Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807018144/bq2010sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807018144/bq2010Isup2.hkl |
CCDC reference: 646641
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.008 Å
- Disorder in solvent or counterion
- R factor = 0.049
- wR factor = 0.107
- Data-to-parameter ratio = 15.0
checkCIF/PLATON results
No syntax errors found
Alert level B CELLV02_ALERT_1_B The supplied cell volume s.u. differs from that calculated from the cell parameter s.u.'s by > 4 Calculated cell volume su = 17.81 Cell volume su given = 13.00
Alert level C PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ... 6724.50 Ang-3 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 23.00 Perc. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 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 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Alexander (1995); Bunzli & Moret (1988); Guerriero et al. (1987); Hu et al. (2003, 2004).
To a methanolic solution (20 ml) of 2,6-diformyl-4-methylphenol(1 mmol) and Gd(NO3)3.6H2O (0.5 mmol), 1,5-diamino-3-azapentane (1 mmol) was added dropwise. After refluxing 3 h, the solvent was removed. Yellow solid was recrystallized in acetonitrile and then yellow block crystals suitable for X-ray analysis were obtained.
The carbon-bound H atoms were generated geometrically (C–H 0.93 to 0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C). The water H atom was located in a difference Fourier map, and was refined with an O–H distance restraint of 0.85±0.01 Å; its temperature factor was refined.
Lanthanide macrocyclic complexes have been received extensive attention, owing to their many possible applications in biological systems, material science and chemical processes (Alexander, 1995;Hu et al., 2003; Hu et al., 2004). A series of lanthanide(III) complexes with macrocyclic Schiff bases have synthesized by one step template condensation of 2,6-diformyl- 4-chlorophenol with 1,5-diamino-3-azapentane in the presence of lanthanide ions (Alexander, 1995). Guerriero et al. (1987) and Bunzli et al. (1988) have reported the crystal structures of the Tb(III) and Eu(III) complexes in which the central ion is nine-coordinate, being bound to five donor atoms from the cyclic polydentate ligand and to four O atoms of two bidentae nitrates.
The title complex (I) (Fig. 1), which is synthesized by template reaction of 2,6-diformyl-4-methylphenol with 1,5-diamino-3-azapentane in the presence of gadolinium(III) nitrate, exhibits a similar coordinate geometry (Fig. 2). Gd1 is encaptured with in the macrocyclic ligand which provided five donor atoms (the two O atoms O1, O2 from the phenolates and the three N atoms N1, N2, N3 from one end of the macrocycle). The ninefold coordination is completed around Gd1 by two bidentate nitrates which locate on the opposite sides of the bisphenoidal positions. The third nitrate is ionic. At the free end of the macrocycle, a further five-membered imidazoling rings is formed by contraction, this makes the ligand more compact hence allowing a more appropriate spatial arrangement of the donor atoms of the macrocyclic ligand around the lanthanide ions. The coordination polyhedron can be described as a distorted tricapped trigonal prism in which N2, O4 and O7 are the caps, as show in Fig.2.
