Assembly of two novel coordination polymers by selecting ditopic or chelating auxiliary ligands with naphthalene-2,6-di­carb­oxy­lic acid: synthesis, structure and luminescence sensing

The Fe^III ion as a ubiquitous metal plays a key role in biochemical processes. Iron deficiency or excess in the human body can induce various diseases. Thus, effective detection of the Fe^III ion has been deemed an issue of focus. To develop more crystalline chemical sensors for the selective detection of Fe³⁺, two novel two-dimensional (2D) coordination polymers, namely, poly[[[μ-bis­(pyridin-4-yl)amine-κ²N:N′](μ-naphthalene-2,6-di­carboxyl­ato-κ²O²:O⁶)zinc(II)] 0.5-hy­drate], {[Zn(C₁₂H₆O₄)(C₁₀H₉N₃)]·0.5H₂O}_n, 1, and poly[(4,4′-dimethyl-2,2′-bi­pyridine-κ²N,N′)(μ-naphthalene-2,6-di­carboxyl­ato-κ²O²:O⁶)hemi(μ-naphthalene-2,6-di­carb­oxy­lic acid-κ²O²:O⁶)copper(II)] [Cu(C₁₂H₆O₄)(C₁₂H₁₂N₂)(C₁₂H₈O₄)_0.5]_n, 2, have been prepared using solvothermal methods. Single-crystal X-ray diffraction analysis shows that com­pound 1 is an undulating twofold inter­penetrated 2D (4,4)-sql network and com­pound 2 is a twofold inter­penetrated 2D honeycomb-type network with a (6,3)-hcb topology. In addition, 1 exhibits highly selective sensing for the Fe³⁺ ion.

Computing details

For both structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[[[µ-bis(pyridin-4-yl)amine-κ²N:N'](µ-naphthalene-2,6-dicarboxylato-κ²O²:O⁶)zinc(II)] 0.5-hydrate] (1)

Crystal data

[Zn(C12H6O4)(C10H9N3)]·0.5H2O	F(000) = 940
Mr = 459.75	Dx = 1.614 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.0556 (10) Å	Cell parameters from 9047 reflections
b = 9.5218 (9) Å	θ = 2.9–27.5°
c = 18.2923 (17) Å	µ = 1.34 mm^−1
β = 100.732 (3)°	T = 298 K
V = 1891.9 (3) Å^3	Block, colourless
Z = 4	0.15 × 0.11 × 0.1 mm

Data collection

Bruker APEXII CCD diffractometer	3020 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 25.1°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→13
Tmin = 0.608, Tmax = 0.746	k = −11→11
39472 measured reflections	l = −21→21
3350 independent reflections

