Dimethyl 2,2′-bipyridine-6,6′-dicarboxyl­ate and bis­(dimethyl 2,2′-bipyridine-6,6′-dicarboxyl­ato-κ²N,N′)copper(I) tetra­fluoro­borate

The single-crystal X-ray structures of dimethyl 2,2′-bipyridine-6,6′-dicarboxylate, C₁₄H₁₂N₂O₄, and the copper(I) coordination complex bis­(dimethyl 2,2′-bipyridine-6,6′-dicarboxylato-κ²N,N′)copper(I) tetra­fluoro­borate, [Cu(C₁₄H₁₂N₂O₄)₂]BF₄, are reported. The uncoordinated ligand crystallizes across an inversion centre and adopts the anti­cipated anti pyridyl arrangement with coplanar pyridyl rings. In contrast, upon coordination of copper(I), the ligand adopts an arrangement of pyridyl donors facilitating chelating metal coordination and an increased inter-pyridyl twisting within each ligand. The distortion of each ligand contrasts with comparable copper(I) complexes of unfunctionalized 2,2′-bipyridine.

S1. Comment

As a part of our ongoing studies of multi-modal ligands for the construction of coordination polymers (Oxtoby et al., 2002, 2003, 2005; Thébault et al., 2006), we have prepared a diester-substituted 2,2'-bipyridyl ligand and a copper(I) complex that serve as potentially useful building blocks for subsequent synthetic procedures.

The diester-substituted 2,2'-bipyridyl molecule, dimethyl 2,2'-bipyridine-6,6'-dicarboxylate, (I), was synthesized by an HCl-catalysed esterification method in MeOH. Single-crystal X-ray diffraction confirmed the identity of the product and demonstrated the lower energy conformation commonly adopted by uncoordinated 2,2'-bipyridyl systems, which has the pyridyl N atoms adopting an anti arrangement to avoid repulsive interactions between the nitrogen lone pairs. The entire molecule is almost planar in the solid state. An inversion centre between atoms C2 and C2ⁱ [symmetry code: (i) -x, 1 - y, 1 - z] ensures coplanarity of the two pyridyl rings, with the two ester groups exhibiting a slight deviation from the plane formed by the bipyridyl moiety with an N1—C6—C7—O8 torsion angle of 9.84 (16)° (Fig. 1).

Compound (I) was complexed to copper(I) in a 2:1 ligand:metal ratio via reaction of [Cu(MeCN)₄]BF₄ with the ligand in MeCN–CH₂Cl₂, to give bis(dimethyl 2,2'-bipyridine-6,6'-dicarboxylate)copper(I) tetrafluoroborate, (II). The crystal structure of (II) (Fig. 2) confirms the anticipated coordination environment in which the metal centre is coordinated solely by the bipyridyl moieties, with the ester groups not participating in metal coordination.

In the structure of (II), there are two short Cu—N bonds of 2.029 (3) and 2.035 (3) Å for Cu—N1 and Cu—N7', respectively, and two slightly longer bonds of 2.074 (3) and 2.077 (3) Å for Cu—N7 and Cu—N1', respectively. Three of the ester carbonyl O atoms point towards the Cu^I centre but no significant interactions are present; the Cu···O distances are longer than 2.8 Å, the combined sum of the van der Waals radii (Standard reference?).

This copper(I) complex adopts a distorted tetrahedral geometry, with an angle of 70° between the planes defined by the two bipyridyl units. This distortion is only slightly greater than the comparable angles observed in bis(2,2'-bipyridine)copper(I) perchlorate (76°; Munakata et al., 1987) and bis(2,2'-bipyridine)copper(I) trifluoromethanesulfonate (85°; Tomislav, 2006). Steric interactions between the bulkier dimethyl 2,2'-biypyridine-6,6'-dicarboxlyate ligands may account for the slight increase in the distortion of the relatively malleable tetrahedral Cu^I coordination environment.

By comparison with the crystal structure of the free ligand, (I), it can be seen that the ligand in (II) adopts a different conformation on complexation, as anticipated, allowing chelation of the metal centre by the bipyridyl species. The coplanarity of the pyridyl rings of the free ligand is also lost on complexation, with an increase in the distortion of the ester groups with respect to the pyridyl rings, resulting from the increased steric constraints of the complex. The C═O and C—O bond lengths of the ester groups in both the free and complexed ligand show no significant deviation, further supporting the absence of ester complexation.

