Propane-1,2-diaminium bis­(pyridine-2,6-dicarboxyl­ato-κ3O2,N,O6)cuprate(II) tetra­hydrate

Aghabozorg, H.; Agah, A.A.; Notash, B.; Mirzaei, M.

doi:10.1107/S1600536811024378

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m992-m993

doi:10.1107/S1600536811024378

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Propane-1,2-diaminium bis(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)cuprate(II) tetrahydrate

Hossein Aghabozorg,^a ^* Ali Akbar Agah,^a Behrouz Notash ^b and Masoud Mirzaei ^c

^aFaculty of Chemistry, Tarbiat Moallem University, 15614, Tehran, Iran, ^bDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran, Iran, and ^cDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad 917751436, Iran
^*Correspondence e-mail: haghabozorg@yahoo.com

(Received 28 February 2011; accepted 21 June 2011; online 30 June 2011)

In the title compound, (C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·4H₂O, the Cu^II atom is six-coordinated in a distorted octahedral geometry by two tridentate pyridine-2,6-dicarboxylate (pydc) ligands. In the crystal, intermolecular O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds, as well as π–π stacking interactions between the pyridine rings of the pydc ligands [centroid–centroid distance = 3.4714 (14) Å] are present. C=O⋯π interactions between the carbonyl groups and pyridine rings [O⋯centroid distances = 3.150 (2) and 3.2233 (19) Å] are also observed.

Related literature

For background to proton-transfer compounds, see: Aghabozorg et al. (2008d ). For related structures, see: Aghabozorg et al. (2008a ,b ,c ).

Experimental

Crystal data

(C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·4H₂O
M_r = 541.97
Orthorhombic, P n a 2₁
a = 20.919 (4) Å
b = 8.2015 (16) Å
c = 12.739 (3) Å
V = 2185.6 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 120 K
0.50 × 0.40 × 0.35 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005 ) T_min = 0.602, T_max = 0.684
9693 measured reflections
5040 independent reflections
4803 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.075
S = 1.09
5040 reflections
350 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.52 e Å⁻³
Absolute structure: Flack (1983 ), 1969 Friedel pairs
Flack parameter: −0.001 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O11ⁱ	0.93	2.59	3.476 (3)	160
C11—H11⋯O7ⁱⁱ	0.93	2.56	3.301 (3)	137
C15—H15A⋯O8ⁱⁱⁱ	0.97	2.30	3.245 (3)	165
C16—H16⋯O5^iv	0.98	2.53	3.321 (3)	138
N3—H3A⋯O6^iv	0.89 (4)	1.93 (4)	2.812 (3)	170 (3)
N3—H3B⋯O11	0.95 (4)	1.88 (4)	2.773 (3)	155 (3)
N3—H3C⋯O2	0.90 (4)	1.91 (4)	2.794 (2)	167 (4)
N4—H4A⋯O10^iv	0.86 (3)	1.94 (3)	2.786 (3)	165 (3)
N4—H4B⋯O12	0.83 (4)	2.00 (4)	2.811 (3)	165 (3)
N4—H4C⋯O4^v	0.84 (2)	2.01 (2)	2.829 (3)	167 (3)
O9—H9A⋯O1	0.84 (2)	1.93 (2)	2.739 (3)	163 (3)
O9—H9B⋯O4^vi	0.82 (2)	2.04 (2)	2.826 (3)	160 (3)
O10—H10A⋯O9	0.78 (4)	1.97 (4)	2.731 (3)	164 (4)
O10—H10B⋯O8^v	0.85 (4)	1.88 (4)	2.724 (3)	170 (3)
O11—H11A⋯O3^v	0.82 (2)	2.41 (3)	3.080 (2)	140 (3)
O11—H11A⋯O7^v	0.82 (2)	2.30 (3)	2.957 (2)	138 (3)
O11—H11B⋯O10	0.82 (4)	1.98 (4)	2.781 (3)	169 (3)
O12—H12A⋯O2^vii	0.79 (2)	1.99 (2)	2.770 (3)	170 (3)
O12—H12B⋯O6^iv	0.81 (2)	2.09 (3)	2.786 (2)	144 (3)
Symmetry codes: (i) $[-x+1, -y+2, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x, y-1, z; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (vi) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811024378/hy2413sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024378/hy2413Isup2.hkl

