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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m958–m959.
Published online 2009 July 22. doi:  10.1107/S1600536809027913
PMCID: PMC2977443

4-(Dimethyl­amino)pyridinium tri­bromido­{3-[bromo/hydro­(0.9/0.1)]-4-(dimethyl­amino)pyridine-κN 1}cobaltate(II)

Abstract

The reaction of a cobalt(II) salt with 4-(dimethyl­amino)pyridinium hydro­bromide perbromide yielded the title compound, (C7H11N2)[CoBr3(C7H9.1Br0.9N2)]. In the anion, the CoII atom is coordinated in a distorted tetra­hedral geometry by three Br atoms and the pyridine N atom of a bromine-substituted 4-(dimethyl­amino)pyridine mol­ecule, whose formation probably results from an incomplete substitution (90%) catalysed by the CoII ion. One of the three bromine atoms bonded to the metal is disordered over two sites in a 0.9:0.1 ratio. An N—H(...)Br hydrogen bond connects the cation and anion.

Related literature

For bis­(4-(dimethyl­amino)pyridinium) tetra­bromidocobaltate, see: Lo & Ng (2009 [triangle]). For other trihalocobaltate(II) anions having a pyridine-type donor ligand, see: Bogdanović et al. (2001 [triangle]); Crane et al. (2004 [triangle]); Divjaković et al. (1982 [triangle]); Hahn et al. (1997 [triangle]); Mueller-Westerhoff et al. (1996 [triangle]); Sumner & Steinmetz (1985 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m958-scheme1.jpg

Experimental

Crystal data

  • (C7H11N2)[CoBr3(C7H9.1Br0.9N2)]
  • M r = 615.02
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m958-efi1.jpg
  • a = 8.3768 (2) Å
  • b = 10.2622 (2) Å
  • c = 12.4691 (3) Å
  • α = 99.028 (2)°
  • β = 98.927 (1)°
  • γ = 106.933 (2)°
  • V = 989.57 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 8.74 mm−1
  • T = 150 K
  • 0.40 × 0.20 × 0.10 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.128, T max = 0.475 (expected range = 0.112–0.417)
  • 7974 measured reflections
  • 4451 independent reflections
  • 3019 reflections with I > 2σ(I)
  • R int = 0.053

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.130
  • S = 0.97
  • 4451 reflections
  • 221 parameters
  • 7 restraints
  • H-atom parameters constrained
  • Δρmax = 1.29 e Å−3
  • Δρmin = −1.04 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

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

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809027913/hy2210sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027913/hy2210Isup2.hkl

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

Acknowledgments

We thank the University of Malaya (RG020/09AFR) for supporting this study.

supplementary crystallographic information

Comment

The reaction of cobalt(II) nitrate and 4-(dimethylamino)pyridinium hydrobromide perbromide yields bis(4-(dimethylamino)pyridinium) tetrabromidocobaltate (Lo & Ng, 2009). A similar reaction with cobalt acetate in place of cobalt nitrate yields a new 4-(dimethylamino)pyridinium salt, [C7H11N2][CoBr3(C7H9.1Br0.9N2)] (Scheme 1, Fig. 1). The CoII atom is coordinated by a bromine-substituted 4-(dimethylamino)pyridine molecule, whose formation probably results from an incomplete (90%) electrophilic substitution of 4-(dimethylamino)pyridine that is probabably catalyzed by the cobaltous ion.

Experimental

Green cobalt acetate (0.70 g, 2.8 mmol) dissolved in water (2 ml) and 4-(dimethylamino)pyridinium hydrobromide perbromide (1.00 g, 2.8 mmol) dissolved in ethanol (50 ml) were mixed and the mixture was heated for one hour. The red solution was filtered; well-formed deep-blue crystals were isolated from the solution after several days.

Refinement

H atoms were placed at calculated positions (C—H = 0.95 and 0.98, N—H = 0.88 Å) and were treated as riding on their parent atoms, with Uiso(H) = 1.2(or 1.5)Ueq(C).

One of the three Br atoms that are bonded to Co1 is disordered over two positions (Br3 and Br3'). The Br3 atom is 3.5 Å from Br4i atom [symmetry code: (i) = 1-x, 1-y, 2-z]. However, as the Br3' atom is only 3.0 Å from Br4i, the atom that is linked to the C2 atom should then be a mixture of Br and H atoms, with the provision that the occupancies of the Br3 and Br4 atoms are identical. As the occupancies refined to nearly 0.9:0.1, the occupancy factors were then fixed as 0.90 and 0.1 for Br3 and Br3', as well as for Br4 and H2. Other ratios, e.g. 0.85:0.15 and 0.95:0.05, gave less satisfactory R indices and large peaks/deep holes in the difference Fourier map. The anisotropic displacement of the minor occupant was restrained to be nearly isotropic; the Co–Br distances were restrained to within 0.01 Å of each other.

