metal-organic compounds
Bis(1,10-phenanthroline-κ2N,N′)(sulfato-O)copper(II) butane-2,3-diol monosolvate
aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
*Correspondence e-mail: zklong76@163.com
The title compound, [Cu(SO4)(C12H8N2)2]·C4H10O2, is comprised of neutral monomeric complex and butane-2,3-diol solvent molecules. In the complex, the CuII ion is in a distorted square-pyramidal coordination environment defined by four N atoms from two chelating 1,10-phenanthroline ligands and one O atom from a monodentate sulfate anion; the O atom is at the apex. The two chelating N2C2 groups subtend a dihedral angle of 85.8 (4)°. In the crystal, the neutral monomeric complex and butane-2,3-diol solvent molecules are held together by O—H⋯O hydrogen bonding, which leads to additional stabilization of the structure. The presence of in the structure suggests the higher symmetry C2/c, but attempts to refine the structure in this resulted in an unsatisfactory model and high R and wR values. The sulfate anion is disordered over two sets of sites with occupancies of 0.55 (1) and 0.45 (1).
Related literature
For the ethane-1,2-diol solvate of the title complex, see: Zhong (2011a), for the propane-1,2-diol solvate, see: Zhong (2011b) and for the propane-1,3-diol solvate, see: Zhong (2012). For related structures of transition metal complexes with a sulfate anion, see: Wang & Zhong (2011); Zhong & Ni (2012); Cui et al. (2010); Lu et al. (2006).
Experimental
Crystal data
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Data collection: CrystalClear (Rigaku, 2007); cell CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
https://doi.org/10.1107/S1600536812049951/bq2380sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049951/bq2380Isup2.hkl
The single crystals of (I) suitable to X-ray analysis were obtained by 0.2 mmol phen, 0.1 mmol CuSO4.5H2O, 2.0 ml propane-1,3-diol and 1.0 ml water mixed and placed in a thick Pyrex tube, which was sealed and heated to 453 K for 72 h.
The H atoms of phen were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms of propane-1,3-diol were placed in geometrically idealized positions and refined as riding atoms, with C—H(CH3) = 0.96 Å, C—H(CH) = 0.98 Å and O—H = 0.82 Å; Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O). The presence of pseudo-symmetry in the structure suggests a higher symmetry
C2/c. But attempts to refine the structure in the C2/c resulted in an unsatisfactory model and high R and wR values. Hence the requirement to solve in Cc. The reported was refined as s full least-squares and obtained by TWIN/BASF procedure in SHELXL (Sheldrick, 2008).In the past few years, we have unexpectedly obtained and characterized some transition metal complexes with bidentate-chelating sulfate auxiliary ligand via alcohol-solvothermal reaction during attempts to synthesize mixed-ligand coordination polymers, such as cobalt complex (Wang & Zhong, 2011), nickel complex (Zhong & Ni, 2012), zinc complex (Cui et al., 2010), cadmium complex (Lu et al., 2006). The title compound [CuSO4(C12H8N2)2].C4H10O2, (I), was obtained by the similar alcohol-solvothermal reaction and its
has not hitherto been reported.The X-ray diffraction experiment found that the title complex is isotypical to the previously reported [CuSO4(C12H8N2)2].C2H6O2 (Zhong, 2011a), (II), [CuSO4(C12H8N2)2].CH2OHCHOHCH3 (Zhong, 2011b), (III), and [CuSO4(C12H8N2)2].CH2OHCH2CH2OH (Zhong, 2012), (IV). The geometry of the phenanthroline and sulfate ligands are in good agreement with those reported in the (II), (III) and (IV). The CuII metal ion is five-coordinated by four N atoms from two chelating phen ligands and an O atoms from a monodentate sulfate ligand, resulting in a distorted CuN4O square-pyramidal environment. The N1, N2, N3 and N4 atoms comprise a square, and the O1 atom site the apex of a square pyramid surrounding each metal atom (Fig 1). The dihedral angle of the two chelating N2C2 groups is 85.8 (4)°, which is larger than those reported in (II) [71.1 (2)°], (III) [84.9 (4)°] and (IV) [71.10 (15) Å], respectively. The Cu—O bond distance [1.922 (11) Å - 1.944 (10) Å], the Cu—N bond distance [2.000 (7) - 2.186 (7) Å], and the N—Cu—N bite angle [79.8 (3) - 81.6 (3)°] are comparable to those observed in (II), (III) and (IV) (Table 1).
In the crystal, the sulfate group is disordered over two positions with refined site occupancies of 0.55 (1) and 0.45 (1), and is hydrogen bonded to the solvent butane-2,3-diol molecule (Table 2 & Fig. 1).
For the ethane-1,2-diol solvate of the title complex, see: Zhong (2011a), for the propane-1,2-diol solvate, see: Zhong (2011b) and for the propane-1,3-diol solvate, see: Zhong (2012). For related structures of transition metal complexes with a sulfate anion, see: Wang & Zhong (2011); Zhong & Ni (2012); Cui et al. (2010); Lu et al. (2006).
