)
120.80(18)
110.06(5)
114.33(4)
100.86(16)
104.38(17)
113.48(4)
115.58(17)
103.69(16)
104.75(4)
2.6766(11)
2.7910(15)
3.0486(18)
117.58(5)
111.25(4)
104.76(4)
117.35(16)
109.94(4)
110.53(4)
1.942(7)
2.5622(12)
2.3736(16)
2.6312(11)
2.052(5)
2.6576(14)
3.089(2)
2.9707(18)
120.7(2)
110.25(15)
105.44(15)
110.01(5)
113.62(4)
111.36(4)
107.08(14)
106.14(3)
108.22(3)
Cu(1)–N(2)
Cu(1)–I(2)
Cu(2)–I(1)
Cu(2)–I(3A)
Cu(3)–I(3)
Cu(3)–I(2)
2.018(5)
2.9956(13)
2.5956(10)
2.6335(14)
2.6502(11)
2.6982(11)
2.9115(12)
Cu(3) / Cu(2A)
N(5)–Cu(1)–I(1)
N(5)–Cu(1)–I(2)
I(1)–Cu(1)–I(2)
S(2B)–Cu(2)–I(2)
S(2B)–Cu(2)–I(3A)
I(2)–Cu(2)–I(3A)
N(4B)–Cu(3)–I(2A)
N(4B)–Cu(3)–I(2)
I(2A)–Cu(3)–I(2)
120.54(16)
91.03(16)
103.54(4)
112.72(5)
101.00(5)
107.39(4)
117.33(14)
105.07(12)
112.63(4)
2.017(5)
2.6569(10)
2.4300(16)
2.6146(10)
2.8712(15)
105.95(16)
109.30(10)
112.58(10)
105.88(5)
115.77(4)
114.23(3)
Cu(1)–N(1)
Cu(1)–I(1A)
Cu(2)–I(2)
Cu(2)–I(2B)
Cu(2)/Cu(2B)
N(3)–Cu(1)–I(1)
N(3)–Cu(1)–I(1A)
I(1)–Cu(1)–I(1A)
S(1A)–Cu(2)–I(1)
S(1A)–Cu(2)–I(2B)
I(1)–Cu(2)–I(2B)
2.056(4)
2.6625(14)
2.5934(14)
2.6408(8)
2.8422(13)
106.65(11)
107.13(11)
114.66(3)
103.76(4)
103.27(5)
112.26(4)
a
Symmetry codes: (A) ꢀ3/2 ꢀ x, 1/2 + y, ꢀ4 ꢀ z; and (B) ꢀ3/2 ꢀ x, ꢀ1/2
+ y, ꢀ4 ꢀ z for 1. (A) ꢀ1 ꢀ x, 2 ꢀ y, ꢀz; and (B) ꢀx, 2 ꢀ y, ꢀz for 2. (A) 2
ꢀ x, ꢀy, ꢀz; and (B): x ꢀ 1, + y, z for 3.
a
Symmetry codes: (A) 1 ꢀ x, 1 ꢀ y, 1 ꢀ z for 4. (A) 2 ꢀ x, 1 ꢀ y, ꢀz; (B) 1
+ x, ꢀ1 + y, z; (C) 1 ꢀ x, 2 ꢀ y, ꢀz; (D) 2 ꢀ x, ꢀy, 1 ꢀz; and (E) 1 ꢀ x, 1 ꢀ
y, 1 ꢀ z for 5. (A) 2 ꢀ x, ꢀ y, ꢀz; and (B) 3 ꢀ x, ꢀy, ꢀz for 6.
such as CH2Cl2 and MeCN, and slightly soluble in DMF and
DMSO. The PXRD showed that the experimental patterns for
each compound correlate well with its simulated ones generated
from single-crystal X-ray diffraction data (Fig. S1–S6†). In the
FT-IR spectra of 3, 4 and 6, the strong bonds at 2253 cmꢀ1 (3),
2256 cmꢀ1 (4), and 2249 cmꢀ1 (6) were assigned to the C^N
stretching vibration of the coordinated MeCN molecule. The
elemental analyses were consistent with their chemical formula.
