metal-organic compounds
Dichlorido{(E)-4-dimethylamino-N′-[(pyridin-2-yl)methylidene-κN]benzohydrazide-κO}zinc
aDepartamento de Química, Facultad de Ciencias, Universidad del Valle, AA 25360, Santiago de Cali, Colombia
*Correspondence e-mail: manuel.chaur@correounivalle.edu.co
In the mononuclear title complex, [ZnCl2(C15H16N4O)], the ZnII cation is five-coordinated in a strongly distorted square-pyramidal environment by two Cl− anions and a neutral tridentate Schiff base ligand. The ZnII cation is chelated by the carbonyl O atom, the imine N atom and the pyridine N atom, which causes a slight loss of planarity for the ligand; the dihedral angle between the aromatic rings is 4.61 (8)°.
Related literature
For related structures, see: Moreno-Fuquen et al. (2012); Chaur et al. (2011); Ma et al. (2011). For the structure of the ligand and its complex with CuCl2, see: Sangeetha, Pal & Pal (2000); Sangeetha, Pal, Anson et al. (2000). For the design of molecular dynamic systems, see: Hirose (2010); Lehn (2006). For the synthetic principles of compounds exhibiting dynamic properties, see Kay et al. (2007). For information storage, see: Kandel (2001).
Experimental
Crystal data
|
Data collection: COLLECT (Nonius, 1998); cell DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536812049355/bh2455sup1.cif
contains datablocks I, global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049355/bh2455Isup2.hkl
(E)-4-(Dimethylamino)-N'-(pyridin-2-ylmethylene)benzohydrazide: 2-pyridinecarboxaldehyde (1.0 equivalent) was added to an ethanol solution of 4-(dimethylamino)benzohydrazine (1.0 equiv.) and a trace amount of glacial acetic acid. The reaction mixture was refluxed for three hours, then the precipitate was collected in a Büchner funnel and recrystallized from ethanol affording the ligand in a 90% yield.
[Zn(C15H16N4O)Cl2]: Two hot ethanolic solutions of the previously prepared Schiff base ligand and ZnCl2 in stoichiometric proportions were mixed and then allowed to cool. The complex salt crystallized out. Then the product was recrystallized from ethanol. Crystals suitable for X-ray diffraction were obtained by slow diffusion of methanol over a DMSO solution of the zinc complex.
All H atoms were placed in idealized positions, with C—H bond lengths fixed to 0.93 (aromatic CH) or 0.96 Å (methyl), and refined as riding with displacement parameters calculated as Uiso(H) = xUeq(carrier C) where x = 1.2 (aromatic CH) or 1.5 (methyl).
Similar to bis-pyridyl
derivatives, pyridine-2-carboxaldehyde acyl (aroyl) are able to undergo configurational (E/Z) isomerization and constitutional changes as well as their structure allows them to coordinate to metallic centers by a tridentade NNO binding site (Chaur et al., 2011). Therefore, the C=N bond of these can be used in double dynamic processes of interest for information storage (Lehn, 2006; Kay et al., 2007). The configurational dynamics of these compounds give access to short term photoactivated metastable states. On the other hand, they can undergo constitutional dynamics by constituent exchange allowing long term storage of information (Kandel, 2001).Thus the pyridyl-acyl
are appealing compounds for the design of systems exhibiting multiple states and interconversion processes that involve configurational/constitutional changes, as well as metal coordination (Ma et al., 2011). These features together with increasing time scales being of interest for the development of both short-term and long-term molecular information storage and processing devices that may be addressed by orthogonal transformations involving either physical stimuli (light, heat; see Hirose, 2010) or chemical effectors (amino components or metal cations).In this regard our group focuses on the design of bis-pyridyl and pyridyl-acyl
as the title compound (Fig. 1), for the implementation of dynamic systems exhibiting reversible multiplex states for information storage (Moreno-Fuquen et al., 2012). The new complex is based on a ligand for which the structure has been previously established (Sangeetha, Pal & Pal, 2000), as well as a Cu(II) complex (Sangeetha, Pal, Anson et al., 2000).The title complex exhibits a distorted five-coordinated square-pyramidal disposition (Fig. 2). The Schiff base ligand is not planar (Fig. 3), resulting in a dihedral angle between the planes of the aromatic and pyridyl rings of 4.61 (8)°, while the free ligand is planar (Sangeetha, Pal & Pal, 2000). The molecules stack forming columns along the [001] direction by intermolecular hydrogen bonds with a distance N3—H3···Cl2 = 3.199 (2) Å. Also it is observed a weak π–π slipped stacking interaction between the aromatic rings, with separations between ring centroids of 3.8075 (1) Å (Fig. 4).
