8 of 10
YIN AND ZHU
1 were collected by filtration, washed with methanol and
dried in air with the 67% yield based on cobalt salt. Ele-
mental analysis (%) calcd for C48H54Co3N24O22S2: C,
36.96; H, 3.49; N, 21.55%. Found: C, 36.91; H, 3.53; N,
21.48%. IR (KBr pellet, cm−1): 3448 (s), 3320 (s), 3097
(s), 1637 (s), 1583 (s), 1560 (m), 1491 (s), 1437 (w), 1392
(s), 1283 (w), 1217 (s), 1111 (s), 1100 (s), 1034 (s), 1009
(s), 869 (w), 809 (w), 796 (w), 718 (s), 663 (m), 636 (m),
564 (w), 509 (w), 464 (w).
20.76%. IR (KBr pellet, cm−1): 3469 (m), 3443 (m), 3367
(m), 3283 (w), 3238 (w), 1676 (m), 1580 (s), 1537 (w),
1482 (w), 1427 (m), 1394 (s), 1274 (w), 1234 (s), 1159 (s),
1101 (m), 1033 (s), 997 (m), 828 (w), 808 (w), 777 (w),
750 (w), 668 (m), 648 (w), 616 (m), 568 (w), 520 (m),
474 (w), 445 (w).
3.7 | Synthesis of {[Co(Hpmad)(SO4)
(H2O)2]·H2O}n (5)
Complex 5 was prepared in a similar way to 1 and 2,
except that Co (CH3COO)2·4H2O was replaced by
CoSO4·7H2O. Red block single crystals of complex were
obtained after 2 months. The red block crystals of 5 were
collected by filtration, washed with methanol and dried
in air with the 59% yield based on cobalt salt. Elemental
analysis (%) calcd for C5H12CoN4O8S: C, 17.30; H, 3.48;
N, 16.14%. Found: C, 17.14; H, 3.47; N, 16.04%. IR (KBr
pellet, cm−1): 3481 (s), 3356 (m), 3092 (w), 1685 (s),
1654 (w), 1583 (s), 1566 (m), 1477 (m), 1408 (w), 1390
(s), 1154 (s), 1085 (s), 990 (w), 842 (w), 808 (w), 708 (w),
651 (m), 612 (m), 496 (w), 474 (w).
3.4 | Synthesis of [Co3(Hpmad)6]·
(3‐sb)2·(CH3COO)2·(H2O)0.5 (2)
Complex 2 was prepared in a similar way to 1, except that
H2(4‐sb) was replaced by H2(3‐sb). The purple black crys-
tals of 2 were obtained after 6 days. The purple black crys-
tals of 2 were collected by filtration, washed with
methanol and dried in air with the 43% yield based on
cobalt salt. Elemental analysis (%) calcd for
C96H102Co6N48O41S4: C, 37.61; H, 3.35; N, 21.93%. Found:
C, 37.67; H, 3.49; N, 21.86%. IR (KBr pellet, cm−1): 3424
(s), 1653 (s), 1641 (s), 1584 (s), 1560 (m), 1492 (s), 1438
(w), 1392 (s), 1285 (w), 1218 (s), 1156 (s), 1100 (s), 1035
(s), 997 (w), 797 (w), 762 (w), 722 (m), 662 (m), 618 (m),
513 (w), 463 (w).
3.8 | X‐ray crystallography
Five single‐crystal X‐ray diffraction data were collected
on Bruker Smart Apex CCD diffractometer with graphite
monochromated Mo‐Kα radiation (λ = 0.71073 Å) and
using the ω‐θ scan mode in the ranges 3.15° ≤ θ ≤
27.00° (1), 1.06° ≤ θ ≤ 27.00° (2), 2.83° ≤ θ ≤ 24.99° (3),
2.19° ≤ θ ≤ 28.36° (4), 3.24° ≤ θ ≤ 25.00° (5), respec-
tively. Raw frame data were integrated with the SAINT
program. The structures were solved by direct methods
using SHELXS‐97 and refined by full‐matrix least‐
squares on F2 using SHELXL‐97.[23] An empirical absorp-
tion correction was applied with the program CrysAlis
RED (Agilent, 2012). All non‐hydrogen atoms were
refined anisotropically. All hydrogen atoms were posi-
tioned geometrically and refined as riding atoms. Crystal-
lographic details for 1–5 have been listed in Table 1. The
selected bond lengths and bond angles are shown in
Table S1. The crystallographic data for the structural
analysis have been deposited in the Cambridge Crystallo-
graphic Data Center with the CCDC reference numbers
of 1862245–1862249.
3.5 | Synthesis of [Co(Hpmad)2(4‐sb)]n (3)
Complex 3 was prepared in a similar way to 1, except that
Co (CH3COO)2·4H2O was replaced by CoCl2·6H2O. Red
block single crystals of 3 were obtained after a month.
The red block crystals of 3 were collected by filtration,
washed with methanol and dried in air with the 53% yield
based on cobalt salt. Elemental analysis (%) calcd for
C17H16CoN8O7S: C, 38.14; H, 3.01; N, 20.93%. Found: C,
38.11; H, 3.10; N, 21.13%. IR (KBr pellet, cm−1): 3453
(m), 3442 (m), 3224 (w), 3103 (w), 1675 (m), 1581 (s),
1479 (w), 1437 (m), 1393 (s), 1239 (s), 1169 (s), 1114
(m), 1035 (s), 1005 (m), 807 (w), 791 (w), 733 (w), 669
(m), 648 (w), 634 (m), 581 (w), 471 (w), 421 (w).
3.6 | Synthesis of [Co(Hpmad)2(3‐sb)]n (4)
Complex 4 was prepared in a similar way to 1, except that
Co (CH3COO)2·4H2O was replaced by CoCl2·6H2O and
H2(4‐sb) was replaced by H2(3‐sb). Red block single crys-
tals of 4 were obtained after 2 days. The red block crystals
of 4 were collected by filtration, washed with methanol
and dried in air with the 61% yield based on cobalt salt.
Elemental analysis (%) calcd for C17H16CoN8O7S: C,
38.14; H, 3.01; N, 20.93%. Found: C, 38.06; H, 3.15; N,
4 | CONCLUSIONS
In summary, five new Hpmad‐based cobalt complexes
have been synthesized by modulating the anion of the
cobalt salt and the third ligand sbH2. The results show