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Acta Crystallogr Sect E Struct Rep Online. 2011 January 1; 67(Pt 1): m1.
Published online 2010 December 4. doi:  10.1107/S1600536810048749
PMCID: PMC3050123

N,N,N′,N′-Tetra­methyl­ethylene­diammonium tetra­chloridocobaltate(II)

Abstract

The asymmetric unit of the title compound, [(CH3)2NH(CH2)2NH(CH3)2][CoCl4], contains a tetra­chlorido­cobalt­ate(II) dianion and two halves of two centrosymmetric, crystallographically-independent, dications. One independent dication is disordered between two conformations in a 0.784 (13):0.216 (13) ratio. In the crystal, inter­molecular N—H(...)Cl hydrogen bonds link cations and anions into chains propagated in [0An external file that holds a picture, illustration, etc.
Object name is e-67-000m1-efi1.jpg1]. These hydrogen bonds contribute to the distorted tetra­hedral geometry at the CoII atom.

Related literature

The synthesis of the title compound was modified from that of Szafran et al. (1998 [triangle]). Related tetra­methyl­ethylene­diammo­nium salts are listed in the Cambridge Structural Database (Allen, 2002 [triangle]).

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Object name is e-67-000m1-scheme1.jpg

Experimental

Crystal data

  • (C6H18N2)[CoCl4]
  • M r = 318.95
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-67-000m1-efi2.jpg
  • a = 6.9179 (3) Å
  • b = 8.2866 (3) Å
  • c = 13.4395 (5) Å
  • α = 72.188 (3)°
  • β = 87.292 (3)°
  • γ = 69.045 (3)°
  • V = 683.31 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.00 mm−1
  • T = 295 K
  • 0.55 × 0.44 × 0.38 mm

Data collection

  • Bruker P4 diffractometer
  • Absorption correction: integration (XSHELL; Bruker, 1999 [triangle]) T min = 0.378, T max = 0.553
  • 3003 measured reflections
  • 2361 independent reflections
  • 2207 reflections with I > 2σ(I)
  • R int = 0.055
  • 3 standard reflections every 100 reflections intensity decay: 3.8%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.097
  • S = 1.08
  • 2361 reflections
  • 129 parameters
  • H-atom parameters constrained
  • Δρmax = 0.53 e Å−3
  • Δρmin = −0.50 e Å−3

Data collection: XSCANS (Bruker, 1996 [triangle]); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL/PC and SHELXL97.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810048749/cv2786sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048749/cv2786Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

During the evaluation of the generality of the procedure of Szafran, Pike, and Singh (1998) for Truman State University's inorganic chemistry course, the title compound, N,N,N',N'-tetramethylethylenediammonium (TMED) tetrachlorocobaltate(II), (I), was the unexpected product. A cobalt(III)-TMED complex had been anticipated. A search of the Cambridge Structural Database (v. 5.31; Allen, 2002) for TMED and TMED-related salts yielded 82 results (from monoatomic to complex anions); the structure of the [CoCl4]2- salt has not been reported, and thus was deemed appropriate for determination.

Two different halves ("A" & "B" suffixes) of the cation are present in the asymmetric unit. The N/C/C/N sections of each cation are planar causing each half to be related to its partner half via a center of inversion in the middle of the cation. Evidence for different conformations of the "A" versus "B" TMED cations include the different methyl C distances from the respective N/C/C/N least-squares plane. The more distant methyl C atoms (C1A and C1B) are 1.313 (6) Å and 1.191 (4) Å, respectively, from their planes. Similarly, C2A and C2B are -0.419 (7) Å and -0.25 (1) Å, respectively, from their planes. Additionally, magnitudes of the corresponding torsion angles involving the methyls are somewhat comparable, but not equal.

