New structures in the bi­pyridine–copper(II) nitrate–methanol system: [(bpy)₂Cu(NO₃)]NO₃·CH₃OH and [(bpy)₂Cu(NO₃)]NO₃

Reaction of 2,2′-bi­pyridine (bpy) and copper(II) nitrate in methanol results in two complexes, namely light-blue bis(2,2′-bi­pyridine)­nitrato­copper(II) nitrate methanol solvate, [Cu(NO₃)(C₁₀H₈N₂)₂]NO₃·CH₃OH, (I), which is unstable in air, and the product of its decomposition, catena-poly­[[[bis(2,2′-bi­pyridine)copper(II)]-μ-nitrato-O:O′] nitrate], {[Cu(NO₃)(C₁₀H₈N₂)₂]NO₃}_n, (II). The crystal structures of both compounds were determined from one crystal at room temperature. Later, the structure of (I) was redetermined at low temperature. In (I) and (II), the Cu atom is coordinated by two bpy and one or two nitrate ions, respectively. The second nitrate ion in (I), along with the methanol solvent mol­ecule, is found in the outer coordination sphere, not bonded to Cu. The nitrate in (I) is chelating, while in (II), it bridges (bpy)₂Cu complexes, forming a one-dimensional chain structure. The Cu cation in (II) lies on a twofold axis and the uncoordinated NO₃⁻ ion is located close to a twofold axis and is therefore disordered. Compound (I) converts into (II) upon loss of solvent.

S1. Comment

Copper–bipyridine complexes have been proposed as catalysts for the hydrolysis of phosphate triesters, such as those found in toxic nerve agents (Morrow & Trogler, 1989). Although a great deal of research has been carried out on the reaction mechanism (Beaudry et al., 1994), a complete structure of the copper–bipyridine complex has not yet been reported. Noak & Gordon (1968) have proposed that the active catalytic structure contains water coordinated (inner sphere) to the central Cu atom, while Catalan et al. (1995) obtained a copper–bipyridin complex with water in the outer coordination sphere. We report here, the single-crystal X-ray structures of two new copper–bipyridine complexes, namely bis(2,2'-bipyridine)nitrocopper(II) nitrate methanol solvate, (I), and catena-poly[[[bis(2,2'-bipyridine)copper(II)]-µ-nitrato-O:O'] nitrate], (II).

The reaction of bipyridine (bpy) with copper(II) nitrate in a 1:1 ratio in methanol (see Experimental) results in a blue crystalline material. Two types of solid products can be identified under an optical microscope, viz. stable intense-blue crystals and light-blue crystalline blocks which are unstable in air. The latter crystals have some clearly visible faces, while the former crystals are effectively shapeless. The crystal structure determination of the intense-blue crystals yields the 1:1 complex [(bpy)Cu(NO₃)₂] previously studied at 193 K (Tadsanaprasittipol et al., 1998).

The unstable light-blue crystals were covered several times with a thin layer of epoxy prior to carrying out the experiment. Indexing of diffraction peaks yielded two related, but still different, lattices. One lattice, (I), was indexed in a triclinic cell, whereas the other set, (II), was indexed in a monoclinic C-centered cell. The monoclinic cell can be reduced to a primitive unit cell with dimensions a = 7.165 (1), b = 10.847 (2), c= 14.633 (3) Å, α = 110.127 (4), β = 101.846 (4) and γ = 96.109 (4)°, which resemble the cell dimensions of the (I) component. The crystal structures of both the triclinic and monoclinic components were determined and resulted in 2:1 complexes with compositions (bpy)₂Cu(NO₃)₂·CH₃OH, (I), and (bpy)₂Cu(NO₃)₂, (II). Essentially, the two crystal structures were determined from one crystal. Interestingly, compound (I) decomposes at some point during the diffraction experiment as a result of evolution of methanol from the crystal. This was in contrast to compound (II), which was stable to the completion of the experiment. Epoxy encapsulation did not prevent decomposition of the crystal, which was stable for about two hours. In multiple experiments, it was noticed that the decomposition of (I) due to the loss of solvent (1–2 h) leads to the formation of compound (II). The diffraction peaks of the resulting `crystals' were broad and the quality of the diffraction pattern was therefore not suitable for structure refinement. The pattern was good enough for the unit cell determination however.

The crystal structure of (I) was redetermined at low temperature from a single-crystal and is described here. Data obtained from the room-temperature experiment were not suitable for publication due to the crystal decomposition. Despite this, the structure was solved and does not differ significantly from the low-temperature structure except in the orientational disorder of the uncoordinated nitrate ion.

The structure of (II) was determined from the double crystal, which contained the two molecules, (I) and (II). An individual single-crystal of (II) suitable for diffraction analysis was not found after numerous attempts. This could mean that (II) only forms from (I) upon the loss of solvent.

Complex (I), with a 2:1 bpy-to-Cu ratio, consists of a [(bpy)₂Cu(NO₃)]⁺ cation, two nitrate ions and a methanl solvent molecule (Fig. 1). The Cu atom in (I) is coordinated by two bpy molecules and one chelating nitrate (N5) anion. The uncoordinated nitrate ion makes a strong hydrogen bond with the hydroxy group and two weak hydrogen bonds with the methyl group of the solvent (Table 2). The pyridine rings in both the N1/N2 and N3/N4 bpy molecules are tilted around the C—C bond by 9.83 (8) and 3.98 (7)°, respectively. The Cu atom and one pair of N atoms from different bpy molecules form almost a straight line, with an N1—Cu1—N4 angle of 176.01 (5)°. In contrast, the Cu atom and the other pair of N atoms are not linear, with an N2—Cu1—N3 angle of 126.64 (5)°. This indicates that the bpy molecules are tilted from each other around the C3—N1—Cu—N4—C18 line by about 60°.

The configuration of the complex [(bpy)₂Cu(NO₃)]⁺ cation is quite similar to that in [(bpy)₂Cu(NO₃)](NO₃)(H₂O), reported by Catalan et al. (1995). However, the stacking differs substantially, most likely due to the stronger and more branched hydrogen-bond network of water versus methanol.

Complex (II) differs from (I) by the absence of the methanol solvent molecule and consists of a [(bpy)₂Cu(NO₃)]⁺ cation and an NO₃^- anion (Fig. 2). However, the coordinated nitrate ion is not chelating, but instead bridges the (bpy)₂Cu complex ions, forming a one-dimensional chain. The Cu coordination polyhedron can be described as a strongly distorted octahedron consisting of four N atoms, with Cu—N distances less than 2 Å, and two weakly bonded O atoms from the bridged nitrate group in apical positions (Table 3 and Fig. 2). This distorted octahedron agrees well with the Cu1 atomic displacement ellipsoid elongated in the direction of the weakly bonded O atoms. This is probably due to disorder of the Cu atom lying slightly off the twofold axis. Both the (bpy)₂Cu and NO₃^- ions are situated on twofold axes, which pass through the center of the bpy molecules and the Cu atom in the complex and along the N11—O11 bond of the bridging nitrate ion. The two bpy molecules, denoted A and B in Fig. 2, are tilted around a twofold axis by 46.66 (6)° from each other. The two pyridine rings are tilted from each other by 3.5 (2)° in bpy A and by 10.8 (2)° in bpy B. The isolated NO₃ ion is situated near the twofold axis and is therefore disordered.

