catena-Poly[[[diaqua­(pyrimidin-2-ylsulfanylacetato)lanthanum(III)]-di-μ-pyrimidin-2-ylsulfanylacetato] trihydrate]

Hao, H.-Q.; Zhang, H.; Chen, J.-G.; Ng, S.W.

doi:10.1107/S1600536805028096

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catena-Poly[[[diaqua(pyrimidin-2-ylsulfanylacetato)lanthanum(III)]-di-μ-pyrimidin-2-ylsulfanylacetato] trihydrate]

H.-Q. Hao, H. Zhang, J.-G. Chen and S. W. Ng

The La atom is ten-coordinate in a capped square–antiprismatic geometry in the title polymeric chain structure, {[La(C₆H₅N₂O₂S)₃(H₂O)₂]·3H₂O}_n. Adjacent chains are linked by hydrogen bonds to give a layer structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805028096/xu6055sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805028096/xu6055Isup2.hkl Contains datablock I

CCDC reference: 287765

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.007 Å
R factor = 0.044
wR factor = 0.110
Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT731_ALERT_1_B Bond    Calc     0.86(5), Rep   0.850(10) ......       5.00 su-Rat
              O4W  -H4W2    1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O5W  -H5W1    1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O5W  -H5W2    1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.86(5), Rep   0.850(10) ......       5.00 su-Rat
              O4W  -H8#     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O5W  -H9#     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.85(5), Rep   0.850(10) ......       5.00 su-Rat
              O5W  -H10#    1.555   1.555

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.56 Ratio
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         10
PLAT731_ALERT_1_C Bond    Calc     0.86(3), Rep   0.850(10) ......       3.00 su-Rat
              O1W  -H1W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O2W  -H2W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O2W  -H2W2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(4), Rep   0.850(10) ......       4.00 su-Rat
              O3W  -H3W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(4), Rep   0.850(10) ......       4.00 su-Rat
              O3W  -H3W2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.86(3), Rep   0.850(10) ......       3.00 su-Rat
              O4W  -H4W1    1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      110(5), Rep      110(2) ......       2.50 su-Rat
              H3W1 -O3W  -H3W2    1.555   1.555   1.555
PLAT732_ALERT_1_C Angle   Calc      111(5), Rep      110(2) ......       2.50 su-Rat
              H5W1 -O5W  -H5W2    1.555   1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.86(3), Rep   0.850(10) ......       3.00 su-Rat
              O1W  -H1#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O2W  -H3#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Rat
              O2W  -H4#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(4), Rep   0.850(10) ......       4.00 su-Rat
              O3W  -H5#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(4), Rep   0.850(10) ......       4.00 su-Rat
              O3W  -H6#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.86(3), Rep   0.850(10) ......       3.00 su-Rat
              O4W  -H7#     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.92(3), Rep   1.920(10) ......       3.00 su-Rat
              H1#  -O3W     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.04(5), Rep     2.03(2) ......       2.50 su-Rat
              H6#  -O3      1.555   3.566
PLAT736_ALERT_1_C H...A   Calc     2.08(6), Rep     2.09(2) ......       3.00 su-Rat
              H9#  -O3W     1.555   3.576
PLAT736_ALERT_1_C H...A   Calc     2.07(5), Rep     2.08(2) ......       2.50 su-Rat
              H10# -N4      1.555   3.666

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

  26 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
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

We have reported several metal derivatives of the 4-pyridylthioacetic acid (Fang et al., 2004; Huang, Zhang, Chen & Ng, 2004; Huang, Zhang, Chen, Zhou et al., 2004; Zhang et al., 2003, 2004a,b); the pyridyl N atom in these complexes typically interact through hydrogen bonds. The studies continue with the 2-pyrimidinyl analog of this heteroarylthioacetic acid; few metal derivatives of this carboxylic acid have been reported (Ng et al., 1993; Ma et al., 2004). The present lanthanum(III) derivative, (I), is chelated by the carboxylate portion of the pyrimidin-2-ylsulfanylacetate, but coordination by water molecules as well as two bridging interactions lead to a ten-coordinate environment of the metal atom (Fig. 1). The geometry is better regarded as a capped square–antiprism (Fig. 2); the capping O atoms are farthest away compared with the other eight O atoms that comprise the square–antiprism (Table 1). The compound adopts a chain motif arising from carboxylate bridging (Fig. 3); adjacent chains are linked through hydrogen bonds involving the lattice water molecules (Table 2) in layers.

