3,5-Diamino-4H-1,2,4-triazol-1-ium (6-carb­oxy­pyridine-2-carboxyl­ato)(pyridine-2,6-dicarboxyl­ato)cuprate(II) trihydrate

Yousuf, S.; Johnson, A.S.; Kazmi, S.A.; Offiong, O.E.; Fun, H.-K.

doi:10.1107/S1600536811011147

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages m509-m510

doi:10.1107/S1600536811011147

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3,5-Diamino-4H-1,2,4-triazol-1-ium (6-carboxypyridine-2-carboxylato)(pyridine-2,6-dicarboxylato)cuprate(II) trihydrate

S. Yousuf,^a A. S. Johnson,^b S. A. Kazmi,^a O. E. Offiong ^b and Hoong-Kun Fun ^c ^*‡

^aH.E.J Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, ^bDepartment of Pure and Applied Chemistry, University of Calabar, Calabar, PMB 1115, Nigeria, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 21 March 2011; accepted 25 March 2011; online 31 March 2011)

In the complex anion of the title compound, (C₂H₆N₅)[Cu(C₇H₄NO₄)(C₇H₃NO₄)]·3H₂O, the Cu^II atom is coordinated by tridentate 6-carboxypyridine-2-carboxylate and pyridine-2,6-dicarboxylate ligands and is surrounded by four O atoms in the equatorial plane and two N atoms in axial positions in a distorted octahedral geometry. In the crystal, the components are linked into a three dimensional network by O—H⋯O, N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds and a π–π interaction with a centroid–centroid distance of 3.6080 (8) Å.

Related literature

For general background to and applications of supramolecular arrangements, see: Lehn (1995 ); Aghajani et al. (2009 ); Tshuva & Lippard (2004 ); Kuzelka et al. (2003 ). For crystal structures of related complexes, see: Aghabozorg et al. (2007 ); Ramos Silva et al. (2008 ); Wang et al. (2004 ); MacDonald et al. (2004 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

(C₂H₆N₅)[Cu(C₇H₄NO₄)(C₇H₃NO₄)]·3H₂O
M_r = 548.92
Orthorhombic, P b c a
a = 11.3091 (2) Å
b = 14.9442 (3) Å
c = 24.6045 (5) Å
V = 4158.29 (14) Å³
Z = 8
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 100 K
0.54 × 0.20 × 0.07 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.583, T_max = 0.921
55434 measured reflections
9184 independent reflections
6619 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.098
S = 1.05
9184 reflections
368 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H1O8⋯O1ⁱ	0.90 (3)	1.71 (2)	2.5536 (15)	157 (2)
N3—H1N3⋯O2Wⁱⁱ	0.76 (2)	2.26 (2)	2.9081 (19)	144 (2)
N5—H1N5⋯O3Wⁱⁱⁱ	0.80 (2)	2.23 (2)	2.8310 (17)	132.3 (18)
N5—H1N5⋯N4^iv	0.80 (2)	2.40 (2)	2.9925 (18)	131.2 (19)
N6—H1N6⋯O2Wⁱⁱ	0.83 (2)	2.47 (2)	3.209 (2)	147.6 (19)
N6—H2N6⋯O3^v	0.93 (2)	2.06 (2)	2.9699 (17)	168.7 (19)
N7—H1N7⋯O3Wⁱⁱⁱ	0.81 (2)	2.15 (2)	2.8570 (19)	145 (2)
N7—H2N7⋯O7^vi	0.82 (2)	1.96 (2)	2.7714 (18)	170 (2)
O1W—H1W1⋯O2	0.79 (2)	2.03 (3)	2.7985 (19)	168 (3)
O1W—H2W1⋯O5^v	0.77 (3)	2.11 (3)	2.8715 (17)	171 (2)
O2W—H1W2⋯O1W	0.90 (3)	1.81 (3)	2.703 (2)	173 (3)
O2W—H2W2⋯O1ⁱ	0.85 (3)	2.58 (3)	3.3968 (18)	162 (3)
O3W—H1W3⋯O6^vii	0.89 (3)	1.90 (3)	2.7712 (17)	169 (2)
O3W—H2W3⋯O3	0.77 (3)	2.04 (3)	2.8113 (16)	177 (2)
C5—H5A⋯O6^viii	0.93	2.35	3.2042 (18)	153
C12—H12A⋯O7ⁱ	0.93	2.47	3.3960 (17)	176
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iv) -x+1, -y+1, -z; (v) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (vi) x+1, y, z; (vii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (viii) -x+1, -y, -z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011147/is2693sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011147/is2693Isup2.hkl