The N atoms in the TMEDs shown in Fig. 1 are not symmetrically disposed about the [CoCl4]2-. The Co1···N1A and Co1···N1AA (= N1A at 1 - x, 1 - y, -z) distances are comparable [4.720 (2) Å and 4.808 (2) Å, respectively], while the Co1···N1B and Co1···N1BA (= N1B at 1 - x, -y, 1 - z) are quite different [4.143 (2) Å and 5.083 (2) Å, respectively] not only from each other, but also from the "A" TMED Co1···N distances.

Examination of the bond lengths and angles reveals numerous significant (\geq 3σ) differences between the "A" and "B" TMED cations. The "B" TMED exhibits disorder [0.784 (13); 0.216 (13)]. In both TMED cations the E conformation (likely due to the preference of dipoles within a molecule to oppose each other) of the methyls, nitrogen, and the amine H atoms shown in Fig. 1 contributes greatly not only to the presence of a center of inversion, but also to the one-dimensional hydrogen bonding present along [0–11].

A highly distorted tetrahedral geometry is present around the Co (cf. the six different Cl—Co—Cl angle values and four distances in Table 1). The ranges of distance and angle values are, respectively, 0.048 Å (\sim 64σ) and 9.21° (~230σ). Two of the Cl's in the [CoCl4]2- moiety are involved in hydrogen bonding with amine H's in either the asymmetric unit or symmetry-related amine H's (Table 2). In both "A" and "B" cations, short (~2.3 Å) H-bond distances are noted for each hydrogen and are shown in Fig. 1. The strong hydrogen bonds (H1AD and H1BD with Cl2 and Cl3, respectively) are concomitant with the long Co1—Cl2 and Co1—Cl3 bond lengths. These interactions are undoubtedly the underlying cause of the severely distorted geometry of the [CoCl4]2- anion.

Experimental

The title compound was synthesized using a method parallel to that of Szafran, Pike, and Singh (1998) for the trans-dichloro bis- ethylenediamine cobalt(III) chloride using CoCl2.H2O and TMED for this work.

Refinement

Approximate positions of the amine H's (H1AD & H1BD) and most of the methyl and methylene H's were first obtained from a difference map, then placed into idealized positions (C—H 0.96-0.97 Å; N—H 0.91 Å), and refined as riding, with Uiso(H) = 1.2-1.5 Ueq of the parent atom.

In the final stages of refinement five reflections with very small or negative Fo's were deemed to be in high disagreement with their Fc's and were eliminated from final refinement.

Figures

Fig. 1.
View of the title compound (asymmetric unit plus inversion-related pairs of both TMEDs) showing the atomic labeling [symmetry codes: (a; left TMED) 1-x, 1-y, -z; (b; right TMED) 1-x, -y, 1-z]. Only the major conformation of the disordered TMED cation ...

Crystal data

(C6H18N2)[CoCl4]Z = 2
Mr = 318.95F(000) = 326
Triclinic, P1Dx = 1.550 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9179 (3) ÅCell parameters from 100 reflections
b = 8.2866 (3) Åθ = 10.4–21.8°
c = 13.4395 (5) ŵ = 2.00 mm1
α = 72.188 (3)°T = 295 K
β = 87.292 (3)°Block cut from larger crystal, blue
γ = 69.045 (3)°0.55 × 0.44 × 0.38 mm
V = 683.31 (5) Å3

Data collection

Bruker P4 diffractometer2207 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.055
graphiteθmax = 25.0°, θmin = 2.7°
θ/2θ scansh = −8→1
Absorption correction: integration (XSHELL; Bruker, 1999)k = −9→9
Tmin = 0.378, Tmax = 0.553l = −15→15
3003 measured reflections3 standard reflections every 100 reflections
2361 independent reflections intensity decay: 3.8%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.097w = 1/[σ2(Fo2) + (0.0551P)2 + 0.3622P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2361 reflectionsΔρmax = 0.53 e Å3
129 parametersΔρmin = −0.50 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.075 (5)

