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Acta Cryst. (2007). E63, m2083    [ doi:10.1107/S1600536807032722 ]

The 2:1 adduct of 8-hydroxyquinoline N-oxide and diaquabis(8-hydroxyquinoline N-oxide)dithiocyanatocobalt(II)

S.-G. Zhang, H.-Y. Xu and J.-M. Shi

Abstract top

In the crystal structure of the title adduct, [Co(NCS)2(C9H7NO2)2(H2O)2]·2C9H7NO2, the uncoordinated 8-hydroxyquinoline molecules and complex molecules are connected by intermolecular O-H...O and C-H...S hydrogen bonds. In the complex molecule, the CoII atom lies on a crystallographic inversion centre and has a slightly distorted octahedral coordination geometry. In addition, weak [pi]-[pi] stacking interactions between the uncoordinated and coordinated ring systems, with ring-centroid separations of 3.7554 (18) Å, consolidate the crystal structure.

Comment top

The thiocyanate anion is a versatile ligand and a large number of complexes have been synthisized with it as a termianl or as a bridging ligand (e.g. Shi et al., 2006). Our interest in complexes containing the thiocyanate ligand resulted in us obtaining the title adduct. Here we report its cystal structure. The crystal structure of 8-hydroxyquinoline N-oxide has previously been reported (Desiderato et al., 1971).

Figure 1 shows a symmetry complete complex molecule and a symmetry unique 8-hydroxyquinoline molecule. Atom Co1 is in a slightly distorted octahedral CoN2O4 coordination geometry. In the crystal structure both the uncoordinated and coordinated 8-hydroxyquinoline molecules contain intramolecular O—H···O and O—H···N hydrogen bonds. Intermolecular O—H···O and C—H···S hydrogen bonds are observed between uncoordinated 8-hydroxyquinoline molecules and complex molecules (Fig. 2). In addition, there is a weak π-π stacking interaction between adjacent C11—C16 and N2/C6—C10 rings, with Cg1···Cg2 = 3.7554 (18) Å and Cg1···Cg2perp = 3.471 Å [Cg1···Cg2 is the distance between the two ring centroids, and Cg1···Cg2perp is the perpendicular distance of the two rings]. The dihedral anagle of the planes of the two rings is 14.6°. The overall result of the hydrogen bonding and π···π stacking interactions leads to the formation of a super-molecular three-dimensional structure.

Related literature top

For related crystal structures, see: Desiderato et al. (1971), Shi et al. (2006).

Experimental top

15 ml H2O solution containing Co(ClO4)2·6H2O (0.1578 g, 0.431 mmol) and NaSCN (0.0702 g, 0.866 mmol) was added into 20 ml 8-hydroxyquinoline N-oxide (0.1321 g, 0.820 mmol) ethanol solution, and stirred for a few minutes. The red single crystals were obtained after the mixed solution had been allowed to stand at room temperature for four weeks. The strong and sharp IR peaks at 1399 cm−1 may be attributed to the stretching vibrations of the C=C and C=N bonds, whereas peak at 2088 cm−1 is assigned to the stretching vibration of thiocyanate group.

