metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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Tris[(2E)-1,3-bis­­(4-chloro­phen­yl)triaz-2-en-1-ido-κ2N1,N3]cobalt(III)

aCollege of Chemistry & Chemical Engineering, South China University of Technology, Guangzhou 510640, People's Republic of China, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: seikweng@um.edu.my

(Received 7 May 2012; accepted 7 May 2012; online 12 May 2012)

Mol­ecules of the title compound, [Co(C12H8Cl2N3)3], lie on a threefold rotation axis. The tris-N,N′-chelated CoIII atom, which is located on the threefold rotation axis, shows a distorted octa­hedral coordination.

Related literature

For tris­(diphenyl­triazenido)cobalt(III), see: Krigbaum & Rubin (1973[Krigbaum, W. R. & Rubin, B. (1973). Acta Cryst. B29, 749-756.]).

[Scheme 1]

Experimental

Crystal data
  • [Co(C12H8Cl2N3)3]

  • Mr = 854.27

  • Trigonal, [R \overline 3]

  • a = 19.383 (3) Å

  • c = 17.546 (2) Å

  • V = 5708.5 (10) Å3

  • Z = 6

  • Mo Kα radiation

  • μ = 0.91 mm−1

  • T = 293 K

  • 0.30 × 0.25 × 0.20 mm

Data collection
  • Bruker SMART APEX diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.771, Tmax = 0.839

  • 8131 measured reflections

  • 2891 independent reflections

  • 1714 reflections with I > 2σ(I)

  • Rint = 0.053

Refinement
  • R[F2 > 2σ(F2)] = 0.053

  • wR(F2) = 0.159

  • S = 1.04

  • 2891 reflections

  • 157 parameters

  • H-atom parameters constrained

  • Δρmax = 0.35 e Å−3

  • Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

The diaryltriazenido anion N,N'-chelates to a large number of metal atoms; for CoIII in particular, three diphenyltriazenido anions chelate to the metal atom to render a trigonal prismatic coordination geometry. Such a geometry appears to be a consequence of the small bite of the chelate (Krigbaum & Rubin, 1973). In chlorine-substituted Co(C12H8Cl2N3)3 (Scheme I), the metal atom lies on a threefold rotation axis that relates one di(4-chlorophenyl)triazenido chelate to the others (Fig. 1). The CoIII atom shows octahedral coordination (Fig. 2). With respect to the delocalized –N–NN– fragment, one phenylene ring is twisted by 9.5 (3) ånd the other by 21.1 (2) °.

Related literature top

For tris(diphenyltriazenido)cobalt(III), see: Krigbaum & Rubin (1973).

Experimental top

4-Chloroaniline (10 mmol) in water (5 ml) was suspended in 1 M hydrochloric acid (30 ml) at 273 K. An aqueous solution (15%) of sodium nitrite (15 mmol) was added dropwise. When the amine had dissolved, a solution of 4-chloroaniline in ethanol (10 mmol) was added at 273 K. The mixture was stirred for 3 h. The reaction mixture was neutralized with a 15% aqueous of sodium acetate to give an orange precipitate. The product was collected and crystallized at 269 K from 9:1 ethyl acetate/n-hexane to give yellow crystals in (65% yield). Calc. for C12H9Cl2N3: C 54.16, H 3.41, N 15.79%. Found: C 54.07, H 3.39, N 15.66.%

To a solution of the ligand (0.798 g, 3 mmol) and triethylamine (0.300 g, 3 mmol) in dichloromethane/acetonitrile (30 ml, 1:1) was added cobalt(II) chloride hexahydrate (0.238 g, 1 mmol). The solvent was allowed to evaporate over several days. Red crystals were isolated in 50% yield. Calc. for C36H24CoN9Cl6: C 50.59, H 2.81, N 14.76%. Found: C 51.19, H 2.68, N 14.81%.

