catena-Poly[[[aqua­copper(II)]-μ-hydroxido-κ2O:O-μ-[3-(4H-1,2,4-triazol-4-yl)benzoato]-κ2N1:N2] monohydrate]

Li, X.-Y.; Zhou, Y.; Wang, H.-C.; Ji, M.; Li, G.-A.; Zhu, A.-Z.

doi:10.1107/S2414314625006388

metal-organic compounds

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ISSN: 2414-3146

Volume 10| Part 7| July 2025| x250638

https://doi.org/10.1107/S2414314625006388

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catena-Poly[[[aquacopper(II)]-μ-hydroxido-κ²O:O-μ-[3-(4H-1,2,4-triazol-4-yl)benzoato]-κ²N¹:N²] monohydrate]

Xiao-Yu Li,^a Ye Zhou,^a Hong-Can Wang,^a Meng Ji,^a Guo-Ao Li ^a and Ai-Xin Zhu ^a ^*

^aFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650050, People's Republic of China
^*Correspondence e-mail: [email protected]

Edited by M. Weil, Vienna University of Technology, Austria (Received 5 May 2025; accepted 17 July 2025; online 29 July 2025)

In the title compound, {[Cu(C₉H₆N₃O₂)(OH)(H₂O)]·H₂O]}_n, the Cu²⁺ cation is situated on a twofold rotation axis and is coordinated by two triazole N atoms from two different 3-(4H-1,2,4-triazol-4-yl)benzoate (3-tba) ligands, by two hydroxyl O atoms and by a water O atom, forming a coordination environment intermediate between a square pyramid and a trigonal bipyramid. The Cu²⁺ ions are connected by 3-tba ligand and a hydroxy group into polymeric chains parallel to [001]. O—H⋯O hydrogen bonds and C—H⋯O interactions consolidate the crystal structure.

Keywords: crystal structure; coordination polymer; triazole-carboxylate; copper complex.

CCDC reference: 2473449

Structure description

Coordination polymers have attracted considerable interest because of their distinctive topologies and various potential applications (Kitagawa et al., 2004 ; Leong & Vittal, 2011 ). Since organic ligands are crucial for the assembly and structural regulation of coordination polymers, they play a decisive role in the design of such compounds. In this regard, bifunctional groups are very useful, such as triazole-carboxylate ligands. For example, 4-(4H-1,2,4-triazol-4-yl)benzoate, 4-(1H-1,2,4-triazol-1-yl)benzoate, 3-(4H-1,2,4-triazol-4-yl)benzoate and 3-(1H-1,2,4-triazol-1-yl)benzoate have been used in the construction of various coordination polymers with different periodicities including dimers, chains, layers or networks (Mu et al., 2014 ; Wang et al., 2020 ; Yang et al., 2016a ,b ). In this contribution, we selected 3-(4H-1,2,4-triazol-4-yl)benzoate (3-tba) as a triazole-carboxylate ligand, generating a new coordination polymer, {[Cu(C₉H₆N₃O₂)(OH)(H₂O)]·H₂O]}_n, which is reported here.

All units in the crystal structure are on special positions. The Cu²⁺ ion and the coordinating water molecule (O1W) are situated on a twofold rotation axis, whereas the hydroxyl group (O3), the non-coordinating water molecule (O2W) and the benzoate entity of the 3-tba ligand are situated on a mirror plane, which also bisects the triazole entity. As shown in Fig. 1, the Cu²⁺ ion is coordinated by two nitrogen atoms from two different 3-tba ligands and three oxygen atoms from two different hydroxyl groups and a coordinating water molecule. The τ₅ index (Addison et al., 1984 ) of 0.40 indicates a coordination environment between a square pyramid (SP) and a trigonal bipyramid (TP) (extreme forms: τ₅ = 0.00 for SP and 1.00 for TP). The Cu—O bond lengths are 1.9434 (9) (2× to the hydroxide O atom) and 2.186 (2) Å (to the coordinating water O atom), and the Cd—N bond length is 2.0254 (14) Å (2× to triazole N atoms). As shown in Fig. 2, the 3-tba ligand and the hydroxyl group display μ₂-bridging modes to link adjacent Cu²⁺ ions into a polymeric chain extending parallel to [001]. These chain are joined via intermolecular O—H⋯O hydrogen-bonding interactions into double sheets parallel to (100) (Table 1, Fig. 3). Since the H atoms of the non-coordinating water molecule (O2W) were not located, the role of this molecule as a donor group is unclear. However, the proximity to oxygen atoms O2 and O3 [2.746 (2) and 2.936 (4) Å] allows conclusions to be drawn as possible acceptor atoms for hydrogen bonding. The cohesion of the crystal structure into a tri-periodic framework is ensured by weak C—H⋯O interactions (Table 1, Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O2ⁱ	0.85	1.90	2.746 (2)	175
O3—H3A⋯O2Wⁱⁱ	0.85	2.09	2.936 (4)	171
C1—H1⋯O1ⁱⁱⁱ	0.93	2.19	3.027 (2)	149
C6—H6⋯O3^iv	0.93	2.50	3.426 (3)	180
C7—H7⋯O1^v	0.93	2.38	3.270 (3)	161
Symmetry codes: (i) ; (ii) ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
Parts of the crystal structure showing the coordination environment of Cu²⁺ in the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (A) x, $[{3\over 2}]$ − y, 1 − z; (B) x, y, $[{1\over 2}]$ − z; (C) x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z.]

Figure 2
The formed polymeric chain in the title compound.

Figure 3
The double-sheet structure formed by O—H⋯O hydrogen-bonding interactions (black dashes lines) viewed along the c axis.

Figure 4
The crystal structure with O—H⋯O hydrogen bonds (black dashed lines) and C—H⋯O hydrogen bonds (purple dashed lines) viewed along the c axis.

Synthesis and crystallization

A mixture of Cu(NO₃)₂·3H₂O (12 mg, 0.05 mmol), 3-Htba (9 mg, 0.05 mmol), water (4 ml) and ammonia solution (0.05 ml, 1 mol l⁻¹) was placed in a Teflon-lined stainless steel vessel (15 ml). The vessel was sealed and heated in an oven at 393 K for 72 h, and then slowly cooled to the room temperature. Blue block-shaped crystals were harvested by filtration, washed with water and dried under ambient condition (yield 36%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Since reliable positions of hydrogen atoms bonded to non-coordinating water molecule O2W could not be derived from difference-Fourier maps, they were excluded from the model but are part of the formula and other structural data.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₉H₆N₃O₂)(OH)(H₂O)]·H₂O
M_r	304.75
Crystal system, space group	Orthorhombic, Pbcm
Temperature (K)	293
a, b, c (Å)	11.456 (2), 14.140 (3), 6.8502 (14)
V (Å³)	1109.6 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.99
Crystal size (mm)	0.25 × 0.22 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS SPIDER
Absorption correction	Multi-scan (ABSCOR; Higashi, 2001 )
T_min, T_max	0.746, 0.896
No. of measured, independent and observed [I > 2σ(I)] reflections	10406, 1374, 1209
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.078, 1.13
No. of reflections	1374
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.45
Computer programs: RAPID-AUTO (Rigaku, 1999 ), CrystalClear (Rigaku, 2002 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2473449

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314625006388/wm4229sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625006388/wm4229Isup3.hkl

checkCIF report

Computing details top

catena-Poly[[[aquacopper(II)]-µ-hydroxido-κ²O:O-µ-[3-(4H-1,2,4-triazol-4-yl)benzoato]-κ²N¹:N²] monohydrate] top

Crystal data top

[Cu(C₉H₆N₃O₂)(OH)(H₂O)]·H₂O	D_x = 1.824 Mg m⁻³
M_r = 304.75	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcm	Cell parameters from 2652 reflections
a = 11.456 (2) Å	θ = 5.2–54.9°
b = 14.140 (3) Å	µ = 1.99 mm⁻¹
c = 6.8502 (14) Å	T = 293 K
V = 1109.6 (4) Å³	Block, blue
Z = 4	0.25 × 0.22 × 0.20 mm
F(000) = 620

Data collection top

Rigaku R-AXIS SPIDER diffractometer	1209 reflections with I > 2σ(I)
ω scans	R_int = 0.038
Absorption correction: multi-scan (ABSCOR; Higashi, 2001)	θ_max = 27.4°, θ_min = 3.4°
T_min = 0.746, T_max = 0.896	h = −14→14
10406 measured reflections	k = −17→18
1374 independent reflections	l = −8→8

