supplementary materials


pk2366 scheme

Acta Cryst. (2012). E68, m51    [ doi:10.1107/S1600536811053128 ]

Bis(morpholin-4-ium) tetrachloridocobalt(II)

W.-Z. Wang, R. H. Ismayilov, G.-H. Lee, Y.-S. Wen and S.-M. Peng

Abstract top

The title compound, (C4H10NO)2[CoCl4], is an ionic compound consisting of two protonated tetrahydro-1,4-oxazine (morpholine) cations and a [CoCl4]2- dianion. The CoII ion is in a tetrahedral coordination geometry. The cations exhibit chair-shaped conformations. A three-dimensional supramolecular architecture is formed through N-H...Cl and C-H...Cl hydrogen bonds between the dianions and the cations.

Comment top

Oligo-α-pyridylamine ligands are very useful in the synthesis of metal string complexes, which are also known as extended metal atom chains (EMACs). EMACs are invaluable for acquiring a fundamental understanding of metal-metal bonds (Kiehl et al., 2004) and for potential applications such as molecular electronic devices. These oligo-α-pyridylamine ligands contain pyridyl and amine groups, and can result in the formation of double helical structures in nonpolar solvents due to hydrogen bonding (Leung et al., 2002). After deprotonation of oligo-α-pyridylamine ligands, the resulting anions can stabilize the linear metal cores. Activation of the H atom was observed in some EMACs. Recently we designed a series of modulated oligo-a-pyridylamino ligands, by including one or more of the nitrogen-rich aromatic rings such as pyrazine, pyrimidine and naphthyridine instead of pyridine rings to the ligands. The modification of ligands significantly improved the reactivity leading to the EMAC, and resulted in complexes with very different redox properties (Wang et al., 2008). Furthermore, by providing more donor nitrogen atoms in aromatic rings, the pyrazine ligands exhibit more coordination forms and are especially versatile in the construction of coordination polymers with potential applications in gas storage, catalysis, magnetism, luminescence, etc. due to their ability to form multidimensional frameworks through multiple metal-binding sites. (Ismayilov et al., 2007; Wang et al., 2007, 2008). Some interesting phenomena were also observed, e.g. the observation of disassembly of ligands during the preparation of EMACs. In this paper we describe a compound (I) from the decomposition of pyrazine-modulated N2-(pyrazin-2-yl)-N6– (6-(pyrazin-2-ylamino)pyridin-2-yl)pyridine-2,6-diamine (H3pzpz) relating to the preparation of heptacobalt complexes (Wang et al., 2007).

The crystal structure of [C4H10NO]2[CoCl4] shown in Fig. 1 consists of two protonated tetrahydro-1,4-oxazine(morpholine) cations [C4H10NO]+ and a [CoCl4]2- dianion, the compound [C4H10NO]2[CoCl4] is a hybrid ionic inorganic-organic compound of Y2X type. The CoII ion is in a tetrahedral coordination geometry. The Co—Cl bond distances are in the range 2.2583 (8) - 2.2818 (8)Å with an average of 2.2675 (8)Å (The Co—Cl in CoCl2 is 2.43 Å). The bond angles between Co—Cl are in the range 106.01 (3) - 113.73 (3)° with an average of 109.43 (3)°, which is very close to the ideal tetrahedral angle value of 109.28° (Fastje & Möller, 2009; Szklarz et al., 2009; Wu et al., 1997).

The cations are six-membered heterocycle rings, protonated tetrahydro- 1,4-oxazine, and exhibit chair-shaped conformations. All bond angles in the rings are in the range 108.8 (3) - 111.9 (2)° with an average of 110.4 (3)°, which is well consistent with a sp3 hybrid orbital angle. The nitrogen atom in tetrahydro-1,4-oxazine was protonated owing to the low basicity of tetrahydro-1,4-oxazine (pKa = 8.4) due to the inductive effect of oxygen atom. The average C—C, C—N and C—O bond distances exhibit a typical value of single bonds, which are 1.503 (4), 1.490 (4) and 1.419 (4) Å, respectively.

