Synthesis, structural characterization, EPR spectros­copy and Hirshfeld surface analysis of a novel Cu²⁺-doped 3,14-diethyl-2,13-di­aza-6,17-diazo­niatri­cyclo­[16.4.0.0^7,12]docosane bis­(perchlorate)

Cyclam derivatives and their metal complexes have been found to exhibit an anti-HIV effect and stimulate the activity of stem cells from bone marrow. The strength of their binding to the CXCR4 receptor correlates with anti-HIV and stem-cell activities. Knowledge of the conformation and crystal packing of various macrocyclic metal complexes has become important in developing new effective anti-HIV drugs. The synthesis and preparation of single crystals of a new Cu²⁺-doped macrocyclic compound, (3,14-diethyl-2,6,13,17-tetra­aza­tri­cyclo­[16.4.0.0^7,12]docosa­ne)copper(II) bis­(perchlorate)–3,14-diethyl-2,13-di­aza-6,17-diazo­niatri­cyclo­[16.4.0.0^7,12]docosane bis­(perchlorate) (0.69/0.31), {[Cu(C₂₂H₄₄N₄)](ClO₄)₂}_0.69·(C₂₂H₄₆N₄²⁺·2ClO₄⁻)_0.31, is reported. Characterization by X-ray diffraction analysis shows that the asymmetric unit contains half of a centrosymmetric mol­ecule. The macrocyclic ligand in the compound adopts the most stable trans-III conformation. The Cu—N distances of 2.015 (3) and 2.047 (3) Å are normal, but the long axial Cu—O bond of 2.795 (3) Å may be due to a combination of the Jahn–Teller effect and the strong in-plane ligand field. The crystal structure is stabilized by hydrogen bonding between secondary N—H groups, the N atoms of the macrocycle and the O atoms of the perchlorate anions. Hirshfeld surface analysis with 2D (two-dimensional) fingerprint plots indicates that the main contributions to the crystal packing are from H...H (58.0%) and H...O/O...H (41.9%) inter­actions. Electron paramagnetic resonance (EPR) properties are also described.

Computing details

Data collection: Pilatus3_SV in X-AREA (Stoe & Cie, 2018); cell refinement: Recipe in X-AREA (Stoe & Cie, 2018); data reduction: Integrate and LANA in X-AREA (Stoe & Cie, 2018); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b) within OLEX2 (Dolomanov et al., 2009); molecular graphics: DIAMOND-4 (Putz & Brandenburg, 2014); software used to prepare material for publication: X-AREA (Stoe & Cie, 2018).

[3,14-Diethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosane]copper(II) bis(perchlorate)–3,14-diethyl-2,13-diaza-6,17-diazoniatricyclo[16.4.0.0^7,12]docosane bis(perchlorate) (0.69/0.31)

Crystal data

{[Cu(C22H44N4)](ClO4)2}0.69·(C22H46N4^2+·2ClO4^−)0.31	F(000) = 645
Mr = 607.98	Dx = 1.486 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54186 Å
a = 9.2244 (7) Å	Cell parameters from 9638 reflections
b = 11.5540 (8) Å	θ = 5.2–67.5°
c = 12.8659 (9) Å	µ = 3.15 mm^−1
β = 97.722 (6)°	T = 100 K
V = 1358.80 (17) Å^3	Block, pinkish violet
Z = 2	0.26 × 0.14 × 0.12 mm

Data collection

Stoe Stadivari with Xenocs Genix3D Cu HF diffractometer	2591 independent reflections
Radiation source: Genix3D Cu HF	1653 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	Rint = 0.064
Detector resolution: 5.81 pixels mm^-1	θmax = 71.6°, θmin = 5.2°
ω scans	h = −10→11
Absorption correction: multi-scan (LANA; Koziskova et al., 2016)	k = −12→14
Tmin = 0.115, Tmax = 0.615	l = −15→9
12575 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.077	H-atom parameters constrained
wR(F^2) = 0.207	w = 1/[σ^2(Fo^2) + (0.1419P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max < 0.001
2591 reflections	Δρmax = 1.09 e Å^−3
187 parameters	Δρmin = −0.47 e Å^−3
62 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.