The identities of 1–6 were finally confirmed by X-ray
crystallography.
phenanthroline).15 Each bphpym ligand in 1 takes a m-h1(N)-
h1(N) mode to coordinate to one of the two Cu atoms of two
[Cu2I2] cores via two Cu–N bonds. Each Cu(I) adopts a tetrahe-
dral coordination geometry, coordinated by three m3-I and one N
ꢀ
atom from one bphpym. The Cu(1)/Cu(2) contact of 2.907(2) A
is longer than those observed in complexes [Cu2I2(dfphbbtz)2]
0
ꢀ
(2.5303(7) A; dfphbbtz ¼ 4,4 -(4,5-difluoro-1,2-phenylene)bis-(1-
benzyl-1H-1,2,3-triazole)),11b [Cu4I4(pcdmpzm)2]n (2.6350(6) A,
ꢀ
pcdmpzm ¼ 1-(4-picolyl)-4-(3,5-dimethylpyrazolylmethyl)-1H-
Crystal structure of [{Cu(m3-I)}2(bphpym)]n (1)
1,2,3-triazole),11c [CuI(bpp)]n (2.713(4) A, bpp ¼ 1,3-bis(4-pyr-
ꢀ
10g
ꢀ
idyl)propane) and {[Cu2I2(bpp)2]$2aniline}n (2.7657(17) A).
Compound 1 crystallizes in the monoclinic space group C2 and
its asymmetric unit consists of half a [(bphpym){Cu(m-I)}2]
molecule. Complex 1 contains a 2D sheet structure (extending
along the bc plane) in which 1D ladder-like [Cu2I2]n chains
(parallel to the b axis) are interlinked by bphpym bridges (Fig. 1).
Each [Cu2I2]n chain is assembled from linking each rhombic
[Cu2I2] via two Cu-m3-I bonds. Such a 1D chain is similar to those
observed in other 2D polymers, [(CuI)2(L)] (L ¼ pyrazine, 1,2-
ꢀ
The mean Cu–N bond distance (2.091(5) A) is longer than that of
0
15b
[Cu(4,4 -bipy)I] (2.025(8) A), but shorter than that found in
ꢀ
ꢀ
[{Cu2I2(tdmpp)}$MeCN]n (2.114(5) A; tdmpp ¼ 1,1,3,3-tetrakis
(3,5-dimethyl-1-pyrazole)propane).10a The average Cu-m3-I bond
ꢀ
length (2.661(8) A) is 0longer than that in [Cu4(m3-I)4(bbbt)2]n
9b
ꢀ
(2.541(2) A; bbbt ¼ 1,1 -(1,4-butanediyl)bis-1H-benzotriazole),
10g
but shorter than those in [Cu4(m3-I)4(bpp)2]n (2.687(2) A) and
ꢀ
0
20g
ꢀ
trans-(4-pyridyl)ethene,
quinoxaline,
pyrimidine,
4,7-
[Cu4(m3-I)4(tdp)2]n (tdp ¼ 4,4 -thiodipyridine) (2.728(1) A).
CrystEngComm, 2012, 14, 1641–1652 | 1645
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Scheme 2 Syntheses of complexes.
Crystal structure of [{Cu(m3-I)}4(bphpye)]n (2)
coordination mode of the bphpye ligand is different from that of
the bphpym ligand in 1. Each bphpye ligand in 2 adopts
a m-h1(S):h1(N)-h1(S):h1(N) mode to bind to each of the four Cu
atoms of the two [Cu2I2] cores via two Cu–N and two Cu–S
bonds, forming two 6-membered chelating rings (CuICuNCS).
