CuII and ZnII β-diketonate coordination polymers based on pyrimidin-2-amine, pyrazine and 1,2-bis­(4-pyridyl)­ethane

Perdih, F.

doi:10.1107/S2052520616014566

Cu^II and Zn^II β-diketonate coordination polymers based on pyrimidin-2-amine, pyrazine and 1,2-bis(4-pyridyl)ethane

Copper(II) and zinc(II) bis(4,4,4-trifluoro-1-phenylbutane-1,3-dionato) compounds with pyrimidin-2-amine (pyr2a), pyrazine (pyz) and 1,2-bis(4-pyridyl)ethane (dpet) were prepared and solid-state structures of coordination polymers [M(tfpb)₂(pyr2a)]_∞ [M = Cu (1), Zn (2); tfpb = 4,4,4-trifluoro-1-phenylbutane-1,3-dionate], [M(tfpb)₂(pyz)]_∞ [M = Cu (3), Zn (4a, 4b)] and [Cu(tfpb)₂(dpet)]_∞ (5), respectively, were determined by single-crystal X-ray analysis. The coordination of metal centers in all compounds is octahedral with nitrogen ligands occupying the axial positions. Compound (1) crystallizes in the triclinic space group $P\bar 1$ , whereas (2) crystallizes in the monoclinic space group P2/n. Differences are due to the different orientation of adjacent M(tfpb)₂ units, whereas the orientation of pyrimidin-2-amine is the same in both compounds. Polymeric chains in (1) and (2) contain intramolecular N—H

O hydrogen bonding between amino and carbonyl groups. Room-temperature structures (3) and (4a) are isomorphous adopting the monoclinic space group C2/m; however, on cooling crystals (4a) to 150 K a single-crystal-to-single-crystal transformation to (4b) possessing the triclinic space group $P\bar 1$ was observed. Compound (5) crystallizes in the triclinic space group $P\bar 1$ and contains a parallel aggregation of chains in contrast to the known structure of the non-fluorinated benzoylacetonato ligand, where chains aggregate in a perpendicular fashion. In the compounds studied intramolecular C—H

O and/or C—H

F interactions are present. The neighboring chains are linked by π

π interactions and in some compounds also by C—H

π interactions [(1), (4b), (5)].

Keywords: β-diketonates; π–π interactions; organic fluorine.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520616014566/eb5048sup1.cif Contains datablocks 1, 2, 3, 4a, 4b, 5, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616014566/eb50481sup2.hkl Contains datablock 1
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616014566/eb50482sup3.hkl Contains datablock 2
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616014566/eb50483sup4.hkl Contains datablock 3
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616014566/eb50484asup5.hkl Contains datablock 4a
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616014566/eb50484bsup6.hkl Contains datablock 4b
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520616014566/eb50485sup7.hkl Contains datablock 5
	Portable Document Format (PDF) file https://doi.org/10.1107/S2052520616014566/eb5048sup8.pdf Figure S1 (packing diagrams), Table S1 (selected hydrogen-bond parameters), Table S2 (geometrical parameters for pi-pi interactions)

CCDC references: 1504157; 1504158; 1504159; 1504160; 1504161; 1504162

Computing details top

Data collection: KappaCCD Reference Manual (Nonius, 1998) for (1), (3); CrysAlis PRO (Agilent, 2013) for (2), (4a), (4b), (5). Cell refinement: DENZO-SMN (Otwinowski & Minor, 1997) for (1), (3); CrysAlis PRO (Agilent, 2013) for (2), (4a), (4b), (5). Data reduction: DENZO-SMN (Otwinowski & Minor, 1997) for (1), (3); CrysAlis PRO (Agilent, 2013) for (2), (4a), (4b), (5). Program(s) used to solve structure: SIR97 (Altomare et al., 1999) for (1), (3), (4a); SHELXS97 (Sheldrick, 2008) for (2), (5); SHELXL2014/7 (Sheldrick, 2015) for (4b). For all compounds, program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015). Molecular graphics: Mercury (Macrae, 2006) for (1), (2), (3).

(1) top

Crystal data top

C₂₄H₁₇CuF₆N₃O₄	Z = 2
M_r = 588.94	F(000) = 594
Triclinic, P1	D_x = 1.597 Mg m⁻³
a = 9.3862 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.7268 (2) Å	Cell parameters from 5428 reflections
c = 13.3463 (3) Å	θ = 1.0–27.5°
α = 70.106 (1)°	µ = 0.97 mm⁻¹
β = 75.783 (2)°	T = 293 K
γ = 84.529 (1)°	Block, green
V = 1224.77 (5) Å³	0.25 × 0.18 × 0.12 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	4579 reflections with I > 2σ(I)
Detector resolution: 0.055 pixels mm^-1	R_int = 0.017
ω scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan SCALEPACK (Otwinowski & Minor, 1997)	h = −12→12
T_min = 0.810, T_max = 1.000	k = −13→13
10114 measured reflections	l = −16→17
5558 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.0806P)² + 0.4928P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.137	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.65 e Å⁻³
5558 reflections	Δρ_min = −0.44 e Å⁻³
347 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.042 (5)

Special details top

Experimental. 184 frames in 5 sets of ω scans. Rotation/frame = 2.0 °. Crystal-detector distance = 25.0 mm. Measuring time = 60 s/°.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.0000	0.5000	0.04368 (15)
Cu2	1.0000	0.0000	0.0000	0.05447 (17)
O1	0.69120 (17)	−0.06552 (15)	0.52965 (14)	0.0457 (4)
O2	0.42753 (17)	−0.17786 (15)	0.53940 (14)	0.0470 (4)
O3	1.0896 (2)	−0.09206 (16)	0.12137 (14)	0.0555 (4)
O4	0.9172 (2)	−0.16084 (17)	0.00255 (15)	0.0576 (4)
N1	0.5887 (2)	0.0107 (2)	0.30140 (17)	0.0495 (4)
N2	0.7575 (3)	0.0295 (2)	0.13082 (18)	0.0575 (5)
N3	0.8376 (3)	0.0217 (3)	0.28180 (19)	0.0621 (6)
H3A	0.8215	0.0163	0.3494	0.093*
H3B	0.9261	0.0279	0.2428	0.093*
F1	0.8963 (3)	−0.3296 (2)	0.6612 (3)	0.1238 (11)
F2	0.8805 (3)	−0.1381 (3)	0.6684 (3)	0.1203 (10)
F3	0.9701 (2)	−0.1652 (3)	0.5200 (2)	0.1277 (10)
F4	1.1676 (3)	−0.3918 (2)	0.3064 (2)	0.1260 (11)
F5	1.1543 (5)	−0.1993 (4)	0.3163 (3)	0.1617 (15)
F6	1.3205 (3)	−0.2477 (3)	0.2021 (3)	0.1367 (12)
C1	0.8658 (3)	−0.2080 (3)	0.6072 (3)	0.0615 (7)
C2	0.7141 (2)	−0.1866 (2)	0.58113 (18)	0.0426 (5)
C3	0.6256 (3)	−0.2930 (2)	0.6125 (2)	0.0494 (5)
H3	0.6572	−0.3746	0.6543	0.059*
C4	0.4868 (2)	−0.2862 (2)	0.58477 (18)	0.0409 (4)
C5	0.4076 (2)	−0.4089 (2)	0.60535 (18)	0.0426 (5)
C6	0.4525 (3)	−0.5331 (2)	0.6646 (3)	0.0597 (7)
H6	0.5332	−0.5413	0.6954	0.072*
C7	0.3777 (3)	−0.6456 (3)	0.6783 (3)	0.0684 (8)
H7	0.4083	−0.7286	0.7186	0.082*
C8	0.2602 (3)	−0.6355 (3)	0.6333 (3)	0.0635 (7)
H8	0.2116	−0.7113	0.6418	0.076*
C9	0.2130 (3)	−0.5121 (3)	0.5749 (3)	0.0647 (7)
H9	0.1319	−0.5049	0.5448	0.078*
C10	0.2862 (3)	−0.3993 (3)	0.5609 (2)	0.0538 (6)
H10	0.2539	−0.3166	0.5216	0.065*
C11	1.1789 (3)	−0.2658 (3)	0.2492 (3)	0.0682 (8)
C12	1.0880 (3)	−0.2174 (2)	0.16384 (18)	0.0475 (5)
C13	1.0191 (3)	−0.3092 (2)	0.1430 (2)	0.0551 (6)
H13	1.0298	−0.3980	0.1829	0.066*
C14	0.9324 (3)	−0.2776 (2)	0.06446 (19)	0.0468 (5)
C15	0.8513 (3)	−0.3826 (3)	0.0526 (2)	0.0535 (6)
C16	0.8424 (4)	−0.5109 (3)	0.1262 (3)	0.0704 (8)
H16	0.8890	−0.5335	0.1841	0.085*
C17	0.7632 (5)	−0.6058 (4)	0.1129 (4)	0.0893 (12)
H17	0.7563	−0.6915	0.1627	0.107*
C18	0.6965 (5)	−0.5742 (4)	0.0284 (4)	0.0965 (13)
H18	0.6443	−0.6382	0.0202	0.116*
C19	0.7057 (5)	−0.4468 (4)	−0.0462 (4)	0.0956 (12)
H19	0.6603	−0.4255	−0.1047	0.115*
C20	0.7823 (4)	−0.3515 (3)	−0.0336 (3)	0.0743 (8)
H20	0.7875	−0.2658	−0.0833	0.089*
C21	0.7246 (3)	0.0205 (2)	0.23715 (19)	0.0466 (5)
C22	0.4786 (3)	0.0123 (3)	0.2545 (2)	0.0603 (6)
H22	0.3831	0.0045	0.2970	0.072*
C23	0.4997 (4)	0.0251 (4)	0.1464 (3)	0.0722 (8)
H23	0.4213	0.0285	0.1144	0.087*
C24	0.6429 (4)	0.0326 (3)	0.0876 (2)	0.0699 (8)
H24	0.6607	0.0401	0.0141	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0420 (2)	0.0309 (2)	0.0590 (3)	0.00510 (14)	−0.02296 (17)	−0.00928 (16)
Cu2	0.0839 (3)	0.0328 (2)	0.0496 (3)	−0.00204 (19)	−0.0349 (2)	−0.00300 (16)
O1	0.0429 (8)	0.0369 (8)	0.0562 (9)	0.0032 (6)	−0.0195 (7)	−0.0093 (7)
O2	0.0449 (8)	0.0327 (7)	0.0640 (10)	0.0049 (6)	−0.0233 (7)	−0.0105 (7)
O3	0.0769 (12)	0.0407 (9)	0.0494 (9)	0.0016 (8)	−0.0302 (8)	−0.0051 (7)
O4	0.0812 (12)	0.0382 (9)	0.0573 (10)	−0.0025 (8)	−0.0311 (9)	−0.0093 (7)
N1	0.0526 (11)	0.0501 (11)	0.0527 (11)	0.0009 (8)	−0.0175 (9)	−0.0222 (9)
N2	0.0638 (13)	0.0613 (13)	0.0482 (11)	−0.0096 (10)	−0.0152 (10)	−0.0148 (10)
N3	0.0528 (12)	0.0843 (17)	0.0527 (12)	−0.0052 (11)	−0.0177 (10)	−0.0219 (11)
F1	0.0843 (14)	0.0627 (12)	0.215 (3)	0.0072 (10)	−0.0951 (18)	0.0076 (15)
F2	0.1043 (17)	0.133 (2)	0.178 (3)	0.0244 (15)	−0.0985 (19)	−0.080 (2)
F3	0.0458 (10)	0.184 (3)	0.1189 (19)	0.0094 (13)	−0.0175 (11)	−0.0097 (18)
F4	0.143 (2)	0.0741 (13)	0.139 (2)	−0.0290 (13)	−0.0984 (18)	0.0455 (13)
F5	0.243 (4)	0.172 (3)	0.121 (2)	0.091 (3)	−0.135 (3)	−0.072 (2)
F6	0.0744 (15)	0.138 (2)	0.162 (3)	−0.0172 (14)	−0.0643 (16)	0.026 (2)
C1	0.0487 (13)	0.0515 (14)	0.0834 (19)	0.0047 (11)	−0.0317 (13)	−0.0107 (13)
C2	0.0419 (10)	0.0409 (11)	0.0476 (11)	0.0080 (8)	−0.0201 (9)	−0.0131 (9)
C3	0.0506 (12)	0.0339 (10)	0.0633 (14)	0.0077 (9)	−0.0278 (11)	−0.0075 (10)
C4	0.0431 (10)	0.0353 (10)	0.0430 (10)	0.0043 (8)	−0.0123 (8)	−0.0107 (8)
C5	0.0421 (10)	0.0365 (11)	0.0471 (11)	0.0026 (8)	−0.0101 (9)	−0.0117 (9)
C6	0.0530 (13)	0.0384 (12)	0.0817 (18)	0.0048 (10)	−0.0219 (13)	−0.0088 (12)
C7	0.0639 (16)	0.0366 (12)	0.094 (2)	0.0010 (11)	−0.0125 (15)	−0.0119 (13)
C8	0.0648 (16)	0.0470 (14)	0.0743 (18)	−0.0148 (12)	−0.0002 (13)	−0.0217 (13)
C9	0.0632 (16)	0.0619 (16)	0.0693 (17)	−0.0145 (13)	−0.0201 (13)	−0.0148 (13)
C10	0.0542 (13)	0.0473 (13)	0.0579 (14)	−0.0038 (10)	−0.0201 (11)	−0.0088 (11)
C11	0.0705 (18)	0.0564 (16)	0.0688 (17)	−0.0011 (13)	−0.0348 (14)	0.0041 (13)
C12	0.0467 (12)	0.0427 (11)	0.0421 (11)	0.0017 (9)	−0.0097 (9)	−0.0010 (9)
C13	0.0583 (14)	0.0379 (11)	0.0583 (14)	0.0002 (10)	−0.0166 (11)	0.0003 (10)
C14	0.0510 (12)	0.0372 (11)	0.0467 (11)	0.0003 (9)	−0.0058 (9)	−0.0109 (9)
C15	0.0513 (13)	0.0438 (12)	0.0610 (14)	−0.0025 (10)	−0.0017 (11)	−0.0188 (11)
C16	0.086 (2)	0.0465 (14)	0.0708 (18)	−0.0130 (14)	−0.0007 (15)	−0.0184 (13)
C17	0.103 (3)	0.0530 (18)	0.105 (3)	−0.0221 (18)	0.004 (2)	−0.0306 (19)
C18	0.087 (2)	0.080 (2)	0.134 (4)	−0.0268 (19)	−0.005 (2)	−0.058 (3)
C19	0.089 (3)	0.093 (3)	0.126 (3)	−0.013 (2)	−0.039 (2)	−0.050 (3)
C20	0.0739 (19)	0.0641 (18)	0.093 (2)	−0.0074 (15)	−0.0294 (17)	−0.0264 (16)
C21	0.0566 (13)	0.0360 (10)	0.0497 (12)	−0.0029 (9)	−0.0181 (10)	−0.0122 (9)
C22	0.0544 (14)	0.0703 (17)	0.0705 (16)	0.0008 (12)	−0.0204 (12)	−0.0372 (14)
C23	0.0715 (18)	0.093 (2)	0.0714 (18)	−0.0030 (16)	−0.0337 (15)	−0.0388 (17)
C24	0.0780 (19)	0.086 (2)	0.0540 (15)	−0.0121 (16)	−0.0219 (14)	−0.0263 (14)

