Aqua­(4-hydroxy­pyridine-2,6-dicarboxyl­ato)(1,10-phenanothroline)copper(II) 4.5-hydrate

Aghabozorg, H.; Motyeian, E.; Soleimannejad, J.; Ghadermazi, M.; Attar Gharamaleki, J.

doi:10.1107/S1600536807067207

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Pages m252-m253

https://doi.org/10.1107/S1600536807067207

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Aqua(4-hydroxypyridine-2,6-dicarboxylato)(1,10-phenanothroline)copper(II) 4.5-hydrate

Hossein Aghabozorg,^a ^* Elham Motyeian,^a Janet Soleimannejad,^b Mohammad Ghadermazi ^c and Jafar Attar Gharamaleki ^a

^aFaculty of Chemistry, Teacher Training University, 49 Mofateh Avenue 15614, Tehran, Iran, ^bFaculty of Science, Department of Chemistry, Ilam University, Ilam, Iran, and ^cDepartment of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Iran
^*Correspondence e-mail: haghabozorg@yahoo.com

(Received 22 November 2007; accepted 16 December 2007; online 21 December 2007)

The title compound, [Cu(C₇H₃NO₅)(C₁₂H₈N₂)(H₂O)]·4.5H₂O or [Cu(hypydc)(phen)(H₂O)]·4.5H₂O (phen is 1,10-phenanthroline and hypydcH₂ is 4-hydroxypyridine-2,6-dicarboxylic acid), was obtained by the reaction of copper(II) nitrate hexahydrate with the proton-transfer compound (phenH)₂(hypydc) in aqueous solution. Both the cationic and the anionic fragments of the proton-transfer compound are involved in complexation. Each Cu^II atom has a distorted octahedral geometry. It is hexacoordinated by three O atoms and three N atoms, from one phen fragment (as bidentate ligand), one (hypydc)²⁻ unit (as tridentate ligand) and a water molecule. In the crystal structure, O—H⋯O and C—H⋯O hydrogen bonds, and π–π stacking interactions [centroid-to-centroid distance 3.5642 (11) Å] between the phen ring systems, contribute to the formation of a three-dimensional 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

[Cu(C₇H₃NO₅)(C₁₂H₈N₂)(H₂O)]·4.5H₂O
M_r = 523.94
Orthorhombic, F d d 2
a = 18.686 (4) Å
b = 44.033 (8) Å
c = 10.3812 (18) Å
V = 8542 (3) Å³
Z = 16
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 296 (2) K
0.34 × 0.24 × 0.12 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.709, T_max = 0.881
59661 measured reflections
10800 independent reflections
9609 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.066
S = 1.01
10800 reflections
300 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), with 4504 Friedel pairs
Flack parameter: 0.007 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O5W	0.85	1.73	2.5771 (14)	174
O6—H6D⋯O1ⁱ	0.85	1.88	2.7059 (12)	162
O6—H6C⋯O4ⁱⁱ	0.85	1.76	2.6048 (11)	174
O1W—H1C⋯O1ⁱⁱⁱ	0.85	1.97	2.8154 (12)	171
O2W—H2C⋯O3^iv	0.85	2.37	3.1062 (16)	145
O2W—H2D⋯O4W	0.85	1.90	2.7470 (16)	172
O3W—H3D⋯O2^v	0.85	1.93	2.7757 (13)	175
O3W—H3C⋯O4	0.85	1.90	2.7496 (13)	175
O4W—H4D⋯O3W	0.85	1.84	2.6834 (15)	171
O4W—H4C⋯O5ⁱ	0.85	2.26	3.0835 (16)	165
O5W—H5C⋯O1W	0.85	2.03	2.8604 (15)	164
O5W—H5D⋯O2W^vi	0.85	1.91	2.7204 (15)	159
C1—H1⋯O5^vii	0.93	2.41	3.1610 (18)	137
C3—H3⋯O3^viii	0.93	2.25	3.130 (2)	158
C8—H8⋯O3W^ix	0.93	2.42	3.315 (2)	161
C10—H10⋯O6	0.93	2.50	2.9995 (17)	114
C10—H10⋯O5W^x	0.93	2.42	3.1809 (19)	139
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, z-1; (iv) $[x-{\script{1\over 4}}, -y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (v) x, y, z-1; (vi) $[-x+{\script{3\over 4}}, y-{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (vii) -x+1, -y, z; (viii) $[x+{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (ix) $[x-{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{3\over 4}}]$ ; (x) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807067207/su2032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807067207/su2032Isup2.hkl

