In the title compound, [Cu(NO3)2(C20H40N4)]·3H2O, the Cu atom lies on a crystallographic inversion centre and has a distorted octahedral geometry, with four N atoms of the macrocyclic ligand in the equatorial positions and two O atoms of the axial nitrate ligands. The long axial Cu—O bond of 2.746 (2) Å may result from the Jahn–Teller effect. The macrocyclic ligand adopts the most stable trans-III configuration with the two six-membered rings in chair form and two five-membered rings in a gauche form.
Supporting information
CCDC reference: 621375
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.003 Å
- H-atom completeness 96%
- Disorder in solvent or counterion
- R factor = 0.030
- wR factor = 0.117
- Data-to-parameter ratio = 16.7
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT245_ALERT_2_C U(iso) H4P Smaller than U(eq) O4 by ... 0.01 AngSq
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 25.00 Perc.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2
H2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3
O
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C20 H46 Cu1 N6 O9
Atom count from the _atom_site data: C20 H44 Cu1 N6 O9
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 1
From the CIF: _chemical_formula_sum C20 H46 Cu N6 O9
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 20.00 20.00 0.00
H 46.00 44.00 2.00
Cu 1.00 1.00 0.00
N 6.00 6.00 0.00
O 9.00 9.00 0.00
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
7 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[5,16-Dimethyl-2,6,13,17-tetraazatricyclo[14,4,0
1.18,0
7.12]docosane-
κ4N]dinitratocopper(II) trihydrate
top
Crystal data top
[Cu(NO3)2(C20H40N4)]·3H2O | Z = 1 |
Mr = 578.17 | F(000) = 309 |
Triclinic, P1 | Dx = 1.463 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.813 (5) Å | Cell parameters from 6079 reflections |
b = 8.746 (7) Å | θ = 3.1–27.5° |
c = 10.715 (7) Å | µ = 0.89 mm−1 |
α = 93.06 (3)° | T = 200 K |
β = 106.86 (2)° | Plate, red–pink |
γ = 108.43 (3)° | 0.20 × 0.18 × 0.10 mm |
V = 656.2 (8) Å3 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 2969 independent reflections |
Graphite monochromator | 2809 reflections with F2 > 2σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.016 |
ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −10→9 |
Tmin = 0.842, Tmax = 0.916 | k = −11→11 |
6435 measured reflections | l = −13→13 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0752P)2 + 0.2496P] where P = (Fo2 + 2Fc2)/3 |
2969 reflections | (Δ/σ)max < 0.001 |
178 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu1 | 0.0000 | 0.0000 | 0.0000 | 0.01594 (13) | |
