Two novel coordination complexes, namely, dichlorido[3,5-dimethyl-1-(pyridin-2-yl-κN)-1H-pyrazole-κN2]zinc(II), [ZnCl2(C10H11N3)], 1, and aquachloridobis[3,5-dimethyl-1-(pyridin-2-yl-κN)-1H-pyrazole-κN2]nickel(II) chloride monohydrate, [NiCl(C10H11N3)(H2O)]Cl·H2O, 2, have been synthesized. The crystal structure analyses revealed that complexes 1 and 2 are mononuclear and have ZnN2Cl2 distorted tetrahedral and NiN4OCl distorted octahedral structures, respectively. Complex 1 displays a dimer in the crystal structure, while complex 2 forms a chain along the [010] direction. The fluorescence properties of both complexes were also investigated. A search of the Cambridge Structural Database for other complexes of the ligand 3,5-dimethyl-1-(pyridin-2-yl)-1H-pyrazole (L) shows that there exist different coordination polyhedra with different arrangements as monomers, dimers and polycyclic structures. Here it has also been demonstrated that there is a relationship between the crystal packing and the fluorescence properties of ZnII and CdII complexes of L.
Supporting information
CCDC references: 2085445; 2085444
Data collection: CrysAlis PRO (Rigaku OD, 2015) for compound1; CrysAlis PRO (Agilent, 2014) for compound2. Cell refinement: CrysAlis PRO (Rigaku OD, 2015) for compound1; CrysAlis PRO (Agilent, 2014) for compound2. Data reduction: CrysAlis PRO (Rigaku OD, 2015) for compound1; CrysAlis PRO (Agilent, 2014) for compound2. Program(s) used to solve structure: SHELXT (Sheldrick, 2015a) for compound1; SIR97 (Altomare et al., 1999) for compound2. Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b) for compound1; SHELXTL (Sheldrick, 2008). for compound2. Molecular graphics: DIAMOND (Brandenburg & Putz, 1999) for compound1. Software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and publCIF (Westrip, 2010) for compound1.
Dichlorido[3,5-dimethyl-1-(pyridin-2-yl-
κN)-1
H-pyrazole-
κN2]zinc(II) (compound1)
top
Crystal data top
[ZnCl2(C10H11N3)] | Z = 2 |
Mr = 309.49 | F(000) = 312 |
Triclinic, P1 | Dx = 1.680 Mg m−3 |
a = 7.4115 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.5345 (4) Å | Cell parameters from 2568 reflections |
c = 10.7790 (5) Å | θ = 3.4–35.3° |
α = 89.682 (4)° | µ = 2.42 mm−1 |
β = 72.145 (5)° | T = 100 K |
γ = 71.405 (5)° | Block, colorless |
V = 611.87 (6) Å3 | 0.32 × 0.26 × 0.2 mm |
Data collection top
Rigaku OD SuperNova Dual source diffractometer with an Atlas detector | 2459 independent reflections |
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source | 2245 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.012 |
Detector resolution: 10.4498 pixels mm-1 | θmax = 26.5°, θmin = 3.1° |
ω–scan | h = −9→9 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | k = −10→9 |
Tmin = 0.559, Tmax = 1.000 | l = −12→13 |
4062 measured reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.067 | w = 1/[σ2(Fo2) + (0.0381P)2 + 0.182P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.016 |
2459 reflections | Δρmax = 0.53 e Å−3 |
147 parameters | Δρmin = −0.27 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.70552 (4) | 0.82724 (3) | 0.28173 (2) | 0.04414 (10) | |
Cl1 | 0.79199 (9) | 0.90792 (7) | 0.44293 (6) | 0.05502 (15) | |
Cl2 | 0.60875 (10) | 1.00140 (7) | 0.14694 (6) | 0.06016 (16) | |
N1 | 0.9263 (2) | 0.60899 (18) | 0.19004 (16) | 0.0404 (4) | |
N2 | 0.8725 (2) | 0.47124 (18) | 0.22315 (16) | 0.0387 (3) | |
