The title compound, [Gd2(C8H22N2O12P4)(C2O4)2(H2O)2]·4H2O, was synthesized by the hydrothermal method. It exhibits a pillar–layer structure, with the layers formed by GdIII ions interconnected by the oxalate ions and the –NH(CH2PO3H)2 units of the tetraphosphonate dianions. The central organic groups of the tetraphosphonate ligands act as the pillars. Each oxalate ion bridges two GdIII ions and each tetraphosphonate ligand bridges six GdIII ions. Inversion centres are located at the mid-points of the central C—C bonds of both types of ligands.
Supporting information
CCDC reference: 636792
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.013 Å
- R factor = 0.045
- wR factor = 0.101
- Data-to-parameter ratio = 12.4
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 5.00 Ratio
Alert level C
PLAT048_ALERT_1_C MoietyFormula Not Given ........................ ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) . 60 Ang.
PLAT213_ALERT_2_C Atom N1 has ADP max/min Ratio ............. 3.60 oblat
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.74
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 13
PLAT417_ALERT_2_C Short Inter D-H..H-D H4 .. H12A .. 2.11 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.15 Ratio
Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
9 ALERT level C = Check and explain
2 ALERT level G = General alerts; check
5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 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
Data collection: APEX2 (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
catena Poly[diaqua bis(oxalic acid)
(tetramethylphosphono-1,4-diaminobutane) digadolinium(III)] tetrahydrate
top
Crystal data top
[Gd2(C2O4)2(C8H22O12N2P4)(H2O)2]·4H2O | Z = 2 |
Mr = 530.40 | F(000) = 516 |
Triclinic, P1 | Dx = 2.305 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5191 (6) Å | Cell parameters from 2718 reflections |
b = 9.6282 (6) Å | θ = 2.3–24.7° |
c = 9.6452 (6) Å | µ = 4.62 mm−1 |
α = 106.939 (3)° | T = 293 K |
β = 98.292 (3)° | Needle, colourless |
γ = 110.123 (2)° | 0.25 × 0.04 × 0.03 mm |
V = 764.05 (8) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2728 independent reflections |
Radiation source: fine-focus sealed tube | 2140 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 25.2°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −11→11 |
Tmin = 0.387, Tmax = 0.893 | k = −11→11 |
6629 measured reflections | l = −11→11 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.0597P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max = 0.001 |
2728 reflections | Δρmax = 1.78 e Å−3 |
220 parameters | Δρmin = −1.92 e Å−3 |
