Crystal structure and photoluminescence properties of a new monomeric copper(II) complex: bis­(3-{[(3-hy­droxy­prop­yl)imino]­meth­yl}-4-nitro­phenolato-κ³O,N,O′)copper(II)

Copper(II)–Schiff base complexes have attracted extensive inter­est due to their structural, electronic, magnetic and luminescence properties. The title novel monomeric Cu^II complex, [Cu(C₁₀H₁₁N₂O₄)₂], has been synthesized by the reaction of 3-{[(3-hy­droxy­prop­yl)imino]­meth­yl}-4-nitro­phenol (H₂L) and copper(II) acetate monohydrate in methanol, and was characterized by elemental analysis, UV and IR spectroscopies, single-crystal X-ray diffraction analysis and a photoluminescence study. The Cu^II atom is located on a centre of inversion and is coordinated by two imine N atoms, two phen­oxy O atoms in a mutual trans disposition and two hy­droxy O atoms in axial positions, forming an elongated octa­hedral geometry. In the crystal, inter­molecular O—H...O hydrogen bonds link the mol­ecules to form a one-dimensional chain structure and π–π contacts also connect the mol­ecules to form a three-dimensional structure. The solid-state photoluminescence properties of the complex and free H₂L have been investigated at room temperature in the visible region. When the complex and H₂L are excited under UV light at 349 nm, the complex displays a strong green emission at 520 nm and H₂L displays a blue emission at 480 nm.

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(3-{[(3-hydroxypropyl)imino]methyl}-4-nitrophenolato-κ³O,N,O')copper(II)

Crystal data

[Cu(C10H11N2O4)2]	F(000) = 526
Mr = 509.95	Dx = 1.667 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.5788 (11) Å	Cell parameters from 812 reflections
b = 6.2806 (5) Å	θ = 3.7–22.9°
c = 15.8478 (19) Å	µ = 1.14 mm^−1
β = 105.272 (12)°	T = 292 K
V = 1015.76 (19) Å^3	Plate, green
Z = 2	0.25 × 0.15 × 0.06 mm