checkCIF report

Comment top

Non-covalent interactions, including hydrogen bonds, are of great importance in stabilizing structures in the solid state. We have synthesized several proton transfer compounds, some with remaining sites as electron donors that can coordinate to metal ions (Aghabozorg, Attar Gharamaleki, Ghadermazi et al., 2007; Aghabozorg, Attar Gharamaleki, Ghasemikhah et al., 2007; Aghabozorg, Daneshvar et al., 2007 and references therein). A wide range of different hydrogen bonds were observed in these compounds and water molecules of crystallization were also involved in hydrogen bonding. Here, we report on the synthesis and crystal structure of the title compound, (I).

The title complex crystallizes in the orthorhombic space group Fdd2, with sixteen molecules in the unit cell. The molecular structure is shown in Fig. 1. Both the cationic and anionic fragments of the starting proton transfer compound are involved in complexation. Each Cu^II atom has a distorted octahedral geometry. It is coordinated by one 1,10-phenanthroline ligand, (phen as bidentate ligand), one 4-hydroxypyridine-2,6-dicarboxylate group, [(hypydc)^2- as a tridentate ligand] and one coordinated water molecule. The axial bond lengths, Cu1—O2 and Cu1—O3 [2.3679 (9) and 2.3205 (11) Å, respectively] are longer than the equitoral metal-ligand bond lengths [1.9996 (8) - 2.0370 (9) Å], probabaly due to the Jahn-Teller effect. The dihedral angle between the planes passing through the (hypydc)^2– and (phen) fragments is 83.41 (4)°, indicating that these to units are almost perpendicular to one another.

In the crystal weak π-π stacking interactions [3.5642 (11) Å [1/4 + x, 1/4 - y, 1/4 + z] between the aromatic rings of the coordinated (phen) fragments are present (Fig. 2). The water molecules of crystallization are involved in the formation of hydrogen bonds, forming chains (Fig. 3 and Table 1). O—H···O and C—H···O hydrogen bonds, ion pairing and π–π stacking interactions all contribute to the formation of a supramolecular structure (Fig. 4).

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

The proton transfer compound, (phenH)₂(hypydc), was prepared by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid, hypydcH₂, with 1,10-phenanthroline, (phen). Cu(NO₃)₂.6H₂O (125 mg, 0.5 mmol) in water (20 ml) and the proton transfer compound, (phenH)₂(hypydc) (500 mg, 1.0 mmol) in water (20 ml), in a 1:2 molar ratio, were mixed. Blue crystals of (I) were obtained by the slow evaporation at room temperature.

Structure description top

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

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL (Bruker, 2005).

Figures top

	Fig. 1. The molecular structure of compound (I), showing the atom numbering scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A view of the π-π stacking interactions between the aromatic rings of the 1,10-phenanthroline (phen) fragments with distances of 3.5639 (11) Å [1/4 + x, 1/4 - y, 1/4 + z].
	Fig. 3. A view of the chain of hydrogen bonded water mlecules in compound (I) with hydrogen bonds shown as dashed lines.
	Fig. 4. The crystal packing of compound (I), with hydrogen bonds shown as dashed lines.

Aqua(4-hydroxypyridine-2,6-dicarboxylato)(1,10-phenanothroline)copper(II) 4.5-hydrate top

Crystal data top

[Cu(C₇H₃NO₅)(C₁₂H₈N₂)(H₂O)]·4.5H₂O	F(000) = 4320
M_r = 523.94	D_x = 1.630 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 30613 reflections
a = 18.686 (4) Å	θ = 2.3–36.4°
b = 44.033 (8) Å	µ = 1.09 mm⁻¹
c = 10.3812 (18) Å	T = 296 K
V = 8542 (3) Å³	Block, pale-blue
Z = 16	0.34 × 0.24 × 0.12 mm

Data collection top

Bruker SMART 1000 diffractometer	10800 independent reflections
Radiation source: fine-focus sealed tube	9609 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 100 pixels mm^-1	θ_max = 38.6°, θ_min = 1.9°
ω scans	h = −30→31
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −72→69
T_min = 0.709, T_max = 0.881	l = −17→17
59661 measured reflections

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0367P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.002
10800 reflections	Δρ_max = 0.50 e Å⁻³
300 parameters	Δρ_min = −0.33 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 4504 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.007 (4)

