Solvent-triggered single-crystal-to-single-crystal transformation from a monomeric to polymeric copper(II) complex based on an aza macrocyclic ligand

Reversible solvent-triggered single-crystal-to-single-crystal (SCSC) transformations are observed between two copper(II) aza­macrocyclic complexes: [Cu(C₁₆H₃₈N₆)(H₂O)₂](C₁₂H₆O₄) (1) and [Cu(C₁₆H₃₈N₆)(C₁₂H₆O₄)] (2). Complex (1) was prepared via self-assembly of a copper(II) aza­macrocyclic complex containing butyl pendant groups, [Cu(C₁₆H₃₈N₆)(ClO₄)₂], with 2,7-naphthalenedi­carb­oxy­lic acid. When monomeric compound (1) was immersed in CH₃OH, coordination polymer (2) was obtained, indicating a solvent-triggered SCSC transformation. Furthermore, when (2) was immersed in water, an reverse SCSC transformation from (2) to (1) occurred. Complex (1) presents a 3D supramolecular structure formed via intermolecular hydrogen-bonding interactions, whereas complex (2) features a 1D zigzag coordination polymer. The reversible SCSC transformation of (1) and (2) was characterized using single-crystal X-ray diffraction and in situ powder X-ray diffraction techniques. Despite its poor porosity, complex (2) displayed interesting CO₂ adsorption behaviour under CO₂ gas.

Computing details

For both structures, data collection: PAL BL2D-SMDC Program(Shin et al., 2016); cell refinement: HKL3000sm(Otwinowski & Minor, 1997); data reduction: HKL3000sm(Otwinowski & Minor, 1997). Program(s) used to solve structure: SHELXT-2018(Sheldrick, 2018) for CuNDC_mono; SHELXT 2018/2 (Sheldrick, 2018) for CuNDC_poly. Program(s) used to refine structure: SHELXL-2018(Sheldrick, 2018) for CuNDC_mono; SHELXL for CuNDC_poly. Molecular graphics: DIAMOND 4(Putz & Brandenburg, 2014) for CuNDC_mono. Software used to prepare material for publication: publCIF(Westrip, 2010) for CuNDC_mono.

(CuNDC_mono)

Crystal data

C16H42CuN6O2·C12H6O4·H2O	Z = 2
Mr = 646.28	F(000) = 690
Triclinic, P1	Dx = 1.341 Mg m^−3
a = 10.946 (2) Å	Synchrotron radiation, λ = 0.610 Å
b = 12.502 (3) Å	Cell parameters from 86556 reflections
c = 13.029 (3) Å	θ = 0.4–33.7°
α = 70.34 (3)°	µ = 0.49 mm^−1
β = 79.99 (3)°	T = 298 K
γ = 73.06 (3)°	Needle, pale purple
V = 1600.4 (7) Å^3	0.13 × 0.05 × 0.03 mm

Data collection

Rayonix MX225HS CCD area detector diffractometer	7396 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.021
ω scan	θmax = 25.0°, θmin = 1.4°
Absorption correction: empirical (using intensity measurements) HKL3000sm Scalepack(Otwinowski et al,2003)	h = −15→15
Tmin = 0.664, Tmax = 1.000	k = −17→17
17649 measured reflections	l = −18→18
8899 independent reflections