Experimental top

Pyrimidin-2-ylsulfanylacetic acid (102 mg, 0.6 mmol) was suspended in a small volume of water–ethanol (2:1 (v/v) and ammonium hydroxide was added dropwise until it dissolved completely. Lanthanum nitrate (86 mg, 0.2 mmol) was added and the mixture was transferred into a Teflon-lined Parr bomb. The bomb was heated at 413 K for 100 h. The cooled contents were filtered; colorless plates separated after two weeks. Elemental analysis found (calculated) for C₁₈H₂₅LaN₆O₁₁S₃: C 29.26 (29.35), H 3.40 (3.42), N 11.32% (11.41%). IR (KBr): 3410, 1601, 1535, 1487, 1426, 622, 550, 472 cm⁻¹. {Bill/David: de we remove the IR data, no assignments]

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. ORTEPII (Johnson, 1976) plot of a portion of the polymeric structure of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms as spheres of arbitrary radii. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) −x, 1 − y, 1 − z.]
	Fig. 2. ORTEPII (Johnson, 1976) plot of the capped square–antiprismatic geometry of La in (I). [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) −x, 1 − y, 1 − z.]
	Fig. 3. ORTEPII (Johnson, 1976) of the chain structure. The lattice water molecules have been omitted.

catena-Poly[[[diaqua(pyrimidin-2-ylsulfanylacetato)lanthanum(III)]-di- µ-pyrimidin-2-ylsulfanylacetato] trihydrate] top

Crystal data top

[La(C₆H₅N₂O₂S)₃(H₂O)₂]·3H₂O	F(000) = 1472
M_r = 736.53	D_x = 1.827 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7684 reflections
a = 8.8145 (3) Å	θ = 2.3–28.6°
b = 11.8211 (5) Å	µ = 1.90 mm⁻¹
c = 25.887 (1) Å	T = 295 K
β = 97.046 (1)°	Block, colorless
V = 2677.0 (2) Å³	0.50 × 0.22 × 0.14 mm
Z = 4

Data collection top

Bruker APEX area-detector diffractometer	6110 independent reflections
Radiation source: fine-focus sealed tube	5749 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→11
T_min = 0.504, T_max = 0.777	k = −15→12
15909 measured reflections	l = −33→32

Refinement top

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ²(F_o²) + (0.0499P)² + 4.1463P] where P = (F_o² + 2F_c²)/3
6110 reflections	(Δ/σ)_max = 0.001
382 parameters	Δρ_max = 1.19 e Å⁻³
15 restraints	Δρ_min = −0.75 e Å⁻³

Crystal data top

[La(C₆H₅N₂O₂S)₃(H₂O)₂]·3H₂O	V = 2677.0 (2) Å³
M_r = 736.53	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.8145 (3) Å	µ = 1.90 mm⁻¹
b = 11.8211 (5) Å	T = 295 K
c = 25.887 (1) Å	0.50 × 0.22 × 0.14 mm
β = 97.046 (1)°

