metal-organic compounds
Bis(1,10-phenanthroline-κ2N,N′)(sulfato-κ2O,O′)cobalt(II) propane-1,2-diol monosolvate
aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
*Correspondence e-mail: zklong76@163.com
In the title compound, [Co(SO4)(C12H8N2)2]·C3H8O2, the CoII atom (site symmetry 2) has a distorted octahedral coordination composed of four N atoms from two chelating 1,10-phenanthroline ligands and two O atoms from an O,O′-bidentate sulfate ligand, in which the S atom has 2. The dihedral angle between the two chelating N2C2 groups is 84.46 (15)°. The complex and solvent molecules are connected through O—H⋯O hydrogen bonds. The solvent molecule is equally disordered over two positions and is also located on a twofold axis.
Related literature
The title complex has been reported with other solvant molecules. In the case of ethane-1,2-diol, see: Zhong et al. (2006); for propane-1,3-diol, see: Zhong (2010); for butane-2,3-diol, see: Wang & Zhong (2011). For crystal engineering aspects of coordination framework structures, see: Batten & Robson (1998); Robin & Fromm (2006).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2007); cell CrystalClear; data reduction: CrystalClear; 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.
Supporting information
https://doi.org/10.1107/S1600536812049616/vn2062sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049616/vn2062Isup2.hkl
0.2 mmol phen, 0.1 mmol melamine, 0.1 mmol CoSO4.7H2O, 2.0 ml propane-1,2-diol and 1.0 ml water were mixed and placed in a thick Pyrex tube, which was sealed and heated to 453 K for 96 h, whereupon red block-shaped crystals of the title compound were obtained.
All non-hydrogen atoms were refined anisotropically. 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-1,2-diol were placed in geometrically idealized positions and refined as riding atoms, with C—H(CH3) = 0.96 Å, C—H(CH2) = 0.97 Å, C—H(CH) = 0.98 Å and O—H = 0.82 Å; Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O). The propane-1,2-diol molecule was found to be disordered over two positions with site occupancy factors of 0.50:0.50. The site occupancy factors were not refined. In order to keep a reasonable geometry distance restraints were used, apart from atomic displacement parameter restraints (ISOR and EADP).
In the past few decades, the supramolecular assembly and crystal engineering of metal-organic coordination frameworks have attracted much attention because of their potential applications in the areas of material chemistry (Batten & Robson, 1998; Robin & Fromm, 2006). Recently, we have unexpectedly obtained some cobalt-phen complexes with interesting four-membered chelating rings during attempts to synthesize mixed-ligand coordination polymers with phen as auxiliary ligand via a alcohol-solvothermal reaction, e.g. [CoSO4(C12H8N2)2]. C2H6O2 (Zhong et al., 2006), (II), [CoSO4(C12H8N2)2].HOCH2 CH2CH2OH (Zhong, 2010), (III) and [CoSO4(C12H8N2)2]. C4H10O2 (Wang & Zhong, 2011), (IV). The
