metal-organic compounds
Bis(μ-4-amino-N-oxidobenzamide)bis[(4-amino-N-oxidobenzamide)aquacobalt] dihydrate
aHubei Key Laboratory for Processing and Application of Catalytic Materials, College of Chemical Engineering, Huanggang Normal University, Huanggang, 438000, People's Republic of China
*Correspondence e-mail: 1379489633@qq.com
The structure of the title compound, [Co2(C7H7N2O2)4(H2O)2]·2H2O, consists of a centrosymmetric binuclear [Co2(4-Apha)4(H2O)2] complex molecule (4-AphaH = 4-aminophenylhydroxamic acid), and two solvent water molecules. Each CoII cation is six coordinate, binding five oxygen atoms from three 4-Apha− ligands and a water molecule in a slightly distorted octahedral geometry. Two of the 4-Apha− ligands bridge two neighbouring CoII ions to form the binuclear complex. A three-dimensional network structure is generated by O—H⋯O, N—H⋯O, and N—H⋯N hydrogen bonds.
Keywords: crystal structure; binuclear structure; cobalt complex.
CCDC reference: 1508944
Structure description
The II cation bound to two bidentate Apha− ligands and a water molecule. The Co1—O4A and Co1A—O4 bonds, [symmetry code: (A) −x, −y, −z], generate the centrosymmetric binuclear [Co2(4-Apha)4(H2O)2] complex, Fig. 1. The structure also has two solvent water molecules. Two of the 4-Apha− ligands bridge the adjacent CoII nuclei in a μ2 fashion while the two others are bidentate, each coordinating to a single CoII atom. A water molecule also binds to the Co nucleus, completing the slightly distorted octahedral coordination geometry. The Co—O distances range from 2.0741 (15) to 2.1655 (15) Å, which agrees well with the values observed in related structures (Chen et al., 2014, 2015). The Co1⋯Co1A distance is 3.1727 (5) Å with a Co1—O4—Co1A angle of 97.44 (6)°.
of the title compound consists of a CoIn the crystal, N—H⋯O hydrogen bonds form between the NH2 groups of 4-Apha− ligands as donors and the O atoms of coordinated or solvate water molecules as acceptors, Table 1. N—H⋯N hydrogen bonds form between the NH groups of the 4-Apha− ligands and the NH2 groups of adjacent ligands. The coordinated and solvent water molecules act as both hydrogen-bond donors and acceptors, Table 1, and this multitude of classical hydrogen bonds combines to generate a three-dimensional supramolecular network structure, Fig. 2.
Synthesis and crystallization
A mixture of 4-AphaH (0.0150 g, 0.1 mmol), Co(CH3COO)2·4H2O (0.0249 g, 0.1 mmol) and H2O/ethanol (v/v = 1:1, 1 ml) was sealed in a 6 ml Pyrex tube. The tube was heated at 60°C for 3 d under autogenous pressure. Slow cooling of the resulting solution to room temperature gave brown prism-like crystals. The yield was 0.0128 g (64%, based on 4-AphaH).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