Refinement

Refinement on F^2	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.063	w = 1/[σ^2(Fo^2) + (0.0282P)^2 + 1.3393P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3350 reflections	Δρmax = 0.22 e Å^−3
283 parameters	Δρmin = −0.31 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.81921 (2)	0.68197 (2)	0.54500 (2)	0.02175 (8)
O1	0.21828 (14)	0.06770 (17)	0.09370 (9)	0.0417 (4)
O2	0.39703 (14)	−0.04452 (16)	0.11804 (8)	0.0378 (4)
O3	0.66253 (18)	0.74991 (17)	0.38502 (10)	0.0544 (5)
O4	0.79147 (14)	0.59343 (17)	0.44749 (8)	0.0404 (4)
N1	0.66614 (14)	0.77501 (17)	0.56474 (9)	0.0247 (4)
N2	0.32981 (14)	0.96120 (18)	0.58118 (10)	0.0297 (4)
H2	0.3373	1.0467	0.5965	0.036*
N3	−0.02952 (14)	0.80532 (16)	0.54781 (9)	0.0233 (3)
C1	0.32588 (19)	0.0580 (2)	0.12630 (11)	0.0287 (5)
C2	0.38160 (19)	0.1735 (2)	0.17746 (11)	0.0273 (4)
C3	0.3040 (2)	0.2796 (2)	0.19696 (12)	0.0333 (5)
H3	0.2195	0.2747	0.1794	0.040*
C4	0.35173 (19)	0.3888 (2)	0.24119 (12)	0.0344 (5)
H4	0.2995	0.4575	0.2538	0.041*
C5	0.47955 (18)	0.3988 (2)	0.26806 (11)	0.0265 (4)
C6	0.55852 (18)	0.2919 (2)	0.24994 (11)	0.0260 (4)
C7	0.50535 (19)	0.1799 (2)	0.20385 (11)	0.0282 (4)
H7	0.5559	0.1092	0.1913	0.034*
C8	0.68630 (19)	0.2995 (2)	0.27878 (11)	0.0303 (5)
H8	0.7385	0.2306	0.2664	0.036*
C9	0.73362 (19)	0.4070 (2)	0.32455 (11)	0.0303 (5)
H9	0.8173	0.4087	0.3447	0.036*
C10	0.65609 (19)	0.5159 (2)	0.34153 (11)	0.0279 (4)
C11	0.53275 (19)	0.5117 (2)	0.31338 (11)	0.0305 (5)
H11	0.4827	0.5844	0.3242	0.037*
C12	0.7065 (2)	0.6314 (2)	0.39428 (11)	0.0308 (5)
C13	0.56050 (18)	0.7026 (2)	0.54888 (12)	0.0293 (4)
H13	0.5646	0.6096	0.5339	0.035*
C14	0.44746 (18)	0.7559 (2)	0.55314 (12)	0.0289 (4)
H14	0.3776	0.6998	0.5416	0.035*
C15	0.43748 (17)	0.8948 (2)	0.57481 (11)	0.0238 (4)
C16	0.54713 (18)	0.9705 (2)	0.59323 (12)	0.0320 (5)
H16	0.5458	1.0629	0.6095	0.038*
C17	0.65626 (18)	0.9087 (2)	0.58727 (12)	0.0311 (5)
H17	0.7278	0.9618	0.5994	0.037*
C18	0.21066 (16)	0.90947 (19)	0.56635 (11)	0.0229 (4)
C19	0.12665 (18)	0.9618 (2)	0.60736 (12)	0.0301 (5)
H19	0.1494	1.0338	0.6415	0.036*
C20	0.01048 (17)	0.9069 (2)	0.59719 (11)	0.0294 (5)
H20	−0.0437	0.9418	0.6260	0.035*
C21	0.04987 (17)	0.7614 (2)	0.50539 (11)	0.0273 (4)
H21	0.0230	0.6941	0.4691	0.033*
C22	0.16804 (18)	0.8098 (2)	0.51240 (11)	0.0276 (4)
H22	0.2192	0.7763	0.4813	0.033*
O1W	0.4755 (6)	0.8144 (8)	0.2542 (4)	0.116 (2)	0.5
