In the title compound, {[Sm(4-pya)
3(H
2O)
2]·2H
2O}
n [4-pya is
trans-3-(4-pyridyl)acrylate, C
8H
6NO
2], each Sm
III atom is ten-coordinated and has a bicapped square-antiprismatic coordination geometry. There is a crystallographic center of symmetry at the mid-point of the Sm
Sm line within each [Sm(4-pya)
3(H
2O)
2]
2 dimer. Each dimer is interconnected by two pairs of bridging 4-pya ligands to form a one-dimensional chain. Neighboring chains are connected
via hydrogen bonds to form a three-dimensional network.
Supporting information
CCDC reference: 290564
4-Hpya was prepared as reported previously (Alcalde et al., 1992). Other reagents were obtained from commercial sources and used as received. A mixture of Sm2O3 (0.06 g, 0.17 mmol), 4-Hpya (0.15 g, 1 mmol) and water (10 ml) was heated in a stainless-steel reactor with a Teflon liner at 413 K for 4 d and then cooled slowly to room temperature. The resulting colorless crystals were collected by filtration, washed with ethanol and then air-dried (yield 8%, 0.018 g). The crystal used for the structure determination was obtained directly from the above preparation. Analysis found: C 43.59, H 3.86, N 6.38%; calculated for C48H52Sm2N6O20: C 43.23, H 3.93, N 6.30%. Spectroscopic analysis: IR (KBr, cm−1): 3238 (m), 3045 (m), 1646 (s), 1601 (s), 1544 (s), 1404 (s), 1253 (m), 990 (m), 822 (m), 744 (m), 590 (m).
The positions of the H atoms of the water molecules were located from difference Fourier maps and were refined freely along with isotropic displacement parameters. All other hydrogen atoms were placed in geometrically idealized positions (C—H = 0.95 Å) and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).
Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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.
catena-Poly[[[diaqua[
trans-3-(4-pyridyl)acrylato]samarium(III)]-di-µ-
trans- 3-(4-pyridyl)acrylato] dihydrate]
top
Crystal data top
[Sm(C8H6NO2)3(H2O)2]·2H2O | Z = 2 |
Mr = 666.83 | F(000) = 666 |
Triclinic, P1 | Dx = 1.672 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 8.2459 (8) Å | Cell parameters from 5348 reflections |
b = 12.6631 (15) Å | θ = 3.1–25.3° |
c = 14.3286 (16) Å | µ = 2.28 mm−1 |
α = 111.782 (2)° | T = 193 K |
β = 98.825 (2)° | Block, colorless |
γ = 100.605 (2)° | 0.35 × 0.15 × 0.10 mm |
V = 1324.7 (3) Å3 | |
Data collection top
Rigaku Mercury diffractometer | 4571 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 25.4°, θmin = 3.1° |
/w scans | h = −9→9 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −12→15 |
