Crystal structure of bis­(4-acetyl­anilinium) tetra­chlorido­cobaltate(II)

Thairiyaraja, M.; Elangovan, A.; Shanmugam, R.; Selvaraju, K.; Thamotharan, S.

doi:10.1107/S2056989015021404

metal-organic compounds

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Volume 71| Part 12| December 2015| Pages m221-m222

https://doi.org/10.1107/S2056989015021404

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Crystal structure of bis(4-acetylanilinium) tetrachloridocobaltate(II)

Manickam Thairiyaraja,^a Arumugam Elangovan,^b Ramasamy Shanmugam,^b Kuthambalam Selvaraju ^a ^* and Subbiah Thamotharan ^c ^*

^aPG & Research Department of Physics, Government Arts College, Ariyalur 621 713, India, ^bDepartment of Chemistry, Thiagarajar College, Madurai 625 009, India, and ^cBiomolecular Crystallography Laboratory, Department of Bioinformatics, School of Chemical and Biotechnology, SASTRA University, Thanjavur 613 401, India
^*Correspondence e-mail: selsphy@yahoo.com, thamu@scbt.sastra.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 9 November 2015; accepted 11 November 2015; online 18 November 2015)

The structure of the title salt, (C₈H₁₀NO)₂[CoCl₄], is isotypic with the analogous cuprate(II) structure. The asymmetric unit contains one 4-acetylanilinium cation and one half of a tetrachloridocobaltate(II) anion for which the Co^II atom and two Cl⁻ ligands lie on a mirror plane. The Co—Cl distances in the distorted tetrahedral anion range from 2.2519 (6) to 2.2954 (9) Å and the Cl—Co—Cl angles range from 106.53 (2) to 110.81 (4)°. In the crystal, cations are self-assembled by intermolecular N—H⋯O hydrogen-bonding interactions, leading to a C(8) chain motif with the chains running parallel to the b axis. π–π stacking interactions between benzene rings, with a centroid-to-centroid distance of 3.709 Å, are also observed along this direction. The CoCl₄²⁻ anions are sandwiched between the cationic chains and interact with each other through intermolecular N—H⋯Cl hydrogen-bonding interactions, forming a three-dimensional network structure.

Keywords: crystal structure; isotypism; cobalt(II); hydrogen bonding; π–π stacking interactions.

CCDC reference: 967676

1. Related literature

For the structure of the isotypic tetrachloridocuprate(II) compound, see: Elangovan et al. (2007 ).

2. Experimental

2.1. Crystal data

(C₈H₁₀NO)₂[CoCl₄]
M_r = 473.07
Orthorhombic, C m c e
a = 19.4605 (6) Å
b = 15.5108 (6) Å
c = 13.7374 (5) Å
V = 4146.6 (3) Å³
Z = 8
Mo Kα radiation
μ = 1.36 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

2.2. Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.687, T_max = 0.773
24499 measured reflections
3329 independent reflections
2439 reflections with I > 2σ(I)
R_int = 0.035

2.3. Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.123
S = 1.05
3329 reflections
131 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.35 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N41—H41A⋯O11ⁱ	0.91 (2)	1.88 (2)	2.781 (3)	174 (3)
N41—H41B⋯Cl2ⁱⁱ	0.92 (2)	2.31 (2)	3.211 (2)	168 (3)
N41—H41C⋯Cl3ⁱⁱⁱ	0.88 (2)	2.48 (2)	3.309 (3)	157 (3)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; method used to solve structure: coordinates taken from an isotypic structure; program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 967676

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015021404/wm5237sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015021404/wm5237Isup2.hkl

checkCIF report

Synthesis and crystallization top

A solution of 4-aminoacetophenone (20 mmol) in 2 ml of HCl and deionized water (10 ml) was added to a 10 ml solution of CoCl₂·6H₂O (10 mmol). The resulting solution was concentrated and kept unperturbed at ambient temperature for crystallization. Dark green block-shaped crystals were obtained after 7 days.

