Dipotassium [N,N′-(propane-1,3-di­yl)dioxamato-κ⁴O,N,N′,O′]copper(II) trihydrate: redetermination at 100 K

Redetermination of the structure of the title compound, K₂[Cu(C₇H₆N₂O₆)]·3H₂O, at 100 K reveals conformational disorder in the almost planar copper-containing mol­ecular dianions and clarifies the complex hydrogen-bonded network involving the water mol­ecules. The asymmetric unit contains two independent formula units. In one of the [Cu(C₇H₆N₂O₆)]²⁻ dianions, the propyl chain is disordered over two orientiations, with site-occupancy factors of 0.852 (5) and 0.148 (5).

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.032
• wR factor = 0.083
• Data-to-parameter ratio = 18.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O17    -   H17A   ...          ?

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.34
PLAT301_ALERT_3_C Main Residue  Disorder .........................       2.00 Perc.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C2     ...       1.54 Ang.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C6     -   C7     ...       1.55 Ang.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C8     -   C9     ...       1.55 Ang.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C13    -   C14    ...       1.55 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          6

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         18

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

The asymmetric unit (Fig. 1) of the title compound contains two independent formula units. Both [Cu(C₇H₆N₂O₆)]^2- anions have similar geometric parameters with Cu^II ions in square-planar CuO₂N₂ environments. Each ligand adopts a tetradentate coordination forming 5–6-5 membered chelate rings around the Cu^II ion (Fig. 1). The four K⁺ ions in the asymmetric unit show a variety of coordination geometries with coordination numbers in the range six to eight, all being coordinated by carbonyl oxygen atoms from the [Cu(C₇H₆N₂O₆)]^2- ion and water of crystallization. The crystal packing is shown in Fig. 2.

The structure at room temperature been reported previously by Zhu et al. (1999). Improved crystallographic data, collected at 100 K, allows us to see structural disorder in the ligand backbone of one [Cu(C₇H₆N₂O₆)]^2- unit, with the minor component present at about 15%. We are also able to locate all H atoms in Fourier difference maps, enabling a good description of the important hydrogen bonded network formed by the six water molecules in the asymmetric unit (Fig. 3).

Related literature

The structure of the title compound at room temperature has been reported previously, see: Zhu et al. (1999). A related monohydrate structure has been reported, see: Fritsky et al. (1999). For other related structures, see: Rodríguez-Romero et al. (1996); Cervera et al. (1998); Pei et al. (1986). For synthesis details, see: Nonoyama et al. (1976)

S2. Experimental

The synthesis of the sodium salt of [Cu(C₇H₆N₂O₆]^2- has been previously described Nonoyama et al. (1976). The title compound was obtained after a partial hydrolysis of the polyamide formed from 1,3-diaminopropane and diethyloxalate. A solution of 1,2-diaminopropane (0.31 g, 4.2 mmol) in absolute ethanol (10 ml) was slowly added to a refluxing solution of diethyloxalate (1.01 g, 6.9 mmol) in absolute ethanol (30 ml). The reaction was refluxed for a further 3 h, then cooled and the white solid was collected by filtration and washed with ethanol (3 x 10 ml). To a warm (323 K) suspension of this solid amide (0.251 g) in distilled water (20 ml) an aqueous solution of KOH (1.0 M) was added drop-wise until the amide had all dissolved, giving a clear solution with pH 12. A solution of CuCl₂.2H₂O (0.65 g, 3.8 mmol) in distilled water (10 ml) was added to the basic amide solution, giving at first a purple then brown solution. After 24 h a fine blue solid is precipitated which is removed by filtration. Brown needle shaped crystals of the product were then obtained by slow vapour diffusion of acetone into the aqueous phase.

S3. Refinement

H atoms bound to C atoms were placed geometrically and allowed to ride during refinement with C—H = 0.97 Å and with U_iso(H) = 1.2 U_eq(C). In one of the complex anions conformational disorder is observed for the propyl chain of the ligand, which was modelled in two orientiations with site occupancy factors 0.852 (5) and 0.148 (5), respectively. H atoms on the water molecules were found in difference Fourier maps, and refined with the O—H and H···H distances restrained to 0.82 (3) and 1.30 (3) Å, respectively. Their displacement parameters were constrained to be 1.2 U_eq for the parent O atom.

