metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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 NiII 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[Wriedt, M. & Näther, C. (2011). Dalton Trans. 40, 886-898.]).

[Scheme 1]

Experimental

Crystal data
  • [Ni(C2N3)2(C4H4N2)4]

  • Mr = 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[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]) Tmin = 0.783, Tmax = 0.927

  • 4159 measured reflections

  • 2142 independent reflections

  • 1582 reflections with I > 2σ(I)

  • Rint = 0.068

Refinement
  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 0.097

  • S = 1.01

  • 2142 reflections

  • 161 parameters

  • H-atom parameters constrained

  • Δρmax = 0.51 e Å−3

  • Δρmin = −0.52 e Å−3

Data collection: X-AREA (Stoe & Cie, 2008[Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 2011[Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.]).; software used to prepare material for publication: XCIF in SHELXTL.

Supporting information


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.

Refinement top

All H atoms were located in difference map but were positioned with idealized geometry and were refined isotropically with Ueq(H) = 1.2 Ueq(C) of the parent atom using a riding model with C—H = 0.95 Å.

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
[Figure 1] 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
Mr = 511.18F(000) = 262
Triclinic, P1Dx = 1.524 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.1796 (12) ÅCell parameters from 4159 reflections
b = 8.4125 (12) Åθ = 2.5–26.0°
c = 8.9643 (11) ŵ = 0.91 mm1
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 tube1582 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.068
phi scanθmax = 26.0°, θmin = 2.5°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 1010
Tmin = 0.783, Tmax = 0.927k = 1010
4159 measured reflectionsl = 1111
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.097 w = 1/[σ2(Fo2) + (0.0348P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2142 reflectionsΔρmax = 0.51 e Å3
161 parametersΔρmin = 0.52 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.025 (4)
Crystal data top
[Ni(C2N3)2(C4H4N2)4]γ = 84.879 (17)°
Mr = 511.18V = 556.97 (13) Å3
Triclinic, P1Z = 1
a = 8.1796 (12) ÅMo Kα radiation
b = 8.4125 (12) ŵ = 0.91 mm1
c = 8.9643 (11) ÅT = 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)
Tmin = 0.783, Tmax = 0.927Rint = 0.068
4159 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.01Δρmax = 0.51 e Å3
2142 reflectionsΔρmin = 0.52 e Å3
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
xyzUiso*/Ueq
Ni10.00000.50000.50000.0161 (2)
N10.1088 (4)0.7246 (3)0.4952 (4)0.0190 (6)
N20.0726 (4)0.7802 (4)0.6384 (4)0.0249 (7)
C10.1491 (5)0.9151 (5)0.6353 (5)0.0295 (9)
H10.12040.95570.73660.035*
C20.2687 (6)0.9998 (5)0.4919 (6)0.0336 (10)
H20.32281.09410.49450.040*
C30.3045 (6)0.9406 (5)0.3470 (5)0.0333 (9)
H30.38530.99200.24490.040*
C40.2185 (5)0.8030 (4)0.3549 (5)0.0254 (8)
H40.23910.76280.25500.031*
N110.2622 (4)0.4283 (3)0.3430 (4)0.0184 (6)
N120.3917 (4)0.4485 (4)0.3946 (4)0.0250 (7)
C110.5593 (5)0.4051 (5)0.3036 (5)0.0264 (8)
H110.65030.42270.33900.032*
C120.6091 (5)0.3350 (5)0.1588 (5)0.0295 (9)
H120.72980.30300.09840.035*
C130.4777 (5)0.3144 (4)0.1079 (5)0.0273 (8)
H130.50350.26690.01070.033*
C140.3019 (4)0.3658 (4)0.2037 (4)0.0201 (7)
H140.20920.35560.16800.024*
N210.0470 (4)0.4009 (4)0.7037 (4)0.0223 (7)
C210.0896 (5)0.3404 (4)0.8065 (5)0.0263 (8)