Tmin = 0.678, Tmax = 0.796 | l = −17→17 |
13165 measured reflections | 720 standard reflections every 6 reflections |
4840 independent reflections | intensity decay: none |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.18 | w = 1/[σ2(Fo2) + (0.0293P)2 + 0.9553P] where P = (Fo2 + 2Fc2)/3 |
4812 reflections | (Δ/σ)max = 0.011 |
338 parameters | Δρmax = 0.95 e Å−3 |
12 restraints | Δρmin = −0.70 e Å−3 |
Crystal data top
[Sm(C8H6NO2)3(H2O)2]·2H2O | γ = 100.605 (2)° |
Mr = 666.83 | V = 1324.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.2459 (8) Å | Mo Kα radiation |
b = 12.6631 (15) Å | µ = 2.28 mm−1 |
c = 14.3286 (16) Å | T = 193 K |
α = 111.782 (2)° | 0.35 × 0.15 × 0.10 mm |
β = 98.825 (2)° | |
Data collection top
Rigaku Mercury diffractometer | 4571 reflections with I > 2σ(I) |
Absorption correction: multi-scan (Jacobson, 1998) | Rint = 0.025 |
Tmin = 0.678, Tmax = 0.796 | 720 standard reflections every 6 reflections |
13165 measured reflections | intensity decay: none |
4840 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.027 | 12 restraints |
wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.18 | Δρmax = 0.95 e Å−3 |
4812 reflections | Δρmin = −0.70 e Å−3 |
338 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Sm1 | 0.781720 (19) | 0.565469 (13) | 0.529619 (11) | 0.01467 (7) | |
O1 | 0.8531 (3) | 0.4493 (2) | 0.63592 (17) | 0.0232 (5) | |
O2 | 0.6943 (3) | 0.5701 (2) | 0.69022 (17) | 0.0201 (5) | |
O3 | 0.5300 (3) | 0.39386 (19) | 0.47128 (17) | 0.0196 (5) | |
O4 | 0.3006 (3) | 0.2467 (2) | 0.41408 (19) | 0.0235 (5) | |
O5 | 0.8865 (3) | 0.41318 (19) | 0.41783 (16) | 0.0187 (5) | |
O6 | 0.9950 (3) | 0.2866 (2) | 0.31192 (18) | 0.0244 (5) | |
O7 | 0.6364 (3) | 0.5384 (2) | 0.35607 (17) | 0.0202 (5) | |
H25 | 0.5329 (18) | 0.499 (3) | 0.335 (2) | 0.024* | |
H26 | 0.679 (3) | 0.533 (3) | 0.3049 (16) | 0.024* | |
O8 | 0.9550 (3) | 0.6918 (2) | 0.46166 (18) | 0.0212 (5) | |
H27 | 1.016 (4) | 0.658 (3) | 0.425 (2) | 0.025* | |
H28 | 0.908 (4) | 0.732 (3) | 0.437 (2) | 0.025* | |
O9 | 1.1028 (5) | 0.0278 (4) | 0.2276 (3) | 0.0782 (12) | |
H29 | 1.142 (7) | 0.086 (3) | 0.286 (2) | 0.094* | |
H30 | 1.017 (5) | 0.039 (5) | 0.195 (4) | 0.094* | |
O10 | 1.1122 (8) | −0.2044 (5) | 0.2021 (9) | 0.183 (4) | |
H31 | 1.168 (13) | −0.153 (8) | 0.185 (10) | 0.220* | |
H32 | 1.033 (10) | −0.179 (9) | 0.227 (8) | 0.220* | |
N1 | 0.7293 (4) | 0.5283 (4) | 1.1685 (3) | 0.0452 (9) | |
N2 | 0.7913 (4) | −0.1654 (3) | 0.3829 (2) | 0.0318 (7) | |