of the title compound [CuSO4(C12H8N2)2].C3H8O2, (I) has hitherto not been reported.Single-crystal X-ray diffraction revealed that the
of (I) contains one neutral monomeric complex [CuSO4(C12H8N2)2] and one solvent propane-1,2-diol molecule, which are connected by an intermolecular O—H···O hydrogen bond with the uncoordinated O atoms of the sulfate group (Fig. 1 & Table 2). In the complex, a twofold rotation axis (symmetry code: 0, y, 1/4) passes through the CoII atom and the S atom. The CoII atom has a distorted CoN4O2 octahedral geometry, with four N atoms from two chelating phenanthroline ligands and two O atoms from an O,O'-bidentate sulfate anion (Fig. 1). The Co—O bond distance [2.124 (3) Å], the Co—N bond distance [2.123 (3) Å], the N—Co—N bite angles [77.50 (13)°] and O—Co—O bite angle [66.91 (16)°] are within normal ranges and are comparable to the closely related structure (II) - (IV). The two chelating N2C2 groups are oriented at 84.46 (15)°, which is much larger than reported in (II), (III) and (IV) [70.16 (6)°, 80.06 (8)° and 83.48 (1)°, respectively]. The solvent molecule is disordered over two sets of sites with occupancies of 0.50 and 0.50.The title complex has been reported with other solvant molecules. In the case of ethane-1,2-diol, see: Zhong et al. (2006); for propane-1,3-diol, see: Zhong (2010); for butane-2,3-diol, see: Wang & Zhong (2011). For crystal engineering aspects of coordination framework structures, see: Batten & Robson (1998); Robin & Fromm (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 30% probability level. Hydrogen bonds O—H···O are shown as dashed lines. |
[Co(SO4)(C12H8N2)2]·C3H8O2 | F(000) = 1220 |
Mr = 591.49 | Dx = 1.520 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5104 reflections |
a = 18.117 (4) Å | θ = 3.1–25.4° |
b = 12.987 (3) Å | µ = 0.80 mm−1 |
c = 12.881 (3) Å | T = 223 K |
β = 121.46 (3)° | Block, red |
V = 2585.2 (13) Å3 | 0.35 × 0.34 × 0.25 mm |
Z = 4 |
Rigaku Mercury CCD diffractometer | 2284 independent reflections |
Radiation source: fine-focus sealed tube | 1465 reflections with I > 2/s(I) |
Graphite Monochromator monochromator | Rint = 0.100 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 25.0°, θmin = 3.1° |
ω scans | h = −20→21 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −14→15 |
Tmin = 0.373, Tmax = 1.000 | l = −15→15 |
11477 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)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.0385P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max = 0.001 |