It was found that (I) easily loses a solvent molecule upon exposure to air and converts to (II). The complex [(bpy)₂Cu(NO₃)]⁺ cations in (I) are stacked on top of each other along the a axis in such a way that atom O3 of the coordinated nitrate anion forms a contact of 3.737 (2) Å with the Cu atom from the next complex (Fig. 3a). During the conversion, one Cu—O bond breaks and a new Cu—O bond forms to the Cu atom of the next complex cation. Thus, in (II), the chelating nitrate group becomes bridging and links the cationic complexes into a one-dimensional chain along the c axis, as shown in Fig. 3(b). Both Cu—O bonds are weak and have equal lengths of 2.696 (4) Å. Therefore, the Cu···Cu distance along the chain is 0.5 Å shorter in (II) (Cu1···Cu1^iv in Table 3) then in (I) (Cu1···Cu1ⁱ in Table 1). This structural reorganization also causes changes in the (bpy)₂Cu configuration. The two bpy molecules move to equatorial positions to make space for the second apical nitrate ion. Thus, the bpy_center—Cu—bpy_center angle is 151.19 (5)° in (I) and linear in (II). In both compounds, the bpy molecules are tilted towards each other due to the steric interaction between the C—H groups next to the coordinated N atoms.

S2. Experimental

Reagent grade Cu(NO₃)₂·2.5H₂O and 2,2'-bipyridine (bpy) were purchased from commercial sources (Aldrich Chemical Company Inc.) and used without further purification. Reagent grade methanol was purchased from a commercial source (EM Science) and used without purification. The complexes were prepared based on the literature procedure of Morrow & Trogler (1989). A 50 ml solution of methanol containing stoichiometric ratios of Cu(NO₃)₂·2.5H₂O and bpy (1:2 ratio) was purged with a blanket of N₂ and heated at reflux for approximately 12 h under constant mixing. After reflux was complete, the reaction solution was rotary evaporated to reduce the volume by half. The remaining solution was left to crystallize. Results for elemental analysis for compounds (I) and (II), theoretical: C 48.0, H 3.2, N 16.8%; found: C 47.6, H 3.1, N 16.6%. Key peaks for IR scan: 778, 1384, 3075 cm^-1. The approximately 0.044 M solution remaining after rotary evaporation was wrapped in aluminium foil to reduce exposure to light and left to crystallize at room temperature. After 3 d at room temperature, crystals of sufficient size for X-ray diffraction experiments were obtained. Crystals were harvested directly from the reaction vessel immediately prior to conducting the diffraction experiment.

S3. Refinement

The H atoms in (I) were refined with C—H distances constrained to be the same. The average C—H distance was refined to 0.917 Å for bpy and 0.943 Å for methanol molecules. The H atoms in (II) were refined as riding with C—H distances of 0.93 Å. U_iso value were refined independently for all H atoms in (I) and were assigned as 1.2U_eq for the attached C atom in (II).

Computing details

For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEP-3 (Farrugia, 1997) and Materials Studio (Accelrys, 2001) for (I); ORTEP-3 (Farrugia,1997) and Materials Studio (Accelrys, 2001) for (II). For both compounds, software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Displacement-ellipsoid plot of (I) at the 50% probability level.
	Fig. 2. Displacement-ellipsoid plot of (II) at the 30% probability level. Disorder of uncoordinated nitrate ion is not shown. [Symmetry codes: (i) 1 - x, y, 1/2 - z; (ii) 1 - x, y, 3/2 - z; (iii) x, y, z - 1.]
	Fig. 3. Chains of [bpy2Cu(NO3)]^+ complexes in (a) (I) and (b) (II). Cu1···O3 contacts between different complexes in (I) are shown as dashed lines (Accelrys, 2001).

(I) bis(2,2'-bipyridine)nitrocopper(II) nitrate methanol solvate

Crystal data

[Cu(NO3)(C10H8N2)2](NO3)·CH4O	Z = 2
Mr = 531.97	F(000) = 546
Triclinic, P1	Dx = 1.578 Mg m^−3
a = 7.6862 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.8902 (9) Å	Cell parameters from 6220 reflections
c = 13.3644 (11) Å	θ = 2.7–31.1°
α = 109.492 (3)°	µ = 1.03 mm^−1
β = 92.902 (4)°	T = 100 K
γ = 101.347 (4)°	Prism, blue
V = 1119.9 (2) Å^3	0.45 × 0.38 × 0.34 mm

Data collection

Smart CCD diffractometer	6676 independent reflections
Radiation source: fine-focus sealed tube	5643 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ϕ and ω scans	θmax = 30.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.634, Tmax = 0.704	k = −16→16
22064 measured reflections	l = −18→19

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0637P)^2 + 0.0117P] where P = (Fo^2 + 2Fc^2)/3
6676 reflections	(Δ/σ)max = 0.001
398 parameters	Δρmax = 0.76 e Å^−3
19 restraints	Δρmin = −0.22 e Å^−3

Special details

Experimental. Omega scan: 606 frames for phi= 0, 120 and 240 °. 2theta = -31 °., omega starts from -31 °. omega step = -0.3 °., expouse = 4 sec/frame Phi scan: 1206 frames for phi from 0, phi step = 0.3 °. 2theta = omega = -31 °., expouse = 4 sec/frame After each scan 50 frames where taken for decomposition and alignment control. Total # of frames = 3224.

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.

Planes from SHELX97 output. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 6.3901 (0.0015) x + 6.8620 (0.0020) y + 3.1090 (0.0053) z = 6.7125 (0.0027)

* 0.0421 (0.0011) N1 * -0.1279 (0.0011) N2 * 0.1105 (0.0013) C1 * 0.0840 (0.0013) C2 * -0.0521 (0.0014) C3 * -0.1161 (0.0014) C4 * -0.0529 (0.0013) C5 * -0.0636 (0.0013) C6 * 0.0538 (0.0013) C7 * 0.1177 (0.0013) C8 * 0.0630 (0.0014) C9 * -0.0584 (0.0012) C10 - 0.1373 (0.0012) Cu1

Rms deviation of fitted atoms = 0.0839

- 6.7166 (0.0025) x + 6.4902 (0.0063) y + 2.5738 (0.0083) z = 6.0330 (0.0059)

Angle to previous plane (with approximate e.s.d.) = 4.82 (0.07)

* -0.0070 (0.0010) N1 * -0.0050 (0.0011) C1 * 0.0124 (0.0011) C2 * -0.0082 (0.0012) C3 * -0.0034 (0.0011) C4 * 0.0112 (0.0010) C5 0.0641 (0.0023) C6 - 0.2397 (0.0021) Cu1

Rms deviation of fitted atoms = 0.0085

- 5.9943 (0.0029) x + 7.2756 (0.0058) y + 3.5380 (0.0080) z = 7.1693 (0.0033)

