Poly[[tetra­aqua­bis(5-carboxy­pyridine-2-carboxyl­ato-κ²N,O)bis­(μ₄-pyridine-2,5-dicarboxyl­ato-κ⁵N,O:O:O′:O′′)dilanthanum(III)] dihydrate]

The title compound, {[La₂(C₇H₄NO₄)₂(C₇H₃NO₄)₂(H₂O)₄]·2H₂O}_n, was prepared by a hydro­thermal reaction at 433 K. The asymmetric unit contains two La^III ions. Each La^III ion is nine-coordinated in a slightly distorted tricapped trigonal–prismatic coordination geometry, formed by two N atoms from 5-carboxy­pyridine-2-carboxyl­ate (Hpydc) and pyridine-2,5-dicarboxyl­ate (pydc) ligands, five O atoms from carboxyl­ate groups of one Hpydc and four pydc ligands, and two water mol­ecules. Adjacent La^III ions are linked together through single bridging carboxyl­ate O atoms and carboxyl­ate groups in a syn–anti mode, forming a two-dimensional layered polymeric structure. Extensive O—H...O hydrogen bonding connects adjacent layers into an infinite three-dimensional supra­molecular network structure. The crystal studied was an inversion twin.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.020 Å
• R factor = 0.064
• wR factor = 0.174
• Data-to-parameter ratio = 11.4

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.500
           From the CIF: _refine_ls_abs_structure_Flack_su    0.040
PLAT033_ALERT_2_C Flack Parameter Value Deviates 2 * su from zero.       0.50
PLAT213_ALERT_2_C Atom O8      has ADP max/min Ratio .............       3.10 prola
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.64 Ratio
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.32
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         20
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C15    -   C16    ...       1.55 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H12A   ..  H21C    ..       2.10 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.01
           From the CIF: _reflns_number_total               5778
           Count of symmetry unique reflns         3026
           Completeness (_total/calc)            190.95%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2752
           Fraction of Friedel pairs measured     0.909
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for La1         (3)       3.69
PLAT794_ALERT_5_G Check Predicted Bond Valency for La2         (3)       3.44
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   2 ALERT type 5 Informative message, check

---

S1. Comment

In recent years, studies on the syntheses, structures and properties of coordination complexes containing lanthanum and aromatic carboxylate have intensely attracted much attention, because they possess potential application on catalysis, separation, gas deposition and luminescence (Chae et al., 2004; Seo et al., 2000; Bradshaw et al., 2004; Lu et al., 2006). As a multi-functional ligand, pyridine-2,5-dicarboxylic acid has been widely used in the preparation of 3 d-4f heterometallic coordination polymers (Liang et al., 2000; Liang et al., 2001) and transition metallic supra-molecular compounds (Min et al., 2001; Xu et al., 2001; Gao et al., 2005). However the investigation on the lanthanum complexes is relative limited (Song et al., 2005). We report here the crystal structure of the title La^III polymeric compound.

A segment of the polymeric structure of the title compound is illustrated in Fig. 1. Each La^III ion is nine-coordinated by two nitrogen atoms from Hpydc and pydc ligands, five oxygen atoms from carboxylate groups of one Hpydc and four pydc ligands and two water molecules. The pydc^2- anion acts as chelating-bridging pentadentate ligand towards four La^III ions. The pyridine nitrogen atom and the ortho-carboxylic oxygen atom chelate one La ion, and this oxygen atom and other two carboxylic oxygen atoms of the pydc ligand bridge another three different La ions. The Hpydc^- anion acts as chelating bidentate ligand towards the La ion with a pyridine nitrogen atom and the ortho carboxylic oxygen atom, which is similar to the coordination mode of Hpydc in [Dy(Hpydc)(pydc)(phen)(H₂O).H₂O]_n [phen=1,10-phenanthroline] (Song et al., 2005) and [Ln(Hpydc)(pydc)] [Ln = Sm, Eu, Gd] (Qin et al., 2005). The La···La separations in the same unit and between adjacent units are 4.339 (9) and 5.619 (9) Å, respectively. The La center is in a slightly distorted tricapped trigonal prism coordination geometry. Adjacent La ions are linked together through single-atom carboxylate oxygen atom and carboxylate group in the syn-anti mode, forming a two-dimensional polymeric layer structure as represented in Fig. 2. Selected geometric parameters are listed in Table 1. The La—O bond lengths fall in range from 2.498 (10) to 2.658 (9) Å.

Extensive N—H···O and O—H···O hydrogen bonding occur in the crystal structure of the title compound, and connect adjacent layers into the infinite three-dimensional supramolecular network structure (Table 2 and Fig. 3).

Related literature

For general background, see: Chae et al. (2004); Seo et al. (2000); Bradshaw et al. (2004); Lu et al. (2006); Liang et al. (2000, 2001); Min et al. (2001); Xu et al. (2001); Gao et al. (2005). For related structures, see: Song et al. (2005); Qin et al. (2005).

S2. Experimental

A mixture of La(NO₃)₃.6H₂O (0.060 g, 0.25 mmol), pyridine-2,5-dicarboxylic acid (0.084 g, 0.50 mmol) and H₂O (15 ml) was sealed in a 25 ml stainless steel reactor with a Teflon liner and heated at 433 K for 72 h. The mixture was cooled slowly to room temperature at a rate of 10 K.h^-1. Straw yellow prism crystals of the title complex were collected by filtration and were obtained in 21% yield. Analysis calculated for C₁₄H₁₃LaN₂O₁₁ (%): C 32.08, H 2.50, N 5.34; found: C 32.11, H 2.53, N 5.36

S3. Refinement

Aromatic H atoms were placed in geometrically idealized positions with C—H = 0.93 Å and refined in the riding-model approximation with U_iso(H) = 1.2U_eq(C). Carboxyl H atoms were placed in calculated position with O—H = 0.82 Å and refined in riding mode with U_iso(H) = 1.5U_eq(O). Water H atoms were placed in calculated positions with O—H = 0.85 Å and refined in riding mode with U_iso(H) = 1.2U_eq(O). The highest peak and deepest hole appear at 1.22 Å from H14 and 0.83 Å from H21A, respectively.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Figures

	Fig. 1. The structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 2. View of the two-dimensional network in the crystal structure of the title compound. H atoms and uncoordinated water molecules have been omitted.
	Fig. 3. View of the packing of the three-dimensional network of the title compound along the b axis (H atoms and uncoordinated water molecules have been omitted for clarity).