N3 | 0.5532 (2) | 0.65702 (19) | 0.32436 (16) | 0.0400 (3) | |
C2 | 1.1206 (3) | 0.5550 (2) | 0.1243 (2) | 0.0423 (4) | |
C5 | 0.6658 (3) | 0.4978 (2) | 0.28763 (18) | 0.0374 (4) | |
C4 | 1.0366 (3) | 0.3306 (2) | 0.1781 (2) | 0.0442 (4) | |
C3 | 1.1936 (3) | 0.3809 (3) | 0.1147 (2) | 0.0481 (5) | |
H3 | 1.3280 | 0.3113 | 0.0717 | 0.058* | |
C9 | 0.3540 (3) | 0.6942 (3) | 0.3823 (2) | 0.0486 (5) | |
H9 | 0.2729 | 0.8075 | 0.4077 | 0.058* | |
C6 | 0.5860 (3) | 0.3708 (3) | 0.3080 (2) | 0.0484 (5) | |
H6 | 0.6693 | 0.2584 | 0.2808 | 0.058* | |
C7 | 0.3819 (3) | 0.4116 (3) | 0.3691 (2) | 0.0514 (5) | |
H7 | 0.3229 | 0.3265 | 0.3856 | 0.062* | |
C8 | 0.2638 (3) | 0.5750 (3) | 0.4060 (2) | 0.0520 (5) | |
H8 | 0.1227 | 0.6047 | 0.4471 | 0.062* | |
C21 | 1.2277 (4) | 0.6748 (3) | 0.0753 (3) | 0.0580 (6) | |
H21A | 1.1297 | 0.7869 | 0.0872 | 0.087* | |
H21B | 1.3042 | 0.6437 | −0.0180 | 0.087* | |
H21C | 1.3199 | 0.6729 | 0.1244 | 0.087* | |
C41 | 1.0408 (4) | 0.1560 (3) | 0.1999 (3) | 0.0638 (7) | |
H41A | 0.9638 | 0.1242 | 0.1511 | 0.096* | |
H41B | 0.9812 | 0.1491 | 0.2935 | 0.096* | |
H41C | 1.1803 | 0.0805 | 0.1692 | 0.096* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.05413 (16) | 0.02706 (13) | 0.05909 (16) | −0.01673 (11) | −0.02577 (12) | 0.00539 (10) |
Cl1 | 0.0641 (3) | 0.0473 (3) | 0.0621 (3) | −0.0241 (3) | −0.0260 (3) | −0.0031 (2) |
Cl2 | 0.0768 (4) | 0.0389 (3) | 0.0728 (4) | −0.0151 (3) | −0.0396 (3) | 0.0139 (2) |
N1 | 0.0478 (9) | 0.0276 (8) | 0.0510 (9) | −0.0168 (7) | −0.0187 (8) | 0.0066 (7) |
N2 | 0.0449 (9) | 0.0256 (7) | 0.0495 (9) | −0.0148 (7) | −0.0173 (7) | 0.0051 (6) |
N3 | 0.0457 (9) | 0.0318 (8) | 0.0460 (8) | −0.0139 (7) | −0.0186 (7) | 0.0004 (6) |
C2 | 0.0482 (11) | 0.0376 (10) | 0.0466 (10) | −0.0183 (9) | −0.0187 (9) | 0.0059 (8) |
C5 | 0.0460 (10) | 0.0321 (9) | 0.0401 (9) | −0.0163 (8) | −0.0187 (8) | 0.0043 (7) |
C4 | 0.0485 (11) | 0.0297 (9) | 0.0583 (12) | −0.0131 (9) | −0.0226 (9) | 0.0045 (8) |
C3 | 0.0446 (11) | 0.0386 (11) | 0.0603 (12) | −0.0134 (9) | −0.0160 (10) | 0.0032 (9) |
C9 | 0.0492 (12) | 0.0414 (11) | 0.0529 (11) | −0.0121 (9) | −0.0163 (10) | −0.0039 (9) |
C6 | 0.0550 (12) | 0.0345 (10) | 0.0612 (12) | −0.0211 (9) | −0.0198 (10) | 0.0057 (9) |
C7 | 0.0573 (13) | 0.0497 (12) | 0.0573 (12) | −0.0305 (11) | −0.0193 (10) | 0.0100 (10) |
C8 | 0.0480 (11) | 0.0578 (13) | 0.0527 (12) | −0.0224 (10) | −0.0146 (10) | 0.0028 (10) |
C21 | 0.0568 (13) | 0.0501 (13) | 0.0708 (15) | −0.0284 (11) | −0.0145 (11) | 0.0117 (11) |
C41 | 0.0566 (14) | 0.0294 (11) | 0.101 (2) | −0.0116 (10) | −0.0216 (13) | 0.0116 (11) |
Geometric parameters (Å, º) top
Zn1—N1 | 2.0514 (16) | C3—H3 | 0.9500 |
Zn1—N3 | 2.0773 (16) | C9—C8 | 1.369 (3) |
Zn1—Cl2 | 2.1840 (6) | C9—H9 | 0.9500 |
Zn1—Cl1 | 2.2094 (6) | C6—C7 | 1.378 (3) |
N1—C2 | 1.320 (3) | C6—H6 | 0.9500 |
N1—N2 | 1.370 (2) | C7—C8 | 1.373 (3) |
N2—C4 | 1.368 (3) | C7—H7 | 0.9500 |
N2—C5 | 1.417 (2) | C8—H8 | 0.9500 |
N3—C5 | 1.334 (2) | C21—H21A | 0.9800 |
N3—C9 | 1.345 (3) | C21—H21B | 0.9800 |
C2—C3 | 1.402 (3) | C21—H21C | 0.9800 |
C2—C21 | 1.486 (3) | C41—H41A | 0.9800 |
C5—C6 | 1.378 (3) | C41—H41B | 0.9800 |
C4—C3 | 1.354 (3) | C41—H41C | 0.9800 |
C4—C41 | 1.499 (3) | | |
| | | |
N1—Zn1—N3 | 77.90 (6) | C2—C3—H3 | 126.4 |
N1—Zn1—Cl2 | 113.82 (5) | N3—C9—C8 | 122.5 (2) |
N3—Zn1—Cl2 | 113.42 (5) | N3—C9—H9 | 118.8 |