2284 reflections | Δρmax = 0.37 e Å−3 |
193 parameters | Δρmin = −0.39 e Å−3 |
38 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0060 (5) |
[Co(SO4)(C12H8N2)2]·C3H8O2 | V = 2585.2 (13) Å3 |
Mr = 591.49 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.117 (4) Å | µ = 0.80 mm−1 |
b = 12.987 (3) Å | T = 223 K |
c = 12.881 (3) Å | 0.35 × 0.34 × 0.25 mm |
β = 121.46 (3)° |
Rigaku Mercury CCD diffractometer | 2284 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 1465 reflections with I > 2/s(I) |
Tmin = 0.373, Tmax = 1.000 | Rint = 0.100 |
11477 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 38 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.37 e Å−3 |
2284 reflections | Δρmin = −0.39 e Å−3 |
193 parameters |
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) | |
Co1 | 0.0000 | 0.32137 (6) | 0.2500 | 0.0348 (3) | |
S1 | 0.0000 | 0.52899 (11) | 0.2500 | 0.0344 (4) | |
O1 | 0.0533 (2) | 0.4578 (2) | 0.3537 (3) | 0.0495 (9) | |
O2 | −0.0552 (2) | 0.5929 (2) | 0.2742 (3) | 0.0604 (10) | |
O3 | −0.0492 (7) | 0.7963 (6) | 0.3204 (8) | 0.071 (3) | 0.50 |
H3 | −0.0428 | 0.7424 | 0.2931 | 0.106* | 0.50 |
O3' | −0.0869 (6) | 0.7996 (6) | 0.2438 (10) | 0.097 (4) | 0.50 |
H3' | −0.0613 | 0.7472 | 0.2804 | 0.145* | 0.50 |
N1 | 0.0830 (2) | 0.3000 (3) | 0.1814 (3) | 0.0379 (9) | |
N2 | 0.0959 (2) | 0.2178 (2) | 0.3803 (3) | 0.0363 (9) | |
C1 | 0.0774 (3) | 0.3442 (4) | 0.0841 (4) | 0.0459 (12) | |
H1A | 0.0340 | 0.3924 | 0.0406 | 0.055* | |
C2 | 0.1339 (3) | 0.3208 (4) | 0.0454 (5) | 0.0537 (14) | |
H2A | 0.1284 | 0.3535 | −0.0225 | 0.064* | |
C3 | 0.1977 (3) | 0.2495 (4) | 0.1074 (5) | 0.0555 (14) | |
H3A | 0.2354 | 0.2331 | 0.0814 | 0.067* | |
C4 | 0.2061 (3) | 0.2012 (3) | 0.2104 (4) | 0.0419 (12) | |
C5 | 0.2732 (3) | 0.1286 (4) | 0.2841 (5) | 0.0538 (14) | |
H5A | 0.3117 | 0.1082 | 0.2608 | 0.065* | |
C6 | 0.2814 (3) | 0.0902 (4) | 0.3853 (5) | 0.0493 (13) | |
H6A | 0.3258 | 0.0440 | 0.4320 | 0.059* | |
C7 | 0.2225 (3) | 0.1189 (3) | 0.4240 (4) | 0.0402 (11) | |
C8 | 0.2298 (3) | 0.0829 (3) | 0.5312 (4) | 0.0506 (13) | |
H8A | 0.2738 | 0.0375 | 0.5816 | 0.061* | |
C9 | 0.1723 (3) | 0.1150 (4) | 0.5605 (4) | 0.0546 (14) | |
H9A | 0.1767 | 0.0924 | 0.6320 | 0.065* | |
C10 | 0.1062 (3) | 0.1819 (3) | 0.4833 (4) | 0.0468 (13) | |
H10A | 0.0671 | 0.2026 | 0.5053 | 0.056* | |
C11 | 0.1546 (3) | 0.1866 (3) | 0.3517 (4) | 0.0320 (10) | |
C12 | 0.1473 (3) | 0.2300 (3) | 0.2447 (4) | 0.0341 (11) | |
C13 | −0.0288 (6) | 0.8772 (5) | 0.2729 (9) | 0.139 (3) | 0.50 |
H13 | −0.0837 | 0.8822 | 0.1948 | 0.167* | 0.50 |
C13' | −0.0288 (6) | 0.8772 (5) | 0.2729 (9) | 0.139 (3) | 0.50 |
H13A | 0.0069 | 0.8799 | 0.3610 | 0.167* | 0.50 |
