A R T I C L E S
Khlobystov et al.
7.68 (d, 2H), 7.42 (d, 2H), 7.26 (m, 1H). Calc for C18H14N2: C 84.38,
H 5.47, N 10.94. Found: C 84.35, H 5.15, N 10.67. MS (EI, m/z):
256 [M]+.
heated in BunOH/o-xylene (4 cm3, 1:1 v/v) at 120 °C for 4 h and then
slowly cooled to room temperature. Colorless blocky crystals (yield
36 mg, 96%) suitable for X-ray diffraction were formed. IR, ν/cm-1
:
2220s, 1607s, 1462s, 1329s, 1286s, 1220s, 1014m, 831w, 787w. Calc
for C36H24Cd2N8O12: C 43.90, H 2.44, N 11.38. Found: C 43.65, H
Complex Synthesis. 1, [Cd(NO3)2(4-phenylpyridine)3](MeCN)2.
A solution of Cd(NO3)2‚4H2O (20 mg, 6.5 × 10-2 mmol) in MeCN (2
cm3) was layered over a solution of 4-phenylpyridine (30 mg, 19.4 ×
10-2 mmol) in dichloromethane (2 cm3). After 3 days, colorless blocky
crystals suitable for X-ray diffraction were formed (yield 35 mg, 77%).
IR, ν/cm-1: 3063w, 3034w, 1609s, 1485m, 1449m, 1416m, 1883s,
1371s, 1290m, 1223w, 762m, 731m, 692m, 618m. Calc for C37H33-
CdN7O6: C 56.68, H 4.24, N 12.50. Found: C 56.10, H 4.12, N 12.31.
2, [Cd(NO3)2(2,4′-bipy)MeCN]2. A solution of Cd(NO3)2‚4H2O (15
mg, 4.9 × 10-2 mmol) in MeCN (2 cm3) was added to a solution of
2,4′-bipy (8 mg, 4.9 × 10-2 mmol) in CH2Cl2 (2 cm3). Slow diffusion
of Et2O vapor into the solution resulted in colorless plate crystals (yield
15 mg, 53%). IR, ν/cm-1: 3050w, 1601s, 1584m, 1565w, 1469m,
1377s, 1312s, 778m, 744m, 511w. Calc for C12H11CdN5O6: C 33.18,
H 2.53, N 16.13. Found: C 32.51, H 2.50, N 15.57. MS (ES, m/z):
759 [M - NO3 + 2H2O]+.
3, [Cd(NO3)2(2,4′-pyph)MeCN]2. A solution of Cd(NO3)2‚4H2O (11
mg, 3.6 × 10-2 mmol) in MeCN (6 cm3) was layered over a solution
of 2,4′-pyph (8 mg, 3.6 × 10-2 mmol) in a 1:1 (v/v) mixture of CH2Cl2
and hexafluorobenzene (2 cm3). The complex [Cd(NO3)2(2,4′-pyph)-
MeCN]2 is formed as the main product (colorless plate crystals). IR,
ν/cm-1: 3114w, 3055w, 1610s, 1589w, 1563w, 1466m, 1436m, 1384s,
1333m, 1232m, 1157w, 1008w, 826m, 784w, 775m, 720m, 611w,
539w. Calc for C18H15CdN5O6: C 42.35, H 2.94, N 13.73. Found: C
42.11, H 3.01, N 13.55. MS (ES, m/z): 912 [M - NO3 + 2H2O]+.
4, [Cd(NO3)2(2,4′-pyac)DMF]2. A solution of Cd(NO3)2‚4H2O (15
mg, 4.9 × 10-2 mmol) in MeCN (2 cm3) was added to a solution of
2,4′-pyac (9 mg, 4.9 × 10-2 mmol) in DMF (2 cm3). Slow diffusion
of Et2O vapor into the solution resulted in colorless blocky crystals
(yield 18 mg, 76%). IR, ν/cm-1: 3444m, 3044w, 2425w, 1655s, 1597s,
1580m, 1563w, 1463m, 1376s, 1299s, 827m, 777m, 744m 557w, 509w.
Calc for C15H15CdN5O7: C 36.73, H 3.06, N 14.29. Found: C 36.00,
H 3.20, N 13.55. MS (ES, m/z): 780 [M - NO3 + 2H2O]+.