N1—Zn1—Cl1 | 106.89 (5) | C8—C9—H9 | 118.8 |
N3—Zn1—Cl1 | 115.74 (5) | C7—C6—C5 | 118.1 (2) |
Cl2—Zn1—Cl1 | 120.83 (2) | C7—C6—H6 | 120.9 |
C2—N1—N2 | 106.69 (15) | C5—C6—H6 | 120.9 |
C2—N1—Zn1 | 138.76 (13) | C8—C7—C6 | 119.99 (19) |
N2—N1—Zn1 | 113.28 (12) | C8—C7—H7 | 120.0 |
C4—N2—N1 | 110.06 (15) | C6—C7—H7 | 120.0 |
C4—N2—C5 | 132.82 (15) | C9—C8—C7 | 118.5 (2) |
N1—N2—C5 | 117.00 (15) | C9—C8—H8 | 120.8 |
C5—N3—C9 | 118.37 (17) | C7—C8—H8 | 120.8 |
C5—N3—Zn1 | 115.84 (13) | C2—C21—H21A | 109.5 |
C9—N3—Zn1 | 125.77 (13) | C2—C21—H21B | 109.5 |
N1—C2—C3 | 109.49 (17) | H21A—C21—H21B | 109.5 |
N1—C2—C21 | 120.34 (18) | C2—C21—H21C | 109.5 |
C3—C2—C21 | 130.2 (2) | H21A—C21—H21C | 109.5 |
N3—C5—C6 | 122.55 (19) | H21B—C21—H21C | 109.5 |
N3—C5—N2 | 114.33 (15) | C4—C41—H41A | 109.5 |
C6—C5—N2 | 123.10 (18) | C4—C41—H41B | 109.5 |
C3—C4—N2 | 106.58 (17) | H41A—C41—H41B | 109.5 |
C3—C4—C41 | 127.3 (2) | C4—C41—H41C | 109.5 |
N2—C4—C41 | 126.10 (19) | H41A—C41—H41C | 109.5 |
C4—C3—C2 | 107.17 (19) | H41B—C41—H41C | 109.5 |
C4—C3—H3 | 126.4 | | |
| | | |
C2—N1—N2—C4 | 0.5 (2) | N1—N2—C4—C3 | −0.9 (2) |
Zn1—N1—N2—C4 | −169.07 (12) | C5—N2—C4—C3 | 174.92 (19) |
C2—N1—N2—C5 | −176.00 (15) | N1—N2—C4—C41 | 177.1 (2) |
Zn1—N1—N2—C5 | 14.38 (19) | C5—N2—C4—C41 | −7.1 (4) |
N2—N1—C2—C3 | 0.0 (2) | N2—C4—C3—C2 | 0.9 (2) |
Zn1—N1—C2—C3 | 165.46 (16) | C41—C4—C3—C2 | −177.1 (2) |
N2—N1—C2—C21 | −179.17 (18) | N1—C2—C3—C4 | −0.6 (2) |
Zn1—N1—C2—C21 | −13.7 (3) | C21—C2—C3—C4 | 178.5 (2) |
C9—N3—C5—C6 | −0.7 (3) | C5—N3—C9—C8 | 0.8 (3) |
Zn1—N3—C5—C6 | −179.35 (15) | Zn1—N3—C9—C8 | 179.27 (16) |
C9—N3—C5—N2 | 177.77 (16) | N3—C5—C6—C7 | −0.1 (3) |
Zn1—N3—C5—N2 | −0.9 (2) | N2—C5—C6—C7 | −178.45 (18) |
C4—N2—C5—N3 | 175.43 (19) | C5—C6—C7—C8 | 0.9 (3) |
N1—N2—C5—N3 | −9.0 (2) | N3—C9—C8—C7 | 0.0 (3) |
C4—N2—C5—C6 | −6.1 (3) | C6—C7—C8—C9 | −0.8 (3) |
N1—N2—C5—C6 | 169.45 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···Cl1i | 0.95 | 2.75 | 3.568 (2) | 145 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Aquachloridobis[3,5-dimethyl-1-(pyridin-2-yl-
κN)-1
H-pyrazole-
κN2]nickel(II) chloride monohydrate (compound2)
top
Crystal data top
[NiCl(C10H11N3)2(H2O)]Cl·H2O | F(000) = 1064 |
Mr = 512.08 | Dx = 1.519 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.2306 (11) Å | Cell parameters from 1291 reflections |
b = 13.2638 (10) Å | θ = 4.4–24.6° |
c = 14.0560 (14) Å | µ = 1.14 mm−1 |
β = 100.981 (8)° | T = 173 K |
V = 2238.5 (3) Å3 | Rod, blue |
Z = 4 | 0.24 × 0.08 × 0.04 mm |
Data collection top
Oxford XCalibur diffractometer | 4070 independent reflections |
Radiation source: fine-focus sealed tube, Spellman generator | 2776 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 15.9809 pixels mm-1 | θmax = 25.4°, θmin = 4.2° |
ω scans | h = −14→14 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −8→15 |
Tmin = 0.994, Tmax = 1.000 | l = −16→16 |
7459 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0325P)2 + 0.0834P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
4070 reflections | Δρmax = 0.50 e Å−3 |
351 parameters | Δρmin = −0.38 e Å−3 |
160 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. The coordinates of the O-bound hydrogen atoms have been refined freely while
the isotropic displacement parameters have been calculated: U(H) = 1.5 U(O).
The O-H distances have been restrained to be equal within a standard deviation
