supplementary materials


hb6916 scheme

Acta Cryst. (2012). E68, m1198    [ doi:10.1107/S1600536812035830 ]

Dimorpholinium tetrachloridocobaltate(II)

X.-X. Cao, H.-L. Cheng, Q.-L. Feng and L.-Z. Chen

Abstract top

In the title molecular salt, (C4H10NO)2[CoCl4], the morpholinium cations adopt chair conformations and the tetrachloridocobaltate(II) anion is significantly distorted from regular tetrahedral geometry [Cl-Co-Cl = 102.183 (19)-117.59 (2)°]. The Co-Cl bond lengths for the chloride ions not accepting hydrogen bonds are significantly shorter than those for the chloride ions accepting such bonds. In the crystal, the components are linked by N-H...O and N-H...Cl and bifurcated N-H...(O,Cl) hydrogen bonds to generate (100) sheets.

Related literature top

For a phase transition in morpholinium tetrafluoridoborate, see: Szklarz et al. (2009); Owczarek et al. (2008). For the structure of dimorpholinium pentachloridoantimonate(III), see: Chen (2009).

Experimental top

CoCl2 (2.37 g, 10 mmol), morpholine (1.01 g, 10 mmol) and 20% aqueous HCl in a molar ratio of 1:1:1 were mixed and dissolved in sufficient water by heating to 353 K forming a clear solution. The reaction mixture was cooled slowly to room temperature, blue blocks of the title compound were formed, collected and washed with dilute aqueous HCl.