For related literature, see: Alexander (1995); Bunzli & Moret (1988); Guerriero et al. (1987); Hu et al. (2003, 2004).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. Thermal ellipsoid plot of (I). Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. Coordination polyhedron in (I). |
[Gd(NO3)2(C26H34N6O2)]NO3·H2O | F(000) = 3320 |
Mr = 823.89 | Dx = 1.628 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5110 reflections |
a = 23.764 (3) Å | θ = 2.6–25.0° |
b = 14.298 (3) Å | µ = 2.05 mm−1 |
c = 19.804 (2) Å | T = 291 K |
β = 91.769 (2)° | Block, yellow |
V = 6724.5 (13) Å3 | 0.30 × 0.26 × 0.24 mm |
Z = 8 |
Bruker SMART CCD area-detector diffractometer | 6596 independent reflections |
Radiation source: sealed tube | 4171 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
φ and ω scans | θmax = 26.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −29→22 |
Tmin = 0.55, Tmax = 0.61 | k = −16→17 |
19136 measured reflections | l = −23→24 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.052P)2] where P = (Fo2 + 2Fc2)/3 |
6596 reflections | (Δ/σ)max < 0.001 |
440 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −1.38 e Å−3 |
[Gd(NO3)2(C26H34N6O2)]NO3·H2O | V = 6724.5 (13) Å3 |
Mr = 823.89 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 23.764 (3) Å | µ = 2.05 mm−1 |
b = 14.298 (3) Å | T = 291 K |
c = 19.804 (2) Å | 0.30 × 0.26 × 0.24 mm |
β = 91.769 (2)° |
Bruker SMART CCD area-detector diffractometer | 6596 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 4171 reflections with I > 2σ(I) |
Tmin = 0.55, Tmax = 0.61 | Rint = 0.046 |
19136 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.41 e Å−3 |
6596 reflections | Δρmin = −1.38 e Å−3 |
440 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.2695 (2) | 0.9536 (4) | 0.1213 (3) | 0.0501 (13) | |
C2 | 0.2875 (2) | 1.0154 (4) | 0.0702 (3) | 0.0563 (14) | |
C3 | 0.3425 (3) | 1.0095 (4) | 0.0459 (3) | 0.0585 (14) | |
H3 | 0.3543 | 1.0526 | 0.0142 | 0.070* | |
C4 | 0.3791 (3) | 0.9403 (4) | 0.0685 (3) | 0.0570 (14) | |
C5 | 0.3604 (3) | 0.8761 (4) | 0.1157 (3) | 0.0589 (15) | |
H5 | 0.3843 | 0.8279 | 0.1298 | 0.071* | |
C6 | 0.3075 (3) | 0.8820 (4) | 0.1422 (3) | 0.0563 (14) | |
C7 | 0.4394 (2) | 0.9327 (5) | 0.0409 (3) | 0.0607 (15) | |
H7A | 0.4659 | 0.9601 | 0.0727 | 0.091* | |
H7B | 0.4409 | 0.9652 | −0.0014 | 0.091* | |
H7C | 0.4487 | 0.8680 | 0.0344 | 0.091* | |
C8 | 0.2520 (3) | 1.0863 (4) | 0.0406 (3) | 0.0652 (16) | |
H8 | 0.2692 | 1.1261 | 0.0103 | 0.078* | |
C9 | 0.1757 (3) | 1.1865 (4) | 0.0145 (3) | 0.0593 (15) | |
