Structural and spectroscopic characterization of a new luminescent Ni^II complex: bis­{2,4-di­chloro-6-[(2-hy­droxy­prop­yl)imino­meth­yl]phenolato-κ³O,N,O′}nickel(II)

The design and preparation of transition-metal complexes with Schiff base lig­ands are of inter­est due to their potential applications in the fields of mol­e­cular magnetism, nonlinear optics, dye-sensitized solar cells (DSSCs), sensing and photoluminescence. Luminescent metal complexes have been suggested as potential phosphors in electroluminescent devices. A new luminescent nickel(II) complex, [Ni(C₁₀H₁₀Cl₂NO₂)₂], has been synthesized and characterized by single-crystal X-ray diffraction and elemental analysis, UV–Vis, FT–IR, ¹H NMR, ¹³C NMR and photoluminescence spectroscopies, and LC–MS/MS. Mol­ecules of the complex in the crystals lie on special positions, on crystallographic binary rotation axes. The Ni^II atoms are six-coordinated by two phenolate O, two imine N and two hy­droxy O atoms from two tridentate Schiff base 2,4-di­chloro-6-[(2-hy­droxy­prop­yl)imino­meth­yl]phenolate ligands, forming an elongated octa­hedral geometry. Furthermore, the complex exhibits a strong green luminescence emission in the solid state at room temperature, as can be seen from the (CIE) chromaticity diagram, and hence the complex may be a promising green OLED (organic light-emitting diode) in the development of electroluminescent materials for flat-panel-display applications.

Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis{2,4-dichloro-6-[(2-hydroxypropyl)iminomethyl]phenolato-κ³O,N,O'}nickel(II)

Crystal data

[Ni(C10H10Cl2NO2)2]	F(000) = 2256
Mr = 552.89	Dx = 1.564 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.5375 (19) Å	Cell parameters from 2317 reflections
b = 10.7332 (6) Å	θ = 3.7–28.1°
c = 22.4073 (19) Å	µ = 1.31 mm^−1
β = 108.073 (10)°	T = 292 K
V = 4695.6 (7) Å^3	Prism, green
Z = 8	0.32 × 0.21 × 0.17 mm

Data collection

Xcalibur, Eos diffractometer	3127 reflections with I > 2σ(I)
Detector resolution: 8.0667 pixels mm^-1	Rint = 0.032
ω scans	θmax = 25.7°, θmin = 3.2°
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by Clark & Reid (1995)]	h = −24→22
Tmin = 0.521, Tmax = 0.685	k = −13→10
7742 measured reflections	l = −27→16
4420 independent reflections

