Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803013114/cf6259sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803013114/cf6259Isup2.hkl |
CCDC reference: 217381
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- Disorder in solvent or counterion
- R factor = 0.043
- wR factor = 0.118
- Data-to-parameter ratio = 15.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ......................... 14.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
To a methanol solution of 4-methyl-2,6-diformylphenol (0.01 mmol) and Gd(NO3)3(H2O)6 (0.005 mmol) was added a methanol solution of 1,3-diaminopropanol (0.01 mmol). After the reaction mixture was refluxed for 10 h, the solvent was removed. The resulting yellow solid was recrystallized from acetonitrile, giving yellow block-shaped crystals of (I) suitable for X-ray analysis.
All H atoms were positioned geometrically and refined with a riding model, with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq of the parent atom.
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); 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.
[Gd(H2O)(NO3)2(C24H28N4O4)](NO3)·0.5CH4O·1.75H2O | F(000) = 3404 |
Mr = 845.35 | Dx = 1.549 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 966 reflections |
a = 24.281 (3) Å | θ = 2.3–19.6° |
b = 17.339 (2) Å | µ = 1.91 mm−1 |
c = 17.715 (2) Å | T = 293 K |
β = 103.63 (1)° | Prism, yellow |
V = 7248.1 (15) Å3 | 0.2 × 0.15 × 0.1 mm |
Z = 8 |
Bruker SMART APEX CCD area-detector diffractometer | 7082 independent reflections |
Radiation source: fine-focus sealed tube | 5746 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −29→27 |
Tmin = 0.72, Tmax = 0.83 | k = −20→21 |
19353 measured reflections | l = −21→21 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.065P)2 + 1.99P] where P = (Fo2 + 2Fc2)/3 |
7082 reflections | (Δ/σ)max < 0.001 |
460 parameters | Δρmax = 0.77 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
[Gd(H2O)(NO3)2(C24H28N4O4)](NO3)·0.5CH4O·1.75H2O | V = 7248.1 (15) Å3 |
Mr = 845.35 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.281 (3) Å | µ = 1.91 mm−1 |
b = 17.339 (2) Å | T = 293 K |
c = 17.715 (2) Å | 0.2 × 0.15 × 0.1 mm |
β = 103.63 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 7082 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 5746 reflections with I > 2σ(I) |
Tmin = 0.72, Tmax = 0.83 | Rint = 0.042 |
19353 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.77 e Å−3 |
7082 reflections | Δρmin = −0.66 e Å−3 |
460 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) | |
Gd1 | 0.327292 (9) | 0.535467 (13) | 0.087375 (13) | 0.04056 (10) | |
C1 | 0.1909 (2) | 0.5932 (3) | 0.0150 (3) | 0.0421 (11) | |
C2 | 0.1334 (2) | 0.5807 (3) | 0.0195 (3) | 0.0466 (12) | |
C3 | 0.0894 (2) | 0.6146 (3) | −0.0352 (3) | 0.0519 (12) | |
H3 | 0.0526 | 0.6061 | −0.0304 | 0.062* | |
C4 | 0.0966 (2) | 0.6589 (3) | −0.0945 (3) | 0.0495 (12) | |
C5 | 0.1522 (2) | 0.6713 (3) | −0.0996 (3) | 0.0473 (11) | |
H5 | 0.1585 | 0.7017 | −0.1399 | 0.057* | |
C6 | 0.1988 (2) | 0.6403 (3) | −0.0472 (3) | 0.0422 (11) | |
