The title compound, [Zn
4(C
7H
4O
3)
4(C
10H
8N
2)
4]·10H
2O, crystallizes as a centrosymmetric tetranuclear cyclic complex containing four Zn
II atoms bridged by four carboxylate groups from salicylate ligands, with a
syn-
anti configuration. Each Zn
II atom has a distorted trigonal-bipyramidal coordination geometry, formed by two N atoms of a 2,2'-bipyridine ligand and three O atoms from two salicylate ligands. The complex is stabilized by intramolecular
-
interactions between pairs of bipyridine rings and a 16-membered gear-wheel-shaped cyclic framework. The hydrogen-bonding network is formed
via the water molecules.
Supporting information
CCDC reference: 254895
Thin yellow prismatic crystals of (I) were obtained by slow evaporation of an aqueous methanol solution (10 ml) of a mixture of salicylic acid (5 mg), 2,2'-bipyridine and ZnCl2 (molar ratio 1:1:1) at room temperature.
All the H atoms, except water molecules, were located from difference Fourier maps, and were placed at idealized positions and treated as riding, with C—H distances of 0.93 Å and Uiso(H) values of 1.2Ueq(parent). Water H atoms bonded to atoms O10 and O11 were located from difference Fourier maps. One of the H atoms attached to each of atoms O7, O8 and O9 shows positional disorder over two sites, viz. H31/H33, H34/H36 and H35/H37, respectively, with occupation factors of 50% each. The positional parameters of the disordered H atoms were calculated on the basis of the positions of the other H atoms (H25, H30 and H32), which were located from difference Fourier maps, and by assuming two possible configurations of the hydrogen-bonding network (Fig. 2). The positional parameters of the water H atoms were fixed, with Uiso(H) = 0.020 Å2, the O—H distances and H—O—H bond angles being 0.71–0.96 Å and 92–116°. The short H32···H4 (which is bonded to C6) contact distance of 2.1 Å suggests that the reported position of atom H32 is slightly shifted from its true position.
Data collection: RAPID-AUTO (Rigaku, 2003); cell refinement: RAPID-AUTO; data reduction: Crystal Structure (Rigaku/MSC, 2004) and
CRYSTALS ( Watkin et al., 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999) and
DIRDIF99 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Scheldrick, 1997); molecular graphics: ORTEP III (Farrugia, 1997); software used to prepare material for publication: Crystal Structure.
Crystal data top
[Zn4(C7H6O3)4(C10H8N2)4]·10H2O | Z = 1 |
Mr = 1610.85 | F(000) = 828.00 |
Triclinic, P1 | Dx = 1.641 Mg m−3 |
Hall symbol: -p_1 | Mo Kα radiation, λ = 0.7107 Å |
a = 12.633 (13) Å | Cell parameters from 13658 reflections |
b = 12.735 (14) Å | θ = 3.1–27.5° |
c = 13.29 (3) Å | µ = 1.54 mm−1 |
α = 61.60 (3)° | T = 296 K |
β = 66.23 (4)° | Prism, colorless |
γ = 63.22 (3)° | 0.30 × 0.20 × 0.10 mm |
V = 1630 (4) Å3 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 5512 reflections with F2 > 2σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.019 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −16→16 |
Tmin = 0.718, Tmax = 0.857 | k = −16→16 |
15951 measured reflections | l = −17→17 |
7327 independent reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.024 | w = 1/[σ2(Fo2) + (0.0387P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.066 | (Δ/σ)max < 0.001 |
S = 1.00 | Δρmax = 0.42 e Å−3 |
7327 reflections | Δρmin = −0.30 e Å−3 |
462 parameters | |
Crystal data top
