A new chiral rare-earth organic framework constructed by tartaric acid: synthesis, structural, thermal investigations and optical properties

Hydro­thermal reactions of rare-earth cerium with L-tartaric acid afford a new coordination polymer, namely, poly[[tri­aqua­(μ₄-L-tartrato)cerium(III)] chlo­ride], {[Ce(C₄H₄O₆)(H₂O)₃]Cl}_n, (1). The structure was determined by single-crystal X-ray diffraction analysis and further characterized by IR and UV–Vis spectroscopy, powder X-ray diffraction and thermogravimetric analysis. Single-crystal X-ray diffraction analysis revealed that the com­pound is a new two-dimensional (2D) double-layered structure with one-dimensional left-handed helical chains. The different inter­molecular inter­actions were confirmed using Hirshfeld surface analysis and mol­ecular fingerprint plots. Mol­ecular 2D fingerprint plots qu­antify the different inter­actions and highlight that H...H (24.8%), H...O/O...H (26.3%), Cl...H/H...Cl (19.6%), O...O (13.8%) and Ce...O/O...Ce (13.6%) inter­actions account for 99.8% of all contacts. Additionally, the photoluminescence properties of the com­pound were investigated in the solid state.

Computing details

Data collection: APEX2 (Bruker, 2011); cell refinement: APEX2 (Bruker, 2011); data reduction: APEX2 (Bruker, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

Poly[[triaqua(µ₄-L-tartrato)cerium(III)] chloride]

Crystal data

[Ce(C4H4O6)(H2O)3]Cl	F(000) = 362
Mr = 377.69	Dx = 2.344 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 9267 reflections
a = 5.9097 (1) Å	θ = 3.2–42.0°
b = 7.7974 (2) Å	µ = 4.53 mm^−1
c = 11.7206 (3) Å	T = 296 K
β = 97.816 (1)°	Prism, colorless
V = 535.07 (2) Å^3	0.17 × 0.09 × 0.07 mm
Z = 2

Data collection

Bruker APEXII diffractometer	2351 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
CCD rotation images, thin slices scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −7→7
Tmin = 0.609, Tmax = 0.750	k = −10→10
8182 measured reflections	l = −15→15
2403 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.019	w = 1/[σ^2(Fo^2) + (0.0034P)^2 + 0.091P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.043	(Δ/σ)max = 0.002
S = 1.04	Δρmax = 0.73 e Å^−3
2403 reflections	Δρmin = −0.42 e Å^−3
162 parameters	Absolute structure: Flack x determined using 1056 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
11 restraints	Absolute structure parameter: 0.003 (14)
0 constraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	1.3911 (6)	1.1276 (6)	1.8203 (4)	0.0212 (9)
C2	1.2482 (6)	0.9622 (5)	1.8126 (4)	0.0172 (8)
H2	1.2889	0.8909	1.7496	0.021*
C3	1.2903 (6)	0.8596 (5)	1.9267 (4)	0.0170 (9)
H3	1.4389	0.8027	1.9302	0.02*
C4	1.1066 (7)	0.7203 (5)	1.9243 (4)	0.0205 (8)
O1	1.6021 (5)	1.1110 (5)	1.8436 (4)	0.0338 (9)
O2	1.2879 (5)	1.2663 (4)	1.8031 (4)	0.0303 (8)
O1W	2.0287 (9)	1.4819 (6)	1.6265 (4)	0.0445 (11)
H1WA	1.981 (14)	1.579 (5)	1.602 (6)	0.053*
H1WB	2.073 (13)	1.428 (7)	1.570 (4)	0.053*
O3	1.0899 (7)	0.6120 (5)	1.8464 (4)	0.0320 (8)
O2W	1.5657 (6)	1.5371 (6)	1.7316 (4)	0.0392 (10)
H2WA	1.559 (10)	1.617 (8)	1.682 (5)	0.047*
H2WB	1.431 (5)	1.507 (8)	1.739 (7)	0.047*
O4	0.9802 (5)	0.7276 (5)	2.0031 (3)	0.0236 (7)
O3W	1.6957 (9)	1.2091 (6)	1.6093 (5)	0.0534 (13)
H3WA	1.634 (11)	1.115 (5)	1.622 (8)	0.064*
H3WB	1.600 (9)	1.271 (8)	1.568 (6)	0.064*
O5	1.0151 (5)	1.0140 (4)	1.7870 (4)	0.0216 (7)
O6	1.2940 (5)	0.9618 (4)	2.0260 (3)	0.0198 (6)
Cl1	1.7297 (2)	1.8177 (3)	1.57477 (12)	0.0390 (3)
Ce	1.88278 (2)	1.33133 (5)	1.79949 (2)	0.01726 (8)
H5	0.952 (8)	0.931 (6)	1.751 (5)	0.022 (13)*
H6	1.207 (10)	1.056 (8)	2.008 (6)	0.025 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0168 (17)	0.021 (2)	0.028 (2)	−0.0069 (13)	0.0097 (16)	−0.0017 (18)
C2	0.0147 (15)	0.0145 (19)	0.023 (2)	−0.0020 (13)	0.0056 (15)	−0.0018 (15)
C3	0.0163 (13)	0.014 (3)	0.0210 (18)	−0.0003 (12)	0.0022 (12)	0.0004 (15)
C4	0.0236 (17)	0.0135 (19)	0.024 (2)	−0.0017 (14)	0.0022 (16)	−0.0004 (16)
O1	0.0152 (13)	0.0302 (19)	0.056 (3)	−0.0047 (12)	0.0060 (14)	0.0021 (17)
O2	0.0209 (14)	0.0183 (14)	0.052 (2)	−0.0027 (10)	0.0074 (15)	0.0035 (15)
O1W	0.070 (3)	0.036 (2)	0.032 (2)	0.011 (2)	0.024 (2)	0.0069 (18)
O3	0.045 (2)	0.0218 (18)	0.031 (2)	−0.0154 (15)	0.0113 (17)	−0.0091 (16)
O2W	0.0246 (14)	0.038 (2)	0.056 (3)	0.0041 (15)	0.0099 (17)	0.022 (2)
O4	0.0243 (13)	0.0252 (18)	0.0219 (17)	−0.0070 (12)	0.0052 (12)	−0.0004 (14)
O3W	0.081 (3)	0.030 (2)	0.039 (3)	0.006 (2)	−0.031 (2)	−0.004 (2)
O5	0.0148 (12)	0.0151 (15)	0.033 (2)	−0.0021 (10)	−0.0021 (13)	−0.0012 (14)
O6	0.0228 (13)	0.0138 (15)	0.0224 (17)	−0.0010 (11)	0.0020 (12)	−0.0015 (12)
Cl1	0.0554 (6)	0.0265 (7)	0.0337 (6)	−0.0087 (8)	0.0008 (4)	0.0046 (8)
Ce	0.01925 (10)	0.01291 (11)	0.01951 (12)	−0.00122 (12)	0.00225 (7)	0.00055 (13)

