Bis­(di­methylamine-κN)bis[4-(1,2,4-triazol-1-yl)benzoato-κO]copper(II)

Liu, L.; Han, Z.-B.

doi:10.1107/S2414314622000463

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 1| January 2022| x220046

https://doi.org/10.1107/S2414314622000463

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Bis(dimethylamine-κN)bis[4-(1,2,4-triazol-1-yl)benzoato-κO]copper(II)

Lin Liu ^a and Zheng-Bo Han ^a ^*

^aCollege of Chemistry, Liaoning University, Shenyang, 110036, People's Republic of China
^*Correspondence e-mail: ceshzb@lnu.edu.cn

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 December 2021; accepted 12 January 2022; online 14 January 2022)

In the title compound, [Cu(C₉H₆N₃O₂)₂(C₂H₇N)₂], the Cu²⁺ cation is situated on an inversion center and is coordinated by the N atoms of two dimethylamine ligands and the carboxylate O atoms of two 4-(1,2,4-triazol-1-yl)benzoate anions, leading to a slightly distorted square-planar N₂O₂ coordination environment. In the crystal, intermolecular N—H⋯N hydrogen bonds between the amine function and the central N atom of the triazole ring lead to the formation of ribbons parallel to [1 $[\overline{1}]$ 1]. Weak intermolecular C—H⋯O hydrogen-bonding interactions are also observed that consolidate the crystal packing.

Keywords: crystal structure; coordination polymer; hydrogen bond.

CCDC reference: 2141669

Structure description

The rational design of coordination polymers is based on the combination of metal ions and versatile organic ligands, resulting in various supramolecular assemblies. The resulting crystal structures determine the potential applications of the coordination polymers. Different polymers based on 4-(1,2,4-triazol-1-yl)benzoic acid complexes have been reported (Du et al., 2014 ). They not only feature structural varieties, but also can be applied in gas storage (Wang et al., 2012 ). In this context we have investigated crystals formed from a copper(II) solution and 4-(1,2,4-triazol-1-yl)benzoic acid under solvothermal conditions.

As shown in Fig. 1, the asymmetric unit of the title compound comprises one Cu^II atom, one 4-(1,2,4-triazol-1-yl)benzoate ligand, and one dimethylamine molecule generated in situ from the decomposition of the solvent dimethyl formamide. The complete molecule is generated by inversion symmetry. The Cu^II atom has a distorted square-planar coordination environment, being coordinated by two symmetry-related benzoato O atoms [Cu—O1 = 1.9611 (14) Å] and two symmetry-related N atoms [Cu—N4 = 2.0096 (19) Å of the amine ligands. The second carboxylate O atom of the anion seems to be too far away [Cu—O2 = 2.80136 (19) Å] to contribute to a significant bonding. Nevertheless, the non-bonding O2 atom is involved as an acceptor in weak C—H⋯O hydrogen-bonding interactions (Table 1, Fig. 2). Stronger N—H⋯N hydrogen bonds between the amine NH group and the central N atom of the triazole ring are also observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯N3ⁱ	0.91	2.17	3.034 (3)	160
C9—H9A⋯O2ⁱⁱ	0.93	2.50	3.428 (3)	173
Symmetry codes: (i) ; (ii) .

Figure 1
The molecular structure of the title compound, with atom labelling and displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry code: (A) −x + 2, −y, −z + 1.]

Figure 2
The crystal packing of the complex molecules. Hydrogen-bonding interactions are shown as dashed lines.

Synthesis and crystallization

A mixture of Cu(NO₃)₂·3H₂O (0.0725 mg, 0.3 mmol), 4-(1,2,4-triazol-1-yl)benzoic acid (0.057 g, 0.3 mmol), dimethylformamide (5 ml), ethanol (5 ml) and water (5 ml) was placed in a Teflon reactor with a 23 ml capacity, which was heated at 433 K for 3 days and then cooled to room temperature at a rate of 10 K h⁻¹. Blue block-shaped crystals of the title compound were obtained in 52% yield after being washed with dimethylformamide and dried in air.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₉H₆N₃O₂)₂(C₂H₇N)₂]
M_r	530.06
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	6.3657 (5), 8.1428 (7), 12.1896 (11)
α, β, γ (°)	72.595 (2), 89.376 (2), 87.805 (2)
V (Å³)	602.47 (9)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.95
Crystal size (mm)	0.36 × 0.32 × 0.27