Data collection top

Bruker APEX area-detector diffractometer	6110 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5749 reflections with I > 2σ(I)
T_min = 0.504, T_max = 0.777	R_int = 0.029
15909 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	15 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	Δρ_max = 1.19 e Å⁻³
6110 reflections	Δρ_min = −0.75 e Å⁻³
382 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
La1	0.24487 (2)	0.48747 (2)	0.49842 (1)	0.0217 (1)
S1	0.5311 (2)	0.3943 (1)	0.69500 (4)	0.0470 (3)
S2	0.4673 (2)	0.0804 (1)	0.55240 (5)	0.0476 (3)
S3	−0.0317 (2)	0.2167 (1)	0.34125 (4)	0.0404 (3)
O1	0.3454 (3)	0.4736 (3)	0.5965 (1)	0.035 (1)
O2	0.5419 (3)	0.4989 (2)	0.5547 (1)	0.031 (1)
O3	0.1503 (3)	0.3031 (2)	0.5376 (1)	0.035 (1)
O4	0.3790 (3)	0.2962 (2)	0.5139 (1)	0.035 (1)
O5	−0.0392 (3)	0.4333 (2)	0.4558 (1)	0.026 (1)
O6	0.1484 (3)	0.3640 (3)	0.4188 (1)	0.035 (1)
O1w	0.3398 (3)	0.6877 (3)	0.5214 (1)	0.037 (1)
O2w	0.1468 (3)	0.6245 (3)	0.4276 (1)	0.038 (1)
O3w	0.0981 (4)	0.8355 (3)	0.5042 (1)	0.050 (1)
O4w	−0.0958 (4)	0.5996 (3)	0.3534 (1)	0.049 (1)
O5w	0.1230 (6)	1.0288 (4)	0.4489 (2)	0.077 (1)
N1	0.7112 (5)	0.2556 (4)	0.6491 (2)	0.046 (1)
N2	0.6024 (5)	0.1919 (4)	0.7227 (2)	0.058 (1)
N3	0.3869 (4)	−0.0388 (3)	0.6313 (1)	0.035 (1)
N4	0.5952 (4)	−0.1016 (3)	0.5896 (1)	0.040 (1)
N5	0.0257 (4)	0.4134 (3)	0.2969 (1)	0.037 (1)
N6	0.1111 (5)	0.2424 (4)	0.2629 (2)	0.053 (1)
C1	0.4845 (4)	0.4851 (3)	0.5959 (1)	0.025 (1)
C2	0.5888 (5)	0.4845 (4)	0.6462 (2)	0.035 (1)
C3	0.6261 (5)	0.2679 (4)	0.6867 (2)	0.037 (1)
C4	0.7790 (7)	0.1555 (5)	0.6472 (2)	0.060 (1)
C5	0.7640 (7)	0.0724 (5)	0.6819 (2)	0.060 (1)
C6	0.6737 (7)	0.0952 (5)	0.7191 (2)	0.065 (2)
C7	0.2768 (4)	0.2565 (3)	0.5380 (2)	0.031 (1)
C8	0.3067 (5)	0.1532 (4)	0.5705 (2)	0.041 (1)
C9	0.4812 (5)	−0.0313 (3)	0.5962 (2)	0.032 (1)
C10	0.4121 (5)	−0.1244 (4)	0.6640 (2)	0.039 (1)
C11	0.5247 (6)	−0.2007 (4)	0.6611 (2)	0.040 (1)
C12	0.6136 (5)	−0.1871 (4)	0.6220 (2)	0.043 (1)
C13	0.0111 (4)	0.3731 (3)	0.4219 (1)	0.025 (1)
C14	−0.1050 (5)	0.3133 (4)	0.3845 (2)	0.034 (1)
C15	0.0412 (5)	0.3026 (4)	0.2959 (2)	0.035 (1)
C16	0.0885 (6)	0.4681 (5)	0.2604 (2)	0.049 (1)
C17	0.1640 (7)	0.4162 (5)	0.2243 (2)	0.056 (1)
C18	0.1719 (7)	0.3016 (5)	0.2273 (2)	0.059 (2)
H1w1	0.275 (3)	0.740 (3)	0.512 (2)	0.044*
H1w2	0.425 (2)	0.707 (3)	0.512 (2)	0.044*
H2w1	0.211 (3)	0.656 (4)	0.410 (1)	0.045*
H2w2	0.064 (3)	0.612 (4)	0.408 (1)	0.045*
H3w1	0.117 (6)	0.890 (3)	0.485 (2)	0.059*
H3w2	0.041 (6)	0.788 (3)	0.487 (2)	0.059*
H4w1	−0.184 (3)	0.588 (4)	0.363 (2)	0.059*
H4w2	−0.082 (5)	0.553 (4)	0.329 (2)	0.059*
H5w1	0.064 (6)	1.080 (4)	0.458 (3)	0.092*
H5w2	0.203 (4)	1.058 (5)	0.439 (3)	0.092*
H2a	0.5967	0.5611	0.6597	0.041*
H2b	0.6900	0.4616	0.6391	0.041*
H4	0.8393	0.1422	0.6207	0.072*
H5	0.8133	0.0032	0.6803	0.072*
H6	0.6612	0.0392	0.7434	0.078*
H8a	0.2179	0.1041	0.5659	0.049*