C7 | 0.2545 (2) | 0.6624 (3) | −0.0572 (3) | 0.0432 (11) | |
H7 | 0.2552 | 0.6978 | −0.0963 | 0.052* | |
C8 | 0.3530 (2) | 0.6729 (3) | −0.0396 (3) | 0.0480 (12) | |
H8A | 0.3578 | 0.7258 | −0.0212 | 0.058* | |
H8B | 0.3469 | 0.6736 | −0.0957 | 0.058* | |
C9 | 0.4058 (2) | 0.6278 (3) | −0.0050 (3) | 0.0463 (11) | |
H9 | 0.4390 | 0.6585 | −0.0084 | 0.056* | |
C10 | 0.4089 (2) | 0.5497 (3) | −0.0437 (3) | 0.0507 (13) | |
H10A | 0.4084 | 0.5568 | −0.0981 | 0.061* | |
H10B | 0.4437 | 0.5234 | −0.0188 | 0.061* | |
C11 | 0.3359 (2) | 0.4635 (3) | −0.0944 (3) | 0.0445 (11) | |
H11 | 0.3514 | 0.4659 | −0.1376 | 0.053* | |
C12 | 0.2875 (2) | 0.4149 (3) | −0.1004 (3) | 0.0425 (11) | |
C13 | 0.2620 (2) | 0.3852 (3) | −0.1731 (3) | 0.0451 (11) | |
H13 | 0.2757 | 0.4008 | −0.2154 | 0.054* | |
C14 | 0.2162 (2) | 0.3325 (3) | −0.1862 (3) | 0.0500 (12) | |
C15 | 0.1968 (2) | 0.3104 (3) | −0.1239 (3) | 0.0490 (12) | |
H15 | 0.1679 | 0.2740 | −0.1307 | 0.059* | |
C16 | 0.2187 (2) | 0.3408 (3) | −0.0491 (3) | 0.0448 (11) | |
C17 | 0.2643 (2) | 0.3944 (3) | −0.0358 (3) | 0.0411 (10) | |
C18 | 0.1935 (2) | 0.3172 (3) | 0.0124 (3) | 0.0488 (12) | |
H18 | 0.1645 | 0.2808 | 0.0007 | 0.059* | |
C19 | 0.1796 (2) | 0.3147 (3) | 0.1428 (3) | 0.0523 (13) | |
H19A | 0.2064 | 0.3156 | 0.1930 | 0.063* | |
H19B | 0.1682 | 0.2615 | 0.1314 | 0.063* | |
C20 | 0.1279 (2) | 0.3614 (3) | 0.1480 (3) | 0.0541 (13) | |
H20 | 0.1085 | 0.3325 | 0.1816 | 0.065* | |
C21 | 0.1401 (2) | 0.4412 (3) | 0.1836 (3) | 0.0536 (13) | |
H21A | 0.1063 | 0.4607 | 0.1975 | 0.064* | |
H21B | 0.1698 | 0.4374 | 0.2309 | 0.064* | |
C22 | 0.1213 (2) | 0.5315 (3) | 0.0784 (3) | 0.0503 (13) | |
H22 | 0.0834 | 0.5249 | 0.0788 | 0.060* | |
C23 | 0.0477 (2) | 0.6953 (3) | −0.1535 (3) | 0.0608 (15) | |
H23A | 0.0271 | 0.6559 | −0.1866 | 0.091* | |
H23B | 0.0623 | 0.7321 | −0.1843 | 0.091* | |
H23C | 0.0228 | 0.7210 | −0.1267 | 0.091* | |
C24 | 0.1913 (2) | 0.3031 (3) | −0.2674 (3) | 0.0605 (14) | |
H24A | 0.1865 | 0.2483 | −0.2659 | 0.091* | |
H24B | 0.2164 | 0.3153 | −0.3002 | 0.091* | |
H24C | 0.1552 | 0.3272 | −0.2875 | 0.091* | |
N1 | 0.30270 (16) | 0.6384 (2) | −0.0179 (2) | 0.0422 (9) | |
N2 | 0.36000 (16) | 0.5038 (2) | −0.0361 (2) | 0.0422 (9) | |
N3 | 0.20788 (18) | 0.3427 (2) | 0.0836 (2) | 0.0478 (10) | |
N4 | 0.15769 (18) | 0.4960 (2) | 0.1304 (3) | 0.0480 (10) | |
N5 | 0.36152 (18) | 0.6432 (2) | 0.2197 (2) | 0.0481 (10) | |
N6 | 0.3043 (2) | 0.4243 (2) | 0.2431 (3) | 0.0533 (11) | |
N7 | 0.55886 (19) | 0.6875 (3) | 0.9824 (3) | 0.0621 (12) | |
O1 | 0.28529 (14) | 0.42178 (19) | 0.03323 (19) | 0.0495 (8) | |
H1A | 0.2578 | 0.4165 | 0.0550 | 0.059* | |
O2 | 0.40624 (13) | 0.61567 (18) | 0.07540 (18) | 0.0457 (8) | |
H2B | 0.4415 | 0.5909 | 0.1013 | 0.055* | |
O3 | 0.23233 (14) | 0.5631 (2) | 0.0647 (2) | 0.0495 (8) | |
H3B | 0.2188 | 0.5187 | 0.0700 | 0.059* | |
O4 | 0.08898 (16) | 0.3703 (2) | 0.0765 (2) | 0.0588 (9) | |
H4 | 0.0751 | 0.3283 | 0.0615 | 0.088* | |
O5 | 0.31832 (15) | 0.65457 (18) | 0.1651 (2) | 0.0515 (8) | |
