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

Thairiyaraja, M.; Elangovan, A.; Arivazhagan, G.; Selvaraju, K.; Thamotharan, S.

doi:10.1107/S2056989015022355

metal-organic compounds

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Volume 71| Part 12| December 2015| Pages m236-m237

https://doi.org/10.1107/S2056989015022355

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

Manickam Thairiyaraja,^a Arumugam Elangovan,^b ^* Ganesh Arivazhagan,^c Kuthambalam Selvaraju ^a ^* and Subbiah Thamotharan ^d ^*

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

Edited by M. Weil, Vienna University of Technology, Austria (Received 16 November 2015; accepted 23 November 2015; online 28 November 2015)

The structure of the title salt, (C₈H₁₀NO)₂[HgCl₄], is isotypic with that of the cuprate(II) and cobaltate(II) analogues. The asymmetric unit contains one 4-acetylanilinium cation and one half of a tetrachloridomercurate(II) anion (point group symmetry m). The Hg—Cl distances are in the range 2.4308 (7)–2.5244 (11) Å and the Cl—Hg—Cl angles in the range of 104.66 (2)–122.94 (4)°, indicating a considerable distortion of the tetrahedral anion. In the crystal, cations are linked by an intermolecular N—H⋯O hydrogen-bonding interaction, leading to a C(8) chain motif with the chains extending parallel to the b axis. There is also a π–π stacking interaction with a centroid-to-centroid distance of 3.735 (2) Å between neighbouring benzene rings along this direction. The anions lie between the chains and interact with the cations through intermolecular N—H⋯Cl hydrogen bonds, leading to the formation of a three-dimensional network structure.

Keywords: crystal structure; isotypism; mercury(II); hydrogen bonding.

CCDC reference: 1047866

1. Related literature

For the structures of the isotypic tetrachloridocuprate(II) and tetrachloridocobaltate(II) analogues, see: Elangovan et al. (2007 ) and Thairiyaraja et al. (2015 ), respectively.

2. Experimental

2.1. Crystal data

(C₈H₁₀NO)₂[HgCl₄]
M_r = 614.73
Orthorhombic, C m c e
a = 19.9231 (6) Å
b = 15.3515 (6) Å
c = 13.7587 (5) Å
V = 4208.1 (3) Å³
Z = 8
Mo Kα radiation
μ = 7.84 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

2.2. Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.202, T_max = 0.303
26289 measured reflections
2988 independent reflections
2152 reflections with I > 2σ(I)
R_int = 0.031

2.3. Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.056
S = 1.04
2988 reflections
131 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.93 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N41—H41A⋯O11ⁱ	0.90 (2)	1.92 (2)	2.792 (3)	162 (4)
N41—H41C⋯Cl2ⁱⁱ	0.90 (2)	2.34 (2)	3.206 (3)	162 (3)
N41—H41B⋯Cl3ⁱⁱⁱ	0.89 (2)	2.49 (2)	3.326 (3)	158 (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; program(s) used to solve structure: coorsdinates taken from an isotypic compound; 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: 1047866

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015022355/wm5243sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015022355/wm5243Isup2.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 HgCl₂ (10 mmol). The resulting solution was concentrated and kept unperturbed at ambient temperature for crystallization. Single crystals suitable for X-ray diffraction were obtained within a week.

Refinement top

Since the title salt is isotypic with its tetrachloridocobaltate and tetrachloridocuprate analogues, it was refined with the coordinates of the tetrachloridocobaltate salt (Thairiyaraja et al., 2015) as a starting model. The ammonium H atoms were located from a difference Fourier map and were 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 geometrically and refined using a riding model approximation with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). At this stage, the maximum residual electron density of 0.77 e Å^-3 suggested the presence of a possible atom site at Wyckofff position 4a at a distance of 2.88 Å near atom H5. This electron density was assumed to be the O atom of a water molecule and was refined with isotropic displacement parameters. However, the resultant model had 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 structures of the isotypic tetrachloridocuprate(II) and tetrachloridocobaltate(II) analogues, see: Elangovan et al. (2007) and Thairiyaraja et al. (2015), respectively.

Structure description top

For the structures of the isotypic tetrachloridocuprate(II) and tetrachloridocobaltate(II) analogues, see: Elangovan et al. (2007) and Thairiyaraja et al. (2015), respectively.

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: coorsdinates taken from an isotypic compound; 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 of the title salt, showing displacement ellipsoids at the 50% probability level. [Symmetry code: (i) -x, y, z.]
	Fig. 2. The crystal packing of the title salt viewed along the a axis. Hydrogen bonds are shown as dashed lines; H atoms bound to C were omitted for clarity.