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2002 )
T_min, T_max	0.727, 0.785
No. of measured, independent and observed [I > 2σ(I)] reflections	3971, 2727, 2345
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.093, 1.03
No. of reflections	2727
No. of parameters	160
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.20
Computer programs: SMART and SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2141669

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622000463/wm4159sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622000463/wm4159Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(dimethylamine-κN)bis[4-(1,2,4-triazol-1-yl)benzoato-κO]copper(II) top

Crystal data top

[Cu(C₉H₆N₃O₂)₂(C₂H₇N)₂]	Z = 1
M_r = 530.06	F(000) = 275
Triclinic, P1	D_x = 1.461 Mg m⁻³
a = 6.3657 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1428 (7) Å	Cell parameters from 1477 reflections
c = 12.1896 (11) Å	θ = 2.6–26.4°
α = 72.595 (2)°	µ = 0.95 mm⁻¹
β = 89.376 (2)°	T = 293 K
γ = 87.805 (2)°	Block, blue
V = 602.47 (9) Å³	0.36 × 0.32 × 0.27 mm

Data collection top

Bruker SMART CCD diffractometer	2727 independent reflections
Radiation source: fine-focus sealed tube	2345 reflections with I > 2σ(I)
Detector resolution: 10.0 pixels mm^-1	R_int = 0.017
ω scan	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
T_min = 0.727, T_max = 0.785	k = −10→10
3971 measured reflections	l = −10→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0482P)² + 0.1332P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2727 reflections	Δρ_max = 0.28 e Å⁻³
160 parameters	Δρ_min = −0.20 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	U_iso*/U_eq
Cu1	1.000000	0.000000	0.500000	0.03668 (13)
O1	0.8278 (3)	0.19597 (19)	0.40688 (13)	0.0456 (4)
N4	0.8929 (3)	−0.1440 (2)	0.40592 (16)	0.0478 (5)
H4	0.834029	−0.069234	0.342060	0.072*
O2	1.0899 (3)	0.2218 (2)	0.28158 (16)	0.0564 (5)
N3	0.3345 (3)	0.9752 (2)	−0.18059 (16)	0.0470 (5)
C8	0.1967 (4)	0.9638 (3)	−0.0944 (2)	0.0475 (5)
H8A	0.069359	1.026329	−0.105518	0.057*
N1	0.4455 (3)	0.7973 (2)	−0.01740 (15)	0.0357 (4)
C1	0.9149 (3)	0.2671 (3)	0.31047 (18)	0.0397 (5)
C2	0.7914 (3)	0.4135 (2)	0.22845 (17)	0.0347 (4)
C3	0.8841 (3)	0.5111 (3)	0.1285 (2)	0.0443 (5)
H3A	1.024977	0.489576	0.114867	0.053*
C4	0.7728 (3)	0.6395 (3)	0.0487 (2)	0.0462 (5)
H4A	0.838250	0.704495	−0.017864	0.055*
C5	0.5630 (3)	0.6712 (2)	0.06815 (17)	0.0332 (4)
C6	0.4692 (3)	0.5793 (3)	0.16901 (19)	0.0429 (5)
H6A	0.329651	0.603747	0.183663	0.052*