Refinement top

H-atoms were placed in calculated positions (C—H 0.93 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of Co(C12H8Cl2N3)3 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry-related atoms are no labeled.
[Figure 2] Fig. 2. Octahedral coordination geometry of CoIII.
Tris[(2E)-1,3-bis(4-chlorophenyl)triaz-2-en-1-ido- κ2N1,N3]cobalt(III) top
Crystal data top
[Co(C12H8Cl2N3)3]Dx = 1.491 Mg m3
Mr = 854.27Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 1211 reflections
Hall symbol: -R 3θ = 2.6–22.1°
a = 19.383 (3) ŵ = 0.91 mm1
c = 17.546 (2) ÅT = 293 K
V = 5708.5 (10) Å3Prism, red
Z = 60.30 × 0.25 × 0.20 mm
F(000) = 2592
Data collection top
Bruker SMART APEX
diffractometer
2891 independent reflections
Radiation source: fine-focus sealed tube1714 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
ω scansθmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2420
Tmin = 0.771, Tmax = 0.839k = 2422
8131 measured reflectionsl = 2222
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)] = 0.053Hydrogen site location: difference Fourier map
wR(F2) = 0.159H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0758P)2 + 0.3669P]
where P = (Fo2 + 2Fc2)/3
2891 reflections(Δ/σ)max = 0.001
157 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
[Co(C12H8Cl2N3)3]Z = 6
Mr = 854.27Mo Kα radiation
Trigonal, R3µ = 0.91 mm1
a = 19.383 (3) ÅT = 293 K
c = 17.546 (2) Å0.30 × 0.25 × 0.20 mm
V = 5708.5 (10) Å3
Data collection top
Bruker SMART APEX
diffractometer
2891 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1714 reflections with I > 2σ(I)
Tmin = 0.771, Tmax = 0.839Rint = 0.053
8131 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.159H-atom parameters constrained
S = 1.04Δρmax = 0.35 e Å3
2891 reflectionsΔρmin = 0.34 e Å3
157 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co10.00000.00000.25642 (4)0.0361 (3)
Cl10.04587 (9)0.28231 (8)0.51099 (7)0.0835 (5)
Cl20.34023 (9)0.12548 (9)0.01594 (8)0.0937 (5)
C10.0269 (2)0.1483 (2)0.35169 (17)0.0349 (8)
C20.0262 (2)0.1092 (2)0.41122 (18)0.0402 (8)
H20.04730.05470.41780.048*
C30.0476 (2)0.1507 (2)0.46038 (19)0.0441 (9)
H30.08300.12450.50010.053*
C40.0162 (2)0.2313 (2)0.4501 (2)0.0477 (10)
C50.0370 (3)0.2714 (2)0.3925 (2)0.0581 (11)
H50.05860.32610.38710.070*
C60.0582 (2)0.2301 (2)0.3430 (2)0.0486 (10)
H60.09350.25690.30340.058*
C70.1553 (2)0.0949 (2)0.15565 (17)0.0368 (8)
C80.1422 (3)0.0343 (3)0.1071 (2)0.0630 (12)
H80.09490.01420.11020.076*
C90.1988 (3)0.0447 (3)0.0536 (3)0.0725 (14)
H90.18930.00330.02050.087*
C100.2671 (3)0.1136 (3)0.0490 (2)0.0547 (11)
C110.2815 (2)0.1764 (3)0.0959 (2)0.0561 (11)
H110.32880.22470.09140.067*
C120.2254 (2)0.1673 (2)0.1496 (2)0.0485 (10)
H120.23470.20940.18150.058*
N10.04549 (18)0.10269 (17)0.30269 (15)0.0398 (7)