[Zn4(C7H6O3)4(C10H8N2)4]·10H2O | γ = 63.22 (3)° |
Mr = 1610.85 | V = 1630 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 12.633 (13) Å | Mo Kα radiation |
b = 12.735 (14) Å | µ = 1.54 mm−1 |
c = 13.29 (3) Å | T = 296 K |
α = 61.60 (3)° | 0.30 × 0.20 × 0.10 mm |
β = 66.23 (4)° | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 7327 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 5512 reflections with F2 > 2σ(F2) |
Tmin = 0.718, Tmax = 0.857 | Rint = 0.019 |
15951 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 462 parameters |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.42 e Å−3 |
7327 reflections | Δρmin = −0.30 e Å−3 |
Special details top
Refinement. Refinement using all reflections. The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Zn1 | 0.12746 (2) | 0.75225 (2) | −0.08242 (2) | 0.01191 (7) | |
Zn2 | 0.13397 (2) | 0.85343 (2) | 0.21368 (2) | 0.01130 (7) | |
O1 | 0.2788 (1) | 0.7757 (1) | −0.2074 (1) | 0.0173 (3) | |
O2 | 0.1576 (1) | 0.8276 (1) | 0.0022 (1) | 0.0151 (3) | |
O3 | 0.2569 (1) | 0.8882 (1) | 0.0566 (1) | 0.0147 (3) | |
O4 | 0.1978 (1) | 0.8484 (1) | 0.3294 (1) | 0.0145 (3) | |
O5 | 0.0284 (1) | 1.0370 (1) | 0.1877 (1) | 0.0135 (3) | |
O6 | −0.0541 (1) | 1.2206 (1) | 0.2090 (1) | 0.0139 (3) | |
O7 | 0.4082 (2) | 0.9709 (2) | 0.0985 (1) | 0.0371 (4) | |
O8 | 0.4544 (1) | 0.7429 (1) | 0.2841 (1) | 0.0309 (4) | |
O9 | 0.5491 (1) | 0.5881 (1) | 0.4876 (1) | 0.0276 (4) | |
O10 | 0.2130 (1) | 0.6165 (1) | 0.5339 (1) | 0.0259 (4) | |
O11 | 0.3446 (1) | 0.6306 (1) | 0.6656 (1) | 0.0223 (3) | |
N1 | 0.1994 (1) | 0.5551 (1) | −0.0053 (1) | 0.0153 (3) | |
N2 | −0.0281 (1) | 0.7015 (1) | 0.0494 (1) | 0.0132 (3) | |
N3 | 0.2125 (1) | 0.6499 (1) | 0.2577 (1) | 0.0143 (3) | |
N4 | −0.0197 (1) | 0.7962 (1) | 0.2762 (1) | 0.0116 (3) | |
C1 | 0.3425 (2) | 0.8742 (2) | −0.1341 (1) | 0.0114 (4) | |
C2 | 0.3504 (2) | 0.8331 (2) | −0.2198 (1) | 0.0113 (4) | |
C3 | 0.4421 (2) | 0.8554 (2) | −0.3266 (2) | 0.0138 (4) | |
C4 | 0.5215 (2) | 0.9135 (2) | −0.3468 (2) | 0.0150 (4) | |
C5 | 0.5155 (2) | 0.9518 (2) | −0.2616 (2) | 0.0168 (4) | |
C6 | 0.4266 (2) | 0.9316 (2) | −0.1573 (2) | 0.0146 (4) | |
C7 | 0.2467 (2) | 0.8617 (2) | −0.0196 (1) | 0.0116 (4) | |
C8 | 0.0811 (2) | 1.0622 (2) | 0.3299 (1) | 0.0114 (4) | |
C9 | 0.1681 (2) | 0.9414 (2) | 0.3661 (1) | 0.0117 (4) | |
C10 | 0.2267 (2) | 0.9166 (2) | 0.4497 (2) | 0.0141 (4) | |
C11 | 0.1993 (2) | 1.0031 (2) | 0.4977 (2) | 0.0153 (4) | |
C12 | 0.1115 (2) | 1.1205 (2) | 0.4643 (2) | 0.0157 (4) | |
C13 | 0.0537 (2) | 1.1478 (2) | 0.3821 (2) | 0.0141 (4) | |
C14 | 0.0156 (2) | 1.1070 (2) | 0.2384 (1) | 0.0115 (4) | |
C15 | 0.1165 (2) | 0.4943 (2) | 0.0682 (1) | 0.0135 (4) | |
C16 | 0.1510 (2) | 0.3634 (2) | 0.1140 (2) | 0.0164 (4) | |
C17 | 0.2731 (2) | 0.2937 (2) | 0.0866 (2) | 0.0210 (4) | |
C18 | 0.3585 (2) | 0.3558 (2) | 0.0142 (2) | 0.0243 (5) | |
C19 | 0.3174 (2) | 0.4860 (2) | −0.0310 (2) | 0.0211 (5) | |
C20 | −0.0115 (2) | 0.5769 (2) | 0.0961 (1) | 0.0124 (4) | |
C21 | −0.1088 (2) | 0.5296 (2) | 0.1661 (2) | 0.0159 (4) | |
C22 | −0.2259 (2) | 0.6139 (2) | 0.1873 (2) | 0.0177 (4) | |
C23 | −0.2419 (2) | 0.7407 (2) | 0.1394 (2) | 0.0186 (4) | |
C24 | −0.1409 (2) | 0.7813 (2) | 0.0707 (2) | 0.0160 (4) | |
C25 | 0.1299 (2) | 0.5920 (2) | 0.2944 (1) | 0.0131 (4) | |
C26 | 0.1653 (2) | 0.4655 (2) | 0.3101 (2) | 0.0179 (4) | |
C27 | 0.2882 (2) | 0.3980 (2) | 0.2889 (2) | 0.0217 (5) | |
