Aqua­(2,2′-bipyridine-κ2N,N′)(3,5-dinitro­benzoato-κO1)copper(II) tetra­hydro­furan monosolvate

Abdullah, N.; Mohamadin, M.I.; Safwan, A.P.; Tiekink, E.R.T.

doi:10.1107/S1600536810030436

Aqua(2,2′-bipyridine-κ²N,N′)(3,5-dinitrobenzoato-κO¹)copper(II) tetrahydrofuran monosolvate

N. Abdullah, M. I. Mohamadin, A. P. Safwan and E. R. T. Tiekink

The title complex, [Cu(C₇H₃N₂O₆)₂(C₁₀H₈N₂)(H₂O)]·C₄H₈O, features a pentacoordinate Cu^II atom bound by two monodentate carboxylate ligands, a bidentate 2,2′-bipyridine molecule [dihedral angle between pyridine rings = 5.0 (2)°] and a water molecule. The resulting N₂O₃ donor set defines a distorted square-pyramidal geometry with the coordinated water molecule in the apical position. In the crystal, the presence of O—H_w

O_c (w = water and c = carbonyl) hydrogen bonding leads to the formation of a supramolecular chain propagating along the c axis, which associates into a double chain via C—H

O and π–π contacts between pyridyl rings [centroid–centroid distance = 3.527 (3) Å]. The solvent molecules, which are disordered over two orientations in a 0.678 (11):0.322 (11) ratio, occupy voids defined by the complex molecules and are held in place via C—H

O interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810030436/hb5590sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810030436/hb5590Isup2.hkl Contains datablock I

CCDC reference: 792243

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.008 Å
Disorder in solvent or counterion
R factor = 0.060
wR factor = 0.134
Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT112_ALERT_2_B ADDSYM Detects Additional (Pseudo) Symm. Elem...          C

Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent .........          5
PLAT314_ALERT_2_C Check Small Angle for H2O: Metal-O1W    -H2W          89.24 Deg.
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          8
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         C5S
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         C8S

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.50
           From the CIF: _reflns_number_total               6223
           Count of symmetry unique reflns         3414
           Completeness (_total/calc)            182.28%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2809
           Fraction of Friedel pairs measured     0.823
           Are heavy atom types Z>Si present        yes
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.      10.16
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         14
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................      50.00 Perc.
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          2
            N5  -CU  -O1  -C1    -45.30  1.50   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         10
            O1  -CU  -N5  -C15   150.50  1.20   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         14
            O1  -CU  -N5  -C19   -27.00  1.50   1.555   1.555   1.555   1.555
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........         16

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   8 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   8 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The title complex solvate, (I), was characterized as part of on-going structural studies of copper carboxylates and their adducts (Ozair et al., 2010).

The crystallographic asymmetric unit of (I) comprises a copper(II) complex and a solvent tetrahydrofuran (thf) molecule of crystallization in a 1:1 ratio. The molecular structure of the complex in (I) is illustrated in Fig. 1 and selected geometric parameters are collected in Table 1. The Cu atom is penta-coordinate, being coordinated by two O atoms derived from two monodentate carboxylate ligand, two N atoms of the chelating 2,2'-bipyridine ligand, and an O atom derived from the coordinated water molecule. The resulting N₂O₃ donor set defines a square pyramidal geometry as indicated by the value of τ = 0.16 which compares to τ = 0 for an ideal square pyramid and τ = 1.0 for an ideal trigonal bipyramid (Addison et al., 1984). In this description, the coordinated water molecule occupies the apical position and each carboxylate-O atom is trans to a pyridine-N atom, Table 2. The four donor atoms defining the square plane have deviations from the least-squares plane through them of -0.089 (2), 0.090 (2), -0.097 (2), and 0.096 (2) Å for atoms O1, O7, N5, and N6, respectively; the r.m.s. deviation for the four atoms is 0.093 Å. The Cu atom lies 0.176 (2) Å out of the square plane in the direction of the O1w atom. Distortions from the ideal geometry are due to the restricted bite distance of the 2,2'-bipyridine ligand [N5–Cu–N6 = 79.95 (18) °] and to the relatively close approach of the carbonyl-O2, O8 atoms. However, the Cu···O2, O4 separations of 2.942 (4) and 3.007 (4) Å, respectively, are not considered to represent significant bonding interactions. Under these circumstances, the disparity in the C–O_carboxylate and C–O_carbonyl bond distances, Table 1, is not as great as might be anticipated for formal C–O_carboxylate and C═O_carbonyl bonds. This is due to i) the weak interaction formed by the carbonyl-O atoms with the Cu atom, and ii) the pivotal role the carbonyl-O atoms play in the supramolecular association operating in the crystal structure (see below). Each of the carbonyl-O2,O8 atoms lies to the same side of the square plane around the Cu atom and in the opposite direction to the coordinated water molecule. The dihedral angle formed between the two carboxylate aromatic rings is 82.1 (2) °, indicating that they are almost orthogonal to each other. Within the carboxylate ligands, each carboxylate group is effectively co-planar with the aromatic ring to which it is bound, with the C1–O1,O2 carboxylate having the greater twist as seen in the O1–C1–C2–C3 torsion angle of 10.0 (7) °. By contrast, one nitro group in each carboxylate ligand, i.e. containing N1 and N4, is significantly twisted out of the plane of the aromatic ring to which it is connected [the O3–N1–C4–C3 and O11–N4–C13–C12 torsion angles are -162.7 (5) and 157.4 (5) °, respectively]. The chelating 2,2'-bipyridine ligand is almost planar with the dihedral angle between the two pyridine rings being 5.0 (2) °; the small twist in the molecule is seen in the N5–C19–C20–N6 torsion angle of -2.6 (7) °.