N20.10592 (17)0.13926 (18)0.25527 (15)0.0407 (7)
N30.09691 (17)0.08162 (18)0.21030 (15)0.0387 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0336 (3)0.0336 (3)0.0410 (4)0.01679 (17)0.0000.000
Cl10.0956 (10)0.0685 (9)0.0929 (9)0.0459 (8)0.0247 (7)0.0207 (7)
Cl20.0941 (10)0.0919 (11)0.0959 (9)0.0471 (9)0.0578 (8)0.0140 (8)
C10.037 (2)0.036 (2)0.0365 (16)0.0218 (17)0.0013 (15)0.0045 (14)
C20.040 (2)0.034 (2)0.0469 (19)0.0193 (17)0.0047 (16)0.0030 (15)
C30.042 (2)0.048 (2)0.0412 (18)0.021 (2)0.0072 (16)0.0016 (17)
C40.051 (2)0.045 (2)0.054 (2)0.029 (2)0.0028 (19)0.0101 (18)
C50.075 (3)0.034 (2)0.067 (2)0.028 (2)0.013 (2)0.0024 (19)
C60.059 (3)0.036 (2)0.052 (2)0.024 (2)0.0180 (19)0.0100 (17)
C70.036 (2)0.037 (2)0.0390 (17)0.0193 (17)0.0046 (15)0.0031 (15)
C80.060 (3)0.041 (2)0.070 (3)0.012 (2)0.025 (2)0.004 (2)
C90.078 (3)0.053 (3)0.074 (3)0.023 (3)0.027 (3)0.013 (2)
C100.057 (3)0.059 (3)0.054 (2)0.033 (2)0.023 (2)0.012 (2)
C110.040 (2)0.052 (3)0.064 (2)0.014 (2)0.0089 (19)0.000 (2)
C120.047 (2)0.041 (2)0.050 (2)0.016 (2)0.0085 (18)0.0059 (17)
N10.0381 (17)0.0350 (17)0.0450 (15)0.0174 (14)0.0081 (13)0.0005 (13)
N20.0401 (18)0.0385 (18)0.0438 (15)0.0199 (15)0.0076 (13)0.0020 (13)
N30.0325 (16)0.0369 (18)0.0445 (14)0.0156 (14)0.0031 (13)0.0061 (13)
Geometric parameters (Å, º) top
Co1—N11.909 (3)C4—C51.373 (5)
Co1—N1i1.909 (3)C5—C61.376 (5)
Co1—N1ii1.909 (3)C5—H50.9300
Co1—N3i1.927 (3)C6—H60.9300
Co1—N31.927 (3)C7—C81.368 (5)
Co1—N3ii1.927 (3)C7—C121.386 (5)
Co1—N2ii2.441 (3)C7—N31.406 (4)
Co1—N2i2.441 (3)C8—C91.381 (6)
Cl1—C41.737 (4)C8—H80.9300
Cl2—C101.741 (4)C9—C101.332 (6)
C1—C21.394 (4)C9—H90.9300
C1—C61.395 (5)C10—C111.377 (6)
C1—N11.403 (4)C11—C121.382 (5)
C2—C31.378 (5)C11—H110.9300
C2—H20.9300C12—H120.9300
C3—C41.376 (5)N1—N21.318 (4)
C3—H30.9300N2—N31.306 (4)
N1—Co1—N1i103.22 (10)C2—C3—H3120.3
N1—Co1—N1ii103.22 (10)C5—C4—C3121.3 (3)
N1i—Co1—N1ii103.22 (10)C5—C4—Cl1120.0 (3)
N1—Co1—N3i163.88 (12)C3—C4—Cl1118.7 (3)
N1i—Co1—N3i64.54 (12)C4—C5—C6119.6 (4)
N1ii—Co1—N3i90.28 (12)C4—C5—H5120.2
N1—Co1—N364.54 (12)C6—C5—H5120.2
N1i—Co1—N390.28 (12)C5—C6—C1120.3 (3)
N1ii—Co1—N3163.88 (12)C5—C6—H6119.8
N3i—Co1—N3103.63 (10)C1—C6—H6119.8
N1—Co1—N3ii90.28 (12)C8—C7—C12119.3 (3)
N1i—Co1—N3ii163.88 (12)C8—C7—N3118.7 (3)
N1ii—Co1—N3ii64.54 (12)C12—C7—N3122.0 (3)
N3i—Co1—N3ii103.63 (10)C7—C8—C9120.3 (4)
N3—Co1—N3ii103.63 (10)C7—C8—H8119.8
N1—Co1—N2ii98.78 (11)C9—C8—H8119.8
N1i—Co1—N2ii134.58 (11)C10—C9—C8120.4 (4)
N1ii—Co1—N2ii32.42 (10)C10—C9—H9119.8
N3i—Co1—N2ii97.33 (11)C8—C9—H9119.8
N3—Co1—N2ii135.13 (11)C9—C10—C11120.7 (4)
N3ii—Co1—N2ii32.14 (10)C9—C10—Cl2120.5 (4)
N1—Co1—N2i134.58 (11)C11—C10—Cl2118.8 (3)
N1i—Co1—N2i32.42 (10)C10—C11—C12119.7 (4)
N1ii—Co1—N2i98.78 (11)C10—C11—H11120.1
