Poly[propane-1,3-diammonium [cuprate(II)-bis­(μ2-pyridine-2,3-dicarboxyl­ato)] trihydrate]

Aghabozorg, H.; Khadivi, R.; Ghadermazi, M.; Pasdar, H.; Hooshmand, S.

doi:10.1107/S1600536807067153

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages m267-m268

doi:10.1107/S1600536807067153

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Poly[propane-1,3-diammonium [cuprate(II)-bis(μ₂-pyridine-2,3-dicarboxylato)] trihydrate]

Hossein Aghabozorg,^a ^* Ramona Khadivi,^b Mohammad Ghadermazi,^c Hoda Pasdar ^b and Shabnam Hooshmand ^d

^aFaculty of Chemistry, Teacher Training University, Tehran, Iran, ^bDepartment of Chemistry, Islamic Azad University, North Tehran Branch, Tehran, Iran, ^cDepartment of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Iran, and ^dDepartment of Chemistry, Ilam University, Ilam, Iran
^*Correspondence e-mail: haghabozorg@yahoo.com

(Received 29 October 2007; accepted 16 December 2007; online 4 January 2008)

The title polymeric compound {(C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·3H₂O}_n or {(pnH₂)[Cu(py-2,3-dc)₂]·3H₂O}_n (pn is propane-1,3-diamine and py-2,3-dcH₂ is pyridine-2,3-dicarboxylic acid), was synthesized by reaction of copper(II) chloride dihydrate with a proton-transfer compound, propane-1,3-diammonium pyridine-2,3-dicarboxylate or (pnH₂)(py-2,3-dc), in aqueous solution. The anion is a six-coordinate complex (site symmetry $[\overline{1}]$ ), with a distorted octahedral geometry around Cu^II, consisting of two bidentate pyridine-2,3-dicarboxylate groups and two O atoms of bridging ligands from (py-2,3-dc)²⁻ fragments, which are located in trans positions. The (pnH₂)²⁺ cation is disordered over two sites by the center of inversion. Intermolecular hydrogen bonds, π–π [centroid–centroid distances of 3.539 (3) Å] and C—O⋯π stacking interactions [O⋯Cg = 3.240 (5) Å; Cg is the center of the pyridine ring], connect the various components into a supramolecular structure.

Related literature

For related literature, see: Aghabozorg, Attar Gharamaleki, Ghadermazi et al. (2007 ); Aghabozorg, Attar Gharamaleki, Ghasemikhah et al. (2007 ); Aghabozorg, Daneshvar et al. (2007 ).

Experimental

Crystal data

(C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·3H₂O
M_r = 523.94
Triclinic, $[P \overline 1]$
a = 6.6857 (12) Å
b = 7.8251 (18) Å
c = 9.9188 (9) Å
α = 82.6561 (10)°
β = 84.0079 (13)°
γ = 71.9520 (17)°
V = 488.20 (15) Å³
Z = 1
Mo Kα radiation
μ = 1.19 mm⁻¹
T = 100 (2) K
0.21 × 0.16 × 0.15 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.775, T_max = 0.836
10997 measured reflections
2348 independent reflections
2310 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.176
S = 1.01
2348 reflections
189 parameters
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.93 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.960 (4)
Cu1—N1	1.970 (4)
Cu1—O4ⁱ	2.549 (4)