of 0.01 Angstroem.
The disorder of one of the ligands has been described by a split model with
the non-disordered ligand acting as geometrical model (SAME restraint). The
ratio of site occupation factors refined to 0.88/0.12. All atoms of the minor
part have been refined isotropically involving the SIMU restraint for similar
refinement of the displacement parameters of atoms with a maximum distance
of 0.8 Angstroem. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | 0.2969 (3) | 0.9197 (2) | 0.4126 (2) | 0.0304 (8) | |
N2 | 0.2467 (3) | 0.7632 (2) | 0.3021 (2) | 0.0261 (8) | |
N3 | 0.3332 (2) | 0.7542 (2) | 0.3803 (2) | 0.0250 (8) | |
C1 | 0.3135 (4) | 1.0019 (3) | 0.4700 (3) | 0.0383 (11) | |
H1 | 0.275204 | 1.062413 | 0.448228 | 0.046* | |
C2 | 0.3837 (4) | 1.0015 (4) | 0.5586 (3) | 0.0462 (13) | |
H2 | 0.395910 | 1.061356 | 0.596227 | 0.055* | |
C3 | 0.4360 (4) | 0.9137 (4) | 0.5922 (3) | 0.0444 (12) | |
H3 | 0.483258 | 0.911524 | 0.654232 | 0.053* | |
C4 | 0.4198 (3) | 0.8301 (3) | 0.5364 (3) | 0.0382 (11) | |
H4 | 0.454059 | 0.768193 | 0.559174 | 0.046* | |
C5 | 0.3521 (3) | 0.8361 (3) | 0.4450 (3) | 0.0294 (10) | |
C6 | 0.1575 (4) | 0.6514 (3) | 0.1698 (3) | 0.0427 (12) | |
H6A | 0.083361 | 0.667835 | 0.182176 | 0.064* | |
H6B | 0.160686 | 0.579501 | 0.154348 | 0.064* | |
H6C | 0.172350 | 0.691515 | 0.115162 | 0.064* | |
C7 | 0.2422 (3) | 0.6743 (3) | 0.2571 (3) | 0.0297 (10) | |
C8 | 0.3254 (3) | 0.6098 (3) | 0.3054 (3) | 0.0326 (10) | |
H8 | 0.338829 | 0.542441 | 0.287785 | 0.039* | |
C9 | 0.3828 (3) | 0.6612 (3) | 0.3815 (3) | 0.0311 (10) | |
C10 | 0.4829 (4) | 0.6274 (3) | 0.4522 (3) | 0.0522 (14) | |
H10A | 0.539775 | 0.680340 | 0.459825 | 0.078* | |
H10B | 0.512561 | 0.565734 | 0.428358 | 0.078* | |
H10C | 0.461998 | 0.613992 | 0.514970 | 0.078* | |
N4 | 0.0443 (3) | 0.8814 (3) | 0.3283 (3) | 0.0248 (10) | 0.879 (4) |
N5 | 0.0766 (3) | 0.8851 (3) | 0.1514 (3) | 0.0268 (9) | 0.879 (4) |
N6 | −0.0304 (3) | 0.8704 (8) | 0.1658 (3) | 0.0251 (10) | 0.879 (4) |
C11 | 0.0354 (4) | 0.8851 (4) | 0.4226 (4) | 0.0295 (13) | 0.879 (4) |
H11A | 0.100498 | 0.897129 | 0.470081 | 0.035* | 0.879 (4) |
C12 | −0.0638 (4) | 0.8722 (4) | 0.4523 (4) | 0.0330 (13) | 0.879 (4) |
H12A | −0.068114 | 0.874616 | 0.519072 | 0.040* | 0.879 (4) |
C13 | −0.1578 (4) | 0.8555 (3) | 0.3818 (4) | 0.0319 (12) | 0.879 (4) |
H13 | −0.227585 | 0.844275 | 0.400253 | 0.038* | 0.879 (4) |
C14 | −0.1509 (6) | 0.8552 (18) | 0.2876 (4) | 0.0295 (13) | 0.879 (4) |
H14 | −0.215894 | 0.846080 | 0.239212 | 0.035* | 0.879 (4) |
C15 | −0.0478 (4) | 0.8682 (3) | 0.2615 (3) | 0.0245 (11) | 0.879 (4) |
C16 | 0.1700 (5) | 0.8942 (5) | 0.0124 (4) | 0.0432 (15) | 0.879 (4) |
H16A | 0.211318 | 0.954765 | 0.037988 | 0.065* | 0.879 (4) |
H16B | 0.147458 | 0.899971 | −0.058116 | 0.065* | 0.879 (4) |
H16C | 0.217545 | 0.834780 | 0.028295 | 0.065* | 0.879 (4) |
C17 | 0.0701 (4) | 0.8839 (3) | 0.0562 (3) | 0.0300 (12) | 0.879 (4) |
C18 | −0.0403 (5) | 0.8691 (9) | 0.0094 (4) | 0.0316 (17) | 0.879 (4) |
H18 | −0.066756 | 0.866262 | −0.058617 | 0.038* | 0.879 (4) |
C19 | −0.1024 (4) | 0.8595 (3) | 0.0785 (3) | 0.0324 (13) | 0.879 (4) |
C20 | −0.2251 (4) | 0.8403 (4) | 0.0636 (4) | 0.0458 (15) | 0.879 (4) |
H20A | −0.261022 | 0.894984 | 0.093035 | 0.069* | 0.879 (4) |
H20B | −0.238388 | 0.776117 | 0.094104 | 0.069* | 0.879 (4) |
H20C | −0.256052 | 0.837055 | −0.005924 | 0.069* | 0.879 (4) |