Refinement top

H atoms of water molecule were located in a difference Fourier map and refined as riding in their as-found positions, with O—H = 0.841–0.846 Å, Uiso(H) = 1.5 Ueq(O). Other H atoms were placed in calculated positions, and refined as riding, with C—H = 0.93 Å, Uiso(H) = 1.2eq(C); O—H = 0.82 Å, Uiso(H) = 1.5 Ueq(O) for hydroxyl groups.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure showing the atom numbering scheme and thermal ellipsoids drawn at the 30% probability level. [Symmetry code: (i) −x + 1, −y, −z + 1]. Only a symmetry unique uncoordinated 8-hydroxyquinoline molecule is shown.
[Figure 2] Fig. 2. Part of the crystal structure showing hydrogen bonds as dahed lines.
8-hydroxyquinoline N-oxide–diaquabis(8-hydroxyquinoline N-oxide-κO1)bis(thiocyanato-κN)cobalt(II) (2/1) top
Crystal data top
[Co(NCS)2(C9H7NO2)2(H2O)2].2C9H7NO2F(000) = 882
Mr = 855.75Dx = 1.518 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3119 reflections
a = 8.6381 (13) Åθ = 2.4–24.1°
b = 17.133 (3) ŵ = 0.64 mm−1
c = 12.6809 (19) ÅT = 298 K
β = 93.967 (2)°Block, red
V = 1872.2 (5) Å30.46 × 0.38 × 0.21 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer		4049 independent reflections
Radiation source: fine-focus sealed tube2959 reflections with I > 2σ(I)
graphiteRint = 0.026
φ and ω scansθmax = 27.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→11
Tmin = 0.758, Tmax = 0.878k = −20→21
10783 measured reflectionsl = −11→16
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0713P)2 + 0.0781P]
where P = (Fo2 + 2Fc2)/3
4049 reflections(Δ/σ)max = 0.002
259 parametersΔρmax = 0.33 e Å−3
3 restraintsΔρmin = −0.21 e Å−3
Crystal data top
[Co(NCS)2(C9H7NO2)2(H2O)2].2C9H7NO2V = 1872.2 (5) Å3
Mr = 855.75Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.6381 (13) ŵ = 0.64 mm−1
b = 17.133 (3) ÅT = 298 K
c = 12.6809 (19) Å0.46 × 0.38 × 0.21 mm
β = 93.967 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer		4049 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2959 reflections with I > 2σ(I)
Tmin = 0.758, Tmax = 0.878Rint = 0.026
10783 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.122Δρmax = 0.33 e Å−3
S = 0.99Δρmin = −0.21 e Å−3
4049 reflectionsAbsolute structure: ?
259 parametersFlack parameter: ?
3 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*/Ueq
O10.30709 (16)0.07591 (9)0.46163 (12)0.0570 (4)
H60.26060.05650.40690.085*
H70.24970.07620.51260.085*
Co10.50000.00000.50000.04581 (15)
O20.63297 (17)0.09338 (8)0.56295 (12)0.0520 (4)
N20.69243 (19)0.15070 (10)0.50537 (13)0.0479 (4)
O51.0743 (2)0.07773 (12)0.61024 (16)0.0881 (6)
H21.03590.03600.62640.132*