O1ⁱⁱ—Cu1—N1ⁱⁱ	83.39 (16)
O1—Cu1—N1ⁱⁱ	96.61 (16)
O4ⁱ—Cu1—O4ⁱⁱⁱ	180
Symmetry codes: (i) x-1, y, z; (ii) -x, -y+2, -z+2; (iii) -x+1, -y+2, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3	0.91	1.96	2.854 (1)	167
N2—H2B⋯O2^iv	0.91	2.01	2.830 (1)	150
N3—H3B⋯N2^v	0.91	1.56	2.283 (1)	134
N3—H3B⋯O2W^vi	0.91	1.95	2.852 (13)	174
N3—H3C⋯O3^iv	0.91	2.42	3.041 (10)	126
N3—H3C⋯O4^iv	0.91	2.08	2.991 (1)	174
N3—H3D⋯O1WA^vii	0.91	2.03	2.934 (1)	170
N3—H3D⋯O1WB^vii	0.91	2.51	3.407 (15)	170
O1WA—H3W⋯O1^viii	0.89	2.11	2.764 (1)	130
O1WA—H4W⋯O3ⁱ	0.97	1.74	2.696 (1)	168
O2W—H1W⋯O1WA	0.87	2.00	2.779 (15)	148
O2W—H1W⋯O1WB	0.87	1.59	2.350 (1)	145
O2W—H2W⋯O3^ix	0.85	1.92	2.768 (1)	179
C5—H5⋯O1WA^x	0.95	2.60	3.534 (13)	169
C8—H8A⋯O2	0.99	2.37	2.891 (11)	112
C8—H8B⋯O4ⁱ	0.99	2.49	3.396 (11)	153
Symmetry codes: (i) x-1, y, z; (iv) -x+1, -y+2, -z+1; (v) -x, -y+2, -z+1; (vi) x-1, y+1, z; (vii) x, y+1, z; (viii) x, y-1, z; (ix) -x+1, -y+1, -z+1; (x) -x, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXTL (Sheldrick, 1998 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067153/om2184sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067153/om2184Isup2.hkl

checkCIF report

Comment top

Intermolecular intractions, such as hydrogen bonding, π-π stacking, ion pairing and donor-acceptor interactions, are famous for making aggregates of molecules. One or more of these interactions may result in the formation of specific and spontaneous self-associations or self-associated compounds. Research has shown that hydrogen bonding plays the key role in preparation of self-assembled compounds.There is a very close relationship between hydrogen bonding and formation of proton transfer compounds (Aghabozorg, Attar Gharamaleki, Ghadermazi et al., 2007; Aghabozorg, Attar Gharamaleki, Ghasemikhah et al., 2007; Aghabozorg, Daneshvar et al., 2007).

Here, we report on the synthesis and X-ray crystal structure of the title compound. Selected bond lengths, bond angles are given in Table 1. The Cu^IIcompound is composed of an anionic complex, [Cu(py-2,3-dc)₂]^2–, propane-1,3-diammonium as a counter-ion, (pnH₂)²⁺, and three uncoordinated water molecules (Fig. 1). The Cu^II atom resides on a center of symmetry and is six-coordinated by two pyridine-2,3-dicarboxylate, (py-2,3-dc)^2–, groups which act as a bidentate ligand through one O atom and one N atom and two O atoms of bridging (py-2,3-dc)^2– ligands that occupy trans positions with [O4ⁱⁱ—Cu1—O4ⁱⁱⁱ = 180°; ii: x - 1, y, z and iii: -x + 1, -y + 2, -z + 2] which create the title polymeric structure. On the other hand, O1—Cu1—N1—C1 and N1—Cu1—O1—C6 torsion angles are 175.1 (3)° and -176.7 (4)°, respectively indicate that two (py-2,3-dc)^2– units are in the plane. In the crystal structure, the spaces between two layers of [Cu(py-2,3-dc)₂]^2– are filled with a layers of (pnH₂)²⁺cations and water molecules (Fig 2). Solvate water molecules are disordered over two sites: O1WA and O1WB with equal occupancies and O2W by the center of inversion.

A notable feature of this compound is the presence of π-π and C—O···π stacking interactions. The π-π stacking between two aromatic rings of (py-2,3-dc)^2– fragments with distances of 3.539 (3) Å (1 - x, 1 - y, 2 - z) are observed (Fig. 3). The C—O···π distances are 3.240 (5) Å (C6–O2···Cg1(1 - x, 2 - y, 2 - z); Cg1 is the centroid for the N1/C1–C5 ring] (Fig. 4). Intermolecular O—H···O, O—H···N, N—H···O, C—H···O and C—H···N hydrogen bonds with D···A ranging from 2.283 (1) Å to 3.534 (13) Å (Table 2) seem to be effective in the stabilization of the crystal structure, resulting in the formation of an interesting supramolecular structure.

Related literature top

For related literature, see: Aghabozorg, Attar Gharamaleki, Ghadermazi et al. (2007); Aghabozorg, Attar Gharamaleki, Ghasemikhah et al. (2007); Aghabozorg, Daneshvar et al. (2007).

Experimental top

A solution of CuCl₂.2H₂O (85 mg, 0.5 mmol) in water (5 ml) was added to an aqueous solution of (pnH₂)(py-2,3-dc) (242 mg, 1 mmol) in water (10 ml) in a 1:2 molar ratio. Blue crystals of title compound were obtained after allowing the mixture to stand for four weeks at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: SHELXTL (Sheldrick, 1998) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 1998).

Figures top

	Fig. 1. The molecular structure of the title complex, with displacement ellipsoids drawn at the 50% probability level. [The labels a, b,c and d denote atoms generated by the symmetry operators (-1 + x, y, z), (1 + x, y, z), (-x, 2 - y, 2 - z) and (1 - x, 2 - y, 2 - z), respectively].
	Fig. 2. A layered packing diagram viewed down the b axis. The space between the two layers of [Cu(py-2,3-dc)₂]^2– fragments is filled with a layer of (pnH₂)²⁺cations and water molecules.
	Fig. 3. π-π Stacking interactions between two aromatic rings. The average distance between the planes is 3.539 (3) Å (1 - x, 1 - y, 2 - z).
	Fig. 4. The stacking interactions of the carbonyl groups of (py-2,3-dc)^2– fragments. The C—O···π distances (measured to the center of ring (N1/C1—C5) are 3.239 (5) Å (1 - x, 2 - y, 2 - z).

Poly[propane-1,3-diammonium [cuprate(II)-bis(µ₂-pyridine-2,3-dicarboxylato] tetrahydrate] top

Crystal data top

(C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·3H₂O	Z = 1
M_r = 523.94	F(000) = 271
Triclinic, P1	D_x = 1.782 Mg m⁻³
a = 6.6857 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8251 (18) Å	Cell parameters from 1234 reflections
c = 9.9188 (9) Å	θ = 3–20°
α = 82.6561 (10)°	µ = 1.19 mm⁻¹
β = 84.0079 (13)°	T = 100 K
γ = 71.9520 (17)°	Prism, blue
V = 488.20 (15) Å³	0.21 × 0.16 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2348 independent reflections
Radiation source: fine-focus sealed tube	2310 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 28.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
T_min = 0.775, T_max = 0.836	k = −10→10
10997 measured reflections	l = −13→13

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)] = 0.063	Hydrogen site location: mixed
wR(F²) = 0.176	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.010P)² + 9.P] where P = (F_o² + 2F_c²)/3
2348 reflections	(Δ/σ)_max < 0.001
189 parameters	Δρ_max = 0.69 e Å⁻³
0 restraints	Δρ_min = −0.93 e Å⁻³

Crystal data top

(C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·3H₂O	γ = 71.9520 (17)°
M_r = 523.94	V = 488.20 (15) Å³
Triclinic, P1	Z = 1
a = 6.6857 (12) Å	Mo Kα radiation
b = 7.8251 (18) Å	µ = 1.19 mm⁻¹
c = 9.9188 (9) Å	T = 100 K
α = 82.6561 (10)°	0.21 × 0.16 × 0.15 mm
β = 84.0079 (13)°

Data collection top

Bruker SMART APEXII CCD diffractometer	2348 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2310 reflections with I > 2σ(I)
T_min = 0.775, T_max = 0.836	R_int = 0.026
10997 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.01	Δρ_max = 0.69 e Å⁻³
2348 reflections	Δρ_min = −0.93 e Å⁻³
189 parameters

Special details top

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	Occ. (<1)
Cu1	0.0000	1.0000	1.0000	0.0083 (2)
O1	0.1529 (5)	1.0909 (5)	0.8418 (4)	0.0137 (7)
O2	0.4743 (6)	1.0337 (6)	0.7330 (4)	0.0233 (9)
O3	0.7857 (6)	0.6603 (5)	0.7152 (4)	0.0189 (8)
O4	0.9507 (6)	0.7923 (5)	0.8365 (4)	0.0184 (8)
N1	0.2805 (6)	0.8300 (5)	1.0351 (4)	0.0099 (8)
C1	0.4291 (7)	0.8457 (6)	0.9349 (5)	0.0098 (9)
C2	0.6352 (8)	0.7332 (6)	0.9342 (5)	0.0108 (9)
C3	0.6889 (8)	0.6039 (6)	1.0472 (5)	0.0119 (9)
H3	0.8292	0.5260	1.0525	0.014*
C4	0.5387 (8)	0.5903 (6)	1.1494 (5)	0.0113 (9)
H4	0.5743	0.5031	1.2259	0.014*
C5	0.3353 (8)	0.7039 (6)	1.1406 (5)	0.0111 (9)
H5	0.2314	0.6924	1.2112	0.013*
C6	0.3515 (8)	1.0015 (7)	0.8261 (5)	0.0135 (9)
C7	0.8024 (7)	0.7337 (7)	0.8180 (5)	0.0135 (10)
N2	0.4757 (13)	0.7636 (12)	0.5189 (9)	0.0129 (16)	0.50
H2A	0.5574	0.7319	0.5913	0.019*	0.50
H2B	0.5369	0.8236	0.4504	0.019*	0.50
H2C	0.4627	0.6624	0.4892	0.019*	0.50
C8	0.2618 (16)	0.8836 (14)	0.5611 (10)	0.0139 (19)	0.50
H8A	0.2673	1.0086	0.5610	0.017*	0.50
H8B	0.2188	0.8415	0.6549	0.017*	0.50
C9	0.1014 (16)	0.8816 (14)	0.4648 (11)	0.014 (2)	0.50
H9A	0.0884	0.7582	0.4704	0.017*	0.50
H9B	0.1506	0.9140	0.3702	0.017*	0.50
C10	−0.1138 (17)	1.0139 (15)	0.4993 (11)	0.017 (2)	0.50
H10A	−0.2226	0.9832	0.4550	0.020*	0.50
H10B	−0.1467	1.0008	0.5990	0.020*	0.50
N3	−0.1232 (14)	1.2052 (12)	0.4541 (9)	0.0135 (16)	0.50
H3B	−0.2596	1.2764	0.4603	0.020*	0.50
H3C	−0.0696	1.2138	0.3662	0.020*	0.50
H3D	−0.0461	1.2422	0.5083	0.020*	0.50
O1WA	0.0811 (17)	0.3649 (16)	0.6306 (12)	0.015 (2)	0.50
O1WB	0.1490 (17)	0.3949 (16)	0.6312 (13)	0.018 (2)	0.50
H3W	0.1276	0.3321	0.7141	0.027*
H4W	−0.0108	0.4794	0.6569	0.027*
O2W	0.4409 (12)	0.4057 (11)	0.4800 (8)	0.0171 (15)	0.50
H1W	0.3664	0.3585	0.5422	0.026*	0.50
H2W	0.3701	0.3870	0.4201	0.026*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0047 (4)	0.0081 (4)	0.0105 (4)	−0.0008 (3)	0.0010 (3)	0.0011 (3)
O1	0.0095 (16)	0.0141 (17)	0.0131 (17)	0.0005 (13)	0.0002 (13)	0.0039 (13)
