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

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 ππ 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.

1. Related literature

For the structures of the isotypic tetra­chlorido­cuprate(II) and tetra­chlorido­cobaltate(II) analogues, see: Elangovan et al. (2007[Elangovan, A., Thamaraichelvan, A., Ramu, A., Athimoolam, S. & Natarajan, S. (2007). Acta Cryst. E63, m224-m226.]) and Thairiyaraja et al. (2015[Thairiyaraja, M., Elangovan, A., Shanmugam, R., Selvaraju, K. & Thamotharan, S. (2015). Acta Cryst. E71, m221-m222.]), respectively.

[Scheme 1]

2. Experimental

2.1. Crystal data

  • (C8H10NO)2[HgCl4]

  • Mr = 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[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.202, Tmax = 0.303

  • 26289 measured reflections

  • 2988 independent reflections

  • 2152 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.77 e Å−3

  • Δρmin = −0.93 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: coorsdinates taken from an isotypic compound; program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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 Uiso(H) = 1.5Ueq(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 Uiso(H) = 1.2Ueq(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

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 details 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 Uiso(H) = 1.5Ueq(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 Uiso(H) = 1.2Ueq(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.

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
[Figure 1] Fig. 1. The molecular components of the title salt, showing displacement ellipsoids at the 50% probability level. [Symmetry code: (i) -x, y, z.]
[Figure 2] 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]Dx = 1.941 Mg m3
Mr = 614.73Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, CmceCell parameters from 9224 reflections
a = 19.9231 (6) Åθ = 2.2–29.3°
b = 15.3515 (6) ŵ = 7.84 mm1
c = 13.7587 (5) ÅT = 293 K
V = 4208.1 (3) Å3Block, orange
Z = 80.30 × 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 tubeRint = 0.031
ω and φ scanθmax = 29.4°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 2727
Tmin = 0.202, Tmax = 0.303k = 1921
26289 measured reflectionsl = 1819
2988 independent reflections
Refinement top
Refinement on F2Primary atom site location: isomorphous structure methods
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.056 w = 1/[σ2(Fo2) + (0.0217P)2 + 6.8872P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2988 reflectionsΔρmax = 0.77 e Å3
131 parametersΔρmin = 0.93 e Å3
3 restraints
Crystal data top
(C8H10NO)2[HgCl4]V = 4208.1 (3) Å3
Mr = 614.73Z = 8
Orthorhombic, CmceMo Kα radiation
a = 19.9231 (6) ŵ = 7.84 mm1
b = 15.3515 (6) ÅT = 293 K
c = 13.7587 (5) Å0.30 × 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)
Tmin = 0.202, Tmax = 0.303Rint = 0.031
26289 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0233 restraints
wR(F2) = 0.056H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.77 e Å3
2988 reflectionsΔρmin = 0.93 e Å3
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
xyzUiso*/Ueq
O110.18874 (11)0.60387 (14)0.87716 (17)0.0544 (6)
N410.37059 (13)0.26610 (16)0.9093 (2)0.0430 (6)
H41A0.359 (2)0.2125 (16)0.889 (3)0.084 (14)*
H41B0.3848 (19)0.270 (2)0.9703 (16)0.072 (13)*
H41C0.4057 (15)0.276 (3)0.870 (2)0.067 (12)*
C10.22199 (12)0.45798 (17)0.87221 (17)0.0297 (5)
C20.20483 (13)0.37068 (17)0.86957 (19)0.0359 (6)
H20.16030.35460.86060.043*
C30.25367 (13)0.30686 (17)0.8803 (2)0.0373 (6)
H30.24230.24810.87840.045*
C40.31897 (12)0.33222 (17)0.89352 (19)0.0321 (5)
C50.33780 (13)0.41877 (18)0.8947 (2)0.0374 (6)
H50.38250.43460.90290.045*
C60.28863 (13)0.48110 (18)0.88350 (19)0.0349 (6)
