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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): m837.
Published online 2010 June 23. doi:  10.1107/S1600536810023342
PMCID: PMC3006849

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 CuII 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 [triangle]); Bernhardt & Sharpe (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m837-scheme1.jpg

Experimental

Crystal data

  • [Cu(NO3)2(C14H36N6)](NO3)2·4H2O
  • M r = 672.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m837-efi1.jpg
  • a = 9.201 (2) Å
  • b = 16.576 (4) Å
  • c = 9.278 (2) Å
  • β = 98.788 (4)°
  • V = 1398.4 (5) Å3
  • 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 [triangle]) 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
  • Δρmax = 1.24 e Å−3
  • Δρmin = −0.81 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810023342/hy2316sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023342/hy2316Isup2.hkl

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

Acknowledgments

The authors acknowledge Henan University of Urban Construction for supporting this work.

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 CuII 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 CuII 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 Uiso(H) = 1.2–1.5 Ueq(C, N). H atoms attached to water molecules were located in a difference Fourier map and refined with Uiso(H) = 1.2Ueq(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)2·4H2OF(000) = 710
Mr = 672.14Dx = 1.596 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2543 reflections
a = 9.201 (2) Åθ = 2.5–27.0°
b = 16.576 (4) ŵ = 0.87 mm1
c = 9.278 (2) ÅT = 123 K
β = 98.788 (4)°Block, red
V = 1398.4 (5) Å30.37 × 0.34 × 0.31 mm
Z = 2

Data collection

Bruker SMART 1000 CCD diffractometer3021 independent reflections
Radiation source: fine-focus sealed tube2269 reflections with I > 2σ(I)
graphiteRint = 0.027
[var phi] and ω scansθmax = 27.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −11→11
Tmin = 0.739, Tmax = 0.774k = −21→17
6071 measured reflectionsl = −10→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0649P)2 + 2.4391P] where P = (Fo2 + 2Fc2)/3
3021 reflections(Δ/σ)max = 0.036
202 parametersΔρmax = 1.24 e Å3
6 restraintsΔρmin = −0.81 e Å3