N4B | 0.1222 (18) | 0.898 (2) | 0.1254 (16) | 0.027 (3)* | 0.121 (4) |
N5B | 0.0308 (18) | 0.880 (2) | 0.2751 (14) | 0.024 (3)* | 0.121 (4) |
N6B | −0.036 (2) | 0.865 (6) | 0.1851 (15) | 0.024 (3)* | 0.121 (4) |
C11B | 0.182 (2) | 0.898 (5) | 0.0538 (19) | 0.047 (6)* | 0.121 (4) |
H11B | 0.259704 | 0.909507 | 0.069110 | 0.056* | 0.121 (4) |
C12B | 0.131 (2) | 0.883 (3) | −0.0404 (19) | 0.033 (11)* | 0.121 (4) |
H12B | 0.173949 | 0.883514 | −0.090125 | 0.040* | 0.121 (4) |
C13B | 0.017 (2) | 0.866 (2) | −0.0631 (17) | 0.032 (9)* | 0.121 (4) |
H13B | −0.019604 | 0.860282 | −0.128805 | 0.038* | 0.121 (4) |
C14B | −0.040 (3) | 0.857 (8) | 0.0091 (18) | 0.030 (3)* | 0.121 (4) |
H14B | −0.117691 | 0.841595 | −0.004607 | 0.036* | 0.121 (4) |
C15B | 0.0154 (19) | 0.871 (3) | 0.1041 (15) | 0.027 (9)* | 0.121 (4) |
C16B | −0.002 (3) | 0.884 (4) | 0.4410 (16) | 0.026 (5)* | 0.121 (4) |
H16D | −0.066232 | 0.886369 | 0.472907 | 0.038* | 0.121 (4) |
H16E | 0.041360 | 0.946678 | 0.454998 | 0.038* | 0.121 (4) |
H16F | 0.045371 | 0.826508 | 0.465257 | 0.038* | 0.121 (4) |
C17B | −0.0400 (19) | 0.874 (2) | 0.3354 (14) | 0.024 (8)* | 0.121 (4) |
C18B | −0.148 (4) | 0.852 (13) | 0.2874 (17) | 0.029 (3)* | 0.121 (4) |
H18B | −0.210534 | 0.836092 | 0.316193 | 0.035* | 0.121 (4) |
C19B | −0.1467 (16) | 0.857 (2) | 0.1931 (15) | 0.018 (7)* | 0.121 (4) |
C20B | −0.245 (2) | 0.839 (3) | 0.114 (2) | 0.034 (5)* | 0.121 (4) |
H20D | −0.313861 | 0.850560 | 0.138884 | 0.051* | 0.121 (4) |
H20E | −0.243855 | 0.769358 | 0.091196 | 0.051* | 0.121 (4) |
H20F | −0.242822 | 0.885368 | 0.060096 | 0.051* | 0.121 (4) |
Cl1 | 0.13307 (9) | 1.08796 (7) | 0.27704 (8) | 0.0388 (3) | |
Cl2 | 0.45368 (9) | 0.34181 (9) | 0.27094 (9) | 0.0478 (3) | |
Ni1 | 0.18951 (4) | 0.91142 (4) | 0.27749 (4) | 0.02430 (16) | |
O1 | 0.3217 (3) | 0.9446 (2) | 0.2126 (2) | 0.0432 (9) | |
H11 | 0.339 (4) | 1.0041 (19) | 0.202 (3) | 0.065* | |
H12 | 0.387 (2) | 0.923 (3) | 0.230 (3) | 0.065* | |
O2 | 0.3326 (3) | 0.3528 (2) | 0.6845 (3) | 0.0566 (10) | |
H21 | 0.275 (3) | 0.350 (3) | 0.708 (4) | 0.085* | |
H22 | 0.370 (4) | 0.304 (3) | 0.712 (4) | 0.085* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.025 (2) | 0.033 (2) | 0.033 (2) | −0.0029 (17) | 0.0035 (15) | −0.0038 (18) |
N2 | 0.023 (2) | 0.0287 (19) | 0.025 (2) | 0.0013 (16) | 0.0024 (14) | 0.0011 (16) |
N3 | 0.0159 (18) | 0.0306 (19) | 0.028 (2) | 0.0039 (15) | 0.0018 (14) | 0.0047 (17) |
C1 | 0.037 (3) | 0.035 (3) | 0.042 (3) | 0.001 (2) | 0.003 (2) | −0.011 (2) |
C2 | 0.041 (3) | 0.057 (3) | 0.040 (3) | −0.012 (3) | 0.005 (2) | −0.022 (3) |
C3 | 0.034 (3) | 0.069 (3) | 0.029 (3) | −0.010 (3) | 0.003 (2) | −0.008 (3) |
C4 | 0.032 (3) | 0.052 (3) | 0.029 (3) | −0.001 (2) | 0.000 (2) | 0.000 (2) |
C5 | 0.021 (2) | 0.039 (3) | 0.028 (3) | −0.005 (2) | 0.0051 (18) | −0.003 (2) |
C6 | 0.047 (3) | 0.038 (3) | 0.040 (3) | 0.001 (2) | 0.001 (2) | −0.007 (2) |
C7 | 0.031 (3) | 0.028 (2) | 0.032 (3) | −0.001 (2) | 0.0078 (19) | −0.001 (2) |
C8 | 0.034 (3) | 0.026 (2) | 0.040 (3) | 0.005 (2) | 0.013 (2) | 0.006 (2) |
C9 | 0.028 (2) | 0.034 (2) | 0.034 (3) | 0.013 (2) | 0.011 (2) | 0.014 (2) |
C10 | 0.051 (3) | 0.064 (3) | 0.040 (3) | 0.028 (3) | 0.005 (2) | 0.007 (3) |
N4 | 0.025 (2) | 0.0242 (19) | 0.025 (2) | 0.0018 (16) | 0.0035 (17) | 0.0008 (19) |
N5 | 0.027 (2) | 0.028 (2) | 0.026 (2) | 0.0016 (18) | 0.0076 (17) | −0.0009 (18) |