checkCIF report

Comment top

Our group has previously reported some proton-transfer systems (Aghabozorg et al., 2008d), using pyridine-2,6-dicarboxylic acid (pydcH₂), propane-1,2-diamine (p-1,2-da) and propane-1,3-diamine (p-1,3-da), which formed the proton-transfer compounds (p-1,2-daH₂)(pydcH)₂.2H₂O (Aghabozorg et al., 2008c), (p-1,2-daH₂)[Ni(pydc)₂].4H₂O (Aghabozorg et al., 2008b), (p-1,3-daH₂)[Cd(pydc)₂].3.5H₂O, (p-1,3-daH₂)[Cu(pydc)₂].4H₂O and (p-1,3-daH2)[Co(pydc)₂].4H₂O (Aghabozorg et al., 2008a).

We describe here the crystal structure of the title compound (Fig. 1). In the complex anion, the Cu^II ion is six-coordinated by two (pydc)^2- ligands in a distorted octahedral geometry. In the crystal, there are N—H···O, O—H···O and weak C—H···O intermolecular hydrogen bonds (Table 1, Fig. 2). There are also π–π stacking interactions between the pyridine rings of the pydc ligands [centroid–centroid distance = 3.4714 (14) Å], as shown in Fig. 3. In addition, there are C═O···π interactions (Fig. 4) between the carbonyl groups and pyridine rings [O···centroid distances = 3.150 (2) and 3.2233 (19) Å].

Related literature top

For background to proton-transfer compounds, see: Aghabozorg et al. (2008d). For related structures, see: Aghabozorg et al. (2008a,b,c).

Experimental top

By mixing Cu(OAc)₂.H₂O (1 mmol), pyridine-2,6-dicarboxylic acid (2 mmol) and propane-1,2-diamine (1 mmol) in 20 ml water, a blue solution was obtained. Blue crystals of the title compound were obtained by allowing the mixture to stand at room temperature for a week.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The packing diagram of the title compound, showing intermolecular N—H···O, O—H···O and weak C—H···O hydrogen bonds (blue dashed lines).
	Fig. 3. The packing diagram of the title compound, showing intermolecular π–π interactions [dashed lines, centroid–centroid distance = 3.4714 (14) Å]. Water molecules and cations have been omitted for clarity.
	Fig. 4. The packing diagram of the title compound, showing C═O···π interactions (dashed lines) between the pyridine rings and the carbonyl groups [O···centroid distances = 3.150 (2) and 3.2233 (19) Å]. Water molecules and cations have been omitted for clarity.

Propane-1,2-diaminium bis(pyridine-2,6-dicarboxylato- κ³O²,N,O⁶)cuprate(II) tetrahydrate top

Crystal data top

(C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·4H₂O	F(000) = 1124
M_r = 541.97	D_x = 1.647 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 5040 reflections
a = 20.919 (4) Å	θ = 2.5–29.1°
b = 8.2015 (16) Å	µ = 1.07 mm⁻¹
c = 12.739 (3) Å	T = 120 K
V = 2185.6 (7) Å³	Block, blue
Z = 4	0.50 × 0.40 × 0.35 mm

Data collection top

Stoe IPDS-2 diffractometer	5040 independent reflections
Radiation source: fine-focus sealed tube	4803 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 29.1°, θ_min = 2.5°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)	h = −24→28
T_min = 0.602, T_max = 0.684	k = −9→11
9693 measured reflections	l = −14→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	w = 1/[σ²(F_o²) + (0.0422P)² + 0.9494P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.003
5040 reflections	Δρ_max = 0.43 e Å⁻³
350 parameters	Δρ_min = −0.52 e Å⁻³
7 restraints	Absolute structure: Flack (1983), 1969 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.001 (10)

Crystal data top

(C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·4H₂O	V = 2185.6 (7) Å³
M_r = 541.97	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 20.919 (4) Å	µ = 1.07 mm⁻¹
b = 8.2015 (16) Å	T = 120 K
c = 12.739 (3) Å	0.50 × 0.40 × 0.35 mm