Data collection

Rigaku OD Xcalibur Eos diffractometer	1303 reflections with I > 2σ(I)
Detector resolution: 8.0667 pixels mm^-1	Rint = 0.046
ω scans	θmax = 25.7°, θmin = 3.5°
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015) based on expressions derived by Clark & Reid (1995)]	h = −12→9
Tmin = 0.823, Tmax = 0.947	k = −7→5
3722 measured reflections	l = −18→19
1908 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H-atom parameters constrained
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.0404P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1908 reflections	Δρmax = 0.46 e Å^−3
152 parameters	Δρmin = −0.44 e Å^−3
0 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.000000	0.500000	0.500000	0.0286 (3)
O1	0.0989 (3)	0.4425 (5)	0.6702 (2)	0.0460 (9)
H1	0.176143	0.416414	0.674076	0.069*
O2	0.1378 (3)	0.3461 (4)	0.4671 (2)	0.0330 (8)
O3	0.5874 (3)	0.8420 (6)	0.3669 (2)	0.0552 (11)
O4	0.6111 (3)	0.5323 (5)	0.3162 (2)	0.0539 (10)
N1	0.1206 (3)	0.7498 (5)	0.5363 (2)	0.0248 (8)
N2	0.5543 (4)	0.6560 (6)	0.3538 (3)	0.0365 (10)
C1	0.0895 (5)	0.6305 (7)	0.7191 (3)	0.0414 (13)
H1A	0.127875	0.601452	0.780692	0.050*
H1B	−0.002340	0.663412	0.711707	0.050*
C2	0.1560 (4)	0.8230 (7)	0.6936 (3)	0.0359 (12)
H2A	0.247528	0.788726	0.700176	0.043*
H2B	0.152832	0.937389	0.734064	0.043*
C3	0.0980 (4)	0.9032 (6)	0.6012 (3)	0.0312 (11)
H3A	0.004588	0.925461	0.591842	0.037*
H3B	0.137556	1.038768	0.593663	0.037*
C4	0.2233 (4)	0.7797 (7)	0.5107 (3)	0.0268 (10)
H4	0.268637	0.905676	0.528558	0.032*
C5	0.2773 (4)	0.6396 (6)	0.4570 (3)	0.0245 (10)
C6	0.3836 (4)	0.7086 (7)	0.4286 (3)	0.0286 (11)
H6	0.414578	0.846620	0.441353	0.034*
C7	0.4442 (4)	0.5766 (7)	0.3818 (3)	0.0295 (11)
C8	0.4019 (4)	0.3672 (7)	0.3639 (3)	0.0328 (11)
H8	0.443455	0.277462	0.332954	0.039*
C9	0.2984 (4)	0.2962 (7)	0.3925 (3)	0.0309 (11)
H9	0.269857	0.156892	0.379817	0.037*
C10	0.2332 (4)	0.4250 (6)	0.4404 (3)	0.0256 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0254 (4)	0.0264 (4)	0.0368 (5)	−0.0030 (4)	0.0132 (4)	−0.0020 (4)
O1	0.047 (2)	0.0414 (19)	0.052 (2)	0.0018 (18)	0.016 (2)	0.0030 (17)
O2	0.0263 (17)	0.0268 (16)	0.049 (2)	−0.0049 (15)	0.0164 (16)	−0.0047 (15)
O3	0.049 (2)	0.056 (2)	0.070 (3)	−0.020 (2)	0.032 (2)	−0.001 (2)
O4	0.040 (2)	0.065 (2)	0.067 (3)	0.004 (2)	0.032 (2)	0.002 (2)
N1	0.0221 (19)	0.0233 (18)	0.031 (2)	0.0027 (18)	0.0097 (17)	−0.0012 (17)
N2	0.026 (2)	0.048 (3)	0.038 (2)	0.002 (2)	0.013 (2)	0.007 (2)
C1	0.045 (3)	0.047 (3)	0.035 (3)	0.006 (3)	0.015 (3)	0.002 (2)
C2	0.034 (3)	0.039 (3)	0.036 (3)	0.003 (2)	0.010 (2)	−0.018 (2)
C3	0.032 (3)	0.025 (2)	0.041 (3)	−0.006 (2)	0.017 (2)	−0.011 (2)
C4	0.026 (2)	0.025 (2)	0.028 (3)	−0.006 (2)	0.004 (2)	0.000 (2)
C5	0.023 (2)	0.026 (2)	0.024 (2)	0.002 (2)	0.007 (2)	−0.003 (2)
C6	0.026 (2)	0.028 (2)	0.031 (3)	−0.002 (2)	0.005 (2)	0.003 (2)
C7	0.020 (2)	0.039 (3)	0.030 (3)	0.000 (2)	0.008 (2)	0.004 (2)
C8	0.029 (3)	0.040 (3)	0.031 (3)	0.009 (2)	0.010 (2)	−0.002 (2)
C9	0.031 (3)	0.024 (2)	0.037 (3)	−0.003 (2)	0.009 (2)	−0.004 (2)
C10	0.018 (2)	0.028 (2)	0.027 (2)	0.002 (2)	0.000 (2)	0.002 (2)

Geometric parameters (Å, º)

