supplementary materials


vn2062 scheme

Acta Cryst. (2013). E69, m26    [ doi:10.1107/S1600536812049616 ]

Bis(1,10-phenanthroline-[kappa]2N,N')(sulfato-[kappa]2O,O')cobalt(II) propane-1,2-diol monosolvate

K.-L. Zhong

Abstract top

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 site symmetry 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.

Comment top

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.

Related literature top

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 top

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.

Refinement top

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).

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: 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).

Figures top
[Figure 1] 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.
Bis(1,10-phenanthroline-κ2N,N')(sulfato- κ2O,O')cobalt(II) propane-1,2-diol monosolvate top
Crystal data top
[Co(SO4)(C12H8N2)2]·C3H8O2F(000) = 1220
Mr = 591.49Dx = 1.520 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5104 reflections
a = 18.117 (4) Åθ = 3.1–25.4°
b = 12.987 (3) ŵ = 0.80 mm1
c = 12.881 (3) ÅT = 223 K
β = 121.46 (3)°Block, red
V = 2585.2 (13) Å30.35 × 0.34 × 0.25 mm
Z = 4
Data collection top
Rigaku Mercury CCD
diffractometer
2284 independent reflections
Radiation source: fine-focus sealed tube1465 reflections with I > 2/s(I)
Graphite Monochromator monochromatorRint = 0.100
Detector resolution: 28.5714 pixels mm-1θmax = 25.0°, θmin = 3.1°
ω scansh = 2021
Absorption correction: multi-scan
(REQAB; Jacobson, 1998)
k = 1415
Tmin = 0.373, Tmax = 1.000l = 1515
11477 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H-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 reflectionsΔρmax = 0.37 e Å3
193 parametersΔρmin = 0.39 e Å3
38 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0060 (5)
Crystal data top
[Co(SO4)(C12H8N2)2]·C3H8O2V = 2585.2 (13) Å3
Mr = 591.49Z = 4
Monoclinic, C2/cMo Kα radiation
a = 18.117 (4) ŵ = 0.80 mm1
b = 12.987 (3) ÅT = 223 K
c = 12.881 (3) Å0.35 × 0.34 × 0.25 mm
β = 121.46 (3)°
Data collection top
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 = 1.000Rint = 0.100
11477 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.129Δρmax = 0.37 e Å3
S = 0.95Δρmin = 0.39 e Å3
2284 reflectionsAbsolute structure: ?
193 parametersFlack parameter: ?
38 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co10.00000.32137 (6)0.25000.0348 (3)
S10.00000.52899 (11)0.25000.0344 (4)
O10.0533 (2)0.4578 (2)0.3537 (3)0.0495 (9)
O20.0552 (2)0.5929 (2)0.2742 (3)0.0604 (10)
O30.0492 (7)0.7963 (6)0.3204 (8)0.071 (3)0.50