N6 | 0.020 (2) | 0.029 (2) | 0.026 (2) | 0.0020 (17) | 0.0030 (17) | 0.000 (3) |
C11 | 0.026 (3) | 0.032 (3) | 0.029 (3) | 0.003 (3) | 0.003 (2) | 0.003 (2) |
C12 | 0.032 (3) | 0.039 (3) | 0.030 (3) | −0.002 (3) | 0.011 (2) | −0.002 (2) |
C13 | 0.027 (3) | 0.029 (3) | 0.043 (3) | −0.003 (2) | 0.016 (2) | −0.005 (2) |
C14 | 0.023 (2) | 0.030 (3) | 0.034 (3) | 0.004 (2) | 0.002 (2) | 0.001 (2) |
C15 | 0.028 (3) | 0.020 (2) | 0.024 (3) | 0.001 (2) | 0.000 (2) | −0.004 (2) |
C16 | 0.045 (3) | 0.048 (3) | 0.042 (4) | 0.013 (3) | 0.021 (3) | 0.009 (4) |
C17 | 0.040 (3) | 0.025 (3) | 0.025 (3) | 0.009 (2) | 0.008 (2) | 0.003 (2) |
C18 | 0.035 (3) | 0.032 (4) | 0.025 (2) | 0.007 (2) | −0.002 (2) | −0.003 (2) |
C19 | 0.033 (3) | 0.030 (3) | 0.030 (3) | 0.001 (2) | −0.004 (2) | −0.004 (2) |
C20 | 0.034 (3) | 0.064 (4) | 0.035 (3) | −0.003 (3) | −0.007 (2) | −0.007 (3) |
Cl1 | 0.0342 (7) | 0.0273 (6) | 0.0575 (8) | 0.0051 (5) | 0.0154 (5) | 0.0030 (5) |
Cl2 | 0.0307 (7) | 0.0489 (7) | 0.0592 (9) | −0.0070 (6) | −0.0031 (5) | 0.0159 (6) |
Ni1 | 0.0196 (3) | 0.0246 (3) | 0.0283 (3) | 0.0016 (2) | 0.0036 (2) | −0.0006 (2) |
O1 | 0.0304 (19) | 0.0392 (18) | 0.065 (2) | 0.0070 (16) | 0.0214 (17) | 0.0130 (18) |
O2 | 0.060 (3) | 0.038 (2) | 0.080 (3) | 0.0051 (18) | 0.033 (2) | 0.0027 (19) |
Geometric parameters (Å, º) top
N1—C5 | 1.333 (5) | C16—H16A | 0.9800 |
N1—C1 | 1.348 (5) | C16—H16B | 0.9800 |
N1—Ni1 | 2.096 (3) | C16—H16C | 0.9800 |
N2—C7 | 1.334 (4) | C17—C18 | 1.399 (7) |
N2—N3 | 1.378 (4) | C18—C19 | 1.347 (7) |
N2—Ni1 | 2.093 (3) | C18—H18 | 0.9500 |
N3—C9 | 1.374 (4) | C19—C20 | 1.497 (6) |
N3—C5 | 1.407 (5) | C20—H20A | 0.9800 |
C1—C2 | 1.372 (6) | C20—H20B | 0.9800 |
C1—H1 | 0.9500 | C20—H20C | 0.9800 |
C2—C3 | 1.368 (6) | N4B—C15B | 1.335 (16) |
C2—H2 | 0.9500 | N4B—C11B | 1.349 (16) |
C3—C4 | 1.350 (5) | N4B—Ni1 | 2.15 (2) |
C3—H3 | 0.9500 | N5B—C17B | 1.326 (16) |
C4—C5 | 1.391 (5) | N5B—N6B | 1.386 (16) |
C4—H4 | 0.9500 | N5B—Ni1 | 1.98 (2) |
C6—C7 | 1.478 (5) | N6B—C19B | 1.377 (15) |
C6—H6A | 0.9800 | N6B—C15B | 1.408 (15) |
C6—H6B | 0.9800 | C11B—C12B | 1.365 (17) |
C6—H6C | 0.9800 | C11B—H11B | 0.9500 |
C7—C8 | 1.402 (5) | C12B—C13B | 1.387 (16) |
C8—C9 | 1.347 (5) | C12B—H12B | 0.9500 |
C8—H8 | 0.9500 | C13B—C14B | 1.347 (17) |
C9—C10 | 1.491 (5) | C13B—H13B | 0.9500 |
C10—H10A | 0.9800 | C14B—C15B | 1.390 (16) |
C10—H10B | 0.9800 | C14B—H14B | 0.9500 |
C10—H10C | 0.9800 | C16B—C17B | 1.474 (16) |
N4—C15 | 1.334 (5) | C16B—H16D | 0.9800 |
N4—C11 | 1.352 (6) | C16B—H16E | 0.9800 |
N4—Ni1 | 2.075 (4) | C16B—H16F | 0.9800 |
N5—C17 | 1.326 (5) | C17B—C18B | 1.400 (17) |
N5—N6 | 1.376 (5) | C18B—C19B | 1.332 (17) |
N5—Ni1 | 2.059 (4) | C18B—H18B | 0.9500 |
N6—C19 | 1.375 (6) | C19B—C20B | 1.496 (15) |
N6—C15 | 1.402 (5) | C20B—H20D | 0.9800 |
C11—C12 | 1.366 (6) | C20B—H20E | 0.9800 |
C11—H11A | 0.9500 | C20B—H20F | 0.9800 |
C12—C13 | 1.385 (6) | Cl1—Ni1 | 2.4408 (11) |
C12—H12A | 0.9500 | Ni1—O1 | 2.050 (3) |
C13—C14 | 1.344 (6) | O1—H11 | 0.84 (2) |
C13—H13 | 0.9500 | O1—H12 | 0.84 (2) |
C14—C15 | 1.389 (6) | O2—H21 | 0.84 (2) |
C14—H14 | 0.9500 | O2—H22 | 0.84 (2) |
C16—C17 | 1.475 (6) | | |
| | | |
C5—N1—C1 | 117.3 (4) | C18—C19—C20 | 127.1 (5) |
C5—N1—Ni1 | 117.1 (3) | N6—C19—C20 | 126.6 (4) |
C1—N1—Ni1 | 125.6 (3) | C19—C20—H20A | 109.5 |
C7—N2—N3 | 105.0 (3) | C19—C20—H20B | 109.5 |