C70.6420 (2)0.22599 (13)0.51917 (16)0.0497 (5)
C150.9009 (2)0.11953 (14)0.73717 (18)0.0545 (5)
O30.4624 (2)0.19045 (10)0.65009 (14)0.0710 (5)
H10.49870.14730.63840.107*
N10.5638 (2)0.01197 (11)0.34865 (16)0.0576 (5)
N30.8489 (2)0.04347 (14)0.75126 (17)0.0678 (6)
C80.8003 (3)0.13268 (18)0.4404 (2)0.0678 (7)
H80.83190.08110.43430.081*
C10.6113 (3)0.02121 (12)0.26736 (18)0.0494 (5)
C160.8379 (3)0.18037 (19)0.7958 (2)0.0733 (8)
C90.8669 (3)0.1907 (3)0.3808 (2)0.0929 (11)
H90.94250.17810.33480.111*
C60.7082 (3)0.28558 (17)0.4597 (2)0.0728 (8)
C20.5277 (3)0.24412 (14)0.59013 (18)0.0566 (6)
C141.0138 (3)0.13580 (16)0.66616 (19)0.0606 (6)
C40.5457 (5)0.37788 (19)0.5420 (3)0.1031 (12)
H40.51250.42900.55060.124*
O40.9025 (2)−0.01479 (11)0.69366 (18)0.0851 (6)
C30.4817 (3)0.31982 (17)0.5988 (2)0.0793 (8)
H30.40530.33220.64430.095*
C131.0592 (3)0.2099 (2)0.6527 (3)0.0868 (9)
H131.13380.22090.60530.104*
C180.6822 (4)0.0881 (3)0.8789 (3)0.1141 (15)
H180.60980.07670.92760.137*
C190.7415 (3)0.0290 (2)0.8207 (3)0.0929 (10)
H190.7069−0.02190.82940.111*
C100.8200 (4)0.2656 (3)0.3908 (2)0.0954 (11)
H100.86340.30430.35080.114*
C120.9966 (5)0.2699 (2)0.7082 (4)0.1114 (13)
H121.02980.32080.69720.134*
C110.8899 (5)0.2572 (2)0.7773 (3)0.1041 (12)
H110.84940.29890.81340.125*
C50.6557 (5)0.36344 (18)0.4736 (3)0.0981 (11)
H50.69680.40410.43590.118*
C170.7273 (4)0.1617 (3)0.8661 (3)0.1088 (14)
H170.68400.20120.90490.131*
S10.67766 (10)0.03564 (5)0.15248 (6)0.0848 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0554 (9)0.0602 (9)0.0560 (9)0.0069 (7)0.0085 (7)−0.0016 (7)
Co10.0487 (2)0.0473 (2)0.0425 (2)0.00069 (17)0.01068 (17)0.00210 (17)
O20.0607 (9)0.0485 (8)0.0474 (8)−0.0054 (7)0.0081 (7)0.0023 (7)
N20.0430 (9)0.0597 (11)0.0413 (9)−0.0064 (8)0.0058 (7)−0.0031 (8)
O50.0686 (11)0.1132 (15)0.0857 (14)0.0141 (11)0.0285 (10)−0.0130 (12)
C70.0521 (12)0.0533 (12)0.0427 (11)−0.0106 (10)−0.0037 (9)0.0011 (10)
C150.0407 (11)0.0715 (15)0.0501 (13)0.0027 (10)−0.0042 (9)−0.0024 (11)
O30.0749 (11)0.0797 (12)0.0614 (11)0.0046 (9)0.0259 (9)−0.0049 (9)
N10.0611 (12)0.0670 (12)0.0460 (10)−0.0026 (9)0.0128 (9)0.0020 (9)
N30.0524 (11)0.0882 (16)0.0613 (13)0.0012 (11)−0.0069 (10)0.0103 (12)
C80.0476 (13)0.0967 (19)0.0603 (15)−0.0067 (12)0.0124 (11)−0.0184 (14)
C10.0536 (12)0.0451 (11)0.0505 (13)0.0002 (9)0.0097 (10)−0.0021 (9)
C160.0552 (14)0.102 (2)0.0603 (16)0.0173 (14)−0.0110 (12)−0.0229 (15)
C90.0602 (17)0.162 (3)0.0589 (18)−0.041 (2)0.0204 (14)−0.014 (2)
C60.0731 (17)0.0812 (18)0.0616 (16)−0.0341 (14)−0.0132 (14)0.0175 (14)
C20.0580 (13)0.0606 (14)0.0500 (13)0.0034 (11)−0.0061 (11)−0.0113 (11)
C140.0453 (12)0.0802 (17)0.0562 (14)0.0019 (12)0.0026 (10)0.0001 (12)