C7	0.5831 (3)	0.4506 (3)	0.24845 (18)	0.0438 (5)
H7A	0.518902	0.388216	0.316208	0.053*
C9	0.4888 (4)	0.8692 (3)	−0.12927 (18)	0.0437 (5)
H9A	0.611277	0.846901	−0.165463	0.052*
N2	0.2529 (3)	0.8588 (2)	0.00657 (16)	0.0467 (5)
C11	1.0630 (5)	−0.2323 (4)	0.3597 (3)	0.0766 (9)
H11A	1.164757	−0.150450	0.321505	0.115*
H11B	1.129585	−0.320275	0.421504	0.115*
H11C	1.005285	−0.283743	0.305845	0.115*
C10	0.7338 (6)	−0.2657 (4)	0.4651 (3)	0.0853 (10)
H10A	0.624985	−0.205376	0.494376	0.128*
H10B	0.674023	−0.317305	0.411925	0.128*
H10C	0.798323	−0.353837	0.527585	0.128*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0456 (2)	0.0340 (2)	0.02439 (18)	0.00871 (14)	−0.00500 (14)	−0.00062 (13)
O1	0.0569 (9)	0.0417 (8)	0.0312 (7)	0.0137 (7)	−0.0080 (7)	−0.0019 (6)
N4	0.0643 (12)	0.0411 (10)	0.0328 (9)	0.0055 (9)	−0.0129 (9)	−0.0034 (8)
O2	0.0430 (9)	0.0580 (10)	0.0580 (11)	0.0168 (8)	−0.0055 (8)	−0.0038 (8)
N3	0.0571 (11)	0.0418 (10)	0.0366 (10)	0.0088 (8)	−0.0123 (9)	−0.0043 (8)
C8	0.0512 (13)	0.0448 (12)	0.0427 (12)	0.0162 (10)	−0.0140 (10)	−0.0089 (10)
N1	0.0387 (9)	0.0317 (8)	0.0330 (8)	0.0042 (7)	−0.0060 (7)	−0.0045 (7)
C1	0.0453 (12)	0.0350 (10)	0.0360 (11)	0.0061 (9)	−0.0121 (9)	−0.0069 (8)
C2	0.0388 (10)	0.0325 (9)	0.0305 (10)	0.0036 (8)	−0.0075 (8)	−0.0060 (8)
C3	0.0333 (10)	0.0467 (12)	0.0446 (12)	0.0055 (9)	−0.0017 (9)	−0.0018 (10)
C4	0.0398 (11)	0.0451 (12)	0.0412 (12)	0.0019 (9)	0.0036 (9)	0.0055 (9)
C5	0.0365 (10)	0.0288 (9)	0.0315 (10)	0.0025 (8)	−0.0064 (8)	−0.0051 (7)
C6	0.0350 (10)	0.0496 (12)	0.0366 (11)	0.0087 (9)	0.0009 (9)	−0.0027 (9)
C7	0.0449 (12)	0.0460 (12)	0.0311 (10)	0.0067 (9)	0.0029 (9)	0.0017 (9)
C9	0.0482 (12)	0.0427 (11)	0.0349 (11)	0.0050 (9)	−0.0043 (9)	−0.0040 (9)
N2	0.0425 (10)	0.0498 (11)	0.0407 (10)	0.0145 (8)	−0.0048 (8)	−0.0049 (8)
C11	0.100 (2)	0.0749 (19)	0.0628 (18)	0.0288 (17)	−0.0177 (17)	−0.0357 (16)
C10	0.103 (3)	0.082 (2)	0.065 (2)	−0.0332 (19)	−0.0135 (18)	−0.0088 (17)

Geometric parameters (Å, º) top

Cu1—O1	1.9611 (14)	C2—C3	1.380 (3)
Cu1—O1ⁱ	1.9612 (14)	C2—C7	1.384 (3)
Cu1—N4	2.0096 (19)	C3—C4	1.375 (3)
Cu1—N4ⁱ	2.0096 (19)	C3—H3A	0.9300
O1—C1	1.276 (3)	C4—C5	1.382 (3)
N4—C10	1.470 (4)	C4—H4A	0.9300
N4—C11	1.475 (4)	C5—C6	1.377 (3)
N4—H4	0.9071	C6—C7	1.382 (3)
O2—C1	1.240 (3)	C6—H6A	0.9300
N3—C9	1.314 (3)	C7—H7A	0.9300
N3—C8	1.345 (3)	C9—H9A	0.9300
C8—N2	1.315 (3)	C11—H11A	0.9600
C8—H8A	0.9300	C11—H11B	0.9600
N1—C9	1.343 (3)	C11—H11C	0.9600
N1—N2	1.368 (2)	C10—H10A	0.9600
N1—C5	1.421 (2)	C10—H10B	0.9600
C1—C2	1.507 (3)	C10—H10C	0.9600

