Bis(dicyanamido-κN)tetra­kis­(pyridazine-κN)nickel(II)

Wöhlert, S.; Wriedt, M.; Jess, I.; Näther, C.

doi:10.1107/S1600536812018363

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m696

doi:10.1107/S1600536812018363

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Bis(dicyanamido-κN)tetrakis(pyridazine-κN)nickel(II)

Susanne Wöhlert,^a Mario Wriedt,^b Inke Jess ^a and Christian Näther ^a ^*

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany, and ^bDepartement of Chemistry, Texas A&M University, College Station, Texas 77843, USA
^*Correspondence e-mail: swoehlert@ac.uni-kiel.de

(Received 23 April 2012; accepted 24 April 2012; online 28 April 2012)

Reaction of nickel(II) chloride with sodium dicyanamide and pyridazine leads to single crystals of the title compound, [Ni{N(CN)₂}₂(C₄H₄N₂)₄], in which the Ni^II cation is octahedrally coordinated by two dicyanamide anions and four pyridazine ligands into a discrete complex that is located on a center of inversion.

Related literature

For the synthesis, structures and properties of dicyanamide coordination compounds, see: Wriedt & Näther (2011 ).

Experimental

Crystal data

[Ni(C₂N₃)₂(C₄H₄N₂)₄]
M_r = 511.18
Triclinic, $[P \overline 1]$
a = 8.1796 (12) Å
b = 8.4125 (12) Å
c = 8.9643 (11) Å
α = 81.364 (16)°
β = 66.027 (15)°
γ = 84.879 (17)°
V = 556.97 (13) Å³
Z = 1
Mo Kα radiation
μ = 0.91 mm⁻¹
T = 170 K
0.10 × 0.08 × 0.06 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ) T_min = 0.783, T_max = 0.927
4159 measured reflections
2142 independent reflections
1582 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.097
S = 1.01
2142 reflections
161 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.52 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: XCIF in SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812018363/bt5900sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018363/bt5900Isup2.hkl

checkCIF report

Comment top

Recently we have reported on the synthesis and characterization of paramagnetic transition metal complexes with dicyanamide as anion (Wriedt & Näther, 2011). As a part of our ongoing study in this field the crystal structure of the title compound was determined. The asymmetric unit of the title compound consits of one nickel(II) cation which is located on a center of inversion as well as one dicyanamide anion and two pyridazine ligands both in general position (Fig. 1). In the crystal structure discrete complexes are formed, in which each nickel(II) cation is coordinated by two terminal coordinated dicyanamide anions and four pyridazine ligands in a slightly distorted octahedral geometry. The Ni—N distances are in the range of 2.058 (3) Å to 2.147 (3) Å with the longer distances to the pyridazine ligands. The shortest intermolecular Ni···Ni distance amounts to 8.1796 Å.

Related literature top

For the synthesis, structures and properties of dicyanamide coordination compounds, see: Wriedt & Näther (2011).

Experimental top

Nickel(II) chloride hexahydrate (NiCl₂x6H₂O), sodium dicyanamide (NaN(CN)₂) and pyridazine were obtained from Alfa Aesar. All chemicals were used without further purification. 0.125 mmol (29.7 mg) NiCl₂x6H₂O, 0.25 mmol (22.3 mg) NaN(CN)₂ were reacted in 1.5 ml pyridazine. Green single crystals of the title compound were obtained after one week.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); 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: XCIF in SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. : Crystal structure of the title compund with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: i = -x, -y + 1, -z + 1.

Bis(dicyanamido-κN)tetrakis(pyridazine-κN)nickel(II) top

Crystal data top

[Ni(C₂N₃)₂(C₄H₄N₂)₄]	Z = 1
M_r = 511.18	F(000) = 262
Triclinic, P1	D_x = 1.524 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1796 (12) Å	Cell parameters from 4159 reflections
b = 8.4125 (12) Å	θ = 2.5–26.0°
c = 8.9643 (11) Å	µ = 0.91 mm⁻¹
α = 81.364 (16)°	T = 170 K
β = 66.027 (15)°	Block, green
γ = 84.879 (17)°	0.10 × 0.08 × 0.06 mm
V = 556.97 (13) Å³

Data collection top

Stoe IPDS-1 diffractometer	2142 independent reflections
Radiation source: fine-focus sealed tube	1582 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
phi scan	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −10→10
T_min = 0.783, T_max = 0.927	k = −10→10
4159 measured reflections	l = −11→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0348P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2142 reflections	Δρ_max = 0.51 e Å⁻³
161 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.025 (4)

Crystal data top

[Ni(C₂N₃)₂(C₄H₄N₂)₄]	γ = 84.879 (17)°
M_r = 511.18	V = 556.97 (13) Å³
Triclinic, P1	Z = 1
a = 8.1796 (12) Å	Mo Kα radiation
b = 8.4125 (12) Å	µ = 0.91 mm⁻¹
c = 8.9643 (11) Å	T = 170 K
α = 81.364 (16)°	0.10 × 0.08 × 0.06 mm
β = 66.027 (15)°

Data collection top

Stoe IPDS-1 diffractometer	2142 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	1582 reflections with I > 2σ(I)
T_min = 0.783, T_max = 0.927	R_int = 0.068
4159 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.01	Δρ_max = 0.51 e Å⁻³
2142 reflections	Δρ_min = −0.52 e Å⁻³
161 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.