Refinement. Data collection and cell refinement on a pale-pink–violet crystal of (I) were made on a Stoe StadiVari diffractometer at 100 K using a Pilatus3R 300 K HPAD detector and a microfocused source Xenocs Genix3D Cu HF (Cu Kα radiation). The structure was solved using the SHELXT program (Sheldrick, 2015a) and refined by the full-matrix least-squares procedure with SHELXL2018 (Sheldrick, 2015b) within the OLEX2 (Dolomanov et al., 2009) program package. A multi-scan absorption corrections were applied using Stoe LANA software (Koziskova et al., 2016). The molecular structures and packing diagram were drawn with DIAMOND-4 (Putz & Brandenburg, 2014).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.500000	0.500000	0.500000	0.0483 (5)	0.688 (4)
N1	0.2819 (3)	0.5387 (3)	0.4689 (3)	0.0559 (9)	0.688 (4)
H1	0.235332	0.457994	0.479276	0.067*	0.688 (4)
N2	0.5067 (3)	0.5153 (3)	0.6566 (3)	0.0533 (9)	0.688 (4)
H2	0.476200	0.436760	0.683324	0.064*	0.688 (4)
N1A	0.2819 (3)	0.5387 (3)	0.4689 (3)	0.0559 (9)	0.312 (4)
H1AA	0.380339	0.545498	0.486947	0.067*	0.156 (2)
H1AB	0.257016	0.464823	0.483422	0.067*	0.312 (4)
N2A	0.5067 (3)	0.5153 (3)	0.6566 (3)	0.0533 (9)	0.312 (4)
H2AA	0.503160	0.529120	0.589204	0.064*	0.156 (2)
H2AB	0.476910	0.448240	0.678584	0.064*	0.312 (4)
C1	0.0859 (5)	0.5449 (4)	0.3140 (4)	0.0613 (12)
H1A	0.031139	0.605421	0.347358	0.074*
H1B	0.052019	0.468830	0.336948	0.074*
C2	0.2473 (4)	0.5574 (4)	0.3535 (3)	0.0554 (10)
H2A	0.277939	0.637751	0.337464	0.066*	0.688 (4)
H2B	0.277939	0.637751	0.337464	0.066*	0.312 (4)
C3	0.2079 (4)	0.6192 (4)	0.5373 (4)	0.0580 (11)
H3A	0.100221	0.605567	0.520704	0.070*	0.688 (4)
H3B	0.100221	0.605567	0.520704	0.070*	0.312 (4)
C4	0.2517 (4)	0.5855 (4)	0.6517 (3)	0.0559 (10)
H4A	0.190395	0.630304	0.694821	0.067*
H4B	0.227765	0.502683	0.659413	0.067*
C5	0.4099 (4)	0.6033 (4)	0.6965 (3)	0.0572 (11)
H5AA	0.441264	0.681565	0.677584	0.069*	0.688 (4)
H5AB	0.419734	0.598474	0.773945	0.069*	0.688 (4)
H5BC	0.441264	0.681565	0.677584	0.069*	0.312 (4)
H5BD	0.419734	0.598474	0.773945	0.069*	0.312 (4)
C6	0.6621 (4)	0.5275 (4)	0.7022 (3)	0.0547 (11)
H6A	0.694042	0.607589	0.686441	0.066*	0.688 (4)
H6B	0.694042	0.607589	0.686441	0.066*	0.312 (4)
C7	0.6915 (5)	0.5106 (4)	0.8197 (4)	0.0594 (11)
H7A	0.660439	0.431931	0.837779	0.071*
H7B	0.633847	0.567326	0.854766	0.071*
C8	0.8557 (5)	0.5266 (4)	0.8591 (4)	0.0610 (12)
H8A	0.885269	0.606919	0.845303	0.073*
H8B	0.873857	0.513193	0.935714	0.073*
C9	0.9459 (5)	0.4429 (4)	0.8043 (4)	0.0629 (12)
H9A	0.923873	0.362713	0.824431	0.076*
H9B	1.051098	0.457447	0.827106	0.076*
C10	0.2347 (5)	0.7453 (4)	0.5135 (4)	0.0603 (11)