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Structural data
CCDC reference: 1508944
https://doi.org/10.1107/S2414314616016400/sj4066sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016400/sj4066Isup2.hkl
Data collection: APEX2 (Bruker, 2005); cell
APEX2 and SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Co2(C7H7N2O2)4(H2O)2]·2H2O | F(000) = 820 |
Mr = 794.51 | Dx = 1.643 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6382 (7) Å | Cell parameters from 2780 reflections |
b = 7.6075 (5) Å | θ = 2.9–27.8° |
c = 19.8693 (13) Å | µ = 1.11 mm−1 |
β = 93.219 (1)° | T = 296 K |
V = 1605.49 (18) Å3 | Prism, brown |
Z = 2 | 0.28 × 0.25 × 0.23 mm |
Bruker APEXII CCD diffractometer | 3123 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.033 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | θmax = 28.4°, θmin = 2.1° |
Tmin = 0.746, Tmax = 0.784 | h = −13→14 |
10770 measured reflections | k = −10→9 |
3984 independent reflections | l = −26→20 |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.086 | w = 1/[σ2(Fo2) + (0.0398P)2 + 1.2061P] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max < 0.001 |
3984 reflections | Δρmax = 0.59 e Å−3 |
226 parameters | Δρmin = −0.48 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.02073 (3) | 0.19515 (4) | 0.02648 (2) | 0.01957 (9) | |
O1 | 0.03470 (15) | 0.1624 (2) | 0.13027 (7) | 0.0276 (3) | |
O3 | 0.02485 (14) | 0.26232 (19) | −0.07576 (7) | 0.0243 (3) | |
O2 | 0.17079 (15) | 0.3594 (2) | 0.05349 (7) | 0.0271 (3) | |
N2 | 0.17829 (18) | 0.3738 (3) | 0.12290 (9) | 0.0280 (4) | |
H2 | 0.2269 | 0.4511 | 0.1423 | 0.034* | |
C8 | 0.12639 (19) | 0.2018 (3) | −0.17786 (10) | 0.0203 (4) | |
O5 | −0.11627 (15) | 0.39954 (19) | 0.04215 (7) | 0.0263 (3) | |
H5A | −0.1234 | 0.4649 | 0.0074 | 0.039* | |
H5B | −0.0824 | 0.4815 | 0.0659 | 0.032* | |
C14 | 0.10440 (19) | 0.1713 (3) | −0.10601 (10) | 0.0194 (4) | |
C7 | 0.1105 (2) | 0.2684 (3) | 0.15950 (10) | 0.0218 (4) | |
C4 | 0.1405 (2) | 0.2830 (3) | 0.37565 (11) | 0.0301 (5) | |
C12 | 0.0396 (2) | 0.2982 (3) | −0.28674 (10) | 0.0267 (5) | |
H12 | −0.0247 | 0.3530 | −0.3125 | 0.032* | |
C11 | 0.1431 (2) | 0.2297 (3) | −0.31795 (10) | 0.0239 (4) | |
C1 | 0.12380 (19) | 0.2772 (3) | 0.23381 (10) | 0.0210 (4) | |
C13 | 0.0319 (2) | 0.2851 (3) | −0.21764 (10) | 0.0242 (4) | |
H13 | −0.0372 | 0.3325 | −0.1974 | 0.029* | |
N1 | 0.1472 (2) | 0.2922 (4) | 0.44496 (10) | 0.0537 (7) | |
H1A | 0.2143 | 0.3404 | 0.4631 | 0.064* | |
H1B | 0.0937 | 0.2416 | 0.4655 | 0.064* | |
C6 | 0.0353 (2) | 0.1913 (3) | 0.27101 (10) | 0.0268 (5) | |