Computing details

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: APEX2 (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The asymmetric unit of the title compound, showing the anionic molecular unit and the potassium counter ions. Displacement ellipsoids drawn at the 70% probability level.
	Fig. 2. A packing diagram showing the relative arangements of the complex anion and the potassium cations. Cu: cyan, K: purple, O: red, N: blue C: black, H: not shown.
	Fig. 3. The coordination spheres of the water molecules and the hydrogen bonding network that they form. Displacement ellipsoids drawn at the 90% probability level. K: purple, O: red, H: white.

Dipotassium [N,N'-(propane-1,3-diyl)dioxamato-κ⁴O,N,N',O']copper(II) trihydrate

Crystal data

K2[Cu(C7H6N2O6)]·3H2O	Z = 4
Mr = 409.98	F(000) = 828
Triclinic, P1	Dx = 2.039 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.4738 (17) Å	Cell parameters from 6896 reflections
b = 10.5498 (15) Å	θ = 2.3–30.6°
c = 12.940 (2) Å	µ = 2.31 mm^−1
α = 72.322 (6)°	T = 100 K
β = 78.691 (7)°	Needle, brown
γ = 87.622 (6)°	0.4 × 0.2 × 0.2 mm
V = 1335.6 (4) Å^3

Data collection

Bruker APEXII CCD diffractometer	7887 independent reflections
Radiation source: fine-focus sealed tube	6530 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ϕ and ω–scans	θmax = 30.6°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −14→14
Tmin = 0.408, Tmax = 0.631	k = −7→14
19933 measured reflections	l = −17→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.035P)^2 + 1.1147P] where P = (Fo^2 + 2Fc^2)/3
7887 reflections	(Δ/σ)max = 0.001
419 parameters	Δρmax = 1.14 e Å^−3
18 restraints	Δρmin = −0.49 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.00614 (2)	0.61853 (2)	0.377692 (19)	0.00882 (6)
O1	−0.11603 (14)	0.70645 (14)	0.46968 (12)	0.0114 (3)
C1	−0.2262 (2)	0.6448 (2)	0.50706 (16)	0.0099 (4)
C2	−0.2405 (2)	0.5175 (2)	0.47506 (16)	0.0104 (4)
O2	−0.31996 (15)	0.67950 (15)	0.56729 (12)	0.0126 (3)
O3	−0.34651 (15)	0.45298 (15)	0.50764 (12)	0.0132 (3)
N1	−0.13270 (17)	0.49092 (17)	0.41369 (14)	0.0117 (3)
C3	−0.1314 (2)	0.3744 (2)	0.37447 (19)	0.0171 (4)
H3A	−0.2191	0.3554	0.3688	0.020*	0.852 (5)
H3B	−0.1027	0.2979	0.4279	0.020*	0.852 (5)
H3A'	−0.1665	0.2994	0.4375	0.020*	0.148 (5)
H3B'	−0.1912	0.3905	0.3236	0.020*	0.148 (5)
C4	−0.0429 (2)	0.3955 (2)	0.26375 (19)	0.0116 (5)	0.852 (5)
H4A	−0.0736	0.4718	0.2115	0.014*	0.852 (5)
H4B	−0.0522	0.3186	0.2394	0.014*	0.852 (5)
C5	0.0999 (2)	0.4176 (2)	0.25727 (19)	0.0176 (4)
H5A	0.1324	0.3420	0.3089	0.021*	0.852 (5)
H5B	0.1468	0.4230	0.1835	0.021*	0.852 (5)
H5A'	0.0908	0.4434	0.1805	0.021*	0.148 (5)
H5B'	0.1772	0.3640	0.2628	0.021*	0.148 (5)
C4'	−0.0081 (14)	0.3338 (14)	0.3198 (11)	0.0116 (5)	0.148 (5)
H4A'	0.0254	0.2666	0.3773	0.014*	0.148 (5)
H4B'	−0.0308	0.2880	0.2711	0.014*	0.148 (5)