Data collection: CrystalClear (Rigaku, 2007); cell
CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure showing the atom-numbering scheme and with displacement ellipsoids drawn at the 35% probability level. Hydrogen bonds O—H···O are shown as dashed lines. |
[Cu(SO4)(C12H8N2)2]·C4H10O2 | F(000) = 1260 |
Mr = 610.13 | Dx = 1.600 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 5509 reflections |
a = 17.352 (4) Å | θ = 3.2–27.5° |
b = 13.070 (3) Å | µ = 1.00 mm−1 |
c = 13.444 (3) Å | T = 223 K |
β = 123.84 (3)° | Block, green |
V = 2532.4 (13) Å3 | 0.32 × 0.27 × 0.21 mm |
Z = 4 |
Rigaku Mercury CCD diffractometer | 4178 independent reflections |
Radiation source: fine-focus sealed tube | 3542 reflections with I > 2σ(I) |
Graphite Monochromator monochromator | Rint = 0.026 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ω scans | h = −15→22 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −16→15 |
Tmin = 0.741, Tmax = 0.818 | l = −17→16 |
7154 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.002 |
4178 reflections | Δρmax = 0.60 e Å−3 |
408 parameters | Δρmin = −0.53 e Å−3 |
124 restraints | Absolute structure: Flack (1983), 1317 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.55 (2) |
[Cu(SO4)(C12H8N2)2]·C4H10O2 | V = 2532.4 (13) Å3 |
Mr = 610.13 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 17.352 (4) Å | µ = 1.00 mm−1 |
b = 13.070 (3) Å | T = 223 K |
c = 13.444 (3) Å | 0.32 × 0.27 × 0.21 mm |
β = 123.84 (3)° |
Rigaku Mercury CCD diffractometer | 4178 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 3542 reflections with I > 2σ(I) |
Tmin = 0.741, Tmax = 0.818 | Rint = 0.026 |
7154 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.135 | Δρmax = 0.60 e Å−3 |
S = 0.99 | Δρmin = −0.53 e Å−3 |
4178 reflections | Absolute structure: Flack (1983), 1317 Friedel pairs |
408 parameters | Absolute structure parameter: 0.55 (2) |
124 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.26519 (10) | 0.30074 (3) | 0.29387 (13) | 0.02436 (16) | |
S1 | 0.2748 (3) | 0.5417 (4) | 0.2771 (4) | 0.0265 (13) | 0.547 (12) |
S1' | 0.2569 (3) | 0.5422 (4) | 0.3106 (4) | 0.0170 (14) | 0.453 (12) |
O1 | 0.2897 (10) | 0.4419 (8) | 0.3416 (12) | 0.043 (3) | 0.547 (12) |
O1' | 0.2430 (10) | 0.4435 (7) | 0.2448 (11) | 0.027 (3) | 0.453 (12) |
O2 | 0.2706 (8) | 0.5188 (9) | 0.1677 (9) | 0.037 (3) | 0.547 (12) |
O2' | 0.2653 (8) | 0.5225 (8) | 0.4213 (8) | 0.023 (3) | 0.453 (12) |
O3 | 0.1922 (11) | 0.5995 (16) | 0.2536 (19) | 0.041 (5) | 0.547 (12) |
O3' | 0.3442 (10) | 0.5860 (12) | 0.3305 (17) | 0.021 (3) | 0.453 (12) |
O4 | 0.3552 (9) | 0.6066 (10) | 0.3586 (11) | 0.021 (3) | 0.547 (12) |
O4' | 0.1754 (13) | 0.6044 (16) | 0.2259 (16) | 0.027 (5) | 0.453 (12) |
O5 | 0.2174 (4) | 0.7813 (3) | 0.3686 (4) | 0.0442 (11) | |
H5B | 0.2079 | 0.7299 | 0.3282 | 0.066* | |
O6 | 0.3460 (5) | 0.8062 (5) | 0.2956 (8) | 0.096 (3) | |
H6 | 0.3455 | 0.7532 | 0.3279 | 0.144* | |
N1 | 0.3506 (5) | 0.2822 (5) | 0.2394 (6) | 0.0244 (14) | |
N2 | 0.3706 (5) | 0.2068 (4) | 0.4426 (6) | 0.0236 (15) | |
N3 | 0.1647 (5) | 0.2096 (5) | 0.1528 (5) | 0.0220 (14) | |
