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The centrosymmetric title compound, C16H32N8O4, crystallizes one half-molecule in the asymmetric unit. Single crystals were grown from water and, even though the compound contains hydrogen-bonding groups, no water mol­ecules of crystallization were found. Two of the four pendant arms form intra­molecularly hydrogen bonds to preorganize the compound into a shape similar to that required for ligation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030023/bv6031sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030023/bv6031Isup2.hkl
Contains datablock I

CCDC reference: 287491

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C)= 0.002 Å
  • R factor = 0.042
  • wR factor = 0.111
  • Data-to-parameter ratio = 17.6

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Comment top

It is well known that macrocyclic ligands produce enhanced thermodynamic stability with metal ions compared with their open-chain analogues. Our interest in this macrocycle is its complexing ability with the heavy post-transition elements, lead and bismuth. The chemistry of lead is of interest in relation to its toxicity and effects on intelligence in human subjects (Bryce-Smith, 1986). Bismuth has become of increasing interest in complexes such as the subsalicylate in treating gastric and duodenal ulcers (Baxter, 1992). The architecture of this ligand (see scheme), having all five-membered chelate rings and four N-donor and four O-donor atoms, should bode well for good complexing ability to lead(II) and bismuth(III). The present ligand has also been used by Amin et al. (1996) in its lanthanide(III) complex form as catalyst for the hydrolytic cleavage of RNA. One of the authors (RCL) was involved in the synthesis of the first example of a bismuth(III) complex with a nitrogen donor macrocycle (Luckay et al., 1995), and on the basis of these studies, the present macrocycle should also show good binding tendencies with bismuth(III). Furthermore, the role of the lone pair in bismuth(III) in determining coordination geometry would be examined. Also of interest is the preorganization of the ligand before ligation of a metal.

There are only three types of hydrogen bonds formed by this compound in its crystalline state (Table 1). That of most interest is the intramolecular hydrogen bond between donor and acceptor atoms N14 and N1, respectively. This preorganizes two of the four pendant arms of the ligand into positions pointing inwards to the center of the ligand (Fig. 1). Although the functional groups pointing inwards (the amines) are different from that of the ligated metal structures where the CO functional group is pointing inwards, this is useful information as it shows that the flexibility of the pendant arms has small energy barriers as the hydrogen bond is relatively weak compared with a coordination bond. The other two hydrogen bonds, which have the hydrogen-bond donor atom N10 in common, connect the individual molecules together to form a three-dimensional hydrogen-bonded network (Fig. 2). When comparing the conformation of the free ligand in the solid state with that of the coordinated state, it does not have the same conformation as in a number of the known metal–ligand complexes (Maumela et al., 1995). Hence, this ligand is not highly preorganized for ligation of metals.

Experimental top

The ligand was synthesized according to the method of Maumela et al. (1995). Characterization of the ligand was consistent with their NMR data reported. Single crystals were grown from a saturated solution of the ligand in water. After four days, colourless rods were deposited using the method of slow evaporation.

