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Acta Cryst. (2010). E66, m888    [ doi:10.1107/S1600536810025699 ]

Diaqua(1,4,8,11-tetraazacyclotetradecane-[kappa]4N1,N4,N8,N11)copper(II) didecanoate dihydrate

N. S. Ahmad Tajidi, N. Abdullah, Z. Arifin, K. W. Tan and S. W. Ng

Abstract top

The CuII atom in the title salt, [Cu(C10H24N4)(H2O)2][CH3(CH2)8CO2]2·2H2O, is chelated by the four N atoms of the 1,4,8,11-tetraazacyclotetradecane (cyclam) ligand and is coordinated by two water molecules in a Jahn-Teller-type tetragonally distorted octahedral geometry. The CuII atom lies on a center of inversion. The cations, anions and uncoordinated water molecules are linked by N-H...O and O-H...O hydrogen bonds, forming a layer structure parallel to (001).

Comment top

The copper(II) ion forms a number of complexes with 1,4,8,11-tetraazacyclotetradecane in which the metal atom is coordinated by the four amino donor-atoms of the cyclic ligand. Among the carboxylate derivatives, neither the acetate nor the benzoate ions bind directly with the copper atom. The copper atom is coordinated instead by water molecules so that the carboxylate group interacts indirectly with the metal atom through the coordinated water molecules (Hunter et al., 2005; Lindoy et al., 2003). The copper(II) atom in the salt, [Cu(H2O)2(C10H24N4)]2+ 2[CH3(CH2)8CO2]-.2H2O (Scheme I), is chelated by the four nitrogen atoms of the cyclam ligand and is coordinated by two water molecules in a Jahn-Teller type of tetragonally distorted octahedral geometry. The copper atom lies on a center of inversion (Fig. 1). The cations, anions and lattice water molecules are linked by N–H···O and O–H···O hydrogen bonds to form a layer structure.

Related literature top

For related (1,4,8,11-tetraazacyclotetradecane)copper carboxylates, see: Lindoy et al. (2003); Hunter et al. (2005).

Experimental top

1,4,8,11-Tetraazacyclotetradecane (0.50 g, 2.50 mmol) dissolved in ethanol (25 ml) was mixed with a suspension of copper decanoate (1.01.80 g, 2.5 mmol) in ethanol (50 ml) to give a purple solution. The solution was heated for an hour and then filtered. Prismatic crystals separated from the solution when it was left to cool slowly.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