H9A | 0.1914 | 1.1923 | −0.0299 | 0.071* | |
H9B | 0.1851 | 1.2426 | 0.0400 | 0.071* | |
C10 | 0.1122 (3) | 1.1764 (4) | 0.0078 (3) | 0.0611 (16) | |
H10A | 0.0958 | 1.2350 | −0.0076 | 0.073* | |
H10B | 0.1028 | 1.1286 | −0.0254 | 0.073* | |
C11 | 0.0258 (3) | 1.1483 (4) | 0.0724 (3) | 0.0575 (15) | |
H11A | 0.0110 | 1.2113 | 0.0686 | 0.069* | |
H11B | 0.0114 | 1.1124 | 0.0341 | 0.069* | |
C12 | 0.0074 (3) | 1.1057 (4) | 0.1351 (3) | 0.0569 (15) | |
H12A | −0.0334 | 1.1062 | 0.1361 | 0.068* | |
H12B | 0.0220 | 1.1411 | 0.1735 | 0.068* | |
C13 | −0.0081 (2) | 0.9434 (4) | 0.1513 (3) | 0.0542 (14) | |
H13 | −0.0445 | 0.9626 | 0.1602 | 0.065* | |
C14 | 0.0023 (2) | 0.8441 (4) | 0.1526 (3) | 0.0537 (13) | |
C15 | −0.0424 (3) | 0.7853 (4) | 0.1679 (3) | 0.0626 (15) | |
H15 | −0.0763 | 0.8134 | 0.1786 | 0.075* | |
C16 | −0.0405 (2) | 0.6898 (4) | 0.1684 (3) | 0.0536 (13) | |
C17 | 0.0090 (3) | 0.6498 (4) | 0.1495 (3) | 0.0586 (15) | |
H17 | 0.0111 | 0.5849 | 0.1472 | 0.070* | |
C18 | 0.0560 (3) | 0.7014 (4) | 0.1337 (3) | 0.0570 (14) | |
C19 | 0.0547 (2) | 0.8007 (4) | 0.1346 (3) | 0.0504 (13) | |
C20 | −0.0906 (3) | 0.6320 (4) | 0.1876 (3) | 0.0613 (16) | |
H20A | −0.1194 | 0.6724 | 0.2039 | 0.092* | |
H20B | −0.0794 | 0.5885 | 0.2223 | 0.092* | |
H20C | −0.1048 | 0.5984 | 0.1487 | 0.092* | |
C21 | 0.1067 (3) | 0.6533 (4) | 0.1148 (3) | 0.0512 (13) | |
H21 | 0.1063 | 0.5882 | 0.1161 | 0.061* | |
C22 | 0.2031 (2) | 0.6402 (4) | 0.0824 (3) | 0.0548 (14) | |
H22A | 0.2052 | 0.6290 | 0.0342 | 0.066* | |
H22B | 0.2023 | 0.5802 | 0.1052 | 0.066* | |
C23 | 0.2554 (2) | 0.6978 (4) | 0.1079 (3) | 0.0516 (13) | |
H23A | 0.2868 | 0.6556 | 0.1166 | 0.062* | |
H23B | 0.2661 | 0.7412 | 0.0730 | 0.062* | |
C24 | 0.2306 (3) | 0.6971 (4) | 0.2291 (3) | 0.0546 (14) | |
H24A | 0.2590 | 0.6506 | 0.2405 | 0.065* | |
H24B | 0.1942 | 0.6666 | 0.2241 | 0.065* | |
C25 | 0.2295 (3) | 0.7747 (4) | 0.2825 (3) | 0.0647 (16) | |
H25A | 0.1912 | 0.7939 | 0.2910 | 0.078* | |
H25B | 0.2476 | 0.7545 | 0.3246 | 0.078* | |
C26 | 0.2897 (2) | 0.8117 (4) | 0.1911 (3) | 0.0499 (13) | |
H26 | 0.3224 | 0.7748 | 0.2064 | 0.060* | |
Gd1 | 0.132602 (11) | 0.996866 (19) | 0.112967 (14) | 0.04773 (10) | |
N1 | 0.0281 (2) | 1.0091 (3) | 0.1389 (2) | 0.0551 (11) | |
N2 | 0.0895 (2) | 1.1511 (3) | 0.0718 (3) | 0.0590 (13) | |
H2 | 0.1009 | 1.1958 | 0.1020 | 0.071* | |
N3 | 0.2000 (2) | 1.1025 (3) | 0.0500 (2) | 0.0542 (12) | |
N4 | 0.2619 (2) | 0.8522 (3) | 0.2508 (2) | 0.0554 (11) | |
H4A | 0.2385 | 0.8989 | 0.2379 | 0.067* | |
H4B | 0.2878 | 0.8752 | 0.2805 | 0.067* | |
N5 | 0.2444 (2) | 0.7482 (4) | 0.1676 (3) | 0.0641 (13) | |
N6 | 0.1521 (2) | 0.6931 (3) | 0.0965 (2) | 0.0584 (12) | |
H6A | 0.1527 | 0.7530 | 0.0924 | 0.070* | |
N7 | 0.1260 (2) | 0.8939 (3) | −0.0123 (2) | 0.0533 (11) | |
N8 | 0.1368 (2) | 1.0475 (4) | 0.2570 (3) | 0.0598 (12) | |
N9 | 0.1283 (2) | 0.3947 (4) | 0.1408 (3) | 0.0589 (13) | |