Special details

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)

xyzUiso*/UeqOcc. (<1)
Co10.08521 (5)0.39063 (4)0.24591 (2)0.03454 (18)
Cl1−0.07188 (15)0.25750 (14)0.37896 (7)0.0711 (3)
Cl20.28898 (11)0.16529 (9)0.17970 (5)0.0440 (2)
Cl30.30208 (13)0.48322 (11)0.31660 (6)0.0556 (2)
Cl4−0.12874 (12)0.63518 (11)0.12131 (7)0.0578 (3)
N1A0.6224 (3)0.2465 (3)0.02177 (19)0.0385 (5)
H1AD0.50670.22820.04970.046*
C1A0.7839 (5)0.1787 (5)0.1090 (3)0.0612 (9)
H1AA0.81910.05020.14060.092*
H1AB0.73150.23930.16060.092*
H1AC0.90530.20280.08230.092*
C2A0.6891 (5)0.1436 (4)−0.0545 (3)0.0556 (8)
H2AA0.57760.1831−0.10650.083*
H2AB0.72570.0161−0.01870.083*
H2AC0.80720.1654−0.08780.083*
C3A0.5641 (4)0.4454 (4)−0.0337 (2)0.0415 (6)
H3AA0.48610.4776−0.09940.050*
H3AB0.68880.4738−0.04930.050*
N1B0.3531 (4)0.2003 (3)0.54857 (19)0.0469 (6)
H1BD0.29850.27730.48370.056*
C1B0.5067 (8)0.2606 (6)0.5827 (3)0.0840 (13)
H1BA0.43720.37650.59350.126*
H1BB0.60360.27160.52990.126*
H1BC0.57940.17350.64710.126*
C2B0.1808 (8)0.2172 (9)0.6196 (4)0.0998 (16)
H2BA0.12460.33910.62330.150*
H2BB0.23240.13380.68830.150*
H2BC0.07410.18930.59320.150*
C3BA0.4254 (8)0.0107 (5)0.5425 (3)0.0415 (15)0.784 (13)
H3BA0.3081−0.01700.52820.050*0.784 (13)
H3BB0.4934−0.07360.60850.050*0.784 (13)
C3BB0.542 (2)0.0458 (19)0.5298 (11)0.040 (5)0.216 (13)
H3BC0.6148−0.03850.59480.048*0.216 (13)
H3BE0.63550.09500.48760.048*0.216 (13)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Co10.0331 (2)0.0344 (3)0.0343 (2)−0.01054 (16)0.00261 (14)−0.01021 (16)
Cl10.0643 (5)0.0794 (6)0.0662 (5)−0.0350 (5)0.0280 (4)−0.0102 (5)
Cl20.0475 (4)0.0414 (4)0.0432 (4)−0.0128 (3)0.0093 (3)−0.0182 (3)
Cl30.0701 (5)0.0565 (5)0.0496 (4)−0.0363 (4)−0.0092 (4)−0.0113 (3)
Cl40.0473 (4)0.0481 (4)0.0596 (5)−0.0079 (3)−0.0117 (3)−0.0002 (4)
N1A0.0317 (10)0.0304 (11)0.0541 (13)−0.0110 (9)0.0104 (9)−0.0154 (10)
C1A0.0536 (19)0.057 (2)0.064 (2)−0.0098 (15)−0.0066 (16)−0.0161 (16)
C2A0.0516 (17)0.0465 (17)0.073 (2)−0.0108 (14)0.0096 (15)−0.0338 (16)
C3A0.0430 (14)0.0333 (13)0.0477 (15)−0.0120 (11)0.0111 (12)−0.0149 (12)
N1B0.0594 (15)0.0358 (13)0.0371 (12)−0.0050 (11)−0.0009 (10)−0.0135 (10)
C1B0.121 (4)0.080 (3)0.066 (2)−0.061 (3)−0.009 (2)−0.012 (2)
C2B0.088 (3)0.145 (5)0.083 (3)−0.048 (3)0.031 (3)−0.055 (3)
C3BA0.046 (3)0.037 (2)0.045 (2)−0.0160 (17)0.0098 (18)−0.0166 (15)
C3BB0.031 (8)0.040 (7)0.047 (8)−0.009 (6)0.012 (5)−0.014 (6)

