Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048386/bv2070sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048386/bv2070Isup2.hkl |
CCDC reference: 1294088
A mixture of N-(2-(picolinamido)phenyl)picolinamide(0.314 g, 0.001 mol) and Ni(NO3)2.6H2O(0.288 g, 0.001 mol) was added to 20 ml e thanol, The mixture was closed in a steel tomb and heated at 418 K for 4 days, Single crystals suitable for X-ray diffraction analysis formed after it cooled down untouched in the air.
All H atoms were located at calculated positions and refined as riding on their parent C atoms with the C—H bond length fixed at 0.93Å with Uiso(H) = 1.2 times Ueq(C). In the final refinement cycles the anistropic parameters of atoms bonding to each other were constrained to be approximately equal.
As shown in Fig. 1, the title compound is a mononuclear complex in which each nickel(II) ion is coordinated by four N atoms from the same N-(2-(picolinamido)phenyl)picolinamide molecule and displays a distorted planar quadrilateral coordination geometry. The coordination bonds of Ni1—N are between 1.920 (4) Å and 2.016 (4) Å, atoms N1, N2, N3, and N4 are approximately coplanar with the central nickel(II) ion with a maximum deviation from the least squares plane of 0.0876 (2) Å for atom N1. Along the a axis, the benzene rings and pyridine rings of adjacent N-(2-(picolinamido)phenyl)picolinamide molecules are nearly parallel to each other impling there may exist π-π interactions between them. In the complex no classical hydrogen bonds are found and the three-dimensional network of the crystal is mainly consolidated by π-π interactions and weak interactions involving O atoms and the H atoms of adjacent pyridine rings.
For related literature, see: Liu et al. (2007).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).
Fig. 1. The molecular unit of (I), showing 50% probability displacement ellipsoids. | |
Fig. 2. The packing diagram of (I), viewed along the c axis. Hydrogen bonds are shown as dashed lines. |
[Ni(C18H12N4O2)] | F(000) = 768.0 |
Mr = 375.01 | Dx = 1.644 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6201 reflections |
a = 7.052 (2) Å | θ = 2.8–27.9° |
b = 18.383 (5) Å | µ = 1.30 mm−1 |
c = 11.826 (3) Å | T = 293 K |
β = 98.827 (4)° | Block, blue |
V = 1514.8 (7) Å3 | 0.31 × 0.27 × 0.22 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2784 independent reflections |
Radiation source: fine-focus sealed tube | 2087 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
φ and ω scans | θmax = 25.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −8→8 |
Tmin = 0.679, Tmax = 0.750 | k = −22→22 |
9286 measured reflections | l = −14→14 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0623P)2 + 1.4239P] where P = (Fo2 + 2Fc2)/3 |
2784 reflections | (Δ/σ)max = 0.003 |
226 parameters | Δρmax = 0.48 e Å−3 |
234 restraints | Δρmin = −0.56 e Å−3 |
[Ni(C18H12N4O2)] | V = 1514.8 (7) Å3 |
Mr = 375.01 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.052 (2) Å | µ = 1.30 mm−1 |