H13B | −0.0613 | 0.9411 | 0.2467 | 0.167* | 0.50 |
C14 | −0.0305 (12) | 0.9804 (8) | 0.3222 (18) | 0.168 (9) | 0.50 |
H14A | 0.0001 | 1.0290 | 0.3021 | 0.252* | 0.50 |
H14B | −0.0032 | 0.9762 | 0.4091 | 0.252* | 0.50 |
H14C | −0.0894 | 1.0025 | 0.2872 | 0.252* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0323 (5) | 0.0367 (5) | 0.0407 (6) | 0.000 | 0.0228 (5) | 0.000 |
S1 | 0.0282 (9) | 0.0352 (9) | 0.0424 (10) | 0.000 | 0.0203 (8) | 0.000 |
O1 | 0.048 (2) | 0.0428 (18) | 0.038 (2) | −0.0012 (15) | 0.0091 (17) | 0.0020 (15) |
O2 | 0.060 (2) | 0.049 (2) | 0.095 (3) | 0.0103 (17) | 0.056 (2) | −0.0082 (19) |
O3 | 0.111 (7) | 0.050 (5) | 0.077 (6) | 0.005 (4) | 0.068 (5) | −0.001 (4) |
O3' | 0.110 (7) | 0.067 (6) | 0.126 (8) | 0.026 (5) | 0.070 (6) | 0.023 (6) |
N1 | 0.038 (2) | 0.042 (2) | 0.041 (2) | 0.0010 (17) | 0.026 (2) | 0.0036 (18) |
N2 | 0.041 (2) | 0.036 (2) | 0.042 (2) | −0.0010 (17) | 0.029 (2) | 0.0011 (17) |
C1 | 0.041 (3) | 0.056 (3) | 0.044 (3) | 0.003 (2) | 0.024 (3) | 0.007 (2) |
C2 | 0.054 (3) | 0.070 (4) | 0.046 (3) | 0.003 (3) | 0.033 (3) | 0.008 (3) |
C3 | 0.050 (3) | 0.080 (4) | 0.052 (3) | 0.004 (3) | 0.038 (3) | −0.003 (3) |
C4 | 0.036 (3) | 0.057 (3) | 0.036 (3) | 0.004 (2) | 0.021 (2) | −0.002 (2) |
C5 | 0.044 (3) | 0.073 (4) | 0.050 (3) | 0.018 (3) | 0.028 (3) | −0.001 (3) |
C6 | 0.037 (3) | 0.059 (3) | 0.047 (3) | 0.015 (2) | 0.018 (3) | 0.001 (3) |
C7 | 0.036 (3) | 0.042 (3) | 0.038 (3) | 0.005 (2) | 0.017 (2) | 0.002 (2) |
C8 | 0.046 (3) | 0.049 (3) | 0.047 (3) | 0.007 (2) | 0.018 (3) | 0.006 (2) |
C9 | 0.063 (4) | 0.059 (3) | 0.046 (3) | 0.005 (3) | 0.031 (3) | 0.015 (3) |
C10 | 0.056 (3) | 0.050 (3) | 0.049 (3) | 0.003 (2) | 0.038 (3) | 0.005 (2) |
C11 | 0.033 (3) | 0.031 (2) | 0.034 (3) | −0.0038 (19) | 0.019 (2) | −0.0020 (19) |
C12 | 0.027 (3) | 0.041 (3) | 0.034 (3) | −0.001 (2) | 0.015 (2) | −0.002 (2) |
C13 | 0.195 (9) | 0.076 (5) | 0.215 (9) | 0.002 (5) | 0.155 (7) | −0.006 (6) |
C13' | 0.195 (9) | 0.076 (5) | 0.215 (9) | 0.002 (5) | 0.155 (7) | −0.006 (6) |
C14 | 0.20 (2) | 0.069 (10) | 0.32 (3) | −0.029 (11) | 0.19 (2) | −0.032 (14) |
Co1—O1 | 2.124 (3) | C3—C4 | 1.402 (6) |
Co1—O1i | 2.124 (3) | C3—H3A | 0.9300 |
Co1—N1 | 2.123 (3) | C4—C12 | 1.400 (6) |
Co1—N1i | 2.123 (3) | C4—C5 | 1.437 (6) |
Co1—N2i | 2.145 (4) | C5—C6 | 1.330 (6) |
Co1—N2 | 2.145 (4) | C5—H5A | 0.9300 |
Co1—S1 | 2.6964 (18) | C6—C7 | 1.442 (6) |
S1—O2i | 1.453 (3) | C6—H6A | 0.9300 |
S1—O2 | 1.453 (3) | C7—C11 | 1.399 (6) |
S1—O1i | 1.492 (3) | C7—C8 | 1.397 (6) |
S1—O1 | 1.492 (3) | C8—C9 | 1.346 (6) |
O3—C13 | 1.361 (4) | C8—H8A | 0.9300 |
O3—H3 | 0.8200 | C9—C10 | 1.391 (6) |
O3'—H3' | 0.8200 | C9—H9A | 0.9300 |
N1—C1 | 1.333 (5) | C10—H10A | 0.9300 |
N1—C12 | 1.363 (5) | C11—C12 | 1.430 (6) |