N2	0.12531 (17)	0.53890 (17)	0.28247 (14)	0.0114 (3)
C6	0.2387 (2)	0.6010 (2)	0.24114 (16)	0.0105 (4)
C7	0.2481 (2)	0.7263 (2)	0.27828 (16)	0.0101 (4)
O4	0.33547 (14)	0.57099 (15)	0.17878 (12)	0.0131 (3)
O5	0.14623 (14)	0.75018 (14)	0.34315 (12)	0.0121 (3)
O6	0.34929 (15)	0.79414 (16)	0.24447 (13)	0.0152 (3)
Cu2	0.00607 (2)	0.87837 (2)	0.118918 (19)	0.00887 (6)
O7	−0.14892 (15)	0.86329 (15)	0.23306 (12)	0.0124 (3)
C8	−0.2332 (2)	0.7783 (2)	0.23232 (16)	0.0097 (4)
O8	−0.33757 (15)	0.74967 (15)	0.29780 (12)	0.0130 (3)
C9	−0.1965 (2)	0.7087 (2)	0.14147 (16)	0.0102 (4)
O9	−0.27554 (15)	0.62825 (15)	0.13377 (12)	0.0139 (3)
N3	−0.07932 (17)	0.74530 (17)	0.08150 (14)	0.0104 (3)
C10	−0.0265 (2)	0.6857 (2)	−0.00552 (16)	0.0110 (4)
H10A	−0.0533	0.7364	−0.0736	0.013*
H10B	−0.0610	0.5957	0.0149	0.013*
C11	0.1224 (2)	0.6827 (2)	−0.02428 (17)	0.0120 (4)
H11A	0.1480	0.6356	0.0453	0.014*
H11B	0.1532	0.6325	−0.0757	0.014*
C12	0.1896 (2)	0.8194 (2)	−0.06914 (17)	0.0132 (4)
H12A	0.2829	0.8086	−0.0876	0.016*
H12B	0.1603	0.8695	−0.1363	0.016*
N4	0.16214 (17)	0.89388 (17)	0.01087 (14)	0.0107 (3)
C13	0.2501 (2)	0.97875 (19)	0.01224 (16)	0.0092 (4)
O10	0.36044 (14)	1.00638 (15)	−0.04981 (12)	0.0129 (3)
C14	0.2045 (2)	1.0457 (2)	0.10437 (16)	0.0110 (4)
O11	0.08988 (15)	1.01213 (14)	0.16221 (12)	0.0117 (3)
O12	0.27828 (16)	1.12601 (15)	0.11610 (12)	0.0148 (3)
K1	−0.49090 (4)	0.77624 (4)	0.04661 (4)	0.01255 (9)
K2	−0.47340 (4)	0.52166 (5)	0.31974 (4)	0.01281 (9)
K3	−0.48490 (5)	0.96678 (4)	0.27047 (4)	0.01381 (9)
K4	−0.08998 (5)	0.98287 (5)	0.37159 (4)	0.01467 (10)
O13	0.15400 (17)	0.96010 (17)	0.43218 (13)	0.0190 (3)
H13B	0.208 (2)	1.018 (2)	0.391 (2)	0.023*
H13A	0.166 (3)	0.899 (2)	0.405 (2)	0.023*
O14	−0.55355 (16)	0.79251 (16)	0.48618 (13)	0.0158 (3)
H14A	−0.4804 (17)	0.767 (3)	0.495 (2)	0.019*
H14B	−0.586 (2)	0.726 (2)	0.480 (2)	0.019*
O15	−0.31804 (17)	1.12393 (17)	0.33581 (13)	0.0174 (3)
H15A	−0.351 (3)	1.142 (3)	0.3924 (14)	0.021*
H15B	−0.338 (3)	1.191 (2)	0.2876 (16)	0.021*
O16	−0.65571 (17)	1.16255 (17)	0.29677 (14)	0.0204 (4)
H16A	−0.693 (3)	1.177 (3)	0.2463 (18)	0.024*
H16B	−0.679 (3)	1.212 (3)	0.333 (2)	0.024*
O17	−0.37629 (17)	0.55354 (18)	−0.01201 (15)	0.0206 (3)
H17A	−0.311 (2)	0.572 (3)	0.008 (2)	0.025*
H17B	−0.350 (3)	0.527 (3)	−0.0664 (18)	0.025*
O18	−0.42834 (18)	0.34400 (19)	0.19062 (15)	0.0243 (4)
H18A	−0.499 (2)	0.309 (3)	0.191 (2)	0.029*
H18B	−0.411 (3)	0.400 (2)	0.1284 (17)	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00652 (12)	0.00991 (12)	0.00891 (11)	−0.00154 (9)	0.00108 (8)	−0.00260 (9)
O1	0.0095 (7)	0.0121 (7)	0.0115 (7)	−0.0012 (5)	0.0008 (5)	−0.0035 (5)
C1	0.0085 (9)	0.0134 (9)	0.0065 (8)	0.0000 (7)	−0.0023 (7)	−0.0003 (7)
C2	0.0084 (9)	0.0121 (9)	0.0097 (9)	−0.0001 (7)	−0.0016 (7)	−0.0017 (7)
O2	0.0101 (7)	0.0164 (7)	0.0114 (7)	0.0009 (6)	−0.0003 (5)	−0.0053 (6)
