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The title complexes, [Ni(C11H14ClN2O)(NCS)], (I), and [Ni(C11H14ClN2O)(N3)]n, (II), are two different structures constructed from the same Schiff base ligand, viz. 4-chloro-2-[2-(dimethyl­amino)­ethyl­imino­meth­yl]­phenol, and different linear triatomic secondary ligands, viz. thio­cyanate for (I) and azide for (II). In mononuclear (I), the NiII atom is four-coordinated in a square-planar geometry by the N,N′,O-donor set of the Schiff base and by the N atom of the terminal thio­cyanate ligand, while in polynuclear (II), the NiII atom is five-coordinated in a square-pyramidal geometry by the N,N′,O-donor set of the Schiff base and by two N atoms from two bridging azide groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106003118/hj3001sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106003118/hj3001Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106003118/hj3001IIsup3.hkl
Contains datablock b

CCDC references: 603182; 603183

Comment top

Transition metal complexes containing bridging ligands are currentlt attracting attention because of their interesting molecular topologies and crystal-packing motifs, as well as the fact that they may be designed with specific functionalities (Mukherjee et al., 2001; Meyer & Pritzkow, 2001; Goher et al., 2002). The prime strategy for designing these polynuclear materials is to use suitable bridging ligands (Koner et al., 2003). Owing to the coordination modes of the thiocyanate and azide anions, these ligands make good bridging groups. However, to the present state of our knowledge, it is hardly possible to determine which coordination mode will be adopted by the thiocyanate or azide anion and whether the sought-after alternating structure will be formed (Bhaduri et al., 2003; Romero et al., 2002; Tercero et al., 2002; Ribas et al., 1999).

In the present paper, the tridentate Schiff base ligand 4-chloro-2-[(2-dimethylaminoethylimino)methyl]phenol was used as the first ligand. The reason we use this ligand is that it can adopt an almost fixed coordination mode through the three N– and O-donor atoms (You & Zhu, 2005; You, 2005). The secondary ligand, viz. thiocyanate or azide, is a well known bridging group. It readily bridges different metal ions through the donor atoms, forming polynuclear complexes. The author reports here two complexes, [Ni(C11H14ClN2O)(NCS)], (I), and [Ni(C11H14ClN2O)(N3)]n, (II). The azide anion acts as a bridging ligand in (II) and ligates two different metal atoms through the same teminal N atom (Fig. 1). This contrasts with the monomeric structure, (I), where the thiocyanate coordinates to a single Ni atom (Fig. 2).

In (I), the Ni atom is four-coordinated in a square-planar geometry by the NNO-donor set of the Schiff base and by the N atom of the thiocyanate ligand. In (II), each repeated unit contains one [Ni(C11H14ClN2O)]+ cation and one bridging azide anion. The Ni atom in (II) is five-coordinated in a square-pyramidal geometry by the NNO-donor set of the Schiff base and by two N atoms from two bridging azide groups.

In (II), all the bond lengths subtended at atom Ni1 are longer than those observed in (I) (Table 1). The coordination of the bridging N atom at the apical position of the Ni atom in (II) leads to the deviation of the metal from the basal donor atoms by 0.070 (2) Å, while in (I), the Ni atom lies nearly in the square plane, with a deviation of 0.009 (2) Å. In each of the complexes, the bond lengths subtended at the metal atoms are within normal ranges and, as expected, the bonds involving the pyridine N atoms are longer than those involving the imine N atoms.

The terminal thiocyanate group always adopts a nearly linear coordination mode to metal ions through the terminal N atom (Moore & Squattrito, 1999; Mondal et al., 2001), while the bridging azide group easily adopts a bent coordination mode to metal ions through one of the terminal N atoms (Zhang et al., 2000). In this paper, the terminal thiocyanate ligand in (I) is nearly linear and shows also a nearly linear coordination mode with the metal atom [the N3—C12—S1 and Ni1—N3—C12 angles are 179.7 (3) and 168.1 (3)°, respectively], while the bridging azide ligand in (II) is also nearly linear but shows a bent coordination mode with the metal atoms [the N3—N4—N5, Ni1—N3—N4 and Ni1i—N3—N4 angles are 177.6 (2), 117.80 (13) and 113.12 (13)°, respectively; symmetry code: (i) x − 1/2, −y + 1/2, −z + 1].