O6 | 0.38519 (14) | 0.5785 (2) | 0.21972 (19) | 0.0523 (8) | |
O7 | 0.37861 (16) | 0.6914 (2) | 0.2699 (2) | 0.0631 (10) | |
O8 | 0.28519 (16) | 0.46850 (19) | 0.1861 (2) | 0.0534 (9) | |
O9 | 0.27416 (17) | 0.4058 (2) | 0.2864 (2) | 0.0657 (10) | |
O10 | 0.35300 (19) | 0.4002 (2) | 0.2552 (2) | 0.0740 (12) | |
O11 | 0.40437 (16) | 0.4476 (2) | 0.1337 (2) | 0.0582 (9) | |
H11A | 0.4016 | 0.4055 | 0.0979 | 0.070* | |
H11B | 0.4022 | 0.4283 | 0.1837 | 0.070* | |
O12 | 0.55077 (19) | 0.7215 (2) | 1.0387 (3) | 0.0779 (12) | |
O13 | 0.58443 (18) | 0.7178 (3) | 0.9383 (3) | 0.0822 (13) | |
O14 | 0.53881 (17) | 0.6243 (2) | 0.9670 (3) | 0.0732 (12) | |
O1W | 0.51608 (16) | 0.5975 (2) | 0.1362 (2) | 0.0747 (12) | |
H1WB | 0.5310 | 0.6068 | 0.0984 | 0.090* | |
H1WC | 0.5242 | 0.6336 | 0.1694 | 0.090* | |
O3W | 0.5361 (7) | 0.2322 (9) | 0.1821 (10) | 0.073 (5) | 0.25 |
H3WA | 0.5264 | 0.1899 | 0.1583 | 0.088* | 0.25 |
H3WB | 0.5713 | 0.2424 | 0.1911 | 0.088* | 0.25 |
O15 | 0.0737 (5) | 0.4257 (6) | 0.8670 (6) | 0.103 (3) | 0.50 |
H15A | 0.0756 | 0.4152 | 0.9127 | 0.123* | 0.50 |
C25 | 0.0274 (7) | 0.4707 (9) | 0.8394 (10) | 0.107 (6) | 0.50 |
H25A | −0.0062 | 0.4431 | 0.8429 | 0.129* | 0.50 |
H25B | 0.0254 | 0.4837 | 0.7861 | 0.129* | 0.50 |
H25C | 0.0303 | 0.5171 | 0.8696 | 0.129* | 0.50 |
O2W | 0.5000 | 0.4771 (5) | 0.2500 | 0.148 (4) | |
H2WA | 0.5244 | 0.4964 | 0.2280 | 0.178* | 0.50 |
H2WC | 0.5057 | 0.4943 | 0.2961 | 0.178* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Gd1 | 0.04522 (16) | 0.04282 (16) | 0.03391 (15) | −0.00028 (10) | 0.00984 (10) | −0.00061 (10) |
C1 | 0.046 (3) | 0.038 (2) | 0.044 (3) | −0.002 (2) | 0.014 (2) | 0.000 (2) |
C2 | 0.049 (3) | 0.043 (3) | 0.049 (3) | −0.003 (2) | 0.014 (2) | 0.001 (2) |
C3 | 0.045 (3) | 0.053 (3) | 0.056 (3) | −0.004 (2) | 0.010 (2) | −0.005 (3) |
C4 | 0.046 (3) | 0.052 (3) | 0.048 (3) | −0.002 (2) | 0.006 (2) | 0.001 (2) |
C5 | 0.053 (3) | 0.046 (3) | 0.041 (3) | −0.001 (2) | 0.007 (2) | 0.003 (2) |
C6 | 0.046 (3) | 0.037 (2) | 0.042 (3) | −0.001 (2) | 0.006 (2) | 0.001 (2) |
C7 | 0.046 (3) | 0.044 (3) | 0.040 (3) | −0.001 (2) | 0.010 (2) | 0.004 (2) |
C8 | 0.051 (3) | 0.052 (3) | 0.043 (3) | −0.007 (2) | 0.016 (2) | −0.001 (2) |
C9 | 0.046 (3) | 0.047 (3) | 0.048 (3) | −0.006 (2) | 0.013 (2) | −0.005 (2) |
C10 | 0.048 (3) | 0.056 (3) | 0.052 (3) | −0.003 (2) | 0.018 (2) | 0.002 (2) |
C11 | 0.047 (3) | 0.048 (3) | 0.041 (3) | 0.002 (2) | 0.015 (2) | 0.000 (2) |
C12 | 0.051 (3) | 0.042 (3) | 0.036 (3) | 0.003 (2) | 0.013 (2) | −0.003 (2) |
C13 | 0.051 (3) | 0.046 (3) | 0.040 (3) | −0.002 (2) | 0.014 (2) | −0.006 (2) |
C14 | 0.060 (3) | 0.049 (3) | 0.042 (3) | 0.000 (2) | 0.015 (2) | −0.007 (2) |
C15 | 0.050 (3) | 0.047 (3) | 0.051 (3) | −0.006 (2) | 0.013 (2) | −0.006 (2) |
C16 | 0.047 (3) | 0.046 (3) | 0.043 (3) | 0.001 (2) | 0.014 (2) | 0.002 (2) |
C17 | 0.047 (3) | 0.040 (2) | 0.035 (3) | 0.002 (2) | 0.008 (2) | −0.002 (2) |
C18 | 0.049 (3) | 0.046 (3) | 0.052 (3) | −0.004 (2) | 0.012 (2) | 0.002 (2) |
C19 | 0.060 (3) | 0.049 (3) | 0.052 (3) | −0.001 (2) | 0.022 (3) | 0.007 (2) |