H8b	0.3254	0.1743	0.6069	0.049*
H10	0.3496	−0.1325	0.6902	0.046*
H11	0.5409	−0.2601	0.6847	0.048*
H12	0.6894	−0.2401	0.6182	0.052*
H14a	−0.1651	0.3698	0.3640	0.041*
H14b	−0.1736	0.2725	0.4044	0.041*
H16	0.0805	0.5466	0.2593	0.059*
H17	0.2076	0.4567	0.1991	0.067*
H18	0.2224	0.2630	0.2031	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0157 (1)	0.0270 (1)	0.0231 (1)	0.0040 (1)	0.0054 (1)	0.0029 (1)
S1	0.0490 (7)	0.0660 (8)	0.0281 (5)	0.0167 (6)	0.0127 (5)	0.0101 (5)
S2	0.0511 (7)	0.0480 (7)	0.0480 (7)	0.0256 (6)	0.0237 (5)	0.0187 (5)
S3	0.0508 (7)	0.0374 (6)	0.0350 (5)	−0.0092 (5)	0.0135 (5)	−0.0091 (4)
O1	0.022 (1)	0.057 (2)	0.028 (1)	0.003 (1)	0.008 (1)	0.006 (1)
O2	0.023 (1)	0.043 (2)	0.027 (1)	0.003 (1)	0.010 (1)	0.004 (1)
O3	0.023 (1)	0.034 (2)	0.050 (2)	0.007 (1)	0.009 (1)	0.010 (1)
O4	0.028 (2)	0.034 (2)	0.047 (2)	0.008 (1)	0.013 (1)	0.008 (1)
O5	0.021 (1)	0.031 (1)	0.026 (1)	0.004 (1)	0.008 (1)	−0.002 (1)
O6	0.022 (1)	0.046 (2)	0.037 (2)	0.004 (1)	0.008 (1)	−0.012 (1)
O1w	0.022 (1)	0.034 (2)	0.056 (2)	0.002 (1)	0.011 (1)	0.001 (1)
O2w	0.028 (2)	0.048 (2)	0.037 (2)	0.004 (1)	0.004 (1)	0.014 (1)
O3w	0.043 (2)	0.035 (2)	0.071 (2)	0.000 (2)	0.013 (2)	0.006 (2)
O4w	0.047 (2)	0.063 (2)	0.040 (2)	0.004 (2)	0.015 (2)	0.006 (2)
O5w	0.073 (3)	0.066 (3)	0.101 (4)	0.012 (2)	0.048 (3)	0.023 (3)
N1	0.051 (2)	0.047 (2)	0.041 (2)	0.006 (2)	0.014 (2)	0.005 (2)
N2	0.058 (3)	0.068 (3)	0.050 (2)	−0.003 (2)	0.013 (2)	0.019 (2)
N3	0.032 (2)	0.036 (2)	0.038 (2)	0.007 (2)	0.009 (2)	0.005 (2)
N4	0.044 (2)	0.038 (2)	0.041 (2)	0.017 (2)	0.014 (2)	0.007 (2)
N5	0.037 (2)	0.042 (2)	0.033 (2)	−0.003 (2)	0.006 (2)	−0.002 (2)
N6	0.067 (3)	0.049 (2)	0.047 (2)	−0.005 (2)	0.028 (2)	−0.013 (2)
C1	0.025 (2)	0.026 (2)	0.026 (2)	0.0049 (14)	0.007 (2)	0.000 (1)
C2	0.036 (2)	0.039 (2)	0.027 (2)	−0.002 (2)	0.000 (2)	−0.001 (2)
C3	0.032 (2)	0.047 (3)	0.030 (2)	−0.005 (2)	0.002 (2)	0.006 (2)
C4	0.072 (4)	0.056 (3)	0.057 (3)	0.009 (3)	0.023 (3)	0.000 (3)
C5	0.064 (4)	0.047 (3)	0.067 (4)	0.004 (3)	−0.003 (3)	−0.002 (3)
C6	0.073 (4)	0.053 (3)	0.066 (4)	−0.007 (3)	−0.003 (3)	0.022 (3)
C7	0.025 (2)	0.030 (2)	0.038 (2)	0.002 (2)	0.004 (2)	−0.002 (2)
C8	0.038 (2)	0.040 (2)	0.046 (2)	0.015 (2)	0.018 (2)	0.013 (2)
C9	0.037 (2)	0.029 (2)	0.032 (2)	0.008 (2)	0.007 (2)	0.000 (2)
C10	0.035 (2)	0.043 (2)	0.039 (2)	−0.001 (2)	0.009 (2)	0.006 (2)
C11	0.051 (3)	0.034 (2)	0.035 (2)	0.008 (2)	0.005 (2)	0.008 (2)
C12	0.043 (3)	0.038 (2)	0.050 (3)	0.019 (2)	0.008 (2)	0.003 (2)
C13	0.025 (2)	0.026 (2)	0.026 (2)	0.004 (1)	0.007 (1)	0.002 (1)
C14	0.027 (2)	0.046 (2)	0.031 (2)	−0.006 (2)	0.007 (2)	−0.008 (2)
C15	0.033 (2)	0.044 (2)	0.027 (2)	−0.004 (2)	0.003 (2)	−0.009 (2)
C16	0.057 (3)	0.046 (3)	0.044 (3)	−0.007 (2)	0.005 (2)	0.000 (2)
C17	0.062 (3)	0.067 (4)	0.043 (3)	−0.023 (3)	0.021 (2)	−0.001 (2)
C18	0.064 (4)	0.075 (4)	0.045 (3)	−0.009 (3)	0.030 (3)	−0.016 (3)