15 restraints | Extinction correction: SHELXL (Sheldrick, 1997) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0049 (8) |
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 | x | y | z | Uiso*/Ueq | |
Gd1 | 0.58737 (5) | 0.72593 (4) | 0.81782 (4) | 0.02119 (15) | |
P1 | 0.2630 (3) | 0.4901 (2) | 0.4847 (2) | 0.0234 (5) | |
P2 | 0.2393 (3) | 0.9714 (2) | 0.3473 (3) | 0.0297 (5) | |
N1 | 0.2567 (9) | 0.6690 (8) | 0.3055 (8) | 0.0276 (18) | |
H1A | 0.312 (9) | 0.625 (9) | 0.276 (8) | 0.02 (2)* | |
O7 | 0.4647 (7) | 0.6667 (6) | 1.0071 (6) | 0.0338 (14) | |
O8 | 0.6016 (7) | 1.1558 (6) | 1.1714 (6) | 0.0307 (13) | |
O9 | 0.4134 (7) | 0.5155 (6) | 1.1446 (6) | 0.0308 (14) | |
O10 | 0.6749 (6) | 0.9783 (6) | 1.0313 (6) | 0.0303 (14) | |
O1 | 0.0893 (6) | 0.3920 (6) | 0.4747 (7) | 0.0363 (15) | |
H1 | 0.0525 | 0.3106 | 0.3991 | 0.054* | |
O2 | 0.3090 (6) | 0.4033 (6) | 0.3569 (6) | 0.0258 (13) | |
O3 | 0.3573 (6) | 0.5350 (6) | 0.6421 (6) | 0.0261 (13) | |
O6 | 0.0686 (7) | 0.9018 (7) | 0.2696 (8) | 0.0473 (17) | |
O5 | 0.3374 (7) | 1.1078 (6) | 0.3124 (7) | 0.0377 (15) | |
O4 | 0.2726 (8) | 1.0112 (7) | 0.5199 (7) | 0.0459 (18) | |
H4 | 0.2506 | 1.0860 | 0.5588 | 0.069* | |
O13 | 0.8584 (8) | 0.7984 (8) | 0.9529 (8) | 0.0448 (16) | |
H13B | 0.9171 | 0.8336 | 0.9053 | 0.067* | |
H13A | 0.888 (14) | 0.822 (14) | 1.047 (4) | 0.10 (5)* | |
O12 | 0.7750 (9) | 0.7605 (8) | 0.2989 (7) | 0.0503 (18) | |
H12B | 0.7705 | 0.6848 | 0.3306 | 0.07 (4)* | |
H12A | 0.8709 | 0.8111 | 0.3077 | 0.08 (4)* | |
O11 | 0.0404 (7) | 0.8710 (7) | 0.7654 (7) | 0.0463 (17) | |
H11B | 0.1328 | 0.9118 | 0.8241 | 0.08 (4)* | |
H11A | 0.0217 | 0.9423 | 0.7425 | 0.09 (5)* | |
C1 | 0.0787 (11) | 0.5600 (10) | 0.0478 (10) | 0.045 (3) | |
H12 | 0.0944 | 0.6628 | 0.0417 | 0.054* | |
H11 | 0.1576 | 0.5291 | 0.0118 | 0.054* | |
C2 | 0.0938 (10) | 0.5714 (9) | 0.2129 (9) | 0.035 (2) | |
H22 | 0.0266 | 0.6188 | 0.2537 | 0.042* | |
H21 | 0.0607 | 0.4656 | 0.2164 | 0.042* | |
C3 | 0.3293 (10) | 0.8288 (9) | 0.2943 (10) | 0.030 (2) | |
H32 | 0.3332 | 0.8114 | 0.1909 | 0.036* | |
H31 | 0.4359 | 0.8796 | 0.3564 | 0.036* | |
C4 | 0.2774 (11) | 0.6785 (9) | 0.4664 (9) | 0.032 (2) | |
H42 | 0.1985 | 0.7073 | 0.5048 | 0.038* | |
H41 | 0.3783 | 0.7614 | 0.5273 | 0.038* | |
C5 | 0.5786 (9) | 1.0380 (8) | 1.0576 (9) | 0.0257 (19) | |
C6 | 0.4646 (9) | 0.5530 (9) | 1.0430 (9) | 0.0215 (18) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Gd1 | 0.0333 (3) | 0.0148 (2) | 0.0241 (3) | 0.01659 (17) | 0.01083 (18) | 0.00941 (17) |
P1 | 0.0332 (13) | 0.0179 (10) | 0.0264 (12) | 0.0159 (9) | 0.0105 (10) | 0.0103 (9) |
P2 | 0.0417 (15) | 0.0219 (11) | 0.0392 (14) | 0.0205 (10) | 0.0179 (12) | 0.0178 (10) |