O1—Cu1—O1ⁱ	180.00 (8)	C3—C4—C5	119.5 (2)
O1—Cu1—N4	89.16 (7)	C3—C4—H4A	120.2
O1ⁱ—Cu1—N4	90.84 (7)	C5—C4—H4A	120.2
O1—Cu1—N4ⁱ	90.84 (7)	C6—C5—C4	119.96 (18)
O1ⁱ—Cu1—N4ⁱ	89.16 (7)	C6—C5—N1	120.69 (18)
N4—Cu1—N4ⁱ	180.00 (7)	C4—C5—N1	119.34 (18)
C1—O1—Cu1	111.32 (13)	C5—C6—C7	119.81 (19)
C10—N4—C11	111.0 (2)	C5—C6—H6A	120.1
C10—N4—Cu1	113.77 (18)	C7—C6—H6A	120.1
C11—N4—Cu1	112.97 (17)	C6—C7—C2	120.9 (2)
C10—N4—H4	108.7	C6—C7—H7A	119.6
C11—N4—H4	103.5	C2—C7—H7A	119.6
Cu1—N4—H4	106.2	N3—C9—N1	110.8 (2)
C9—N3—C8	102.46 (18)	N3—C9—H9A	124.6
N2—C8—N3	116.0 (2)	N1—C9—H9A	124.6
N2—C8—H8A	122.0	C8—N2—N1	101.72 (18)
N3—C8—H8A	122.0	N4—C11—H11A	109.5
C9—N1—N2	109.03 (17)	N4—C11—H11B	109.5
C9—N1—C5	129.63 (18)	H11A—C11—H11B	109.5
N2—N1—C5	121.27 (17)	N4—C11—H11C	109.5
O2—C1—O1	124.09 (19)	H11A—C11—H11C	109.5
O2—C1—C2	119.7 (2)	H11B—C11—H11C	109.5
O1—C1—C2	116.21 (18)	N4—C10—H10A	109.5
C3—C2—C7	118.30 (18)	N4—C10—H10B	109.5
C3—C2—C1	119.88 (19)	H10A—C10—H10B	109.5
C7—C2—C1	121.79 (19)	N4—C10—H10C	109.5
C4—C3—C2	121.5 (2)	H10A—C10—H10C	109.5
C4—C3—H3A	119.3	H10B—C10—H10C	109.5
C2—C3—H3A	119.3

C9—N3—C8—N2	−0.1 (3)	C9—N1—C5—C4	17.1 (3)
Cu1—O1—C1—O2	−2.6 (3)	N2—N1—C5—C4	−166.2 (2)
Cu1—O1—C1—C2	176.67 (13)	C4—C5—C6—C7	−2.7 (3)
O2—C1—C2—C3	−8.7 (3)	N1—C5—C6—C7	176.47 (19)
O1—C1—C2—C3	172.0 (2)	C5—C6—C7—C2	0.5 (4)
O2—C1—C2—C7	169.3 (2)	C3—C2—C7—C6	1.6 (3)
O1—C1—C2—C7	−10.0 (3)	C1—C2—C7—C6	−176.4 (2)
C7—C2—C3—C4	−1.6 (4)	C8—N3—C9—N1	0.0 (3)
C1—C2—C3—C4	176.4 (2)	N2—N1—C9—N3	0.0 (3)
C2—C3—C4—C5	−0.5 (4)	C5—N1—C9—N3	177.02 (19)
C3—C4—C5—C6	2.7 (3)	N3—C8—N2—N1	0.1 (3)
C3—C4—C5—N1	−176.5 (2)	C9—N1—N2—C8	0.0 (2)
C9—N1—C5—C6	−162.0 (2)	C5—N1—N2—C8	−177.35 (18)
N2—N1—C5—C6	14.7 (3)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N3ⁱⁱ	0.91	2.17	3.034 (3)	160
C9—H9A···O2ⁱⁱⁱ	0.93	2.50	3.428 (3)	173

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z.

Funding information

Funding for this research was provided by: Scientific Research Foundation of the Education Department of Liaoning Province (grant No. LJC202004).

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