Diaqua­bis[4-(4H-1,2,4-triazol-4-yl)­benzoato-κ²O,O′]cobalt(II), and the cadmium(II) and copper(II) analogues: new self-complementary hydrogen-bond donor/acceptor modules for designing hydrogen-bonded frameworks

In the isostructural title complexes, [M(C₉H₆N₃O₂)₂(H₂O)₂] [M = Co^II, (I), Cd^II, (II), and Cu^II, (III); the metal centres reside on a twofold axis in the space group C2/c for (I) and (II)], the metal centres are surrounded by four O atoms from two O,O′-bidentate carboxyl­ate groups and by two trans-coordinated aqua ligands, forming a distorted octa­hedral environment. The mol­ecules possess four hydrogen-bond donor (two aqua ligands) and four hydrogen-bond acceptor sites (two triazole groups), and aggregate by self-association, forming two-dimensional hydrogen-bonded frameworks [via O—H...N inter­actions; O...N = 2.749 (3)–2.872 (3) Å]. The layers are parallel and are tightly packed with short inter­layer distances of 4.93, 4.95 and 5.01 Å for (I), (II) and (III), respectively.

Computing details

For all compounds, data collection: SMART-NT (Bruker, 1998). Cell refinement: SMART-NT or SAINT??? (Bruker, 1998) for (I), (III); SMART-NT or SAINT???? (Bruker, 1998) for (II). Data reduction: SMART-NT or SAINT??? for (I), (III); SMART-NT or SAINT???? for (II). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Diamond (Brandenburg, 1999); software used to prepare material for publication: WinGX (Version 1.700.00; Farrugia, 1999).

(I) Diaquabis[4-(4H-1,2,4-triazol-4-yl)benzoato-κ²O,O']cobalt(II)

Crystal data

[Co(C9H6N3O2)2(H2O)2]	F(000) = 964
Mr = 471.30	Dx = 1.753 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.5266 (9) Å	Cell parameters from 7599 reflections
b = 9.8617 (7) Å	θ = 2.6–27.6°
c = 14.4429 (9) Å	µ = 1.02 mm^−1
β = 112.083 (3)°	T = 213 K
V = 1785.3 (2) Å^3	Prism, pink
Z = 4	0.18 × 0.16 × 0.16 mm

Data collection

Siemens SMART CCD diffractometer	2057 independent reflections
Radiation source: fine-focus sealed tube	1607 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 27.6°, θmin = 2.6°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.838, Tmax = 0.854	k = −12→12
7599 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.043P)^2] where P = (Fo^2 + 2Fc^2)/3
2057 reflections	(Δ/σ)max = 0.001
141 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Co1	0.0000	0.07711 (3)	0.2500	0.01897 (11)
O1	0.14414 (9)	−0.03691 (12)	0.29607 (10)	0.0249 (3)
O2	0.14914 (9)	0.18553 (11)	0.30013 (9)	0.0223 (3)
O3	0.00316 (10)	0.10071 (15)	0.39246 (10)	0.0339 (3)
H1	0.0537	0.0556	0.4347	0.051*
H2	−0.0571	0.0800	0.3944	0.051*
N1	0.80877 (11)	−0.01767 (16)	0.45657 (12)	0.0260 (3)
N2	0.80936 (11)	0.11569 (15)	0.42598 (12)	0.0241 (3)
N3	0.64489 (10)	0.06013 (13)	0.40370 (10)	0.0179 (3)
C1	0.71053 (14)	−0.04841 (17)	0.44199 (14)	0.0238 (4)
H1A	0.6878	−0.1334	0.4559	0.029*
C2	0.71094 (13)	0.15929 (17)	0.39482 (14)	0.0218 (4)
H2A	0.6888	0.2468	0.3698	0.026*
C3	0.53209 (12)	0.06498 (16)	0.37981 (12)	0.0171 (3)
C4	0.47489 (13)	−0.05533 (16)	0.35866 (14)	0.0223 (4)
H4A	0.5095	−0.1380	0.3587	0.027*
C5	0.36607 (13)	−0.05241 (15)	0.33750 (14)	0.0215 (4)
H5A	0.3269	−0.1337	0.3241	0.026*
C6	0.31456 (12)	0.07019 (17)	0.33599 (12)	0.0181 (3)
C7	0.37303 (13)	0.19015 (16)	0.35553 (14)	0.0214 (4)
H7A	0.3381	0.2733	0.3531	0.026*
C8	0.48238 (13)	0.18840 (16)	0.37852 (13)	0.0217 (4)
H8A	0.5220	0.2694	0.3929	0.026*
C9	0.19648 (12)	0.07302 (16)	0.30986 (12)	0.0181 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.00907 (16)	0.01947 (16)	0.0285 (2)	0.000	0.00718 (14)	0.000
O1	0.0121 (6)	0.0215 (6)	0.0410 (8)	−0.0024 (4)	0.0099 (6)	−0.0014 (5)
O2	0.0125 (6)	0.0207 (6)	0.0332 (7)	0.0014 (4)	0.0080 (6)	−0.0005 (5)
O3	0.0137 (6)	0.0605 (9)	0.0287 (7)	0.0091 (6)	0.0091 (6)	0.0097 (6)
N1	0.0143 (7)	0.0334 (8)	0.0293 (9)	0.0055 (6)	0.0071 (7)	0.0010 (7)
N2	0.0120 (7)	0.0344 (8)	0.0258 (8)	−0.0009 (6)	0.0070 (6)	−0.0004 (6)
N3	0.0097 (6)	0.0233 (7)	0.0207 (7)	0.0011 (5)	0.0057 (6)	0.0002 (5)
C1	0.0164 (8)	0.0262 (8)	0.0283 (10)	0.0046 (6)	0.0078 (8)	0.0043 (7)
C2	0.0140 (8)	0.0262 (8)	0.0259 (10)	−0.0017 (6)	0.0081 (8)	0.0001 (7)
C3	0.0093 (7)	0.0235 (8)	0.0188 (8)	0.0006 (6)	0.0057 (7)	0.0006 (6)
C4	0.0146 (8)	0.0201 (8)	0.0337 (10)	0.0023 (6)	0.0108 (8)	−0.0002 (7)
C5	0.0142 (8)	0.0185 (8)	0.0328 (10)	−0.0020 (6)	0.0102 (8)	−0.0008 (6)
C6	0.0110 (7)	0.0227 (7)	0.0206 (8)	0.0002 (6)	0.0060 (7)	0.0006 (6)
C7	0.0131 (8)	0.0197 (8)	0.0314 (10)	0.0014 (6)	0.0085 (8)	−0.0026 (7)
C8	0.0130 (8)	0.0201 (8)	0.0308 (10)	−0.0028 (6)	0.0071 (8)	−0.0043 (7)
C9	0.0108 (7)	0.0225 (7)	0.0214 (8)	−0.0003 (6)	0.0065 (7)	0.0005 (7)