C28 | 0.3731 (2) | 0.4563 (2) | 0.2548 (2) | 0.0227 (5) | |
C29 | 0.3318 (2) | 0.5831 (2) | 0.2389 (2) | 0.0197 (4) | |
C30 | −0.0001 (2) | 0.6712 (2) | 0.3168 (1) | 0.0122 (4) | |
C31 | −0.0963 (2) | 0.6221 (2) | 0.3767 (2) | 0.0162 (4) | |
C32 | −0.2146 (2) | 0.7029 (2) | 0.3938 (2) | 0.0181 (4) | |
C33 | −0.2348 (2) | 0.8312 (2) | 0.3501 (2) | 0.0164 (4) | |
C34 | −0.1350 (2) | 0.8743 (2) | 0.2917 (2) | 0.0135 (4) | |
H1 | 0.4485 | 0.8299 | −0.3844 | 0.017* | |
H2 | 0.5799 | 0.9275 | −0.4179 | 0.018* | |
H3 | 0.5699 | 0.9899 | −0.2745 | 0.020* | |
H4 | 0.4222 | 0.9570 | −0.1003 | 0.018* | |
H5 | 0.2860 | 0.8388 | 0.4730 | 0.017* | |
H6 | 0.2396 | 0.9830 | 0.5527 | 0.018* | |
H7 | 0.0921 | 1.1793 | 0.4968 | 0.019* | |
H8 | −0.0057 | 1.2259 | 0.3603 | 0.017* | |
H9 | 0.4562 | 0.4115 | 0.2428 | 0.027* | |
H10 | 0.3138 | 0.3140 | 0.2974 | 0.026* | |
H11 | 0.0928 | 0.3230 | 0.1625 | 0.020* | |
H12 | 0.2975 | 0.2061 | 0.1164 | 0.025* | |
H13 | 0.4412 | 0.3110 | −0.0034 | 0.029* | |
H14 | 0.3741 | 0.5278 | −0.0816 | 0.025* | |
H15 | 0.1071 | 0.4273 | 0.3345 | 0.022* | |
H16 | −0.0811 | 0.5356 | 0.4051 | 0.019* | |
H17 | −0.3191 | 0.7987 | 0.1528 | 0.022* | |
H18 | −0.1524 | 0.8673 | 0.0382 | 0.019* | |
H19 | −0.0955 | 0.4432 | 0.1981 | 0.019* | |
H20 | −0.1485 | 0.9606 | 0.2621 | 0.016* | |
H21 | −0.3138 | 0.8874 | 0.3597 | 0.020* | |
H22 | −0.2923 | 0.5847 | 0.2331 | 0.021* | |
H23 | −0.2798 | 0.6714 | 0.4342 | 0.022* | |
H24 | 0.3888 | 0.6230 | 0.2144 | 0.024* | |
H25 | 0.4962 | 0.6096 | 0.5390 | 0.020* | |
H26 | 0.2916 | 0.6452 | 0.6351 | 0.020* | |
H27 | 0.3237 | 0.6749 | 0.6972 | 0.020* | |
H28 | 0.2096 | 0.6813 | 0.4715 | 0.020* | |
H29 | 0.2673 | 0.5726 | 0.5143 | 0.020* | |
H30 | 0.3813 | 0.7643 | 0.3093 | 0.020* | |
H31 | 0.4565 | 1.0097 | 0.0344 | 0.020* | 0.50 |
H32 | 0.3598 | 0.9519 | 0.0731 | 0.020* | |
H33 | 0.4549 | 0.8890 | 0.1240 | 0.020* | 0.50 |
H34 | 0.4580 | 0.7948 | 0.2223 | 0.020* | 0.50 |
H35 | 0.5307 | 0.6534 | 0.4212 | 0.020* | 0.50 |
H36 | 0.4988 | 0.6972 | 0.3386 | 0.020* | 0.50 |
H37 | 0.5232 | 0.5407 | 0.4910 | 0.020* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0141 (1) | 0.0132 (1) | 0.0107 (1) | −0.00781 (9) | −0.00370 (8) | −0.00215 (9) |
Zn2 | 0.0121 (1) | 0.0116 (1) | 0.0111 (1) | −0.00527 (9) | −0.00236 (8) | −0.00380 (9) |
O1 | 0.0200 (8) | 0.0234 (7) | 0.0154 (7) | −0.0144 (6) | 0.0013 (5) | −0.0098 (6) |
O2 | 0.0152 (7) | 0.0212 (7) | 0.0135 (6) | −0.0110 (6) | −0.0011 (5) | −0.0068 (6) |
O3 | 0.0162 (7) | 0.0188 (7) | 0.0127 (6) | −0.0098 (6) | −0.0014 (5) | −0.0062 (6) |
O4 | 0.0165 (7) | 0.0131 (6) | 0.0162 (6) | −0.0036 (6) | −0.0069 (5) | −0.0056 (6) |
O5 | 0.0174 (7) | 0.0121 (6) | 0.0132 (6) | −0.0056 (6) | −0.0054 (5) | −0.0040 (5) |
O6 | 0.0170 (7) | 0.0109 (6) | 0.0143 (6) | −0.0036 (6) | −0.0076 (5) | −0.0026 (5) |
O7 | 0.045 (1) | 0.053 (1) | 0.0291 (9) | −0.0343 (9) | −0.0048 (8) | −0.0123 (8) |
O8 | 0.0176 (8) | 0.0367 (9) | 0.0356 (9) | −0.0050 (7) | −0.0059 (7) | −0.0149 (8) |
O9 | 0.0200 (8) | 0.0342 (9) | 0.0260 (8) | −0.0088 (7) | −0.0008 (6) | −0.0128 (7) |
O10 | 0.0323 (9) | 0.0176 (7) | 0.0214 (7) | −0.0068 (7) | −0.0055 (6) | −0.0042 (6) |
O11 | 0.0259 (9) | 0.0222 (7) | 0.0219 (7) | −0.0050 (7) | −0.0061 (6) | −0.0125 (6) |
N1 | 0.0153 (9) | 0.0163 (8) | 0.0146 (8) | −0.0065 (7) | −0.0056 (6) | −0.0029 (7) |
N2 | 0.0173 (9) | 0.0132 (8) | 0.0115 (7) | −0.0071 (7) | −0.0047 (6) | −0.0029 (7) |