Geometric parameters (Å, º) top

La1—O1	2.590 (3)	N2—C6	1.314 (8)
La1—O2	2.838 (3)	N2—C3	1.329 (6)
La1—O2ⁱ	2.466 (3)	N3—C9	1.309 (5)
La1—O3	2.584 (3)	N3—C10	1.319 (5)
La1—O4	2.560 (3)	N4—C12	1.311 (6)
La1—O5	2.687 (3)	N4—C9	1.331 (5)
La1—O5ⁱⁱ	2.469 (2)	N5—C15	1.317 (6)
La1—O6	2.583 (3)	N5—C16	1.323 (6)
La1—O1w	2.556 (3)	N6—C15	1.322 (5)
La1—O2w	2.518 (3)	N6—C18	1.321 (7)
S1—C3	1.740 (5)	C1—C2	1.498 (5)
S1—C2	1.775 (4)	C4—C5	1.349 (8)
S2—C9	1.734 (4)	C5—C6	1.348 (9)
S2—C8	1.769 (4)	C7—C8	1.488 (6)
S3—C15	1.734 (4)	C10—C11	1.351 (6)
S3—C14	1.776 (4)	C11—C12	1.362 (6)
O1—C1	1.236 (5)	C13—C14	1.496 (5)
O2—C1	1.247 (5)	C16—C17	1.358 (7)
O3—C7	1.243 (5)	C17—C18	1.359 (8)
O4—C7	1.249 (5)	C2—H2a	0.97
O5—C13	1.254 (4)	C2—H2b	0.97
O6—C13	1.227 (4)	C4—H4	0.93
O1w—H1w1	0.85 (1)	C5—H5	0.93
O1w—H1w2	0.85 (1)	C6—H6	0.93
O2w—H2w1	0.85 (1)	C8—H8a	0.97
O2w—H2w2	0.85 (1)	C8—H8b	0.97
O3w—H3w1	0.85 (1)	C10—H10	0.93
O3w—H3w2	0.85 (1)	C11—H11	0.93
O4w—H4w1	0.85 (1)	C12—H12	0.93
O4w—H4w2	0.85 (1)	C14—H14a	0.97
O5w—H5w1	0.85 (1)	C14—H14b	0.97
O5w—H5w2	0.85 (1)	C16—H16	0.93
N1—C3	1.308 (6)	C17—H17	0.93
N1—C4	1.329 (7)	C18—H18	0.93

O1—La1—O2	46.9 (1)	N1—C3—N2	126.9 (5)
O1—La1—O2ⁱ	111.0 (1)	N1—C3—S1	121.1 (3)
O1—La1—O3	69.5 (1)	N2—C3—S1	112.0 (4)
O1—La1—O4	72.2 (1)	N1—C4—C5	122.8 (5)
O1—La1—O5	125.2 (1)	C4—C5—C6	116.4 (6)
O1—La1—O5ⁱⁱ	74.7 (1)	N2—C6—C5	123.6 (5)
O1—La1—O6	141.8 (1)	O4—C7—O3	122.1 (4)
O1—La1—O1w	76.6 (1)	O4—C7—C8	120.1 (4)
O1—La1—O2w	143.1 (1)	O3—C7—C8	117.7 (4)
O2—La1—O2ⁱ	64.2 (1)	C7—C8—S2	110.0 (3)
O2—La1—O3	99.2 (1)	N3—C9—N4	126.9 (4)
O2—La1—O4	65.3 (1)	N3—C9—S2	120.4 (3)
O2—La1—O5	167.5 (1)	N4—C9—S2	112.7 (3)
O2—La1—O5ⁱⁱ	114.9 (1)	N3—C10—C11	123.0 (4)
O2—La1—O6	129.0 (1)	C10—C11—C12	117.1 (4)
O2—La1—O1w	65.3 (1)	N4—C12—C11	121.9 (4)
O2—La1—O2w	123.8 (1)	O6—C13—O5	122.1 (4)
O2ⁱ—La1—O3	125.35 (1)	O6—C13—C14	121.3 (3)
O2ⁱ—La1—O4	77.1 (1)	O5—C13—C14	116.6 (3)