5, {[Cd(NO3)2(2,4′-pyacph)]MeCN}∞. A solution of Cd(NO3)2‚
4H2O (12 mg, 3.9 × 10-5 mol) in CH3CN (2 cm3) was layered over a
solution of 2,4′-pyacph (10 mg, 3.9 × 10-5 mol) in CH2Cl2 (2 cm3).
Colorless columnar crystals suitable for X-ray diffraction were formed
overnight (yield 35 mg, 93%). IR (ν, cm-1): 2229w, 1615s, 1452s,
1384vs, 1292s, 814w. Calc for C40H30Cd2N10O12: C 45.03, H 2.81, N
13.13. Found: C 45.45, H 2.90, N 12.98. MS (ES/MeOH): m/z 941
[M - NO3 + H2O].
2.50, N 11.98. MS (ES, m/z): 941 [M - NO3 + H2O]+.
-
9, {[Cd(NO3)2(2,4′-pyphac)2H2O]}∞. A solution of Cd(NO3)2‚4H2O
(12 mg, 3.9 × 10-2 mmol) in MeCN (2 cm3) was layered over a solution
of 2,4′-pyphac (10 mg, 3.9 × 10-2 mmol) in CH2Cl2 (2 cm3). Colorless
plate crystals suitable for X-ray diffraction were formed overnight (yield
33 mg, 90%). IR, ν/cm-1: 2220m, 1607m, 1463m, 1463m, 1384s,
1329w, 1289w, 1220w, 1013w, 831w, 787w. Calc for C36H26CdN6O7:
C 56.32, H 3.39, N 10.95. Found: C 56.35, H 3.30, N 10.59. MS (ES,
m/z): 705 [M - NO3 + H2O]+.
The mononuclear complex 9 was irreversibly transformed into the
complex {[Cd(NO3)2(2,4′-pyphac)]2}∞ (8) when heated in a mixture
of BunOH/o-xylene at 120 °C.
X-ray Crystallography. Single-crystal X-ray experiments were
performed on Bruker SMART CCD area detector diffractometers
equipped with an Oxford Cryosystems open-flow cryostat using
graphite-monochromated Mo KR radiation (λ ) 0.71073 Å) for
compounds 1, 2, and 4-8 and synchrotron radiation (λ ) 0.6942 Å
and λ ) 0.6892 Å for compounds 3 and 9, respectively). Structures 3
and 5 were solved by heavy atom methods, and structures 1, 2, 4, and
6-9 were solved by direct methods;23 all remaining non-hydrogen
atoms were located in difference Fourier syntheses.24
Crystal data for 1: C37H33CdN7O6, Mr ) 784.10, triclinic, space
group P1h, a ) 12.8471(7) Å, b ) 13.0727(7) Å, c ) 13.0765(7) Å, R
) 113.780(2)°, â ) 95.372(2)°, γ ) 112.184(2)°, V ) 1780.9(2) Å3.
Crystal data for 2: C24H22Cd2N10O12, Mr ) 867.32, triclinic, space
group P1h, a ) 7.8735(7) Å, b ) 8.1441(7) Å, c ) 12.9572(11) Å, R
) 78.804(1)°, â ) 78.681(1)°, γ ) 68.581(1)°, V ) 751.6(2) Å3.
Crystal data for 3: C36H30Cd2N10O12, Mr ) 1019.52, triclinic, space
group P1h, a ) 8.992(4) Å, b ) 10.657(6) Å, c ) 10.684(6) Å, R )
77.01(6)°, â ) 74.64(6)°, γ ) 88.29(7)°, V ) 961.6(9) Å3.
Crystal data for 4: C30H30Cd2N10O14, Mr ) 979.44, triclinic, space
group P1h, a ) 8.4570(13) Å, b ) 9.581(2) Å, c ) 12.026(2) Å, R )
88.117(2)°, â ) 88.678(3)°, γ ) 82.132(2)°, V ) 964.6(3) Å3.
Crystal data for 5: C40H30Cd2N10O12, Mr ) 1067.54, monoclinic,
space group C2/c, a ) 26.583(8) Å, b ) 8.143(2) Å, c ) 21.270(6) Å,
â ) 117.112(2)°, V ) 4098(4) Å3.
