Poly[[hexa­aqua­(μ₂-fumarato-κ⁴O¹,O^1′:O⁴,O^4′)bis­(μ₃-maleato-κ⁴O¹,O^1′:O⁴:O^4′)disamarium(III)] hexa­hydrate]

In the title coordination polymer, {[Sm₂(C₄H₂O₄)₃(H₂O)₆]·6H₂O}_n, the Sm^III ion is nine-coordinated by four O atoms from three different maleate ligands, two O atoms from one fumarate ligand and three O atoms from three water mol­ecules. The fumarate ligand lies on an inversion center. Adjacent Sm^III ions are bridged by the maleate and fumarate ligands, forming a layer parallel to (011). The layers are further linked by inter­molecular O—H...O hydrogen bonds into a three-dimensional supra­molecular network.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.017
• wR factor = 0.066
• Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .          4

Alert level C
PLAT417_ALERT_2_C Short Inter D-H..H-D       H11B   ..  H12B    ..       2.11 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4
PLAT918_ALERT_3_C Reflection(s) # with I(obs) much smaller I(calc)          4
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ          ?
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         25

Alert level G
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Sm1     .......       3.09

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Diacids have been widely used to form metal–organic frameworks. Recently, we reported several compounds based on malonate ligand and different transition metal ions (Li et al., 2006; Ye et al., 2007; Zhu et al., 2007). Hererin, we report the crystal structure of the title compound based on maleate ligand.

The structure of the title compound is shown in Fig. 1. The bond lengths and angles are normal and comparable with those reported for a similar structure (Hansson & Thörnqwist, 1975). The Sm^III ion is nine-coordinated by four O atoms from three maleate ligands, two O atoms from one fumarate ligand and three coordinated water molecules. The two carboxylate groups of the fumarate ligand and one of the carboxylate groups of the maleate ligand exhibit a chelating coordination mode, while the other carboxylate group of the maleate ligand binds Sm^III ions in a bidentate bridging mode. Adjacent Sm^III ions are bridged by the maleate and fumarate ligands, forming a layer parallel to (0 1 1) (Fig. 2). Additionly, abundant O—H···O hydrogen bonds stabilize the crystal structure of the title compound (Table 1).

Related literature

For the structures of transition metal complexes with malonate ligands, see: Li et al. (2006); Ye et al. (2007); Zhu et al. (2007). For a related structure, see: Hansson & Thörnqwist (1975).

S2. Experimental

Maleic acid and Sm(NO₃)₃ of analytical grade are used without further purification. Sm(NO₃)₃ (67.24 mg, 0.2 mmol) and maleic acid (69.64 mg, 0.6 mmol) were dissolved in water (10 ml), and the pH value was adjusted to about 3 using a dilute NaOH solution. The mixture was stirred for half an hour and then filtered. The filtrate was allowed to stand at room temperature for two weeks, giving colorless block-shaped crystals.

S3. Refinement

C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding atoms, with U_iso(H) = 1.2 U_eq(C). H atoms of the water molecules were initially located in a difference Fourier map, but were idealized and refined as riding atoms, with O—H = 0.85 Å and U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The asymmetric unit of the title compound, with the symmetry-related atoms to complete the Sm coordination. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (A) -x, 1-y, 1-z; (B) 2-x, 2-y, -z; (C) 1+x, y, z; (D) 1-x, 2-y, -z.]
	Fig. 2. Crystal packing diagram of the title cmopound, showing the two-dimensional network.

Poly[[hexaaqua(µ₂-fumarato- κ⁴O¹,O^1':O⁴,O^4')bis(µ₃-maleato- κ⁴O¹,O^1':O⁴:O^4')disamarium(III)] hexahydrate]

Crystal data

[Sm2(C4H2O4)3(H2O)6]·6H2O	Z = 1
Mr = 859.08	F(000) = 418
Triclinic, P1	Dx = 2.100 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.150 (3) Å	Cell parameters from 6497 reflections
b = 10.679 (6) Å	θ = 3.3–27.5°
c = 11.214 (6) Å	µ = 4.38 mm^−1
α = 69.99 (3)°	T = 290 K
β = 79.64 (2)°	Block, colorless
γ = 89.74 (2)°	0.08 × 0.07 × 0.06 mm
V = 679.4 (6) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	3071 independent reflections
Radiation source: rotation anode	2950 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→7
Tmin = 0.732, Tmax = 0.782	k = −13→13
6707 measured reflections	l = −14→13