Each Cu(I) adopts a tetrahedral coordination geometry, coor-
dinated by three m3-I and one N (or S) atom from one bphpye
ligand. In the four-membered Cu2I2 (coordinated by two
ꢁ
Compound 2 crystallizes in the triclinic space group P1 and its
asymmetric unit consists of half a [{Cu(m3-I)}4(bphpye)] mole-
cule. Compound 2 has a 2D fish-scale network (extending along
the ab plane) in which 1D ladder [Cu2I2]n chains (extending along
the a axis) are interconnected by bphpye bridges (Fig. 2). Such
a [Cu2I2]n chain in 2 is similar to that in 1. However, the
1646 | CrystEngComm, 2012, 14, 1641–1652
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Fig. 1 View of the 2D network of 1 (extending along the bc plane) with 50% thermal ellipsoids. All phenyl groups and hydrogen atoms are omitted for
clarity. Symmetry codes: (A) ꢀ3/2 ꢀ x, 1/2 + y, ꢀ4 ꢀ z; (B) ꢀ3/2 ꢀ x, ꢀ1/2 + y, ꢀ4 ꢀ z; and (C) x, 1 + y, z.
ꢀ
ꢀ
Cu–S bond length (2.3520(18) A) is shorter than those in [(Cu4I4)
S atoms) ring, the Cu(1)/Cu(1B) contact of 2.6388(16) A is
ꢀ
ꢀ
shorter than the Cu(2)/Cu(2A) distance (3.0486(18) A) in the
Cu2I2 (coordinated by two N atoms) ring and the Cu(1)/Cu(2)
interaction (2.7910(15) A) in Cu2I2 (coordinated by one N and one
(mptq)2]n (2.362(3) A; mptq ¼ 8((2-pyridylmethyl)thio)quino-
line)20d and [(Cu4I4)(pysmpy)2]n (2.4311(13) A; pysmpy ¼ 2-[(o-
ꢀ
pyridyl)-sulfanylmethyl]-pyrimidine).21b
ꢀ
S atoms) ring. In the six-membered Cu2ISNC ring, the separation
ꢀ
of Cu(1)/Cu(2A) (or Cu(2)/Cu(1A)) (3.3470(16) A) is the
Crystal structure of [{(MeCN)Cu3(m-I)2(m4-I)}2(bphpypr)2]n (3)
ꢀ
longest. The mean Cu–N bond length (2.046(4) A) is shorter than
ꢁ
Compound 3 crystallizes in the triclinic space group P1 and its
10a
ꢀ
that of 1 and [{Cu2I2(tdmpp)}$MeCN]n
(2.114(5) A), but
0
15b
slightly longer than that in [Cu(4,4 -bipy)I] (2.025(8) A). The
ꢀ
asymmetric unit consists of half a [{Cu3(m-I)2(m4-I)}2(bphpypr)2]
molecule. 3 consists of a 1D double chain (extending along the
b axis) in which hexanuclear {(MeCN)Cu3(m-I)2(m4-I)}2 units
(Fig. 3) are interlinked to adjacent ones by two pairs of bphpypr
ligands (Fig. 4). There is a crystallographic center of inversion
located at the middle of Cu(3) and Cu(3A) in such a unit. Each
unit may be viewed as a double butterfly-shaped structure in
which two butterfly-shaped [Cu3(m-I)2(m4-I)] subunits are linked
by Cu(3)–I(2) and Cu(3A)–I(2A) bonds. Although a few Cu/I
complexes with hexagonal prism-shaped Cu6I6 structures12 have
been reported, this double butterfly-shaped {Cu3(m-I)2(m4-I)}2
structure is unprecedented. Each bphpypr ligand in 3 binds to
three Cu(I) atoms through the N,S,N-tridentate mode. The Cu6I6
ꢀ
average Cu-m3-I bond length (2.660(3) A) is close to that of 1, but
longer than that of [Cu4(m3-I)4(bbbt)2]n (2.541(2) A).9b The mean
ꢀ
Fig. 2 View of the 2D network of 2 (extending along the ab plane) with
50% thermal ellipsoids. All phenyl groups and H atoms are omitted for
clarity. Symmetry codes: (A) ꢀ1 ꢀ x, 2 ꢀ y, ꢀz; (B) ꢀx, 2 ꢀ y, ꢀz; and (C)
ꢀ1 + x, y, z.
Fig. 3 View of the coordination environments of the copper atoms in 3
with 50% thermal ellipsoids. Symmetry codes: (A) 2 ꢀ x, ꢀy, ꢀz; (B) x, ꢀ
1 + y, z; and (C) 2 ꢀ x, 1 ꢀ y, ꢀz.