N3i—Co1—N2i32.14 (10)C12—C11—H11120.1
N3—Co1—N2i97.33 (11)C11—C12—C7119.5 (4)
N3ii—Co1—N2i135.13 (11)C11—C12—H12120.3
N2ii—Co1—N2i119.993 (4)C7—C12—H12120.3
C2—C1—C6118.9 (3)N2—N1—C1119.2 (3)
C2—C1—N1118.0 (3)N2—N1—Co196.6 (2)
C6—C1—N1123.1 (3)C1—N1—Co1141.9 (2)
C3—C2—C1120.5 (3)N3—N2—N1102.6 (3)
C3—C2—H2119.7N2—N3—C7120.3 (3)
C1—C2—H2119.7N2—N3—Co196.14 (19)
C4—C3—C2119.3 (3)C7—N3—Co1143.3 (3)
C4—C3—H3120.3
C6—C1—C2—C30.3 (5)N2i—Co1—N1—N275.96 (18)
N1—C1—C2—C3179.0 (3)N1i—Co1—N1—C1113.8 (3)
C1—C2—C3—C40.1 (5)N1ii—Co1—N1—C16.5 (4)
C2—C3—C4—C51.0 (6)N3i—Co1—N1—C1152.7 (4)
C2—C3—C4—Cl1178.3 (3)N3—Co1—N1—C1162.3 (4)
C3—C4—C5—C61.4 (6)N3ii—Co1—N1—C157.4 (4)
Cl1—C4—C5—C6177.8 (3)N2ii—Co1—N1—C126.2 (4)
C4—C5—C6—C11.0 (6)N2i—Co1—N1—C1123.4 (3)
C2—C1—C6—C50.2 (6)C1—N1—N2—N3168.8 (3)
N1—C1—C6—C5179.4 (4)Co1—N1—N2—N32.3 (3)
C12—C7—C8—C91.1 (6)N1—N2—N3—C7173.3 (3)
N3—C7—C8—C9178.9 (4)N1—N2—N3—Co12.3 (3)
C7—C8—C9—C100.5 (8)C8—C7—N3—N2176.9 (3)
C8—C9—C10—C111.9 (8)C12—C7—N3—N23.0 (5)
C8—C9—C10—Cl2177.4 (4)C8—C7—N3—Co110.5 (6)
C9—C10—C11—C121.6 (7)C12—C7—N3—Co1169.6 (3)
Cl2—C10—C11—C12177.7 (3)N1—Co1—N3—N21.69 (19)
C10—C11—C12—C70.1 (6)N1i—Co1—N3—N2106.2 (2)
C8—C7—C12—C111.4 (6)N1ii—Co1—N3—N241.0 (5)
N3—C7—C12—C11178.6 (3)N3i—Co1—N3—N2170.04 (19)
C2—C1—N1—N2167.4 (3)N3ii—Co1—N3—N282.0 (3)
C6—C1—N1—N213.3 (5)N2ii—Co1—N3—N274.52 (18)
C2—C1—N1—Co134.7 (5)N2i—Co1—N3—N2138.0 (2)
C6—C1—N1—Co1144.5 (3)N1—Co1—N3—C7171.9 (4)
N1i—Co1—N1—N285.6 (3)N1i—Co1—N3—C767.4 (4)
N1ii—Co1—N1—N2167.2 (2)N1ii—Co1—N3—C7145.5 (4)
N3i—Co1—N1—N246.6 (5)N3i—Co1—N3—C73.5 (4)
N3—Co1—N1—N21.67 (19)N3ii—Co1—N3—C7104.4 (3)
N3ii—Co1—N1—N2103.3 (2)N2ii—Co1—N3—C7111.9 (4)
N2ii—Co1—N1—N2134.4 (2)N2i—Co1—N3—C735.6 (4)
Symmetry codes: (i) x+y, x, z; (ii) y, xy, z.

Experimental details

Crystal data
Chemical formula[Co(C12H8Cl2N3)3]
Mr854.27
Crystal system, space groupTrigonal, R3
Temperature (K)293
a, c (Å)19.383 (3), 17.546 (2)
V3)5708.5 (10)
Z6
Radiation typeMo Kα
µ (mm1)0.91
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.771, 0.839
No. of measured, independent and
observed [I > 2σ(I)] reflections
8131, 2891, 1714
Rint0.053
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.159, 1.04
No. of reflections2891
No. of parameters157
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.34

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

 

Acknowledgements

We thank South China University of Technology and the Ministry of Higher Education of Malaysia (grant No. UM·C/HIR/MOHE/SC/12) for supporting this study.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationKrigbaum, W. R. & Rubin, B. (1973). Acta Cryst. B29, 749–756.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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