H6 | −0.0302 | 0.1307 | 0.2484 | 0.032* | |
C5 | 0.0426 (2) | 0.1937 (3) | 0.34055 (11) | 0.0326 (5) | |
H5 | −0.0199 | 0.1340 | 0.3650 | 0.039* | |
N3 | 0.1540 (2) | 0.2500 (3) | −0.38711 (9) | 0.0324 (4) | |
H3A | 0.0772 | 0.2451 | −0.4051 | 0.039* | |
H3B | 0.2181 | 0.2073 | −0.4059 | 0.039* | |
C10 | 0.2395 (2) | 0.1511 (3) | −0.27810 (11) | 0.0272 (5) | |
H10 | 0.3100 | 0.1073 | −0.2981 | 0.033* | |
C9 | 0.2312 (2) | 0.1375 (3) | −0.20921 (11) | 0.0255 (4) | |
H9 | 0.2964 | 0.0849 | −0.1833 | 0.031* | |
C2 | 0.2233 (2) | 0.3625 (3) | 0.26928 (11) | 0.0280 (5) | |
H2A | 0.2847 | 0.4187 | 0.2456 | 0.034* | |
C3 | 0.2321 (2) | 0.3649 (3) | 0.33879 (11) | 0.0314 (5) | |
H3 | 0.2996 | 0.4215 | 0.3613 | 0.038* | |
O6 | 0.4080 (2) | 0.2162 (4) | 0.02767 (13) | 0.0874 (9) | |
H6A | 0.3381 | 0.2481 | 0.0425 | 0.105* | |
H6B | 0.4146 | 0.3256 | 0.0198 | 0.105* | |
N4 | 0.16524 (16) | 0.0421 (2) | −0.07437 (8) | 0.0211 (4) | |
H4 | 0.2273 | −0.0089 | −0.0923 | 0.025* | |
O4 | 0.12774 (13) | −0.01100 (19) | −0.01141 (6) | 0.0209 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.02660 (16) | 0.01796 (14) | 0.01431 (13) | −0.00035 (11) | 0.00260 (10) | −0.00054 (10) |
O1 | 0.0365 (9) | 0.0277 (8) | 0.0183 (7) | −0.0102 (7) | −0.0017 (6) | −0.0001 (6) |
O3 | 0.0322 (8) | 0.0240 (7) | 0.0171 (7) | 0.0064 (6) | 0.0044 (6) | 0.0008 (6) |
O2 | 0.0339 (9) | 0.0311 (8) | 0.0165 (7) | −0.0052 (7) | 0.0030 (6) | 0.0001 (6) |
N2 | 0.0336 (10) | 0.0317 (10) | 0.0188 (9) | −0.0110 (8) | 0.0008 (7) | −0.0033 (7) |
C8 | 0.0241 (10) | 0.0198 (10) | 0.0172 (9) | −0.0028 (8) | 0.0035 (7) | 0.0008 (8) |
O5 | 0.0352 (9) | 0.0211 (7) | 0.0231 (8) | 0.0015 (6) | 0.0055 (6) | 0.0016 (6) |
C14 | 0.0226 (10) | 0.0187 (10) | 0.0171 (9) | −0.0031 (8) | 0.0016 (7) | −0.0011 (7) |
C7 | 0.0248 (10) | 0.0210 (10) | 0.0196 (10) | 0.0012 (8) | 0.0006 (8) | −0.0010 (8) |
C4 | 0.0310 (12) | 0.0380 (13) | 0.0206 (10) | 0.0021 (10) | −0.0029 (9) | −0.0011 (9) |
C12 | 0.0271 (11) | 0.0321 (12) | 0.0210 (10) | 0.0018 (9) | 0.0024 (8) | 0.0057 (9) |
C11 | 0.0287 (11) | 0.0253 (11) | 0.0183 (10) | −0.0047 (9) | 0.0058 (8) | 0.0010 (8) |
C1 | 0.0231 (10) | 0.0221 (11) | 0.0177 (9) | 0.0004 (8) | −0.0012 (7) | −0.0014 (8) |
C13 | 0.0233 (11) | 0.0280 (11) | 0.0220 (10) | 0.0030 (9) | 0.0059 (8) | 0.0013 (8) |
N1 | 0.0495 (14) | 0.093 (2) | 0.0175 (10) | −0.0225 (14) | −0.0037 (9) | −0.0022 (11) |
C6 | 0.0274 (11) | 0.0310 (11) | 0.0214 (10) | −0.0051 (9) | −0.0030 (8) | −0.0029 (9) |
C5 | 0.0322 (12) | 0.0444 (14) | 0.0212 (10) | −0.0109 (11) | 0.0009 (9) | 0.0019 (10) |
N3 | 0.0341 (11) | 0.0459 (12) | 0.0177 (9) | −0.0006 (9) | 0.0065 (8) | 0.0020 (8) |