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Fig. 4 View of a section of the 1D chain (extending along the b axis) of 3 with labeling scheme and 50% thermal ellipsoids. All hydrogen atoms are
omitted for clarity. Symmetry codes: (A) 1 ꢀ x, 1 ꢀ y, 1 ꢀ z.
21b
(2.4311(13) A). It is worth noting that the phenyl and pyr-
ꢀ
unit contains two different types of iodide ligands, four of which
are doubly bridging (m2) and two are quadruply bridging (m4). Cu
(1) or Cu(1A) is coordinated by one m-I atom, one m4-I atom, one
N atom from one MeCN molecule and one N atom from the
bphpypr ligand, forming a distorted tetrahedral coordination
geometry. While the tetrahedral coordination sphere of Cu(2) or
Cu(2A) is completed by two m-I atoms, one m4-I atom and one S
atom from one bphpypr ligand. Cu(3) or Cu(3A) adopts
a tetrahedral coordination geometry, coordinated by one m-I
atom, two m4-I atoms and one N atom from one bphpypr ligand.
imidyl rings of the bphpypr ligands produce evident p–p inter-
ꢀ
actions (3.768(4), 3.710(3), 3.769(4) and 3.709(3) A) with the
corresponding ones of the neighboring chains, forming a 2D
supramolecular network (Fig. S7†).
Crystal structure of [{((MeCN)Cu)(m-I)}2(bphpyb)]n (4)
ꢁ
Compound 4 crystallizes in the triclinic space group P1 and its
asymmetric unit contains half a [{((MeCN)Cu)(m-I)}2(bphpyb)]
molecule. Compound 4 has a 1D zigzag chain (parallel to the [110]
plane) in which each rhombic [(MeCN)Cu(m-I)]2 unit is bridged by
a pair of bphpyb ligands (Fig. 5). In 4, two m-I ligands bridge two
Cu(I) atoms, thus forming a {((MeCN)Cu)(m-I)}2 core with
a crystallographic center of symmetry being at the midpoint of Cu
(1) and Cu(1A) atoms. Each Cu atom is tetrahedrally coordinated
by two m-I, one N atom from one bphpyb ligand and one
N atom from one MeCN molecule. The Cu/Cu separation
ꢀ
The Cu/Cu contacts (2.9115(12)–3.089(2) A) are longer than
11b
ꢀ
those found in 1, [Cu2I2(dfphbbtz)2] (2.5303(7) A),
11c
[Cu4I4(pcdmpzm)2]n (2.6350(6) A), [CuI(bpp)]n (2.713(4) A)
ꢀ
ꢀ
and {[Cu2I2(bpp)2]$2aniline}n (2.7657(17) A).10g The mean Cu–N
ꢀ
ꢀ
bond length (2.004(5) A) is slightly shorter than those of the
corresponding ones of 1 and 2. In the middle the ‘‘[Cu(2)I(2)Cu
(3)I(3)Cu(2A)I(2A)Cu(3A)I(3A)]’’ chair-like core, the Cu-m-I
ꢀ
bond distances (2.6335(14)–2.6982(11) A) are close to the Cu-m4-
ꢀ
I bond distances (2.6312(11)–2.6982(11) A). The Cu(1)-m4-I(2)
ꢀ
(2.6852(10) A) (Table 3) is shorter than those in 3, 1, [CuI(bpp)]n
ꢀ
ꢀ
ꢀ
bond length (2.9956(13) A) is much longer than the Cu(1)–I(1)
(2.713(4) A) and {[Cu2I2(bpp)2]$2aniline}n (2.7657(17) A),10g but
11b
ꢀ
bond length (2.5622(12) A) in the ‘‘Cu(1)I(2)Cu(2)I(1)’’ rhomb.