O1 | 0.22107 (16) | 0.9625 (3) | 0.15061 (18) | 0.0525 (9) | |
O2 | 0.09826 (15) | 0.8486 (2) | 0.12235 (18) | 0.0485 (8) | |
O3 | 0.09112 (17) | 0.9594 (3) | −0.00056 (19) | 0.0583 (10) | |
O4 | 0.17109 (19) | 0.8926 (3) | 0.0223 (2) | 0.0637 (11) | |
O5 | 0.11340 (17) | 0.8315 (3) | −0.0522 (2) | 0.0648 (11) | |
O6 | 0.13705 (18) | 1.1068 (3) | 0.2101 (2) | 0.0640 (11) | |
O7 | 0.13078 (17) | 0.9602 (3) | 0.2391 (2) | 0.0616 (10) | |
O8 | 0.1408 (2) | 1.0668 (3) | 0.3166 (3) | 0.0853 (14) | |
O9 | 0.14265 (19) | 0.3210 (3) | 0.1536 (2) | 0.0661 (12) | |
O10 | 0.15358 (18) | 0.4520 (3) | 0.1704 (2) | 0.0627 (11) | |
O11 | 0.0879 (2) | 0.4096 (3) | 0.1042 (2) | 0.0685 (12) | |
O1W | 0.0000 | 0.3603 (5) | 0.2500 | 0.069 (2) | 0.80 |
H1WA | 0.0081 | 0.3026 | 0.2474 | 0.083* | 0.40 |
H1WB | 0.0145 | 0.3896 | 0.2175 | 0.083* | 0.40 |
O2W | 0.8107 (3) | 0.9370 (5) | 0.1122 (3) | 0.0629 (17) | 0.60 |
H2WD | 0.8465 | 0.9383 | 0.1129 | 0.075* | 0.60 |
H2WB | 0.7981 | 0.9918 | 0.1189 | 0.075* | 0.60 |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.048 (3) | 0.049 (3) | 0.053 (3) | 0.013 (2) | −0.006 (2) | 0.011 (2) |
C2 | 0.040 (3) | 0.055 (4) | 0.074 (4) | 0.009 (2) | 0.002 (3) | 0.003 (3) |
C3 | 0.057 (3) | 0.052 (3) | 0.067 (3) | 0.007 (3) | −0.001 (3) | −0.003 (3) |
C4 | 0.050 (3) | 0.062 (4) | 0.058 (3) | 0.010 (3) | −0.004 (3) | 0.013 (3) |
C5 | 0.054 (4) | 0.057 (3) | 0.065 (3) | 0.007 (3) | −0.004 (3) | 0.010 (3) |
C6 | 0.050 (3) | 0.057 (3) | 0.062 (3) | 0.007 (3) | 0.005 (3) | −0.004 (3) |
C7 | 0.035 (3) | 0.074 (4) | 0.073 (4) | 0.013 (3) | 0.007 (3) | 0.010 (3) |
C8 | 0.072 (5) | 0.064 (4) | 0.059 (3) | 0.009 (3) | −0.007 (3) | −0.009 (3) |
C9 | 0.059 (4) | 0.061 (4) | 0.056 (3) | 0.013 (3) | −0.010 (3) | −0.007 (3) |
C10 | 0.066 (4) | 0.053 (3) | 0.063 (4) | −0.004 (3) | −0.016 (3) | −0.014 (3) |
C11 | 0.060 (4) | 0.052 (3) | 0.059 (3) | −0.007 (3) | −0.019 (3) | 0.000 (3) |
C12 | 0.049 (3) | 0.054 (3) | 0.067 (4) | −0.007 (3) | −0.008 (3) | 0.024 (3) |
C13 | 0.035 (3) | 0.060 (3) | 0.067 (3) | −0.004 (3) | 0.001 (2) | 0.014 (3) |
C14 | 0.037 (3) | 0.064 (4) | 0.061 (3) | 0.003 (3) | 0.005 (2) | 0.011 (3) |
C15 | 0.054 (4) | 0.066 (4) | 0.068 (4) | 0.002 (3) | 0.008 (3) | 0.026 (3) |
C16 | 0.046 (3) | 0.060 (3) | 0.055 (3) | 0.014 (3) | 0.010 (2) | 0.013 (3) |
C17 | 0.055 (4) | 0.062 (4) | 0.059 (3) | 0.005 (3) | 0.005 (3) | 0.006 (3) |
C18 | 0.063 (4) | 0.053 (3) | 0.055 (3) | −0.002 (3) | 0.000 (3) | 0.006 (2) |
C19 | 0.036 (3) | 0.046 (3) | 0.069 (3) | −0.002 (2) | 0.003 (2) | 0.005 (2) |
C20 | 0.061 (4) | 0.053 (3) | 0.071 (4) | 0.025 (3) | 0.027 (3) | 0.018 (3) |
C21 | 0.061 (4) | 0.033 (3) | 0.059 (3) | 0.001 (2) | −0.006 (3) | 0.008 (2) |
C22 | 0.052 (4) | 0.057 (3) | 0.056 (3) | −0.008 (3) | 0.017 (3) | 0.007 (3) |
C23 | 0.039 (3) | 0.059 (3) | 0.057 (3) | −0.009 (2) | 0.013 (2) | 0.003 (3) |
C24 | 0.046 (3) | 0.063 (4) | 0.056 (3) | 0.001 (3) | 0.004 (3) | −0.018 (3) |