H10A	0.199757	0.760185	0.438569	0.072*
H10B	0.341361	0.760243	0.525170	0.072*
C11	0.1591 (5)	0.8294 (4)	0.5803 (4)	0.0667 (13)
H11A	0.202642	0.822664	0.653820	0.100*
H11B	0.054600	0.810906	0.574000	0.100*
H11C	0.171477	0.908709	0.555893	0.100*
Cl1	0.69860 (19)	0.75428 (10)	0.43307 (9)	0.0582 (5)	0.953 (4)
O1	0.8297 (4)	0.6880 (3)	0.4545 (4)	0.0933 (13)	0.953 (4)
O2	0.6262 (5)	0.7274 (3)	0.3313 (3)	0.0902 (13)	0.953 (4)
O3	0.6078 (4)	0.7263 (3)	0.5071 (4)	0.0756 (10)	0.953 (4)
O4	0.7334 (5)	0.8747 (3)	0.4364 (3)	0.0768 (11)	0.953 (4)
Cl1A	0.631 (4)	0.737 (2)	0.443 (2)	0.0582 (5)	0.047 (4)
O1A	0.733 (7)	0.661 (5)	0.404 (6)	0.0933 (13)	0.047 (4)
O2A	0.505 (6)	0.757 (6)	0.369 (5)	0.0902 (13)	0.047 (4)
O3A	0.598 (8)	0.695 (7)	0.537 (4)	0.0756 (10)	0.047 (4)
O4A	0.701 (8)	0.847 (4)	0.461 (6)	0.0768 (11)	0.047 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0346 (7)	0.0470 (8)	0.0622 (8)	0.0016 (5)	0.0032 (5)	−0.0017 (5)
N1	0.0433 (18)	0.053 (2)	0.071 (2)	0.0007 (15)	0.0072 (15)	−0.0004 (17)
N2	0.0417 (18)	0.051 (2)	0.066 (2)	0.0000 (15)	0.0037 (14)	−0.0003 (16)
N1A	0.0433 (18)	0.053 (2)	0.071 (2)	0.0007 (15)	0.0072 (15)	−0.0004 (17)
N2A	0.0417 (18)	0.051 (2)	0.066 (2)	0.0000 (15)	0.0037 (14)	−0.0003 (16)
C1	0.046 (2)	0.059 (3)	0.078 (3)	0.0029 (19)	0.007 (2)	0.000 (2)
C2	0.044 (2)	0.050 (2)	0.072 (3)	0.0020 (18)	0.0064 (18)	0.003 (2)
C3	0.039 (2)	0.056 (3)	0.078 (3)	0.0036 (18)	0.0044 (19)	0.001 (2)
C4	0.043 (2)	0.052 (2)	0.072 (3)	0.0008 (19)	0.0076 (18)	−0.003 (2)
C5	0.048 (2)	0.053 (3)	0.070 (3)	0.0045 (19)	0.0063 (19)	−0.001 (2)
C6	0.046 (2)	0.047 (2)	0.071 (3)	−0.0029 (18)	0.0043 (19)	−0.0003 (19)
C7	0.048 (2)	0.057 (3)	0.073 (3)	−0.001 (2)	0.0052 (19)	−0.002 (2)
C8	0.047 (2)	0.060 (3)	0.074 (3)	−0.0010 (19)	−0.001 (2)	−0.002 (2)
C9	0.046 (2)	0.066 (3)	0.075 (3)	−0.001 (2)	0.002 (2)	0.000 (2)
C10	0.049 (2)	0.050 (3)	0.082 (3)	0.000 (2)	0.008 (2)	0.002 (2)
C11	0.061 (3)	0.055 (3)	0.082 (3)	0.001 (2)	0.005 (2)	−0.003 (2)
Cl1	0.0552 (9)	0.0493 (7)	0.0703 (8)	0.0002 (6)	0.0095 (6)	−0.0019 (5)
O1	0.052 (2)	0.070 (2)	0.160 (4)	0.0029 (18)	0.020 (2)	−0.007 (2)
O2	0.118 (3)	0.069 (3)	0.081 (3)	−0.022 (2)	0.006 (2)	0.0022 (19)
O3	0.068 (2)	0.072 (3)	0.088 (3)	0.0021 (18)	0.017 (2)	0.009 (2)
O4	0.090 (3)	0.052 (2)	0.088 (3)	−0.0077 (17)	0.0098 (19)	0.0013 (18)
Cl1A	0.0552 (9)	0.0493 (7)	0.0703 (8)	0.0002 (6)	0.0095 (6)	−0.0019 (5)
O1A	0.052 (2)	0.070 (2)	0.160 (4)	0.0029 (18)	0.020 (2)	−0.007 (2)
O2A	0.118 (3)	0.069 (3)	0.081 (3)	−0.022 (2)	0.006 (2)	0.0022 (19)
O3A	0.068 (2)	0.072 (3)	0.088 (3)	0.0021 (18)	0.017 (2)	0.009 (2)
O4A	0.090 (3)	0.052 (2)	0.088 (3)	−0.0077 (17)	0.0098 (19)	0.0013 (18)