Geometric parameters (Å, º)

Co1—O1	2.1291 (12)	C1—H1A	0.9400
Co1—O2	2.1539 (11)	C2—H2A	0.9400
Co1—O3	2.0552 (13)	C3—C4	1.386 (2)
O1—C9	1.269 (2)	C3—C8	1.387 (2)
O2—C9	1.2622 (19)	C4—C5	1.387 (2)
O3—H1	0.8500	C4—H4A	0.9400
O3—H2	0.8500	C5—C6	1.391 (2)
N1—C1	1.301 (2)	C5—H5A	0.9400
N1—N2	1.388 (2)	C6—C7	1.392 (2)
N2—C2	1.307 (2)	C6—C9	1.497 (2)
N3—C2	1.363 (2)	C7—C8	1.389 (2)
N3—C1	1.368 (2)	C7—H7A	0.9400
N3—C3	1.4330 (19)	C8—H8A	0.9400
O3—Co1—O3^i	166.99 (8)	N2—C2—N3	110.51 (15)
O3—Co1—O1^i	92.56 (5)	N2—C2—H2A	124.7
O3—Co1—O1	94.30 (5)	N3—C2—H2A	124.7
O3^i—Co1—O1	92.56 (5)	C4—C3—C8	121.36 (14)
O1^i—Co1—O1	116.25 (6)	C4—C3—N3	118.69 (13)
O3—Co1—O2	86.73 (5)	C8—C3—N3	119.95 (14)
O3^i—Co1—O2	86.82 (5)	C3—C4—C5	119.28 (14)
O1^i—Co1—O2	177.69 (5)	C3—C4—H4A	120.4
O1—Co1—O2	61.65 (4)	C5—C4—H4A	120.4
O3—Co1—O2^i	86.82 (5)	C4—C5—C6	120.35 (15)
O1—Co1—O2^i	177.69 (5)	C4—C5—H5A	119.8
O2—Co1—O2^i	120.47 (6)	C6—C5—H5A	119.8
C9—O1—Co1	89.38 (9)	C5—C6—C7	119.50 (14)
C9—O2—Co1	88.45 (9)	C5—C6—C9	120.04 (15)
Co1—O3—H1	111.5	C7—C6—C9	120.43 (14)
Co1—O3—H2	110.3	C8—C7—C6	120.72 (14)
H1—O3—H2	111.9	C8—C7—H7A	119.6
C1—N1—N2	107.28 (14)	C6—C7—H7A	119.6
C2—N2—N1	107.11 (13)	C3—C8—C7	118.77 (14)
C2—N3—C1	104.53 (14)	C3—C8—H8A	120.6
C2—N3—C3	129.03 (14)	C7—C8—H8A	120.6
C1—N3—C3	126.44 (14)	O2—C9—O1	120.25 (14)
N1—C1—N3	110.57 (15)	O2—C9—C6	119.54 (14)
N1—C1—H1A	124.7	O1—C9—C6	120.20 (14)
N3—C1—H1A	124.7
O3—Co1—O1—C9	−86.93 (10)	C8—C3—C4—C5	−1.1 (3)
O3^i—Co1—O1—C9	82.01 (10)	N3—C3—C4—C5	178.65 (15)
O1^i—Co1—O1—C9	178.08 (11)	C3—C4—C5—C6	1.0 (3)
O2—Co1—O1—C9	−2.99 (9)	C4—C5—C6—C7	0.2 (3)
O3—Co1—O2—C9	99.68 (10)	C4—C5—C6—C9	178.03 (15)
O3^i—Co1—O2—C9	−91.62 (10)	C5—C6—C7—C8	−1.4 (3)
O1—Co1—O2—C9	3.01 (9)	C9—C6—C7—C8	−179.14 (16)
O2^i—Co1—O2—C9	−175.94 (10)	C4—C3—C8—C7	0.0 (3)
C1—N1—N2—C2	0.36 (19)	N3—C3—C8—C7	−179.74 (15)
N2—N1—C1—N3	−0.7 (2)	C6—C7—C8—C3	1.2 (3)
C2—N3—C1—N1	0.8 (2)	Co1—O2—C9—O1	−5.15 (15)
C3—N3—C1—N1	−178.84 (15)	Co1—O2—C9—C6	173.77 (14)
N1—N2—C2—N3	0.12 (19)	Co1—O1—C9—O2	5.21 (16)
C1—N3—C2—N2	−0.53 (19)	Co1—O1—C9—C6	−173.70 (14)
C3—N3—C2—N2	179.06 (15)	C5—C6—C9—O2	−173.83 (15)
C2—N3—C3—C4	155.98 (17)	C7—C6—C9—O2	3.9 (2)
C1—N3—C3—C4	−24.5 (3)	C5—C6—C9—O1	5.1 (3)
C2—N3—C3—C8	−24.2 (3)	C7—C6—C9—O1	−177.14 (15)
C1—N3—C3—C8	155.29 (17)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···N1^ii	0.85	1.97	2.780 (2)	159
O3—H2···N2^iii	0.85	2.05	2.843 (2)	154
C4—H4A···O3^iv	0.94	2.63	3.428 (2)	143

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

(II) Diaquabis[4-(4H-1,2,4-triazol-4-yl)benzoato-κ²O,O']cadmium(II)

Crystal data

[Cd(C9H6N3O2)2(H2O)2]	F(000) = 1048
Mr = 524.77	Dx = 1.870 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.7301 (6) Å	Cell parameters from 6196 reflections
b = 9.8915 (5) Å	θ = 2.6–27.9°
c = 14.8111 (10) Å	µ = 1.23 mm^−1
β = 112.063 (3)°	T = 296 K
V = 1864.21 (18) Å^3	Prism, colorless
Z = 4	0.18 × 0.16 × 0.16 mm

Data collection

Siemens SMART CCD diffractometer	2213 independent reflections
Radiation source: fine-focus sealed tube	1941 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 27.9°, θmin = 2.6°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −18→12
Tmin = 0.810, Tmax = 0.828	k = −11→12
6196 measured reflections	l = −18→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0474P)^2 + 1.5785P] where P = (Fo^2 + 2Fc^2)/3
2213 reflections	(Δ/σ)max < 0.001
141 parameters	Δρmax = 0.67 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cd1	0.0000	0.08044 (3)	0.2500	0.03738 (12)
O1	0.15745 (14)	−0.0332 (2)	0.29622 (16)	0.0412 (5)
O2	0.16224 (13)	0.18906 (19)	0.30451 (14)	0.0376 (4)
O3	0.00698 (16)	0.1188 (3)	0.40408 (15)	0.0520 (6)
H1	0.0576	0.0737	0.4463	0.078*
H2	−0.0533	0.0981	0.4060	0.078*
N1	0.80989 (17)	−0.0116 (3)	0.45761 (18)	0.0420 (6)
N2	0.81063 (17)	0.1206 (3)	0.42637 (17)	0.0378 (5)
N3	0.64934 (16)	0.0651 (2)	0.40523 (15)	0.0278 (4)
C1	0.7141 (2)	−0.0411 (3)	0.4444 (2)	0.0394 (6)
H1A	0.6923	−0.1241	0.4597	0.047*
C2	0.71409 (19)	0.1627 (3)	0.39526 (19)	0.0331 (6)
H2A	0.6922	0.2482	0.3696	0.040*
C3	0.53806 (18)	0.0699 (2)	0.38105 (18)	0.0262 (5)
C4	0.4824 (2)	−0.0497 (3)	0.3619 (2)	0.0356 (6)
H4A	0.5165	−0.1314	0.3637	0.043*
C5	0.3752 (2)	−0.0466 (3)	0.3400 (2)	0.0353 (6)
H5A	0.3372	−0.1269	0.3271	0.042*
C6	0.32420 (19)	0.0742 (2)	0.33720 (18)	0.0286 (5)
C7	0.38106 (18)	0.1938 (3)	0.35575 (19)	0.0326 (5)
H7A	0.3467	0.2757	0.3527	0.039*
C8	0.48841 (19)	0.1924 (3)	0.37879 (19)	0.0327 (6)
H8A	0.5267	0.2725	0.3926	0.039*
C9	0.20695 (19)	0.0769 (2)	0.31081 (19)	0.0295 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01693 (15)	0.0448 (2)	0.0498 (2)	0.000	0.01183 (12)	0.000
O1	0.0192 (9)	0.0345 (10)	0.0689 (14)	−0.0015 (8)	0.0156 (9)	−0.0021 (9)
O2	0.0176 (8)	0.0346 (10)	0.0593 (12)	0.0008 (7)	0.0130 (8)	−0.0003 (9)
O3	0.0238 (10)	0.0874 (16)	0.0461 (12)	0.0141 (10)	0.0147 (9)	0.0154 (11)
N1	0.0220 (11)	0.0523 (15)	0.0499 (14)	0.0106 (10)	0.0115 (10)	0.0063 (12)
N2	0.0199 (10)	0.0511 (14)	0.0422 (12)	0.0020 (10)	0.0115 (9)	−0.0002 (11)
N3	0.0160 (9)	0.0357 (12)	0.0325 (11)	0.0026 (8)	0.0098 (8)	0.0014 (8)
C1	0.0249 (13)	0.0403 (15)	0.0526 (17)	0.0084 (11)	0.0139 (12)	0.0093 (13)
C2	0.0207 (11)	0.0389 (15)	0.0407 (14)	−0.0011 (10)	0.0127 (10)	0.0023 (11)
C3	0.0149 (10)	0.0357 (13)	0.0286 (11)	0.0025 (9)	0.0087 (9)	0.0018 (9)
C4	0.0232 (12)	0.0272 (13)	0.0581 (17)	0.0028 (10)	0.0171 (12)	0.0007 (11)
C5	0.0226 (12)	0.0275 (13)	0.0579 (17)	−0.0043 (10)	0.0177 (12)	−0.0016 (11)
C6	0.0181 (11)	0.0348 (14)	0.0344 (13)	−0.0008 (9)	0.0115 (10)	−0.0009 (10)
C7	0.0178 (11)	0.0300 (13)	0.0483 (15)	0.0016 (10)	0.0106 (10)	−0.0033 (11)
C8	0.0202 (11)	0.0312 (13)	0.0451 (14)	−0.0035 (10)	0.0104 (10)	−0.0052 (11)
C9	0.0168 (11)	0.0352 (14)	0.0367 (13)	−0.0009 (10)	0.0102 (10)	−0.0007 (10)

Geometric parameters (Å, º)

Cd1—O1	2.3008 (19)	C1—H1A	0.9300
Cd1—O2	2.3275 (17)	C2—H2A	0.9300
Cd1—O3	2.280 (2)	C3—C4	1.379 (4)
O1—C9	1.258 (3)	C3—C8	1.384 (3)
O2—C9	1.255 (3)	C4—C5	1.383 (3)
O3—H1	0.8640	C4—H4A	0.9300
O3—H2	0.8630	C5—C6	1.378 (4)
N1—C1	1.288 (4)	C5—H5A	0.9300
N1—N2	1.388 (4)	C6—C7	1.387 (3)
N2—C2	1.298 (3)	C6—C9	1.507 (3)
N3—C2	1.357 (3)	C7—C8	1.383 (3)
N3—C1	1.358 (3)	C7—H7A	0.9300
N3—C3	1.433 (3)	C8—H8A	0.9300
O3—Cd1—O3^i	160.83 (12)	N2—C2—N3	110.9 (2)
O3—Cd1—O1^i	93.48 (8)	N2—C2—H2A	124.6
O3—Cd1—O1	95.85 (7)	N3—C2—H2A	124.6
O3^i—Cd1—O1	93.48 (8)	C4—C3—C8	121.0 (2)
O1^i—Cd1—O1	121.51 (10)	C4—C3—N3	118.7 (2)
O3—Cd1—O2	84.32 (7)	C8—C3—N3	120.3 (2)
O3^i—Cd1—O2	86.86 (7)	C3—C4—C5	119.3 (2)
O1^i—Cd1—O2	176.96 (7)	C3—C4—H4A	120.4
O1—Cd1—O2	56.80 (7)	C5—C4—H4A	120.4
O3—Cd1—O2^i	86.86 (7)	C6—C5—C4	120.6 (2)
O1—Cd1—O2^i	176.96 (7)	C6—C5—H5A	119.7
O2—Cd1—O2^i	125.02 (9)	C4—C5—H5A	119.7
C9—O1—Cd1	90.85 (15)	C5—C6—C7	119.5 (2)
C9—O2—Cd1	89.73 (14)	C5—C6—C9	120.3 (2)
Cd1—O3—H1	111.0	C7—C6—C9	120.2 (2)
Cd1—O3—H2	108.3	C8—C7—C6	120.6 (2)
H1—O3—H2	111.9	C8—C7—H7A	119.7
C1—N1—N2	107.3 (2)	C6—C7—H7A	119.7
C2—N2—N1	106.6 (2)	C7—C8—C3	119.0 (2)
C2—N3—C1	104.3 (2)	C7—C8—H8A	120.5
C2—N3—C3	129.0 (2)	C3—C8—H8A	120.5
C1—N3—C3	126.7 (2)	O2—C9—O1	122.3 (2)
N1—C1—N3	110.9 (3)	O2—C9—C6	118.7 (2)
N1—C1—H1A	124.6	O1—C9—C6	119.0 (2)
N3—C1—H1A	124.6
C1—N1—N2—C2	−0.5 (3)	C4—C5—C6—C9	178.4 (3)
N2—N1—C1—N3	0.2 (3)	C5—C6—C7—C8	−1.2 (4)
C2—N3—C1—N1	0.1 (3)	C9—C6—C7—C8	−179.2 (2)
C3—N3—C1—N1	−179.6 (2)	C6—C7—C8—C3	1.4 (4)
N1—N2—C2—N3	0.6 (3)	C4—C3—C8—C7	−0.8 (4)
C1—N3—C2—N2	−0.5 (3)	N3—C3—C8—C7	−179.6 (2)
C3—N3—C2—N2	179.3 (2)	Cd1—O2—C9—O1	−5.4 (3)
C2—N3—C3—C4	155.6 (3)	Cd1—O2—C9—C6	174.9 (2)
C1—N3—C3—C4	−24.6 (4)	Cd1—O1—C9—O2	5.4 (3)
C2—N3—C3—C8	−25.5 (4)	Cd1—O1—C9—C6	−174.8 (2)
C1—N3—C3—C8	154.2 (3)	C5—C6—C9—O2	−176.8 (3)
C8—C3—C4—C5	0.1 (4)	C7—C6—C9—O2	1.2 (4)
N3—C3—C4—C5	179.0 (2)	C5—C6—C9—O1	3.5 (4)
C3—C4—C5—C6	0.1 (5)	C7—C6—C9—O1	−178.6 (2)
C4—C5—C6—C7	0.5 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···N1^ii	0.86	1.94	2.788 (2)	166
O3—H2···N2^iii	0.86	2.01	2.836 (2)	159
C4—H4A···O3^iv	0.93	2.56	3.331 (2)	141

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

(III) Diaquabis[4-(4H-1,2,4-triazol-4-yl)benzoato-κ²O,O']copper(II)

Crystal data

[Cu(C9H6N3O2)2(H2O)2]	F(000) = 972
Mr = 475.91	Dx = 1.746 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.4483 (4) Å	Cell parameters from 4301 reflections
b = 10.0101 (3) Å	θ = 2.5–27.9°
c = 14.4749 (5) Å	µ = 1.26 mm^−1
β = 111.674 (2)°	T = 296 K
V = 1810.83 (10) Å^3	Prism, green
Z = 4	0.50 × 0.20 × 0.20 mm

Data collection

Siemens SMART CCD diffractometer	4301 independent reflections
Radiation source: fine-focus sealed tube	3232 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 27.9°, θmin = 2.5°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −16→17
Tmin = 0.571, Tmax = 0.787	k = −10→13
13821 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0483P)^2 + 0.7524P] where P = (Fo^2 + 2Fc^2)/3
4301 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.55 e Å^−3

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cu1	0.245975 (19)	0.66068 (3)	0.24870 (2)	0.02728 (11)
O1	0.39100 (12)	0.72780 (17)	0.28705 (13)	0.0348 (4)
O2	0.41565 (13)	0.51206 (18)	0.31827 (15)	0.0444 (5)
O3	0.09854 (11)	0.60241 (16)	0.20779 (12)	0.0300 (4)
O4	0.08660 (13)	0.82128 (16)	0.19047 (15)	0.0418 (5)
O5	0.23969 (13)	0.6187 (2)	0.11294 (13)	0.0415 (4)
H1	0.3001	0.6297	0.1079	0.062*
H2	0.1930	0.6659	0.0695	0.062*
O6	0.25190 (14)	0.6661 (2)	0.38628 (14)	0.0508 (6)
H3	0.1905	0.6776	0.3891	0.076*
H4	0.2947	0.7258	0.4204	0.076*
N1	1.05531 (15)	0.7948 (2)	0.45891 (15)	0.0339 (5)
N2	1.06570 (15)	0.6653 (2)	0.42989 (15)	0.0329 (5)
N3	0.89811 (13)	0.69928 (19)	0.40789 (13)	0.0252 (4)
N4	−0.57351 (15)	0.7263 (2)	0.03454 (16)	0.0398 (5)
N5	−0.56489 (15)	0.6002 (2)	0.07641 (15)	0.0373 (5)
N6	−0.40455 (14)	0.67049 (18)	0.09400 (14)	0.0264 (4)
C1	0.95508 (18)	0.8121 (2)	0.44445 (18)	0.0325 (5)
H1A	0.9262	0.8910	0.4574	0.039*
C2	0.97164 (17)	0.6107 (2)	0.40034 (17)	0.0293 (5)
H2A	0.9565	0.5235	0.3773	0.035*
C3	0.78610 (16)	0.6788 (2)	0.38397 (16)	0.0245 (5)
C4	0.71836 (17)	0.7872 (2)	0.35558 (18)	0.0305 (5)
H4A	0.7454	0.8715	0.3511	0.037*
C5	0.60993 (17)	0.7702 (2)	0.33377 (18)	0.0305 (5)
H5A	0.5643	0.8434	0.3153	0.037*
C6	0.56891 (17)	0.6446 (2)	0.33925 (17)	0.0268 (5)
C7	0.63819 (18)	0.5365 (2)	0.36612 (19)	0.0329 (5)
H7A	0.6112	0.4517	0.3689	0.039*
C8	0.74681 (18)	0.5527 (2)	0.38885 (19)	0.0326 (5)
H8A	0.7927	0.4796	0.4072	0.039*
C9	0.45090 (17)	0.6253 (2)	0.31374 (17)	0.0286 (5)
C10	−0.47793 (18)	0.7655 (3)	0.04653 (18)	0.0351 (6)
H10A	−0.4616	0.8475	0.0255	0.042*
C11	−0.46379 (18)	0.5702 (3)	0.11054 (18)	0.0333 (5)
H11A	−0.4356	0.4903	0.1422	0.040*
C12	−0.29169 (16)	0.6793 (2)	0.11892 (16)	0.0243 (5)
C13	−0.24369 (18)	0.8039 (2)	0.13370 (18)	0.0311 (5)
H13A	−0.2843	0.8805	0.1291	0.037*
C14	−0.13485 (18)	0.8134 (2)	0.15541 (18)	0.0304 (5)
H14A	−0.1026	0.8971	0.1643	0.036*
C15	−0.07326 (16)	0.6996 (2)	0.16412 (16)	0.0251 (5)
C16	−0.12287 (17)	0.5747 (2)	0.15096 (18)	0.0284 (5)
H16A	−0.0820	0.4978	0.1580	0.034*
C17	−0.23173 (18)	0.5640 (2)	0.12766 (18)	0.0306 (5)
H17A	−0.2644	0.4806	0.1179	0.037*
C18	0.04455 (16)	0.7110 (2)	0.18885 (16)	0.0258 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01299 (15)	0.03152 (18)	0.03728 (18)	0.00017 (10)	0.00922 (12)	0.00061 (12)
O1	0.0154 (8)	0.0384 (10)	0.0504 (11)	−0.0003 (7)	0.0120 (7)	0.0022 (8)
O2	0.0239 (9)	0.0382 (10)	0.0712 (13)	−0.0057 (8)	0.0176 (9)	0.0044 (9)
O3	0.0139 (7)	0.0310 (9)	0.0437 (10)	−0.0002 (6)	0.0091 (7)	0.0005 (7)
O4	0.0230 (9)	0.0307 (10)	0.0722 (13)	−0.0036 (7)	0.0182 (9)	0.0018 (8)
O5	0.0198 (8)	0.0676 (12)	0.0379 (10)	0.0105 (8)	0.0118 (8)	0.0090 (9)
O6	0.0209 (9)	0.0921 (17)	0.0417 (11)	−0.0145 (9)	0.0143 (8)	−0.0165 (10)
N1	0.0187 (9)	0.0417 (12)	0.0396 (12)	−0.0073 (8)	0.0088 (9)	−0.0032 (9)
N2	0.0176 (9)	0.0458 (13)	0.0353 (11)	0.0004 (8)	0.0098 (8)	−0.0002 (9)
N3	0.0144 (9)	0.0311 (10)	0.0301 (10)	−0.0015 (7)	0.0082 (8)	−0.0016 (8)
N4	0.0190 (10)	0.0576 (15)	0.0413 (12)	0.0058 (9)	0.0092 (9)	0.0017 (11)
N5	0.0185 (10)	0.0568 (14)	0.0367 (12)	−0.0040 (9)	0.0104 (9)	−0.0032 (10)
N6	0.0155 (9)	0.0355 (11)	0.0278 (10)	0.0015 (7)	0.0076 (8)	−0.0007 (8)
C1	0.0231 (11)	0.0327 (13)	0.0426 (14)	−0.0049 (9)	0.0130 (11)	−0.0049 (10)
C2	0.0175 (11)	0.0354 (13)	0.0353 (13)	0.0019 (9)	0.0102 (10)	0.0004 (10)
C3	0.0134 (10)	0.0334 (12)	0.0269 (11)	−0.0006 (8)	0.0076 (9)	0.0004 (9)
C4	0.0208 (11)	0.0265 (11)	0.0454 (14)	−0.0020 (9)	0.0136 (10)	0.0013 (10)
C5	0.0204 (11)	0.0285 (12)	0.0438 (14)	0.0034 (9)	0.0134 (10)	0.0004 (10)
C6	0.0158 (10)	0.0370 (13)	0.0283 (12)	−0.0013 (9)	0.0089 (9)	0.0004 (9)
C7	0.0211 (11)	0.0290 (12)	0.0482 (15)	−0.0026 (9)	0.0124 (11)	0.0059 (11)
C8	0.0189 (11)	0.0287 (12)	0.0483 (15)	0.0032 (9)	0.0104 (11)	0.0069 (10)
C9	0.0164 (11)	0.0390 (13)	0.0312 (12)	−0.0029 (9)	0.0098 (10)	−0.0035 (10)
C10	0.0199 (11)	0.0451 (15)	0.0385 (14)	0.0052 (10)	0.0086 (10)	0.0029 (11)
C11	0.0223 (11)	0.0436 (14)	0.0341 (13)	−0.0052 (10)	0.0107 (10)	−0.0012 (11)
C12	0.0136 (10)	0.0353 (12)	0.0244 (11)	0.0002 (8)	0.0074 (9)	−0.0008 (9)
C13	0.0225 (11)	0.0271 (12)	0.0446 (14)	0.0051 (9)	0.0136 (11)	0.0005 (10)
C14	0.0221 (11)	0.0257 (12)	0.0451 (14)	−0.0026 (9)	0.0145 (10)	−0.0012 (10)
C15	0.0153 (10)	0.0311 (11)	0.0286 (11)	0.0002 (8)	0.0079 (9)	0.0007 (9)
C16	0.0193 (11)	0.0262 (11)	0.0395 (13)	0.0027 (9)	0.0106 (10)	−0.0013 (10)
C17	0.0205 (11)	0.0288 (12)	0.0418 (14)	−0.0027 (9)	0.0109 (10)	−0.0035 (10)
C18	0.0172 (10)	0.0300 (11)	0.0316 (12)	−0.0013 (9)	0.0104 (9)	−0.0011 (10)

Geometric parameters (Å, º)

Cu1—O1	1.9400 (15)	C2—H2A	0.9300
Cu1—O3	1.9377 (14)	C3—C4	1.378 (3)
Cu1—O5	1.9806 (17)	C3—C8	1.381 (3)
Cu1—O6	1.9642 (18)	C4—C5	1.384 (3)
O1—C9	1.273 (3)	C4—H4A	0.9300
O2—C9	1.240 (3)	C5—C6	1.387 (3)
O3—C18	1.279 (3)	C5—H5A	0.9300
O4—C18	1.237 (3)	C6—C7	1.387 (3)
O5—H1	0.8500	C6—C9	1.503 (3)
O5—H2	0.8500	C7—C8	1.383 (3)
O6—H3	0.8500	C7—H7A	0.9300
O6—H4	0.8500	C8—H8A	0.9300
N1—C1	1.297 (3)	C10—H10A	0.9300
N1—N2	1.386 (3)	C11—H11A	0.9300
N2—C2	1.297 (3)	C12—C13	1.384 (3)
N3—C1	1.357 (3)	C12—C17	1.387 (3)
N3—C2	1.362 (3)	C13—C14	1.382 (3)
N3—C3	1.430 (3)	C13—H13A	0.9300
N4—C10	1.293 (3)	C14—C15	1.387 (3)
N4—N5	1.386 (3)	C14—H14A	0.9300
N5—C11	1.299 (3)	C15—C16	1.396 (3)
N6—C11	1.357 (3)	C15—C18	1.494 (3)
N6—C10	1.360 (3)	C16—C17	1.380 (3)
N6—C12	1.427 (3)	C16—H16A	0.9300
C1—H1A	0.9300	C17—H17A	0.9300
O3—Cu1—O1	177.14 (6)	C5—C6—C7	118.9 (2)
O3—Cu1—O6	88.40 (7)	C5—C6—C9	120.6 (2)
O1—Cu1—O6	92.31 (7)	C7—C6—C9	120.5 (2)
O3—Cu1—O5	88.22 (7)	C8—C7—C6	121.1 (2)
O1—Cu1—O5	91.57 (7)	C8—C7—H7A	119.4
O6—Cu1—O5	169.33 (8)	C6—C7—H7A	119.4
C9—O1—Cu1	105.33 (14)	C3—C8—C7	119.0 (2)
C18—O3—Cu1	104.21 (13)	C3—C8—H8A	120.5
Cu1—O5—H1	111.5	C7—C8—H8A	120.5
Cu1—O5—H2	111.5	O2—C9—O1	122.8 (2)
H1—O5—H2	109.4	O2—C9—C6	119.6 (2)
Cu1—O6—H3	112.1	O1—C9—C6	117.6 (2)
Cu1—O6—H4	112.0	N4—C10—N6	110.8 (2)
H3—O6—H4	109.9	N4—C10—H10A	124.6
C1—N1—N2	106.90 (19)	N6—C10—H10A	124.6
C2—N2—N1	107.38 (19)	N5—C11—N6	111.2 (2)
C1—N3—C2	104.52 (18)	N5—C11—H11A	124.4
C1—N3—C3	127.30 (19)	N6—C11—H11A	124.4
C2—N3—C3	128.18 (19)	C13—C12—C17	120.9 (2)
C10—N4—N5	107.4 (2)	C13—C12—N6	119.10 (19)
C11—N5—N4	106.47 (19)	C17—C12—N6	120.01 (19)
C11—N6—C10	104.05 (19)	C14—C13—C12	119.5 (2)
C11—N6—C12	129.78 (19)	C14—C13—H13A	120.3
C10—N6—C12	126.17 (19)	C12—C13—H13A	120.3
N1—C1—N3	110.8 (2)	C13—C14—C15	120.7 (2)
N1—C1—H1A	124.6	C13—C14—H14A	119.7
N3—C1—H1A	124.6	C15—C14—H14A	119.7
N2—C2—N3	110.4 (2)	C14—C15—C16	118.93 (19)
N2—C2—H2A	124.8	C14—C15—C18	120.3 (2)
N3—C2—H2A	124.8	C16—C15—C18	120.8 (2)
C4—C3—C8	120.8 (2)	C17—C16—C15	120.9 (2)
C4—C3—N3	118.71 (19)	C17—C16—H16A	119.5
C8—C3—N3	120.5 (2)	C15—C16—H16A	119.5
C3—C4—C5	119.7 (2)	C16—C17—C12	119.1 (2)
C3—C4—H4A	120.1	C16—C17—H17A	120.5
C5—C4—H4A	120.1	C12—C17—H17A	120.5
C4—C5—C6	120.4 (2)	O4—C18—O3	122.34 (19)
C4—C5—H5A	119.8	O4—C18—C15	120.6 (2)
C6—C5—H5A	119.8	O3—C18—C15	117.01 (19)
O6—Cu1—O1—C9	85.23 (16)	C7—C6—C9—O2	1.1 (3)
O5—Cu1—O1—C9	−84.83 (15)	C5—C6—C9—O1	0.1 (3)
O6—Cu1—O3—C18	90.46 (15)	C7—C6—C9—O1	−178.1 (2)
O5—Cu1—O3—C18	−99.66 (14)	N5—N4—C10—N6	0.7 (3)
C1—N1—N2—C2	−0.6 (3)	C11—N6—C10—N4	−0.4 (3)
C10—N4—N5—C11	−0.6 (3)	C12—N6—C10—N4	179.5 (2)
N2—N1—C1—N3	0.6 (3)	N4—N5—C11—N6	0.4 (3)
C2—N3—C1—N1	−0.4 (3)	C10—N6—C11—N5	0.0 (3)
C3—N3—C1—N1	179.0 (2)	C12—N6—C11—N5	−179.9 (2)
N1—N2—C2—N3	0.4 (3)	C11—N6—C12—C13	−153.1 (2)
C1—N3—C2—N2	0.0 (3)	C10—N6—C12—C13	26.9 (3)
C3—N3—C2—N2	−179.4 (2)	C11—N6—C12—C17	27.1 (3)
C1—N3—C3—C4	28.3 (3)	C10—N6—C12—C17	−152.8 (2)
C2—N3—C3—C4	−152.4 (2)	C17—C12—C13—C14	1.4 (4)
C1—N3—C3—C8	−151.9 (2)	N6—C12—C13—C14	−178.4 (2)
C2—N3—C3—C8	27.3 (3)	C12—C13—C14—C15	−1.1 (4)
C8—C3—C4—C5	1.4 (4)	C13—C14—C15—C16	−0.2 (3)
N3—C3—C4—C5	−178.9 (2)	C13—C14—C15—C18	−179.2 (2)
C3—C4—C5—C6	−0.7 (4)	C14—C15—C16—C17	1.3 (3)
C4—C5—C6—C7	−0.5 (4)	C18—C15—C16—C17	−179.7 (2)
C4—C5—C6—C9	−178.8 (2)	C15—C16—C17—C12	−1.0 (4)
C5—C6—C7—C8	1.1 (4)	C13—C12—C17—C16	−0.3 (3)
C9—C6—C7—C8	179.4 (2)	N6—C12—C17—C16	179.4 (2)
C4—C3—C8—C7	−0.9 (4)	Cu1—O3—C18—O4	5.7 (3)
N3—C3—C8—C7	179.4 (2)	Cu1—O3—C18—C15	−174.38 (15)
C6—C7—C8—C3	−0.4 (4)	C14—C15—C18—O4	−8.5 (3)
Cu1—O1—C9—O2	−4.6 (3)	C16—C15—C18—O4	172.6 (2)
Cu1—O1—C9—C6	174.65 (16)	C14—C15—C18—O3	171.6 (2)
C5—C6—C9—O2	179.4 (2)	C16—C15—C18—O3	−7.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···N5^i	0.85	2.05	2.872 (3)	163
O5—H2···N1^ii	0.85	1.99	2.790 (3)	157
O6—H3···N2^iii	0.85	1.98	2.799 (3)	162
O6—H4···N4^iv	0.85	1.98	2.749 (3)	149
C2—H2A···O4^v	0.93	2.23	3.158 (3)	175
C4—H4A···O5^vi	0.93	2.52	3.368 (3)	152
C13—H13A···O2^vii	0.93	2.54	3.371 (3)	150

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