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.040P)² + 0.7023P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
1374 reflections	Δρ_max = 0.48 e Å⁻³
101 parameters	Δρ_min = −0.45 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	0.33189 (3)	0.750000	0.500000	0.01519 (13)
N1	0.28663 (14)	0.63184 (10)	0.3510 (2)	0.0197 (3)
N2	0.2127 (2)	0.49830 (15)	0.250000	0.0194 (4)
C1	0.24192 (17)	0.55131 (12)	0.4081 (2)	0.0218 (4)
H1	0.231667	0.533087	0.537449	0.026*
C2	0.1535 (2)	0.40752 (18)	0.250000	0.0190 (5)
C3	0.2189 (2)	0.32508 (17)	0.250000	0.0187 (5)
H3	0.300014	0.327427	0.250000	0.022*
C4	0.1603 (2)	0.23812 (17)	0.250000	0.0182 (5)
C5	0.0387 (3)	0.23727 (18)	0.250000	0.0235 (5)
H5	−0.000599	0.179720	0.250000	0.028*
C6	−0.0245 (2)	0.3205 (2)	0.250000	0.0284 (6)
H6	−0.105621	0.318531	0.250000	0.034*
C7	0.0329 (2)	0.40733 (19)	0.250000	0.0261 (6)
H7	−0.008844	0.463720	0.250000	0.031*
C8	0.2265 (2)	0.14552 (17)	0.250000	0.0207 (5)
O1	0.16904 (17)	0.07078 (13)	0.250000	0.0247 (4)
O2	0.33717 (18)	0.14919 (15)	0.250000	0.0361 (5)
O3	0.32341 (16)	0.81461 (12)	0.250000	0.0186 (4)
H3A	0.371738	0.860229	0.250000	0.022*
O1W	0.5227 (2)	0.750000	0.500000	0.0501 (8)
H1W	0.565365	0.778680	0.582500	0.060*
O2W	0.4674 (3)	−0.0136 (2)	0.250000	0.0820 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0241 (2)	0.00965 (18)	0.01184 (18)	0.000	0.000	−0.00046 (9)
N1	0.0339 (8)	0.0132 (7)	0.0122 (7)	−0.0031 (6)	−0.0007 (6)	−0.0003 (6)
N2	0.0297 (11)	0.0099 (9)	0.0186 (10)	−0.0024 (8)	0.000	0.000
C1	0.0359 (10)	0.0133 (8)	0.0161 (8)	−0.0029 (7)	0.0003 (7)	0.0008 (6)
C2	0.0278 (13)	0.0106 (11)	0.0186 (12)	−0.0039 (9)	0.000	0.000
C3	0.0222 (12)	0.0143 (11)	0.0196 (11)	−0.0020 (9)	0.000	0.000
C4	0.0247 (13)	0.0127 (12)	0.0172 (13)	−0.0007 (9)	0.000	0.000
C5	0.0269 (13)	0.0160 (12)	0.0277 (14)	−0.0067 (10)	0.000	0.000
C6	0.0200 (13)	0.0249 (14)	0.0403 (15)	−0.0017 (11)	0.000	0.000
C7	0.0278 (14)	0.0158 (12)	0.0348 (14)	0.0037 (10)	0.000	0.000
C8	0.0296 (14)	0.0140 (12)	0.0185 (11)	0.0005 (10)	0.000	0.000
O1	0.0344 (11)	0.0109 (9)	0.0288 (10)	−0.0020 (7)	0.000	0.000
O2	0.0267 (11)	0.0192 (10)	0.0624 (15)	0.0028 (8)	0.000	0.000
O3	0.0302 (10)	0.0106 (8)	0.0151 (8)	−0.0030 (7)	0.000	0.000
O1W	0.0236 (12)	0.091 (2)	0.0357 (13)	0.000	0.000	−0.0226 (12)
O2W	0.0488 (17)	0.0304 (15)	0.167 (4)	−0.0002 (13)	0.000	0.000

Geometric parameters (Å, º) top

Cu1—O3ⁱ	1.9434 (9)	C3—H3	0.9300
Cu1—O3	1.9434 (9)	C4—C5	1.393 (4)
Cu1—N1ⁱⁱ	2.0254 (14)	C4—C8	1.513 (3)
Cu1—N1	2.0254 (14)	C5—C6	1.382 (4)
Cu1—O1W	2.186 (2)	C5—H5	0.9300
N1—C1	1.309 (2)	C6—C7	1.393 (4)
N1—N1ⁱⁱⁱ	1.384 (3)	C6—H6	0.9300
N2—C1	1.359 (2)	C7—H7	0.9300
N2—C1ⁱⁱⁱ	1.359 (2)	C8—O1	1.245 (3)
N2—C2	1.452 (3)	C8—O2	1.269 (3)
C1—H1	0.9300	O3—H3A	0.8501
C2—C7	1.382 (4)	O1W—H1W	0.8500
C2—C3	1.385 (4)	O1W—H1Wⁱⁱ	0.8499
C3—C4	1.401 (3)