N3 | 0.2294 (7) | 0.0697 (3) | −0.0816 (3) | 0.0696 (14) | |
C1 | 0.7771 (4) | 0.4988 (3) | 0.7022 (2) | 0.0184 (4) | |
C2 | 0.7835 (4) | 0.4750 (3) | 0.7964 (3) | 0.0240 (8) | |
H2 | 0.8237 | 0.4105 | 0.7998 | 0.029* | |
C3 | 0.7338 (4) | 0.5428 (3) | 0.8756 (3) | 0.0250 (8) | |
H3 | 0.6910 | 0.6041 | 0.8669 | 0.030* | |
C4 | 0.7365 (5) | 0.5351 (3) | 0.9754 (3) | 0.0282 (8) | |
C5 | 0.6781 (5) | 0.6164 (4) | 1.0492 (3) | 0.0345 (9) | |
H5 | 0.6396 | 0.6764 | 1.0351 | 0.041* | |
C6 | 0.6766 (6) | 0.6094 (4) | 1.1426 (4) | 0.0506 (6) | |
H6 | 0.6357 | 0.6656 | 1.1915 | 0.061* | |
C7 | 0.7863 (6) | 0.4511 (4) | 1.0978 (4) | 0.0506 (6) | |
H7 | 0.8261 | 0.3932 | 1.1149 | 0.061* | |
C8 | 0.7915 (5) | 0.4496 (4) | 1.0014 (3) | 0.0339 (9) | |
H8 | 0.8317 | 0.3915 | 0.9538 | 0.041* | |
C9 | 0.4602 (4) | 0.2839 (3) | 0.4367 (2) | 0.0184 (4) | |
C10 | 0.5702 (4) | 0.2026 (3) | 0.4264 (3) | 0.0201 (7) | |
H10 | 0.6901 | 0.2341 | 0.4470 | 0.024* | |
C11 | 0.5067 (4) | 0.0868 (3) | 0.3892 (3) | 0.0237 (7) | |
H11 | 0.3868 | 0.0571 | 0.3644 | 0.028* | |
C12 | 0.6071 (4) | 0.0005 (3) | 0.3833 (3) | 0.0235 (7) | |
C13 | 0.5276 (5) | −0.1110 (3) | 0.3732 (3) | 0.0280 (8) | |
H13 | 0.4081 | −0.1336 | 0.3648 | 0.034* | |
C14 | 0.6238 (5) | −0.1889 (3) | 0.3753 (3) | 0.0313 (9) | |
H14 | 0.5676 | −0.2636 | 0.3712 | 0.038* | |
C15 | 0.8654 (5) | −0.0597 (3) | 0.3876 (3) | 0.0328 (9) | |
H15 | 0.9835 | −0.0421 | 0.3901 | 0.039* | |
C16 | 0.7809 (5) | 0.0259 (3) | 0.3892 (3) | 0.0278 (8) | |
H16 | 0.8405 | 0.1003 | 0.3942 | 0.033* | |
C17 | 0.8716 (4) | 0.3278 (3) | 0.3312 (2) | 0.0184 (4) | |
C18 | 0.7059 (4) | 0.2804 (3) | 0.2541 (3) | 0.0221 (7) | |
H18 | 0.6088 | 0.3015 | 0.2757 | 0.027* | |
C19 | 0.6880 (5) | 0.2100 (3) | 0.1566 (3) | 0.0298 (8) | |
H19 | 0.7853 | 0.1869 | 0.1369 | 0.036* | |
C20 | 0.5275 (6) | 0.1645 (3) | 0.0754 (3) | 0.0383 (10) | |
C21 | 0.5313 (7) | 0.1257 (4) | −0.0281 (3) | 0.0522 (13) | |
H21 | 0.6368 | 0.1305 | −0.0473 | 0.063* | |
C22 | 0.3791 (6) | 0.0798 (4) | −0.1032 (4) | 0.0506 (6) | |
H22 | 0.3835 | 0.0544 | −0.1738 | 0.061* | |
C23 | 0.2235 (6) | 0.1081 (4) | 0.0171 (3) | 0.0506 (6) | |
H23 | 0.1154 | 0.1025 | 0.0331 | 0.061* | |
C24 | 0.3689 (6) | 0.1562 (4) | 0.0986 (3) | 0.0462 (11) | |
H24 | 0.3600 | 0.1827 | 0.1684 | 0.055* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sm1 | 0.01735 (10) | 0.01504 (10) | 0.01451 (10) | 0.00717 (7) | 0.00520 (7) | 0.00734 (7) |
O1 | 0.0270 (13) | 0.0300 (13) | 0.0220 (12) | 0.0168 (11) | 0.0130 (10) | 0.0137 (11) |