H1WA	0.5493	0.8372	0.2724	0.174*	0.5
H1WB	0.4648	0.8420	0.2093	0.174*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01634 (12)	0.02300 (13)	0.02494 (13)	0.00070 (9)	0.00132 (8)	−0.00038 (9)
O1	0.0335 (9)	0.0397 (9)	0.0477 (9)	−0.0085 (7)	−0.0031 (7)	−0.0056 (7)
O2	0.0372 (8)	0.0327 (8)	0.0404 (9)	−0.0018 (7)	−0.0010 (7)	−0.0118 (7)
O3	0.0815 (14)	0.0235 (9)	0.0513 (11)	−0.0046 (9)	−0.0058 (9)	−0.0070 (8)
O4	0.0347 (8)	0.0510 (10)	0.0324 (8)	0.0011 (7)	−0.0017 (7)	−0.0151 (7)
N1	0.0172 (8)	0.0250 (9)	0.0318 (9)	0.0006 (7)	0.0043 (7)	0.0008 (7)
N2	0.0189 (8)	0.0202 (8)	0.0509 (11)	−0.0019 (7)	0.0092 (7)	−0.0083 (8)
N3	0.0192 (8)	0.0243 (9)	0.0265 (8)	−0.0001 (6)	0.0044 (6)	−0.0009 (7)
C1	0.0349 (12)	0.0281 (11)	0.0234 (10)	−0.0091 (9)	0.0059 (9)	0.0010 (9)
C2	0.0316 (11)	0.0259 (11)	0.0241 (10)	−0.0054 (8)	0.0044 (8)	0.0003 (8)
C3	0.0268 (11)	0.0356 (12)	0.0358 (12)	−0.0013 (9)	0.0015 (9)	−0.0037 (10)
C4	0.0305 (11)	0.0330 (12)	0.0390 (12)	0.0063 (9)	0.0047 (9)	−0.0069 (10)
C5	0.0299 (11)	0.0247 (10)	0.0250 (10)	0.0011 (8)	0.0048 (8)	0.0004 (8)
C6	0.0279 (10)	0.0251 (10)	0.0246 (10)	−0.0010 (8)	0.0043 (8)	0.0007 (8)
C7	0.0327 (11)	0.0234 (10)	0.0282 (10)	0.0009 (8)	0.0053 (8)	−0.0033 (8)
C8	0.0303 (11)	0.0281 (11)	0.0319 (11)	0.0031 (9)	0.0037 (9)	−0.0024 (9)
C9	0.0301 (11)	0.0290 (11)	0.0296 (11)	−0.0044 (9)	0.0003 (8)	0.0003 (9)
C10	0.0368 (11)	0.0241 (10)	0.0218 (10)	−0.0067 (9)	0.0025 (8)	0.0008 (8)
C11	0.0375 (12)	0.0247 (11)	0.0288 (11)	0.0024 (9)	0.0051 (9)	−0.0031 (9)
C12	0.0366 (12)	0.0280 (11)	0.0284 (11)	−0.0099 (9)	0.0078 (9)	−0.0042 (9)
C13	0.0228 (10)	0.0203 (10)	0.0445 (12)	0.0006 (8)	0.0056 (9)	−0.0012 (9)
C14	0.0192 (10)	0.0206 (10)	0.0468 (12)	−0.0041 (8)	0.0056 (9)	−0.0001 (9)
C15	0.0188 (9)	0.0246 (10)	0.0287 (10)	−0.0008 (8)	0.0060 (8)	0.0014 (8)
C16	0.0247 (10)	0.0250 (11)	0.0466 (13)	−0.0033 (8)	0.0072 (9)	−0.0123 (10)
C17	0.0186 (10)	0.0310 (11)	0.0429 (12)	−0.0054 (8)	0.0036 (9)	−0.0084 (9)
C18	0.0183 (9)	0.0187 (9)	0.0315 (10)	0.0018 (7)	0.0039 (8)	0.0020 (8)
C19	0.0229 (10)	0.0271 (11)	0.0400 (12)	−0.0006 (8)	0.0050 (9)	−0.0142 (9)
C20	0.0202 (10)	0.0333 (11)	0.0360 (11)	0.0022 (8)	0.0087 (8)	−0.0102 (9)
C21	0.0236 (10)	0.0288 (11)	0.0294 (10)	−0.0011 (8)	0.0050 (8)	−0.0086 (9)
C22	0.0229 (10)	0.0316 (11)	0.0303 (10)	0.0022 (8)	0.0098 (8)	−0.0062 (9)
O1W	0.098 (4)	0.135 (5)	0.117 (5)	0.026 (4)	0.023 (3)	0.073 (4)