Poly[[tetraaquabis(5-carboxypyridine-2-carboxylato-κ²N,O)bis(µ₄– pyridine-2,5-dicarboxylato-κ⁵N,O:O:O':O'')dilanthanum(III)] dihydrate]

Crystal data

[La2(C7H4NO4)2(C7H3NO4)2(H2O)4]·2H2O	F(000) = 1024
Mr = 1048.35	Dx = 2.088 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3211 reflections
a = 9.2203 (18) Å	θ = 2.2–20.5°
b = 19.744 (4) Å	µ = 2.63 mm^−1
c = 9.3552 (19) Å	T = 293 K
β = 101.72 (3)°	Prism, yellow
V = 1667.5 (6) Å^3	0.35 × 0.34 × 0.27 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	5778 independent reflections
Radiation source: fine-focus sealed tube	5491 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
φ and ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.428, Tmax = 0.490	k = −23→23
12319 measured reflections	l = −11→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.064	H-atom parameters constrained
wR(F^2) = 0.174	w = 1/[σ^2(Fo^2) + (0.0958P)^2 + 9.9455P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
5778 reflections	Δρmax = 1.82 e Å^−3
505 parameters	Δρmin = −3.93 e Å^−3
1 restraint	Absolute structure: Flack (1983), 2752 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.50 (4)