C25 | 0.056 (4) | 0.069 (4) | 0.069 (4) | 0.020 (3) | 0.009 (3) | −0.005 (3) |
C26 | 0.030 (3) | 0.064 (3) | 0.055 (3) | −0.003 (2) | −0.003 (2) | −0.006 (2) |
Gd1 | 0.03673 (14) | 0.04502 (15) | 0.06105 (16) | 0.00045 (12) | −0.00490 (10) | 0.00840 (13) |
N1 | 0.048 (3) | 0.050 (3) | 0.067 (3) | −0.009 (2) | −0.005 (2) | 0.020 (2) |
N2 | 0.057 (3) | 0.047 (3) | 0.071 (3) | −0.004 (2) | −0.028 (2) | 0.007 (2) |
N3 | 0.043 (3) | 0.060 (3) | 0.059 (3) | 0.007 (2) | −0.007 (2) | −0.014 (2) |
N4 | 0.046 (3) | 0.060 (3) | 0.060 (3) | −0.001 (2) | −0.006 (2) | 0.009 (2) |
N5 | 0.061 (3) | 0.065 (3) | 0.066 (3) | 0.000 (3) | 0.000 (3) | 0.001 (2) |
N6 | 0.066 (3) | 0.046 (3) | 0.063 (3) | −0.002 (2) | 0.004 (3) | 0.004 (2) |
N7 | 0.048 (3) | 0.050 (3) | 0.063 (3) | 0.002 (2) | 0.011 (2) | 0.002 (2) |
N8 | 0.049 (3) | 0.067 (3) | 0.064 (3) | 0.009 (3) | 0.012 (2) | 0.008 (3) |
N9 | 0.054 (3) | 0.057 (3) | 0.065 (3) | −0.001 (2) | −0.022 (2) | 0.026 (2) |
O1 | 0.048 (2) | 0.053 (2) | 0.057 (2) | 0.0023 (17) | 0.0058 (18) | 0.0030 (17) |
O2 | 0.047 (2) | 0.0388 (18) | 0.061 (2) | 0.0012 (16) | 0.0111 (17) | 0.0042 (15) |
O3 | 0.055 (2) | 0.062 (2) | 0.057 (2) | −0.008 (2) | −0.0115 (18) | 0.0004 (18) |
O4 | 0.062 (3) | 0.064 (3) | 0.065 (2) | 0.006 (2) | 0.004 (2) | 0.0013 (19) |
O5 | 0.061 (3) | 0.067 (3) | 0.066 (3) | −0.004 (2) | 0.003 (2) | 0.036 (2) |
O6 | 0.063 (3) | 0.065 (3) | 0.064 (2) | 0.008 (2) | −0.005 (2) | 0.014 (2) |
O7 | 0.054 (3) | 0.067 (3) | 0.065 (2) | 0.010 (2) | 0.0086 (19) | 0.026 (2) |
O8 | 0.064 (3) | 0.075 (3) | 0.118 (4) | 0.006 (2) | 0.019 (3) | 0.005 (3) |
O9 | 0.066 (3) | 0.069 (3) | 0.062 (2) | 0.021 (2) | −0.018 (2) | −0.014 (2) |
O10 | 0.062 (3) | 0.058 (2) | 0.066 (2) | −0.015 (2) | −0.022 (2) | 0.021 (2) |
O11 | 0.067 (3) | 0.070 (3) | 0.067 (3) | −0.011 (2) | −0.017 (2) | 0.017 (2) |
O1W | 0.067 (5) | 0.072 (5) | 0.071 (5) | 0.000 | 0.016 (4) | 0.000 |
O2W | 0.047 (4) | 0.067 (4) | 0.074 (4) | 0.005 (3) | 0.002 (3) | 0.005 (3) |
C1—O1 | 1.311 (6) | C21—N6 | 1.284 (8) |
C1—C6 | 1.417 (7) | C21—H21 | 0.9300 |
C1—C2 | 1.421 (8) | C22—N6 | 1.462 (8) |
C2—C3 | 1.408 (8) | C22—C23 | 1.563 (8) |
C2—C8 | 1.433 (8) | C22—H22A | 0.9700 |
C3—C4 | 1.383 (8) | C22—H22B | 0.9700 |
C3—H3 | 0.9300 | C23—N5 | 1.415 (7) |
C4—C5 | 1.392 (8) | C23—H23A | 0.9700 |
C4—C7 | 1.552 (8) | C23—H23B | 0.9700 |
C5—C6 | 1.380 (8) | C24—N5 | 1.465 (8) |
C5—H5 | 0.9300 | C24—C25 | 1.533 (8) |
C6—C26 | 1.467 (8) | C24—H24A | 0.9700 |
C7—H7A | 0.9600 | C24—H24B | 0.9700 |
C7—H7B | 0.9600 | C25—N4 | 1.497 (8) |
C7—H7C | 0.9600 | C25—H25A | 0.9700 |
C8—N3 | 1.275 (8) | C25—H25B | 0.9700 |
C8—H8 | 0.9300 | C26—N5 | 1.473 (7) |
C9—N3 | 1.499 (7) | C26—N4 | 1.490 (7) |
C9—C10 | 1.516 (8) | C26—H26 | 0.9800 |
C9—H9A | 0.9700 | Gd1—O1 | 2.263 (4) |
C9—H9B | 0.9700 | Gd1—O2 | 2.281 (3) |
C10—N2 | 1.439 (8) | Gd1—O6 | 2.483 (4) |
C10—H10A | 0.9700 | Gd1—O3 | 2.485 (4) |
C10—H10B | 0.9700 | Gd1—O4 | 2.527 (4) |