Geometric parameters (Å, º) top

Cu1—O2ⁱ	1.9412 (16)	C5—C6	1.385 (3)
Cu1—O2	1.9412 (16)	C5—C10	1.389 (3)
Cu1—O1	1.9469 (15)	C6—C7	1.390 (4)
Cu1—O1ⁱ	1.9469 (15)	C6—H6	0.9300
Cu1—N1	2.542 (2)	C7—C8	1.360 (5)
Cu2—O3	1.9307 (16)	C7—H7	0.9300
Cu2—O3ⁱⁱ	1.9308 (16)	C8—C9	1.382 (4)
Cu2—O4	1.9455 (18)	C8—H8	0.9300
Cu2—O4ⁱⁱ	1.9456 (18)	C9—C10	1.383 (4)
Cu2—N2	2.572 (2)	C9—H9	0.9300
O1—C2	1.272 (3)	C10—H10	0.9300
O2—C4	1.261 (3)	C11—C12	1.512 (3)
O3—C12	1.269 (3)	C12—C13	1.365 (4)
O4—C14	1.262 (3)	C13—C14	1.414 (4)
N1—C22	1.329 (3)	C13—H13	0.9300
N1—C21	1.342 (3)	C14—C15	1.489 (3)
N2—C24	1.332 (4)	C15—C20	1.385 (4)
N2—C21	1.347 (3)	C15—C16	1.388 (4)
N3—C21	1.341 (3)	C16—C17	1.397 (5)
N3—H3A	0.8600	C16—H16	0.9300
N3—H3B	0.8600	C17—C18	1.351 (6)
F1—C1	1.301 (3)	C17—H17	0.9300
F2—C1	1.319 (4)	C18—C19	1.386 (6)
F3—C1	1.298 (4)	C18—H18	0.9300
F4—C11	1.307 (3)	C19—C20	1.381 (4)
F5—C11	1.290 (4)	C19—H19	0.9300
F6—C11	1.325 (4)	C20—H20	0.9300
C1—C2	1.525 (3)	C22—C23	1.367 (4)
C2—C3	1.362 (3)	C22—H22	0.9300
C3—C4	1.428 (3)	C23—C24	1.375 (5)
C3—H3	0.9300	C23—H23	0.9300
C4—C5	1.483 (3)	C24—H24	0.9300

O2ⁱ—Cu1—O2	180.0	C6—C7—H7	119.7
O2ⁱ—Cu1—O1	87.43 (6)	C7—C8—C9	119.8 (3)
O2—Cu1—O1	92.57 (6)	C7—C8—H8	120.1
O2ⁱ—Cu1—O1ⁱ	92.57 (6)	C9—C8—H8	120.1
O2—Cu1—O1ⁱ	87.43 (6)	C8—C9—C10	120.2 (3)
O1—Cu1—O1ⁱ	180.0	C8—C9—H9	119.9
O2ⁱ—Cu1—N1	89.47 (7)	C10—C9—H9	119.9
O2—Cu1—N1	90.53 (7)	C9—C10—C5	120.4 (2)
O1—Cu1—N1	91.27 (7)	C9—C10—H10	119.8
O1ⁱ—Cu1—N1	88.72 (7)	C5—C10—H10	119.8
O3—Cu2—O3ⁱⁱ	180.0	F5—C11—F4	108.2 (3)
O3—Cu2—O4	93.42 (7)	F5—C11—F6	103.9 (3)
O3ⁱⁱ—Cu2—O4	86.58 (7)	F4—C11—F6	105.1 (3)
O3—Cu2—O4ⁱⁱ	86.57 (7)	F5—C11—C12	113.1 (3)
O3ⁱⁱ—Cu2—O4ⁱⁱ	93.43 (7)	F4—C11—C12	115.4 (3)
O4—Cu2—O4ⁱⁱ	180.0	F6—C11—C12	110.3 (3)
O3—Cu2—N2	91.33 (8)	O3—C12—C13	129.8 (2)
O3ⁱⁱ—Cu2—N2	88.67 (8)	O3—C12—C11	111.9 (2)
O4—Cu2—N2	87.02 (8)	C13—C12—C11	118.3 (2)
O4ⁱⁱ—Cu2—N2	92.98 (8)	C12—C13—C14	124.1 (2)
C2—O1—Cu1	122.19 (14)	C12—C13—H13	117.9
C4—O2—Cu1	127.82 (15)	C14—C13—H13	117.9
C12—O3—Cu2	122.25 (16)	O4—C14—C13	122.7 (2)
C14—O4—Cu2	127.42 (17)	O4—C14—C15	116.5 (2)
C22—N1—C21	116.4 (2)	C13—C14—C15	120.8 (2)
C22—N1—Cu1	112.57 (18)	C20—C15—C16	119.1 (3)
C21—N1—Cu1	130.93 (16)	C20—C15—C14	119.3 (3)
C24—N2—C21	115.7 (2)	C16—C15—C14	121.7 (3)
C24—N2—Cu2	111.03 (18)	C15—C16—C17	119.8 (4)
C21—N2—Cu2	132.25 (18)	C15—C16—H16	120.1
C21—N3—H3A	120.0	C17—C16—H16	120.1
C21—N3—H3B	120.0	C18—C17—C16	120.6 (4)
H3A—N3—H3B	120.0	C18—C17—H17	119.7
F3—C1—F1	108.9 (3)	C16—C17—H17	119.7
F3—C1—F2	103.7 (3)	C17—C18—C19	120.3 (3)
F1—C1—F2	105.0 (3)	C17—C18—H18	119.9
F3—C1—C2	112.1 (2)	C19—C18—H18	119.9
F1—C1—C2	115.0 (2)	C18—C19—C20	119.8 (4)
F2—C1—C2	111.3 (2)	C18—C19—H19	120.1
O1—C2—C3	129.5 (2)	C20—C19—H19	120.1
O1—C2—C1	111.6 (2)	C19—C20—C15	120.5 (4)
C3—C2—C1	118.9 (2)	C19—C20—H20	119.8
C2—C3—C4	123.6 (2)	C15—C20—H20	119.8
C2—C3—H3	118.2	N3—C21—N1	117.7 (2)
C4—C3—H3	118.2	N3—C21—N2	116.9 (2)
O2—C4—C3	122.5 (2)	N1—C21—N2	125.4 (2)
O2—C4—C5	116.77 (19)	N1—C22—C23	122.8 (3)
C3—C4—C5	120.65 (19)	N1—C22—H22	118.6
C6—C5—C10	118.7 (2)	C23—C22—H22	118.6
C6—C5—C4	122.6 (2)	C22—C23—C24	116.5 (3)
C10—C5—C4	118.7 (2)	C22—C23—H23	121.8
C5—C6—C7	120.4 (3)	C24—C23—H23	121.8
C5—C6—H6	119.8	N2—C24—C23	123.2 (3)
C7—C6—H6	119.8	N2—C24—H24	118.4
C8—C7—C6	120.5 (3)	C23—C24—H24	118.4
C8—C7—H7	119.7

