Poly[[tetra­aqua­tri-μ-oxolato-dithulium] dihydrate]

The structure of the oxalate-bridged title complex, [Tm₂(C₂O₄)₃(H₂O)₄]·2H₂O, consists of layers built from Tm₂(C₂O₄)₃ units. The coordination polyhedron of Tm can be described as a distorted dicapped trigonal prism. Each oxalate is located on an inversion centre.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.019
• wR factor = 0.046
• Data-to-parameter ratio = 11.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT369_ALERT_2_B Long   C(sp2)-C(sp2) Bond  C3     -   C3_b   ...       1.57 Ang.

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C1_a   ...       1.56 Ang.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C2     -   C2_c   ...       1.54 Ang.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 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
   3 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Poly[[tetraaquatri-µ-oxolato-dithulium] dihydrate]

Crystal data

[Tm2(C2O4)3(H2O)4]·2H2O	Z = 1
Mr = 710.02	F(000) = 330
Triclinic, P1	Dx = 3.085 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.289 (3) Å	Cell parameters from 926 reflections
b = 6.660 (3) Å	θ = 3.2–25.1°
c = 9.628 (4) Å	µ = 11.63 mm^−1
α = 75.043 (6)°	T = 295 K
β = 80.778 (6)°	Block, colourless
γ = 81.575 (6)°	0.18 × 0.16 × 0.12 mm
V = 382.2 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	1345 independent reflections
Radiation source: fine-focus sealed tube	1284 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
φ and ω scans	θmax = 25.1°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −7→5
Tmin = 0.153, Tmax = 0.248	k = −8→7
2179 measured reflections	l = −12→7

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.046	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0212P)^2 + 0.1731P] where P = (Fo^2 + 2Fc^2)/3
1345 reflections	(Δ/σ)max = 0.001
118 parameters	Δρmax = 1.06 e Å^−3
0 restraints	Δρmin = −0.97 e Å^−3

Special details

Experimental. The hydrogen atoms of water located on the difference Fourier map and moved along the O—H bond to give a ideal distance (0.85 Å). They were refined using a riding model with U_eq. = 1.5 U_eq.(O).

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 (Ų)

	x	y	z	Uiso*/Ueq
Tm1	0.30208 (3)	0.30847 (3)	0.307083 (18)	0.01235 (9)
O1	0.1512 (5)	0.1653 (5)	0.5484 (3)	0.0141 (7)
O2	−0.0620 (6)	−0.0706 (5)	0.6874 (3)	0.0183 (7)
C1	0.0250 (7)	0.0273 (7)	0.5692 (5)	0.0123 (9)
O3	0.5733 (5)	0.2581 (5)	0.4564 (3)	0.0162 (7)
O4	0.7192 (5)	0.4081 (5)	0.5953 (4)	0.0193 (7)
C2	0.5850 (8)	0.4037 (6)	0.5142 (5)	0.0141 (9)
O5	0.5850 (6)	0.4962 (5)	0.1638 (3)	0.0210 (7)
O6	0.7186 (6)	0.6475 (5)	−0.0626 (3)	0.0192 (7)
C3	0.5895 (8)	0.5426 (7)	0.0290 (5)	0.0161 (10)
O7	0.5439 (6)	0.0324 (5)	0.2464 (4)	0.0233 (8)
H7A	0.6213	−0.0431	0.3092	0.028*
H7B	0.6165	0.0533	0.1626	0.028*
O8	−0.0185 (6)	0.5348 (6)	0.2654 (4)	0.0271 (8)
H8A	−0.0415	0.6464	0.2946	0.033*
H8B	−0.1229	0.5236	0.2229	0.033*
O9	0.7727 (11)	0.0842 (9)	−0.0234 (6)	0.0726 (18)
H9A	0.7269	0.0575	−0.0942	0.087*
H9B	0.8630	0.1740	−0.0535	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tm1	0.01466 (13)	0.01431 (13)	0.00900 (13)	−0.00685 (8)	0.00063 (8)	−0.00282 (8)
O1	0.0155 (17)	0.0145 (15)	0.0131 (16)	−0.0087 (13)	0.0010 (13)	−0.0025 (12)
O2	0.0223 (19)	0.0217 (17)	0.0116 (16)	−0.0095 (15)	0.0005 (14)	−0.0029 (13)
C1	0.010 (2)	0.011 (2)	0.015 (2)	0.0016 (17)	−0.0016 (18)	−0.0029 (17)
O3	0.0181 (18)	0.0171 (16)	0.0154 (16)	−0.0009 (13)	−0.0055 (13)	−0.0061 (13)
O4	0.0166 (18)	0.0190 (16)	0.0266 (18)	0.0002 (14)	−0.0099 (14)	−0.0099 (14)
C2	0.016 (2)	0.010 (2)	0.015 (2)	−0.0057 (19)	0.0045 (18)	−0.0040 (17)
O5	0.026 (2)	0.0291 (18)	0.0102 (16)	−0.0151 (15)	−0.0019 (14)	−0.0020 (14)
O6	0.0189 (18)	0.0273 (18)	0.0111 (16)	−0.0133 (15)	0.0006 (13)	0.0002 (13)
C3	0.018 (3)	0.014 (2)	0.016 (2)	−0.0046 (19)	−0.0008 (19)	−0.0035 (18)
O7	0.024 (2)	0.0231 (18)	0.0216 (18)	0.0017 (15)	−0.0031 (15)	−0.0063 (14)
O8	0.022 (2)	0.033 (2)	0.034 (2)	0.0010 (16)	−0.0108 (16)	−0.0203 (16)
O9	0.088 (5)	0.099 (4)	0.045 (3)	−0.035 (4)	0.012 (3)	−0.040 (3)