N4 | 0.1742 (5) | 0.2848 (5) | 0.3410 (6) | 0.0232 (14) | |
C1 | 0.3444 (6) | 0.3269 (7) | 0.1484 (8) | 0.0282 (17) | |
H1A | 0.3000 | 0.3772 | 0.1053 | 0.034* | |
C2 | 0.4087 (7) | 0.2967 (7) | 0.1148 (9) | 0.038 (2) | |
H2A | 0.4052 | 0.3285 | 0.0505 | 0.046* | |
C3 | 0.4728 (6) | 0.2229 (7) | 0.1768 (8) | 0.0375 (18) | |
H3A | 0.5100 | 0.2000 | 0.1517 | 0.045* | |
C4 | 0.4826 (7) | 0.1813 (8) | 0.2797 (9) | 0.038 (2) | |
C5 | 0.5554 (7) | 0.1082 (5) | 0.3559 (8) | 0.032 (2) | |
H5A | 0.5958 | 0.0858 | 0.3355 | 0.039* | |
C6 | 0.5640 (6) | 0.0738 (6) | 0.4535 (8) | 0.036 (2) | |
H6A | 0.6112 | 0.0273 | 0.5009 | 0.043* | |
C7 | 0.5031 (6) | 0.1051 (6) | 0.4909 (8) | 0.0281 (18) | |
C8 | 0.5105 (7) | 0.0762 (5) | 0.5960 (9) | 0.032 (2) | |
H8A | 0.5567 | 0.0309 | 0.6490 | 0.038* | |
C9 | 0.4489 (6) | 0.1151 (7) | 0.6208 (8) | 0.038 (2) | |
H9A | 0.4540 | 0.0982 | 0.6915 | 0.046* | |
C10 | 0.3805 (6) | 0.1789 (7) | 0.5391 (7) | 0.0277 (18) | |
H10A | 0.3384 | 0.2035 | 0.5554 | 0.033* | |
C11 | 0.4289 (5) | 0.1747 (6) | 0.4123 (7) | 0.0270 (18) | |
C12 | 0.4198 (5) | 0.2096 (5) | 0.3075 (7) | 0.0183 (15) | |
C13 | 0.1532 (6) | 0.1797 (6) | 0.0470 (7) | 0.0293 (19) | |
H13A | 0.1933 | 0.2046 | 0.0273 | 0.035* | |
C14 | 0.0804 (6) | 0.1109 (6) | −0.0329 (7) | 0.032 (2) | |
H14A | 0.0736 | 0.0927 | −0.1043 | 0.039* | |
C15 | 0.0208 (6) | 0.0714 (7) | −0.0069 (8) | 0.033 (2) | |
H15A | −0.0248 | 0.0245 | −0.0575 | 0.040* | |
C16 | 0.0311 (6) | 0.1046 (6) | 0.1007 (8) | 0.0284 (18) | |
C17 | −0.0306 (6) | 0.0719 (6) | 0.1307 (7) | 0.035 (2) | |
H17A | −0.0777 | 0.0261 | 0.0808 | 0.042* | |
C18 | −0.0226 (6) | 0.1067 (7) | 0.2327 (8) | 0.037 (2) | |
H18A | −0.0630 | 0.0823 | 0.2521 | 0.045* | |
C19 | 0.0465 (5) | 0.1794 (6) | 0.3089 (6) | 0.0215 (15) | |
C20 | 0.0547 (6) | 0.2284 (8) | 0.4077 (7) | 0.0346 (18) | |
H20A | 0.0129 | 0.2132 | 0.4283 | 0.042* | |
C21 | 0.1237 (7) | 0.2981 (6) | 0.4733 (9) | 0.036 (2) | |
H21A | 0.1324 | 0.3270 | 0.5420 | 0.043* | |
C22 | 0.1777 (6) | 0.3233 (7) | 0.4369 (6) | 0.0324 (19) | |
H22A | 0.2228 | 0.3726 | 0.4816 | 0.039* | |
C23 | 0.1077 (6) | 0.2146 (6) | 0.2782 (7) | 0.0281 (18) | |
C24 | 0.1010 (5) | 0.1709 (6) | 0.1728 (6) | 0.0194 (15) | |
C25 | 0.2642 (9) | 0.9498 (6) | 0.4054 (10) | 0.059 (3) | |
H25A | 0.2309 | 0.9594 | 0.4425 | 0.089* | |
H25B | 0.2663 | 1.0133 | 0.3711 | 0.089* | |
H25C | 0.3262 | 0.9275 | 0.4643 | 0.089* | |
C26 | 0.2142 (7) | 0.8676 (6) | 0.3052 (8) | 0.053 (2) | |
H26A | 0.1498 | 0.8877 | 0.2462 | 0.063* | |
C27 | 0.2654 (7) | 0.8516 (5) | 0.2453 (8) | 0.058 (2) | |
H27A | 0.2238 | 0.8072 | 0.1771 | 0.069* | |
C28 | 0.2703 (13) | 0.9468 (10) | 0.1881 (16) | 0.101 (5) | |
H28A | 0.3013 | 0.9326 | 0.1487 | 0.151* | |
H28B | 0.3040 | 0.9982 | 0.2482 | 0.151* | |
H28C | 0.2086 | 0.9709 | 0.1304 | 0.151* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0249 (3) | 0.0219 (2) | 0.0321 (3) | −0.0008 (5) | 0.0194 (2) | −0.0011 (5) |
S1 | 0.026 (3) | 0.027 (2) | 0.029 (2) | −0.0005 (17) | 0.017 (2) | −0.0049 (19) |
S1' | 0.017 (3) | 0.014 (2) | 0.017 (2) | −0.0005 (17) | 0.008 (2) | −0.0029 (18) |
