N,N,N′,N′-Tetra­methyl-N,N′-dipropyl­ethane-1,2-diaminium tetra­chlorido­cobaltate(II)

Närhi, S.M.; Kostamo, J.; Asikkala, J.; Oilunkaniemi, R.; Laitinen, R.S.

doi:10.1107/S1600536811050744

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page m1887

https://doi.org/10.1107/S1600536811050744

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N,N,N′,N′-Tetramethyl-N,N′-dipropylethane-1,2-diaminium tetrachloridocobaltate(II)

Sari M. Närhi,^a Jatta Kostamo,^a Janne Asikkala,^a Raija Oilunkaniemi ^a ^* and Risto S. Laitinen ^a

^aDepartment of Chemistry, PO Box 3000, FI-90014 University of Oulu, Finland
^*Correspondence e-mail: raija.oilunkaniemi@oulu.fi

(Received 9 November 2011; accepted 25 November 2011; online 30 November 2011)

The crystal structure of the title compound, (C₁₂H₃₀N₂)[CoCl₄], is composed of discrete (C₁₂H₃₀N₂)²⁺ cations and [CoCl₄]²⁻ anions. The asymmetric unit contains a half-cation and a half-anion. The atoms of the cation occupy general positions about an inversion centre, which is located at the midpoint of the central C—C bond. The Co atoms lie on a twofold rotation axis. The slightly distorted tetrahedral coordination environment around the metal atom consists of two Cl atoms and their symmetry-related pairs.

Related literature

For the synthesis and structural characterization of C₁₂H₃₀N₂²⁺·Cl₂²⁻, see: Närhi et al. (2011 ).

Experimental

Crystal data

(C₁₂H₃₀N₂)[CoCl₄]
M_r = 403.11
Monoclinic, C 2/c
a = 13.583 (3) Å
b = 9.2334 (18) Å
c = 14.981 (3) Å
β = 101.83 (3)°
V = 1839.1 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.51 mm⁻¹
T = 120 K
0.25 × 0.20 × 0.10 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.705, T_max = 0.864
11798 measured reflections
1799 independent reflections
1596 reflections with I > 2σ(I)
R_int = 0.098

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.107
S = 1.08
1799 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—Cl1	2.2731 (9)
Co1—Cl2	2.2759 (8)

Data collection: COLLECT (Bruker, 2008 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811050744/hp2021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050744/hp2021Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of (C₁₂H₃₀N₂)[CoCl₄] consists of half of the cation and half of the anion (see Fig. 1). The N—C bond lengths in the cation range from 1.501 (3) to 1.530 (3) Å and the C—C bond lengths from 1.509 (4) to 1.525 (4) Å. These can be compared to the bond lengths in the related chloride and bromide (Närhi et al. 2011). In the title compound, the two n-propyl chains are almost coplanar with the N1—C1—C1ⁱⁱ—N1ⁱⁱ skeleton with all torsional angles ca 180 °, whereas in (C₁₂H₃₀N₂)Cl₂ and (C₁₂H₃₀N₂)Br₂ the n-propyl chains are in the anti-configuration with respect to the corresponding NCCN skeleton (Närhi et al. 2011). The cobalt atom shows a slightly distorted tetrahedral coordination geometry and the Co—Cl bond lengths of 2.2731 (9) Å and 2.2759 (8) Å are quite normal.

The packing of the title compound consists of layers of cations. The isolated anions lay between these layers with several hydrogen bonds connecting the anions and cations, as shown in Fig. 2. The packing of the molecules is shown in Fig. 3.

Related literature top

For the synthesis and structural characterization of C₁₂H₃₀N₂²⁺.Cl₂^2- see Närhi et al. (2011).

Experimental top

Addition of solution of (C₁₂H₃₀N₂)Cl₂ (0.118 g, 0.432 mmol) in 5 ml MeOH to solution of CoCl₂ ^. 6 H₂O (0.103 g, 0.433 mmol) in 5 ml MeOH gave a purple solution from which the title compound was obtained as crystalline blue precipitate.

Structure description top

For the synthesis and structural characterization of C₁₂H₃₀N₂²⁺.Cl₂^2- see Närhi et al. (2011).

Computing details top

Data collection: COLLECT (Bruker, 2008); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound indicating the numbering of the atoms. The thermal ellipsoids have been drawn at 50% probability. Symmetry code: (i) = -x, y, 0.5 - z (ii) = 0.5 - x, 0.5 - y, -z.
	Fig. 2. The closest contacts between an anion and the closest cations. The spacefilling presentation is shown in the insert.
	Fig. 3. The packing of the molecules viewed along the a axis.