Geometric parameters (Å, °)

Co1—Cl12.2500 (8)N1B—C1B1.469 (5)
Co1—Cl22.2980 (7)N1B—C2B1.485 (5)
Co1—Cl32.2686 (8)N1B—C3BA1.496 (4)
Co1—Cl42.2615 (8)N1B—C3BB1.542 (13)
N1A—C2A1.483 (4)N1B—H1BD0.9100
N1A—C1A1.487 (4)C1B—H1BA0.9600
N1A—C3A1.496 (3)C1B—H1BB0.9598
N1A—H1AD0.9100C1B—H1BC0.9599
C1A—H1AA0.9600C2B—H2BA0.9600
C1A—H1AB0.9600C2B—H2BB0.9600
C1A—H1AC0.9601C2B—H2BC0.9600
C2A—H2AA0.9601C3BA—C3BAii1.510 (9)
C2A—H2AB0.9600C3BA—H3BA0.9600
C2A—H2AC0.9599C3BA—H3BB0.9601
C3A—C3Ai1.509 (5)C3BB—C3BBii1.51 (3)
C3A—H3AA0.9700C3BB—H3BC0.9600
C3A—H3AB0.9700C3BB—H3BE0.9600
Cl1—Co1—Cl4115.50 (4)N1B—C2B—H2BA109.6
Cl1—Co1—Cl2106.29 (4)N1B—C2B—H2BB109.4
Cl1—Co1—Cl3106.99 (4)H2BA—C2B—H2BB109.5
Cl2—Co1—Cl3107.06 (3)N1B—C2B—H2BC109.4
Cl2—Co1—Cl4112.81 (3)H2BA—C2B—H2BC109.5
Cl3—Co1—Cl4107.76 (3)H2BB—C2B—H2BC109.5
C1A—N1A—C2A111.2 (2)C3BB—C3BA—C3BBii90.0 (15)
C1A—N1A—C3A112.5 (2)C3BB—C3BA—N1B74.6 (8)
C2A—N1A—C3A109.8 (2)C3BBii—C3BA—N1B131.5 (8)
C2A—N1A—H1AD107.6C3BB—C3BA—C3BAii51.4 (9)
C1A—N1A—H1AD107.7N1B—C3BA—C3BAii110.7 (4)
C3A—N1A—H1AD107.6C3BB—C3BA—H3BA158.9
N1A—C1A—H1AA109.4C3BBii—C3BA—H3BA71.7
N1A—C1A—H1AB109.5N1B—C3BA—H3BA109.6
H1AA—C1A—H1AB109.5C3BAii—C3BA—H3BA109.6
N1A—C1A—H1AC109.5C3BB—C3BA—H3BB88.9
H1AA—C1A—H1AC109.5C3BBii—C3BA—H3BB115.9
H1AB—C1A—H1AC109.5N1B—C3BA—H3BB109.6
N1A—C2A—H2AA109.4C3BAii—C3BA—H3BB109.2
N1A—C2A—H2AB109.6H3BA—C3BA—H3BB108.1
H2AA—C2A—H2AB109.5C3BBii—C3BA—H3BC107.1
N1A—C2A—H2AC109.4N1B—C3BA—H3BC93.1
H2AA—C2A—H2AC109.5C3BAii—C3BA—H3BC77.4
H2AB—C2A—H2AC109.5H3BA—C3BA—H3BC150.8
N1A—C3A—C3Ai110.3 (3)C3BA—C3BB—C3BAii90.0 (15)
N1A—C3A—H3AA109.7C3BA—C3BB—C3BBii51.5 (12)
C3Ai—C3A—H3AA109.8C3BA—C3BB—N1B69.3 (8)
N1A—C3A—H3AB109.5C3BAii—C3BB—N1B130.1 (12)
C3Ai—C3A—H3AB109.4C3BBii—C3BB—N1B106.5 (14)
H3AA—C3A—H3AB108.1C3BA—C3BB—H3BB46.1
C1B—N1B—C2B109.6 (3)C3BAii—C3BB—H3BB108.4
C1B—N1B—C3BA117.8 (3)C3BBii—C3BB—H3BB79.3
C2B—N1B—C3BA106.6 (4)N1B—C3BB—H3BB89.6
