Bis(nitrato-κO)(5,7,12,14-tetra­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-6,13-diaminium-κ⁴ N ¹,N ⁴,N ⁸,N ¹¹)copper(II) dinitrate tetra­hydrate

Abstract

In the title compound, [Cu(NO₃)₂(C₁₄H₃₆N₆)](NO₃)₂·4H₂O, the Cu^II atom, lying on an inversion center, is six-coordinated in a distorted octa­hedral environment by four N atoms from a centrosymmetric 14-membered tetra­aza­cyclo­tetra­decane macrocyclic ligand and two O atoms from two nitrate anions. The supra­molecular network is consolidated by extensive O—H⋯O and N—H⋯O hydrogen-bonding inter­actions.

Related literature

For Cu(II) complexes of related macrocyclic ligands, see: Bernhardt (1999 ▶); Bernhardt & Sharpe (1998 ▶).

Experimental

Crystal data

• [Cu(NO₃)₂(C₁₄H₃₆N₆)](NO₃)₂·4H₂O

• M _r = 672.14

• Monoclinic,

• a = 9.201 (2) Å

• b = 16.576 (4) Å

• c = 9.278 (2) Å

• β = 98.788 (4)°

• V = 1398.4 (5) ų

• Z = 2

• Mo Kα radiation

• μ = 0.87 mm⁻¹

• T = 123 K

• 0.37 × 0.34 × 0.31 mm

Data collection

• Bruker SMART 1000 CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.739, T _max = 0.774

• 6071 measured reflections

• 3021 independent reflections

• 2269 reflections with I > 2σ(I)

• R _int = 0.027

Refinement

• R[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 0.133

• S = 1.03

• 3021 reflections

• 202 parameters

• 6 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 1.24 e Å⁻³

• Δρ_min = −0.81 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O3	0.93	2.43	3.155 (4)	134
N1—H1C⋯O2Wi	0.93	2.28	3.096 (4)	146
N2—H2A⋯O3	0.93	2.52	3.244 (4)	135
N2—H2A⋯O4ii	0.93	2.47	3.249 (4)	141
N3—H3D⋯O4	0.91	2.08	2.924 (4)	155
N3—H3E⋯O1Wiii	0.91	1.86	2.748 (4)	164
N3—H3F⋯O2i	0.91	2.06	2.902 (4)	154
N3—H3F⋯O3i	0.91	2.32	3.108 (4)	145
O1W—H1WA⋯O2i	0.84 (4)	2.01 (3)	2.823 (4)	160 (5)
O1W—H1WB⋯O5iv	0.84 (2)	1.97 (2)	2.795 (4)	168 (5)
O2W—H2WA⋯O6ii	0.93 (5)	2.00 (5)	2.913 (5)	166 (5)
O2W—H2WB⋯O6v	0.92 (2)	2.18 (2)	3.084 (5)	167 (5)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

In the past, much attention has been given to the copper complexes of macrocyclic trans-5(R),7(R),12(R), 14(R)-tetramethyl-6, 13-dinitro-1,4,8,11-tetraazacyclotetradecane and related ligands (Bernhardt, 1999; Bernhardt & Sharpe, 1998). Recently, we have synthesized a Cu(II) complex based on 5,7,12,14-tetramethyl-6,13- diamino-1,4,8,11-tetraazacyclotetradecane and its structure is reported here.

The asymmetric unit of the title compound (Fig. 1) contains one Cu^II ion lying on an inversion center, one half of a 14-membered tetraazacyclotetradecane macrocyclic ligand, one coordinated nitrate anion, one uncoordinated nitrate anion and two solvent water molecules. The Cu^II ion has a slightly distorted octahedral coordination geometry, with two O atoms from two nitrate anions in the axial positions. The equatorial positions are occupied by four N atoms from the centrosymmetric 14-membered tetraazacyclotetradecane macrocyclic ligand [Cu1—N1 2.025 (2) and Cu1—N2 2.020 (2) Å]. The two uncoordinated nitrate anions are located above and below the 14-membered tetraazacyclotetradecane macrocycle and linked to the macrocycle via N—H···O hydrogen bonds (Table 1).