Geometric parameters (Å, º)

Zn1—O2^i	1.9520 (14)	C6—C8	1.415 (3)
Zn1—O4	1.9450 (14)	C7—H7	0.9300
Zn1—N1	2.0016 (16)	C8—H8	0.9300
Zn1—N3^ii	2.0365 (16)	C8—C9	1.363 (3)
O1—C1	1.231 (2)	C9—H9	0.9300
O2—Zn1^iii	1.9519 (14)	C9—C10	1.416 (3)
O2—C1	1.280 (3)	C10—C11	1.365 (3)
O3—C12	1.228 (3)	C10—C12	1.500 (3)
O4—C12	1.273 (3)	C11—H11	0.9300
N1—C13	1.341 (3)	C13—H13	0.9300
N1—C17	1.349 (3)	C13—C14	1.364 (3)
N2—H2	0.8600	C14—H14	0.9300
N2—C15	1.372 (2)	C14—C15	1.391 (3)
N2—C18	1.385 (2)	C15—C16	1.397 (3)
N3—Zn1^iv	2.0364 (16)	C16—H16	0.9300
N3—C20	1.341 (3)	C16—C17	1.365 (3)
N3—C21	1.342 (2)	C17—H17	0.9300
C1—C2	1.500 (3)	C18—C19	1.391 (3)
C2—C3	1.413 (3)	C18—C22	1.387 (3)
C2—C7	1.365 (3)	C19—H19	0.9300
C3—H3	0.9300	C19—C20	1.367 (3)
C3—C4	1.362 (3)	C20—H20	0.9300
C4—H4	0.9300	C21—H21	0.9300
C4—C5	1.410 (3)	C21—C22	1.369 (3)
C5—C6	1.420 (3)	C22—H22	0.9300
C5—C11	1.417 (3)	O1W—H1WA	0.8499
C6—C7	1.418 (3)	O1W—H1WB	0.8507
O2^i—Zn1—N1	116.94 (7)	C8—C9—C10	120.37 (19)
O2^i—Zn1—N3^ii	96.56 (6)	C10—C9—H9	119.8
O4—Zn1—O2^i	108.14 (7)	C9—C10—C12	120.70 (18)
O4—Zn1—N1	111.28 (7)	C11—C10—C9	119.91 (18)
O4—Zn1—N3^ii	105.17 (7)	C11—C10—C12	119.27 (19)
N1—Zn1—N3^ii	117.27 (7)	C5—C11—H11	119.4
C1—O2—Zn1^iii	112.95 (13)	C10—C11—C5	121.27 (19)
C12—O4—Zn1	123.10 (14)	C10—C11—H11	119.4
C13—N1—Zn1	117.71 (13)	O3—C12—O4	125.7 (2)
C13—N1—C17	115.77 (16)	O3—C12—C10	119.68 (19)
C17—N1—Zn1	126.31 (13)	O4—C12—C10	114.61 (19)
C15—N2—H2	115.5	N1—C13—H13	117.7
C15—N2—C18	128.90 (17)	N1—C13—C14	124.51 (19)
C18—N2—H2	115.5	C14—C13—H13	117.7
C20—N3—Zn1^iv	126.81 (13)	C13—C14—H14	120.3
C20—N3—C21	116.44 (16)	C13—C14—C15	119.48 (18)
C21—N3—Zn1^iv	115.34 (13)	C15—C14—H14	120.3
O1—C1—O2	124.02 (19)	N2—C15—C14	125.36 (17)
O1—C1—C2	119.68 (19)	N2—C15—C16	118.00 (17)
O2—C1—C2	116.27 (18)	C14—C15—C16	116.62 (17)
C3—C2—C1	118.89 (18)	C15—C16—H16	120.0
C7—C2—C1	121.43 (19)	C17—C16—C15	119.91 (19)
C7—C2—C3	119.66 (18)	C17—C16—H16	120.0
C2—C3—H3	119.7	N1—C17—C16	123.68 (18)
C4—C3—C2	120.60 (19)	N1—C17—H17	118.2
C4—C3—H3	119.7	C16—C17—H17	118.2
C3—C4—H4	119.6	N2—C18—C19	118.24 (17)
C3—C4—C5	120.71 (19)	N2—C18—C22	124.58 (17)
C5—C4—H4	119.6	C22—C18—C19	117.18 (17)
C4—C5—C6	119.36 (18)	C18—C19—H19	120.2
C4—C5—C11	122.33 (19)	C20—C19—C18	119.61 (18)
C11—C5—C6	118.32 (18)	C20—C19—H19	120.2
C7—C6—C5	118.25 (18)	N3—C20—C19	123.46 (18)
C8—C6—C5	119.39 (18)	N3—C20—H20	118.3
C8—C6—C7	122.35 (18)	C19—C20—H20	118.3
C2—C7—C6	121.41 (19)	N3—C21—H21	118.1
C2—C7—H7	119.3	N3—C21—C22	123.79 (18)
C6—C7—H7	119.3	C22—C21—H21	118.1
C6—C8—H8	119.7	C18—C22—H22	120.4
C9—C8—C6	120.67 (19)	C21—C22—C18	119.29 (18)
C9—C8—H8	119.7	C21—C22—H22	120.4
C8—C9—H9	119.8	H1WA—O1W—H1WB	104.5