C40.122 (3)0.0600 (18)0.121 (3)0.002 (2)−0.039 (3)−0.007 (2)
O40.0760 (13)0.0685 (12)0.1083 (17)0.0125 (9)−0.0125 (12)−0.0076 (11)
C30.0859 (19)0.0710 (18)0.078 (2)0.0145 (15)−0.0143 (16)−0.0179 (15)
C130.0696 (18)0.105 (2)0.085 (2)−0.0220 (17)−0.0049 (16)0.0168 (19)
C180.063 (2)0.229 (5)0.0507 (18)0.002 (3)0.0101 (15)0.012 (3)
C190.0594 (16)0.140 (3)0.077 (2)−0.0225 (18)−0.0114 (16)0.042 (2)
C100.083 (2)0.138 (3)0.0649 (19)−0.063 (2)0.0007 (16)0.023 (2)
C120.107 (3)0.078 (2)0.142 (4)−0.015 (2)−0.043 (3)−0.005 (2)
C110.097 (2)0.091 (3)0.118 (3)0.024 (2)−0.038 (2)−0.044 (2)
C50.120 (3)0.0609 (18)0.107 (3)−0.0371 (19)−0.035 (2)0.0288 (17)
C170.0613 (19)0.203 (4)0.062 (2)0.029 (2)0.0004 (15)−0.039 (3)
S10.1174 (6)0.0820 (5)0.0604 (4)−0.0090 (4)0.0450 (4)−0.0001 (4)
Geometric parameters (Å, °) top
O1—Co12.1431 (14)C1—S11.621 (2)
O1—H60.8463C16—C171.389 (5)
O1—H70.8407C16—C111.416 (5)
Co1—N1i2.044 (2)C9—C101.354 (5)
Co1—N12.044 (2)C9—H90.9300
Co1—O22.0951 (14)C6—C101.390 (4)
Co1—O2i2.0951 (14)C6—C51.424 (4)
Co1—O1i2.1431 (14)C2—C31.363 (3)
O2—N21.346 (2)C14—C131.344 (4)
N2—C81.322 (3)C4—C51.353 (5)
N2—C71.376 (3)C4—C31.367 (4)
O5—C141.348 (3)C4—H40.9300
O5—H20.8200C3—H30.9300
C7—C61.413 (3)C13—C121.377 (5)
C7—C21.416 (3)C13—H130.9300
C15—N31.394 (3)C18—C171.333 (5)
C15—C141.401 (3)C18—C191.373 (5)
C15—C161.411 (3)C18—H180.9300
O3—C21.342 (3)C19—H190.9300
O3—H10.8200C10—H100.9300
N1—C11.146 (3)C12—C111.333 (5)
N3—O41.338 (3)C12—H120.9300
N3—C191.345 (4)C11—H110.9300
C8—C91.397 (4)C5—H50.9300
C8—H80.9300C17—H170.9300
Co1—O1—H6105.4C10—C9—H9120.5
Co1—O1—H7108.6C8—C9—H9120.5
H6—O1—H7111.2C10—C6—C7118.8 (3)
N1i—Co1—N1180.0C10—C6—C5123.4 (3)
N1i—Co1—O283.99 (7)C7—C6—C5117.8 (3)
N1—Co1—O296.01 (7)O3—C2—C3118.0 (2)
N1i—Co1—O2i96.01 (7)O3—C2—C7123.3 (2)
N1—Co1—O2i83.99 (7)C3—C2—C7118.7 (2)
O2—Co1—O2i180.00 (5)C13—C14—O5120.3 (3)
N1i—Co1—O191.03 (7)C13—C14—C15119.5 (3)
N1—Co1—O188.97 (7)O5—C14—C15120.3 (2)
O2—Co1—O191.16 (6)C5—C4—C3122.2 (3)
O2i—Co1—O188.84 (6)C5—C4—H4118.9
N1i—Co1—O1i88.97 (7)C3—C4—H4118.9
N1—Co1—O1i91.03 (7)C2—C3—C4121.2 (3)
O2—Co1—O1i88.84 (6)C2—C3—H3119.4
O2i—Co1—O1i91.16 (6)C4—C3—H3119.4
O1—Co1—O1i180.00 (8)C14—C13—C12120.8 (3)
N2—O2—Co1124.75 (12)C14—C13—H13119.6
C8—N2—O2118.6 (2)C12—C13—H13119.6
C8—N2—C7122.7 (2)C17—C18—C19120.7 (3)
O2—N2—C7118.60 (16)C17—C18—H18119.7
C14—O5—H2109.5C19—C18—H18119.7
N2—C7—C6117.8 (2)N3—C19—C18121.0 (3)
N2—C7—C2121.80 (19)N3—C19—H19119.5
C6—C7—C2120.4 (2)C18—C19—H19119.5
N3—C15—C14120.9 (2)C9—C10—C6121.2 (3)
N3—C15—C16118.9 (2)C9—C10—H10119.4
C14—C15—C16120.2 (2)C6—C10—H10119.4
C2—O3—H1109.5C11—C12—C13121.8 (4)