O2 | 0.0222 (12) | 0.0250 (12) | 0.0175 (11) | 0.0104 (10) | 0.0065 (10) | 0.0110 (10) |
O3 | 0.0254 (12) | 0.0160 (11) | 0.0199 (12) | 0.0076 (10) | 0.0062 (10) | 0.0087 (10) |
O4 | 0.0188 (12) | 0.0206 (12) | 0.0338 (14) | 0.0079 (10) | 0.0074 (10) | 0.0123 (11) |
O5 | 0.0219 (12) | 0.0177 (11) | 0.0165 (11) | 0.0084 (9) | 0.0049 (9) | 0.0055 (9) |
O6 | 0.0220 (12) | 0.0247 (13) | 0.0242 (13) | 0.0096 (10) | 0.0064 (10) | 0.0056 (10) |
O7 | 0.0184 (12) | 0.0286 (13) | 0.0177 (12) | 0.0072 (10) | 0.0064 (10) | 0.0128 (10) |
O8 | 0.0231 (12) | 0.0226 (13) | 0.0276 (13) | 0.0132 (10) | 0.0106 (11) | 0.0157 (11) |
O9 | 0.062 (3) | 0.073 (3) | 0.060 (3) | 0.000 (2) | −0.010 (2) | 0.002 (2) |
O10 | 0.079 (4) | 0.084 (4) | 0.297 (10) | 0.043 (3) | 0.003 (5) | −0.012 (5) |
N1 | 0.0357 (19) | 0.068 (3) | 0.0241 (17) | −0.0066 (18) | 0.0021 (15) | 0.0218 (18) |
N2 | 0.048 (2) | 0.0274 (17) | 0.0269 (17) | 0.0247 (15) | 0.0095 (15) | 0.0121 (14) |
N3 | 0.091 (4) | 0.034 (2) | 0.052 (3) | 0.000 (2) | −0.031 (2) | 0.0101 (19) |
C1 | 0.0211 (10) | 0.0206 (10) | 0.0171 (9) | 0.0076 (8) | 0.0053 (8) | 0.0105 (8) |
C2 | 0.0256 (18) | 0.0321 (19) | 0.0217 (18) | 0.0127 (16) | 0.0070 (15) | 0.0162 (16) |
C3 | 0.0268 (18) | 0.0304 (19) | 0.0227 (18) | 0.0081 (16) | 0.0051 (15) | 0.0162 (16) |
C4 | 0.0287 (19) | 0.036 (2) | 0.0210 (18) | 0.0036 (16) | 0.0060 (16) | 0.0146 (16) |
C5 | 0.042 (2) | 0.037 (2) | 0.0227 (19) | 0.0061 (19) | 0.0101 (18) | 0.0111 (17) |
C6 | 0.0548 (15) | 0.0495 (14) | 0.0379 (13) | 0.0026 (12) | −0.0008 (11) | 0.0176 (11) |
C7 | 0.0548 (15) | 0.0495 (14) | 0.0379 (13) | 0.0026 (12) | −0.0008 (11) | 0.0176 (11) |
C8 | 0.034 (2) | 0.048 (2) | 0.030 (2) | 0.0127 (19) | 0.0109 (17) | 0.0242 (19) |
C9 | 0.0211 (10) | 0.0206 (10) | 0.0171 (9) | 0.0076 (8) | 0.0053 (8) | 0.0105 (8) |
C10 | 0.0202 (17) | 0.0235 (18) | 0.0235 (17) | 0.0108 (14) | 0.0086 (14) | 0.0136 (15) |
C11 | 0.0256 (18) | 0.0217 (18) | 0.0258 (18) | 0.0102 (15) | 0.0067 (15) | 0.0099 (15) |
C12 | 0.0310 (19) | 0.0207 (17) | 0.0194 (17) | 0.0121 (15) | 0.0062 (15) | 0.0065 (14) |
C13 | 0.037 (2) | 0.0231 (18) | 0.0278 (19) | 0.0127 (16) | 0.0125 (17) | 0.0107 (16) |
C14 | 0.053 (3) | 0.0217 (18) | 0.029 (2) | 0.0190 (18) | 0.0167 (19) | 0.0151 (16) |
C15 | 0.036 (2) | 0.034 (2) | 0.028 (2) | 0.0196 (18) | 0.0050 (17) | 0.0087 (17) |
C16 | 0.036 (2) | 0.0189 (17) | 0.0263 (19) | 0.0123 (16) | 0.0030 (16) | 0.0057 (15) |
C17 | 0.0211 (10) | 0.0206 (10) | 0.0171 (9) | 0.0076 (8) | 0.0053 (8) | 0.0105 (8) |