checkCIF report

Comment top

Non-covalent supramolecular arrangements due to the non-covalent interactions between two or more molecular sub-units are responsible for influencing different structural properties and the addition of metal in the coordination is considered to be an effective tool to study and control the connectivity and linkages (Lehn et al., 1995). The study of the construction of metal organic frameworks indicates that under suitable conditions, the transfer of the acidic protons to appropriate bases will result in increased intermolecular interactions and as a result enhanced stabilization of the resulting system (Aghajani et al., 2009). The study of metal carboxylates has always been fascinating for the researchers because they play important roles not only in synthetic chemistry, considering the vast array of coordination modes of the carboxylate group, but also in biological activities (Tshuva et al., 2004; Kuzelka et al., 2003) and physiological effects (Aghabozorg et al., 2007). In our ongoing research to study the packing features of molecules containing metal chelate and triazole rings, the title Cu complex (I) was prepared from 3,5-diamino-1,2,4-triazole and dipicolinic acid.

The title complex, (C₂H₆N₅)⁺[Cu(C₇H₄NO₄)(C₇H₃NO₄)]^-.3H₂O, contains two tridentate dipicolinate ligands (one neutral and one protonated) coordinated with Cu(II) to reveal a distorted octahedral geometry, one independent protonated triazole and three water molecules (Fig. 1). The coordination environment around the Cu(II) ion is such that the two dipiconilate ligands are assembled perpendicular to each other with two axially oriented N atoms [Cu1—N1 = 1.9057 (12) Å, Cu1—N2 = 1.9723 (2) Å] and four O atoms on the basal positions [Cu1—O1 = 2.0889 (10) Å, Cu1—O2 = 2.0453 (10) Å, Cu1—O3 = 2.2727 (10) Å, Cu1—O4 = 2.3939 (10) Å]. Coordination of Cu^II ion with N1, O1, O2 and N2, O3, O4 of the two chelating dipicolinate ligands is responsible for the formation of four five-membered rings, A, (Cu1/O1/C1/C2/N1, with a maximum deviation of 0.049 (1) Å for atom O1), B (Cu1/N1/C6/C7/O2, with a maximum deviation of -0.042 (1) Å for atom O2), C (Cu1/O3/C8/C9/N2, with a maximum deviation of -0.043 (1) Å for atom C8) and D (Cu1/N2/C13/C14/O4, with a maximum deviation of -0.040 (1) Å for atom N2). The dihedral angles between them are 4.34 (6)° (A/B), 82.15 (6)° (A/C), 84.95 (6)° (A/D), 79.10 (6)° (B/C), 81.79 (6)° (B/D) and 3.58 (5)° (C/D). The independent triazole ring (N3/C15/N4/N5/C16) is essentially planar. All bond lengths are in agreement with another related structure (Ramos Silva et al., 2008). O—H···O, N—H···O, N—H···N and C—H···O hydrogen bonds play important roles in stabilizing the crystal structure by forming a two-dimensional-network, which is further extended to three-dimensional-network due to the intermolecular linkages made by water solvates (Table 2 and Fig. 2). The three-dimensional network is further strengthened by significant π–π interactions between (N1/C1–C5) pyridine (centroid Cg5) and triazole (N3/C15/N4/N5/C16) (centroid Cg7) rings [Cg5···Cg7^vii distance = 3.6080 (8) Å; (vii) -1/2 + x, 1/2 - y, -z].

Related literature top

For general background to and applications of supramolecular arrangements, see: Lehn (1995); Aghajani et al. (2009); Tshuva & Lippard (2004); Kuzelka et al. (2003). For crystal structures of related complexes, see: Aghabozorg et al. (2007); Ramos Silva et al. (2008); Wang et al. (2004); MacDonald et al. (2004). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

Pyridine-2,6-dicarboxylic acid (dipicolinic acid, H2dipic) and 3,5-diamino-1,2,4-triazole (datrz) were purchased from Merck and Molekula, respectively. Copper (II) sulfate pentahydrate (CuSO₄.5H₂O) and HPLC grade methanol were Uni- Chem and M TEDIA products, respectively. Deionized water was also used in the procedures when needed.

Synthesis of (Hdatrz)⁺[Cu(Hdipic)(dipic)]^-.3H₂O 1 mmol (0.099 g) of 3,5-diamino-1,2,4-triazole(datrz) and 1 mmol of dipicolinic acid (0.167 g) were dissolved in a mixture of methanol/water solution (1:10, 11 ml). The resulting solution was heated to 600 °C with stirring. An aqueous solution (1 ml) containing 0.5 mmol (0.125 g) of CuSO₄.5H₂O was added to the stirred solution. The greenish suspension was allowed to stir further for 1 hr, and then filtered while hot. The filtrate was kept at room temperature. Well shaped blue crystals of the title compound were formed by slow evaporation of the solution after 5 days. Percentage yield based on copper is 51.67%.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title crystal, showing 50% probability displacement ellipsoids and the atom-numbering scheme. The intramolecular hydrogen bonds are shown by dashed lines.
	Fig. 2. The crystal packing of the title compound, showing a three-dimensional molecular network. Only hydrogen atoms involved in hydrogen bonding are shown.