N3 | 0.0150 (9) | 0.0130 (8) | 0.0141 (7) | −0.0032 (7) | −0.0035 (6) | −0.0056 (7) |
N4 | 0.0134 (8) | 0.0117 (7) | 0.0113 (7) | −0.0035 (7) | −0.0047 (6) | −0.0044 (6) |
C1 | 0.0107 (9) | 0.0110 (9) | 0.0112 (8) | −0.0038 (7) | −0.0036 (7) | −0.0020 (7) |
C2 | 0.0099 (9) | 0.0086 (8) | 0.0129 (8) | −0.0014 (7) | −0.0044 (7) | −0.0022 (7) |
C3 | 0.014 (1) | 0.0124 (9) | 0.0131 (9) | −0.0010 (8) | −0.0037 (7) | −0.0056 (8) |
C4 | 0.010 (1) | 0.0140 (9) | 0.0137 (9) | −0.0019 (8) | −0.0009 (7) | −0.0032 (8) |
C5 | 0.013 (1) | 0.018 (1) | 0.020 (1) | −0.0078 (8) | −0.0042 (8) | −0.0044 (8) |
C6 | 0.015 (1) | 0.0157 (9) | 0.0141 (9) | −0.0054 (8) | −0.0048 (7) | −0.0049 (8) |
C7 | 0.013 (1) | 0.0085 (8) | 0.0118 (8) | −0.0030 (7) | −0.0044 (7) | −0.0017 (7) |
C8 | 0.012 (1) | 0.0135 (9) | 0.0093 (8) | −0.0069 (8) | −0.0016 (7) | −0.0023 (7) |
C9 | 0.0113 (9) | 0.0138 (9) | 0.0106 (8) | −0.0063 (8) | −0.0008 (7) | −0.0041 (7) |
C10 | 0.013 (1) | 0.0149 (9) | 0.0125 (9) | −0.0057 (8) | −0.0041 (7) | −0.0013 (8) |
C11 | 0.017 (1) | 0.021 (1) | 0.0105 (8) | −0.0095 (8) | −0.0039 (7) | −0.0033 (8) |
C12 | 0.020 (1) | 0.018 (1) | 0.0133 (9) | −0.0086 (8) | −0.0026 (7) | −0.0069 (8) |
C13 | 0.015 (1) | 0.0139 (9) | 0.0124 (9) | −0.0071 (8) | −0.0027 (7) | −0.0024 (8) |
C14 | 0.0115 (9) | 0.0130 (9) | 0.0095 (8) | −0.0077 (8) | −0.0011 (7) | −0.0012 (7) |
C15 | 0.017 (1) | 0.0153 (9) | 0.0107 (8) | −0.0069 (8) | −0.0060 (7) | −0.0029 (8) |
C16 | 0.021 (1) | 0.0152 (9) | 0.0152 (9) | −0.0080 (8) | −0.0065 (8) | −0.0029 (8) |
C17 | 0.026 (1) | 0.0130 (9) | 0.022 (1) | −0.0035 (9) | −0.0108 (9) | −0.0030 (8) |
C18 | 0.017 (1) | 0.021 (1) | 0.026 (1) | −0.0010 (9) | −0.0076 (9) | −0.0050 (9) |
C19 | 0.015 (1) | 0.023 (1) | 0.021 (1) | −0.0075 (9) | −0.0052 (8) | −0.0032 (9) |
C20 | 0.017 (1) | 0.0130 (9) | 0.0097 (8) | −0.0068 (8) | −0.0054 (7) | −0.0029 (7) |
C21 | 0.022 (1) | 0.0145 (9) | 0.0124 (9) | −0.0102 (8) | −0.0047 (8) | −0.0016 (8) |
C22 | 0.018 (1) | 0.022 (1) | 0.0147 (9) | −0.0114 (9) | −0.0007 (8) | −0.0059 (8) |
C23 | 0.017 (1) | 0.018 (1) | 0.0176 (9) | −0.0043 (8) | −0.0027 (8) | −0.0068 (8) |
C24 | 0.020 (1) | 0.0121 (9) | 0.0145 (9) | −0.0059 (8) | −0.0032 (8) | −0.0037 (8) |
C25 | 0.017 (1) | 0.0123 (9) | 0.0094 (8) | −0.0043 (8) | −0.0041 (7) | −0.0029 (7) |
C26 | 0.022 (1) | 0.0140 (9) | 0.0184 (9) | −0.0061 (8) | −0.0070 (8) | −0.0041 (8) |
C27 | 0.026 (1) | 0.0119 (9) | 0.024 (1) | −0.0001 (9) | −0.0101 (9) | −0.0065 (9) |
C28 | 0.016 (1) | 0.019 (1) | 0.025 (1) | 0.0019 (9) | −0.0039 (8) | −0.0100 (9) |
C29 | 0.017 (1) | 0.019 (1) | 0.021 (1) | −0.0055 (9) | −0.0023 (8) | −0.0075 (9) |
C30 | 0.017 (1) | 0.0112 (9) | 0.0103 (8) | −0.0051 (8) | −0.0045 (7) | −0.0034 (7) |
C31 | 0.021 (1) | 0.0133 (9) | 0.0160 (9) | −0.0076 (8) | −0.0063 (8) | −0.0029 (8) |
C32 | 0.018 (1) | 0.022 (1) | 0.0174 (9) | −0.0118 (9) | −0.0029 (8) | −0.0053 (8) |
C33 | 0.013 (1) | 0.019 (1) | 0.0174 (9) | −0.0025 (8) | −0.0042 (7) | −0.0089 (8) |
C34 | 0.016 (1) | 0.0119 (9) | 0.0143 (9) | −0.0034 (8) | −0.0054 (7) | −0.0051 (8) |
Geometric parameters (Å, º) top
Zn1—O1 | 1.996 (5) | C8—C14 | 1.487 (3) |
Zn1—O2 | 2.008 (5) | C9—C10 | 1.414 (4) |
Zn1—N1 | 2.105 (5) | C10—C11 | 1.374 (4) |
Zn1—N2 | 2.154 (5) | C10—H5 | 0.9300 |
Zn1—O6i | 2.052 (5) | C11—C12 | 1.391 (5) |
Zn2—O3 | 2.023 (5) | C11—H6 | 0.9300 |
Zn2—O4 | 1.969 (5) | C12—C13 | 1.378 (4) |