O1 | 0.054 (5) | 0.037 (5) | 0.044 (5) | −0.006 (3) | 0.031 (4) | 0.005 (3) |
O1' | 0.045 (5) | 0.009 (4) | 0.029 (5) | 0.001 (3) | 0.023 (4) | 0.004 (3) |
O2 | 0.043 (5) | 0.049 (5) | 0.029 (4) | −0.002 (3) | 0.025 (3) | −0.002 (3) |
O2' | 0.022 (4) | 0.024 (4) | 0.015 (4) | −0.009 (3) | 0.006 (3) | 0.001 (3) |
O3 | 0.034 (6) | 0.042 (6) | 0.047 (7) | 0.000 (4) | 0.022 (4) | 0.005 (4) |
O3' | 0.017 (5) | 0.016 (5) | 0.028 (5) | −0.001 (3) | 0.011 (4) | −0.003 (4) |
O4 | 0.017 (4) | 0.019 (5) | 0.021 (5) | 0.004 (3) | 0.007 (3) | −0.004 (3) |
O4' | 0.029 (6) | 0.028 (6) | 0.024 (6) | 0.002 (4) | 0.016 (4) | 0.003 (4) |
O5 | 0.066 (3) | 0.038 (2) | 0.041 (2) | 0.001 (2) | 0.037 (2) | −0.0007 (19) |
O6 | 0.076 (4) | 0.060 (4) | 0.188 (7) | 0.039 (3) | 0.096 (5) | 0.071 (4) |
N1 | 0.023 (3) | 0.026 (3) | 0.027 (3) | −0.003 (3) | 0.016 (3) | −0.002 (3) |
N2 | 0.027 (3) | 0.017 (3) | 0.038 (4) | −0.001 (2) | 0.025 (3) | 0.000 (2) |
N3 | 0.019 (3) | 0.026 (3) | 0.011 (3) | 0.002 (2) | 0.002 (2) | −0.001 (2) |
N4 | 0.022 (3) | 0.027 (3) | 0.019 (3) | −0.008 (3) | 0.010 (3) | −0.007 (3) |
C1 | 0.033 (4) | 0.026 (3) | 0.047 (5) | 0.009 (3) | 0.036 (4) | 0.008 (3) |
C2 | 0.034 (4) | 0.055 (5) | 0.035 (4) | 0.002 (3) | 0.025 (4) | −0.009 (3) |
C3 | 0.038 (4) | 0.046 (4) | 0.048 (4) | 0.005 (3) | 0.035 (4) | −0.011 (4) |
C4 | 0.043 (5) | 0.035 (4) | 0.048 (5) | 0.003 (4) | 0.033 (4) | −0.007 (3) |
C5 | 0.034 (5) | 0.017 (3) | 0.044 (5) | 0.008 (3) | 0.021 (4) | −0.004 (3) |
C6 | 0.023 (4) | 0.025 (4) | 0.054 (5) | 0.009 (3) | 0.018 (4) | −0.016 (3) |
C7 | 0.023 (4) | 0.019 (3) | 0.031 (4) | 0.007 (3) | 0.009 (3) | 0.007 (3) |
C8 | 0.029 (5) | 0.015 (3) | 0.033 (5) | −0.002 (3) | 0.006 (4) | 0.008 (3) |
C9 | 0.034 (5) | 0.053 (5) | 0.039 (5) | −0.006 (4) | 0.028 (4) | 0.001 (4) |
C10 | 0.026 (4) | 0.034 (4) | 0.026 (4) | −0.009 (4) | 0.016 (4) | −0.014 (3) |
C11 | 0.019 (4) | 0.022 (3) | 0.031 (4) | −0.006 (3) | 0.008 (3) | −0.004 (3) |
C12 | 0.013 (3) | 0.016 (3) | 0.034 (4) | 0.001 (3) | 0.018 (3) | −0.002 (3) |
C13 | 0.031 (4) | 0.030 (3) | 0.026 (4) | −0.001 (4) | 0.015 (4) | −0.013 (3) |
C14 | 0.039 (5) | 0.020 (3) | 0.020 (4) | 0.001 (3) | 0.005 (4) | −0.009 (3) |
C15 | 0.021 (5) | 0.043 (4) | 0.028 (4) | −0.005 (4) | 0.009 (4) | −0.003 (4) |
C16 | 0.022 (4) | 0.030 (4) | 0.029 (4) | 0.007 (3) | 0.012 (3) | 0.015 (4) |
C17 | 0.026 (4) | 0.036 (4) | 0.030 (4) | 0.002 (3) | 0.007 (4) | −0.013 (3) |
C18 | 0.022 (4) | 0.060 (5) | 0.034 (5) | −0.005 (4) | 0.018 (4) | 0.009 (4) |
C19 | 0.009 (3) | 0.033 (3) | 0.020 (3) | 0.005 (3) | 0.007 (3) | 0.007 (3) |
C20 | 0.029 (4) | 0.051 (4) | 0.019 (3) | 0.012 (3) | 0.010 (3) | 0.005 (3) |
C21 | 0.044 (5) | 0.036 (4) | 0.033 (4) | 0.007 (3) | 0.025 (4) | −0.013 (3) |
C22 | 0.024 (4) | 0.039 (4) | 0.017 (4) | −0.001 (3) | 0.001 (3) | −0.006 (3) |
C23 | 0.033 (4) | 0.023 (4) | 0.019 (4) | 0.001 (3) | 0.008 (3) | 0.003 (3) |
C24 | 0.026 (4) | 0.017 (3) | 0.019 (3) | 0.000 (3) | 0.015 (3) | 0.002 (3) |
C25 | 0.104 (6) | 0.036 (4) | 0.074 (5) | −0.044 (4) | 0.071 (5) | −0.042 (4) |
C26 | 0.070 (5) | 0.046 (4) | 0.069 (5) | 0.016 (4) | 0.055 (5) | 0.009 (4) |