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

xyzUiso*/Ueq
C10.8753 (4)0.0883 (2)0.2521 (3)0.0169 (7)
H1A0.94130.13560.26950.020*
H1B0.78860.10390.18070.020*
C20.7676 (3)0.13149 (18)0.4684 (3)0.0136 (6)
H20.84770.17220.49300.016*
C30.6400 (4)0.1717 (2)0.3687 (3)0.0234 (8)
H3A0.67490.19210.28090.035*
H3B0.60190.21670.42050.035*
H3C0.56160.13220.34080.035*
C40.7205 (3)0.10160 (19)0.6114 (3)0.0129 (6)
H40.65740.05270.58880.016*
C50.8448 (3)0.08013 (19)0.7366 (3)0.0137 (6)
H50.79730.06420.82240.016*
C60.9474 (3)0.15076 (19)0.7843 (3)0.0167 (7)
H6A1.00860.13780.87740.025*
H6B0.88890.19910.79600.025*
H6C1.01050.16080.71020.025*
C71.0453 (3)−0.0192 (2)0.8066 (3)0.0170 (7)
H7A1.0050−0.03660.89470.020*
H7B1.11440.02590.83420.020*
Cu11.00000.00000.50000.01124 (16)
N10.8274 (3)0.06223 (16)0.3922 (2)0.0120 (5)
H1C0.75090.02560.36830.014*
N20.9236 (3)0.00785 (15)0.6924 (3)0.0128 (5)
H2A0.8545−0.03340.68820.015*
N30.6297 (3)0.16570 (17)0.6691 (3)0.0173 (6)
H3D0.67220.21470.66110.026*
H3E0.62410.15550.76450.026*
H3F0.53760.16570.61670.026*
N50.7860 (3)0.36290 (18)0.6169 (3)0.0214 (6)
O40.6922 (3)0.33861 (18)0.6897 (3)0.0377 (7)
O50.8513 (3)0.31313 (17)0.5511 (3)0.0399 (7)
O60.8117 (3)0.43623 (16)0.6061 (4)0.0402 (7)
O1W0.1266 (3)0.33514 (16)0.4647 (3)0.0236 (5)
O2W0.4173 (4)0.0272 (3)0.8131 (4)0.0592 (10)
H1WA0.168 (5)0.291 (2)0.489 (6)0.071*
H1WB0.039 (3)0.334 (3)0.481 (6)0.071*
H2WA0.494 (5)−0.008 (3)0.846 (6)0.071*
H2WB0.396 (6)0.045 (3)0.901 (3)0.071*
N40.7300 (3)−0.14301 (18)0.4733 (3)0.0233 (6)
O10.8658 (2)−0.13506 (15)0.4843 (2)0.0226 (5)
O20.6711 (3)−0.21048 (15)0.4441 (3)0.0252 (6)
O30.6522 (3)−0.08487 (18)0.4963 (4)0.0520 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0194 (16)0.0188 (17)0.0124 (14)0.0044 (13)0.0023 (11)0.0043 (12)
C20.0175 (15)0.0104 (15)0.0122 (14)0.0038 (12)0.0004 (11)0.0000 (11)
C30.0233 (18)0.032 (2)0.0150 (15)0.0136 (15)0.0039 (13)0.0031 (14)
C40.0113 (14)0.0153 (16)0.0120 (13)0.0026 (12)0.0014 (11)−0.0013 (11)
C50.0141 (15)0.0155 (16)0.0117 (13)0.0025 (12)0.0021 (11)0.0011 (11)
C60.0171 (15)0.0130 (16)0.0192 (15)0.0000 (12)−0.0003 (12)−0.0031 (12)
C70.0175 (15)0.0232 (18)0.0094 (13)0.0068 (13)−0.0009 (11)0.0019 (11)
Cu10.0120 (3)0.0135 (3)0.0079 (2)0.0030 (2)0.00051 (17)0.0002 (2)
N10.0121 (12)0.0128 (13)0.0112 (11)0.0008 (10)0.0022 (9)−0.0003 (10)
N20.0123 (12)0.0143 (14)0.0113 (11)0.0017 (10)−0.0001 (9)0.0009 (10)
N30.0161 (13)0.0226 (16)0.0134 (12)0.0050 (11)0.0030 (10)−0.0006 (11)
N50.0167 (14)0.0227 (16)0.0244 (14)0.0033 (12)0.0021 (11)0.0008 (12)
O40.0357 (16)0.0389 (17)0.0442 (16)0.0024 (13)0.0241 (13)0.0093 (13)
O50.0442 (17)0.0260 (15)0.0558 (18)−0.0001 (13)0.0282 (14)−0.0111 (13)
O60.0382 (16)0.0149 (14)0.071 (2)−0.0009 (12)0.0184 (14)−0.0028 (13)
O1W0.0252 (13)0.0268 (14)0.0192 (12)−0.0001 (11)0.0047 (10)0.0005 (10)
O2W0.051 (2)0.068 (3)0.056 (2)0.0019 (19)−0.0006 (17)−0.0158 (19)
N40.0187 (14)0.0206 (16)0.0305 (16)−0.0036 (12)0.0031 (12)−0.0016 (12)
O10.0153 (11)0.0264 (14)0.0268 (12)−0.0057 (10)0.0053 (9)−0.0017 (10)
O20.0212 (12)0.0197 (13)0.0327 (13)−0.0060 (10)−0.0022 (10)−0.0022 (10)
O30.0230 (15)0.0230 (16)0.111 (3)0.0001 (12)0.0151 (16)−0.0074 (17)

Geometric parameters (Å, °)