Bis(4-acetylanilinium) tetrachloridomercurate(II) top

Crystal data top

(C₈H₁₀NO)₂[HgCl₄]	D_x = 1.941 Mg m⁻³
M_r = 614.73	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Cmce	Cell parameters from 9224 reflections
a = 19.9231 (6) Å	θ = 2.2–29.3°
b = 15.3515 (6) Å	µ = 7.84 mm⁻¹
c = 13.7587 (5) Å	T = 293 K
V = 4208.1 (3) Å³	Block, orange
Z = 8	0.30 × 0.25 × 0.20 mm
F(000) = 2352

Data collection top

Bruker SMART APEX CCD diffractometer	2152 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
ω and φ scan	θ_max = 29.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −27→27
T_min = 0.202, T_max = 0.303	k = −19→21
26289 measured reflections	l = −18→19
2988 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)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0217P)² + 6.8872P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2988 reflections	Δρ_max = 0.77 e Å⁻³
131 parameters	Δρ_min = −0.93 e Å⁻³
3 restraints

Crystal data top

(C₈H₁₀NO)₂[HgCl₄]	V = 4208.1 (3) Å³
M_r = 614.73	Z = 8
Orthorhombic, Cmce	Mo Kα radiation
a = 19.9231 (6) Å	µ = 7.84 mm⁻¹
b = 15.3515 (6) Å	T = 293 K
c = 13.7587 (5) Å	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2988 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2152 reflections with I > 2σ(I)
T_min = 0.202, T_max = 0.303	R_int = 0.031
26289 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	3 restraints
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.77 e Å⁻³
2988 reflections	Δρ_min = −0.93 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	0.18874 (11)	0.60387 (14)	0.87716 (17)	0.0544 (6)
N41	0.37059 (13)	0.26610 (16)	0.9093 (2)	0.0430 (6)
H41A	0.359 (2)	0.2125 (16)	0.889 (3)	0.084 (14)*
H41B	0.3848 (19)	0.270 (2)	0.9703 (16)	0.072 (13)*
H41C	0.4057 (15)	0.276 (3)	0.870 (2)	0.067 (12)*
C1	0.22199 (12)	0.45798 (17)	0.87221 (17)	0.0297 (5)
C2	0.20483 (13)	0.37068 (17)	0.86957 (19)	0.0359 (6)
H2	0.1603	0.3546	0.8606	0.043*
C3	0.25367 (13)	0.30686 (17)	0.8803 (2)	0.0373 (6)
H3	0.2423	0.2481	0.8784	0.045*
C4	0.31897 (12)	0.33222 (17)	0.89352 (19)	0.0321 (5)
C5	0.33780 (13)	0.41877 (18)	0.8947 (2)	0.0374 (6)
H5	0.3825	0.4346	0.9029	0.045*
C6	0.28863 (13)	0.48110 (18)	0.88350 (19)	0.0349 (6)
H6	0.3005	0.5397	0.8835	0.042*
C11	0.17064 (14)	0.52843 (18)	0.86546 (19)	0.0341 (6)
C12	0.09920 (13)	0.5071 (2)	0.8458 (2)	0.0482 (8)
H12A	0.0742	0.5600	0.8372	0.072*
H12B	0.0811	0.4750	0.8996	0.072*
H12C	0.0962	0.4725	0.7878	0.072*
Hg1	0.0000	0.24841 (2)	0.85591 (2)	0.04734 (7)
Cl1	0.0000	0.34199 (7)	1.00252 (8)	0.0479 (2)
Cl2	0.0000	0.33901 (7)	0.70279 (8)	0.0455 (2)
Cl3	0.10720 (4)	0.17292 (6)	0.86099 (7)	0.0607 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O11	0.0515 (12)	0.0266 (12)	0.0850 (17)	0.0019 (9)	−0.0071 (11)	−0.0038 (10)
N41	0.0335 (11)	0.0344 (16)	0.061 (2)	0.0014 (9)	−0.0018 (11)	0.0055 (12)
C1	0.0341 (12)	0.0274 (14)	0.0275 (14)	−0.0026 (9)	0.0008 (10)	−0.0008 (10)
C2	0.0309 (12)	0.0321 (15)	0.0448 (16)	−0.0053 (10)	−0.0016 (11)	−0.0005 (11)
C3	0.0361 (13)	0.0236 (14)	0.0523 (18)	−0.0041 (10)	−0.0008 (12)	0.0023 (11)
C4	0.0331 (12)	0.0269 (14)	0.0365 (14)	0.0009 (10)	−0.0009 (10)	0.0030 (11)
C5	0.0326 (12)	0.0351 (16)	0.0445 (16)	−0.0062 (11)	−0.0037 (11)	0.0013 (12)
C6	0.0387 (14)	0.0248 (14)	0.0410 (15)	−0.0054 (10)	−0.0025 (11)	−0.0022 (11)
C11	0.0387 (13)	0.0299 (15)	0.0336 (14)	0.0010 (10)	0.0017 (11)	−0.0014 (11)
C12	0.0359 (13)	0.0407 (17)	0.068 (2)	0.0042 (12)	0.0015 (14)	−0.0065 (15)
Hg1	0.03172 (8)	0.05938 (13)	0.05092 (11)	0.000	0.000	−0.00393 (9)
Cl1	0.0538 (5)	0.0448 (6)	0.0453 (6)	0.000	0.000	−0.0061 (5)
Cl2	0.0420 (5)	0.0490 (6)	0.0455 (6)	0.000	0.000	−0.0018 (5)
Cl3	0.0383 (4)	0.0555 (5)	0.0883 (6)	0.0145 (3)	−0.0098 (4)	−0.0202 (4)