ꢀ
longer than those in Cu2I2(dfphbbtz)2 (2.5303(7) A)
ꢀ
[Cu4I4(L)2]n (2.6350(6) A).
and
11c
ꢀ
The Cu–S bond distance (2.3736(16) A) is shorter than those in
ꢀ
2, [(Cu4I4)(mptq)2]n (2.362(3) A)
The mean Cu–N bond
20d
ꢀ
distance (2.060(3) A) is in-between that in 2 and that in 1. The
and [(Cu4I4)(pysmpy)2]n
Fig. 5 View of a portion of the 1D chain (parallel to the [110] plane) of 4 with labeling scheme and 50% thermal ellipsoids. All hydrogen atoms are
omitted for clarity. Symmetry code: (A) 1 ꢀ x, 1 ꢀ y, 1 ꢀ z.
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Fig. 6 View of a section of one of the 1D chains of 5 with 50% thermal ellipsoids. All hydrogen atoms are omitted for clarity. Symmetry codes: 2 ꢀ x,
1 ꢀ y, ꢀz; (B) 1 + x, ꢀ1 + y, z; and (C) 1 ꢀ x, 2 ꢀ y, ꢀz.
ꢀ
(2.8346(17) A) in the two puckered rings, while in the other,
[(MeCN)Cu(m-I)]2 unit is asymmetric, as the Cu(1)–I(1) and
Cu(1)–I(1A) bond distances are different. The average Cu–I
ꢀ
bond length (2.6513(8) A) is slightly longer than that in
ꢀ
the Cu(3)/Cu(3B) contact (2.989(2) A) is shorter than the
ꢀ
Cu(3)/Cu(4) contact (2.906(2) A). Their mean value (2.909(2)
22a
ꢀ
[(dmpzm)Cu(m-I)]2 (2.615(1) A).
ꢀ
A) is longer than those found in 4, [CuI(bpp)]n (2.713(4) A) and
ꢀ
The Cu(1)–N(2)(bphpyb)
10g
{[Cu2I2(bpp)2]$2aniline}n (2.7657(17) A), but comparable to
ꢀ
ꢀ
(2.077(3) A) is slightly longer than the Cu(1)–N(3)(MeCN) bond
ꢀ
(2.043(3) A). Intriguingly, each 1D chain connects with others via
ꢀ
those in 1 and 3. The mean Cu–N bond distance (2.057(6) A) is
ꢀ
ꢀ
the p–p interactions (3.568(2) A, 3.568(2) A) between the phenyl
and pyrimidyl rings of the bphpypr ligands to form a 2D supra-
molecular network (Fig. S8†).
in-between those of 1 and 2. In the puckered ring of the chair-
like [Cu2(m-I)(m3-I)]2 unit, the Cu(2)-m3-I(2A) bond length of
ꢀ
2.7097(12) A is the longest. The mean Cu-m-I bond distance
ꢀ
(2.688(2) A) is longer than those of 4 and [(dmpzm)Cu(m-I)]2
22a
ꢀ
(2.615(2) (1) A).
The average Cu-m3-I bond distance
(2.644(2) A) is close to those of 1 and 2, but shorter than the one
Crystal structure of [{Cu2(m-I)(m3-I)}2(bphpyp)2]n (5)
ꢀ
9b
in [Cu4(m3-I)4(bbbt)2]n (2.541(2) A). The average Cu–S bond
ꢀ
length (2.330(2) A) is shorter than those of the corresponding
ꢀ
ꢁ
Compound 5 crystallizes in the triclinic space group P1 and its
asymmetric unit consists of two halves of crystallographically
independent [{Cu2(m-I)(m3-I)}2(bphpyp)2] molecules. The two
[{Cu2(m-I)(m3-I)}2(bphpyp)2] molecules form two distinct 1D
double chains in each of which each chair-like [Cu2(m-I)(m3-I)]2
unit is connected to adjacent ones by two pairs of bphpyp ligands
via the N,S,N-tridentate coordination mode. Because the two
chains are structurally very similar, only one of them is presented
in Fig. 6. The pertinent bond lengths and angles of the
two structures are compared in Table 3. All Cu atoms adopt
a distorted tetrahedral coordination geometry, coordinated by
one m-I, one m3-I, and one N and S atoms from one bphpyp
ligand (Cu(1), Cu(1A), Cu(4), Cu(4B)) or by one m-I, two
m3-I, and one N atom from one bphpyp ligand (Cu(2), Cu
(2A), Cu(3), Cu(3B)). In one chain, the Cu(2)/Cu(2A) contact
ones in 2 and 3.