C20 | 0.062 (3) | 0.051 (3) | 0.057 (3) | −0.002 (2) | 0.028 (3) | 0.008 (2) |
C21 | 0.061 (3) | 0.056 (3) | 0.050 (3) | −0.001 (3) | 0.026 (3) | 0.003 (2) |
C22 | 0.051 (3) | 0.048 (3) | 0.056 (3) | −0.002 (2) | 0.021 (3) | −0.004 (2) |
C23 | 0.047 (3) | 0.068 (4) | 0.063 (4) | 0.003 (3) | 0.004 (3) | 0.007 (3) |
C24 | 0.061 (3) | 0.070 (4) | 0.047 (3) | −0.013 (3) | 0.006 (3) | −0.015 (3) |
N1 | 0.047 (2) | 0.046 (2) | 0.034 (2) | −0.0043 (18) | 0.0107 (18) | −0.0014 (17) |
N2 | 0.044 (2) | 0.043 (2) | 0.040 (2) | −0.0039 (18) | 0.0125 (18) | −0.0015 (19) |
N3 | 0.058 (3) | 0.045 (2) | 0.043 (2) | 0.0008 (19) | 0.017 (2) | 0.0021 (18) |
N4 | 0.057 (3) | 0.043 (2) | 0.046 (2) | 0.002 (2) | 0.016 (2) | 0.0058 (19) |
N5 | 0.054 (3) | 0.050 (3) | 0.044 (3) | 0.000 (2) | 0.019 (2) | −0.005 (2) |
N6 | 0.067 (3) | 0.048 (3) | 0.043 (3) | −0.001 (2) | 0.010 (2) | 0.002 (2) |
N7 | 0.051 (3) | 0.064 (3) | 0.074 (4) | −0.011 (2) | 0.019 (3) | −0.009 (3) |
O1 | 0.056 (2) | 0.056 (2) | 0.041 (2) | −0.0088 (16) | 0.0202 (16) | −0.0048 (16) |
O2 | 0.0486 (19) | 0.053 (2) | 0.0345 (18) | −0.0040 (15) | 0.0079 (14) | 0.0011 (14) |
O3 | 0.0467 (19) | 0.0537 (19) | 0.049 (2) | −0.0017 (16) | 0.0118 (16) | 0.0116 (17) |
O4 | 0.060 (2) | 0.055 (2) | 0.062 (3) | −0.0062 (17) | 0.0145 (19) | 0.0008 (18) |
O5 | 0.053 (2) | 0.050 (2) | 0.053 (2) | 0.0062 (16) | 0.0157 (18) | 0.0032 (16) |
O6 | 0.061 (2) | 0.050 (2) | 0.043 (2) | 0.0015 (17) | 0.0076 (17) | −0.0027 (16) |
O7 | 0.074 (3) | 0.059 (2) | 0.056 (2) | −0.0049 (19) | 0.016 (2) | −0.0186 (19) |
O8 | 0.063 (2) | 0.056 (2) | 0.042 (2) | 0.0001 (16) | 0.0136 (18) | 0.0078 (16) |
O9 | 0.074 (3) | 0.075 (3) | 0.050 (2) | −0.006 (2) | 0.018 (2) | 0.0144 (19) |
O10 | 0.074 (3) | 0.080 (3) | 0.067 (3) | 0.008 (2) | 0.015 (2) | 0.022 (2) |
O11 | 0.067 (2) | 0.055 (2) | 0.053 (2) | 0.0114 (17) | 0.0137 (19) | −0.0015 (17) |
O12 | 0.098 (3) | 0.071 (3) | 0.071 (3) | −0.019 (2) | 0.031 (3) | −0.014 (2) |
O13 | 0.075 (3) | 0.090 (3) | 0.086 (3) | −0.028 (2) | 0.029 (3) | −0.016 (3) |
O14 | 0.068 (3) | 0.059 (3) | 0.098 (3) | −0.007 (2) | 0.031 (2) | −0.013 (2) |
O1W | 0.061 (2) | 0.087 (3) | 0.070 (3) | −0.003 (2) | 0.003 (2) | 0.010 (2) |
O3W | 0.068 (10) | 0.059 (10) | 0.098 (14) | −0.007 (8) | 0.031 (9) | −0.013 (9) |
O15 | 0.119 (9) | 0.085 (7) | 0.094 (8) | 0.026 (6) | 0.002 (7) | −0.009 (6) |
C25 | 0.094 (12) | 0.128 (15) | 0.103 (13) | −0.035 (10) | 0.032 (10) | −0.073 (11) |
O2W | 0.127 (8) | 0.113 (7) | 0.180 (11) | 0.000 | −0.012 (7) | 0.000 |
Gd1—O3 | 2.296 (3) | C17—O1 | 1.299 (5) |
Gd1—O1 | 2.321 (3) | C18—N3 | 1.304 (6) |
Gd1—O11 | 2.403 (3) | C18—H18 | 0.930 |
Gd1—O2 | 2.418 (3) | C19—N3 | 1.467 (6) |
Gd1—O8 | 2.510 (3) | C19—C20 | 1.514 (7) |
Gd1—O5 | 2.520 (3) | C19—H19A | 0.970 |
Gd1—O6 | 2.545 (3) | C19—H19B | 0.970 |
Gd1—N1 | 2.548 (4) | C20—O4 | 1.398 (6) |
Gd1—N2 | 2.556 (4) | C20—C21 | 1.521 (7) |
Gd1—N5 | 2.959 (4) | C20—H20 | 0.980 |
Gd1—H3B | 2.5943 | C21—N4 | 1.471 (6) |
C1—O3 | 1.282 (6) | C21—H21A | 0.970 |
C1—C6 | 1.420 (6) | C21—H21B | 0.970 |