O2ⁱ—La1—O5ⁱⁱ	153.8 (1)	C13—C14—S3	116.0 (3)
O2ⁱ—La1—O5	121.5 (1)	N5—C15—N6	127.3 (4)
O2ⁱ—La1—O6	77.9 (1)	N5—C15—S3	121.3 (3)
O2ⁱ—La1—O1w	79.6 (1)	N6—C15—S3	111.3 (4)
O2ⁱ—La1—O2w	76.7 (1)	N5—C16—C17	123.6 (5)
O3—La1—O4	50.1 (1)	C16—C17—C18	116.0 (5)
O3—La1—O5	68.3 (1)	N6—C18—C17	123.0 (5)
O3—La1—O5ⁱⁱ	80.8 (1)	La1—O1w—H1w1	114 (3)
O3—La1—O6	75.3 (1)	La1—O1w—H1w2	117 (3)
O3—La1—O1w	143.3 (1)	H1w1—O1w—H1w2	109 (2)
O3—La1—O2w	136.8 (1)	La1—O2w—H2w1	118 (3)
O4—La1—O5	104.1 (1)	La1—O2w—H2w2	121 (3)
O4—La1—O5ⁱⁱ	127.8 (1)	H2w1—O2w—H2w2	110 (2)
O4—La1—O6	74.1 (1)	H3w1—O3w—H3w2	110 (2)
O4—La1—O1w	130.5 (1)	H4w1—O4w—H4w2	109 (2)
O4—La1—O2w	142.4 (1)	H5w1—O5w—H5w2	110 (2)
O5—La1—O5ⁱⁱ	65.5 (1)	C1—C2—H2a	108.5
O5—La1—O6	48.6 (1)	S1—C2—H2a	108.5
O5—La1—O1w	125.3 (1)	C1—C2—H2b	108.5
O5—La1—O2w	68.6 (1)	S1—C2—H2b	108.5
O5ⁱⁱ—La1—O6	114.1 (1)	H2a—C2—H2b	107.5
O5ⁱⁱ—La1—O1w	77.0 (1)	N1—C4—H4	118.6
O5ⁱⁱ—La1—O2w	84.2 (1)	C5—C4—H4	118.6
O6—La1—O1w	140.8 (1)	C4—C5—H5	121.8
O6—La1—O2w	74.5 (1)	C6—C5—H5	121.8
O1w—La1—O2w	69.3 (1)	N2—C6—H6	118.2
C3—S1—C2	104.1 (2)	C5—C6—H6	118.2
C9—S2—C8	101.1 (2)	C7—C8—H8a	109.7
C15—S3—C14	104.1 (2)	S2—C8—H8a	109.7
C1—O1—La1	101.6 (2)	C7—C8—H8b	109.7
C1—O2—La1ⁱ	154.5 (3)	S2—C8—H8b	109.7
C1—O2—La1	89.3 (2)	H8a—C8—H8b	108.2
La1ⁱ—O2—La1	115.82 (10)	N3—C10—H10	118.5
C7—O3—La1	92.6 (2)	C11—C10—H10	118.5
C7—O4—La1	93.6 (2)	C10—C11—H11	121.4
C13—O5—La1ⁱⁱ	153.6 (2)	C12—C11—H11	121.4
C13—O5—La1	91.8 (2)	N4—C12—H12	119.0
La1ⁱⁱ—O5—La1	114.49 (9)	C11—C12—H12	119.0
C13—O6—La1	97.5 (2)	C13—C14—H14a	108.3
C3—N1—C4	115.4 (4)	S3—C14—H14a	108.3
C6—N2—C3	114.8 (5)	C13—C14—H14b	108.3
C9—N3—C10	115.2 (4)	S3—C14—H14b	108.3
C12—N4—C9	115.8 (4)	H14a—C14—H14b	107.4
C15—N5—C16	114.8 (4)	N5—C16—H16	118.2
C15—N6—C18	115.3 (5)	C17—C16—H16	118.2
O1—C1—O2	122.2 (4)	C16—C17—H17	122.0
O1—C1—C2	119.5 (4)	C18—C17—H17	122.0
O2—C1—C2	118.3 (4)	N6—C18—H18	118.5
C1—C2—S1	115.0 (3)	C17—C18—H18	118.5