Extensive hydrogen bonds between chloride atoms Cl(1), Cl(2) and Cl(3) in the [CoCl4]2- dianion and nitrogen and oxygen atoms N(1), N(2), O(1) and O(2) in both tetrahydro-1,4-oxazine cations were observed (Table 1). [CoCl4]2- dianions were paired through the hydrogen bonds between Cl(1), Cl(2) and N(1) atoms, resulting in an 8-membered ring N(1)···Cl(1)—Co—Cl(2)···N(1)···Cl(1)—Co—Cl(2) (Fig. 2) which were further linked to a 2-D sheet extending in the bc plane through hydrogen bonds between Cl(3) and N(2) atoms. A group of weak hydrogen bonds involving carbon atoms were observed between layers, which build the title compound (I) into a 3-D network (Fig. 3).

Related literature top

For background to this class of compound, see: Ismayilov et al. (2007); Kiehl et al. (2004); Leung et al. (2002); Wang et al. (2007, 2008). For the synthesis, see: Wang et al. (2007, 2008). For related structures, see: Fastje & Möller (2009); Szklarz et al. (2009); Wu et al. (1997).

Experimental top

Anhydrous CoCl2 (254 mg, 1.95 mmol), H3pzpz (300 mg, 0.84 mmol) and naphthalene (65 g) were placed in an Erlenmeyer flask. The mixture was heated under argon and then a solution of potassium tert-butoxide (311 mg, 2.77 mmol) in n-butyl alcohol (5 ml) was added dropwise. The reaction was continued for another 12 h. After cooling the product was transferred to hexane to wash out the remaining naphthalene, and then 100 ml ca CH2Cl2 was used to extract the complex. A dark green product, mainly the heptacobalt(II) metal string complex, [Co77-pzpz)4Cl2], was obtained after evaporation. The title compound was obtained as a side product from the reaction. Light blue single crystals suitable for X-ray diffraction were obtained by diffusion of ether into a chloroform solution of the green product.