Refinement top

All H atoms were positioned geometrically (C—H = 0.99 Å and N—H = 0.88 Å) and constrained to ride on their parent atoms; Uiso(H) values were set at 1.2 times Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001; Atwood and Barbour, 2003); software used to prepare material for publication: X-SEED.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing atom labels and 50% probability displacement ellipsoids for non-H atoms. Unlabeled atoms are related by the symmetry operator (1 − x, 1 − y, 1 − z). The red dashed lines represent the intramolecular hydrogen bonds.
[Figure 2] Fig. 2. The molecular packing of the title compound via hydrogen bonds, shown as red dashed lines. Molecules shown in closed-capped representation.
1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane top
Crystal data top
C16H32N8O4F(000) = 432
Mr = 400.50Dx = 1.377 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2706 reflections
a = 5.9691 (7) Åθ = 6.4–28.1°
b = 17.795 (2) ŵ = 0.10 mm1
c = 9.4230 (12) ÅT = 100 K
β = 105.190 (2)°Rod-shaped, colourless
V = 966.0 (2) Å30.25 × 0.21 × 0.12 mm
Z = 2
Data collection top
Bruker APEX CCD area-detector
diffractometer
1903 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.030
Graphite monochromatorθmax = 28.2°, θmin = 2.3°
ω scansh = 67
5989 measured reflectionsk = 2322
2230 independent reflectionsl = 127
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0652P)2 + 0.116P]
where P = (Fo2 + 2Fc2)/3
2230 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C16H32N8O4V = 966.0 (2) Å3
Mr = 400.50Z = 2
Monoclinic, P21/cMo Kα radiation
a = 5.9691 (7) ŵ = 0.10 mm1
b = 17.795 (2) ÅT = 100 K
c = 9.4230 (12) Å0.25 × 0.21 × 0.12 mm
β = 105.190 (2)°
Data collection top
Bruker APEX CCD area-detector
diffractometer
1903 reflections with I > 2σ(I)
5989 measured reflectionsRint = 0.030
2230 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.111H-atom parameters constrained
S = 1.05Δρmax = 0.39 e Å3
2230 reflectionsΔρmin = 0.20 e Å3
127 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O90.06228 (17)0.71086 (5)0.66999 (10)0.0190 (2)
O130.60801 (17)0.63037 (5)0.05167 (10)0.0192 (2)
N10.38291 (18)0.62848 (5)0.53673 (11)0.0126 (2)
N40.35284 (18)0.51512 (6)0.28716 (11)0.0124 (2)
N140.62562 (19)0.64100 (6)0.29415 (12)0.0160 (3)
H14A0.71320.68150.30500.019*
H14B0.58360.62240.36980.019*
N100.0326 (2)0.78487 (6)0.46780 (12)0.0183 (3)
H10A0.15210.80450.49270.022*
H10B0.00030.79920.38610.022*
C60.5019 (2)0.61926 (7)0.69382 (13)0.0141 (3)
H6A0.38980.60010.74610.017*
H6B0.55770.66890.73610.017*
C30.1615 (2)0.55950 (7)0.31657 (14)0.0136 (3)
H3A0.01290.53260.27730.016*
H3B0.15140.60860.26570.016*
C20.1998 (2)0.57234 (7)0.48091 (13)0.0131 (3)
H2A0.05320.58970.50040.016*
H2B0.24400.52430.53380.016*
C120.5564 (2)0.60775 (7)0.16271 (14)0.0137 (3)
C70.3021 (2)0.70506 (6)0.49790 (13)0.0135 (3)
H7A0.25660.70900.38930.016*
H7B0.43480.73950.53480.016*
C80.0996 (2)0.73311 (7)0.55437 (13)0.0141 (3)
C110.4077 (2)0.53773 (7)0.15164 (14)0.0146 (3)
H11A0.26040.54630.07560.018*
H11B0.48900.49560.11770.018*
C50.2933 (2)0.43453 (7)0.28141 (14)0.0138 (3)
H5B0.18630.42360.18410.017*
H5A0.20840.42430.35660.017*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O90.0251 (5)0.0196 (5)0.0146 (5)0.0028 (4)0.0090 (4)0.0015 (4)
O130.0234 (5)0.0194 (5)0.0172 (5)0.0024 (4)0.0096 (4)0.0021 (4)
N10.0158 (5)0.0099 (5)0.0115 (5)0.0002 (4)0.0024 (4)0.0000 (4)
N40.0155 (5)0.0111 (5)0.0120 (5)0.0002 (4)0.0058 (4)0.0003 (4)
N140.0171 (6)0.0142 (5)0.0175 (6)0.0032 (4)0.0059 (4)0.0009 (4)