Data collection top

Stoe IPDS-2 diffractometer	5040 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)	4803 reflections with I > 2σ(I)
T_min = 0.602, T_max = 0.684	R_int = 0.029
9693 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.075	Δρ_max = 0.43 e Å⁻³
S = 1.09	Δρ_min = −0.52 e Å⁻³
5040 reflections	Absolute structure: Flack (1983), 1969 Friedel pairs
350 parameters	Absolute structure parameter: −0.001 (10)
7 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.730311 (10)	0.99084 (3)	0.53964 (3)	0.00819 (6)
O1	0.65641 (8)	0.7928 (2)	0.57097 (13)	0.0156 (3)
O2	0.60721 (7)	0.67722 (19)	0.70796 (13)	0.0133 (3)
O3	0.81368 (7)	1.15817 (19)	0.58997 (13)	0.0121 (3)
O4	0.86763 (7)	1.22026 (19)	0.73603 (13)	0.0126 (3)
O5	0.65879 (7)	1.16886 (17)	0.53346 (15)	0.0134 (3)
O6	0.59524 (8)	1.2936 (2)	0.41726 (14)	0.0151 (3)
O7	0.80165 (7)	0.83190 (19)	0.48615 (13)	0.0109 (3)
O8	0.85015 (8)	0.7555 (2)	0.33667 (13)	0.0129 (3)
O9	0.56195 (10)	0.7606 (4)	0.42357 (17)	0.0426 (7)
O10	0.44108 (9)	0.8652 (2)	0.46858 (15)	0.0162 (3)
O11	0.42267 (8)	0.5941 (2)	0.59618 (14)	0.0171 (3)
O12	0.46500 (9)	0.3499 (2)	0.38944 (16)	0.0216 (4)
N1	0.73387 (8)	0.9634 (2)	0.69332 (17)	0.0079 (3)
N2	0.72136 (9)	1.0156 (2)	0.38998 (18)	0.0077 (4)
N3	0.54048 (9)	0.4390 (2)	0.59580 (16)	0.0124 (3)
N4	0.44690 (9)	0.1638 (2)	0.57235 (16)	0.0116 (4)
C1	0.64760 (10)	0.7709 (3)	0.66754 (17)	0.0096 (4)
C2	0.69142 (10)	0.8648 (2)	0.74089 (18)	0.0088 (4)
C3	0.69152 (10)	0.8437 (2)	0.84916 (18)	0.0094 (4)
H3	0.6616	0.7763	0.8813	0.011*
C4	0.73706 (10)	0.9252 (3)	0.90831 (18)	0.0112 (4)
H4	0.7382	0.9122	0.9808	0.013*
C5	0.78101 (11)	1.0265 (3)	0.85857 (19)	0.0099 (4)
H5	0.8121	1.0813	0.8971	0.012*
C6	0.77765 (10)	1.0443 (2)	0.75039 (18)	0.0079 (4)
C7	0.82336 (9)	1.1500 (2)	0.68727 (18)	0.0089 (4)
C8	0.63972 (10)	1.1994 (3)	0.44162 (19)	0.0109 (4)
C9	0.67591 (10)	1.1157 (2)	0.35435 (18)	0.0093 (4)
C10	0.66963 (11)	1.1435 (2)	0.24765 (18)	0.0110 (4)
H10	0.6379	1.2123	0.2221	0.013*
C11	0.71196 (11)	1.0660 (3)	0.17933 (17)	0.0118 (4)
H11	0.7089	1.0839	0.1074	0.014*
C12	0.75891 (11)	0.9616 (3)	0.21866 (18)	0.0097 (4)
H12	0.7875	0.9093	0.1739	0.012*
C13	0.76179 (10)	0.9379 (3)	0.32665 (17)	0.0090 (4)
C14	0.80893 (10)	0.8320 (2)	0.38701 (19)	0.0097 (4)
C15	0.53174 (11)	0.3070 (3)	0.67483 (19)	0.0135 (4)
H15B	0.5001	0.3411	0.7259	0.016*
H15A	0.5717	0.2899	0.7117	0.016*
C16	0.51050 (10)	0.1466 (2)	0.62550 (18)	0.0114 (4)
H16	0.5423	0.1141	0.5730	0.014*
C17	0.50603 (13)	0.0132 (3)	0.7083 (2)	0.0188 (5)
H17B	0.4754	0.0440	0.7607	0.023*
H17C	0.5471	−0.0017	0.7406	0.023*
H17A	0.4928	−0.0869	0.6758	0.023*
H3A	0.5597 (15)	0.404 (4)	0.538 (3)	0.023*
H4A	0.4377 (15)	0.074 (4)	0.540 (3)	0.023*
H9A	0.5887 (14)	0.790 (4)	0.468 (2)	0.023*
H10A	0.4750 (18)	0.846 (4)	0.446 (3)	0.023*
H11A	0.3889 (11)	0.562 (4)	0.572 (3)	0.023*
H12A	0.4484 (15)	0.340 (4)	0.3341 (18)	0.023*