Special details

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
La1	0.46937 (8)	0.05700 (3)	0.39796 (8)	0.0112 (2)
La2	0.28724 (8)	0.07667 (3)	0.93428 (8)	0.0107 (2)
N1	0.5695 (13)	−0.0629 (6)	0.5397 (14)	0.016 (3)
N2	−0.2524 (13)	0.0334 (6)	0.3592 (13)	0.014 (3)
N3	0.0116 (13)	0.1009 (6)	0.9728 (13)	0.015 (3)
N4	0.1862 (13)	0.1969 (6)	0.7924 (13)	0.014 (3)
O1	0.3674 (11)	−0.0545 (5)	0.2910 (11)	0.015 (2)
O2	0.2676 (12)	−0.1539 (5)	0.3372 (12)	0.024 (2)
O3	0.9397 (13)	−0.0864 (6)	0.8710 (13)	0.024 (3)
O4	0.8767 (12)	−0.1922 (5)	0.9100 (13)	0.026 (3)
H4B	0.9385	−0.1884	0.9860	0.038*
O5	0.2708 (11)	0.0173 (5)	0.5298 (11)	0.014 (2)
O6	0.1288 (10)	0.0513 (5)	0.6871 (10)	0.0148 (19)
O7	−0.3646 (11)	−0.0298 (6)	0.0010 (12)	0.021 (2)
O8	−0.4868 (10)	0.0364 (5)	0.1292 (10)	0.011 (2)
O9	0.4727 (13)	0.2909 (5)	1.0127 (13)	0.029 (3)
O10	0.3905 (11)	0.1868 (5)	1.0408 (11)	0.016 (2)
O11	−0.1719 (12)	0.2227 (5)	0.4463 (12)	0.020 (2)
O12	−0.0761 (13)	0.3223 (5)	0.3902 (13)	0.026 (3)
H12A	−0.1476	0.3221	0.3218	0.040*
O13	0.2497 (11)	0.0993 (5)	1.2010 (11)	0.015 (2)
O14	0.1265 (12)	0.1662 (6)	1.3299 (12)	0.023 (2)
O15	−0.3697 (10)	0.0818 (5)	0.6455 (10)	0.0145 (19)
O16	−0.5110 (11)	0.1124 (5)	0.7993 (11)	0.017 (2)
O17	0.3846 (11)	−0.0285 (5)	0.8125 (11)	0.016 (2)
H17A	0.4683	−0.0311	0.8705	0.019*
H17C	0.3985	−0.0053	0.7400	0.019*
O18	0.1967 (11)	−0.0318 (5)	1.0239 (11)	0.016 (2)
H18A	0.2358	−0.0457	1.1090	0.019*
H18C	0.1178	−0.0542	0.9929	0.019*
O19	0.3764 (12)	0.1608 (5)	0.5188 (12)	0.018 (2)
H19A	0.2862	0.1573	0.4756	0.022*
H19B	0.3869	0.1431	0.6031	0.022*
O20	0.5648 (11)	0.1658 (5)	0.3042 (12)	0.019 (2)
H20A	0.5504	0.1549	0.2145	0.022*
H20B	0.6562	0.1606	0.3414	0.022*
O21	0.7230 (12)	0.3388 (5)	0.1594 (13)	0.027 (3)
H21B	0.6464	0.3190	0.1118	0.033*
H21C	0.7003	0.3796	0.1734	0.033*
O22	0.1319 (14)	0.7993 (6)	0.0723 (16)	0.040 (3)
H22A	0.1775	0.8147	0.1540	0.048*
H22B	0.1779	0.8119	0.0068	0.048*
C1	0.3653 (16)	−0.1095 (7)	0.3636 (16)	0.016 (3)
C2	0.4906 (16)	−0.1192 (7)	0.4931 (16)	0.015 (3)
C3	0.5209 (16)	−0.1821 (8)	0.5549 (17)	0.017 (3)
H3A	0.4613	−0.2191	0.5205	0.021*
C4	0.6448 (16)	−0.1899 (7)	0.6723 (17)	0.018 (3)
H4A	0.6699	−0.2318	0.7156	0.021*
C5	0.7253 (16)	−0.1331 (7)	0.7187 (17)	0.016 (3)
C6	0.8590 (16)	−0.1344 (7)	0.8433 (17)	0.017 (3)
C7	0.6853 (16)	−0.0696 (8)	0.6544 (16)	0.016 (3)
H7A	0.7393	−0.0315	0.6913	0.019*
C8	0.1461 (15)	0.0313 (7)	0.5627 (16)	0.014 (3)
C9	0.0120 (16)	0.0184 (7)	0.4480 (16)	0.013 (3)
C10	0.0192 (16)	−0.0138 (7)	0.3160 (16)	0.015 (3)
H10A	0.1094	−0.0302	0.3007	0.018*
C11	−0.1064 (15)	−0.0214 (7)	0.2089 (17)	0.014 (3)
H11A	−0.1001	−0.0431	0.1221	0.017*
C12	−0.2384 (16)	0.0021 (7)	0.2280 (16)	0.014 (3)
C13	−0.3733 (15)	0.0021 (7)	0.1096 (16)	0.014 (3)
C14	−0.1313 (15)	0.0397 (7)	0.4643 (16)	0.014 (3)
H14	−0.1410	0.0590	0.5526	0.017*
C15	0.1360 (16)	0.1339 (7)	1.2190 (16)	0.014 (3)
C16	−0.0017 (16)	0.1304 (7)	1.0937 (16)	0.013 (3)
C17	−0.1335 (16)	0.1583 (7)	1.1211 (17)	0.016 (3)
H17B	−0.1360	0.1813	1.2073	0.019*
C18	−0.2594 (16)	0.1499 (7)	1.0130 (16)	0.014 (3)
H18B	−0.3503	0.1665	1.0259	0.017*
C19	−0.2479 (16)	0.1164 (7)	0.8852 (16)	0.014 (3)
C20	−0.3863 (15)	0.1042 (7)	0.7739 (16)	0.013 (3)
C21	−0.1135 (15)	0.0917 (7)	0.8690 (15)	0.014 (3)
H21A	−0.1075	0.0679	0.7846	0.017*
C22	0.3880 (16)	0.2428 (7)	0.9726 (16)	0.017 (3)
C23	0.2723 (16)	0.2512 (7)	0.8339 (16)	0.016 (3)
C24	0.2569 (17)	0.3121 (7)	0.7608 (17)	0.018 (3)
H24A	0.3219	0.3478	0.7911	0.022*
C25	0.1432 (17)	0.3188 (7)	0.6423 (17)	0.017 (3)
H25A	0.1294	0.3596	0.5917	0.021*
C26	0.0477 (16)	0.2643 (7)	0.5970 (16)	0.015 (3)
C27	−0.0788 (16)	0.2672 (7)	0.4702 (16)	0.015 (3)
C28	0.0747 (16)	0.2054 (7)	0.6777 (16)	0.015 (3)