b = 18.383 (5) Å | T = 293 K |
c = 11.826 (3) Å | 0.31 × 0.27 × 0.22 mm |
β = 98.827 (4)° |
Bruker SMART CCD area-detector diffractometer | 2784 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 2087 reflections with I > 2σ(I) |
Tmin = 0.679, Tmax = 0.750 | Rint = 0.035 |
9286 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 234 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.48 e Å−3 |
2784 reflections | Δρmin = −0.56 e Å−3 |
226 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 | 0.27023 (8) | 0.49353 (2) | 0.04659 (5) | 0.0392 (2) | |
N4 | 0.3749 (5) | 0.54985 (19) | 0.1888 (3) | 0.0491 (5) | |
C18 | 0.3852 (7) | 0.5336 (3) | 0.2993 (4) | 0.0525 (6) | |
H18 | 0.3490 | 0.4871 | 0.3189 | 0.063* | |
C17 | 0.4466 (7) | 0.5821 (2) | 0.3866 (4) | 0.0557 (6) | |
H17 | 0.4515 | 0.5686 | 0.4627 | 0.067* | |
C16 | 0.5004 (7) | 0.6508 (3) | 0.3581 (4) | 0.0562 (6) | |
H16 | 0.5412 | 0.6848 | 0.4148 | 0.067* | |
C15 | 0.4931 (7) | 0.6685 (3) | 0.2443 (4) | 0.0537 (6) | |
H15 | 0.5306 | 0.7144 | 0.2234 | 0.064* | |
C14 | 0.4297 (7) | 0.6176 (2) | 0.1617 (4) | 0.0496 (5) | |
C13 | 0.4132 (7) | 0.6356 (2) | 0.0369 (4) | 0.0492 (5) | |
C6 | 0.2871 (7) | 0.5805 (2) | −0.1482 (4) | 0.0479 (5) | |
C5 | 0.3207 (7) | 0.6352 (2) | −0.2235 (4) | 0.0513 (6) | |
H5 | 0.3875 | 0.6768 | −0.1959 | 0.062* | |
C4 | 0.2551 (7) | 0.6281 (3) | −0.3395 (4) | 0.0545 (6) | |
H4 | 0.2796 | 0.6647 | −0.3896 | 0.065* | |
C3 | 0.1537 (7) | 0.5672 (3) | −0.3814 (4) | 0.0556 (6) | |
H3 | 0.1078 | 0.5636 | −0.4592 | 0.067* | |
C2 | 0.1194 (7) | 0.5110 (2) | −0.3080 (4) | 0.0530 (6) | |
H2 | 0.0524 | 0.4697 | −0.3367 | 0.064* | |
C1 | 0.1860 (7) | 0.5172 (2) | −0.1916 (4) | 0.0487 (5) | |
C7 | 0.0884 (7) | 0.3988 (2) | −0.1232 (4) | 0.0508 (5) | |
C8 | 0.0954 (7) | 0.3593 (2) | −0.0110 (4) | 0.0509 (5) | |
C9 | 0.0197 (7) | 0.2900 (3) | −0.0066 (4) | 0.0548 (6) | |
H9 | −0.0386 | 0.2672 | −0.0731 | 0.066* | |
C10 | 0.0318 (7) | 0.2553 (2) | 0.0974 (4) | 0.0570 (6) | |
H10 | −0.0191 | 0.2089 | 0.1017 | 0.068* | |
C11 | 0.1188 (7) | 0.2894 (2) | 0.1942 (4) | 0.0554 (6) | |
H11 | 0.1289 | 0.2664 | 0.2649 | 0.067* | |
C12 | 0.1923 (7) | 0.3591 (2) | 0.1851 (4) | 0.0524 (6) | |
H12 | 0.2520 | 0.3823 | 0.2509 | 0.063* | |
N3 | 0.1797 (5) | 0.39376 (18) | 0.0844 (3) | 0.0492 (5) | |
N1 | 0.1611 (5) | 0.46607 (19) | −0.1063 (3) | 0.0477 (5) | |
N2 | 0.3430 (5) | 0.57963 (18) | −0.0291 (3) | 0.0467 (5) | |
O1 | 0.0220 (5) | 0.36873 (16) | −0.2133 (3) | 0.0565 (6) | |
O2 | 0.4605 (4) | 0.69673 (16) | 0.0071 (3) | 0.0542 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0475 (4) | 0.0257 (3) | 0.0445 (3) | 0.0000 (2) | 0.0071 (2) | −0.0003 (2) |
N4 | 0.0594 (12) | 0.0381 (9) | 0.0502 (8) | −0.0017 (9) | 0.0098 (10) | −0.0048 (7) |
C18 | 0.0640 (13) | 0.0437 (11) | 0.0501 (8) | −0.0017 (11) | 0.0093 (12) | −0.0053 (8) |
C17 | 0.0667 (14) | 0.0470 (12) | 0.0532 (10) | −0.0011 (11) | 0.0087 (12) | −0.0080 (9) |