C11—C12 | 1.462 (8) | Gd1—O7 | 2.553 (4) |
C11—N2 | 1.515 (8) | Gd1—N2 | 2.554 (4) |
C11—H11A | 0.9700 | Gd1—N3 | 2.555 (5) |
C11—H11B | 0.9700 | Gd1—N1 | 2.558 (5) |
C12—N1 | 1.467 (7) | Gd1—N7 | 2.884 (5) |
C12—H12A | 0.9700 | Gd1—N8 | 2.941 (6) |
C12—H12B | 0.9700 | N2—H2 | 0.9100 |
C13—N1 | 1.302 (7) | N4—H4A | 0.9000 |
C13—C14 | 1.442 (8) | N4—H4B | 0.9000 |
C13—H13 | 0.9300 | N6—H6A | 0.8600 |
C14—C15 | 1.394 (8) | N7—O5 | 1.223 (6) |
C14—C19 | 1.446 (8) | N7—O4 | 1.254 (6) |
C15—C16 | 1.365 (8) | N7—O3 | 1.277 (6) |
C15—H15 | 0.9300 | N8—O8 | 1.213 (7) |
C16—C17 | 1.371 (8) | N8—O6 | 1.258 (6) |
C16—C20 | 1.507 (8) | N8—O7 | 1.304 (7) |
C17—C18 | 1.383 (9) | N9—O9 | 1.133 (6) |
C17—H17 | 0.9300 | N9—O10 | 1.164 (6) |
C18—C19 | 1.420 (8) | N9—O11 | 1.204 (6) |
C18—C21 | 1.445 (9) | N9—O1W | 3.824 (6) |
C19—O2 | 1.271 (6) | O1W—H1WA | 0.8499 |
C20—H20A | 0.9600 | O1W—H1WB | 0.8501 |
C20—H20B | 0.9600 | O2W—H2WD | 0.8499 |
C20—H20C | 0.9600 | O2W—H2WB | 0.8500 |
O1—C1—C6 | 120.1 (5) | N5—C26—H26 | 109.3 |
O1—C1—C2 | 122.9 (5) | N4—C26—H26 | 109.3 |
C6—C1—C2 | 117.0 (5) | O1—Gd1—O2 | 95.90 (13) |
C3—C2—C1 | 120.6 (5) | O1—Gd1—O6 | 82.25 (13) |
C3—C2—C8 | 116.4 (6) | O2—Gd1—O6 | 122.13 (13) |
C1—C2—C8 | 123.0 (6) | O1—Gd1—O3 | 126.15 (14) |
C4—C3—C2 | 120.9 (6) | O2—Gd1—O3 | 74.96 (13) |
C4—C3—H3 | 119.5 | O6—Gd1—O3 | 147.48 (13) |
C2—C3—H3 | 119.5 | O1—Gd1—O4 | 75.71 (14) |
C3—C4—C5 | 118.5 (6) | O2—Gd1—O4 | 69.41 (13) |
C3—C4—C7 | 120.9 (5) | O6—Gd1—O4 | 156.35 (14) |
C5—C4—C7 | 120.5 (5) | O3—Gd1—O4 | 51.10 (14) |
C6—C5—C4 | 121.9 (5) | O1—Gd1—O7 | 71.15 (13) |
C6—C5—H5 | 119.0 | O2—Gd1—O7 | 73.31 (14) |
C4—C5—H5 | 119.0 | O6—Gd1—O7 | 51.25 (14) |
C5—C6—C1 | 120.9 (5) | O3—Gd1—O7 | 145.32 (14) |
C5—C6—C26 | 119.6 (5) | O4—Gd1—O7 | 126.28 (14) |
C1—C6—C26 | 119.5 (5) | O1—Gd1—N2 | 130.66 (15) |
C4—C7—H7A | 109.5 | O2—Gd1—N2 | 133.42 (14) |
C4—C7—H7B | 109.5 | O6—Gd1—N2 | 73.01 (14) |
H7A—C7—H7B | 109.5 | O3—Gd1—N2 | 75.73 (15) |
C4—C7—H7C | 109.5 | O4—Gd1—N2 | 115.63 (16) |
H7A—C7—H7C | 109.5 | O7—Gd1—N2 | 118.06 (16) |
H7B—C7—H7C | 109.5 | O1—Gd1—N3 | 72.45 (14) |
N3—C8—C2 | 129.1 (7) | O2—Gd1—N3 | 145.13 (14) |
N3—C8—H8 | 115.5 | O6—Gd1—N3 | 89.51 (14) |
C2—C8—H8 | 115.5 | O3—Gd1—N3 | 85.59 (14) |
N3—C9—C10 | 109.5 (5) | O4—Gd1—N3 | 75.83 (14) |
N3—C9—H9A | 109.8 | O7—Gd1—N3 | 128.93 (14) |
C10—C9—H9A | 109.8 | N2—Gd1—N3 | 65.50 (16) |
N3—C9—H9B | 109.8 | O1—Gd1—N1 | 147.86 (14) |
C10—C9—H9B | 109.8 | O2—Gd1—N1 | 72.23 (13) |
H9A—C9—H9B | 108.2 | O6—Gd1—N1 | 79.62 (15) |
N2—C10—C9 | 110.2 (5) | O3—Gd1—N1 | 80.55 (15) |
N2—C10—H10A | 109.6 | O4—Gd1—N1 | 123.92 (15) |
C9—C10—H10A | 109.6 | O7—Gd1—N1 | 76.80 (14) |
N2—C10—H10B | 109.6 | N2—Gd1—N1 | 67.85 (15) |
C9—C10—H10B | 109.6 | N3—Gd1—N1 | 133.27 (14) |
H10A—C10—H10B | 108.1 | O1—Gd1—N7 | 101.41 (14) |
C12—C11—N2 | 110.1 (5) | O2—Gd1—N7 | 65.53 (13) |
C12—C11—H11A | 109.6 | O6—Gd1—N7 | 171.41 (12) |