O3	0.0090 (7)	0.0157 (7)	0.0139 (7)	−0.0040 (6)	0.0011 (5)	−0.0048 (6)
N1	0.0080 (8)	0.0122 (8)	0.0141 (8)	−0.0024 (6)	0.0022 (6)	−0.0053 (6)
C3	0.0127 (11)	0.0148 (10)	0.0234 (11)	−0.0039 (8)	0.0048 (8)	−0.0100 (8)
C4	0.0120 (12)	0.0135 (11)	0.0109 (11)	−0.0007 (8)	−0.0018 (8)	−0.0062 (8)
C5	0.0139 (11)	0.0164 (10)	0.0230 (11)	−0.0037 (8)	0.0039 (8)	−0.0110 (9)
C4'	0.0120 (12)	0.0135 (11)	0.0109 (11)	−0.0007 (8)	−0.0018 (8)	−0.0062 (8)
N2	0.0087 (8)	0.0126 (8)	0.0127 (8)	−0.0026 (6)	0.0021 (6)	−0.0060 (6)
C6	0.0094 (9)	0.0125 (9)	0.0092 (9)	0.0002 (7)	−0.0021 (7)	−0.0023 (7)
C7	0.0095 (9)	0.0121 (9)	0.0080 (8)	−0.0014 (7)	−0.0024 (7)	−0.0014 (7)
O4	0.0076 (7)	0.0173 (7)	0.0137 (7)	−0.0016 (6)	0.0017 (5)	−0.0058 (6)
O5	0.0092 (7)	0.0126 (7)	0.0130 (7)	−0.0032 (5)	0.0020 (5)	−0.0040 (5)
O6	0.0110 (7)	0.0193 (8)	0.0148 (7)	−0.0055 (6)	0.0008 (6)	−0.0055 (6)
Cu2	0.00750 (12)	0.01079 (12)	0.00748 (11)	−0.00203 (9)	0.00116 (9)	−0.00287 (9)
O7	0.0102 (7)	0.0154 (7)	0.0106 (7)	−0.0036 (6)	0.0026 (5)	−0.0048 (5)
C8	0.0084 (9)	0.0107 (9)	0.0082 (8)	0.0005 (7)	−0.0011 (7)	−0.0007 (7)
O8	0.0094 (7)	0.0148 (7)	0.0126 (7)	−0.0007 (6)	0.0012 (5)	−0.0030 (6)
C9	0.0099 (9)	0.0111 (9)	0.0086 (8)	0.0002 (7)	−0.0015 (7)	−0.0016 (7)
O9	0.0106 (7)	0.0174 (7)	0.0141 (7)	−0.0040 (6)	−0.0005 (6)	−0.0060 (6)
N3	0.0101 (8)	0.0117 (8)	0.0090 (7)	−0.0006 (6)	0.0007 (6)	−0.0038 (6)
C10	0.0102 (10)	0.0137 (9)	0.0100 (9)	−0.0012 (7)	0.0001 (7)	−0.0057 (7)
C11	0.0106 (10)	0.0122 (9)	0.0139 (9)	−0.0002 (7)	0.0000 (7)	−0.0062 (7)
C12	0.0107 (10)	0.0166 (10)	0.0128 (9)	−0.0028 (8)	0.0022 (7)	−0.0074 (8)
N4	0.0087 (8)	0.0131 (8)	0.0105 (8)	−0.0019 (6)	0.0016 (6)	−0.0055 (6)
C13	0.0084 (9)	0.0096 (9)	0.0084 (8)	0.0005 (7)	−0.0016 (7)	−0.0012 (7)
O10	0.0078 (7)	0.0161 (7)	0.0138 (7)	−0.0019 (5)	0.0010 (5)	−0.0044 (6)
C14	0.0118 (10)	0.0122 (9)	0.0075 (8)	−0.0014 (7)	−0.0015 (7)	−0.0008 (7)
O11	0.0117 (7)	0.0134 (7)	0.0094 (7)	−0.0031 (5)	0.0006 (5)	−0.0036 (5)
O12	0.0157 (8)	0.0163 (7)	0.0124 (7)	−0.0060 (6)	−0.0006 (6)	−0.0047 (6)
K1	0.0095 (2)	0.0138 (2)	0.0122 (2)	−0.00217 (15)	0.00079 (15)	−0.00224 (15)
K2	0.0096 (2)	0.0169 (2)	0.01092 (19)	−0.00272 (16)	−0.00020 (15)	−0.00333 (16)
K3	0.0124 (2)	0.0141 (2)	0.0147 (2)	−0.00086 (16)	−0.00016 (16)	−0.00532 (16)
K4	0.0165 (2)	0.0160 (2)	0.0129 (2)	−0.00074 (17)	−0.00389 (17)	−0.00549 (16)
O13	0.0205 (9)	0.0201 (8)	0.0172 (8)	−0.0005 (7)	−0.0001 (6)	−0.0091 (6)
O14	0.0123 (8)	0.0182 (8)	0.0176 (8)	−0.0001 (6)	−0.0019 (6)	−0.0069 (6)
O15	0.0183 (8)	0.0209 (8)	0.0140 (7)	0.0029 (6)	−0.0021 (6)	−0.0076 (6)
O16	0.0217 (9)	0.0240 (9)	0.0229 (9)	0.0084 (7)	−0.0108 (7)	−0.0149 (7)
O17	0.0146 (9)	0.0279 (9)	0.0236 (9)	−0.0017 (7)	−0.0023 (7)	−0.0149 (7)
O18	0.0201 (9)	0.0256 (9)	0.0222 (9)	0.0027 (7)	0.0012 (7)	−0.0035 (7)