Refinement

Refinement on F^2	50 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.171	w = 1/[σ^2(Fo^2) + (0.1181P)^2 + 0.0613P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
8899 reflections	Δρmax = 0.76 e Å^−3
399 parameters	Δρmin = −0.91 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
Cu1	0.74253 (2)	0.74501 (2)	−0.00637 (2)	0.03540 (10)
O1	0.94326 (16)	0.61210 (14)	0.05384 (13)	0.0467 (4)
H1O1	1.016 (2)	0.620 (2)	0.004 (2)	0.070*
H2O1	0.951 (3)	0.5310 (10)	0.080 (2)	0.070*
O2	0.5256 (2)	0.89356 (19)	−0.07982 (18)	0.0669 (5)
H1O2	0.486 (3)	0.912 (3)	−0.0138 (18)	0.100*
H2O2	0.456 (2)	0.880 (3)	−0.106 (3)	0.100*
N1	0.66639 (17)	0.61025 (16)	0.01233 (14)	0.0396 (4)
H1	0.736112	0.538455	0.023860	0.048*
N2	0.66757 (17)	0.73820 (15)	0.14723 (13)	0.0365 (3)
H2	0.587434	0.799866	0.142621	0.044*
N3	0.76986 (19)	0.87602 (17)	0.16186 (15)	0.0448 (4)
N4	0.80889 (18)	0.88598 (15)	−0.02700 (14)	0.0394 (4)
H4	0.736692	0.955532	−0.044052	0.047*
N5	0.81055 (18)	0.75610 (16)	−0.16173 (14)	0.0396 (4)
H5	0.888265	0.692335	−0.160548	0.047*
N6	0.6805 (2)	0.6363 (2)	−0.18439 (16)	0.0536 (5)
C1	0.5778 (2)	0.5989 (2)	0.11367 (18)	0.0445 (5)
H1A	0.565089	0.520199	0.141581	0.053*
H1AB	0.495164	0.653978	0.097674	0.053*
C2	0.6348 (2)	0.62386 (19)	0.19818 (17)	0.0419 (4)
H2A	0.573523	0.626787	0.261262	0.050*
H2AB	0.711078	0.562385	0.222212	0.050*
C3	0.7516 (2)	0.7590 (2)	0.21295 (17)	0.0428 (4)
H3A	0.712195	0.751308	0.286911	0.051*
H3AB	0.833621	0.701577	0.216469	0.051*
C4	0.8644 (2)	0.8856 (2)	0.06896 (19)	0.0462 (5)
H4A	0.939193	0.819935	0.085845	0.055*
H4AB	0.891150	0.957437	0.052645	0.055*
C5	0.9017 (2)	0.8948 (2)	−0.12506 (18)	0.0454 (5)
H5A	0.983284	0.839132	−0.106132	0.054*
H5AB	0.915519	0.973123	−0.153178	0.054*
C6	0.8480 (2)	0.8686 (2)	−0.21097 (17)	0.0467 (5)
H6A	0.773890	0.931285	−0.238270	0.056*
H6AB	0.912021	0.863297	−0.271896	0.056*
C7	0.7189 (3)	0.7439 (2)	−0.22794 (18)	0.0502 (5)
H7A	0.643141	0.808704	−0.232902	0.060*
H7AB	0.758784	0.749714	−0.301525	0.060*
C8	0.6009 (3)	0.6228 (3)	−0.0845 (2)	0.0549 (6)
H8A	0.568776	0.554031	−0.069709	0.066*
H8AB	0.527716	0.690396	−0.093446	0.066*
C9	0.7909 (3)	0.9292 (2)	0.2403 (2)	0.0524 (6)
H9A	0.718567	0.929758	0.295172	0.063*
H9AB	0.791985	1.010199	0.201751	0.063*
C10	0.9132 (3)	0.8689 (3)	0.2983 (2)	0.0643 (7)
H10A	0.986240	0.866794	0.244290	0.077*
H10B	0.911714	0.788535	0.339606	0.077*
C11	0.9290 (4)	0.9323 (3)	0.3766 (3)	0.0755 (8)
H11A	1.019004	0.914282	0.387586	0.091*
H11B	0.899598	1.016392	0.343575	0.091*
C12	0.8559 (6)	0.8968 (5)	0.4832 (3)	0.1223 (19)
H12A	0.851984	0.949395	0.523670	0.183*
H12B	0.897511	0.818332	0.523638	0.183*
H12C	0.770588	0.899417	0.471846	0.183*
C13	0.7717 (3)	0.5302 (3)	−0.1978 (3)	0.0662 (7)
H13A	0.737565	0.463340	−0.155725	0.079*
H13B	0.850560	0.521054	−0.167811	0.079*
C14	0.8019 (6)	0.5286 (4)	−0.3127 (4)	0.1160 (15)
H14A	0.866486	0.457053	−0.314662	0.139*
H14B	0.838007	0.594270	−0.354620	0.139*
C15	0.6868 (7)	0.5355 (5)	−0.3662 (4)	0.1465 (19)
H15A	0.657100	0.464792	−0.330667	0.176*
H15B	0.617999	0.601796	−0.356860	0.176*
C16	0.7189 (10)	0.5489 (7)	−0.4861 (5)	0.218 (4)
H16A	0.663796	0.516475	−0.510233	0.327*
H16B	0.806561	0.508160	−0.498133	0.327*
H16C	0.706815	0.630622	−0.526396	0.327*
O3	0.83009 (17)	0.36242 (15)	0.08615 (12)	0.0506 (4)
O4	0.93372 (16)	0.39340 (15)	0.20262 (12)	0.0481 (4)
O5	0.7453 (2)	0.2086 (2)	0.79533 (14)	0.0697 (6)
O6	0.59965 (16)	0.10487 (15)	0.86034 (12)	0.0469 (4)
C17	0.8509 (2)	0.35402 (18)	0.18148 (16)	0.0391 (4)
C18	0.76806 (19)	0.29441 (17)	0.27645 (15)	0.0376 (4)
C19	0.7812 (2)	0.28976 (18)	0.38141 (16)	0.0384 (4)
H19	0.841430	0.322966	0.392969	0.046*
C20	0.70458 (19)	0.23525 (17)	0.47177 (15)	0.0365 (4)
C21	0.7181 (2)	0.22774 (19)	0.58096 (15)	0.0389 (4)
H21	0.777109	0.261634	0.593351	0.047*