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.129	w = 1/[σ^2(Fo^2) + (0.0441P)^2 + 4.9249P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
4420 reflections	Δρmax = 0.96 e Å^−3
287 parameters	Δρmin = −0.48 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.500000	0.94958 (7)	0.750000	0.0279 (2)
Cl1	0.54771 (7)	1.15988 (12)	0.94460 (5)	0.0517 (3)
Cl2	0.30179 (8)	1.0281 (2)	0.96063 (7)	0.1007 (7)
O1	0.50449 (16)	0.8076 (3)	0.68720 (13)	0.0367 (7)
O2	0.49229 (14)	1.0783 (2)	0.81378 (12)	0.0313 (7)
N1	0.39456 (18)	0.9443 (3)	0.71840 (15)	0.0320 (8)
C1	0.4526 (2)	0.7924 (4)	0.62759 (19)	0.0428 (12)
H1A	0.461837	0.717088	0.607678	0.051*
H1B	0.454575	0.862248	0.600710	0.051*
C2	0.3824 (2)	0.7847 (4)	0.6339 (2)	0.0428 (12)
H2A	0.382276	0.721245	0.664696	0.051*
H2B	0.350644	0.758498	0.594005	0.051*
C3	0.3569 (2)	0.9072 (5)	0.6535 (2)	0.0456 (12)
H3A	0.361152	0.972646	0.625136	0.055*
H3B	0.308672	0.898814	0.649568	0.055*
C4	0.3588 (2)	0.9615 (4)	0.7555 (2)	0.0376 (10)
H4	0.312089	0.945846	0.739480	0.045*
C5	0.3846 (2)	1.0033 (4)	0.82048 (19)	0.0346 (10)
C6	0.3394 (2)	0.9951 (5)	0.8565 (2)	0.0488 (13)
H6	0.296078	0.960868	0.838905	0.059*
C7	0.3588 (3)	1.0369 (5)	0.9168 (2)	0.0542 (14)
C8	0.4222 (3)	1.0881 (5)	0.9440 (2)	0.0487 (13)
H8	0.435033	1.115878	0.985345	0.058*
C9	0.4666 (2)	1.0977 (4)	0.90923 (19)	0.0362 (10)
C10	0.4498 (2)	1.0594 (4)	0.84608 (18)	0.0311 (10)
Ni2	0.500000	0.45155 (7)	0.750000	0.0275 (2)
Cl3	0.70002 (6)	0.66331 (13)	0.74089 (7)	0.0579 (4)
Cl4	0.67063 (8)	0.42402 (18)	0.52341 (7)	0.0819 (6)
O3	0.55891 (14)	0.5803 (2)	0.72366 (13)	0.0326 (7)
O4	0.44015 (15)	0.3063 (3)	0.76858 (14)	0.0375 (7)
N2	0.44185 (18)	0.4452 (3)	0.65718 (16)	0.0330 (8)
C11	0.3686 (2)	0.2922 (4)	0.7356 (2)	0.0405 (11)
H11A	0.343523	0.360106	0.746926	0.049*
H11B	0.352385	0.214891	0.748466	0.049*
C12	0.3541 (2)	0.2912 (4)	0.6655 (2)	0.0454 (12)
H12A	0.306440	0.269108	0.645841	0.054*
H12B	0.381921	0.227162	0.654872	0.054*
C13	0.3682 (2)	0.4154 (4)	0.6385 (2)	0.0432 (12)
H13A	0.350323	0.412019	0.593009	0.052*
H13B	0.344280	0.481296	0.652679	0.052*
C14	0.4702 (2)	0.4524 (4)	0.6140 (2)	0.0368 (10)
H14	0.442685	0.436358	0.573133	0.044*
C15	0.5413 (2)	0.4833 (4)	0.6228 (2)	0.0361 (10)
C16	0.5688 (2)	0.4496 (5)	0.5754 (2)	0.0454 (12)
H16	0.541716	0.407314	0.540169	0.054*
C17	0.6345 (3)	0.4778 (5)	0.5800 (2)	0.0481 (13)
C18	0.6749 (2)	0.5468 (5)	0.6297 (2)	0.0476 (13)