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
Ni1	0.0000	0.5000	0.5000	0.0161 (2)
N1	0.1088 (4)	0.7246 (3)	0.4952 (4)	0.0190 (6)
N2	0.0726 (4)	0.7802 (4)	0.6384 (4)	0.0249 (7)
C1	0.1491 (5)	0.9151 (5)	0.6353 (5)	0.0295 (9)
H1	0.1204	0.9557	0.7366	0.035*
C2	0.2687 (6)	0.9998 (5)	0.4919 (6)	0.0336 (10)
H2	0.3228	1.0941	0.4945	0.040*
C3	0.3045 (6)	0.9406 (5)	0.3470 (5)	0.0333 (9)
H3	0.3853	0.9920	0.2449	0.040*
C4	0.2185 (5)	0.8030 (4)	0.3549 (5)	0.0254 (8)
H4	0.2391	0.7628	0.2550	0.031*
N11	0.2622 (4)	0.4283 (3)	0.3430 (4)	0.0184 (6)
N12	0.3917 (4)	0.4485 (4)	0.3946 (4)	0.0250 (7)
C11	0.5593 (5)	0.4051 (5)	0.3036 (5)	0.0264 (8)
H11	0.6503	0.4227	0.3390	0.032*
C12	0.6091 (5)	0.3350 (5)	0.1588 (5)	0.0295 (9)
H12	0.7298	0.3030	0.0984	0.035*
C13	0.4777 (5)	0.3144 (4)	0.1079 (5)	0.0273 (8)
H13	0.5035	0.2669	0.0107	0.033*
C14	0.3019 (4)	0.3658 (4)	0.2037 (4)	0.0201 (7)
H14	0.2092	0.3556	0.1680	0.024*
N21	0.0470 (4)	0.4009 (4)	0.7037 (4)	0.0223 (7)
C21	0.0896 (5)	0.3404 (4)	0.8065 (5)	0.0263 (8)
N22	0.1310 (7)	0.2874 (5)	0.9320 (5)	0.0581 (13)
C22	0.1948 (5)	0.1418 (5)	0.9515 (5)	0.0300 (9)
N23	0.2467 (6)	0.0160 (5)	0.9879 (5)	0.0480 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0151 (4)	0.0195 (4)	0.0144 (4)	−0.0010 (3)	−0.0066 (3)	−0.0020 (3)
N1	0.0177 (14)	0.0215 (15)	0.0193 (16)	0.0027 (12)	−0.0090 (12)	−0.0047 (12)
N2	0.0227 (16)	0.0314 (17)	0.0223 (17)	−0.0058 (13)	−0.0082 (13)	−0.0083 (13)
C1	0.032 (2)	0.029 (2)	0.033 (2)	0.0018 (17)	−0.0151 (18)	−0.0137 (17)
C2	0.037 (2)	0.0228 (19)	0.047 (3)	−0.0085 (17)	−0.021 (2)	−0.0029 (18)
C3	0.033 (2)	0.028 (2)	0.032 (2)	−0.0079 (17)	−0.0069 (18)	0.0039 (17)
C4	0.029 (2)	0.0245 (18)	0.021 (2)	−0.0027 (16)	−0.0087 (16)	0.0008 (15)
N11	0.0157 (15)	0.0224 (15)	0.0174 (16)	−0.0012 (12)	−0.0062 (12)	−0.0043 (12)
N12	0.0211 (16)	0.0290 (17)	0.0291 (18)	0.0023 (13)	−0.0131 (14)	−0.0083 (14)
C11	0.0145 (17)	0.032 (2)	0.033 (2)	−0.0030 (15)	−0.0085 (16)	−0.0050 (17)
C12	0.0207 (19)	0.030 (2)	0.031 (2)	0.0018 (16)	−0.0031 (16)	−0.0047 (17)
C13	0.0249 (19)	0.028 (2)	0.021 (2)	−0.0026 (16)	0.0003 (15)	−0.0065 (16)
C14	0.0172 (17)	0.0242 (18)	0.0162 (19)	−0.0016 (14)	−0.0036 (14)	−0.0025 (14)
N21	0.0219 (16)	0.0263 (16)	0.0191 (18)	−0.0035 (13)	−0.0079 (14)	−0.0034 (13)
C21	0.035 (2)	0.028 (2)	0.018 (2)	−0.0030 (16)	−0.0129 (17)	−0.0034 (15)
N22	0.113 (4)	0.037 (2)	0.053 (3)	0.007 (2)	−0.065 (3)	−0.0054 (19)
C22	0.037 (2)	0.035 (2)	0.024 (2)	−0.0021 (19)	−0.0190 (18)	−0.0022 (17)
N23	0.059 (3)	0.050 (2)	0.043 (2)	0.020 (2)	−0.030 (2)	−0.0134 (19)