Refinement top

All H atoms were placed in calculated positions, with C—H = 0.97 Å and N—H = 0.90 Å, and refined using a riding model, with Uiso(H)=1.2Ueq(C, N).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The packing viewed along the a axis. Hydrogen bonds are drawn as dashed lines
Dimorpholinium tetrachloridocobaltate(II) top
Crystal data top
(C4H10NO)2[CoCl4]F(000) = 772
Mr = 376.99Dx = 1.629 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2761 reflections
a = 6.5952 (13) Åθ = 2.5–26.0°
b = 13.696 (3) ŵ = 1.80 mm1
c = 17.039 (3) ÅT = 291 K
β = 92.930 (2)°Block, blue
V = 1537.1 (5) Å30.26 × 0.12 × 0.08 mm
Z = 4
Data collection top
Rigaku SCXmini
diffractometer
2997 independent reflections
Radiation source: fine-focus sealed tube2761 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
Detector resolution: 13.66612 pixels mm-1θmax = 26.0°, θmin = 1.9°
ω scansh = 78
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1616
Tmin = 0.90, Tmax = 1.00l = 2020
11708 measured reflections
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)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.055P)2 + 0.0459P]
where P = (Fo2 + 2Fc2)/3
2997 reflections(Δ/σ)max = 0.001
154 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
(C4H10NO)2[CoCl4]V = 1537.1 (5) Å3
Mr = 376.99Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.5952 (13) ŵ = 1.80 mm1
b = 13.696 (3) ÅT = 291 K
c = 17.039 (3) Å0.26 × 0.12 × 0.08 mm
β = 92.930 (2)°
Data collection top
Rigaku SCXmini
diffractometer
2997 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
2761 reflections with I > 2σ(I)
Tmin = 0.90, Tmax = 1.00Rint = 0.019
11708 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.074Δρmax = 0.25 e Å3
S = 1.07Δρmin = 0.42 e Å3
2997 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
C10.1713 (3)0.61037 (13)0.55358 (11)0.0444 (4)
H1A0.23540.66390.58010.053*
H1B0.27560.56290.53880.053*
C20.0788 (3)0.64794 (13)0.48120 (10)0.0404 (4)
H2A0.02100.59430.45260.048*
H2B0.18190.67910.44720.048*
C30.2348 (3)0.67437 (14)0.56019 (11)0.0479 (4)
H3A0.33490.72260.57760.057*
H3B0.30430.62210.53420.057*
C40.1303 (3)0.63460 (14)0.62962 (10)0.0471 (4)
H4A0.22960.60330.66530.056*
H4B0.06960.68800.65760.056*
C51.1478 (3)0.07758 (13)0.35868 (11)0.0472 (4)
H5A1.19970.01420.37540.057*
H5B1.25970.12360.36160.057*
C61.0622 (3)0.07100 (13)0.27501 (11)0.0459 (4)
H6A1.02230.13550.25640.055*
H6B1.16520.04630.24150.055*
C70.7310 (3)0.03294 (13)0.32823 (11)0.0427 (4)
H7A0.62260.01500.32800.051*
H7B0.67200.09570.31370.051*
C80.8328 (3)0.03920 (13)0.40899 (10)0.0428 (4)
H8A0.73460.05880.44640.051*
H8B0.88540.02450.42450.051*
Cl10.10686 (6)0.80041 (3)0.33040 (2)0.04020 (12)
Cl20.55058 (7)0.83591 (3)0.45501 (2)0.04426 (13)
Cl30.59472 (7)0.79781 (4)0.23183 (2)0.04472 (13)
Cl40.45151 (7)0.59332 (3)0.36450 (3)0.04461 (13)
Co10.44468 (3)0.757637 (14)0.342708 (12)0.02945 (10)
N10.0826 (2)0.71964 (10)0.50476 (8)0.0392 (3)
H1C0.14380.74060.46180.047*
H1D0.02660.77160.52770.047*
N20.8819 (2)0.00444 (10)0.27066 (8)0.0395 (3)
H2C0.82310.00640.22180.047*
H2D0.92310.05720.28040.047*
O10.02319 (19)0.56588 (8)0.60621 (7)0.0402 (3)
O20.9955 (2)0.10839 (9)0.40987 (7)0.0454 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0361 (9)0.0437 (9)0.0533 (11)0.0013 (7)0.0020 (8)0.0055 (8)
C20.0476 (10)0.0389 (8)0.0335 (9)0.0042 (7)0.0083 (7)0.0026 (7)
C30.0440 (10)0.0619 (11)0.0373 (9)0.0188 (8)0.0023 (8)0.0045 (8)
C40.0601 (11)0.0511 (10)0.0292 (9)0.0191 (9)0.0060 (8)0.0041 (7)
C50.0418 (10)0.0453 (9)0.0544 (11)0.0079 (8)0.0031 (8)0.0097 (8)
C60.0550 (11)0.0393 (8)0.0448 (10)0.0053 (8)0.0159 (8)0.0002 (8)
C70.0412 (9)0.0418 (9)0.0450 (10)0.0019 (7)0.0015 (8)0.0046 (7)
C80.0515 (10)0.0412 (9)0.0363 (9)0.0102 (7)0.0061 (8)0.0041 (7)
Cl10.0353 (2)0.0502 (2)0.0352 (2)0.00980 (16)0.00288 (17)0.01069 (17)