Zn2—O5 | 2.040 (5) | C12—H7 | 0.9300 |
Zn2—N3 | 2.181 (5) | C13—H8 | 0.9300 |
Zn2—N4 | 2.095 (5) | C14—O5 | 1.277 (3) |
O1—C2 | 1.319 (3) | C14—O6 | 1.269 (2) |
O2—C7 | 1.263 (3) | C14—C8 | 1.487 (3) |
O3—C7 | 1.275 (3) | C15—C16 | 1.390 (3) |
O4—C9 | 1.335 (3) | C15—C20 | 1.488 (5) |
O5—C14 | 1.277 (3) | C16—C17 | 1.386 (3) |
O6—C14 | 1.269 (2) | C16—H11 | 0.9300 |
O7—H31 | 0.8914 | C17—C18 | 1.386 (3) |
O7—H32 | 0.9612 | C17—H12 | 0.9300 |
O7—H33 | 0.9063 | C18—C19 | 1.381 (3) |
O8—H30 | 0.8061 | C18—H13 | 0.9300 |
O8—H34 | 0.7709 | C19—H14 | 0.9300 |
O8—H36 | 0.8997 | C20—C21 | 1.397 (3) |
O9—H25 | 0.7961 | C21—C22 | 1.393 (5) |
O9—H35 | 0.9033 | C21—H19 | 0.9300 |
O9—H37 | 0.7828 | C22—C23 | 1.374 (3) |
O10—H28 | 0.8466 | C22—H22 | 0.9300 |
O10—H29 | 0.7065 | C23—C24 | 1.390 (3) |
O11—H26 | 0.8250 | C23—H17 | 0.9300 |
O11—H27 | 0.7526 | C24—H18 | 0.9300 |
N1—C15 | 1.356 (3) | C25—C26 | 1.395 (3) |
N1—C19 | 1.344 (2) | C25—C30 | 1.484 (5) |
N2—C20 | 1.348 (3) | C26—C27 | 1.380 (3) |
N2—C24 | 1.337 (2) | C26—H15 | 0.9300 |
N3—C25 | 1.346 (3) | C27—C28 | 1.383 (4) |
N3—C29 | 1.342 (2) | C27—H10 | 0.9300 |
N4—C30 | 1.349 (3) | C28—C29 | 1.389 (3) |
N4—C34 | 1.342 (2) | C28—H9 | 0.9300 |
C1—C2 | 1.418 (4) | C29—H24 | 0.9300 |
C1—C6 | 1.407 (4) | C30—N4 | 1.349 (3) |
C1—C7 | 1.504 (2) | C30—C25 | 1.484 (5) |
C2—C3 | 1.423 (2) | C30—C31 | 1.391 (3) |
C3—C4 | 1.376 (4) | C31—C30 | 1.391 (3) |
C3—H1 | 0.9299 | C31—C32 | 1.380 (3) |
C4—C5 | 1.395 (4) | C31—H16 | 0.9300 |
C4—H2 | 0.9299 | C32—C33 | 1.383 (3) |
C5—C6 | 1.384 (5) | C32—H23 | 0.9299 |
C5—H3 | 0.9300 | C33—C34 | 1.386 (3) |
C6—H4 | 0.9300 | C33—H21 | 0.9300 |
C8—C9 | 1.416 (5) | C34—H20 | 0.9300 |
C8—C13 | 1.406 (4) | | |
| | | |
O1—Zn1—O2 | 89.42 (7) | C11—C10—C9 | 122.5 (2) |
O1—Zn1—N1 | 96.08 (6) | C11—C10—H5 | 118.7598 |
O1—Zn1—N2 | 171.73 (7) | H5—C10—C9 | 118.7674 |
O2—Zn1—N1 | 107.28 (8) | C12—C11—C10 | 120.2 (2) |
O2—Zn1—N2 | 97.02 (7) | C12—C11—H6 | 119.8740 |
N1—Zn1—N2 | 77.10 (6) | H6—C11—C10 | 119.8770 |
O1—Zn1—O6i | 88.49 (8) | C13—C12—C11 | 118.6 (2) |
O2—Zn1—O6i | 148.42 (6) | C13—C12—H7 | 120.7043 |
N1—Zn1—O6i | 104.3 (1) | H7—C12—C11 | 120.7077 |
N2—Zn1—O6i | 88.75 (7) | H8—C13—C8 | 118.7185 |
O3—Zn2—O4 | 107.50 (7) | H8—C13—C12 | 118.7267 |
O3—Zn2—O5 | 96.02 (5) | O5—C14—C8 | 122.8 (2) |
O3—Zn2—N3 | 92.81 (5) | O5—C14—O6 | 119.3 (2) |
O3—Zn2—N4 | 133.48 (8) | O6—C14—C8 | 117.9 (2) |
O4—Zn2—O5 | 91.26 (7) | C16—C15—N1 | 121.2 (2) |
O4—Zn2—N3 | 92.82 (7) | C16—C15—C20 | 123.2 (2) |
O4—Zn2—N4 | 118.09 (6) | C20—C15—N1 | 115.5 (2) |
O5—Zn2—N3 | 168.69 (7) | C17—C16—C15 | 119.4 (2) |
O5—Zn2—N4 | 91.91 (6) | C17—C16—H11 | 120.3126 |
N3—Zn2—N4 | 76.86 (7) | H11—C16—C15 | 120.3133 |
C2—O1—Zn1 | 128.5 (1) | C18—C17—C16 | 119.4 (2) |
C7—O2—Zn1 | 130.5 (1) | C18—C17—H12 | 120.3040 |
C7—O3—Zn2 | 115.2 (1) | H12—C17—C16 | 120.3032 |
C9—O4—Zn2 | 127.2 (1) | C19—C18—C17 | 118.2 (2) |
C14—O5—Zn2 | 128.6 (1) | C19—C18—H13 | 120.8921 |
H31—O7—H32 | 107.8813 | H13—C18—C17 | 120.8946 |
H31—O7—H33 | 105.5714 | H14—C19—N1 | 118.4221 |
H32—O7—H33 | 92.3286 | H14—C19—C18 | 118.4160 |
H30—O8—H34 | 98.8129 | C21—C20—N2 | 121.7 (2) |
H30—O8—H36 | 115.8014 | C21—C20—C15 | 122.7 (2) |
H34—O8—H36 | 138.0266 | C22—C21—C20 | 118.9 (2) |
H25—O9—H35 | 103.6160 | C22—C21—H19 | 120.5374 |
H25—O9—H37 | 96.2263 | H19—C21—C20 | 120.5393 |
H35—O9—H37 | 101.5451 | C23—C22—C21 | 118.9 (2) |