It is interesting to compare the twisted arrangement of the dimethyl 2,2'-bipyridine-6,6'-dicarboxylate ligand in (II) with previously reported examples. Two N—C—C—N torsion angles of 10.4 (5) and 25.1 (6)° are observed for these ligands in complex (II), revealing a significantly greater twist than observed in the three structures of metal complexes of dimethyl 2,2'-bipyridine-6,6'-dicarboxylate (Anderberg et al., 2002; Kinnunen et al., 2000, 2002) reported prior to this study (average C—N—N—C torsion angles ca 5°). The twist in (II) is also greater than that observed in bis(2,2'-bipyridine)copper(I) trifluoromethanesulfonate (Tomislav, 2006) and the analogous perchlorate salt (Munakata et al., 1987), in which the 2,2'-bipyridine ligands remain essentially planar with average C—N—N—C torsion angles of 2.9 and 1.8°, respectively.

In summary, two single-crystal X-ray structures of dimethyl 2,2'-bipyridine-6,6'-dicarboxylate and its copper(I) complex, bis(dimethyl 2,2'-bipyridine-6,6'-dicarboxylate)copper(I) tetrafluoroborate, are reported and the relative twisting of the bipyridyl moiety compared.

Related literature

For related literature, see: Anderberg et al. (2002); Kinnunen et al. (2000, 2002); Munakata et al. (1987); Oxtoby et al. (2002, 2003, 2005); Thébault et al. (2006); Tomislav (2006).

S2. Experimental

2,2'-Bipyridine-6,6'-dicarboxylic acid (122 mg, 0.5 mmol) and concentrated sulfuric acid (0.5 ml) in methanol (20 ml) were heated at reflux for 3 d. The solvent was reduced to half the original volume and cooled, causing dimethyl 2,2'-bipyridine-6,6'-dicarboxylate (100 mg, 75%) to precipitate as a white crystalline solid. Single crystals suitable for X-ray diffraction were grown by slow cooling of a methanolic solution of the ester. Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 8.75 (d, 2H), 8.16 (d, 2H), 8.00 (t, 2H), 4.04 (s, 6H); 13 C NMR (CDCl₃, δ, p.p.m.): 166.1, 155.9, 146.0, 138.5, 125.9, 125.3, 53.3; ES–MS: m/z 273 (M⁺ + H); IR (KBr disc, ν, cm^-1): 3476 (s), 1740 (m), 1636 (m), 1580 (m), 1295 (w), 1252 (m), 1146 (m), 831 (w), 765 (m), 703 (m), 629 (m).

Dimethyl 2,2'-bipyridine-6,6'-dicarboxylate (13.5 mg, 0.05 mmol) in dichloromethane (5 ml) and [Cu(MeCN)₄](BF₄) (8 mg, 0.025 mmol) in acetonitrile (5 ml) were stirred together at room temperature for ca 30 min. The solvents were removed to give the product as a dark-red solid (15 mg). Single crystals of (II) were obtained by slow diffusion of [Diethyl?] ether into a chloroform solution of the complex. Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 8.71 (d, 4H), 8.18 (m, 6H), 1.94 (s, 12H); FAB-MS: m/z 607 (M⁺), 335 (M⁺ - L); IR (KBr disc, ν, cm^-1): 3503 (s), 1730 (s), 1635 (m), 1592 (m), 1447 (w), 1372 (w), 1336 (m), 1310 (w), 1296 (w), 1264 (w), 1137 (w), 1116 (m), 1076 (s), 769 (m), 721 (w), 701 (w), 668 (w), 630 (w).

S3. Refinement

H atoms were included in geometrically calculated positions, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for the pyridyl CH, and with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for the methyl H atoms, and constrained as part of a riding model.

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT and SHELXTL (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL. Software used to prepare material for publication: enCIFer (Allen et al., 2004) and PLATON (Spek, 2003) for (I); SHELXL97 and PLATON (Spek, 2003) for (II).

Figures

	Fig. 1. A view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Unlabelled atoms are related to labelled atoms by the symmetry operator (x, 1 - y, 1 - z).
	Fig. 2. A view of the structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

(I) Dimethyl 2,2'-bipyridine-6,6'-dicarboxylate

Crystal data

C14H12N2O4	F(000) = 284
Mr = 272.26	Dx = 1.509 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.4182 (15) Å	Cell parameters from 1954 reflections
b = 6.8889 (11) Å	θ = 2.6–27.5°
c = 9.7931 (15) Å	µ = 0.11 mm^−1
β = 109.448 (2)°	T = 150 K
V = 599.1 (3) Å^3	Hexagonal prism, colourless
Z = 2	0.67 × 0.61 × 0.21 mm

Data collection

Bruker SMART1000 CCD area-detector diffractometer	1167 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.057
Graphite monochromator	θmax = 27.5°, θmin = 2.6°
ω scans	h = −12→10
3716 measured reflections	k = −8→5
1360 independent reflections	l = −12→12

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.038	w = 1/[σ^2(Fo^2) + (0.0629P)^2 + 0.0616P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.113	(Δ/σ)max = 0.001
S = 1.13	Δρmax = 0.41 e Å^−3
1360 reflections	Δρmin = −0.22 e Å^−3
92 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.015 (5)
Primary atom site location: structure-invariant direct methods

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.