H28A	0.0109	0.1691	0.6503	0.018*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La1	0.0075 (4)	0.0194 (4)	0.0072 (4)	0.0004 (3)	0.0030 (3)	−0.0004 (3)
La2	0.0075 (4)	0.0192 (4)	0.0057 (4)	0.0007 (3)	0.0022 (3)	−0.0004 (3)
N1	0.013 (6)	0.022 (6)	0.012 (7)	0.001 (5)	0.002 (5)	0.000 (5)
N2	0.010 (6)	0.024 (6)	0.008 (6)	0.002 (5)	0.003 (5)	−0.003 (5)
N3	0.012 (6)	0.024 (6)	0.008 (6)	0.000 (5)	0.002 (5)	−0.001 (5)
N4	0.012 (6)	0.023 (6)	0.008 (6)	0.000 (5)	0.003 (5)	0.001 (5)
O1	0.013 (5)	0.024 (5)	0.008 (5)	0.001 (4)	0.003 (4)	0.001 (4)
O2	0.018 (6)	0.032 (6)	0.019 (6)	−0.008 (5)	−0.005 (5)	0.002 (5)
O3	0.023 (6)	0.026 (6)	0.020 (6)	−0.004 (5)	−0.004 (5)	−0.001 (5)
O4	0.022 (6)	0.032 (6)	0.018 (6)	−0.003 (5)	−0.005 (5)	0.003 (4)
O5	0.011 (5)	0.025 (5)	0.009 (5)	0.002 (4)	0.005 (4)	−0.001 (4)
O6	0.011 (4)	0.024 (5)	0.010 (5)	0.001 (4)	0.004 (4)	−0.001 (4)
O7	0.012 (5)	0.037 (6)	0.011 (6)	0.004 (5)	−0.003 (4)	−0.009 (5)
O8	0.003 (4)	0.023 (5)	0.007 (5)	0.002 (3)	−0.001 (4)	−0.004 (4)
O9	0.023 (6)	0.031 (6)	0.028 (7)	−0.007 (5)	−0.006 (5)	0.002 (5)
O10	0.014 (5)	0.023 (5)	0.010 (5)	0.001 (4)	0.001 (4)	0.001 (4)
O11	0.013 (5)	0.029 (6)	0.015 (6)	−0.001 (5)	−0.002 (4)	−0.002 (4)
O12	0.021 (6)	0.035 (6)	0.017 (6)	−0.003 (5)	−0.011 (5)	0.009 (4)
O13	0.016 (5)	0.023 (5)	0.010 (5)	−0.002 (4)	0.008 (4)	0.000 (4)
O14	0.017 (6)	0.035 (6)	0.016 (6)	0.005 (5)	0.001 (5)	−0.012 (5)
O15	0.011 (5)	0.024 (5)	0.008 (5)	0.002 (4)	0.001 (4)	−0.002 (4)
O16	0.011 (5)	0.027 (5)	0.012 (5)	0.000 (4)	0.002 (4)	0.001 (4)
O17	0.014 (5)	0.025 (5)	0.009 (5)	0.004 (4)	0.004 (4)	0.003 (4)
O18	0.012 (5)	0.028 (5)	0.010 (5)	−0.005 (4)	0.006 (4)	0.003 (4)
O19	0.014 (5)	0.028 (6)	0.012 (6)	0.003 (4)	0.000 (4)	0.002 (5)
O20	0.013 (5)	0.030 (6)	0.013 (6)	−0.002 (4)	0.001 (4)	0.001 (4)
O21	0.022 (6)	0.024 (5)	0.030 (7)	−0.005 (4)	−0.009 (5)	0.006 (5)
O22	0.034 (8)	0.045 (7)	0.036 (8)	0.000 (6)	−0.003 (6)	−0.002 (6)
C1	0.012 (7)	0.023 (7)	0.011 (8)	0.001 (6)	0.003 (6)	−0.001 (6)
C2	0.011 (7)	0.023 (7)	0.011 (8)	0.000 (6)	0.003 (6)	0.001 (6)
C3	0.014 (8)	0.024 (7)	0.014 (8)	0.000 (6)	0.002 (6)	0.001 (6)
C4	0.013 (8)	0.026 (7)	0.014 (8)	0.001 (6)	0.001 (6)	0.001 (6)
C5	0.012 (7)	0.024 (7)	0.011 (7)	0.001 (6)	0.003 (6)	0.001 (6)
C6	0.014 (8)	0.025 (7)	0.012 (8)	0.003 (6)	0.003 (6)	0.001 (6)
C7	0.012 (7)	0.024 (7)	0.012 (8)	0.001 (6)	0.003 (6)	0.000 (6)
C8	0.011 (7)	0.023 (7)	0.009 (7)	0.001 (6)	0.003 (6)	0.000 (6)
C9	0.008 (7)	0.024 (7)	0.008 (7)	0.000 (6)	0.002 (6)	0.000 (6)
C10	0.011 (7)	0.024 (7)	0.010 (7)	0.000 (6)	0.004 (6)	−0.001 (6)
C11	0.010 (7)	0.024 (7)	0.008 (8)	0.001 (5)	0.003 (6)	−0.002 (6)
C12	0.012 (7)	0.023 (7)	0.008 (7)	−0.001 (6)	0.000 (6)	−0.005 (6)
C13	0.008 (7)	0.023 (7)	0.009 (8)	−0.001 (5)	0.002 (6)	−0.001 (6)
C14	0.010 (7)	0.024 (8)	0.008 (7)	−0.001 (5)	0.003 (5)	−0.002 (5)
C15	0.011 (7)	0.022 (7)	0.010 (8)	−0.001 (5)	0.002 (6)	0.000 (6)
C16	0.010 (7)	0.023 (7)	0.007 (7)	0.001 (6)	0.005 (6)	0.001 (5)
C17	0.013 (7)	0.025 (7)	0.011 (7)	0.001 (6)	0.003 (6)	−0.001 (6)
C18	0.011 (7)	0.024 (7)	0.008 (7)	−0.001 (6)	0.004 (6)	−0.001 (6)
C19	0.012 (7)	0.023 (7)	0.008 (7)	−0.001 (6)	0.004 (6)	0.000 (6)
C20	0.010 (7)	0.022 (6)	0.008 (7)	−0.001 (6)	0.002 (6)	0.003 (6)
C21	0.011 (7)	0.024 (8)	0.009 (7)	0.001 (5)	0.004 (5)	−0.001 (5)
C22	0.013 (7)	0.024 (7)	0.013 (8)	0.001 (6)	0.002 (6)	−0.002 (6)
C23	0.012 (7)	0.024 (7)	0.012 (8)	0.001 (6)	0.003 (6)	−0.001 (6)
C24	0.015 (8)	0.025 (7)	0.013 (8)	−0.002 (6)	−0.001 (6)	0.000 (6)
C25	0.015 (7)	0.023 (7)	0.012 (8)	−0.001 (6)	0.000 (6)	0.002 (6)
C26	0.011 (7)	0.024 (7)	0.010 (7)	0.000 (5)	0.003 (6)	−0.001 (6)
C27	0.012 (7)	0.024 (7)	0.010 (7)	0.000 (6)	0.003 (6)	0.000 (5)
C28	0.012 (7)	0.024 (7)	0.010 (8)	0.000 (6)	0.003 (6)	−0.001 (6)