For related structures, see: Moreno-Fuquen et al. (2012); Chaur et al. (2011); Ma et al. (2011). For the structure of the ligand and its complex with CuCl2, see: Sangeetha, Pal & Pal (2000); Sangeetha, Pal, Anson et al. (2000). For the design of molecular dynamic systems, see: Hirose (2010); Lehn (2006). For the synthetic principles of compounds exhibiting dynamic properties, see Kay et al. (2007). For information storage, see: Kandel (2001).
Data collection: COLLECT (Nonius, 1998); cell
DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).[ZnCl2(C15H16N4O)] | F(000) = 824 |
Mr = 404.59 | Dx = 1.609 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 18477 reflections |
a = 16.1822 (7) Å | θ = 1.0–27.5° |
b = 13.5864 (7) Å | µ = 1.80 mm−1 |
c = 7.5989 (2) Å | T = 173 K |
β = 91.123 (3)° | Plate, orange |
V = 1670.36 (12) Å3 | 0.40 × 0.22 × 0.10 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 3803 independent reflections |
Radiation source: fine-focus sealed tube | 3252 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
φ and ω scans | θmax = 27.5°, θmin = 1.3° |
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009) | h = −18→20 |
Tmin = 0.538, Tmax = 0.764 | k = −17→16 |
14366 measured reflections | l = −9→8 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0401P)2 + 0.7957P] where P = (Fo2 + 2Fc2)/3 |
3803 reflections | (Δ/σ)max = 0.001 |
210 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.74 e Å−3 |
0 constraints |
[ZnCl2(C15H16N4O)] | V = 1670.36 (12) Å3 |
Mr = 404.59 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.1822 (7) Å | µ = 1.80 mm−1 |
b = 13.5864 (7) Å | T = 173 K |
c = 7.5989 (2) Å | 0.40 × 0.22 × 0.10 mm |
β = 91.123 (3)° |
Nonius KappaCCD diffractometer | 3803 independent reflections |
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009) | 3252 reflections with I > 2σ(I) |
Tmin = 0.538, Tmax = 0.764 | Rint = 0.055 |
14366 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.33 e Å−3 |
3803 reflections | Δρmin = −0.74 e Å−3 |
210 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.00605 (14) | 0.89834 (18) | 0.1655 (3) | 0.0286 (5) | |
H1A | 0.0063 | 0.9667 | 0.1708 | 0.034* | |
C2 | −0.06416 (14) | 0.85138 (19) | 0.0983 (3) | 0.0307 (5) | |
H2A | −0.1101 | 0.8875 | 0.0608 | 0.037* | |
C3 | −0.06401 (14) | 0.75050 (19) | 0.0887 (3) | 0.0291 (5) | |
H3A | −0.1098 | 0.7172 | 0.0428 | 0.035* | |
C4 | 0.00513 (13) | 0.69839 (17) | 0.1480 (3) | 0.0241 (5) | |
H4A | 0.0064 | 0.6300 | 0.1422 | 0.029* | |
C5 | 0.07173 (12) | 0.75049 (16) | 0.2157 (3) | 0.0206 (4) | |
C6 | 0.14641 (13) | 0.70244 (16) | 0.2877 (3) | 0.0223 (4) | |
H6A | 0.1522 | 0.6344 | 0.2903 | 0.027* | |
C7 | 0.32992 (13) | 0.79835 (16) | 0.4744 (3) | 0.0219 (4) | |
C8 | 0.40823 (13) | 0.76645 (17) | 0.5528 (3) | 0.0226 (4) | |
C9 | 0.42999 (13) | 0.66764 (18) | 0.5805 (3) | 0.0250 (5) | |
H9A | 0.3925 | 0.6183 | 0.5502 | 0.030* | |
C10 | 0.50558 (14) | 0.64279 (19) | 0.6515 (3) | 0.0284 (5) | |
H10A | 0.5182 | 0.5768 | 0.6697 | 0.034* | |
C11 | 0.56503 (13) | 0.71553 (19) | 0.6978 (3) | 0.0256 (5) | |