O3ⁱ—Cu1—O3	174.27 (11)	C2—C3—H3	120.7
O3ⁱ—Cu1—N1ⁱⁱ	86.03 (6)	C4—C3—H3	120.7
O3—Cu1—N1ⁱⁱ	92.49 (6)	C5—C4—C3	119.1 (2)
O3ⁱ—Cu1—N1	92.50 (6)	C5—C4—C8	119.6 (2)
O3—Cu1—N1	86.04 (6)	C3—C4—C8	121.3 (2)
N1ⁱⁱ—Cu1—N1	150.33 (9)	C6—C5—C4	121.1 (2)
O3ⁱ—Cu1—O1W	92.87 (5)	C6—C5—H5	119.4
O3—Cu1—O1W	92.87 (5)	C4—C5—H5	119.4
N1ⁱⁱ—Cu1—O1W	104.83 (5)	C5—C6—C7	120.2 (3)
N1—Cu1—O1W	104.83 (5)	C5—C6—H6	119.9
C1—N1—N1ⁱⁱⁱ	107.40 (10)	C7—C6—H6	119.9
C1—N1—Cu1	131.86 (12)	C2—C7—C6	118.3 (3)
N1ⁱⁱⁱ—N1—Cu1	120.26 (4)	C2—C7—H7	120.9
C1—N2—C1ⁱⁱⁱ	105.7 (2)	C6—C7—H7	120.9
C1—N2—C2	127.06 (10)	O1—C8—O2	124.3 (2)
C1ⁱⁱⁱ—N2—C2	127.06 (10)	O1—C8—C4	118.0 (2)
N1—C1—N2	109.75 (15)	O2—C8—C4	117.7 (2)
N1—C1—H1	125.1	Cu1ⁱⁱⁱ—O3—Cu1	123.58 (9)
N2—C1—H1	125.1	Cu1ⁱⁱⁱ—O3—H3A	108.9
C7—C2—C3	122.6 (2)	Cu1—O3—H3A	108.9
C7—C2—N2	118.0 (2)	Cu1—O1W—H1W	125.1
C3—C2—N2	119.4 (2)	Cu1—O1W—H1Wⁱⁱ	125.078 (7)
C2—C3—C4	118.7 (2)	H1W—O1W—H1Wⁱⁱ	109.8

N1ⁱⁱⁱ—N1—C1—N2	0.11 (19)	C2—C3—C4—C8	180.0
Cu1—N1—C1—N2	172.00 (15)	C3—C4—C5—C6	0.0
C1ⁱⁱⁱ—N2—C1—N1	−0.2 (3)	C8—C4—C5—C6	180.0
C2—N2—C1—N1	−175.4 (2)	C4—C5—C6—C7	0.0
C1—N2—C2—C7	87.1 (2)	C3—C2—C7—C6	0.0
C1ⁱⁱⁱ—N2—C2—C7	−87.1 (2)	N2—C2—C7—C6	180.0
C1—N2—C2—C3	−92.9 (2)	C5—C6—C7—C2	0.0
C1ⁱⁱⁱ—N2—C2—C3	92.9 (2)	C5—C4—C8—O1	0.0
C7—C2—C3—C4	0.0	C3—C4—C8—O1	180.0
N2—C2—C3—C4	180.0	C5—C4—C8—O2	180.0
C2—C3—C4—C5	0.0	C3—C4—C8—O2	0.0

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, −z+1; (iii) x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2^iv	0.85	1.90	2.746 (2)	175
O3—H3A···O2W^v	0.85	2.09	2.936 (4)	171
C1—H1···O1^vi	0.93	2.19	3.027 (2)	149
C6—H6···O3^vii	0.93	2.50	3.426 (3)	180
C7—H7···O1^viii	0.93	2.38	3.270 (3)	161

Symmetry codes: (iv) −x+1, −y+1, −z+1; (v) x, y+1, z; (vi) x, −y+1/2, z+1/2; (vii) −x, y−1/2, −z+1/2; (viii) −x, y+1/2, −z+1/2.

Funding information

Funding for this research was provided by: Graduate Student Research Innovation Fund Project and Research Training Program of Yunnan Normal University (grant No. YJSJJ23-B84; award No. HGKX202403).

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