H30.04280.74240.29310.106*0.50
O3'0.0869 (6)0.7996 (6)0.2438 (10)0.097 (4)0.50
H3'0.06130.74720.28040.145*0.50
N10.0830 (2)0.3000 (3)0.1814 (3)0.0379 (9)
N20.0959 (2)0.2178 (2)0.3803 (3)0.0363 (9)
C10.0774 (3)0.3442 (4)0.0841 (4)0.0459 (12)
H1A0.03400.39240.04060.055*
C20.1339 (3)0.3208 (4)0.0454 (5)0.0537 (14)
H2A0.12840.35350.02250.064*
C30.1977 (3)0.2495 (4)0.1074 (5)0.0555 (14)
H3A0.23540.23310.08140.067*
C40.2061 (3)0.2012 (3)0.2104 (4)0.0419 (12)
C50.2732 (3)0.1286 (4)0.2841 (5)0.0538 (14)
H5A0.31170.10820.26080.065*
C60.2814 (3)0.0902 (4)0.3853 (5)0.0493 (13)
H6A0.32580.04400.43200.059*
C70.2225 (3)0.1189 (3)0.4240 (4)0.0402 (11)
C80.2298 (3)0.0829 (3)0.5312 (4)0.0506 (13)
H8A0.27380.03750.58160.061*
C90.1723 (3)0.1150 (4)0.5605 (4)0.0546 (14)
H9A0.17670.09240.63200.065*
C100.1062 (3)0.1819 (3)0.4833 (4)0.0468 (13)
H10A0.06710.20260.50530.056*
C110.1546 (3)0.1866 (3)0.3517 (4)0.0320 (10)
C120.1473 (3)0.2300 (3)0.2447 (4)0.0341 (11)
C130.0288 (6)0.8772 (5)0.2729 (9)0.139 (3)0.50
H130.08370.88220.19480.167*0.50
C13'0.0288 (6)0.8772 (5)0.2729 (9)0.139 (3)0.50
H13A0.00690.87990.36100.167*0.50
H13B0.06130.94110.24670.167*0.50
C140.0305 (12)0.9804 (8)0.3222 (18)0.168 (9)0.50
H14A0.00011.02900.30210.252*0.50
H14B0.00320.97620.40910.252*0.50
H14C0.08941.00250.28720.252*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0323 (5)0.0367 (5)0.0407 (6)0.0000.0228 (5)0.000
S10.0282 (9)0.0352 (9)0.0424 (10)0.0000.0203 (8)0.000
O10.048 (2)0.0428 (18)0.038 (2)0.0012 (15)0.0091 (17)0.0020 (15)
O20.060 (2)0.049 (2)0.095 (3)0.0103 (17)0.056 (2)0.0082 (19)
O30.111 (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)
N10.038 (2)0.042 (2)0.041 (2)0.0010 (17)0.026 (2)0.0036 (18)
N20.041 (2)0.036 (2)0.042 (2)0.0010 (17)0.029 (2)0.0011 (17)
C10.041 (3)0.056 (3)0.044 (3)0.003 (2)0.024 (3)0.007 (2)
C20.054 (3)0.070 (4)0.046 (3)0.003 (3)0.033 (3)0.008 (3)
C30.050 (3)0.080 (4)0.052 (3)0.004 (3)0.038 (3)0.003 (3)
C40.036 (3)0.057 (3)0.036 (3)0.004 (2)0.021 (2)0.002 (2)
C50.044 (3)0.073 (4)0.050 (3)0.018 (3)0.028 (3)0.001 (3)
C60.037 (3)0.059 (3)0.047 (3)0.015 (2)0.018 (3)0.001 (3)
C70.036 (3)0.042 (3)0.038 (3)0.005 (2)0.017 (2)0.002 (2)
C80.046 (3)0.049 (3)0.047 (3)0.007 (2)0.018 (3)0.006 (2)
C90.063 (4)0.059 (3)0.046 (3)0.005 (3)0.031 (3)0.015 (3)
C100.056 (3)0.050 (3)0.049 (3)0.003 (2)0.038 (3)0.005 (2)
C110.033 (3)0.031 (2)0.034 (3)0.0038 (19)0.019 (2)0.0020 (19)
C120.027 (3)0.041 (3)0.034 (3)0.001 (2)0.015 (2)0.002 (2)
C130.195 (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)
C140.20 (2)0.069 (10)0.32 (3)0.029 (11)0.19 (2)0.032 (14)