C22	0.64625 (19)	0.17184 (18)	0.66792 (15)	0.0367 (4)
C23	0.5557 (2)	0.1210 (2)	0.64888 (17)	0.0437 (4)
H23	0.506786	0.082624	0.707764	0.052*
C24	0.5392 (2)	0.1278 (2)	0.54513 (18)	0.0480 (5)
H24	0.478545	0.094639	0.534304	0.058*
C25	0.6133 (2)	0.18446 (19)	0.45376 (16)	0.0408 (4)
C26	0.6015 (2)	0.1904 (2)	0.34512 (18)	0.0499 (5)
H26	0.541975	0.157439	0.332145	0.060*
C27	0.6763 (2)	0.2438 (2)	0.25931 (16)	0.0458 (5)
H27	0.666807	0.247039	0.188704	0.055*
C28	0.6659 (2)	0.1620 (2)	0.78357 (16)	0.0422 (4)
O7	0.7517 (4)	0.1956 (3)	1.0086 (2)	0.1104 (11)
H1O7	0.787 (5)	0.184 (4)	0.940 (2)	0.166*
H2O7	0.764 (6)	0.271 (2)	1.002 (4)	0.166*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03728 (15)	0.04265 (16)	0.02994 (14)	−0.01520 (10)	−0.00062 (9)	−0.01235 (10)
O1	0.0410 (8)	0.0468 (8)	0.0445 (8)	−0.0072 (6)	0.0022 (6)	−0.0098 (6)
O2	0.0599 (12)	0.0614 (11)	0.0647 (12)	−0.0062 (9)	0.0100 (9)	−0.0156 (9)
N1	0.0403 (9)	0.0468 (9)	0.0368 (8)	−0.0147 (7)	−0.0044 (7)	−0.0154 (7)
N2	0.0372 (8)	0.0399 (8)	0.0350 (8)	−0.0129 (7)	0.0012 (6)	−0.0139 (6)
N3	0.0506 (10)	0.0525 (10)	0.0422 (9)	−0.0201 (8)	0.0023 (8)	−0.0250 (8)
N4	0.0407 (9)	0.0409 (8)	0.0363 (8)	−0.0107 (7)	0.0012 (7)	−0.0132 (7)
N5	0.0420 (9)	0.0437 (9)	0.0321 (8)	−0.0103 (7)	−0.0039 (6)	−0.0102 (6)
N6	0.0601 (13)	0.0672 (13)	0.0441 (10)	−0.0211 (10)	−0.0097 (9)	−0.0236 (9)
C1	0.0421 (11)	0.0514 (12)	0.0455 (11)	−0.0225 (9)	0.0022 (8)	−0.0156 (9)
C2	0.0463 (11)	0.0448 (10)	0.0372 (10)	−0.0183 (9)	0.0036 (8)	−0.0135 (8)
C3	0.0472 (11)	0.0531 (11)	0.0344 (9)	−0.0160 (9)	−0.0001 (8)	−0.0200 (8)
C4	0.0502 (12)	0.0548 (12)	0.0441 (11)	−0.0241 (10)	0.0021 (9)	−0.0220 (9)
C5	0.0492 (12)	0.0468 (11)	0.0415 (11)	−0.0201 (9)	0.0058 (9)	−0.0130 (9)
C6	0.0560 (13)	0.0471 (11)	0.0346 (10)	−0.0155 (10)	−0.0001 (9)	−0.0089 (8)
C7	0.0556 (13)	0.0624 (14)	0.0341 (10)	−0.0165 (11)	−0.0117 (9)	−0.0114 (9)
C8	0.0560 (14)	0.0752 (16)	0.0476 (12)	−0.0308 (12)	−0.0116 (10)	−0.0208 (11)
C9	0.0555 (14)	0.0628 (14)	0.0548 (13)	−0.0207 (11)	0.0008 (10)	−0.0357 (11)
C10	0.0656 (17)	0.0786 (18)	0.0614 (16)	−0.0250 (14)	−0.0060 (13)	−0.0310 (14)
C11	0.086 (2)	0.089 (2)	0.0648 (18)	−0.0296 (18)	−0.0181 (15)	−0.0280 (16)
C12	0.190 (6)	0.135 (4)	0.058 (2)	−0.076 (4)	−0.008 (3)	−0.020 (2)
C13	0.0675 (17)	0.0670 (16)	0.0723 (17)	−0.0132 (13)	−0.0181 (14)	−0.0287 (14)
C14	0.156 (4)	0.096 (3)	0.095 (3)	−0.016 (3)	0.012 (3)	−0.053 (2)
C15	0.202 (4)	0.143 (3)	0.107 (3)	−0.004 (3)	−0.048 (3)	−0.070 (3)
C16	0.356 (8)	0.190 (6)	0.112 (4)	−0.049 (6)	−0.035 (5)	−0.061 (4)
O3	0.0597 (10)	0.0616 (10)	0.0284 (7)	−0.0181 (8)	0.0027 (6)	−0.0116 (6)
O4	0.0491 (9)	0.0557 (9)	0.0382 (8)	−0.0183 (7)	0.0049 (6)	−0.0123 (7)
O5	0.0823 (14)	0.1112 (16)	0.0353 (8)	−0.0578 (13)	0.0003 (8)	−0.0212 (9)
O6	0.0517 (9)	0.0559 (9)	0.0302 (7)	−0.0167 (7)	0.0038 (6)	−0.0104 (6)
C17	0.0416 (10)	0.0392 (9)	0.0305 (9)	−0.0049 (8)	0.0031 (7)	−0.0103 (7)
C18	0.0381 (10)	0.0407 (9)	0.0308 (8)	−0.0065 (8)	−0.0012 (7)	−0.0104 (7)
C19	0.0407 (10)	0.0453 (10)	0.0316 (9)	−0.0154 (8)	0.0007 (7)	−0.0126 (7)
C20	0.0381 (10)	0.0426 (9)	0.0300 (8)	−0.0115 (8)	−0.0012 (7)	−0.0121 (7)
C21	0.0415 (10)	0.0479 (10)	0.0308 (9)	−0.0170 (8)	−0.0009 (7)	−0.0125 (7)
C22	0.0375 (9)	0.0429 (10)	0.0288 (8)	−0.0095 (8)	0.0000 (7)	−0.0115 (7)
C23	0.0404 (10)	0.0538 (12)	0.0367 (10)	−0.0179 (9)	0.0028 (8)	−0.0112 (8)
C24	0.0462 (12)	0.0662 (14)	0.0398 (10)	−0.0284 (10)	0.0000 (8)	−0.0160 (9)
C25	0.0378 (10)	0.0525 (11)	0.0345 (9)	−0.0148 (8)	−0.0022 (7)	−0.0138 (8)
C26	0.0460 (12)	0.0731 (15)	0.0395 (10)	−0.0241 (11)	−0.0066 (8)	−0.0192 (10)
C27	0.0468 (11)	0.0626 (13)	0.0304 (9)	−0.0154 (10)	−0.0063 (8)	−0.0141 (8)
C28	0.0436 (11)	0.0509 (11)	0.0299 (9)	−0.0095 (9)	−0.0001 (7)	−0.0131 (8)
O7	0.192 (3)	0.114 (2)	0.0488 (12)	−0.078 (2)	−0.0060 (16)	−0.0230 (13)