Refinement top

H atoms attached to C and N atoms were positioned geometrically and refined using a riding model, with C—H = 0.99 Å, N—H = 0.92Å and Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 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 of (I) with ellisoids at the 30% probability level.
[Figure 2] Fig. 2. An 8-membered ring generated by hydrogen bonds (dashed lines) in (I). Atoms labelled with the suffixes i are at the symmetry equivalent position (-x + 1, -y + 1, -z + 1). Ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. A packing diagram of (I) viewed down the c axis. Dashed lines represent hydrogen bonds. Atoms labelled with the suffixes i, ii, and iii are at symmetry equivalent positions (-x + 1, -y + 1, -z + 1), (x, -y + 3/2, z - 1/2) and (-x + 2, y + 1/2, -z + 3/2), respectively.
Bis(morpholin-4-ium) tetrachloridocobalt(II) top
Crystal data top
(C4H10NO)2[CoCl4]F(000) = 772
Mr = 376.99Dx = 1.634 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2047 reflections
a = 9.7545 (5) Åθ = 2.4–24.0°
b = 15.0283 (8) ŵ = 1.81 mm1
c = 10.4785 (5) ÅT = 100 K
β = 94.064 (3)°Prism, blue
V = 1532.22 (13) Å30.20 × 0.16 × 0.06 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2661 independent reflections
Radiation source: fine-focus sealed tube2001 reflections with I > 2σ(I)
graphiteRint = 0.047
φ and ω scansθmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1110
Tmin = 0.714, Tmax = 0.899k = 1717
10714 measured reflectionsl = 1212
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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059H-atom parameters constrained
S = 0.89 w = 1/[σ2(Fo2) + (0.012P)2 + 2.9504P]
where P = (Fo2 + 2Fc2)/3
2661 reflections(Δ/σ)max = 0.001
154 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
(C4H10NO)2[CoCl4]V = 1532.22 (13) Å3
Mr = 376.99Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.7545 (5) ŵ = 1.81 mm1
b = 15.0283 (8) ÅT = 100 K
c = 10.4785 (5) Å0.20 × 0.16 × 0.06 mm
β = 94.064 (3)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2661 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
2001 reflections with I > 2σ(I)
Tmin = 0.714, Tmax = 0.899Rint = 0.047
10714 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.059Δρmax = 0.32 e Å3
S = 0.89Δρmin = 0.32 e Å3
2661 reflectionsAbsolute structure: ?
154 parametersFlack parameter: ?
0 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
Co0.68020 (4)0.58131 (3)0.71185 (4)0.01425 (11)
Cl10.49824 (8)0.64671 (5)0.79526 (7)0.01891 (18)
Cl20.70544 (8)0.43579 (5)0.76441 (7)0.02066 (19)
Cl30.87551 (8)0.65335 (5)0.78680 (7)0.01802 (18)
Cl40.65461 (8)0.60624 (5)0.49825 (7)0.01990 (19)
O10.0543 (2)0.71540 (14)0.4880 (2)0.0254 (6)
N10.3114 (2)0.62863 (16)0.5349 (2)0.0180 (6)
H1A0.32450.59980.45920.022*
H1B0.38550.61640.59140.022*
C10.1733 (3)0.7481 (2)0.4313 (3)0.0251 (8)
H1C0.16550.81340.42070.030*
H1D0.17800.72130.34540.030*
C20.3035 (3)0.7266 (2)0.5115 (3)0.0196 (7)
H2C0.38420.74630.46670.024*
H2D0.30430.75860.59420.024*
C30.1836 (3)0.5950 (2)0.5878 (3)0.0177 (7)
H3A0.17490.62020.67420.021*
H3B0.18760.52930.59540.021*
C40.0621 (3)0.6215 (2)0.5008 (3)0.0224 (8)
H4A0.06970.59430.41550.027*
H4B0.02300.59900.53560.027*
O20.7598 (2)0.98715 (13)0.6677 (2)0.0219 (5)
N20.8070 (3)0.81133 (16)0.5829 (2)0.0182 (6)
H2A0.82190.75250.60390.022*
H2B0.80780.81670.49550.022*
C50.8865 (3)0.9630 (2)0.6206 (3)0.0259 (8)
H5A0.96051.00030.66220.031*
H5B0.88300.97450.52740.031*
C60.9189 (3)0.8666 (2)0.6456 (3)0.0257 (8)
H6A1.00760.85110.61080.031*
H6B0.92670.85500.73880.031*
C70.6702 (3)0.8394 (2)0.6240 (3)0.0196 (7)
H7A0.66390.82550.71570.024*
H7B0.59640.80660.57420.024*
C80.6522 (3)0.9378 (2)0.6026 (3)0.0232 (8)