Geometric parameters (Å, º)

Cu1—N1	1.9131 (18)	C8—C9	1.546 (3)
Cu1—N2	1.9287 (17)	O8—K3	2.6797 (16)
Cu1—O5	1.9536 (15)	O8—K2	2.7571 (16)
Cu1—O1	1.9721 (15)	C9—O9	1.248 (2)
O1—C1	1.281 (2)	C9—N3	1.320 (3)
O1—K4	2.8057 (16)	O9—K2	2.8185 (16)
C1—O2	1.244 (2)	O9—K1	2.9041 (16)
C1—C2	1.542 (3)	N3—C10	1.459 (3)
C2—O3	1.257 (3)	C10—C11	1.530 (3)
C2—N1	1.319 (3)	C10—H10A	0.970
O2—K2^i	2.9294 (16)	C10—H10B	0.970
O3—K2^i	2.6995 (16)	C11—C12	1.527 (3)
O3—K2	2.8844 (16)	C11—H11A	0.970
N1—C3	1.464 (3)	C11—H11B	0.970
C3—C4'	1.460 (14)	C12—N4	1.459 (3)
C3—C4	1.504 (3)	C12—H12A	0.970
C3—H3A	0.970	C12—H12B	0.970
C3—H3B	0.970	N4—C13	1.317 (3)
C3—H3A'	0.970	C13—O10	1.260 (2)
C3—H3B'	0.970	C13—C14	1.552 (3)
C4—C5	1.506 (3)	O10—K1^iii	2.7329 (16)
C4—H4A	0.970	O10—K3^iii	2.8305 (16)
C4—H4B	0.970	O10—K1^ii	2.9128 (16)
C5—C4'	1.416 (14)	C14—O12	1.232 (3)
C5—N2	1.460 (3)	C14—O11	1.284 (3)
C5—H5A	0.970	O11—K4	2.9194 (16)
C5—H5B	0.970	O12—K1^iii	2.7365 (16)
C5—H5A'	0.970	K1—O17	2.8332 (18)
C5—H5B'	0.970	K2—O18	2.837 (2)
C4'—H4A'	0.970	K3—O16	2.7320 (17)
C4'—H4B'	0.970	K3—O14	2.8096 (17)
N2—C6	1.314 (3)	K3—O15	2.8617 (18)
C6—O4	1.259 (2)	K4—O13^iv	2.7360 (17)
C6—C7	1.551 (3)	K4—O13	2.7969 (19)
C7—O6	1.231 (3)	K4—O15	2.8027 (17)
C7—O5	1.289 (2)	O13—H13B	0.83 (2)
O4—K1^ii	2.7890 (16)	O13—H13A	0.82 (2)
O4—K2^ii	2.8939 (16)	O14—H14A	0.82 (2)
O6—K3^ii	2.7037 (16)	O14—H14B	0.83 (3)
O6—K1^ii	2.8247 (16)	O15—H15A	0.83 (3)
O6—K2^ii	3.3506 (17)	O15—H15B	0.84 (3)
Cu2—N4	1.9080 (18)	O16—H16A	0.80 (3)
Cu2—N3	1.9214 (18)	O16—H16B	0.81 (2)
Cu2—O7	1.9443 (15)	O17—H17A	0.82 (2)
Cu2—O11	1.9625 (15)	O17—H17B	0.83 (2)
O7—C8	1.287 (2)	O18—H18A	0.83 (2)
O7—K4	2.6567 (16)	O18—H18B	0.83 (2)
C8—O8	1.230 (2)
N1—Cu1—N2	96.64 (8)	C11—C12—H12B	109.3
N1—Cu1—O5	178.92 (7)	H12A—C12—H12B	107.9
N2—Cu1—O5	84.42 (7)	C13—N4—C12	119.52 (17)
N1—Cu1—O1	84.37 (7)	C13—N4—Cu2	115.16 (14)
N2—Cu1—O1	177.61 (7)	C12—N4—Cu2	125.31 (14)
O5—Cu1—O1	94.58 (6)	O10—C13—N4	127.39 (19)