H28—O10—H29 | 101.1932 | C23—C22—H22 | 120.5421 |
H26—O11—H27 | 111.0059 | H22—C22—C21 | 120.5380 |
C15—N1—Zn1 | 115.8 (1) | C24—C23—C22 | 119.1 (2) |
C15—N1—C19 | 118.6 (2) | C24—C23—H17 | 120.4372 |
C19—N1—Zn1 | 125.4 (1) | H17—C23—C22 | 120.4430 |
C20—N2—Zn1 | 114.1 (1) | H18—C24—N2 | 118.6953 |
C20—N2—C24 | 118.7 (2) | H18—C24—C23 | 118.6999 |
C24—N2—Zn1 | 125.8 (1) | C26—C25—N3 | 121.7 (2) |
C25—N3—Zn2 | 114.0 (1) | C26—C25—C30 | 122.6 (2) |
C25—N3—C29 | 119.0 (2) | C30—C25—N3 | 115.8 (2) |
C29—N3—Zn2 | 126.5 (2) | C27—C26—C25 | 118.9 (2) |
C30—N4—Zn2 | 117.0 (1) | C27—C26—H15 | 120.5491 |
C30—N4—C34 | 118.9 (2) | H15—C26—C25 | 120.5493 |
C34—N4—Zn2 | 123.6 (2) | C28—C27—C26 | 119.5 (2) |
C2—C1—C7 | 123.2 (2) | C28—C27—H10 | 120.2612 |
C2—C1—C6 | 118.8 (2) | H10—C27—C26 | 120.2652 |
C6—C1—C7 | 118.0 (2) | C29—C28—C27 | 118.7 (2) |
C3—C2—C1 | 117.6 (2) | C29—C28—H9 | 120.6316 |
C3—C2—O1 | 117.8 (2) | H9—C28—C27 | 120.6312 |
C4—C3—C2 | 121.9 (2) | H24—C29—N3 | 118.9215 |
C4—C3—H1 | 119.0727 | H24—C29—C28 | 118.9245 |
H1—C3—C2 | 119.0767 | N4—C30—C25 | 115.3 (2) |
C5—C4—C3 | 120.6 (2) | N4—C30—C31 | 121.4 (2) |
C5—C4—H2 | 119.6793 | C25—C30—C31 | 123.4 (2) |
H2—C4—C3 | 119.6799 | C30—C31—C32 | 119.4 (2) |
C6—C5—C4 | 118.4 (2) | C30—C31—H16 | 120.2860 |
C6—C5—H3 | 120.7821 | C32—C31—H16 | 120.2905 |
H3—C5—C4 | 120.7756 | C33—C32—C31 | 119.2 (2) |
H4—C6—C1 | 118.6919 | C33—C32—H23 | 120.4126 |
H4—C6—C5 | 118.6844 | H23—C32—C31 | 120.4136 |
C9—C8—C14 | 124.5 (2) | C34—C33—C32 | 118.7 (2) |
C9—C8—C13 | 118.9 (2) | C34—C33—H21 | 120.6584 |
C13—C8—C14 | 116.6 (2) | H21—C33—C32 | 120.6489 |
C10—C9—O4 | 117.4 (2) | H20—C34—N4 | 118.7739 |
C10—C9—C8 | 117.2 (2) | H20—C34—C33 | 118.7802 |
| | | |
O2—Zn1—O1—C2 | −6.0 (1) | C2—C3—C4—C5 | 0.7 (2) |
O1—Zn1—O2—C7 | −5.3 (1) | C3—C4—C5—C6 | −1.0 (2) |
O1—Zn1—N1—C15 | −164.6 (2) | C4—C5—C6—C1 | 0.0 (2) |
O4—Zn2—O3—C7 | 162.1 (1) | C13—C8—C9—O4 | 175.9 (2) |
O3—Zn2—O4—C9 | 98.0 (1) | C9—C8—C13—C12 | 2.4 (3) |
O3—Zn2—O5—C14 | −110.1 (1) | C9—C8—C14—O5 | 3.3 (3) |
O3—Zn2—N3—C25 | −130.6 (1) | C9—C8—C14—O6 | −175.4 (2) |
O3—Zn2—N4—C30 | 84.7 (2) | O4—C9—C10—C11 | −177.0 (2) |
Zn1—O1—C2—C1 | 10.0 (2) | C9—C10—C11—C12 | −0.3 (3) |
Zn1—O2—C7—O3 | −168.4 (1) | C10—C11—C12—C13 | −0.4 (3) |
Zn1—O2—C7—C1 | 12.3 (2) | C11—C12—C13—C8 | −0.7 (3) |
Zn2—O3—C7—O2 | 6.2 (2) | N1—C15—C16—C17 | 1.8 (4) |
Zn2—O3—C7—C1 | −174.5 (1) | N1—C15—C20—N2 | −3.0 (3) |
Zn2—O4—C9—C8 | 1.7 (3) | C15—C16—C17—C18 | 0.1 (4) |
Zn2—O5—C14—O6 | 179.2 (1) | C16—C17—C18—C19 | −2.0 (4) |
Zn2—O5—C14—C8 | 0.6 (3) | C17—C18—C19—N1 | 2.1 (5) |
Zn1—N1—C15—C16 | 172.6 (2) | N2—C20—C21—C22 | 0.4 (4) |
Zn1—N1—C19—C18 | −174.0 (2) | C20—C21—C22—C23 | −0.5 (4) |
Zn1—N2—C20—C15 | 12.0 (3) | C21—C22—C23—C24 | 0.5 (4) |
Zn1—N2—C24—C23 | 166.5 (2) | C22—C23—C24—N2 | −0.3 (4) |
Zn2—N3—C25—C26 | 170.7 (2) | N3—C25—C26—C27 | 0.9 (3) |
Zn2—N3—C29—C28 | −170.8 (2) | N3—C25—C30—N4 | 12.4 (3) |
Zn2—N4—C30—C25 | −9.3 (3) | C25—C26—C27—C28 | 1.2 (4) |
Zn2—N4—C34—C33 | −169.6 (2) | C26—C27—C28—C29 | −2.3 (4) |
C6—C1—C2—O1 | 178.5 (1) | C27—C28—C29—N3 | 1.4 (4) |
C2—C1—C6—C5 | 1.3 (2) | N4—C30—C31—C32 | 0.8 (4) |
C2—C1—C7—O2 | −8.7 (2) | C30—C31—C32—C33 | 0.5 (4) |
C2—C1—C7—O3 | 172.0 (1) | C31—C32—C33—C34 | −0.8 (4) |
O1—C2—C3—C4 | −179.4 (2) | C32—C33—C34—N4 | −0.1 (3) |
Symmetry code: (i) −x, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H31···O7ii | 0.90 | 1.90 | 2.755 (7) | 158 |