C7—N2—Ni1 | 140.3 (3) | H20A—C20—H20B | 109.5 |
N3—N2—Ni1 | 113.2 (2) | C19—C20—H20C | 109.5 |
C9—N3—N2 | 110.9 (3) | H20A—C20—H20C | 109.5 |
C9—N3—C5 | 131.9 (3) | H20B—C20—H20C | 109.5 |
N2—N3—C5 | 117.1 (3) | C15B—N4B—C11B | 118.4 (18) |
N1—C1—C2 | 122.5 (4) | C15B—N4B—Ni1 | 114.8 (14) |
N1—C1—H1 | 118.8 | C11B—N4B—Ni1 | 125.7 (17) |
C2—C1—H1 | 118.8 | C17B—N5B—N6B | 103.2 (15) |
C3—C2—C1 | 119.2 (4) | C17B—N5B—Ni1 | 139.5 (15) |
C3—C2—H2 | 120.4 | N6B—N5B—Ni1 | 117.2 (12) |
C1—C2—H2 | 120.4 | C19B—N6B—N5B | 110.9 (15) |
C4—C3—C2 | 119.4 (4) | C19B—N6B—C15B | 131.9 (18) |
C4—C3—H3 | 120.3 | N5B—N6B—C15B | 116.7 (15) |
C2—C3—H3 | 120.3 | N4B—C11B—C12B | 121 (2) |
C3—C4—C5 | 119.1 (4) | N4B—C11B—H11B | 119.5 |
C3—C4—H4 | 120.5 | C12B—C11B—H11B | 119.5 |
C5—C4—H4 | 120.5 | C11B—C12B—C13B | 120 (2) |
N1—C5—C4 | 122.4 (4) | C11B—C12B—H12B | 120.1 |
N1—C5—N3 | 114.3 (3) | C13B—C12B—H12B | 120.1 |
C4—C5—N3 | 123.3 (4) | C14B—C13B—C12B | 119.2 (19) |
C7—C6—H6A | 109.5 | C14B—C13B—H13B | 120.4 |
C7—C6—H6B | 109.5 | C12B—C13B—H13B | 120.4 |
H6A—C6—H6B | 109.5 | C13B—C14B—C15B | 119 (2) |
C7—C6—H6C | 109.5 | C13B—C14B—H14B | 120.6 |
H6A—C6—H6C | 109.5 | C15B—C14B—H14B | 120.6 |
H6B—C6—H6C | 109.5 | N4B—C15B—C14B | 122.1 (17) |
N2—C7—C8 | 110.4 (4) | N4B—C15B—N6B | 113.9 (17) |
N2—C7—C6 | 122.3 (4) | C14B—C15B—N6B | 123.8 (18) |
C8—C7—C6 | 127.3 (4) | C17B—C16B—H16D | 109.5 |
C9—C8—C7 | 107.2 (3) | C17B—C16B—H16E | 109.5 |
C9—C8—H8 | 126.4 | H16D—C16B—H16E | 109.5 |
C7—C8—H8 | 126.4 | C17B—C16B—H16F | 109.5 |
C8—C9—N3 | 106.4 (3) | H16D—C16B—H16F | 109.5 |
C8—C9—C10 | 127.9 (4) | H16E—C16B—H16F | 109.5 |
N3—C9—C10 | 125.6 (4) | N5B—C17B—C18B | 112.2 (16) |
C9—C10—H10A | 109.5 | N5B—C17B—C16B | 121 (2) |
C9—C10—H10B | 109.5 | C18B—C17B—C16B | 126.5 (19) |
H10A—C10—H10B | 109.5 | C19B—C18B—C17B | 106.0 (18) |
C9—C10—H10C | 109.5 | C19B—C18B—H18B | 127.0 |
H10A—C10—H10C | 109.5 | C17B—C18B—H18B | 127.0 |
H10B—C10—H10C | 109.5 | C18B—C19B—N6B | 106.6 (17) |
C15—N4—C11 | 118.6 (4) | C18B—C19B—C20B | 124.5 (19) |
C15—N4—Ni1 | 116.6 (3) | N6B—C19B—C20B | 127.9 (19) |
C11—N4—Ni1 | 124.4 (3) | C19B—C20B—H20D | 109.5 |
C17—N5—N6 | 105.7 (4) | C19B—C20B—H20E | 109.5 |
C17—N5—Ni1 | 140.6 (3) | H20D—C20B—H20E | 109.5 |
N6—N5—Ni1 | 113.5 (3) | C19B—C20B—H20F | 109.5 |
C19—N6—N5 | 110.4 (4) | H20D—C20B—H20F | 109.5 |
C19—N6—C15 | 131.8 (4) | H20E—C20B—H20F | 109.5 |
N5—N6—C15 | 117.8 (4) | N5B—Ni1—O1 | 153.1 (6) |
N4—C11—C12 | 122.5 (4) | O1—Ni1—N5 | 96.31 (14) |
N4—C11—H11A | 118.7 | O1—Ni1—N4 | 173.55 (14) |
C12—C11—H11A | 118.7 | N5—Ni1—N4 | 77.64 (15) |
C11—C12—C13 | 117.7 (4) | N5B—Ni1—N2 | 95.9 (9) |
C11—C12—H12A | 121.1 | O1—Ni1—N2 | 90.48 (12) |
C13—C12—H12A | 121.1 | N5—Ni1—N2 | 97.53 (14) |
C14—C13—C12 | 120.5 (4) | N4—Ni1—N2 | 92.51 (13) |
C14—C13—H13 | 119.8 | N5B—Ni1—N1 | 118.0 (6) |
C12—C13—H13 | 119.8 | O1—Ni1—N1 | 88.88 (13) |
C13—C14—C15 | 119.4 (5) | N5—Ni1—N1 | 172.23 (14) |
C13—C14—H14 | 120.3 | N4—Ni1—N1 | 97.37 (14) |
C15—C14—H14 | 120.3 | N2—Ni1—N1 | 76.59 (12) |
N4—C15—C14 | 121.2 (4) | N5B—Ni1—N4B | 77.1 (8) |
N4—C15—N6 | 114.2 (4) | O1—Ni1—N4B | 76.1 (6) |
C14—C15—N6 | 124.6 (4) | N2—Ni1—N4B | 98.1 (8) |
C17—C16—H16A | 109.5 | N1—Ni1—N4B | 164.1 (6) |
C17—C16—H16B | 109.5 | N5B—Ni1—Cl1 | 85.6 (9) |
H16A—C16—H16B | 109.5 | O1—Ni1—Cl1 | 92.26 (9) |
C17—C16—H16C | 109.5 | N5—Ni1—Cl1 | 90.99 (11) |