Angle to previous plane (with approximate e.s.d.) = 9.83 (0.08)

* -0.0041 (0.0010) N2 * 0.0037 (0.0010) C6 * -0.0008 (0.0011) C7 * -0.0017 (0.0011) C8 * 0.0013 (0.0011) C9 * 0.0016 (0.0011) C10 0.0920 (0.0022) C5 0.1627 (0.0020) Cu1

Rms deviation of fitted atoms = 0.0025

- 6.3614 (0.0026) x + 6.1417 (0.0067) y + 4.2441 (0.0078) z = 6.7940 (0.0052)

Angle to previous plane (with approximate e.s.d.) = 6.76 (0.09)

* 0.0000 (0.0000) N1 * 0.0000 (0.0000) N2 * 0.0000 (0.0000) Cu1

Rms deviation of fitted atoms = 0.0000

1.2357 (0.0033) x - 8.0851 (0.0071) y + 12.1464 (0.0040) z = 2.2391 (0.0089)

Angle to previous plane (with approximate e.s.d.) = 86.76 (0.04)

* 0.0000 (0.0000) O1 * 0.0000 (0.0000) O2 * 0.0000 (0.0000) Cu1

Rms deviation of fitted atoms = 0.0000

4.4318 (0.0036) x - 8.7036 (0.0128) y + 9.0536 (0.0088) z = 1.6736 (0.0174)

Angle to previous plane (with approximate e.s.d.) = 27.09 (0.10)

* -0.6331 (0.0012) O1 * -0.2960 (0.0012) O2 * 0.3418 (0.0005) N4 * 0.5873 (0.0008) O3 - 1.4482 (0.0011) Cu1

Rms deviation of fitted atoms = 0.4874

7.0275 (0.0022) x + 2.4614 (0.0081) y - 1.3254 (0.0080) z = 2.7952 (0.0066)

Angle to previous plane (with approximate e.s.d.) = 71.00 (0.05)

* 0.0000 (0.0000) N3 * 0.0000 (0.0000) N4 * 0.0000 (0.0000) Cu1

Rms deviation of fitted atoms = 0.0000

1.2357 (0.0033) x - 8.0851 (0.0071) y + 12.1464 (0.0040) z = 2.2391 (0.0089)

Angle to previous plane (with approximate e.s.d.) = 87.30 (0.05)

* 0.0000 (0.0000) O1 * 0.0000 (0.0000) O2 * 0.0000 (0.0000) Cu1

Rms deviation of fitted atoms = 0.0000

- 6.3614 (0.0026) x + 6.1417 (0.0067) y + 4.2441 (0.0078) z = 6.7940 (0.0052)

Angle to previous plane (with approximate e.s.d.) = 86.76 (0.04)

* 0.0000 (0.0000) N1 * 0.0000 (0.0000) N2 * 0.0000 (0.0000) Cu1

Rms deviation of fitted atoms = 0.0000

7.0275 (0.0022) x + 2.4614 (0.0081) y - 1.3254 (0.0080) z = 2.7952 (0.0066)

Angle to previous plane (with approximate e.s.d.) = 54.90 (0.04)

* 0.0000 (0.0000) N3 * 0.0000 (0.0000) N4 * 0.0000 (0.0000) Cu1

Rms deviation of fitted atoms = 0.0000

6.9453 (0.0008) x + 2.8532 (0.0024) y - 2.0530 (0.0060) z = 2.5236 (0.0054)

Angle to previous plane (with approximate e.s.d.) = 3.30 (0.06)

* 0.0247 (0.0012) N3 * -0.0568 (0.0012) N4 * 0.0416 (0.0013) C11 * 0.0295 (0.0014) C12 * -0.0198 (0.0013) C13 * -0.0500 (0.0013) C14 * -0.0195 (0.0014) C15 * -0.0225 (0.0014) C16 * 0.0281 (0.0014) C17 * 0.0412 (0.0014) C18 * 0.0252 (0.0014) C19 * -0.0217 (0.0013) C20 0.0569 (0.0013) Cu1

Rms deviation of fitted atoms = 0.0339

6.9883 (0.0021) x + 2.6503 (0.0074) y - 1.6155 (0.0088) z = 2.7266 (0.0089)

Angle to previous plane (with approximate e.s.d.) = 1.94 (0.05)

* 0.0017 (0.0010) N3 * -0.0050 (0.0011) C11 * 0.0035 (0.0012) C12 * 0.0010 (0.0011) C13 * -0.0043 (0.0011) C14 * 0.0030 (0.0010) C15 0.0236 (0.0023) C16 0.0094 (0.0022) Cu1

Rms deviation of fitted atoms = 0.0034

6.8815 (0.0023) x + 3.0953 (0.0076) y - 2.4934 (0.0085) z = 2.2749 (0.0083)

Angle to previous plane (with approximate e.s.d.) = 3.96 (0.07)

* -0.0070 (0.0010) N4 * 0.0027 (0.0010) C16 * 0.0042 (0.0011) C17 * -0.0069 (0.0012) C18 * 0.0027 (0.0012) C19 * 0.0043 (0.0011) C20 0.0347 (0.0024) C15 0.1765 (0.0022) Cu1

Rms deviation of fitted atoms = 0.0049

6.9453 (0.0008) x + 2.8532 (0.0024) y - 2.0530 (0.0060) z = 2.5236 (0.0054)

Angle to previous plane (with approximate e.s.d.) = 2.02 (0.06)

* 0.0247 (0.0012) N3 * -0.0568 (0.0012) N4 * 0.0416 (0.0013) C11 * 0.0295 (0.0014) C12 * -0.0198 (0.0013) C13 * -0.0500 (0.0013) C14 * -0.0195 (0.0014) C15 * -0.0225 (0.0014) C16 * 0.0281 (0.0014) C17 * 0.0412 (0.0014) C18 * 0.0252 (0.0014) C19 * -0.0217 (0.0013) C20 0.0569 (0.0013) Cu1

Rms deviation of fitted atoms = 0.0339

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.