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

Poly[(4,4'-dimethyl-2,2'-bipyridine-κ²N,N')(µ-naphthalene-2,6-dicarboxylato-κ²O²:O⁶)hemi(µ-naphthalene-2,6-\# dicarboxylic acid-κ²O²:O⁶)copper(II)] (2)

Crystal data

[Cu(C12H6O4)(C12H12N2)(C12H8O4)0.5]	Z = 2
Mr = 570.03	F(000) = 586
Triclinic, P1	Dx = 1.515 Mg m^−3
a = 11.0642 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.1234 (4) Å	Cell parameters from 9878 reflections
c = 11.6697 (4) Å	θ = 3.0–27.6°
α = 61.912 (1)°	µ = 0.92 mm^−1
β = 86.182 (1)°	T = 150 K
γ = 80.602 (1)°	Block, blue
V = 1249.97 (8) Å^3	0.12 × 0.11 × 0.1 mm

Data collection

Bruker APEXII CCD diffractometer	4537 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 27.6°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
Tmin = 0.652, Tmax = 0.746	k = −14→14
30448 measured reflections	l = −15→15
5778 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.065	w = 1/[σ^2(Fo^2) + (0.0014P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.79	(Δ/σ)max = 0.001
5778 reflections	Δρmax = 0.32 e Å^−3
401 parameters	Δρmin = −0.31 e Å^−3
33 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.62316 (2)	0.56483 (2)	0.73767 (2)	0.01693 (7)
O1	0.70966 (10)	0.37657 (13)	0.92661 (12)	0.0263 (3)
O2	0.87286 (11)	0.45640 (14)	0.95408 (14)	0.0326 (3)
H2	0.820968	0.526349	0.939250	0.049*
O3	0.56788 (10)	0.69878 (13)	0.79878 (12)	0.0236 (3)
O4	0.72750 (11)	0.66667 (14)	0.92574 (13)	0.0337 (3)
O5	0.77943 (9)	0.63468 (12)	0.67803 (12)	0.0216 (3)
O6	0.68382 (11)	0.75759 (13)	0.48627 (13)	0.0312 (3)
N1	0.44948 (11)	0.53005 (14)	0.73974 (14)	0.0174 (3)
N2	0.65250 (11)	0.42775 (14)	0.67005 (13)	0.0154 (3)
C1	0.34977 (14)	0.58882 (19)	0.77608 (18)	0.0242 (4)
H1	0.359592	0.645438	0.814411	0.029*
C2	0.23247 (15)	0.5700 (2)	0.75975 (18)	0.0256 (4)
H2A	0.163572	0.613114	0.786818	0.031*
C3	0.21610 (14)	0.48787 (18)	0.70374 (17)	0.0214 (4)
C4	0.32009 (13)	0.42570 (17)	0.66731 (16)	0.0178 (4)
H4	0.312626	0.368305	0.629152	0.021*
C5	0.43509 (13)	0.44826 (17)	0.68719 (16)	0.0154 (3)
C6	0.55084 (13)	0.38279 (16)	0.65519 (15)	0.0146 (3)
C7	0.55744 (14)	0.28249 (17)	0.61630 (17)	0.0187 (4)
H7	0.484334	0.255266	0.604051	0.022*
C8	0.67030 (14)	0.22102 (18)	0.59492 (17)	0.0210 (4)
C9	0.77433 (14)	0.26641 (18)	0.61288 (17)	0.0214 (4)
H9	0.853562	0.226487	0.600557	0.026*
C10	0.76149 (13)	0.36945 (18)	0.64857 (17)	0.0196 (4)
H10	0.833195	0.400638	0.658418	0.024*
C11	0.08993 (14)	0.4658 (2)	0.68228 (19)	0.0309 (5)
H11A	0.066068	0.523573	0.590697	0.046*
H11B	0.030814	0.490863	0.736685	0.046*
H11C	0.091176	0.368680	0.705567	0.046*
C12	0.67752 (16)	0.1096 (2)	0.5554 (2)	0.0338 (5)