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)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.066	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0342P)^2 + 3.0041P] where P = (Fo^2 + 2Fc^2)/3
3071 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.58 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6917 (6)	1.1675 (4)	0.0453 (3)	0.0173 (7)
C2	0.7911 (7)	1.3067 (4)	0.0028 (4)	0.0256 (8)
H2	0.7026	1.3681	0.0269	0.031*
C3	0.9922 (7)	1.3525 (4)	−0.0657 (4)	0.0291 (9)
H3	1.0311	1.4423	−0.0853	0.035*
C4	1.1596 (6)	1.2717 (4)	−0.1134 (3)	0.0190 (7)
C5	0.2343 (6)	0.6379 (4)	0.4136 (3)	0.0176 (7)
C6	0.0980 (7)	0.5175 (4)	0.5083 (4)	0.0254 (8)
H6	0.1523	0.4658	0.5807	0.031*
O1	0.6917 (5)	1.0926 (3)	0.1584 (3)	0.0230 (6)
O2	0.6003 (5)	1.1329 (4)	−0.0303 (3)	0.0321 (7)
O3	1.1332 (4)	1.1467 (3)	−0.0770 (3)	0.0211 (5)
O4	1.3316 (5)	1.3327 (3)	−0.1921 (3)	0.0326 (7)
O5	0.4186 (5)	0.6652 (3)	0.4363 (3)	0.0253 (6)
O6	0.1671 (4)	0.7103 (3)	0.3142 (3)	0.0224 (5)
O7	0.8126 (4)	0.8515 (3)	0.3427 (3)	0.0223 (5)
H7B	0.8962	0.7909	0.3325	0.033*
H7A	0.8156	0.8534	0.4176	0.033*
O8	0.3684 (5)	0.9438 (3)	0.4042 (3)	0.0289 (6)
H8A	0.3148	1.0200	0.3882	0.043*
H8B	0.3346	0.9100	0.4861	0.043*
O9	0.1952 (4)	1.0193 (3)	0.1778 (3)	0.0236 (6)
H9A	0.0669	0.9933	0.2236	0.035*
H9B	0.1633	1.0477	0.1027	0.035*
O10	0.8053 (6)	0.1975 (3)	0.3360 (3)	0.0339 (7)
H10A	0.7981	0.1545	0.2853	0.051*
H10B	0.7485	0.2727	0.3128	0.051*
O11	0.2212 (5)	0.1916 (3)	0.3961 (3)	0.0322 (7)
H11B	0.3085	0.2599	0.3771	0.048*
H11A	0.1137	0.2035	0.3560	0.048*
O12	0.5308 (6)	0.4066 (3)	0.3112 (3)	0.0384 (8)
H12A	0.5696	0.4872	0.2639	0.058*
H12B	0.5062	0.4142	0.3894	0.058*
Sm1	0.50414 (3)	0.869449 (17)	0.223642 (16)	0.01447 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0152 (16)	0.0201 (17)	0.0163 (16)	0.0006 (13)	0.0001 (12)	−0.0074 (13)
C2	0.028 (2)	0.0164 (17)	0.029 (2)	0.0044 (15)	0.0018 (16)	−0.0079 (15)
C3	0.035 (2)	0.0138 (17)	0.033 (2)	−0.0033 (15)	0.0089 (17)	−0.0089 (16)
C4	0.0210 (17)	0.0184 (16)	0.0152 (16)	−0.0009 (14)	−0.0014 (13)	−0.0038 (13)
C5	0.0164 (16)	0.0167 (16)	0.0163 (16)	0.0012 (13)	−0.0015 (13)	−0.0023 (13)
C6	0.0252 (19)	0.0207 (18)	0.0224 (18)	−0.0066 (15)	0.0005 (15)	0.0002 (15)
O1	0.0281 (14)	0.0196 (13)	0.0172 (12)	−0.0039 (11)	−0.0035 (11)	−0.0013 (10)
O2	0.0257 (15)	0.051 (2)	0.0247 (15)	−0.0029 (14)	−0.0051 (12)	−0.0194 (14)
O3	0.0207 (13)	0.0153 (12)	0.0247 (13)	−0.0003 (10)	−0.0003 (10)	−0.0055 (10)
O4	0.0282 (15)	0.0187 (14)	0.0409 (18)	−0.0034 (12)	0.0135 (13)	−0.0076 (13)
O5	0.0186 (13)	0.0246 (14)	0.0274 (14)	−0.0048 (11)	−0.0072 (11)	−0.0006 (11)
O6	0.0169 (12)	0.0215 (13)	0.0219 (13)	−0.0008 (10)	−0.0043 (10)	0.0017 (10)
O7	0.0154 (12)	0.0271 (14)	0.0234 (13)	0.0044 (10)	−0.0063 (10)	−0.0062 (11)
O8	0.0423 (17)	0.0262 (15)	0.0168 (13)	0.0084 (13)	−0.0019 (12)	−0.0074 (11)
O9	0.0168 (12)	0.0270 (14)	0.0216 (13)	0.0030 (11)	−0.0029 (10)	−0.0021 (11)
O10	0.0396 (18)	0.0385 (18)	0.0292 (16)	0.0048 (14)	−0.0105 (13)	−0.0168 (14)
O11	0.0342 (17)	0.0299 (16)	0.0337 (16)	0.0009 (13)	−0.0113 (13)	−0.0101 (13)
O12	0.051 (2)	0.0229 (15)	0.0373 (18)	−0.0064 (14)	−0.0083 (15)	−0.0057 (13)
Sm1	0.01201 (10)	0.01535 (10)	0.01502 (10)	−0.00140 (6)	−0.00158 (6)	−0.00444 (7)