O7—H32···O3 | 0.96 | 1.94 | 2.882 (4) | 168 |
O7—H33···O8 | 0.91 | 2.06 | 2.771 (7) | 135 |
O8—H30···O4 | 0.81 | 2.03 | 2.819 (7) | 165 |
O8—H34···O7 | 0.77 | 2.04 | 2.771 (7) | 157 |
O8—H36···O9 | 0.90 | 1.96 | 2.836 (7) | 163 |
O9—H35···O8 | 0.91 | 2.00 | 2.836 (7) | 153 |
O9—H37···O9iii | 0.78 | 2.08 | 2.855 (4) | 176 |
O9—H25···O11 | 0.80 | 1.98 | 2.756 (6) | 163 |
O10—H28···O4 | 0.85 | 2.06 | 2.902 (7) | 175 |
O10—H29···O9iii | 0.71 | 2.30 | 2.977 (7) | 161 |
O11—H26···O10 | 0.83 | 2.19 | 2.962 (7) | 155 |
O11—H27···O1iv | 0.75 | 1.97 | 2.721 (3) | 174 |
Symmetry codes: (ii) −x+1, −y+2, −z; (iii) −x+1, −y+1, −z+1; (iv) x, y, z+1. |
Experimental details
Crystal data |
Chemical formula | [Zn4(C7H6O3)4(C10H8N2)4]·10H2O |
Mr | 1610.85 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 12.633 (13), 12.735 (14), 13.29 (3) |
α, β, γ (°) | 61.60 (3), 66.23 (4), 63.22 (3) |
V (Å3) | 1630 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.54 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.718, 0.857 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 15951, 7327, 5512 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.066, 1.00 |
No. of reflections | 7327 |
No. of parameters | 462 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.30 |
Selected geometric parameters (Å, º) topZn1—O1 | 1.996 (5) | Zn2—O3 | 2.023 (5) |
Zn1—O2 | 2.008 (5) | Zn2—O4 | 1.969 (5) |
Zn1—N1 | 2.105 (5) | Zn2—O5 | 2.040 (5) |
Zn1—N2 | 2.154 (5) | Zn2—N3 | 2.181 (5) |
Zn1—O6i | 2.052 (5) | Zn2—N4 | 2.095 (5) |
| | | |
O1—Zn1—O2 | 89.42 (7) | O3—Zn2—O4 | 107.50 (7) |
O1—Zn1—N1 | 96.08 (6) | O3—Zn2—O5 | 96.02 (5) |
O1—Zn1—N2 | 171.73 (7) | O3—Zn2—N3 | 92.81 (5) |
O2—Zn1—N1 | 107.28 (8) | O3—Zn2—N4 | 133.48 (8) |
O2—Zn1—N2 | 97.02 (7) | O4—Zn2—O5 | 91.26 (7) |
N1—Zn1—N2 | 77.10 (6) | O4—Zn2—N3 | 92.82 (7) |
O1—Zn1—O6i | 88.49 (8) | O4—Zn2—N4 | 118.09 (6) |
O2—Zn1—O6i | 148.42 (6) | O5—Zn2—N3 | 168.69 (7) |
N1—Zn1—O6i | 104.3 (1) | O5—Zn2—N4 | 91.91 (6) |
N2—Zn1—O6i | 88.75 (7) | N3—Zn2—N4 | 76.86 (7) |
Symmetry code: (i) −x, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H31···O7ii | 0.90 | 1.90 | 2.755 (7) | 158 |
O7—H32···O3 | 0.96 | 1.94 | 2.882 (4) | 168 |
O7—H33···O8 | 0.91 | 2.06 | 2.771 (7) | 135 |
O8—H30···O4 | 0.81 | 2.03 | 2.819 (7) | 165 |
O8—H34···O7 | 0.77 | 2.04 | 2.771 (7) | 157 |
O8—H36···O9 | 0.90 | 1.96 | 2.836 (7) | 163 |
O9—H35···O8 | 0.91 | 2.00 | 2.836 (7) | 153 |
O9—H37···O9iii | 0.78 | 2.08 | 2.855 (4) | 176 |
O9—H25···O11 | 0.80 | 1.98 | 2.756 (6) | 163 |
O10—H28···O4 | 0.85 | 2.06 | 2.902 (7) | 175 |
O10—H29···O9iii | 0.71 | 2.30 | 2.977 (7) | 161 |
O11—H26···O10 | 0.83 | 2.19 | 2.962 (7) | 155 |
O11—H27···O1iv | 0.75 | 1.97 | 2.721 (3) | 174 |
Symmetry codes: (ii) −x+1, −y+2, −z; (iii) −x+1, −y+1, −z+1; (iv) x, y, z+1. |
Zinc is an important and beneficial element for human growth. It is well known that the ZnII atom can inhibit replication of rhinoviruses (Korant et al., 1974), and ZnII complexes have antibacterial and antiviral activities; for example, the complex of zinc acetate with erythromycin is used for acne therapy (Feucht et al., 1980). A large number of ZnII complexes have been investigated (Yaghi et al., 1997; Karanovic et al., 2002; Gronlund et al., 1995). One of the best ways to understand of the effective antimicrobial species is to gain knowledge about the structure and coordination geometry of the complexes.