3,5-Diamino-4H-1,2,4-triazol-1-ium (6-carboxypyridine-2-carboxylato)(pyridine-2,6-dicarboxylato)cuprate(II) trihydrate top

Crystal data top

(C₂H₆N₅)[Cu(C₇H₄NO₄)(C₇H₃NO₄)]·3H₂O	D_x = 1.754 Mg m⁻³
M_r = 548.92	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9982 reflections
a = 11.3091 (2) Å	θ = 2.4–34.3°
b = 14.9442 (3) Å	µ = 1.13 mm⁻¹
c = 24.6045 (5) Å	T = 100 K
V = 4158.29 (14) Å³	Block, blue
Z = 8	0.54 × 0.20 × 0.07 mm
F(000) = 2248

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	9184 independent reflections
Radiation source: fine-focus sealed tube	6619 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 35.2°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −16→18
T_min = 0.583, T_max = 0.921	k = −24→24
55434 measured reflections	l = −35→39

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0419P)² + 1.6423P] where P = (F_o² + 2F_c²)/3
9184 reflections	(Δ/σ)_max = 0.001
368 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

(C₂H₆N₅)[Cu(C₇H₄NO₄)(C₇H₃NO₄)]·3H₂O	V = 4158.29 (14) Å³
M_r = 548.92	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.3091 (2) Å	µ = 1.13 mm⁻¹
b = 14.9442 (3) Å	T = 100 K
c = 24.6045 (5) Å	0.54 × 0.20 × 0.07 mm

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	9184 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	6619 reflections with I > 2σ(I)
T_min = 0.583, T_max = 0.921	R_int = 0.040
55434 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.61 e Å⁻³
9184 reflections	Δρ_min = −0.62 e Å⁻³
368 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.215732 (15)	0.157389 (11)	0.147781 (7)	0.00961 (5)
O1	0.08015 (9)	0.08189 (7)	0.18273 (4)	0.0134 (2)
O2	0.36032 (9)	0.18850 (7)	0.10156 (4)	0.01296 (19)
O3	0.07633 (9)	0.24435 (7)	0.10732 (4)	0.01269 (19)
O4	0.35335 (9)	0.12522 (7)	0.21908 (4)	0.0141 (2)
O5	−0.02108 (10)	−0.04545 (7)	0.16838 (5)	0.0178 (2)
O6	0.49003 (10)	0.12228 (8)	0.04550 (5)	0.0209 (2)
O7	−0.02109 (9)	0.37240 (7)	0.12527 (4)	0.0146 (2)
O8	0.43168 (10)	0.20192 (7)	0.28899 (4)	0.0153 (2)
N1	0.22886 (10)	0.04926 (8)	0.10717 (5)	0.0101 (2)
N2	0.21368 (10)	0.26548 (8)	0.19377 (5)	0.0093 (2)
N3	0.74524 (12)	0.52025 (8)	0.08876 (5)	0.0135 (2)
N4	0.57456 (11)	0.54813 (8)	0.04709 (5)	0.0132 (2)
N5	0.61177 (11)	0.45979 (8)	0.03913 (5)	0.0131 (2)
N6	0.66479 (13)	0.66858 (9)	0.09430 (6)	0.0173 (3)
N7	0.77259 (13)	0.36686 (10)	0.06458 (7)	0.0211 (3)
C1	0.06033 (13)	0.00591 (9)	0.15837 (6)	0.0122 (2)
C2	0.14997 (12)	−0.01609 (9)	0.11494 (6)	0.0102 (2)
C3	0.15723 (12)	−0.09465 (9)	0.08511 (6)	0.0120 (2)
H3A	0.1014	−0.1397	0.0895	0.014*
C4	0.25034 (13)	−0.10441 (9)	0.04841 (6)	0.0126 (3)
H4A	0.2568	−0.1565	0.0280	0.015*
C5	0.33380 (12)	−0.03646 (9)	0.04217 (6)	0.0125 (3)
H5A	0.3973	−0.0430	0.0185	0.015*
C6	0.31922 (12)	0.04136 (9)	0.07243 (6)	0.0110 (2)
C7	0.39802 (13)	0.12317 (10)	0.07216 (6)	0.0128 (3)
C8	0.05761 (12)	0.31610 (9)	0.13374 (6)	0.0109 (2)
C9	0.14039 (12)	0.33297 (9)	0.18110 (6)	0.0096 (2)
C10	0.14068 (12)	0.41254 (9)	0.21033 (6)	0.0121 (2)
H10A	0.0887	0.4585	0.2013	0.015*
C11	0.21941 (12)	0.42253 (9)	0.25307 (6)	0.0127 (2)
H11A	0.2219	0.4757	0.2727	0.015*
C12	0.29478 (12)	0.35219 (9)	0.26639 (6)	0.0122 (2)
H12A	0.3481	0.3574	0.2950	0.015*
C13	0.28853 (12)	0.27413 (9)	0.23597 (6)	0.0108 (2)
C14	0.36167 (12)	0.19255 (9)	0.24695 (6)	0.0116 (2)
C15	0.65778 (12)	0.58205 (9)	0.07748 (6)	0.0123 (3)
C16	0.71346 (12)	0.44283 (10)	0.06413 (6)	0.0125 (2)
O1W	0.54413 (15)	0.26343 (9)	0.16261 (7)	0.0380 (4)
O2W	0.64627 (12)	0.10349 (10)	0.18324 (6)	0.0293 (3)
O3W	0.08779 (10)	0.22067 (8)	−0.00591 (5)	0.0171 (2)
H1O8	0.467 (2)	0.1503 (17)	0.2979 (11)	0.054 (8)*
H1N3	0.7969 (19)	0.5288 (15)	0.1077 (9)	0.032 (6)*
H1N5	0.5722 (17)	0.4258 (14)	0.0218 (9)	0.023 (5)*
H1N6	0.7083 (18)	0.6739 (15)	0.1215 (10)	0.028 (6)*
H2N6	0.5929 (19)	0.6983 (14)	0.0952 (8)	0.026 (5)*
H1N7	0.7412 (19)	0.3244 (14)	0.0499 (8)	0.022 (5)*
H2N7	0.837 (2)	0.3643 (15)	0.0799 (9)	0.033 (6)*
H1W1	0.491 (2)	0.2500 (19)	0.1436 (11)	0.049 (8)*
H2W1	0.546 (2)	0.3146 (17)	0.1640 (10)	0.031 (6)*
H1W2	0.611 (3)	0.157 (2)	0.1794 (14)	0.076 (10)*
H2W2	0.618 (3)	0.0882 (19)	0.2141 (13)	0.067 (9)*
H1W3	0.054 (2)	0.2667 (17)	−0.0225 (10)	0.044 (7)*
H2W3	0.082 (2)	0.2265 (15)	0.0251 (11)	0.037 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01071 (8)	0.00748 (8)	0.01064 (8)	0.00011 (6)	0.00135 (6)	−0.00198 (6)
O1	0.0145 (5)	0.0100 (4)	0.0157 (5)	−0.0004 (4)	0.0043 (4)	−0.0022 (4)
O2	0.0146 (5)	0.0096 (4)	0.0147 (5)	−0.0009 (4)	0.0026 (4)	−0.0022 (4)
O3	0.0147 (5)	0.0113 (4)	0.0122 (5)	−0.0003 (4)	−0.0010 (4)	−0.0022 (4)
O4	0.0171 (5)	0.0100 (4)	0.0151 (5)	0.0020 (4)	−0.0017 (4)	−0.0012 (4)
O5	0.0169 (5)	0.0141 (5)	0.0223 (6)	−0.0037 (4)	0.0070 (4)	−0.0014 (4)
O6	0.0181 (5)	0.0179 (5)	0.0268 (6)	−0.0039 (4)	0.0116 (5)	−0.0058 (5)
O7	0.0134 (5)	0.0142 (5)	0.0163 (5)	0.0027 (4)	−0.0024 (4)	0.0013 (4)
O8	0.0183 (5)	0.0120 (5)	0.0157 (5)	0.0036 (4)	−0.0069 (4)	−0.0006 (4)
N1	0.0104 (5)	0.0095 (5)	0.0104 (5)	0.0004 (4)	0.0003 (4)	−0.0007 (4)
N2	0.0095 (5)	0.0088 (5)	0.0096 (5)	0.0003 (4)	0.0006 (4)	0.0002 (4)
N3	0.0120 (5)	0.0125 (5)	0.0160 (6)	−0.0003 (4)	−0.0038 (5)	−0.0010 (5)
N4	0.0125 (5)	0.0118 (5)	0.0155 (6)	0.0013 (4)	−0.0004 (4)	−0.0013 (4)
N5	0.0123 (5)	0.0108 (5)	0.0161 (6)	0.0001 (4)	−0.0026 (4)	−0.0020 (4)
N6	0.0174 (6)	0.0127 (6)	0.0217 (7)	0.0010 (5)	−0.0021 (5)	−0.0050 (5)
N7	0.0168 (7)	0.0120 (6)	0.0346 (8)	0.0021 (5)	−0.0115 (6)	−0.0028 (5)
C1	0.0141 (6)	0.0089 (6)	0.0136 (6)	0.0012 (5)	0.0017 (5)	0.0002 (5)
C2	0.0099 (6)	0.0090 (6)	0.0118 (6)	0.0008 (5)	0.0003 (4)	−0.0003 (4)
C3	0.0134 (6)	0.0089 (6)	0.0139 (6)	−0.0001 (5)	−0.0004 (5)	−0.0001 (5)
C4	0.0142 (6)	0.0109 (6)	0.0127 (6)	0.0019 (5)	−0.0017 (5)	−0.0017 (5)
C5	0.0126 (6)	0.0124 (6)	0.0125 (6)	0.0022 (5)	0.0008 (5)	−0.0021 (5)
C6	0.0115 (6)	0.0101 (6)	0.0113 (6)	0.0013 (5)	0.0009 (5)	−0.0005 (5)
C7	0.0143 (6)	0.0113 (6)	0.0128 (6)	−0.0008 (5)	0.0013 (5)	−0.0011 (5)
C8	0.0112 (6)	0.0110 (6)	0.0105 (6)	−0.0016 (5)	0.0007 (5)	0.0023 (5)
C9	0.0097 (5)	0.0086 (6)	0.0106 (6)	−0.0001 (4)	0.0007 (4)	−0.0001 (4)
C10	0.0122 (6)	0.0087 (6)	0.0155 (7)	0.0017 (5)	0.0005 (5)	−0.0010 (5)
C11	0.0141 (6)	0.0090 (6)	0.0150 (6)	0.0004 (5)	0.0008 (5)	−0.0026 (5)
C12	0.0134 (6)	0.0111 (6)	0.0122 (6)	−0.0001 (5)	−0.0018 (5)	−0.0018 (5)
C13	0.0108 (6)	0.0106 (6)	0.0108 (6)	0.0014 (5)	−0.0004 (5)	−0.0005 (4)
C14	0.0118 (6)	0.0116 (6)	0.0114 (6)	−0.0001 (5)	0.0003 (5)	0.0019 (5)
C15	0.0119 (6)	0.0116 (6)	0.0136 (6)	0.0010 (5)	0.0008 (5)	0.0003 (5)
C16	0.0116 (6)	0.0112 (6)	0.0146 (7)	−0.0005 (5)	−0.0020 (5)	0.0000 (5)
O1W	0.0469 (9)	0.0118 (6)	0.0554 (10)	−0.0030 (6)	−0.0334 (8)	0.0027 (6)
O2W	0.0308 (7)	0.0313 (7)	0.0256 (7)	0.0163 (6)	0.0061 (6)	0.0020 (6)
O3W	0.0232 (6)	0.0141 (5)	0.0140 (6)	0.0026 (4)	0.0017 (4)	−0.0017 (4)

Geometric parameters (Å, º) top

Cu1—N1	1.9057 (12)	N6—H2N6	0.93 (2)
Cu1—N2	1.9723 (12)	N7—C16	1.318 (2)
Cu1—O2	2.0453 (10)	N7—H1N7	0.81 (2)
Cu1—O1	2.0889 (10)	N7—H2N7	0.82 (2)
Cu1—O3	2.2727 (10)	C1—C2	1.509 (2)
Cu1—O4	2.3939 (10)	C2—C3	1.3870 (19)
O1—C1	1.3034 (17)	C3—C4	1.395 (2)
O2—C7	1.2877 (17)	C3—H3A	0.9300
O3—C8	1.2716 (17)	C4—C5	1.395 (2)
O4—C14	1.2213 (17)	C4—H4A	0.9300
O5—C1	1.2237 (17)	C5—C6	1.3907 (19)
O6—C7	1.2301 (17)	C5—H5A	0.9300
O7—C8	1.2425 (17)	C6—C7	1.513 (2)
O8—C14	1.3102 (17)	C8—C9	1.516 (2)
O8—H1O8	0.90 (3)	C9—C10	1.3896 (19)
N1—C2	1.3365 (17)	C10—C11	1.386 (2)
N1—C6	1.3375 (18)	C10—H10A	0.9300
N2—C9	1.3422 (17)	C11—C12	1.3925 (19)
N2—C13	1.3459 (17)	C11—H11A	0.9300
N3—C16	1.3547 (19)	C12—C13	1.3878 (19)
N3—C15	1.3813 (19)	C12—H12A	0.9300
N3—H1N3	0.76 (2)	C13—C14	1.4978 (19)
N4—C15	1.3045 (18)	O1W—H1W1	0.78 (3)
N4—N5	1.3994 (17)	O1W—H2W1	0.77 (2)
N5—C16	1.3285 (18)	O2W—H1W2	0.90 (3)
N5—H1N5	0.80 (2)	O2W—H2W2	0.85 (3)
N6—C15	1.3602 (19)	O3W—H1W3	0.89 (3)
N6—H1N6	0.83 (2)	O3W—H2W3	0.77 (3)

N1—Cu1—N2	174.99 (5)	C2—C3—C4	118.42 (13)
N1—Cu1—O2	80.73 (4)	C2—C3—H3A	120.8
N2—Cu1—O2	98.17 (4)	C4—C3—H3A	120.8
N1—Cu1—O1	79.34 (4)	C3—C4—C5	120.39 (13)
N2—Cu1—O1	101.40 (4)	C3—C4—H4A	119.8
O2—Cu1—O1	159.80 (4)	C5—C4—H4A	119.8
N1—Cu1—O3	108.01 (4)	C6—C5—C4	118.01 (13)
N2—Cu1—O3	76.99 (4)	C6—C5—H5A	121.0
O2—Cu1—O3	100.43 (4)	C4—C5—H5A	121.0
O1—Cu1—O3	88.85 (4)	N1—C6—C5	120.44 (13)
N1—Cu1—O4	99.40 (4)	N1—C6—C7	112.42 (12)
N2—Cu1—O4	75.63 (4)	C5—C6—C7	127.13 (13)
O2—Cu1—O4	86.18 (4)	O6—C7—O2	126.01 (14)
O1—Cu1—O4	93.85 (4)	O6—C7—C6	119.46 (13)
O3—Cu1—O4	152.47 (4)	O2—C7—C6	114.53 (12)
C1—O1—Cu1	114.05 (9)	O7—C8—O3	127.20 (13)
C7—O2—Cu1	113.87 (9)	O7—C8—C9	117.30 (13)
C8—O3—Cu1	111.94 (9)	O3—C8—C9	115.50 (12)
C14—O4—Cu1	107.22 (9)	N2—C9—C10	121.43 (13)
C14—O8—H1O8	111.8 (17)	N2—C9—C8	115.77 (12)
C2—N1—C6	122.47 (12)	C10—C9—C8	122.80 (12)
C2—N1—Cu1	119.51 (9)	C11—C10—C9	119.10 (13)
C6—N1—Cu1	118.00 (9)	C11—C10—H10A	120.4
C9—N2—C13	119.69 (12)	C9—C10—H10A	120.4
C9—N2—Cu1	119.31 (9)	C10—C11—C12	119.38 (13)
C13—N2—Cu1	120.92 (9)	C10—C11—H11A	120.3
C16—N3—C15	106.92 (12)	C12—C11—H11A	120.3
C16—N3—H1N3	128.6 (17)	C13—C12—C11	118.45 (13)
C15—N3—H1N3	124.2 (17)	C13—C12—H12A	120.8
C15—N4—N5	103.28 (11)	C11—C12—H12A	120.8
C16—N5—N4	112.06 (12)	N2—C13—C12	121.93 (12)
C16—N5—H1N5	127.6 (14)	N2—C13—C14	114.09 (12)
N4—N5—H1N5	120.4 (14)	C12—C13—C14	123.97 (12)
C15—N6—H1N6	111.6 (15)	O4—C14—O8	125.31 (13)
C15—N6—H2N6	114.3 (13)	O4—C14—C13	121.79 (13)
H1N6—N6—H2N6	117.0 (19)	O8—C14—C13	112.90 (12)
C16—N7—H1N7	116.6 (15)	N4—C15—N6	125.87 (13)
C16—N7—H2N7	119.6 (16)	N4—C15—N3	111.84 (13)
H1N7—N7—H2N7	124 (2)	N6—C15—N3	122.19 (13)
O5—C1—O1	125.68 (13)	N7—C16—N5	127.42 (14)
O5—C1—C2	120.75 (13)	N7—C16—N3	126.69 (13)
O1—C1—C2	113.57 (12)	N5—C16—N3	105.89 (13)
N1—C2—C3	120.22 (12)	H1W1—O1W—H2W1	107 (3)
N1—C2—C1	112.99 (12)	H1W2—O2W—H2W2	100 (3)
C3—C2—C1	126.79 (12)	H1W3—O3W—H2W3	109 (2)

N1—Cu1—O1—C1	−6.84 (10)	N1—C2—C3—C4	1.9 (2)
N2—Cu1—O1—C1	178.21 (10)	C1—C2—C3—C4	−176.87 (13)
O2—Cu1—O1—C1	−16.30 (18)	C2—C3—C4—C5	0.1 (2)
O3—Cu1—O1—C1	101.73 (10)	C3—C4—C5—C6	−1.6 (2)
O4—Cu1—O1—C1	−105.69 (10)	C2—N1—C6—C5	0.6 (2)
N1—Cu1—O2—C7	−5.71 (10)	Cu1—N1—C6—C5	179.32 (10)
N2—Cu1—O2—C7	169.34 (10)	C2—N1—C6—C7	−178.28 (12)
O1—Cu1—O2—C7	3.71 (18)	Cu1—N1—C6—C7	0.41 (15)
O3—Cu1—O2—C7	−112.48 (10)	C4—C5—C6—N1	1.3 (2)
O4—Cu1—O2—C7	94.47 (10)	C4—C5—C6—C7	−179.91 (14)
N1—Cu1—O3—C8	176.48 (9)	Cu1—O2—C7—O6	−171.91 (13)
N2—Cu1—O3—C8	−3.90 (9)	Cu1—O2—C7—C6	7.35 (15)
O2—Cu1—O3—C8	−99.97 (9)	N1—C6—C7—O6	173.99 (13)
O1—Cu1—O3—C8	98.08 (9)	C5—C6—C7—O6	−4.8 (2)
O4—Cu1—O3—C8	1.95 (14)	N1—C6—C7—O2	−5.33 (18)
N1—Cu1—O4—C14	174.94 (10)	C5—C6—C7—O2	175.84 (14)
N2—Cu1—O4—C14	−4.45 (9)	Cu1—O3—C8—O7	−172.04 (12)
O2—Cu1—O4—C14	95.00 (10)	Cu1—O3—C8—C9	7.09 (14)
O1—Cu1—O4—C14	−105.24 (9)	C13—N2—C9—C10	0.7 (2)
O3—Cu1—O4—C14	−10.33 (14)	Cu1—N2—C9—C10	−176.17 (10)
N2—Cu1—N1—C2	103.6 (6)	C13—N2—C9—C8	−178.69 (12)
O2—Cu1—N1—C2	−178.65 (11)	Cu1—N2—C9—C8	4.45 (16)
O1—Cu1—N1—C2	4.64 (10)	O7—C8—C9—N2	171.23 (12)
O3—Cu1—N1—C2	−80.62 (11)	O3—C8—C9—N2	−7.99 (18)
O4—Cu1—N1—C2	96.82 (10)	O7—C8—C9—C10	−8.1 (2)
N2—Cu1—N1—C6	−75.1 (6)	O3—C8—C9—C10	172.64 (13)
O2—Cu1—N1—C6	2.62 (10)	N2—C9—C10—C11	0.7 (2)
O1—Cu1—N1—C6	−174.09 (11)	C8—C9—C10—C11	−179.93 (13)
O3—Cu1—N1—C6	100.66 (10)	C9—C10—C11—C12	−1.2 (2)
O4—Cu1—N1—C6	−81.90 (10)	C10—C11—C12—C13	0.3 (2)
N1—Cu1—N2—C9	175.3 (5)	C9—N2—C13—C12	−1.7 (2)
O2—Cu1—N2—C9	98.28 (10)	Cu1—N2—C13—C12	175.13 (10)
O1—Cu1—N2—C9	−86.74 (10)	C9—N2—C13—C14	177.65 (12)
O3—Cu1—N2—C9	−0.61 (10)	Cu1—N2—C13—C14	−5.54 (16)
O4—Cu1—N2—C9	−177.83 (11)	C11—C12—C13—N2	1.2 (2)
N1—Cu1—N2—C13	−1.5 (6)	C11—C12—C13—C14	−178.06 (13)
O2—Cu1—N2—C13	−78.54 (11)	Cu1—O4—C14—O8	−177.73 (12)
O1—Cu1—N2—C13	96.45 (11)	Cu1—O4—C14—C13	3.18 (16)
O3—Cu1—N2—C13	−177.43 (11)	N2—C13—C14—O4	0.74 (19)
O4—Cu1—N2—C13	5.36 (10)	C12—C13—C14—O4	−179.95 (14)
C15—N4—N5—C16	0.02 (16)	N2—C13—C14—O8	−178.46 (12)
Cu1—O1—C1—O5	−172.99 (12)	C12—C13—C14—O8	0.9 (2)
Cu1—O1—C1—C2	7.53 (15)	N5—N4—C15—N6	176.70 (14)
C6—N1—C2—C3	−2.3 (2)	N5—N4—C15—N3	0.33 (16)
Cu1—N1—C2—C3	179.01 (10)	C16—N3—C15—N4	−0.57 (17)
C6—N1—C2—C1	176.63 (12)	C16—N3—C15—N6	−177.08 (14)
Cu1—N1—C2—C1	−2.03 (16)	N4—N5—C16—N7	−179.65 (15)
O5—C1—C2—N1	176.49 (13)	N4—N5—C16—N3	−0.36 (16)
O1—C1—C2—N1	−4.00 (17)	C15—N3—C16—N7	179.84 (15)
O5—C1—C2—C3	−4.6 (2)	C15—N3—C16—N5	0.54 (16)
O1—C1—C2—C3	174.87 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1O8···O1ⁱ	0.90 (3)	1.71 (2)	2.5536 (15)	157 (2)
N3—H1N3···O2Wⁱⁱ	0.76 (2)	2.26 (2)	2.9081 (19)	144 (2)
N5—H1N5···O3Wⁱⁱⁱ	0.80 (2)	2.23 (2)	2.8310 (17)	132.3 (18)
N5—H1N5···N4^iv	0.80 (2)	2.40 (2)	2.9925 (18)	131.2 (19)
N6—H1N6···O2Wⁱⁱ	0.83 (2)	2.47 (2)	3.209 (2)	147.6 (19)
N6—H2N6···O3^v	0.93 (2)	2.06 (2)	2.9699 (17)	168.7 (19)
N7—H1N7···O3Wⁱⁱⁱ	0.81 (2)	2.15 (2)	2.8570 (19)	145 (2)
N7—H2N7···O7^vi	0.82 (2)	1.96 (2)	2.7714 (18)	170 (2)
O1W—H1W1···O2	0.79 (2)	2.03 (3)	2.7985 (19)	168 (3)
O1W—H2W1···O5^v	0.77 (3)	2.11 (3)	2.8715 (17)	171 (2)
O2W—H1W2···O1W	0.90 (3)	1.81 (3)	2.703 (2)	173 (3)
O2W—H2W2···O1ⁱ	0.85 (3)	2.58 (3)	3.3968 (18)	162 (3)
O3W—H1W3···O6^vii	0.89 (3)	1.90 (3)	2.7712 (17)	169 (2)
O3W—H2W3···O3	0.77 (3)	2.04 (3)	2.8113 (16)	177 (2)
C5—H5A···O6^viii	0.93	2.35	3.2042 (18)	153
C12—H12A···O7ⁱ	0.93	2.47	3.3960 (17)	176

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

Experimental details

Crystal data
Chemical formula	(C₂H₆N₅)[Cu(C₇H₄NO₄)(C₇H₃NO₄)]·3H₂O
M_r	548.92
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	11.3091 (2), 14.9442 (3), 24.6045 (5)
V (Å³)	4158.29 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.13
Crystal size (mm)	0.54 × 0.20 × 0.07

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.583, 0.921
No. of measured, independent and observed [I > 2σ(I)] reflections	55434, 9184, 6619
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.811

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.098, 1.05
No. of reflections	9184
No. of parameters	368
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.62

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008), SHELXTL and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1O8···O1ⁱ	0.90 (3)	1.71 (2)	2.5536 (15)	157 (2)
N3—H1N3···O2Wⁱⁱ	0.76 (2)	2.26 (2)	2.9081 (19)	144 (2)
N5—H1N5···O3Wⁱⁱⁱ	0.80 (2)	2.23 (2)	2.8310 (17)	132.3 (18)
N5—H1N5···N4^iv	0.80 (2)	2.40 (2)	2.9925 (18)	131.2 (19)
N6—H1N6···O2Wⁱⁱ	0.83 (2)	2.47 (2)	3.209 (2)	147.6 (19)
N6—H2N6···O3^v	0.93 (2)	2.06 (2)	2.9699 (17)	168.7 (19)
N7—H1N7···O3Wⁱⁱⁱ	0.81 (2)	2.15 (2)	2.8570 (19)	145 (2)
N7—H2N7···O7^vi	0.82 (2)	1.96 (2)	2.7714 (18)	170 (2)
O1W—H1W1···O2	0.79 (2)	2.03 (3)	2.7985 (19)	168 (3)
O1W—H2W1···O5^v	0.77 (3)	2.11 (3)	2.8715 (17)	171 (2)
O2W—H1W2···O1W	0.90 (3)	1.81 (3)	2.703 (2)	173 (3)
O2W—H2W2···O1ⁱ	0.85 (3)	2.58 (3)	3.3968 (18)	162 (3)
O3W—H1W3···O6^vii	0.89 (3)	1.90 (3)	2.7712 (17)	169 (2)
O3W—H2W3···O3	0.77 (3)	2.04 (3)	2.8113 (16)	177 (2)
C5—H5A···O6^viii	0.93	2.35	3.2042 (18)	153
C12—H12A···O7ⁱ	0.93	2.47	3.3960 (17)	176

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

AJ thanks The Academy of Sciences for the Developing World (TWAS) for the award of a Research and Advanced Training Fellowship and the H·E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, for providing research facilities. SY thanks the School of Physics, Universiti Sains Malaysia, for providing X-ray diffraction research facilities. HKF thanks the Malaysian Government and Universiti Sains Malaysia (USM) for the Research University Grant No. 1001/PFIZIK/811160.

References

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Volume 67| Part 4| April 2011| Pages m509-m510

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3,5-Di­amino-4H-1,2,4-triazol-1-ium (6-carb­­oxy­pyridine-2-carboxyl­ato)(pyridine-2,6-di­carboxyl­ato)cuprate(II) trihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

metal-organic compounds

3,5-Diamino-4H-1,2,4-triazol-1-ium (6-carboxypyridine-2-carboxylato)(pyridine-2,6-dicarboxylato)cuprate(II) trihydrate