Crystal data top

[Cu(C₇H₃NO₅)(C₁₂H₈N₂)(H₂O)]·4.5H₂O	V = 8542 (3) Å³
M_r = 523.94	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 18.686 (4) Å	µ = 1.09 mm⁻¹
b = 44.033 (8) Å	T = 296 K
c = 10.3812 (18) Å	0.34 × 0.24 × 0.12 mm

Data collection top

Bruker SMART 1000 diffractometer	10800 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	9609 reflections with I > 2σ(I)
T_min = 0.709, T_max = 0.881	R_int = 0.032
59661 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.066	Δρ_max = 0.50 e Å⁻³
S = 1.01	Δρ_min = −0.33 e Å⁻³
10800 reflections	Absolute structure: Flack (1983), 4504 Friedel pairs
300 parameters	Absolute structure parameter: 0.007 (4)
1 restraint

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
Cu1	0.260204 (6)	0.052661 (3)	1.031738 (12)	0.01475 (3)
N1	0.33349 (5)	0.086905 (19)	1.03093 (10)	0.02096 (15)
N2	0.19432 (5)	0.08711 (2)	1.07530 (9)	0.01972 (16)
N3	0.32981 (5)	0.019941 (19)	0.98387 (8)	0.01433 (14)
O1	0.37788 (5)	−0.00342 (2)	1.29870 (8)	0.02511 (17)
O2	0.29904 (5)	0.03122 (2)	1.22904 (7)	0.02473 (16)
O3	0.26351 (6)	0.054290 (19)	0.80826 (9)	0.02719 (19)
O4	0.30653 (5)	0.026752 (19)	0.64661 (7)	0.02505 (17)
O5	0.47567 (5)	−0.04570 (2)	0.88292 (8)	0.02523 (17)
H5A	0.4872	−0.0449	0.8038	0.030*
O6	0.17682 (4)	0.024272 (16)	1.02325 (8)	0.01793 (12)
H6D	0.1690	0.0174	0.9480	0.022*
H6C	0.1854	0.0080	1.0643	0.022*
C1	0.40278 (7)	0.08587 (3)	1.00820 (13)	0.0302 (3)
H1	0.4249	0.0670	1.0000	0.036*
C2	0.44453 (9)	0.11231 (4)	0.99596 (15)	0.0413 (4)
H2	0.4934	0.1109	0.9799	0.050*
C3	0.41253 (9)	0.14022 (3)	1.00797 (14)	0.0401 (4)
H3	0.4394	0.1579	0.9992	0.048*
C4	0.33932 (8)	0.14188 (3)	1.03349 (13)	0.0307 (2)
C5	0.29961 (11)	0.16990 (3)	1.05229 (13)	0.0414 (4)
H5	0.3235	0.1884	1.0460	0.050*
C6	0.22947 (10)	0.16978 (3)	1.07841 (15)	0.0397 (4)
H6	0.2059	0.1882	1.0906	0.048*
C7	0.18977 (8)	0.14200 (3)	1.08811 (12)	0.0312 (3)
C8	0.11568 (10)	0.14002 (4)	1.11384 (15)	0.0404 (4)
H8	0.0889	0.1575	1.1272	0.048*
C9	0.08381 (8)	0.11233 (4)	1.11891 (14)	0.0357 (3)
H9	0.0351	0.1108	1.1360	0.043*
C10	0.12452 (7)	0.08614 (3)	1.09834 (12)	0.0265 (2)
H10	0.1019	0.0673	1.1009	0.032*
C11	0.22684 (7)	0.11447 (2)	1.07039 (11)	0.0222 (2)
C12	0.30164 (6)	0.11451 (2)	1.04432 (10)	0.02191 (19)
C13	0.34558 (6)	0.01134 (3)	1.21286 (9)	0.01798 (18)
C14	0.36451 (5)	0.00388 (2)	1.07388 (9)	0.01544 (16)
C15	0.41397 (5)	−0.01821 (2)	1.04245 (10)	0.01813 (17)
H15	0.4377	−0.0290	1.1065	0.022*
C16	0.42769 (5)	−0.02401 (2)	0.91269 (10)	0.01755 (17)
C17	0.39083 (6)	−0.00763 (2)	0.81932 (10)	0.01653 (16)
H17	0.3987	−0.0112	0.7322	0.020*
C18	0.34222 (6)	0.01404 (2)	0.85910 (9)	0.01394 (16)
C19	0.30013 (6)	0.03315 (2)	0.76368 (9)	0.01689 (17)
O1W	0.5000	0.0000	0.45689 (13)	0.0277 (2)*
H1C	0.5384	0.0026	0.4143	0.033*
O2W	0.13216 (6)	0.15930 (2)	0.41663 (14)	0.0457 (3)