C27 | 0.104 (7) | 0.031 (3) | 0.082 (6) | 0.038 (4) | 0.079 (6) | 0.028 (4) |
C28 | 0.149 (10) | 0.089 (8) | 0.110 (8) | 0.024 (7) | 0.100 (7) | 0.021 (6) |
Cu1—O1 | 1.922 (11) | C7—C11 | 1.445 (11) |
Cu1—O1' | 1.944 (10) | C8—C9 | 1.382 (14) |
Cu1—N1 | 2.000 (7) | C8—H8A | 0.9300 |
Cu1—N4 | 2.014 (7) | C9—C10 | 1.364 (12) |
Cu1—N3 | 2.091 (6) | C9—H9A | 0.9300 |
Cu1—N2 | 2.186 (7) | C10—H10A | 0.9300 |
S1—O2 | 1.463 (10) | C11—C12 | 1.404 (12) |
S1—O4 | 1.471 (12) | C13—C14 | 1.430 (11) |
S1—O3 | 1.490 (15) | C13—H13A | 0.9300 |
S1—O1 | 1.506 (11) | C14—C15 | 1.365 (14) |
S1'—O2' | 1.435 (10) | C14—H14A | 0.9300 |
S1'—O4' | 1.470 (15) | C15—C16 | 1.423 (14) |
S1'—O3' | 1.498 (14) | C15—H15A | 0.9300 |
S1'—O1' | 1.507 (10) | C16—C24 | 1.361 (12) |
O5—C26 | 1.396 (9) | C16—C17 | 1.405 (12) |
O5—H5B | 0.8200 | C17—C18 | 1.377 (12) |
O6—C27 | 1.307 (9) | C17—H17A | 0.9300 |
O6—H6 | 0.8200 | C18—C19 | 1.423 (12) |
N1—C1 | 1.306 (10) | C18—H18A | 0.9300 |
N1—C12 | 1.399 (10) | C19—C20 | 1.408 (11) |
N2—C10 | 1.265 (11) | C19—C23 | 1.412 (11) |
N2—C11 | 1.350 (11) | C20—C21 | 1.366 (13) |
N3—C24 | 1.372 (10) | C20—H20A | 0.9300 |
N3—C13 | 1.379 (10) | C21—C22 | 1.318 (14) |
N4—C23 | 1.341 (10) | C21—H21A | 0.9300 |
N4—C22 | 1.352 (11) | C22—H22A | 0.9300 |
C1—C2 | 1.472 (12) | C23—C24 | 1.472 (11) |
C1—H1A | 0.9300 | C25—C26 | 1.555 (13) |
C2—C3 | 1.352 (13) | C25—H25A | 0.9600 |
C2—H2A | 0.9300 | C25—H25B | 0.9600 |
C3—C4 | 1.406 (13) | C25—H25C | 0.9600 |
C3—H3A | 0.9300 | C26—C27 | 1.510 (9) |
C4—C12 | 1.384 (11) | C26—H26A | 0.9800 |
C4—C5 | 1.455 (13) | C27—C28 | 1.490 (14) |
C5—C6 | 1.314 (13) | C27—H27A | 0.9800 |
C5—H5A | 0.9300 | C28—H28A | 0.9600 |
C6—C7 | 1.460 (12) | C28—H28B | 0.9600 |
C6—H6A | 0.9300 | C28—H28C | 0.9600 |
C7—C8 | 1.398 (14) | ||
O1—Cu1—O1' | 32.6 (2) | N2—C10—C9 | 124.3 (8) |
O1—Cu1—N1 | 99.6 (4) | N2—C10—H10A | 117.9 |
O1'—Cu1—N1 | 92.2 (4) | C9—C10—H10A | 117.9 |
O1—Cu1—N4 | 93.5 (4) | N2—C11—C12 | 121.1 (7) |
O1'—Cu1—N4 | 99.5 (4) | N2—C11—C7 | 119.1 (8) |
N1—Cu1—N4 | 166.8 (3) | C12—C11—C7 | 119.7 (8) |
O1—Cu1—N3 | 140.1 (4) | C4—C12—N1 | 121.5 (7) |
O1'—Cu1—N3 | 109.3 (4) | C4—C12—C11 | 121.2 (7) |
N1—Cu1—N3 | 90.7 (3) | N1—C12—C11 | 116.9 (7) |
N4—Cu1—N3 | 79.8 (3) | N3—C13—C14 | 120.9 (8) |
O1—Cu1—N2 | 108.5 (4) | N3—C13—H13A | 119.6 |
O1'—Cu1—N2 | 139.1 (4) | C14—C13—H13A | 119.6 |
N1—Cu1—N2 | 81.6 (3) | C15—C14—C13 | 121.6 (8) |
N4—Cu1—N2 | 93.3 (3) | C15—C14—H14A | 119.2 |
N3—Cu1—N2 | 111.08 (12) | C13—C14—H14A | 119.2 |
O2—S1—O4 | 111.2 (9) | C14—C15—C16 | 117.5 (7) |
O2—S1—O3 | 112.8 (11) | C14—C15—H15A | 121.3 |
O4—S1—O3 | 105.5 (12) | C16—C15—H15A | 121.3 |
O2—S1—O1 | 107.4 (7) | C24—C16—C17 | 120.5 (8) |
O4—S1—O1 | 106.5 (8) | C24—C16—C15 | 118.5 (8) |
O3—S1—O1 | 113.4 (12) | C17—C16—C15 | 121.0 (8) |
O2'—S1'—O4' | 113.7 (11) | C18—C17—C16 | 121.0 (8) |
O2'—S1'—O3' | 112.0 (9) | C18—C17—H17A | 119.5 |
O4'—S1'—O3' | 111.5 (12) | C16—C17—H17A | 119.5 |
O2'—S1'—O1' | 110.2 (7) | C17—C18—C19 | 121.0 (8) |
O4'—S1'—O1' | 104.4 (10) | C17—C18—H18A | 119.5 |
O3'—S1'—O1' | 104.3 (10) | C19—C18—H18A | 119.5 |
