Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039384/hb2501sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039384/hb2501Isup2.hkl |
CCDC reference: 1283836
H2mbdpz (102 mg, 0.5 mmol) in ethanol (10 ml) was added to a solution of NiCl2 (12.9 mg, 0.1 mmol) in H2O (10 ml). The mixture was refuxed for 2 h with stirring, yielding a brown precipitate. The solution was then filtered to remove the precipitate, which was subsequently washed with water, methanol and acetone, and finally dried. The solid was dissolved in DMF, producing a clear solution, which was allowed to stand undisturbed at room temperature for a few weeks at which time green blocks of (I) were obtained.
The H atoms were refined with a riding model [C—H = 0.93–0.97Å (geometrically placed) and N—H = 0.96–0.98Å (located in a difference map); Uiso(H) = 1.2Ueq or 1.5 Ueq(carrier)]. The methyl groups were allowed to rotate but not to tip. The maximum difference peak is 1.12Å from Cl2.
Interest in one dimensional chain structures arises partly because these structures are expected to play a crucial role as precursors in the formation of two- and three-dimensional structures (Neeraj et al., 1999). In the past, the majority of one-dimensional coordination networks were found to be composed of bis-monodentate tectons (Yaghi et al., 1998; Hennigar et al., 1997), while few examples of complexes with bis-bidentate (Veltan & Rehahn, 1996; Kaes et al., 1998), and bis-tridentate tectons (Constable & Cargill Thompson, 1992; Neels et al., 1997; Loi et al., 1999) were published.
In this paper, we report the crystal structure of the title compound, (I), (Fig. 1), containing the bis-bidentate organic tecton 4,4'-methylene-bis(3,5-dimethylpyrazole) and Cl ligands. The Ni atom is coordinated by three Cl- ions and two N-bonded H2mbdpz ligands (Table 1). The four nearest atoms result in a cis-NiCl2N2 square planar geometry and a third chloride ion with a much longer Ni—Cl bond distance completes a distorted NiCl3N2 square pyramid. The alternating (NiCl2)2 groups and pairs of bridging H2mbdpz ligands form an infinite one-dimensional chain (Fig. 2). The dihedral angle between the two pyrazole rings within one ligand is 81.8 (3)°. which is slightly smaller than that in the free ligand. The Ni···Ni non-bonding distance between adjacent metal ions in the chain is 3.728 (4) Å. The structure is completed by N—H···Cl hydrogen bonds (Table 2).
For related literature, see: Constable & Cargill Thompson (1992); Hennigar et al. (1997); Kaes et al. (1998); Loi et al. (1999) Neels et al. (1997); Neeraj et al. (1999); Veltan & Rehahn (1996); Yaghi et al. (1998).
Data collection: APEX2 (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(C11H16N4)] | Z = 2 |
Mr = 333.89 | F(000) = 344 |
Triclinic, P1 | Dx = 1.665 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.759 (3) Å | Cell parameters from 3212 reflections |
b = 8.879 (3) Å | θ = 2.3–25.1° |
c = 9.735 (3) Å | µ = 1.85 mm−1 |
α = 79.269 (6)° | T = 298 K |
β = 63.584 (5)° | Block, green |
γ = 86.922 (5)° | 0.28 × 0.22 × 0.15 mm |
V = 665.8 (4) Å3 |
Bruker APEX II CCD diffractometer | 2312 independent reflections |
Radiation source: fine-focus sealed tube | 1534 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 0 pixels mm-1 | θmax = 25.1°, θmin = 2.3° |