Geometric parameters (Å, º) top

O11—C11	1.224 (3)	C4—C5	1.381 (4)
N41—C4	1.461 (3)	C5—C6	1.378 (4)
N41—H41A	0.901 (19)	C5—H5	0.9300
N41—H41B	0.887 (19)	C6—H6	0.9300
N41—H41C	0.899 (19)	C11—C12	1.486 (4)
C1—C6	1.383 (4)	C12—H12A	0.9600
C1—C2	1.384 (4)	C12—H12B	0.9600
C1—C11	1.492 (4)	C12—H12C	0.9600
C2—C3	1.389 (4)	Hg1—Cl3ⁱ	2.4308 (7)
C2—H2	0.9300	Hg1—Cl3	2.4308 (7)
C3—C4	1.370 (4)	Hg1—Cl1	2.4764 (11)
C3—H3	0.9300	Hg1—Cl2	2.5244 (11)

C4—N41—H41A	114 (3)	C4—C5—H5	120.9
C4—N41—H41B	109 (2)	C5—C6—C1	121.1 (2)
H41A—N41—H41B	116 (3)	C5—C6—H6	119.4
C4—N41—H41C	110 (3)	C1—C6—H6	119.4
H41A—N41—H41C	100 (3)	O11—C11—C12	121.0 (3)
H41B—N41—H41C	108 (3)	O11—C11—C1	118.4 (2)
C6—C1—C2	119.3 (2)	C12—C11—C1	120.6 (2)
C6—C1—C11	118.6 (2)	C11—C12—H12A	109.5
C2—C1—C11	122.1 (2)	C11—C12—H12B	109.5
C1—C2—C3	120.5 (2)	H12A—C12—H12B	109.5
C1—C2—H2	119.8	C11—C12—H12C	109.5
C3—C2—H2	119.8	H12A—C12—H12C	109.5
C4—C3—C2	118.6 (2)	H12B—C12—H12C	109.5
C4—C3—H3	120.7	Cl3ⁱ—Hg1—Cl3	122.94 (4)
C2—C3—H3	120.7	Cl3ⁱ—Hg1—Cl1	104.66 (2)
C3—C4—C5	122.2 (2)	Cl3—Hg1—Cl1	104.66 (2)
C3—C4—N41	119.4 (2)	Cl3ⁱ—Hg1—Cl2	106.66 (3)
C5—C4—N41	118.4 (2)	Cl3—Hg1—Cl2	106.66 (3)
C6—C5—C4	118.3 (2)	Cl1—Hg1—Cl2	111.11 (4)
C6—C5—H5	120.9

C6—C1—C2—C3	1.4 (4)	C4—C5—C6—C1	0.6 (4)
C11—C1—C2—C3	−177.2 (2)	C2—C1—C6—C5	−1.8 (4)
C1—C2—C3—C4	0.1 (4)	C11—C1—C6—C5	176.9 (2)
C2—C3—C4—C5	−1.3 (4)	C6—C1—C11—O11	−5.2 (4)
C2—C3—C4—N41	177.3 (3)	C2—C1—C11—O11	173.4 (3)
C3—C4—C5—C6	0.9 (4)	C6—C1—C11—C12	175.3 (2)
N41—C4—C5—C6	−177.6 (3)	C2—C1—C11—C12	−6.1 (4)

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	0.90 (2)	1.92 (2)	2.792 (3)	162 (4)
N41—H41C···Cl2ⁱⁱⁱ	0.90 (2)	2.34 (2)	3.206 (3)	162 (3)
N41—H41B···Cl3^iv	0.89 (2)	2.49 (2)	3.326 (3)	158 (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	0.901 (19)	1.92 (2)	2.792 (3)	162 (4)
N41—H41C···Cl2ⁱⁱ	0.899 (19)	2.34 (2)	3.206 (3)	162 (3)
N41—H41B···Cl3ⁱⁱⁱ	0.887 (19)	2.49 (2)	3.326 (3)	158 (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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 12| December 2015| Pages m236-m237

https://doi.org/10.1107/S2056989015022355

Open

access