The final difference Fourier map had a peak in the vicinity of Br2 and a hole in the vicinty of Br4. The magnitudes of both could be decreased by lowering the 2θ limit to 50°.

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 70% probability level. Minor disordered sites are omitted for clarity.

Crystal data

(C7H11N2)[CoBr3(C7H9.1Br0.9N2)]Z = 2
Mr = 615.02F(000) = 591.2
Triclinic, P1Dx = 2.064 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.3768 (2) ÅCell parameters from 6987 reflections
b = 10.2622 (2) Åθ = 2.4–28.3°
c = 12.4691 (3) ŵ = 8.74 mm1
α = 99.028 (2)°T = 150 K
β = 98.927 (1)°Block, brown
γ = 106.933 (2)°0.40 × 0.20 × 0.10 mm
V = 989.57 (4) Å3

Data collection

Bruker APEXII CCD diffractometer4451 independent reflections
Radiation source: fine-focus sealed tube3019 reflections with I > 2σ(I)
graphiteRint = 0.053
[var phi] and ω scansθmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→10
Tmin = 0.128, Tmax = 0.475k = −12→13
7974 measured reflectionsl = −16→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 0.97w = 1/[σ2(Fo2) + (0.0634P)2] where P = (Fo2 + 2Fc2)/3
4451 reflections(Δ/σ)max = 0.001
221 parametersΔρmax = 1.29 e Å3
7 restraintsΔρmin = −1.04 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
Br10.26488 (9)0.68358 (8)0.54136 (5)0.0375 (2)
Br20.64945 (8)0.59464 (7)0.69989 (5)0.03080 (18)
Br30.49021 (18)0.89737 (12)0.84679 (11)0.0315 (3)0.90
Br3'0.531 (2)0.8775 (13)0.8695 (11)0.068 (5)0.10
Br40.30233 (9)0.25573 (8)0.96716 (6)0.0350 (2)0.90
Co10.41492 (10)0.67837 (9)0.72097 (7)0.0271 (2)
N10.2478 (6)0.5344 (5)0.7796 (4)0.0280 (12)
N2−0.0965 (6)0.2792 (5)0.9321 (4)0.0276 (12)
N30.6361 (7)0.7246 (6)0.4462 (5)0.0414 (15)
H30.55800.67230.47510.050*
N41.0006 (7)0.9742 (6)0.3157 (4)0.0318 (12)
C10.2977 (8)0.4510 (6)0.8403 (5)0.0267 (13)
H10.41350.45400.84920.032*
C20.1936 (7)0.3618 (6)0.8904 (5)0.0226 (12)
H2'0.23680.30260.92930.027*0.10
C30.0191 (7)0.3572 (6)0.8846 (5)0.0248 (13)
C4−0.0282 (8)0.4425 (7)0.8152 (5)0.0320 (15)
H4−0.14380.44040.80150.038*
C50.0825 (8)0.5267 (7)0.7677 (6)0.0338 (15)
H50.04200.58300.72390.041*
C6−0.0620 (10)0.1971 (10)1.0125 (8)0.063 (3)
H6A0.04490.25031.06600.094*
H6B−0.05160.11010.97370.094*