Refinement top

Since the title complex is isotypic with its tetrachloridocuprate counterpart, it was refined with the coordinates of the latter (Elangovan et al., 2007) as starting parameters. The amino H atoms were located from a difference Fourier map and refined with a distance restraint of N—H = 0.89 (2) Å. The methyl H atoms were constrained to an ideal geometry (C—H = 0.96 Å) with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C–C bond. The remaining H atoms were positioned in geometrically calculated positions and refined using a riding model with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). At this stage, the maximum residual electron density of 1.35 e Å^-3 indicated the presence of a possible atom at Wyckofff position 4a at a distance of 2.81Å near atom H5. This peak was assumed to be the O atom of a water molecule and was refined with isotropic displacement parameters. However, the resultant model had slightly higher reliability factors and a very high isotropic atomic displacement parameter for this O atom. As a consequence, this water O atom was not included in the final model.

Related literature top

For the structure of the isotypic tetrachloridocuprate(II) compound, see: Elangovan et al. (2007).

Structure description top

For the structure of the isotypic tetrachloridocuprate(II) compound, see: Elangovan et al. (2007).

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: coordinates taken from an isotypic structure; program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular components in the structure of the title salt. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x, y, z.]
	Fig. 2. The crystal packing of the title salt viewed along the c axis. Hydrogen bonds are shown as dashed lines; H atoms bound to C were omitted for clarity.

Bis(4-acetylanilinium) tetrachloridocobaltate(II) top

Crystal data top

(C₈H₁₀NO)₂[CoCl₄]	D_x = 1.516 Mg m⁻³
M_r = 473.07	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Cmce	Cell parameters from 14227 reflections
a = 19.4605 (6) Å	θ = 2.0–30.0°
b = 15.5108 (6) Å	µ = 1.36 mm⁻¹
c = 13.7374 (5) Å	T = 293 K
V = 4146.6 (3) Å³	Block, green
Z = 8	0.3 × 0.2 × 0.2 mm
F(000) = 1928

Data collection top

Bruker SMART APEX CCD diffractometer	2439 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
ω and φ scan	θ_max = 30.9°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −27→28
T_min = 0.687, T_max = 0.773	k = −18→22
24499 measured reflections	l = −19→18
3329 independent reflections

Refinement top

Refinement on F²	Primary atom site location: isomorphous structure methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0558P)² + 6.0921P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3329 reflections	Δρ_max = 1.35 e Å⁻³
131 parameters	Δρ_min = −0.66 e Å⁻³
3 restraints