O1 | 0.1797 (3) | −0.2240 (2) | 0.00098 (18) | 0.0340 (4) | |
O2 | 0.2211 (3) | −0.2795 (2) | 0.20003 (16) | 0.0335 (4) | |
O3 | 0.2222 (3) | −0.4498 (2) | 0.04641 (19) | 0.0341 (4) | |
O4 | −0.0160 (4) | −0.5639 (3) | 0.2688 (2) | 0.0493 (6) | |
O5 | −0.0376 (6) | −0.3449 (5) | 0.4723 (4) | 0.0422 (9) | 0.50 |
N1 | 0.0250 (2) | −0.03671 (19) | 0.18891 (15) | 0.0153 (3) | |
H1N | 0.0836 | −0.1147 | 0.2005 | 0.018* | |
N2 | 0.2353 (2) | 0.20037 (19) | 0.08223 (15) | 0.0153 (3) | |
H2N | 0.1927 | 0.2873 | 0.0899 | 0.018* | |
N3 | 0.2077 (2) | −0.3193 (2) | 0.08223 (18) | 0.0219 (4) | |
C1 | 0.1703 (3) | 0.1115 (2) | 0.28035 (18) | 0.0167 (4) | |
H1A | 0.1093 | 0.1951 | 0.2861 | 0.020* | |
C2 | 0.2534 (3) | 0.0784 (3) | 0.4198 (2) | 0.0242 (4) | |
H2A | 0.1502 | 0.0389 | 0.4588 | 0.029* | |
H2B | 0.3092 | −0.0080 | 0.4153 | 0.029* | |
C3 | 0.4067 (4) | 0.2325 (3) | 0.5074 (2) | 0.0304 (5) | |
H3A | 0.3483 | 0.3152 | 0.5193 | 0.036* | |
H3B | 0.4631 | 0.2067 | 0.5955 | 0.036* | |
C4 | 0.5625 (3) | 0.3020 (3) | 0.4467 (2) | 0.0281 (5) | |
H4A | 0.6306 | 0.2243 | 0.4441 | 0.034* | |
H4B | 0.6559 | 0.4055 | 0.5025 | 0.034* | |
C5 | 0.4804 (3) | 0.3339 (3) | 0.3063 (2) | 0.0243 (4) | |
H5A | 0.4241 | 0.4202 | 0.3096 | 0.029* | |
H5B | 0.5840 | 0.3729 | 0.2675 | 0.029* | |
C6 | 0.3276 (3) | 0.1782 (2) | 0.21965 (18) | 0.0166 (4) | |
H6A | 0.3887 | 0.0944 | 0.2145 | 0.020* | |
C7 | 0.3737 (3) | 0.2485 (3) | 0.0084 (2) | 0.0225 (4) | |
H7A | 0.4343 | 0.1649 | 0.0072 | 0.027* | |
H7B | 0.4753 | 0.3533 | 0.0550 | 0.027* | |
C8 | 0.2796 (3) | 0.2669 (2) | −0.13312 (19) | 0.0209 (4) | |
H8A | 0.3812 | 0.3238 | −0.1695 | 0.025* | |
H8B | 0.2036 | 0.3381 | −0.1311 | 0.025* | |
C9 | 0.1502 (3) | 0.1094 (2) | −0.22755 (19) | 0.0168 (4) | |
H9A | 0.1084 | 0.1385 | −0.3177 | 0.020* | |
C10 | 0.2519 (3) | −0.0120 (3) | −0.2355 (2) | 0.0253 (4) | |
H10A | 0.1628 | −0.1109 | −0.2971 | 0.030* | |
H10B | 0.2983 | −0.0402 | −0.1477 | 0.030* | |
H10C | 0.3600 | 0.0373 | −0.2667 | 0.030* | |
H4P | 0.058 (5) | −0.493 (4) | 0.250 (3) | 0.036 (8)* | |
H4O | −0.087 (6) | −0.614 (5) | 0.194 (4) | 0.052 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01456 (19) | 0.01781 (19) | 0.01349 (19) | 0.00250 (13) | 0.00538 (13) | 0.00097 (12) |
O1 | 0.0451 (10) | 0.0340 (9) | 0.0345 (9) | 0.0213 (8) | 0.0202 (8) | 0.0144 (7) |
O2 | 0.0456 (10) | 0.0325 (9) | 0.0225 (8) | 0.0194 (8) | 0.0052 (7) | 0.0014 (6) |
O3 | 0.0390 (10) | 0.0233 (8) | 0.0460 (10) | 0.0155 (7) | 0.0184 (8) | 0.0006 (7) |
O4 | 0.0717 (16) | 0.0382 (11) | 0.0344 (11) | 0.0143 (11) | 0.0168 (11) | 0.0096 (9) |
O5 | 0.043 (2) | 0.043 (2) | 0.047 (2) | 0.0174 (17) | 0.0201 (18) | 0.0121 (17) |