H60.30050.53970.88350.042*
C110.17064 (14)0.52843 (18)0.86546 (19)0.0341 (6)
C120.09920 (13)0.5071 (2)0.8458 (2)0.0482 (8)
H12A0.07420.56000.83720.072*
H12B0.08110.47500.89960.072*
H12C0.09620.47250.78780.072*
Hg10.00000.24841 (2)0.85591 (2)0.04734 (7)
Cl10.00000.34199 (7)1.00252 (8)0.0479 (2)
Cl20.00000.33901 (7)0.70279 (8)0.0455 (2)
Cl30.10720 (4)0.17292 (6)0.86099 (7)0.0607 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O110.0515 (12)0.0266 (12)0.0850 (17)0.0019 (9)0.0071 (11)0.0038 (10)
N410.0335 (11)0.0344 (16)0.061 (2)0.0014 (9)0.0018 (11)0.0055 (12)
C10.0341 (12)0.0274 (14)0.0275 (14)0.0026 (9)0.0008 (10)0.0008 (10)
C20.0309 (12)0.0321 (15)0.0448 (16)0.0053 (10)0.0016 (11)0.0005 (11)
C30.0361 (13)0.0236 (14)0.0523 (18)0.0041 (10)0.0008 (12)0.0023 (11)
C40.0331 (12)0.0269 (14)0.0365 (14)0.0009 (10)0.0009 (10)0.0030 (11)
C50.0326 (12)0.0351 (16)0.0445 (16)0.0062 (11)0.0037 (11)0.0013 (12)
C60.0387 (14)0.0248 (14)0.0410 (15)0.0054 (10)0.0025 (11)0.0022 (11)
C110.0387 (13)0.0299 (15)0.0336 (14)0.0010 (10)0.0017 (11)0.0014 (11)
C120.0359 (13)0.0407 (17)0.068 (2)0.0042 (12)0.0015 (14)0.0065 (15)
Hg10.03172 (8)0.05938 (13)0.05092 (11)0.0000.0000.00393 (9)
Cl10.0538 (5)0.0448 (6)0.0453 (6)0.0000.0000.0061 (5)
Cl20.0420 (5)0.0490 (6)0.0455 (6)0.0000.0000.0018 (5)
Cl30.0383 (4)0.0555 (5)0.0883 (6)0.0145 (3)0.0098 (4)0.0202 (4)
Geometric parameters (Å, º) top
O11—C111.224 (3)C4—C51.381 (4)
N41—C41.461 (3)C5—C61.378 (4)
N41—H41A0.901 (19)C5—H50.9300
N41—H41B0.887 (19)C6—H60.9300
N41—H41C0.899 (19)C11—C121.486 (4)
C1—C61.383 (4)C12—H12A0.9600
C1—C21.384 (4)C12—H12B0.9600
C1—C111.492 (4)C12—H12C0.9600
C2—C31.389 (4)Hg1—Cl3i2.4308 (7)
C2—H20.9300Hg1—Cl32.4308 (7)
C3—C41.370 (4)Hg1—Cl12.4764 (11)
C3—H30.9300Hg1—Cl22.5244 (11)
C4—N41—H41A114 (3)C4—C5—H5120.9
C4—N41—H41B109 (2)C5—C6—C1121.1 (2)
H41A—N41—H41B116 (3)C5—C6—H6119.4
C4—N41—H41C110 (3)C1—C6—H6119.4
H41A—N41—H41C100 (3)O11—C11—C12121.0 (3)
H41B—N41—H41C108 (3)O11—C11—C1118.4 (2)
C6—C1—C2119.3 (2)C12—C11—C1120.6 (2)
C6—C1—C11118.6 (2)C11—C12—H12A109.5
C2—C1—C11122.1 (2)C11—C12—H12B109.5
C1—C2—C3120.5 (2)H12A—C12—H12B109.5
C1—C2—H2119.8C11—C12—H12C109.5
C3—C2—H2119.8H12A—C12—H12C109.5
C4—C3—C2118.6 (2)H12B—C12—H12C109.5
C4—C3—H3120.7Cl3i—Hg1—Cl3122.94 (4)
C2—C3—H3120.7Cl3i—Hg1—Cl1104.66 (2)
C3—C4—C5122.2 (2)Cl3—Hg1—Cl1104.66 (2)
C3—C4—N41119.4 (2)Cl3i—Hg1—Cl2106.66 (3)
C5—C4—N41118.4 (2)Cl3—Hg1—Cl2106.66 (3)
C6—C5—C4118.3 (2)Cl1—Hg1—Cl2111.11 (4)
C6—C5—H5120.9
C6—C1—C2—C31.4 (4)C4—C5—C6—C10.6 (4)
C11—C1—C2—C3177.2 (2)C2—C1—C6—C51.8 (4)
C1—C2—C3—C40.1 (4)C11—C1—C6—C5176.9 (2)
C2—C3—C4—C51.3 (4)C6—C1—C11—O115.2 (4)
C2—C3—C4—N41177.3 (3)C2—C1—C11—O11173.4 (3)
C3—C4—C5—C60.9 (4)C6—C1—C11—C12175.3 (2)
N41—C4—C5—C6177.6 (3)C2—C1—C11—C126.1 (4)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N41—H41A···O11ii0.90 (2)1.92 (2)2.792 (3)162 (4)
N41—H41C···Cl2iii0.90 (2)2.34 (2)3.206 (3)162 (3)
N41—H41B···Cl3iv0.89 (2)2.49 (2)3.326 (3)158 (3)
Symmetry codes: (ii) x+1/2, y1/2, 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···AD—HH···AD···AD—H···A
N41—H41A···O11i0.901 (19)1.92 (2)2.792 (3)162 (4)
N41—H41C···Cl2ii0.899 (19)2.34 (2)3.206 (3)162 (3)
N41—H41B···Cl3iii0.887 (19)2.49 (2)3.326 (3)158 (3)
Symmetry codes: (i) x+1/2, y1/2, 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

First citationBruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationElangovan, A., Thamaraichelvan, A., Ramu, A., Athimoolam, S. & Natarajan, S. (2007). Acta Cryst. E63, m224–m226.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationThairiyaraja, M., Elangovan, A., Shanmugam, R., Selvaraju, K. & Thamotharan, S. (2015). Acta Cryst. E71, m221–m222.  CSD CrossRef 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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