Crystal data top

(C₈H₁₀NO)₂[CoCl₄]	V = 4146.6 (3) Å³
M_r = 473.07	Z = 8
Orthorhombic, Cmce	Mo Kα radiation
a = 19.4605 (6) Å	µ = 1.36 mm⁻¹
b = 15.5108 (6) Å	T = 293 K
c = 13.7374 (5) Å	0.3 × 0.2 × 0.2 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3329 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2439 reflections with I > 2σ(I)
T_min = 0.687, T_max = 0.773	R_int = 0.035
24499 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	3 restraints
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 1.35 e Å⁻³
3329 reflections	Δρ_min = −0.66 e Å⁻³
131 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
O11	0.19113 (10)	0.60656 (11)	0.87507 (15)	0.0548 (5)
N41	0.37078 (11)	0.26577 (13)	0.90637 (18)	0.0421 (5)
H41A	0.3519 (18)	0.2142 (15)	0.891 (3)	0.082 (12)*
H41B	0.4081 (14)	0.276 (2)	0.867 (2)	0.068 (10)*
H41C	0.3860 (16)	0.268 (2)	0.9661 (14)	0.065 (10)*
C1	0.22194 (11)	0.46100 (12)	0.87145 (14)	0.0299 (4)
C2	0.20229 (11)	0.37474 (14)	0.86968 (16)	0.0353 (4)
H2	0.1563	0.3603	0.8613	0.042*
C3	0.25125 (12)	0.30994 (13)	0.88036 (16)	0.0366 (5)
H3	0.2384	0.2522	0.8793	0.044*
C4	0.31896 (11)	0.33283 (13)	0.89257 (15)	0.0322 (4)
C5	0.33997 (11)	0.41822 (14)	0.89347 (17)	0.0371 (5)
H5	0.3861	0.4324	0.9011	0.045*
C6	0.29092 (11)	0.48178 (13)	0.88278 (16)	0.0358 (4)
H6	0.3042	0.5394	0.8832	0.043*
C11	0.17101 (12)	0.53274 (14)	0.86411 (15)	0.0352 (4)
C12	0.09695 (12)	0.51393 (16)	0.8452 (2)	0.0483 (6)
H12A	0.0727	0.5670	0.8343	0.072*
H12B	0.0776	0.4848	0.9004	0.072*
H12C	0.0929	0.4779	0.7886	0.072*
Co1	0.0000	0.25104 (3)	0.86031 (3)	0.03357 (13)
Cl1	0.0000	0.33842 (5)	0.99225 (6)	0.04207 (19)
Cl2	0.0000	0.33034 (6)	0.71924 (6)	0.0462 (2)
Cl3	0.09841 (3)	0.17486 (5)	0.86639 (6)	0.0601 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O11	0.0497 (10)	0.0283 (8)	0.0863 (14)	0.0022 (7)	−0.0056 (9)	−0.0036 (8)
N41	0.0326 (10)	0.0337 (10)	0.0599 (14)	0.0014 (8)	−0.0043 (9)	0.0067 (9)
C1	0.0330 (9)	0.0256 (8)	0.0311 (10)	−0.0005 (7)	0.0005 (8)	−0.0006 (7)
C2	0.0280 (9)	0.0304 (9)	0.0476 (12)	−0.0044 (8)	−0.0006 (8)	0.0006 (8)
C3	0.0337 (10)	0.0261 (9)	0.0499 (12)	−0.0046 (8)	−0.0011 (9)	0.0022 (8)
C4	0.0311 (10)	0.0297 (9)	0.0358 (10)	0.0002 (8)	−0.0012 (8)	0.0030 (8)
C5	0.0306 (10)	0.0329 (10)	0.0479 (12)	−0.0054 (8)	−0.0054 (9)	0.0005 (9)
C6	0.0371 (11)	0.0270 (9)	0.0432 (12)	−0.0060 (8)	−0.0026 (9)	−0.0009 (8)
C11	0.0387 (11)	0.0310 (9)	0.0360 (11)	0.0017 (8)	0.0020 (9)	−0.0008 (8)
C12	0.0355 (12)	0.0417 (12)	0.0676 (17)	0.0053 (10)	0.0028 (11)	−0.0038 (11)
Co1	0.0253 (2)	0.0355 (2)	0.0399 (2)	0.000	0.000	−0.00463 (16)
Cl1	0.0469 (4)	0.0377 (4)	0.0416 (4)	0.000	0.000	−0.0080 (3)
Cl2	0.0456 (4)	0.0525 (5)	0.0405 (4)	0.000	0.000	0.0007 (3)
Cl3	0.0399 (3)	0.0581 (4)	0.0824 (5)	0.0193 (3)	−0.0109 (3)	−0.0218 (3)

Geometric parameters (Å, º) top

O11—C11	1.220 (3)	C4—C5	1.386 (3)
N41—C4	1.461 (3)	C5—C6	1.380 (3)
N41—H41A	0.904 (18)	C5—H5	0.9300
N41—H41B	0.921 (18)	C6—H6	0.9300
N41—H41C	0.872 (17)	C11—C12	1.493 (3)
C1—C6	1.389 (3)	C12—H12A	0.9600
C1—C2	1.392 (3)	C12—H12B	0.9600
C1—C11	1.494 (3)	C12—H12C	0.9600
C2—C3	1.393 (3)	Co1—Cl3ⁱ	2.2519 (6)
C2—H2	0.9300	Co1—Cl3	2.2519 (6)
C3—C4	1.375 (3)	Co1—Cl1	2.2631 (9)
C3—H3	0.9300	Co1—Cl2	2.2954 (9)