H18	0.719243	0.569347	0.631525	0.057*
C19	0.6479 (2)	0.5818 (4)	0.6768 (2)	0.0404 (11)
C20	0.5815 (2)	0.5497 (4)	0.6766 (2)	0.0330 (10)
H4A	0.459 (2)	0.237 (3)	0.779 (2)	0.050*
H1	0.519 (2)	0.737 (2)	0.701 (2)	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0350 (4)	0.0194 (4)	0.0314 (4)	0.000	0.0134 (3)	0.000
Cl1	0.0576 (8)	0.0540 (8)	0.0434 (6)	−0.0137 (7)	0.0157 (6)	−0.0060 (6)
Cl2	0.0610 (10)	0.197 (2)	0.0597 (9)	−0.0077 (12)	0.0411 (8)	−0.0009 (11)
O1	0.048 (2)	0.0244 (16)	0.0356 (16)	0.0037 (15)	0.0094 (14)	−0.0045 (14)
O2	0.0381 (17)	0.0251 (16)	0.0369 (15)	−0.0040 (13)	0.0205 (13)	−0.0028 (12)
N1	0.039 (2)	0.0244 (18)	0.0339 (19)	0.0011 (17)	0.0125 (16)	0.0013 (16)
C1	0.058 (3)	0.035 (3)	0.035 (2)	0.004 (2)	0.015 (2)	−0.004 (2)
C2	0.048 (3)	0.035 (3)	0.043 (3)	−0.004 (2)	0.011 (2)	−0.009 (2)
C3	0.045 (3)	0.048 (3)	0.039 (3)	0.006 (2)	0.006 (2)	−0.006 (2)
C4	0.033 (2)	0.030 (2)	0.048 (3)	−0.001 (2)	0.012 (2)	0.001 (2)
C5	0.037 (3)	0.035 (2)	0.035 (2)	0.003 (2)	0.0146 (19)	0.007 (2)
C6	0.036 (3)	0.065 (3)	0.048 (3)	−0.002 (3)	0.017 (2)	0.009 (3)
C7	0.050 (3)	0.080 (4)	0.042 (3)	0.004 (3)	0.028 (2)	0.010 (3)
C8	0.051 (3)	0.062 (3)	0.039 (3)	0.006 (3)	0.023 (2)	0.004 (2)
C9	0.042 (3)	0.031 (2)	0.038 (2)	−0.001 (2)	0.015 (2)	0.003 (2)
C10	0.043 (3)	0.021 (2)	0.034 (2)	0.005 (2)	0.018 (2)	0.0039 (19)
Ni2	0.0255 (4)	0.0198 (4)	0.0404 (4)	0.000	0.0148 (3)	0.000
Cl3	0.0381 (7)	0.0510 (8)	0.0892 (10)	−0.0115 (6)	0.0265 (7)	−0.0143 (7)
Cl4	0.0729 (10)	0.1293 (16)	0.0606 (9)	0.0225 (10)	0.0454 (8)	0.0049 (9)
O3	0.0335 (17)	0.0225 (15)	0.0479 (17)	−0.0019 (13)	0.0217 (14)	−0.0011 (13)
O4	0.0310 (17)	0.0235 (16)	0.059 (2)	−0.0014 (14)	0.0162 (15)	0.0056 (15)
N2	0.034 (2)	0.0240 (18)	0.043 (2)	0.0013 (16)	0.0153 (17)	0.0028 (17)
C11	0.026 (2)	0.030 (2)	0.067 (3)	−0.001 (2)	0.015 (2)	0.002 (2)
C12	0.028 (2)	0.044 (3)	0.061 (3)	−0.011 (2)	0.010 (2)	−0.004 (3)
C13	0.033 (3)	0.047 (3)	0.049 (3)	−0.003 (2)	0.011 (2)	0.001 (2)
C14	0.035 (3)	0.035 (2)	0.038 (2)	0.002 (2)	0.009 (2)	0.000 (2)
C15	0.034 (3)	0.034 (3)	0.044 (3)	0.007 (2)	0.018 (2)	0.007 (2)
C16	0.051 (3)	0.051 (3)	0.037 (2)	0.010 (3)	0.018 (2)	0.004 (2)
C17	0.053 (3)	0.055 (3)	0.047 (3)	0.012 (3)	0.031 (3)	0.008 (3)
C18	0.038 (3)	0.048 (3)	0.069 (3)	0.009 (2)	0.034 (3)	0.016 (3)
C19	0.036 (3)	0.026 (2)	0.063 (3)	0.003 (2)	0.021 (2)	0.006 (2)
C20	0.033 (2)	0.024 (2)	0.048 (3)	0.006 (2)	0.022 (2)	0.008 (2)