H12A	0.745635	0.117181	0.495366	0.051*
H12B	0.600670	0.119646	0.512364	0.051*
H12C	0.690964	0.019257	0.632617	0.051*
C13	0.81920 (15)	0.36247 (19)	0.94994 (17)	0.0242 (4)
C14	0.90396 (15)	0.23282 (19)	0.97504 (17)	0.0228 (4)
C15	0.86075 (15)	0.13322 (19)	0.96017 (17)	0.0239 (4)
H15	0.777411	0.146616	0.935955	0.029*
C16	1.02769 (15)	0.21448 (19)	1.01345 (18)	0.0260 (4)
H16	1.057683	0.284584	1.023048	0.031*
C17	1.10355 (15)	0.09404 (19)	1.03659 (18)	0.0269 (4)
H17	1.185646	0.080641	1.064455	0.032*
C18	1.06189 (14)	−0.00947 (19)	1.01977 (17)	0.0222 (4)
C19	0.62418 (15)	0.72392 (18)	0.87507 (17)	0.0216 (4)
C20	0.55944 (14)	0.83489 (17)	0.90631 (17)	0.0184 (4)
C21	0.60057 (14)	0.84466 (17)	1.00953 (16)	0.0183 (4)
H21	0.665587	0.777868	1.062317	0.022*
C22	0.54924 (13)	0.95074 (17)	1.03949 (16)	0.0162 (3)
C23	0.46012 (14)	0.93163 (18)	0.82916 (17)	0.0204 (4)
H23	0.429902	0.923993	0.758908	0.024*
C24	0.40783 (14)	1.03562 (18)	0.85546 (17)	0.0201 (4)
H24	0.341592	1.100091	0.802792	0.024*
C25	0.76658 (14)	0.73466 (18)	0.56299 (18)	0.0198 (4)
C26	0.92622 (16)	0.8442 (2)	0.6051 (2)	0.0166 (5)	0.897 (4)
H26	0.926074	0.777032	0.693891	0.020*	0.897 (4)
C27	0.8564 (3)	0.8372 (3)	0.5170 (4)	0.0178 (6)	0.897 (4)
C28	0.85907 (18)	0.9349 (2)	0.3845 (2)	0.0196 (5)	0.897 (4)
H28	0.811275	0.929124	0.323058	0.024*	0.897 (4)
C29	0.92936 (16)	1.0375 (2)	0.34353 (19)	0.0205 (5)	0.897 (4)
H29	0.930656	1.101763	0.253904	0.025*	0.897 (4)
C30	1.0009 (2)	1.0490 (3)	0.4342 (3)	0.0159 (6)	0.897 (4)
C27A	0.864 (2)	0.820 (2)	0.555 (2)	0.018 (8)	0.103 (4)
C26A	0.8874 (17)	0.908 (2)	0.454 (2)	0.017 (4)	0.103 (4)
H26A	0.852826	0.914378	0.378940	0.020*	0.103 (4)
C30A	1.0266 (19)	0.983 (2)	0.565 (2)	0.010 (6)	0.103 (4)
C29A	1.0072 (15)	0.8800 (19)	0.678 (2)	0.027 (5)	0.103 (4)
H29A	1.046909	0.862421	0.755014	0.033*	0.103 (4)
C28A	0.9267 (15)	0.799 (2)	0.678 (2)	0.017 (4)	0.103 (4)
H28A	0.908931	0.724870	0.758818	0.020*	0.103 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01635 (10)	0.01852 (12)	0.02194 (12)	−0.00282 (8)	−0.00001 (8)	−0.01429 (10)
O1	0.0265 (6)	0.0241 (7)	0.0248 (7)	0.0032 (5)	−0.0017 (5)	−0.0106 (6)
O2	0.0303 (7)	0.0310 (8)	0.0434 (9)	0.0112 (6)	−0.0130 (6)	−0.0264 (8)
O3	0.0243 (6)	0.0254 (7)	0.0310 (8)	−0.0005 (5)	−0.0025 (5)	−0.0220 (6)
O4	0.0338 (7)	0.0347 (8)	0.0441 (9)	0.0135 (6)	−0.0165 (6)	−0.0314 (8)
O5	0.0191 (6)	0.0221 (7)	0.0277 (8)	−0.0059 (5)	−0.0008 (5)	−0.0141 (6)
O6	0.0341 (7)	0.0300 (8)	0.0311 (8)	−0.0149 (6)	−0.0078 (6)	−0.0115 (7)
N1	0.0171 (6)	0.0184 (8)	0.0206 (8)	−0.0010 (6)	0.0019 (6)	−0.0129 (7)