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

	x	y	z	Uiso*/Ueq
N1	0.19692 (9)	0.43661 (14)	0.56343 (10)	0.0176 (3)
C2	0.07443 (11)	0.55029 (15)	0.52528 (11)	0.0166 (3)
C3	0.08300 (13)	0.75356 (16)	0.53162 (13)	0.0200 (3)
H3	−0.0061	0.8299	0.5020	0.024*
C4	0.22295 (13)	0.84109 (16)	0.58167 (13)	0.0209 (3)
H4	0.2316	0.9785	0.5868	0.025*
C5	0.35080 (12)	0.72472 (16)	0.62438 (12)	0.0196 (3)
H5	0.4485	0.7804	0.6606	0.023*
C6	0.33170 (11)	0.52426 (16)	0.61262 (11)	0.0173 (3)
C7	0.46470 (12)	0.38823 (17)	0.65597 (12)	0.0183 (3)
O8	0.45856 (9)	0.21621 (12)	0.63260 (10)	0.0273 (3)
O9	0.59166 (8)	0.48458 (12)	0.72497 (9)	0.0234 (3)
C10	0.72757 (13)	0.36866 (17)	0.77504 (14)	0.0233 (3)
H8A	0.8136	0.4527	0.8235	0.035*
H8B	0.7440	0.3046	0.6922	0.035*
H8D	0.7170	0.2703	0.8433	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0141 (5)	0.0153 (5)	0.0236 (5)	0.0001 (3)	0.0065 (4)	0.0001 (4)
C2	0.0144 (6)	0.0143 (5)	0.0216 (5)	−0.0003 (4)	0.0068 (4)	0.0003 (4)
C3	0.0158 (5)	0.0148 (5)	0.0295 (6)	0.0023 (4)	0.0076 (4)	0.0009 (5)
C4	0.0212 (6)	0.0130 (5)	0.0294 (6)	−0.0006 (4)	0.0095 (4)	−0.0006 (4)
C5	0.0148 (5)	0.0175 (6)	0.0261 (6)	−0.0029 (4)	0.0063 (4)	−0.0015 (4)
C6	0.0140 (5)	0.0164 (5)	0.0219 (6)	0.0007 (4)	0.0066 (4)	−0.0001 (4)
C7	0.0154 (5)	0.0161 (6)	0.0236 (6)	−0.0005 (4)	0.0069 (4)	0.0001 (4)
O8	0.0183 (4)	0.0150 (5)	0.0452 (6)	0.0006 (3)	0.0063 (4)	−0.0041 (4)
O9	0.0126 (4)	0.0149 (4)	0.0389 (5)	0.0011 (3)	0.0034 (3)	−0.0012 (3)
C10	0.0141 (5)	0.0178 (6)	0.0349 (6)	0.0034 (4)	0.0040 (4)	0.0013 (5)

Geometric parameters (Å, º)

N1—C2	1.3405 (14)	C5—H5	0.9500
N1—C6	1.3419 (13)	C6—C7	1.5077 (15)
C2—C3	1.4028 (15)	C7—O8	1.2046 (15)
C2—C2^i	1.493 (2)	C7—O9	1.3375 (13)
C3—C4	1.3824 (16)	O9—C10	1.4486 (13)
C3—H3	0.9500	C10—H8A	0.9800
C4—C5	1.3900 (16)	C10—H8B	0.9800
C4—H4	0.9500	C10—H8D	0.9800
C5—C6	1.3924 (15)
C2—N1—C6	117.43 (9)	N1—C6—C5	123.82 (10)
N1—C2—C3	122.64 (9)	N1—C6—C7	114.79 (9)
N1—C2—C2^i	116.57 (12)	C5—C6—C7	121.39 (9)
C3—C2—C2^i	120.79 (11)	O8—C7—O9	124.22 (10)
C4—C3—C2	119.02 (10)	O8—C7—C6	125.11 (9)
C4—C3—H3	120.5	O9—C7—C6	110.67 (9)
C2—C3—H3	120.5	C7—O9—C10	115.98 (9)
C3—C4—C5	118.90 (10)	O9—C10—H8A	109.5
C3—C4—H4	120.5	O9—C10—H8B	109.5
C5—C4—H4	120.5	H8A—C10—H8B	109.5
C4—C5—C6	118.16 (10)	O9—C10—H8D	109.5
C4—C5—H5	120.9	H8A—C10—H8D	109.5
C6—C5—H5	120.9	H8B—C10—H8D	109.5
C6—N1—C2—C3	1.65 (16)	C4—C5—C6—N1	−0.53 (17)
C6—N1—C2—C2^i	−178.37 (11)	C4—C5—C6—C7	179.69 (10)
N1—C2—C3—C4	−1.24 (17)	N1—C6—C7—O8	9.84 (16)
C2^i—C2—C3—C4	178.77 (12)	C5—C6—C7—O8	−170.36 (11)
C2—C3—C4—C5	−0.11 (17)	N1—C6—C7—O9	−169.94 (9)
C3—C4—C5—C6	0.94 (17)	C5—C6—C7—O9	9.86 (14)
C2—N1—C6—C5	−0.76 (16)	O8—C7—O9—C10	−1.02 (16)
C2—N1—C6—C7	179.04 (9)	C6—C7—O9—C10	178.76 (9)