C1—C2 | 1.433 (7) | C22—N4 | 1.275 (7) |
C2—C3 | 1.391 (7) | C22—H22 | 0.9300 |
C2—C22 | 1.431 (7) | C23—H23A | 0.960 |
C3—C4 | 1.346 (7) | C23—H23B | 0.960 |
C3—H3 | 0.930 | C23—H23C | 0.960 |
C4—C5 | 1.390 (7) | C24—H24A | 0.960 |
C4—C23 | 1.521 (7) | C24—H24B | 0.960 |
C5—C6 | 1.391 (7) | C24—H24C | 0.960 |
C5—H5 | 0.930 | N5—O7 | 1.219 (5) |
C6—C7 | 1.457 (7) | N5—O6 | 1.260 (5) |
C7—N1 | 1.281 (6) | N5—O5 | 1.264 (5) |
C7—H7 | 0.930 | N6—O9 | 1.221 (5) |
C8—N1 | 1.491 (6) | N6—O10 | 1.226 (6) |
C8—C9 | 1.503 (7) | N6—O8 | 1.265 (5) |
C8—H8A | 0.970 | N7—O14 | 1.203 (6) |
C8—H8B | 0.970 | N7—O12 | 1.214 (6) |
C9—O2 | 1.438 (6) | N7—O13 | 1.226 (6) |
C9—C10 | 1.527 (7) | O1—H1A | 0.850 |
C9—H9 | 0.980 | O2—H2B | 0.970 |
C10—N2 | 1.461 (6) | O3—H3B | 0.850 |
C10—H10A | 0.970 | O4—H4 | 0.820 |
C10—H10B | 0.970 | O11—H11A | 0.960 |
C11—N2 | 1.269 (6) | O11—H11B | 0.960 |
C11—C12 | 1.431 (7) | O1W—H1WB | 0.850 |
C11—H11 | 0.9300 | O1W—H1WC | 0.850 |
C12—C13 | 1.390 (6) | O3W—H3WA | 0.850 |
C12—C17 | 1.435 (6) | O3W—H3WB | 0.850 |
C13—C14 | 1.414 (7) | O15—C25 | 1.361 (18) |
C13—H13 | 0.930 | O15—H15A | 0.820 |
C14—C15 | 1.355 (7) | C25—H25A | 0.960 |
C14—C24 | 1.510 (7) | C25—H25B | 0.960 |
C15—C16 | 1.409 (7) | C25—H25C | 0.960 |
C15—H15 | 0.930 | O2W—H2WA | 0.850 |
C16—C17 | 1.420 (7) | O2W—H2WC | 0.850 |
C16—C18 | 1.430 (7) | ||
O3—Gd1—O1 | 77.25 (12) | C11—C12—C17 | 123.9 (4) |
O3—Gd1—O11 | 149.46 (12) | C12—C13—C14 | 123.6 (5) |
O1—Gd1—O11 | 80.43 (12) | C12—C13—H13 | 118.2 |
O3—Gd1—O2 | 130.49 (11) | C14—C13—H13 | 118.2 |
O1—Gd1—O2 | 137.11 (11) | C15—C14—C13 | 117.3 (5) |
O11—Gd1—O2 | 79.90 (12) | C15—C14—C24 | 122.8 (5) |
O3—Gd1—O8 | 70.18 (12) | C13—C14—C24 | 119.8 (5) |
O1—Gd1—O8 | 71.55 (11) | C14—C15—C16 | 122.3 (5) |
O11—Gd1—O8 | 83.16 (12) | C14—C15—H15 | 118.9 |
O2—Gd1—O8 | 142.09 (11) | C16—C15—H15 | 118.9 |
O3—Gd1—O5 | 73.27 (12) | C15—C16—C17 | 120.5 (4) |
O1—Gd1—O5 | 146.71 (11) | C15—C16—C18 | 118.3 (4) |
O11—Gd1—O5 | 119.58 (12) | C17—C16—C18 | 121.2 (4) |
O2—Gd1—O5 | 75.46 (11) | O1—C17—C16 | 120.9 (4) |
O8—Gd1—O5 | 84.05 (11) | O1—C17—C12 | 121.3 (4) |
O3—Gd1—O6 | 114.46 (12) | C16—C17—C12 | 117.8 (4) |
O1—Gd1—O6 | 136.33 (11) | N3—C18—C16 | 125.0 (5) |
O11—Gd1—O6 | 69.78 (12) | N3—C18—H18 | 117.5 |
O2—Gd1—O6 | 68.59 (11) | C16—C18—H18 | 117.5 |
O8—Gd1—O6 | 73.77 (11) | N3—C19—C20 | 113.6 (4) |
O5—Gd1—O6 | 49.94 (11) | N3—C19—H19A | 108.8 |
O3—Gd1—N1 | 70.95 (12) | C20—C19—H19A | 108.8 |
O1—Gd1—N1 | 106.73 (12) | N3—C19—H19B | 108.8 |
O11—Gd1—N1 | 136.33 (13) | C20—C19—H19B | 108.8 |
O2—Gd1—N1 | 65.61 (11) | H19A—C19—H19B | 107.7 |
O8—Gd1—N1 | 140.40 (12) | O4—C20—C19 | 113.4 (4) |
O5—Gd1—N1 | 77.90 (12) | O4—C20—C21 | 107.4 (4) |
O6—Gd1—N1 | 116.89 (12) | C19—C20—C21 | 115.4 (5) |
O3—Gd1—N2 | 113.39 (12) | O4—C20—H20 | 106.7 |
O1—Gd1—N2 | 70.06 (12) | C19—C20—H20 | 106.7 |
O11—Gd1—N2 | 77.42 (13) | C21—C20—H20 | 106.7 |
O2—Gd1—N2 | 68.63 (11) | N4—C21—C20 | 112.2 (4) |
O8—Gd1—N2 | 139.20 (12) | N4—C21—H21A | 109.2 |
O5—Gd1—N2 | 136.69 (12) | C20—C21—H21A | 109.2 |