Cu1—O1^i	2.648 (4)	C2—H2A	0.9700
Cu1—O1	2.648 (4)	C2—H2B	0.9700
Cu1—O2	1.931 (3)	C2—C3	1.516 (6)
Cu1—O2^i	1.931 (3)	C3—H3A	0.9700
Cu1—N1	2.008 (3)	C3—H3B	0.9700
Cu1—N1^i	2.008 (3)	C4—H4	0.9300
O1—H1	0.8200	C4—C5	1.443 (5)
O1—C1	1.431 (5)	C5—C6	1.386 (6)
O2—C10	1.292 (5)	C5—C10	1.428 (6)
O3—N2	1.221 (4)	C6—H6	0.9300
O4—N2	1.228 (4)	C6—C7	1.378 (5)
N1—C3	1.474 (5)	C7—C8	1.394 (6)
N1—C4	1.269 (5)	C8—H8	0.9300
N2—C7	1.441 (5)	C8—C9	1.365 (6)
C1—H1A	0.9700	C9—H9	0.9300
C1—H1B	0.9700	C9—C10	1.409 (5)
C1—C2	1.507 (6)
O1—Cu1—O1^i	180.0	C1—C2—H2B	108.5
O2^i—Cu1—O1^i	94.75 (11)	C1—C2—C3	115.3 (4)
O2—Cu1—O1	94.75 (11)	H2A—C2—H2B	107.5
O2—Cu1—O1^i	85.25 (11)	C3—C2—H2A	108.5
O2^i—Cu1—O1	85.25 (11)	C3—C2—H2B	108.5
O2—Cu1—O2^i	180.00 (9)	N1—C3—C2	111.0 (3)
O2—Cu1—N1^i	89.97 (12)	N1—C3—H3A	109.4
O2^i—Cu1—N1^i	90.03 (12)	N1—C3—H3B	109.4
O2^i—Cu1—N1	89.97 (12)	C2—C3—H3A	109.4
O2—Cu1—N1	90.03 (12)	C2—C3—H3B	109.4
N1^i—Cu1—O1^i	76.37 (12)	H3A—C3—H3B	108.0
N1—Cu1—O1	76.37 (12)	N1—C4—H4	116.4
N1—Cu1—O1^i	103.63 (12)	N1—C4—C5	127.1 (4)
N1^i—Cu1—O1	103.63 (12)	C5—C4—H4	116.4
N1^i—Cu1—N1	180.0	C6—C5—C4	118.8 (4)
Cu1—O1—H1	102.9	C6—C5—C10	119.3 (4)
C1—O1—Cu1	112.0 (3)	C10—C5—C4	121.6 (4)
C1—O1—H1	109.5	C5—C6—H6	119.4
C10—O2—Cu1	127.4 (3)	C7—C6—C5	121.2 (4)
C3—N1—Cu1	120.2 (3)	C7—C6—H6	119.4
C4—N1—Cu1	123.8 (3)	C6—C7—N2	119.1 (4)
C4—N1—C3	115.8 (4)	C6—C7—C8	120.5 (4)
O3—N2—O4	122.2 (4)	C8—C7—N2	120.4 (4)
O3—N2—C7	119.8 (4)	C7—C8—H8	120.6
O4—N2—C7	118.0 (4)	C9—C8—C7	118.9 (4)
O1—C1—H1A	108.7	C9—C8—H8	120.6
O1—C1—H1B	108.7	C8—C9—H9	118.6
O1—C1—C2	114.4 (4)	C8—C9—C10	122.7 (4)
H1A—C1—H1B	107.6	C10—C9—H9	118.6
C2—C1—H1A	108.7	O2—C10—C5	123.2 (4)
C2—C1—H1B	108.7	O2—C10—C9	119.5 (4)
C1—C2—H2A	108.5	C9—C10—C5	117.3 (4)
Cu1—O1—C1—C2	−57.7 (5)	C3—N1—C4—C5	171.3 (4)
Cu1—O2—C10—C5	21.1 (6)	C4—N1—C3—C2	−92.6 (4)
Cu1—O2—C10—C9	−159.0 (3)	C4—C5—C6—C7	175.9 (4)
Cu1—N1—C3—C2	83.0 (4)	C4—C5—C10—O2	4.4 (6)
Cu1—N1—C4—C5	−4.1 (6)	C4—C5—C10—C9	−175.5 (4)
O1—C1—C2—C3	64.3 (5)	C5—C6—C7—N2	180.0 (4)
O3—N2—C7—C6	−4.5 (6)	C5—C6—C7—C8	−1.7 (7)
O3—N2—C7—C8	177.3 (4)	C6—C5—C10—O2	177.7 (4)
O4—N2—C7—C6	176.2 (4)	C6—C5—C10—C9	−2.3 (6)
O4—N2—C7—C8	−2.0 (6)	C6—C7—C8—C9	0.8 (7)
N1—C4—C5—C6	173.8 (4)	C7—C8—C9—C10	−0.7 (7)
N1—C4—C5—C10	−12.9 (7)	C8—C9—C10—O2	−178.5 (4)
N2—C7—C8—C9	179.1 (4)	C8—C9—C10—C5	1.4 (6)
C1—C2—C3—N1	−68.0 (5)	C10—C5—C6—C7	2.5 (6)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4^ii	0.82	2.24	3.023 (4)	160

Symmetry code: (ii) −x+1, −y+1, −z+1.