Geometric parameters (Å, º)

Ni1—O1	2.096 (3)	Ni2—O3	2.041 (3)
Ni1—O1^i	2.096 (3)	Ni2—O3^i	2.041 (3)
Ni1—O2^i	2.029 (3)	Ni2—O4	2.106 (3)
Ni1—O2	2.029 (3)	Ni2—O4^i	2.106 (3)
Ni1—N1	2.060 (3)	Ni2—N2	2.053 (3)
Ni1—N1^i	2.060 (3)	Ni2—N2^i	2.053 (3)
Cl1—C9	1.741 (5)	Cl3—C19	1.737 (5)
Cl2—C7	1.749 (4)	Cl4—C17	1.754 (4)
O1—C1	1.436 (5)	O3—C20	1.319 (4)
O1—H1	0.831 (19)	O4—C11	1.434 (5)
O2—C10	1.312 (4)	O4—H4A	0.836 (19)
N1—C3	1.474 (5)	N2—C13	1.474 (5)
N1—C4	1.282 (5)	N2—C14	1.277 (5)
C1—H1A	0.9700	C11—H11A	0.9700
C1—H1B	0.9700	C11—H11B	0.9700
C1—C2	1.495 (6)	C11—C12	1.505 (6)
C2—H2A	0.9700	C12—H12A	0.9700
C2—H2B	0.9700	C12—H12B	0.9700
C2—C3	1.530 (6)	C12—C13	1.529 (6)
C3—H3A	0.9700	C13—H13A	0.9700
C3—H3B	0.9700	C13—H13B	0.9700
C4—H4	0.9300	C14—H14	0.9300
C4—C5	1.457 (6)	C14—C15	1.450 (6)
C5—C6	1.408 (6)	C15—C16	1.398 (5)
C5—C10	1.416 (6)	C15—C20	1.422 (6)
C6—H6	0.9300	C16—H16	0.9300
C6—C7	1.362 (6)	C16—C17	1.355 (6)
C7—C8	1.370 (7)	C17—C18	1.379 (7)
C8—H8	0.9300	C18—H18	0.9300
C8—C9	1.374 (6)	C18—C19	1.389 (6)
C9—C10	1.410 (5)	C19—C20	1.405 (6)
O1^i—Ni1—O1	86.70 (16)	O3—Ni2—O3^i	94.75 (15)
O2—Ni1—O1	175.92 (11)	O3—Ni2—O4^i	90.54 (11)
O2^i—Ni1—O1^i	175.92 (11)	O3^i—Ni2—O4^i	173.47 (11)
O2^i—Ni1—O1	89.59 (11)	O3—Ni2—O4	173.47 (11)
O2—Ni1—O1^i	89.59 (11)	O3^i—Ni2—O4	90.54 (11)
O2^i—Ni1—O2	94.17 (15)	O3—Ni2—N2^i	96.02 (12)
O2—Ni1—N1^i	94.59 (12)	O3—Ni2—N2	86.57 (12)
O2^i—Ni1—N1	94.59 (12)	O3^i—Ni2—N2^i	86.57 (12)
O2^i—Ni1—N1^i	87.55 (12)	O3^i—Ni2—N2	96.02 (12)
O2—Ni1—N1	87.55 (12)	O4—Ni2—O4^i	84.44 (16)
N1^i—Ni1—O1	87.15 (13)	N2^i—Ni2—O4^i	89.08 (13)
N1^i—Ni1—O1^i	90.57 (13)	N2—Ni2—O4^i	88.10 (13)
N1—Ni1—O1^i	87.15 (13)	N2^i—Ni2—O4	88.10 (13)
N1—Ni1—O1	90.57 (13)	N2—Ni2—O4	89.08 (13)
N1^i—Ni1—N1	176.86 (19)	N2^i—Ni2—N2	176.19 (19)
Ni1—O1—H1	120 (3)	C20—O3—Ni2	116.7 (2)
C1—O1—Ni1	122.2 (3)	Ni2—O4—H4A	118 (3)
C1—O1—H1	108 (3)	C11—O4—Ni2	123.0 (3)
C10—O2—Ni1	119.6 (2)	C11—O4—H4A	111 (3)
C3—N1—Ni1	121.4 (3)	C13—N2—Ni2	121.2 (3)
C4—N1—Ni1	121.7 (3)	C14—N2—Ni2	120.5 (3)
C4—N1—C3	116.6 (4)	C14—N2—C13	117.8 (4)
O1—C1—H1A	109.2	O4—C11—H11A	109.2
O1—C1—H1B	109.2	O4—C11—H11B	109.2
O1—C1—C2	112.2 (4)	O4—C11—C12	112.2 (3)
H1A—C1—H1B	107.9	H11A—C11—H11B	107.9
C2—C1—H1A	109.2	C12—C11—H11A	109.2
C2—C1—H1B	109.2	C12—C11—H11B	109.2
C1—C2—H2A	108.8	C11—C12—H12A	108.7
C1—C2—H2B	108.8	C11—C12—H12B	108.7
C1—C2—C3	114.0 (4)	C11—C12—C13	114.1 (4)
H2A—C2—H2B	107.7	H12A—C12—H12B	107.6
C3—C2—H2A	108.8	C13—C12—H12A	108.7
C3—C2—H2B	108.8	C13—C12—H12B	108.7