Cu1—O1—C2—C3	8.9 (4)	F6—C11—C12—C13	110.2 (3)
Cu1—O1—C2—C1	−172.05 (17)	O3—C12—C13—C14	0.4 (5)
F3—C1—C2—O1	−55.7 (3)	C11—C12—C13—C14	−179.2 (3)
F1—C1—C2—O1	179.2 (3)	Cu2—O4—C14—C13	−1.5 (4)
F2—C1—C2—O1	59.9 (3)	Cu2—O4—C14—C15	177.38 (16)
F3—C1—C2—C3	123.5 (3)	C12—C13—C14—O4	3.6 (4)
F1—C1—C2—C3	−1.6 (4)	C12—C13—C14—C15	−175.2 (2)
F2—C1—C2—C3	−120.9 (3)	O4—C14—C15—C20	9.0 (4)
O1—C2—C3—C4	4.2 (4)	C13—C14—C15—C20	−172.1 (3)
C1—C2—C3—C4	−174.8 (2)	O4—C14—C15—C16	−170.6 (2)
Cu1—O2—C4—C3	−1.7 (3)	C13—C14—C15—C16	8.3 (4)
Cu1—O2—C4—C5	−179.71 (14)	C20—C15—C16—C17	−0.6 (5)
C2—C3—C4—O2	−8.3 (4)	C14—C15—C16—C17	179.0 (3)
C2—C3—C4—C5	169.7 (2)	C15—C16—C17—C18	0.7 (6)
O2—C4—C5—C6	−173.1 (2)	C16—C17—C18—C19	−0.2 (6)
C3—C4—C5—C6	8.8 (4)	C17—C18—C19—C20	−0.5 (7)
O2—C4—C5—C10	8.8 (3)	C18—C19—C20—C15	0.6 (6)
C3—C4—C5—C10	−169.3 (2)	C16—C15—C20—C19	0.0 (5)
C10—C5—C6—C7	0.5 (4)	C14—C15—C20—C19	−179.7 (3)
C4—C5—C6—C7	−177.7 (2)	C22—N1—C21—N3	178.7 (2)
C5—C6—C7—C8	0.4 (5)	Cu1—N1—C21—N3	2.1 (3)
C6—C7—C8—C9	−1.1 (5)	C22—N1—C21—N2	−1.2 (4)
C7—C8—C9—C10	0.8 (5)	Cu1—N1—C21—N2	−177.79 (18)
C8—C9—C10—C5	0.1 (4)	C24—N2—C21—N3	−177.8 (3)
C6—C5—C10—C9	−0.7 (4)	Cu2—N2—C21—N3	15.2 (3)
C4—C5—C10—C9	177.5 (2)	C24—N2—C21—N1	2.0 (4)
Cu2—O3—C12—C13	−5.7 (4)	Cu2—N2—C21—N1	−164.95 (18)
Cu2—O3—C12—C11	173.96 (19)	C21—N1—C22—C23	−0.9 (4)
F5—C11—C12—O3	46.3 (4)	Cu1—N1—C22—C23	176.4 (3)
F4—C11—C12—O3	171.6 (3)	N1—C22—C23—C24	1.8 (5)
F6—C11—C12—O3	−69.5 (4)	C21—N2—C24—C23	−1.0 (5)
F5—C11—C12—C13	−134.0 (3)	Cu2—N2—C24—C23	168.8 (3)
F4—C11—C12—C13	−8.7 (4)	C22—C23—C24—N2	−0.8 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.86	2.32	3.100 (3)	151
N3—H3B···O3	0.86	2.54	3.226 (3)	137
C10—H10···O2	0.93	2.41	2.727 (4)	100
C22—H22···O1ⁱ	0.93	2.53	3.140 (3)	123
C24—H24···O3ⁱⁱ	0.93	2.56	3.185 (4)	125
C3—H3···F1	0.93	2.37	2.735 (4)	103
C13—H13···F4	0.93	2.35	2.725 (4)	104

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

(2) top

Crystal data top

C₂₄H₁₇F₆N₃O₄Zn	F(000) = 596
M_r = 590.77	D_x = 1.552 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.5334 (4) Å	Cell parameters from 5290 reflections
b = 9.2949 (2) Å	θ = 2.8–29.4°
c = 13.0287 (5) Å	µ = 1.05 mm⁻¹
β = 115.198 (5)°	T = 293 K
V = 1263.79 (8) Å³	Plate, colorless
Z = 2	0.50 × 0.30 × 0.03 mm

Data collection top

SuperNova, Dual, Cu at zero, Atlas diffractometer	2260 reflections with I > 2σ(I)
Detector resolution: 10.4933 pixels mm^-1	R_int = 0.038
ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan CrysAlis Pro; Oxford Diffraction, 2013	h = −14→14
T_min = 0.849, T_max = 1.000	k = −12→11
12548 measured reflections	l = −16→16
2861 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0386P)² + 0.3634P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2861 reflections	Δρ_max = 0.26 e Å⁻³
203 parameters	Δρ_min = −0.24 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.5000	0.5000	0.0000	0.04178 (12)
O1	0.49666 (12)	0.31644 (14)	0.08326 (11)	0.0436 (3)
O2	0.35739 (13)	0.58194 (15)	0.03574 (12)	0.0469 (3)
N1	0.65295 (15)	0.60274 (17)	0.16441 (13)	0.0413 (4)
N2	0.7500	0.3916 (3)	0.2500	0.0606 (7)
H2A	0.6896	0.3453	0.1968	0.091*	0.5
H2B	0.8104	0.3453	0.3032	0.091*	0.5
F1A	0.3481 (12)	0.1068 (12)	0.2110 (12)	0.140 (4)	0.66 (2)
F2A	0.3965 (15)	0.0435 (7)	0.0767 (10)	0.153 (4)	0.66 (2)
F3A	0.5387 (7)	0.1054 (9)	0.2357 (10)	0.122 (3)	0.66 (2)
F1B	0.317 (2)	0.0900 (19)	0.164 (3)	0.157 (8)	0.34 (2)
F2B	0.447 (3)	0.0395 (15)	0.107 (2)	0.156 (9)	0.34 (2)
F3B	0.508 (4)	0.141 (3)	0.265 (2)	0.209 (12)	0.34 (2)
C1	0.4208 (3)	0.1358 (3)	0.1609 (3)	0.0815 (9)
C2	0.4083 (2)	0.2881 (2)	0.11364 (17)	0.0452 (5)
C3	0.3097 (2)	0.3717 (2)	0.1105 (2)	0.0540 (5)
H3	0.2508	0.3300	0.1328	0.065*
C4	0.29043 (18)	0.5176 (2)	0.07562 (17)	0.0433 (5)
C5	0.18948 (19)	0.6052 (3)	0.09068 (18)	0.0514 (5)
C6	0.1013 (2)	0.5462 (3)	0.1249 (2)	0.0630 (6)
H6	0.1020	0.4478	0.1382	0.076*
C7	0.0118 (2)	0.6339 (4)	0.1395 (2)	0.0819 (9)
H7	−0.0477	0.5936	0.1617	0.098*
C8	0.0106 (3)	0.7770 (5)	0.1216 (3)	0.1039 (12)
H8	−0.0501	0.8348	0.1310	0.125*
C9	0.0979 (4)	0.8368 (4)	0.0899 (4)	0.1191 (14)
H9	0.0981	0.9357	0.0794	0.143*
C10	0.1867 (3)	0.7506 (3)	0.0733 (3)	0.0873 (9)
H10	0.2449	0.7922	0.0500	0.105*
C11	0.7500	0.5343 (3)	0.2500	0.0396 (6)
C12	0.6541 (2)	0.7458 (2)	0.16808 (18)	0.0512 (5)
H12	0.5866	0.7956	0.1124	0.061*
C13	0.7500	0.8233 (3)	0.2500	0.0586 (8)
H13	0.7500	0.9233	0.2500	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.03641 (19)	0.04281 (19)	0.0529 (2)	0.00513 (13)	0.02555 (15)	0.00917 (14)
O1	0.0355 (7)	0.0450 (7)	0.0502 (8)	0.0007 (6)	0.0180 (6)	0.0082 (6)
O2	0.0405 (8)	0.0489 (8)	0.0582 (9)	0.0065 (6)	0.0276 (7)	0.0040 (7)
N1	0.0373 (9)	0.0421 (9)	0.0451 (9)	0.0029 (7)	0.0183 (7)	0.0006 (7)
N2	0.0476 (15)	0.0401 (13)	0.0661 (17)	0.000	−0.0026 (13)	0.000
F1A	0.172 (8)	0.109 (6)	0.216 (7)	0.042 (5)	0.158 (7)	0.090 (5)
F2A	0.248 (9)	0.043 (3)	0.190 (6)	−0.040 (4)	0.113 (6)	−0.022 (4)
F3A	0.110 (4)	0.089 (4)	0.167 (8)	0.037 (3)	0.059 (4)	0.076 (4)
F1B	0.139 (10)	0.067 (5)	0.31 (2)	−0.037 (6)	0.138 (13)	0.029 (10)
F2B	0.243 (16)	0.069 (7)	0.25 (2)	0.084 (10)	0.198 (17)	0.071 (10)
F3B	0.30 (3)	0.115 (10)	0.115 (10)	0.003 (12)	−0.007 (13)	0.071 (9)
C1	0.093 (2)	0.0577 (17)	0.117 (3)	0.0015 (16)	0.067 (2)	0.0209 (18)
C2	0.0458 (11)	0.0456 (11)	0.0454 (11)	−0.0076 (9)	0.0206 (9)	0.0019 (9)
C3	0.0527 (13)	0.0534 (12)	0.0691 (14)	−0.0074 (10)	0.0387 (11)	0.0008 (11)
C4	0.0315 (10)	0.0569 (13)	0.0407 (11)	−0.0043 (8)	0.0146 (8)	−0.0074 (9)
C5	0.0363 (11)	0.0677 (14)	0.0498 (12)	−0.0009 (9)	0.0178 (9)	−0.0142 (10)
C6	0.0440 (13)	0.0981 (18)	0.0523 (13)	0.0030 (12)	0.0256 (11)	−0.0056 (13)
C7	0.0468 (14)	0.144 (3)	0.0628 (16)	0.0011 (16)	0.0312 (12)	−0.0245 (18)
C8	0.0587 (18)	0.127 (3)	0.134 (3)	0.0100 (19)	0.048 (2)	−0.052 (3)
C9	0.088 (2)	0.086 (2)	0.204 (4)	0.0109 (19)	0.082 (3)	−0.035 (2)
C10	0.0609 (17)	0.0709 (18)	0.147 (3)	0.0031 (13)	0.0606 (19)	−0.0169 (18)
C11	0.0328 (14)	0.0427 (15)	0.0468 (15)	0.000	0.0203 (12)	0.000
C12	0.0568 (13)	0.0456 (11)	0.0511 (12)	0.0102 (10)	0.0228 (10)	0.0054 (10)
C13	0.076 (2)	0.0377 (15)	0.0595 (19)	0.000	0.0260 (17)	0.000

