ARTICLE IN PRESS
1444
D.-G. Ding et al. / Journal of Solid State Chemistry 182 (2009) 1443–1449
2.2. Preparation of [Cd(taa)Cl]
n
1
Table 2
Selected bond lengths ( A˚ ) and angles (deg) for complex 1, 2, and 3.
A mixture of Htaa (0.50 mmol, 82 mg) and CdAc
2
ꢁ 2H
2
O
a
Compound 1
(
0.50 mmol, 135 mg) in 10 mL of H O, was kept in a Teflon-lined
2
Cd(1)–O(1)
2.472(4)
2.291(5)
Cd(1)–Cl(1)
2.6497(16)
2.395(5)
2.567(5)
autoclave at 175 1C for 72 h. After slowly cooling to room
temperature, colorless prism crystals were obtained as a mono-
phasic product. The crystals were manually selected and used for
physical measurements. Yield: 92 mg (68% based on Cd). Anal.
Cd(1)–N(3)]1
Cd(1)–N(2)]2
Cd(1)–O(2)]3
Cd(1)–O(1)]3
2.428(4)
Cd(1)–Cl(1)]4
2.6481(17)
170.09(16)
87.25(16)
85.09(15)
89.86(17)
52.17(14)
93.48(13)
152.58(11)
154.53(11)
97.55(12)
165.88(11)
81.31(5)
N(3)]1–Cd(1)–N(2)]2
N(2)]2–Cd(1)–O(1)]3
N(2)]2–Cd(1)–O(1)
N(3)]1–Cd(1)–O(2)]3
O(1)]3–Cd(1)–O(2)]3
N(3)]1–Cd(1)–Cl(1)]4
O(1)]3–Cd(1)–Cl(1)]4
O(2)]3–Cd(1)–Cl(1)]4
N(2)]2–Cd(1)–Cl(1)
O(1)–Cd(1)–Cl(1)
Cl(1)]4–Cd(1)–Cl(1)
N(3)]1–Cd(1)–O(1)]3
N(3)]1–Cd(1)–O(1)
O(1)]3–Cd(1)–O(1)
N(2)]2–Cd(1)–O(2)]3
O(1)–Cd(1)–O(2)]3
N(2)]2–Cd(1)–Cl(1)]4
O(1)–Cd(1)–Cl(1)]4
N(3)]1–Cd(1)–Cl(1)
O(1)]3–Cd(1)–Cl(1)
O(2)]3–Cd(1)–Cl(1)
92.08(16)
85.47(15)
68.41(17)
97.48(17)
120.16(15)
82.75(12)
85.29(11)
90.90(12)
125.45(11)
73.39(11)
found (calcd.) for C
5.56 (15.33). IR (KBr, cm ): 3432(m), 3123(m), 2935(w), 1603(s),
520(m), 1425(m), 1394(m), 1316(s), 1217(w), 1183(w), 1139(m),
039(m), 989(w), 890(w), 794(m), 704(m), 665(m), 586(w).
4 4 3 2
H N O ClCd: C, 17.71 (17.52); H, 1.54 (1.46); N,
ꢀ1
1
1
1
2
n
.3. Preparation of [Hg(taa)Cl] 2
b
Compound 2
An aqueous solution (6 mL) of Htaa (16.5 mg, 0.1 mmol) was
dropwise added into an aqueous solution (1 mL) of Hg(NO
/2H O (334 mg, 0.1 mmol). The resulting reaction mixture was
put at room temperature. Colorless needle-like crystals suitable
for X-ray diffraction were obtained three days later. Yield: 28 mg
Hg(1)–O(1)
2.591(3)
2.117(4)
2.615(3)
2.615(3)
180.0(3)
88.84(13)
91.16(13)
180.0
Hg(1)–O(1)]3
2.591(3)
2.117(4)
3
)
2
ꢁ
Hg(1)–N(3)]1
Hg(1)–N(3)]2
Hg(2)–O(1)
Hg(2)–Cl(1)
2.3333(13)
2.3333(13)
91.16(13)
88.84(13)
180.00(9)
85.06(8)
94.94(8)
180.0
1
2
Hg(2)–O(1)]4
Hg(2)–Cl(1)]4
N(3)]1–Hg(1)–N(3)]2
N(3)]2–Hg(1)–O(1)]3
N(3)]2–Hg(1)–O(1)
Cl(1)]4–Hg(2)–Cl(1)
Cl(1)–Hg(2)–O(1)
Cl(1)–Hg(2)–O(1)]4
N(3)]1–Hg(1)–O(1)]3
N(3)]1–Hg(1)–O(1)
O(1)]3–Hg(1)–O(1)
Cl(1)]4–Hg(2)–O(1)
Cl(1)]4–Hg(2)–O(1)]4
O(1)–Hg(2)–O(1)]4
(
(
3
1
76% based on Hg). Anal. found (calcd.) for C
13.26); H, 1.23 (1.11); N, 11.76 (11.60). IR (KBr, cm ): 3444(m),
120(w), 2926(m), 2857(w), 1620(s), 1523(w), 1387(s), 1308(m),
214(w), 1176(w), 1133(m), 1027(w), 882(w), 796(w), 671(m),
83(w).