C12 | 0.54238 (14) | 0.81434 (19) | 0.6719 (3) | 0.0282 (5) | |
H12A | 0.5794 | 0.8640 | 0.7032 | 0.034* | |
C13 | 0.46628 (13) | 0.83866 (18) | 0.6010 (3) | 0.0270 (5) | |
H13A | 0.4530 | 0.9047 | 0.5845 | 0.032* | |
C14 | 0.70184 (15) | 0.7651 (2) | 0.8079 (3) | 0.0408 (7) | |
H14A | 0.7102 | 0.8067 | 0.7077 | 0.061* | |
H14B | 0.7531 | 0.7341 | 0.8414 | 0.061* | |
H14C | 0.6825 | 0.8040 | 0.9042 | 0.061* | |
C15 | 0.65998 (16) | 0.5884 (2) | 0.8059 (4) | 0.0396 (6) | |
H15A | 0.6212 | 0.5644 | 0.8897 | 0.059* | |
H15B | 0.7149 | 0.5843 | 0.8552 | 0.059* | |
H15C | 0.6564 | 0.5492 | 0.7009 | 0.059* | |
N1 | 0.07305 (11) | 0.84965 (14) | 0.2226 (2) | 0.0232 (4) | |
N2 | 0.20292 (10) | 0.76034 (14) | 0.3464 (2) | 0.0216 (4) | |
N3 | 0.27499 (11) | 0.72631 (14) | 0.4181 (2) | 0.0232 (4) | |
H3B | 0.2857 | 0.6645 | 0.4278 | 0.028* | |
N4 | 0.64094 (12) | 0.69027 (16) | 0.7633 (3) | 0.0328 (5) | |
O1 | 0.31050 (10) | 0.88558 (12) | 0.4524 (2) | 0.0295 (4) | |
Cl1 | 0.13487 (3) | 1.01282 (4) | 0.52926 (7) | 0.02717 (13) | |
Cl2 | 0.23435 (3) | 0.98562 (4) | 0.07806 (7) | 0.02852 (14) | |
Zn1 | 0.189086 (15) | 0.914569 (19) | 0.32708 (3) | 0.02243 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0269 (12) | 0.0245 (13) | 0.0343 (12) | 0.0053 (9) | −0.0051 (9) | −0.0028 (9) |
C2 | 0.0244 (12) | 0.0315 (14) | 0.0360 (12) | 0.0074 (10) | −0.0066 (9) | −0.0026 (10) |
C3 | 0.0229 (11) | 0.0323 (14) | 0.0317 (11) | −0.0025 (10) | −0.0045 (9) | −0.0051 (10) |
C4 | 0.0247 (11) | 0.0212 (12) | 0.0263 (10) | −0.0005 (9) | −0.0021 (8) | −0.0015 (9) |
C5 | 0.0212 (10) | 0.0209 (11) | 0.0196 (9) | −0.0010 (9) | 0.0001 (8) | −0.0004 (8) |
C6 | 0.0223 (11) | 0.0193 (11) | 0.0252 (10) | 0.0011 (9) | −0.0027 (8) | −0.0010 (8) |
C7 | 0.0212 (10) | 0.0224 (12) | 0.0221 (10) | −0.0005 (9) | 0.0006 (8) | −0.0015 (8) |
C8 | 0.0179 (10) | 0.0283 (12) | 0.0216 (10) | 0.0019 (9) | 0.0004 (8) | −0.0007 (9) |
C9 | 0.0214 (11) | 0.0264 (12) | 0.0271 (10) | −0.0007 (9) | −0.0012 (8) | 0.0005 (9) |
C10 | 0.0245 (12) | 0.0259 (13) | 0.0345 (12) | 0.0054 (9) | −0.0036 (9) | 0.0031 (10) |
C11 | 0.0181 (10) | 0.0376 (14) | 0.0210 (10) | 0.0018 (10) | −0.0001 (8) | 0.0021 (9) |
C12 | 0.0218 (11) | 0.0338 (13) | 0.0290 (11) | −0.0046 (10) | −0.0028 (9) | 0.0015 (10) |
C13 | 0.0237 (11) | 0.0275 (13) | 0.0297 (11) | 0.0023 (10) | −0.0024 (9) | 0.0032 (9) |
C14 | 0.0225 (12) | 0.061 (2) | 0.0390 (14) | −0.0028 (12) | −0.0078 (10) | 0.0057 (13) |
C15 | 0.0289 (13) | 0.0446 (17) | 0.0448 (14) | 0.0154 (12) | −0.0089 (11) | −0.0008 (12) |
N1 | 0.0226 (9) | 0.0215 (10) | 0.0252 (9) | −0.0005 (8) | −0.0012 (7) | 0.0009 (7) |
N2 | 0.0184 (9) | 0.0235 (10) | 0.0228 (8) | 0.0015 (7) | −0.0003 (7) | 0.0018 (7) |
N3 | 0.0183 (9) | 0.0211 (10) | 0.0299 (9) | 0.0039 (8) | −0.0050 (7) | 0.0009 (7) |
N4 | 0.0207 (10) | 0.0404 (13) | 0.0371 (10) | 0.0009 (9) | −0.0056 (8) | 0.0058 (9) |
O1 | 0.0233 (8) | 0.0224 (9) | 0.0424 (9) | 0.0016 (7) | −0.0081 (7) | 0.0008 (7) |
Cl1 | 0.0256 (3) | 0.0239 (3) | 0.0319 (3) | 0.0018 (2) | −0.0017 (2) | −0.0059 (2) |
