(5,16-Dimethyl-2,6,13,17-tetra­azatricyclo­[14,4,0^1,18,0^7,12]docosane-κ⁴N)dinitratocopper(II) trihydrate

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.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](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

---

Computing details

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

Crystal data

[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) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	2969 independent reflections
Graphite monochromator	2809 reflections with F^2 > 2σ(F^2)
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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	w = 1/[σ^2(Fo^2) + (0.0752P)^2 + 0.2496P] where P = (Fo^2 + 2Fc^2)/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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—C9^i	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—N2^i	94.96 (7)	H2A—C2—H2B	108.0
N1—Cu1—O1^i	95.92 (6)	C4—C3—H3A	109.5
N2—Cu1—O1^i	82.17 (9)	C2—C3—H3A	109.5
N3—O1—Cu1	129.37 (14)	C4—C3—H3B	109.5
C1—N1—C9^i	114.46 (15)	C2—C3—H3B	109.5
C1—N1—Cu1	108.90 (12)	H3A—C3—H3B	108.0
C9^i—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
N1^i—C9—C8	109.32 (16)	C9—C8—H8A	108.2
N1^i—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	N1^i—C9—H9A	107.5
C9^i—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)
N2^i—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)
N1^i—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)
N2^i—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—C9^i	145.27 (14)	Cu1—N2—C6—C1	−43.64 (16)
N2^i—Cu1—N1—C9^i	−34.73 (14)	C7—N2—C6—C5	63.2 (2)
O1—Cu1—N1—C9^i	−116.31 (14)	Cu1—N2—C6—C5	−166.58 (14)
N1—Cu1—N2—C7	145.82 (14)	N1—C1—C6—N2	53.49 (19)
N1^i—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)
N1^i—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)
C9^i—N1—C1—C6	−174.50 (14)	N2—C7—C8—C9	−71.5 (2)
Cu1—N1—C1—C6	−36.83 (16)	C7—C8—C9—N1^i	68.7 (2)
C9^i—N1—C1—C2	63.2 (2)	C7—C8—C9—C10	−56.5 (2)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

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···O3^ii	0.93	2.32	3.133 (3)	145
O4—H4P···O2	0.79 (4)	2.10 (3)	2.870 (3)	169 (4)
O4—H4O···O1^iii	0.84 (4)	2.25 (4)	3.036 (2)	158 (4)

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