C10 | 0.0262 (11) | 0.0305 (12) | 0.0258 (11) | 0.0030 (9) | 0.0087 (9) | 0.0005 (9) |
C9 | 0.0261 (11) | 0.0276 (11) | 0.0230 (10) | 0.0050 (9) | 0.0025 (8) | 0.0030 (9) |
C2 | 0.0258 (11) | 0.0341 (12) | 0.0241 (11) | −0.0061 (9) | 0.0018 (8) | −0.0017 (9) |
C3 | 0.0264 (12) | 0.0399 (13) | 0.0270 (11) | −0.0069 (10) | −0.0061 (9) | −0.0062 (10) |
O6 | 0.0394 (13) | 0.137 (3) | 0.0859 (18) | −0.0009 (15) | 0.0076 (12) | −0.0290 (18) |
N4 | 0.0234 (9) | 0.0241 (9) | 0.0163 (8) | 0.0018 (7) | 0.0046 (6) | 0.0012 (7) |
O4 | 0.0279 (8) | 0.0221 (7) | 0.0129 (6) | 0.0004 (6) | 0.0023 (5) | 0.0021 (5) |
Co1—O2 | 2.0741 (15) | C11—N3 | 1.394 (3) |
Co1—O1 | 2.0742 (14) | C11—C10 | 1.395 (3) |
Co1—O3 | 2.0975 (14) | C1—C6 | 1.392 (3) |
Co1—O4 | 2.1021 (14) | C1—C2 | 1.398 (3) |
Co1—O4i | 2.1198 (15) | C13—H13 | 0.9300 |
Co1—O5 | 2.1655 (15) | N1—H1A | 0.8628 |
O1—C7 | 1.259 (2) | N1—H1B | 0.8150 |
O3—C14 | 1.270 (2) | C6—C5 | 1.380 (3) |
O2—N2 | 1.381 (2) | C6—H6 | 0.9300 |
N2—C7 | 1.323 (3) | C5—H5 | 0.9600 |
N2—H2 | 0.8600 | N3—H3A | 0.8745 |
C8—C9 | 1.396 (3) | N3—H3B | 0.8598 |
C8—C13 | 1.396 (3) | C10—C9 | 1.380 (3) |
C8—C14 | 1.478 (3) | C10—H10 | 0.9300 |
O5—H5A | 0.8500 | C9—H9 | 0.9300 |
O5—H5B | 0.8500 | C2—C3 | 1.379 (3) |
C14—N4 | 1.317 (3) | C2—H2A | 0.9300 |
C7—C1 | 1.477 (3) | C3—H3 | 0.9300 |
C4—N1 | 1.377 (3) | O6—H6A | 0.8499 |
C4—C5 | 1.397 (3) | O6—H6B | 0.8501 |
C4—C3 | 1.398 (3) | N4—O4 | 1.394 (2) |
C12—C13 | 1.384 (3) | N4—H4 | 0.8600 |
C12—C11 | 1.395 (3) | O4—Co1i | 2.1199 (15) |
C12—H12 | 0.9300 | ||
O2—Co1—O1 | 78.69 (6) | N3—C11—C12 | 120.6 (2) |
O2—Co1—O3 | 92.65 (6) | C10—C11—C12 | 118.77 (19) |
O1—Co1—O3 | 171.07 (6) | C6—C1—C2 | 117.76 (18) |
O2—Co1—O4 | 96.76 (6) | C6—C1—C7 | 118.68 (18) |
O1—Co1—O4 | 104.87 (6) | C2—C1—C7 | 123.52 (19) |
O3—Co1—O4 | 78.10 (5) | C12—C13—C8 | 120.90 (19) |
O2—Co1—O4i | 172.41 (5) | C12—C13—H13 | 119.5 |
O1—Co1—O4i | 94.15 (5) | C8—C13—H13 | 119.5 |
O3—Co1—O4i | 94.60 (6) | C4—N1—H1A | 115.7 |
O4—Co1—O4i | 82.56 (6) | C4—N1—H1B | 118.6 |
O2—Co1—O5 | 92.56 (6) | H1A—N1—H1B | 125.2 |
O1—Co1—O5 | 87.39 (6) | C5—C6—C1 | 121.6 (2) |
O3—Co1—O5 | 90.87 (5) | C5—C6—H6 | 119.2 |
O4—Co1—O5 | 165.83 (5) | C1—C6—H6 | 119.2 |
O4i—Co1—O5 | 89.58 (6) | C6—C5—C4 | 120.3 (2) |
C7—O1—Co1 | 112.97 (13) | C6—C5—H5 | 120.0 |
C14—O3—Co1 | 112.10 (12) | C4—C5—H5 | 119.7 |
N2—O2—Co1 | 107.85 (11) | C11—N3—H3A | 105.8 |
C7—N2—O2 | 119.88 (17) | C11—N3—H3B | 119.9 |
C7—N2—H2 | 120.1 | H3A—N3—H3B | 123.5 |
O2—N2—H2 | 120.1 | C9—C10—C11 | 120.6 (2) |
C9—C8—C13 | 118.33 (18) | C9—C10—H10 | 119.7 |
C9—C8—C14 | 123.36 (18) | C11—C10—H10 | 119.7 |
