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The title compound, [NiCl2(C6H8N2)2], contains centrosymmetric mol­ecules with two phenyl­ene­di­amine ligands coordinated in a bidentate fashion. The Ni-N distances are 2.088 (1) and 2.096 (1) Å, and the Ni-Cl distance of 2.4635 (4) Å. The plane of each phenyl­enedi­amine mol­ecule makes a dihedral angle of 26.53 (7)° with the NiN4 plane. Extensive hydrogen bonding leads to distinct cleavage in the bc plane.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012476/qa0378sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012476/qa0378Isup2.hkl
Contains datablock I

CCDC reference: 152663

Comment top

The title compound, (I), was prepared for use as a starting material in the synthesis of Haldane Gap systems (Haldane, 1983). The latter can be realised by linear-chain systems of antiferromagnetically coupled S = 1 species.

Experimental top

The title compound was prepared by the reaction of 1,2-phenylenediamine dihydrochloride (0.989 g, 5.46 mmol) with NiCl2·6H2O (0.386 g, 2.00 mmol) in water (30 ml) under a nitrogen atmosphere for 5 d. The solution was then stored in a sealed tube at room temperature. After 8 d, brown rod-shaped crystals had formed. They were removed by filtration and washed with cold water.

Computing details top

Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

(I) top
Crystal data top
[NiCl2(C6H8N2)2]F(000) = 356
Mr = 345.90Dx = 1.546 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.3793 (2) ÅCell parameters from 4572 reflections
b = 5.9240 (1) Åθ = 2.0–28.2°
c = 12.1901 (1) ŵ = 1.66 mm1
β = 115.31°T = 213 K
V = 742.84 (2) Å3Block, green
Z = 20.35 × 0.20 × 0.15 mm
Data collection top
CCD
diffractometer
1758 independent reflections
Radiation source: fine-focus sealed tube1702 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 28.2°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 1996)
h = 1510
Tmin = 0.650, Tmax = 0.780k = 77
4572 measured reflectionsl = 1516
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)] = 0.023All H-atom parameters refined
wR(F2) = 0.057 w = 1/[σ2(Fo2) + (0.0134P)2 + 0.3976P]
where P = (Fo2 + 2Fc2)/3
S = 1.22(Δ/σ)max = 0.001
1758 reflectionsΔρmax = 0.25 e Å3
121 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0137 (12)
Crystal data top
[NiCl2(C6H8N2)2]V = 742.84 (2) Å3
Mr = 345.90Z = 2
Monoclinic, P21/cMo Kα radiation
a = 11.3793 (2) ŵ = 1.66 mm1
b = 5.9240 (1) ÅT = 213 K
c = 12.1901 (1) Å0.35 × 0.20 × 0.15 mm
β = 115.31°
Data collection top
CCD
diffractometer
1758 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 1996)
1702 reflections with I > 2σ(I)
Tmin = 0.650, Tmax = 0.780Rint = 0.022
4572 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.057All H-atom parameters refined
S = 1.22Δρmax = 0.25 e Å3
1758 reflectionsΔρmin = 0.19 e Å3
121 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
Ni0.00000.00000.50000.02065 (10)
N10.15376 (14)0.1992 (2)0.50529 (12)0.0256 (3)
C10.24839 (15)0.2187 (3)0.63023 (14)0.0258 (3)