S1—O1—Cu1 | 134.8 (9) | C20—C19—C23 | 115.4 (7) |
S1'—O1'—Cu1 | 133.3 (8) | C20—C19—C18 | 125.8 (8) |
C26—O5—H5B | 109.5 | C23—C19—C18 | 118.5 (7) |
C27—O6—H6 | 109.5 | C21—C20—C19 | 120.3 (8) |
C1—N1—C12 | 120.6 (7) | C21—C20—H20A | 119.9 |
C1—N1—Cu1 | 126.8 (6) | C19—C20—H20A | 119.9 |
C12—N1—Cu1 | 112.6 (5) | C22—C21—C20 | 118.4 (8) |
C10—N2—C11 | 121.6 (7) | C22—C21—H21A | 120.8 |
C10—N2—Cu1 | 131.8 (6) | C20—C21—H21A | 120.8 |
C11—N2—Cu1 | 106.6 (5) | C21—C22—N4 | 126.6 (8) |
C24—N3—C13 | 115.4 (6) | C21—C22—H22A | 116.7 |
C24—N3—Cu1 | 112.8 (5) | N4—C22—H22A | 116.7 |
C13—N3—Cu1 | 131.8 (6) | N4—C23—C19 | 124.2 (8) |
C23—N4—C22 | 114.9 (8) | N4—C23—C24 | 116.8 (8) |
C23—N4—Cu1 | 115.1 (6) | C19—C23—C24 | 119.0 (7) |
C22—N4—Cu1 | 129.3 (6) | C16—C24—N3 | 126.2 (7) |
N1—C1—C2 | 119.2 (8) | C16—C24—C23 | 119.7 (7) |
N1—C1—H1A | 120.4 | N3—C24—C23 | 113.9 (7) |
C2—C1—H1A | 120.4 | C26—C25—H25A | 109.5 |
C3—C2—C1 | 120.4 (9) | C26—C25—H25B | 109.5 |
C3—C2—H2A | 119.8 | H25A—C25—H25B | 109.5 |
C1—C2—H2A | 119.8 | C26—C25—H25C | 109.5 |
C2—C3—C4 | 119.4 (8) | H25A—C25—H25C | 109.5 |
C2—C3—H3A | 120.3 | H25B—C25—H25C | 109.5 |
C4—C3—H3A | 120.3 | O5—C26—C27 | 112.2 (6) |
C12—C4—C3 | 118.7 (8) | O5—C26—C25 | 102.5 (7) |
C12—C4—C5 | 119.4 (9) | C27—C26—C25 | 110.4 (9) |
C3—C4—C5 | 121.9 (9) | O5—C26—H26A | 110.5 |
C6—C5—C4 | 119.9 (9) | C27—C26—H26A | 110.5 |
C6—C5—H5A | 120.1 | C25—C26—H26A | 110.5 |
C4—C5—H5A | 120.1 | O6—C27—C28 | 107.1 (9) |
C5—C6—C7 | 123.2 (8) | O6—C27—C26 | 124.3 (7) |
C5—C6—H6A | 118.4 | C28—C27—C26 | 112.2 (8) |
C7—C6—H6A | 118.4 | O6—C27—H27A | 103.6 |
C8—C7—C11 | 116.9 (8) | C28—C27—H27A | 103.6 |
C8—C7—C6 | 126.6 (8) | C26—C27—H27A | 103.6 |
C11—C7—C6 | 116.4 (8) | C27—C28—H28A | 109.5 |
C9—C8—C7 | 119.8 (8) | C27—C28—H28B | 109.5 |
C9—C8—H8A | 120.1 | H28A—C28—H28B | 109.5 |
C7—C8—H8A | 120.1 | C27—C28—H28C | 109.5 |
C10—C9—C8 | 118.3 (8) | H28A—C28—H28C | 109.5 |
C10—C9—H9A | 120.9 | H28B—C28—H28C | 109.5 |
C8—C9—H9A | 120.9 | ||
O2—S1—O1—Cu1 | −23.9 (15) | C11—C7—C8—C9 | −0.8 (12) |
O4—S1—O1—Cu1 | −143.0 (11) | C6—C7—C8—C9 | 177.9 (8) |
O3—S1—O1—Cu1 | 101.4 (15) | C7—C8—C9—C10 | 1.9 (12) |
O1'—Cu1—O1—S1 | −14.2 (12) | C11—N2—C10—C9 | −0.1 (13) |
N1—Cu1—O1—S1 | 64.7 (12) | Cu1—N2—C10—C9 | 176.6 (6) |
N4—Cu1—O1—S1 | −116.4 (12) | C8—C9—C10—N2 | −1.5 (13) |
N3—Cu1—O1—S1 | −38.2 (16) | C10—N2—C11—C12 | −177.2 (7) |
N2—Cu1—O1—S1 | 149.0 (11) | Cu1—N2—C11—C12 | 5.4 (8) |
O2'—S1'—O1'—Cu1 | −18.3 (14) | C10—N2—C11—C7 | 1.3 (11) |
O4'—S1'—O1'—Cu1 | −140.8 (13) | Cu1—N2—C11—C7 | −176.1 (6) |
O3'—S1'—O1'—Cu1 | 102.1 (13) | C8—C7—C11—N2 | −0.8 (11) |
O1—Cu1—O1'—S1' | −17.4 (12) | C6—C7—C11—N2 | −179.6 (7) |
N1—Cu1—O1'—S1' | −121.9 (12) | C8—C7—C11—C12 | 177.7 (7) |
N4—Cu1—O1'—S1' | 64.2 (12) | C6—C7—C11—C12 | −1.1 (11) |
N3—Cu1—O1'—S1' | 146.6 (11) | C3—C4—C12—N1 | −3.4 (13) |
N2—Cu1—O1'—S1' | −42.2 (15) | C5—C4—C12—N1 | 177.7 (7) |
O1—Cu1—N1—C1 | −65.3 (8) | C3—C4—C12—C11 | −176.6 (8) |
O1'—Cu1—N1—C1 | −33.4 (8) | C5—C4—C12—C11 | 4.5 (12) |
N4—Cu1—N1—C1 | 119.4 (13) | C1—N1—C12—C4 | −1.3 (12) |
N3—Cu1—N1—C1 | 76.0 (7) | Cu1—N1—C12—C4 | 176.2 (6) |
N2—Cu1—N1—C1 | −172.8 (8) | C1—N1—C12—C11 | 172.3 (8) |
O1—Cu1—N1—C12 | 117.4 (6) | Cu1—N1—C12—C11 | −10.3 (8) |
O1'—Cu1—N1—C12 | 149.3 (6) | N2—C11—C12—C4 | 176.3 (8) |
N4—Cu1—N1—C12 | −57.9 (17) | C7—C11—C12—C4 | −2.2 (11) |
N3—Cu1—N1—C12 | −101.3 (5) | N2—C11—C12—N1 | 2.8 (10) |
N2—Cu1—N1—C12 | 10.0 (5) | C7—C11—C12—N1 | −175.7 (7) |
O1—Cu1—N2—C10 | 77.2 (8) | C24—N3—C13—C14 | −1.5 (10) |
O1'—Cu1—N2—C10 | 91.0 (9) | Cu1—N3—C13—C14 | 176.2 (5) |
N1—Cu1—N2—C10 | 174.6 (8) | N3—C13—C14—C15 | −0.9 (12) |
N4—Cu1—N2—C10 | −17.6 (8) | C13—C14—C15—C16 | 2.7 (12) |
N3—Cu1—N2—C10 | −97.9 (7) | C14—C15—C16—C24 | −2.0 (12) |
O1—Cu1—N2—C11 | −105.6 (6) | C14—C15—C16—C17 | 176.5 (8) |
O1'—Cu1—N2—C11 | −91.8 (7) | C24—C16—C17—C18 | 0.6 (13) |
N1—Cu1—N2—C11 | −8.2 (5) | C15—C16—C17—C18 | −177.8 (8) |
N4—Cu1—N2—C11 | 159.6 (5) | C16—C17—C18—C19 | 2.1 (13) |
N3—Cu1—N2—C11 | 79.2 (6) | C17—C18—C19—C20 | 172.6 (9) |
O1—Cu1—N3—C24 | −94.2 (8) | C17—C18—C19—C23 | −0.5 (12) |
O1'—Cu1—N3—C24 | −107.6 (6) | C23—C19—C20—C21 | −5.8 (12) |
N1—Cu1—N3—C24 | 159.8 (5) | C18—C19—C20—C21 | −179.1 (8) |
N4—Cu1—N3—C24 | −11.0 (5) | C19—C20—C21—C22 | 4.8 (13) |
N2—Cu1—N3—C24 | 78.6 (6) | C20—C21—C22—N4 | −2.1 (14) |
O1—Cu1—N3—C13 | 88.0 (9) | C23—N4—C22—C21 | 0.6 (13) |
O1'—Cu1—N3—C13 | 74.6 (8) | Cu1—N4—C22—C21 | −168.9 (7) |
N1—Cu1—N3—C13 | −18.0 (7) | C22—N4—C23—C19 | −1.9 (12) |
N4—Cu1—N3—C13 | 171.2 (7) | Cu1—N4—C23—C19 | 169.2 (6) |
N2—Cu1—N3—C13 | −99.2 (7) | C22—N4—C23—C24 | 179.7 (7) |
O1—Cu1—N4—C23 | 151.3 (7) | Cu1—N4—C23—C24 | −9.2 (9) |
O1'—Cu1—N4—C23 | 119.0 (7) | C20—C19—C23—N4 | 4.5 (12) |
N1—Cu1—N4—C23 | −33.4 (18) | C18—C19—C23—N4 | 178.3 (8) |
N3—Cu1—N4—C23 | 10.9 (5) | C20—C19—C23—C24 | −177.2 (7) |
N2—Cu1—N4—C23 | −99.9 (6) | C18—C19—C23—C24 | −3.4 (11) |
O1—Cu1—N4—C22 | −39.2 (8) | C17—C16—C24—N3 | −179.0 (7) |
O1'—Cu1—N4—C22 | −71.4 (8) | C15—C16—C24—N3 | −0.6 (12) |
N1—Cu1—N4—C22 | 136.2 (13) | C17—C16—C24—C23 | −4.6 (12) |
N3—Cu1—N4—C22 | −179.6 (8) | C15—C16—C24—C23 | 173.9 (8) |
N2—Cu1—N4—C22 | 69.6 (8) | C13—N3—C24—C16 | 2.3 (11) |
C12—N1—C1—C2 | 2.7 (12) | Cu1—N3—C24—C16 | −175.9 (6) |
Cu1—N1—C1—C2 | −174.3 (6) | C13—N3—C24—C23 | −172.4 (7) |
N1—C1—C2—C3 | 0.6 (13) | Cu1—N3—C24—C23 | 9.4 (8) |
C1—C2—C3—C4 | −5.2 (13) | N4—C23—C24—C16 | −175.6 (7) |
C2—C3—C4—C12 | 6.5 (14) | C19—C23—C24—C16 | 6.0 (11) |
C2—C3—C4—C5 | −174.7 (8) | N4—C23—C24—N3 | −0.5 (10) |
C12—C4—C5—C6 | −3.6 (13) | C19—C23—C24—N3 | −178.9 (7) |
C3—C4—C5—C6 | 177.6 (9) | O5—C26—C27—O6 | −42.6 (15) |
C4—C5—C6—C7 | 0.2 (13) | C25—C26—C27—O6 | 71.1 (12) |
C5—C6—C7—C8 | −176.6 (9) | O5—C26—C27—C28 | −174.2 (10) |
C5—C6—C7—C11 | 2.0 (12) | C25—C26—C27—C28 | −60.6 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5B···O3 | 0.82 | 1.92 | 2.73 (2) | 172 |
O5—H5B···O4′ | 0.82 | 2.01 | 2.83 (2) | 176 |
O6—H6···O3′ | 0.82 | 2.19 | 2.919 (16) | 148 |
O6—H6···O4 | 0.82 | 1.95 | 2.720 (14) | 156 |
Experimental details
Crystal data | |
Chemical formula | [Cu(SO4)(C12H8N2)2]·C4H10O2 |
Mr | 610.13 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 223 |