The most prominent interactions operating in the crystal structure of (I) are O–H···O contacts occurring between the hydrogen atoms of the coordinated water molecule and the carbonyl-O atoms of a translationally related molecule; Table 2. As illustrated in Fig. 2, the water-bound hydrogen atoms effectively form a bridge between the adjacent carbonyl atoms resulting in a ten-membered {···HOH···OCOCuOCO} synthon. The result of this hydrogen bonding is the formation of a supramolecular chain along the c axis. Each supramolecular chain is connected into a double chain along c with helical topology via C–H···O contacts whereby two bipyridine-H atoms form interactions with a carbonyl-O of the second chain, and a third bipyridine-H atom forms a C–H···O contact with a nitro-O within the chain, Fig. 3 and Table 2. This arrangement brings into close proximity the 2,2'-bipyridine molecules which interdigitate, Fig. 3, allowing for the formation of π–π interactions [ring centroid(N6,C20–C24)···ring centroid(N6,C20–C24)ⁱ = 3.527 (3) Å for i: -x + 1/2, y, z - 1/2]. The double chains pack in the ac plane to form layers that stack along the b axis, Fig. 4. Within each layer, there are voids and these are occupied by the solvent thf molecules which are held in place by C–H···O interactions, Table 2 and Fig. 4. Interactions between layers are primarily of the type C–H···O as detailed in Table 2.

Related literature top

For background to the study of copper carboxylates, see: Ozair et al. (2010). For the preparation, see: Fountain & Hatfield (1965). For additional geometric analysis, see: Addison et al. (1984).

Experimental top

Copper(II) acetate monohydrate (Merck; 1.995 g, 0.01 mol) and 3,5-dinitrobenzoic acid (Merck, 4.24 g, 0.02 mol) were reacted in an 1:2 molar ratio hot ethanol (60 ml) for 30 minutes following a literature precedent (Fountain & Hatfield, 1965). The resulting blue powder, [Cu₂(3,5-(NO₂)₂C₆H₃COO)₄], was isolated in 23% yield and reacted with 2,2'-bipyridine (mole ratio = 1:1) in THF (15 ml) at room temperature. Blue-green prisms of (I) formed when the solvent was allowed to slowly evaporate off at room temperature after 2 days.

Structure description top

The title complex solvate, (I), was characterized as part of on-going structural studies of copper carboxylates and their adducts (Ozair et al., 2010).

For background to the study of copper carboxylates, see: Ozair et al. (2010). For the preparation, see: Fountain & Hatfield (1965). For additional geometric analysis, see: Addison et al. (1984).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level. The disordered thf molecule is not illustrated.
	Fig. 2. A portion of the supramolecular chain aligned along the c axis found in the crystal structure of (I) mediated by O–H···O hydrogen bonding (orange dashed lines). Colour code: Cu, orange; O, red; N, blue; C, grey; and H, green.
	Fig. 3. Double chain with helical topology in (I) mediated by O–H···O and C–H···O contacts shown as orange and blue dashed lines, respectively. Colour code: Cu, orange; O, red; N, blue; C, grey; and H, green.
	Fig. 4. View of the unit-cell contents of (I) viewed in projection down the c axis. The double chains form layers in the ac plane which have large voids that are occupied by the solvent thf molecules; only the major component of the disordered molecules are shown. In the lower two layers, the solvent molecules are shown in space filling mode. In the upper two layers, the C–H···O interactions connecting the thf molecules to the layers are shown as green dashed lines. Colour code: Cu, orange; O, red; N, blue; C, grey; and H, green.

Aqua(2,2'-bipyridine-κ²N,N')(3,5-dinitrobenzoato- κO¹)copper(II) tetrahydrofuran monosolvate top

Crystal data top

[Cu(C₇H₃N₂O₆)₂(C₁₀H₈N₂)(H₂O)]·C₄H₈O	F(000) = 1500
M_r = 732.08	D_x = 1.614 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 7872 reflections
a = 19.6424 (7) Å	θ = 2.6–28.0°
b = 23.2687 (8) Å	µ = 0.81 mm⁻¹
c = 6.5897 (2) Å	T = 100 K
V = 3011.84 (17) Å³	Prism, green
Z = 4	0.26 × 0.07 × 0.07 mm

Data collection top

Bruker SMART APEX CCD diffractometer	6223 independent reflections
Radiation source: fine-focus sealed tube	5759 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 26.5°, θ_min = 0.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→23
T_min = 0.865, T_max = 1.000	k = −29→29
25602 measured reflections	l = −8→8

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)] = 0.060	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.0125P)² + 10.1609P] where P = (F_o² + 2F_c²)/3
S = 1.28	(Δ/σ)_max < 0.001
6223 reflections	Δρ_max = 0.50 e Å⁻³
444 parameters	Δρ_min = −0.50 e Å⁻³
14 restraints	Absolute structure: Flack (1983), 2809 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (2)

Crystal data top

[Cu(C₇H₃N₂O₆)₂(C₁₀H₈N₂)(H₂O)]·C₄H₈O	V = 3011.84 (17) Å³
M_r = 732.08	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 19.6424 (7) Å	µ = 0.81 mm⁻¹
b = 23.2687 (8) Å	T = 100 K
c = 6.5897 (2) Å	0.26 × 0.07 × 0.07 mm

Data collection top

Bruker SMART APEX CCD diffractometer	6223 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5759 reflections with I > 2σ(I)
T_min = 0.865, T_max = 1.000	R_int = 0.035
25602 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.0125P)² + 10.1609P] where P = (F_o² + 2F_c²)/3
S = 1.28	Δρ_max = 0.50 e Å⁻³
6223 reflections	Δρ_min = −0.50 e Å⁻³
444 parameters	Absolute structure: Flack (1983), 2809 Friedel pairs
14 restraints	Absolute structure parameter: 0.02 (2)

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)
Cu	0.42505 (3)	0.74892 (3)	0.81422 (13)	0.01710 (13)
O1	0.48462 (18)	0.68415 (15)	0.8897 (5)	0.0203 (8)
O2	0.43340 (18)	0.68207 (18)	1.1923 (6)	0.0276 (9)
O3	0.7080 (2)	0.59152 (17)	0.8280 (8)	0.0349 (10)
O4	0.7241 (2)	0.51293 (17)	0.9989 (6)	0.0277 (9)
O5	0.5108 (2)	0.5410 (2)	1.6840 (6)	0.0362 (11)
O6	0.6025 (2)	0.4906 (2)	1.6345 (8)	0.0475 (13)
O7	0.49031 (18)	0.80342 (17)	0.9272 (6)	0.0223 (8)
O8	0.41911 (19)	0.8246 (2)	1.1836 (6)	0.0313 (10)
O9	0.4959 (2)	0.95628 (19)	1.7149 (7)	0.0326 (10)
O10	0.5952 (2)	0.9953 (2)	1.6972 (8)	0.0447 (13)
O11	0.7198 (2)	0.88618 (18)	0.9376 (7)	0.0344 (10)
O12	0.73480 (19)	0.96655 (16)	1.0991 (7)	0.0300 (10)
O1W	0.4763 (3)	0.7479 (2)	0.5176 (6)	0.0417 (11)
H2W	0.450 (3)	0.774 (2)	0.478 (11)	0.063*
H1W	0.478 (4)	0.723 (2)	0.426 (8)	0.063*
N1	0.6927 (2)	0.5575 (2)	0.9613 (7)	0.0232 (10)
N2	0.5602 (3)	0.5278 (2)	1.5819 (8)	0.0303 (11)
N3	0.5503 (2)	0.9650 (2)	1.6327 (7)	0.0240 (10)
N4	0.7016 (2)	0.92304 (18)	1.0584 (8)	0.0209 (10)
N5	0.3550 (2)	0.80942 (19)	0.7545 (6)	0.0169 (9)
N6	0.3428 (2)	0.6991 (2)	0.7701 (6)	0.0198 (10)
C1	0.4777 (2)	0.6669 (2)	1.0699 (8)	0.0192 (11)
C2	0.5301 (3)	0.6231 (2)	1.1368 (8)	0.0180 (11)
C3	0.5867 (3)	0.6110 (2)	1.0177 (8)	0.0173 (10)
H3	0.5934	0.6296	0.8911	0.021*
C4	0.6333 (2)	0.5706 (2)	1.0894 (8)	0.0175 (10)
C5	0.6267 (3)	0.5431 (2)	1.2735 (8)	0.0199 (12)
H5	0.6593	0.5159	1.3196	0.024*
C6	0.5703 (3)	0.5571 (2)	1.3865 (8)	0.0243 (12)
C7	0.5218 (3)	0.5960 (2)	1.3246 (10)	0.0248 (11)
H7	0.4836	0.6043	1.4077	0.030*
C8	0.4735 (3)	0.8296 (2)	1.0928 (8)	0.0225 (11)
C9	0.5270 (3)	0.8696 (2)	1.1773 (8)	0.0210 (11)
C10	0.5142 (3)	0.8988 (2)	1.3576 (8)	0.0181 (11)
H10	0.4721	0.8937	1.4260	0.022*
C11	0.5628 (3)	0.9350 (2)	1.4367 (9)	0.0219 (11)
C12	0.6256 (3)	0.9422 (2)	1.3450 (8)	0.0178 (11)
H12	0.6599	0.9654	1.4048	0.021*
C13	0.6362 (3)	0.9144 (2)	1.1637 (9)	0.0205 (11)
C14	0.5891 (2)	0.8771 (2)	1.0798 (8)	0.0178 (10)
H14	0.5989	0.8570	0.9579	0.021*
C15	0.3682 (3)	0.8653 (2)	0.7354 (8)	0.0257 (12)
H15	0.4139	0.8784	0.7420	0.031*
C16	0.3158 (4)	0.9047 (3)	0.7059 (9)	0.0345 (15)
H16	0.3260	0.9444	0.6915	0.041*
C17	0.2505 (4)	0.8867 (3)	0.6977 (9)	0.0320 (14)
H17	0.2147	0.9136	0.6792	0.038*
C18	0.2362 (3)	0.8287 (3)	0.7166 (8)	0.0252 (12)
H18	0.1906	0.8152	0.7129	0.030*
C19	0.2910 (3)	0.7905 (2)	0.7414 (7)	0.0161 (10)
C20	0.2837 (3)	0.7281 (2)	0.7550 (7)	0.0187 (11)
C21	0.2213 (3)	0.6990 (3)	0.7491 (8)	0.0256 (12)
H21	0.1797	0.7197	0.7411	0.031*
C22	0.2212 (3)	0.6388 (3)	0.7554 (8)	0.0289 (13)
H22	0.1795	0.6182	0.7526	0.035*
C23	0.2816 (3)	0.6102 (3)	0.7655 (8)	0.0292 (13)
H23	0.2826	0.5694	0.7675	0.035*
C24	0.3417 (3)	0.6415 (3)	0.7727 (7)	0.0259 (13)
H24	0.3836	0.6213	0.7799	0.031*
O1S	0.6126 (3)	0.6981 (3)	0.5879 (10)	0.0375 (19)*	0.678 (11)
C1S	0.6344 (5)	0.7402 (3)	0.7275 (13)	0.029 (2)*	0.678 (11)
H1S1	0.6734	0.7259	0.8083	0.035*	0.678 (11)
H1S2	0.5970	0.7507	0.8211	0.035*	0.678 (11)
C2S	0.6551 (5)	0.7910 (4)	0.6005 (15)	0.039 (2)*	0.678 (11)
H2S1	0.6153	0.8155	0.5682	0.047*	0.678 (11)
H2S2	0.6898	0.8145	0.6711	0.047*	0.678 (11)
C4S	0.6573 (6)	0.7039 (5)	0.4224 (18)	0.059 (3)*	0.678 (11)
H4S1	0.6331	0.6944	0.2950	0.070*	0.678 (11)
H4S2	0.6958	0.6767	0.4377	0.070*	0.678 (11)
C3S	0.6839 (6)	0.7640 (4)	0.4117 (17)	0.053 (3)*	0.678 (11)
H3S1	0.6675	0.7839	0.2882	0.064*	0.678 (11)
H3S2	0.7343	0.7647	0.4132	0.064*	0.678 (11)
O2S	0.6819 (9)	0.7085 (7)	0.296 (3)	0.070 (6)*	0.322 (11)
C5S	0.6454 (10)	0.7603 (7)	0.299 (3)	0.041 (5)*	0.322 (11)
H5S1	0.5993	0.7537	0.2429	0.049*	0.322 (11)
H5S2	0.6686	0.7888	0.2115	0.049*	0.322 (11)
C8S	0.6827 (10)	0.6886 (8)	0.496 (2)	0.032 (5)*	0.322 (11)
H8S1	0.7301	0.6874	0.5465	0.038*	0.322 (11)
H8S2	0.6638	0.6492	0.5013	0.038*	0.322 (11)
C7S	0.6406 (14)	0.7281 (9)	0.626 (4)	0.058 (7)*	0.322 (11)
H7S1	0.5940	0.7128	0.6442	0.069*	0.322 (11)
H7S2	0.6618	0.7333	0.7612	0.069*	0.322 (11)
C6S	0.6395 (15)	0.7838 (9)	0.511 (3)	0.058 (7)*	0.322 (11)
H6S1	0.6785	0.8088	0.5462	0.070*	0.322 (11)
H6S2	0.5963	0.8051	0.5310	0.070*	0.322 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0121 (2)	0.0260 (3)	0.0132 (2)	0.0013 (3)	−0.0011 (3)	−0.0022 (3)
O1	0.0154 (18)	0.0217 (19)	0.024 (2)	0.0063 (15)	−0.0003 (14)	−0.0014 (15)
O2	0.0168 (19)	0.040 (2)	0.026 (2)	0.0046 (17)	−0.0002 (16)	−0.0089 (18)
O3	0.031 (2)	0.035 (2)	0.039 (2)	0.0110 (17)	0.013 (2)	0.012 (2)
O4	0.027 (2)	0.022 (2)	0.034 (2)	0.0091 (17)	−0.0020 (18)	−0.0005 (17)
O5	0.039 (2)	0.043 (3)	0.026 (2)	−0.012 (2)	0.007 (2)	0.0052 (19)
O6	0.037 (3)	0.054 (3)	0.051 (3)	0.001 (2)	−0.006 (2)	0.032 (3)
O7	0.0161 (18)	0.030 (2)	0.021 (2)	0.0004 (16)	−0.0012 (15)	−0.0019 (17)
O8	0.0181 (19)	0.054 (3)	0.022 (2)	−0.0079 (19)	0.0015 (17)	−0.0053 (19)
O9	0.029 (2)	0.037 (2)	0.031 (2)	−0.0051 (19)	0.0120 (19)	−0.0090 (19)
O10	0.024 (2)	0.059 (3)	0.051 (3)	−0.013 (2)	0.009 (2)	−0.029 (3)
O11	0.024 (2)	0.029 (2)	0.050 (3)	−0.0030 (18)	0.016 (2)	−0.010 (2)
O12	0.023 (2)	0.0222 (19)	0.045 (3)	−0.0030 (16)	0.0079 (19)	−0.0043 (19)
O1W	0.063 (3)	0.041 (3)	0.021 (2)	0.009 (3)	0.016 (2)	−0.002 (2)
N1	0.019 (2)	0.023 (2)	0.027 (2)	0.0073 (19)	−0.0023 (19)	−0.003 (2)
N2	0.028 (3)	0.039 (3)	0.024 (3)	−0.011 (2)	0.000 (2)	0.007 (2)
N3	0.019 (2)	0.028 (3)	0.025 (2)	0.001 (2)	0.004 (2)	−0.006 (2)
N4	0.0121 (19)	0.016 (2)	0.035 (3)	0.0009 (17)	0.0024 (19)	−0.001 (2)
N5	0.018 (2)	0.022 (2)	0.010 (2)	0.0017 (17)	−0.0014 (16)	0.0017 (17)
N6	0.017 (2)	0.030 (2)	0.012 (2)	0.0038 (18)	−0.0020 (17)	0.0009 (17)
C1	0.014 (2)	0.026 (3)	0.017 (3)	−0.001 (2)	−0.001 (2)	−0.009 (2)
C2	0.019 (2)	0.019 (3)	0.017 (3)	−0.002 (2)	0.001 (2)	−0.007 (2)
C3	0.019 (2)	0.016 (2)	0.017 (2)	−0.004 (2)	−0.004 (2)	−0.009 (2)
C4	0.014 (2)	0.016 (2)	0.022 (3)	−0.0012 (19)	0.000 (2)	−0.007 (2)
C5	0.023 (3)	0.011 (2)	0.026 (3)	−0.0038 (19)	−0.008 (2)	−0.004 (2)
C6	0.024 (3)	0.030 (3)	0.019 (2)	−0.008 (2)	−0.003 (2)	0.005 (2)
C7	0.022 (2)	0.034 (3)	0.018 (3)	−0.005 (2)	0.000 (3)	−0.003 (3)
C8	0.018 (3)	0.033 (3)	0.017 (3)	−0.001 (2)	−0.005 (2)	0.002 (2)
C9	0.013 (2)	0.032 (3)	0.018 (3)	0.001 (2)	−0.002 (2)	0.010 (2)
C10	0.014 (2)	0.020 (2)	0.020 (3)	0.000 (2)	0.001 (2)	0.001 (2)
C11	0.016 (2)	0.027 (3)	0.023 (3)	0.002 (2)	−0.001 (2)	−0.004 (2)
C12	0.015 (2)	0.017 (2)	0.021 (3)	0.0021 (18)	−0.001 (2)	−0.001 (2)
C13	0.016 (2)	0.016 (2)	0.030 (3)	0.001 (2)	0.000 (2)	0.011 (2)
C14	0.018 (2)	0.017 (2)	0.018 (2)	0.006 (2)	−0.002 (2)	0.005 (2)
C15	0.036 (3)	0.023 (3)	0.018 (2)	−0.002 (2)	−0.006 (2)	−0.001 (2)
C16	0.058 (4)	0.023 (3)	0.022 (3)	0.013 (3)	−0.009 (3)	0.004 (2)
C17	0.045 (4)	0.034 (3)	0.017 (3)	0.024 (3)	−0.010 (3)	−0.003 (2)
C18	0.022 (3)	0.042 (3)	0.011 (2)	0.012 (2)	−0.005 (2)	−0.005 (2)
C19	0.020 (3)	0.023 (3)	0.006 (2)	0.006 (2)	−0.0025 (19)	−0.003 (2)
C20	0.014 (2)	0.032 (3)	0.010 (2)	0.002 (2)	0.0001 (18)	−0.008 (2)
C21	0.021 (3)	0.047 (3)	0.010 (2)	−0.008 (3)	−0.001 (2)	−0.009 (2)
C22	0.032 (3)	0.040 (3)	0.014 (3)	−0.015 (3)	−0.004 (2)	−0.003 (2)
C23	0.045 (3)	0.029 (3)	0.014 (3)	−0.013 (3)	−0.003 (2)	0.000 (2)
C24	0.024 (3)	0.040 (3)	0.013 (3)	0.000 (2)	0.000 (2)	−0.005 (2)

Geometric parameters (Å, º) top

Cu—O7	1.951 (4)	C13—C14	1.384 (7)
Cu—O1	1.972 (4)	C14—H14	0.9500
Cu—N5	2.007 (4)	C15—C16	1.392 (8)
Cu—N6	2.010 (4)	C15—H15	0.9500
Cu—O1W	2.198 (4)	C16—C17	1.351 (10)
C1—O1	1.261 (6)	C16—H16	0.9500
C1—O2	1.238 (6)	C17—C18	1.382 (8)
O3—N1	1.220 (6)	C17—H17	0.9500
O4—N1	1.231 (6)	C18—C19	1.406 (7)
O5—N2	1.221 (7)	C18—H18	0.9500
O6—N2	1.248 (7)	C19—C20	1.461 (8)
C8—O7	1.293 (7)	C20—C21	1.402 (7)
C8—O8	1.230 (6)	C21—C22	1.400 (8)
O9—N3	1.214 (6)	C21—H21	0.9500
O10—N3	1.207 (6)	C22—C23	1.363 (9)
O11—N4	1.224 (6)	C22—H22	0.9500
O12—N4	1.234 (6)	C23—C24	1.387 (8)
O1W—H2W	0.84 (5)	C23—H23	0.9500
O1W—H1W	0.84 (5)	C24—H24	0.9500
N1—C4	1.473 (6)	O1S—C4S	1.406 (8)
N2—C6	1.470 (7)	O1S—C1S	1.410 (8)
N3—C11	1.489 (7)	C1S—C2S	1.505 (8)
N4—C13	1.473 (7)	C1S—H1S1	0.9900
N5—C15	1.331 (7)	C1S—H1S2	0.9900
N5—C19	1.336 (6)	C2S—C3S	1.504 (9)
N6—C24	1.340 (7)	C2S—H2S1	0.9900
N6—C20	1.346 (6)	C2S—H2S2	0.9900
C1—C2	1.514 (7)	C4S—C3S	1.496 (9)
C2—C3	1.389 (7)	C4S—H4S1	0.9900
C2—C7	1.399 (8)	C4S—H4S2	0.9900
C3—C4	1.394 (7)	C3S—H3S1	0.9900
C3—H3	0.9500	C3S—H3S2	0.9900
C4—C5	1.378 (7)	O2S—C8S	1.397 (10)
C5—C6	1.374 (8)	O2S—C5S	1.401 (10)
C5—H5	0.9500	C5S—C6S	1.503 (10)
C6—C7	1.376 (8)	C5S—H5S1	0.9900
C7—H7	0.9500	C5S—H5S2	0.9900
C8—C9	1.511 (7)	C8S—C7S	1.506 (10)
C9—C10	1.392 (7)	C8S—H8S1	0.9900
C9—C14	1.388 (7)	C8S—H8S2	0.9900
C10—C11	1.375 (7)	C7S—C6S	1.503 (10)
C10—H10	0.9500	C7S—H7S1	0.9900
C11—C12	1.383 (7)	C7S—H7S2	0.9900
C12—C13	1.376 (8)	C6S—H6S1	0.9900
C12—H12	0.9500	C6S—H6S2	0.9900

O7—Cu—O1	90.62 (16)	C17—C16—C15	120.2 (6)
O7—Cu—N5	93.96 (16)	C17—C16—H16	119.9
O1—Cu—N5	172.85 (17)	C15—C16—H16	119.9
O7—Cu—N6	163.43 (16)	C16—C17—C18	119.5 (5)
O1—Cu—N6	94.15 (17)	C16—C17—H17	120.3
N5—Cu—N6	79.95 (18)	C18—C17—H17	120.3
O7—Cu—O1W	92.59 (18)	C17—C18—C19	118.2 (5)
O1—Cu—O1W	86.83 (17)	C17—C18—H18	120.9
N5—Cu—O1W	98.43 (18)	C19—C18—H18	120.9
N6—Cu—O1W	103.51 (19)	N5—C19—C18	121.3 (5)
C1—O1—Cu	114.6 (3)	N5—C19—C20	114.5 (4)
C8—O7—Cu	117.4 (3)	C18—C19—C20	124.2 (5)
Cu—O1W—H2W	89 (6)	N6—C20—C21	120.9 (5)
Cu—O1W—H1W	132 (6)	N6—C20—C19	114.8 (5)
H2W—O1W—H1W	108 (5)	C21—C20—C19	124.3 (5)
O3—N1—O4	124.7 (5)	C22—C21—C20	118.9 (5)
O3—N1—C4	118.2 (4)	C22—C21—H21	120.5
O4—N1—C4	117.1 (5)	C20—C21—H21	120.5
O5—N2—O6	123.4 (5)	C23—C22—C21	119.3 (5)
O5—N2—C6	118.2 (5)	C23—C22—H22	120.4
O6—N2—C6	118.4 (5)	C21—C22—H22	120.4
O10—N3—O9	125.7 (5)	C22—C23—C24	119.0 (5)
O10—N3—C11	117.3 (4)	C22—C23—H23	120.5
O9—N3—C11	117.0 (5)	C24—C23—H23	120.5
O11—N4—O12	124.2 (4)	N6—C24—C23	122.6 (5)
O11—N4—C13	117.7 (4)	N6—C24—H24	118.7
O12—N4—C13	118.1 (4)	C23—C24—H24	118.7
C15—N5—C19	119.9 (5)	C4S—O1S—C1S	104.5 (8)
C15—N5—Cu	124.8 (4)	O1S—C1S—C2S	105.4 (7)
C19—N5—Cu	115.2 (3)	O1S—C1S—H1S1	110.7
C24—N6—C20	119.2 (5)	C2S—C1S—H1S1	110.7
C24—N6—Cu	126.0 (4)	O1S—C1S—H1S2	110.7
C20—N6—Cu	114.5 (4)	C2S—C1S—H1S2	110.7
O2—C1—O1	126.8 (5)	H1S1—C1S—H1S2	108.8
O2—C1—C2	118.7 (5)	C3S—C2S—C1S	103.5 (8)
O1—C1—C2	114.5 (4)	C3S—C2S—H2S1	111.1
C3—C2—C7	120.0 (5)	C1S—C2S—H2S1	111.1
C3—C2—C1	121.1 (5)	C3S—C2S—H2S2	111.1
C7—C2—C1	118.9 (5)	C1S—C2S—H2S2	111.1
C2—C3—C4	118.1 (5)	H2S1—C2S—H2S2	109.0
C2—C3—H3	120.9	O1S—C4S—C3S	110.2 (9)
C4—C3—H3	120.9	O1S—C4S—H4S1	109.6
C5—C4—C3	123.3 (5)	C3S—C4S—H4S1	109.6
C5—C4—N1	118.9 (5)	O1S—C4S—H4S2	109.6
C3—C4—N1	117.8 (5)	C3S—C4S—H4S2	109.6
C6—C5—C4	116.3 (5)	H4S1—C4S—H4S2	108.1
C6—C5—H5	121.9	C4S—C3S—C2S	102.7 (8)
C4—C5—H5	121.9	C4S—C3S—H3S1	111.2
C7—C6—C5	123.6 (5)	C2S—C3S—H3S1	111.2
C7—C6—N2	118.2 (5)	C4S—C3S—H3S2	111.2
C5—C6—N2	118.2 (5)	C2S—C3S—H3S2	111.2
C6—C7—C2	118.7 (5)	H3S1—C3S—H3S2	109.1
C6—C7—H7	120.7	C8S—O2S—C5S	106.1 (17)
C2—C7—H7	120.7	O2S—C5S—C6S	111.5 (18)
O8—C8—O7	126.0 (5)	O2S—C5S—H5S1	109.3
O8—C8—C9	119.0 (5)	C6S—C5S—H5S1	109.3
O7—C8—C9	115.1 (5)	O2S—C5S—H5S2	109.3
C10—C9—C14	119.5 (5)	C6S—C5S—H5S2	109.3
C10—C9—C8	119.3 (5)	H5S1—C5S—H5S2	108.0
C14—C9—C8	121.1 (5)	O2S—C8S—C7S	109.3 (17)
C11—C10—C9	119.8 (5)	O2S—C8S—H8S1	109.8
C11—C10—H10	120.1	C7S—C8S—H8S1	109.8
C9—C10—H10	120.1	O2S—C8S—H8S2	109.8
C10—C11—C12	121.8 (5)	C7S—C8S—H8S2	109.8
C10—C11—N3	120.0 (5)	H8S1—C8S—H8S2	108.3
C12—C11—N3	118.0 (5)	C6S—C7S—C8S	104.2 (18)
C13—C12—C11	117.2 (5)	C6S—C7S—H7S1	110.9
C13—C12—H12	121.4	C8S—C7S—H7S1	110.9
C11—C12—H12	121.4	C6S—C7S—H7S2	110.9
C12—C13—C14	122.7 (5)	C8S—C7S—H7S2	110.9
C12—C13—N4	118.5 (5)	H7S1—C7S—H7S2	108.9
C14—C13—N4	118.8 (5)	C7S—C6S—C5S	98.9 (18)
C13—C14—C9	118.7 (5)	C7S—C6S—H6S1	112.0
C13—C14—H14	120.6	C5S—C6S—H6S1	112.0
C9—C14—H14	120.6	C7S—C6S—H6S2	112.0
N5—C15—C16	120.9 (6)	C5S—C6S—H6S2	112.0
N5—C15—H15	119.6	H6S1—C6S—H6S2	109.7
C16—C15—H15	119.6

O7—Cu—O1—C1	84.5 (4)	C14—C9—C10—C11	0.5 (7)
N5—Cu—O1—C1	−45.3 (15)	C8—C9—C10—C11	179.5 (5)
N6—Cu—O1—C1	−79.6 (4)	C9—C10—C11—C12	−2.0 (8)
O1W—Cu—O1—C1	177.1 (4)	C9—C10—C11—N3	−178.2 (5)
O1—Cu—O7—C8	−109.3 (4)	O10—N3—C11—C10	178.4 (5)
N5—Cu—O7—C8	65.2 (4)	O9—N3—C11—C10	−0.7 (8)
N6—Cu—O7—C8	−2.4 (8)	O10—N3—C11—C12	2.1 (8)
O1W—Cu—O7—C8	163.8 (4)	O9—N3—C11—C12	−177.0 (5)
O7—Cu—N5—C15	20.9 (4)	C10—C11—C12—C13	4.0 (8)
O1—Cu—N5—C15	150.5 (12)	N3—C11—C12—C13	−179.8 (5)
N6—Cu—N5—C15	−174.7 (5)	C11—C12—C13—C14	−4.6 (8)
O1W—Cu—N5—C15	−72.3 (5)	C11—C12—C13—N4	177.6 (5)
O7—Cu—N5—C19	−156.7 (3)	O11—N4—C13—C12	157.4 (5)
O1—Cu—N5—C19	−27.0 (15)	O12—N4—C13—C12	−21.8 (7)
N6—Cu—N5—C19	7.8 (3)	O11—N4—C13—C14	−20.5 (7)
O1W—Cu—N5—C19	110.1 (4)	O12—N4—C13—C14	160.3 (5)
O7—Cu—N6—C24	−113.5 (6)	C12—C13—C14—C9	3.3 (8)
O1—Cu—N6—C24	−7.2 (4)	N4—C13—C14—C9	−178.9 (4)
N5—Cu—N6—C24	176.9 (4)	C10—C9—C14—C13	−1.1 (7)
O1W—Cu—N6—C24	80.6 (4)	C8—C9—C14—C13	179.9 (5)
O7—Cu—N6—C20	60.4 (8)	C19—N5—C15—C16	1.3 (8)
O1—Cu—N6—C20	166.7 (3)	Cu—N5—C15—C16	−176.1 (4)
N5—Cu—N6—C20	−9.2 (3)	N5—C15—C16—C17	0.5 (9)
O1W—Cu—N6—C20	−105.5 (4)	C15—C16—C17—C18	−0.7 (9)
Cu—O1—C1—O2	8.5 (7)	C16—C17—C18—C19	−0.7 (9)
Cu—O1—C1—C2	−171.8 (3)	C15—N5—C19—C18	−2.9 (7)
O2—C1—C2—C3	−170.3 (5)	Cu—N5—C19—C18	174.8 (4)
O1—C1—C2—C3	10.0 (7)	C15—N5—C19—C20	177.1 (4)
O2—C1—C2—C7	7.8 (7)	Cu—N5—C19—C20	−5.2 (5)
O1—C1—C2—C7	−172.0 (5)	C17—C18—C19—N5	2.6 (8)
C7—C2—C3—C4	1.3 (7)	C17—C18—C19—C20	−177.4 (5)
C1—C2—C3—C4	179.3 (4)	C24—N6—C20—C21	2.3 (7)
C2—C3—C4—C5	−1.2 (7)	Cu—N6—C20—C21	−172.1 (4)
C2—C3—C4—N1	179.3 (4)	C24—N6—C20—C19	−176.6 (4)
O3—N1—C4—C5	−161.2 (5)	Cu—N6—C20—C19	9.1 (5)
O4—N1—C4—C5	17.8 (7)	N5—C19—C20—N6	−2.6 (7)
O3—N1—C4—C3	18.3 (7)	C18—C19—C20—N6	177.4 (4)
O4—N1—C4—C3	−162.7 (5)	N5—C19—C20—C21	178.6 (4)
C3—C4—C5—C6	0.4 (7)	C18—C19—C20—C21	−1.4 (8)
N1—C4—C5—C6	179.9 (4)	N6—C20—C21—C22	−1.2 (8)
C4—C5—C6—C7	0.3 (8)	C19—C20—C21—C22	177.5 (5)
C4—C5—C6—N2	178.6 (5)	C20—C21—C22—C23	−0.5 (8)
O5—N2—C6—C7	−2.9 (8)	C21—C22—C23—C24	1.1 (8)
O6—N2—C6—C7	176.9 (5)	C20—N6—C24—C23	−1.7 (7)
O5—N2—C6—C5	178.7 (5)	Cu—N6—C24—C23	172.0 (4)
O6—N2—C6—C5	−1.5 (8)	C22—C23—C24—N6	0.0 (8)
C5—C6—C7—C2	−0.2 (8)	C4S—O1S—C1S—C2S	37.4 (10)
N2—C6—C7—C2	−178.5 (5)	O1S—C1S—C2S—C3S	−34.0 (10)
C3—C2—C7—C6	−0.6 (8)	C1S—O1S—C4S—C3S	−26.8 (13)
C1—C2—C7—C6	−178.7 (5)	O1S—C4S—C3S—C2S	5.2 (14)
Cu—O7—C8—O8	−2.2 (8)	C1S—C2S—C3S—C4S	16.9 (12)
Cu—O7—C8—C9	177.9 (3)	C8S—O2S—C5S—C6S	17 (2)
O8—C8—C9—C10	1.5 (8)	C5S—O2S—C8S—C7S	4 (2)
O7—C8—C9—C10	−178.6 (5)	O2S—C8S—C7S—C6S	−23 (3)
O8—C8—C9—C14	−179.6 (5)	C8S—C7S—C6S—C5S	30 (3)
O7—C8—C9—C14	0.3 (7)	O2S—C5S—C6S—C7S	−30 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w···O2ⁱ	0.84 (5)	2.01 (6)	2.766 (6)	150 (7)
O1w—H2w···O8ⁱ	0.84 (5)	2.35 (7)	3.048 (6)	141 (6)
C18—H18···O8ⁱⁱ	0.95	2.17	3.060 (7)	155
C21—H21···O2ⁱⁱ	0.95	2.41	3.087 (7)	128
C15—H15···O9ⁱ	0.95	2.43	3.285 (7)	150
C1s—H1s2···O7	0.99	2.53	3.451 (10)	155
C3—H3···O1s	0.95	2.58	3.520 (8)	169
C2s—H2s2···O11	0.99	2.49	3.385 (11)	150
C5—H5···O4ⁱⁱⁱ	0.95	2.58	3.360 (7)	140
C12—H12···O12ⁱⁱⁱ	0.95	2.43	3.263 (7)	146
C16—H16···O12^iv	0.95	2.47	3.234 (8)	138

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

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₃N₂O₆)₂(C₁₀H₈N₂)(H₂O)]·C₄H₈O
M_r	732.08
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	100
a, b, c (Å)	19.6424 (7), 23.2687 (8), 6.5897 (2)
V (Å³)	3011.84 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.26 × 0.07 × 0.07

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.865, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	25602, 6223, 5759
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.134, 1.28
No. of reflections	6223
No. of parameters	444
No. of restraints	14
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0125P)² + 10.1609P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.50
Absolute structure	Flack (1983), 2809 Friedel pairs
Absolute structure parameter	0.02 (2)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cu—O7	1.951 (4)	C1—O1	1.261 (6)
Cu—O1	1.972 (4)	C1—O2	1.238 (6)
Cu—N5	2.007 (4)	C8—O7	1.293 (7)
Cu—N6	2.010 (4)	C8—O8	1.230 (6)
Cu—O1W	2.198 (4)