Geometric parameters (Å, º) top
Co1—O12.124 (3)C3—C41.402 (6)
Co1—O1i2.124 (3)C3—H3A0.9300
Co1—N12.123 (3)C4—C121.400 (6)
Co1—N1i2.123 (3)C4—C51.437 (6)
Co1—N2i2.145 (4)C5—C61.330 (6)
Co1—N22.145 (4)C5—H5A0.9300
Co1—S12.6964 (18)C6—C71.442 (6)
S1—O2i1.453 (3)C6—H6A0.9300
S1—O21.453 (3)C7—C111.399 (6)
S1—O1i1.492 (3)C7—C81.397 (6)
S1—O11.492 (3)C8—C91.346 (6)
O3—C131.361 (4)C8—H8A0.9300
O3—H30.8200C9—C101.391 (6)
O3'—H3'0.8200C9—H9A0.9300
N1—C11.333 (5)C10—H10A0.9300
N1—C121.363 (5)C11—C121.430 (6)
N2—C101.324 (5)C13—C13i1.443 (7)
N2—C111.356 (5)C13—C141.489 (9)
C1—C21.386 (6)C13—H130.9800
C1—H1A0.9300C14—H14A0.9600
C2—C31.366 (6)C14—H14B0.9600
C2—H2A0.9300C14—H14C0.9600
O1—Co1—O1i66.91 (16)C1—C2—H2A120.2
O1—Co1—N1100.51 (13)C2—C3—C4119.9 (4)
O1i—Co1—N192.02 (13)C2—C3—H3A120.1
O1—Co1—N1i92.02 (13)C4—C3—H3A120.1
O1i—Co1—N1i100.51 (13)C12—C4—C3117.0 (4)
N1—Co1—N1i165.01 (18)C12—C4—C5119.2 (4)
O1—Co1—N2i158.77 (12)C3—C4—C5123.8 (4)
O1i—Co1—N2i96.57 (12)C6—C5—C4121.1 (4)
N1—Co1—N2i93.03 (13)C6—C5—H5A119.5
N1i—Co1—N2i77.50 (13)C4—C5—H5A119.5
O1—Co1—N296.57 (12)C5—C6—C7121.2 (4)
O1i—Co1—N2158.77 (12)C5—C6—H6A119.4
N1—Co1—N277.50 (13)C7—C6—H6A119.4
N1i—Co1—N293.03 (13)C11—C7—C8117.7 (4)
N2i—Co1—N2102.31 (18)C11—C7—C6119.0 (4)
O1—Co1—S133.45 (8)C8—C7—C6123.3 (4)
O1i—Co1—S133.45 (8)C9—C8—C7119.0 (4)
N1—Co1—S197.50 (9)C9—C8—H8A120.5
N1i—Co1—S197.50 (9)C7—C8—H8A120.5
N2i—Co1—S1128.85 (9)C8—C9—C10119.7 (5)
N2—Co1—S1128.85 (9)C8—C9—H9A120.1
O2i—S1—O2110.3 (3)C10—C9—H9A120.1
O2i—S1—O1i111.01 (19)N2—C10—C9123.8 (4)
O2—S1—O1i110.46 (19)N2—C10—H10A118.1
O2i—S1—O1110.46 (19)C9—C10—H10A118.1
O2—S1—O1111.01 (19)N2—C11—C7123.3 (4)
O1i—S1—O1103.4 (2)N2—C11—C12116.9 (4)
O2i—S1—Co1124.83 (13)C7—C11—C12119.7 (4)
O2—S1—Co1124.83 (13)N1—C12—C4122.9 (4)
O1i—S1—Co151.70 (12)N1—C12—C11117.4 (4)
O1—S1—Co151.70 (12)C4—C12—C11119.8 (4)
S1—O1—Co194.85 (16)O3—C13—C13i127.5 (5)
C13—O3—H3109.5O3—C13—C14115.6 (8)
C1—N1—C12118.1 (4)C13i—C13—C14110.8 (7)
C1—N1—Co1127.8 (3)O3—C13—H1398.3
C12—N1—Co1114.1 (3)C13i—C13—H1398.3
C10—N2—C11116.5 (4)C14—C13—H1398.3
C10—N2—Co1129.7 (3)C13—C14—H14A109.5
C11—N2—Co1113.9 (3)C13—C14—H14B109.5
N1—C1—C2122.4 (4)H14A—C14—H14B109.5
N1—C1—H1A118.8C13—C14—H14C109.5
C2—C1—H1A118.8H14A—C14—H14C109.5
C3—C2—C1119.7 (5)H14B—C14—H14C109.5
C3—C2—H2A120.2
O1—Co1—S1—O2i89.6 (2)N2i—Co1—N2—C1094.6 (4)
O1i—Co1—S1—O2i90.4 (2)S1—Co1—N2—C1085.4 (4)
N1—Co1—S1—O2i8.1 (2)O1—Co1—N2—C11103.3 (3)
N1i—Co1—S1—O2i171.9 (2)O1i—Co1—N2—C1165.9 (5)
N2i—Co1—S1—O2i108.2 (2)N1—Co1—N2—C114.0 (3)
N2—Co1—S1—O2i71.8 (2)N1i—Co1—N2—C11164.3 (3)
O1—Co1—S1—O290.4 (2)N2i—Co1—N2—C1186.4 (3)