The amino and water H-atoms were located in a difference Fourier map, and were refined with distance restraints of N–H 0.86±0.01, O–H 0.84±0.01 Å; their displacement parameters were freely refined.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of [Cu(H2O)2(C10H24N4)]2+ 2[CH3(CH2)8CO2]-.2H2O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Diaqua(1,4,8,11-tetraazacyclotetradecane-\ κ4N1,N4,N8,N11)copper(II) didecanoate dihydrate top
Crystal data top
[Cu(C10H24N4)(H2O)2](C10H19O2)2·2H2OZ = 1
Mr = 678.44F(000) = 371
Triclinic, P1Dx = 1.217 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9820 (6) ÅCell parameters from 3079 reflections
b = 8.8006 (8) Åθ = 2.4–28.1°
c = 15.3291 (13) ŵ = 0.64 mm−1
α = 95.045 (1)°T = 100 K
β = 93.158 (1)°Plate, purple
γ = 98.423 (1)°0.30 × 0.20 × 0.02 mm
V = 925.93 (14) Å3
Data collection top
Bruker SMART APEX
diffractometer		4230 independent reflections
Radiation source: fine-focus sealed tube3736 reflections with I > 2σ(I)
graphiteRint = 0.034
ω scansθmax = 27.5°, θmin = 1.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.832, Tmax = 0.987k = −11→11
8967 measured reflectionsl = −19→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0348P)2 + 0.1911P]
where P = (Fo2 + 2Fc2)/3
4230 reflections(Δ/σ)max = 0.001
220 parametersΔρmax = 0.33 e Å−3
6 restraintsΔρmin = −0.43 e Å−3
Crystal data top
[Cu(C10H24N4)(H2O)2](C10H19O2)2·2H2Oγ = 98.423 (1)°
Mr = 678.44V = 925.93 (14) Å3
Triclinic, P1Z = 1
a = 6.9820 (6) ÅMo Kα radiation
b = 8.8006 (8) ŵ = 0.64 mm−1
c = 15.3291 (13) ÅT = 100 K
α = 95.045 (1)°0.30 × 0.20 × 0.02 mm
β = 93.158 (1)°
Data collection top
Bruker SMART APEX
diffractometer		4230 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3736 reflections with I > 2σ(I)
Tmin = 0.832, Tmax = 0.987Rint = 0.034
8967 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.086Δρmax = 0.33 e Å−3
S = 1.06Δρmin = −0.43 e Å−3
4230 reflectionsAbsolute structure: ?
220 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.50000.50000.50000.01105 (9)
O10.9257 (2)0.05590 (14)0.38643 (8)0.0242 (3)
O20.93155 (17)0.28063 (13)0.33012 (8)0.0179 (3)
O1W0.81745 (18)0.48550 (14)0.57137 (9)0.0204 (3)
H110.900 (3)0.555 (2)0.5970 (13)0.035 (6)*
H120.870 (3)0.4065 (17)0.5704 (15)0.037 (7)*
O2W0.95494 (18)0.20230 (14)0.54959 (9)0.0185 (3)
H210.945 (3)0.160 (2)0.4983 (8)0.040 (7)*
H220.982 (3)0.1320 (19)0.5783 (13)0.029 (6)*
N10.55275 (19)0.35212 (15)0.39806 (9)0.0135 (3)
H10.6723 (15)0.342 (2)0.4045 (12)0.022 (5)*
N20.6209 (2)0.68731 (15)0.44674 (9)0.0130 (3)
H20.7437 (14)0.692 (2)0.4559 (12)0.017 (5)*