C1—N1—Co1174.2 (2)C11—C12—H12119.1
O4—N3—C19120.0 (3)C13—C12—H12119.1
O4—N3—C15120.0 (2)C12—C11—C16120.2 (3)
C19—N3—C15120.0 (3)C12—C11—H11119.9
N2—C8—C9120.4 (3)C16—C11—H11119.9
N2—C8—H8119.8C4—C5—C6119.6 (3)
C9—C8—H8119.8C4—C5—H5120.2
N1—C1—S1179.1 (2)C6—C5—H5120.2
C17—C16—C15118.4 (3)C18—C17—C16121.0 (4)
C17—C16—C11124.1 (3)C18—C17—H17119.5
C15—C16—C11117.5 (3)C16—C17—H17119.5
C10—C9—C8119.1 (3)
N1i—Co1—O2—N2−162.65 (15)N2—C7—C2—C3−179.1 (2)
N1—Co1—O2—N217.35 (15)C6—C7—C2—C30.8 (3)
O1—Co1—O2—N2−71.73 (14)N3—C15—C14—C13178.6 (2)
O1i—Co1—O2—N2108.27 (14)C16—C15—C14—C13−1.4 (4)
Co1—O2—N2—C8−65.6 (2)N3—C15—C14—O5−0.1 (3)
Co1—O2—N2—C7116.45 (17)C16—C15—C14—O5179.9 (2)
C8—N2—C7—C60.8 (3)O3—C2—C3—C4178.5 (3)
O2—N2—C7—C6178.66 (18)C7—C2—C3—C4−1.2 (4)
C8—N2—C7—C2−179.2 (2)C5—C4—C3—C20.9 (5)
O2—N2—C7—C2−1.4 (3)O5—C14—C13—C12179.0 (3)
C14—C15—N3—O4−2.6 (3)C15—C14—C13—C120.3 (4)
C16—C15—N3—O4177.5 (2)O4—N3—C19—C18−178.5 (3)
C14—C15—N3—C19179.3 (2)C15—N3—C19—C18−0.4 (4)
C16—C15—N3—C19−0.7 (3)C17—C18—C19—N31.5 (5)
O2—N2—C8—C9−178.8 (2)C8—C9—C10—C60.6 (5)
C7—N2—C8—C9−1.0 (4)C7—C6—C10—C9−0.7 (4)
N3—C15—C16—C170.6 (4)C5—C6—C10—C9179.6 (3)
C14—C15—C16—C17−179.4 (2)C14—C13—C12—C110.3 (5)
N3—C15—C16—C11−178.2 (2)C13—C12—C11—C160.2 (5)
C14—C15—C16—C111.9 (4)C17—C16—C11—C12−180.0 (3)
N2—C8—C9—C100.2 (4)C15—C16—C11—C12−1.3 (4)
N2—C7—C6—C100.0 (3)C3—C4—C5—C6−0.2 (5)
C2—C7—C6—C10−179.9 (2)C10—C6—C5—C4179.6 (3)
N2—C7—C6—C5179.8 (2)C7—C6—C5—C4−0.1 (4)
C2—C7—C6—C5−0.2 (4)C19—C18—C17—C16−1.6 (6)
N2—C7—C2—O31.2 (3)C15—C16—C17—C180.6 (5)
C6—C7—C2—O3−178.8 (2)C11—C16—C17—C18179.2 (3)
Symmetry codes: (i) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H7···O5ii0.842.022.849 (2)168
O1—H6···O4i0.851.972.786 (3)162
C5—H5···S1iii0.932.773.695 (4)173
C12—H12···S1iv0.932.853.768 (4)170
O3—H1···O20.821.812.527 (2)145
O3—H1···N20.822.462.878 (2)113
O5—H2···O40.821.722.460 (3)150
O5—H2···N30.822.342.796 (3)116
Symmetry codes: (ii) x−1, y, z; (i) −x+1, −y, −z+1; (iii) −x+3/2, y+1/2, −z+1/2; (iv) x+1/2, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H7···O5i0.842.022.849 (2)168
O1—H6···O4ii0.851.972.786 (3)162
C5—H5···S1iii0.932.773.695 (4)173
C12—H12···S1iv0.932.853.768 (4)170
O3—H1···O20.821.812.527 (2)145
O3—H1···N20.822.462.878 (2)113
O5—H2···O40.821.722.460 (3)150
O5—H2···N30.822.342.796 (3)116
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+1; (iii) −x+3/2, y+1/2, −z+1/2; (iv) x+1/2, −y+1/2, z+1/2.
Acknowledgements top

The authors thank the Natural Science Foundation of Shandong Province of China (grant No. Y2005B25).

references
References top

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