H2C	0.0889	0.1635	0.4349	0.055*
H2D	0.1336	0.1403	0.4299	0.055*
O3W	0.24433 (5)	0.05872 (2)	0.44855 (9)	0.02822 (19)
H3D	0.2586	0.0500	0.3801	0.034*
H3C	0.2628	0.0496	0.5126	0.034*
O4W	0.13298 (7)	0.09704 (2)	0.43343 (14)	0.0474 (3)
H4D	0.1683	0.0853	0.4474	0.057*
H4C	0.0974	0.0857	0.4167	0.057*
O5W	0.51596 (5)	−0.04686 (2)	0.64555 (9)	0.03011 (19)
H5C	0.5200	−0.0331	0.5886	0.036*
H5D	0.5500	−0.0593	0.6321	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01572 (5)	0.01249 (5)	0.01605 (5)	0.00093 (4)	0.00172 (5)	−0.00189 (4)
N1	0.0232 (4)	0.0187 (4)	0.0210 (4)	−0.0040 (3)	0.0044 (4)	−0.0048 (3)
N2	0.0230 (4)	0.0173 (4)	0.0189 (4)	0.0048 (3)	0.0015 (3)	−0.0016 (3)
N3	0.0163 (4)	0.0136 (3)	0.0131 (3)	0.0001 (3)	0.0000 (3)	−0.0003 (3)
O1	0.0224 (4)	0.0370 (5)	0.0159 (4)	0.0013 (3)	−0.0015 (3)	0.0065 (3)
O2	0.0276 (4)	0.0306 (4)	0.0161 (3)	0.0069 (3)	0.0018 (3)	−0.0014 (3)
O3	0.0394 (5)	0.0240 (4)	0.0181 (4)	0.0176 (3)	−0.0018 (3)	−0.0007 (3)
O4	0.0408 (5)	0.0205 (4)	0.0138 (3)	0.0097 (3)	−0.0028 (3)	−0.0010 (3)
O5	0.0265 (4)	0.0256 (4)	0.0236 (4)	0.0144 (3)	0.0046 (3)	0.0027 (3)
O6	0.0200 (3)	0.0177 (3)	0.0161 (3)	−0.0011 (2)	−0.0013 (3)	0.0014 (3)
C1	0.0249 (5)	0.0303 (6)	0.0355 (7)	−0.0083 (4)	0.0074 (5)	−0.0087 (5)
C2	0.0321 (7)	0.0500 (9)	0.0418 (8)	−0.0241 (6)	0.0079 (6)	−0.0082 (6)
C3	0.0560 (9)	0.0340 (7)	0.0305 (7)	−0.0281 (6)	0.0005 (6)	−0.0032 (5)
C4	0.0498 (7)	0.0198 (5)	0.0224 (5)	−0.0125 (4)	−0.0037 (5)	−0.0018 (4)
C5	0.0805 (12)	0.0144 (5)	0.0292 (7)	−0.0099 (6)	−0.0146 (6)	0.0009 (4)
C6	0.0702 (11)	0.0155 (5)	0.0333 (6)	0.0079 (6)	−0.0147 (7)	−0.0050 (4)
C7	0.0498 (8)	0.0179 (5)	0.0258 (5)	0.0117 (5)	−0.0070 (5)	−0.0043 (4)
C8	0.0524 (9)	0.0340 (7)	0.0347 (7)	0.0262 (7)	−0.0054 (6)	−0.0075 (5)
C9	0.0300 (7)	0.0421 (8)	0.0352 (7)	0.0180 (6)	0.0017 (5)	−0.0053 (6)
C10	0.0229 (5)	0.0303 (6)	0.0264 (5)	0.0083 (4)	0.0028 (4)	−0.0017 (4)
C11	0.0333 (6)	0.0153 (4)	0.0181 (4)	0.0040 (4)	−0.0016 (4)	−0.0024 (3)
C12	0.0327 (5)	0.0158 (4)	0.0173 (4)	−0.0043 (4)	−0.0003 (4)	−0.0026 (3)
C13	0.0176 (5)	0.0235 (5)	0.0129 (4)	−0.0025 (4)	0.0001 (3)	0.0006 (3)
C14	0.0147 (4)	0.0165 (4)	0.0151 (4)	−0.0011 (3)	−0.0001 (3)	0.0017 (3)
C15	0.0165 (4)	0.0202 (4)	0.0178 (4)	0.0027 (3)	−0.0002 (3)	0.0043 (3)
C16	0.0164 (4)	0.0159 (4)	0.0204 (4)	0.0031 (3)	0.0015 (3)	0.0024 (3)
C17	0.0174 (4)	0.0158 (4)	0.0163 (4)	0.0019 (3)	0.0010 (3)	−0.0001 (3)
C18	0.0166 (4)	0.0118 (4)	0.0135 (4)	0.0005 (3)	−0.0009 (3)	0.0002 (3)
C19	0.0220 (4)	0.0132 (4)	0.0155 (4)	0.0028 (3)	−0.0021 (3)	0.0006 (3)
O2W	0.0372 (6)	0.0250 (5)	0.0747 (8)	0.0000 (4)	0.0068 (6)	−0.0087 (5)
O3W	0.0340 (5)	0.0279 (4)	0.0227 (4)	0.0101 (3)	0.0024 (3)	0.0032 (3)
O4W	0.0441 (7)	0.0248 (5)	0.0735 (9)	0.0095 (4)	−0.0168 (6)	−0.0081 (5)
O5W	0.0278 (5)	0.0364 (5)	0.0262 (4)	0.0049 (4)	0.0036 (3)	−0.0030 (3)