Geometric parameters (Å, º)

C1—O2	1.244 (6)	O2W—Ce	2.512 (4)
C1—O1	1.247 (5)	O2W—H2WA	0.849 (14)
C1—C2	1.538 (6)	O2W—H2WB	0.845 (14)
C2—O5	1.428 (5)	O4—Ce^iii	2.481 (4)
C2—C3	1.548 (6)	O3W—Ce	2.535 (5)
C2—H2	0.98	O3W—H3WA	0.841 (15)
C3—O6	1.408 (5)	O3W—H3WB	0.843 (14)
C3—C4	1.534 (6)	O5—Ce^i	2.605 (3)
C3—H3	0.98	O5—H5	0.83 (3)
C4—O3	1.238 (6)	O6—Ce^iii	2.625 (3)
C4—O4	1.265 (5)	O6—H6	0.90 (7)
O1—Ce	2.490 (3)	Ce—O2^iv	2.442 (3)
O2—Ce^i	2.442 (3)	Ce—O4^v	2.481 (4)
O1W—Ce	2.590 (4)	Ce—O3^vi	2.531 (4)
O1W—H1WA	0.847 (14)	Ce—O5^iv	2.605 (3)
O1W—H1WB	0.850 (14)	Ce—O6^v	2.625 (3)
O3—Ce^ii	2.531 (3)
O2—C1—O1	125.4 (4)	O2^iv—Ce—O4^v	73.81 (12)
O2—C1—C2	117.8 (3)	O2^iv—Ce—O1	122.16 (11)
O1—C1—C2	116.8 (4)	O4^v—Ce—O1	73.95 (13)
O5—C2—C1	106.3 (3)	O2^iv—Ce—O2W	145.62 (12)
O5—C2—C3	111.4 (3)	O4^v—Ce—O2W	129.66 (13)
C1—C2—C3	111.1 (4)	O1—Ce—O2W	90.98 (12)
O5—C2—H2	109.3	O2^iv—Ce—O3^vi	74.42 (13)
C1—C2—H2	109.3	O4^v—Ce—O3^vi	89.58 (15)
C3—C2—H2	109.3	O1—Ce—O3^vi	150.16 (13)
O6—C3—C4	110.3 (3)	O2W—Ce—O3^vi	80.48 (15)
O6—C3—C2	113.8 (3)	O2^iv—Ce—O3W	104.28 (16)
C4—C3—C2	108.7 (3)	O4^v—Ce—O3W	138.18 (16)
O6—C3—H3	107.9	O1—Ce—O3W	72.54 (17)
C4—C3—H3	107.9	O2W—Ce—O3W	75.20 (17)
C2—C3—H3	107.9	O3^vi—Ce—O3W	131.01 (16)
O3—C4—O4	125.0 (4)	O2^iv—Ce—O1W	71.20 (15)
O3—C4—C3	118.8 (4)	O4^v—Ce—O1W	140.97 (15)
O4—C4—C3	116.2 (4)	O1—Ce—O1W	141.00 (17)
C1—O1—Ce	123.9 (3)	O2W—Ce—O1W	77.07 (14)
C1—O2—Ce^i	129.9 (2)	O3^vi—Ce—O1W	64.87 (16)
Ce—O1W—H1WA	123 (5)	O3W—Ce—O1W	68.54 (19)
Ce—O1W—H1WB	124 (5)	O2^iv—Ce—O5^iv	60.18 (10)
H1WA—O1W—H1WB	108 (2)	O4^v—Ce—O5^iv	71.34 (12)
C4—O3—Ce^ii	137.5 (3)	O1—Ce—O5^iv	64.53 (10)
Ce—O2W—H2WA	130 (4)	O2W—Ce—O5^iv	143.65 (15)
Ce—O2W—H2WB	118 (4)	O3^vi—Ce—O5^iv	133.89 (14)