O2	0.0120 (18)	0.029 (2)	0.019 (2)	0.0007 (16)	0.0054 (15)	0.0113 (16)
O3	0.0152 (18)	0.024 (2)	0.0127 (18)	−0.0001 (15)	0.0009 (14)	−0.0029 (15)
O4	0.0134 (17)	0.0167 (18)	0.023 (2)	−0.0041 (14)	0.0063 (15)	−0.0012 (15)
N1	0.0093 (18)	0.0090 (18)	0.0103 (19)	−0.0011 (15)	0.0015 (15)	−0.0022 (14)
C1	0.008 (2)	0.012 (2)	0.010 (2)	−0.0044 (17)	−0.0004 (16)	−0.0005 (17)
C2	0.011 (2)	0.011 (2)	0.011 (2)	−0.0048 (17)	−0.0024 (17)	0.0010 (17)
C3	0.013 (2)	0.010 (2)	0.013 (2)	−0.0022 (17)	−0.0039 (18)	−0.0027 (17)
C4	0.014 (2)	0.009 (2)	0.012 (2)	−0.0034 (17)	−0.0036 (17)	0.0005 (17)
C5	0.016 (2)	0.010 (2)	0.010 (2)	−0.0061 (18)	−0.0015 (17)	−0.0026 (17)
C6	0.006 (2)	0.017 (2)	0.013 (2)	−0.0005 (18)	0.0021 (17)	0.0030 (18)
C7	0.007 (2)	0.015 (2)	0.012 (2)	0.0036 (17)	−0.0006 (17)	0.0041 (18)
N2	0.011 (4)	0.016 (4)	0.010 (4)	−0.003 (3)	0.002 (3)	0.000 (3)
C8	0.014 (5)	0.014 (5)	0.012 (4)	−0.002 (4)	0.004 (4)	−0.004 (4)
C9	0.012 (5)	0.012 (5)	0.017 (5)	−0.003 (4)	0.002 (4)	0.000 (4)
C10	0.018 (5)	0.013 (5)	0.016 (5)	−0.004 (4)	0.004 (4)	0.000 (4)
N3	0.015 (4)	0.012 (4)	0.012 (4)	−0.002 (3)	0.000 (3)	0.001 (3)
O1WA	0.014 (6)	0.018 (5)	0.010 (4)	−0.002 (4)	0.005 (4)	0.000 (3)
O1WB	0.016 (6)	0.016 (5)	0.016 (4)	0.001 (4)	0.006 (4)	0.001 (3)
O2W	0.014 (3)	0.020 (4)	0.017 (4)	−0.007 (3)	0.002 (3)	−0.002 (3)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.960 (4)	C5—H5	0.9500
Cu1—O1	1.960 (4)	N2—C8	1.499 (12)
Cu1—N1ⁱ	1.970 (4)	N2—H2A	0.9100
Cu1—N1	1.970 (4)	N2—H2B	0.9100
Cu1—O4ⁱⁱ	2.549 (4)	N2—H2C	0.9100
Cu1—O4ⁱⁱⁱ	2.549 (4)	C8—C9	1.513 (14)
O1—C6	1.298 (6)	C8—H8A	0.9900
O2—C6	1.225 (6)	C8—H8B	0.9900
O3—C7	1.263 (7)	C9—C10	1.524 (14)
O4—C7	1.252 (7)	C9—H9A	0.9900
O4—Cu1^iv	2.549 (4)	C9—H9B	0.9900
N1—C5	1.340 (6)	C10—N3	1.491 (13)
N1—C1	1.352 (6)	C10—H10A	0.9900
C1—C2	1.386 (7)	C10—H10B	0.9900
C1—C6	1.520 (7)	N3—H3B	0.9100
C2—C3	1.406 (7)	N3—H3C	0.9100
C2—C7	1.520 (7)	N3—H3D	0.9100
C3—C4	1.369 (7)	O1WA—H3W	0.8934
C3—H3	0.9500	O1WA—H4W	0.9660
C4—C5	1.379 (7)	O2W—H1W	0.8700
C4—H4	0.9500	O2W—H2W	0.8498

O1ⁱ—Cu1—O1	180.000 (1)	N1—C5—C4	121.7 (5)
O1ⁱ—Cu1—N1ⁱ	83.39 (16)	C4—C5—Cu1	152.8 (4)
O1—Cu1—N1ⁱ	96.61 (16)	N1—C5—H5	119.1
O1ⁱ—Cu1—N1	96.61 (16)	C4—C5—H5	119.1
O1—Cu1—N1	83.39 (16)	Cu1—C5—H5	88.0
N1ⁱ—Cu1—N1	180.000 (1)	O2—C6—O1	125.3 (5)
O1ⁱ—Cu1—O4ⁱⁱ	96.02 (14)	O2—C6—C1	119.8 (4)
O1—Cu1—O4ⁱⁱ	83.98 (14)	O1—C6—C1	114.9 (4)
N1ⁱ—Cu1—O4ⁱⁱ	90.52 (15)	O2—C6—Cu1	165.3 (4)
N1—Cu1—O4ⁱⁱ	89.48 (15)	C1—C6—Cu1	74.8 (3)
O1ⁱ—Cu1—O4ⁱⁱⁱ	83.98 (14)	O4—C7—O3	126.2 (5)
O1—Cu1—O4ⁱⁱⁱ	96.02 (14)	O4—C7—C2	118.0 (5)
N1ⁱ—Cu1—O4ⁱⁱⁱ	89.48 (15)	O3—C7—C2	115.5 (4)
N1—Cu1—O4ⁱⁱⁱ	90.52 (15)	N2—C8—C9	110.5 (8)
O4ⁱⁱ—Cu1—O4ⁱⁱⁱ	180.000 (1)	N2—C8—H8A	109.5
C6—O1—Cu1	114.8 (3)	C9—C8—H8A	109.5
C7—O4—Cu1^iv	134.2 (3)	N2—C8—H8B	109.5
C5—N1—C1	118.9 (4)	C9—C8—H8B	109.5
C5—N1—Cu1	128.3 (3)	H8A—C8—H8B	108.1
C1—N1—Cu1	112.8 (3)	C8—C9—C10	111.4 (9)
N1—C1—C2	122.9 (4)	C8—C9—H9A	109.3
N1—C1—C6	113.9 (4)	C10—C9—H9A	109.3
C2—C1—C6	123.2 (4)	C8—C9—H9B	109.3
C2—C1—Cu1	163.3 (4)	C10—C9—H9B	109.3
C6—C1—Cu1	73.4 (3)	H9A—C9—H9B	108.0
C1—C2—C3	116.9 (4)	N3—C10—C9	112.5 (8)
C1—C2—C7	124.9 (4)	N3—C10—H10A	109.1
C3—C2—C7	118.1 (4)	C9—C10—H10A	109.1
C4—C3—C2	119.9 (5)	N3—C10—H10B	109.1
C4—C3—H3	120.0	C9—C10—H10B	109.1
C2—C3—H3	120.0	H10A—C10—H10B	107.8
C3—C4—C5	119.6 (5)	H3W—O1WA—H4W	91.9
C3—C4—H4	120.2	H1W—O2W—H2W	88.7
C5—C4—H4	120.2

N1ⁱ—Cu1—O1—C6	−176.6 (4)	C3—C4—C5—Cu1	1.2 (10)
N1—Cu1—O1—C6	3.4 (4)	O1ⁱ—Cu1—C5—N1	176.7 (4)
O4ⁱⁱ—Cu1—O1—C6	−86.8 (4)	O1—Cu1—C5—N1	−3.3 (4)
O4ⁱⁱⁱ—Cu1—O1—C6	93.2 (4)	N1ⁱ—Cu1—C5—N1	180.000 (3)
O1ⁱ—Cu1—N1—C5	−3.2 (4)	O4ⁱⁱ—Cu1—C5—N1	81.2 (4)
O1—Cu1—N1—C5	176.8 (4)	O4ⁱⁱⁱ—Cu1—C5—N1	−98.8 (4)
O4ⁱⁱ—Cu1—N1—C5	−99.2 (4)	O1ⁱ—Cu1—C5—C4	173.2 (8)
O4ⁱⁱⁱ—Cu1—N1—C5	80.8 (4)	O1—Cu1—C5—C4	−6.8 (8)
O1ⁱ—Cu1—N1—C1	175.0 (3)	N1ⁱ—Cu1—C5—C4	176.5 (7)
O1—Cu1—N1—C1	−5.0 (3)	N1—Cu1—C5—C4	−3.5 (7)
O4ⁱⁱ—Cu1—N1—C1	79.0 (3)	O4ⁱⁱ—Cu1—C5—C4	77.6 (7)
O4ⁱⁱⁱ—Cu1—N1—C1	−101.0 (3)	O4ⁱⁱⁱ—Cu1—C5—C4	−102.4 (7)
C5—N1—C1—C2	2.0 (7)	Cu1—O1—C6—O2	178.7 (5)
Cu1—N1—C1—C2	−176.4 (4)	Cu1—O1—C6—C1	−1.2 (6)
C5—N1—C1—C6	−176.0 (4)	N1—C1—C6—O2	177.1 (5)
Cu1—N1—C1—C6	5.6 (5)	C2—C1—C6—O2	−1.0 (8)
C5—N1—C1—Cu1	178.4 (6)	Cu1—C1—C6—O2	−179.1 (6)
O1ⁱ—Cu1—C1—N1	−5.9 (4)	N1—C1—C6—O1	−3.0 (7)
O1—Cu1—C1—N1	174.1 (4)	C2—C1—C6—O1	179.0 (5)
N1ⁱ—Cu1—C1—N1	180.000 (3)	Cu1—C1—C6—O1	0.8 (4)
O4ⁱⁱ—Cu1—C1—N1	−99.6 (3)	N1—C1—C6—Cu1	−3.8 (4)
O4ⁱⁱⁱ—Cu1—C1—N1	80.4 (3)	C2—C1—C6—Cu1	178.2 (5)
O1ⁱ—Cu1—C1—C2	4.7 (13)	O1ⁱ—Cu1—C6—O2	176.0 (15)
O1—Cu1—C1—C2	−175.3 (13)	O1—Cu1—C6—O2	−4.0 (15)
N1ⁱ—Cu1—C1—C2	−169.4 (11)	N1ⁱ—Cu1—C6—O2	−0.1 (18)
N1—Cu1—C1—C2	10.6 (11)	N1—Cu1—C6—O2	179.9 (18)
O4ⁱⁱ—Cu1—C1—C2	−89.0 (12)	O4ⁱⁱ—Cu1—C6—O2	86.3 (17)
O4ⁱⁱⁱ—Cu1—C1—C2	91.0 (12)	O4ⁱⁱⁱ—Cu1—C6—O2	−93.7 (17)
O1ⁱ—Cu1—C1—C6	179.4 (3)	O1ⁱ—Cu1—C6—O1	180.000 (2)
O1—Cu1—C1—C6	−0.6 (3)	N1ⁱ—Cu1—C6—O1	3.9 (4)
N1ⁱ—Cu1—C1—C6	5.3 (5)	N1—Cu1—C6—O1	−176.1 (4)
N1—Cu1—C1—C6	−174.7 (5)	O4ⁱⁱ—Cu1—C6—O1	90.3 (4)
O4ⁱⁱ—Cu1—C1—C6	85.7 (3)	O4ⁱⁱⁱ—Cu1—C6—O1	−89.7 (4)
O4ⁱⁱⁱ—Cu1—C1—C6	−94.3 (3)	O1ⁱ—Cu1—C6—C1	−1.1 (5)
N1—C1—C2—C3	−2.9 (7)	O1—Cu1—C6—C1	178.9 (5)
C6—C1—C2—C3	175.0 (4)	N1ⁱ—Cu1—C6—C1	−177.2 (3)
Cu1—C1—C2—C3	−11.1 (15)	N1—Cu1—C6—C1	2.8 (3)
N1—C1—C2—C7	174.0 (5)	O4ⁱⁱ—Cu1—C6—C1	−90.8 (3)
C6—C1—C2—C7	−8.2 (8)	O4ⁱⁱⁱ—Cu1—C6—C1	89.2 (3)
Cu1—C1—C2—C7	165.8 (10)	Cu1^iv—O4—C7—O3	164.8 (4)
C1—C2—C3—C4	1.8 (7)	Cu1^iv—O4—C7—C2	−21.4 (7)
C7—C2—C3—C4	−175.3 (4)	C1—C2—C7—O4	109.8 (6)
C2—C3—C4—C5	0.0 (7)	C3—C2—C7—O4	−73.4 (6)
C1—N1—C5—C4	0.0 (7)	C1—C2—C7—O3	−75.7 (6)
Cu1—N1—C5—C4	178.1 (4)	C3—C2—C7—O3	101.1 (5)
C1—N1—C5—Cu1	−178.1 (7)	N2—C8—C9—C10	−175.6 (8)
C3—C4—C5—N1	−1.0 (7)	C8—C9—C10—N3	76.1 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.91	1.96	2.854 (1)	167
N2—H2B···O2^v	0.91	2.01	2.830 (1)	150
N3—H3B···N2^vi	0.91	1.56	2.283 (1)	134
N3—H3B···O2W^vii	0.91	1.95	2.852 (13)	174
N3—H3C···O3^v	0.91	2.42	3.041 (10)	126
N3—H3C···O4^v	0.91	2.08	2.991 (1)	174
N3—H3D···O1WA^viii	0.91	2.03	2.934 (1)	170
N3—H3D···O1WB^viii	0.91	2.51	3.407 (15)	170
O1WA—H3W···O1^ix	0.89	2.11	2.764 (1)	130
O1WA—H4W···O3ⁱⁱ	0.97	1.74	2.696 (1)	168
O2W—H1W···O1WA	0.87	2.00	2.779 (15)	148
O2W—H1W···O1WB	0.87	1.59	2.350 (1)	145
O2W—H2W···O3^x	0.85	1.92	2.768 (1)	179
C5—H5···O1WA^xi	0.95	2.60	3.534 (13)	169
C8—H8A···O2	0.99	2.37	2.891 (11)	112
C8—H8B···O4ⁱⁱ	0.99	2.49	3.396 (11)	153

Symmetry codes: (ii) x−1, y, z; (v) −x+1, −y+2, −z+1; (vi) −x, −y+2, −z+1; (vii) x−1, y+1, z; (viii) x, y+1, z; (ix) x, y−1, z; (x) −x+1, −y+1, −z+1; (xi) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	(C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·3H₂O
M_r	523.94
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.6857 (12), 7.8251 (18), 9.9188 (9)
α, β, γ (°)	82.6561 (10), 84.0079 (13), 71.9520 (17)
V (Å³)	488.20 (15)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.19
Crystal size (mm)	0.21 × 0.16 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.775, 0.836
No. of measured, independent and observed [I > 2σ(I)] reflections	10997, 2348, 2310
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.176, 1.01
No. of reflections	2348
No. of parameters	189
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.93

Computer programs: APEX2 (Bruker, 2005), SHELXTL (Sheldrick, 1998) and Mercury (Macrae et al., 2006).

Selected geometric parameters (Å, º) top

Cu1—O1	1.960 (4)	Cu1—O4ⁱ	2.549 (4)
Cu1—N1	1.970 (4)

O1ⁱⁱ—Cu1—N1ⁱⁱ	83.39 (16)	O4ⁱ—Cu1—O4ⁱⁱⁱ	180.000 (1)
O1—Cu1—N1ⁱⁱ	96.61 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.910	1.960	2.854 (1)	167
N2—H2B···O2^iv	0.910	2.005	2.830 (1)	150
N3—H3B···N2^v	0.910	1.559	2.283 (1)	134
N3—H3B···O2W^vi	0.91	1.95	2.852 (13)	174
N3—H3C···O3^iv	0.91	2.42	3.041 (10)	126
N3—H3C···O4^iv	0.910	2.084	2.991 (1)	174
N3—H3D···O1WA^vii	0.910	2.034	2.934 (1)	170
N3—H3D···O1WB^vii	0.91	2.51	3.407 (15)	170
O1WA—H3W···O1^viii	0.893	2.105	2.764 (1)	130
O1WA—H4W···O3ⁱ	0.966	1.744	2.696 (1)	168
O2W—H1W···O1WA	0.87	2.00	2.779 (15)	148
O2W—H1W···O1WB	0.870	1.585	2.350 (1)	145
O2W—H2W···O3^ix	0.850	1.919	2.768 (1)	179
C5—H5···O1WA^x	0.95	2.60	3.534 (13)	169
C8—H8A···O2	0.99	2.37	2.891 (11)	112
C8—H8B···O4ⁱ	0.99	2.49	3.396 (11)	153

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

Acknowledgements

Financial support from Ilam University and the Teacher Training University is gratefully acknowledged.

References

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