H3B	0.4992 (17)	0.477 (4)	0.577 (3)	0.023*
H4B	0.4502 (15)	0.233 (4)	0.525 (3)	0.023*
H9B	0.5786 (16)	0.726 (4)	0.3696 (19)	0.023*
H10B	0.4158 (17)	0.830 (4)	0.421 (3)	0.023*
H11B	0.4249 (16)	0.680 (4)	0.564 (3)	0.023*
H12B	0.4996 (11)	0.316 (4)	0.372 (3)	0.023*
H3C	0.5641 (17)	0.520 (4)	0.622 (3)	0.023*
H4C	0.4190 (13)	0.200 (4)	0.613 (2)	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.00687 (10)	0.01264 (10)	0.00506 (10)	0.00041 (8)	−0.00005 (12)	0.00104 (10)
O1	0.0129 (7)	0.0252 (8)	0.0088 (8)	−0.0069 (6)	−0.0014 (6)	−0.0002 (6)
O2	0.0105 (7)	0.0159 (7)	0.0134 (8)	−0.0052 (5)	0.0017 (6)	−0.0014 (6)
O3	0.0133 (7)	0.0152 (7)	0.0079 (8)	−0.0031 (5)	−0.0008 (6)	0.0008 (6)
O4	0.0088 (7)	0.0169 (7)	0.0122 (8)	−0.0040 (6)	−0.0002 (6)	−0.0021 (6)
O5	0.0113 (6)	0.0217 (7)	0.0072 (7)	0.0036 (5)	0.0009 (7)	0.0002 (7)
O6	0.0115 (7)	0.0202 (8)	0.0135 (8)	0.0066 (6)	−0.0001 (6)	0.0019 (6)
O7	0.0096 (7)	0.0150 (7)	0.0081 (8)	0.0023 (5)	0.0003 (6)	0.0009 (5)
O8	0.0090 (7)	0.0178 (7)	0.0120 (8)	0.0024 (6)	0.0027 (6)	0.0000 (6)
O9	0.0142 (9)	0.100 (2)	0.0136 (10)	0.0126 (11)	−0.0035 (8)	−0.0176 (12)
O10	0.0133 (8)	0.0181 (7)	0.0172 (9)	−0.0011 (6)	−0.0005 (7)	−0.0052 (6)
O11	0.0118 (7)	0.0214 (8)	0.0180 (9)	0.0024 (6)	−0.0011 (7)	0.0026 (7)
O12	0.0146 (8)	0.0367 (10)	0.0135 (9)	0.0005 (7)	−0.0046 (7)	0.0009 (7)
N1	0.0060 (8)	0.0104 (8)	0.0073 (9)	0.0005 (6)	−0.0002 (7)	0.0003 (8)
N2	0.0049 (7)	0.0120 (8)	0.0063 (9)	−0.0024 (6)	−0.0006 (7)	0.0007 (7)
N3	0.0096 (8)	0.0148 (8)	0.0128 (9)	−0.0006 (6)	−0.0004 (7)	−0.0032 (7)
N4	0.0073 (7)	0.0147 (8)	0.0128 (9)	0.0011 (6)	−0.0003 (7)	−0.0017 (7)
C1	0.0069 (8)	0.0116 (9)	0.0104 (10)	0.0006 (7)	−0.0001 (8)	0.0003 (7)
C2	0.0062 (8)	0.0097 (8)	0.0104 (10)	0.0007 (7)	−0.0001 (8)	−0.0002 (7)
C3	0.0093 (9)	0.0114 (9)	0.0074 (9)	0.0006 (7)	0.0025 (8)	0.0023 (7)
C4	0.0146 (10)	0.0142 (9)	0.0050 (9)	0.0024 (8)	0.0014 (8)	−0.0005 (7)
C5	0.0112 (9)	0.0101 (8)	0.0085 (11)	0.0025 (7)	−0.0005 (8)	−0.0015 (7)
C6	0.0073 (8)	0.0098 (8)	0.0066 (10)	0.0007 (7)	−0.0006 (7)	−0.0004 (7)
C7	0.0064 (8)	0.0090 (8)	0.0113 (10)	0.0007 (6)	0.0007 (8)	−0.0001 (7)
C8	0.0088 (9)	0.0132 (8)	0.0107 (10)	0.0000 (7)	0.0022 (8)	−0.0002 (7)
C9	0.0076 (9)	0.0117 (9)	0.0085 (9)	−0.0009 (7)	−0.0007 (8)	0.0006 (7)
C10	0.0125 (9)	0.0099 (8)	0.0105 (10)	−0.0009 (7)	0.0002 (8)	0.0009 (7)
C11	0.0156 (10)	0.0131 (9)	0.0066 (10)	−0.0028 (8)	−0.0009 (8)	−0.0004 (7)
C12	0.0116 (9)	0.0109 (8)	0.0065 (10)	−0.0032 (8)	0.0019 (8)	−0.0014 (7)
C13	0.0077 (9)	0.0097 (9)	0.0095 (11)	−0.0012 (7)	−0.0009 (8)	0.0021 (7)
C14	0.0107 (9)	0.0079 (8)	0.0105 (10)	−0.0032 (7)	−0.0005 (8)	0.0004 (7)
C15	0.0117 (9)	0.0175 (9)	0.0112 (10)	−0.0023 (8)	−0.0013 (8)	−0.0018 (8)
C16	0.0091 (9)	0.0144 (9)	0.0108 (10)	0.0000 (7)	−0.0008 (8)	−0.0015 (7)
C17	0.0220 (11)	0.0188 (10)	0.0156 (13)	0.0035 (8)	−0.0001 (10)	0.0023 (9)