All H atoms were located from difference Fourier map and refined with C—H bond length restrained to be the same for all bonds. Methanol C—H bonds were restrained separately and O—H bond was not restrained.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.23697 (2)	0.84996 (2)	0.72600 (2)	0.01783 (7)
N1	0.20965 (17)	0.90586 (11)	0.60414 (10)	0.0176 (2)
N2	0.03918 (17)	0.70911 (11)	0.63335 (10)	0.0178 (2)
C1	0.3068 (2)	1.00953 (13)	0.59701 (13)	0.0204 (3)
H1	0.383 (2)	1.0646 (13)	0.6562 (11)	0.016 (4)*
C2	0.2943 (2)	1.03614 (14)	0.50417 (13)	0.0225 (3)
H2	0.359 (2)	1.1072 (13)	0.5014 (16)	0.023 (5)*
C3	0.1821 (2)	0.95205 (15)	0.41525 (13)	0.0246 (3)
H3	0.180 (3)	0.9696 (18)	0.3529 (11)	0.025 (5)*
C4	0.0809 (2)	0.84512 (14)	0.42264 (12)	0.0223 (3)
H4	0.004 (2)	0.7905 (15)	0.3646 (12)	0.026 (5)*
C5	0.0959 (2)	0.82492 (13)	0.51849 (12)	0.0173 (3)
C6	−0.0085 (2)	0.71725 (12)	0.53801 (12)	0.0174 (3)
C7	−0.1515 (2)	0.63364 (14)	0.46644 (13)	0.0211 (3)
H7	−0.186 (3)	0.641 (2)	0.4030 (12)	0.039 (6)*
C8	−0.2482 (2)	0.54013 (14)	0.49463 (13)	0.0236 (3)
H8	−0.3473 (19)	0.4880 (15)	0.4492 (13)	0.021 (5)*
C9	−0.2005 (2)	0.53210 (14)	0.59280 (14)	0.0244 (3)
H9	−0.267 (3)	0.4715 (16)	0.6124 (17)	0.037 (6)*
C10	−0.0561 (2)	0.61838 (14)	0.66021 (13)	0.0211 (3)
H10	−0.018 (2)	0.6158 (17)	0.7257 (11)	0.024 (5)*
N3	0.20821 (17)	1.00164 (11)	0.85517 (10)	0.0187 (2)
N4	0.28029 (17)	0.79062 (11)	0.84546 (10)	0.0188 (2)
C11	0.1674 (2)	1.10588 (14)	0.85359 (13)	0.0219 (3)
H11	0.153 (3)	1.1169 (17)	0.7885 (11)	0.025 (5)*
C12	0.1542 (2)	1.20003 (14)	0.94589 (14)	0.0245 (3)
H12	0.134 (3)	1.2717 (14)	0.9415 (18)	0.037 (6)*
C13	0.1819 (2)	1.18545 (15)	1.04342 (14)	0.0242 (3)
H13	0.179 (3)	1.2488 (14)	1.1031 (12)	0.031 (5)*
C14	0.2227 (2)	1.07764 (14)	1.04623 (12)	0.0216 (3)
H14	0.234 (2)	1.0618 (16)	1.1091 (10)	0.015 (4)*
C15	0.23571 (19)	0.98758 (13)	0.95023 (12)	0.0179 (3)
C16	0.2819 (2)	0.87042 (13)	0.94511 (12)	0.0184 (3)
C17	0.3268 (2)	0.84372 (15)	1.03520 (13)	0.0223 (3)
H17	0.331 (3)	0.9019 (15)	1.1019 (11)	0.031 (5)*
C18	0.3707 (2)	0.73237 (15)	1.02250 (14)	0.0249 (3)
H18	0.389 (3)	0.7073 (19)	1.0788 (13)	0.036 (6)*
C19	0.3713 (2)	0.65154 (15)	0.92011 (14)	0.0253 (3)
H19	0.404 (3)	0.5799 (15)	0.913 (2)	0.048 (7)*
C20	0.3259 (2)	0.68346 (14)	0.83389 (13)	0.0225 (3)
H20	0.326 (3)	0.6331 (15)	0.7651 (10)	0.021 (5)*
N5	0.58575 (18)	0.83052 (11)	0.68538 (10)	0.0197 (3)
O1	0.52226 (15)	0.91958 (10)	0.74332 (9)	0.0207 (2)
O2	0.47839 (17)	0.73615 (10)	0.62568 (10)	0.0312 (3)
O3	0.74983 (15)	0.84163 (11)	0.69178 (10)	0.0256 (2)
N6	0.4511 (2)	0.33854 (12)	0.73714 (11)	0.0259 (3)
O4	0.28982 (18)	0.29812 (13)	0.74079 (12)	0.0384 (3)
O5	0.50345 (19)	0.44698 (11)	0.74038 (12)	0.0365 (3)
O6	0.55977 (19)	0.27295 (12)	0.73075 (13)	0.0410 (3)
C1M	0.9560 (3)	0.43745 (17)	0.84539 (18)	0.0343 (4)
H1M	0.888 (3)	0.3582 (14)	0.8351 (17)	0.029 (5)*
H2M	1.043 (3)	0.461 (2)	0.9044 (17)	0.062 (8)*
H3M	1.011 (3)	0.434 (2)	0.7825 (15)	0.053 (7)*
O1M	0.8485 (2)	0.52427 (12)	0.86747 (12)	0.0354 (3)
H4M	0.764 (3)	0.497 (2)	0.831 (2)	0.039 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01944 (11)	0.01741 (10)	0.01623 (10)	0.00382 (7)	0.00093 (7)	0.00577 (7)
N1	0.0173 (6)	0.0181 (5)	0.0174 (6)	0.0052 (4)	0.0019 (5)	0.0054 (5)
N2	0.0167 (6)	0.0181 (5)	0.0189 (6)	0.0061 (4)	0.0041 (5)	0.0053 (5)
C1	0.0199 (7)	0.0182 (6)	0.0208 (7)	0.0031 (5)	0.0016 (6)	0.0047 (6)
C2	0.0219 (8)	0.0220 (7)	0.0250 (7)	0.0042 (5)	0.0052 (6)	0.0104 (6)
C3	0.0260 (8)	0.0287 (8)	0.0207 (7)	0.0043 (6)	0.0045 (6)	0.0114 (6)
C4	0.0226 (8)	0.0239 (7)	0.0172 (7)	0.0026 (6)	0.0013 (6)	0.0048 (6)
C5	0.0149 (7)	0.0183 (6)	0.0188 (6)	0.0048 (5)	0.0035 (5)	0.0056 (5)
C6	0.0159 (7)	0.0167 (6)	0.0187 (6)	0.0055 (5)	0.0042 (5)	0.0037 (5)
C7	0.0200 (8)	0.0208 (7)	0.0193 (7)	0.0049 (5)	0.0018 (6)	0.0030 (6)
C8	0.0200 (8)	0.0194 (7)	0.0258 (8)	0.0029 (5)	0.0038 (6)	0.0017 (6)
C9	0.0229 (8)	0.0198 (7)	0.0299 (8)	0.0038 (6)	0.0075 (6)	0.0081 (6)
C10	0.0207 (8)	0.0217 (7)	0.0232 (7)	0.0070 (5)	0.0061 (6)	0.0092 (6)
N3	0.0161 (6)	0.0203 (6)	0.0196 (6)	0.0047 (4)	0.0031 (5)	0.0064 (5)
N4	0.0188 (6)	0.0185 (5)	0.0182 (6)	0.0046 (4)	0.0013 (5)	0.0054 (5)
C11	0.0208 (8)	0.0228 (7)	0.0232 (7)	0.0071 (5)	0.0034 (6)	0.0081 (6)
C12	0.0216 (8)	0.0212 (7)	0.0302 (8)	0.0088 (6)	0.0054 (6)	0.0058 (6)
C13	0.0203 (8)	0.0226 (7)	0.0251 (8)	0.0063 (6)	0.0053 (6)	0.0012 (6)
C14	0.0180 (7)	0.0255 (7)	0.0184 (7)	0.0041 (5)	0.0029 (6)	0.0045 (6)
C15	0.0125 (7)	0.0212 (6)	0.0194 (7)	0.0029 (5)	0.0030 (5)	0.0068 (6)
C16	0.0133 (7)	0.0211 (6)	0.0202 (7)	0.0025 (5)	0.0036 (5)	0.0071 (6)
C17	0.0203 (8)	0.0275 (7)	0.0195 (7)	0.0040 (6)	0.0041 (6)	0.0092 (6)
C18	0.0227 (8)	0.0308 (8)	0.0258 (8)	0.0059 (6)	0.0020 (6)	0.0163 (7)
C19	0.0248 (8)	0.0241 (7)	0.0307 (8)	0.0076 (6)	0.0034 (7)	0.0131 (7)
C20	0.0231 (8)	0.0203 (7)	0.0241 (7)	0.0057 (5)	0.0034 (6)	0.0072 (6)
N5	0.0222 (7)	0.0207 (6)	0.0187 (6)	0.0069 (5)	0.0050 (5)	0.0084 (5)
O1	0.0200 (6)	0.0211 (5)	0.0202 (5)	0.0084 (4)	0.0032 (4)	0.0041 (4)
O2	0.0315 (7)	0.0204 (5)	0.0336 (7)	0.0023 (5)	0.0019 (5)	0.0013 (5)
O3	0.0196 (6)	0.0343 (6)	0.0274 (6)	0.0122 (5)	0.0076 (5)	0.0125 (5)
N6	0.0284 (8)	0.0254 (6)	0.0216 (6)	0.0023 (5)	−0.0009 (5)	0.0082 (5)
O4	0.0275 (7)	0.0474 (8)	0.0430 (8)	−0.0014 (6)	0.0023 (6)	0.0252 (7)
O5	0.0385 (8)	0.0250 (6)	0.0478 (8)	0.0050 (5)	0.0105 (6)	0.0157 (6)
O6	0.0355 (8)	0.0284 (6)	0.0527 (9)	0.0096 (5)	−0.0101 (7)	0.0069 (6)
C1M	0.0301 (10)	0.0286 (8)	0.0445 (11)	0.0058 (7)	0.0046 (8)	0.0137 (8)
O1M	0.0364 (8)	0.0283 (6)	0.0378 (8)	0.0092 (6)	0.0000 (6)	0.0065 (6)