Geometric parameters (Å, º)

La1—O1	2.520 (10)	O16—La2^iv	2.551 (10)
La1—O5	2.531 (10)	O17—H17A	0.8500
La1—O8^i	2.658 (9)	O17—H17C	0.8500
La1—O13^ii	2.584 (10)	O18—H18A	0.8500
La1—O15^i	2.531 (9)	O18—H18C	0.8500
La1—O19	2.570 (11)	O19—H19A	0.8500
La1—O20	2.543 (10)	O19—H19B	0.8501
La1—N1	2.778 (13)	O20—H20A	0.8500
La1—N2^i	2.703 (12)	O20—H20B	0.8500
La2—O6	2.522 (9)	O21—H21B	0.8500
La2—O8^iii	2.599 (9)	O21—H21C	0.8500
La2—O10	2.498 (10)	O22—H22A	0.8500
La2—O13	2.626 (10)	O22—H22B	0.8500
La2—O16^i	2.551 (10)	C1—C2	1.51 (2)
La2—O17	2.613 (10)	C2—C3	1.38 (2)
La2—O18	2.505 (10)	C3—C4	1.42 (2)
La2—N3	2.681 (12)	C3—H3A	0.9300
La2—N4	2.786 (12)	C4—C5	1.37 (2)
N1—C2	1.351 (19)	C4—H4A	0.9300
N1—C7	1.357 (19)	C5—C7	1.41 (2)
N2—C14	1.335 (18)	C5—C6	1.51 (2)
N2—C12	1.403 (19)	C7—H7A	0.9300
N2—La1^iv	2.703 (12)	C8—C9	1.49 (2)
N3—C16	1.300 (19)	C9—C10	1.40 (2)
N3—C21	1.361 (18)	C9—C14	1.42 (2)
N4—C28	1.337 (19)	C10—C11	1.38 (2)
N4—C23	1.344 (19)	C10—H10A	0.9300
O1—C1	1.282 (17)	C11—C12	1.35 (2)
O2—C1	1.246 (18)	C11—H11A	0.9300
O3—C6	1.201 (18)	C12—C13	1.488 (19)
O4—C6	1.296 (18)	C14—H14	0.9300
O4—H4B	0.8200	C15—C16	1.545 (19)
O5—C8	1.279 (17)	C16—C17	1.40 (2)
O6—C8	1.270 (17)	C17—C18	1.39 (2)
O7—C13	1.211 (18)	C17—H17B	0.9300
O8—C13	1.290 (17)	C18—C19	1.39 (2)
O8—La2^v	2.599 (9)	C18—H18B	0.9300
O8—La1^iv	2.658 (9)	C19—C21	1.37 (2)
O9—C22	1.237 (18)	C19—C20	1.494 (19)
O10—C22	1.276 (18)	C21—H21A	0.9300
O11—C27	1.216 (18)	C22—C23	1.512 (19)
O12—C27	1.323 (18)	C23—C24	1.38 (2)
O12—H12A	0.8200	C24—C25	1.37 (2)
O13—C15	1.291 (17)	C24—H24A	0.9300
O13—La1^vi	2.584 (10)	C25—C26	1.40 (2)
O14—C15	1.237 (18)	C25—H25A	0.9300
O15—C20	1.317 (18)	C26—C28	1.38 (2)
O15—La1^iv	2.531 (9)	C26—C27	1.486 (19)
O16—C20	1.232 (18)	C28—H28A	0.9300
O1—La1—O5	71.0 (3)	C15—O13—La2	118.8 (9)
O1—La1—O15^i	129.4 (3)	La1^vi—O13—La2	112.8 (4)
O5—La1—O15^i	87.8 (3)	C20—O15—La1^iv	138.1 (8)
O1—La1—O20	136.7 (3)	C20—O16—La2^iv	149.6 (10)
O5—La1—O20	139.9 (3)	La2—O17—H17A	96.8
O15^i—La1—O20	88.4 (3)	La2—O17—H17C	92.3
O1—La1—O19	137.8 (3)	H17A—O17—H17C	106.2
O5—La1—O19	72.1 (3)	La2—O18—H18A	118.8
O15^i—La1—O19	68.2 (3)	La2—O18—H18C	130.6
O20—La1—O19	69.4 (4)	H18A—O18—H18C	108.8
O1—La1—O13^ii	79.9 (3)	La1—O19—H19A	96.2
O5—La1—O13^ii	84.7 (3)	La1—O19—H19B	95.5
O15^i—La1—O13^ii	145.0 (3)	H19A—O19—H19B	108.9
O20—La1—O13^ii	76.0 (3)	La1—O20—H20A	97.6
O19—La1—O13^ii	76.9 (3)	La1—O20—H20B	98.1
O1—La1—O8^i	66.8 (3)	H20A—O20—H20B	108.5
O5—La1—O8^i	132.7 (3)	H21B—O21—H21C	108.2
O15^i—La1—O8^i	136.2 (3)	H22A—O22—H22B	108.5
O20—La1—O8^i	70.9 (3)	O2—C1—O1	125.4 (13)
O19—La1—O8^i	131.8 (3)	O2—C1—C2	118.4 (13)
O13^ii—La1—O8^i	67.8 (3)	O1—C1—C2	116.2 (12)
O1—La1—N2^i	94.8 (3)	N1—C2—C3	123.9 (13)
O5—La1—N2^i	144.3 (3)	N1—C2—C1	115.4 (12)
O15^i—La1—N2^i	76.1 (3)	C3—C2—C1	120.7 (13)
O20—La1—N2^i	72.3 (3)	C2—C3—C4	118.9 (13)
O19—La1—N2^i	127.4 (3)	C2—C3—H3A	120.5
O13^ii—La1—N2^i	126.0 (3)	C4—C3—H3A	120.5
O8^i—La1—N2^i	61.0 (3)	C5—C4—C3	117.2 (14)
O1—La1—N1	60.4 (4)	C5—C4—H4A	121.4
O5—La1—N1	73.0 (3)	C3—C4—H4A	121.4
O15^i—La1—N1	69.6 (3)	C4—C5—C7	121.1 (14)