O6—Gd1—N2 | 129.47 (12) | N4—C21—H21B | 109.2 |
N1—Gd1—N2 | 65.83 (12) | C20—C21—H21B | 109.2 |
O3—Gd1—N5 | 95.17 (12) | H21A—C21—H21B | 107.9 |
O1—Gd1—N5 | 151.35 (11) | N4—C22—C2 | 126.2 (5) |
O11—Gd1—N5 | 94.51 (12) | N4—C22—H22 | 116.9 |
O2—Gd1—N5 | 68.04 (11) | C2—C22—H22 | 116.9 |
O8—Gd1—N5 | 79.87 (11) | C4—C23—H23A | 109.5 |
O5—Gd1—N5 | 25.07 (11) | C4—C23—H23B | 109.5 |
O6—Gd1—N5 | 25.04 (11) | H23A—C23—H23B | 109.5 |
N1—Gd1—N5 | 96.41 (12) | C4—C23—H23C | 109.5 |
N2—Gd1—N5 | 136.67 (12) | H23A—C23—H23C | 109.5 |
O3—Gd1—H3B | 18.8 | H23B—C23—H23C | 109.5 |
O1—Gd1—H3B | 61.4 | C14—C24—H24A | 109.5 |
O11—Gd1—H3B | 131.0 | C14—C24—H24B | 109.5 |
O2—Gd1—H3B | 149.1 | H24A—C24—H24B | 109.5 |
O8—Gd1—H3B | 57.5 | C14—C24—H24C | 109.5 |
O5—Gd1—H3B | 86.6 | H24A—C24—H24C | 109.5 |
O6—Gd1—H3B | 117.8 | H24B—C24—H24C | 109.5 |
N1—Gd1—H3B | 86.3 | C7—N1—C8 | 115.4 (4) |
N2—Gd1—H3B | 112.7 | C7—N1—Gd1 | 130.7 (3) |
N5—Gd1—H3B | 104.6 | C8—N1—Gd1 | 113.9 (3) |
O3—C1—C6 | 122.7 (4) | C11—N2—C10 | 116.9 (4) |
O3—C1—C2 | 121.2 (4) | C11—N2—Gd1 | 129.6 (3) |
C6—C1—C2 | 116.2 (4) | C10—N2—Gd1 | 112.6 (3) |
C3—C2—C22 | 120.3 (5) | C18—N3—C19 | 121.1 (4) |
C3—C2—C1 | 119.7 (5) | C22—N4—C21 | 121.3 (4) |
C22—C2—C1 | 120.0 (5) | O7—N5—O6 | 122.2 (4) |
C4—C3—C2 | 124.4 (5) | O7—N5—O5 | 122.0 (4) |
C4—C3—H3 | 117.8 | O6—N5—O5 | 115.8 (4) |
C2—C3—H3 | 117.8 | O7—N5—Gd1 | 173.6 (3) |
C3—C4—C5 | 116.4 (5) | O6—N5—Gd1 | 58.7 (2) |
C3—C4—C23 | 123.3 (5) | O5—N5—Gd1 | 57.6 (2) |
C5—C4—C23 | 120.3 (5) | O9—N6—O10 | 119.8 (4) |
C4—C5—C6 | 123.2 (5) | O9—N6—O8 | 120.0 (5) |
C4—C5—H5 | 118.4 | O10—N6—O8 | 120.2 (5) |
C6—C5—H5 | 118.4 | O14—N7—O12 | 119.5 (5) |
C5—C6—C1 | 120.1 (4) | O14—N7—O13 | 119.0 (5) |
C5—C6—C7 | 116.8 (4) | O12—N7—O13 | 121.3 (5) |
C1—C6—C7 | 123.0 (4) | C17—O1—Gd1 | 137.5 (3) |
N1—C7—C6 | 127.2 (4) | C17—O1—H1A | 102.2 |
N1—C7—H7 | 116.4 | Gd1—O1—H1A | 102.6 |
C6—C7—H7 | 116.4 | C9—O2—Gd1 | 110.5 (2) |
N1—C8—C9 | 111.0 (4) | C9—O2—H2B | 109.5 |
N1—C8—H8A | 109.4 | Gd1—O2—H2B | 109.4 |
C9—C8—H8A | 109.4 | C1—O3—Gd1 | 143.0 (3) |
N1—C8—H8B | 109.4 | C1—O3—H3B | 100.6 |
C9—C8—H8B | 109.4 | Gd1—O3—H3B | 100.9 |
H8A—C8—H8B | 108.0 | C20—O4—H4 | 109.5 |
O2—C9—C8 | 106.6 (4) | N5—O5—Gd1 | 97.3 (3) |
O2—C9—C10 | 109.0 (4) | N5—O6—Gd1 | 96.2 (3) |
C8—C9—C10 | 114.0 (4) | N6—O8—Gd1 | 134.8 (3) |
O2—C9—H9 | 109.1 | Gd1—O11—H11A | 109.3 |
C8—C9—H9 | 109.1 | Gd1—O11—H11B | 109.2 |
C10—C9—H9 | 109.1 | H11A—O11—H11B | 109.5 |
N2—C10—C9 | 108.4 (4) | H1WB—O1W—H1WC | 109.5 |
N2—C10—H10A | 110.0 | H3WA—O3W—H3WB | 114.9 |
C9—C10—H10A | 110.0 | C25—O15—H15A | 109.5 |
N2—C10—H10B | 110.0 | O15—C25—H25A | 109.5 |
C9—C10—H10B | 110.0 | O15—C25—H25B | 109.5 |
H10A—C10—H10B | 108.4 | H25A—C25—H25B | 109.5 |
N2—C11—C12 | 126.7 (5) | O15—C25—H25C | 109.5 |
N2—C11—H11 | 116.6 | H25A—C25—H25C | 109.5 |
C12—C11—H11 | 116.6 | H25B—C25—H25C | 109.5 |
C13—C12—C11 | 117.8 (4) | H2WA—O2W—H2WC | 109.4 |
C13—C12—C17 | 118.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O12i | 0.85 | 2.35 | 3.000 (6) | 133 |
O1W—H1WB···O14i | 0.85 | 2.40 | 3.207 (6) | 159 |