H8A0.65050.95050.50990.028*
H8B0.56300.95670.63320.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0151 (2)0.0141 (2)0.0135 (2)0.00047 (19)0.00119 (17)0.00033 (17)
Cl10.0197 (4)0.0212 (4)0.0161 (4)0.0040 (3)0.0027 (3)0.0015 (3)
Cl20.0282 (5)0.0152 (4)0.0190 (4)0.0025 (3)0.0045 (3)0.0005 (3)
Cl30.0165 (4)0.0196 (4)0.0175 (4)0.0021 (3)0.0015 (3)0.0018 (3)
Cl40.0242 (5)0.0225 (4)0.0130 (4)0.0032 (3)0.0010 (3)0.0004 (3)
O10.0180 (13)0.0232 (13)0.0358 (14)0.0090 (10)0.0089 (11)0.0097 (10)
N10.0140 (15)0.0217 (15)0.0179 (14)0.0042 (12)0.0025 (12)0.0014 (11)
C10.029 (2)0.0201 (18)0.0277 (19)0.0023 (16)0.0087 (17)0.0110 (15)
C20.020 (2)0.0171 (18)0.0218 (17)0.0042 (14)0.0053 (15)0.0008 (14)
C30.0257 (19)0.0131 (17)0.0146 (15)0.0001 (14)0.0036 (14)0.0018 (13)
C40.0151 (18)0.0252 (19)0.0277 (18)0.0011 (15)0.0066 (15)0.0039 (15)
O20.0200 (13)0.0208 (12)0.0252 (12)0.0009 (10)0.0033 (10)0.0135 (10)
N20.0224 (16)0.0127 (14)0.0194 (14)0.0002 (12)0.0002 (12)0.0008 (11)
C50.024 (2)0.0232 (19)0.031 (2)0.0098 (15)0.0019 (16)0.0087 (15)
C60.0123 (18)0.028 (2)0.036 (2)0.0012 (15)0.0037 (16)0.0058 (15)
C70.0169 (18)0.0225 (18)0.0197 (17)0.0057 (14)0.0031 (14)0.0019 (14)
C80.0177 (18)0.0231 (19)0.0287 (19)0.0009 (15)0.0021 (15)0.0066 (15)
Geometric parameters (Å, °) top
Co—Cl12.2583 (8)C4—H4A0.9900
Co—Cl22.2644 (8)C4—H4B0.9900
Co—Cl42.2656 (8)O2—C81.420 (4)
Co—Cl32.2818 (8)O2—C51.410 (4)
O1—C11.428 (4)N2—C61.486 (4)
O1—C41.419 (4)N2—C71.492 (4)
N1—C31.488 (4)N2—H2A0.9200
N1—C21.494 (4)N2—H2B0.9200
N1—H1A0.9200C5—C61.503 (4)
N1—H1B0.9200C5—H5A0.9900
C1—C21.507 (4)C5—H5B0.9900
C1—H1C0.9900C6—H6A0.9900
C1—H1D0.9900C6—H6B0.9900
C2—H2C0.9900C7—C81.503 (4)
C2—H2D0.9900C7—H7A0.9900
C3—C41.498 (4)C7—H7B0.9900
C3—H3A0.9900C8—H8A0.9900
C3—H3B0.9900C8—H8B0.9900
Cl1—Co—Cl2113.65 (3)O1—C4—H4B109.4
Cl1—Co—Cl4106.01 (3)C3—C4—H4B109.4
Cl2—Co—Cl4113.73 (3)H4A—C4—H4B108.0
Cl1—Co—Cl3108.68 (3)C8—O2—C5109.5 (2)
Cl2—Co—Cl3107.50 (3)C6—N2—C7111.0 (2)
Cl4—Co—Cl3107.00 (3)C6—N2—H2A109.4
C1—O1—C4109.9 (2)C7—N2—H2A109.4
C3—N1—C2111.2 (2)C6—N2—H2B109.4
C3—N1—H1A109.4C7—N2—H2B109.4
C2—N1—H1A109.4H2A—N2—H2B108.0
C3—N1—H1B109.4O2—C5—C6111.5 (3)
C2—N1—H1B109.4O2—C5—H5A109.3
H1A—N1—H1B108.0C6—C5—H5A109.3
O1—C1—C2111.9 (2)O2—C5—H5B109.3
O1—C1—H1C109.2C6—C5—H5B109.3
C2—C1—H1C109.2H5A—C5—H5B108.0
O1—C1—H1D109.2N2—C6—C5108.8 (3)
C2—C1—H1D109.2N2—C6—H6A109.9
H1C—C1—H1D107.9C5—C6—H6A109.9
N1—C2—C1109.5 (2)N2—C6—H6B109.9
N1—C2—H2C109.8C5—C6—H6B109.9
C1—C2—H2C109.8H6A—C6—H6B108.3
N1—C2—H2D109.8N2—C7—C8109.4 (2)
C1—C2—H2D109.8N2—C7—H7A109.8
H2C—C2—H2D108.2C8—C7—H7A109.8
N1—C3—C4109.3 (2)N2—C7—H7B109.8
N1—C3—H3A109.8C8—C7—H7B109.8
C4—C3—H3A109.8H7A—C7—H7B108.2
N1—C3—H3B109.8O2—C8—C7111.6 (3)
C4—C3—H3B109.8O2—C8—H8A109.3
H3A—C3—H3B108.3C7—C8—H8A109.3
O1—C4—C3111.0 (3)O2—C8—H8B109.3
O1—C4—H4A109.4C7—C8—H8B109.3
C3—C4—H4A109.4H8A—C8—H8B108.0
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl2i0.922.403.275 (3)159.
N1—H1B···Cl10.922.383.184 (2)146.
N2—H2A···Cl30.922.453.232 (3)142.
N2—H2B···Cl3ii0.922.373.264 (3)163.
C2—H2C···Cl1ii0.992.713.603 (3)151.
C3—H3B···Cl4i0.992.773.556 (3)136.
C5—H5A···Cl3iii0.992.833.767 (3)158.
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z−1/2; (iii) −x+2, y+1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl2i0.922.403.275 (3)159.
N1—H1B···Cl10.922.383.184 (2)146.
N2—H2A···Cl30.922.453.232 (3)142.
N2—H2B···Cl3ii0.922.373.264 (3)163.
C2—H2C···Cl1ii0.992.713.603 (3)151.
C3—H3B···Cl4i0.992.773.556 (3)136.
C5—H5A···Cl3iii0.992.833.767 (3)158.
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z−1/2; (iii) −x+2, y+1/2, −z+3/2.
references
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