C4—N41—H41A	109 (2)	C4—C5—H5	120.7
C4—N41—H41B	110 (2)	C5—C6—C1	120.96 (19)
H41A—N41—H41B	110 (3)	C5—C6—H6	119.5
C4—N41—H41C	109 (2)	C1—C6—H6	119.5
H41A—N41—H41C	112 (3)	O11—C11—C12	121.0 (2)
H41B—N41—H41C	106 (3)	O11—C11—C1	118.6 (2)
C6—C1—C2	119.37 (19)	C12—C11—C1	120.44 (19)
C6—C1—C11	118.42 (18)	C11—C12—H12A	109.5
C2—C1—C11	122.2 (2)	C11—C12—H12B	109.5
C1—C2—C3	120.3 (2)	H12A—C12—H12B	109.5
C1—C2—H2	119.9	C11—C12—H12C	109.5
C3—C2—H2	119.9	H12A—C12—H12C	109.5
C4—C3—C2	118.82 (19)	H12B—C12—H12C	109.5
C4—C3—H3	120.6	Cl3ⁱ—Co1—Cl3	116.52 (4)
C2—C3—H3	120.6	Cl3ⁱ—Co1—Cl1	106.53 (2)
C3—C4—C5	122.04 (19)	Cl3—Co1—Cl1	106.53 (2)
C3—C4—N41	119.57 (19)	Cl3ⁱ—Co1—Cl2	108.21 (3)
C5—C4—N41	118.39 (19)	Cl3—Co1—Cl2	108.21 (3)
C6—C5—C4	118.5 (2)	Cl1—Co1—Cl2	110.81 (4)
C6—C5—H5	120.7

C6—C1—C2—C3	0.8 (3)	C4—C5—C6—C1	0.1 (3)
C11—C1—C2—C3	−177.6 (2)	C2—C1—C6—C5	−0.8 (3)
C1—C2—C3—C4	0.0 (3)	C11—C1—C6—C5	177.7 (2)
C2—C3—C4—C5	−0.7 (3)	C6—C1—C11—O11	−5.0 (3)
C2—C3—C4—N41	178.4 (2)	C2—C1—C11—O11	173.4 (2)
C3—C4—C5—C6	0.7 (3)	C6—C1—C11—C12	175.8 (2)
N41—C4—C5—C6	−178.5 (2)	C2—C1—C11—C12	−5.8 (3)

Symmetry code: (i) −x, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N41—H41A···O11ⁱⁱ	0.91 (2)	1.88 (2)	2.781 (3)	174 (3)
N41—H41B···Cl2ⁱⁱⁱ	0.92 (2)	2.31 (2)	3.211 (2)	168 (3)
N41—H41C···Cl3^iv	0.88 (2)	2.48 (2)	3.309 (3)	157 (3)

Symmetry codes: (ii) −x+1/2, y−1/2, z; (iii) x+1/2, y, −z+3/2; (iv) −x+1/2, −y+1/2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N41—H41A···O11ⁱ	0.905 (18)	1.880 (19)	2.781 (3)	174 (3)
N41—H41B···Cl2ⁱⁱ	0.920 (18)	2.305 (19)	3.211 (2)	168 (3)
N41—H41C···Cl3ⁱⁱⁱ	0.875 (17)	2.48 (2)	3.309 (3)	157 (3)

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x+1/2, y, −z+3/2; (iii) −x+1/2, −y+1/2, −z+2.

Acknowledgements

ST is very grateful to the management of SASTRA University for infrastructural and financial support (Professor TRR fund).

References

Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Elangovan, A., Thamaraichelvan, A., Ramu, A., Athimoolam, S. & Natarajan, S. (2007). Acta Cryst. E63, m224–m226. Web of Science CSD CrossRef IUCr Journals Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 12| December 2015| Pages m221-m222

https://doi.org/10.1107/S2056989015021404

Open

access