ω scans | h = −10→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −7→10 |
Tmin = 0.626, Tmax = 0.769 | l = −11→11 |
3330 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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.208 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.1397P)2] where P = (Fo2 + 2Fc2)/3 |
2312 reflections | (Δ/σ)max < 0.001 |
169 parameters | Δρmax = 0.73 e Å−3 |
40 restraints | Δρmin = −1.05 e Å−3 |
[NiCl2(C11H16N4)] | γ = 86.922 (5)° |
Mr = 333.89 | V = 665.8 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.759 (3) Å | Mo Kα radiation |
b = 8.879 (3) Å | µ = 1.85 mm−1 |
c = 9.735 (3) Å | T = 298 K |
α = 79.269 (6)° | 0.28 × 0.22 × 0.15 mm |
β = 63.584 (5)° |
Bruker APEX II CCD diffractometer | 2312 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1534 reflections with I > 2σ(I) |
Tmin = 0.626, Tmax = 0.769 | Rint = 0.033 |
3330 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 40 restraints |
wR(F2) = 0.208 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.73 e Å−3 |
2312 reflections | Δρmin = −1.05 e Å−3 |
169 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 | ||
Ni2 | 0.36689 (12) | 0.08445 (11) | 0.90152 (10) | 0.0275 (4) | |
Cl1 | 0.1129 (2) | 0.0033 (2) | 1.1136 (2) | 0.0370 (5) | |
Cl2 | 0.4813 (3) | −0.1538 (2) | 0.9274 (2) | 0.0384 (6) | |
C8 | 0.6764 (9) | 0.5680 (8) | 0.1917 (8) | 0.0277 (16) | |
N2 | 0.8976 (7) | 0.7132 (6) | 0.1257 (7) | 0.0324 (15) | |
C10 | 0.9389 (9) | 0.5714 (9) | 0.1731 (8) | 0.0299 (17) | |
C3 | 0.7286 (9) | 0.2395 (8) | 0.4362 (8) | 0.0295 (17) | |
N4 | 0.7209 (8) | 0.1467 (8) | 0.6655 (7) | 0.0371 (17) | |
N3 | 0.5559 (8) | 0.1395 (8) | 0.6870 (7) | 0.0373 (16) | |
C4 | 0.8261 (10) | 0.2016 (10) | 0.5168 (9) | 0.039 (2) | |
C6 | 0.7886 (10) | 0.3010 (9) | 0.2662 (8) | 0.0339 (19) | |
H39A | 0.7122 | 0.2606 | 0.2331 | 0.041* | |
H39B | 0.9005 | 0.2615 | 0.2101 | 0.041* | |
C7 | 0.8005 (9) | 0.4745 (8) | 0.2170 (8) | 0.0289 (17) | |
C1 | 0.4016 (10) | 0.1983 (10) | 0.5276 (9) | 0.042 (2) | |
H1C | 0.3209 | 0.1224 | 0.6070 | 0.063* | |
H1A | 0.4272 | 0.1766 | 0.4267 | 0.063* | |
H1B | 0.3538 | 0.2979 | 0.5364 | 0.063* | |
C2 | 0.5595 (10) | 0.1951 (8) | 0.5472 (9) | 0.0306 (17) | |
C5 | 1.0141 (10) | 0.2126 (12) | 0.4657 (10) | 0.049 (2) | |
H45A | 1.0450 | 0.3135 | 0.4691 | 0.074* | |
H45B | 1.0742 | 0.1934 | 0.3611 | 0.074* | |
H45C | 1.0438 | 0.1380 | 0.5342 | 0.074* | |
C9 | 0.5025 (10) | 0.5253 (9) | 0.2176 (10) | 0.041 (2) | |
H30A | 0.4218 | 0.5337 | 0.3219 | 0.061* | |
H30B | 0.5007 | 0.4215 | 0.2028 | 0.061* | |
H30C | 0.4728 | 0.5929 | 0.1446 | 0.061* | |
C11 | 1.1094 (10) | 0.5454 (11) | 0.1706 (10) | 0.045 (2) | |
H47A | 1.1901 | 0.6217 | 0.0919 | 0.068* | |
H47B | 1.1461 | 0.4453 | 0.1477 | 0.068* | |
H47C | 1.1020 | 0.5524 | 0.2706 | 0.068* | |
N1 | 0.7387 (7) | 0.7146 (6) | 0.1358 (7) | 0.0348 (16) | |
H4 | 0.7577 | 0.1015 | 0.7460 | 0.070 (6)* | |
H2 | 0.9769 | 0.7979 | 0.0653 | 0.069 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni2 | 0.0317 (6) | 0.0230 (6) | 0.0266 (6) | 0.0017 (4) | −0.0143 (4) | 0.0015 (4) |
Cl1 | 0.0349 (11) | 0.0368 (12) | 0.0387 (11) | −0.0040 (9) | −0.0201 (9) | 0.0060 (9) |
Cl2 | 0.0499 (13) | 0.0277 (11) | 0.0434 (12) | 0.0046 (9) | −0.0264 (10) | −0.0058 (9) |