Crystal structure of [{((MeCN)Cu)(m3-I)}2{Cu(m-I)}2(bphpyh)2]n (6)
ꢁ
Compound 6 crystallizes in the triclinic space group P1 and its
asymmetric unit consists of half a [{((MeCN)Cu)(m3-I)}2{Cu(m-
I)}2(bphpyh)2] species. In 6, each [Cu(m-I)]2 rhomb and
[{(MeCN)Cu}(m3-I)]2 fragment are linked alternately by Cu-m3-I
bonds, forming a 1D rhomboid tandem chain extending along
the a axis. Such a chain is further interconnected by dphpyh
ligands to form a 2D network extending along the ac plane
(Fig. 7). It is notable that the rhomboid tandem [Cu2I2]n chain is
rare in the CuI system.26 Such a 1D [Cu2I2]n chain is different
from those in complexes 1–5, which may be due to the different
ꢀ
(2.8998(19) A) is longer than the Cu(1)/Cu(2) contact
Fig. 7 View of the 2D network of 6 (extending along the ac plane) with 50% thermal ellipsoids. All H atoms are omitted for clarity. Symmetry codes: 2 ꢀ
x, ꢀy, ꢀz; and (B) 3 ꢀ x, ꢀy, ꢀz.
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spacer lengths of [(phpy)(CH2)n(phpy)] ligands. The bphpyh
ligand in 6 takes a m-h1(S):h1(N)-h1(S):h1(N) mode to coordinate
to four Cu atoms of two of the [Cu2I2] units via two Cu–N and
two Cu–S bonds, forming two 6-membered chelating rings
(CuICuNCS). The tetrahedral coordination sphere of the Cu(I)
atom is completed by three m3-I atoms and one S atom, or by two
m3-I atoms, one N atom from MeCN and one N atom from the
bphpyh ligand. The mean Cu(1)/Cu(1A) (coordinated by
Scheme 3 The coordination modes of ligands [(phpy)(CH2)n(phpy)].
ꢀ
N from bphpyh) contact (2.8712(15) A) is longer than that of
the Cu(2)/Cu(2B) (coordinated by S from bphpyh) contact
ꢀ
(2.8422(13) A). Their mean value (2.8567 A) is longer than that in
ꢀ
Scheme 4 The [CunIn] structural motifs in 1–6.
4, but shorter than those in 1 and 3. The Cu(1)–N(1) (bphpyh)
ꢀ
(2.056(4) A) and Cu(1)–N(3) (MeCN) (2.017(5) A) bond
ꢀ
1 (or 3, 4) to 6, which may be ascribed to the different [CunIn]
units and the different coordination modes of ligands. Although
the ladder [Cu2I2] chains in 1 and 2 are similar, the different
coordination bonds may result in the blue shift from 1 to 2.
Complex 6 has lower-energy transition compared to 1–5, which
may be due to the weaker coordination interaction between Cu
and S atoms in 6.
distances are shorter than those of the corresponding ones in 4.
ꢀ
The mean Cu-m-I bond distance of 2.617(2) A is shorter
than those observed in 4 and 5. The Cu-m3-I bond distance
ꢀ
(2.645(2) A) is close to those of 1, 2 and 5. The mean Cu(2)–S
ꢀ
bond distance (2.4300(16) A) is longer than those in 2 and 3.