Geometric parameters (Å, º)

C1—O1	1.247 (5)	O9—H9A	0.8500
C1—O2	1.249 (5)	O9—H9B	0.8500
C1—C2	1.493 (5)	O10—H10A	0.8500
C2—C3	1.328 (6)	O10—H10B	0.8501
C2—H2	0.9300	O11—H11B	0.8500
C3—C4	1.484 (5)	O11—H11A	0.8500
C3—H3	0.9300	O12—H12A	0.8500
C4—O3	1.256 (5)	O12—H12B	0.8944
C4—O4	1.265 (5)	Sm1—O1	2.464 (3)
C5—O6	1.258 (5)	Sm1—O2^ii	2.377 (3)
C5—O5	1.262 (5)	Sm1—O3^iii	2.566 (3)
C5—C6	1.496 (5)	Sm1—O4^iii	2.486 (3)
C6—C6^i	1.327 (8)	Sm1—O5	2.593 (3)
C6—H6	0.9300	Sm1—O6	2.512 (3)
O7—H7B	0.8500	Sm1—O7	2.480 (3)
O7—H7A	0.8499	Sm1—O8	2.432 (3)
O8—H8A	0.8500	Sm1—O9	2.489 (3)
O8—H8B	0.8500
O1—C1—O2	122.4 (4)	O2^ii—Sm1—O7	145.71 (10)
O1—C1—C2	118.2 (3)	O8—Sm1—O7	73.67 (10)
O2—C1—C2	119.2 (4)	O1—Sm1—O7	71.50 (10)
C3—C2—C1	127.1 (4)	O2^ii—Sm1—O4^iii	76.01 (12)
C3—C2—H2	116.4	O8—Sm1—O4^iii	137.15 (11)
C1—C2—H2	116.4	O1—Sm1—O4^iii	126.86 (10)
C2—C3—C4	125.2 (4)	O7—Sm1—O4^iii	80.70 (11)
C2—C3—H3	117.4	O2^ii—Sm1—O9	71.17 (11)
C4—C3—H3	117.4	O8—Sm1—O9	69.13 (10)
O3—C4—O4	120.7 (3)	O1—Sm1—O9	77.68 (10)
O3—C4—C3	121.5 (3)	O7—Sm1—O9	136.11 (10)
O4—C4—C3	117.7 (3)	O4^iii—Sm1—O9	143.16 (11)
O3—C4—Sm1^iii	62.2 (2)	O2^ii—Sm1—O6	79.19 (10)
O4—C4—Sm1^iii	58.6 (2)	O8—Sm1—O6	84.11 (11)
C3—C4—Sm1^iii	175.8 (3)	O1—Sm1—O6	152.27 (10)
O6—C5—O5	120.8 (3)	O7—Sm1—O6	121.53 (9)
O6—C5—C6	121.1 (3)	O4^iii—Sm1—O6	80.77 (10)
O5—C5—C6	118.1 (3)	O9—Sm1—O6	77.11 (10)
C6^i—C6—C5	121.8 (5)	O2^ii—Sm1—O3^iii	74.78 (10)
C6^i—C6—H6	119.1	O8—Sm1—O3^iii	140.72 (10)
C5—C6—H6	119.1	O1—Sm1—O3^iii	76.69 (9)
C1—O1—Sm1	115.9 (2)	O7—Sm1—O3^iii	71.03 (10)
C1—O2—Sm1^ii	161.0 (3)	O4^iii—Sm1—O3^iii	51.38 (9)