N2—C10 | 1.324 (5) | C13—C13i | 1.443 (7) |
N2—C11 | 1.356 (5) | C13—C14 | 1.489 (9) |
C1—C2 | 1.386 (6) | C13—H13 | 0.9800 |
C1—H1A | 0.9300 | C14—H14A | 0.9600 |
C2—C3 | 1.366 (6) | C14—H14B | 0.9600 |
C2—H2A | 0.9300 | C14—H14C | 0.9600 |
O1—Co1—O1i | 66.91 (16) | C1—C2—H2A | 120.2 |
O1—Co1—N1 | 100.51 (13) | C2—C3—C4 | 119.9 (4) |
O1i—Co1—N1 | 92.02 (13) | C2—C3—H3A | 120.1 |
O1—Co1—N1i | 92.02 (13) | C4—C3—H3A | 120.1 |
O1i—Co1—N1i | 100.51 (13) | C12—C4—C3 | 117.0 (4) |
N1—Co1—N1i | 165.01 (18) | C12—C4—C5 | 119.2 (4) |
O1—Co1—N2i | 158.77 (12) | C3—C4—C5 | 123.8 (4) |
O1i—Co1—N2i | 96.57 (12) | C6—C5—C4 | 121.1 (4) |
N1—Co1—N2i | 93.03 (13) | C6—C5—H5A | 119.5 |
N1i—Co1—N2i | 77.50 (13) | C4—C5—H5A | 119.5 |
O1—Co1—N2 | 96.57 (12) | C5—C6—C7 | 121.2 (4) |
O1i—Co1—N2 | 158.77 (12) | C5—C6—H6A | 119.4 |
N1—Co1—N2 | 77.50 (13) | C7—C6—H6A | 119.4 |
N1i—Co1—N2 | 93.03 (13) | C11—C7—C8 | 117.7 (4) |
N2i—Co1—N2 | 102.31 (18) | C11—C7—C6 | 119.0 (4) |
O1—Co1—S1 | 33.45 (8) | C8—C7—C6 | 123.3 (4) |
O1i—Co1—S1 | 33.45 (8) | C9—C8—C7 | 119.0 (4) |
N1—Co1—S1 | 97.50 (9) | C9—C8—H8A | 120.5 |
N1i—Co1—S1 | 97.50 (9) | C7—C8—H8A | 120.5 |
N2i—Co1—S1 | 128.85 (9) | C8—C9—C10 | 119.7 (5) |
N2—Co1—S1 | 128.85 (9) | C8—C9—H9A | 120.1 |
O2i—S1—O2 | 110.3 (3) | C10—C9—H9A | 120.1 |
O2i—S1—O1i | 111.01 (19) | N2—C10—C9 | 123.8 (4) |
O2—S1—O1i | 110.46 (19) | N2—C10—H10A | 118.1 |
O2i—S1—O1 | 110.46 (19) | C9—C10—H10A | 118.1 |
O2—S1—O1 | 111.01 (19) | N2—C11—C7 | 123.3 (4) |
O1i—S1—O1 | 103.4 (2) | N2—C11—C12 | 116.9 (4) |
O2i—S1—Co1 | 124.83 (13) | C7—C11—C12 | 119.7 (4) |
O2—S1—Co1 | 124.83 (13) | N1—C12—C4 | 122.9 (4) |
O1i—S1—Co1 | 51.70 (12) | N1—C12—C11 | 117.4 (4) |
O1—S1—Co1 | 51.70 (12) | C4—C12—C11 | 119.8 (4) |
S1—O1—Co1 | 94.85 (16) | O3—C13—C13i | 127.5 (5) |
C13—O3—H3 | 109.5 | O3—C13—C14 | 115.6 (8) |
C1—N1—C12 | 118.1 (4) | C13i—C13—C14 | 110.8 (7) |
C1—N1—Co1 | 127.8 (3) | O3—C13—H13 | 98.3 |
C12—N1—Co1 | 114.1 (3) | C13i—C13—H13 | 98.3 |
C10—N2—C11 | 116.5 (4) | C14—C13—H13 | 98.3 |
C10—N2—Co1 | 129.7 (3) | C13—C14—H14A | 109.5 |
C11—N2—Co1 | 113.9 (3) | C13—C14—H14B | 109.5 |
N1—C1—C2 | 122.4 (4) | H14A—C14—H14B | 109.5 |
N1—C1—H1A | 118.8 | C13—C14—H14C | 109.5 |
C2—C1—H1A | 118.8 | H14A—C14—H14C | 109.5 |
C3—C2—C1 | 119.7 (5) | H14B—C14—H14C | 109.5 |
C3—C2—H2A | 120.2 | ||
O1—Co1—S1—O2i | 89.6 (2) | N2i—Co1—N2—C10 | −94.6 (4) |
O1i—Co1—S1—O2i | −90.4 (2) | S1—Co1—N2—C10 | 85.4 (4) |
N1—Co1—S1—O2i | −8.1 (2) | O1—Co1—N2—C11 | −103.3 (3) |
N1i—Co1—S1—O2i | 171.9 (2) | O1i—Co1—N2—C11 | −65.9 (5) |
N2i—Co1—S1—O2i | −108.2 (2) | N1—Co1—N2—C11 | −4.0 (3) |
N2—Co1—S1—O2i | 71.8 (2) | N1i—Co1—N2—C11 | 164.3 (3) |
O1—Co1—S1—O2 | −90.4 (2) | N2i—Co1—N2—C11 | 86.4 (3) |