C8 | 0.033 (4) | 0.022 (4) | 0.024 (4) | 0.004 (3) | −0.011 (3) | 0.000 (3) |
N2 | 0.029 (3) | 0.026 (4) | 0.039 (4) | −0.001 (3) | −0.016 (3) | 0.005 (3) |
C10 | 0.029 (4) | 0.033 (4) | 0.026 (4) | −0.001 (3) | −0.011 (3) | −0.003 (3) |
C3 | 0.033 (4) | 0.020 (4) | 0.033 (4) | 0.001 (3) | −0.014 (3) | −0.001 (3) |
N4 | 0.032 (4) | 0.044 (4) | 0.038 (4) | −0.004 (3) | −0.022 (3) | 0.003 (3) |
N3 | 0.036 (4) | 0.038 (4) | 0.035 (4) | 0.009 (3) | −0.017 (3) | −0.001 (3) |
C4 | 0.045 (5) | 0.039 (5) | 0.030 (4) | 0.005 (4) | −0.019 (4) | 0.003 (4) |
C6 | 0.041 (5) | 0.028 (4) | 0.031 (4) | 0.012 (4) | −0.017 (4) | −0.003 (3) |
C7 | 0.035 (4) | 0.023 (4) | 0.030 (4) | 0.002 (3) | −0.016 (3) | −0.004 (3) |
C1 | 0.048 (5) | 0.044 (5) | 0.037 (5) | 0.005 (4) | −0.023 (4) | −0.003 (4) |
C2 | 0.036 (4) | 0.023 (4) | 0.036 (4) | 0.003 (3) | −0.021 (4) | −0.002 (3) |
C5 | 0.041 (5) | 0.064 (7) | 0.046 (5) | 0.003 (5) | −0.027 (4) | 0.000 (5) |
C9 | 0.038 (5) | 0.031 (5) | 0.065 (6) | −0.007 (4) | −0.032 (4) | −0.008 (4) |
C11 | 0.040 (5) | 0.047 (6) | 0.046 (5) | 0.013 (4) | −0.019 (4) | −0.006 (4) |
N1 | 0.032 (4) | 0.031 (4) | 0.039 (4) | −0.001 (3) | −0.016 (3) | 0.002 (3) |
Ni2—N3 | 1.992 (6) | N3—C2 | 1.346 (9) |
Ni2—N1i | 2.013 (6) | C4—C5 | 1.497 (11) |
Ni2—Cl1 | 2.294 (2) | C6—C7 | 1.520 (10) |
Ni2—Cl2 | 2.311 (2) | C6—H39A | 0.9700 |
Ni2—Cl2ii | 2.713 (2) | C6—H39B | 0.9700 |
Cl2—Ni2ii | 2.713 (2) | C1—C2 | 1.476 (10) |
C8—N1 | 1.355 (9) | C1—H1C | 0.9600 |
C8—C7 | 1.413 (10) | C1—H1A | 0.9600 |
C8—C9 | 1.488 (10) | C1—H1B | 0.9600 |
N2—C10 | 1.346 (9) | C5—H45A | 0.9600 |
N2—N1 | 1.351 (7) | C5—H45B | 0.9600 |
N2—H2 | 0.9600 | C5—H45C | 0.9600 |
C10—C7 | 1.381 (10) | C9—H30A | 0.9600 |
C10—C11 | 1.489 (10) | C9—H30B | 0.9600 |
C3—C4 | 1.387 (11) | C9—H30C | 0.9600 |
C3—C2 | 1.413 (10) | C11—H47A | 0.9600 |
C3—C6 | 1.494 (10) | C11—H47B | 0.9600 |
N4—C4 | 1.334 (9) | C11—H47C | 0.9600 |
N4—N3 | 1.369 (8) | N1—Ni2i | 2.013 (6) |
N4—H4 | 0.9864 | ||
N3—Ni2—N1i | 88.6 (2) | C7—C6—H39B | 108.1 |
N3—Ni2—Cl1 | 164.9 (2) | H39A—C6—H39B | 107.3 |
N1i—Ni2—Cl1 | 88.90 (16) | C10—C7—C8 | 105.6 (7) |
N3—Ni2—Cl2 | 89.5 (2) | C10—C7—C6 | 127.7 (7) |
N1i—Ni2—Cl2 | 174.54 (19) | C8—C7—C6 | 126.4 (7) |
Cl1—Ni2—Cl2 | 91.59 (8) | C2—C1—H1C | 109.5 |
N3—Ni2—Cl2ii | 100.5 (2) | C2—C1—H1A | 109.5 |
N1i—Ni2—Cl2ii | 100.84 (19) | H1C—C1—H1A | 109.5 |
Cl1—Ni2—Cl2ii | 94.60 (8) | C2—C1—H1B | 109.5 |
Cl2—Ni2—Cl2ii | 84.54 (8) | H1C—C1—H1B | 109.5 |
Ni2—Cl2—Ni2ii | 95.46 (8) | H1A—C1—H1B | 109.5 |
N1—C8—C7 | 109.2 (7) | N3—C2—C3 | 109.7 (6) |
N1—C8—C9 | 121.4 (6) | N3—C2—C1 | 120.3 (7) |
C7—C8—C9 | 129.4 (7) | C3—C2—C1 | 129.9 (7) |
C10—N2—N1 | 111.6 (4) | C4—C5—H45A | 109.5 |
C10—N2—H2 | 125.4 | C4—C5—H45B | 109.5 |
N1—N2—H2 | 120.8 | H45A—C5—H45B | 109.5 |
N2—C10—C7 | 107.3 (6) | C4—C5—H45C | 109.5 |
N2—C10—C11 | 120.0 (7) | H45A—C5—H45C | 109.5 |
C7—C10—C11 | 132.7 (8) | H45B—C5—H45C | 109.5 |
C4—C3—C2 | 105.0 (7) | C8—C9—H30A | 109.5 |
C4—C3—C6 | 128.1 (7) | C8—C9—H30B | 109.5 |
C2—C3—C6 | 126.7 (7) | H30A—C9—H30B | 109.5 |
C4—N4—N3 | 111.0 (6) | C8—C9—H30C | 109.5 |
C4—N4—H4 | 124.8 | H30A—C9—H30C | 109.5 |
N3—N4—H4 | 123.5 | H30B—C9—H30C | 109.5 |
C2—N3—N4 | 106.1 (6) | C10—C11—H47A | 109.5 |
C2—N3—Ni2 | 133.1 (5) | C10—C11—H47B | 109.5 |