Our interest in the coordination chemistry of salicylic acid stems from the fact that the carboxylate group plays an important role in interactions with metals that affect biological activity. Salicylic acid, one of metabolites of aspirin, has been used in dermatology as a fungicidal treatment (Diehl, 1996), and inhibits the oxidative stress (Sagone & Husney, 1987). In recent years, ligands with carboxylate groups have been employed in the design of novel complex frameworks. Many zinc compounds of this kind have been prepared. We report here the structure of the title compound, (I), which is a ternary zinc complex of salicylic acid and 2,2'-bipyridine.
In (I), there are two independent zinc centers, namely Zn1 and Zn2, and a tetranuclear unit is formed in which these atoms are related by a center of symmetry (Fig. 1). Each ZnII atom is bonded to two N atoms from a 2,2'-bipyridine moiety, one phenolate O atom and two carboxylate O atoms from two salicylate ligands. The two independent ZnII atoms show similar coordination geometry, i.e. distorted trigonal bipyramidal. Atoms Zn1, N1, O2 and O6i [symmetry code: (i) −x, 2 − y, −z] occupy the equatorial plane, and atoms O1 and N2 are in axial positions, with an O1—Zn1—N2 bond angle of 171.73 (7)°. Around atom Zn2, atoms N4, O3 and O4 form the trigonal plane, and atoms O5 and N3 occupy the axial positions, with an O5—Zn2—N3 angle of 168.69 (7)°. In the above geometry, atoms Zn1 and Zn2 deviate from the trigonal plane by 0.017 (3) Å (toward O1) and 0.111 (3) Å (toward N5), respectively.
The Zn1—O1(phenolate) bond distance in the axial direction is longer than the Zn2—O4(phenolate) bond in the equatorial plane (Table 1). This difference may be due to the Jahn–Teller effect of the d10 metal atom. Similarly, the Zn2—O5(carboxylate) bond in the axial direction is longer than the Zn1—O2(carboxylate) bond in the equatorial plane. In its role as bridging atom, atom O3 is connected to atom Zn2 more tightly than atom O6i is to Zn1, where both atom O3 and atom O6i are in the trigonal plane. This difference may be due to the bipyridine molecules being twisted to different degrees. In the bipyridine group in which atoms N1 and N2 are bonded to atom Zn1, the two pyridine rings are nearly coplanar, with a dihedral angle of only 3.6 (3)°. In the bipyridine group with N3 and N4 bonded to Zn2, the two ring planes intersect at 13.38 (6)° to each other.
The carboxylate group in each salicylate ligand bridges neighboring ZnII atoms to form a tetrameric cyclic complex containing four Zn atoms, four 2,2'-bipyridine molecules and four salicylate ligands in a syn–anti configuration (Clegg et al., 1988). Four repeating (–Zn—O—C—O–) units construct a hexadeca gear-wheel-shaped cyclic framework, which stabilizes the complex molecule. The structure is further stabilized by intramolecular π–π interactions between bipyridine ligands, with contact distances from 3.336 (5) Å (C15···C26) to 3.592 (5) Å (C21···C31). Intermolecular π–π interactions between the salicylate ligands of adjacent complexes are also present, with a mean distance of 3.564 (2) Å.
A linear array of three metal ions bridged by carboxylate ligands in syn–anti or syn–syn configurations was mentioned by Clegg et al. (1988). They reported the crystal structures of the complexes of general formula [MZn2(crot)6(base)2] (M = Zn, Mn, Co, Ni and Cd), which contained two monodentate monoatomic crotonate bridges. Moreover, a trinuclear linear array of ZnII atoms was also described, with formula [Zn3(CH3COO)6(py)2] or [Zn3(CH3COO)6(bppz)2] [bppz is 2,5-bis(2-pyridyl)pyrazine; Singh et al., 1997; Neels et al., 1999]. However, to our knowledge, the present structure of (I) is the first report that tetranuclear ZnII atoms are circularly arrayed with aromatic ligand species.
The average Zn—O(carboxylate) bond distance of (I) was compared with the similar circular wheel-shaped zinc(II) complexes of formula [Zn2(RCOO)4L2], in which two ZnII atoms are connected by benzoate ligands in a syn–syn configuration (Zeleňák et al., 2004). The value of 2.031 (3) Å in (I) is slightly shorter than the average values of 2.048 (8) Å {RCOO− is benzoate and L is [1-(3,4-dimethoxyphenyl)methyl]-6,7-dimethoxyisoquinoline}, 2.038 and 2.041 Å (RCOO− is acetate and L is pyridine), and 2.034, 2.039 and 2.042 Å (RCOO− is indomethacin and L is 1-methylpyrrolidinone, pyridine or dimethylacetamide), which are cited by Zeleňák et al. (2004).
The intramolecular Zn1···Zn2 [4.7249 (5) Å] and Zn1···Zn2i [4.5310 (3) Å] distances in (I) are much longer than those in the above-mentioned complexes. The longer Zn···Zn separations may be attributed to the further coordination of zinc with the phenolate O atom in each salicylate ligand. Moreover, the bridging mode of syn–anti configuration (Clegg et al., 1988) is reasonable to explain the further separation of each two zinc atoms. Compared with a previous example (Dana et al., 2003) containing the same ligand molecule (2,2'-bipyridine), the ZnII atom of this study seems to be more strongly coordinated to the N atoms, with Zn—N bond lengths ranging from 2.143 (5) to 2.185 (4) Å.
All of the water molecules participate in the formation of a characteristic hydrogen-bonding network including the O atoms of the salicylate ligands (Table 2). One of the water H atoms attached to O7, O8 and O9 were disordered over two sites, as the result of O7—H31···O7(1 − x, 2 − y, −z) and O9—H37···O9(1 − x, 1 − y, 1 − z) hydrogen bonds. The positional disorder of the water H atoms can be explained by assuming two possible configurations of the hydrogen-bonding network (Fig. 2).