Experimental

An aqueous solution of 5,7,12,14-tetramethyl-6,13-diamino-1,4,8,11-tetraazacyclotetradecane (0.27 g, 1.0 mmol), Cu(NO₃)₂ (0.10 g, 0.5 mmol) and Na₂CO₃ (0.05 g, 0.5 mmol) was heated to reflux for 24 h. The reaction mixture was cooled to room temperature and red crystals of the title compound were obtained by slow evaporation of the solvent at room temperature.

Refinement

H atoms bound to C and N atoms were placed at calculated positions and were treated as riding on the parent atoms, with C—H = 1.00 (CH), 0.99 (CH₂) and 0.98 (CH₃) Å and N—H = 0.93 (NH) and 0.91 (NH₃) Å and with U_iso(H) = 1.2–1.5 U_eq(C, N). H atoms attached to water molecules were located in a difference Fourier map and refined with U_iso(H) = 1.2U_eq(O). The highest residual electron density was found 0.91 Å from O3 the deepest hole 0.52 Å from H2WA.

Figures

Fig. 1.

The molecular structure of the title compound. Displacement ellipsoids are shown at the 30% probability level. H atoms have been omitted for clarity. [Symmetry code: (i) 2-x, -y, 1-z.]

Crystal data

[Cu(NO3)2(C14H36N6)](NO3)2·4H2O	F(000) = 710
Mr = 672.14	Dx = 1.596 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2543 reflections
a = 9.201 (2) Å	θ = 2.5–27.0°
b = 16.576 (4) Å	µ = 0.87 mm−1
c = 9.278 (2) Å	T = 123 K
β = 98.788 (4)°	Block, red
V = 1398.4 (5) Å3	0.37 × 0.34 × 0.31 mm
Z = 2

Data collection

Bruker SMART 1000 CCD diffractometer	3021 independent reflections
Radiation source: fine-focus sealed tube	2269 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 27.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
Tmin = 0.739, Tmax = 0.774	k = −21→17
6071 measured reflections	l = −10→11

Refinement

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0649P)2 + 2.4391P] where P = (Fo2 + 2Fc2)/3
3021 reflections	(Δ/σ)max = 0.036
202 parameters	Δρmax = 1.24 e Å−3
6 restraints	Δρmin = −0.81 e Å−3

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

	x	y	z	Uiso*/Ueq
C1	0.8753 (4)	0.0883 (2)	0.2521 (3)	0.0169 (7)
H1A	0.9413	0.1356	0.2695	0.020*
H1B	0.7886	0.1039	0.1807	0.020*
C2	0.7676 (3)	0.13149 (18)	0.4684 (3)	0.0136 (6)
H2	0.8477	0.1722	0.4930	0.016*
C3	0.6400 (4)	0.1717 (2)	0.3687 (3)	0.0234 (8)
H3A	0.6749	0.1921	0.2809	0.035*
H3B	0.6019	0.2167	0.4205	0.035*
H3C	0.5616	0.1322	0.3408	0.035*
C4	0.7205 (3)	0.10160 (19)	0.6114 (3)	0.0129 (6)
H4	0.6574	0.0527	0.5888	0.016*
C5	0.8448 (3)	0.08013 (19)	0.7366 (3)	0.0137 (6)
H5	0.7973	0.0642	0.8224	0.016*
C6	0.9474 (3)	0.15076 (19)	0.7843 (3)	0.0167 (7)
H6A	1.0086	0.1378	0.8774	0.025*
H6B	0.8889	0.1991	0.7960	0.025*
H6C	1.0105	0.1608	0.7102	0.025*
C7	1.0453 (3)	−0.0192 (2)	0.8066 (3)	0.0170 (7)
H7A	1.0050	−0.0366	0.8947	0.020*
H7B	1.1144	0.0259	0.8342	0.020*
Cu1	1.0000	0.0000	0.5000	0.01124 (16)
N1	0.8274 (3)	0.06223 (16)	0.3922 (2)	0.0120 (5)
H1C	0.7509	0.0256	0.3683	0.014*
N2	0.9236 (3)	0.00785 (15)	0.6924 (3)	0.0128 (5)
H2A	0.8545	−0.0334	0.6882	0.015*
N3	0.6297 (3)	0.16570 (17)	0.6691 (3)	0.0173 (6)
H3D	0.6722	0.2147	0.6611	0.026*
H3E	0.6241	0.1555	0.7645	0.026*
H3F	0.5376	0.1657	0.6167	0.026*
N5	0.7860 (3)	0.36290 (18)	0.6169 (3)	0.0214 (6)
O4	0.6922 (3)	0.33861 (18)	0.6897 (3)	0.0377 (7)
O5	0.8513 (3)	0.31313 (17)	0.5511 (3)	0.0399 (7)
O6	0.8117 (3)	0.43623 (16)	0.6061 (4)	0.0402 (7)
O1W	0.1266 (3)	0.33514 (16)	0.4647 (3)	0.0236 (5)
O2W	0.4173 (4)	0.0272 (3)	0.8131 (4)	0.0592 (10)
H1WA	0.168 (5)	0.291 (2)	0.489 (6)	0.071*
H1WB	0.039 (3)	0.334 (3)	0.481 (6)	0.071*
H2WA	0.494 (5)	−0.008 (3)	0.846 (6)	0.071*
H2WB	0.396 (6)	0.045 (3)	0.901 (3)	0.071*
N4	0.7300 (3)	−0.14301 (18)	0.4733 (3)	0.0233 (6)
O1	0.8658 (2)	−0.13506 (15)	0.4843 (2)	0.0226 (5)
O2	0.6711 (3)	−0.21048 (15)	0.4441 (3)	0.0252 (6)
O3	0.6522 (3)	−0.08487 (18)	0.4963 (4)	0.0520 (9)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0194 (16)	0.0188 (17)	0.0124 (14)	0.0044 (13)	0.0023 (11)	0.0043 (12)
C2	0.0175 (15)	0.0104 (15)	0.0122 (14)	0.0038 (12)	0.0004 (11)	0.0000 (11)
C3	0.0233 (18)	0.032 (2)	0.0150 (15)	0.0136 (15)	0.0039 (13)	0.0031 (14)
C4	0.0113 (14)	0.0153 (16)	0.0120 (13)	0.0026 (12)	0.0014 (11)	−0.0013 (11)
C5	0.0141 (15)	0.0155 (16)	0.0117 (13)	0.0025 (12)	0.0021 (11)	0.0011 (11)
C6	0.0171 (15)	0.0130 (16)	0.0192 (15)	0.0000 (12)	−0.0003 (12)	−0.0031 (12)
C7	0.0175 (15)	0.0232 (18)	0.0094 (13)	0.0068 (13)	−0.0009 (11)	0.0019 (11)
Cu1	0.0120 (3)	0.0135 (3)	0.0079 (2)	0.0030 (2)	0.00051 (17)	0.0002 (2)
N1	0.0121 (12)	0.0128 (13)	0.0112 (11)	0.0008 (10)	0.0022 (9)	−0.0003 (10)
N2	0.0123 (12)	0.0143 (14)	0.0113 (11)	0.0017 (10)	−0.0001 (9)	0.0009 (10)
N3	0.0161 (13)	0.0226 (16)	0.0134 (12)	0.0050 (11)	0.0030 (10)	−0.0006 (11)
N5	0.0167 (14)	0.0227 (16)	0.0244 (14)	0.0033 (12)	0.0021 (11)	0.0008 (12)
O4	0.0357 (16)	0.0389 (17)	0.0442 (16)	0.0024 (13)	0.0241 (13)	0.0093 (13)
O5	0.0442 (17)	0.0260 (15)	0.0558 (18)	−0.0001 (13)	0.0282 (14)	−0.0111 (13)
O6	0.0382 (16)	0.0149 (14)	0.071 (2)	−0.0009 (12)	0.0184 (14)	−0.0028 (13)
O1W	0.0252 (13)	0.0268 (14)	0.0192 (12)	−0.0001 (11)	0.0047 (10)	0.0005 (10)
O2W	0.051 (2)	0.068 (3)	0.056 (2)	0.0019 (19)	−0.0006 (17)	−0.0158 (19)
N4	0.0187 (14)	0.0206 (16)	0.0305 (16)	−0.0036 (12)	0.0031 (12)	−0.0016 (12)
O1	0.0153 (11)	0.0264 (14)	0.0268 (12)	−0.0057 (10)	0.0053 (9)	−0.0017 (10)
O2	0.0212 (12)	0.0197 (13)	0.0327 (13)	−0.0060 (10)	−0.0022 (10)	−0.0022 (10)
O3	0.0230 (15)	0.0230 (16)	0.111 (3)	0.0001 (12)	0.0151 (16)	−0.0074 (17)