C4—O3—Sm1^iii	92.2 (2)	O9—Sm1—O3^iii	130.71 (9)
C4—O4—Sm1^iii	95.7 (2)	O6—Sm1—O3^iii	129.48 (9)
C5—O5—Sm1	92.2 (2)	O2^ii—Sm1—O5	121.78 (11)
C5—O6—Sm1	96.1 (2)	O8—Sm1—O5	70.25 (11)
Sm1—O7—H7B	110.4	O1—Sm1—O5	134.92 (9)
Sm1—O7—H7A	131.5	O7—Sm1—O5	70.75 (9)
H7B—O7—H7A	106.8	O4^iii—Sm1—O5	69.11 (11)
Sm1—O8—H8A	118.2	O9—Sm1—O5	115.51 (9)
Sm1—O8—H8B	137.9	O6—Sm1—O5	50.82 (9)
H8A—O8—H8B	102.8	O3^iii—Sm1—O5	112.47 (9)
Sm1—O9—H9A	118.7	O2^ii—Sm1—C4^iii	74.35 (11)
Sm1—O9—H9B	120.7	O8—Sm1—C4^iii	146.16 (11)
H9A—O9—H9B	100.2	O1—Sm1—C4^iii	101.68 (11)
H10A—O10—H10B	113.0	O7—Sm1—C4^iii	73.74 (10)
H11B—O11—H11A	115.2	O4^iii—Sm1—C4^iii	25.73 (10)
H12A—O12—H12B	100.4	O9—Sm1—C4^iii	144.26 (10)
O2^ii—Sm1—O8	139.41 (11)	O6—Sm1—C4^iii	105.51 (11)
O2^ii—Sm1—O1	103.29 (11)	O3^iii—Sm1—C4^iii	25.66 (9)
O8—Sm1—O1	76.25 (10)	O5—Sm1—C4^iii	90.53 (11)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+2, −z; (iii) −x+2, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O6^iv	0.85	1.88	2.680 (4)	156
O7—H7A···O11^v	0.85	1.95	2.774 (5)	164
O8—H8A···O11^vi	0.85	1.94	2.770 (5)	164
O8—H8B···O10^v	0.85	1.97	2.792 (5)	164
O9—H9A···O7^vii	0.85	2.10	2.893 (4)	155
O9—H9B···O3^vii	0.85	1.97	2.808 (4)	168
O10—H10A···O1^viii	0.85	1.97	2.783 (4)	160
O10—H10B···O12	0.85	1.95	2.761 (5)	159
O11—H11B···O12	0.85	1.93	2.775 (5)	171
O11—H11A···O10^vii	0.85	1.95	2.755 (5)	157
O12—H12A···O4^iii	0.85	1.87	2.705 (5)	168
O12—H12B···O5^v	0.89	1.98	2.744 (5)	142

Symmetry codes: (iii) −x+2, −y+2, −z; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1; (vi) x, y+1, z; (vii) x−1, y, z; (viii) x, y−1, z.