N2—C11—H11A | 109.6 | O3—Gd1—N7 | 26.18 (13) |
C12—C11—H11B | 109.6 | O4—Gd1—N7 | 25.71 (13) |
N2—C11—H11B | 109.6 | O7—Gd1—N7 | 137.25 (14) |
H11A—C11—H11B | 108.2 | N2—Gd1—N7 | 98.95 (15) |
C11—C12—N1 | 109.1 (5) | N3—Gd1—N7 | 84.27 (14) |
C11—C12—H12A | 109.9 | N1—Gd1—N7 | 100.38 (15) |
N1—C12—H12A | 109.9 | O1—Gd1—N8 | 74.39 (14) |
C11—C12—H12B | 109.9 | O2—Gd1—N8 | 98.69 (14) |
N1—C12—H12B | 109.9 | O6—Gd1—N8 | 25.03 (13) |
H12A—C12—H12B | 108.3 | O3—Gd1—N8 | 158.56 (14) |
N1—C13—C14 | 126.9 (6) | O4—Gd1—N8 | 146.35 (14) |
N1—C13—H13 | 116.6 | O7—Gd1—N8 | 26.26 (14) |
C14—C13—H13 | 116.6 | N2—Gd1—N8 | 95.62 (16) |
C15—C14—C13 | 117.8 (5) | N3—Gd1—N8 | 108.96 (14) |
C15—C14—C19 | 117.5 (6) | N1—Gd1—N8 | 78.01 (15) |
C13—C14—C19 | 124.5 (5) | N7—Gd1—N8 | 163.50 (15) |
C16—C15—C14 | 125.4 (6) | C13—N1—C12 | 117.8 (5) |
C16—C15—H15 | 117.3 | C13—N1—Gd1 | 129.8 (4) |
C14—C15—H15 | 117.3 | C12—N1—Gd1 | 112.3 (3) |
C15—C16—C17 | 116.3 (6) | C10—N2—C11 | 114.6 (4) |
C15—C16—C20 | 121.6 (5) | C10—N2—Gd1 | 109.9 (4) |
C17—C16—C20 | 122.1 (5) | C11—N2—Gd1 | 111.4 (3) |
C16—C17—C18 | 123.0 (6) | C10—N2—H2 | 106.8 |
C16—C17—H17 | 118.5 | C11—N2—H2 | 106.8 |
C18—C17—H17 | 118.5 | Gd1—N2—H2 | 106.8 |
C17—C18—C19 | 120.8 (6) | C8—N3—C9 | 116.0 (6) |
C17—C18—C21 | 119.3 (5) | C8—N3—Gd1 | 126.1 (4) |
C19—C18—C21 | 119.9 (5) | C9—N3—Gd1 | 117.6 (4) |
O2—C19—C18 | 121.2 (5) | C26—N4—C25 | 107.0 (4) |
O2—C19—C14 | 122.0 (5) | C26—N4—H4A | 110.3 |
C18—C19—C14 | 116.8 (5) | C25—N4—H4A | 110.3 |
C16—C20—H20A | 109.5 | C26—N4—H4B | 110.3 |
C16—C20—H20B | 109.5 | C25—N4—H4B | 110.3 |
H20A—C20—H20B | 109.5 | H4A—N4—H4B | 108.6 |
C16—C20—H20C | 109.5 | C23—N5—C24 | 119.5 (5) |
H20A—C20—H20C | 109.5 | C23—N5—C26 | 115.2 (5) |
H20B—C20—H20C | 109.5 | C24—N5—C26 | 103.0 (4) |
N6—C21—C18 | 125.2 (5) | C21—N6—C22 | 122.3 (5) |
N6—C21—H21 | 117.4 | C21—N6—H6A | 118.9 |
C18—C21—H21 | 117.4 | C22—N6—H6A | 118.9 |
N6—C22—C23 | 108.7 (5) | O5—N7—O4 | 122.1 (5) |
N6—C22—H22A | 110.0 | O5—N7—O3 | 120.3 (5) |
C23—C22—H22A | 110.0 | O4—N7—O3 | 117.4 (5) |
N6—C22—H22B | 110.0 | O5—N7—Gd1 | 159.1 (4) |
C23—C22—H22B | 110.0 | O4—N7—Gd1 | 61.0 (3) |
H22A—C22—H22B | 108.3 | O3—N7—Gd1 | 59.2 (3) |
N5—C23—C22 | 111.9 (5) | O8—N8—O6 | 124.3 (6) |
N5—C23—H23A | 109.2 | O8—N8—O7 | 119.2 (5) |
C22—C23—H23A | 109.2 | O6—N8—O7 | 116.5 (5) |
N5—C23—H23B | 109.2 | O8—N8—Gd1 | 177.1 (4) |
C22—C23—H23B | 109.2 | O6—N8—Gd1 | 56.7 (3) |
H23A—C23—H23B | 107.9 | O7—N8—Gd1 | 60.0 (3) |
N5—C24—C25 | 102.8 (5) | O9—N9—O10 | 113.2 (5) |
N5—C24—H24A | 111.2 | O9—N9—O11 | 121.9 (6) |
C25—C24—H24A | 111.2 | O10—N9—O11 | 124.6 (5) |
N5—C24—H24B | 111.2 | O9—N9—O1W | 89.7 (4) |
C25—C24—H24B | 111.2 | O10—N9—O1W | 102.3 (4) |
H24A—C24—H24B | 109.1 | O11—N9—O1W | 74.2 (3) |
N4—C25—C24 | 103.1 (5) | C1—O1—Gd1 | 134.0 (3) |
N4—C25—H25A | 111.1 | C19—O2—Gd1 | 144.3 (3) |
C24—C25—H25A | 111.1 | N7—O3—Gd1 | 94.6 (3) |
N4—C25—H25B | 111.1 | N7—O4—Gd1 | 93.3 (3) |