Symmetry code: (i) −x, −y+1, −z+1.

(II) bis(dimethyl 2,2'-bipyridine-6,6'-dicarboxylato-κ²N,N')copper(I) tetrafluoroborate

Crystal data

[Cu(C14H12N2O4)2]BF4	F(000) = 1416
Mr = 694.86	Dx = 1.591 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.777 (2) Å	Cell parameters from 2605 reflections
b = 27.434 (6) Å	θ = 3.1–23.2°
c = 13.965 (3) Å	µ = 0.84 mm^−1
β = 103.254 (3)°	T = 150 K
V = 2900.1 (12) Å^3	Triangular prism, purple
Z = 4	0.26 × 0.22 × 0.07 mm

Data collection

Bruker SMART1000 CCD area-detector diffractometer	5406 independent reflections
Radiation source: sealed tube	3654 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ω scans	θmax = 26.1°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker 2001)	h = −9→9
Tmin = 0.812, Tmax = 0.944	k = −30→33
14165 measured reflections	l = −17→16

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0527P)^2 + 5.7924P] where P = (Fo^2 + 2Fc^2)/3
5406 reflections	(Δ/σ)max = 0.001
415 parameters	Δρmax = 0.85 e Å^−3
0 restraints	Δρmin = −0.57 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
Cu1	0.61325 (7)	0.146688 (18)	0.61022 (4)	0.02274 (16)
N1	0.6341 (4)	0.08238 (12)	0.5420 (2)	0.0212 (8)
C2	0.7036 (5)	0.04740 (15)	0.6083 (3)	0.0230 (9)
C3	0.7691 (6)	0.00345 (15)	0.5809 (3)	0.0284 (10)
H3A	0.8204	−0.0199	0.6293	0.034*
C4	0.7580 (6)	−0.00556 (16)	0.4827 (3)	0.0310 (11)
H4A	0.8035	−0.0350	0.4626	0.037*
C5	0.6805 (6)	0.02849 (16)	0.4137 (3)	0.0276 (10)
H5A	0.6686	0.0225	0.3454	0.033*
C6	0.6204 (6)	0.07167 (15)	0.4461 (3)	0.0229 (9)
N7	0.7186 (4)	0.10672 (12)	0.7361 (2)	0.0198 (8)
C8	0.7126 (6)	0.05902 (15)	0.7133 (3)	0.0232 (9)
C9	0.7114 (6)	0.02268 (17)	0.7825 (3)	0.0320 (11)
H9A	0.7098	−0.0107	0.7643	0.038*
C10	0.7123 (7)	0.03579 (18)	0.8776 (3)	0.0384 (12)
H10A	0.7091	0.0116	0.9258	0.046*
C11	0.7179 (6)	0.08461 (17)	0.9024 (3)	0.0345 (11)
H11A	0.7178	0.0946	0.9675	0.041*
C12	0.7238 (6)	0.11857 (16)	0.8303 (3)	0.0238 (10)
C13	0.5394 (6)	0.10976 (17)	0.3722 (3)	0.0236 (10)
O14	0.5523 (4)	0.15309 (11)	0.3849 (2)	0.0306 (7)
O15	0.4485 (4)	0.08837 (11)	0.2905 (2)	0.0326 (8)
C16	0.3791 (7)	0.12001 (18)	0.2074 (3)	0.0379 (12)
H16A	0.3155	0.1004	0.1518	0.057*
H16B	0.4768	0.1372	0.1886	0.057*
H16C	0.2981	0.1438	0.2257	0.057*
C17	0.7368 (6)	0.17135 (16)	0.8596 (3)	0.0262 (10)
O18	0.6949 (4)	0.18574 (12)	0.9327 (2)	0.0378 (8)
O19	0.8037 (4)	0.19936 (11)	0.7991 (2)	0.0289 (7)
C20	0.8168 (6)	0.25045 (16)	0.8245 (3)	0.0324 (11)
H20A	0.8673	0.2683	0.7766	0.049*
H20B	0.8931	0.2545	0.8904	0.049*
H20C	0.6989	0.2633	0.8238	0.049*
N1'	0.4228 (4)	0.19077 (12)	0.6488 (2)	0.0208 (8)
C2'	0.4482 (5)	0.23856 (15)	0.6346 (3)	0.0217 (9)
C3'	0.3551 (6)	0.27486 (16)	0.6706 (3)	0.0270 (10)
H3'A	0.3741	0.3082	0.6581	0.032*
C4'	0.2347 (6)	0.26162 (17)	0.7246 (3)	0.0324 (11)
H4'A	0.1712	0.2858	0.7511	0.039*
C5'	0.2076 (6)	0.21257 (16)	0.7398 (3)	0.0284 (10)
H5'A	0.1242	0.2026	0.7760	0.034*
C6'	0.3037 (6)	0.17838 (15)	0.7014 (3)	0.0236 (10)
N7'	0.6923 (5)	0.21254 (12)	0.5688 (2)	0.0222 (8)
C8'	0.5888 (5)	0.25011 (16)	0.5818 (3)	0.0225 (9)
C9'	0.6166 (6)	0.29705 (15)	0.5497 (3)	0.0256 (10)
H9'A	0.5428	0.3232	0.5598	0.031*
C10'	0.7519 (6)	0.30489 (17)	0.5033 (3)	0.0320 (11)
H10B	0.7731	0.3367	0.4815	0.038*
C11'	0.8577 (6)	0.26616 (16)	0.4886 (3)	0.0286 (10)
H11B	0.9515	0.2708	0.4563	0.034*
C12'	0.8225 (6)	0.22063 (15)	0.5221 (3)	0.0228 (9)
C13'	0.2813 (5)	0.12446 (16)	0.7154 (3)	0.0249 (10)
O14'	0.3282 (4)	0.09342 (11)	0.6673 (2)	0.0286 (7)
O15'	0.2051 (4)	0.11643 (11)	0.7912 (2)	0.0325 (8)
C16'	0.1783 (7)	0.06533 (18)	0.8105 (4)	0.0452 (14)
H16D	0.1222	0.0625	0.8664	0.068*
H16E	0.2926	0.0485	0.8260	0.068*
H16F	0.1020	0.0504	0.7522	0.068*
C17'	0.9326 (6)	0.17690 (16)	0.5110 (3)	0.0262 (10)
O18'	0.9474 (4)	0.14162 (11)	0.5630 (2)	0.0287 (7)
O19'	1.0148 (4)	0.18273 (11)	0.4373 (2)	0.0343 (8)
C20'	1.1190 (7)	0.14104 (18)	0.4209 (4)	0.0383 (12)
H20D	1.1756	0.1481	0.3665	0.057*
H20E	1.0420	0.1125	0.4044	0.057*
H20F	1.2099	0.1343	0.4807	0.057*
B1	1.1467 (8)	−0.0783 (2)	0.8171 (5)	0.0447 (16)
F1	1.0588 (5)	−0.10343 (14)	0.8740 (3)	0.0748 (11)
F2	1.2880 (5)	−0.05292 (13)	0.8718 (2)	0.0702 (11)
F3	1.0419 (5)	−0.04841 (13)	0.7514 (2)	0.0753 (11)
F4	1.2087 (5)	−0.11437 (14)	0.7590 (3)	0.0775 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0302 (3)	0.0158 (3)	0.0232 (3)	0.0024 (2)	0.0082 (2)	0.0003 (2)
N1	0.0206 (18)	0.0198 (19)	0.0228 (19)	−0.0018 (15)	0.0046 (15)	−0.0026 (15)
C2	0.025 (2)	0.020 (2)	0.023 (2)	−0.0026 (19)	0.0024 (18)	−0.0015 (18)
C3	0.036 (3)	0.016 (2)	0.029 (2)	0.0033 (19)	0.001 (2)	0.0021 (18)
C4	0.036 (3)	0.022 (2)	0.033 (3)	0.006 (2)	0.002 (2)	−0.006 (2)
C5	0.034 (3)	0.026 (3)	0.023 (2)	0.003 (2)	0.007 (2)	−0.0065 (19)
C6	0.026 (2)	0.022 (2)	0.022 (2)	−0.0023 (18)	0.0069 (18)	0.0004 (17)
N7	0.0220 (19)	0.0176 (19)	0.0189 (18)	−0.0011 (15)	0.0026 (15)	−0.0025 (14)
C8	0.028 (2)	0.020 (2)	0.020 (2)	0.0005 (19)	0.0030 (18)	−0.0020 (17)
C9	0.046 (3)	0.021 (2)	0.027 (3)	−0.001 (2)	0.004 (2)	0.0029 (19)
C10	0.057 (3)	0.030 (3)	0.029 (3)	−0.002 (2)	0.012 (2)	0.012 (2)