H6C−0.15590.17561.05180.094*
C7−0.2699 (8)0.2868 (7)0.9146 (6)0.0377 (16)
H7A−0.32130.25960.83490.057*
H7B−0.26610.38240.94330.057*
H7C−0.33850.22340.95370.057*
C80.7904 (10)0.7112 (7)0.4577 (5)0.0362 (16)
H80.81480.64410.49620.043*
C90.9138 (9)0.7919 (7)0.4155 (5)0.0320 (15)
H91.02360.78110.42540.038*
C100.8813 (7)0.8921 (6)0.3568 (4)0.0240 (13)
C110.7136 (9)0.9012 (7)0.3454 (5)0.0360 (16)
H110.68260.96550.30620.043*
C120.5987 (9)0.8172 (8)0.3908 (6)0.0405 (17)
H120.48710.82430.38310.049*
C130.9613 (11)1.0765 (8)0.2567 (6)0.051 (2)
H13A0.91621.13660.30380.076*
H13B0.87581.02820.18810.076*
H13C1.06541.13340.23840.076*
C141.1733 (9)0.9648 (8)0.3293 (6)0.048 (2)
H14A1.22140.97680.40840.073*
H14B1.24521.03800.29940.073*
H14C1.16890.87330.28930.073*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0327 (4)0.0541 (5)0.0345 (4)0.0205 (3)0.0109 (3)0.0188 (3)
Br20.0220 (3)0.0369 (4)0.0365 (4)0.0102 (3)0.0092 (3)0.0119 (3)
Br30.0321 (5)0.0292 (5)0.0328 (5)0.0089 (4)0.0070 (3)0.0071 (4)
Br3'0.076 (9)0.060 (7)0.057 (7)0.001 (5)0.034 (6)0.001 (5)
Br40.0253 (4)0.0469 (5)0.0403 (4)0.0144 (3)0.0087 (3)0.0237 (4)
Co10.0236 (5)0.0288 (5)0.0310 (5)0.0068 (4)0.0110 (3)0.0108 (4)
N10.025 (3)0.030 (3)0.031 (3)0.008 (2)0.009 (2)0.011 (2)
N20.022 (3)0.031 (3)0.029 (3)0.003 (2)0.010 (2)0.013 (2)
N30.033 (3)0.047 (4)0.034 (3)−0.005 (3)0.011 (3)0.007 (3)
N40.026 (3)0.038 (3)0.026 (3)0.002 (2)0.003 (2)0.010 (2)
C10.017 (3)0.033 (4)0.028 (3)0.007 (3)0.007 (2)0.002 (3)
C20.023 (3)0.023 (3)0.025 (3)0.009 (2)0.008 (2)0.010 (2)
C30.020 (3)0.025 (3)0.024 (3)0.000 (2)0.006 (2)0.000 (2)
C40.023 (3)0.035 (4)0.039 (4)0.007 (3)0.004 (3)0.015 (3)
C50.024 (3)0.039 (4)0.046 (4)0.014 (3)0.011 (3)0.020 (3)
C60.036 (5)0.085 (7)0.083 (6)0.017 (5)0.021 (4)0.058 (5)
C70.024 (4)0.042 (4)0.049 (4)0.008 (3)0.017 (3)0.010 (3)
C80.055 (5)0.029 (4)0.023 (3)0.011 (3)0.007 (3)0.007 (3)
C90.036 (4)0.031 (4)0.027 (3)0.012 (3)0.001 (3)0.002 (3)
C100.027 (3)0.025 (3)0.015 (3)0.003 (3)0.002 (2)0.003 (2)
C110.033 (4)0.045 (4)0.030 (4)0.014 (3)0.002 (3)0.013 (3)
C120.023 (4)0.059 (5)0.033 (4)0.007 (3)0.002 (3)0.008 (3)
C130.060 (5)0.035 (4)0.050 (5)−0.001 (4)0.008 (4)0.022 (4)
C140.031 (4)0.056 (5)0.045 (5)−0.003 (4)0.013 (3)−0.002 (4)