C16 | 0.0660 (14) | 0.0458 (11) | 0.0566 (10) | −0.0014 (11) | 0.0085 (12) | −0.0101 (10) |
C15 | 0.0625 (13) | 0.0408 (10) | 0.0578 (10) | −0.0023 (10) | 0.0088 (12) | −0.0086 (9) |
C14 | 0.0584 (11) | 0.0359 (9) | 0.0549 (8) | −0.0023 (8) | 0.0095 (10) | −0.0059 (7) |
C13 | 0.0583 (11) | 0.0329 (8) | 0.0569 (9) | −0.0038 (8) | 0.0101 (9) | −0.0018 (7) |
C6 | 0.0558 (11) | 0.0379 (9) | 0.0507 (8) | 0.0020 (8) | 0.0108 (9) | 0.0026 (7) |
C5 | 0.0587 (13) | 0.0433 (10) | 0.0528 (10) | 0.0032 (10) | 0.0117 (11) | 0.0052 (9) |
C4 | 0.0617 (13) | 0.0495 (11) | 0.0530 (10) | 0.0045 (10) | 0.0113 (11) | 0.0056 (10) |
C3 | 0.0625 (13) | 0.0521 (12) | 0.0525 (10) | 0.0041 (11) | 0.0095 (11) | 0.0028 (9) |
C2 | 0.0598 (13) | 0.0480 (11) | 0.0514 (9) | 0.0028 (10) | 0.0089 (11) | −0.0007 (9) |
C1 | 0.0559 (11) | 0.0408 (9) | 0.0499 (7) | 0.0020 (8) | 0.0095 (9) | −0.0012 (7) |
C7 | 0.0559 (11) | 0.0366 (9) | 0.0601 (9) | −0.0029 (8) | 0.0097 (9) | −0.0076 (7) |
C8 | 0.0544 (11) | 0.0338 (8) | 0.0656 (10) | −0.0025 (8) | 0.0129 (10) | −0.0034 (7) |
C9 | 0.0577 (13) | 0.0363 (10) | 0.0717 (12) | −0.0031 (9) | 0.0139 (11) | −0.0023 (9) |
C10 | 0.0599 (13) | 0.0378 (11) | 0.0748 (13) | −0.0027 (10) | 0.0155 (12) | 0.0026 (9) |
C11 | 0.0595 (13) | 0.0372 (11) | 0.0714 (12) | −0.0016 (10) | 0.0158 (12) | 0.0065 (9) |
C12 | 0.0573 (13) | 0.0353 (10) | 0.0664 (11) | −0.0011 (10) | 0.0151 (12) | 0.0063 (8) |
N3 | 0.0540 (12) | 0.0323 (9) | 0.0629 (10) | −0.0015 (9) | 0.0136 (11) | 0.0020 (7) |
N1 | 0.0549 (11) | 0.0367 (9) | 0.0518 (8) | −0.0018 (8) | 0.0090 (9) | −0.0044 (7) |
N2 | 0.0562 (11) | 0.0325 (8) | 0.0519 (8) | −0.0019 (8) | 0.0098 (9) | 0.0012 (7) |
O1 | 0.0618 (13) | 0.0426 (11) | 0.0642 (11) | −0.0040 (10) | 0.0072 (11) | −0.0110 (9) |
O2 | 0.0641 (13) | 0.0352 (10) | 0.0633 (12) | −0.0068 (10) | 0.0101 (12) | −0.0001 (9) |
Ni1—N1 | 1.920 (4) | C5—H5 | 0.9300 |
Ni1—N2 | 1.926 (3) | C4—C3 | 1.378 (7) |
Ni1—N4 | 2.016 (4) | C4—H4 | 0.9300 |
Ni1—N3 | 2.015 (3) | C3—C2 | 1.395 (6) |
N4—C18 | 1.332 (6) | C3—H3 | 0.9300 |
N4—C14 | 1.357 (5) | C2—C1 | 1.389 (7) |
C18—C17 | 1.382 (6) | C2—H2 | 0.9300 |
C18—H18 | 0.9300 | C1—N1 | 1.409 (6) |
C17—C16 | 1.374 (7) | C7—O1 | 1.228 (5) |
C17—H17 | 0.9300 | C7—N1 | 1.342 (5) |
C16—C15 | 1.378 (7) | C7—C8 | 1.506 (7) |
C16—H16 | 0.9300 | C8—N3 | 1.350 (6) |
C15—C14 | 1.375 (6) | C8—C9 | 1.385 (6) |
C15—H15 | 0.9300 | C9—C10 | 1.377 (6) |
C14—C13 | 1.500 (6) | C9—H9 | 0.9300 |
C13—O2 | 1.238 (5) | C10—C11 | 1.365 (7) |
C13—N2 | 1.339 (5) | C10—H10 | 0.9300 |
C6—C5 | 1.388 (6) | C11—C12 | 1.392 (6) |
C6—N2 | 1.403 (6) | C11—H11 | 0.9300 |
C6—C1 | 1.419 (6) | C12—N3 | 1.341 (6) |
C5—C4 | 1.386 (6) | C12—H12 | 0.9300 |
N1—Ni1—N2 | 82.83 (15) | C4—C3—C2 | 120.6 (5) |
N1—Ni1—N4 | 164.32 (15) | C4—C3—H3 | 119.7 |
N2—Ni1—N4 | 82.89 (15) | C2—C3—H3 | 119.7 |
N1—Ni1—N3 | 82.82 (16) | C1—C2—C3 | 119.4 (5) |
N2—Ni1—N3 | 165.30 (16) | C1—C2—H2 | 120.3 |
N4—Ni1—N3 | 111.72 (15) | C3—C2—H2 | 120.3 |
C18—N4—C14 | 117.6 (4) | C2—C1—N1 | 126.5 (4) |