N2	0.0153 (6)	0.0155 (7)	0.0168 (8)	−0.0030 (5)	0.0010 (5)	−0.0087 (6)
C1	0.0231 (9)	0.0287 (11)	0.0272 (11)	−0.0010 (8)	0.0024 (7)	−0.0196 (9)
C2	0.0182 (8)	0.0320 (11)	0.0289 (11)	0.0016 (7)	0.0045 (7)	−0.0182 (10)
C3	0.0162 (8)	0.0221 (10)	0.0211 (10)	−0.0024 (7)	0.0008 (7)	−0.0063 (8)
C4	0.0186 (8)	0.0161 (9)	0.0192 (9)	−0.0036 (7)	0.0003 (7)	−0.0084 (8)
C5	0.0160 (7)	0.0144 (9)	0.0149 (9)	−0.0016 (6)	0.0006 (6)	−0.0064 (7)
C6	0.0151 (7)	0.0139 (9)	0.0145 (9)	−0.0026 (6)	0.0007 (6)	−0.0062 (7)
C7	0.0177 (8)	0.0168 (9)	0.0246 (10)	−0.0037 (7)	0.0016 (7)	−0.0120 (8)
C8	0.0243 (9)	0.0169 (9)	0.0226 (10)	−0.0019 (7)	0.0032 (7)	−0.0106 (8)
C9	0.0165 (8)	0.0212 (10)	0.0271 (10)	0.0010 (7)	0.0032 (7)	−0.0132 (9)
C10	0.0138 (7)	0.0229 (10)	0.0228 (10)	−0.0023 (7)	0.0009 (7)	−0.0114 (8)
C11	0.0167 (8)	0.0391 (12)	0.0382 (12)	−0.0052 (8)	0.0022 (8)	−0.0189 (11)
C12	0.0316 (10)	0.0294 (12)	0.0529 (14)	−0.0050 (9)	0.0102 (9)	−0.0307 (11)
C13	0.0282 (9)	0.0276 (11)	0.0154 (10)	0.0040 (8)	−0.0014 (7)	−0.0112 (9)
C14	0.0253 (9)	0.0228 (10)	0.0156 (9)	0.0023 (7)	−0.0001 (7)	−0.0070 (8)
C15	0.0199 (8)	0.0266 (11)	0.0193 (10)	0.0007 (7)	−0.0009 (7)	−0.0070 (9)
C16	0.0272 (9)	0.0252 (11)	0.0248 (11)	−0.0013 (8)	−0.0023 (8)	−0.0115 (9)
C17	0.0210 (9)	0.0284 (11)	0.0282 (11)	−0.0019 (8)	−0.0036 (7)	−0.0107 (9)
C18	0.0207 (8)	0.0242 (10)	0.0178 (9)	−0.0015 (7)	0.0006 (7)	−0.0073 (8)
C19	0.0257 (9)	0.0190 (10)	0.0245 (10)	−0.0023 (7)	−0.0007 (7)	−0.0140 (9)
C20	0.0206 (8)	0.0169 (9)	0.0216 (10)	−0.0045 (7)	0.0023 (7)	−0.0120 (8)
C21	0.0194 (8)	0.0161 (9)	0.0199 (9)	−0.0003 (7)	−0.0019 (7)	−0.0092 (8)
C22	0.0182 (8)	0.0154 (9)	0.0164 (9)	−0.0038 (7)	0.0010 (6)	−0.0083 (8)
C23	0.0235 (8)	0.0229 (10)	0.0200 (10)	−0.0040 (7)	−0.0028 (7)	−0.0137 (8)
C24	0.0209 (8)	0.0195 (9)	0.0211 (10)	0.0016 (7)	−0.0055 (7)	−0.0112 (8)
C25	0.0183 (8)	0.0192 (10)	0.0303 (11)	−0.0055 (7)	0.0049 (7)	−0.0182 (9)
C26	0.0163 (9)	0.0168 (11)	0.0149 (13)	−0.0009 (8)	−0.0001 (8)	−0.0064 (10)
C27	0.0154 (12)	0.0174 (15)	0.0260 (19)	−0.0037 (10)	0.0029 (12)	−0.0145 (13)
C28	0.0213 (10)	0.0252 (12)	0.0189 (13)	−0.0077 (9)	−0.0019 (9)	−0.0140 (11)
C29	0.0210 (10)	0.0263 (12)	0.0159 (11)	−0.0077 (8)	−0.0013 (8)	−0.0099 (9)
C30	0.0125 (11)	0.0197 (14)	0.0208 (13)	−0.0036 (10)	−0.0003 (9)	−0.0134 (11)
C27A	0.020 (9)	0.015 (9)	0.023 (10)	−0.002 (4)	0.008 (5)	−0.012 (6)
C26A	0.022 (7)	0.020 (8)	0.013 (8)	0.007 (6)	−0.005 (6)	−0.013 (7)
C30A	0.008 (7)	0.009 (7)	0.017 (7)	−0.004 (4)	−0.001 (4)	−0.009 (5)
C29A	0.028 (8)	0.030 (9)	0.034 (9)	−0.005 (6)	−0.003 (6)	−0.023 (7)
C28A	0.016 (5)	0.015 (6)	0.024 (6)	−0.008 (4)	−0.004 (4)	−0.010 (4)