Geometric parameters (Å, º) top

Zn1—O1	2.0310 (13)	C2—C3	1.364 (3)
Zn1—O1ⁱ	2.0310 (13)	C3—C4	1.417 (3)
Zn1—O2	2.0382 (13)	C3—H3	0.9300
Zn1—O2ⁱ	2.0382 (13)	C4—C5	1.500 (3)
Zn1—N1ⁱ	2.3226 (16)	C5—C10	1.369 (4)
Zn1—N1	2.3226 (16)	C5—C6	1.386 (3)
O1—C2	1.268 (2)	C6—C7	1.390 (4)
O2—C4	1.251 (2)	C6—H6	0.9300
N1—C12	1.331 (3)	C7—C8	1.349 (5)
N1—C11	1.356 (2)	C7—H7	0.9300
N2—C11	1.327 (4)	C8—C9	1.359 (5)
N2—H2A	0.8600	C8—H8	0.9300
N2—H2B	0.8600	C9—C10	1.388 (4)
F1A—C1	1.292 (8)	C9—H9	0.9300
F2A—C1	1.325 (9)	C10—H10	0.9300
F3A—C1	1.322 (9)	C11—N1ⁱⁱ	1.356 (2)
F1B—C1	1.290 (16)	C12—C13	1.370 (3)
F2B—C1	1.249 (16)	C12—H12	0.9300
F3B—C1	1.30 (2)	C13—C12ⁱⁱ	1.370 (3)
C1—C2	1.526 (3)	C13—H13	0.9300

O1—Zn1—O1ⁱ	180.0	O1—C2—C1	111.6 (2)
O1—Zn1—O2	89.49 (5)	C3—C2—C1	118.4 (2)
O1ⁱ—Zn1—O2	90.50 (5)	C2—C3—C4	124.76 (19)
O1—Zn1—O2ⁱ	90.51 (5)	C2—C3—H3	117.6
O1ⁱ—Zn1—O2ⁱ	89.50 (5)	C4—C3—H3	117.6
O2—Zn1—O2ⁱ	180.0	O2—C4—C3	123.37 (19)
O1—Zn1—N1ⁱ	88.14 (5)	O2—C4—C5	116.46 (18)
O1ⁱ—Zn1—N1ⁱ	91.86 (5)	C3—C4—C5	120.11 (19)
O2—Zn1—N1ⁱ	89.68 (6)	C10—C5—C6	118.4 (2)
O2ⁱ—Zn1—N1ⁱ	90.32 (6)	C10—C5—C4	118.6 (2)
O1—Zn1—N1	91.86 (5)	C6—C5—C4	123.0 (2)
O1ⁱ—Zn1—N1	88.14 (5)	C5—C6—C7	120.1 (3)
O2—Zn1—N1	90.32 (6)	C5—C6—H6	120.0
O2ⁱ—Zn1—N1	89.68 (6)	C7—C6—H6	120.0
N1ⁱ—Zn1—N1	180.00 (7)	C8—C7—C6	120.6 (3)
C2—O1—Zn1	122.81 (13)	C8—C7—H7	119.7
C4—O2—Zn1	128.11 (13)	C6—C7—H7	119.7
C12—N1—C11	116.57 (18)	C7—C8—C9	120.0 (3)
C12—N1—Zn1	115.85 (13)	C7—C8—H8	120.0
C11—N1—Zn1	127.06 (14)	C9—C8—H8	120.0
C11—N2—H2A	120.0	C8—C9—C10	120.2 (3)
C11—N2—H2B	120.0	C8—C9—H9	119.9
H2A—N2—H2B	120.0	C10—C9—H9	119.9
F2B—C1—F1B	103.3 (13)	C5—C10—C9	120.7 (3)
F2B—C1—F3B	110.3 (15)	C5—C10—H10	119.6
F1B—C1—F3B	107.4 (14)	C9—C10—H10	119.6
F1A—C1—F3A	105.5 (7)	N2—C11—N1	117.98 (12)
F1A—C1—F2A	109.2 (7)	N2—C11—N1ⁱⁱ	117.97 (12)
F3A—C1—F2A	105.1 (6)	N1—C11—N1ⁱⁱ	124.0 (2)
F2B—C1—C2	116.4 (8)	N1—C12—C13	123.1 (2)
F1B—C1—C2	112.8 (10)	N1—C12—H12	118.5
F1A—C1—C2	115.3 (5)	C13—C12—H12	118.5
F3B—C1—C2	106.5 (9)	C12—C13—C12ⁱⁱ	116.6 (3)
F3A—C1—C2	112.8 (4)	C12—C13—H13	121.7
F2A—C1—C2	108.5 (5)	C12ⁱⁱ—C13—H13	121.7
O1—C2—C3	129.99 (19)

Zn1—O1—C2—C3	−7.7 (3)	O2—C4—C5—C10	−7.6 (3)
Zn1—O1—C2—C1	172.83 (19)	C3—C4—C5—C10	169.7 (2)
F2B—C1—C2—O1	−43.3 (16)	O2—C4—C5—C6	174.50 (19)
F1B—C1—C2—O1	−162.3 (16)	C3—C4—C5—C6	−8.2 (3)
F1A—C1—C2—O1	168.9 (9)	C10—C5—C6—C7	0.8 (4)
F3B—C1—C2—O1	80 (2)	C4—C5—C6—C7	178.7 (2)
F3A—C1—C2—O1	47.6 (7)	C5—C6—C7—C8	−0.7 (4)
F2A—C1—C2—O1	−68.4 (8)	C6—C7—C8—C9	−0.5 (5)
F2B—C1—C2—C3	137.2 (16)	C7—C8—C9—C10	1.5 (6)
F1B—C1—C2—C3	18.1 (16)	C6—C5—C10—C9	0.2 (5)
F1A—C1—C2—C3	−10.7 (9)	C4—C5—C10—C9	−177.8 (3)
F3B—C1—C2—C3	−99 (2)	C8—C9—C10—C5	−1.4 (6)
F3A—C1—C2—C3	−131.9 (6)	C12—N1—C11—N2	178.58 (13)
F2A—C1—C2—C3	112.1 (7)	Zn1—N1—C11—N2	−10.11 (13)
O1—C2—C3—C4	−3.5 (4)	C12—N1—C11—N1ⁱⁱ	−1.42 (13)
C1—C2—C3—C4	175.9 (2)	Zn1—N1—C11—N1ⁱⁱ	169.89 (13)
Zn1—O2—C4—C3	4.2 (3)	C11—N1—C12—C13	2.9 (3)
Zn1—O2—C4—C5	−178.58 (12)	Zn1—N1—C12—C13	−169.37 (13)
C2—C3—C4—O2	5.6 (4)	N1—C12—C13—C12ⁱⁱ	−1.56 (14)
C2—C3—C4—C5	−171.5 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1ⁱⁱ	0.86	2.10	2.8878 (14)	152
N2—H2A···O1	0.86	2.10	2.8878 (14)	152
C10—H10···O2	0.93	2.40	2.719 (4)	100
C12—H12···O1ⁱ	0.93	2.53	3.039 (3)	114
C3—H3···F1A	0.93	2.37	2.735 (12)	103

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

(3) top

Crystal data top

C₂₄H₁₆CuF₆N₂O₄	F(000) = 578
M_r = 573.93	D_x = 1.474 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 16.6980 (4) Å	Cell parameters from 1565 reflections
b = 7.5724 (2) Å	θ = 1.0–27.5°
c = 11.9436 (3) Å	µ = 0.92 mm⁻¹
β = 121.097 (2)°	T = 293 K
V = 1293.17 (6) Å³	Prism, green
Z = 2	0.25 × 0.18 × 0.13 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	1511 reflections with I > 2σ(I)
Detector resolution: 0.055 pixels mm^-1	R_int = 0.016
ω scans	θ_max = 27.5°, θ_min = 5.1°
Absorption correction: multi-scan SCALEPACK (Otwinowski & Minor, 1997)	h = −21→21
T_min = 0.820, T_max = 1.000	k = −9→9
2852 measured reflections	l = −15→15
1571 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.044	w = 1/[σ²(F_o²) + (0.0919P)² + 0.3544P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.129	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.41 e Å⁻³
1571 reflections	Δρ_min = −0.40 e Å⁻³
122 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.078 (13)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.0000	0.0000	0.0000	0.0563 (3)
F1	−0.0937 (3)	0.0000	0.3519 (4)	0.242 (4)
F2	−0.1780 (2)	−0.1337 (7)	0.1778 (4)	0.231 (2)
O1	−0.07818 (15)	0.0000	0.0774 (2)	0.0657 (5)
O2	0.11542 (15)	0.0000	0.1710 (2)	0.0648 (5)
N1	0.0000	0.3173 (3)	0.0000	0.0654 (6)
C1	−0.1221 (4)	0.0000	0.2317 (5)	0.141 (3)
C2	−0.0446 (2)	0.0000	0.1987 (3)	0.0713 (8)
C3	0.0452 (3)	0.0000	0.2981 (4)	0.0843 (11)
H3	0.0566	0.0000	0.3830	0.101*
C4	0.1235 (2)	0.0000	0.2816 (3)	0.0613 (6)
C5	0.2196 (3)	0.0000	0.3953 (3)	0.0741 (8)
C6	0.2919 (4)	0.0536 (10)	0.3757 (6)	0.100 (3)	0.5
H6	0.2786	0.0820	0.2920	0.120*	0.5
C7	0.3819 (4)	0.0642 (13)	0.4789 (8)	0.131 (4)	0.5
H7	0.4295	0.0994	0.4652	0.157*	0.5
C8	0.4019 (5)	0.023 (8)	0.6034 (7)	0.139 (9)	0.5
H8	0.4632	0.0298	0.6732	0.167*	0.5
C9	0.3339 (5)	−0.028 (4)	0.6249 (6)	0.111 (7)	0.5
H9	0.3487	−0.0608	0.7086	0.133*	0.5
C10	0.2410 (4)	−0.0328 (15)	0.5220 (4)	0.088 (3)	0.5
H10	0.1935	−0.0577	0.5385	0.106*	0.5
C11	0.06978 (16)	0.4086 (3)	0.0067 (3)	0.0703 (5)
H11	0.1201	0.3486	0.0115	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0539 (3)	0.0681 (4)	0.0494 (3)	0.000	0.0284 (2)	0.000
F1	0.129 (3)	0.539 (11)	0.106 (3)	0.000	0.094 (2)	0.000
F2	0.144 (2)	0.393 (7)	0.205 (4)	−0.102 (3)	0.125 (2)	−0.020 (3)
O1	0.0584 (10)	0.0840 (14)	0.0591 (11)	0.000	0.0335 (9)	0.000
O2	0.0586 (10)	0.0842 (14)	0.0525 (10)	0.000	0.0293 (9)	0.000
N1	0.0621 (13)	0.0593 (13)	0.0701 (14)	0.000	0.0308 (11)	0.000
C1	0.075 (3)	0.280 (10)	0.087 (3)	0.000	0.055 (3)	0.000
C2	0.0708 (17)	0.092 (2)	0.0648 (17)	0.000	0.0445 (15)	0.000
C3	0.076 (2)	0.129 (3)	0.0542 (15)	0.000	0.0387 (15)	0.000
C4	0.0654 (15)	0.0655 (15)	0.0509 (13)	0.000	0.0286 (12)	0.000
C5	0.0711 (18)	0.085 (2)	0.0557 (16)	0.000	0.0255 (14)	0.000
C6	0.064 (2)	0.142 (9)	0.078 (3)	0.008 (3)	0.026 (2)	0.012 (3)
C7	0.065 (3)	0.184 (12)	0.113 (5)	0.008 (4)	0.024 (3)	0.011 (5)
C8	0.093 (4)	0.17 (3)	0.084 (3)	0.012 (10)	−0.005 (3)	−0.013 (10)
C9	0.103 (4)	0.13 (2)	0.059 (2)	0.008 (6)	0.015 (2)	0.003 (4)
C10	0.100 (3)	0.095 (10)	0.0540 (19)	0.006 (3)	0.028 (2)	0.003 (2)
C11	0.0604 (10)	0.0682 (13)	0.0813 (14)	0.0037 (9)	0.0359 (10)	−0.0010 (11)

Geometric parameters (Å, º) top

Cu1—O1	1.951 (2)	C3—H3	0.9300
Cu1—O1ⁱ	1.951 (2)	C4—C5	1.473 (5)
Cu1—O2	1.954 (2)	C5—C10	1.387 (6)
Cu1—O2ⁱ	1.954 (2)	C5—C6	1.403 (7)
Cu1—N1ⁱ	2.403 (3)	C6—C7	1.367 (8)
Cu1—N1	2.403 (3)	C6—H6	0.9300
F1—C1	1.258 (6)	C7—C8	1.382 (17)
F2—C1	1.301 (5)	C7—H7	0.9300
O1—C2	1.254 (4)	C8—C9	1.34 (2)
O2—C4	1.257 (3)	C8—H8	0.9300
N1—C11ⁱⁱ	1.321 (3)	C9—C10	1.395 (8)
N1—C11	1.321 (3)	C9—H9	0.9300
C1—F2ⁱⁱⁱ	1.301 (5)	C10—H10	0.9300
C1—C2	1.534 (5)	C11—C11^iv	1.384 (5)
C2—C3	1.349 (5)	C11—H11	0.9300
C3—C4	1.418 (5)

O1—Cu1—O1ⁱ	180.0	C3—C2—C1	118.4 (3)
O1—Cu1—O2	92.56 (9)	C2—C3—C4	124.3 (3)
O1ⁱ—Cu1—O2	87.43 (9)	C2—C3—H3	117.9
O1—Cu1—O2ⁱ	87.43 (9)	C4—C3—H3	117.9
O1ⁱ—Cu1—O2ⁱ	92.57 (9)	O2—C4—C3	122.7 (3)
O2—Cu1—O2ⁱ	180.0	O2—C4—C5	116.3 (3)
O1—Cu1—N1ⁱ	90.0	C3—C4—C5	121.0 (3)
O1ⁱ—Cu1—N1ⁱ	90.0	C10—C5—C6	118.3 (5)
O2—Cu1—N1ⁱ	90.0	C10—C5—C4	123.4 (4)
O2ⁱ—Cu1—N1ⁱ	90.0	C6—C5—C4	117.9 (4)
O1—Cu1—N1	90.0	C7—C6—C5	120.4 (6)
O1ⁱ—Cu1—N1	90.0	C7—C6—H6	119.8
O2—Cu1—N1	90.0	C5—C6—H6	119.8
O2ⁱ—Cu1—N1	90.0	C6—C7—C8	119.9 (9)
N1ⁱ—Cu1—N1	180.0	C6—C7—H7	120.0
C2—O1—Cu1	122.6 (2)	C8—C7—H7	120.0
C4—O2—Cu1	127.6 (2)	C9—C8—C7	120.8 (6)
C11ⁱⁱ—N1—C11	116.9 (3)	C9—C8—H8	119.6
C11ⁱⁱ—N1—Cu1	121.53 (14)	C7—C8—H8	119.6
C11—N1—Cu1	121.53 (14)	C8—C9—C10	120.3 (10)
F1—C1—F2	108.4 (3)	C8—C9—H9	119.9
F1—C1—F2ⁱⁱⁱ	108.4 (3)	C10—C9—H9	119.9
F2—C1—F2ⁱⁱⁱ	102.2 (6)	C5—C10—C9	119.9 (7)
F1—C1—C2	115.0 (4)	C5—C10—H10	120.0
F2—C1—C2	111.0 (3)	C9—C10—H10	120.0
F2ⁱⁱⁱ—C1—C2	111.0 (3)	N1—C11—C11^iv	121.53 (14)
O1—C2—C3	130.3 (3)	N1—C11—H11	119.2
O1—C2—C1	111.3 (3)	C11^iv—C11—H11	119.2

Cu1—O1—C2—C3	0.0000 (10)	O2—C4—C5—C10	−167.6 (6)
Cu1—O1—C2—C1	180.0000	C3—C4—C5—C10	12.4 (6)
F1—C1—C2—O1	180.0000 (10)	O2—C4—C5—C6	19.1 (3)
F2—C1—C2—O1	56.5 (4)	C3—C4—C5—C6	−160.9 (3)
F2ⁱⁱⁱ—C1—C2—O1	−56.5 (4)	C10—C5—C6—C7	3.2 (9)
F1—C1—C2—C3	0.0000 (10)	C4—C5—C6—C7	176.9 (6)
F2—C1—C2—C3	−123.5 (4)	C5—C6—C7—C8	0 (3)
F2ⁱⁱⁱ—C1—C2—C3	123.5 (4)	C6—C7—C8—C9	0 (5)
O1—C2—C3—C4	0.0000 (10)	C7—C8—C9—C10	−3 (6)
C1—C2—C3—C4	180.0000	C6—C5—C10—C9	−6.0 (19)
Cu1—O2—C4—C3	0.0000 (10)	C4—C5—C10—C9	−179.2 (16)
Cu1—O2—C4—C5	180.0000 (10)	C8—C9—C10—C5	6 (4)
C2—C3—C4—O2	0.0000 (10)	C11ⁱⁱ—N1—C11—C11^iv	−0.0010
C2—C3—C4—C5	180.0000 (10)	Cu1—N1—C11—C11^iv	180.0000

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F1	0.93	2.34	2.708 (8)	103

(4a) top

Crystal data top

C₂₄H₁₆F₆N₂O₄Zn	F(000) = 580
M_r = 575.76	D_x = 1.500 Mg m⁻³
Monoclinic, C2/m	Cu Kα radiation, λ = 1.54184 Å
a = 16.8348 (15) Å	Cell parameters from 1425 reflections
b = 7.2272 (4) Å	θ = 4.2–72.6°
c = 12.2602 (8) Å	µ = 2.04 mm⁻¹
β = 121.311 (5)°	T = 293 K
V = 1274.43 (17) Å³	Plate, colorless
Z = 2	0.40 × 0.08 × 0.05 mm

Data collection top

SuperNova, Dual, Cu at zero, Atlas diffractometer	1315 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1188 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.036
Detector resolution: 10.4933 pixels mm^-1	θ_max = 70.1°, θ_min = 4.2°
ω scans	h = −19→20
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −8→4
T_min = 0.036, T_max = 1.000	l = −14→14
4190 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.0681P)² + 0.5567P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.118	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.31 e Å⁻³
1315 reflections	Δρ_min = −0.34 e Å⁻³
123 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
12 restraints	Extinction coefficient: 0.0052 (5)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.0000	0.0000	0.0000	0.0516 (3)
F1A	−0.0943 (5)	0.0000	0.3507 (6)	0.228 (6)	0.884 (12)
F2A	−0.1788 (3)	−0.1450 (11)	0.1780 (6)	0.222 (4)	0.884 (12)
F1B	−0.191 (2)	0.0000	0.158 (3)	0.084 (10)	0.116 (12)
F2B	−0.1003 (19)	−0.149 (4)	0.316 (3)	0.113 (11)	0.116 (12)
O1	−0.08021 (17)	0.0000	0.0803 (2)	0.0598 (6)
O2	0.11637 (17)	0.0000	0.1784 (2)	0.0589 (6)
N1	0.0000	0.3087 (4)	0.0000	0.0530 (7)
C1	−0.1234 (5)	0.0000	0.2303 (7)	0.149 (4)
C2	−0.0467 (3)	0.0000	0.1978 (4)	0.0652 (10)
C3	0.0434 (3)	0.0000	0.2964 (4)	0.0781 (13)
H3	0.0539	0.0000	0.3788	0.094*
C4	0.1220 (3)	0.0000	0.2840 (3)	0.0551 (8)
C5	0.2170 (3)	0.0000	0.3984 (4)	0.0651 (10)
C6	0.2354 (4)	0.0000	0.5219 (4)	0.0930 (16)
H6	0.1863	0.0000	0.5363	0.112*
C7	0.3254 (5)	0.0000	0.6241 (5)	0.117 (2)
H7	0.3360	0.0000	0.7065	0.141*
C8	0.3973 (5)	0.0000	0.6082 (7)	0.130 (3)
H8	0.4579	0.0000	0.6780	0.156*
C9	0.3803 (5)	0.0000	0.4872 (8)	0.182 (4)
H9	0.4299	0.0000	0.4741	0.218*
C10	0.2901 (4)	0.0000	0.3826 (6)	0.123 (3)
H10	0.2802	0.0000	0.3006	0.148*
C11	0.07138 (18)	0.4049 (4)	0.0124 (3)	0.0604 (6)
H11	0.1227	0.3421	0.0214	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0556 (4)	0.0535 (4)	0.0471 (4)	0.000	0.0278 (3)	0.000
F1A	0.137 (5)	0.49 (2)	0.105 (4)	0.000	0.098 (4)	0.000
F2A	0.147 (4)	0.354 (10)	0.211 (6)	−0.104 (5)	0.125 (4)	−0.001 (5)
F1B	0.064 (12)	0.107 (14)	0.102 (13)	0.000	0.058 (9)	0.000
F2B	0.114 (13)	0.139 (15)	0.125 (14)	−0.027 (8)	0.089 (10)	0.036 (8)
O1	0.0561 (14)	0.0669 (15)	0.0573 (14)	0.000	0.0301 (12)	0.000
O2	0.0515 (13)	0.0775 (16)	0.0492 (13)	0.000	0.0272 (11)	0.000
N1	0.0522 (15)	0.0473 (14)	0.0566 (16)	0.000	0.0262 (13)	0.000
C1	0.076 (4)	0.305 (14)	0.080 (4)	0.000	0.051 (4)	0.000
C2	0.064 (2)	0.077 (2)	0.064 (2)	0.000	0.0398 (19)	0.000
C3	0.074 (3)	0.118 (4)	0.052 (2)	0.000	0.039 (2)	0.000
C4	0.062 (2)	0.0521 (18)	0.0498 (18)	0.000	0.0285 (16)	0.000
C5	0.064 (2)	0.067 (2)	0.052 (2)	0.000	0.0214 (18)	0.000
C6	0.094 (4)	0.117 (4)	0.052 (2)	0.000	0.026 (2)	0.000
C7	0.120 (5)	0.122 (5)	0.055 (3)	0.000	0.008 (3)	0.000
C8	0.085 (4)	0.148 (6)	0.087 (4)	0.000	−0.005 (3)	0.000
C9	0.062 (4)	0.332 (14)	0.111 (6)	0.000	0.017 (4)	0.000
C10	0.058 (3)	0.222 (8)	0.074 (3)	0.000	0.022 (2)	0.000
C11	0.0540 (14)	0.0554 (13)	0.0709 (15)	0.0035 (11)	0.0319 (12)	−0.0004 (12)

Geometric parameters (Å, º) top

Zn1—O2	2.042 (2)	C2—C3	1.362 (6)
Zn1—O2ⁱ	2.042 (2)	C3—C4	1.409 (6)
Zn1—O1ⁱ	2.043 (3)	C3—H3	0.9300
Zn1—O1	2.043 (3)	C4—C5	1.481 (5)
Zn1—N1ⁱ	2.231 (3)	C5—C10	1.341 (7)
Zn1—N1	2.231 (3)	C5—C6	1.379 (6)
F1A—C1	1.291 (9)	C6—C7	1.376 (8)
F2A—C1	1.325 (7)	C6—H6	0.9300
F1B—C1	1.02 (3)	C7—C8	1.322 (10)
F2B—C1	1.41 (2)	C7—H7	0.9300
O1—C2	1.244 (5)	C8—C9	1.357 (11)
O2—C4	1.248 (4)	C8—H8	0.9300
N1—C11	1.327 (3)	C9—C10	1.388 (8)
N1—C11ⁱⁱ	1.327 (3)	C9—H9	0.9300
C1—F2Aⁱⁱⁱ	1.325 (7)	C10—H10	0.9300
C1—F2Bⁱⁱⁱ	1.41 (2)	C11—C11^iv	1.374 (5)
C1—C2	1.536 (7)	C11—H11	0.9300

O2—Zn1—O2ⁱ	180.0	F2Bⁱⁱⁱ—C1—C2	104.6 (11)
O2—Zn1—O1ⁱ	90.57 (10)	O1—C2—C3	130.8 (4)
O2ⁱ—Zn1—O1ⁱ	89.43 (10)	O1—C2—C1	111.3 (4)
O2—Zn1—O1	89.43 (10)	C3—C2—C1	117.9 (4)
O2ⁱ—Zn1—O1	90.57 (10)	C2—C3—C4	125.4 (4)
O1ⁱ—Zn1—O1	180.0	C2—C3—H3	117.3
O2—Zn1—N1ⁱ	90.0	C4—C3—H3	117.3
O2ⁱ—Zn1—N1ⁱ	90.0	O2—C4—C3	122.9 (4)
O1ⁱ—Zn1—N1ⁱ	90.0	O2—C4—C5	116.4 (3)
O1—Zn1—N1ⁱ	90.0	C3—C4—C5	120.7 (4)
O2—Zn1—N1	90.0	C10—C5—C6	117.4 (5)
O2ⁱ—Zn1—N1	90.0	C10—C5—C4	118.9 (4)
O1ⁱ—Zn1—N1	90.0	C6—C5—C4	123.7 (4)
O1—Zn1—N1	90.0	C7—C6—C5	120.8 (6)
N1ⁱ—Zn1—N1	180.0	C7—C6—H6	119.6
C2—O1—Zn1	122.8 (3)	C5—C6—H6	119.6
C4—O2—Zn1	128.7 (2)	C8—C7—C6	121.7 (6)
C11—N1—C11ⁱⁱ	116.8 (3)	C8—C7—H7	119.1
C11—N1—Zn1	121.60 (15)	C6—C7—H7	119.1
C11ⁱⁱ—N1—Zn1	121.60 (15)	C7—C8—C9	118.1 (6)
F1A—C1—F2A	107.8 (4)	C7—C8—H8	120.9
F1A—C1—F2Aⁱⁱⁱ	107.8 (4)	C9—C8—H8	120.9
F2A—C1—F2Aⁱⁱⁱ	104.5 (9)	C8—C9—C10	121.2 (7)
F1B—C1—F2B	113.5 (14)	C8—C9—H9	119.4
F1B—C1—F2Bⁱⁱⁱ	113.5 (14)	C10—C9—H9	119.4
F2B—C1—F2Bⁱⁱⁱ	99 (3)	C5—C10—C9	120.8 (7)
F1B—C1—C2	119 (2)	C5—C10—H10	119.6
F1A—C1—C2	115.2 (6)	C9—C10—H10	119.6
F2A—C1—C2	110.5 (4)	N1—C11—C11^iv	121.60 (15)
F2Aⁱⁱⁱ—C1—C2	110.5 (4)	N1—C11—H11	119.2
F2B—C1—C2	104.6 (11)	C11^iv—C11—H11	119.2

Zn1—O1—C2—C3	0.0000 (10)	Zn1—O2—C4—C5	180.0000 (10)
Zn1—O1—C2—C1	180.0000 (10)	C2—C3—C4—O2	0.0000 (10)
F1B—C1—C2—O1	0.0000 (10)	C2—C3—C4—C5	180.0000 (10)
F1A—C1—C2—O1	180.0000 (10)	O2—C4—C5—C10	0.0000 (10)
F2A—C1—C2—O1	57.5 (5)	C3—C4—C5—C10	180.0000 (10)
F2Aⁱⁱⁱ—C1—C2—O1	−57.5 (5)	O2—C4—C5—C6	180.0000 (10)
F2B—C1—C2—O1	128.2 (13)	C3—C4—C5—C6	0.0000 (10)
F2Bⁱⁱⁱ—C1—C2—O1	−128.2 (13)	C10—C5—C6—C7	0.000 (2)
F1B—C1—C2—C3	180.0000 (10)	C4—C5—C6—C7	180.000 (2)
F1A—C1—C2—C3	0.0000 (10)	C5—C6—C7—C8	0.000 (2)
F2A—C1—C2—C3	−122.5 (5)	C6—C7—C8—C9	0.000 (2)
F2Aⁱⁱⁱ—C1—C2—C3	122.5 (5)	C7—C8—C9—C10	0.000 (3)
F2B—C1—C2—C3	−51.8 (13)	C6—C5—C10—C9	0.000 (2)
F2Bⁱⁱⁱ—C1—C2—C3	51.8 (13)	C4—C5—C10—C9	180.000 (2)
O1—C2—C3—C4	0.0000 (10)	C8—C9—C10—C5	0.000 (2)
C1—C2—C3—C4	180.0000	C11ⁱⁱ—N1—C11—C11^iv	0.0030
Zn1—O2—C4—C3	0.0000 (10)	Zn1—N1—C11—C11^iv	180.0020

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

(4b) top

Crystal data top

C₂₄H₁₆F₆N₂O₄Zn	Z = 1
M_r = 575.76	F(000) = 290
Triclinic, P1	D_x = 1.560 Mg m⁻³
a = 7.2110 (5) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.9713 (7) Å	Cell parameters from 2128 reflections
c = 10.9554 (9) Å	θ = 4.2–74.3°
α = 92.223 (7)°	µ = 2.12 mm⁻¹
β = 106.931 (7)°	T = 150 K
γ = 113.347 (7)°	Plate, colorless
V = 612.83 (9) Å³	0.40 × 0.08 × 0.05 mm

Data collection top

SuperNova, Dual, Cu at zero, Atlas diffractometer	2314 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2102 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.051
Detector resolution: 10.4933 pixels mm^-1	θ_max = 70.1°, θ_min = 4.3°
ω scans	h = −6→8
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −10→10
T_min = 0.521, T_max = 1.000	l = −13→13
4001 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.050	w = 1/[σ²(F_o²) + (0.0849P)² + 0.0966P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.138	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.58 e Å⁻³
2314 reflections	Δρ_min = −0.85 e Å⁻³
170 parameters	Extinction correction: SHELXL-2014/7 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.020 (2)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.0000	0.5000	0.0000	0.0249 (2)
F1	0.4625 (7)	1.0429 (3)	0.3574 (3)	0.1305 (18)
F2	0.4973 (6)	1.0430 (4)	0.1723 (3)	0.1198 (16)
F3	0.2160 (9)	1.0447 (4)	0.1919 (4)	0.1283 (16)
O1	0.1567 (3)	0.7438 (2)	0.08081 (18)	0.0285 (4)
O2	0.0506 (3)	0.4405 (2)	0.18159 (18)	0.0302 (4)
N1	0.3074 (3)	0.4995 (3)	0.0001 (2)	0.0257 (5)
C1	0.3556 (10)	0.9822 (5)	0.2327 (4)	0.0812 (18)
C2	0.2478 (5)	0.7950 (3)	0.2015 (3)	0.0342 (6)
C3	0.2587 (5)	0.7080 (4)	0.3019 (3)	0.0414 (8)
H3	0.3412	0.7694	0.3869	0.050*
C4	0.1572 (4)	0.5345 (3)	0.2887 (3)	0.0283 (6)
C5	0.1657 (5)	0.4559 (4)	0.4057 (3)	0.0346 (6)
C6	0.3103 (6)	0.5387 (5)	0.5290 (3)	0.0469 (8)
H6	0.4066	0.6515	0.5417	0.056*
C7	0.3121 (7)	0.4543 (6)	0.6336 (3)	0.0611 (11)
H7	0.4125	0.5105	0.7170	0.073*
C8	0.1739 (8)	0.2939 (6)	0.6189 (4)	0.0655 (12)
H8	0.1788	0.2383	0.6910	0.079*
C9	0.0254 (8)	0.2121 (6)	0.4977 (4)	0.0645 (11)
H9	−0.0754	0.1010	0.4872	0.077*
C10	0.0234 (6)	0.2918 (4)	0.3917 (3)	0.0475 (8)
H10	−0.0762	0.2337	0.3086	0.057*
C11	0.4682 (4)	0.6362 (3)	−0.0064 (3)	0.0300 (6)
H11	0.4503	0.7354	−0.0116	0.036*
C12	0.3387 (4)	0.3635 (3)	0.0057 (3)	0.0283 (6)
H12	0.2268	0.2637	0.0093	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0176 (3)	0.0257 (3)	0.0215 (3)	0.0047 (2)	0.00019 (19)	−0.00298 (19)
F1	0.209 (4)	0.0367 (13)	0.0471 (15)	−0.0193 (18)	0.0082 (19)	−0.0156 (11)
F2	0.116 (3)	0.0650 (17)	0.0784 (19)	−0.0497 (18)	0.0177 (19)	0.0093 (15)
F3	0.219 (5)	0.0475 (16)	0.124 (3)	0.068 (3)	0.049 (3)	0.0067 (18)
O1	0.0241 (9)	0.0244 (9)	0.0254 (9)	0.0043 (8)	0.0017 (7)	−0.0031 (7)
O2	0.0292 (10)	0.0284 (10)	0.0240 (9)	0.0091 (8)	0.0015 (7)	0.0001 (7)
N1	0.0174 (10)	0.0301 (12)	0.0233 (10)	0.0073 (9)	0.0024 (8)	0.0017 (9)
C1	0.117 (4)	0.032 (2)	0.041 (2)	−0.008 (2)	0.009 (2)	−0.0065 (16)
C2	0.0280 (14)	0.0262 (14)	0.0331 (14)	−0.0007 (11)	0.0074 (11)	−0.0043 (11)
C3	0.0418 (17)	0.0363 (16)	0.0215 (13)	0.0006 (14)	0.0003 (12)	−0.0065 (11)
C4	0.0195 (12)	0.0355 (14)	0.0235 (12)	0.0095 (11)	0.0025 (10)	−0.0023 (11)
C5	0.0330 (15)	0.0441 (17)	0.0273 (14)	0.0201 (13)	0.0060 (12)	0.0033 (12)
C6	0.0479 (19)	0.064 (2)	0.0230 (14)	0.0255 (17)	0.0033 (13)	−0.0011 (14)
C7	0.072 (3)	0.094 (3)	0.0244 (15)	0.049 (3)	0.0067 (16)	0.0078 (18)
C8	0.092 (3)	0.089 (3)	0.0412 (19)	0.060 (3)	0.026 (2)	0.031 (2)
C9	0.083 (3)	0.063 (2)	0.058 (2)	0.037 (2)	0.028 (2)	0.032 (2)
C10	0.056 (2)	0.0470 (19)	0.0388 (17)	0.0241 (17)	0.0118 (15)	0.0132 (15)
C11	0.0250 (13)	0.0288 (13)	0.0319 (13)	0.0089 (11)	0.0074 (11)	0.0031 (11)
C12	0.0229 (12)	0.0265 (13)	0.0297 (13)	0.0068 (10)	0.0062 (10)	0.0024 (10)

Geometric parameters (Å, º) top

Zn1—O1ⁱ	2.0381 (18)	C4—C5	1.484 (4)
Zn1—O1	2.0381 (18)	C5—C10	1.392 (5)
Zn1—O2ⁱ	2.0469 (19)	C5—C6	1.397 (4)
Zn1—O2	2.0469 (19)	C6—C7	1.397 (5)
Zn1—N1ⁱ	2.218 (2)	C6—H6	0.9500
Zn1—N1	2.218 (2)	C7—C8	1.357 (7)
F1—C1	1.323 (5)	C7—H7	0.9500
F2—C1	1.327 (7)	C8—C9	1.387 (6)
F3—C1	1.316 (8)	C8—H8	0.9500
O1—C2	1.264 (3)	C9—C10	1.386 (5)
O2—C4	1.251 (3)	C9—H9	0.9500
N1—C12	1.327 (4)	C10—H10	0.9500
N1—C11	1.335 (4)	C11—C12ⁱⁱ	1.388 (4)
C1—C2	1.519 (5)	C11—H11	0.9500
C2—C3	1.375 (4)	C12—C11ⁱⁱ	1.388 (4)
C3—C4	1.413 (4)	C12—H12	0.9500
C3—H3	0.9500

O1ⁱ—Zn1—O1	180.00 (6)	C2—C3—H3	117.4
O1ⁱ—Zn1—O2ⁱ	89.60 (8)	C4—C3—H3	117.4
O1—Zn1—O2ⁱ	90.40 (8)	O2—C4—C3	123.2 (3)
O1ⁱ—Zn1—O2	90.40 (8)	O2—C4—C5	116.7 (2)
O1—Zn1—O2	89.60 (8)	C3—C4—C5	120.1 (3)
O2ⁱ—Zn1—O2	180.0	C10—C5—C6	118.5 (3)
O1ⁱ—Zn1—N1ⁱ	89.94 (8)	C10—C5—C4	118.4 (3)
O1—Zn1—N1ⁱ	90.06 (8)	C6—C5—C4	123.1 (3)
O2ⁱ—Zn1—N1ⁱ	90.02 (8)	C7—C6—C5	119.5 (4)
O2—Zn1—N1ⁱ	89.98 (8)	C7—C6—H6	120.2
O1ⁱ—Zn1—N1	90.06 (8)	C5—C6—H6	120.2
O1—Zn1—N1	89.94 (8)	C8—C7—C6	121.6 (4)
O2ⁱ—Zn1—N1	89.98 (8)	C8—C7—H7	119.2
O2—Zn1—N1	90.02 (8)	C6—C7—H7	119.2
N1ⁱ—Zn1—N1	180.0	C7—C8—C9	119.3 (4)
C2—O1—Zn1	123.16 (19)	C7—C8—H8	120.3
C4—O2—Zn1	128.54 (18)	C9—C8—H8	120.3
C12—N1—C11	117.2 (2)	C10—C9—C8	120.2 (4)
C12—N1—Zn1	121.53 (17)	C10—C9—H9	119.9
C11—N1—Zn1	121.25 (19)	C8—C9—H9	119.9
F3—C1—F1	108.5 (5)	C9—C10—C5	120.8 (4)
F3—C1—F2	105.7 (4)	C9—C10—H10	119.6
F1—C1—F2	105.8 (4)	C5—C10—H10	119.6
F3—C1—C2	111.3 (4)	N1—C11—C12ⁱⁱ	121.4 (3)
F1—C1—C2	114.0 (4)	N1—C11—H11	119.3
F2—C1—C2	110.9 (5)	C12ⁱⁱ—C11—H11	119.3
O1—C2—C3	130.0 (3)	N1—C12—C11ⁱⁱ	121.4 (2)
O1—C2—C1	111.3 (3)	N1—C12—H12	119.3
C3—C2—C1	118.7 (3)	C11ⁱⁱ—C12—H12	119.3
C2—C3—C4	125.2 (3)

Zn1—O1—C2—C3	−2.2 (5)	C3—C4—C5—C10	164.5 (3)
Zn1—O1—C2—C1	178.6 (3)	O2—C4—C5—C6	166.9 (3)
F3—C1—C2—O1	59.8 (5)	C3—C4—C5—C6	−15.8 (5)
F1—C1—C2—O1	−176.9 (5)	C10—C5—C6—C7	1.6 (5)
F2—C1—C2—O1	−57.5 (5)	C4—C5—C6—C7	−178.1 (3)
F3—C1—C2—C3	−119.5 (4)	C5—C6—C7—C8	−1.2 (6)
F1—C1—C2—C3	3.8 (7)	C6—C7—C8—C9	−0.8 (7)
F2—C1—C2—C3	123.1 (4)	C7—C8—C9—C10	2.3 (7)
O1—C2—C3—C4	−2.8 (6)	C8—C9—C10—C5	−1.8 (7)
C1—C2—C3—C4	176.4 (4)	C6—C5—C10—C9	−0.1 (6)
Zn1—O2—C4—C3	2.7 (4)	C4—C5—C10—C9	179.6 (3)
Zn1—O2—C4—C5	179.95 (18)	C12—N1—C11—C12ⁱⁱ	−0.8 (4)
C2—C3—C4—O2	2.5 (5)	Zn1—N1—C11—C12ⁱⁱ	179.64 (19)
C2—C3—C4—C5	−174.7 (3)	C11—N1—C12—C11ⁱⁱ	0.8 (4)
O2—C4—C5—C10	−12.9 (4)	Zn1—N1—C12—C11ⁱⁱ	−179.65 (19)

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

(5) top

Crystal data top

C₃₂H₂₂CuF₆N₂O₄	Z = 1
M_r = 676.05	F(000) = 343
Triclinic, P1	D_x = 1.565 Mg m⁻³
a = 8.6460 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6246 (4) Å	Cell parameters from 2665 reflections
c = 9.6615 (5) Å	θ = 3.0–30.2°
α = 65.711 (5)°	µ = 0.84 mm⁻¹
β = 78.619 (4)°	T = 293 K
γ = 88.191 (4)°	Plate, green
V = 717.29 (6) Å³	0.20 × 0.10 × 0.03 mm