Cl2 | 0.0302 (3) | 0.0234 (3) | 0.0321 (3) | 0.0013 (2) | 0.0022 (2) | 0.0035 (2) |
Zn1 | 0.02174 (15) | 0.01823 (15) | 0.02718 (15) | 0.00072 (10) | −0.00272 (10) | −0.00081 (9) |
C1—N1 | 1.335 (3) | C10—H10A | 0.9300 |
C1—C2 | 1.391 (3) | C11—N4 | 1.360 (3) |
C1—H1A | 0.9300 | C11—C12 | 1.404 (3) |
C2—C3 | 1.373 (4) | C12—C13 | 1.375 (3) |
C2—H2A | 0.9300 | C12—H12A | 0.9300 |
C3—C4 | 1.392 (3) | C13—H13A | 0.9300 |
C3—H3A | 0.9300 | C14—N4 | 1.452 (3) |
C4—C5 | 1.380 (3) | C14—H14A | 0.9600 |
C4—H4A | 0.9300 | C14—H14B | 0.9600 |
C5—N1 | 1.348 (3) | C14—H14C | 0.9600 |
C5—C6 | 1.470 (3) | C15—N4 | 1.453 (3) |
C6—N2 | 1.280 (3) | C15—H15A | 0.9600 |
C6—H6A | 0.9300 | C15—H15B | 0.9600 |
C7—O1 | 1.237 (3) | C15—H15C | 0.9600 |
C7—N3 | 1.384 (3) | N1—Zn1 | 2.2080 (18) |
C7—C8 | 1.456 (3) | N2—N3 | 1.358 (2) |
C8—C13 | 1.402 (3) | N2—Zn1 | 2.1122 (19) |
C8—C9 | 1.403 (3) | N3—H3B | 0.8600 |
C9—C10 | 1.369 (3) | O1—Zn1 | 2.2019 (15) |
C9—H9A | 0.9300 | Cl1—Zn1 | 2.2282 (6) |
C10—C11 | 1.419 (3) | Cl2—Zn1 | 2.2590 (6) |
N1—C1—C2 | 123.0 (2) | C12—C13—H13A | 119.2 |
N1—C1—H1A | 118.5 | C8—C13—H13A | 119.2 |
C2—C1—H1A | 118.5 | N4—C14—H14A | 109.5 |
C3—C2—C1 | 118.4 (2) | N4—C14—H14B | 109.5 |
C3—C2—H2A | 120.8 | H14A—C14—H14B | 109.5 |
C1—C2—H2A | 120.8 | N4—C14—H14C | 109.5 |
C2—C3—C4 | 119.5 (2) | H14A—C14—H14C | 109.5 |
C2—C3—H3A | 120.2 | H14B—C14—H14C | 109.5 |
C4—C3—H3A | 120.2 | N4—C15—H15A | 109.5 |
C5—C4—C3 | 118.5 (2) | N4—C15—H15B | 109.5 |
C5—C4—H4A | 120.8 | H15A—C15—H15B | 109.5 |
C3—C4—H4A | 120.8 | N4—C15—H15C | 109.5 |
N1—C5—C4 | 122.6 (2) | H15A—C15—H15C | 109.5 |
N1—C5—C6 | 114.65 (18) | H15B—C15—H15C | 109.5 |
C4—C5—C6 | 122.8 (2) | C1—N1—C5 | 118.04 (19) |
N2—C6—C5 | 115.7 (2) | C1—N1—Zn1 | 126.75 (16) |
N2—C6—H6A | 122.2 | C5—N1—Zn1 | 115.20 (14) |
C5—C6—H6A | 122.2 | C6—N2—N3 | 122.18 (19) |
O1—C7—N3 | 118.41 (19) | C6—N2—Zn1 | 120.75 (15) |
O1—C7—C8 | 123.9 (2) | N3—N2—Zn1 | 117.03 (14) |
N3—C7—C8 | 117.7 (2) | N2—N3—C7 | 115.11 (18) |
C13—C8—C9 | 117.7 (2) | N2—N3—H3B | 122.4 |
C13—C8—C7 | 118.2 (2) | C7—N3—H3B | 122.4 |
C9—C8—C7 | 124.1 (2) | C11—N4—C14 | 120.9 (2) |
C10—C9—C8 | 121.0 (2) | C11—N4—C15 | 120.5 (2) |
C10—C9—H9A | 119.5 | C14—N4—C15 | 118.4 (2) |
C8—C9—H9A | 119.5 | C7—O1—Zn1 | 116.88 (14) |
C9—C10—C11 | 121.5 (2) | N2—Zn1—O1 | 72.54 (6) |
C9—C10—H10A | 119.3 | N2—Zn1—N1 | 73.56 (7) |
C11—C10—H10A | 119.3 | O1—Zn1—N1 | 146.03 (7) |
N4—C11—C12 | 121.6 (2) | N2—Zn1—Cl1 | 126.09 (5) |
N4—C11—C10 | 121.2 (2) | O1—Zn1—Cl1 | 99.73 (5) |
C12—C11—C10 | 117.2 (2) | N1—Zn1—Cl1 | 98.25 (5) |
C13—C12—C11 | 120.9 (2) | N2—Zn1—Cl2 | 116.52 (5) |
C13—C12—H12A | 119.5 | O1—Zn1—Cl2 | 97.90 (5) |
C11—C12—H12A | 119.5 | N1—Zn1—Cl2 | 99.04 (5) |
C12—C13—C8 | 121.6 (2) | Cl1—Zn1—Cl2 | 117.39 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···Cl2i | 0.86 | 2.49 | 3.199 (2) | 140 |
Symmetry code: (i) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C15H16N4O)] |
Mr | 404.59 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 16.1822 (7), 13.5864 (7), 7.5989 (2) |
β (°) | 91.123 (3) |
V (Å3) | 1670.36 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.80 |