Geometric parameters (Å, º)

Cu1—O1	2.3327 (12)	C14—C15	1.361 (2)
Cu1—O3	1.9359 (11)	C14—C16	1.422 (2)
Cu1—O5	1.9614 (11)	C15—H15	0.9500
Cu1—N1	2.0176 (12)	C15—C18^i	1.421 (2)
Cu1—N2	1.9976 (13)	C16—H16	0.9500
O1—C13	1.2286 (19)	C16—C17	1.376 (2)
O2—H2	0.8400	C17—H17	0.9500
O2—C13	1.304 (2)	C17—C18	1.405 (2)
O3—C19	1.2743 (19)	C18—C18^i	1.425 (3)
O4—C19	1.249 (2)	C19—C20	1.507 (2)
O5—C25	1.276 (2)	C20—C21	1.372 (2)
O6—C25	1.234 (2)	C20—C23	1.418 (2)
N1—C1	1.3370 (19)	C21—H21	0.9500
N1—C5	1.347 (2)	C21—C22	1.407 (2)
N2—C6	1.3552 (19)	C22—C22^ii	1.425 (3)
N2—C10	1.3398 (19)	C22—C24^ii	1.424 (2)
C1—H1	0.9500	C23—H23	0.9500
C1—C2	1.387 (2)	C23—C24	1.363 (2)
C2—H2A	0.9500	C24—H24	0.9500
C2—C3	1.388 (2)	C25—C27	1.516 (3)
C3—C4	1.391 (2)	C25—C27A	1.518 (9)
C3—C11	1.513 (2)	C26—H26	0.9500
C4—H4	0.9500	C26—C27	1.365 (3)
C4—C5	1.391 (2)	C26—C30^iii	1.422 (3)
C5—C6	1.482 (2)	C27—C28	1.412 (4)
C6—C7	1.379 (2)	C28—H28	0.9500
C7—H7	0.9500	C28—C29	1.365 (3)
C7—C8	1.389 (2)	C29—H29	0.9500
C8—C9	1.395 (2)	C29—C30	1.427 (3)
C8—C12	1.502 (2)	C30—C30^iii	1.405 (5)
C9—H9	0.9500	C27A—C26A	1.17 (3)
C9—C10	1.377 (2)	C27A—C28A	1.53 (3)
C10—H10	0.9500	C26A—H26A	0.9500
C11—H11A	0.9800	C26A—C30A^iii	1.58 (3)
C11—H11B	0.9800	C30A—C30A^iii	1.52 (5)
C11—H11C	0.9800	C30A—C29A	1.31 (3)
C12—H12A	0.9800	C29A—H29A	0.9500
C12—H12B	0.9800	C29A—C28A	1.37 (2)
C12—H12C	0.9800	C28A—H28A	0.9500
C13—C14	1.497 (2)
O3—Cu1—O1	101.39 (5)	C15—C14—C16	120.62 (16)
O3—Cu1—O5	92.57 (5)	C16—C14—C13	120.42 (17)
O3—Cu1—N1	90.26 (5)	C14—C15—H15	119.4
O3—Cu1—N2	171.05 (5)	C14—C15—C18^i	121.16 (16)
O5—Cu1—O1	93.44 (5)	C18^i—C15—H15	119.4
O5—Cu1—N1	162.09 (5)	C14—C16—H16	120.4
O5—Cu1—N2	95.25 (5)	C17—C16—C14	119.28 (17)
N1—Cu1—O1	103.33 (5)	C17—C16—H16	120.4
N2—Cu1—O1	82.52 (5)	C16—C17—H17	119.4
N2—Cu1—N1	80.96 (5)	C16—C17—C18	121.26 (16)
C13—O1—Cu1	119.56 (12)	C18—C17—H17	119.4
C13—O2—H2	109.5	C15^i—C18—C18^i	118.2 (2)
C19—O3—Cu1	127.62 (11)	C17—C18—C15^i	122.36 (15)
C25—O5—Cu1	109.74 (10)	C17—C18—C18^i	119.4 (2)
C1—N1—Cu1	126.80 (12)	O3—C19—C20	116.43 (14)
C1—N1—C5	118.60 (13)	O4—C19—O3	126.70 (16)
C5—N1—Cu1	114.30 (10)	O4—C19—C20	116.88 (15)
C6—N2—Cu1	115.22 (10)	C21—C20—C19	118.89 (15)
C10—N2—Cu1	126.59 (11)	C21—C20—C23	119.52 (15)
C10—N2—C6	117.96 (14)	C23—C20—C19	121.56 (15)
N1—C1—H1	118.9	C20—C21—H21	119.0
N1—C1—C2	122.26 (16)	C20—C21—C22	121.92 (15)
C2—C1—H1	118.9	C22—C21—H21	119.0
C1—C2—H2A	120.1	C21—C22—C22^ii	118.47 (18)
C1—C2—C3	119.79 (15)	C21—C22—C24^ii	122.82 (15)
C3—C2—H2A	120.1	C24^ii—C22—C22^ii	118.71 (18)
C2—C3—C4	117.81 (14)	C20—C23—H23	119.9
C2—C3—C11	121.70 (15)	C24—C23—C20	120.21 (15)
C4—C3—C11	120.49 (16)	C24—C23—H23	119.9
C3—C4—H4	120.3	C22^ii—C24—H24	119.4
C5—C4—C3	119.46 (16)	C23—C24—C22^ii	121.15 (15)
C5—C4—H4	120.3	C23—C24—H24	119.4
N1—C5—C4	122.08 (14)	O5—C25—C27	118.3 (2)
N1—C5—C6	114.81 (13)	O5—C25—C27A	103.6 (7)
C4—C5—C6	123.10 (15)	O6—C25—O5	125.04 (15)
N2—C6—C5	114.15 (14)	O6—C25—C27	116.7 (2)
N2—C6—C7	121.79 (14)	O6—C25—C27A	131.0 (8)
C7—C6—C5	124.05 (14)	C27—C26—H26	119.6
C6—C7—H7	119.8	C27—C26—C30^iii	120.8 (2)
C6—C7—C8	120.41 (15)	C30^iii—C26—H26	119.6
C8—C7—H7	119.8	C26—C27—C25	120.0 (3)
C7—C8—C9	117.21 (16)	C26—C27—C28	119.6 (2)
C7—C8—C12	120.37 (15)	C28—C27—C25	120.1 (2)
C9—C8—C12	122.41 (15)	C27—C28—H28	119.6
C8—C9—H9	120.2	C29—C28—C27	120.9 (2)
C10—C9—C8	119.59 (15)	C29—C28—H28	119.6
C10—C9—H9	120.2	C28—C29—H29	119.7
N2—C10—C9	123.01 (15)	C28—C29—C30	120.5 (2)
N2—C10—H10	118.5	C30—C29—H29	119.7
C9—C10—H10	118.5	C26^iii—C30—C29	121.9 (2)
C3—C11—H11A	109.5	C30^iii—C30—C26^iii	119.6 (3)
C3—C11—H11B	109.5	C30^iii—C30—C29	118.5 (3)
C3—C11—H11C	109.5	C25—C27A—C28A	121.4 (12)
H11A—C11—H11B	109.5	C26A—C27A—C25	119.4 (18)
H11A—C11—H11C	109.5	C26A—C27A—C28A	119.1 (14)
H11B—C11—H11C	109.5	C27A—C26A—H26A	117.8
C8—C12—H12A	109.5	C27A—C26A—C30A^iii	124 (2)
C8—C12—H12B	109.5	C30A^iii—C26A—H26A	117.8
C8—C12—H12C	109.5	C29A—C30A—C30A^iii	126 (2)
H12A—C12—H12B	109.5	C30A—C29A—H29A	121.8
H12A—C12—H12C	109.5	C30A—C29A—C28A	116 (2)
H12B—C12—H12C	109.5	C28A—C29A—H29A	121.8
O1—C13—O2	124.41 (16)	C27A—C28A—H28A	118.1
O1—C13—C14	121.72 (17)	C29A—C28A—C27A	123.8 (18)
O2—C13—C14	113.86 (15)	C29A—C28A—H28A	118.1
C15—C14—C13	118.96 (15)

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