C10.5260 (3)0.4008 (2)0.30884 (11)0.0184 (4)
H1A0.38790.41040.29630.022*
H1B0.56020.32110.26530.022*
C20.6516 (3)0.5543 (2)0.29990 (11)0.0200 (4)
H2A0.65090.57220.23700.024*
H2B0.78690.54800.32050.024*
C30.5859 (3)0.6912 (2)0.35105 (11)0.0186 (4)
H3A0.65700.78810.33320.022*
H3B0.44570.69020.33670.022*
C40.5625 (2)0.82300 (18)0.49625 (12)0.0179 (4)
H4A0.42970.83610.47540.021*
H4B0.65220.91740.48710.021*
C50.5685 (2)0.79793 (18)0.59202 (12)0.0181 (4)
H5A0.70390.79670.61450.022*
H5B0.51780.88260.62590.022*
C60.9049 (2)0.13621 (18)0.32350 (11)0.0137 (3)
C70.8332 (3)0.04950 (19)0.23452 (11)0.0172 (4)
H7A0.68950.03110.23090.021*
H7B0.8776−0.05250.23130.021*
C80.8998 (2)0.1307 (2)0.15509 (11)0.0177 (4)
H8A0.82650.07600.10150.021*
H8B0.86900.23720.16130.021*
C91.1168 (2)0.1371 (2)0.14399 (12)0.0194 (4)
H9A1.19020.20060.19490.023*
H9B1.14990.03140.14370.023*
C101.1795 (2)0.2040 (2)0.06012 (11)0.0189 (4)
H10A1.14260.30840.05980.023*
H10B1.10780.13890.00930.023*
C111.3965 (3)0.2155 (2)0.04841 (12)0.0204 (4)
H11A1.46840.28660.09680.024*
H11B1.43560.11250.05250.024*
C121.4536 (2)0.2727 (2)−0.03877 (11)0.0188 (4)
H12A1.40840.3732−0.04390.023*
H12B1.38570.1989−0.08700.023*
C131.6711 (3)0.2921 (2)−0.05047 (11)0.0196 (4)
H13A1.73940.3678−0.00320.024*
H13B1.71740.1922−0.04440.024*
C141.7228 (3)0.3460 (2)−0.13872 (12)0.0253 (4)
H14A1.67230.4440−0.14540.030*
H14B1.65700.2685−0.18570.030*
C151.9396 (3)0.3709 (3)−0.15119 (14)0.0329 (5)
H15A1.96170.4047−0.20950.049*
H15B1.99080.2740−0.14580.049*
H15C2.00580.4501−0.10620.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01256 (15)0.00841 (14)0.01241 (16)0.00162 (10)0.00342 (11)0.00065 (10)
O10.0374 (8)0.0185 (6)0.0167 (7)0.0035 (5)−0.0007 (6)0.0043 (5)
O20.0220 (6)0.0131 (5)0.0184 (6)0.0051 (5)−0.0005 (5)−0.0012 (5)
O1W0.0139 (6)0.0158 (6)0.0306 (8)0.0045 (5)−0.0032 (5)−0.0027 (5)
O2W0.0200 (6)0.0159 (6)0.0200 (7)0.0046 (5)0.0001 (5)0.0010 (5)
N10.0089 (7)0.0154 (7)0.0157 (7)0.0023 (5)0.0020 (6)−0.0020 (5)
N20.0096 (7)0.0127 (6)0.0176 (7)0.0030 (5)0.0031 (6)0.0028 (5)
C10.0170 (9)0.0250 (9)0.0133 (9)0.0061 (7)0.0014 (7)−0.0026 (7)
C20.0177 (9)0.0310 (10)0.0133 (9)0.0062 (7)0.0045 (7)0.0074 (7)
C30.0170 (9)0.0211 (8)0.0193 (9)0.0037 (7)0.0017 (7)0.0098 (7)
C40.0144 (8)0.0085 (7)0.0312 (10)0.0019 (6)0.0050 (7)0.0014 (7)
C50.0148 (8)0.0109 (7)0.0270 (10)0.0001 (6)0.0039 (7)−0.0052 (7)
C60.0098 (8)0.0163 (8)0.0155 (9)0.0034 (6)0.0040 (6)−0.0002 (6)
C70.0184 (9)0.0157 (8)0.0163 (9)−0.0006 (6)0.0040 (7)−0.0016 (7)
C80.0179 (9)0.0211 (8)0.0133 (8)0.0003 (7)0.0030 (7)−0.0002 (7)