O2ⁱ—La1—O1—C1	4.6 (3)	O2w—La1—O6—C13	−76.2 (2)
O5ⁱⁱ—La1—O1—C1	−148.5 (3)	O1w—La1—O6—C13	−99.3 (3)
O2w—La1—O1—C1	−91.2 (3)	O4—La1—O6—C13	124.7 (3)
O1w—La1—O1—C1	−68.5 (2)	O3—La1—O6—C13	72.6 (2)
O4—La1—O1—C1	72.6 (2)	O1—La1—O6—C13	95.8 (3)
O3—La1—O1—C1	125.8 (3)	O5—La1—O6—C13	−1.3 (2)
O6—La1—O1—C1	101.8 (3)	O2—La1—O6—C13	162.6 (2)
O5—La1—O1—C1	167.5 (2)	La1—O1—C1—O2	−0.1 (4)
O2—La1—O1—C1	0.1 (2)	La1—O1—C1—C2	178.9 (3)
O2ⁱ—La1—O2—C1	−175.4 (3)	La1ⁱ—O2—C1—O1	−170.2 (4)
O5ⁱⁱ—La1—O2—C1	33.7 (2)	La1—O2—C1—O1	0.1 (4)
O2w—La1—O2—C1	133.8 (2)	La1ⁱ—O2—C1—C2	10.8 (8)
O1w—La1—O2—C1	94.6 (2)	La1—O2—C1—C2	−178.9 (3)
O4—La1—O2—C1	−88.3 (2)	O1—C1—C2—S1	33.9 (5)
O3—La1—O2—C1	−50.5 (2)	O2—C1—C2—S1	−147.1 (3)
O6—La1—O2—C1	−129.0 (2)	C3—S1—C2—C1	93.1 (3)
O1—La1—O2—C1	0.0 (2)	C4—N1—C3—N2	0.7 (7)
O5—La1—O2—C1	−55.3 (4)	C4—N1—C3—S1	179.4 (4)
O5ⁱⁱ—La1—O2—La1ⁱ	−151.0 (1)	C6—N2—C3—N1	0.0 (8)
O2w—La1—O2—La1ⁱ	−50.9 (2)	C6—N2—C3—S1	−178.8 (4)
O1w—La1—O2—La1ⁱ	−90.1 (1)	C2—S1—C3—N1	−2.7 (4)
O4—La1—O2—La1ⁱ	87.1 (1)	C2—S1—C3—N2	176.2 (3)
O3—La1—O2—La1ⁱ	124.9 (1)	C3—N1—C4—C5	−1.1 (8)
O6—La1—O2—La1ⁱ	46.4 (2)	N1—C4—C5—C6	0.9 (9)
O1—La1—O2—La1ⁱ	175.3 (2)	C3—N2—C6—C5	−0.3 (9)
O5—La1—O2—La1ⁱ	120.0 (3)	C4—C5—C6—N2	−0.2 (9)
O2ⁱ—La1—O3—C7	25.3 (3)	La1—O4—C7—O3	13.4 (4)
O5ⁱⁱ—La1—O3—C7	−153.4 (3)	La1—O4—C7—C8	−163.7 (4)
O2w—La1—O3—C7	135.4 (2)	La1—O3—C7—O4	−13.3 (4)
O1w—La1—O3—C7	−100.1 (3)	La1—O3—C7—C8	163.9 (3)
O4—La1—O3—C7	7.1 (2)	O4—C7—C8—S2	−18.4 (5)
O6—La1—O3—C7	88.5 (2)	O3—C7—C8—S2	164.4 (3)
O1—La1—O3—C7	−76.4 (2)	C9—S2—C8—C7	178.3 (3)
O5—La1—O3—C7	139.4 (3)	C10—N3—C9—N4	1.6 (7)
O2—La1—O3—C7	−39.5 (3)	C10—N3—C9—S2	−177.2 (3)
O2ⁱ—La1—O4—C7	−171.9 (3)	C12—N4—C9—N3	0.2 (7)
O5ⁱⁱ—La1—O4—C7	17.5 (3)	C12—N4—C9—S2	179.0 (4)
O2w—La1—O4—C7	−125.3 (2)	C8—S2—C9—N3	−2.2 (4)
O1w—La1—O4—C7	124.3 (2)	C8—S2—C9—N4	178.8 (4)
O3—La1—O4—C7	−7.1 (2)	C9—N3—C10—C11	−1.4 (7)
O6—La1—O4—C7	−91.0 (2)	N3—C10—C11—C12	−0.5 (7)
O1—La1—O4—C7	70.8 (2)	C9—N4—C12—C11	−2.3 (7)
O5—La1—O4—C7	−52.2 (3)	C10—C11—C12—N4	2.5 (7)
O2—La1—O4—C7	120.8 (3)	La1—O6—C13—O5	2.5 (4)
O2ⁱ—La1—O5—C13	31.2 (2)	La1—O6—C13—C14	−178.3 (3)
O5ⁱⁱ—La1—O5—C13	−177.5 (3)	La1ⁱⁱ—O5—C13—O6	−177.3 (4)
O2w—La1—O5—C13	89.1 (2)	La1—O5—C13—O6	−2.4 (4)
O1w—La1—O5—C13	131.2 (2)	La1ⁱⁱ—O5—C13—C14	3.4 (7)
O4—La1—O5—C13	−52.1 (2)	La1—O5—C13—C14	178.4 (3)
O3—La1—O5—C13	−88.0 (2)	O6—C13—C14—S3	7.3 (5)
O6—La1—O5—C13	1.3 (2)	O5—C13—C14—S3	−173.4 (3)
O1—La1—O5—C13	−130.1 (2)	C15—S3—C14—C13	−74.9 (4)
O2—La1—O5—C13	−82.8 (4)	C16—N5—C15—N6	−0.1 (7)
O2ⁱ—La1—O5—La1ⁱⁱ	−151.3 (1)	C16—N5—C15—S3	179.2 (3)
O2w—La1—O5—La1ⁱⁱ	−93.4 (1)	C18—N6—C15—N5	0.2 (7)
O1w—La1—O5—La1ⁱⁱ	−51.3 (2)	C18—N6—C15—S3	−179.2 (4)
O4—La1—O5—La1ⁱⁱ	125.4 (1)	C14—S3—C15—N5	−4.2 (4)
O3—La1—O5—La1ⁱⁱ	89.6 (1)	C14—S3—C15—N6	175.2 (3)
O6—La1—O5—La1ⁱⁱ	178.8 (2)	C15—N5—C16—C17	−0.2 (7)
O1—La1—O5—La1ⁱⁱ	47.5 (2)	N5—C16—C17—C18	0.3 (9)
O2—La1—O5—La1ⁱⁱ	94.8 (3)	C15—N6—C18—C17	0.0 (8)
O2ⁱ—La1—O6—C13	−155.6 (3)	C16—C17—C18—N6	−0.2 (9)
O5ⁱⁱ—La1—O6—C13	−0.1 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O3w	0.85 (1)	1.92 (1)	2.749 (5)	165 (4)
O1w—H1w2···O4ⁱ	0.85 (1)	1.93 (2)	2.751 (4)	164 (4)
O2w—H2w1···N1ⁱ	0.85 (1)	2.05 (2)	2.852 (5)	158 (4)
O2w—H2w2···O4w	0.85 (1)	1.88 (2)	2.709 (5)	167 (4)
O3w—H3w1···O5w	0.85 (1)	1.89 (2)	2.718 (5)	166 (6)
O3w—H3w2···O3ⁱⁱ	0.85 (1)	2.03 (2)	2.840 (5)	158 (5)
O4w—H4w1···O1ⁱⁱ	0.85 (1)	2.01 (2)	2.823 (4)	160 (5)
O4w—H4w2···N5	0.85 (1)	2.13 (3)	2.918 (5)	154 (5)
O5w—H5w1···O3wⁱⁱⁱ	0.85 (1)	2.09 (2)	2.903 (6)	162 (6)
O5w—H5w2···N4ⁱ	0.85 (1)	2.08 (2)	2.918 (6)	169 (6)