Geometric parameters (Å, º) top

Cu1—N2	1.926 (2)	N4—C16	1.499 (3)
Cu1—N1	1.972 (2)	N4—H4A	0.86 (3)
Cu1—O5	2.0920 (14)	N4—H4B	0.83 (4)
Cu1—O7	2.0953 (16)	N4—H4C	0.84 (2)
Cu1—O1	2.2775 (17)	C1—C2	1.519 (3)
Cu1—O3	2.3100 (16)	C2—C3	1.390 (3)
O1—C1	1.257 (3)	C3—C4	1.386 (3)
O2—C1	1.253 (3)	C3—H3	0.9300
O3—C7	1.258 (3)	C4—C5	1.392 (3)
O4—C7	1.255 (3)	C4—H4	0.9300
O5—C8	1.261 (3)	C5—C6	1.387 (3)
O6—C8	1.248 (3)	C5—H5	0.9300
O7—C14	1.272 (3)	C6—C7	1.521 (3)
O8—C14	1.245 (3)	C8—C9	1.510 (3)
O9—H9A	0.84 (2)	C9—C10	1.384 (3)
O9—H9B	0.82 (2)	C10—C11	1.395 (3)
O10—H10A	0.78 (4)	C10—H10	0.9300
O10—H10B	0.85 (4)	C11—C12	1.396 (3)
O11—H11A	0.82 (2)	C11—H11	0.9300
O11—H11B	0.82 (4)	C12—C13	1.390 (3)
O12—H12A	0.79 (2)	C12—H12	0.9300
O12—H12B	0.81 (2)	C13—C14	1.523 (3)
N1—C6	1.344 (3)	C15—C16	1.524 (3)
N1—C2	1.345 (3)	C15—H15B	0.9700
N2—C13	1.331 (3)	C15—H15A	0.9700
N2—C9	1.336 (3)	C16—C17	1.523 (3)
N3—C15	1.490 (3)	C16—H16	0.9800
N3—H3A	0.89 (4)	C17—H17B	0.9600
N3—H3B	0.95 (4)	C17—H17C	0.9600
N3—H3C	0.90 (4)	C17—H17A	0.9600

N2—Cu1—N1	176.55 (8)	C3—C4—H4	120.2
N2—Cu1—O5	79.62 (8)	C5—C4—H4	120.2
N1—Cu1—O5	98.27 (8)	C6—C5—C4	118.8 (2)
N2—Cu1—O7	79.21 (8)	C6—C5—H5	120.6
N1—Cu1—O7	103.00 (7)	C4—C5—H5	120.6
O5—Cu1—O7	158.64 (7)	N1—C6—C5	121.3 (2)
N2—Cu1—O1	100.52 (7)	N1—C6—C7	115.1 (2)
N1—Cu1—O1	76.72 (7)	C5—C6—C7	123.6 (2)
O5—Cu1—O1	91.08 (6)	O4—C7—O3	125.6 (2)
O7—Cu1—O1	95.55 (6)	O4—C7—C6	117.6 (2)
N2—Cu1—O3	106.59 (7)	O3—C7—C6	116.74 (18)
N1—Cu1—O3	76.33 (7)	O6—C8—O5	126.1 (2)
O5—Cu1—O3	97.80 (6)	O6—C8—C9	118.2 (2)
O7—Cu1—O3	85.54 (6)	O5—C8—C9	115.73 (19)
O1—Cu1—O3	152.56 (7)	N2—C9—C10	120.2 (2)
C1—O1—Cu1	111.91 (14)	N2—C9—C8	112.7 (2)
C7—O3—Cu1	111.32 (13)	C10—C9—C8	126.90 (19)
C8—O5—Cu1	113.56 (15)	C9—C10—C11	118.5 (2)
C14—O7—Cu1	114.06 (14)	C9—C10—H10	120.7
H9A—O9—H9B	113 (3)	C11—C10—H10	120.7
H10A—O10—H10B	104 (3)	C10—C11—C12	120.1 (2)
H11A—O11—H11B	98 (3)	C10—C11—H11	119.9
H12A—O12—H12B	97 (4)	C12—C11—H11	119.9
C6—N1—C2	120.2 (2)	C13—C12—C11	118.1 (2)
C6—N1—Cu1	120.43 (15)	C13—C12—H12	120.9
C2—N1—Cu1	119.39 (16)	C11—C12—H12	120.9
C13—N2—C9	122.7 (2)	N2—C13—C12	120.4 (2)
C13—N2—Cu1	119.20 (17)	N2—C13—C14	112.2 (2)
C9—N2—Cu1	118.04 (17)	C12—C13—C14	127.39 (19)
C15—N3—H3A	113 (2)	O8—C14—O7	126.5 (2)
C15—N3—H3B	107 (2)	O8—C14—C13	118.4 (2)
H3A—N3—H3B	108 (3)	O7—C14—C13	115.11 (19)
C15—N3—H3C	111 (2)	N3—C15—C16	112.60 (19)
H3A—N3—H3C	108 (3)	N3—C15—H15B	109.1
H3B—N3—H3C	111 (3)	C16—C15—H15B	109.1
C16—N4—H4A	109 (2)	N3—C15—H15A	109.1
C16—N4—H4B	109 (2)	C16—C15—H15A	109.1
H4A—N4—H4B	105 (3)	H15B—C15—H15A	107.8
C16—N4—H4C	112 (2)	N4—C16—C17	109.01 (18)
H4A—N4—H4C	116 (3)	N4—C16—C15	111.34 (17)
H4B—N4—H4C	106 (3)	C17—C16—C15	110.6 (2)
O2—C1—O1	126.1 (2)	N4—C16—H16	108.6
O2—C1—C2	117.73 (19)	C17—C16—H16	108.6
O1—C1—C2	116.18 (19)	C15—C16—H16	108.6
N1—C2—C3	121.4 (2)	C16—C17—H17B	109.5
N1—C2—C1	115.23 (19)	C16—C17—H17C	109.5
C3—C2—C1	123.26 (19)	H17B—C17—H17C	109.5
C4—C3—C2	118.7 (2)	C16—C17—H17A	109.5
C4—C3—H3	120.6	H17B—C17—H17A	109.5
C2—C3—H3	120.6	H17C—C17—H17A	109.5
C3—C4—C5	119.6 (2)

N2—Cu1—O1—C1	−171.17 (16)	O1—C1—C2—C3	−174.4 (2)
N1—Cu1—O1—C1	6.72 (15)	N1—C2—C3—C4	−0.8 (3)
O5—Cu1—O1—C1	−91.53 (16)	C1—C2—C3—C4	174.61 (18)
O7—Cu1—O1—C1	108.80 (15)	C2—C3—C4—C5	0.5 (3)
O3—Cu1—O1—C1	17.8 (2)	C3—C4—C5—C6	0.5 (3)
N2—Cu1—O3—C7	−179.84 (14)	C2—N1—C6—C5	1.1 (3)
N1—Cu1—O3—C7	2.05 (14)	Cu1—N1—C6—C5	−179.91 (16)
O5—Cu1—O3—C7	98.72 (14)	C2—N1—C6—C7	179.27 (18)
O7—Cu1—O3—C7	−102.50 (14)	Cu1—N1—C6—C7	−1.7 (3)
O1—Cu1—O3—C7	−9.0 (2)	C4—C5—C6—N1	−1.3 (3)
N2—Cu1—O5—C8	5.37 (15)	C4—C5—C6—C7	−179.37 (18)
N1—Cu1—O5—C8	−171.87 (15)	Cu1—O3—C7—O4	175.85 (16)
O7—Cu1—O5—C8	13.2 (3)	Cu1—O3—C7—C6	−3.5 (2)
O1—Cu1—O5—C8	−95.13 (15)	N1—C6—C7—O4	−175.73 (19)
O3—Cu1—O5—C8	110.91 (15)	C5—C6—C7—O4	2.4 (3)
N2—Cu1—O7—C14	4.09 (14)	N1—C6—C7—O3	3.6 (3)
N1—Cu1—O7—C14	−178.60 (14)	C5—C6—C7—O3	−178.2 (2)
O5—Cu1—O7—C14	−3.7 (3)	Cu1—O5—C8—O6	175.81 (18)
O1—Cu1—O7—C14	103.77 (14)	Cu1—O5—C8—C9	−5.7 (2)
O3—Cu1—O7—C14	−103.75 (15)	C13—N2—C9—C10	−0.5 (3)
O5—Cu1—N1—C6	−96.10 (17)	Cu1—N2—C9—C10	176.89 (15)
O7—Cu1—N1—C6	82.02 (18)	C13—N2—C9—C8	−175.35 (18)
O1—Cu1—N1—C6	174.75 (19)	Cu1—N2—C9—C8	2.1 (2)
O3—Cu1—N1—C6	−0.02 (16)	O6—C8—C9—N2	−178.67 (19)
O5—Cu1—N1—C2	82.93 (17)	O5—C8—C9—N2	2.7 (3)
O7—Cu1—N1—C2	−98.95 (17)	O6—C8—C9—C10	6.9 (3)
O1—Cu1—N1—C2	−6.22 (16)	O5—C8—C9—C10	−171.7 (2)
O3—Cu1—N1—C2	179.00 (18)	N2—C9—C10—C11	−0.5 (3)
O5—Cu1—N2—C13	173.65 (16)	C8—C9—C10—C11	173.5 (2)
O7—Cu1—N2—C13	−3.47 (15)	C9—C10—C11—C12	0.7 (3)
O1—Cu1—N2—C13	−97.18 (16)	C10—C11—C12—C13	0.1 (3)
O3—Cu1—N2—C13	78.52 (16)	C9—N2—C13—C12	1.4 (3)
O5—Cu1—N2—C9	−3.87 (15)	Cu1—N2—C13—C12	−176.00 (16)
O7—Cu1—N2—C9	179.02 (16)	C9—N2—C13—C14	179.81 (18)
O1—Cu1—N2—C9	85.30 (16)	Cu1—N2—C13—C14	2.4 (2)
O3—Cu1—N2—C9	−99.00 (16)	C11—C12—C13—N2	−1.2 (3)
Cu1—O1—C1—O2	175.48 (17)	C11—C12—C13—C14	−179.30 (19)
Cu1—O1—C1—C2	−6.0 (2)	Cu1—O7—C14—O8	175.91 (17)
C6—N1—C2—C3	0.0 (3)	Cu1—O7—C14—C13	−4.0 (2)
Cu1—N1—C2—C3	−179.01 (15)	N2—C13—C14—O8	−178.59 (18)
C6—N1—C2—C1	−175.74 (18)	C12—C13—C14—O8	−0.3 (3)
Cu1—N1—C2—C1	5.2 (2)	N2—C13—C14—O7	1.3 (3)
O2—C1—C2—N1	179.95 (19)	C12—C13—C14—O7	179.6 (2)
O1—C1—C2—N1	1.3 (3)	N3—C15—C16—N4	−61.9 (2)
O2—C1—C2—C3	4.3 (3)	N3—C15—C16—C17	176.67 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O11ⁱ	0.93	2.59	3.476 (3)	160
C11—H11···O7ⁱⁱ	0.93	2.56	3.301 (3)	137
C15—H15A···O8ⁱⁱⁱ	0.97	2.30	3.245 (3)	165
C16—H16···O5^iv	0.98	2.53	3.321 (3)	138
N3—H3A···O6^iv	0.89 (4)	1.93 (4)	2.812 (3)	170 (3)
N3—H3B···O11	0.95 (4)	1.88 (4)	2.773 (3)	155 (3)
N3—H3C···O2	0.90 (4)	1.91 (4)	2.794 (2)	167 (4)
N4—H4A···O10^iv	0.86 (3)	1.94 (3)	2.786 (3)	165 (3)
N4—H4B···O12	0.83 (4)	2.00 (4)	2.811 (3)	165 (3)
N4—H4C···O4^v	0.84 (2)	2.01 (2)	2.829 (3)	167 (3)
O9—H9A···O1	0.84 (2)	1.93 (2)	2.739 (3)	163 (3)
O9—H9B···O4^vi	0.82 (2)	2.04 (2)	2.826 (3)	160 (3)
O10—H10A···O9	0.78 (4)	1.97 (4)	2.731 (3)	164 (4)
O10—H10B···O8^v	0.85 (4)	1.88 (4)	2.724 (3)	170 (3)
O11—H11A···O3^v	0.82 (2)	2.41 (3)	3.080 (2)	140 (3)
O11—H11A···O7^v	0.82 (2)	2.30 (3)	2.957 (2)	138 (3)
O11—H11B···O10	0.82 (4)	1.98 (4)	2.781 (3)	169 (3)
O12—H12A···O2^vii	0.79 (2)	1.99 (2)	2.770 (3)	170 (3)
O12—H12B···O6^iv	0.81 (2)	2.09 (3)	2.786 (2)	144 (3)

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

Experimental details

Crystal data
Chemical formula	(C₃H₁₂N₂)[Cu(C₇H₃NO₄)₂]·4H₂O
M_r	541.97
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	120
a, b, c (Å)	20.919 (4), 8.2015 (16), 12.739 (3)
V (Å³)	2185.6 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.50 × 0.40 × 0.35

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)
T_min, T_max	0.602, 0.684
No. of measured, independent and observed [I > 2σ(I)] reflections	9693, 5040, 4803
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.075, 1.09
No. of reflections	5040
No. of parameters	350
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.52
Absolute structure	Flack (1983), 1969 Friedel pairs
Absolute structure parameter	−0.001 (10)

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O11ⁱ	0.93	2.59	3.476 (3)	160
C11—H11···O7ⁱⁱ	0.93	2.56	3.301 (3)	137
C15—H15A···O8ⁱⁱⁱ	0.97	2.30	3.245 (3)	165
C16—H16···O5^iv	0.98	2.53	3.321 (3)	138
N3—H3A···O6^iv	0.89 (4)	1.93 (4)	2.812 (3)	170 (3)
N3—H3B···O11	0.95 (4)	1.88 (4)	2.773 (3)	155 (3)
N3—H3C···O2	0.90 (4)	1.91 (4)	2.794 (2)	167 (4)
N4—H4A···O10^iv	0.86 (3)	1.94 (3)	2.786 (3)	165 (3)
N4—H4B···O12	0.83 (4)	2.00 (4)	2.811 (3)	165 (3)
N4—H4C···O4^v	0.84 (2)	2.01 (2)	2.829 (3)	167 (3)
O9—H9A···O1	0.84 (2)	1.93 (2)	2.739 (3)	163 (3)
O9—H9B···O4^vi	0.82 (2)	2.04 (2)	2.826 (3)	160 (3)
O10—H10A···O9	0.78 (4)	1.97 (4)	2.731 (3)	164 (4)
O10—H10B···O8^v	0.85 (4)	1.88 (4)	2.724 (3)	170 (3)
O11—H11A···O3^v	0.82 (2)	2.41 (3)	3.080 (2)	140 (3)
O11—H11A···O7^v	0.82 (2)	2.30 (3)	2.957 (2)	138 (3)
O11—H11B···O10	0.82 (4)	1.98 (4)	2.781 (3)	169 (3)
O12—H12A···O2^vii	0.79 (2)	1.989 (19)	2.770 (3)	170 (3)
O12—H12B···O6^iv	0.81 (2)	2.09 (3)	2.786 (2)	144 (3)

Acknowledgements

We are grateful to Tarbiat Moallem University for financial support.

References

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