Dimorpholinium tetra­chlorido­cobaltate(II)

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

doi:10.1107/S1600536812035830

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page m1198

doi:10.1107/S1600536812035830

Open

access

Dimorpholinium tetrachloridocobaltate(II)

Xing-Xing Cao,^a He-Long Cheng,^a Qing-Liu Feng ^a and Li-Zhuang Chen ^a ^*

^aSchool of Biology and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: clz1977@sina.com

(Received 26 July 2012; accepted 15 August 2012; online 23 August 2012)

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

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

Crystal data

(C₄H₁₀NO)₂[CoCl₄]
M_r = 376.99
Monoclinic, P 2₁ /c
a = 6.5952 (13) Å
b = 13.696 (3) Å
c = 17.039 (3) Å
β = 92.930 (2)°
V = 1537.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.80 mm⁻¹
T = 291 K
0.26 × 0.12 × 0.08 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.90, T_max = 1.00
11708 measured reflections
2997 independent reflections
2761 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.074
S = 1.07
2997 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—Cl1	2.3029 (6)
Co1—Cl2	2.2720 (6)
Co1—Cl3	2.2455 (6)
Co1—Cl4	2.2811 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Cl1	0.90	2.39	3.1819 (15)	148
N1—H1D⋯O2ⁱ	0.90	1.97	2.8294 (19)	160
N2—H2C⋯O1ⁱⁱ	0.90	2.47	3.0577 (18)	123
N2—H2C⋯Cl4ⁱⁱⁱ	0.90	2.57	3.3322 (15)	143
N2—H2D⋯Cl1^iv	0.90	2.43	3.3003 (15)	164
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x+1, y-1, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812035830/hb6916sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035830/hb6916Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	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
M_r = 376.99	D_x = 1.629 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2761 reflections
a = 6.5952 (13) Å	θ = 2.5–26.0°
b = 13.696 (3) Å	µ = 1.80 mm⁻¹
c = 17.039 (3) Å	T = 291 K
β = 92.930 (2)°	Block, blue
V = 1537.1 (5) Å³	0.26 × 0.12 × 0.08 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2997 independent reflections
Radiation source: fine-focus sealed tube	2761 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 13.66612 pixels mm^-1	θ_max = 26.0°, θ_min = 1.9°
ω scans	h = −7→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
T_min = 0.90, T_max = 1.00	l = −20→20
11708 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.055P)² + 0.0459P] where P = (F_o² + 2F_c²)/3
2997 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

(C₄H₁₀NO)₂[CoCl₄]	V = 1537.1 (5) Å³
M_r = 376.99	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.5952 (13) Å	µ = 1.80 mm⁻¹
b = 13.696 (3) Å	T = 291 K
c = 17.039 (3) Å	0.26 × 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)
T_min = 0.90, T_max = 1.00	R_int = 0.019
11708 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.07	Δρ_max = 0.25 e Å⁻³
2997 reflections	Δρ_min = −0.42 e Å⁻³
154 parameters

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

	x	y	z	U_iso*/U_eq
C1	−0.1713 (3)	0.61037 (13)	0.55358 (11)	0.0444 (4)
H1A	−0.2354	0.6639	0.5801	0.053*
H1B	−0.2756	0.5629	0.5388	0.053*
C2	−0.0788 (3)	0.64794 (13)	0.48120 (10)	0.0404 (4)
H2A	−0.0210	0.5943	0.4526	0.048*
H2B	−0.1819	0.6791	0.4472	0.048*
C3	0.2348 (3)	0.67437 (14)	0.56019 (11)	0.0479 (4)
H3A	0.3349	0.7226	0.5776	0.057*
H3B	0.3043	0.6221	0.5342	0.057*
C4	0.1303 (3)	0.63460 (14)	0.62962 (10)	0.0471 (4)
H4A	0.2296	0.6033	0.6653	0.056*
H4B	0.0696	0.6880	0.6576	0.056*
C5	1.1478 (3)	0.07758 (13)	0.35868 (11)	0.0472 (4)
H5A	1.1997	0.0142	0.3754	0.057*
H5B	1.2597	0.1236	0.3616	0.057*
C6	1.0622 (3)	0.07100 (13)	0.27501 (11)	0.0459 (4)
H6A	1.0223	0.1355	0.2564	0.055*
H6B	1.1652	0.0463	0.2415	0.055*
C7	0.7310 (3)	0.03294 (13)	0.32823 (11)	0.0427 (4)
H7A	0.6226	−0.0150	0.3280	0.051*
H7B	0.6720	0.0957	0.3137	0.051*
C8	0.8328 (3)	0.03920 (13)	0.40899 (10)	0.0428 (4)
H8A	0.7346	0.0588	0.4464	0.051*
H8B	0.8854	−0.0245	0.4245	0.051*
Cl1	0.10686 (6)	0.80041 (3)	0.33040 (2)	0.04020 (12)
Cl2	0.55058 (7)	0.83591 (3)	0.45501 (2)	0.04426 (13)
Cl3	0.59472 (7)	0.79781 (4)	0.23183 (2)	0.04472 (13)
Cl4	0.45151 (7)	0.59332 (3)	0.36450 (3)	0.04461 (13)
Co1	0.44468 (3)	0.757637 (14)	0.342708 (12)	0.02945 (10)
N1	0.0826 (2)	0.71964 (10)	0.50476 (8)	0.0392 (3)
H1C	0.1438	0.7406	0.4618	0.047*
H1D	0.0266	0.7716	0.5277	0.047*
N2	0.8819 (2)	0.00444 (10)	0.27066 (8)	0.0395 (3)
H2C	0.8231	0.0064	0.2218	0.047*
H2D	0.9231	−0.0572	0.2804	0.047*
O1	−0.02319 (19)	0.56588 (8)	0.60621 (7)	0.0402 (3)
O2	0.9955 (2)	0.10839 (9)	0.40987 (7)	0.0454 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0361 (9)	0.0437 (9)	0.0533 (11)	−0.0013 (7)	0.0020 (8)	0.0055 (8)
C2	0.0476 (10)	0.0389 (8)	0.0335 (9)	0.0042 (7)	−0.0083 (7)	−0.0026 (7)
C3	0.0440 (10)	0.0619 (11)	0.0373 (9)	−0.0188 (8)	−0.0023 (8)	0.0045 (8)
C4	0.0601 (11)	0.0511 (10)	0.0292 (9)	−0.0191 (9)	−0.0060 (8)	0.0041 (7)
C5	0.0418 (10)	0.0453 (9)	0.0544 (11)	−0.0079 (8)	0.0031 (8)	−0.0097 (8)
C6	0.0550 (11)	0.0393 (8)	0.0448 (10)	−0.0053 (8)	0.0159 (8)	0.0002 (8)
C7	0.0412 (9)	0.0418 (9)	0.0450 (10)	−0.0019 (7)	0.0015 (8)	−0.0046 (7)
C8	0.0515 (10)	0.0412 (9)	0.0363 (9)	−0.0102 (7)	0.0061 (8)	−0.0041 (7)
Cl1	0.0353 (2)	0.0502 (2)	0.0352 (2)	0.00980 (16)	0.00288 (17)	0.01069 (17)
Cl2	0.0559 (3)	0.0427 (2)	0.0342 (2)	−0.01302 (18)	0.00315 (19)	−0.00842 (17)
Cl3	0.0403 (2)	0.0616 (3)	0.0330 (2)	−0.00275 (18)	0.00952 (18)	0.00554 (18)
Cl4	0.0543 (3)	0.0295 (2)	0.0487 (3)	−0.00623 (16)	−0.0107 (2)	0.00300 (16)
Co1	0.03183 (15)	0.02976 (14)	0.02686 (15)	−0.00168 (7)	0.00255 (10)	0.00081 (7)
N1	0.0550 (9)	0.0368 (7)	0.0266 (7)	−0.0064 (6)	0.0108 (6)	0.0019 (6)
N2	0.0549 (9)	0.0347 (7)	0.0283 (7)	0.0001 (6)	−0.0038 (6)	−0.0015 (5)
O1	0.0462 (7)	0.0356 (6)	0.0384 (6)	−0.0088 (5)	−0.0005 (5)	0.0075 (5)
O2	0.0522 (7)	0.0415 (6)	0.0428 (7)	−0.0124 (6)	0.0053 (6)	−0.0148 (5)

Geometric parameters (Å, º) top

C1—O1	1.428 (2)	C6—N2	1.497 (2)
C1—C2	1.495 (2)	C6—H6A	0.9700
C1—H1A	0.9700	C6—H6B	0.9700
C1—H1B	0.9700	C7—N2	1.485 (2)
C2—N1	1.488 (2)	C7—C8	1.503 (2)
C2—H2A	0.9700	C7—H7A	0.9700
C2—H2B	0.9700	C7—H7B	0.9700
C3—N1	1.479 (2)	C8—O2	1.431 (2)
C3—C4	1.502 (2)	C8—H8A	0.9700
C3—H3A	0.9700	C8—H8B	0.9700
C3—H3B	0.9700	Co1—Cl1	2.3029 (6)
C4—O1	1.424 (2)	Co1—Cl2	2.2720 (6)
C4—H4A	0.9700	Co1—Cl3	2.2455 (6)
C4—H4B	0.9700	Co1—Cl4	2.2811 (6)
C5—O2	1.427 (2)	N1—H1C	0.9000
C5—C6	1.509 (3)	N1—H1D	0.9000
C5—H5A	0.9700	N2—H2C	0.9000
C5—H5B	0.9700	N2—H2D	0.9000

O1—C1—C2	111.70 (14)	C5—C6—H6B	109.7
O1—C1—H1A	109.3	H6A—C6—H6B	108.2
C2—C1—H1A	109.3	N2—C7—C8	109.66 (14)
O1—C1—H1B	109.3	N2—C7—H7A	109.7
C2—C1—H1B	109.3	C8—C7—H7A	109.7
H1A—C1—H1B	107.9	N2—C7—H7B	109.7
N1—C2—C1	108.73 (14)	C8—C7—H7B	109.7
N1—C2—H2A	109.9	H7A—C7—H7B	108.2
C1—C2—H2A	109.9	O2—C8—C7	110.32 (14)
N1—C2—H2B	109.9	O2—C8—H8A	109.6
C1—C2—H2B	109.9	C7—C8—H8A	109.6
H2A—C2—H2B	108.3	O2—C8—H8B	109.6
N1—C3—C4	109.34 (15)	C7—C8—H8B	109.6
N1—C3—H3A	109.8	H8A—C8—H8B	108.1
C4—C3—H3A	109.8	Cl3—Co1—Cl2	117.59 (2)
N1—C3—H3B	109.8	Cl3—Co1—Cl4	111.892 (19)
C4—C3—H3B	109.8	Cl2—Co1—Cl4	109.01 (2)
H3A—C3—H3B	108.3	Cl3—Co1—Cl1	109.083 (19)
O1—C4—C3	111.56 (14)	Cl2—Co1—Cl1	102.183 (19)
O1—C4—H4A	109.3	Cl4—Co1—Cl1	106.068 (18)
C3—C4—H4A	109.3	C3—N1—C2	110.39 (13)
O1—C4—H4B	109.3	C3—N1—H1C	109.6
C3—C4—H4B	109.3	C2—N1—H1C	109.6
H4A—C4—H4B	108.0	C3—N1—H1D	109.6
O2—C5—C6	110.74 (15)	C2—N1—H1D	109.6
O2—C5—H5A	109.5	H1C—N1—H1D	108.1
C6—C5—H5A	109.5	C7—N2—C6	111.39 (13)
O2—C5—H5B	109.5	C7—N2—H2C	109.3
C6—C5—H5B	109.5	C6—N2—H2C	109.3
H5A—C5—H5B	108.1	C7—N2—H2D	109.3
N2—C6—C5	109.93 (14)	C6—N2—H2D	109.3
N2—C6—H6A	109.7	H2C—N2—H2D	108.0
C5—C6—H6A	109.7	C4—O1—C1	110.33 (13)
N2—C6—H6B	109.7	C5—O2—C8	110.38 (12)

O1—C1—C2—N1	−58.22 (18)	C8—C7—N2—C6	−53.66 (19)
N1—C3—C4—O1	57.4 (2)	C5—C6—N2—C7	52.48 (19)
O2—C5—C6—N2	−55.95 (19)	C3—C4—O1—C1	−58.9 (2)
N2—C7—C8—O2	58.34 (18)	C2—C1—O1—C4	59.74 (19)
C4—C3—N1—C2	−56.12 (19)	C6—C5—O2—C8	61.60 (19)
C1—C2—N1—C3	56.46 (18)	C7—C8—O2—C5	−62.79 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl1	0.90	2.39	3.1819 (15)	148
N1—H1D···O2ⁱ	0.90	1.97	2.8294 (19)	160
N2—H2C···O1ⁱⁱ	0.90	2.47	3.0577 (18)	123
N2—H2C···Cl4ⁱⁱⁱ	0.90	2.57	3.3322 (15)	143
N2—H2D···Cl1^iv	0.90	2.43	3.3003 (15)	164

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, −y+1/2, z−1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x+1, y−1, z.

Experimental details

Crystal data
Chemical formula	(C₄H₁₀NO)₂[CoCl₄]
M_r	376.99
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	6.5952 (13), 13.696 (3), 17.039 (3)
β (°)	92.930 (2)
V (Å³)	1537.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.80
Crystal size (mm)	0.26 × 0.12 × 0.08

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.90, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	11708, 2997, 2761
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.074, 1.07
No. of reflections	2997
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.42

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—Cl1	2.3029 (6)	Co1—Cl3	2.2455 (6)
Co1—Cl2	2.2720 (6)	Co1—Cl4	2.2811 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl1	0.90	2.39	3.1819 (15)	148
N1—H1D···O2ⁱ	0.90	1.97	2.8294 (19)	160
N2—H2C···O1ⁱⁱ	0.90	2.47	3.0577 (18)	123
N2—H2C···Cl4ⁱⁱⁱ	0.90	2.57	3.3322 (15)	143
N2—H2D···Cl1^iv	0.90	2.43	3.3003 (15)	164

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, −y+1/2, z−1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) x+1, y−1, z.

Acknowledgements

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

Chen, L. Z. (2009). Acta Cryst. E65, m689. Web of Science CSD CrossRef IUCr Journals Google Scholar
Owczarek, M., Szklarz, P., Jakubas, R. & Lis, T. (2008). Acta Cryst. E64, o667. Web of Science CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Szklarz, P., Owczarek, M., Bator, G., Lis, T., Gatner, K. & Jakubas, R. (2009). J. Mol. Struct. 929, 48. Web of Science CSD CrossRef Google Scholar