O2W—H2WA···O6ii | 0.85 | 2.60 | 3.232 (6) | 132 |
O2W—H2WC···O1Wii | 0.85 | 2.28 | 2.990 (7) | 141 |
O2W—H2WC···O11ii | 0.85 | 2.39 | 2.765 (4) | 108 |
O1W—H1WC···O7ii | 0.85 | 2.56 | 3.154 (6) | 128 |
O11—H11A···O13iii | 0.96 | 2.28 | 3.177 (6) | 155 |
O11—H11A···O14iii | 0.96 | 2.11 | 2.794 (5) | 127 |
O4—H4···O12iv | 0.82 | 1.96 | 2.771 (5) | 171 |
C18—H18···O13iv | 0.93 | 2.28 | 3.172 (7) | 161 |
C20—H20···O7v | 0.98 | 2.59 | 3.309 (6) | 130 |
C19—H19A···O9 | 0.97 | 2.57 | 3.390 (7) | 142 |
C21—H21B···O9 | 0.97 | 2.55 | 3.391 (7) | 145 |
O11—H11B···O10 | 0.96 | 2.00 | 2.852 (6) | 147 |
O2W—H2WA···O1W | 0.85 | 2.37 | 2.990 (7) | 130 |
O2—H2B···O1W | 0.97 | 1.77 | 2.649 (5) | 148 |
O1—H1A···N3 | 0.85 | 1.91 | 2.646 (5) | 144 |
O3—H3B···N4 | 0.85 | 2.06 | 2.643 (5) | 125 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, y, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) x−1/2, y−1/2, z−1; (v) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Gd(H2O)(NO3)2(C24H28N4O4)](NO3)·0.5CH4O·1.75H2O |
Mr | 845.35 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 24.281 (3), 17.339 (2), 17.715 (2) |
β (°) | 103.63 (1) |
V (Å3) | 7248.1 (15) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.91 |
Crystal size (mm) | 0.2 × 0.15 × 0.1 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.72, 0.83 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19353, 7082, 5746 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.118, 1.08 |
No. of reflections | 7082 |
No. of parameters | 460 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.77, −0.66 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O12i | 0.85 | 2.35 | 3.000 (6) | 133 |
O1W—H1WB···O14i | 0.85 | 2.40 | 3.207 (6) | 159 |
O2W—H2WA···O6ii | 0.85 | 2.60 | 3.232 (6) | 132 |
O2W—H2WC···O1Wii | 0.85 | 2.28 | 2.990 (7) | 141 |
O2W—H2WC···O11ii | 0.85 | 2.39 | 2.765 (4) | 108 |
O1W—H1WC···O7ii | 0.85 | 2.56 | 3.154 (6) | 128 |
O11—H11A···O13iii | 0.96 | 2.28 | 3.177 (6) | 155 |
O11—H11A···O14iii | 0.96 | 2.11 | 2.794 (5) | 127 |
O4—H4···O12iv | 0.82 | 1.96 | 2.771 (5) | 171 |
C18—H18···O13iv | 0.93 | 2.28 | 3.172 (7) | 161 |
C20—H20···O7v | 0.98 | 2.59 | 3.309 (6) | 130 |
C19—H19A···O9 | 0.97 | 2.57 | 3.390 (7) | 142 |
C21—H21B···O9 | 0.97 | 2.55 | 3.391 (7) | 145 |
O11—H11B···O10 | 0.96 | 2.00 | 2.852 (6) | 147 |
O2W—H2WA···O1W | 0.85 | 2.37 | 2.990 (7) | 130 |
O2—H2B···O1W | 0.97 | 1.77 | 2.649 (5) | 148 |
O1—H1A···N3 | 0.85 | 1.91 | 2.646 (5) | 144 |
O3—H3B···N4 | 0.85 | 2.06 | 2.643 (5) | 125 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, y, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) x−1/2, y−1/2, z−1; (v) −x+1/2, y−1/2, −z+1/2. |