Data collection top

SuperNova, Dual, Cu at zero, Atlas diffractometer	2634 reflections with I > 2σ(I)
Detector resolution: 10.4933 pixels mm^-1	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan CrysAlis Pro; Oxford Diffraction, 2013	h = −11→11
T_min = 0.841, T_max = 1.000	k = −12→12
6726 measured reflections	l = −12→12
3286 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.113	w = 1/[σ²(F_o²) + (0.0536P)² + 0.0947P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3286 reflections	Δρ_max = 0.61 e Å⁻³
205 parameters	Δρ_min = −0.24 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.0000	0.0000	0.5000	0.03739 (16)
F1	0.1566 (3)	0.3201 (2)	−0.0094 (2)	0.0810 (6)
F2	0.3538 (2)	0.3601 (2)	0.0747 (2)	0.0774 (6)
F3	0.1793 (2)	0.52517 (19)	0.0212 (2)	0.0737 (6)
N1	−0.1793 (3)	0.0273 (2)	0.3312 (3)	0.0468 (5)
O1	0.1416 (2)	0.15236 (19)	0.3088 (2)	0.0441 (4)
O2	−0.0987 (2)	0.16151 (18)	0.55026 (19)	0.0413 (4)
C1	0.1987 (3)	0.3766 (3)	0.0839 (3)	0.0522 (7)
C2	0.1067 (3)	0.2909 (3)	0.2493 (3)	0.0370 (5)
C3	−0.0014 (3)	0.3685 (3)	0.3113 (3)	0.0405 (6)
H3	−0.0122	0.4710	0.2507	0.049*
C4	−0.0962 (3)	0.3023 (3)	0.4602 (3)	0.0336 (5)
C5	−0.2047 (3)	0.3956 (3)	0.5237 (3)	0.0357 (5)
C6	−0.2315 (3)	0.5472 (3)	0.4366 (3)	0.0481 (7)
H6	−0.1770	0.5966	0.3346	0.058*
C7	−0.3386 (4)	0.6250 (3)	0.5004 (4)	0.0552 (7)
H7	−0.3564	0.7259	0.4405	0.066*
C8	−0.4178 (3)	0.5558 (3)	0.6496 (4)	0.0556 (8)
H8	−0.4902	0.6087	0.6915	0.067*
C9	−0.3906 (4)	0.4070 (4)	0.7386 (4)	0.0705 (10)
H9	−0.4435	0.3594	0.8413	0.085*
C10	−0.2846 (4)	0.3285 (3)	0.6751 (4)	0.0583 (8)
H10	−0.2669	0.2279	0.7361	0.070*
C11	−0.3251 (3)	0.0754 (3)	0.3497 (4)	0.0537 (7)
H11	−0.3554	0.1114	0.4262	0.064*
C12	−0.4334 (3)	0.0754 (3)	0.2637 (4)	0.0539 (7)
H12	−0.5341	0.1084	0.2842	0.065*
C13	−0.3922 (3)	0.0259 (3)	0.1458 (3)	0.0466 (6)
C14	−0.2383 (4)	−0.0205 (3)	0.1221 (3)	0.0555 (7)
H14	−0.2034	−0.0529	0.0434	0.067*
C15	−0.1382 (3)	−0.0181 (3)	0.2165 (4)	0.0547 (7)
H15	−0.0364	−0.0500	0.1991	0.066*
C16	−0.5100 (3)	0.0233 (3)	0.0555 (3)	0.0503 (7)
H16	−0.6086	0.0584	0.0802	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0428 (3)	0.0318 (2)	0.0374 (3)	0.01444 (18)	−0.00477 (18)	−0.01649 (19)
F1	0.1174 (17)	0.0898 (14)	0.0427 (11)	0.0138 (12)	−0.0121 (10)	−0.0365 (10)
F2	0.0538 (11)	0.0931 (14)	0.0660 (12)	0.0161 (10)	0.0133 (9)	−0.0260 (11)
F3	0.0913 (13)	0.0507 (10)	0.0517 (11)	0.0164 (9)	0.0137 (10)	−0.0076 (8)
N1	0.0450 (13)	0.0510 (13)	0.0470 (14)	0.0057 (10)	−0.0056 (10)	−0.0246 (11)
O1	0.0457 (10)	0.0414 (10)	0.0462 (11)	0.0179 (8)	−0.0076 (8)	−0.0209 (8)
O2	0.0514 (10)	0.0335 (9)	0.0357 (10)	0.0155 (8)	−0.0036 (8)	−0.0144 (7)
C1	0.0597 (18)	0.0498 (16)	0.0429 (16)	0.0191 (14)	−0.0020 (13)	−0.0196 (13)
C2	0.0403 (13)	0.0392 (13)	0.0354 (13)	0.0096 (11)	−0.0094 (11)	−0.0192 (11)
C3	0.0485 (14)	0.0338 (12)	0.0359 (14)	0.0135 (11)	−0.0056 (11)	−0.0132 (11)
C4	0.0363 (12)	0.0331 (12)	0.0364 (13)	0.0108 (10)	−0.0116 (10)	−0.0179 (10)
C5	0.0349 (12)	0.0344 (12)	0.0398 (14)	0.0077 (10)	−0.0061 (10)	−0.0184 (11)
C6	0.0549 (16)	0.0383 (14)	0.0455 (16)	0.0138 (12)	−0.0031 (13)	−0.0158 (12)
C7	0.0624 (18)	0.0382 (14)	0.065 (2)	0.0208 (13)	−0.0089 (15)	−0.0241 (14)
C8	0.0531 (17)	0.0525 (17)	0.067 (2)	0.0171 (14)	0.0008 (15)	−0.0370 (16)
C9	0.080 (2)	0.0533 (18)	0.060 (2)	0.0146 (16)	0.0215 (17)	−0.0221 (16)
C10	0.071 (2)	0.0374 (14)	0.0509 (18)	0.0141 (14)	0.0116 (15)	−0.0145 (13)
C11	0.0565 (17)	0.0561 (17)	0.0555 (18)	0.0154 (14)	−0.0098 (14)	−0.0315 (15)
C12	0.0488 (16)	0.0564 (17)	0.0601 (19)	0.0152 (13)	−0.0107 (14)	−0.0286 (15)
C13	0.0474 (15)	0.0406 (14)	0.0440 (16)	0.0038 (12)	−0.0077 (12)	−0.0104 (12)
C14	0.0626 (18)	0.0630 (18)	0.0451 (17)	0.0062 (15)	−0.0028 (14)	−0.0302 (15)
C15	0.0450 (16)	0.0683 (19)	0.0540 (18)	0.0109 (14)	−0.0034 (13)	−0.0319 (15)
C16	0.0535 (16)	0.0428 (14)	0.0465 (17)	0.0072 (13)	−0.0062 (13)	−0.0126 (12)

Geometric parameters (Å, º) top

Cu1—O2	1.9377 (15)	C6—C7	1.381 (4)
Cu1—O2ⁱ	1.9377 (15)	C6—H6	0.9300
Cu1—O1	2.0135 (18)	C7—C8	1.356 (4)
Cu1—O1ⁱ	2.0135 (18)	C7—H7	0.9300
Cu1—N1	2.398 (2)	C8—C9	1.375 (4)
Cu1—N1ⁱ	2.398 (2)	C8—H8	0.9300
F1—C1	1.337 (3)	C9—C10	1.380 (4)
F2—C1	1.335 (3)	C9—H9	0.9300
F3—C1	1.324 (3)	C10—H10	0.9300
N1—C11	1.333 (3)	C11—C12	1.369 (4)
N1—C15	1.334 (3)	C11—H11	0.9300
O1—C2	1.270 (3)	C12—C13	1.388 (4)
O2—C4	1.272 (3)	C12—H12	0.9300
C1—C2	1.524 (4)	C13—C14	1.396 (4)
C2—C3	1.375 (3)	C13—C16	1.473 (4)
C3—C4	1.400 (3)	C14—C15	1.383 (4)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.496 (3)	C15—H15	0.9300
C5—C10	1.373 (4)	C16—C16ⁱⁱ	1.303 (5)
C5—C6	1.392 (3)	C16—H16	0.9300

O2—Cu1—O2ⁱ	180.0	C10—C5—C4	118.7 (2)
O2—Cu1—O1	91.50 (7)	C6—C5—C4	123.4 (2)
O2ⁱ—Cu1—O1	88.50 (7)	C7—C6—C5	120.5 (3)
O2—Cu1—O1ⁱ	88.50 (7)	C7—C6—H6	119.7
O2ⁱ—Cu1—O1ⁱ	91.50 (7)	C5—C6—H6	119.7
O1—Cu1—O1ⁱ	180.0	C8—C7—C6	120.7 (3)
O2—Cu1—N1	90.08 (7)	C8—C7—H7	119.7
O2ⁱ—Cu1—N1	89.92 (7)	C6—C7—H7	119.7
O1—Cu1—N1	84.93 (7)	C7—C8—C9	119.7 (2)
O1ⁱ—Cu1—N1	95.07 (7)	C7—C8—H8	120.1
O2—Cu1—N1ⁱ	89.92 (7)	C9—C8—H8	120.1
O2ⁱ—Cu1—N1ⁱ	90.08 (7)	C8—C9—C10	119.9 (3)
O1—Cu1—N1ⁱ	95.07 (7)	C8—C9—H9	120.1
O1ⁱ—Cu1—N1ⁱ	84.93 (7)	C10—C9—H9	120.1
N1—Cu1—N1ⁱ	180.0	C5—C10—C9	121.4 (3)
C11—N1—C15	116.0 (2)	C5—C10—H10	119.3
C11—N1—Cu1	124.53 (18)	C9—C10—H10	119.3
C15—N1—Cu1	119.28 (18)	N1—C11—C12	124.5 (3)
C2—O1—Cu1	120.46 (15)	N1—C11—H11	117.7
C4—O2—Cu1	127.26 (15)	C12—C11—H11	117.7
F3—C1—F2	106.6 (2)	C11—C12—C13	119.7 (3)
F3—C1—F1	106.6 (2)	C11—C12—H12	120.1
F2—C1—F1	106.2 (2)	C13—C12—H12	120.1
F3—C1—C2	115.1 (2)	C12—C13—C14	116.4 (3)
F2—C1—C2	111.5 (2)	C12—C13—C16	119.5 (2)
F1—C1—C2	110.3 (2)	C14—C13—C16	124.1 (3)
O1—C2—C3	129.4 (2)	C15—C14—C13	119.5 (3)
O1—C2—C1	112.4 (2)	C15—C14—H14	120.2
C3—C2—C1	118.2 (2)	C13—C14—H14	120.2
C2—C3—C4	123.9 (2)	N1—C15—C14	123.8 (3)
C2—C3—H3	118.1	N1—C15—H15	118.1
C4—C3—H3	118.1	C14—C15—H15	118.1
O2—C4—C3	123.8 (2)	C16ⁱⁱ—C16—C13	126.5 (4)
O2—C4—C5	115.1 (2)	C16ⁱⁱ—C16—H16	116.8
C3—C4—C5	121.1 (2)	C13—C16—H16	116.8
C10—C5—C6	117.8 (2)

Cu1—O1—C2—C3	14.8 (3)	C4—C5—C6—C7	177.2 (2)
Cu1—O1—C2—C1	−163.53 (17)	C5—C6—C7—C8	0.9 (5)
F3—C1—C2—O1	−173.5 (2)	C6—C7—C8—C9	0.5 (5)
F2—C1—C2—O1	−51.8 (3)	C7—C8—C9—C10	−0.9 (5)
F1—C1—C2—O1	65.9 (3)	C6—C5—C10—C9	1.3 (5)
F3—C1—C2—C3	8.0 (4)	C4—C5—C10—C9	−177.7 (3)
F2—C1—C2—C3	129.7 (3)	C8—C9—C10—C5	0.0 (5)
F1—C1—C2—C3	−112.6 (3)	C15—N1—C11—C12	2.4 (4)
O1—C2—C3—C4	0.2 (4)	Cu1—N1—C11—C12	−172.6 (2)
C1—C2—C3—C4	178.4 (2)	N1—C11—C12—C13	−1.5 (5)
Cu1—O2—C4—C3	−9.0 (3)	C11—C12—C13—C14	−0.5 (4)
Cu1—O2—C4—C5	170.37 (15)	C11—C12—C13—C16	178.8 (3)
C2—C3—C4—O2	−4.2 (4)	C12—C13—C14—C15	1.3 (4)
C2—C3—C4—C5	176.4 (2)	C16—C13—C14—C15	−178.0 (3)
O2—C4—C5—C10	6.3 (3)	C11—N1—C15—C14	−1.5 (4)
C3—C4—C5—C10	−174.3 (3)	Cu1—N1—C15—C14	173.8 (2)
O2—C4—C5—C6	−172.6 (2)	C13—C14—C15—N1	−0.3 (5)
C3—C4—C5—C6	6.8 (4)	C12—C13—C16—C16ⁱⁱ	−178.3 (4)
C10—C5—C6—C7	−1.7 (4)	C14—C13—C16—C16ⁱⁱ	1.0 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···F3	0.93	2.36	2.741 (3)	104
C10—H10···O2	0.93	2.37	2.700 (4)	101

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

CuII and ZnII β-diketonate coordination polymers based on pyrimidin-2-amine, pyrazine and 1,2-bis­(4-pyridyl)­ethane

Supporting information

Cu^II and Zn^II β-diketonate coordination polymers based on pyrimidin-2-amine, pyrazine and 1,2-bis(4-pyridyl)ethane