O20—La1—N1	141.2 (3)	C4—C5—C6	122.4 (13)
O19—La1—N1	125.3 (4)	C7—C5—C6	116.5 (13)
O13^ii—La1—N1	138.8 (3)	O3—C6—O4	125.5 (14)
O8^i—La1—N1	102.8 (3)	O3—C6—C5	121.6 (13)
N2^i—La1—N1	71.6 (4)	O4—C6—C5	112.8 (12)
O10—La2—O18	137.5 (3)	N1—C7—C5	121.4 (14)
O10—La2—O6	129.9 (3)	N1—C7—H7A	119.3
O18—La2—O6	88.1 (3)	C5—C7—H7A	119.3
O10—La2—O16^i	72.5 (3)	O6—C8—O5	125.1 (13)
O18—La2—O16^i	136.8 (3)	O6—C8—C9	118.3 (12)
O6—La2—O16^i	86.9 (3)	O5—C8—C9	116.5 (13)
O10—La2—O16^i	72.5 (3)	C10—C9—C14	116.1 (13)
O18—La2—O16^i	136.8 (3)	C10—C9—C8	122.1 (13)
O6—La2—O16^i	86.9 (3)	C14—C9—C8	121.8 (13)
O16^i—La2—O16^i	0.0 (4)	C11—C10—C9	120.4 (14)
O10—La2—O8^iii	78.5 (3)	C11—C10—H10A	119.8
O18—La2—O8^iii	77.1 (3)	C9—C10—H10A	119.8
O6—La2—O8^iii	144.6 (3)	C12—C11—C10	121.0 (14)
O16^i—La2—O8^iii	82.6 (3)	C12—C11—H11A	119.5
O16^i—La2—O8^iii	82.6 (3)	C10—C11—H11A	119.5
O10—La2—O17	136.8 (3)	C11—C12—N2	120.9 (13)
O18—La2—O17	68.5 (4)	C11—C12—C13	122.8 (14)
O6—La2—O17	68.2 (3)	N2—C12—C13	116.1 (12)
O16^i—La2—O17	69.8 (3)	O7—C13—O8	125.8 (13)
O16^i—La2—O17	69.8 (3)	O7—C13—C12	115.9 (13)
O8^iii—La2—O17	76.4 (3)	O8—C13—C12	118.2 (12)
O10—La2—O13	65.6 (3)	N2—C14—C9	123.3 (13)
O18—La2—O13	73.1 (3)	N2—C14—H14	118.4
O6—La2—O13	137.9 (3)	C9—C14—H14	118.4
O16^i—La2—O13	132.3 (3)	O14—C15—O13	125.5 (13)
O16^i—La2—O13	132.3 (3)	O14—C15—C16	118.2 (13)
O8^iii—La2—O13	68.1 (3)	O13—C15—C16	116.2 (12)
O17—La2—O13	132.3 (3)	N3—C16—C17	125.0 (14)
O10—La2—N3	94.9 (3)	N3—C16—C15	118.1 (13)
O18—La2—N3	73.6 (3)	C17—C16—C15	116.9 (13)
O6—La2—N3	76.7 (3)	C18—C17—C16	116.6 (14)
O16^i—La2—N3	145.4 (3)	C18—C17—H17B	121.7
O16^i—La2—N3	145.4 (3)	C16—C17—H17B	121.7
O8^iii—La2—N3	127.4 (3)	C17—C18—C19	119.0 (14)
O17—La2—N3	128.3 (3)	C17—C18—H18B	120.5
O13—La2—N3	62.0 (3)	C19—C18—H18B	120.5
O10—La2—N4	60.8 (4)	C21—C19—C18	119.6 (14)
O18—La2—N4	141.8 (3)	C21—C19—C20	122.0 (13)
O6—La2—N4	69.9 (3)	C18—C19—C20	118.2 (13)
O16^i—La2—N4	74.7 (3)	O16—C20—O15	120.4 (13)
O16^i—La2—N4	74.7 (3)	O16—C20—C19	122.9 (13)
O8^iii—La2—N4	137.6 (3)	O15—C20—C19	116.7 (12)
O17—La2—N4	125.5 (4)	N3—C21—C19	121.9 (13)
O13—La2—N4	102.2 (3)	N3—C21—H21A	119.0
N3—La2—N4	71.2 (4)	C19—C21—H21A	119.0
C2—N1—C7	117.4 (13)	O9—C22—O10	124.5 (14)
C2—N1—La1	116.2 (9)	O9—C22—C23	117.9 (13)
C7—N1—La1	126.4 (10)	O10—C22—C23	117.5 (12)
C14—N2—C12	118.3 (12)	N4—C23—C24	124.0 (14)
C14—N2—La1^iv	124.0 (9)	N4—C23—C22	115.7 (13)
C12—N2—La1^iv	116.8 (8)	C24—C23—C22	120.4 (13)
C16—N3—C21	117.7 (12)	C25—C24—C23	118.1 (14)
C16—N3—La2	117.2 (9)	C25—C24—H24A	120.9
C21—N3—La2	124.7 (9)	C23—C24—H24A	120.9
C28—N4—C23	116.4 (13)	C24—C25—C26	120.2 (14)
C28—N4—La2	128.1 (10)	C24—C25—H25A	119.9
C23—N4—La2	114.9 (9)	C26—C25—H25A	119.9
C1—O1—La1	125.0 (9)	C28—C26—C25	116.7 (13)
C6—O4—H4B	109.5	C28—C26—C27	119.5 (13)
C8—O5—La1	145.6 (9)	C25—C26—C27	123.7 (13)
C8—O6—La2	138.2 (8)	O11—C27—O12	125.6 (13)
C13—O8—La2^v	128.2 (8)	O11—C27—C26	122.0 (13)
C13—O8—La1^iv	119.9 (8)	O12—C27—C26	112.4 (12)
La2^v—O8—La1^iv	111.2 (3)	N4—C28—C26	124.6 (14)
C22—O10—La2	126.1 (9)	N4—C28—H28A	117.7
C27—O12—H12A	109.5	C26—C28—H28A	117.7
C15—O13—La1^vi	128.2 (9)
O1—La1—N1—C2	−12.5 (9)	La1—O1—C1—O2	146.7 (12)
O5—La1—N1—C2	64.9 (10)	La1—O1—C1—C2	−31.7 (17)
O15^i—La1—N1—C2	159.0 (11)	C7—N1—C2—C3	0 (2)
O20—La1—N1—C2	−141.6 (10)	La1—N1—C2—C3	−177.3 (12)
O19—La1—N1—C2	117.4 (10)	C7—N1—C2—C1	−178.7 (13)
O13^ii—La1—N1—C2	4.7 (13)	La1—N1—C2—C1	4.0 (16)
O8^i—La1—N1—C2	−66.2 (11)	O2—C1—C2—N1	−162.9 (14)
N2^i—La1—N1—C2	−119.4 (11)	O1—C1—C2—N1	15.6 (19)
O1—La1—N1—C7	170.5 (13)	O2—C1—C2—C3	18 (2)
O5—La1—N1—C7	−112.0 (12)	O1—C1—C2—C3	−163.1 (14)
O15^i—La1—N1—C7	−18.0 (11)	N1—C2—C3—C4	−2 (2)
O20—La1—N1—C7	41.5 (14)	C1—C2—C3—C4	176.8 (13)
O19—La1—N1—C7	−59.6 (13)	C2—C3—C4—C5	1 (2)
O13^ii—La1—N1—C7	−172.3 (10)	C3—C4—C5—C7	1 (2)
O8^i—La1—N1—C7	116.9 (12)	C3—C4—C5—C6	179.6 (13)
N2^i—La1—N1—C7	63.6 (11)	C4—C5—C6—O3	170.4 (15)
O10—La2—N3—C16	−39.9 (11)	C7—C5—C6—O3	−11 (2)
O18—La2—N3—C16	98.3 (11)	C4—C5—C6—O4	−8 (2)
O6—La2—N3—C16	−169.8 (11)	C7—C5—C6—O4	170.9 (14)
O16^i—La2—N3—C16	−105.9 (11)	C2—N1—C7—C5	2 (2)
O16^i—La2—N3—C16	−105.9 (11)	La1—N1—C7—C5	179.4 (11)
O8^iii—La2—N3—C16	39.4 (12)	C4—C5—C7—N1	−3 (2)
O17—La2—N3—C16	142.4 (10)	C6—C5—C7—N1	178.4 (13)
O13—La2—N3—C16	19.0 (10)	La2—O6—C8—O5	0 (2)
N4—La2—N3—C16	−96.7 (11)	La2—O6—C8—C9	175.4 (9)
O10—La2—N3—C21	132.3 (10)	La1—O5—C8—O6	−104.4 (18)
O18—La2—N3—C21	−89.5 (10)	La1—O5—C8—C9	79.9 (19)
O6—La2—N3—C21	2.4 (10)	O6—C8—C9—C10	−169.6 (13)
O16^i—La2—N3—C21	66.3 (12)	O5—C8—C9—C10	6 (2)
O16^i—La2—N3—C21	66.3 (12)	O6—C8—C9—C14	12 (2)
O8^iii—La2—N3—C21	−148.4 (9)	O5—C8—C9—C14	−172.0 (13)
O17—La2—N3—C21	−45.4 (12)	C14—C9—C10—C11	2 (2)
O13—La2—N3—C21	−168.8 (11)	C8—C9—C10—C11	−176.3 (13)
N4—La2—N3—C21	75.5 (10)	C9—C10—C11—C12	0 (2)
O10—La2—N4—C28	−172.5 (13)	C10—C11—C12—N2	−2 (2)
O18—La2—N4—C28	−41.6 (15)	C10—C11—C12—C13	172.9 (14)
O6—La2—N4—C28	16.9 (11)	C14—N2—C12—C11	1 (2)
O16^i—La2—N4—C28	109.2 (12)	La1^iv—N2—C12—C11	−169.3 (11)
O16^i—La2—N4—C28	109.2 (12)	C14—N2—C12—C13	−174.5 (12)
O8^iii—La2—N4—C28	169.3 (10)	La1^iv—N2—C12—C13	15.7 (15)
O17—La2—N4—C28	58.7 (13)	La2^v—O8—C13—O7	−16 (2)
O13—La2—N4—C28	−119.8 (12)	La1^iv—O8—C13—O7	153.7 (12)
N3—La2—N4—C28	−65.4 (12)	La2^v—O8—C13—C12	162.2 (9)
O10—La2—N4—C23	16.5 (10)	La1^iv—O8—C13—C12	−27.8 (16)
O18—La2—N4—C23	147.4 (9)	C11—C12—C13—O7	11 (2)
O6—La2—N4—C23	−154.0 (11)	N2—C12—C13—O7	−174.1 (13)
O16^i—La2—N4—C23	−61.7 (10)	C11—C12—C13—O8	−167.7 (14)
O16^i—La2—N4—C23	−61.7 (10)	N2—C12—C13—O8	7.3 (19)
O8^iii—La2—N4—C23	−1.6 (13)	C12—N2—C14—C9	2 (2)
O17—La2—N4—C23	−112.3 (10)	La1^iv—N2—C14—C9	171.2 (10)
O13—La2—N4—C23	69.2 (11)	C10—C9—C14—N2	−4 (2)
N3—La2—N4—C23	123.7 (11)	C8—C9—C14—N2	175.0 (13)
O5—La1—O1—C1	−56.9 (11)	La1^vi—O13—C15—O14	17 (2)
O15^i—La1—O1—C1	13.5 (12)	La2—O13—C15—O14	−155.8 (12)
O20—La1—O1—C1	158.6 (10)	La1^vi—O13—C15—C16	−158.9 (9)
O19—La1—O1—C1	−87.4 (11)	La2—O13—C15—C16	28.0 (15)
O13^ii—La1—O1—C1	−144.7 (11)	C21—N3—C16—C17	−5 (2)
O8^i—La1—O1—C1	145.2 (11)	La2—N3—C16—C17	167.4 (12)
N2^i—La1—O1—C1	89.5 (11)	C21—N3—C16—C15	173.2 (12)
N1—La1—O1—C1	23.8 (10)	La2—N3—C16—C15	−14.0 (16)
O1—La1—O5—C8	−120.5 (16)	O14—C15—C16—N3	174.7 (14)
O15^i—La1—O5—C8	106.3 (16)	O13—C15—C16—N3	−8.8 (19)
O20—La1—O5—C8	21.3 (18)	O14—C15—C16—C17	−7 (2)
O19—La1—O5—C8	38.4 (16)	O13—C15—C16—C17	169.9 (13)
O13^ii—La1—O5—C8	−39.5 (16)	N3—C16—C17—C18	4 (2)
O8^i—La1—O5—C8	−92.5 (16)	C15—C16—C17—C18	−174.7 (13)
N2^i—La1—O5—C8	168.6 (15)	C16—C17—C18—C19	−1 (2)
N1—La1—O5—C8	175.6 (17)	C17—C18—C19—C21	1 (2)
O10—La2—O6—C8	95.6 (14)	C17—C18—C19—C20	176.4 (13)
O18—La2—O6—C8	−105.5 (13)	La2^iv—O16—C20—O15	110.5 (19)
O16^i—La2—O6—C8	31.6 (13)	La2^iv—O16—C20—C19	−67 (2)
O16^i—La2—O6—C8	31.6 (13)	La1^iv—O15—C20—O16	8 (2)
O8^iii—La2—O6—C8	−41.0 (16)	La1^iv—O15—C20—C19	−174.1 (9)
O17—La2—O6—C8	−37.9 (13)	C21—C19—C20—O16	163.5 (14)
O13—La2—O6—C8	−167.5 (12)	C18—C19—C20—O16	−12 (2)
N3—La2—O6—C8	−179.1 (14)	C21—C19—C20—O15	−15 (2)
N4—La2—O6—C8	106.4 (14)	C18—C19—C20—O15	170.0 (13)
O18—La2—O10—C22	−156.8 (11)	C16—N3—C21—C19	4 (2)
O6—La2—O10—C22	−9.0 (13)	La2—N3—C21—C19	−167.7 (10)
O16^i—La2—O10—C22	61.3 (11)	C18—C19—C21—N3	−2 (2)
O16^i—La2—O10—C22	61.3 (11)	C20—C19—C21—N3	−177.7 (12)
O8^iii—La2—O10—C22	147.1 (12)	La2—O10—C22—O9	−158.6 (12)
O17—La2—O10—C22	91.6 (12)	La2—O10—C22—C23	22.0 (18)
O13—La2—O10—C22	−141.9 (12)	C28—N4—C23—C24	−4 (2)
N3—La2—O10—C22	−85.8 (12)	La2—N4—C23—C24	168.3 (12)
N4—La2—O10—C22	−20.6 (11)	C28—N4—C23—C22	174.1 (12)
O10—La2—O13—C15	85.7 (10)	La2—N4—C23—C22	−13.8 (16)
O18—La2—O13—C15	−104.7 (9)	O9—C22—C23—N4	178.0 (14)
O6—La2—O13—C15	−37.5 (11)	O10—C22—C23—N4	−3 (2)
O16^i—La2—O13—C15	116.3 (9)	O9—C22—C23—C24	−4 (2)
O16^i—La2—O13—C15	116.3 (9)	O10—C22—C23—C24	175.3 (14)
O8^iii—La2—O13—C15	172.6 (10)	N4—C23—C24—C25	3 (2)
O17—La2—O13—C15	−142.4 (9)	C22—C23—C24—C25	−175.0 (14)
N3—La2—O13—C15	−24.7 (9)	C23—C24—C25—C26	−1 (2)
N4—La2—O13—C15	36.0 (10)	C24—C25—C26—C28	0 (2)
O10—La2—O13—La1^vi	−88.4 (4)	C24—C25—C26—C27	179.6 (14)
O18—La2—O13—La1^vi	81.1 (4)	C28—C26—C27—O11	10 (2)
O6—La2—O13—La1^vi	148.4 (4)	C25—C26—C27—O11	−169.3 (15)
O16^i—La2—O13—La1^vi	−57.8 (5)	C28—C26—C27—O12	−169.6 (13)
O16^i—La2—O13—La1^vi	−57.8 (5)	C25—C26—C27—O12	11 (2)
O8^iii—La2—O13—La1^vi	−1.5 (4)	C23—N4—C28—C26	3 (2)
O17—La2—O13—La1^vi	43.5 (6)	La2—N4—C28—C26	−167.7 (11)
N3—La2—O13—La1^vi	161.2 (5)	C25—C26—C28—N4	−1 (2)
N4—La2—O13—La1^vi	−138.1 (4)	C27—C26—C28—N4	179.2 (13)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O22—H22B···O21^vii	0.85	2.03	2.88 (2)	176
O22—H22A···O2^viii	0.85	1.85	2.702 (17)	177
O21—H21C···O17^ix	0.85	1.99	2.833 (15)	171
O21—H21B···O9^ii	0.85	1.77	2.612 (15)	171
O20—H20B···O11^i	0.85	2.09	2.759 (14)	136
O20—H20A···O8^i	0.85	2.47	3.020 (14)	123
O20—H20A···O10^ii	0.85	2.06	2.687 (14)	130
O19—H19B···O16^i	0.85	1.98	2.787 (15)	158
O19—H19A···O14^ii	0.85	1.80	2.605 (15)	157
O18—H18C···O3^iv	0.85	1.91	2.728 (15)	162
O18—H18A···O1^vi	0.85	1.89	2.706 (14)	161
O17—H17C···O16^i	0.85	2.49	2.955 (14)	115
O17—H17C···O5	0.85	2.12	2.791 (14)	135
O17—H17A···O7^iii	0.85	1.76	2.608 (14)	174
O12—H12A···O21^iv	0.82	1.76	2.564 (15)	166
O4—H4B···O22^x	0.82	1.82	2.534 (14)	145

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