N1 | 0.0168 (8) | 0.0146 (7) | 0.0145 (7) | 0.0046 (6) | 0.0061 (6) | 0.0013 (6) |
N2 | 0.0140 (7) | 0.0163 (7) | 0.0152 (7) | 0.0035 (6) | 0.0061 (6) | 0.0020 (6) |
N3 | 0.0182 (8) | 0.0208 (8) | 0.0267 (9) | 0.0075 (7) | 0.0066 (7) | 0.0030 (7) |
C1 | 0.0185 (9) | 0.0159 (8) | 0.0142 (8) | 0.0045 (7) | 0.0050 (7) | 0.0002 (6) |
C2 | 0.0269 (10) | 0.0264 (10) | 0.0141 (9) | 0.0042 (8) | 0.0042 (8) | 0.0046 (7) |
C3 | 0.0334 (12) | 0.0323 (12) | 0.0142 (9) | 0.0038 (10) | 0.0002 (9) | 0.0003 (8) |
C4 | 0.0216 (10) | 0.0312 (11) | 0.0205 (10) | 0.0014 (9) | −0.0006 (8) | 0.0015 (8) |
C5 | 0.0226 (10) | 0.0220 (10) | 0.0192 (10) | 0.0003 (8) | 0.0018 (8) | 0.0025 (7) |
C6 | 0.0158 (8) | 0.0166 (8) | 0.0159 (9) | 0.0053 (7) | 0.0035 (7) | 0.0027 (7) |
C7 | 0.0167 (9) | 0.0285 (10) | 0.0189 (9) | 0.0020 (8) | 0.0075 (8) | 0.0039 (8) |
C8 | 0.0233 (10) | 0.0181 (9) | 0.0185 (9) | 0.0022 (7) | 0.0082 (8) | 0.0037 (7) |
C9 | 0.0177 (9) | 0.0182 (9) | 0.0168 (9) | 0.0049 (7) | 0.0100 (7) | 0.0049 (7) |
C10 | 0.0281 (11) | 0.0227 (10) | 0.0320 (11) | 0.0103 (8) | 0.0178 (9) | 0.0056 (8) |
Geometric parameters (Å, º) top
Cu1—N2 | 2.021 (2) | N1—H1N | 0.9300 |
Cu1—N1 | 2.029 (2) | N2—H2N | 0.9300 |
Cu1—O1 | 2.746 (2) | C1—H1A | 1.0000 |
O1—N3 | 1.258 (2) | C2—H2A | 0.9900 |
O2—N3 | 1.256 (3) | C2—H2B | 0.9900 |
O3—N3 | 1.234 (3) | C3—H3A | 0.9900 |
N1—C1 | 1.489 (3) | C3—H3B | 0.9900 |
N1—C9i | 1.501 (2) | C4—H4A | 0.9900 |
N2—C7 | 1.489 (3) | C4—H4B | 0.9900 |
N2—C6 | 1.493 (3) | C5—H5A | 0.9900 |
C1—C6 | 1.524 (3) | C5—H5B | 0.9900 |
C1—C2 | 1.529 (3) | C6—H6A | 1.0000 |
C2—C3 | 1.525 (3) | C7—H7A | 0.9900 |
C3—C4 | 1.520 (3) | C7—H7B | 0.9900 |
C4—C5 | 1.533 (3) | C8—H8A | 0.9900 |
C5—C6 | 1.528 (3) | C8—H8B | 0.9900 |
C7—C8 | 1.523 (3) | C9—H9A | 1.0000 |
C8—C9 | 1.524 (3) | C10—H10A | 0.9800 |
C9—C10 | 1.526 (3) | C10—H10B | 0.9800 |
O4—H4P | 0.79 (4) | C10—H10C | 0.9800 |
O4—H4O | 0.84 (4) | | |
| | | |
N2—Cu1—N1 | 85.04 (7) | C1—C2—H2A | 109.4 |
N2—Cu1—O1 | 97.83 (9) | C3—C2—H2B | 109.4 |
N1—Cu1—O1 | 84.08 (6) | C1—C2—H2B | 109.4 |
N1—Cu1—N2i | 94.96 (7) | H2A—C2—H2B | 108.0 |
N1—Cu1—O1i | 95.92 (6) | C4—C3—H3A | 109.5 |
N2—Cu1—O1i | 82.17 (9) | C2—C3—H3A | 109.5 |
N3—O1—Cu1 | 129.37 (14) | C4—C3—H3B | 109.5 |
C1—N1—C9i | 114.46 (15) | C2—C3—H3B | 109.5 |
C1—N1—Cu1 | 108.90 (12) | H3A—C3—H3B | 108.0 |
C9i—N1—Cu1 | 120.16 (12) | C3—C4—H4A | 109.3 |
C7—N2—C6 | 112.03 (16) | C5—C4—H4A | 109.3 |
C7—N2—Cu1 | 117.40 (13) | C3—C4—H4B | 109.3 |
C6—N2—Cu1 | 107.32 (12) | C5—C4—H4B | 109.3 |
O3—N3—O2 | 120.65 (18) | H4A—C4—H4B | 108.0 |
O3—N3—O1 | 120.26 (19) | C6—C5—H5A | 109.5 |
O2—N3—O1 | 119.08 (18) | C4—C5—H5A | 109.5 |