Geometric parameters (Å, º) top

Cu1—O6	1.9996 (8)	C5—H5	0.9300
Cu1—N3	2.0036 (9)	C6—C7	1.434 (2)
Cu1—N2	2.0052 (9)	C6—H6	0.9300
Cu1—N1	2.0370 (9)	C7—C11	1.4082 (16)
Cu1—O3	2.3219 (10)	C7—C8	1.413 (2)
Cu1—O2	2.3693 (9)	C8—C9	1.358 (3)
N1—C1	1.3168 (16)	C8—H8	0.9300
N1—C12	1.3604 (14)	C9—C10	1.3979 (17)
N2—C10	1.3267 (16)	C9—H9	0.9300
N2—C11	1.3505 (15)	C10—H10	0.9300
N3—C14	1.3392 (13)	C11—C12	1.4237 (17)
N3—C18	1.3412 (12)	C13—C14	1.5213 (14)
O1—C13	1.2572 (13)	C14—C15	1.3810 (14)
O2—C13	1.2453 (14)	C15—C16	1.3948 (15)
O3—C19	1.2445 (12)	C15—H15	0.9300
O4—C19	1.2533 (12)	C16—C17	1.3906 (14)
O5—C16	1.3460 (13)	C17—C18	1.3806 (14)
O5—H5A	0.8500	C17—H17	0.9300
O6—H6D	0.8500	C18—C19	1.5194 (14)
O6—H6C	0.8500	O1W—H1C	0.8500
C1—C2	1.4072 (18)	O2W—H2C	0.8501
C1—H1	0.9300	O2W—H2D	0.8501
C2—C3	1.372 (3)	O3W—H3D	0.8500
C2—H2	0.9300	O3W—H3C	0.8500
C3—C4	1.395 (2)	O4W—H4D	0.8501
C3—H3	0.9300	O4W—H4C	0.8498
C4—C12	1.4005 (15)	O5W—H5C	0.8501
C4—C5	1.453 (2)	O5W—H5D	0.8499
C5—C6	1.338 (3)