N1 | 0.047 (5) | 0.019 (4) | 0.033 (4) | 0.027 (4) | 0.017 (4) | 0.013 (3) |
O7 | 0.052 (4) | 0.028 (3) | 0.041 (4) | 0.029 (3) | 0.020 (3) | 0.021 (3) |
O8 | 0.040 (4) | 0.026 (3) | 0.029 (3) | 0.020 (3) | 0.004 (3) | 0.007 (3) |
O9 | 0.049 (4) | 0.028 (3) | 0.040 (4) | 0.030 (3) | 0.026 (3) | 0.022 (3) |
O10 | 0.034 (3) | 0.023 (3) | 0.035 (4) | 0.023 (3) | 0.005 (3) | 0.002 (3) |
O1 | 0.035 (4) | 0.029 (3) | 0.043 (4) | 0.013 (3) | 0.018 (3) | 0.007 (3) |
O2 | 0.040 (4) | 0.026 (3) | 0.026 (3) | 0.023 (3) | 0.018 (3) | 0.014 (3) |
O3 | 0.036 (3) | 0.015 (3) | 0.028 (3) | 0.014 (2) | 0.004 (3) | 0.006 (2) |
O6 | 0.042 (4) | 0.031 (3) | 0.077 (5) | 0.023 (3) | 0.018 (4) | 0.022 (3) |
O5 | 0.055 (4) | 0.024 (3) | 0.049 (4) | 0.022 (3) | 0.025 (3) | 0.024 (3) |
O4 | 0.086 (5) | 0.035 (4) | 0.044 (4) | 0.046 (4) | 0.032 (4) | 0.019 (3) |
O13 | 0.049 (4) | 0.046 (4) | 0.040 (5) | 0.029 (3) | 0.010 (4) | 0.006 (3) |
O12 | 0.066 (6) | 0.040 (4) | 0.057 (5) | 0.026 (4) | 0.026 (4) | 0.025 (4) |
O11 | 0.037 (4) | 0.035 (4) | 0.053 (5) | 0.013 (3) | −0.005 (4) | 0.007 (3) |
C1 | 0.059 (7) | 0.038 (5) | 0.040 (6) | 0.022 (5) | 0.003 (5) | 0.019 (5) |
C2 | 0.048 (6) | 0.021 (4) | 0.034 (5) | 0.018 (4) | −0.001 (5) | 0.010 (4) |
C3 | 0.039 (5) | 0.024 (4) | 0.040 (5) | 0.018 (4) | 0.017 (4) | 0.020 (4) |
C4 | 0.053 (6) | 0.024 (4) | 0.018 (5) | 0.017 (4) | 0.002 (4) | 0.010 (4) |
C5 | 0.035 (5) | 0.011 (4) | 0.035 (5) | 0.014 (4) | 0.012 (4) | 0.006 (4) |
C6 | 0.029 (5) | 0.018 (4) | 0.024 (5) | 0.015 (4) | 0.008 (4) | 0.010 (4) |
Geometric parameters (Å, º) top
Gd1—O5i | 2.301 (5) | O9—Gd1iv | 2.452 (5) |
Gd1—O3 | 2.322 (5) | O10—C5 | 1.257 (9) |
Gd1—O2ii | 2.337 (5) | O1—H1 | 0.8200 |
Gd1—O7 | 2.406 (5) | O2—Gd1ii | 2.337 (5) |
Gd1—O8iii | 2.437 (5) | O5—Gd1i | 2.301 (5) |
Gd1—O9iv | 2.452 (5) | O4—H4 | 0.8200 |
Gd1—O10 | 2.456 (5) | O13—H13B | 0.8200 |
Gd1—O13 | 2.470 (7) | O13—H13A | 0.85 (2) |
P1—O2 | 1.489 (5) | O12—H12B | 0.8595 |
P1—O3 | 1.501 (5) | O12—H12A | 0.8517 |
P1—O1 | 1.569 (6) | O11—H11B | 0.8590 |
P1—C4 | 1.834 (8) | O11—H11A | 0.8447 |
P2—O5 | 1.488 (5) | C1—C1v | 1.490 (17) |
P2—O6 | 1.503 (7) | C1—C2 | 1.546 (11) |
P2—O4 | 1.553 (6) | C1—H12 | 0.9700 |
P2—C3 | 1.846 (8) | C1—H11 | 0.9700 |
N1—C2 | 1.482 (11) | C2—H22 | 0.9700 |
N1—C3 | 1.498 (9) | C2—H21 | 0.9700 |
N1—C4 | 1.508 (10) | C3—H32 | 0.9700 |
N1—H1A | 0.82 (8) | C3—H31 | 0.9700 |
O7—C6 | 1.240 (9) | C4—H42 | 0.9700 |
O8—C5 | 1.254 (9) | C4—H41 | 0.9700 |
O8—Gd1iii | 2.437 (5) | C5—C5iii | 1.517 (16) |
O9—C6 | 1.246 (9) | C6—C6iv | 1.524 (14) |
| | | |
O5i—Gd1—O3 | 98.9 (2) | C4—N1—H1A | 103 (5) |
O5i—Gd1—O2ii | 76.27 (18) | C6—O7—Gd1 | 120.5 (5) |