C90.0176 (9)0.0240 (9)0.0168 (9)0.0027 (7)0.0032 (7)0.0017 (7)
C100.0174 (9)0.0234 (9)0.0156 (9)0.0009 (7)0.0036 (7)0.0024 (7)
C110.0192 (9)0.0259 (9)0.0162 (9)0.0025 (7)0.0054 (7)0.0021 (7)
C120.0165 (9)0.0242 (9)0.0150 (9)0.0003 (7)0.0031 (7)0.0018 (7)
C130.0186 (9)0.0250 (9)0.0154 (9)0.0024 (7)0.0033 (7)0.0027 (7)
C140.0210 (10)0.0367 (11)0.0182 (10)0.0012 (8)0.0044 (7)0.0071 (8)
C150.0250 (10)0.0443 (12)0.0316 (12)0.0039 (9)0.0138 (9)0.0104 (9)
Geometric parameters (Å, °) top
Cu1—N12.029 (1)C5—H5B0.9900
Cu1—N1i2.029 (1)C6—C71.524 (2)
Cu1—N22.000 (1)C7—C81.526 (2)
Cu1—N2i2.000 (1)C7—H7A0.9900
Cu1—O1w2.443 (1)C7—H7B0.9900
O1—C61.259 (2)C8—C91.527 (2)
O2—C61.2515 (19)C8—H8A0.9900
O1W—H110.832 (10)C8—H8B0.9900
O1W—H120.831 (9)C9—C101.520 (2)
O2W—H210.834 (9)C9—H9A0.9900
O2W—H220.828 (9)C9—H9B0.9900
N1—C11.479 (2)C10—C111.525 (2)
N1—C5i1.485 (2)C10—H10A0.9900
N1—H10.855 (9)C10—H10B0.9900
N2—C31.478 (2)C11—C121.522 (2)
N2—C41.478 (2)C11—H11A0.9900
N2—H20.854 (9)C11—H11B0.9900
C1—C21.520 (2)C12—C131.525 (2)
C1—H1A0.9900C12—H12A0.9900
C1—H1B0.9900C12—H12B0.9900
C2—C31.521 (2)C13—C141.517 (2)
C2—H2A0.9900C13—H13A0.9900
C2—H2B0.9900C13—H13B0.9900
C3—H3A0.9900C14—C151.522 (3)
C3—H3B0.9900C14—H14A0.9900
C4—C51.503 (3)C14—H14B0.9900
C4—H4A0.9900C15—H15A0.9800
C4—H4B0.9900C15—H15B0.9800
C5—N1i1.485 (2)C15—H15C0.9800
C5—H5A0.9900
N2—Cu1—N2i180.000 (1)O2—C6—C7118.55 (15)
N2—Cu1—N193.73 (6)O1—C6—C7116.87 (14)
N2i—Cu1—N186.27 (6)C6—C7—C8115.27 (13)
N2—Cu1—N1i86.27 (6)C6—C7—H7A108.5
N2i—Cu1—N1i93.73 (6)C8—C7—H7A108.5
N1—Cu1—N1i180.00 (5)C6—C7—H7B108.5
N2—Cu1—O1W88.48 (5)C8—C7—H7B108.5
N2i—Cu1—O1W91.52 (5)H7A—C7—H7B107.5
N1—Cu1—O1W90.25 (5)C9—C8—C7113.07 (15)
N1i—Cu1—O1W89.75 (5)C9—C8—H8A109.0
Cu1—O1W—H11130.2 (16)C7—C8—H8A109.0
Cu1—O1W—H12124.9 (16)C9—C8—H8B109.0
H11—O1W—H12105 (2)C7—C8—H8B109.0
H21—O2W—H22102 (2)H8A—C8—H8B107.8
C1—N1—C5i112.07 (13)C10—C9—C8113.02 (15)
C1—N1—Cu1117.07 (10)C10—C9—H9A109.0
C5i—N1—Cu1106.17 (10)C8—C9—H9A109.0
C1—N1—H1105.4 (13)C10—C9—H9B109.0
C5i—N1—H1108.8 (13)C8—C9—H9B109.0
Cu1—N1—H1107.0 (13)H9A—C9—H9B107.8
C3—N2—C4111.44 (13)C9—C10—C11114.15 (15)
C3—N2—Cu1117.71 (10)C9—C10—H10A108.7
C4—N2—Cu1107.26 (10)C11—C10—H10A108.7
C3—N2—H2105.7 (13)C9—C10—H10B108.7
C4—N2—H2107.8 (13)C11—C10—H10B108.7
Cu1—N2—H2106.5 (13)H10A—C10—H10B107.6
N1—C1—C2111.30 (14)C12—C11—C10113.15 (15)
N1—C1—H1A109.4C12—C11—H11A108.9
C2—C1—H1A109.4C10—C11—H11A108.9
N1—C1—H1B109.4C12—C11—H11B108.9
C2—C1—H1B109.4C10—C11—H11B108.9
H1A—C1—H1B108.0H11A—C11—H11B107.8
C1—C2—C3113.84 (14)C11—C12—C13114.24 (15)
C1—C2—H2A108.8C11—C12—H12A108.7