C1—N11.499 (4)C7—C1i1.505 (4)
C1—C7i1.505 (4)C7—H7A0.9900
C1—H1A0.9900C7—H7B0.9900
C1—H1B0.9900Cu1—N22.020 (2)
C2—N11.496 (4)Cu1—N12.025 (2)
C2—C31.532 (4)Cu1—O12.550 (2)
C2—C41.539 (4)N1—H1C0.9300
C2—H21.0000N2—H2A0.9300
C3—H3A0.9800N3—H3D0.9100
C3—H3B0.9800N3—H3E0.9100
C3—H3C0.9800N3—H3F0.9100
C4—N31.500 (4)N5—O51.235 (4)
C4—C51.542 (4)N5—O41.241 (4)
C4—H41.0000N5—O61.245 (4)
C5—N21.491 (4)O1W—H1WA0.84 (4)
C5—C61.526 (4)O1W—H1WB0.84 (2)
C5—H51.0000O2W—H2WA0.93 (5)
C6—H6A0.9800O2W—H2WB0.91 (2)
C6—H6B0.9800N4—O31.239 (4)
C6—H6C0.9800N4—O11.245 (4)
C7—N21.488 (3)N4—O21.254 (4)
N1—C1—C7i108.5 (2)N2—C7—H7A109.9
N1—C1—H1A110.0C1i—C7—H7A109.9
C7i—C1—H1A110.0N2—C7—H7B109.9
N1—C1—H1B110.0C1i—C7—H7B109.9
C7i—C1—H1B110.0H7A—C7—H7B108.3
H1A—C1—H1B108.4N2i—Cu1—N187.06 (10)
N1—C2—C3110.6 (2)N2—Cu1—N192.94 (10)
N1—C2—C4109.4 (2)O1—Cu1—N194.74 (9)
C3—C2—C4111.7 (3)O1—Cu1—N282.89 (8)
N1—C2—H2108.3O1—Cu1—N1i85.26 (9)
C3—C2—H2108.3O1—Cu1—N2i97.11 (8)
C4—C2—H2108.3C2—N1—C1111.5 (2)
C2—C3—H3A109.5C2—N1—Cu1118.36 (17)
C2—C3—H3B109.5C1—N1—Cu1105.27 (18)
H3A—C3—H3B109.5C2—N1—H1C107.1
C2—C3—H3C109.5C1—N1—H1C107.1
H3A—C3—H3C109.5Cu1—N1—H1C107.1
H3B—C3—H3C109.5C7—N2—C5113.0 (2)
N3—C4—C2109.0 (2)C7—N2—Cu1106.55 (18)
N3—C4—C5106.5 (2)C5—N2—Cu1123.02 (18)
C2—C4—C5116.8 (3)C7—N2—H2A104.1
N3—C4—H4108.1C5—N2—H2A104.1
C2—C4—H4108.1Cu1—N2—H2A104.1
C5—C4—H4108.1C4—N3—H3D109.5
N2—C5—C6113.0 (2)C4—N3—H3E109.5
N2—C5—C4108.3 (2)H3D—N3—H3E109.5
C6—C5—C4113.3 (3)C4—N3—H3F109.5
N2—C5—H5107.3H3D—N3—H3F109.5
C6—C5—H5107.3H3E—N3—H3F109.5
C4—C5—H5107.3O5—N5—O4118.9 (3)
C5—C6—H6A109.5O5—N5—O6120.0 (3)
C5—C6—H6B109.5O4—N5—O6121.1 (3)
H6A—C6—H6B109.5H1WA—O1W—H1WB109 (4)
C5—C6—H6C109.5H2WA—O2W—H2WB99 (4)
H6A—C6—H6C109.5O3—N4—O1120.2 (3)
H6B—C6—H6C109.5O3—N4—O2119.3 (3)
N2—C7—C1i109.0 (2)O1—N4—O2120.5 (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—C237.9 (2)
N1—C2—C4—C572.4 (3)N2i—Cu1—N1—C1−16.78 (19)
C3—C2—C4—C5−164.7 (3)N2—Cu1—N1—C1163.22 (19)
N3—C4—C5—N2171.2 (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—C754.5 (3)
C2—C4—C5—C659.3 (3)C4—C5—N2—C7−179.2 (2)
C3—C2—N1—C156.7 (3)C6—C5—N2—Cu1−75.7 (3)
C4—C2—N1—C1−179.9 (2)C4—C5—N2—Cu150.7 (3)
C3—C2—N1—Cu1178.9 (2)N1i—Cu1—N2—C711.4 (2)
C4—C2—N1—Cu1−57.6 (3)N1—Cu1—N2—C7−168.6 (2)
C7i—C1—N1—C2171.5 (2)N1i—Cu1—N2—C5144.2 (2)
C7i—C1—N1—Cu142.0 (3)N1—Cu1—N2—C5−35.8 (2)

Symmetry codes: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···O30.932.433.155 (4)134
N1—H1C···O2Wii0.932.283.096 (4)146
N2—H2A···O30.932.523.244 (4)135
N2—H2A···O4iii0.932.473.249 (4)141
N3—H3D···O40.912.082.924 (4)155
N3—H3E···O1Wiv0.911.862.748 (4)164
N3—H3F···O2ii0.912.062.902 (4)154
N3—H3F···O3ii0.912.323.108 (4)145
O1W—H1WA···O2ii0.84 (4)2.01 (3)2.823 (4)160 (5)
O1W—H1WB···O5v0.84 (2)1.97 (2)2.795 (4)168 (5)
O2W—H2WA···O6iii0.93 (5)2.00 (5)2.913 (5)166 (5)
O2W—H2WB···O6vi0.92 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2316).

References

  • Bernhardt, P. V. (1999). Inorg. Chem.38, 3481–3483. [PubMed]
  • Bernhardt, P. V. & Sharpe, P. C. (1998). Inorg. Chem.37, 1629–1236.
  • Bruker (2001). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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