C18—N4—Ni1 | 131.4 (3) | C2—C1—C6 | 120.0 (4) |
C14—N4—Ni1 | 110.8 (3) | N1—C1—C6 | 113.4 (4) |
N4—C18—C17 | 123.4 (5) | O1—C7—N1 | 129.1 (5) |
N4—C18—H18 | 118.3 | O1—C7—C8 | 120.3 (4) |
C17—C18—H18 | 118.3 | N1—C7—C8 | 110.7 (4) |
C18—C17—C16 | 118.5 (5) | N3—C8—C9 | 121.5 (4) |
C18—C17—H17 | 120.8 | N3—C8—C7 | 117.5 (4) |
C16—C17—H17 | 120.8 | C9—C8—C7 | 121.1 (4) |
C17—C16—C15 | 119.1 (4) | C10—C9—C8 | 119.3 (5) |
C17—C16—H16 | 120.5 | C10—C9—H9 | 120.4 |
C15—C16—H16 | 120.5 | C8—C9—H9 | 120.4 |
C14—C15—C16 | 119.4 (4) | C11—C10—C9 | 119.6 (4) |
C14—C15—H15 | 120.3 | C11—C10—H10 | 120.2 |
C16—C15—H15 | 120.3 | C9—C10—H10 | 120.2 |
N4—C14—C15 | 122.0 (4) | C10—C11—C12 | 118.9 (5) |
N4—C14—C13 | 116.9 (4) | C10—C11—H11 | 120.6 |
C15—C14—C13 | 121.1 (4) | C12—C11—H11 | 120.6 |
O2—C13—N2 | 128.5 (4) | N3—C12—C11 | 122.1 (5) |
O2—C13—C14 | 119.7 (4) | N3—C12—H12 | 119.0 |
N2—C13—C14 | 111.7 (4) | C11—C12—H12 | 119.0 |
C5—C6—N2 | 127.0 (4) | C12—N3—C8 | 118.7 (4) |
C5—C6—C1 | 119.2 (4) | C12—N3—Ni1 | 130.5 (3) |
N2—C6—C1 | 113.7 (4) | C8—N3—Ni1 | 110.8 (3) |
C6—C5—C4 | 120.2 (5) | C7—N1—C1 | 126.5 (4) |
C6—C5—H5 | 119.9 | C7—N1—Ni1 | 118.1 (3) |
C4—C5—H5 | 119.9 | C1—N1—Ni1 | 115.0 (3) |
C3—C4—C5 | 120.5 (5) | C13—N2—C6 | 126.7 (4) |
C3—C4—H4 | 119.7 | C13—N2—Ni1 | 117.5 (3) |
C5—C4—H4 | 119.7 | C6—N2—Ni1 | 114.9 (3) |
Experimental details
Crystal data | |
Chemical formula | [Ni(C18H12N4O2)] |
Mr | 375.01 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.052 (2), 18.383 (5), 11.826 (3) |
β (°) | 98.827 (4) |
V (Å3) | 1514.8 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.30 |
Crystal size (mm) | 0.31 × 0.27 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.679, 0.750 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9286, 2784, 2087 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.119, 1.00 |
No. of reflections | 2784 |
No. of parameters | 226 |
No. of restraints | 234 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.56 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996).
As shown in Fig. 1, the title compound is a mononuclear complex in which each nickel(II) ion is coordinated by four N atoms from the same N-(2-(picolinamido)phenyl)picolinamide molecule and displays a distorted planar quadrilateral coordination geometry. The coordination bonds of Ni1—N are between 1.920 (4) Å and 2.016 (4) Å, atoms N1, N2, N3, and N4 are approximately coplanar with the central nickel(II) ion with a maximum deviation from the least squares plane of 0.0876 (2) Å for atom N1. Along the a axis, the benzene rings and pyridine rings of adjacent N-(2-(picolinamido)phenyl)picolinamide molecules are nearly parallel to each other impling there may exist π-π interactions between them. In the complex no classical hydrogen bonds are found and the three-dimensional network of the crystal is mainly consolidated by π-π interactions and weak interactions involving O atoms and the H atoms of adjacent pyridine rings.