N100.0220 (6)0.0183 (6)0.0173 (6)0.0074 (4)0.0100 (5)0.0049 (4)
C60.0177 (7)0.0126 (6)0.0116 (6)0.0001 (4)0.0033 (5)0.0012 (5)
C30.0142 (6)0.0127 (6)0.0138 (6)0.0012 (4)0.0033 (5)0.0002 (5)
C20.0144 (6)0.0118 (6)0.0138 (6)0.0002 (4)0.0048 (5)0.0005 (5)
C120.0128 (6)0.0128 (6)0.0162 (6)0.0030 (4)0.0048 (5)0.0020 (5)
C70.0179 (6)0.0106 (6)0.0126 (6)0.0011 (4)0.0051 (5)0.0005 (4)
C80.0185 (6)0.0109 (6)0.0125 (6)0.0013 (5)0.0033 (5)0.0027 (4)
C110.0189 (6)0.0136 (6)0.0117 (6)0.0011 (5)0.0048 (5)0.0009 (5)
C50.0157 (6)0.0118 (6)0.0134 (6)0.0020 (5)0.0027 (5)0.0000 (5)
Geometric parameters (Å, º) top
O9—C81.2331 (15)C6—H6B0.9900
O13—C121.2332 (15)C3—C21.5222 (17)
N1—C71.4599 (15)C3—H3A0.9900
N1—C21.4724 (15)C3—H3B0.9900
N1—C61.4737 (16)C2—H2A0.9900
N4—C111.4559 (16)C2—H2B0.9900
N4—C31.4733 (16)C12—C111.5174 (17)
N4—C51.4749 (15)C7—C81.5267 (18)
N14—C121.3366 (16)C7—H7A0.9900
N14—H14A0.8800C7—H7B0.9900
N14—H14B0.8800C11—H11A0.9900
N10—C81.3413 (16)C11—H11B0.9900
N10—H10A0.8800C5—C6i1.5214 (17)
N10—H10B0.8800C5—H5B0.9900
C6—C5i1.5214 (17)C5—H5A0.9900
C6—H6A0.9900
C7—N1—C2112.23 (10)N1—C2—H2B109.3
C7—N1—C6113.35 (9)C3—C2—H2B109.3
C2—N1—C6113.62 (10)H2A—C2—H2B108.0
C11—N4—C3112.36 (10)O13—C12—N14123.82 (12)
C11—N4—C5110.12 (9)O13—C12—C11118.77 (11)
C3—N4—C5109.69 (10)N14—C12—C11117.41 (11)
C12—N14—H14A120.0N1—C7—C8117.23 (10)
C12—N14—H14B120.0N1—C7—H7A108.0
H14A—N14—H14B120.0C8—C7—H7A108.0
C8—N10—H10A120.0N1—C7—H7B108.0
C8—N10—H10B120.0C8—C7—H7B108.0
H10A—N10—H10B120.0H7A—C7—H7B107.2
N1—C6—C5i112.37 (10)O9—C8—N10122.98 (12)
N1—C6—H6A109.1O9—C8—C7123.08 (11)
C5i—C6—H6A109.1N10—C8—C7113.93 (11)
N1—C6—H6B109.1N4—C11—C12115.38 (10)
C5i—C6—H6B109.1N4—C11—H11A108.4
H6A—C6—H6B107.9C12—C11—H11A108.4
N4—C3—C2110.77 (10)N4—C11—H11B108.4
N4—C3—H3A109.5C12—C11—H11B108.4
C2—C3—H3A109.5H11A—C11—H11B107.5
N4—C3—H3B109.5N4—C5—C6i115.47 (10)
C2—C3—H3B109.5N4—C5—H5B108.4
H3A—C3—H3B108.1C6i—C5—H5B108.4
N1—C2—C3111.40 (10)N4—C5—H5A108.4
N1—C2—H2A109.3C6i—C5—H5A108.4
C3—C2—H2A109.3H5B—C5—H5A107.5
C7—N1—C6—C5i142.57 (11)N1—C7—C8—O929.78 (17)
C2—N1—C6—C5i87.74 (12)N1—C7—C8—N10151.01 (11)
C11—N4—C3—C2144.92 (10)C3—N4—C11—C1279.79 (13)
C5—N4—C3—C292.24 (11)C5—N4—C11—C12157.60 (10)
C7—N1—C2—C376.28 (12)O13—C12—C11—N4179.48 (11)
C6—N1—C2—C3153.48 (10)N14—C12—C11—N41.11 (16)
N4—C3—C2—N174.14 (12)C11—N4—C5—C6i76.65 (13)
C2—N1—C7—C860.26 (14)C3—N4—C5—C6i159.19 (10)
C6—N1—C7—C870.12 (14)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N14—H14B···N10.882.223.018 (1)152
N10—H10A···O13ii0.882.032.897 (1)168
N10—H10B···O9iii0.882.173.006 (1)158
Symmetry codes: (ii) x1, y+3/2, z+1/2; (iii) x, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaC16H32N8O4
Mr400.50
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)5.9691 (7), 17.795 (2), 9.4230 (12)
β (°) 105.190 (2)
V3)966.0 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.25 × 0.21 × 0.12
Data collection
DiffractometerBruker APEX CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5989, 2230, 1903
Rint0.030
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.111, 1.05
No. of reflections2230
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.20

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001; Atwood and Barbour, 2003), X-SEED.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N14—H14B···N10.882.223.018 (1)151.5
N10—H10A···O13i0.882.032.897 (1)168.4
N10—H10B···O9ii0.882.173.006 (1)158.2
Symmetry codes: (i) x1, y+3/2, z+1/2; (ii) x, y+3/2, z1/2.
 

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