C11	0.048 (3)	0.034 (3)	0.021 (2)	−0.004 (2)	0.006 (2)	−0.002 (2)
C12	0.024 (2)	0.022 (2)	0.024 (2)	0.0005 (19)	0.0026 (18)	0.0000 (18)
C13	0.024 (2)	0.027 (3)	0.021 (2)	−0.0014 (19)	0.0085 (18)	−0.0031 (18)
O14	0.0443 (19)	0.0214 (19)	0.0226 (16)	0.0034 (14)	0.0006 (14)	−0.0022 (13)
O15	0.045 (2)	0.0237 (17)	0.0234 (17)	−0.0043 (15)	−0.0039 (14)	0.0002 (13)
C16	0.054 (3)	0.031 (3)	0.022 (2)	0.000 (2)	−0.005 (2)	0.005 (2)
C17	0.027 (2)	0.029 (3)	0.020 (2)	0.002 (2)	−0.0015 (19)	−0.0018 (19)
O18	0.051 (2)	0.034 (2)	0.0327 (19)	0.0078 (16)	0.0184 (16)	−0.0067 (15)
O19	0.0361 (18)	0.0211 (17)	0.0298 (17)	−0.0034 (14)	0.0082 (14)	−0.0071 (13)
C20	0.039 (3)	0.021 (2)	0.033 (3)	−0.002 (2)	0.000 (2)	−0.006 (2)
N1'	0.0231 (19)	0.0182 (19)	0.0209 (18)	−0.0003 (15)	0.0044 (15)	−0.0015 (14)
C2'	0.023 (2)	0.021 (2)	0.019 (2)	0.0016 (18)	0.0005 (18)	0.0007 (17)
C3'	0.034 (3)	0.016 (2)	0.030 (2)	0.0044 (19)	0.008 (2)	−0.0016 (18)
C4'	0.037 (3)	0.025 (3)	0.035 (3)	0.012 (2)	0.009 (2)	−0.004 (2)
C5'	0.031 (3)	0.028 (3)	0.027 (2)	0.004 (2)	0.010 (2)	−0.0042 (19)
C6'	0.025 (2)	0.022 (2)	0.023 (2)	0.0008 (18)	0.0031 (19)	−0.0033 (18)
N7'	0.027 (2)	0.022 (2)	0.0154 (18)	−0.0043 (16)	0.0004 (15)	−0.0019 (14)
C8'	0.024 (2)	0.024 (2)	0.016 (2)	0.0012 (19)	−0.0011 (17)	−0.0045 (17)
C9'	0.034 (3)	0.019 (2)	0.022 (2)	0.0014 (19)	0.001 (2)	−0.0024 (18)
C10'	0.046 (3)	0.022 (3)	0.026 (3)	−0.005 (2)	0.005 (2)	0.0034 (19)
C11'	0.035 (3)	0.026 (3)	0.026 (2)	−0.004 (2)	0.010 (2)	−0.0029 (19)
C12'	0.029 (2)	0.022 (2)	0.017 (2)	−0.0041 (19)	0.0053 (18)	−0.0020 (17)
C13'	0.019 (2)	0.025 (2)	0.029 (2)	0.0003 (19)	0.0033 (19)	0.000 (2)
O14'	0.0294 (17)	0.0231 (17)	0.0342 (18)	−0.0029 (13)	0.0089 (14)	−0.0059 (14)
O15'	0.042 (2)	0.0219 (17)	0.0385 (19)	−0.0018 (15)	0.0189 (16)	0.0025 (14)
C16'	0.052 (3)	0.027 (3)	0.063 (4)	−0.003 (2)	0.027 (3)	0.008 (2)
C17'	0.022 (2)	0.028 (3)	0.026 (2)	−0.0012 (19)	0.0021 (19)	−0.001 (2)
O18'	0.0273 (16)	0.0293 (19)	0.0304 (17)	0.0025 (14)	0.0086 (14)	0.0053 (14)
O19'	0.0415 (19)	0.0322 (19)	0.0372 (19)	0.0027 (15)	0.0257 (16)	0.0031 (14)
C20'	0.044 (3)	0.034 (3)	0.043 (3)	0.008 (2)	0.023 (2)	0.001 (2)
B1	0.041 (4)	0.050 (4)	0.040 (4)	−0.010 (3)	0.003 (3)	0.009 (3)
F1	0.084 (3)	0.078 (3)	0.060 (2)	−0.036 (2)	0.012 (2)	0.0071 (19)
F2	0.076 (2)	0.075 (3)	0.052 (2)	−0.037 (2)	−0.0005 (18)	0.0027 (18)
F3	0.100 (3)	0.055 (2)	0.056 (2)	0.023 (2)	−0.012 (2)	0.0161 (18)
F4	0.072 (3)	0.060 (2)	0.103 (3)	0.002 (2)	0.026 (2)	−0.008 (2)