O1i—Co1—S1—O2 | 89.6 (2) | S1—Co1—N2—C11 | −93.6 (3) |
N1—Co1—S1—O2 | 171.9 (2) | C12—N1—C1—C2 | 0.4 (7) |
N1i—Co1—S1—O2 | −8.1 (2) | Co1—N1—C1—C2 | −177.4 (3) |
N2i—Co1—S1—O2 | 71.8 (2) | N1—C1—C2—C3 | 0.5 (8) |
N2—Co1—S1—O2 | −108.2 (2) | C1—C2—C3—C4 | −0.6 (8) |
O1—Co1—S1—O1i | 180.0 | C2—C3—C4—C12 | −0.3 (7) |
N1—Co1—S1—O1i | 82.27 (19) | C2—C3—C4—C5 | −177.3 (5) |
N1i—Co1—S1—O1i | −97.73 (19) | C12—C4—C5—C6 | −1.3 (7) |
N2i—Co1—S1—O1i | −17.8 (2) | C3—C4—C5—C6 | 175.6 (5) |
N2—Co1—S1—O1i | 162.2 (2) | C4—C5—C6—C7 | 0.8 (8) |
O1i—Co1—S1—O1 | 180.0 | C5—C6—C7—C11 | 1.5 (7) |
N1—Co1—S1—O1 | −97.73 (19) | C5—C6—C7—C8 | −178.2 (5) |
N1i—Co1—S1—O1 | 82.27 (19) | C11—C7—C8—C9 | −0.4 (7) |
N2i—Co1—S1—O1 | 162.2 (2) | C6—C7—C8—C9 | 179.2 (4) |
N2—Co1—S1—O1 | −17.8 (2) | C7—C8—C9—C10 | 0.8 (7) |
O2i—S1—O1—Co1 | −118.82 (17) | C11—N2—C10—C9 | −0.6 (7) |
O2—S1—O1—Co1 | 118.44 (18) | Co1—N2—C10—C9 | −179.5 (3) |
O1i—S1—O1—Co1 | 0.0 | C8—C9—C10—N2 | −0.4 (8) |
O1i—Co1—O1—S1 | 0.0 | C10—N2—C11—C7 | 1.0 (6) |
N1—Co1—O1—S1 | 87.70 (17) | Co1—N2—C11—C7 | −179.9 (3) |
N1i—Co1—O1—S1 | −100.56 (16) | C10—N2—C11—C12 | −176.1 (4) |
N2i—Co1—O1—S1 | −41.1 (4) | Co1—N2—C11—C12 | 3.0 (5) |
N2—Co1—O1—S1 | 166.15 (15) | C8—C7—C11—N2 | −0.6 (7) |
O1—Co1—N1—C1 | −83.2 (4) | C6—C7—C11—N2 | 179.8 (4) |
O1i—Co1—N1—C1 | −16.3 (4) | C8—C7—C11—C12 | 176.5 (4) |
N1i—Co1—N1—C1 | 130.6 (4) | C6—C7—C11—C12 | −3.1 (6) |
N2i—Co1—N1—C1 | 80.4 (4) | C1—N1—C12—C4 | −1.4 (6) |
N2—Co1—N1—C1 | −177.6 (4) | Co1—N1—C12—C4 | 176.7 (3) |
S1—Co1—N1—C1 | −49.4 (4) | C1—N1—C12—C11 | 177.4 (4) |
O1—Co1—N1—C12 | 99.0 (3) | Co1—N1—C12—C11 | −4.5 (5) |
O1i—Co1—N1—C12 | 165.9 (3) | C3—C4—C12—N1 | 1.3 (7) |
N1i—Co1—N1—C12 | −47.3 (3) | C5—C4—C12—N1 | 178.4 (4) |
N2i—Co1—N1—C12 | −97.5 (3) | C3—C4—C12—C11 | −177.5 (4) |
N2—Co1—N1—C12 | 4.5 (3) | C5—C4—C12—C11 | −0.4 (6) |
S1—Co1—N1—C12 | 132.7 (3) | N2—C11—C12—N1 | 1.0 (6) |
O1—Co1—N2—C10 | 75.6 (4) | C7—C11—C12—N1 | −176.3 (4) |
O1i—Co1—N2—C10 | 113.1 (5) | N2—C11—C12—C4 | 179.9 (4) |
N1—Co1—N2—C10 | 175.0 (4) | C7—C11—C12—C4 | 2.6 (6) |
N1i—Co1—N2—C10 | −16.8 (4) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.82 | 1.95 | 2.698 (9) | 150 |
O3′—H3′···O2 | 0.82 | 2.01 | 2.730 (10) | 146 |
Experimental details
Crystal data | |
Chemical formula | [Co(SO4)(C12H8N2)2]·C3H8O2 |
Mr | 591.49 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 223 |
a, b, c (Å) | 18.117 (4), 12.987 (3), 12.881 (3) |
β (°) | 121.46 (3) |
V (Å3) | 2585.2 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.35 × 0.34 × 0.25 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.373, 1.000 |
No. of measured, independent and observed [I > 2/s(I)] reflections | 11477, 2284, 1465 |
Rint | 0.100 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.129, 0.95 |
