Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024324/is2165sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024324/is2165Isup2.hkl |
CCDC reference: 650570
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.006 Å
- R factor = 0.050
- wR factor = 0.144
- Data-to-parameter ratio = 14.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 500 Deg.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1 (2) 1.89
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature, see: Brammer (2004); Carlucci et al. (2003); Ghosh et al. (2004); Hong et al. (2005); Luo et al. (2003); Moulton & Zaworotko (2001); Woodward et al. (2005).
The title complex was prepared by the addition of a stoichiometric amount of NiSO4 (0.18 g, 20 mmol), NaOH (0.12 g, 30 mmol) and HCl (1 mol/L, 0.1 ml) to a hot aqueous solution of bpe (0.031 g, 12 mmol). The resulting solution was filtered, and green single crystals were obtained at room temperature over several days.
H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) refined using a riding model, with Uiso(H) = 1.2Ueq(C). The deepest hole in the difference Fourier map is located 0.95 Å from atom Ni1.
Recently, there are of great interest in the design and synthesis of coordination complexes, such one-dimensional chains and ladders, two-dimensional grids, three-dimensional networks, interpenetrated modes and helical staircase networks, which are used as functional materials potentially applied in magnetism, molecular adsorption, optoelectronic devices, sensors, luminescent materials and catalysis (Moulton & Zaworotko, 2001; Carlucci et al., 2003; Brammer, 2004). The flexible bridging ligand 1,2-bis(4-pyridyl)ethane (bpe) is useful in the formation of various frameworks (Luo et al., 2003; Ghosh et al., 2004; Hong et al., 2005). We report here the crystal structure of the title Ni complex polymer, [NiCl2(bpe)]n, (I).
The NiII center has a distorted tetrahedral geometry, which is coordinated by two N atoms from two bpe ligands and two Cl ligands, forming a one-dimensional helical chain (Fig. 1 and 2). The dihedral angle between two pyridine rings, C1—C5/N1 and C7—C11/N2, is 61.93 (3)°. One bpe is almost planar as shown by the C8—C9—C12—C12ii torsion angle of -6.1 (9)°, while the other is not planar but parallel, the C2—C3—C6—C6i angle and the interplanar distance between the pyridine rings being 105.4 (6)° and 1.452 (2) Å, respectively [symmetry codes: (i) -x + 1, -y, -z + 1; (ii) -x, -y + 2, -z + 2]. The angles of C3—C6—C6i and C9—C12—C12ii are also different, they are 111.6 (4) and 115.2 (5)°. The Ni···Nii and Ni···Niii distances are 13.441 (3) and 13.279 (3) Å, respectively.
For related literature, see: Brammer (2004); Carlucci et al. (2003); Ghosh et al. (2004); Hong et al. (2005); Luo et al. (2003); Moulton & Zaworotko (2001); Woodward et al. (2005).
Data collection: SMART (Bruker,1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[NiCl2(C12H12N2)] | Z = 2 |
Mr = 313.85 | F(000) = 320 |
Triclinic, P1 | Dx = 1.580 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.3979 (17) Å | Cell parameters from 1592 reflections |
b = 8.806 (3) Å | θ = 2.7–25.5° |
c = 14.018 (4) Å | µ = 1.85 mm−1 |
α = 87.988 (5)° | T = 298 K |
β = 84.165 (5)° | Block, green |
γ = 84.475 (5)° | 0.38 × 0.30 × 0.30 mm |
V = 659.6 (4) Å3 |
Bruker APEXII area-detector diffractometer | 2297 independent reflections |
Radiation source: fine-focus sealed tube | 1942 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: none pixels mm-1 | θmax = 25.1°, θmin = 1.5° |
φ and ω scan | h = −4→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −9→10 |
Tmin = 0.511, Tmax = 0.574 | l = −16→16 |
3306 measured reflections |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1008P)2 + 0.3P] where P = (Fo2 + 2Fc2)/3 |
2297 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.98 e Å−3 |
0 restraints | Δρmin = −1.04 e Å−3 |
[NiCl2(C12H12N2)] | γ = 84.475 (5)° |
Mr = 313.85 | V = 659.6 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.3979 (17) Å | Mo Kα radiation |
b = 8.806 (3) Å | µ = 1.85 mm−1 |
c = 14.018 (4) Å | T = 298 K |
α = 87.988 (5)° | 0.38 × 0.30 × 0.30 mm |
β = 84.165 (5)° |
Bruker APEXII area-detector diffractometer | 2297 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1942 reflections with I > 2σ(I) |
Tmin = 0.511, Tmax = 0.574 | Rint = 0.022 |
3306 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.98 e Å−3 |
2297 reflections | Δρmin = −1.04 e Å−3 |
154 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.88487 (9) | 0.54655 (5) | 0.74751 (3) | 0.0401 (2) | |
Cl1 | 1.0080 (2) | 0.70646 (11) | 0.62712 (7) | 0.0507 (3) | |
Cl2 | 1.1490 (2) | 0.42178 (12) | 0.84309 (7) | 0.0505 (3) | |
N1 | 0.7275 (6) | 0.3808 (3) | 0.6836 (2) | 0.0379 (7) | |
N2 | 0.6308 (6) | 0.6763 (4) | 0.8355 (2) | 0.0397 (7) | |
C1 | 0.5435 (8) | 0.4129 (4) | 0.6284 (3) | 0.0431 (9) | |
H1 | 0.4844 | 0.5148 | 0.6205 | 0.052* | |
C2 | 0.4336 (8) | 0.3063 (5) | 0.5819 (3) | 0.0460 (10) | |
H2 | 0.3057 | 0.3359 | 0.5435 | 0.055* | |
C3 | 0.5183 (8) | 0.1532 (5) | 0.5935 (3) | 0.0442 (9) | |
C4 | 0.7074 (9) | 0.1187 (5) | 0.6504 (3) | 0.0541 (11) | |
H4 | 0.7696 | 0.0175 | 0.6592 | 0.065* | |
C5 | 0.8075 (9) | 0.2329 (5) | 0.6952 (3) | 0.0491 (10) | |
H5 | 0.9343 | 0.2062 | 0.7346 | 0.059* | |
C6 | 0.4100 (9) | 0.0308 (5) | 0.5416 (3) | 0.0517 (11) | |
H6A | 0.2548 | 0.0729 | 0.5177 | 0.062* | |
H6B | 0.3724 | −0.0523 | 0.5864 | 0.062* | |
C7 | 0.4599 (9) | 0.7752 (5) | 0.7981 (3) | 0.0536 (11) | |
H7 | 0.4614 | 0.7852 | 0.7317 | 0.064* | |
C8 | 0.2811 (9) | 0.8629 (6) | 0.8555 (3) | 0.0604 (13) | |
H8 | 0.1651 | 0.9306 | 0.8274 | 0.072* | |
C9 | 0.2740 (8) | 0.8505 (5) | 0.9545 (3) | 0.0481 (10) | |
C10 | 0.4500 (9) | 0.7474 (5) | 0.9904 (3) | 0.0551 (11) | |
H10 | 0.4521 | 0.7342 | 1.0565 | 0.066* | |
C11 | 0.6215 (9) | 0.6641 (5) | 0.9308 (3) | 0.0497 (10) | |
H11 | 0.7379 | 0.5953 | 0.9578 | 0.060* | |
C12 | 0.0849 (9) | 0.9404 (5) | 1.0231 (3) | 0.0575 (12) | |
H12A | −0.0171 | 0.8695 | 1.0596 | 0.069* | |
H12B | 0.1743 | 0.9897 | 1.0681 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0508 (4) | 0.0359 (3) | 0.0341 (3) | −0.0033 (2) | −0.0084 (2) | −0.0001 (2) |
Cl1 | 0.0616 (7) | 0.0437 (6) | 0.0459 (6) | −0.0056 (5) | −0.0051 (5) | 0.0136 (4) |
Cl2 | 0.0571 (7) | 0.0537 (6) | 0.0419 (6) | −0.0005 (5) | −0.0174 (4) | 0.0064 (4) |
N1 | 0.0468 (18) | 0.0331 (17) | 0.0346 (16) | −0.0041 (13) | −0.0069 (13) | −0.0018 (13) |
N2 | 0.0473 (18) | 0.0357 (17) | 0.0371 (17) | −0.0009 (14) | −0.0109 (14) | −0.0021 (13) |
C1 | 0.053 (2) | 0.033 (2) | 0.043 (2) | −0.0005 (17) | −0.0095 (18) | 0.0001 (17) |
C2 | 0.052 (2) | 0.046 (2) | 0.042 (2) | −0.0053 (18) | −0.0135 (18) | −0.0006 (18) |
C3 | 0.054 (2) | 0.043 (2) | 0.037 (2) | −0.0115 (18) | −0.0039 (17) | −0.0038 (17) |
C4 | 0.073 (3) | 0.032 (2) | 0.060 (3) | −0.004 (2) | −0.018 (2) | −0.001 (2) |
C5 | 0.061 (3) | 0.037 (2) | 0.053 (2) | −0.0020 (18) | −0.022 (2) | −0.0007 (18) |
C6 | 0.064 (3) | 0.048 (2) | 0.046 (2) | −0.018 (2) | −0.007 (2) | −0.0066 (19) |
C7 | 0.067 (3) | 0.057 (3) | 0.034 (2) | 0.012 (2) | −0.0090 (19) | 0.0016 (19) |
C8 | 0.064 (3) | 0.064 (3) | 0.048 (3) | 0.022 (2) | −0.008 (2) | 0.005 (2) |
C9 | 0.056 (3) | 0.045 (2) | 0.041 (2) | 0.0023 (19) | −0.0028 (18) | −0.0019 (18) |
C10 | 0.068 (3) | 0.060 (3) | 0.035 (2) | 0.011 (2) | −0.0083 (19) | −0.0005 (19) |
C11 | 0.059 (3) | 0.048 (2) | 0.041 (2) | 0.0075 (19) | −0.0082 (19) | −0.0005 (18) |
C12 | 0.066 (3) | 0.058 (3) | 0.044 (2) | 0.012 (2) | −0.001 (2) | 0.001 (2) |
Ni1—N1 | 2.034 (3) | C5—H5 | 0.9300 |
Ni1—N2 | 2.040 (3) | C6—C6i | 1.520 (9) |
Ni1—Cl2 | 2.2402 (12) | C6—H6A | 0.9700 |
Ni1—Cl1 | 2.2490 (12) | C6—H6B | 0.9700 |
N1—C1 | 1.324 (5) | C7—C8 | 1.385 (6) |
N1—C5 | 1.342 (5) | C7—H7 | 0.9300 |
N2—C11 | 1.333 (5) | C8—C9 | 1.386 (6) |
N2—C7 | 1.340 (5) | C8—H8 | 0.9300 |
C1—C2 | 1.373 (6) | C9—C10 | 1.371 (6) |
C1—H1 | 0.9300 | C9—C12 | 1.514 (6) |
C2—C3 | 1.391 (6) | C10—C11 | 1.359 (6) |
C2—H2 | 0.9300 | C10—H10 | 0.9300 |
C3—C4 | 1.363 (6) | C11—H11 | 0.9300 |
C3—C6 | 1.515 (5) | C12—C12ii | 1.500 (9) |
C4—C5 | 1.384 (6) | C12—H12A | 0.9700 |
C4—H4 | 0.9300 | C12—H12B | 0.9700 |
N1—Ni1—N2 | 112.52 (13) | C3—C6—C6i | 111.6 (4) |
N1—Ni1—Cl2 | 105.23 (9) | C3—C6—H6A | 109.3 |
N2—Ni1—Cl2 | 105.99 (10) | C6i—C6—H6A | 109.3 |
N1—Ni1—Cl1 | 105.07 (10) | C3—C6—H6B | 109.3 |
N2—Ni1—Cl1 | 104.95 (10) | C6i—C6—H6B | 109.3 |
Cl2—Ni1—Cl1 | 123.23 (5) | H6A—C6—H6B | 108.0 |
C1—N1—C5 | 116.7 (3) | N2—C7—C8 | 121.8 (4) |
C1—N1—Ni1 | 122.1 (3) | N2—C7—H7 | 119.1 |
C5—N1—Ni1 | 121.2 (3) | C8—C7—H7 | 119.1 |
C11—N2—C7 | 117.4 (3) | C7—C8—C9 | 120.4 (4) |
C11—N2—Ni1 | 122.4 (3) | C7—C8—H8 | 119.8 |
C7—N2—Ni1 | 120.1 (3) | C9—C8—H8 | 119.8 |
N1—C1—C2 | 124.7 (4) | C10—C9—C8 | 116.3 (4) |
N1—C1—H1 | 117.7 | C10—C9—C12 | 119.4 (4) |
C2—C1—H1 | 117.7 | C8—C9—C12 | 124.3 (4) |
C1—C2—C3 | 118.4 (4) | C11—C10—C9 | 120.9 (4) |
C1—C2—H2 | 120.8 | C11—C10—H10 | 119.6 |
C3—C2—H2 | 120.8 | C9—C10—H10 | 119.6 |
C4—C3—C2 | 117.4 (4) | N2—C11—C10 | 123.2 (4) |
C4—C3—C6 | 121.6 (4) | N2—C11—H11 | 118.4 |
C2—C3—C6 | 120.9 (4) | C10—C11—H11 | 118.4 |
C3—C4—C5 | 120.6 (4) | C12ii—C12—C9 | 115.2 (5) |
C3—C4—H4 | 119.7 | C12ii—C12—H12A | 108.5 |
C5—C4—H4 | 119.7 | C9—C12—H12A | 108.5 |
N1—C5—C4 | 122.1 (4) | C12ii—C12—H12B | 108.5 |
N1—C5—H5 | 119.0 | C9—C12—H12B | 108.5 |
C4—C5—H5 | 119.0 | H12A—C12—H12B | 107.5 |
N2—Ni1—N1—C1 | 58.7 (3) | C6—C3—C4—C5 | 178.4 (4) |
Cl2—Ni1—N1—C1 | 173.7 (3) | C1—N1—C5—C4 | 1.3 (7) |
Cl1—Ni1—N1—C1 | −54.9 (3) | Ni1—N1—C5—C4 | −178.3 (4) |
N2—Ni1—N1—C5 | −121.7 (3) | C3—C4—C5—N1 | −1.2 (8) |
Cl2—Ni1—N1—C5 | −6.7 (4) | C4—C3—C6—C6i | −72.3 (7) |
Cl1—Ni1—N1—C5 | 124.7 (3) | C2—C3—C6—C6i | 105.4 (6) |
N1—Ni1—N2—C11 | 106.5 (3) | C11—N2—C7—C8 | 0.6 (7) |
Cl2—Ni1—N2—C11 | −8.0 (4) | Ni1—N2—C7—C8 | 178.6 (4) |
Cl1—Ni1—N2—C11 | −139.8 (3) | N2—C7—C8—C9 | −0.1 (8) |
N1—Ni1—N2—C7 | −71.4 (4) | C7—C8—C9—C10 | −0.5 (8) |
Cl2—Ni1—N2—C7 | 174.1 (3) | C7—C8—C9—C12 | −179.5 (5) |
Cl1—Ni1—N2—C7 | 42.3 (3) | C8—C9—C10—C11 | 0.5 (7) |
C5—N1—C1—C2 | −1.0 (7) | C12—C9—C10—C11 | 179.6 (5) |
Ni1—N1—C1—C2 | 178.6 (3) | C7—N2—C11—C10 | −0.6 (7) |
N1—C1—C2—C3 | 0.6 (7) | Ni1—N2—C11—C10 | −178.5 (4) |
C1—C2—C3—C4 | −0.4 (6) | C9—C10—C11—N2 | 0.0 (8) |
C1—C2—C3—C6 | −178.1 (4) | C10—C9—C12—C12ii | 174.9 (6) |
C2—C3—C4—C5 | 0.7 (7) | C8—C9—C12—C12ii | −6.1 (9) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [NiCl2(C12H12N2)] |
Mr | 313.85 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 5.3979 (17), 8.806 (3), 14.018 (4) |
α, β, γ (°) | 87.988 (5), 84.165 (5), 84.475 (5) |
V (Å3) | 659.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.85 |
Crystal size (mm) | 0.38 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.511, 0.574 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3306, 2297, 1942 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.144, 1.04 |
No. of reflections | 2297 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.98, −1.04 |
Computer programs: SMART (Bruker,1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
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Recently, there are of great interest in the design and synthesis of coordination complexes, such one-dimensional chains and ladders, two-dimensional grids, three-dimensional networks, interpenetrated modes and helical staircase networks, which are used as functional materials potentially applied in magnetism, molecular adsorption, optoelectronic devices, sensors, luminescent materials and catalysis (Moulton & Zaworotko, 2001; Carlucci et al., 2003; Brammer, 2004). The flexible bridging ligand 1,2-bis(4-pyridyl)ethane (bpe) is useful in the formation of various frameworks (Luo et al., 2003; Ghosh et al., 2004; Hong et al., 2005). We report here the crystal structure of the title Ni complex polymer, [NiCl2(bpe)]n, (I).
The NiII center has a distorted tetrahedral geometry, which is coordinated by two N atoms from two bpe ligands and two Cl ligands, forming a one-dimensional helical chain (Fig. 1 and 2). The dihedral angle between two pyridine rings, C1—C5/N1 and C7—C11/N2, is 61.93 (3)°. One bpe is almost planar as shown by the C8—C9—C12—C12ii torsion angle of -6.1 (9)°, while the other is not planar but parallel, the C2—C3—C6—C6i angle and the interplanar distance between the pyridine rings being 105.4 (6)° and 1.452 (2) Å, respectively [symmetry codes: (i) -x + 1, -y, -z + 1; (ii) -x, -y + 2, -z + 2]. The angles of C3—C6—C6i and C9—C12—C12ii are also different, they are 111.6 (4) and 115.2 (5)°. The Ni···Nii and Ni···Niii distances are 13.441 (3) and 13.279 (3) Å, respectively.