C1—O1—Cu1	112.10 (13)	O10—C13—C14	120.66 (18)
C1—O1—K4	123.41 (12)	N4—C13—C14	111.95 (17)
Cu1—O1—K4	108.76 (6)	C13—O10—K1^iii	117.31 (13)
O2—C1—O1	124.89 (19)	C13—O10—K3^iii	140.13 (13)
O2—C1—C2	118.74 (18)	K1^iii—O10—K3^iii	92.13 (5)
O1—C1—C2	116.37 (17)	C13—O10—K1^ii	101.51 (12)
O3—C2—N1	128.1 (2)	K1^iii—O10—K1^ii	105.99 (5)
O3—C2—C1	119.79 (18)	K3^iii—O10—K1^ii	94.69 (5)
N1—C2—C1	112.15 (18)	O12—C14—O11	125.32 (19)
C1—O2—K2^i	115.85 (13)	O12—C14—C13	118.82 (18)
C2—O3—K2^i	122.56 (13)	O11—C14—C13	115.86 (17)
C2—O3—K2	105.64 (12)	C14—O11—Cu2	112.40 (13)
K2^i—O3—K2	106.34 (5)	C14—O11—K4	147.63 (13)
C2—N1—C3	118.80 (18)	Cu2—O11—K4	96.76 (6)
C2—N1—Cu1	114.97 (14)	C14—O12—K1^iii	119.12 (13)
C3—N1—Cu1	126.13 (14)	O10^iii—K1—O12^iii	61.29 (5)
C4'—C3—N1	119.0 (6)	O10^iii—K1—O4^v	142.77 (5)
N1—C3—C4	111.94 (18)	O12^iii—K1—O4^v	152.08 (5)
C4'—C3—H3A	128.5	O10^iii—K1—O6^v	85.83 (5)
N1—C3—H3A	109.2	O12^iii—K1—O6^v	147.06 (5)
C4—C3—H3A	109.2	O4^v—K1—O6^v	58.72 (4)
C4'—C3—H3B	73.0	O10^iii—K1—O17	125.98 (5)
N1—C3—H3B	109.2	O12^iii—K1—O17	74.14 (5)
C4—C3—H3B	109.2	O4^v—K1—O17	78.11 (5)
H3A—C3—H3B	107.9	O6^v—K1—O17	130.91 (5)
C4'—C3—H3A'	107.6	O10^iii—K1—O9	84.50 (5)
N1—C3—H3A'	107.6	O12^iii—K1—O9	76.14 (5)
C4—C3—H3A'	137.1	O4^v—K1—O9	90.53 (5)
C4'—C3—H3B'	107.6	O6^v—K1—O9	100.13 (5)
N1—C3—H3B'	107.6	O17—K1—O9	55.10 (5)
C4—C3—H3B'	76.5	O10^iii—K1—O10^v	74.01 (5)
H3A'—C3—H3B'	107.0	O12^iii—K1—O10^v	90.17 (5)
C3—C4—C5	117.3 (2)	O4^v—K1—O10^v	108.66 (5)
C3—C4—H4A	108.0	O6^v—K1—O10^v	82.08 (5)
C5—C4—H4A	108.0	O17—K1—O10^v	137.51 (5)
C3—C4—H4B	108.0	O9—K1—O10^v	158.22 (5)
C5—C4—H4B	108.0	O3^i—K2—O8	93.93 (5)
H4A—C4—H4B	107.2	O3^i—K2—O9	151.45 (5)
C4'—C5—N2	120.2 (6)	O8—K2—O9	59.29 (4)
N2—C5—C4	112.26 (19)	O3^i—K2—O18	136.49 (5)
C4'—C5—H5A	72.3	O8—K2—O18	129.53 (5)
N2—C5—H5A	109.2	O9—K2—O18	70.65 (5)
C4—C5—H5A	109.2	O3^i—K2—O3	73.66 (5)
C4'—C5—H5B	127.7	O8—K2—O3	75.51 (4)
N2—C5—H5B	109.2	O9—K2—O3	105.64 (5)