Cl20.0559 (3)0.0427 (2)0.0342 (2)0.01302 (18)0.00315 (19)0.00842 (17)
Cl30.0403 (2)0.0616 (3)0.0330 (2)0.00275 (18)0.00952 (18)0.00554 (18)
Cl40.0543 (3)0.0295 (2)0.0487 (3)0.00623 (16)0.0107 (2)0.00300 (16)
Co10.03183 (15)0.02976 (14)0.02686 (15)0.00168 (7)0.00255 (10)0.00081 (7)
N10.0550 (9)0.0368 (7)0.0266 (7)0.0064 (6)0.0108 (6)0.0019 (6)
N20.0549 (9)0.0347 (7)0.0283 (7)0.0001 (6)0.0038 (6)0.0015 (5)
O10.0462 (7)0.0356 (6)0.0384 (6)0.0088 (5)0.0005 (5)0.0075 (5)
O20.0522 (7)0.0415 (6)0.0428 (7)0.0124 (6)0.0053 (6)0.0148 (5)
Geometric parameters (Å, º) top
C1—O11.428 (2)C6—N21.497 (2)
C1—C21.495 (2)C6—H6A0.9700
C1—H1A0.9700C6—H6B0.9700
C1—H1B0.9700C7—N21.485 (2)
C2—N11.488 (2)C7—C81.503 (2)
C2—H2A0.9700C7—H7A0.9700
C2—H2B0.9700C7—H7B0.9700
C3—N11.479 (2)C8—O21.431 (2)
C3—C41.502 (2)C8—H8A0.9700
C3—H3A0.9700C8—H8B0.9700
C3—H3B0.9700Co1—Cl12.3029 (6)
C4—O11.424 (2)Co1—Cl22.2720 (6)
C4—H4A0.9700Co1—Cl32.2455 (6)
C4—H4B0.9700Co1—Cl42.2811 (6)
C5—O21.427 (2)N1—H1C0.9000
C5—C61.509 (3)N1—H1D0.9000
C5—H5A0.9700N2—H2C0.9000
C5—H5B0.9700N2—H2D0.9000
O1—C1—C2111.70 (14)C5—C6—H6B109.7
O1—C1—H1A109.3H6A—C6—H6B108.2
C2—C1—H1A109.3N2—C7—C8109.66 (14)
O1—C1—H1B109.3N2—C7—H7A109.7
C2—C1—H1B109.3C8—C7—H7A109.7
H1A—C1—H1B107.9N2—C7—H7B109.7
N1—C2—C1108.73 (14)C8—C7—H7B109.7
N1—C2—H2A109.9H7A—C7—H7B108.2
C1—C2—H2A109.9O2—C8—C7110.32 (14)
N1—C2—H2B109.9O2—C8—H8A109.6
C1—C2—H2B109.9C7—C8—H8A109.6
H2A—C2—H2B108.3O2—C8—H8B109.6
N1—C3—C4109.34 (15)C7—C8—H8B109.6
N1—C3—H3A109.8H8A—C8—H8B108.1
C4—C3—H3A109.8Cl3—Co1—Cl2117.59 (2)
N1—C3—H3B109.8Cl3—Co1—Cl4111.892 (19)
C4—C3—H3B109.8Cl2—Co1—Cl4109.01 (2)
H3A—C3—H3B108.3Cl3—Co1—Cl1109.083 (19)
O1—C4—C3111.56 (14)Cl2—Co1—Cl1102.183 (19)
O1—C4—H4A109.3Cl4—Co1—Cl1106.068 (18)
C3—C4—H4A109.3C3—N1—C2110.39 (13)
O1—C4—H4B109.3C3—N1—H1C109.6
C3—C4—H4B109.3C2—N1—H1C109.6
H4A—C4—H4B108.0C3—N1—H1D109.6
O2—C5—C6110.74 (15)C2—N1—H1D109.6
O2—C5—H5A109.5H1C—N1—H1D108.1
C6—C5—H5A109.5C7—N2—C6111.39 (13)
O2—C5—H5B109.5C7—N2—H2C109.3
C6—C5—H5B109.5C6—N2—H2C109.3
H5A—C5—H5B108.1C7—N2—H2D109.3
N2—C6—C5109.93 (14)C6—N2—H2D109.3
N2—C6—H6A109.7H2C—N2—H2D108.0
C5—C6—H6A109.7C4—O1—C1110.33 (13)
N2—C6—H6B109.7C5—O2—C8110.38 (12)
O1—C1—C2—N158.22 (18)C8—C7—N2—C653.66 (19)
N1—C3—C4—O157.4 (2)C5—C6—N2—C752.48 (19)
O2—C5—C6—N255.95 (19)C3—C4—O1—C158.9 (2)
N2—C7—C8—O258.34 (18)C2—C1—O1—C459.74 (19)
C4—C3—N1—C256.12 (19)C6—C5—O2—C861.60 (19)
C1—C2—N1—C356.46 (18)C7—C8—O2—C562.79 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···Cl10.902.393.1819 (15)148
N1—H1D···O2i0.901.972.8294 (19)160
N2—H2C···O1ii0.902.473.0577 (18)123
N2—H2C···Cl4iii0.902.573.3322 (15)143
N2—H2D···Cl1iv0.902.433.3003 (15)164
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1/2, z1/2; (iii) x+1, y1/2, z+1/2; (iv) x+1, y1, z.
Selected bond lengths (Å) top
Co1—Cl12.3029 (6)Co1—Cl32.2455 (6)
Co1—Cl22.2720 (6)Co1—Cl42.2811 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···Cl10.902.393.1819 (15)148
N1—H1D···O2i0.901.972.8294 (19)160
N2—H2C···O1ii0.902.473.0577 (18)123
N2—H2C···Cl4iii0.902.573.3322 (15)143
N2—H2D···Cl1iv0.902.433.3003 (15)164
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1/2, z1/2; (iii) x+1, y1/2, z+1/2; (iv) x+1, y1, z.
Acknowledgements top

This work was supported by a start-up grant from Jiangsu University of Science and Technology and the Foundation of Jiangsu Educational Committee (grant No. 11KJB150004), China.

references
References top

Chen, L. Z. (2009). Acta Cryst. E65, m689.

Owczarek, M., Szklarz, P., Jakubas, R. & Lis, T. (2008). Acta Cryst. E64, o667.

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

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

Szklarz, P., Owczarek, M., Bator, G., Lis, T., Gatner, K. & Jakubas, R. (2009). J. Mol. Struct. 929, 48.