Geometric parameters (Å, °)

C1—N1	1.499 (4)	C7—C1i	1.505 (4)
C1—C7i	1.505 (4)	C7—H7A	0.9900
C1—H1A	0.9900	C7—H7B	0.9900
C1—H1B	0.9900	Cu1—N2	2.020 (2)
C2—N1	1.496 (4)	Cu1—N1	2.025 (2)
C2—C3	1.532 (4)	Cu1—O1	2.550 (2)
C2—C4	1.539 (4)	N1—H1C	0.9300
C2—H2	1.0000	N2—H2A	0.9300
C3—H3A	0.9800	N3—H3D	0.9100
C3—H3B	0.9800	N3—H3E	0.9100
C3—H3C	0.9800	N3—H3F	0.9100
C4—N3	1.500 (4)	N5—O5	1.235 (4)
C4—C5	1.542 (4)	N5—O4	1.241 (4)
C4—H4	1.0000	N5—O6	1.245 (4)
C5—N2	1.491 (4)	O1W—H1WA	0.84 (4)
C5—C6	1.526 (4)	O1W—H1WB	0.84 (2)
C5—H5	1.0000	O2W—H2WA	0.93 (5)
C6—H6A	0.9800	O2W—H2WB	0.91 (2)
C6—H6B	0.9800	N4—O3	1.239 (4)
C6—H6C	0.9800	N4—O1	1.245 (4)
C7—N2	1.488 (3)	N4—O2	1.254 (4)
N1—C1—C7i	108.5 (2)	N2—C7—H7A	109.9
N1—C1—H1A	110.0	C1i—C7—H7A	109.9
C7i—C1—H1A	110.0	N2—C7—H7B	109.9
N1—C1—H1B	110.0	C1i—C7—H7B	109.9
C7i—C1—H1B	110.0	H7A—C7—H7B	108.3
H1A—C1—H1B	108.4	N2i—Cu1—N1	87.06 (10)
N1—C2—C3	110.6 (2)	N2—Cu1—N1	92.94 (10)
N1—C2—C4	109.4 (2)	O1—Cu1—N1	94.74 (9)
C3—C2—C4	111.7 (3)	O1—Cu1—N2	82.89 (8)
N1—C2—H2	108.3	O1—Cu1—N1i	85.26 (9)
C3—C2—H2	108.3	O1—Cu1—N2i	97.11 (8)
C4—C2—H2	108.3	C2—N1—C1	111.5 (2)
C2—C3—H3A	109.5	C2—N1—Cu1	118.36 (17)
C2—C3—H3B	109.5	C1—N1—Cu1	105.27 (18)
H3A—C3—H3B	109.5	C2—N1—H1C	107.1
C2—C3—H3C	109.5	C1—N1—H1C	107.1
H3A—C3—H3C	109.5	Cu1—N1—H1C	107.1
H3B—C3—H3C	109.5	C7—N2—C5	113.0 (2)
N3—C4—C2	109.0 (2)	C7—N2—Cu1	106.55 (18)
N3—C4—C5	106.5 (2)	C5—N2—Cu1	123.02 (18)
C2—C4—C5	116.8 (3)	C7—N2—H2A	104.1
N3—C4—H4	108.1	C5—N2—H2A	104.1
C2—C4—H4	108.1	Cu1—N2—H2A	104.1
C5—C4—H4	108.1	C4—N3—H3D	109.5
N2—C5—C6	113.0 (2)	C4—N3—H3E	109.5
N2—C5—C4	108.3 (2)	H3D—N3—H3E	109.5
C6—C5—C4	113.3 (3)	C4—N3—H3F	109.5
N2—C5—H5	107.3	H3D—N3—H3F	109.5
