Bis(pyridazine-κN)bis­(seleno­cyanato-κN)zinc

Abstract

The asymmetric unit of the title compound, [Zn(NCSe)₂(C₄H₄N₂)₂], consists of one Zn^II cation, located on a twofold rotation axis, one seleno­cyanate anion and one pyridazine ligand in general positions. The Zn^II atom is coordinated by two N-atoms of two pyridazine ligands and two terminal N-bonded seleno­cyanate anions within a slightly distorted tetra­hedral coordination environment. In the crystal, discrete complex mol­ecules are arranged in layers parallel to the ac plane, with Zn^II⋯Zn^II distances of 8.0906 (6) Å along the a axis and of 9.0490 (7) or 9.3604 (7) Å along the c axis. The complex mol­ecules are further linked via weak Se⋯Se inter­actions, with Se⋯Se distances of 3.8235 (9) Å.

Related literature

For related structures see: Boeckmann et al. (2011 ▶); Bhosekar et al. (2010 ▶); Wriedt & Näther (2010 ▶); Zhu et al. (2008 ▶).

Experimental

Crystal data

• [Zn(NCSe)₂(C₄H₄N₂)₂]

• M _r = 435.51

• Monoclinic,

• a = 15.1521 (10) Å

• b = 5.6783 (4) Å

• c = 17.4855 (13) Å

• β = 94.981 (6)°

• V = 1498.74 (18) ų

• Z = 4

• Mo Kα radiation

• μ = 6.49 mm⁻¹

• T = 293 K

• 0.09 × 0.06 × 0.04 mm

Data collection

• Stoe IPDS-2 diffractometer

• Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T _min = 0.373, T _max = 0.664

• 9054 measured reflections

• 1634 independent reflections

• 1287 reflections with I > 2σ(I)

• R _int = 0.028

Refinement

• R[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 0.097

• S = 1.13

• 1634 reflections

• 87 parameters

• H-atom parameters constrained

• Δρ_max = 0.49 e Å⁻³

• Δρ_min = −0.39 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 2011 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

Table 1. Selected geometric parameters (Å, °).

Zn1—N1	1.925 (4)
Zn1—N11	2.022 (3)

N1—Zn1—N1i	117.5 (3)
N1—Zn1—N11i	111.40 (17)
N1—Zn1—N11	106.96 (16)
N11i—Zn1—N11	101.48 (18)

Symmetry code: (i) .

supplementary crystallographic information

Comment

The structure determination of the title compound was performed as a part of a project on the synthesis of new selenocyanato coordination compounds (Wriedt & Näther, 2010). In our ongoing investigations we have reacted zinc(II)nitrate with potassium(I)selenocyanate and pyridazine in acetonitrile, which leads to the phase pure formation of bis(selenocyanato-N)-bis(pyridazine-N)zinc(II).

The title compound is isotypic to its thiocyanato analogon reported recently (Bhosekar et al., 2010). In the crystal structure the zinc atoms are surrounded by two N-atoms of two symmetry equivalent pyridazine ligands and two N-bonded symmetry equivalent thiocyanato anions in a slightly distorted tetrahedral geometry (Fig. 1 and Tab. 1). The discrete complexes are arranged in layers parallel along the ac plane with Zn^II···Zn^II distances of 8.0906 (6) Å along the a axis and of 9.0490 (7) or 9.3604 (7) Å along the c axis. Within these layers these complexes are further connected via weak Se···Se interactions of 3.8235 (9) Å (Fig. 2). Crystal structures of related thio- and selenocyanato compounds with pyridine as neutral coligand have already been described in literature (Zhu et al., 2008; Boeckmann et al., 2011).

Experimental

The title compound was prepared by the reaction of 74.35 mg Zn(NO₃)₂ × 6 H₂O (0.25 mmol), 72.0 mg KSeCN (0.50 mmol) and 18.1 µL pyridazine (0.25 mmol) in 1.00 ml acetonitrile at RT in a closed 3 ml snap cap vial. After one week colourless blocks of the title compound were obtained.

Refinement

All H atoms were located in difference map but were positioned with idealized geometry and were refined using a riding model with U_eq(H) = 1.2 U_eq(C) and with C—H = 0.93 Å.

Figures

Fig. 1.

: Crystal structure of the title compund with labelling and displacement ellipsoids drawn at the 30% probability level. Symmetry codes: i = -x + 1, y, -z + 1/2.

Fig. 2.

: Packing diagram of title compound with view along the crystallographic b axis. Intermolecular Se···Se interactions are shown as dashed lines.