H16A—C16—H16C | 109.5 | N4—Ni1—Cl1 | 85.68 (10) |
H16B—C16—H16C | 109.5 | N2—Ni1—Cl1 | 170.71 (9) |
N5—C17—C18 | 110.1 (4) | N1—Ni1—Cl1 | 94.59 (9) |
N5—C17—C16 | 121.6 (4) | N4B—Ni1—Cl1 | 91.2 (8) |
C18—C17—C16 | 128.3 (5) | Ni1—O1—H11 | 122 (3) |
C19—C18—C17 | 107.5 (5) | Ni1—O1—H12 | 125 (3) |
C19—C18—H18 | 126.3 | H11—O1—H12 | 97 (4) |
C17—C18—H18 | 126.3 | H21—O2—H22 | 102 (5) |
C18—C19—N6 | 106.3 (5) | | |
| | | |
C7—N2—N3—C9 | 1.5 (4) | N5—N6—C15—N4 | 0.2 (10) |
Ni1—N2—N3—C9 | −167.4 (2) | C19—N6—C15—C14 | −1.2 (18) |
C7—N2—N3—C5 | −175.9 (3) | N5—N6—C15—C14 | 179.2 (13) |
Ni1—N2—N3—C5 | 15.2 (4) | N6—N5—C17—C18 | 0.3 (8) |
C5—N1—C1—C2 | −0.1 (6) | Ni1—N5—C17—C18 | −173.7 (6) |
Ni1—N1—C1—C2 | 178.7 (3) | N6—N5—C17—C16 | −178.0 (6) |
N1—C1—C2—C3 | −2.5 (7) | Ni1—N5—C17—C16 | 7.9 (8) |
C1—C2—C3—C4 | 1.8 (7) | N5—C17—C18—C19 | −0.9 (10) |
C2—C3—C4—C5 | 1.4 (7) | C16—C17—C18—C19 | 177.3 (6) |
C1—N1—C5—C4 | 3.5 (6) | C17—C18—C19—N6 | 1.1 (10) |
Ni1—N1—C5—C4 | −175.5 (3) | C17—C18—C19—C20 | −178.5 (5) |
C1—N1—C5—N3 | −178.3 (3) | N5—N6—C19—C18 | −0.9 (10) |
Ni1—N1—C5—N3 | 2.7 (4) | C15—N6—C19—C18 | 179.5 (10) |
C3—C4—C5—N1 | −4.2 (6) | N5—N6—C19—C20 | 178.7 (5) |
C3—C4—C5—N3 | 177.8 (4) | C15—N6—C19—C20 | −0.9 (14) |
C9—N3—C5—N1 | 171.3 (4) | C17B—N5B—N6B—C19B | 5 (7) |
N2—N3—C5—N1 | −12.0 (5) | Ni1—N5B—N6B—C19B | −172 (4) |
C9—N3—C5—C4 | −10.6 (7) | C17B—N5B—N6B—C15B | 177 (6) |
N2—N3—C5—C4 | 166.2 (4) | Ni1—N5B—N6B—C15B | 1 (8) |
N3—N2—C7—C8 | −0.5 (4) | C15B—N4B—C11B—C12B | 8 (7) |
Ni1—N2—C7—C8 | 163.3 (3) | Ni1—N4B—C11B—C12B | 176 (4) |
N3—N2—C7—C6 | 178.2 (4) | N4B—C11B—C12B—C13B | 0 (8) |
Ni1—N2—C7—C6 | −17.9 (7) | C11B—C12B—C13B—C14B | −5 (8) |
N2—C7—C8—C9 | −0.6 (5) | C12B—C13B—C14B—C15B | 3 (10) |
C6—C7—C8—C9 | −179.3 (4) | C11B—N4B—C15B—C14B | −10 (7) |
C7—C8—C9—N3 | 1.4 (5) | Ni1—N4B—C15B—C14B | −179 (6) |
C7—C8—C9—C10 | −176.6 (4) | C11B—N4B—C15B—N6B | 175 (5) |
N2—N3—C9—C8 | −1.8 (4) | Ni1—N4B—C15B—N6B | 6 (5) |
C5—N3—C9—C8 | 175.1 (4) | C13B—C14B—C15B—N4B | 4 (11) |
N2—N3—C9—C10 | 176.3 (4) | C13B—C14B—C15B—N6B | 179 (7) |
C5—N3—C9—C10 | −6.8 (7) | C19B—N6B—C15B—N4B | 167 (7) |
C17—N5—N6—C19 | 0.3 (8) | N5B—N6B—C15B—N4B | −5 (8) |
Ni1—N5—N6—C19 | 176.2 (5) | C19B—N6B—C15B—C14B | −9 (12) |
C17—N5—N6—C15 | 180.0 (6) | N5B—N6B—C15B—C14B | −180 (7) |
Ni1—N5—N6—C15 | −4.1 (9) | N6B—N5B—C17B—C18B | 2 (9) |
C15—N4—C11—C12 | 2.4 (7) | Ni1—N5B—C17B—C18B | 177 (8) |
Ni1—N4—C11—C12 | 175.0 (3) | N6B—N5B—C17B—C16B | 178 (5) |
N4—C11—C12—C13 | −0.5 (7) | Ni1—N5B—C17B—C16B | −7 (6) |
C11—C12—C13—C14 | −1.9 (13) | N5B—C17B—C18B—C19B | −8 (14) |
C12—C13—C14—C15 | 2 (2) | C16B—C17B—C18B—C19B | 176 (6) |
C11—N4—C15—C14 | −2.0 (13) | C17B—C18B—C19B—N6B | 10 (13) |
Ni1—N4—C15—C14 | −175.2 (12) | C17B—C18B—C19B—C20B | −180 (6) |
C11—N4—C15—N6 | 177.1 (6) | N5B—N6B—C19B—C18B | −10 (10) |
Ni1—N4—C15—N6 | 3.9 (6) | C15B—N6B—C19B—C18B | 179 (11) |
C13—C14—C15—N4 | 0 (2) | N5B—N6B—C19B—C20B | −179 (4) |
C13—C14—C15—N6 | −179.2 (12) | C15B—N6B—C19B—C20B | 10 (12) |
C19—N6—C15—N4 | 179.7 (8) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O2i | 0.84 (2) | 1.91 (2) | 2.722 (4) | 162 (4) |
O1—H12···Cl2ii | 0.84 (2) | 2.23 (3) | 3.036 (3) | 161 (4) |
O2—H21···Cl1iii | 0.84 (2) | 2.29 (2) | 3.078 (4) | 157 (3) |
O2—H22···Cl2iv | 0.84 (2) | 2.27 (2) | 3.106 (4) | 171 (5) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+3/2, z+1/2; (iv) x, −y+1/2, z+1/2. |