C6—C5—H5	107.3	H3E—N3—H3F	109.5
C4—C5—H5	107.3	O5—N5—O4	118.9 (3)
C5—C6—H6A	109.5	O5—N5—O6	120.0 (3)
C5—C6—H6B	109.5	O4—N5—O6	121.1 (3)
H6A—C6—H6B	109.5	H1WA—O1W—H1WB	109 (4)
C5—C6—H6C	109.5	H2WA—O2W—H2WB	99 (4)
H6A—C6—H6C	109.5	O3—N4—O1	120.2 (3)
H6B—C6—H6C	109.5	O3—N4—O2	119.3 (3)
N2—C7—C1i	109.0 (2)	O1—N4—O2	120.5 (3)
N1—C2—C4—N3	−167.0 (2)	N2i—Cu1—N1—C2	−142.1 (2)
C3—C2—C4—N3	−44.1 (3)	N2—Cu1—N1—C2	37.9 (2)
N1—C2—C4—C5	72.4 (3)	N2i—Cu1—N1—C1	−16.78 (19)
C3—C2—C4—C5	−164.7 (3)	N2—Cu1—N1—C1	163.22 (19)
N3—C4—C5—N2	171.2 (2)	C1i—C7—N2—C5	−175.9 (3)
C2—C4—C5—N2	−66.9 (3)	C1i—C7—N2—Cu1	−37.9 (3)
N3—C4—C5—C6	−62.6 (3)	C6—C5—N2—C7	54.5 (3)
C2—C4—C5—C6	59.3 (3)	C4—C5—N2—C7	−179.2 (2)
C3—C2—N1—C1	56.7 (3)	C6—C5—N2—Cu1	−75.7 (3)
C4—C2—N1—C1	−179.9 (2)	C4—C5—N2—Cu1	50.7 (3)
C3—C2—N1—Cu1	178.9 (2)	N1i—Cu1—N2—C7	11.4 (2)
C4—C2—N1—Cu1	−57.6 (3)	N1—Cu1—N2—C7	−168.6 (2)
C7i—C1—N1—C2	171.5 (2)	N1i—Cu1—N2—C5	144.2 (2)
C7i—C1—N1—Cu1	42.0 (3)	N1—Cu1—N2—C5	−35.8 (2)

Symmetry codes: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3	0.93	2.43	3.155 (4)	134
N1—H1C···O2Wii	0.93	2.28	3.096 (4)	146
N2—H2A···O3	0.93	2.52	3.244 (4)	135
N2—H2A···O4iii	0.93	2.47	3.249 (4)	141
N3—H3D···O4	0.91	2.08	2.924 (4)	155
N3—H3E···O1Wiv	0.91	1.86	2.748 (4)	164
N3—H3F···O2ii	0.91	2.06	2.902 (4)	154
N3—H3F···O3ii	0.91	2.32	3.108 (4)	145
O1W—H1WA···O2ii	0.84 (4)	2.01 (3)	2.823 (4)	160 (5)
O1W—H1WB···O5v	0.84 (2)	1.97 (2)	2.795 (4)	168 (5)
O2W—H2WA···O6iii	0.93 (5)	2.00 (5)	2.913 (5)	166 (5)
O2W—H2WB···O6vi	0.92 (2)	2.18 (2)	3.084 (5)	167 (5)

Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x+3/2, y−1/2, −z+3/2; (iv) x+1/2, −y+1/2, z+1/2; (v) x−1, y, z; (vi) x−1/2, −y+1/2, z+1/2.