Geometric parameters (Å, º) top

Ni1—N21	2.058 (3)	C4—H4	0.9500
Ni1—N21ⁱ	2.058 (3)	N11—C14	1.333 (4)
Ni1—N11ⁱ	2.125 (3)	N11—N12	1.349 (4)
Ni1—N11	2.125 (3)	N12—C11	1.330 (5)
Ni1—N1ⁱ	2.147 (3)	C11—C12	1.399 (5)
Ni1—N1	2.147 (3)	C11—H11	0.9500
N1—C4	1.327 (5)	C12—C13	1.359 (5)
N1—N2	1.342 (4)	C12—H12	0.9500
N2—C1	1.336 (5)	C13—C14	1.410 (5)
C1—C2	1.394 (6)	C13—H13	0.9500
C1—H1	0.9500	C14—H14	0.9500
C2—C3	1.372 (6)	N21—C21	1.148 (5)
C2—H2	0.9500	C21—N22	1.308 (5)
C3—C4	1.385 (5)	N22—C22	1.304 (6)
C3—H3	0.9500	C22—N23	1.155 (6)

N21—Ni1—N21ⁱ	180.00 (8)	C2—C3—H3	121.2
N21—Ni1—N11ⁱ	89.44 (11)	C4—C3—H3	121.2
N21ⁱ—Ni1—N11ⁱ	90.56 (11)	N1—C4—C3	123.2 (3)
N21—Ni1—N11	90.56 (11)	N1—C4—H4	118.4
N21ⁱ—Ni1—N11	89.44 (11)	C3—C4—H4	118.4
N11ⁱ—Ni1—N11	180.0	C14—N11—N12	120.5 (3)
N21—Ni1—N1ⁱ	88.23 (11)	C14—N11—Ni1	124.5 (2)
N21ⁱ—Ni1—N1ⁱ	91.77 (11)	N12—N11—Ni1	115.0 (2)
N11ⁱ—Ni1—N1ⁱ	87.48 (11)	C11—N12—N11	118.6 (3)
N11—Ni1—N1ⁱ	92.52 (10)	N12—C11—C12	123.7 (3)
N21—Ni1—N1	91.77 (11)	N12—C11—H11	118.1
N21ⁱ—Ni1—N1	88.23 (11)	C12—C11—H11	118.1
N11ⁱ—Ni1—N1	92.52 (10)	C13—C12—C11	117.3 (3)
N11—Ni1—N1	87.48 (11)	C13—C12—H12	121.3
N1ⁱ—Ni1—N1	180.0	C11—C12—H12	121.3
C4—N1—N2	120.1 (3)	C12—C13—C14	117.9 (3)
C4—N1—Ni1	121.1 (2)	C12—C13—H13	121.0
N2—N1—Ni1	118.7 (2)	C14—C13—H13	121.0
C1—N2—N1	118.4 (3)	N11—C14—C13	121.9 (3)
N2—C1—C2	123.8 (3)	N11—C14—H14	119.1
N2—C1—H1	118.1	C13—C14—H14	119.1
C2—C1—H1	118.1	C21—N21—Ni1	173.1 (3)
C3—C2—C1	116.9 (3)	N21—C21—N22	173.1 (4)
C3—C2—H2	121.6	C22—N22—C21	122.1 (4)
C1—C2—H2	121.6	N23—C22—N22	171.8 (4)
C2—C3—C4	117.6 (4)

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Ni(C₂N₃)₂(C₄H₄N₂)₄]
M_r	511.18
Crystal system, space group	Triclinic, P1
Temperature (K)	170
a, b, c (Å)	8.1796 (12), 8.4125 (12), 8.9643 (11)
α, β, γ (°)	81.364 (16), 66.027 (15), 84.879 (17)
V (Å³)	556.97 (13)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.10 × 0.08 × 0.06

Data collection
Diffractometer	Stoe IPDS1 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)
T_min, T_max	0.783, 0.927
No. of measured, independent and observed [I > 2σ(I)] reflections	4159, 2142, 1582
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.097, 1.01
No. of reflections	2142
No. of parameters	161
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.52

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011)., XCIF in SHELXTL (Sheldrick, 2008).

Acknowledgements

We gratefully acknowledge financial support by the DFG (project No. NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

References

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Wriedt, M. & Näther, C. (2011). Dalton Trans. 40, 886–898. Web of Science CSD CrossRef CAS PubMed Google Scholar