Geometric parameters (Å, °)

Co1—Br12.4086 (11)C4—H40.9500
Co1—Br22.3958 (10)C5—H50.9500
Co1—Br32.3814 (13)C6—H6A0.9800
Co1—Br3'2.376 (9)C6—H6B0.9800
Br4—C21.888 (6)C6—H6C0.9800
Co1—N12.032 (5)C7—H7A0.9800
N1—C11.340 (8)C7—H7B0.9800
N1—C51.347 (8)C7—H7C0.9800
N2—C31.343 (7)C8—C91.356 (9)
N2—C61.454 (9)C8—H80.9500
N2—C71.461 (8)C9—C101.416 (8)
N3—C81.328 (9)C9—H90.9500
N3—C121.338 (9)C10—C111.421 (9)
N3—H30.8800C11—C121.353 (9)
N4—C101.333 (7)C11—H110.9500
N4—C131.456 (9)C12—H120.9500
N4—C141.463 (9)C13—H13A0.9800
C1—C21.368 (8)C13—H13B0.9800
C1—H10.9500C13—H13C0.9800
C2—C31.439 (8)C14—H14A0.9800
C2—H2'0.9500C14—H14B0.9800
C3—C41.415 (9)C14—H14C0.9800
C4—C51.350 (9)
N1—Co1—Br3'105.5 (5)N2—C6—H6A109.5
N1—Co1—Br3107.98 (15)N2—C6—H6B109.5
Br3'—Co1—Br312.5 (4)H6A—C6—H6B109.5
N1—Co1—Br2106.97 (14)N2—C6—H6C109.5
Br3'—Co1—Br2104.7 (4)H6A—C6—H6C109.5
Br3—Co1—Br2114.67 (5)H6B—C6—H6C109.5
N1—Co1—Br1105.94 (15)N2—C7—H7A109.5
Br3'—Co1—Br1123.1 (4)N2—C7—H7B109.5
Br3—Co1—Br1111.17 (5)H7A—C7—H7B109.5
Br2—Co1—Br1109.64 (4)N2—C7—H7C109.5
C1—N1—C5116.2 (5)H7A—C7—H7C109.5
C1—N1—Co1122.3 (4)H7B—C7—H7C109.5
C5—N1—Co1121.2 (4)N3—C8—C9121.1 (6)
C3—N2—C6125.9 (5)N3—C8—H8119.5
C3—N2—C7119.4 (5)C9—C8—H8119.5
C6—N2—C7114.3 (5)C8—C9—C10120.9 (6)
C8—N3—C12120.3 (6)C8—C9—H9119.5
C8—N3—H3119.9C10—C9—H9119.5
C12—N3—H3119.9N4—C10—C9122.3 (6)
C10—N4—C13120.2 (6)N4—C10—C11121.8 (6)
C10—N4—C14121.2 (6)C9—C10—C11115.9 (6)
C13—N4—C14118.6 (6)C12—C11—C10119.2 (6)
N1—C1—C2124.6 (5)C12—C11—H11120.4
N1—C1—H1117.7C10—C11—H11120.4
C2—C1—H1117.7N3—C12—C11122.6 (6)
C1—C2—C3120.5 (5)N3—C12—H12118.7
C1—C2—Br4114.0 (4)C11—C12—H12118.7
C3—C2—Br4125.5 (4)N4—C13—H13A109.5
C1—C2—H2'119.8N4—C13—H13B109.5
C3—C2—H2'119.8H13A—C13—H13B109.5
N2—C3—C4120.3 (5)N4—C13—H13C109.5
N2—C3—C2127.4 (6)H13A—C13—H13C109.5
C4—C3—C2112.2 (5)H13B—C13—H13C109.5
C5—C4—C3123.4 (6)N4—C14—H14A109.5
C5—C4—H4118.3N4—C14—H14B109.5
C3—C4—H4118.3H14A—C14—H14B109.5
N1—C5—C4122.9 (6)N4—C14—H14C109.5
N1—C5—H5118.6H14A—C14—H14C109.5
C4—C5—H5118.6H14B—C14—H14C109.5
Br3'—Co1—N1—C1−83.8 (6)Br4—C2—C3—C4−176.4 (5)
Br3—Co1—N1—C1−96.6 (5)N2—C3—C4—C5177.9 (6)
Br2—Co1—N1—C127.3 (5)C2—C3—C4—C5−5.0 (9)
Br1—Co1—N1—C1144.2 (4)C1—N1—C5—C41.3 (9)
Br3'—Co1—N1—C590.1 (7)Co1—N1—C5—C4−173.0 (5)
Br3—Co1—N1—C577.3 (5)C3—C4—C5—N11.8 (11)
Br2—Co1—N1—C5−158.8 (5)C12—N3—C8—C91.0 (10)
Br1—Co1—N1—C5−41.9 (5)N3—C8—C9—C10−0.6 (10)
C5—N1—C1—C2−0.6 (9)C13—N4—C10—C9−179.5 (6)
Co1—N1—C1—C2173.6 (5)C14—N4—C10—C90.0 (9)
N1—C1—C2—C3−3.0 (9)C13—N4—C10—C11−0.2 (9)
N1—C1—C2—Br4178.6 (5)C14—N4—C10—C11179.3 (6)
C6—N2—C3—C4−174.2 (7)C8—C9—C10—N4179.1 (6)
C7—N2—C3—C4−2.0 (9)C8—C9—C10—C11−0.3 (9)
C6—N2—C3—C29.1 (10)N4—C10—C11—C12−178.6 (6)
C7—N2—C3—C2−178.7 (6)C9—C10—C11—C120.7 (9)
C1—C2—C3—N2−177.7 (6)C8—N3—C12—C11−0.5 (10)
Br4—C2—C3—N20.5 (9)C10—C11—C12—N3−0.3 (11)
C1—C2—C3—C45.4 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3···Br10.882.743.434 (6)137

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2210).

References

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