N,N,N',N'-Tetramethyl-N,N'- dipropylethane-1,2-diaminium tetrachloridocobaltate(II) top

Crystal data top

(C₁₂H₃₀N₂)[CoCl₄]	F(000) = 844
M_r = 403.11	D_x = 1.456 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1596 reflections
a = 13.583 (3) Å	θ = 3.1–26.0°
b = 9.2334 (18) Å	µ = 1.51 mm⁻¹
c = 14.981 (3) Å	T = 120 K
β = 101.83 (3)°	Plate, blue
V = 1839.1 (6) Å³	0.25 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD diffractometer	1799 independent reflections
Radiation source: fine-focus sealed tube	1596 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.098
φ scans, and ω scans with κ offsets	θ_max = 26.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −15→16
T_min = 0.705, T_max = 0.864	k = −11→11
11798 measured reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0551P)² + 2.1498P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1799 reflections	Δρ_max = 0.41 e Å⁻³
91 parameters	Δρ_min = −0.45 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0131 (12)

Crystal data top

(C₁₂H₃₀N₂)[CoCl₄]	V = 1839.1 (6) Å³
M_r = 403.11	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.583 (3) Å	µ = 1.51 mm⁻¹
b = 9.2334 (18) Å	T = 120 K
c = 14.981 (3) Å	0.25 × 0.20 × 0.10 mm
β = 101.83 (3)°

Data collection top

Bruker–Nonius KappaCCD diffractometer	1799 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	1596 reflections with I > 2σ(I)
T_min = 0.705, T_max = 0.864	R_int = 0.098
11798 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.08	Δρ_max = 0.41 e Å⁻³
1799 reflections	Δρ_min = −0.45 e Å⁻³
91 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Co1	0.0000	0.27789 (5)	0.2500	0.0254 (2)
Cl1	0.12341 (5)	0.42242 (8)	0.32854 (5)	0.0369 (2)
Cl2	0.06661 (5)	0.13400 (8)	0.15413 (5)	0.0348 (2)
N1	0.24693 (16)	0.4259 (2)	0.07011 (14)	0.0271 (5)
C1	0.2084 (2)	0.3026 (3)	0.00547 (18)	0.0289 (6)
H1A	0.1775	0.3430	−0.0550	0.035*
H1B	0.1556	0.2494	0.0288	0.035*
C2	0.2940 (2)	0.3728 (3)	0.16405 (18)	0.0346 (7)
H2A	0.3542	0.3158	0.1612	0.052*
H2B	0.2457	0.3122	0.1874	0.052*
H2C	0.3129	0.4559	0.2047	0.052*
C3	0.3208 (2)	0.5173 (3)	0.03321 (19)	0.0322 (6)
H3A	0.3404	0.6007	0.0734	0.048*
H3B	0.2897	0.5514	−0.0280	0.048*
H3C	0.3805	0.4595	0.0302	0.048*
C4	0.15188 (19)	0.5122 (3)	0.07434 (18)	0.0309 (6)
H4A	0.1194	0.5404	0.0114	0.037*
H4B	0.1047	0.4474	0.0975	0.037*
C5	0.1662 (2)	0.6471 (3)	0.1325 (2)	0.0379 (7)
H5A	0.2160	0.7117	0.1130	0.046*
H5B	0.1915	0.6209	0.1972	0.046*
C6	0.0652 (2)	0.7244 (3)	0.1219 (2)	0.0420 (7)
H6A	0.0388	0.7451	0.0573	0.063*
H6B	0.0743	0.8154	0.1563	0.063*
H6C	0.0177	0.6625	0.1454	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0235 (3)	0.0307 (3)	0.0215 (3)	0.000	0.00327 (19)	0.000
Cl1	0.0295 (4)	0.0445 (5)	0.0335 (4)	−0.0022 (3)	−0.0012 (3)	−0.0116 (3)
Cl2	0.0375 (4)	0.0359 (4)	0.0341 (4)	−0.0039 (3)	0.0148 (3)	−0.0067 (3)
N1	0.0294 (11)	0.0279 (12)	0.0234 (11)	−0.0014 (9)	0.0042 (8)	−0.0016 (9)
C1	0.0251 (13)	0.0304 (14)	0.0292 (14)	−0.0022 (11)	0.0009 (10)	−0.0011 (11)
C2	0.0360 (15)	0.0416 (16)	0.0249 (13)	0.0076 (12)	0.0027 (11)	0.0036 (12)
C3	0.0308 (14)	0.0323 (15)	0.0330 (14)	−0.0063 (11)	0.0056 (11)	−0.0002 (11)
C4	0.0276 (13)	0.0348 (15)	0.0293 (14)	−0.0027 (11)	0.0037 (10)	0.0000 (11)
C5	0.0345 (15)	0.0369 (17)	0.0397 (16)	−0.0003 (12)	0.0014 (12)	−0.0016 (13)
C6	0.0363 (17)	0.0354 (17)	0.0523 (19)	0.0036 (12)	0.0044 (14)	−0.0043 (14)

Geometric parameters (Å, º) top

Co1—Cl1	2.2731 (9)	C2—H2C	0.9800
Co1—Cl1ⁱ	2.2731 (9)	C3—H3A	0.9800
Co1—Cl2	2.2759 (8)	C3—H3B	0.9800
Co1—Cl2ⁱ	2.2759 (8)	C3—H3C	0.9800
N1—C3	1.501 (3)	C4—C5	1.509 (4)
N1—C2	1.504 (3)	C4—H4A	0.9900
N1—C1	1.516 (3)	C4—H4B	0.9900
N1—C4	1.530 (3)	C5—C6	1.525 (4)
C1—C1ⁱⁱ	1.524 (5)	C5—H5A	0.9900
C1—H1A	0.9900	C5—H5B	0.9900
C1—H1B	0.9900	C6—H6A	0.9800
C2—H2A	0.9800	C6—H6B	0.9800
C2—H2B	0.9800	C6—H6C	0.9800

Cl1—Co1—Cl1ⁱ	108.10 (5)	N1—C3—H3A	109.5
Cl1—Co1—Cl2	108.84 (3)	N1—C3—H3B	109.5
Cl1ⁱ—Co1—Cl2	111.25 (3)	H3A—C3—H3B	109.5
Cl1—Co1—Cl2ⁱ	111.25 (3)	N1—C3—H3C	109.5
Cl1ⁱ—Co1—Cl2ⁱ	108.84 (3)	H3A—C3—H3C	109.5
Cl2—Co1—Cl2ⁱ	108.57 (4)	H3B—C3—H3C	109.5
C3—N1—C2	109.9 (2)	C5—C4—N1	116.4 (2)
C3—N1—C1	110.8 (2)	C5—C4—H4A	108.2
C2—N1—C1	112.2 (2)	N1—C4—H4A	108.2
C3—N1—C4	110.9 (2)	C5—C4—H4B	108.2
C2—N1—C4	109.4 (2)	N1—C4—H4B	108.2
C1—N1—C4	103.54 (19)	H4A—C4—H4B	107.3
N1—C1—C1ⁱⁱ	112.4 (3)	C4—C5—C6	108.7 (2)
N1—C1—H1A	109.1	C4—C5—H5A	110.0
C1ⁱⁱ—C1—H1A	109.1	C6—C5—H5A	110.0
N1—C1—H1B	109.1	C4—C5—H5B	110.0
C1ⁱⁱ—C1—H1B	109.1	C6—C5—H5B	110.0
H1A—C1—H1B	107.9	H5A—C5—H5B	108.3
N1—C2—H2A	109.5	C5—C6—H6A	109.5
N1—C2—H2B	109.5	C5—C6—H6B	109.5
H2A—C2—H2B	109.5	H6A—C6—H6B	109.5
N1—C2—H2C	109.5	C5—C6—H6C	109.5
H2A—C2—H2C	109.5	H6A—C6—H6C	109.5
H2B—C2—H2C	109.5	H6B—C6—H6C	109.5

C3—N1—C1—C1ⁱⁱ	63.7 (3)	C2—N1—C4—C5	61.9 (3)
C2—N1—C1—C1ⁱⁱ	−59.5 (3)	C1—N1—C4—C5	−178.3 (2)
C4—N1—C1—C1ⁱⁱ	−177.4 (3)	N1—C4—C5—C6	175.3 (2)
C3—N1—C4—C5	−59.4 (3)

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

Experimental details

Crystal data
Chemical formula	(C₁₂H₃₀N₂)[CoCl₄]
M_r	403.11
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	120
a, b, c (Å)	13.583 (3), 9.2334 (18), 14.981 (3)
β (°)	101.83 (3)
V (Å³)	1839.1 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.51
Crystal size (mm)	0.25 × 0.20 × 0.10

Data collection
Diffractometer	Bruker–Nonius KappaCCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.705, 0.864
No. of measured, independent and observed [I > 2σ(I)] reflections	11798, 1799, 1596
R_int	0.098
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.107, 1.08
No. of reflections	1799
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.45

Computer programs: COLLECT (Bruker, 2008), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Co1—Cl1

2.2731 (9)

Co1—Cl2

2.2759 (8)

Acknowledgements

Financial support from the Academy of Finland is gratefully acknowledged.

References

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