Photoluminescent properties of 1–6
The photoluminescent properties of 1–6 along with bphpym,
bphpye, bphpypr, bphpyb, bphpyp, and bphpyh in the solid state
at ambient temperature were studied. Complexes 1–6 show
strong photoluminescence upon irradiation of ultraviolet light in
the solid state. The excitation and emission spectra of the six Cu
(I) complexes are recorded in Fig. 8. For 1–6, upon excitation at
368, 375, 352, 373, 368 and 355 nm, they exhibited strong pho-
toluminescence with emission maxima at ca. 565, 550, 567, 569,
Conclusions
In summary, the assembly of copper(I) iodide and six bis(4-
phenylpyrimidine-2-thio)alkane ligands with different spacer
lengths [(phpy)(CH2)n(phpy)] (n ¼ 1–6) afforded six [CunIn]-
based coordination polymers 1–6 with different topological
structures. The spacer length of the [(phpy)(CH2)n(phpy)] ligands
has exerted a significant influence on their conformations,
coordination modes, and the [CunIn] motifs. In 1–6, there are
three coordination modes: m-h1(N)-h1(N) (1 and 4), m-h1(N),
h1(S)-h1(N),h1(S) (2 and 6) and m-h1(N),h1(S)-h1(N) (3 and 5)
(Scheme 3). The dihedral angles of the two pyrimidyl rings of the
[(phpy)(CH2)n(phpy)] ligands in 1, 3, and 5 are 75.9ꢁ (1), 89.3ꢁ (2)
and 50.3ꢁ (3) while those in 2, 4, and 6 are parallel to each other.
It seems that ligands with a shorter or longer (CH2)n (n ¼ 1, 2 and
6) spacer length cleave the 3D framework of bulk CuI into 1D
[CunIn]-based chains, e.g. staircase [Cu2I2]n chains (1 and 2) and
rhomboid tandem [Cu2I2]n chains (6). While oligomeric units
such as dinuclear [Cu(m-I)]2 units (4), chair-like tetranuclear
[Cu4(m-I)2(m3-I)2] units (5), and double butterfly-shaped hex-
anuclear [Cu3(m-I)2(m4-I)]2 units (3) are formed when those with
the medium (CH2)n (n ¼ 3, 4 and 5) spacer length are employed
(Scheme 4). These resulting [CunIn] species are further linked by
these ligands to form the 1D chain (3, 4 and 5), or 2D layer (1, 2
and 6). However, each Cu atom in 1–6 adopts a tetrahedral
coordination sphere. In addition, it is also possible that the
choice of acetonitrile as the reaction solvent, which has resulted
in coordination of acetonitrile in 3, 4, and 6, may have been
a significant determinant of the structures formed. In the lumi-
nescent spectra of 1–6, the emission maxima are red shifted from
2 to 4 to 6 while the emission maxima are blue-shifted from 1 (or
3) to 5. These results provided some interesting insight into how
the spacer length controlled the assembly of [CunIn]-based
coordination polymers along with their luminescent properties.
It is anticipated that construction of these ligands with other Cu
(I) salts would produce more [CunIn]-based coordination poly-
mers with more intriguing structural arrays and physical
properties.
552 and 599 nm, respectively. Red shift occurred obviously
em
compared to the ligands bphpym (lmax
em
¼
366 nm),
em
bphpye (lmax ¼ 397 nm), bphpypr (lmax ¼ 366 nm), bphpyb
em
em
(lmax ¼ 374 nm), bphpyp (lmax ¼ 363 nm), and bphpyh
em
(lmax ¼ 369 nm). The emission bands might be assigned as
a combination of a cluster-centered (CC*) excited state con-
taining mixed halide-to-metal charge-transfer (XMCT) and d–s
transitions by Cu(I)–Cu(I) interactions.11b,27 The emission peaks
for 2 and 5 (or for 1, 3 and 4) are quite similar with only 2 nm
(or 4 nm) difference in the yellow range. It should be noted that
the red shift occurred in the fluorescent spectra from 2 (or 5),
Fig. 8 Excitation (dashed line) and emission (solid line) spectra of 1–6 in
the solid state at room temperature.
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Acknowledgements
The authors thank the National Natural Science Foundation of
China (20871088, 20871038 and 90922018), the Nature Science
Key Basic Research of Jiangsu Province for Higher Education
(09KJA150002), the Specialized Research Fund for the Doctoral
Program of Higher Education of Ministry of Education
(20093201110017), and the State Key Laboratory of Organo-
metallic Chemistry of Shanghai Institute of Organic Chemistry
(08-25) for financial support. J. P. Lang also highly appreciates
the support for the Qin-Lan and the ‘‘333’’ Projects of Jiangsu
Province, the Priority Academic Program Development of
Jiangsu Higher Education Institutions, and the ‘‘SooChow
Scholar’’ Program and Program for Innovative Research Team
of Suzhou University.
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