Geometric parameters (Å, º)

Tm1—O4^i	2.295 (3)	O4—C2	1.246 (6)
Tm1—O6^ii	2.318 (3)	C2—C2^i	1.541 (9)
Tm1—O2^iii	2.329 (3)	O5—C3	1.251 (6)
Tm1—O3	2.336 (3)	O6—C3	1.243 (6)
Tm1—O7	2.342 (3)	C3—C3^ii	1.567 (9)
Tm1—O8	2.357 (4)	O7—H7A	0.8487
Tm1—O5	2.368 (3)	O7—H7B	0.8495
Tm1—O1	2.371 (3)	O8—H8A	0.8459
O1—C1	1.258 (5)	O8—H8B	0.8491
O2—C1	1.241 (6)	O9—H9A	0.8491
C1—C1^iii	1.557 (9)	O9—H9B	0.8494
O3—C2	1.252 (5)
O4^i—Tm1—O6^ii	120.85 (12)	O7—Tm1—O1	103.61 (11)
O4^i—Tm1—O2^iii	134.00 (12)	O8—Tm1—O1	90.74 (12)
O6^ii—Tm1—O2^iii	78.16 (11)	O5—Tm1—O1	144.07 (11)
O4^i—Tm1—O3	70.23 (11)	C1—O1—Tm1	118.1 (3)
O6^ii—Tm1—O3	137.37 (12)	C1—O2—Tm1^iii	119.8 (3)
O2^iii—Tm1—O3	126.22 (11)	O2—C1—O1	127.2 (4)
O4^i—Tm1—O7	142.34 (12)	O2—C1—C1^iii	116.8 (5)
O6^ii—Tm1—O7	76.70 (12)	O1—C1—C1^iii	116.0 (5)
O2^iii—Tm1—O7	79.36 (13)	C2—O3—Tm1	116.8 (3)
O3—Tm1—O7	75.20 (12)	C2—O4—Tm1^i	119.5 (3)
O4^i—Tm1—O8	68.00 (12)	O4—C2—O3	126.6 (4)
O6^ii—Tm1—O8	75.63 (12)	O4—C2—C2^i	115.9 (5)
O2^iii—Tm1—O8	79.15 (13)	O3—C2—C2^i	117.6 (5)
O3—Tm1—O8	136.99 (11)	C3—O5—Tm1	118.4 (3)
O7—Tm1—O8	147.80 (12)	C3—O6—Tm1^ii	119.5 (3)
O4^i—Tm1—O5	77.00 (12)	O6—C3—O5	127.5 (4)
O6^ii—Tm1—O5	69.44 (11)	O6—C3—C3^ii	117.0 (5)
O2^iii—Tm1—O5	144.68 (11)	O5—C3—C3^ii	115.4 (5)
O3—Tm1—O5	74.54 (12)	Tm1—O7—H7A	118.9
O7—Tm1—O5	79.86 (13)	Tm1—O7—H7B	118.2
O8—Tm1—O5	105.17 (13)	H7A—O7—H7B	110.4
O4^i—Tm1—O1	79.68 (12)	Tm1—O8—H8A	120.1
O6^ii—Tm1—O1	146.48 (11)	Tm1—O8—H8B	129.6
O2^iii—Tm1—O1	69.17 (11)	H8A—O8—H8B	110.3
O3—Tm1—O1	72.01 (12)	H9A—O9—H9B	110.5

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O1^iv	0.85	2.07	2.906 (5)	166
O7—H7A···O3^iv	0.85	2.57	3.059 (5)	118
O7—H7B···O9	0.85	1.88	2.724 (6)	177
O8—H8A···O1^v	0.85	2.17	2.963 (5)	155
O8—H8B···O5^vi	0.85	2.05	2.888 (5)	167
O9—H9A···O2^vii	0.85	2.57	3.184 (6)	130
O9—H9B···O8^ii	0.85	2.60	3.347 (7)	148

Symmetry codes: (ii) −x+1, −y+1, −z; (iv) −x+1, −y, −z+1; (v) −x, −y+1, −z+1; (vi) x−1, y, z; (vii) x+1, y, z−1.