No. of reflections | 2284 |
No. of parameters | 193 |
No. of restraints | 38 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.39 |
Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.82 | 1.95 | 2.698 (9) | 150.4 |
O3'—H3'···O2 | 0.82 | 2.01 | 2.730 (10) | 146.2 |
Acknowledgements
This work was supported by the Scientific Research Foundation of Nanjing College of Chemical Technology (grant No. NHKY-2010–17).
References
Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460–1494. Web of Science CrossRef Google Scholar
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Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Robin, A.-Y. & Fromm, K. M. (2006). Coord. Chem. Rev. 250, 2127–2157. Web of Science CrossRef CAS Google Scholar
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In the past few decades, the supramolecular assembly and crystal engineering of metal-organic coordination frameworks have attracted much attention because of their potential applications in the areas of material chemistry (Batten & Robson, 1998; Robin & Fromm, 2006). Recently, we have unexpectedly obtained some cobalt-phen complexes with interesting four-membered chelating rings during attempts to synthesize mixed-ligand coordination polymers with phen as auxiliary ligand via a alcohol-solvothermal reaction, e.g. [CoSO4(C12H8N2)2]. C2H6O2 (Zhong et al., 2006), (II), [CoSO4(C12H8N2)2].HOCH2 CH2CH2OH (Zhong, 2010), (III) and [CoSO4(C12H8N2)2]. C4H10O2 (Wang & Zhong, 2011), (IV). The crystal structure of the title compound [CuSO4(C12H8N2)2].C3H8O2, (I) has hitherto not been reported.
Single-crystal X-ray diffraction revealed that the asymmetric unit of (I) contains one neutral monomeric complex [CuSO4(C12H8N2)2] and one solvent propane-1,2-diol molecule, which are connected by an intermolecular O—H···O hydrogen bond with the uncoordinated O atoms of the sulfate group (Fig. 1 & Table 2). In the complex, a twofold rotation axis (symmetry code: 0, y, 1/4) passes through the CoII atom and the S atom. The CoII atom has a distorted CoN4O2 octahedral geometry, with four N atoms from two chelating phenanthroline ligands and two O atoms from an O,O'-bidentate sulfate anion (Fig. 1). The Co—O bond distance [2.124 (3) Å], the Co—N bond distance [2.123 (3) Å], the N—Co—N bite angles [77.50 (13)°] and O—Co—O bite angle [66.91 (16)°] are within normal ranges and are comparable to the closely related structure (II) - (IV). The two chelating N2C2 groups are oriented at 84.46 (15)°, which is much larger than reported in (II), (III) and (IV) [70.16 (6)°, 80.06 (8)° and 83.48 (1)°, respectively]. The solvent molecule is disordered over two sets of sites with occupancies of 0.50 and 0.50.