Zinc mercury(II) tetra­kis­(seleno­cyanate)

Sun, H.-Q.; Wang, X.-Q.; Zhang, W.-W.

doi:10.1107/S1600536813022502

inorganic compounds

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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page i59

doi:10.1107/S1600536813022502

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Zinc mercury(II) tetrakis(selenocyanate)

Hai-Qing Sun,^a ^* Xin-Qiang Wang ^b and Wei-Wei Zhang ^a

^aSchool of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, People's Republic of China, and ^bState Key Laboratory of Crystal Materials (Shandong University), Jinan 250100, People's Republic of China
^*Correspondence e-mail: sunhaiqing@sina.com

(Received 1 August 2013; accepted 10 August 2013; online 17 August 2013)

The title crystal, [HgZn(NCSe)₄]_n, a coordination polymer, has a diamond-like network. In the crystal, the metal ions, Zn²⁺ and Hg²⁺, are both located on fourfold inversion axes and mimic the role of C atoms in the structure of diamond, and the linear selenocyanate bridges replace the C—C bonds. The C—N—Zn unit is almost linear and the C—Se—Hg unit is nearly a right angle. Thus, the HgZn₄ (or ZnHg₄) arrangement is midway between a tetrahedron and a square plane, with two types of Hg—Zn—Hg (or Zn—Hg—Zn) angles of 92.38 (6) and 156.45 (6)°.

Related literature

For background to coordination polymers, see: Batten et al. (2009 ). For diamond-like networks, see: Sun et al. (2006 ); Evans et al. (1999 ). For similar structures, see: Wang et al. (2001 , 2007 ); Sun et al. (2005 , 2006); Tian et al. (1999 ); Xu et al. (1999 ); Yan et al. (1999 ); Yuan et al. (1997 ).

Experimental

Crystal data

[HgZn(NCSe)₄]
M_r = 685.88
Tetragonal, $[I \overline 4]$
a = 11.2716 (1) Å
c = 4.6981 (1) Å
V = 596.89 (2) Å³
Z = 2
Mo Kα radiation
μ = 27.02 mm⁻¹
T = 293 K
0.13 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (APEX2; Bruker, 2005 ) T_min = 0.127, T_max = 0.173
2476 measured reflections
1244 independent reflections
1113 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.053
S = 0.86
1244 reflections
33 parameters
Δρ_max = 1.35 e Å⁻³
Δρ_min = −0.81 e Å⁻³
Absolute structure: Flack (1983 ), 467 Friedel pairs
Absolute structure parameter: 0.026 (10)

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813022502/br2230sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813022502/br2230Isup2.hkl

checkCIF report

Comment top

Coordination polymers, which contain ions linked by coordinated ligands into an infinite array, have extensive applications such as porosity, magnetism, non-linear optical activity, reactive networks, heterogenous catalysis and luminescence (Batten et al. 2009). [AB(SCN)₄]_n and [AB(SeCN)₄]_n (where A and B = Zn, Cd, Hg or Mn) are coordination polymers that have non-linear optical property (Wang et al., 2007, 2001; Sun et al., 2006, 2005; Yuan et al. 1997). [ZnHg(SeCN)₄]_n is a new member of this group.

All the [AB(SCN)₄]_n and [AB(SeCN)₄]_n have similar structure. The [ZnHg(SeCN)₄]_n is of no exception. The Zn and Hg atoms are connected by SeCN^- ions, forming an infinite three-dimensional network (see Fig. 1). Each Zn or Hg node is 4-coordinated with Zn—N or Hg—Se bond. The ZnN₄ and HgSe₄ tetrahedra are slightly distorted from an ideal one. The Zn—N—C—Se is nearly linear, but the C—Se—Hg is bent. The whole structure might be defined as a diamond-like network with Zn and Hg nodes and bent bonds. The HgZn₄ (or ZnHg₄) tetrahedra have a significant distortion from an ideal one, with two types of Hg—Zn—Hg (or Zn—Hg—Zn) angles, 92.38 (6)° and 156.45 (6)°. Along the c-direction there are irregular octagon channels.

Related literature top

For background to coordination polymers, see: Batten et al. (2009). For diamond-like networks, see: Sun et al. (2006); Evans et al. (1999). For similar structures, see: Wang et al. (2001, 2007); Sun et al. (2005, 2006); Tian et al. (1999); Xu et al. (1999); Yan et al. (1999); Yuan et al. (1997)

Experimental top

Sodium metasilicate nonahydrate (Na₂SiO₃.9H₂O), ZnCl₂ and KSeCN solution were mixed together with stirring for 1 h. Then the sol is put into a test tube. Glacial acetic acid was added to adjust pH to 3.1. The above solution was sealed and gelled on standing for 72 h. Then some HgCl₂ solution was added on top of the gel. Within 20 d the ZMSC crystal grew in the gel medium.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

Fig. 1. Packing diagram of [ZnHg(NCSe)₄]_n (viewed down the c axis), with displacement ellipsoids drawn at the 50% probability level.