C13—C8—C14 | 118.04 (18) | C10—C9—C8 | 120.9 (2) |
Co1—O5—H5A | 109.5 | C10—C9—H9 | 119.6 |
Co1—O5—H5B | 109.8 | C8—C9—H9 | 119.6 |
H5A—O5—H5B | 92.2 | C3—C2—C1 | 121.2 (2) |
O3—C14—N4 | 120.23 (18) | C3—C2—H2A | 119.4 |
O3—C14—C8 | 121.16 (18) | C1—C2—H2A | 119.4 |
N4—C14—C8 | 118.54 (18) | C2—C3—C4 | 120.6 (2) |
O1—C7—N2 | 119.28 (18) | C2—C3—H3 | 119.7 |
O1—C7—C1 | 120.88 (18) | C4—C3—H3 | 119.7 |
N2—C7—C1 | 119.83 (18) | H6A—O6—H6B | 82.3 |
N1—C4—C5 | 121.3 (2) | C14—N4—O4 | 119.12 (17) |
N1—C4—C3 | 120.2 (2) | C14—N4—H4 | 120.4 |
C5—C4—C3 | 118.5 (2) | O4—N4—H4 | 120.4 |
C13—C12—C11 | 120.4 (2) | N4—O4—Co1 | 107.06 (11) |
C13—C12—H12 | 119.8 | N4—O4—Co1i | 108.24 (10) |
C11—C12—H12 | 119.8 | Co1—O4—Co1i | 97.44 (6) |
N3—C11—C10 | 120.5 (2) | ||
Co1—O2—N2—C7 | 10.8 (2) | C2—C1—C6—C5 | 1.9 (3) |
Co1—O3—C14—N4 | 5.4 (2) | C7—C1—C6—C5 | 179.7 (2) |
Co1—O3—C14—C8 | −177.58 (14) | C1—C6—C5—C4 | −0.3 (4) |
C9—C8—C14—O3 | 164.1 (2) | N1—C4—C5—C6 | 177.8 (2) |
C13—C8—C14—O3 | −21.9 (3) | C3—C4—C5—C6 | −1.7 (4) |
C9—C8—C14—N4 | −18.8 (3) | N3—C11—C10—C9 | 177.3 (2) |
C13—C8—C14—N4 | 155.16 (19) | C12—C11—C10—C9 | 1.5 (3) |
Co1—O1—C7—N2 | −5.6 (3) | C11—C10—C9—C8 | 0.1 (3) |
Co1—O1—C7—C1 | 173.90 (15) | C13—C8—C9—C10 | −2.0 (3) |
O2—N2—C7—O1 | −3.8 (3) | C14—C8—C9—C10 | 171.9 (2) |
O2—N2—C7—C1 | 176.66 (18) | C6—C1—C2—C3 | −1.4 (3) |
C13—C12—C11—N3 | −177.0 (2) | C7—C1—C2—C3 | −179.1 (2) |
C13—C12—C11—C10 | −1.2 (3) | C1—C2—C3—C4 | −0.6 (4) |
O1—C7—C1—C6 | −11.9 (3) | N1—C4—C3—C2 | −177.3 (2) |
N2—C7—C1—C6 | 167.6 (2) | C5—C4—C3—C2 | 2.2 (4) |
O1—C7—C1—C2 | 165.8 (2) | O3—C14—N4—O4 | 9.8 (3) |
N2—C7—C1—C2 | −14.7 (3) | C8—C14—N4—O4 | −167.29 (17) |
C11—C12—C13—C8 | −0.7 (3) | C14—N4—O4—Co1 | −18.85 (19) |
C9—C8—C13—C12 | 2.3 (3) | C14—N4—O4—Co1i | 85.25 (17) |
C14—C8—C13—C12 | −172.0 (2) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O2ii | 0.85 | 1.85 | 2.681 (2) | 164 |
N1—H1B···O6iii | 0.81 | 2.41 | 3.106 (3) | 144 |
N1—H1A···O4iv | 0.86 | 2.20 | 3.060 (3) | 174 |
O5—H5B···O3ii | 0.85 | 2.05 | 2.817 (2) | 150 |
N3—H3A···O6v | 0.87 | 2.20 | 3.047 (3) | 163 |
N3—H3B···O5vi | 0.86 | 2.24 | 3.103 (2) | 178 |
O6—H6A···O2 | 0.85 | 1.99 | 2.822 (3) | 164 |
O6—H6A···N2 | 0.85 | 2.58 | 3.392 (3) | 160 |
N4—H4···N3vii | 0.86 | 2.28 | 3.063 (3) | 152 |
Symmetry codes: (ii) −x, −y+1, −z; (iii) x−1/2, −y+1/2, z+1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) x−1/2, −y+1/2, z−1/2; (vi) x+1/2, −y+1/2, z−1/2; (vii) −x+1/2, y−1/2, −z−1/2. |
Acknowledgements
This research was supported by Doctoral Fund Project of Huanggang Normal University (grant No. 2015001803).
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