N4—N3—Ni2 | 120.0 (5) | H47A—C11—H47B | 109.5 |
N4—C4—C3 | 108.0 (7) | C10—C11—H47C | 109.5 |
N4—C4—C5 | 119.9 (7) | H47A—C11—H47C | 109.5 |
C3—C4—C5 | 132.0 (7) | H47B—C11—H47C | 109.5 |
C3—C6—C7 | 116.8 (6) | N2—N1—C8 | 106.2 (5) |
C3—C6—H39A | 108.1 | N2—N1—Ni2i | 119.9 (3) |
C7—C6—H39A | 108.1 | C8—N1—Ni2i | 133.3 (5) |
C3—C6—H39B | 108.1 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Cl1iii | 0.96 | 2.45 | 3.227 (6) | 138 |
N2—H2···Cl1i | 0.96 | 2.59 | 3.123 (6) | 116 |
N4—H4···Cl1ii | 0.99 | 2.19 | 3.167 (7) | 169 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+2; (iii) x+1, y+1, z−1. |
Experimental details
Crystal data | |
Chemical formula | [NiCl2(C11H16N4)] |
Mr | 333.89 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.759 (3), 8.879 (3), 9.735 (3) |
α, β, γ (°) | 79.269 (6), 63.584 (5), 86.922 (5) |
V (Å3) | 665.8 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.85 |
Crystal size (mm) | 0.28 × 0.22 × 0.15 |
Data collection | |
Diffractometer | Bruker APEX II CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.626, 0.769 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3330, 2312, 1534 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.208, 0.97 |
No. of reflections | 2312 |
No. of parameters | 169 |
No. of restraints | 40 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.73, −1.05 |
Computer programs: APEX2 (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
Ni2—N3 | 1.992 (6) | Ni2—Cl2 | 2.311 (2) |
Ni2—N1i | 2.013 (6) | Ni2—Cl2ii | 2.713 (2) |
Ni2—Cl1 | 2.294 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···Cl1iii | 0.96 | 2.45 | 3.227 (6) | 138 |
N2—H2···Cl1i | 0.96 | 2.59 | 3.123 (6) | 116 |
N4—H4···Cl1ii | 0.99 | 2.19 | 3.167 (7) | 169 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+2; (iii) x+1, y+1, z−1. |
Interest in one dimensional chain structures arises partly because these structures are expected to play a crucial role as precursors in the formation of two- and three-dimensional structures (Neeraj et al., 1999). In the past, the majority of one-dimensional coordination networks were found to be composed of bis-monodentate tectons (Yaghi et al., 1998; Hennigar et al., 1997), while few examples of complexes with bis-bidentate (Veltan & Rehahn, 1996; Kaes et al., 1998), and bis-tridentate tectons (Constable & Cargill Thompson, 1992; Neels et al., 1997; Loi et al., 1999) were published.
In this paper, we report the crystal structure of the title compound, (I), (Fig. 1), containing the bis-bidentate organic tecton 4,4'-methylene-bis(3,5-dimethylpyrazole) and Cl ligands. The Ni atom is coordinated by three Cl- ions and two N-bonded H2mbdpz ligands (Table 1). The four nearest atoms result in a cis-NiCl2N2 square planar geometry and a third chloride ion with a much longer Ni—Cl bond distance completes a distorted NiCl3N2 square pyramid. The alternating (NiCl2)2 groups and pairs of bridging H2mbdpz ligands form an infinite one-dimensional chain (Fig. 2). The dihedral angle between the two pyrazole rings within one ligand is 81.8 (3)°. which is slightly smaller than that in the free ligand. The Ni···Ni non-bonding distance between adjacent metal ions in the chain is 3.728 (4) Å. The structure is completed by N—H···Cl hydrogen bonds (Table 2).