Geometric parameters (Å, º)

Cu1—N1	1.970 (1)	C11—C12	1.386 (2)
Cu1—N4	1.987 (1)	C11—H11	0.926 (11)
Cu1—N2	2.018 (1)	C12—C13	1.383 (3)
Cu1—N3	2.098 (1)	C12—H12	0.916 (11)
Cu1—O1	2.157 (1)	C13—C14	1.390 (2)
Cu1—O2	2.665 (1)	C13—H13	0.902 (11)
N1—C1	1.345 (2)	C14—C15	1.393 (2)
N1—C5	1.354 (2)	C14—H14	0.924 (10)
N2—C10	1.343 (2)	C15—C16	1.485 (2)
N2—C6	1.348 (2)	C16—C17	1.388 (2)
C1—C2	1.382 (2)	C17—C18	1.388 (2)
C1—H1	0.924 (10)	C17—H17	0.922 (11)
C2—C3	1.386 (2)	C18—C19	1.386 (2)
C2—H2	0.905 (11)	C18—H18	0.911 (11)
C3—C4	1.391 (2)	C19—C20	1.377 (2)
C3—H3	0.925 (11)	C19—H19	0.911 (11)
C4—C5	1.383 (2)	C20—H20	0.914 (10)
C4—H4	0.915 (11)	N5—O3	1.2374 (17)
C5—C6	1.480 (2)	N5—O2	1.2442 (17)
C6—C7	1.393 (2)	N5—O1	1.2860 (16)
C7—C8	1.383 (2)	N6—O6	1.2376 (19)
C7—H7	0.914 (11)	N6—O4	1.248 (2)
C8—C9	1.383 (2)	N6—O5	1.2582 (18)
C8—H8	0.921 (10)	C1M—O1M	1.412 (2)
C9—C10	1.389 (2)	C1M—H1M	0.944 (14)
C9—H9	0.920 (11)	C1M—H2M	0.933 (15)
C10—H10	0.921 (10)	C1M—H3M	0.952 (15)
N3—C11	1.3435 (19)	O1M—H4M	0.74 (3)
N3—C15	1.347 (2)	Cu1—Cu1^i	7.6862 (6)
N4—C20	1.3491 (19)	Cu1—Cu1^ii	7.6862 (6)
N4—C16	1.3507 (19)	Cu1—Cu1^iii	7.5234 (6)
N1—Cu1—N4	176.01 (5)	C9—C10—H10	121.9 (12)
N1—Cu1—N2	81.64 (5)	C11—N3—C15	118.67 (13)
N4—Cu1—N2	99.45 (5)	C20—N4—C16	118.93 (13)
N1—Cu1—N3	102.09 (5)	N3—C11—C12	122.64 (15)
N4—Cu1—N3	80.39 (5)	N3—C11—H11	118.7 (12)
N2—Cu1—N3	126.64 (5)	C12—C11—H11	118.6 (12)
N1—Cu1—O1	89.43 (5)	Cu1—C11—H11	87.0 (12)
N4—Cu1—O1	87.35 (5)	C13—C12—C11	118.68 (15)
N2—Cu1—O1	141.56 (4)	C13—C12—H12	121.5 (15)
N3—Cu1—O1	91.77 (4)	C11—C12—H12	119.8 (15)
N1—Cu1—O2	86.76 (5)	C12—C13—C14	119.32 (14)
N4—Cu1—O2	89.39 (5)	C12—C13—H13	117.9 (13)
N2—Cu1—O2	89.82 (4)	C14—C13—H13	122.7 (13)
N3—Cu1—O2	143.16 (4)	C13—C14—C15	118.77 (15)
O1—Cu1—O2	52.22 (4)	C13—C14—H14	122.1 (11)
C1—N1—C5	119.51 (13)	C15—C14—H14	119.0 (11)
C1—N1—Cu1	125.07 (10)	N3—C15—C14	121.91 (14)
C5—N1—Cu1	115.05 (10)	N3—C15—C16	115.31 (12)
C10—N2—C6	118.67 (13)	C14—C15—C16	122.78 (14)
C10—N2—Cu1	127.46 (11)	N4—C16—C17	121.47 (14)
C6—N2—Cu1	113.58 (10)	N4—C16—C15	115.23 (13)
N1—C1—C2	121.83 (14)	C17—C16—C15	123.29 (13)
N1—C1—H1	118.8 (11)	C16—C17—C18	119.20 (14)
C2—C1—H1	119.4 (11)	C16—C17—H17	118.9 (13)
C1—C2—C3	118.95 (15)	C18—C17—H17	121.8 (13)
C1—C2—H2	120.5 (13)	C19—C18—C17	119.10 (15)
C3—C2—H2	120.6 (13)	C19—C18—H18	118.4 (14)
C2—C3—C4	119.28 (15)	C17—C18—H18	122.3 (14)
C2—C3—H3	117.8 (13)	C20—C19—C18	118.95 (15)
C4—C3—H3	123.0 (12)	C20—C19—H19	123.0 (16)
C5—C4—C3	119.10 (14)	C18—C19—H19	118.0 (16)
C5—C4—H4	121.5 (13)	N4—C20—C19	122.34 (15)
C3—C4—H4	119.4 (13)	N4—C20—H20	116.0 (12)
N1—C5—C4	121.29 (14)	C19—C20—H20	121.6 (12)
N1—C5—C6	114.23 (13)	O3—N5—O2	122.87 (13)
C4—C5—C6	124.47 (13)	O3—N5—O1	118.98 (12)
N2—C6—C7	121.99 (14)	O2—N5—O1	118.14 (13)
N2—C6—C5	114.86 (12)	N5—O1—Cu1	106.06 (9)
C7—C6—C5	123.07 (14)	N5—O2—Cu1	83.01 (8)
C8—C7—C6	118.90 (15)	N5—O3—Cu1^i	173.72 (10)
C8—C7—H7	119.4 (14)	O6—N6—O4	120.52 (15)
C6—C7—H7	121.7 (14)	O6—N6—O5	119.88 (15)
C7—C8—C9	119.26 (15)	O4—N6—O5	119.60 (15)
C7—C8—H8	118.8 (12)	O1m—C1m—H1m	111.5 (13)
C9—C8—H8	121.9 (12)	O1m—C1m—H2m	107.6 (17)
C8—C9—C10	118.84 (15)	H1m—C1m—H2m	109 (2)
C8—C9—H9	119.1 (14)	O1m—C1m—H3m	110.6 (16)
C10—C9—H9	122.0 (14)	H1m—C1m—H3m	108 (2)
N2—C10—C9	122.34 (15)	H2m—C1m—H3m	110 (2)
N2—C10—H10	115.8 (12)	C1m—O1m—H4m	108 (2)
N1—C5—C6—N2	−7.04 (18)	N3—C15—C16—N4	−3.58 (19)
C4—C5—C6—C7	−9.5 (2)	C14—C15—C16—C17	−4.1 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1m—H4m···O5	0.74 (3)	2.15 (3)	2.882 (2)	170 (3)
C1m—H3m···O4^i	0.95 (2)	2.90 (2)	3.431 (3)	116 (2)
C1m—H1m···O6	0.94 (1)	2.65 (2)	3.261 (3)	123 (2)

