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

Yu, G.; Zhan, S.-Z.; Ng, S.W.

doi:10.1107/S1600536812020569

metal-organic compounds

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Volume 68| Part 6| June 2012| Page m758

doi:10.1107/S1600536812020569

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

Gang Yu,^a Shu-Zhong Zhan ^a and Seik Weng Ng ^b,^c ^*

^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 Co^III 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 ).

Experimental

Crystal data

[Co(C₁₂H₈Cl₂N₃)₃]
M_r = 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 ) T_min = 0.771, T_max = 0.839
8131 measured reflections
2891 independent reflections
1714 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.159
S = 1.04
2891 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812020569/bt5911sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020569/bt5911Isup2.hkl

checkCIF report

Comment top

The diaryltriazenido anion N,N'-chelates to a large number of metal atoms; for Co^III 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 Co^III atom shows octahedral coordination (Fig. 2). With respect to the delocalized –N–N═N– 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%.

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

	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.
	Fig. 2. Octahedral coordination geometry of Co^III.

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

Crystal data top

[Co(C₁₂H₈Cl₂N₃)₃]	D_x = 1.491 Mg m⁻³
M_r = 854.27	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 1211 reflections
Hall symbol: -R 3	θ = 2.6–22.1°
a = 19.383 (3) Å	µ = 0.91 mm⁻¹
c = 17.546 (2) Å	T = 293 K
V = 5708.5 (10) Å³	Prism, red
Z = 6	0.30 × 0.25 × 0.20 mm
F(000) = 2592

Data collection top

Bruker SMART APEX diffractometer	2891 independent reflections
Radiation source: fine-focus sealed tube	1714 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→20
T_min = 0.771, T_max = 0.839	k = −24→22
8131 measured reflections	l = −22→22

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)] = 0.053	Hydrogen site location: difference Fourier map
wR(F²) = 0.159	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0758P)² + 0.3669P] where P = (F_o² + 2F_c²)/3
2891 reflections	(Δ/σ)_max = 0.001
157 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Co(C₁₂H₈Cl₂N₃)₃]	Z = 6
M_r = 854.27	Mo Kα radiation
Trigonal, R3	µ = 0.91 mm⁻¹
a = 19.383 (3) Å	T = 293 K
c = 17.546 (2) Å	0.30 × 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)
T_min = 0.771, T_max = 0.839	R_int = 0.053
8131 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 1.04	Δρ_max = 0.35 e Å⁻³
2891 reflections	Δρ_min = −0.34 e Å⁻³
157 parameters

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

	x	y	z	U_iso*/U_eq
Co1	0.0000	0.0000	0.25642 (4)	0.0361 (3)
Cl1	−0.04587 (9)	0.28231 (8)	0.51099 (7)	0.0835 (5)
Cl2	0.34023 (9)	0.12548 (9)	−0.01594 (8)	0.0937 (5)
C1	0.0269 (2)	0.1483 (2)	0.35169 (17)	0.0349 (8)
C2	−0.0262 (2)	0.1092 (2)	0.41122 (18)	0.0402 (8)
H2	−0.0473	0.0547	0.4178	0.048*
C3	−0.0476 (2)	0.1507 (2)	0.46038 (19)	0.0441 (9)
H3	−0.0830	0.1245	0.5001	0.053*
C4	−0.0162 (2)	0.2313 (2)	0.4501 (2)	0.0477 (10)
C5	0.0370 (3)	0.2714 (2)	0.3925 (2)	0.0581 (11)
H5	0.0586	0.3261	0.3871	0.070*
C6	0.0582 (2)	0.2301 (2)	0.3430 (2)	0.0486 (10)
H6	0.0935	0.2569	0.3034	0.058*
C7	0.1553 (2)	0.0949 (2)	0.15565 (17)	0.0368 (8)
C8	0.1422 (3)	0.0343 (3)	0.1071 (2)	0.0630 (12)
H8	0.0949	−0.0142	0.1102	0.076*
C9	0.1988 (3)	0.0447 (3)	0.0536 (3)	0.0725 (14)
H9	0.1893	0.0033	0.0205	0.087*
C10	0.2671 (3)	0.1136 (3)	0.0490 (2)	0.0547 (11)
C11	0.2815 (2)	0.1764 (3)	0.0959 (2)	0.0561 (11)
H11	0.3288	0.2247	0.0914	0.067*
C12	0.2254 (2)	0.1673 (2)	0.1496 (2)	0.0485 (10)
H12	0.2347	0.2094	0.1815	0.058*
N1	0.04549 (18)	0.10269 (17)	0.30269 (15)	0.0398 (7)
N2	0.10592 (17)	0.13926 (18)	0.25527 (15)	0.0407 (7)
N3	0.09691 (17)	0.08162 (18)	0.21030 (15)	0.0387 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0336 (3)	0.0336 (3)	0.0410 (4)	0.01679 (17)	0.000	0.000
Cl1	0.0956 (10)	0.0685 (9)	0.0929 (9)	0.0459 (8)	0.0247 (7)	−0.0207 (7)
Cl2	0.0941 (10)	0.0919 (11)	0.0959 (9)	0.0471 (9)	0.0578 (8)	0.0140 (8)
C1	0.037 (2)	0.036 (2)	0.0365 (16)	0.0218 (17)	0.0013 (15)	0.0045 (14)
C2	0.040 (2)	0.034 (2)	0.0469 (19)	0.0193 (17)	0.0047 (16)	0.0030 (15)
C3	0.042 (2)	0.048 (2)	0.0412 (18)	0.021 (2)	0.0072 (16)	−0.0016 (17)
C4	0.051 (2)	0.045 (2)	0.054 (2)	0.029 (2)	0.0028 (19)	−0.0101 (18)
C5	0.075 (3)	0.034 (2)	0.067 (2)	0.028 (2)	0.013 (2)	0.0024 (19)
C6	0.059 (3)	0.036 (2)	0.052 (2)	0.024 (2)	0.0180 (19)	0.0100 (17)
C7	0.036 (2)	0.037 (2)	0.0390 (17)	0.0193 (17)	0.0046 (15)	0.0031 (15)
C8	0.060 (3)	0.041 (2)	0.070 (3)	0.012 (2)	0.025 (2)	−0.004 (2)
C9	0.078 (3)	0.053 (3)	0.074 (3)	0.023 (3)	0.027 (3)	−0.013 (2)
C10	0.057 (3)	0.059 (3)	0.054 (2)	0.033 (2)	0.023 (2)	0.012 (2)
C11	0.040 (2)	0.052 (3)	0.064 (2)	0.014 (2)	0.0089 (19)	0.000 (2)
C12	0.047 (2)	0.041 (2)	0.050 (2)	0.016 (2)	0.0085 (18)	−0.0059 (17)
N1	0.0381 (17)	0.0350 (17)	0.0450 (15)	0.0174 (14)	0.0081 (13)	0.0005 (13)
N2	0.0401 (18)	0.0385 (18)	0.0438 (15)	0.0199 (15)	0.0076 (13)	0.0020 (13)
N3	0.0325 (16)	0.0369 (18)	0.0445 (14)	0.0156 (14)	0.0031 (13)	−0.0061 (13)

Geometric parameters (Å, º) top

Co1—N1	1.909 (3)	C4—C5	1.373 (5)
Co1—N1ⁱ	1.909 (3)	C5—C6	1.376 (5)
Co1—N1ⁱⁱ	1.909 (3)	C5—H5	0.9300
Co1—N3ⁱ	1.927 (3)	C6—H6	0.9300
Co1—N3	1.927 (3)	C7—C8	1.368 (5)
Co1—N3ⁱⁱ	1.927 (3)	C7—C12	1.386 (5)
Co1—N2ⁱⁱ	2.441 (3)	C7—N3	1.406 (4)
Co1—N2ⁱ	2.441 (3)	C8—C9	1.381 (6)
Cl1—C4	1.737 (4)	C8—H8	0.9300
Cl2—C10	1.741 (4)	C9—C10	1.332 (6)
C1—C2	1.394 (4)	C9—H9	0.9300
C1—C6	1.395 (5)	C10—C11	1.377 (6)
C1—N1	1.403 (4)	C11—C12	1.382 (5)
C2—C3	1.378 (5)	C11—H11	0.9300
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.376 (5)	N1—N2	1.318 (4)
C3—H3	0.9300	N2—N3	1.306 (4)

N1—Co1—N1ⁱ	103.22 (10)	C2—C3—H3	120.3
N1—Co1—N1ⁱⁱ	103.22 (10)	C5—C4—C3	121.3 (3)
N1ⁱ—Co1—N1ⁱⁱ	103.22 (10)	C5—C4—Cl1	120.0 (3)
N1—Co1—N3ⁱ	163.88 (12)	C3—C4—Cl1	118.7 (3)
N1ⁱ—Co1—N3ⁱ	64.54 (12)	C4—C5—C6	119.6 (4)
N1ⁱⁱ—Co1—N3ⁱ	90.28 (12)	C4—C5—H5	120.2
N1—Co1—N3	64.54 (12)	C6—C5—H5	120.2
N1ⁱ—Co1—N3	90.28 (12)	C5—C6—C1	120.3 (3)
N1ⁱⁱ—Co1—N3	163.88 (12)	C5—C6—H6	119.8
N3ⁱ—Co1—N3	103.63 (10)	C1—C6—H6	119.8
N1—Co1—N3ⁱⁱ	90.28 (12)	C8—C7—C12	119.3 (3)
N1ⁱ—Co1—N3ⁱⁱ	163.88 (12)	C8—C7—N3	118.7 (3)
N1ⁱⁱ—Co1—N3ⁱⁱ	64.54 (12)	C12—C7—N3	122.0 (3)
N3ⁱ—Co1—N3ⁱⁱ	103.63 (10)	C7—C8—C9	120.3 (4)
N3—Co1—N3ⁱⁱ	103.63 (10)	C7—C8—H8	119.8
N1—Co1—N2ⁱⁱ	98.78 (11)	C9—C8—H8	119.8
N1ⁱ—Co1—N2ⁱⁱ	134.58 (11)	C10—C9—C8	120.4 (4)
N1ⁱⁱ—Co1—N2ⁱⁱ	32.42 (10)	C10—C9—H9	119.8
N3ⁱ—Co1—N2ⁱⁱ	97.33 (11)	C8—C9—H9	119.8
N3—Co1—N2ⁱⁱ	135.13 (11)	C9—C10—C11	120.7 (4)
N3ⁱⁱ—Co1—N2ⁱⁱ	32.14 (10)	C9—C10—Cl2	120.5 (4)
N1—Co1—N2ⁱ	134.58 (11)	C11—C10—Cl2	118.8 (3)
N1ⁱ—Co1—N2ⁱ	32.42 (10)	C10—C11—C12	119.7 (4)
N1ⁱⁱ—Co1—N2ⁱ	98.78 (11)	C10—C11—H11	120.1
N3ⁱ—Co1—N2ⁱ	32.14 (10)	C12—C11—H11	120.1
N3—Co1—N2ⁱ	97.33 (11)	C11—C12—C7	119.5 (4)
N3ⁱⁱ—Co1—N2ⁱ	135.13 (11)	C11—C12—H12	120.3
N2ⁱⁱ—Co1—N2ⁱ	119.993 (4)	C7—C12—H12	120.3
C2—C1—C6	118.9 (3)	N2—N1—C1	119.2 (3)
C2—C1—N1	118.0 (3)	N2—N1—Co1	96.6 (2)
C6—C1—N1	123.1 (3)	C1—N1—Co1	141.9 (2)
C3—C2—C1	120.5 (3)	N3—N2—N1	102.6 (3)
C3—C2—H2	119.7	N2—N3—C7	120.3 (3)
C1—C2—H2	119.7	N2—N3—Co1	96.14 (19)
C4—C3—C2	119.3 (3)	C7—N3—Co1	143.3 (3)
C4—C3—H3	120.3

C6—C1—C2—C3	0.3 (5)	N2ⁱ—Co1—N1—N2	75.96 (18)
N1—C1—C2—C3	−179.0 (3)	N1ⁱ—Co1—N1—C1	−113.8 (3)
C1—C2—C3—C4	0.1 (5)	N1ⁱⁱ—Co1—N1—C1	−6.5 (4)
C2—C3—C4—C5	−1.0 (6)	N3ⁱ—Co1—N1—C1	−152.7 (4)
C2—C3—C4—Cl1	178.3 (3)	N3—Co1—N1—C1	162.3 (4)
C3—C4—C5—C6	1.4 (6)	N3ⁱⁱ—Co1—N1—C1	57.4 (4)
Cl1—C4—C5—C6	−177.8 (3)	N2ⁱⁱ—Co1—N1—C1	26.2 (4)
C4—C5—C6—C1	−1.0 (6)	N2ⁱ—Co1—N1—C1	−123.4 (3)
C2—C1—C6—C5	0.2 (6)	C1—N1—N2—N3	−168.8 (3)
N1—C1—C6—C5	179.4 (4)	Co1—N1—N2—N3	−2.3 (3)
C12—C7—C8—C9	1.1 (6)	N1—N2—N3—C7	−173.3 (3)
N3—C7—C8—C9	−178.9 (4)	N1—N2—N3—Co1	2.3 (3)
C7—C8—C9—C10	0.5 (8)	C8—C7—N3—N2	−176.9 (3)
C8—C9—C10—C11	−1.9 (8)	C12—C7—N3—N2	3.0 (5)
C8—C9—C10—Cl2	177.4 (4)	C8—C7—N3—Co1	10.5 (6)
C9—C10—C11—C12	1.6 (7)	C12—C7—N3—Co1	−169.6 (3)
Cl2—C10—C11—C12	−177.7 (3)	N1—Co1—N3—N2	−1.69 (19)
C10—C11—C12—C7	0.1 (6)	N1ⁱ—Co1—N3—N2	−106.2 (2)
C8—C7—C12—C11	−1.4 (6)	N1ⁱⁱ—Co1—N3—N2	41.0 (5)
N3—C7—C12—C11	178.6 (3)	N3ⁱ—Co1—N3—N2	−170.04 (19)
C2—C1—N1—N2	−167.4 (3)	N3ⁱⁱ—Co1—N3—N2	82.0 (3)
C6—C1—N1—N2	13.3 (5)	N2ⁱⁱ—Co1—N3—N2	74.52 (18)
C2—C1—N1—Co1	34.7 (5)	N2ⁱ—Co1—N3—N2	−138.0 (2)
C6—C1—N1—Co1	−144.5 (3)	N1—Co1—N3—C7	171.9 (4)
N1ⁱ—Co1—N1—N2	85.6 (3)	N1ⁱ—Co1—N3—C7	67.4 (4)
N1ⁱⁱ—Co1—N1—N2	−167.2 (2)	N1ⁱⁱ—Co1—N3—C7	−145.5 (4)
N3ⁱ—Co1—N1—N2	46.6 (5)	N3ⁱ—Co1—N3—C7	3.5 (4)
N3—Co1—N1—N2	1.67 (19)	N3ⁱⁱ—Co1—N3—C7	−104.4 (3)
N3ⁱⁱ—Co1—N1—N2	−103.3 (2)	N2ⁱⁱ—Co1—N3—C7	−111.9 (4)
N2ⁱⁱ—Co1—N1—N2	−134.4 (2)	N2ⁱ—Co1—N3—C7	35.6 (4)

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₂H₈Cl₂N₃)₃]
M_r	854.27
Crystal system, space group	Trigonal, R3
Temperature (K)	293
a, c (Å)	19.383 (3), 17.546 (2)
V (Å³)	5708.5 (10)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.771, 0.839
No. of measured, independent and observed [I > 2σ(I)] reflections	8131, 2891, 1714
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.159, 1.04
No. of reflections	2891
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

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