Geometric parameters (Å, º)

Cu1—N1	2.029 (3)	N1'—C2'	1.347 (5)
Cu1—N7'	2.035 (3)	N1'—C6'	1.351 (5)
Cu1—N7	2.074 (3)	C2'—C3'	1.392 (6)
Cu1—N1'	2.077 (3)	C2'—C8'	1.486 (6)
N1—C6	1.351 (5)	C3'—C4'	1.379 (6)
N1—C2	1.356 (5)	C3'—H3'A	0.9500
C2—C3	1.396 (6)	C4'—C5'	1.386 (6)
C2—C8	1.487 (6)	C4'—H4'A	0.9500
C3—C4	1.377 (6)	C5'—C6'	1.382 (6)
C3—H3A	0.9500	C5'—H5'A	0.9500
C4—C5	1.378 (6)	C6'—C13'	1.507 (6)
C4—H4A	0.9500	N7'—C12'	1.342 (5)
C5—C6	1.387 (6)	N7'—C8'	1.345 (5)
C5—H5A	0.9500	C8'—C9'	1.397 (6)
C6—C13	1.502 (6)	C9'—C10'	1.373 (6)
N7—C8	1.345 (5)	C9'—H9'A	0.9500
N7—C12	1.347 (5)	C10'—C11'	1.388 (6)
C8—C9	1.390 (6)	C10'—H10B	0.9500
C9—C10	1.375 (6)	C11'—C12'	1.383 (6)
C9—H9A	0.9500	C11'—H11B	0.9500
C10—C11	1.382 (7)	C12'—C17'	1.502 (6)
C10—H10A	0.9500	C13'—O14'	1.193 (5)
C11—C12	1.380 (6)	C13'—O15'	1.345 (5)
C11—H11A	0.9500	O15'—C16'	1.452 (5)
C12—C17	1.502 (6)	C16'—H16D	0.9800
C13—O14	1.203 (5)	C16'—H16E	0.9800
C13—O15	1.333 (5)	C16'—H16F	0.9800
O15—C16	1.450 (5)	C17'—O18'	1.199 (5)
C16—H16A	0.9800	C17'—O19'	1.340 (5)
C16—H16B	0.9800	O19'—C20'	1.450 (5)
C16—H16C	0.9800	C20'—H20D	0.9800
C17—O18	1.207 (5)	C20'—H20E	0.9800
C17—O19	1.333 (5)	C20'—H20F	0.9800
O19—C20	1.444 (5)	B1—F1	1.350 (7)
C20—H20A	0.9800	B1—F3	1.355 (7)
C20—H20B	0.9800	B1—F2	1.375 (7)
C20—H20C	0.9800	B1—F4	1.432 (8)
N1—Cu1—N7'	125.21 (13)	C2'—N1'—C6'	117.9 (3)
N1—Cu1—N7	83.09 (13)	C2'—N1'—Cu1	113.0 (3)
N7'—Cu1—N7	128.60 (13)	C6'—N1'—Cu1	127.8 (3)
N1—Cu1—N1'	140.05 (13)	N1'—C2'—C3'	122.4 (4)
N7'—Cu1—N1'	80.61 (13)	N1'—C2'—C8'	115.5 (4)
N7—Cu1—N1'	104.76 (13)	C3'—C2'—C8'	122.0 (4)
C6—N1—C2	116.8 (3)	C4'—C3'—C2'	119.0 (4)
C6—N1—Cu1	131.1 (3)	C4'—C3'—H3'A	120.5
C2—N1—Cu1	110.9 (3)	C2'—C3'—H3'A	120.5
N1—C2—C3	122.5 (4)	C3'—C4'—C5'	119.0 (4)
N1—C2—C8	116.3 (4)	C3'—C4'—H4'A	120.5
C3—C2—C8	121.2 (4)	C5'—C4'—H4'A	120.5
C4—C3—C2	119.0 (4)	C6'—C5'—C4'	119.0 (4)
C4—C3—H3A	120.5	C6'—C5'—H5'A	120.5
C2—C3—H3A	120.5	C4'—C5'—H5'A	120.5