N1—C3—C2	113.2 (4)	N2—C13—C12	112.4 (4)
N1—C3—H3A	108.9	N2—C13—H13A	109.1
N1—C3—H3B	108.9	N2—C13—H13B	109.1
C2—C3—H3A	108.9	C12—C13—H13A	109.1
C2—C3—H3B	108.9	C12—C13—H13B	109.1
H3A—C3—H3B	107.7	H13A—C13—H13B	107.9
N1—C4—H4	117.0	N2—C14—H14	117.1
N1—C4—C5	126.1 (4)	N2—C14—C15	125.9 (4)
C5—C4—H4	117.0	C15—C14—H14	117.1
C6—C5—C4	116.9 (4)	C16—C15—C14	117.7 (4)
C6—C5—C10	120.1 (4)	C16—C15—C20	120.5 (4)
C10—C5—C4	122.7 (4)	C20—C15—C14	121.8 (4)
C5—C6—H6	119.8	C15—C16—H16	119.6
C7—C6—C5	120.4 (5)	C17—C16—C15	120.8 (5)
C7—C6—H6	119.8	C17—C16—H16	119.6
C6—C7—Cl2	119.9 (4)	C16—C17—Cl4	120.3 (4)
C6—C7—C8	121.3 (4)	C16—C17—C18	121.2 (4)
C8—C7—Cl2	118.8 (4)	C18—C17—Cl4	118.4 (4)
C7—C8—H8	120.5	C17—C18—H18	120.8
C7—C8—C9	118.9 (4)	C17—C18—C19	118.4 (4)
C9—C8—H8	120.5	C19—C18—H18	120.8
C8—C9—Cl1	118.7 (4)	C18—C19—Cl3	118.4 (4)
C8—C9—C10	123.2 (4)	C18—C19—C20	123.2 (4)
C10—C9—Cl1	118.1 (3)	C20—C19—Cl3	118.4 (3)
O2—C10—C5	123.3 (4)	O3—C20—C15	123.1 (4)
O2—C10—C9	120.7 (4)	O3—C20—C19	121.2 (4)
C9—C10—C5	115.9 (4)	C19—C20—C15	115.8 (4)
Ni1—O1—C1—C2	−53.3 (5)	Ni2—O3—C20—C15	39.1 (5)
Ni1—O2—C10—C5	−37.6 (5)	Ni2—O3—C20—C19	−141.0 (3)
Ni1—O2—C10—C9	144.0 (3)	Ni2—O4—C11—C12	53.0 (4)
Ni1—N1—C3—C2	50.4 (5)	Ni2—N2—C13—C12	−55.5 (5)
Ni1—N1—C4—C5	9.2 (6)	Ni2—N2—C14—C15	−9.6 (6)
Cl1—C9—C10—O2	−4.7 (5)	Cl3—C19—C20—O3	0.0 (6)
Cl1—C9—C10—C5	176.7 (3)	Cl3—C19—C20—C15	179.9 (3)
Cl2—C7—C8—C9	−178.6 (4)	Cl4—C17—C18—C19	−175.4 (3)
O1—C1—C2—C3	69.4 (5)	O4—C11—C12—C13	−66.9 (5)
N1—C4—C5—C6	−169.0 (4)	N2—C14—C15—C16	160.3 (4)
N1—C4—C5—C10	16.1 (7)	N2—C14—C15—C20	−22.0 (7)
C1—C2—C3—N1	−68.4 (5)	C11—C12—C13—N2	68.7 (5)
C3—N1—C4—C5	−177.3 (4)	C13—N2—C14—C15	178.5 (4)
C4—N1—C3—C2	−123.2 (4)	C14—N2—C13—C12	116.4 (4)
C4—C5—C6—C7	−177.4 (5)	C14—C15—C16—C17	178.7 (4)
C4—C5—C10—O2	−0.1 (7)	C14—C15—C20—O3	4.6 (6)
C4—C5—C10—C9	178.4 (4)	C14—C15—C20—C19	−175.3 (4)
C5—C6—C7—Cl2	179.2 (4)	C15—C16—C17—Cl4	174.7 (4)
C5—C6—C7—C8	0.2 (8)	C15—C16—C17—C18	−3.9 (8)
C6—C5—C10—O2	−174.9 (4)	C16—C15—C20—O3	−177.8 (4)
C6—C5—C10—C9	3.6 (6)	C16—C15—C20—C19	2.4 (6)
C6—C7—C8—C9	0.4 (8)	C16—C17—C18—C19	3.2 (7)
C7—C8—C9—Cl1	−178.7 (4)	C17—C18—C19—Cl3	177.5 (4)
C7—C8—C9—C10	1.2 (7)	C17—C18—C19—C20	0.4 (7)
C8—C9—C10—O2	175.4 (4)	C18—C19—C20—O3	177.1 (4)
C8—C9—C10—C5	−3.2 (6)	C18—C19—C20—C15	−3.1 (6)
C10—C5—C6—C7	−2.3 (7)	C20—C15—C16—C17	1.0 (7)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3	0.84 (3)	1.87 (3)	2.702 (4)	172 (4)
O4—H4A···O2^ii	0.84 (2)	1.91 (2)	2.736 (4)	168 (4)

Symmetry code: (ii) x, y−1, z.