Crystal data for 6: C36H24Cd2N8O12, Mr ) 985.44, triclinic, space
group P1h, a ) 8.3796(9) Å, b ) 8.4698(9) Å, c ) 12.8983(14) Å, R
) 83.743(2)°, â ) 76.014(2)°, γ ) 85.366(2)°, V ) 881.5(3) Å3.
Crystal data for 7: C41.6H39.2Cd2N8O14.4, Mr ) 1106.40, monoclinic,
space group P21/c, a ) 13.2770(8) Å, b ) 13.2606(8) Å, c )
14.3240(8) Å, â ) 114.656(1)°, V ) 2292.0(4) Å3.
Crystal data for 8: C36H24Cd2N8O12, Mr ) 985.44, monoclinic, space
group P21/c, a ) 8.5354(8) Å, b ) 15.0114(14) Å, c ) 14.7187(13)
Å, â ) 99.674(2)°, V ) 1859.1(5) Å3.
6, {[Cd(NO3)2(2,4′-pyacph)]}∞. A mixture of Cd(NO3)2‚4H2O (12
mg, 3.9 × 10-5 mol) and 2,4′-pyacph (10 mg, 3.9 × 10-5 mol) was
heated in BunOH/o-xylene (4 cm3, 1:1 v/v) at 130 °C for 30 min and
then slowly cooled to room temperature. Colorless platy crystals suitable
for X-ray diffraction were formed (yield 34 mg, 90%). Complex 5 is
quantitatively transformed to 6 when heated in the mother liquor at
130 °C over 1 h. IR (ν, cm-1): 2218w, 1614s, 1467s, 1384vs, 813w.
Calc for C36H24Cd2N8O12: C 43.90, H 2.44, N 11.38. Found: C 43.34,
H 2.44, N 11.17. MS (ES/MeOH): m/z 941 [M - NO3 + H2O].
7, {[Cd(NO3)2(2,4′-pyacph)PriOH]2}∞. A solution of Cd(NO3)2‚
4H2O (12 mg, 3.9 × 10-2 mmol) in PriOH (2 cm3) was layered over
a solution of 2,4′-pyacph (10 mg, 3.9 × 10-2 mmol) in CH2Cl2/toluene
(1:1 v/v 2 cm3). Colorless block-shaped crystals (yield 35 mg, 91%)
Crystal data for 9: C36H26CdN6O7, Mr ) 767.03, monoclinic, space
group Cc, a ) 38.754(8) Å, b ) 10.189(2) Å, c ) 8.479(2) Å, â )
102.13(3)°, V ) 3273.3(11) Å3.
Crystallographic data (excluding structure factors) for the structures
reported in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication nos. 192297
(1), 192298 (2), 192299 (3), 192300 (4), 168544 (5), 168543 (6),
168545 (7), 168546 (8), and 192301 (9). Copies of the data can be
obtained free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail:
deposit@ccdc.cam.ac.uk).
suitable for X-ray diffraction were formed over 5 days. IR, ν/cm-1
:
3400m, 2222w, 1612s, 1492w, 1384vs, 1287w, 815w. Calc C36H24-
Cd2N8O12: C 43.90, H 2.44, N 11.38. Found: C 44.03, H 2.67, N 11.09.
-
MS (ES, m/z): 941 [M - NO3 + H2O]+.
The compound {[Cd(NO3)2(2,4′-pyacph)(PriOH)]2}∞ (7) co-crystal-
lized with the complex {[Cd(NO3)2(2,4′-pyacph)]2}∞ (6) and then
gradually lost PriOH, transforming almost completely to 6.
(22) Coudret, C. Synth. Commun. 1996, 3543.
(23) Sheldrick, G. M. SHELXS-97. Acta Crystallogr. Sect. A 1990, 46, 467.
(24) Sheldrick, G. M. SHELXL-97; Universita¨t Go¨ttingen: Germany, 1997.
8, {[Cd(NO3)2(2,4′-pyphac)]}∞. A mixture of Cd(NO3)2‚4H2O (12
mg, 3.9 × 10-2mmol) and 2,4′-pyphac (10 mg, 3.9 × 10-2mmol) was
9
6760 J. AM. CHEM. SOC. VOL. 125, NO. 22, 2003