Geometric parameters (Å, º)

Cu1—N1^i	2.047 (3)	C4—C5	1.509 (5)
Cu1—N1	2.047 (3)	C5—H5AA	0.9900
Cu1—N2	2.015 (3)	C5—H5AB	0.9900
Cu1—N2^i	2.015 (3)	C5—H5BC	0.9900
N1—H1	1.0429	C5—H5BD	0.9900
N1—C2	1.492 (5)	C6—H6A	1.0000
N1—C3	1.505 (5)	C6—H6B	1.0000
N2—H2	1.0228	C6—C7	1.512 (6)
N2—C5	1.489 (5)	C7—H7A	0.9900
N2—C6	1.481 (5)	C7—H7B	0.9900
N1A—H1AA	0.9100	C7—C8	1.543 (6)
N1A—H1AB	0.9100	C8—H8A	0.9900
N1A—C2	1.492 (5)	C8—H8B	0.9900
N1A—C3	1.505 (5)	C8—C9	1.510 (7)
N2A—H2AA	0.8779	C9—H9A	0.9900
N2A—H2AB	0.8809	C9—H9B	0.9900
N2A—C5	1.489 (5)	C10—H10A	0.9900
N2A—C6	1.481 (5)	C10—H10B	0.9900
C1—H1A	0.9937	C10—C11	1.527 (6)
C1—H1B	0.9908	C11—H11A	0.9800
C1—C2	1.514 (6)	C11—H11B	0.9800
C1—C9^i	1.517 (6)	C11—H11C	0.9800
C2—H2A	1.0000	Cl1—O1	1.426 (4)
C2—H2B	1.0000	Cl1—O2	1.423 (4)
C2—C6^i	1.528 (6)	Cl1—O3	1.388 (4)
C3—H3A	1.0000	Cl1—O4	1.428 (4)
C3—H3B	1.0000	Cl1A—O1A	1.423 (11)
C3—C4	1.523 (6)	Cl1A—O2A	1.419 (11)
C3—C10	1.515 (6)	Cl1A—O3A	1.386 (11)
C4—H4A	0.9900	Cl1A—O4A	1.434 (11)
C4—H4B	0.9900
N1^i—Cu1—N1	180.0	N2—C5—H5AA	109.3
N2^i—Cu1—N1^i	94.20 (14)	N2—C5—H5AB	109.3
N2—Cu1—N1	94.20 (14)	N2A—C5—C4	111.7 (3)
N2^i—Cu1—N1	85.80 (14)	N2A—C5—H5BC	109.3
N2—Cu1—N1^i	85.80 (14)	N2A—C5—H5BD	109.3
N2^i—Cu1—N2	180.0	C4—C5—H5AA	109.3
Cu1—N1—H1	101.0	C4—C5—H5AB	109.3
C2—N1—Cu1	107.4 (2)	C4—C5—H5BC	109.3
C2—N1—H1	102.7	C4—C5—H5BD	109.3
C2—N1—C3	116.1 (3)	H5AA—C5—H5AB	107.9
C3—N1—Cu1	122.1 (3)	H5BC—C5—H5BD	107.9
C3—N1—H1	104.6	N2—C6—C2^i	108.3 (3)
Cu1—N2—H2	106.6	N2—C6—H6A	107.7
C5—N2—Cu1	117.7 (3)	N2—C6—C7	114.7 (3)
C5—N2—H2	106.5	N2A—C6—H6B	107.7
C6—N2—Cu1	107.6 (3)	N2A—C6—C7	114.7 (3)
C6—N2—H2	104.3	C2^i—C6—H6A	107.7
C6—N2—C5	113.0 (3)	C2^i—C6—H6B	107.7
H1AA—N1A—H1AB	107.4	C7—C6—C2^i	110.5 (3)
C2—N1A—H1AA	108.3	C7—C6—H6A	107.7
C2—N1A—H1AB	108.3	C7—C6—H6B	107.7
C2—N1A—C3	116.1 (3)	C6—C7—H7A	109.6
C3—N1A—H1AA	108.3	C6—C7—H7B	109.6
C3—N1A—H1AB	108.3	C6—C7—C8	110.4 (4)