Crystal data

[Zn(NCSe)2(C4H4N2)2]	F(000) = 832
Mr = 435.51	Dx = 1.930 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9054 reflections
a = 15.1521 (10) Å	θ = 2.3–27.0°
b = 5.6783 (4) Å	µ = 6.49 mm−1
c = 17.4855 (13) Å	T = 293 K
β = 94.981 (6)°	Block, colourless
V = 1498.74 (18) Å3	0.09 × 0.06 × 0.04 mm
Z = 4

Data collection

Stoe IPDS-2 diffractometer	1634 independent reflections
Radiation source: fine-focus sealed tube	1287 reflections with I > 2σ(I)
graphite	Rint = 0.028
ω scans	θmax = 27.0°, θmin = 2.3°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −19→19
Tmin = 0.373, Tmax = 0.664	k = −7→7
9054 measured reflections	l = −22→22

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0314P)2 + 3.5658P] where P = (Fo2 + 2Fc2)/3
1634 reflections	(Δ/σ)max < 0.001
87 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.39 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
Zn1	0.5000	0.29445 (12)	0.2500	0.0599 (2)
N1	0.4362 (3)	0.4703 (8)	0.3215 (3)	0.0882 (13)
C1	0.4026 (4)	0.5649 (9)	0.3694 (3)	0.0746 (13)
Se1	0.35126 (4)	0.71204 (11)	0.44311 (3)	0.0895 (2)
N11	0.5806 (2)	0.0691 (6)	0.31236 (18)	0.0529 (7)
N12	0.6478 (3)	−0.0093 (8)	0.2760 (2)	0.0805 (12)
C11	0.6957 (4)	−0.1819 (13)	0.3105 (5)	0.110 (2)
H11	0.7432	−0.2417	0.2863	0.131*
C12	0.6781 (5)	−0.2768 (11)	0.3808 (5)	0.108 (2)
H12	0.7132	−0.3968	0.4033	0.129*
C13	0.6107 (5)	−0.1931 (11)	0.4148 (4)	0.1007 (19)
H13	0.5958	−0.2522	0.4616	0.121*
C14	0.5640 (3)	−0.0171 (9)	0.3784 (3)	0.0747 (13)
H14	0.5169	0.0465	0.4022	0.090*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Zn1	0.0636 (4)	0.0529 (4)	0.0629 (4)	0.000	0.0043 (3)	0.000
N1	0.092 (3)	0.080 (3)	0.092 (3)	0.027 (2)	0.000 (2)	−0.027 (2)
C1	0.081 (3)	0.061 (3)	0.079 (3)	0.018 (2)	−0.009 (2)	−0.005 (2)
Se1	0.1106 (5)	0.0806 (4)	0.0785 (4)	0.0227 (3)	0.0144 (3)	−0.0112 (3)
N11	0.0485 (17)	0.0543 (19)	0.0559 (18)	0.0004 (14)	0.0047 (14)	−0.0038 (15)
N12	0.059 (2)	0.093 (3)	0.093 (3)	0.011 (2)	0.023 (2)	−0.005 (2)
C11	0.062 (3)	0.110 (5)	0.158 (7)	0.019 (3)	0.016 (4)	−0.023 (5)
C12	0.093 (4)	0.082 (4)	0.140 (6)	0.013 (4)	−0.039 (4)	0.011 (4)
C13	0.125 (5)	0.085 (4)	0.090 (4)	0.016 (4)	−0.005 (4)	0.019 (3)
C14	0.086 (3)	0.073 (3)	0.067 (3)	0.010 (3)	0.017 (2)	0.007 (2)

Geometric parameters (Å, °)

Zn1—N1	1.925 (4)	N12—C11	1.332 (8)
Zn1—N1i	1.925 (4)	C11—C12	1.389 (11)
Zn1—N11i	2.022 (3)	C11—H11	0.9300
Zn1—N11	2.022 (3)	C12—C13	1.315 (9)
N1—C1	1.150 (6)	C12—H12	0.9300
C1—Se1	1.772 (5)	C13—C14	1.351 (8)
N11—C14	1.299 (5)	C13—H13	0.9300
N11—N12	1.324 (5)	C14—H14	0.9300
N1—Zn1—N1i	117.5 (3)	N12—C11—C12	123.2 (6)
N1—Zn1—N11i	111.40 (17)	N12—C11—H11	118.4
N1i—Zn1—N11i	106.96 (16)	C12—C11—H11	118.4
N1—Zn1—N11	106.96 (16)	C13—C12—C11	118.4 (6)
N1i—Zn1—N11	111.40 (17)	C13—C12—H12	120.8
N11i—Zn1—N11	101.48 (18)	C11—C12—H12	120.8
C1—N1—Zn1	173.8 (4)	C12—C13—C14	116.8 (6)
N1—C1—Se1	179.7 (6)	C12—C13—H13	121.6
C14—N11—N12	121.1 (4)	C14—C13—H13	121.6
C14—N11—Zn1	124.3 (3)	N11—C14—C13	124.3 (5)
N12—N11—Zn1	114.1 (3)	N11—C14—H14	117.8
N11—N12—C11	116.2 (5)	C13—C14—H14	117.8

Symmetry codes: (i) −x+1, y, −z+1/2.