Symmetry code: (i) x+1, y, z.

(II) catena-poly[[[bis(2,2'-bipyridine)copper(II)]-µ-nitrato-O:O'] nitrate]

Crystal data

[Cu(NO3)(C10H8N2)2](NO3)	F(000) = 1020
Mr = 499.93	Dx = 1.619 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.347 (3) Å	Cell parameters from 2067 reflections
b = 26.540 (6) Å	θ = 3.0–23.3°
c = 7.1648 (16) Å	µ = 1.12 mm^−1
β = 119.129 (4)°	T = 295 K
V = 2051.0 (8) Å^3	Prism, light-blue
Z = 4	0.38 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer	1645 independent reflections
Radiation source: fine-focus sealed tube	1063 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.100
ω scans	θmax = 24.2°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.623, Tmax = 0.800	k = −30→30
7462 measured reflections	l = −8→8

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0673P)^2] where P = (Fo^2 + 2Fc^2)/3
1645 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. Omega scan: 606 frames for phi= 0, 120 and 240 °. 2theta = -31 °., omega starts from -31 °. omega step = -0.3 °., expouse = 10 sec/frame At the end 50 frames where taken for decomposition and alignment control. Total # of frames = 1868.

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.

Planes from SHELX97 output. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

8.8355 (0.0084) x + 0.0000 (0.0003) y - 6.8676 (0.0025) z = 2.7008 (0.0046)

* -0.0670 (0.0037) N1A * -0.0289 (0.0044) C1A * 0.0129 (0.0043) C2A * 0.0279 (0.0046) C3A * 0.0265 (0.0049) C4A * -0.0040 (0.0042) C5A * 0.0670 (0.0037) N1A_$2 * 0.0289 (0.0044) C1A_$2 * -0.0129 (0.0043) C2A_$2 * -0.0279 (0.0046) C3A_$2 * -0.0265 (0.0049) C4A_$2 * 0.0040 (0.0042) C5A_$2 0.0000 (0.0001) Cu1

Rms deviation of fitted atoms = 0.0341

8.9285 (0.0181) x - 0.8103 (0.0525) y - 6.8408 (0.0047) z = 1.9373 (0.0521)

Angle to previous plane (with approximate e.s.d.) = 1.87 (0.18)

* -0.0180 (0.0029) N1A * 0.0080 (0.0034) C1A * 0.0062 (0.0037) C2A * -0.0101 (0.0037) C3A * 0.0001 (0.0035) C4A * 0.0138 (0.0032) C5A 0.1455 (0.0094) N1A_$2 0.1095 (0.0063) Cu1

Rms deviation of fitted atoms = 0.0109

8.9285 (0.0181) x + 0.8103 (0.0525) y - 6.8408 (0.0047) z = 3.5708 (0.0508)

Angle to previous plane (with approximate e.s.d.) = 3.50 (0.23)

* 0.0180 (0.0029) N1A_$2 * -0.0080 (0.0034) C1A_$2 * -0.0062 (0.0037) C2A_$2 * 0.0101 (0.0037) C3A_$2 * -0.0001 (0.0035) C4A_$2 * -0.0138 (0.0031) C5A_$2 - 0.1455 (0.0094) N1A -0.1095 (0.0063) Cu1

Rms deviation of fitted atoms = 0.0109

8.8355 (0.0084) x + 0.0000 (0.0003) y - 6.8676 (0.0025) z = 2.7008 (0.0046)

Angle to previous plane (with approximate e.s.d.) = 1.87 (0.18)

* -0.0670 (0.0037) N1A * -0.0289 (0.0044) C1A * 0.0129 (0.0043) C2A * 0.0279 (0.0046) C3A * 0.0265 (0.0049) C4A * -0.0040 (0.0042) C5A * 0.0670 (0.0037) N1A_$2 * 0.0289 (0.0044) C1A_$2 * -0.0129 (0.0043) C2A_$2 * -0.0279 (0.0046) C3A_$2 * -0.0265 (0.0049) C4A_$2 * 0.0040 (0.0042) C5A_$2 0.0000 (0.0001) Cu1

Rms deviation of fitted atoms = 0.0341

0.2088 (0.0101) x + 0.0000 (0.0000) y + 6.1988 (0.0033) z = 1.6541 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 46.66 (0.06)

* 0.1177 (0.0037) N1B * 0.1028 (0.0043) C1B * 0.0155 (0.0038) C2B * -0.0985 (0.0043) C3B * -0.1250 (0.0044) C4B * -0.0048 (0.0044) C5B * -0.1177 (0.0037) N1B_$2 * -0.1028 (0.0043) C1B_$2 * -0.0155 (0.0038) C2B_$2 * 0.0985 (0.0043) C3B_$2 * 0.1250 (0.0044) C4B_$2 * 0.0048 (0.0044) C5B_$2 0.0000 (0.0000) Cu1