C3—C4—C5	119.5 (4)	N1'—C6'—C5'	122.6 (4)
C3—C4—H4A	120.2	N1'—C6'—C13'	115.5 (4)
C5—C4—H4A	120.2	C5'—C6'—C13'	121.8 (4)
C4—C5—C6	118.5 (4)	C12'—N7'—C8'	118.7 (4)
C4—C5—H5A	120.8	C12'—N7'—Cu1	126.6 (3)
C6—C5—H5A	120.8	C8'—N7'—Cu1	114.4 (3)
N1—C6—C5	123.6 (4)	N7'—C8'—C9'	121.4 (4)
N1—C6—C13	117.1 (4)	N7'—C8'—C2'	115.8 (4)
C5—C6—C13	119.3 (4)	C9'—C8'—C2'	122.8 (4)
C8—N7—C12	117.2 (4)	C10'—C9'—C8'	119.2 (4)
C8—N7—Cu1	109.2 (3)	C10'—C9'—H9'A	120.4
C12—N7—Cu1	128.2 (3)	C8'—C9'—H9'A	120.4
N7—C8—C9	122.6 (4)	C9'—C10'—C11'	119.6 (4)
N7—C8—C2	115.7 (4)	C9'—C10'—H10B	120.2
C9—C8—C2	121.7 (4)	C11'—C10'—H10B	120.2
C10—C9—C8	119.0 (4)	C12'—C11'—C10'	118.1 (4)
C10—C9—H9A	120.5	C12'—C11'—H11B	120.9
C8—C9—H9A	120.5	C10'—C11'—H11B	120.9
C9—C10—C11	119.2 (4)	N7'—C12'—C11'	122.9 (4)
C9—C10—H10A	120.4	N7'—C12'—C17'	115.4 (4)
C11—C10—H10A	120.4	C11'—C12'—C17'	121.6 (4)
C12—C11—C10	118.4 (4)	O14'—C13'—O15'	125.0 (4)
C12—C11—H11A	120.8	O14'—C13'—C6'	124.6 (4)
C10—C11—H11A	120.8	O15'—C13'—C6'	110.3 (4)
N7—C12—C11	123.5 (4)	C13'—O15'—C16'	114.4 (4)
N7—C12—C17	118.9 (4)	O15'—C16'—H16D	109.5
C11—C12—C17	117.6 (4)	O15'—C16'—H16E	109.5
O14—C13—O15	124.8 (4)	H16D—C16'—H16E	109.5
O14—C13—C6	125.4 (4)	O15'—C16'—H16F	109.5
O15—C13—C6	109.8 (4)	H16D—C16'—H16F	109.5
C13—O15—C16	116.6 (3)	H16E—C16'—H16F	109.5
O15—C16—H16A	109.5	O18'—C17'—O19'	124.3 (4)
O15—C16—H16B	109.5	O18'—C17'—C12'	124.1 (4)
H16A—C16—H16B	109.5	O19'—C17'—C12'	111.6 (4)
O15—C16—H16C	109.5	C17'—O19'—C20'	114.2 (3)
H16A—C16—H16C	109.5	O19'—C20'—H20D	109.5
H16B—C16—H16C	109.5	O19'—C20'—H20E	109.5
O18—C17—O19	124.6 (4)	H20D—C20'—H20E	109.5
O18—C17—C12	122.1 (4)	O19'—C20'—H20F	109.5
O19—C17—C12	113.2 (4)	H20D—C20'—H20F	109.5
C17—O19—C20	114.8 (3)	H20E—C20'—H20F	109.5
O19—C20—H20A	109.5	F1—B1—F3	113.6 (5)
O19—C20—H20B	109.5	F1—B1—F2	112.3 (5)
H20A—C20—H20B	109.5	F3—B1—F2	110.5 (5)
O19—C20—H20C	109.5	F1—B1—F4	105.2 (5)
H20A—C20—H20C	109.5	F3—B1—F4	105.2 (5)
H20B—C20—H20C	109.5	F2—B1—F4	109.6 (5)