C4—C5—H5B	109.2	O18—K2—O3	114.72 (5)
H5A—C5—H5B	107.9	O3^i—K2—O4^v	91.61 (5)
C4'—C5—H5A'	107.3	O8—K2—O4^v	112.26 (5)
N2—C5—H5A'	107.3	O9—K2—O4^v	90.16 (5)
C4—C5—H5A'	76.2	O18—K2—O4^v	71.87 (5)
C4'—C5—H5B'	107.3	O3—K2—O4^v	164.10 (4)
N2—C5—H5B'	107.3	O3^i—K2—O2^i	58.66 (4)
C4—C5—H5B'	137.4	O8—K2—O2^i	152.46 (5)
H5A'—C5—H5B'	106.9	O9—K2—O2^i	148.07 (4)
C5—C4'—C3	126.7 (10)	O18—K2—O2^i	77.98 (5)
C5—C4'—H4A'	105.6	O3—K2—O2^i	92.55 (4)
C3—C4'—H4A'	105.6	O4^v—K2—O2^i	74.27 (4)
C5—C4'—H4B'	105.6	O3^i—K2—O6^v	68.82 (4)
C3—C4'—H4B'	105.6	O8—K2—O6^v	68.37 (4)
H4A'—C4'—H4B'	106.1	O9—K2—O6^v	90.39 (4)
C6—N2—C5	119.85 (18)	O18—K2—O6^v	120.48 (5)
C6—N2—Cu1	114.65 (14)	O3—K2—O6^v	124.74 (4)
C5—N2—Cu1	125.48 (14)	O4^v—K2—O6^v	51.68 (4)
O4—C6—N2	128.8 (2)	O2^i—K2—O6^v	100.65 (4)
O4—C6—C7	118.82 (18)	O8—K3—O6^v	80.17 (5)
N2—C6—C7	112.39 (17)	O8—K3—O16	166.04 (5)
O6—C7—O5	125.6 (2)	O6^v—K3—O16	99.19 (5)
O6—C7—C6	118.86 (18)	O8—K3—O14	69.03 (5)
O5—C7—C6	115.55 (18)	O6^v—K3—O14	77.95 (5)
C6—O4—K1^ii	117.31 (13)	O16—K3—O14	97.13 (5)
C6—O4—K2^ii	100.63 (12)	O8—K3—O10^iii	78.67 (5)
K1^ii—O4—K2^ii	83.00 (4)	O6^v—K3—O10^iii	86.26 (5)
C7—O5—Cu1	112.98 (13)	O16—K3—O10^iii	115.27 (5)
C7—O6—K3^ii	149.85 (14)	O14—K3—O10^iii	145.90 (5)
C7—O6—K1^ii	117.26 (13)	O8—K3—O15	96.70 (5)
K3^ii—O6—K1^ii	92.87 (5)	O6^v—K3—O15	170.50 (5)
C7—O6—K2^ii	90.70 (12)	O16—K3—O15	81.66 (5)
K3^ii—O6—K2^ii	96.66 (5)	O14—K3—O15	92.55 (5)
K1^ii—O6—K2^ii	74.62 (4)	O10^iii—K3—O15	102.00 (5)
N4—Cu2—N3	97.12 (7)	O7—K4—O13^iv	149.28 (5)
N4—Cu2—O7	177.77 (7)	O7—K4—O13	122.30 (5)
N3—Cu2—O7	84.63 (7)	O13^iv—K4—O13	79.99 (6)
N4—Cu2—O11	84.61 (7)	O7—K4—O15	84.01 (5)
N3—Cu2—O11	178.08 (6)	O13^iv—K4—O15	81.34 (5)
O7—Cu2—O11	93.63 (6)	O13—K4—O15	150.97 (5)
C8—O7—Cu2	112.87 (13)	O7—K4—O1	68.72 (5)
C8—O7—K4	138.61 (13)	O13^iv—K4—O1	94.44 (5)
Cu2—O7—K4	106.22 (6)	O13—K4—O1	86.35 (5)
O8—C8—O7	124.83 (19)	O15—K4—O1	117.16 (5)
O8—C8—C9	119.32 (18)	O7—K4—O11	61.23 (4)