Zinc mercury(II) tetrakis(selenocyanate) top

Crystal data top

[HgZn(NCSe)₄]	D_x = 3.816 Mg m⁻³
M_r = 685.88	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 1556 reflections
Hall symbol: I -4	θ = 2.6–34.8°
a = 11.2716 (1) Å	µ = 27.02 mm⁻¹
c = 4.6981 (1) Å	T = 293 K
V = 596.89 (2) Å³	Prism, colourless
Z = 2	0.13 × 0.12 × 0.10 mm
F(000) = 596

Data collection top

Bruker APEXII CCD area-detector diffractometer	1244 independent reflections
Radiation source: fine-focus sealed tube	1113 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 38.1°, θ_min = 2.6°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −16→19
T_min = 0.127, T_max = 0.173	k = −17→11
2476 measured reflections	l = −6→7

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²)]
R[F² > 2σ(F²)] = 0.026	(Δ/σ)_max < 0.001
wR(F²) = 0.053	Δρ_max = 1.35 e Å⁻³
S = 0.86	Δρ_min = −0.81 e Å⁻³
1244 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
33 parameters	Extinction coefficient: 0.0047 (3)
0 restraints	Absolute structure: Flack (1983), 467 Friedel pairs
Primary atom site location: isomorphous structure methods	Absolute structure parameter: 0.026 (10)

Crystal data top

[HgZn(NCSe)₄]	Z = 2
M_r = 685.88	Mo Kα radiation
Tetragonal, I4	µ = 27.02 mm⁻¹
a = 11.2716 (1) Å	T = 293 K
c = 4.6981 (1) Å	0.13 × 0.12 × 0.10 mm
V = 596.89 (2) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	1244 independent reflections
Absorption correction: multi-scan (APEX2; Bruker, 2005)	1113 reflections with I > 2σ(I)
T_min = 0.127, T_max = 0.173	R_int = 0.029
2476 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.053	Δρ_max = 1.35 e Å⁻³
S = 0.86	Δρ_min = −0.81 e Å⁻³
1244 reflections	Absolute structure: Flack (1983), 467 Friedel pairs
33 parameters	Absolute structure parameter: 0.026 (10)

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Hg1	0.0000	0.0000	0.0000	0.02909 (11)
Se1	0.12160 (4)	0.15390 (4)	0.31572 (11)	0.03115 (13)
Zn1	0.0000	0.5000	−0.2500	0.0289 (2)
N1	0.0462 (4)	0.3643 (3)	−0.0118 (16)	0.0374 (9)
C1	0.0756 (4)	0.2818 (4)	0.1106 (10)	0.0280 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.02405 (11)	0.02405 (11)	0.0392 (2)	0.000	0.000	0.000
Se1	0.0322 (2)	0.0250 (2)	0.0363 (3)	−0.00208 (18)	−0.0073 (2)	0.00031 (19)
Zn1	0.0242 (3)	0.0242 (3)	0.0382 (6)	0.000	0.000	0.000
N1	0.040 (2)	0.0242 (16)	0.048 (2)	0.0011 (14)	−0.004 (3)	−0.004 (2)
C1	0.0241 (19)	0.0219 (18)	0.038 (2)	−0.0019 (15)	0.0023 (17)	−0.0046 (17)

Geometric parameters (Å, º) top

Hg1—Se1	2.6623 (5)	Zn1—N1^iv	1.966 (6)
Hg1—Se1ⁱ	2.6623 (5)	Zn1—N1^v	1.966 (6)
Hg1—Se1ⁱⁱ	2.6623 (5)	Zn1—N1^vi	1.966 (6)
Hg1—Se1ⁱⁱⁱ	2.6623 (5)	Zn1—N1	1.966 (6)
Se1—C1	1.810 (5)	N1—C1	1.141 (7)

Se1—Hg1—Se1ⁱ	108.084 (11)	N1^iv—Zn1—N1^vi	110.6 (4)
Se1—Hg1—Se1ⁱⁱ	112.28 (2)	N1^v—Zn1—N1^vi	108.91 (18)
Se1ⁱ—Hg1—Se1ⁱⁱ	108.084 (11)	N1^iv—Zn1—N1	108.91 (18)
Se1—Hg1—Se1ⁱⁱⁱ	108.084 (11)	N1^v—Zn1—N1	110.6 (4)
Se1ⁱ—Hg1—Se1ⁱⁱⁱ	112.28 (2)	N1^vi—Zn1—N1	108.91 (18)
Se1ⁱⁱ—Hg1—Se1ⁱⁱⁱ	108.084 (11)	C1—N1—Zn1	175.5 (6)
C1—Se1—Hg1	94.29 (14)	N1—C1—Se1	178.1 (5)
N1^iv—Zn1—N1^v	108.91 (18)

Se1ⁱ—Hg1—Se1—C1	−14.76 (14)	N1^iv—Zn1—N1—C1	69 (5)
Se1ⁱⁱ—Hg1—Se1—C1	−133.89 (14)	N1^vi—Zn1—N1—C1	−52 (5)
Se1ⁱⁱⁱ—Hg1—Se1—C1	106.99 (14)	Hg1—Se1—C1—N1	140 (12)

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

Experimental details

Crystal data
Chemical formula	[HgZn(NCSe)₄]
M_r	685.88
Crystal system, space group	Tetragonal, I4
Temperature (K)	293
a, c (Å)	11.2716 (1), 4.6981 (1)
V (Å³)	596.89 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	27.02
Crystal size (mm)	0.13 × 0.12 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (APEX2; Bruker, 2005)
T_min, T_max	0.127, 0.173
No. of measured, independent and observed [I > 2σ(I)] reflections	2476, 1244, 1113
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.868

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.053, 0.86
No. of reflections	1244
No. of parameters	33
Δρ_max, Δρ_min (e Å⁻³)	1.35, −0.81
Absolute structure	Flack (1983), 467 Friedel pairs
Absolute structure parameter	0.026 (10)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 2012).

Acknowledgements

The authors thank the Open Project of the State Key Laboratory of Crystal Materials (grant No. KF0804) and the Excellent Mid-youthful Scientist Encouraging Foundation of Shandong province (grant No. BS2010CL037) for financial support.

References

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