Rms deviation of fitted atoms = 0.0913

- 0.2179 (0.0215) x + 2.4893 (0.0485) y - 6.1685 (0.0064) z = 0.2742 (0.0410)

Angle to previous plane (with approximate e.s.d.) = 5.38 (0.15)

* -0.0096 (0.0031) N1B * 0.0127 (0.0034) C1B * -0.0041 (0.0035) C2B * -0.0072 (0.0036) C3B * 0.0100 (0.0035) C4B * -0.0018 (0.0032) C5B 0.2269 (0.0084) N1B_$2 0.2477 (0.0058) Cu1

Rms deviation of fitted atoms = 0.0084

0.2179 (0.0216) x + 2.4893 (0.0485) y + 6.1685 (0.0064) z = 3.5764 (0.0374)

Angle to previous plane (with approximate e.s.d.) = 10.76 (0.19)

* -0.0096 (0.0031) N1B_$2 * 0.0127 (0.0034) C1B_$2 * -0.0041 (0.0035) C2B_$2 * -0.0072 (0.0036) C3B_$2 * 0.0100 (0.0035) C4B_$2 * -0.0018 (0.0032) C5B_$2 0.2269 (0.0084) N1B 0.2477 (0.0058) Cu1

Rms deviation of fitted atoms = 0.0084

0.2088 (0.0101) x + 0.0000 (0.0000) y + 6.1988 (0.0033) z = 1.6541 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 5.38 (0.15)

* 0.1177 (0.0037) N1B * 0.1028 (0.0043) C1B * 0.0155 (0.0038) C2B * -0.0985 (0.0043) C3B * -0.1250 (0.0044) C4B * -0.0048 (0.0044) C5B * -0.1177 (0.0037) N1B_$2 * -0.1028 (0.0043) C1B_$2 * -0.0155 (0.0038) C2B_$2 * 0.0985 (0.0043) C3B_$2 * 0.1250 (0.0044) C4B_$2 * 0.0048 (0.0044) C5B_$2 0.0000 (0.0000) Cu1

Rms deviation of fitted atoms = 0.0913

8.3797 (0.0266) x + 0.0000 (0.0006) y - 6.9636 (0.0052) z = 2.4490 (0.0147)

Angle to previous plane (with approximate e.s.d.) = 43.71 (0.08)

* 0.0000 (0.0000) Cu1 * 0.0000 (0.0001) N1A * 0.0000 (0.0000) N1A_$2 - 4.5235 (0.0038) O12 - 2.4401 (0.0048) O12_$4

Rms deviation of fitted atoms = 0.0000

- 0.9030 (0.0350) x + 0.0000 (0.0000) y + 6.4970 (0.0087) z = 1.1727 (0.0153)

Angle to previous plane (with approximate e.s.d.) = 38.55 (0.19)

* 0.0000 (0.0000) Cu1 * 0.0000 (0.0000) N1B * 0.0000 (0.0000) N1B_$2 3.8776 (0.0077) O12 2.6193 (0.0043) O12_$4

Rms deviation of fitted atoms = 0.0000

11.7641 (0.0061) x + 0.0000 (0.0011) y - 1.4221 (0.0102) z = 5.5266 (0.0015)

Angle to previous plane (with approximate e.s.d.) = 76.51 (0.19)

* 0.0000 (0.0000) Cu1 * 0.0000 (0.0001) O12_$3 * 0.0000 (0.0000) O12_$4

Rms deviation of fitted atoms = 0.0000

8.3797 (0.0266) x + 0.0000 (0.0006) y - 6.9636 (0.0052) z = 2.4490 (0.0147)

Angle to previous plane (with approximate e.s.d.) = 64.94 (0.15)

* 0.0000 (0.0000) Cu1 * 0.0000 (0.0001) N1A * 0.0000 (0.0000) N1A_$2 - 4.5235 (0.0038) O12 - 2.4401 (0.0048) O12_$4

Rms deviation of fitted atoms = 0.0000

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.

Disorder of nitrate ion (located near 2-fold axis) along with elongated atomic displacement ellipsoids for Cu1 (situated on 2-fold axis) pointed out that the symmetry may be lower. Thus, non-centrosymmetric space group Cc was tested but without success. Nitrate ion was still disordered and displacement ellipsoids for Cu atoms were even worse. Therefore, C2/c space group was accepted as final.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5000	0.87294 (3)	0.2500	0.0599 (4)
N1A	0.3827 (4)	0.92935 (14)	0.1088 (7)	0.0461 (10)
C1A	0.2654 (5)	0.9258 (2)	−0.0477 (9)	0.0578 (15)
H1A	0.2310	0.8939	−0.0917	0.069*
C2A	0.1923 (5)	0.9678 (2)	−0.1478 (10)	0.0661 (16)
H2A	0.1105	0.9641	−0.2554	0.079*
C3A	0.2438 (7)	1.0146 (2)	−0.0837 (11)	0.0689 (17)
H3A	0.1965	1.0432	−0.1461	0.083*
C4A	0.3646 (6)	1.01917 (19)	0.0720 (10)	0.0606 (16)
H4A	0.3999	1.0510	0.1145	0.073*
C5A	0.4357 (4)	0.97592 (17)	0.1679 (8)	0.0454 (12)
N1B	0.6099 (3)	0.81709 (14)	0.2653 (6)	0.0431 (10)
C1B	0.7172 (5)	0.8205 (2)	0.2593 (8)	0.0507 (13)
H1B	0.7507	0.8523	0.2664	0.061*
C2B	0.7795 (5)	0.7791 (2)	0.2431 (8)	0.0558 (14)
H2B	0.8545	0.7827	0.2433	0.067*
C3B	0.7272 (5)	0.7321 (2)	0.2265 (8)	0.0561 (15)
H3B	0.7671	0.7034	0.2157	0.067*
C4B	0.6170 (5)	0.72795 (18)	0.2259 (7)	0.0508 (13)
H4B	0.5806	0.6965	0.2113	0.061*
C5B	0.5585 (4)	0.77104 (16)	0.2472 (7)	0.0398 (11)
N11	0.5000	0.8452 (2)	0.7500	0.0464 (14)
O11	0.5000	0.79903 (18)	0.7500	0.0608 (14)
O12	0.4504 (4)	0.86910 (14)	0.8399 (6)	0.0697 (11)
N21	−0.0133 (13)	0.8848 (7)	0.162 (3)	0.188 (5)	0.50
O21	−0.1257 (10)	0.8732 (5)	0.060 (2)	0.119 (4)	0.50
O22	0.0374 (14)	0.8857 (9)	0.357 (2)	0.188 (5)	0.50
O23	0.0404 (11)	0.8941 (5)	0.059 (3)	0.180 (7)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0474 (6)	0.0286 (5)	0.1049 (9)	0.000	0.0380 (6)	0.000
N1A	0.052 (3)	0.034 (2)	0.065 (3)	0.0029 (19)	0.038 (2)	0.000 (2)
C1A	0.057 (4)	0.050 (3)	0.080 (4)	0.008 (3)	0.044 (3)	0.001 (3)
C2A	0.053 (4)	0.087 (4)	0.068 (4)	0.020 (3)	0.037 (3)	0.021 (4)
C3A	0.090 (5)	0.057 (4)	0.085 (5)	0.029 (4)	0.062 (4)	0.023 (3)
C4A	0.093 (5)	0.036 (3)	0.083 (4)	0.009 (3)	0.067 (4)	0.010 (3)
C5A	0.066 (3)	0.036 (3)	0.056 (3)	0.006 (2)	0.047 (3)	0.004 (2)
N1B	0.045 (2)	0.039 (2)	0.048 (3)	0.0039 (18)	0.025 (2)	0.0044 (19)
C1B	0.051 (3)	0.057 (3)	0.050 (3)	0.005 (3)	0.029 (3)	0.005 (3)
C2B	0.052 (3)	0.076 (4)	0.044 (3)	0.017 (3)	0.026 (3)	0.004 (3)
C3B	0.065 (4)	0.057 (4)	0.046 (3)	0.025 (3)	0.028 (3)	0.004 (3)
C4B	0.074 (4)	0.034 (3)	0.044 (3)	0.010 (3)	0.028 (3)	0.002 (2)
C5B	0.048 (3)	0.037 (3)	0.034 (3)	0.003 (2)	0.020 (2)	0.002 (2)
N11	0.048 (4)	0.040 (4)	0.050 (4)	0.000	0.024 (3)	0.000
O11	0.070 (4)	0.039 (3)	0.081 (4)	0.000	0.043 (3)	0.000
O12	0.097 (3)	0.056 (2)	0.088 (3)	0.028 (2)	0.070 (3)	0.016 (2)
N21	0.111 (13)	0.166 (9)	0.205 (13)	−0.03 (2)	0.013 (11)	0.01 (3)
O21	0.076 (7)	0.104 (8)	0.187 (13)	−0.027 (7)	0.071 (8)	−0.027 (9)
O22	0.111 (13)	0.166 (9)	0.205 (13)	−0.03 (2)	0.013 (11)	0.01 (3)
O23	0.077 (8)	0.143 (12)	0.31 (2)	0.011 (7)	0.085 (10)	0.083 (13)