Geometric parameters (Å, º)

Cu1—N5	2.0046 (18)	C9—H9AB	0.9700
Cu1—N2	2.0102 (17)	C10—C11	1.543 (4)
Cu1—N1	2.0159 (18)	C10—H10A	0.9700
Cu1—N4	2.0164 (18)	C10—H10B	0.9700
Cu1—O1	2.4079 (19)	C11—C12	1.474 (5)
O1—H1O1	0.940 (10)	C11—H11A	0.9700
O1—H2O1	0.938 (10)	C11—H11B	0.9700
O2—H1O2	0.963 (10)	C12—H12A	0.9600
O2—H2O2	0.962 (10)	C12—H12B	0.9600
N1—C1	1.488 (3)	C12—H12C	0.9600
N1—C8	1.499 (3)	C13—C14	1.481 (5)
N1—H1	0.9800	C13—H13A	0.9700
N2—C2	1.480 (3)	C13—H13B	0.9700
N2—C3	1.486 (3)	C14—C15	1.511 (8)
N2—H2	0.9800	C14—H14A	0.9700
N3—C4	1.446 (3)	C14—H14B	0.9700
N3—C3	1.446 (3)	C15—C16	1.503 (7)
N3—C9	1.472 (3)	C15—H15A	0.9700
N4—C4	1.480 (3)	C15—H15B	0.9700
N4—C5	1.482 (3)	C16—H16A	0.9600
N4—H4	0.9800	C16—H16B	0.9600
N5—C6	1.481 (3)	C16—H16C	0.9600
N5—C7	1.501 (3)	O3—C17	1.266 (2)
N5—H5	0.9800	O4—C17	1.256 (3)
N6—C8	1.423 (3)	O5—C28	1.233 (3)
N6—C7	1.429 (3)	O6—C28	1.267 (3)
N6—C13	1.453 (4)	C17—C18	1.514 (3)
C1—C2	1.511 (3)	C18—C19	1.380 (3)
C1—H1A	0.9700	C18—C27	1.415 (3)
C1—H1AB	0.9700	C19—C20	1.416 (3)
C2—H2A	0.9700	C19—H19	0.9300
C2—H2AB	0.9700	C20—C25	1.417 (3)
C3—H3A	0.9700	C20—C21	1.425 (3)
C3—H3AB	0.9700	C21—C22	1.367 (3)
C4—H4A	0.9700	C21—H21	0.9300
C4—H4AB	0.9700	C22—C23	1.416 (3)
C5—C6	1.515 (3)	C22—C28	1.518 (3)
C5—H5A	0.9700	C23—C24	1.366 (3)
C5—H5AB	0.9700	C23—H23	0.9300
C6—H6A	0.9700	C24—C25	1.417 (3)
C6—H6AB	0.9700	C24—H24	0.9300
C7—H7A	0.9700	C25—C26	1.419 (3)
C7—H7AB	0.9700	C26—C27	1.366 (3)
C8—H8A	0.9700	C26—H26	0.9300
C8—H8AB	0.9700	C27—H27	0.9300
C9—C10	1.520 (4)	O7—H1O7	0.956 (10)
C9—H9A	0.9700	O7—H2O7	0.957 (10)
N5—Cu1—N2	177.69 (7)	N6—C8—H8AB	108.7
N5—Cu1—N1	93.73 (8)	N1—C8—H8AB	108.7
N2—Cu1—N1	86.15 (7)	H8A—C8—H8AB	107.6
N5—Cu1—N4	86.63 (8)	N3—C9—C10	115.6 (2)
N2—Cu1—N4	93.36 (7)	N3—C9—H9A	108.4
N1—Cu1—N4	176.77 (7)	C10—C9—H9A	108.4
N5—Cu1—O1	89.49 (7)	N3—C9—H9AB	108.4
N2—Cu1—O1	92.82 (7)	C10—C9—H9AB	108.4
N1—Cu1—O1	91.38 (7)	H9A—C9—H9AB	107.5
N4—Cu1—O1	91.82 (7)	C9—C10—C11	112.0 (3)
Cu1—O1—H1O1	116.2 (18)	C9—C10—H10A	109.2
Cu1—O1—H2O1	119.9 (18)	C11—C10—H10A	109.2
H1O1—O1—H2O1	104.6 (17)	C9—C10—H10B	109.2
H1O2—O2—H2O2	101.5 (18)	C11—C10—H10B	109.2
C1—N1—C8	111.83 (18)	H10A—C10—H10B	107.9
C1—N1—Cu1	107.21 (13)	C12—C11—C10	111.6 (3)
C8—N1—Cu1	113.82 (15)	C12—C11—H11A	109.3
C1—N1—H1	107.9	C10—C11—H11A	109.3
C8—N1—H1	107.9	C12—C11—H11B	109.3
Cu1—N1—H1	107.9	C10—C11—H11B	109.3
C2—N2—C3	112.59 (17)	H11A—C11—H11B	108.0
C2—N2—Cu1	107.49 (13)	C11—C12—H12A	109.5
C3—N2—Cu1	113.69 (13)	C11—C12—H12B	109.5
C2—N2—H2	107.6	H12A—C12—H12B	109.5
C3—N2—H2	107.6	C11—C12—H12C	109.5
Cu1—N2—H2	107.6	H12A—C12—H12C	109.5
C4—N3—C3	114.03 (18)	H12B—C12—H12C	109.5
C4—N3—C9	112.23 (18)	N6—C13—C14	114.3 (3)
C3—N3—C9	113.17 (19)	N6—C13—H13A	108.7
C4—N4—C5	112.16 (18)	C14—C13—H13A	108.7
C4—N4—Cu1	115.38 (14)	N6—C13—H13B	108.7
C5—N4—Cu1	106.43 (13)	C14—C13—H13B	108.7
C4—N4—H4	107.5	H13A—C13—H13B	107.6
C5—N4—H4	107.5	C13—C14—C15	113.4 (4)
Cu1—N4—H4	107.5	C13—C14—H14A	108.9
C6—N5—C7	111.82 (17)	C15—C14—H14A	108.9
C6—N5—Cu1	107.76 (13)	C13—C14—H14B	108.9
C7—N5—Cu1	113.71 (14)	C15—C14—H14B	108.9
C6—N5—H5	107.8	H14A—C14—H14B	107.7
C7—N5—H5	107.8	C16—C15—C14	111.2 (6)
Cu1—N5—H5	107.8	C16—C15—H15A	109.4
C8—N6—C7	116.0 (2)	C14—C15—H15A	109.4
C8—N6—C13	116.0 (2)	C16—C15—H15B	109.4
C7—N6—C13	118.0 (2)	C14—C15—H15B	109.4
N1—C1—C2	109.04 (17)	H15A—C15—H15B	108.0
N1—C1—H1A	109.9	C15—C16—H16A	109.5
C2—C1—H1A	109.9	C15—C16—H16B	109.5
N1—C1—H1AB	109.9	H16A—C16—H16B	109.5
C2—C1—H1AB	109.9	C15—C16—H16C	109.5
H1A—C1—H1AB	108.3	H16A—C16—H16C	109.5
N2—C2—C1	107.93 (17)	H16B—C16—H16C	109.5
N2—C2—H2A	110.1	O4—C17—O3	124.7 (2)
C1—C2—H2A	110.1	O4—C17—C18	117.82 (18)
N2—C2—H2AB	110.1	O3—C17—C18	117.5 (2)
C1—C2—H2AB	110.1	C19—C18—C27	119.25 (19)
H2A—C2—H2AB	108.4	C19—C18—C17	119.76 (19)
N3—C3—N2	108.68 (18)	C27—C18—C17	120.99 (18)
N3—C3—H3A	110.0	C18—C19—C20	121.04 (19)
N2—C3—H3A	110.0	C18—C19—H19	119.5
N3—C3—H3AB	110.0	C20—C19—H19	119.5
N2—C3—H3AB	110.0	C19—C20—C25	119.27 (17)
H3A—C3—H3AB	108.3	C19—C20—C21	121.96 (18)
N3—C4—N4	109.53 (18)	C25—C20—C21	118.76 (18)
N3—C4—H4A	109.8	C22—C21—C20	121.48 (19)
N4—C4—H4A	109.8	C22—C21—H21	119.3
N3—C4—H4AB	109.8	C20—C21—H21	119.3
N4—C4—H4AB	109.8	C21—C22—C23	119.21 (18)
H4A—C4—H4AB	108.2	C21—C22—C28	120.20 (19)
N4—C5—C6	108.48 (19)	C23—C22—C28	120.57 (18)
N4—C5—H5A	110.0	C24—C23—C22	120.84 (19)
C6—C5—H5A	110.0	C24—C23—H23	119.6
N4—C5—H5AB	110.0	C22—C23—H23	119.6
C6—C5—H5AB	110.0	C23—C24—C25	121.0 (2)
H5A—C5—H5AB	108.4	C23—C24—H24	119.5
N5—C6—C5	109.19 (17)	C25—C24—H24	119.5
N5—C6—H6A	109.8	C24—C25—C20	118.72 (18)
C5—C6—H6A	109.8	C24—C25—C26	122.6 (2)
N5—C6—H6AB	109.8	C20—C25—C26	118.62 (19)
C5—C6—H6AB	109.8	C27—C26—C25	121.0 (2)
H6A—C6—H6AB	108.3	C27—C26—H26	119.5
N6—C7—N5	114.10 (18)	C25—C26—H26	119.5
N6—C7—H7A	108.7	C26—C27—C18	120.85 (19)
N5—C7—H7A	108.7	C26—C27—H27	119.6
N6—C7—H7AB	108.7	C18—C27—H27	119.6
N5—C7—H7AB	108.7	O5—C28—O6	125.5 (2)
H7A—C7—H7AB	107.6	O5—C28—C22	117.83 (19)
N6—C8—N1	114.3 (2)	O6—C28—C22	116.7 (2)
N6—C8—H8A	108.7	H1O7—O7—H2O7	104 (2)
N1—C8—H8A	108.7
C8—N1—C1—C2	−162.79 (19)	N6—C13—C14—C15	−61.6 (5)
Cu1—N1—C1—C2	−37.4 (2)	C13—C14—C15—C16	172.8 (4)
C3—N2—C2—C1	−166.52 (18)	O4—C17—C18—C19	3.0 (3)
Cu1—N2—C2—C1	−40.54 (19)	O3—C17—C18—C19	−175.81 (19)
N1—C1—C2—N2	52.5 (2)	O4—C17—C18—C27	−177.5 (2)
C4—N3—C3—N2	−79.6 (2)	O3—C17—C18—C27	3.7 (3)
C9—N3—C3—N2	150.46 (18)	C27—C18—C19—C20	0.0 (3)
C2—N2—C3—N3	−175.38 (16)	C17—C18—C19—C20	179.61 (18)
Cu1—N2—C3—N3	62.1 (2)	C18—C19—C20—C25	0.2 (3)
C3—N3—C4—N4	76.8 (2)	C18—C19—C20—C21	178.9 (2)
C9—N3—C4—N4	−152.9 (2)	C19—C20—C21—C22	−178.0 (2)
C5—N4—C4—N3	−179.61 (17)	C25—C20—C21—C22	0.7 (3)
Cu1—N4—C4—N3	−57.5 (2)	C20—C21—C22—C23	−0.5 (3)
C4—N4—C5—C6	168.01 (18)	C20—C21—C22—C28	178.08 (19)
Cu1—N4—C5—C6	41.0 (2)	C21—C22—C23—C24	−0.3 (3)
C7—N5—C6—C5	161.1 (2)	C28—C22—C23—C24	−178.8 (2)
Cu1—N5—C6—C5	35.5 (2)	C22—C23—C24—C25	0.8 (4)
N4—C5—C6—N5	−51.8 (2)	C23—C24—C25—C20	−0.5 (4)
C8—N6—C7—N5	68.9 (3)	C23—C24—C25—C26	178.2 (2)
C13—N6—C7—N5	−75.3 (3)	C19—C20—C25—C24	178.5 (2)
C6—N5—C7—N6	179.5 (2)	C21—C20—C25—C24	−0.2 (3)
Cu1—N5—C7—N6	−58.1 (2)	C19—C20—C25—C26	−0.2 (3)
C7—N6—C8—N1	−68.4 (3)	C21—C20—C25—C26	−179.0 (2)
C13—N6—C8—N1	76.5 (3)	C24—C25—C26—C27	−178.7 (2)
C1—N1—C8—N6	178.8 (2)	C20—C25—C26—C27	0.0 (4)
Cu1—N1—C8—N6	57.2 (3)	C25—C26—C27—C18	0.3 (4)
C4—N3—C9—C10	−65.9 (3)	C19—C18—C27—C26	−0.3 (3)
C3—N3—C9—C10	64.9 (3)	C17—C18—C27—C26	−179.8 (2)
N3—C9—C10—C11	178.5 (2)	C21—C22—C28—O5	2.0 (3)
C9—C10—C11—C12	82.9 (4)	C23—C22—C28—O5	−179.5 (2)
C8—N6—C13—C14	149.4 (3)	C21—C22—C28—O6	−177.2 (2)
C7—N6—C13—C14	−66.4 (4)	C23—C22—C28—O6	1.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O3^i	0.94 (1)	1.91 (1)	2.843 (2)	175 (3)
O1—H2O1···O4	0.94 (1)	1.94 (2)	2.788 (3)	149 (2)
O2—H1O2···O6^ii	0.96 (1)	2.02 (2)	2.953 (3)	161 (3)
N1—H1···O3	0.98	2.08	3.015 (3)	159
N2—H2···O6^ii	0.98	2.05	3.007 (3)	166
N4—H4···O6^iii	0.98	2.18	3.115 (3)	160
N5—H5···O4^i	0.98	2.01	2.952 (3)	160
O7—H1O7···O5	0.96 (1)	1.92 (4)	2.740 (3)	143 (5)
O7—H2O7···O3^iv	0.96 (1)	2.16 (3)	2.979 (3)	143 (4)

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

(CuNDC_poly)

Crystal data

C28H44CuN6O4·2(CH4O)	Dx = 1.271 Mg m^−3
Mr = 656.31	Synchrotron radiation, λ = 0.610 Å
Orthorhombic, Pbcn	Cell parameters from 83896 reflections
a = 11.386 (2) Å	θ = 0.4–33.7°
b = 14.063 (3) Å	µ = 0.46 mm^−1
c = 21.427 (4) Å	T = 298 K
V = 3430.9 (12) Å^3	Block, pale purple
Z = 4	0.06 × 0.04 × 0.03 mm
F(000) = 1404

Data collection

Rayonix MX225HS CCD area detector diffractometer	2914 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.070
ω scan	θmax = 25.0°, θmin = 1.6°
Absorption correction: empirical (using intensity measurements) HKL3000sm Scalepack(Otwinowski et.al,2003)	h = −15→15
Tmin = 0.954, Tmax = 1.000	k = −19→19
32900 measured reflections	l = −29→29
4785 independent reflections

Refinement

Refinement on F^2	13 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.178	w = 1/[σ^2(Fo^2) + (0.0974P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
4785 reflections	Δρmax = 0.63 e Å^−3
201 parameters	Δρmin = −0.54 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
Cu1	0.500000	0.500000	0.500000	0.04297 (16)
N1	0.44740 (17)	0.60336 (12)	0.55847 (8)	0.0446 (4)
H1	0.474456	0.664109	0.541283	0.054*
N2	0.66607 (17)	0.49968 (12)	0.53310 (9)	0.0466 (5)
H2	0.707252	0.553551	0.514046	0.056*
N3	0.62088 (19)	0.59324 (14)	0.62615 (9)	0.0545 (5)
C1	0.3175 (2)	0.60387 (17)	0.55705 (11)	0.0564 (6)
H1A	0.288035	0.664315	0.572236	0.068*
H1B	0.286941	0.553788	0.583618	0.068*
C2	0.4956 (2)	0.59479 (19)	0.62260 (11)	0.0521 (6)
H2A	0.466956	0.647737	0.647296	0.063*
H2B	0.465478	0.536847	0.641224	0.063*
C3	0.6755 (3)	0.51042 (16)	0.60193 (12)	0.0560 (6)
H3A	0.640597	0.455104	0.621584	0.067*
H3B	0.758022	0.511577	0.613226	0.067*
C4	0.7218 (2)	0.41184 (17)	0.50972 (12)	0.0558 (6)
H4A	0.698695	0.358187	0.535389	0.067*
H4B	0.806570	0.417815	0.511445	0.067*
C5	0.6810 (3)	0.68365 (18)	0.61216 (14)	0.0692 (7)
H5A	0.656059	0.705512	0.571332	0.083*
H5B	0.764924	0.671971	0.610162	0.083*
C6	0.6585 (3)	0.7612 (2)	0.65886 (16)	0.0843 (9)
H6A	0.705416	0.816151	0.647478	0.101*
H6B	0.576610	0.779686	0.656037	0.101*
C7	0.6842 (3)	0.7368 (3)	0.72303 (17)	0.0929 (10)
H7A	0.761004	0.707227	0.725345	0.112*
H7B	0.626615	0.691294	0.737900	0.112*
C8	0.6820 (4)	0.8277 (3)	0.7660 (2)	0.1183 (14)
H8A	0.719965	0.879478	0.744987	0.177*
H8B	0.722560	0.814297	0.804325	0.177*
H8C	0.602060	0.844579	0.775035	0.177*
O1	0.55905 (18)	0.61898 (11)	0.42101 (7)	0.0590 (5)
O2	0.52363 (18)	0.75269 (12)	0.47301 (9)	0.0628 (5)
C9	0.5384 (2)	0.70618 (16)	0.42361 (10)	0.0475 (5)
C10	0.52700 (19)	0.75897 (15)	0.36242 (10)	0.0429 (5)
C11	0.51451 (18)	0.71173 (15)	0.30735 (11)	0.0434 (5)
H11	0.515570	0.645601	0.307495	0.052*
C12	0.500000	0.7598 (2)	0.250000	0.0404 (6)
C13	0.500000	0.8609 (2)	0.250000	0.0453 (7)
C14	0.5135 (2)	0.90907 (16)	0.30770 (11)	0.0545 (6)
H14	0.514098	0.975193	0.308343	0.065*
C15	0.5258 (2)	0.86009 (16)	0.36231 (11)	0.0509 (6)
H15	0.533323	0.893082	0.399713	0.061*
O3	0.3728 (3)	0.8881 (2)	0.50859 (10)	0.1090 (9)
H3	0.398 (4)	0.837 (3)	0.4928 (10)	0.163*
C16	0.3928 (4)	0.8878 (3)	0.57022 (16)	0.1062 (10)
H16A	0.470418	0.911556	0.578314	0.159*
H16B	0.386251	0.824085	0.585847	0.159*
H16C	0.336172	0.927666	0.590653	0.159*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0449 (3)	0.0426 (2)	0.0414 (2)	0.00713 (15)	−0.00073 (14)	−0.00420 (15)
N1	0.0473 (11)	0.0393 (9)	0.0472 (10)	0.0027 (8)	0.0022 (8)	−0.0028 (8)
N2	0.0456 (10)	0.0452 (10)	0.0492 (12)	0.0026 (8)	−0.0020 (8)	−0.0002 (8)
N3	0.0615 (13)	0.0546 (11)	0.0473 (10)	−0.0043 (10)	−0.0025 (9)	−0.0068 (9)
C1	0.0520 (15)	0.0539 (13)	0.0633 (15)	0.0050 (11)	0.0080 (11)	−0.0125 (11)
C2	0.0646 (16)	0.0502 (13)	0.0415 (11)	−0.0020 (11)	0.0069 (10)	−0.0039 (11)
C3	0.0579 (15)	0.0594 (14)	0.0506 (13)	0.0030 (11)	−0.0090 (11)	−0.0002 (11)
C4	0.0458 (13)	0.0528 (13)	0.0689 (15)	0.0078 (11)	−0.0047 (11)	−0.0051 (11)
C5	0.0729 (19)	0.0618 (15)	0.0728 (17)	−0.0154 (13)	−0.0100 (14)	−0.0066 (13)
C6	0.076 (2)	0.0777 (19)	0.100 (2)	−0.0081 (17)	−0.0045 (17)	−0.0218 (19)
C7	0.079 (2)	0.112 (3)	0.088 (2)	−0.001 (2)	0.0032 (18)	−0.024 (2)
C8	0.113 (2)	0.132 (2)	0.1102 (18)	0.0021 (16)	−0.0029 (16)	−0.0388 (16)
O1	0.0820 (13)	0.0436 (9)	0.0513 (9)	0.0074 (8)	0.0030 (9)	0.0056 (7)
O2	0.0956 (14)	0.0491 (10)	0.0436 (9)	0.0044 (9)	0.0031 (8)	0.0028 (8)
C9	0.0495 (13)	0.0435 (12)	0.0497 (12)	−0.0037 (10)	−0.0010 (10)	0.0027 (10)
C10	0.0439 (12)	0.0382 (11)	0.0466 (12)	−0.0015 (9)	0.0025 (9)	0.0018 (9)
C11	0.0472 (13)	0.0340 (10)	0.0491 (12)	−0.0006 (8)	0.0048 (9)	0.0025 (9)
C12	0.0402 (16)	0.0357 (14)	0.0453 (16)	0.000	0.0027 (11)	0.000
C13	0.0528 (19)	0.0382 (15)	0.0449 (16)	0.000	0.0012 (13)	0.000
C14	0.0778 (18)	0.0328 (10)	0.0529 (13)	−0.0044 (10)	−0.0008 (11)	−0.0026 (11)
C15	0.0638 (15)	0.0415 (12)	0.0473 (12)	−0.0053 (10)	−0.0011 (10)	−0.0040 (10)
O3	0.129 (2)	0.1249 (18)	0.0730 (11)	0.0658 (16)	−0.0197 (12)	−0.0134 (12)
C16	0.135 (2)	0.112 (2)	0.0724 (12)	0.0603 (18)	−0.0217 (15)	−0.0213 (16)

Geometric parameters (Å, º)

Cu1—N1	2.0103 (17)	C6—H6A	0.9700
Cu1—N1^i	2.0103 (17)	C6—H6B	0.9700
Cu1—N2^i	2.019 (2)	C7—C8	1.576 (5)
Cu1—N2	2.019 (2)	C7—H7A	0.9700
N1—C1	1.480 (3)	C7—H7B	0.9700
N1—C2	1.484 (3)	C8—H8A	0.9600
N1—H1	0.9800	C8—H8B	0.9600
N2—C4	1.476 (3)	C8—H8C	0.9600
N2—C3	1.486 (3)	O1—C9	1.250 (3)
N2—H2	0.9800	O2—C9	1.256 (3)
N3—C3	1.419 (3)	C9—C10	1.512 (3)
N3—C2	1.429 (3)	C10—C11	1.362 (3)
N3—C5	1.475 (3)	C10—C15	1.422 (3)
C1—C4^i	1.515 (3)	C11—C12	1.412 (3)
C1—H1A	0.9700	C11—H11	0.9300
C1—H1B	0.9700	C12—C13	1.422 (4)
C2—H2A	0.9700	C13—C14^ii	1.418 (3)
C2—H2B	0.9700	C13—C14	1.418 (3)
C3—H3A	0.9700	C14—C15	1.365 (3)
C3—H3B	0.9700	C14—H14	0.9300
C4—H4A	0.9700	C15—H15	0.9300
C4—H4B	0.9700	O3—C16	1.340 (4)
C5—C6	1.503 (4)	O3—H3	0.85 (5)
C5—H5A	0.9700	C16—H16A	0.9600
C5—H5B	0.9700	C16—H16B	0.9600
C6—C7	1.447 (5)	C16—H16C	0.9600
N1—Cu1—N1^i	180.00 (7)	C6—C5—H5B	108.7
N1—Cu1—N2^i	86.46 (7)	H5A—C5—H5B	107.6
N1^i—Cu1—N2^i	93.54 (7)	C7—C6—C5	115.2 (3)
N1—Cu1—N2	93.54 (7)	C7—C6—H6A	108.5
N1^i—Cu1—N2	86.46 (7)	C5—C6—H6A	108.5
N2^i—Cu1—N2	180.0	C7—C6—H6B	108.5
C1—N1—C2	112.90 (18)	C5—C6—H6B	108.5
C1—N1—Cu1	106.77 (13)	H6A—C6—H6B	107.5
C2—N1—Cu1	114.08 (14)	C6—C7—C8	111.1 (3)
C1—N1—H1	107.6	C6—C7—H7A	109.4
C2—N1—H1	107.6	C8—C7—H7A	109.4
Cu1—N1—H1	107.6	C6—C7—H7B	109.4
C4—N2—C3	112.99 (18)	C8—C7—H7B	109.4
C4—N2—Cu1	106.55 (14)	H7A—C7—H7B	108.0
C3—N2—Cu1	114.59 (15)	C7—C8—H8A	109.5
C4—N2—H2	107.5	C7—C8—H8B	109.5
C3—N2—H2	107.5	H8A—C8—H8B	109.5
Cu1—N2—H2	107.5	C7—C8—H8C	109.5
C3—N3—C2	115.5 (2)	H8A—C8—H8C	109.5
C3—N3—C5	115.4 (2)	H8B—C8—H8C	109.5
C2—N3—C5	116.1 (2)	O1—C9—O2	125.0 (2)
N1—C1—C4^i	108.27 (19)	O1—C9—C10	117.3 (2)
N1—C1—H1A	110.0	O2—C9—C10	117.6 (2)
C4^i—C1—H1A	110.0	C11—C10—C15	119.0 (2)
N1—C1—H1B	110.0	C11—C10—C9	121.4 (2)
C4^i—C1—H1B	110.0	C15—C10—C9	119.5 (2)
H1A—C1—H1B	108.4	C10—C11—C12	122.2 (2)
N3—C2—N1	114.82 (19)	C10—C11—H11	118.9
N3—C2—H2A	108.6	C12—C11—H11	118.9
N1—C2—H2A	108.6	C11^ii—C12—C11	122.7 (3)
N3—C2—H2B	108.6	C11^ii—C12—C13	118.63 (14)
N1—C2—H2B	108.6	C11—C12—C13	118.63 (14)
H2A—C2—H2B	107.5	C14^ii—C13—C14	123.0 (3)
N3—C3—N2	114.49 (19)	C14^ii—C13—C12	118.52 (15)
N3—C3—H3A	108.6	C14—C13—C12	118.52 (15)
N2—C3—H3A	108.6	C15—C14—C13	121.2 (2)
N3—C3—H3B	108.6	C15—C14—H14	119.4
N2—C3—H3B	108.6	C13—C14—H14	119.4
H3A—C3—H3B	107.6	C14—C15—C10	120.5 (2)
N2—C4—C1^i	108.41 (19)	C14—C15—H15	119.8
N2—C4—H4A	110.0	C10—C15—H15	119.8
C1^i—C4—H4A	110.0	C16—O3—H3	109.5
N2—C4—H4B	110.0	O3—C16—H16A	109.5
C1^i—C4—H4B	110.0	O3—C16—H16B	109.5
H4A—C4—H4B	108.4	H16A—C16—H16B	109.5
N3—C5—C6	114.3 (2)	O3—C16—H16C	109.5
N3—C5—H5A	108.7	H16A—C16—H16C	109.5
C6—C5—H5A	108.7	H16B—C16—H16C	109.5
N3—C5—H5B	108.7
C2—N1—C1—C4^i	−166.13 (19)	O2—C9—C10—C11	−164.6 (2)
Cu1—N1—C1—C4^i	−40.0 (2)	O1—C9—C10—C15	−168.2 (2)
C3—N3—C2—N1	−69.2 (3)	O2—C9—C10—C15	13.5 (3)
C5—N3—C2—N1	70.6 (3)	C15—C10—C11—C12	−0.2 (3)
C1—N1—C2—N3	179.52 (19)	C9—C10—C11—C12	177.96 (18)
Cu1—N1—C2—N3	57.4 (2)	C10—C11—C12—C11^ii	−179.2 (2)
C2—N3—C3—N2	68.4 (3)	C10—C11—C12—C13	0.8 (2)
C5—N3—C3—N2	−71.7 (3)	C11^ii—C12—C13—C14^ii	−0.55 (15)
C4—N2—C3—N3	−178.8 (2)	C11—C12—C13—C14^ii	179.45 (15)
Cu1—N2—C3—N3	−56.5 (2)	C11^ii—C12—C13—C14	179.45 (15)
C3—N2—C4—C1^i	166.6 (2)	C11—C12—C13—C14	−0.55 (15)
Cu1—N2—C4—C1^i	39.9 (2)	C14^ii—C13—C14—C15	179.7 (3)
C3—N3—C5—C6	−153.7 (2)	C12—C13—C14—C15	−0.3 (3)
C2—N3—C5—C6	66.5 (3)	C13—C14—C15—C10	1.0 (4)
N3—C5—C6—C7	54.5 (4)	C11—C10—C15—C14	−0.7 (3)
C5—C6—C7—C8	168.7 (3)	C9—C10—C15—C14	−178.9 (2)
O1—C9—C10—C11	13.7 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.98	2.00	2.918 (3)	155
N2—H2···O3^iii	0.98	2.11	2.971 (3)	145
O3—H3···O2	0.85	1.90	2.675 (3)	151

Symmetry code: (iii) x+1/2, −y+3/2, −z+1.