O3—Gd1—O2ii | 80.85 (19) | C5—O8—Gd1iii | 119.6 (5) |
O5i—Gd1—O7 | 148.5 (2) | C6—O9—Gd1iv | 120.2 (5) |
O3—Gd1—O7 | 86.62 (19) | C5—O10—Gd1 | 118.5 (5) |
O2ii—Gd1—O7 | 135.15 (17) | P1—O1—H1 | 109.5 |
O5i—Gd1—O8iii | 78.21 (19) | P1—O2—Gd1ii | 171.8 (3) |
O3—Gd1—O8iii | 73.57 (18) | P1—O3—Gd1 | 141.1 (3) |
O2ii—Gd1—O8iii | 140.25 (18) | P2—O5—Gd1i | 159.0 (4) |
O7—Gd1—O8iii | 73.66 (18) | P2—O4—H4 | 109.5 |
O5i—Gd1—O9iv | 145.7 (2) | Gd1—O13—H13B | 109.5 |
O3—Gd1—O9iv | 79.08 (18) | Gd1—O13—H13A | 123 (9) |
O2ii—Gd1—O9iv | 69.60 (17) | H13B—O13—H13A | 122.3 |
O7—Gd1—O9iv | 65.78 (18) | H12B—O12—H12A | 105.7 |
O8iii—Gd1—O9iv | 131.85 (19) | H11B—O11—H11A | 109.4 |
O5i—Gd1—O10 | 82.8 (2) | C1v—C1—C2 | 109.4 (10) |
O3—Gd1—O10 | 138.43 (18) | C1v—C1—H12 | 109.8 |
O2ii—Gd1—O10 | 138.35 (19) | C2—C1—H12 | 109.8 |
O7—Gd1—O10 | 73.11 (19) | C1v—C1—H11 | 109.8 |
O8iii—Gd1—O10 | 66.11 (18) | C2—C1—H11 | 109.8 |
O9iv—Gd1—O10 | 121.41 (18) | H12—C1—H11 | 108.2 |
O5i—Gd1—O13 | 92.9 (2) | N1—C2—C1 | 110.5 (7) |
O3—Gd1—O13 | 148.7 (2) | N1—C2—H22 | 109.5 |
O2ii—Gd1—O13 | 73.9 (2) | C1—C2—H22 | 109.5 |
O7—Gd1—O13 | 98.3 (2) | N1—C2—H21 | 109.5 |
O8iii—Gd1—O13 | 137.6 (2) | C1—C2—H21 | 109.5 |
O9iv—Gd1—O13 | 75.0 (2) | H22—C2—H21 | 108.1 |
O10—Gd1—O13 | 71.68 (19) | N1—C3—P2 | 119.1 (6) |
O2—P1—O3 | 118.3 (3) | N1—C3—H32 | 107.6 |
O2—P1—O1 | 110.0 (3) | P2—C3—H32 | 107.6 |
O3—P1—O1 | 107.2 (3) | N1—C3—H31 | 107.6 |
O2—P1—C4 | 107.7 (3) | P2—C3—H31 | 107.6 |
O3—P1—C4 | 105.3 (3) | H32—C3—H31 | 107.0 |
O1—P1—C4 | 107.9 (4) | N1—C4—P1 | 112.3 (5) |
O5—P2—O6 | 115.2 (4) | N1—C4—H42 | 109.1 |
O5—P2—O4 | 111.2 (3) | P1—C4—H42 | 109.1 |
O6—P2—O4 | 112.6 (4) | N1—C4—H41 | 109.1 |
O5—P2—C3 | 102.7 (3) | P1—C4—H41 | 109.1 |
O6—P2—C3 | 113.1 (4) | H42—C4—H41 | 107.9 |
O4—P2—C3 | 100.6 (4) | O8—C5—O10 | 125.4 (8) |
C2—N1—C3 | 115.1 (6) | O8—C5—C5iii | 117.0 (9) |
C2—N1—C4 | 112.2 (7) | O10—C5—C5iii | 117.5 (9) |
C3—N1—C4 | 112.4 (6) | O7—C6—O9 | 126.7 (7) |
C2—N1—H1A | 110 (5) | O7—C6—C6iv | 118.0 (8) |
C3—N1—H1A | 103 (5) | O9—C6—C6iv | 115.2 (8) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+2, −z+2; (iv) −x+1, −y+1, −z+2; (v) −x, −y+1, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O11vi | 0.82 | 1.81 | 2.628 (8) | 177 |
O13—H13B···O11vii | 0.82 | 1.94 | 2.751 (10) | 168 |
O4—H4···O12i | 0.82 | 1.81 | 2.602 (8) | 161 |
O11—H11B···O10iii | 0.86 | 1.87 | 2.720 (8) | 172 |
O12—H12A···O6vii | 0.85 | 1.92 | 2.752 (10) | 165 |
O11—H11A···O6viii | 0.84 | 1.99 | 2.805 (9) | 161 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (iii) −x+1, −y+2, −z+2; (vi) −x, −y+1, −z+1; (vii) x+1, y, z; (viii) −x, −y+2, −z+1. |