C1B—N1B—C3BB85.6 (7)C3BA—C3BB—H3BC93.1
C2B—N1B—C3BB137.0 (7)C3BAii—C3BB—H3BC115.0
C1B—N1B—H1BD107.5C3BBii—C3BB—H3BC111.4
C2B—N1B—H1BD107.3N1B—C3BB—H3BC111.2
C3BA—N1B—H1BD107.5H3BB—C3BB—H3BC47.0
C3BB—N1B—H1BD105.5C3BA—C3BB—H3BE155.7
N1B—C1B—H1BA109.4C3BAii—C3BB—H3BE71.7
N1B—C1B—H1BB109.5C3BBii—C3BB—H3BE108.8
H1BA—C1B—H1BB109.5N1B—C3BB—H3BE110.1
N1B—C1B—H1BC109.5H3BB—C3BB—H3BE154.5
H1BA—C1B—H1BC109.5H3BC—C3BB—H3BE108.8
H1BB—C1B—H1BC109.5
N1A—C3A—C3Ai—N1Ai180.0C3BB—N1B—C3BA—C3BAii−37.3 (9)
C1A—N1A—C3A—C3Ai−73.0 (4)C3BBii—C3BA—C3BB—C3BAii0.001 (2)
C2A—N1A—C3A—C3Ai162.5 (3)N1B—C3BA—C3BB—C3BAii−133.5 (9)
N1B—C3BA—C3BAii—N1Bii180.0N1B—C3BA—C3BB—C3BBii−133.5 (9)
N1B—C3BB—C3BBii—N1Bii180.0C3BAii—C3BA—C3BB—C3BBii−0.001 (2)
C1B—N1B—C3BA—C3BAii−66.5 (5)C3BBii—C3BA—C3BB—N1B133.5 (9)
C1B—N1B—C3BB—C3BBii−169.3 (14)C3BAii—C3BA—C3BB—N1B133.5 (9)
C2B—N1B—C3BA—C3BAii170.0 (4)C1B—N1B—C3BB—C3BA154.4 (8)
C2B—N1B—C3BB—C3BBii76.5 (15)C2B—N1B—C3BB—C3BA40.2 (13)
C1B—N1B—C3BA—C3BB−29.1 (9)C1B—N1B—C3BB—C3BAii−134.0 (19)
C2B—N1B—C3BA—C3BB−152.7 (9)C2B—N1B—C3BB—C3BAii111.8 (16)
C1B—N1B—C3BA—C3BBii−105.0 (15)C3BA—N1B—C3BB—C3BAii72 (2)
C2B—N1B—C3BA—C3BBii131.5 (15)C3BA—N1B—C3BB—C3BBii36.3 (11)
C3BB—N1B—C3BA—C3BBii−75.8 (19)

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

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1A—H1AD···Cl20.912.313.170 (2)157
N1B—H1BD···Cl30.912.373.222 (3)155

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2786).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Bruker (1996). XSCANS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (1999). XSHELL Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Szafran, Z., Pike, R. M. & Singh, M. M. (1998). Microscale Inorganic Chemistry: A Comprehensive Laboratory Experience, pp. 239–243. New York: John Wiley & Sons.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography