catena-Poly[[(2-amino­pyrimidine-κN ¹)(thio­cyanato-κS)mercury(II)]-μ-thio­cyanato-κ² S:N]

Abstract

In the title coordination polymer, [Hg(NCS)₂(C₄H₅N₃)], the Hg^II atom is four-coordinated by one aromatic N atom from a 2-amino­pyrimidine ligand, one S atom from a terminal thio­cyanate ligand, and one S atom and one N atom from a bridging thio­cyanate ligand. The crystal structure features polymeric chains running along the b axis which are stabilized by N—H⋯N hydrogen bonds.

Related literature  

For related structures with amino­pyridine as a ligand, see: Albada et al. (2002 ▶); Castillo et al. (2011 ▶); Cheng et al. (2009 ▶); Cui et al. (2011 ▶); Gao & Ng (2010 ▶); Lee et al. (2003 ▶); Li et al. (2006 ▶); Lin & Zeng (2007 ▶); Masaki et al. (2002 ▶); Qu et al. (2008 ▶); Zhu et al. (2002 ▶, 2003 ▶).

Experimental  

Crystal data  

• [Hg(NCS)₂(C₄H₅N₃)]

• M _r = 411.88

• Monoclinic,

• a = 25.819 (2) Å

• b = 6.0060 (4) Å

• c = 20.1176 (15) Å

• β = 136.222 (4)°

• V = 2158.4 (3) ų

• Z = 8

• Mo Kα radiation

• μ = 14.62 mm⁻¹

• T = 298 K

• 0.25 × 0.22 × 0.11 mm

Data collection  

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: numerical (SADABS; Bruker, 2001 ▶) T _min = 0.039, T _max = 0.222

• 7675 measured reflections

• 2131 independent reflections

• 1671 reflections with I > 2σ(I)

• R _int = 0.078

Refinement  

• R[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 0.088

• S = 1.10

• 2131 reflections

• 127 parameters

• H-atom parameters constrained

• Δρ_max = 0.72 e Å⁻³

• Δρ_min = −1.23 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N5i	0.86	2.21	3.052 (14)	167
N1—H1B⋯N3ii	0.86	2.15	3.004 (13)	176

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Numerous complexes with 2-aminopyrimidine as a ligand have been prepared, such as that of cobalt (Li et al., 2006), manganese (Lee et al., 2003), nickel (Masaki et al., 2002), zinc (Gao et al., 2010; Qu et al., 2008; Lin & Zeng, 2007), cadmium (Castillo et al., 2011; Cheng et al., 2009), silver (Zhu et al., 2003; Cui et al., 2011) and copper (Zhu et al., 2002; Albada et al., 2002). Here, we report the synthesis and structure of the title compound.

In the title coordination polymer, (Fig. 1), the Hg^II atom is four-coordinated in a butterfly configuration by one N atom from one 2-aminopyrimidine, one S atom from one terminal SCN ligand, one S atom from one bridging SCN and one N atom from one bridging SCN ligand.

In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 2, Fig. 2) stabilize the structure.

Experimental

A solution of 2-aminopyrimidine (0.19 g, 2.0 mmol) in methanol (20 ml) was added to a solution of Hg(SCN)₂ (0.43 g, 1.0 mmol) in methanol (20 ml) and the resulting colorless solution was stirred for 20 min at 313 K. This solution was left to evaporate slowly at room temperature. After one week, colourless prismatic crystals of the title compound were isolated (yield; 0.33 g, 72.8%).

Refinement

All H atoms were positioned geometrically, with C—H = 0.93 Å and N—H = 0.86 Å and constrained to ride on their parent atoms with U_iso(H)=1.2U_eq(C,N).

Figures

Fig. 1.

The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (a) x,-1 + y,z].

Fig. 2.

Unit-cell packing diagram for title molecule. Hydrogen bonds are shown as dashed lines.

Crystal data

[Hg(NCS)2(C4H5N3)]	F(000) = 1504
Mr = 411.88	Dx = 2.535 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7675 reflections
a = 25.819 (2) Å	θ = 2.9–26.0°
b = 6.0060 (4) Å	µ = 14.62 mm−1
c = 20.1176 (15) Å	T = 298 K
β = 136.222 (4)°	Prism, colorless
V = 2158.4 (3) Å3	0.25 × 0.22 × 0.11 mm
Z = 8

Data collection

Bruker APEXII CCD area-detector diffractometer	2131 independent reflections
Radiation source: fine-focus sealed tube	1671 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
ω scans	θmax = 26.0°, θmin = 2.9°
Absorption correction: numerical (SADABS; Bruker, 2001)	h = −31→27
Tmin = 0.039, Tmax = 0.222	k = −7→7
7675 measured reflections	l = −23→24

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0349P)2] where P = (Fo2 + 2Fc2)/3
2131 reflections	(Δ/σ)max = 0.008
127 parameters	Δρmax = 0.72 e Å−3
0 restraints	Δρmin = −1.23 e Å−3

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
Hg1	0.16617 (2)	0.10942 (6)	0.33894 (3)	0.05561 (16)
S1	0.1305 (2)	0.3052 (4)	0.4049 (2)	0.0707 (8)
S2	0.25302 (16)	−0.0298 (4)	0.3378 (2)	0.0641 (7)
C1	0.0285 (5)	0.2478 (15)	0.1021 (6)	0.049 (2)
C2	0.0007 (6)	−0.0719 (16)	0.1318 (7)	0.055 (2)
H2	0.0126	−0.1780	0.1749	0.067*
C3	−0.0648 (5)	−0.0935 (19)	0.0381 (7)	0.058 (3)
H3	−0.0961	−0.2152	0.0153	0.069*
C4	−0.0821 (5)	0.0738 (17)	−0.0211 (7)	0.054 (3)
H4	−0.1278	0.0675	−0.0855	0.065*
C5	0.1323 (6)	0.5655 (15)	0.3790 (8)	0.055 (3)
C6	0.2379 (5)	−0.3009 (18)	0.3346 (6)	0.047 (2)
N1	0.0752 (5)	0.4154 (14)	0.1322 (6)	0.073 (3)
H1A	0.1176	0.4234	0.1916	0.088*
H1B	0.0629	0.5155	0.0923	0.088*
N2	0.0491 (4)	0.0940 (11)	0.1659 (5)	0.0437 (16)
N3	−0.0368 (4)	0.2472 (13)	0.0082 (5)	0.051 (2)
N4	0.1294 (7)	0.7461 (14)	0.3608 (9)	0.090 (4)
N5	0.2301 (5)	−0.4879 (17)	0.3329 (7)	0.070 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Hg1	0.0759 (3)	0.03563 (19)	0.0604 (2)	0.0129 (2)	0.0510 (2)	0.0059 (2)
S1	0.123 (3)	0.0400 (12)	0.097 (2)	−0.0033 (15)	0.096 (2)	−0.0014 (14)
S2	0.0652 (17)	0.0482 (13)	0.0875 (19)	−0.0009 (13)	0.0581 (16)	−0.0002 (13)
C1	0.047 (5)	0.049 (5)	0.041 (5)	0.004 (4)	0.029 (5)	−0.001 (4)
C2	0.062 (6)	0.050 (6)	0.063 (6)	−0.005 (5)	0.048 (6)	0.002 (5)
C3	0.047 (5)	0.073 (7)	0.058 (6)	−0.013 (5)	0.039 (5)	−0.005 (6)
C4	0.039 (5)	0.072 (7)	0.045 (5)	−0.006 (5)	0.028 (4)	−0.004 (5)
C5	0.080 (7)	0.045 (6)	0.074 (7)	0.010 (5)	0.067 (6)	0.013 (5)
C6	0.033 (5)	0.050 (5)	0.049 (5)	0.001 (4)	0.026 (5)	−0.005 (4)
N1	0.062 (5)	0.058 (5)	0.043 (4)	−0.017 (4)	0.018 (4)	0.007 (4)
N2	0.047 (4)	0.036 (4)	0.042 (4)	0.004 (3)	0.030 (3)	0.006 (3)
N3	0.037 (4)	0.062 (5)	0.042 (4)	−0.007 (4)	0.024 (4)	−0.005 (4)
N4	0.163 (11)	0.036 (5)	0.164 (11)	0.016 (6)	0.148 (10)	0.014 (6)
N5	0.063 (6)	0.051 (5)	0.089 (7)	−0.004 (5)	0.053 (6)	−0.016 (5)

Geometric parameters (Å, º)

Hg1—S1	2.399 (5)	N3—C4	1.343 (16)
Hg1—S2	2.409 (5)	N4—C5	1.130 (13)
Hg1—N2	2.464 (7)	N5—C6	1.137 (15)
Hg1—N4i	2.542 (13)	N1—H1B	0.8600
S1—C5	1.659 (11)	N1—H1A	0.8600
S2—C6	1.665 (11)	C2—C3	1.352 (15)
N1—C1	1.334 (16)	C3—C4	1.364 (16)
N2—C1	1.341 (12)	C2—H2	0.9300
N2—C2	1.337 (16)	C3—H3	0.9300
N3—C1	1.346 (12)	C4—H4	0.9300
Hg1···N5ii	2.980 (13)	C2···S1iii	3.679 (16)
Hg1···H1A	2.9200	C3···S1iii	3.569 (15)
S1···N4i	3.468 (10)	C4···S1iii	3.630 (15)
S1···C2iii	3.679 (16)	C4···N5vii	3.44 (2)
S1···C3iii	3.569 (15)	C4···C1vi	3.400 (19)
S1···C4iii	3.630 (15)	C5···C6ii	3.52 (2)
S2···N5ii	3.297 (11)	C5···N5ii	3.27 (2)
S2···H3iv	3.1900	C6···C5i	3.52 (2)
N1···N5ii	3.052 (14)	C1···H1Bv	3.0900
N1···N3v	3.004 (13)	C4···H1Bv	3.0700
N3···N1v	3.004 (13)	C6···H1Ai	2.7900
N4···C6ii	3.22 (3)	C6···H3iv	3.0200
N4···S1ii	3.468 (10)	C6···H4iv	3.0200
N4···C2ii	3.370 (16)	H1A···Hg1	2.9200
N5···N1i	3.052 (14)	H1A···N5ii	2.2100
N5···C4iv	3.44 (2)	H1A···C6ii	2.7900
N5···Hg1i	2.980 (13)	H1B···N3v	2.1500
N5···S2i	3.297 (11)	H1B···C1v	3.0900
N5···C5i	3.27 (2)	H1B···C4v	3.0700
N3···H1Bv	2.1500	H2···N4i	2.6500
N4···H2ii	2.6500	H3···S2vii	3.1900
N5···H1Ai	2.2100	H3···C6vii	3.0200
N5···H4iv	2.7700	H4···N5vii	2.7700
C1···C4vi	3.400 (19)	H4···C6vii	3.0200
S1—Hg1—S2	155.11 (12)	C1—N1—H1B	120.00
S1—Hg1—N2	103.3 (3)	N1—C1—N2	118.8 (8)
S1—Hg1—N4i	89.1 (4)	N1—C1—N3	116.4 (9)
S2—Hg1—N2	100.0 (3)	N2—C1—N3	124.8 (10)
S2—Hg1—N4i	99.8 (5)	N2—C2—C3	123.5 (10)
N2—Hg1—N4i	89.0 (4)	C2—C3—C4	116.0 (11)
Hg1—S1—C5	100.3 (6)	N3—C4—C3	123.8 (10)
Hg1—S2—C6	98.4 (6)	S1—C5—N4	175 (2)
Hg1—N2—C1	124.1 (7)	S2—C6—N5	177.0 (15)
Hg1—N2—C2	119.5 (6)	N2—C2—H2	118.00
C1—N2—C2	116.4 (8)	C3—C2—H2	118.00
C1—N3—C4	115.4 (9)	C2—C3—H3	122.00
Hg1ii—N4—C5	159.2 (18)	C4—C3—H3	122.00
H1A—N1—H1B	120.00	N3—C4—H4	118.00
C1—N1—H1A	120.00	C3—C4—H4	118.00
S2—Hg1—S1—C5	79.5 (5)	S2—Hg1—N4i—C5i	18 (3)
N2—Hg1—S1—C5	−80.0 (5)	N2—Hg1—N4i—C5i	118 (3)
N4i—Hg1—S1—C5	−168.8 (6)	Hg1—N2—C1—N1	3.2 (18)
S1—Hg1—S2—C6	118.0 (4)	C2—N2—C1—N1	−179.2 (13)
N2—Hg1—S2—C6	−82.3 (4)	Hg1—N2—C1—N3	−176.8 (10)
N4i—Hg1—S2—C6	8.4 (4)	C2—N2—C1—N3	1 (2)
S1—Hg1—N2—C1	91.2 (11)	C1—N2—C2—C3	2 (2)
S1—Hg1—N2—C2	−86.3 (10)	Hg1—N2—C2—C3	180.0 (12)
S2—Hg1—N2—C1	−80.2 (10)	C4—N3—C1—N2	−2 (2)
S2—Hg1—N2—C2	102.3 (11)	C4—N3—C1—N1	178.3 (13)
N4i—Hg1—N2—C1	−179.9 (11)	C1—N3—C4—C3	0 (2)
N4i—Hg1—N2—C2	2.5 (11)	N2—C2—C3—C4	−4 (2)
S1—Hg1—N4i—C5i	−139 (3)	C2—C3—C4—N3	3 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N5ii	0.86	2.21	3.052 (14)	167
N1—H1B···N3v	0.86	2.15	3.004 (13)	176

Symmetry codes: (ii) x, y+1, z; (v) −x, −y+1, −z.