H2AA—N2A—H2AB	120.4	H7A—C7—H7B	108.1
C5—N2A—H2AA	105.8	C8—C7—H7A	109.6
C5—N2A—H2AB	105.2	C8—C7—H7B	109.6
C6—N2A—H2AA	106.2	C7—C8—H8A	109.6
C6—N2A—H2AB	106.5	C7—C8—H8B	109.6
C6—N2A—C5	113.0 (3)	H8A—C8—H8B	108.1
H1A—C1—H1B	107.2	C9—C8—C7	110.4 (4)
C2—C1—H1A	108.8	C9—C8—H8A	109.6
C2—C1—H1B	108.7	C9—C8—H8B	109.6
C2—C1—C9^i	112.1 (4)	C1^i—C9—H9A	109.4
C9^i—C1—H1A	109.1	C1^i—C9—H9B	109.4
C9^i—C1—H1B	110.8	C8—C9—C1^i	111.3 (4)
N1—C2—C1	112.9 (3)	C8—C9—H9A	109.4
N1—C2—H2A	108.2	C8—C9—H9B	109.4
N1—C2—C6^i	108.5 (3)	H9A—C9—H9B	108.0
N1A—C2—C1	112.9 (3)	C3—C10—H10A	108.9
N1A—C2—H2B	108.2	C3—C10—H10B	108.9
C1—C2—H2A	108.2	C3—C10—C11	113.5 (4)
C1—C2—H2B	108.2	H10A—C10—H10B	107.7
C1—C2—C6^i	110.8 (3)	C11—C10—H10A	108.9
C6^i—C2—H2A	108.2	C11—C10—H10B	108.9
C6^i—C2—H2B	108.2	C10—C11—H11A	109.5
N1—C3—H3A	107.0	C10—C11—H11B	109.5
N1—C3—C4	108.9 (3)	C10—C11—H11C	109.5
N1—C3—C10	112.1 (4)	H11A—C11—H11B	109.5
N1A—C3—H3B	107.0	H11A—C11—H11C	109.5
N1A—C3—C4	108.9 (3)	H11B—C11—H11C	109.5
N1A—C3—C10	112.1 (4)	O1—Cl1—O4	109.6 (2)
C4—C3—H3A	107.0	O2—Cl1—O1	110.0 (3)
C4—C3—H3B	107.0	O2—Cl1—O4	108.4 (2)
C10—C3—H3A	107.0	O3—Cl1—O1	108.4 (3)
C10—C3—H3B	107.0	O3—Cl1—O2	109.2 (3)
C10—C3—C4	114.3 (4)	O3—Cl1—O4	111.2 (2)
C3—C4—H4A	108.1	O1A—Cl1A—O4A	108 (3)
C3—C4—H4B	108.1	O2A—Cl1A—O1A	113 (3)
H4A—C4—H4B	107.3	O2A—Cl1A—O4A	106 (2)
C5—C4—C3	116.8 (4)	O3A—Cl1A—O1A	109 (3)
C5—C4—H4A	108.1	O3A—Cl1A—O2A	112 (3)
C5—C4—H4B	108.1	O3A—Cl1A—O4A	109 (3)
N2—C5—C4	111.7 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	1.04	2.02	3.028 (5)	162
N1—H1···O3^i	1.04	2.57	3.228 (5)	121
N2—H2···O2^i	1.02	2.12	3.072 (5)	155
N1A—H1AA···N2A	0.91	2.36	2.976 (5)	125
N1A—H1AB···O1A^i	0.91	2.05	2.84 (7)	145
N1A—H1AB···O3A^i	0.91	2.31	2.92 (8)	124
N2A—H2AA···N1A	0.88	2.39	2.976 (5)	124
N2A—H2AB···O1A^i	0.88	2.43	3.03 (7)	126
N2A—H2AB···O2A^i	0.88	2.46	3.17 (7)	137

Symmetry code: (i) −x+1, −y+1, −z+1.