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The design and synthesis of macrocyclic ligands and their lanthanide complexes are an interesting area of research, due to their importance in basic and applied chemistry (Alexander, 1995). The ability of macrocyclic ligands to recognize lanthanide(III) ions makes them valuable for the development of applications such as selective separation of metals (Zhu & Izatt, 1990), luminescence probes in biological systems (Faulkner et al., 2001) and supramolecular devices (Chen et al., 2002). Gadolinium macrocyclic complexes have been extensively investigated, owing to their potential application in magnetic resonance imaging (Caravan et al., 1999). 18- and 20-membered macrocycles, derived from [2 + 2]-condensation of 2,6-diformylphenol and diamines, have good complexing properties for lanthanide ions (Alexander, 1995), but only a few gadolinium complexes have been reported (Drew et al., 1995).
We report here the crystal structure of a new gadolinium complex, [Gd(H4L)(NO3)2(H2O)](NO3)·0.5MeOH·1.75H2O, (I), with the neutral Schiff base ligand H4L derived from 4-methyl-2,6-diformylphenol and 1,3-diaminopropanol. The same complex as a dihydrate, [Gd(H4L)(NO3)2(H2O)](NO3)·2H2O, has been reported previously (Spodine et al., 2000), but (I) is a different solvate, belonging to a different crystal system (monoclinic, space group C2/c, compared with orthorhombic, Pbca).
In (I), atom Gd1 is coordinated by a monodentate nitrate ion, a bidentate nitrate ion, a water molecule, and the neutral Schiff base macrocycle H4L, namely 5,17-dihydroxy-11,23-dimethylbicyclo[18.3.1.19,13]hexacosa- 1(25),2,7,9,11,13 (26),21,23-octaene-25,26-diol, which provides an N2O3 donor set to encapsulate only one gadolinium ion. The coordination polyhedron can be described as a distorted monocapped square antiprism, in which atoms N1, N2, O1 and O3 of H4L form the basal plane [mean deviation = 0.0595 (2) Å], the upper plane consists of O2, O11 (water molecule), O8 (from monodentate nitrate) and O5 (from bidentate nitrate) [mean deviation = 0.2160 (2) Å], and another oxygen atom (O6) from the bidentate nitrate occupies the capping position.
The coordination distance is 2.418 (3) Å for the alcohol atom O2, slightly longer than those for the phenol atoms O1 [2.321 (3) Å] and O3 [2.296 (4) Å]. The Gd—O distances for the three-coordinate O atoms from the monodentate and the bidentate nitrate ions are in the range 2.509 (4)–2.545 (3) Å, and for O11 from the water molecule it is 2.403 (4) Å. Of the nine coordination distances, the longest are those for the two imino atoms N1 [2.549 (3) Å] and N2 ([2.556 (4) Å]. Among all the nine coordination distances, only two (for water atom O11 and the phenol atom O1) are shorter than those of the previously reported complex (Spondine et al., 2000), while the others show no significant differences. The two crystal structures belong to different crystal systems (monoclinic and orthorhomic, with space groups C2/c and Pbca, respectively), and have different solvent content. There is a larger dihedral angle between the two aromatic rings of 55.5 (2)° in the macrocyclic ligand of our complex, compared to 41.6° for the previous complex. The crystal structure of (I) is stabilized by intramolecular and intermolecular hydrogen bonds of the types O—H···O and C—H···O, where O atoms belong to water molecules, nitrate ions or the macrocyclic ligand (Table 1).