C24—C25—H25B | 111.1 | N8—O6—Gd1 | 98.3 (4) |
H25A—C25—H25B | 109.1 | N8—O7—Gd1 | 93.7 (3) |
C6—C26—N5 | 115.8 (5) | N9—O1W—H1WA | 84.5 |
C6—C26—N4 | 113.7 (5) | H1WA—O1W—H1WB | 109.5 |
N5—C26—N4 | 98.7 (4) | H2WD—O2W—H2WB | 109.5 |
C6—C26—H26 | 109.3 |
Experimental details
Crystal data | |
Chemical formula | [Gd(NO3)2(C26H34N6O2)]NO3·H2O |
Mr | 823.89 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 291 |
a, b, c (Å) | 23.764 (3), 14.298 (3), 19.804 (2) |
β (°) | 91.769 (2) |
V (Å3) | 6724.5 (13) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.05 |
Crystal size (mm) | 0.30 × 0.26 × 0.24 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.55, 0.61 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19136, 6596, 4171 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.107, 0.98 |
No. of reflections | 6596 |
No. of parameters | 440 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −1.38 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
Gd1—O1 | 2.263 (4) | Gd1—O7 | 2.553 (4) |
Gd1—O2 | 2.281 (3) | Gd1—N2 | 2.554 (4) |
Gd1—O6 | 2.483 (4) | Gd1—N3 | 2.555 (5) |
Gd1—O3 | 2.485 (4) | Gd1—N1 | 2.558 (5) |
Gd1—O4 | 2.527 (4) |
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Lanthanide macrocyclic complexes have been received extensive attention, owing to their many possible applications in biological systems, material science and chemical processes (Alexander, 1995;Hu et al., 2003; Hu et al., 2004). A series of lanthanide(III) complexes with macrocyclic Schiff bases have synthesized by one step template condensation of 2,6-diformyl- 4-chlorophenol with 1,5-diamino-3-azapentane in the presence of lanthanide ions (Alexander, 1995). Guerriero et al. (1987) and Bunzli et al. (1988) have reported the crystal structures of the Tb(III) and Eu(III) complexes in which the central ion is nine-coordinate, being bound to five donor atoms from the cyclic polydentate ligand and to four O atoms of two bidentae nitrates.
The title complex (I) (Fig. 1), which is synthesized by template reaction of 2,6-diformyl-4-methylphenol with 1,5-diamino-3-azapentane in the presence of gadolinium(III) nitrate, exhibits a similar coordinate geometry (Fig. 2). Gd1 is encaptured with in the macrocyclic ligand which provided five donor atoms (the two O atoms O1, O2 from the phenolates and the three N atoms N1, N2, N3 from one end of the macrocycle). The ninefold coordination is completed around Gd1 by two bidentate nitrates which locate on the opposite sides of the bisphenoidal positions. The third nitrate is ionic. At the free end of the macrocycle, a further five-membered imidazoling rings is formed by contraction, this makes the ligand more compact hence allowing a more appropriate spatial arrangement of the donor atoms of the macrocyclic ligand around the lanthanide ions. The coordination polyhedron can be described as a distorted tricapped trigonal prism in which N2, O4 and O7 are the caps, as show in Fig.2.