N220.1310 (7)0.2874 (5)0.9320 (5)0.0581 (13)
C220.1948 (5)0.1418 (5)0.9515 (5)0.0300 (9)
N230.2467 (6)0.0160 (5)0.9879 (5)0.0480 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0151 (4)0.0195 (4)0.0144 (4)0.0010 (3)0.0066 (3)0.0020 (3)
N10.0177 (14)0.0215 (15)0.0193 (16)0.0027 (12)0.0090 (12)0.0047 (12)
N20.0227 (16)0.0314 (17)0.0223 (17)0.0058 (13)0.0082 (13)0.0083 (13)
C10.032 (2)0.029 (2)0.033 (2)0.0018 (17)0.0151 (18)0.0137 (17)
C20.037 (2)0.0228 (19)0.047 (3)0.0085 (17)0.021 (2)0.0029 (18)
C30.033 (2)0.028 (2)0.032 (2)0.0079 (17)0.0069 (18)0.0039 (17)
C40.029 (2)0.0245 (18)0.021 (2)0.0027 (16)0.0087 (16)0.0008 (15)
N110.0157 (15)0.0224 (15)0.0174 (16)0.0012 (12)0.0062 (12)0.0043 (12)
N120.0211 (16)0.0290 (17)0.0291 (18)0.0023 (13)0.0131 (14)0.0083 (14)
C110.0145 (17)0.032 (2)0.033 (2)0.0030 (15)0.0085 (16)0.0050 (17)
C120.0207 (19)0.030 (2)0.031 (2)0.0018 (16)0.0031 (16)0.0047 (17)
C130.0249 (19)0.028 (2)0.021 (2)0.0026 (16)0.0003 (15)0.0065 (16)
C140.0172 (17)0.0242 (18)0.0162 (19)0.0016 (14)0.0036 (14)0.0025 (14)
N210.0219 (16)0.0263 (16)0.0191 (18)0.0035 (13)0.0079 (14)0.0034 (13)
C210.035 (2)0.028 (2)0.018 (2)0.0030 (16)0.0129 (17)0.0034 (15)
N220.113 (4)0.037 (2)0.053 (3)0.007 (2)0.065 (3)0.0054 (19)
C220.037 (2)0.035 (2)0.024 (2)0.0021 (19)0.0190 (18)0.0022 (17)
N230.059 (3)0.050 (2)0.043 (2)0.020 (2)0.030 (2)0.0134 (19)
Geometric parameters (Å, º) top
Ni1—N212.058 (3)C4—H40.9500
Ni1—N21i2.058 (3)N11—C141.333 (4)
Ni1—N11i2.125 (3)N11—N121.349 (4)
Ni1—N112.125 (3)N12—C111.330 (5)
Ni1—N1i2.147 (3)C11—C121.399 (5)
Ni1—N12.147 (3)C11—H110.9500
N1—C41.327 (5)C12—C131.359 (5)
N1—N21.342 (4)C12—H120.9500
N2—C11.336 (5)C13—C141.410 (5)
C1—C21.394 (6)C13—H130.9500
C1—H10.9500C14—H140.9500
C2—C31.372 (6)N21—C211.148 (5)
C2—H20.9500C21—N221.308 (5)
C3—C41.385 (5)N22—C221.304 (6)
C3—H30.9500C22—N231.155 (6)
N21—Ni1—N21i180.00 (8)C2—C3—H3121.2
N21—Ni1—N11i89.44 (11)C4—C3—H3121.2
N21i—Ni1—N11i90.56 (11)N1—C4—C3123.2 (3)
N21—Ni1—N1190.56 (11)N1—C4—H4118.4
N21i—Ni1—N1189.44 (11)C3—C4—H4118.4
N11i—Ni1—N11180.0C14—N11—N12120.5 (3)
N21—Ni1—N1i88.23 (11)C14—N11—Ni1124.5 (2)
N21i—Ni1—N1i91.77 (11)N12—N11—Ni1115.0 (2)
N11i—Ni1—N1i87.48 (11)C11—N12—N11118.6 (3)
N11—Ni1—N1i92.52 (10)N12—C11—C12123.7 (3)
N21—Ni1—N191.77 (11)N12—C11—H11118.1
N21i—Ni1—N188.23 (11)C12—C11—H11118.1
N11i—Ni1—N192.52 (10)C13—C12—C11117.3 (3)
N11—Ni1—N187.48 (11)C13—C12—H12121.3
N1i—Ni1—N1180.0C11—C12—H12121.3
C4—N1—N2120.1 (3)C12—C13—C14117.9 (3)
C4—N1—Ni1121.1 (2)C12—C13—H13121.0
N2—N1—Ni1118.7 (2)C14—C13—H13121.0
C1—N2—N1118.4 (3)N11—C14—C13121.9 (3)
N2—C1—C2123.8 (3)N11—C14—H14119.1
N2—C1—H1118.1C13—C14—H14119.1
C2—C1—H1118.1C21—N21—Ni1173.1 (3)
C3—C2—C1116.9 (3)N21—C21—N22173.1 (4)
C3—C2—H2121.6C22—N22—C21122.1 (4)
C1—C2—H2121.6N23—C22—N22171.8 (4)
C2—C3—C4117.6 (4)
Symmetry code: (i) x, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Ni(C2N3)2(C4H4N2)4]
Mr511.18
Crystal system, space groupTriclinic, 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)
V3)556.97 (13)
Z1
Radiation typeMo Kα
µ (mm1)0.91
Crystal size (mm)0.10 × 0.08 × 0.06
Data collection
DiffractometerStoe IPDS1
diffractometer
Absorption correctionNumerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
Tmin, Tmax0.783, 0.927
No. of measured, independent and
observed [I > 2σ(I)] reflections
4159, 2142, 1582
Rint0.068
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.097, 1.01
No. of reflections2142
No. of parameters161
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds