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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.039
• wR factor = 0.123
• Data-to-parameter ratio = 25.4

checkCIF/PLATON results

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Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.04 Report
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....        Co1 Check
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .         50 Ang3
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.651 Report

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C16 H20 Cl4 Co1 N2 O2
            Atom count from _chemical_formula_moiety:
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.       6.09 Why ?
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          3 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          3 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         33 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Synthesis and crystallization

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.

S2. Refinement

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

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

Structure description

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

Synthesis and crystallization

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 details

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.

Computing details

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

	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)

Crystal data

(C8H10NO)2[CoCl4]	Dx = 1.516 Mg m^−3
Mr = 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) Å^3	Block, green
Z = 8	0.3 × 0.2 × 0.2 mm
F(000) = 1928

Data collection

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

Refinement

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—Cl3^i	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	Cl3^i—Co1—Cl3	116.52 (4)
C2—C3—H3	120.6	Cl3^i—Co1—Cl1	106.53 (2)
C3—C4—C5	122.04 (19)	Cl3—Co1—Cl1	106.53 (2)
C3—C4—N41	119.57 (19)	Cl3^i—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)

D—H···A	D—H	H···A	D···A	D—H···A
N41—H41A···O11^ii	0.91 (2)	1.88 (2)	2.781 (3)	174 (3)
N41—H41B···Cl2^iii	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.