Crystal size (mm) | 0.40 × 0.22 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (MULscanABS in PLATON; Spek, 2009) |
Tmin, Tmax | 0.538, 0.764 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14366, 3803, 3252 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.084, 1.06 |
No. of reflections | 3803 |
No. of parameters | 210 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.74 |
Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
Acknowledgements
The author is grateful to the Service de radiocristallographie de l'Institut de Chimie (Strasbourg) and to the Universidad del Valle in Cali, Colombia, for partial financial support.
References
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Similar to bis-pyridyl hydrazones derivatives, pyridine-2-carboxaldehyde acyl (aroyl) hydrazones are able to undergo configurational (E/Z) isomerization and constitutional changes as well as their structure allows them to coordinate to metallic centers by a tridentade NNO binding site (Chaur et al., 2011). Therefore, the C=N bond of these hydrazones can be used in double dynamic processes of interest for information storage (Lehn, 2006; Kay et al., 2007). The configurational dynamics of these compounds give access to short term photoactivated metastable states. On the other hand, they can undergo constitutional dynamics by constituent exchange allowing long term storage of information (Kandel, 2001).
Thus the pyridyl-acyl hydrazones are appealing compounds for the design of systems exhibiting multiple states and interconversion processes that involve configurational/constitutional changes, as well as metal coordination (Ma et al., 2011). These features together with increasing time scales being of interest for the development of both short-term and long-term molecular information storage and processing devices that may be addressed by orthogonal transformations involving either physical stimuli (light, heat; see Hirose, 2010) or chemical effectors (amino components or metal cations).
In this regard our group focuses on the design of bis-pyridyl and pyridyl-acyl hydrazones, as the title compound (Fig. 1), for the implementation of dynamic systems exhibiting reversible multiplex states for information storage (Moreno-Fuquen et al., 2012). The new complex is based on a ligand for which the structure has been previously established (Sangeetha, Pal & Pal, 2000), as well as a Cu(II) complex (Sangeetha, Pal, Anson et al., 2000).
The title complex exhibits a distorted five-coordinated square-pyramidal disposition (Fig. 2). The Schiff base ligand is not planar (Fig. 3), resulting in a dihedral angle between the planes of the aromatic and pyridyl rings of 4.61 (8)°, while the free ligand is planar (Sangeetha, Pal & Pal, 2000). The molecules stack forming columns along the [001] direction by intermolecular hydrogen bonds with a distance N3—H3···Cl2 = 3.199 (2) Å. Also it is observed a weak π–π slipped stacking interaction between the aromatic rings, with separations between ring centroids of 3.8075 (1) Å (Fig. 4).