C60.33793 (17)0.3950 (3)0.67172 (17)0.0328 (4)
Cl10.06884 (5)0.29160 (7)0.60437 (4)0.03327 (12)
N20.14354 (14)0.1131 (2)0.66630 (12)0.0249 (3)
C40.41579 (18)0.2542 (4)0.87636 (18)0.0412 (4)
C20.24329 (15)0.0582 (3)0.71265 (14)0.0254 (3)
C30.32741 (17)0.0765 (3)0.83549 (15)0.0334 (4)
C50.42118 (19)0.4133 (4)0.79457 (19)0.0411 (4)
H20.473 (2)0.270 (4)0.961 (2)0.053 (7)*
H60.342 (2)0.504 (3)0.616 (2)0.036 (6)*
H2B0.173 (2)0.236 (4)0.651 (2)0.040 (6)*
H1B0.131 (2)0.335 (4)0.4713 (19)0.038 (6)*
H2A0.119 (2)0.153 (4)0.721 (2)0.040 (6)*
H30.318 (2)0.032 (3)0.8894 (19)0.035 (5)*
H50.480 (2)0.534 (4)0.820 (2)0.046 (6)*
H1A0.184 (2)0.125 (4)0.462 (2)0.041 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.02621 (15)0.01932 (15)0.01932 (14)0.00204 (10)0.01250 (11)0.00226 (10)
N10.0322 (7)0.0232 (7)0.0252 (6)0.0017 (6)0.0160 (6)0.0039 (5)
C10.0253 (7)0.0268 (8)0.0283 (8)0.0042 (6)0.0145 (6)0.0018 (6)
C60.0299 (8)0.0328 (9)0.0390 (9)0.0003 (7)0.0179 (7)0.0019 (8)
Cl10.0536 (3)0.0254 (2)0.0309 (2)0.01126 (17)0.02775 (19)0.00333 (15)
N20.0324 (7)0.0227 (7)0.0231 (6)0.0039 (6)0.0153 (6)0.0039 (5)
C40.0307 (9)0.0552 (12)0.0314 (9)0.0010 (8)0.0072 (7)0.0037 (8)
C20.0256 (7)0.0277 (8)0.0262 (7)0.0052 (6)0.0142 (6)0.0022 (6)
C30.0300 (8)0.0428 (10)0.0269 (8)0.0051 (7)0.0116 (7)0.0038 (7)
C50.0307 (9)0.0445 (11)0.0456 (11)0.0071 (8)0.0138 (8)0.0083 (9)
Geometric parameters (Å, º) top
Ni—N1i2.0883 (14)C1—C61.394 (2)
Ni—N12.0883 (14)C1—C21.402 (2)
Ni—N2i2.0964 (13)C6—C51.392 (3)
Ni—N22.0964 (13)N2—C21.445 (2)
Ni—Cl1i2.4635 (4)C4—C31.393 (3)
Ni—Cl12.4635 (4)C4—C51.392 (3)
N1—C11.446 (2)C2—C31.394 (2)
N1i—Ni—N1180.0Cl1i—Ni—Cl1180.0
N1i—Ni—N2i81.64 (5)C1—N1—Ni108.34 (10)
N1—Ni—N2i98.36 (5)C6—C1—C2119.71 (15)
N1i—Ni—N298.36 (5)C6—C1—N1122.80 (15)
N1—Ni—N281.64 (5)C2—C1—N1117.39 (14)
N2i—Ni—N2180.00 (6)C5—C6—C1120.26 (17)
N1i—Ni—Cl1i92.01 (4)C2—N2—Ni108.09 (10)
N1—Ni—Cl1i87.99 (4)C3—C4—C5120.11 (17)
N2i—Ni—Cl1i90.75 (4)C3—C2—C1119.80 (16)
N2—Ni—Cl1i89.25 (4)C3—C2—N2122.55 (15)
N1i—Ni—Cl187.99 (4)C1—C2—N2117.53 (14)
N1—Ni—Cl192.01 (4)C4—C3—C2120.14 (17)
N2i—Ni—Cl189.25 (4)C6—C5—C4119.97 (18)
N2—Ni—Cl190.75 (4)
Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formula[NiCl2(C6H8N2)2]
Mr345.90
Crystal system, space groupMonoclinic, P21/c
Temperature (K)213
a, b, c (Å)11.3793 (2), 5.9240 (1), 12.1901 (1)
β (°) 115.31
V3)742.84 (2)
Z2
Radiation typeMo Kα
µ (mm1)1.66
Crystal size (mm)0.35 × 0.20 × 0.15
Data collection
DiffractometerCCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Bruker, 1996)
Tmin, Tmax0.650, 0.780
No. of measured, independent and
observed [I > 2σ(I)] reflections
4572, 1758, 1702
Rint0.022
(sin θ/λ)max1)0.665
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.057, 1.22
No. of reflections1758
No. of parameters121
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.25, 0.19

Computer programs: SMART (Bruker, 1996), SAINT (Bruker, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.

 

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