O7—C8—C9	115.85 (17)	O13^iv—K4—O11	149.49 (5)
C8—O8—K3	108.63 (12)	O13—K4—O11	77.03 (5)
C8—O8—K2	120.21 (13)	O15—K4—O11	110.54 (5)
K3—O8—K2	113.34 (6)	O1—K4—O11	103.79 (4)
O9—C9—N3	128.80 (19)	K4^iv—O13—K4	100.01 (6)
O9—C9—C8	119.22 (18)	K4^iv—O13—H13B	106.5 (18)
N3—C9—C8	111.97 (18)	K4—O13—H13B	114 (2)
C9—O9—K2	117.15 (13)	K4^iv—O13—H13A	143.5 (19)
C9—O9—K1	108.51 (12)	K4—O13—H13A	86 (2)
K2—O9—K1	82.31 (4)	H13B—O13—H13A	104 (2)
C9—N3—C10	119.53 (17)	K3—O14—H14A	98.1 (19)
C9—N3—Cu2	114.60 (14)	K3—O14—H14B	105.8 (19)
C10—N3—Cu2	125.86 (14)	H14A—O14—H14B	102 (2)
N3—C10—C11	111.04 (16)	K4—O15—K3	108.62 (6)
N3—C10—H10A	109.4	K4—O15—H15A	108.3 (19)
C11—C10—H10A	109.4	K3—O15—H15A	114 (2)
N3—C10—H10B	109.4	K4—O15—H15B	135.9 (19)
C11—C10—H10B	109.4	K3—O15—H15B	88.7 (19)
H10A—C10—H10B	108.0	H15A—O15—H15B	101 (2)
C12—C11—C10	114.65 (17)	K3—O16—H16A	105.0 (19)
C12—C11—H11A	108.6	K3—O16—H16B	144.0 (19)
C10—C11—H11A	108.6	H16A—O16—H16B	111 (2)
C12—C11—H11B	108.6	K1—O17—H17A	86 (2)
C10—C11—H11B	108.6	K1—O17—H17B	142 (2)
H11A—C11—H11B	107.6	H17A—O17—H17B	107 (2)
N4—C12—C11	111.76 (17)	K2—O18—H18A	110 (2)
N4—C12—H12A	109.3	K2—O18—H18B	98 (2)
C11—C12—H12A	109.3	H18A—O18—H18B	104 (2)
N4—C12—H12B	109.3

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13B···O16^ii	0.83 (2)	2.05 (2)	2.884 (3)	177 (2)
O13—H13A···O5	0.82 (2)	2.00 (2)	2.800 (2)	166 (3)
O14—H14A···O2	0.82 (2)	2.13 (2)	2.918 (2)	163 (2)
O14—H14B···O3^i	0.82 (2)	1.99 (2)	2.806 (2)	169 (2)
O15—H15A···O14^vi	0.82 (2)	1.98 (2)	2.795 (2)	171 (2)
O15—H15B···O18^vii	0.84 (2)	2.05 (2)	2.870 (3)	167 (2)
O16—H16A···O12^v	0.80 (3)	2.00 (3)	2.701 (2)	147 (2)
O16—H16B···O2^vi	0.80 (3)	1.97 (3)	2.740 (2)	162 (2)
O17—H17A···O9	0.83 (2)	2.00 (3)	2.654 (2)	136 (2)
O17—H17B···O4^viii	0.84 (2)	2.01 (3)	2.807 (2)	163 (2)
O18—H18A···O16^ix	0.84 (2)	2.24 (3)	2.953 (3)	144 (2)
O18—H18B···O17	0.83 (2)	2.02 (2)	2.842 (3)	173 (2)

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