C3—C2—H2A108.8C13—C12—H12A108.7
C1—C2—H2B108.8C11—C12—H12B108.7
C3—C2—H2B108.8C13—C12—H12B108.7
H2A—C2—H2B107.7H12A—C12—H12B107.6
N2—C3—C2111.53 (13)C14—C13—C12112.92 (15)
N2—C3—H3A109.3C14—C13—H13A109.0
C2—C3—H3A109.3C12—C13—H13A109.0
N2—C3—H3B109.3C14—C13—H13B109.0
C2—C3—H3B109.3C12—C13—H13B109.0
H3A—C3—H3B108.0H13A—C13—H13B107.8
N2—C4—C5108.50 (13)C13—C14—C15114.09 (16)
N2—C4—H4A110.0C13—C14—H14A108.7
C5—C4—H4A110.0C15—C14—H14A108.7
N2—C4—H4B110.0C13—C14—H14B108.7
C5—C4—H4B110.0C15—C14—H14B108.7
H4A—C4—H4B108.4H14A—C14—H14B107.6
N1i—C5—C4108.31 (13)C14—C15—H15A109.5
N1i—C5—H5A110.0C14—C15—H15B109.5
C4—C5—H5A110.0H15A—C15—H15B109.5
N1i—C5—H5B110.0C14—C15—H15C109.5
C4—C5—H5B110.0H15A—C15—H15C109.5
H5A—C5—H5B108.4H15B—C15—H15C109.5
O2—C6—O1124.52 (15)
N2—Cu1—N1—C1−39.47 (12)C4—N2—C3—C2178.27 (13)
N2i—Cu1—N1—C1140.53 (12)Cu1—N2—C3—C2−57.23 (16)
O1W—Cu1—N1—C1−127.96 (11)C1—C2—C3—N270.00 (18)
N2—Cu1—N1—C5i−165.46 (11)C3—N2—C4—C5170.11 (13)
N2i—Cu1—N1—C5i14.54 (11)Cu1—N2—C4—C539.93 (15)
O1W—Cu1—N1—C5i106.05 (11)N2—C4—C5—N1i−54.24 (17)
N1—Cu1—N2—C339.47 (12)O2—C6—C7—C831.5 (2)
N1i—Cu1—N2—C3−140.53 (12)O1—C6—C7—C8−151.30 (16)
O1W—Cu1—N2—C3129.61 (11)C6—C7—C8—C969.42 (19)
N1—Cu1—N2—C4166.02 (11)C7—C8—C9—C10174.47 (14)
N1i—Cu1—N2—C4−13.98 (11)C8—C9—C10—C11178.58 (14)
O1W—Cu1—N2—C4−103.84 (10)C9—C10—C11—C12176.14 (14)
C5i—N1—C1—C2−179.84 (13)C10—C11—C12—C13177.40 (14)
Cu1—N1—C1—C257.16 (16)C11—C12—C13—C14178.81 (15)
N1—C1—C2—C3−70.19 (19)C12—C13—C14—C15178.29 (16)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.86 (1)2.30 (1)3.025 (2)144 (2)
N2—H2···O2wii0.85 (1)2.18 (1)2.974 (2)154 (2)
O1w—H11···O2ii0.83 (1)1.95 (1)2.774 (2)172 (2)
O1w—H12···O2w0.83 (1)1.98 (1)2.799 (2)169 (2)
O2w—H21···O10.83 (1)1.86 (1)2.694 (2)177 (2)
O2w—H22···O1iii0.83 (1)1.97 (1)2.771 (2)163 (2)
Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y, −z+1.
Table 1
Selected geometric parameters (Å) top
Cu1—N12.029 (1)Cu1—O1w2.443 (1)
Cu1—N22.000 (1)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.86 (1)2.30 (1)3.025 (2)144 (2)
N2—H2···O2wi0.85 (1)2.18 (1)2.974 (2)154 (2)
O1w—H11···O2i0.83 (1)1.95 (1)2.774 (2)172 (2)
O1w—H12···O2w0.83 (1)1.98 (1)2.799 (2)169 (2)
O2w—H21···O10.83 (1)1.86 (1)2.694 (2)177 (2)
O2w—H22···O1ii0.83 (1)1.97 (1)2.771 (2)163 (2)
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z+1.
Acknowledgements top

We thank the University of Malaya (RG039/09SUS) and Ministry of Higher Education (FP017/2009) for for supporting this study.

references
References top

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