O6—Cu1—N3	92.60 (4)	C5—C6—H6	119.2
O6—Cu1—N2	90.26 (4)	C7—C6—H6	119.2
N3—Cu1—N2	176.79 (4)	C11—C7—C8	116.97 (13)
O6—Cu1—N1	170.57 (3)	C11—C7—C6	118.07 (14)
N3—Cu1—N1	95.44 (4)	C8—C7—C6	124.96 (13)
N2—Cu1—N1	81.59 (4)	C9—C8—C7	119.51 (12)
O6—Cu1—O3	89.77 (4)	C9—C8—H8	120.2
N3—Cu1—O3	75.95 (3)	C7—C8—H8	120.2
N2—Cu1—O3	102.61 (3)	C8—C9—C10	119.75 (14)
N1—Cu1—O3	87.43 (4)	C8—C9—H9	120.1
O6—Cu1—O2	91.59 (3)	C10—C9—H9	120.1
N3—Cu1—O2	74.28 (3)	N2—C10—C9	122.41 (13)
N2—Cu1—O2	107.13 (4)	N2—C10—H10	118.8
N1—Cu1—O2	95.31 (4)	C9—C10—H10	118.8
O3—Cu1—O2	150.22 (3)	N2—C11—C7	122.80 (12)
C1—N1—C12	118.64 (10)	N2—C11—C12	116.73 (9)
C1—N1—Cu1	129.51 (8)	C7—C11—C12	120.46 (11)
C12—N1—Cu1	111.52 (7)	N1—C12—C4	122.74 (12)
C10—N2—C11	118.55 (10)	N1—C12—C11	116.62 (9)
C10—N2—Cu1	128.30 (9)	C4—C12—C11	120.64 (11)
C11—N2—Cu1	112.97 (8)	O2—C13—O1	127.08 (10)
C14—N3—C18	119.19 (9)	O2—C13—C14	116.23 (9)
C14—N3—Cu1	121.39 (7)	O1—C13—C14	116.69 (10)
C18—N3—Cu1	119.41 (7)	N3—C14—C15	122.08 (9)
C13—O2—Cu1	112.17 (7)	N3—C14—C13	115.80 (9)
C19—O3—Cu1	111.29 (7)	C15—C14—C13	122.12 (9)
C16—O5—H5A	111.1	C14—C15—C16	118.69 (9)
Cu1—O6—H6D	113.4	C14—C15—H15	120.7
Cu1—O6—H6C	111.0	C16—C15—H15	120.7
H6D—O6—H6C	101.1	O5—C16—C17	122.54 (10)
N1—C1—C2	122.19 (13)	O5—C16—C15	118.30 (9)
N1—C1—H1	118.9	C17—C16—C15	119.16 (9)
C2—C1—H1	118.9	C18—C17—C16	118.41 (9)
C3—C2—C1	119.41 (15)	C18—C17—H17	120.8
C3—C2—H2	120.3	C16—C17—H17	120.8
C1—C2—H2	120.3	N3—C18—C17	122.45 (9)
C2—C3—C4	119.43 (12)	N3—C18—C19	115.64 (8)
C2—C3—H3	120.3	C17—C18—C19	121.90 (9)
C4—C3—H3	120.3	O3—C19—O4	125.54 (10)
C3—C4—C12	117.59 (12)	O3—C19—C18	117.16 (9)
C3—C4—C5	124.80 (12)	O4—C19—C18	117.27 (9)
C12—C4—C5	117.60 (13)	H2C—O2W—H2D	102.1
C6—C5—C4	121.61 (12)	H3D—O3W—H3C	108.3
C6—C5—H5	119.2	H4D—O4W—H4C	106.6
C4—C5—H5	119.2	H5C—O5W—H5D	106.2
C5—C6—C7	121.61 (13)