H2WA—O2W—H2WB	108 (2)	O3W—Ce—O5^iv	72.06 (14)
C4—O4—Ce^iii	123.0 (3)	O1W—Ce—O5^iv	104.60 (13)
Ce—O3W—H3WA	108 (6)	O2^iv—Ce—O6^v	124.05 (13)
Ce—O3W—H3WB	118 (6)	O4^v—Ce—O6^v	60.90 (10)
H3WA—O3W—H3WB	109 (3)	O1—Ce—O6^v	76.04 (12)
C2—O5—Ce^i	123.1 (2)	O2W—Ce—O6^v	68.93 (13)
C2—O5—H5	104 (4)	O3^vi—Ce—O6^v	74.20 (11)
Ce^i—O5—H5	131 (4)	O3W—Ce—O6^v	131.18 (15)
C3—O6—Ce^iii	117.5 (2)	O1W—Ce—O6^v	130.12 (14)
C3—O6—H6	109 (5)	O5^iv—Ce—O6^v	124.48 (11)
Ce^iii—O6—H6	102 (4)
O2—C1—C2—O5	−0.6 (6)	O2—C1—O1—Ce	−21.3 (7)
O1—C1—C2—O5	179.2 (4)	C2—C1—O1—Ce	158.9 (3)
O2—C1—C2—C3	−122.0 (4)	O1—C1—O2—Ce^i	−164.6 (4)
O1—C1—C2—C3	57.8 (5)	C2—C1—O2—Ce^i	15.2 (7)
O5—C2—C3—O6	−74.5 (4)	O4—C4—O3—Ce^ii	−11.7 (9)
C1—C2—C3—O6	43.9 (4)	C3—C4—O3—Ce^ii	169.3 (4)
O5—C2—C3—C4	48.8 (4)	O3—C4—O4—Ce^iii	147.8 (4)
C1—C2—C3—C4	167.2 (3)	C3—C4—O4—Ce^iii	−33.2 (5)
O6—C3—C4—O3	−175.5 (4)	C1—C2—O5—Ce^i	−12.0 (4)
C2—C3—C4—O3	59.1 (5)	C3—C2—O5—Ce^i	109.3 (3)
O6—C3—C4—O4	5.5 (5)	C4—C3—O6—Ce^iii	21.0 (4)
C2—C3—C4—O4	−119.9 (4)	C2—C3—O6—Ce^iii	143.5 (2)

Symmetry codes: (i) x−1, y, z; (ii) x−1, y−1, z; (iii) −x+3, y−1/2, −z+4; (iv) x+1, y, z; (v) −x+3, y+1/2, −z+4; (vi) x+1, y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···Cl1	0.85	2.37	3.1710 (1)	157
O1W—H1WB···Cl1^vii	0.85	2.35	3.1871 (1)	167
O3W—H3WA···Cl1^viii	0.84	2.46	3.0884 (1)	132
O3W—H3WB···Cl1^ix	0.84	2.42	3.1966 (1)	154
O5—H5···Cl1^ii	0.83 (3)	2.46 (3)	3.1991 (1)	149
O2W—H2WA···Cl1	0.85	2.32	3.0973 (1)	152
O6—H6···O4^x	0.90 (7)	1.73 (7)	2.6241 (7)	170.00
O2W—H2WB···O1W^i	0.85	2.56	3.2728 (1)	142
O2W—H2WB···O2	0.85	2.23	2.8685 (1)	132

Symmetry codes: (i) x−1, y, z; (ii) x−1, y−1, z; (vii) −x+4, y−1/2, −z+3; (viii) x, y−1, z; (ix) −x+3, y−1/2, −z+3; (x) −x+2, y+1/2, −z+4.