O1i—Co1—S1—O289.6 (2)S1—Co1—N2—C1193.6 (3)
N1—Co1—S1—O2171.9 (2)C12—N1—C1—C20.4 (7)
N1i—Co1—S1—O28.1 (2)Co1—N1—C1—C2177.4 (3)
N2i—Co1—S1—O271.8 (2)N1—C1—C2—C30.5 (8)
N2—Co1—S1—O2108.2 (2)C1—C2—C3—C40.6 (8)
O1—Co1—S1—O1i180.0C2—C3—C4—C120.3 (7)
N1—Co1—S1—O1i82.27 (19)C2—C3—C4—C5177.3 (5)
N1i—Co1—S1—O1i97.73 (19)C12—C4—C5—C61.3 (7)
N2i—Co1—S1—O1i17.8 (2)C3—C4—C5—C6175.6 (5)
N2—Co1—S1—O1i162.2 (2)C4—C5—C6—C70.8 (8)
O1i—Co1—S1—O1180.0C5—C6—C7—C111.5 (7)
N1—Co1—S1—O197.73 (19)C5—C6—C7—C8178.2 (5)
N1i—Co1—S1—O182.27 (19)C11—C7—C8—C90.4 (7)
N2i—Co1—S1—O1162.2 (2)C6—C7—C8—C9179.2 (4)
N2—Co1—S1—O117.8 (2)C7—C8—C9—C100.8 (7)
O2i—S1—O1—Co1118.82 (17)C11—N2—C10—C90.6 (7)
O2—S1—O1—Co1118.44 (18)Co1—N2—C10—C9179.5 (3)
O1i—S1—O1—Co10.0C8—C9—C10—N20.4 (8)
O1i—Co1—O1—S10.0C10—N2—C11—C71.0 (6)
N1—Co1—O1—S187.70 (17)Co1—N2—C11—C7179.9 (3)
N1i—Co1—O1—S1100.56 (16)C10—N2—C11—C12176.1 (4)
N2i—Co1—O1—S141.1 (4)Co1—N2—C11—C123.0 (5)
N2—Co1—O1—S1166.15 (15)C8—C7—C11—N20.6 (7)
O1—Co1—N1—C183.2 (4)C6—C7—C11—N2179.8 (4)
O1i—Co1—N1—C116.3 (4)C8—C7—C11—C12176.5 (4)
N1i—Co1—N1—C1130.6 (4)C6—C7—C11—C123.1 (6)
N2i—Co1—N1—C180.4 (4)C1—N1—C12—C41.4 (6)
N2—Co1—N1—C1177.6 (4)Co1—N1—C12—C4176.7 (3)
S1—Co1—N1—C149.4 (4)C1—N1—C12—C11177.4 (4)
O1—Co1—N1—C1299.0 (3)Co1—N1—C12—C114.5 (5)
O1i—Co1—N1—C12165.9 (3)C3—C4—C12—N11.3 (7)
N1i—Co1—N1—C1247.3 (3)C5—C4—C12—N1178.4 (4)
N2i—Co1—N1—C1297.5 (3)C3—C4—C12—C11177.5 (4)
N2—Co1—N1—C124.5 (3)C5—C4—C12—C110.4 (6)
S1—Co1—N1—C12132.7 (3)N2—C11—C12—N11.0 (6)
O1—Co1—N2—C1075.6 (4)C7—C11—C12—N1176.3 (4)
O1i—Co1—N2—C10113.1 (5)N2—C11—C12—C4179.9 (4)
N1—Co1—N2—C10175.0 (4)C7—C11—C12—C42.6 (6)
N1i—Co1—N2—C1016.8 (4)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O20.821.952.698 (9)150
O3—H3···O20.822.012.730 (10)146
Selected bond lengths (Å) top
Co1—O12.124 (3)Co1—N22.145 (4)
Co1—N12.123 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O20.821.952.698 (9)150.4
O3'—H3'···O20.822.012.730 (10)146.2
Acknowledgements top

This work was supported by the Scientific Research Foundation of Nanjing College of Chemical Technology (grant No. NHKY-2010–17).

references
References top

Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460–1494.

Jacobson, R. (1998). REQAB. Molecular Structure Corporation, The Woodlands, Texas, USA.

Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Robin, A.-Y. & Fromm, K. M. (2006). Coord. Chem. Rev. 250, 2127–2157.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Wang, S.-J. & Zhong, K.-L. (2011). Acta Cryst. E67, m446.

Zhong, K.-L. (2010). Acta Cryst. E66, m247.

Zhong, K.-L., Zhu, Y.-M. & Lu, W.-J. (2006). Acta Cryst. E62, m631–m633.