4 4 3 2
H N O ClHg: C, 13.52
ꢀ1
94.94(8)
85.06(8)
c
Compound 3
Ag(1)–O(1)]2
5
2.285(3)
2.345(3)
Ag(1)–O(2)]3
2.331(3)
2.532(3)
Ag(1)–N(2)
Ag(1)–O(3)
Ag(2)–N(3)]1
2.174(3)
Ag(2)–N(3)
2.174(3)
O(1)]2–Ag(1)–O(2)]3
O(2)]3–Ag(1)–N(2)
138.00(12)
92.29(10)
O(1)]2–Ag(1)–N(2)
N(3)–Ag(2)–N(3)]1
107.50(12)
179.999(1)
3 0.5 n
2.4. Preparation of [Ag1.5(taa)(NO ) ] 3
a
Symmetry transformations used to generate equivalent atoms in compound
An aqueous solution (6 mL) of Htaa (16.5 mg, 0.1 mmol) was
dropwise added into an aqueous solution (1 mL) of AgNO
340 mg, 0.2 mmol). A white precipitate was immediately formed.
1
: (]1) ꢀx+1, yꢀ1/2, ꢀz+1/2; (]2) x+1, y, z; (]3) ꢀx+2, ꢀy+1, ꢀz+1; (]4) ꢀx+2,
3
ꢀ
y+1, ꢀz.
(
b
Symmetry transformations used to generate equivalent atoms in compound
The precipitate was filtered, and the filtrate was put at room
temperature. Colorless needle-like crystals suitable for X-ray
diffraction were obtained one day later. Yield: 27 mg (85% based
2: (]1) xꢀ1, ꢀy+1/2, zꢀ1/2; (]2) ꢀx+1, yꢀ1/2, ꢀz+1/2; (]3) ꢀx, ꢀy, ꢀz; (]4) ꢀx, ꢀy,
ꢀz+1.
c
Symmetry transformations used to generate equivalent atoms in compound
3: (]1) –x+2, ꢀy, ꢀz+2; (]2) ꢀx+1, y, ꢀz+3/2; (]3) x, ꢀy, z+1/2.
4 4 3.5
on Htaa). Anal. found (calcd.) for C H N O3.5Ag1.5: C, 15.21
ꢀ
1
(
15.05); H, 1.34 (1.26); N, 15.65 (15.37). IR (KBr, cm ): 3447(m),
3
096(m), 1627(s), 1514(m), 1388(s), 1315(m), 1272(m), 1211(m),
2.5. Single-crystal structure determination
1171(m), 1135(m), 1030(m), 961(m), 895(m), 798(m), 680(s),
5
82(w).
The intensity data for 1–3 were collected at 291 K(2) on a
Bruker Smart CCD diffractometer using graphite-monochromated
˚
Table 1
MoKa radiation (l ¼ 0.71073 A). All of the structures were solved
Crystallographic data for compounds 1, 2, and 3.
by direct methods and expanded using Fourier techniques. The
non-hydrogen atoms were refined with anisotropic thermal
parameters. The hydrogen atoms were assigned with common
isotropic displacement factors and included in the final refine-
1
2
3
Empirical
Mr
C
4
H
4
3
N O
2
ClCd
C
4
H
4
3
N O
2
ClHg
C
4 4 3.5
H N O3.5Ag1.5
273.9
Monoclinic
P2 /c
362.1
Monoclinic
P2 /c
318.9
ment by using geometrical constraints. Position disorder has been
Crystal system
Monoclinic
C2/c
ꢀ
Space group
a ( A˚ )
b ( A˚ )
c ( A˚ )
1
1
found for the oxygen atoms of NO
3
anion for compound 3. The
6.9552(14)
12.592(3)
7.9427(16)
6.8780(12)
13.132(2)
15.899(3)
7.2573(15)
13.543(3)
final cycle of full-matrix least squares refinement was based
on the observed reflections and variable parameters. All calcula-
tions were performed using the SHELXL crystallographic software
package [12]. Table 1 shows crystallographic data of 1–3. Selected
bond distances and angles for compound 1–3 are listed in Table 2.
8.1870(15)
a
b
g
(1)
(1)
(1)
108.81(3)
111.282(2)
111.32(3)
V (A˚
3
)
658.5(2)
4
689.1(2)
4
1455.7(5)
8
Z
ꢀ
1
m
(mm
)
3.663
2.763
520
2.669
3.491
648
4.051
2.910
1208
3
.
Results and discussion
ꢀ
3
D
c
(g cm
)
F (000)
Reflections
Unique
5617
3376
1214
7972
3.1. Description of the crystal structures
1254
1.043
0.0382
0.0874
1580
Goodness-of-fit
1.031
0.0200
0.0533
1.077
0.0339
0.0769
3
.1.1. Crystal structure of [Cd(taa)Cl]
Single-crystal X-ray structural analysis reveals that compound
crystallizes in the monoclinic space group P2 /c, and consists
n
1
1
R (I42s(I))
wR
2
(all data)
1
1
P
P
¼ [P
P
2
0
2
c
2
2 2 1/2
) ]
R
1
¼
0
||F |ꢀ|F
c
||/ |F
0
|; wR
2
w(F
ꢀF
) / w(F
0
.
of 1D helical chains. The asymmetric unit contains one Cd(II) ion,