Geometric parameters (Å, º)

Cu1—N1B^i	1.977 (4)	C1B—C2B	1.377 (7)
Cu1—N1B	1.977 (4)	C1B—H1B	0.9300
Cu1—N1A^i	1.984 (4)	C2B—C3B	1.384 (8)
Cu1—N1A	1.984 (4)	C2B—H2B	0.9300
Cu1—O12^ii	2.696 (4)	C3B—C4B	1.364 (7)
Cu1—O12^iii	2.696 (4)	C3B—H3B	0.9300
N1A—C1A	1.336 (7)	C4B—C5B	1.400 (6)
N1A—C5A	1.366 (6)	C4B—H4B	0.9300
C1A—C2A	1.393 (7)	C5B—C5B^i	1.465 (9)
C1A—H1A	0.9300	N11—O11	1.226 (7)
C2A—C3A	1.370 (8)	N11—O12^iii	1.255 (4)
C2A—H2A	0.9300	N11—O12	1.255 (4)
C3A—C4A	1.365 (8)	N21—O22	1.225 (8)
C3A—H3A	0.9300	N21—O23	1.233 (9)
C4A—C5A	1.405 (7)	N21—O21	1.252 (9)
C4A—H4A	0.9300	Cu1—Cu1^iv	7.1648 (16)
C5A—C5A^i	1.444 (10)	Cu1—Cu1^ii	7.1648 (16)
N1B—C1B	1.349 (6)	Cu1—Cu1^v	7.637 (2)
N1B—C5B	1.354 (6)	Cu1—Cu1^vi	7.637 (2)
N1B^i—Cu1—N1B	82.8 (2)	C5A—C4A—H4A	120.0
N1B^i—Cu1—N1A^i	154.88 (16)	N1A—C5A—C4A	119.8 (5)
N1B—Cu1—N1A^i	103.08 (16)	N1A—C5A—C5A^i	115.1 (3)
N1B^i—Cu1—N1A	103.08 (16)	C4A—C5A—C5A^i	125.2 (3)
N1B—Cu1—N1A	154.88 (16)	C1B—N1B—C5B	118.6 (4)
N1A^i—Cu1—N1A	82.0 (2)	C1B—N1B—Cu1	127.3 (3)
N1B^i—Cu1—O12^ii	97.23 (14)	C5B—N1B—Cu1	113.2 (3)
N1B—Cu1—O12^ii	79.48 (13)	N1B—C1B—C2B	123.1 (5)
N1A^i—Cu1—O12^ii	107.83 (15)	N1B—C1B—H1B	118.4
N1A—Cu1—O12^ii	75.57 (14)	C2B—C1B—H1B	118.4
N1B^i—Cu1—O12^iii	79.48 (13)	Cu1—C1B—H1B	87.1
N1B—Cu1—O12^iii	97.23 (14)	C1B—C2B—C3B	118.0 (5)
N1A^i—Cu1—O12^iii	75.57 (14)	C1B—C2B—H2B	121.0
N1A—Cu1—O12^iii	107.83 (15)	C3B—C2B—H2B	121.0
O12^ii—Cu1—O12^iii	175.67 (16)	C4B—C3B—C2B	119.8 (5)
C1A—N1A—C5A	119.0 (4)	C4B—C3B—H3B	120.1
C1A—N1A—Cu1	126.8 (3)	C2B—C3B—H3B	120.1
C5A—N1A—Cu1	113.8 (3)	C3B—C4B—C5B	120.0 (5)
N1A—C1A—C2A	122.8 (5)	C3B—C4B—H4B	120.0
N1A—C1A—H1A	118.6	C5B—C4B—H4B	120.0
C2A—C1A—H1A	118.6	N1B—C5B—C4B	120.3 (4)
Cu1—C1A—H1A	86.5	N1B—C5B—C5B^i	114.9 (3)
C3A—C2A—C1A	118.3 (6)	C4B—C5B—C5B^i	124.8 (3)
C3A—C2A—H2A	120.8	O11—N11—O12^iii	120.3 (3)
C1A—C2A—H2A	120.8	O11—N11—O12	120.3 (3)
C4A—C3A—C2A	120.0 (6)	O12^iii—N11—O12	119.4 (5)
C4A—C3A—H3A	120.0	N11—O12—Cu1^iv	132.1 (3)
C2A—C3A—H3A	120.0	O22—N21—O23	123.7 (10)
C3A—C4A—C5A	120.1 (5)	O22—N21—O21	118.3 (10)
C3A—C4A—H4A	120.0	O23—N21—O21	118.0 (9)
N1B—C5B—C5B^i—N1B^i	11.8 (8)	N1A—C5A—C5A^i—N1A^i	5.5 (8)
C4B—C5B—C5B^i—C4B^i	11.5 (11)	C4A—C5A—C5A^i—C4A^i	3.5 (10)

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