a, b, c (Å) | 17.352 (4), 13.070 (3), 13.444 (3) |
β (°) | 123.84 (3) |
V (Å3) | 2532.4 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.00 |
Crystal size (mm) | 0.32 × 0.27 × 0.21 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.741, 0.818 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7154, 4178, 3542 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.135, 0.99 |
No. of reflections | 4178 |
No. of parameters | 408 |
No. of restraints | 124 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.53 |
Absolute structure | Flack (1983), 1317 Friedel pairs |
Absolute structure parameter | 0.55 (2) |
Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Cu1—O1 | 1.922 (11) | Cu1—N4 | 2.014 (7) |
Cu1—O1' | 1.944 (10) | Cu1—N3 | 2.091 (6) |
Cu1—N1 | 2.000 (7) | Cu1—N2 | 2.186 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5B···O3 | 0.82 | 1.92 | 2.73 (2) | 172 |
O5—H5B···O4' | 0.82 | 2.01 | 2.83 (2) | 176 |
O6—H6···O3' | 0.82 | 2.19 | 2.919 (16) | 148 |
O6—H6···O4 | 0.82 | 1.95 | 2.720 (14) | 156 |
Acknowledgements
This work was supported by the Scientific Research Foundation of Nanjing College of Chemical Technology (grant No. NHKY-2010–17).
References
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In the past few years, we have unexpectedly obtained and characterized some transition metal complexes with bidentate-chelating sulfate auxiliary ligand via alcohol-solvothermal reaction during attempts to synthesize mixed-ligand coordination polymers, such as cobalt complex (Wang & Zhong, 2011), nickel complex (Zhong & Ni, 2012), zinc complex (Cui et al., 2010), cadmium complex (Lu et al., 2006). The title compound [CuSO4(C12H8N2)2].C4H10O2, (I), was obtained by the similar alcohol-solvothermal reaction and its crystal structure has not hitherto been reported.
The X-ray diffraction experiment found that the title complex is isotypical to the previously reported [CuSO4(C12H8N2)2].C2H6O2 (Zhong, 2011a), (II), [CuSO4(C12H8N2)2].CH2OHCHOHCH3 (Zhong, 2011b), (III), and [CuSO4(C12H8N2)2].CH2OHCH2CH2OH (Zhong, 2012), (IV). The geometry of the phenanthroline and sulfate ligands are in good agreement with those reported in the (II), (III) and (IV). The CuII metal ion is five-coordinated by four N atoms from two chelating phen ligands and an O atoms from a monodentate sulfate ligand, resulting in a distorted CuN4O square-pyramidal environment. The N1, N2, N3 and N4 atoms comprise a square, and the O1 atom site the apex of a square pyramid surrounding each metal atom (Fig 1). The dihedral angle of the two chelating N2C2 groups is 85.8 (4)°, which is larger than those reported in (II) [71.1 (2)°], (III) [84.9 (4)°] and (IV) [71.10 (15) Å], respectively. The Cu—O bond distance [1.922 (11) Å - 1.944 (10) Å], the Cu—N bond distance [2.000 (7) - 2.186 (7) Å], and the N—Cu—N bite angle [79.8 (3) - 81.6 (3)°] are comparable to those observed in (II), (III) and (IV) (Table 1).
In the crystal, the sulfate group is disordered over two positions with refined site occupancies of 0.55 (1) and 0.45 (1), and is hydrogen bonded to the solvent butane-2,3-diol molecule (Table 2 & Fig. 1).