N1—C1—C6 | 107.45 (15) | C6—C5—H5B | 109.5 |
N1—C1—C2 | 113.26 (16) | C4—C5—H5B | 109.5 |
C6—C1—C2 | 110.51 (17) | H5A—C5—H5B | 108.1 |
C3—C2—C1 | 110.98 (18) | N2—C6—H6A | 108.2 |
C4—C3—C2 | 110.93 (19) | C1—C6—H6A | 108.2 |
C3—C4—C5 | 111.44 (19) | C5—C6—H6A | 108.2 |
C6—C5—C4 | 110.55 (17) | N2—C7—H7A | 109.1 |
N2—C6—C1 | 107.48 (16) | C8—C7—H7A | 109.1 |
N2—C6—C5 | 113.92 (16) | N2—C7—H7B | 109.1 |
C1—C6—C5 | 110.62 (17) | C8—C7—H7B | 109.1 |
N2—C7—C8 | 112.35 (17) | H7A—C7—H7B | 107.9 |
C7—C8—C9 | 116.18 (17) | C7—C8—H8A | 108.2 |
N1i—C9—C8 | 109.32 (16) | C9—C8—H8A | 108.2 |
N1i—C9—C10 | 111.96 (16) | C7—C8—H8B | 108.2 |
C8—C9—C10 | 112.68 (18) | C9—C8—H8B | 108.2 |
H4P—O4—H4O | 101 (3) | H8A—C8—H8B | 107.4 |
C1—N1—H1N | 103.7 | N1i—C9—H9A | 107.5 |
C9i—N1—H1N | 103.7 | C8—C9—H9A | 107.5 |
Cu1—N1—H1N | 103.7 | C10—C9—H9A | 107.5 |
C7—N2—H2N | 106.5 | C9—C10—H10A | 109.5 |
C6—N2—H2N | 106.5 | C9—C10—H10B | 109.5 |
Cu1—N2—H2N | 106.5 | H10A—C10—H10B | 109.5 |
N1—C1—H1A | 108.5 | C9—C10—H10C | 109.5 |
C6—C1—H1A | 108.5 | H10A—C10—H10C | 109.5 |
C2—C1—H1A | 108.5 | H10B—C10—H10C | 109.5 |
C3—C2—H2A | 109.4 | | |
| | | |
N2—Cu1—O1—N3 | 97.99 (19) | Cu1—N1—C1—C2 | −159.17 (14) |
N2i—Cu1—O1—N3 | −82.01 (19) | N1—C1—C2—C3 | 177.75 (17) |
N1—Cu1—O1—N3 | 13.85 (18) | C6—C1—C2—C3 | 57.1 (2) |
N1i—Cu1—O1—N3 | −166.15 (18) | C1—C2—C3—C4 | −56.0 (3) |
N2—Cu1—N1—C1 | 10.43 (12) | C2—C3—C4—C5 | 55.5 (3) |
N2i—Cu1—N1—C1 | −169.57 (12) | C3—C4—C5—C6 | −55.9 (3) |
O1—Cu1—N1—C1 | 108.85 (13) | C7—N2—C6—C1 | −173.90 (15) |
N2—Cu1—N1—C9i | 145.27 (14) | Cu1—N2—C6—C1 | −43.64 (16) |
N2i—Cu1—N1—C9i | −34.73 (14) | C7—N2—C6—C5 | 63.2 (2) |
O1—Cu1—N1—C9i | −116.31 (14) | Cu1—N2—C6—C5 | −166.58 (14) |
N1—Cu1—N2—C7 | 145.82 (14) | N1—C1—C6—N2 | 53.49 (19) |
N1i—Cu1—N2—C7 | −34.18 (14) | C2—C1—C6—N2 | 177.52 (15) |
O1—Cu1—N2—C7 | 62.50 (14) | N1—C1—C6—C5 | 178.44 (15) |
N1—Cu1—N2—C6 | 18.65 (12) | C2—C1—C6—C5 | −57.5 (2) |
N1i—Cu1—N2—C6 | −161.35 (12) | C4—C5—C6—N2 | 177.97 (18) |
O1—Cu1—N2—C6 | −64.67 (12) | C4—C5—C6—C1 | 56.8 (2) |
Cu1—O1—N3—O3 | 152.16 (16) | C6—N2—C7—C8 | 178.46 (15) |
Cu1—O1—N3—O2 | −28.0 (3) | Cu1—N2—C7—C8 | 53.6 (2) |
C9i—N1—C1—C6 | −174.50 (14) | N2—C7—C8—C9 | −71.5 (2) |
Cu1—N1—C1—C6 | −36.83 (16) | C7—C8—C9—N1i | 68.7 (2) |
C9i—N1—C1—C2 | 63.2 (2) | C7—C8—C9—C10 | −56.5 (2) |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2 | 0.93 | 2.05 | 2.975 (3) | 171 |
N2—H2N···O3ii | 0.93 | 2.32 | 3.133 (3) | 145 |
O4—H4P···O2 | 0.79 (4) | 2.10 (3) | 2.870 (3) | 169 (4) |
O4—H4O···O1iii | 0.84 (4) | 2.25 (4) | 3.036 (2) | 158 (4) |
Symmetry codes: (ii) x, y+1, z; (iii) −x, −y−1, −z. |