O6—Cu1—N1—C1	−149.7 (2)	C7—C8—C9—C10	−0.2 (2)
N3—Cu1—N1—C1	−1.22 (12)	C11—N2—C10—C9	−0.67 (18)
N2—Cu1—N1—C1	−179.99 (13)	Cu1—N2—C10—C9	−175.40 (10)
O3—Cu1—N1—C1	−76.84 (12)	C8—C9—C10—N2	0.9 (2)
O2—Cu1—N1—C1	73.44 (12)	C10—N2—C11—C7	−0.28 (16)
O6—Cu1—N1—C12	23.5 (3)	Cu1—N2—C11—C7	175.23 (9)
N3—Cu1—N1—C12	171.95 (8)	C10—N2—C11—C12	−179.47 (11)
N2—Cu1—N1—C12	−6.81 (8)	Cu1—N2—C11—C12	−3.95 (13)
O3—Cu1—N1—C12	96.34 (8)	C8—C7—C11—N2	0.96 (17)
O2—Cu1—N1—C12	−113.39 (8)	C6—C7—C11—N2	−178.83 (11)
O6—Cu1—N2—C10	5.57 (10)	C8—C7—C11—C12	−179.88 (12)
N3—Cu1—N2—C10	158.3 (7)	C6—C7—C11—C12	0.32 (17)
N1—Cu1—N2—C10	−179.17 (11)	C1—N1—C12—C4	0.74 (18)
O3—Cu1—N2—C10	95.39 (10)	Cu1—N1—C12—C4	−173.26 (9)
O2—Cu1—N2—C10	−86.17 (10)	C1—N1—C12—C11	−179.24 (11)
O6—Cu1—N2—C11	−169.41 (8)	Cu1—N1—C12—C11	6.76 (13)
N3—Cu1—N2—C11	−16.7 (7)	C3—C4—C12—N1	−0.05 (19)
N1—Cu1—N2—C11	5.85 (8)	C5—C4—C12—N1	−178.80 (11)
O3—Cu1—N2—C11	−79.58 (8)	C3—C4—C12—C11	179.93 (12)
O2—Cu1—N2—C11	98.86 (8)	C5—C4—C12—C11	1.18 (18)
O6—Cu1—N3—C14	−93.65 (8)	N2—C11—C12—N1	−2.01 (16)
N2—Cu1—N3—C14	113.7 (7)	C7—C11—C12—N1	178.79 (10)
N1—Cu1—N3—C14	91.27 (8)	N2—C11—C12—C4	178.01 (10)
O3—Cu1—N3—C14	177.24 (8)	C7—C11—C12—C4	−1.19 (17)
O2—Cu1—N3—C14	−2.73 (7)	Cu1—O2—C13—O1	177.76 (10)
O6—Cu1—N3—C18	86.62 (8)	Cu1—O2—C13—C14	−3.11 (12)
N2—Cu1—N3—C18	−66.1 (7)	C18—N3—C14—C15	1.41 (15)
N1—Cu1—N3—C18	−88.46 (8)	Cu1—N3—C14—C15	−178.33 (7)
O3—Cu1—N3—C18	−2.49 (8)	C18—N3—C14—C13	−178.14 (9)
O2—Cu1—N3—C18	177.53 (8)	Cu1—N3—C14—C13	2.13 (12)
O6—Cu1—O2—C13	95.47 (8)	O2—C13—C14—N3	1.10 (14)
N3—Cu1—O2—C13	3.22 (8)	O1—C13—C14—N3	−179.67 (10)
N2—Cu1—O2—C13	−173.77 (8)	O2—C13—C14—C15	−178.44 (10)
N1—Cu1—O2—C13	−90.96 (8)	O1—C13—C14—C15	0.78 (15)
O3—Cu1—O2—C13	3.16 (12)	N3—C14—C15—C16	−0.40 (15)
O6—Cu1—O3—C19	−86.68 (9)	C13—C14—C15—C16	179.12 (10)
N3—Cu1—O3—C19	6.06 (8)	C14—C15—C16—O5	−179.62 (10)
N2—Cu1—O3—C19	−176.89 (8)	C14—C15—C16—C17	−0.57 (15)
N1—Cu1—O3—C19	102.33 (9)	O5—C16—C17—C18	179.53 (10)
O2—Cu1—O3—C19	6.11 (13)	C15—C16—C17—C18	0.52 (15)
C12—N1—C1—C2	−0.7 (2)	C14—N3—C18—C17	−1.47 (15)
Cu1—N1—C1—C2	172.03 (11)	Cu1—N3—C18—C17	178.27 (8)
N1—C1—C2—C3	0.0 (2)	C14—N3—C18—C19	179.53 (9)
C1—C2—C3—C4	0.7 (2)	Cu1—N3—C18—C19	−0.73 (12)
C2—C3—C4—C12	−0.7 (2)	C16—C17—C18—N3	0.50 (15)
C2—C3—C4—C5	178.00 (14)	C16—C17—C18—C19	179.45 (9)
C3—C4—C5—C6	−178.98 (15)	Cu1—O3—C19—O4	173.59 (10)
C12—C4—C5—C6	−0.3 (2)	Cu1—O3—C19—C18	−8.18 (12)
C4—C5—C6—C7	−0.5 (2)	N3—C18—C19—O3	6.64 (14)
C5—C6—C7—C11	0.5 (2)	C17—C18—C19—O3	−172.37 (10)
C5—C6—C7—C8	−179.23 (14)	N3—C18—C19—O4	−174.98 (10)
C11—C7—C8—C9	−0.7 (2)	C17—C18—C19—O4	6.01 (15)
C6—C7—C8—C9	179.07 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O5W	0.85	1.73	2.5771 (14)	174
O6—H6D···O1ⁱ	0.85	1.88	2.7059 (12)	162
O6—H6C···O4ⁱⁱ	0.85	1.76	2.6048 (11)	174
O1W—H1C···O1ⁱⁱⁱ	0.85	1.97	2.8154 (12)	171
O2W—H2C···O3^iv	0.85	2.37	3.1062 (16)	145
O2W—H2D···O4W	0.85	1.90	2.7470 (16)	172
O3W—H3D···O2^v	0.85	1.93	2.7757 (13)	175
O3W—H3C···O4	0.85	1.90	2.7496 (13)	175
O4W—H4D···O3W	0.85	1.84	2.6834 (15)	171
O4W—H4C···O5ⁱ	0.85	2.26	3.0835 (16)	165
O5W—H5C···O1W	0.85	2.03	2.8604 (15)	164
O5W—H5D···O2W^vi	0.85	1.91	2.7204 (15)	159
C1—H1···O5^vii	0.93	2.41	3.1610 (18)	137
C3—H3···O3^viii	0.93	2.25	3.130 (2)	158
C8—H8···O3W^ix	0.93	2.42	3.315 (2)	161
C10—H10···O6	0.93	2.50	2.9995 (17)	114
C10—H10···O5Wⁱⁱ	0.93	2.42	3.1809 (19)	139