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

Experimental details

Crystal data
Chemical formula	[La(C₆H₅N₂O₂S)₃(H₂O)₂]·3H₂O
M_r	736.53
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	8.8145 (3), 11.8211 (5), 25.887 (1)
β (°)	97.046 (1)
V (Å³)	2677.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.90
Crystal size (mm)	0.50 × 0.22 × 0.14

Data collection
Diffractometer	Bruker APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.504, 0.777
No. of measured, independent and observed [I > 2σ(I)] reflections	15909, 6110, 5749
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.110, 1.16
No. of reflections	6110
No. of parameters	382
No. of restraints	15
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.19, −0.75

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top

La1—O1	2.590 (3)	La1—O5	2.687 (3)
La1—O2	2.838 (3)	La1—O5ⁱⁱ	2.469 (2)
La1—O2ⁱ	2.466 (3)	La1—O6	2.583 (3)
La1—O3	2.584 (3)	La1—O1w	2.556 (3)
La1—O4	2.560 (3)	La1—O2w	2.518 (3)

O1—La1—O2	46.9 (1)	O2ⁱ—La1—O2w	76.7 (1)
O1—La1—O2ⁱ	111.0 (1)	O3—La1—O4	50.1 (1)
O1—La1—O3	69.5 (1)	O3—La1—O5	68.3 (1)
O1—La1—O4	72.2 (1)	O3—La1—O5ⁱⁱ	80.8 (1)
O1—La1—O5	125.2 (1)	O3—La1—O6	75.3 (1)
O1—La1—O5ⁱⁱ	74.7 (1)	O3—La1—O1w	143.3 (1)
O1—La1—O6	141.8 (1)	O3—La1—O2w	136.8 (1)
O1—La1—O1w	76.6 (1)	O4—La1—O5	104.1 (1)
O1—La1—O2w	143.1 (1)	O4—La1—O5ⁱⁱ	127.8 (1)
O2—La1—O2ⁱ	64.2 (1)	O4—La1—O6	74.1 (1)
O2—La1—O3	99.2 (1)	O4—La1—O1w	130.5 (1)
O2—La1—O4	65.3 (1)	O4—La1—O2w	142.4 (1)
O2—La1—O5	167.5 (1)	O5—La1—O5ⁱⁱ	65.5 (1)
O2—La1—O5ⁱⁱ	114.9 (1)	O5—La1—O6	48.6 (1)
O2—La1—O6	129.0 (1)	O5—La1—O1w	125.3 (1)
O2—La1—O1w	65.3 (1)	O5—La1—O2w	68.6 (1)
O2—La1—O2w	123.8 (1)	O5ⁱⁱ—La1—O6	114.1 (1)
O2ⁱ—La1—O3	125.35 (1)	O5ⁱⁱ—La1—O1w	77.0 (1)
O2ⁱ—La1—O4	77.1 (1)	O5ⁱⁱ—La1—O2w	84.2 (1)
O2ⁱ—La1—O5ⁱⁱ	153.8 (1)	O6—La1—O1w	140.8 (1)
O2ⁱ—La1—O5	121.5 (1)	O6—La1—O2w	74.5 (1)
O2ⁱ—La1—O6	77.9 (1)	O1w—La1—O2w	69.3 (1)
O2ⁱ—La1—O1w	79.6 (1)