In conclusion, the similar small ligands used as the secondary ligand in the preparation of the title complexes severely influence the final structures.

Experimental top

For the preparation of complex (I), 5-chloro-2-hydroxybenzaldehyde (0.1 mmol, 15.6 mg) and N,N-dimethylethane-1,2-diamine (0.1 mmol, 8.8 mg) were dissolved in methanol (10 ml). The mixture was stirred at room temperature for about 10 min to give a clear yellow solution, to which was added an aqueous solution (2 ml) of NH4NCS (0.1 mmol, 7.6 mg) and a methanol solution (5 ml) of Ni(CH3COO)2·4H2O (0.1 mmol, 24.9 mg) with stirring. The mixture was stirred for another 10 min at room temperature. After the filtrate had been kept in air for 3 d, green needle-shaped crystals were formed. Complex (II) was prepared by a procedure similar to that described for (I), with NH4NCS replaced by NaN3 (0.1 mmol, 6.5 mg). Green block-shaped crystals of (II) were obtained after evaporating the solvents from the filtrate in air for 8 d.

Refinement top

All H atoms in (I) and (II) were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) values of 1.2 or 1.5 times Ueq(C). The C9H2, C10H3 and C11H3 groups in (I) were disordered over two distinct sites, with occupancies of 0.492 (3) and 0.508 (3). The C—C and C—N distances of the disordered groups were restrained to 1.53 (1) and 1.46 (1) Å, respectively.

Computing details top

For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Only the major components of the disordered moiety (C8–C11/N2) is shown.
[Figure 2] Fig. 2. The structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labeled with the suffixes A and B are at the symmetry positions (x − 1/2, −y + 1/2, −z + 1) and (x + 1/2, −y + 1/2, −z + 1), respectively. H atoms have been omitted.
(I) {4-chloro-2-[2-(dimethylamino)ethyliminomethyl]phenolato}thiocyanatonickel(II) top
Crystal data top
[Ni(C11H14ClN2O)(NCS)]F(000) = 704
Mr = 342.48Dx = 1.576 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.980 (1) ÅCell parameters from 2348 reflections
b = 10.936 (2) Åθ = 2.3–25.4°
c = 18.955 (3) ŵ = 1.67 mm1
β = 93.901 (2)°T = 298 K
V = 1443.6 (4) Å3Needle, green
Z = 40.22 × 0.12 × 0.08 mm
Data collection top
Bruker SMART APEX area-detector
diffractometer
3293 independent reflections
Radiation source: fine-focus sealed tube2526 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 99
Tmin = 0.711, Tmax = 0.878k = 1414
12176 measured reflectionsl = 2324
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0528P)2 + 0.4314P]
where P = (Fo2 + 2Fc2)/3
3293 reflections(Δ/σ)max < 0.001
204 parametersΔρmax = 0.35 e Å3
14 restraintsΔρmin = 0.38 e Å3
Crystal data top
[Ni(C11H14ClN2O)(NCS)]V = 1443.6 (4) Å3
Mr = 342.48Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.980 (1) ŵ = 1.67 mm1
b = 10.936 (2) ÅT = 298 K
c = 18.955 (3) Å0.22 × 0.12 × 0.08 mm
β = 93.901 (2)°
Data collection top
Bruker SMART APEX area-detector
diffractometer
3293 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
2526 reflections with I > 2σ(I)
Tmin = 0.711, Tmax = 0.878Rint = 0.043
12176 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04514 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.03Δρmax = 0.35 e Å3
3293 reflectionsΔρmin = 0.38 e Å3
204 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*/UeqOcc. (<1)
Ni10.26818 (6)0.84248 (4)0.31685 (2)0.03870 (15)
Cl10.21309 (15)1.17273 (9)0.64156 (5)0.0589 (3)
S10.17535 (18)0.95182 (10)0.08135 (5)0.0670 (3)
O10.2580 (3)0.9998 (2)0.35102 (11)0.0459 (5)
N10.2937 (4)0.7710 (2)0.40486 (13)0.0413 (6)
N20.2772 (5)0.6768 (2)0.27882 (15)0.0518 (7)
N30.2388 (5)0.9070 (3)0.22490 (15)0.0554 (8)
C10.2615 (4)0.9523 (3)0.47462 (15)0.0337 (6)
C20.2506 (4)1.0343 (3)0.41686 (16)0.0372 (7)
C30.2300 (5)1.1586 (3)0.43193 (19)0.0472 (8)
H30.22401.21430.39480.057*
C40.2185 (5)1.2012 (3)0.49960 (19)0.0491 (8)
H40.20371.28430.50790.059*
C50.2291 (4)1.1189 (3)0.55558 (16)0.0409 (7)
C60.2504 (4)0.9972 (3)0.54399 (16)0.0384 (7)
H60.25780.94320.58200.046*
C70.2849 (5)0.8250 (3)0.46474 (16)0.0408 (7)
H70.29480.77640.50510.049*
C120.2125 (5)0.9260 (3)0.16522 (18)0.0472 (8)
C80.3243 (8)0.6397 (3)0.4040 (2)0.0770 (13)
H8A0.42310.61770.44030.092*
H8B0.20680.59800.41430.092*
C90.3815 (17)0.6020 (7)0.3364 (3)0.056 (3)0.492 (15)
H9A0.35220.51600.32920.067*0.492 (15)
H9B0.51900.61270.33440.067*0.492 (15)
C100.425 (4)0.657 (3)0.2286 (18)0.089 (11)0.492 (15)
H10A0.45000.57060.22480.133*0.492 (15)
H10B0.54120.69790.24520.133*0.492 (15)
H10C0.38160.68830.18310.133*0.492 (15)
C110.091 (3)0.646 (2)0.243 (2)0.087 (10)0.492 (15)
H11A0.10630.57820.21120.131*0.492 (15)
H11B0.04170.71500.21620.131*0.492 (15)
H11C0.00210.62340.27710.131*0.492 (15)
C9'0.241 (2)0.5917 (6)0.3375 (3)0.063 (3)0.508 (15)
H9'A0.10380.58090.34020.075*0.508 (15)
H9'B0.29680.51250.32840.075*0.508 (15)
C10'0.440 (4)0.660 (3)0.2342 (16)0.074 (9)0.508 (15)
H10D0.42810.58320.21010.111*0.508 (15)
H10E0.55820.66180.26340.111*0.508 (15)
H10F0.44070.72520.20010.111*0.508 (15)
C11'0.106 (4)0.640 (3)0.234 (2)0.098 (10)0.508 (15)
H11D0.09780.55230.23280.147*0.508 (15)
H11E0.11510.67080.18710.147*0.508 (15)
H11F0.00700.67250.25360.147*0.508 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0440 (3)0.0414 (3)0.0306 (2)0.00188 (18)0.00186 (16)0.00263 (17)
Cl10.0691 (6)0.0627 (6)0.0459 (5)0.0018 (5)0.0119 (4)0.0157 (4)
S10.1067 (9)0.0628 (6)0.0311 (5)0.0050 (6)0.0020 (5)0.0014 (4)
O10.0670 (15)0.0421 (13)0.0285 (11)0.0037 (11)0.0020 (10)0.0002 (9)
N10.0533 (16)0.0345 (14)0.0360 (15)0.0026 (12)0.0022 (12)0.0021 (11)
N20.072 (2)0.0434 (17)0.0405 (17)0.0040 (15)0.0050 (15)0.0076 (13)
N30.075 (2)0.0547 (19)0.0358 (16)0.0007 (16)0.0007 (14)0.0031 (14)
C10.0305 (15)0.0379 (16)0.0325 (15)0.0030 (12)0.0010 (12)0.0009 (13)
C20.0353 (16)0.0401 (17)0.0353 (16)0.0022 (13)0.0044 (13)0.0000 (14)
C30.058 (2)0.0386 (18)0.0441 (19)0.0002 (15)0.0009 (15)0.0052 (15)
C40.054 (2)0.0392 (18)0.053 (2)0.0009 (16)0.0023 (17)0.0072 (16)
C50.0366 (17)0.0502 (19)0.0362 (17)0.0034 (14)0.0044 (13)0.0088 (15)
C60.0368 (16)0.0462 (19)0.0322 (15)0.0026 (14)0.0026 (12)0.0008 (13)
C70.0521 (19)0.0385 (18)0.0315 (16)0.0032 (14)0.0001 (14)0.0047 (13)
C120.063 (2)0.0392 (18)0.0396 (19)0.0002 (16)0.0065 (16)0.0065 (15)
C80.133 (4)0.039 (2)0.058 (3)0.009 (2)0.002 (3)0.0028 (18)
C90.072 (7)0.041 (4)0.056 (5)0.001 (4)0.015 (4)0.007 (4)
C100.064 (14)0.09 (2)0.11 (2)0.006 (11)0.003 (12)0.028 (17)
C110.052 (10)0.053 (10)0.16 (2)0.020 (7)0.021 (12)0.069 (13)
C9'0.095 (9)0.041 (4)0.055 (5)0.015 (5)0.027 (5)0.007 (4)
C10'0.048 (10)0.089 (19)0.086 (14)0.017 (10)0.014 (9)0.056 (14)
C11'0.055 (11)0.12 (2)0.119 (16)0.019 (10)0.025 (11)0.063 (16)
Geometric parameters (Å, º) top
Ni1—N11.840 (3)C5—C61.359 (4)
Ni1—O11.842 (2)C6—H60.9300
Ni1—N31.879 (3)C7—H70.9300
Ni1—N21.953 (3)C8—C91.429 (7)
Cl1—C51.744 (3)C8—C9'1.451 (7)
S1—C121.618 (4)C8—H8A0.9700
O1—C21.308 (4)C8—H8B0.9700
N1—C71.285 (4)C9—H9A0.9700
N1—C81.452 (4)C9—H9B0.9700
N2—C101.468 (9)C10—H10A0.9600
N2—C111.469 (9)C10—H10B0.9600
N2—C11'1.473 (9)C10—H10C0.9600
N2—C10'1.475 (8)C11—H11A0.9600
N2—C9'1.484 (7)C11—H11B0.9600
N2—C91.511 (7)C11—H11C0.9600
N3—C121.153 (4)C9'—H9'A0.9700
C1—C61.410 (4)C9'—H9'B0.9700
C1—C21.413 (4)C10'—H10D0.9600
C1—C71.415 (4)C10'—H10E0.9600
C2—C31.399 (4)C10'—H10F0.9600
C3—C41.372 (5)C11'—H11D0.9600
C3—H30.9300C11'—H11E0.9600
C4—C51.389 (5)C11'—H11F0.9600
C4—H40.9300
N1—Ni1—O194.70 (10)C5—C6—H6119.8
N1—Ni1—N3176.86 (12)C1—C6—H6119.8
O1—Ni1—N388.34 (12)N1—C7—C1125.6 (3)
N1—Ni1—N286.38 (12)N1—C7—H7117.2
O1—Ni1—N2178.89 (11)C1—C7—H7117.2
N3—Ni1—N290.58 (12)N3—C12—S1179.7 (3)
C2—O1—Ni1127.6 (2)C9—C8—N1110.2 (4)
C7—N1—C8118.7 (3)C9'—C8—N1108.4 (4)
C7—N1—Ni1126.7 (2)C9—C8—H8A109.6
C8—N1—Ni1114.6 (2)C9'—C8—H8A138.6
C10—N2—C11108 (2)N1—C8—H8A109.6
C10—N2—C11'100 (2)C9—C8—H8B109.6
C11—N2—C10'114 (2)C9'—C8—H8B73.1
C11'—N2—C10'105 (2)N1—C8—H8B109.6
C10—N2—C9'123.6 (16)H8A—C8—H8B108.1
C11—N2—C9'90.7 (16)C8—C9—N2110.0 (5)
C11'—N2—C9'94.9 (18)C8—C9—H9A109.7
C10'—N2—C9'122.0 (15)N2—C9—H9A109.7
C10—N2—C993.5 (17)C8—C9—H9B109.7
C11—N2—C9125.4 (14)N2—C9—H9B109.7
C11'—N2—C9126.8 (15)H9A—C9—H9B108.2
C10'—N2—C989.7 (15)N2—C10—H10A109.5
C10—N2—Ni1114.8 (14)N2—C10—H10B109.5
C11—N2—Ni1109.7 (11)N2—C10—H10C109.5
C11'—N2—Ni1114.9 (12)N2—C11—H11A109.5
C10'—N2—Ni1111.7 (12)N2—C11—H11B109.5
C9'—N2—Ni1107.1 (3)N2—C11—H11C109.5
C9—N2—Ni1105.2 (3)C8—C9'—N2110.2 (5)
C12—N3—Ni1168.1 (3)C8—C9'—H9'A109.6
C6—C1—C2119.9 (3)N2—C9'—H9'A109.6
C6—C1—C7118.7 (3)C8—C9'—H9'B109.6
C2—C1—C7121.5 (3)N2—C9'—H9'B109.6
O1—C2—C3119.1 (3)H9'A—C9'—H9'B108.1
O1—C2—C1123.6 (3)N2—C10'—H10D109.5
C3—C2—C1117.3 (3)N2—C10'—H10E109.5
C4—C3—C2122.3 (3)H10D—C10'—H10E109.5
C4—C3—H3118.9N2—C10'—H10F109.5
C2—C3—H3118.9H10D—C10'—H10F109.5
C3—C4—C5119.4 (3)H10E—C10'—H10F109.5
C3—C4—H4120.3N2—C11'—H11D109.5
C5—C4—H4120.3N2—C11'—H11E109.5
C6—C5—C4120.8 (3)H11D—C11'—H11E109.5
C6—C5—Cl1119.8 (3)N2—C11'—H11F109.5
C4—C5—Cl1119.5 (3)H11D—C11'—H11F109.5
C5—C6—C1120.3 (3)H11E—C11'—H11F109.5
(II) catena-poly[{4-chloro-2-[2- (dimethylamino)ethyliminomethyl]phenolato}nickel(II)]-µ-azido] top
Crystal data top
[Ni(C11H14ClN2O)(N3)]Dx = 1.569 Mg m3
Mr = 326.43Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 6155 reflections
a = 6.750 (1) Åθ = 2.5–26.9°
b = 19.893 (2) ŵ = 1.60 mm1
c = 20.585 (2) ÅT = 298 K
V = 2764.1 (6) Å3Block, green
Z = 80.20 × 0.19 × 0.10 mm
F(000) = 1344
Data collection top
Bruker SMART APEX area-detector
diffractometer
3166 independent reflections
Radiation source: fine-focus sealed tube2647 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 88
Tmin = 0.741, Tmax = 0.857k = 2525
22079 measured reflectionsl = 2626
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0353P)2 + 0.6214P]
where P = (Fo2 + 2Fc2)/3
3166 reflections(Δ/σ)max < 0.001
174 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
[Ni(C11H14ClN2O)(N3)]V = 2764.1 (6) Å3
Mr = 326.43Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 6.750 (1) ŵ = 1.60 mm1
b = 19.893 (2) ÅT = 298 K
c = 20.585 (2) Å0.20 × 0.19 × 0.10 mm
Data collection top
Bruker SMART APEX area-detector
diffractometer
3166 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
2647 reflections with I > 2σ(I)
Tmin = 0.741, Tmax = 0.857Rint = 0.033
22079 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.074H-atom parameters constrained
S = 1.07Δρmax = 0.38 e Å3
3166 reflectionsΔρmin = 0.21 e Å3
174 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
Ni10.94020 (3)0.190305 (11)0.485400 (11)0.03505 (9)
Cl10.57260 (8)0.05102 (3)0.71792 (3)0.05522 (15)
O10.94054 (19)0.17193 (7)0.57661 (6)0.0443 (3)
N10.8552 (2)0.09955 (7)0.46320 (7)0.0361 (3)
N20.9382 (2)0.20582 (8)0.38551 (8)0.0392 (4)
N31.0629 (2)0.27877 (8)0.50320 (8)0.0441 (4)
N40.9563 (2)0.32630 (9)0.50753 (8)0.0450 (4)
N50.8584 (3)0.37395 (11)0.51166 (11)0.0712 (6)
C10.7835 (2)0.06319 (8)0.57265 (9)0.0358 (4)
C20.8607 (3)0.12037 (9)0.60545 (9)0.0376 (4)
C30.8468 (3)0.12059 (10)0.67399 (9)0.0467 (5)
H30.89870.15690.69680.056*
C40.7601 (3)0.06952 (10)0.70788 (10)0.0466 (5)
H40.75270.07140.75300.056*
C50.6828 (3)0.01456 (9)0.67456 (9)0.0418 (4)
C60.6948 (3)0.01107 (9)0.60863 (9)0.0408 (4)
H60.64390.02620.58710.049*
C70.7893 (3)0.05572 (8)0.50330 (9)0.0378 (4)
H70.74130.01570.48610.045*
C80.8476 (3)0.08672 (9)0.39328 (9)0.0443 (4)
H8A0.74490.05420.38340.053*
H8B0.97350.06920.37810.053*
C90.8028 (3)0.15327 (10)0.36089 (9)0.0435 (4)
H9A0.81840.14890.31420.052*
H9B0.66680.16600.36970.052*
C101.1404 (3)0.19725 (11)0.35898 (11)0.0564 (6)
H10A1.18930.15350.37020.085*
H10B1.22610.23090.37700.085*
H10C1.13680.20180.31260.085*
C110.8645 (3)0.27248 (10)0.36505 (10)0.0521 (5)
H11A0.85150.27350.31860.078*
H11B0.95640.30660.37860.078*
H11C0.73780.28070.38470.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.04247 (15)0.03269 (14)0.03001 (14)0.00599 (9)0.00206 (9)0.00441 (9)
Cl10.0563 (3)0.0577 (3)0.0516 (3)0.0084 (2)0.0013 (2)0.0124 (2)
O10.0534 (8)0.0429 (7)0.0366 (7)0.0101 (6)0.0069 (6)0.0027 (6)
N10.0358 (8)0.0367 (8)0.0358 (8)0.0019 (6)0.0031 (6)0.0072 (6)
N20.0382 (8)0.0426 (8)0.0369 (8)0.0017 (6)0.0041 (6)0.0038 (7)
N30.0459 (10)0.0387 (9)0.0478 (9)0.0065 (7)0.0002 (7)0.0055 (7)
N40.0432 (10)0.0459 (10)0.0459 (10)0.0120 (8)0.0052 (7)0.0108 (7)
N50.0580 (12)0.0577 (12)0.0980 (17)0.0058 (11)0.0054 (11)0.0271 (11)
C10.0345 (9)0.0354 (9)0.0375 (9)0.0030 (7)0.0041 (7)0.0032 (7)
C20.0366 (9)0.0375 (9)0.0387 (10)0.0023 (8)0.0063 (8)0.0002 (8)
C30.0558 (12)0.0450 (11)0.0392 (10)0.0030 (9)0.0094 (9)0.0050 (8)
C40.0505 (11)0.0521 (11)0.0370 (10)0.0024 (9)0.0026 (8)0.0008 (9)
C50.0377 (10)0.0416 (10)0.0459 (11)0.0034 (8)0.0010 (8)0.0073 (8)
C60.0399 (10)0.0374 (9)0.0450 (10)0.0009 (8)0.0040 (8)0.0023 (8)
C70.0371 (10)0.0321 (9)0.0441 (10)0.0010 (8)0.0051 (8)0.0070 (7)
C80.0496 (11)0.0453 (11)0.0381 (10)0.0003 (9)0.0024 (9)0.0101 (8)
C90.0457 (11)0.0511 (11)0.0336 (9)0.0008 (9)0.0031 (8)0.0061 (8)
C100.0450 (12)0.0685 (15)0.0558 (13)0.0005 (10)0.0086 (10)0.0065 (11)
C110.0624 (13)0.0485 (12)0.0453 (11)0.0060 (10)0.0060 (10)0.0032 (9)
Geometric parameters (Å, º) top
Ni1—O11.913 (2)C3—H30.9300
Ni1—N11.949 (2)C4—C51.392 (3)
Ni1—N31.979 (2)C4—H40.9300
Ni1—N22.079 (2)C5—C61.361 (3)
Cl1—C51.747 (2)C6—H60.9300
O1—C21.302 (2)C7—H70.9300
N1—C71.280 (2)C8—C91.513 (3)
N1—C81.463 (2)C8—H8A0.9700
N2—C111.478 (2)C8—H8B0.9700
N2—C91.478 (2)C9—H9A0.9700
N2—C101.480 (3)C9—H9B0.9700
N3—N41.192 (2)C10—H10A0.9600
N4—N51.159 (3)C10—H10B0.9600
C1—C61.408 (3)C10—H10C0.9600
C1—C21.422 (2)C11—H11A0.9600
C1—C71.436 (3)C11—H11B0.9600
C2—C31.414 (3)C11—H11C0.9600
C3—C41.364 (3)
O1—Ni1—N193.07 (6)C4—C5—Cl1119.63 (15)
O1—Ni1—N389.30 (6)C5—C6—C1120.82 (17)
N1—Ni1—N3172.04 (7)C5—C6—H6119.6
O1—Ni1—N2177.50 (6)C1—C6—H6119.6
N1—Ni1—N284.48 (6)N1—C7—C1125.46 (16)
N3—Ni1—N293.08 (7)N1—C7—H7117.3
C2—O1—Ni1126.70 (12)C1—C7—H7117.3
C7—N1—C8120.23 (15)N1—C8—C9106.73 (14)
C7—N1—Ni1125.59 (12)N1—C8—H8A110.4
C8—N1—Ni1113.75 (12)C9—C8—H8A110.4
C11—N2—C9109.20 (15)N1—C8—H8B110.4
C11—N2—C10107.98 (16)C9—C8—H8B110.4
C9—N2—C10111.23 (15)H8A—C8—H8B108.6
C11—N2—Ni1114.66 (12)N2—C9—C8110.14 (15)
C9—N2—Ni1103.77 (11)N2—C9—H9A109.6
C10—N2—Ni1110.00 (13)C8—C9—H9A109.6
N4—N3—Ni1117.80 (13)N2—C9—H9B109.6
N5—N4—N3177.6 (2)C8—C9—H9B109.6
C6—C1—C2119.69 (17)H9A—C9—H9B108.1
C6—C1—C7117.29 (16)N2—C10—H10A109.5
C2—C1—C7123.01 (16)N2—C10—H10B109.5
O1—C2—C3118.69 (17)H10A—C10—H10B109.5
O1—C2—C1124.44 (17)N2—C10—H10C109.5
C3—C2—C1116.86 (17)H10A—C10—H10C109.5
C4—C3—C2122.44 (18)H10B—C10—H10C109.5
C4—C3—H3118.8N2—C11—H11A109.5
C2—C3—H3118.8N2—C11—H11B109.5
C3—C4—C5119.58 (19)H11A—C11—H11B109.5
C3—C4—H4120.2N2—C11—H11C109.5
C5—C4—H4120.2H11A—C11—H11C109.5
C6—C5—C4120.59 (18)H11B—C11—H11C109.5
C6—C5—Cl1119.78 (15)

Experimental details

(I)(II)
Crystal data
Chemical formula[Ni(C11H14ClN2O)(NCS)][Ni(C11H14ClN2O)(N3)]
Mr342.48326.43
Crystal system, space groupMonoclinic, P21/cOrthorhombic, Pbca
Temperature (K)298298
a, b, c (Å)6.980 (1), 10.936 (2), 18.955 (3)6.750 (1), 19.893 (2), 20.585 (2)
α, β, γ (°)90, 93.901 (2), 9090, 90, 90
V3)1443.6 (4)2764.1 (6)
Z48
Radiation typeMo KαMo Kα
µ (mm1)1.671.60
Crystal size (mm)0.22 × 0.12 × 0.080.20 × 0.19 × 0.10
Data collection
DiffractometerBruker SMART APEX area-detector
diffractometer
Bruker SMART APEX area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Multi-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.711, 0.8780.741, 0.857
No. of measured, independent and
observed [I > 2σ(I)] reflections
12176, 3293, 2526 22079, 3166, 2647
Rint0.0430.033
(sin θ/λ)max1)0.6500.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.113, 1.03 0.030, 0.074, 1.07
No. of reflections32933166
No. of parameters204174
No. of restraints140
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.380.38, 0.21

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.

Selected geometric parameters (Å, º) for (I) top
Ni1—N11.840 (3)Ni1—N31.879 (3)
Ni1—O11.842 (2)Ni1—N21.953 (3)
N1—Ni1—O194.70 (10)N1—Ni1—N286.38 (12)
N1—Ni1—N3176.86 (12)O1—Ni1—N2178.89 (11)
O1—Ni1—N388.34 (12)N3—Ni1—N290.58 (12)
Selected geometric parameters (Å, º) for (II) top
Ni1—O11.913 (2)Ni1—N31.979 (2)
Ni1—N11.949 (2)Ni1—N22.079 (2)
O1—Ni1—N193.07 (6)O1—Ni1—N2177.50 (6)
O1—Ni1—N389.30 (6)N1—Ni1—N284.48 (6)
N1—Ni1—N3172.04 (7)N3—Ni1—N293.08 (7)
 

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