Symmetry codes: (i) −x+1/2, −y, z−1/2; (ii) −x+1/2, −y, z+1/2; (iii) −x+1, −y, z−1; (iv) x−1/4, −y+1/4, z−1/4; (v) x, y, z−1; (vi) −x+3/4, y−1/4, z+1/4; (vii) −x+1, −y, z; (viii) x+1/4, −y+1/4, z+1/4; (ix) x−1/4, −y+1/4, z+3/4.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₃NO₅)(C₁₂H₈N₂)(H₂O)]·4.5H₂O
M_r	523.94
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	296
a, b, c (Å)	18.686 (4), 44.033 (8), 10.3812 (18)
V (Å³)	8542 (3)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.34 × 0.24 × 0.12

Data collection
Diffractometer	Bruker SMART 1000
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.709, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	59661, 10800, 9609
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.878

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.066, 1.01
No. of reflections	10800
No. of parameters	300
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.33
Absolute structure	Flack (1983), 4504 Friedel pairs
Absolute structure parameter	0.007 (4)

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O5W	0.85	1.73	2.5771 (14)	174
O6—H6D···O1ⁱ	0.85	1.88	2.7059 (12)	162
O6—H6C···O4ⁱⁱ	0.85	1.76	2.6048 (11)	174
O1W—H1C···O1ⁱⁱⁱ	0.85	1.97	2.8154 (12)	171
O2W—H2C···O3^iv	0.85	2.37	3.1062 (16)	145
O2W—H2D···O4W	0.85	1.90	2.7470 (16)	172
O3W—H3D···O2^v	0.85	1.93	2.7757 (13)	175
O3W—H3C···O4	0.85	1.90	2.7496 (13)	175
O4W—H4D···O3W	0.85	1.84	2.6834 (15)	171
O4W—H4C···O5ⁱ	0.85	2.26	3.0835 (16)	165
O5W—H5C···O1W	0.85	2.03	2.8604 (15)	164.
O5W—H5D···O2W^vi	0.85	1.91	2.7204 (15)	159
C1—H1···O5^vii	0.93	2.41	3.1610 (18)	137
C3—H3···O3^viii	0.93	2.25	3.130 (2)	158
C8—H8···O3W^ix	0.93	2.42	3.315 (2)	161
C10—H10···O6	0.93	2.50	2.9995 (17)	114
C10—H10···O5Wⁱⁱ	0.93	2.42	3.1809 (19)	139

Acknowledgements

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

References

Aghabozorg, H., Attar Gharamaleki, J., Ghadermazi, M., Ghasemikhah, P. & Soleimannejad, J. (2007). Acta Cryst. E63, m1803–m1804. Web of Science CSD CrossRef IUCr Journals Google Scholar
Aghabozorg, H., Attar Gharamaleki, J., Ghasemikhah, P., Ghadermazi, M. & Soleimannejad, J. (2007). Acta Cryst. E63, m1710–m1711. Web of Science CSD CrossRef IUCr Journals Google Scholar
Aghabozorg, H., Daneshvar, S., Motyeian, E., Ghadermazi, M. & Attar Gharamaleki, J. (2007). Acta Cryst. E63, m2468–m2469. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (1998). SADABS (Version 2004/1), SAINT (Version 6.01) and SMART (Version 5.059). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2005). SHELXTL. Version 6.10. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

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Volume 64| Part 1| January 2008| Pages m252-m253

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

Aqua­(4-hy­droxy­pyridine-2,6-di­carboxyl­ato)(1,10-phenanothroline)copper(II) 4.5-hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Aqua(4-hydroxypyridine-2,6-dicarboxylato)(1,10-phenanothroline)copper(II) 4.5-hydrate