C18 | 0.0246 (18) | 0.0222 (17) | 0.0205 (17) | 0.0065 (14) | 0.0027 (14) | 0.0107 (15) |
C19 | 0.037 (2) | 0.0264 (19) | 0.0246 (19) | 0.0089 (17) | 0.0031 (16) | 0.0098 (16) |
C20 | 0.054 (3) | 0.0217 (19) | 0.027 (2) | 0.0034 (18) | −0.0075 (19) | 0.0067 (16) |
C21 | 0.080 (4) | 0.037 (2) | 0.025 (2) | 0.011 (2) | −0.006 (2) | 0.0066 (19) |
C22 | 0.0548 (15) | 0.0495 (14) | 0.0379 (13) | 0.0026 (12) | −0.0008 (11) | 0.0176 (11) |
C23 | 0.0548 (15) | 0.0495 (14) | 0.0379 (13) | 0.0026 (12) | −0.0008 (11) | 0.0176 (11) |
C24 | 0.045 (3) | 0.038 (2) | 0.040 (2) | −0.002 (2) | −0.012 (2) | 0.013 (2) |
Geometric parameters (Å, º) top
Sm1—O5 | 2.404 (2) | C3—C4 | 1.465 (5) |
Sm1—O7 | 2.457 (2) | C3—H3 | 0.9500 |
Sm1—O4i | 2.471 (2) | C4—C5 | 1.393 (5) |
Sm1—O3 | 2.488 (2) | C4—C8 | 1.396 (5) |
Sm1—O2 | 2.499 (2) | C5—C6 | 1.376 (6) |
Sm1—O8 | 2.508 (2) | C5—H5 | 0.9500 |
Sm1—O6ii | 2.519 (2) | C6—H6 | 0.9500 |
Sm1—O1 | 2.557 (2) | C7—C8 | 1.381 (6) |
Sm1—O5ii | 2.659 (2) | C7—H7 | 0.9500 |
Sm1—O3i | 2.712 (2) | C8—H8 | 0.9500 |
O1—C1 | 1.254 (4) | C9—C10 | 1.475 (4) |
O2—C1 | 1.272 (4) | C10—C11 | 1.327 (5) |
O3—C9 | 1.273 (4) | C10—H10 | 0.9500 |
O3—Sm1i | 2.712 (2) | C11—C12 | 1.473 (5) |
O4—C9 | 1.259 (4) | C11—H11 | 0.9500 |
O4—Sm1i | 2.471 (2) | C12—C13 | 1.387 (5) |
O5—C17 | 1.278 (4) | C12—C16 | 1.393 (5) |
O5—Sm1ii | 2.659 (2) | C13—C14 | 1.380 (5) |
O6—C17 | 1.249 (4) | C13—H13 | 0.9500 |
O6—Sm1ii | 2.519 (2) | C14—H14 | 0.9500 |
O7—H25 | 0.848 (10) | C15—C16 | 1.387 (5) |
O7—H26 | 0.848 (10) | C15—H15 | 0.9500 |
O8—H27 | 0.84 (3) | C16—H16 | 0.9500 |
O8—H28 | 0.84 (4) | C17—C18 | 1.480 (5) |
O9—H29 | 0.85 (3) | C18—C19 | 1.316 (5) |
O9—H30 | 0.85 (5) | C18—H18 | 0.9500 |
O10—H31 | 0.86 (12) | C19—C20 | 1.479 (5) |
O10—H32 | 0.85 (10) | C19—H19 | 0.9500 |
N1—C7 | 1.336 (6) | C20—C21 | 1.385 (6) |
N1—C6 | 1.334 (6) | C20—C24 | 1.393 (6) |
N2—C14 | 1.337 (5) | C21—C22 | 1.387 (6) |
N2—C15 | 1.338 (5) | C21—H21 | 0.9500 |
N3—C23 | 1.327 (6) | C22—H22 | 0.9500 |
N3—C22 | 1.313 (7) | C23—C24 | 1.394 (6) |
C1—C2 | 1.483 (4) | C23—H23 | 0.9500 |
C2—C3 | 1.320 (5) | C24—H24 | 0.9500 |
C2—H2 | 0.9500 | | |
| | | |
O5—Sm1—O7 | 77.38 (7) | C3—C2—C1 | 120.5 (3) |
O5—Sm1—O4i | 154.64 (8) | C3—C2—H2 | 119.8 |
O7—Sm1—O4i | 83.76 (8) | C1—C2—H2 | 119.8 |
O5—Sm1—O3 | 79.83 (7) | C2—C3—C4 | 128.0 (3) |
O7—Sm1—O3 | 74.40 (7) | C2—C3—H3 | 116.0 |
O4i—Sm1—O3 | 111.35 (7) | C4—C3—H3 | 116.0 |
O5—Sm1—O2 | 125.51 (7) | C5—C4—C8 | 117.0 (3) |
O7—Sm1—O2 | 135.99 (7) | C5—C4—C3 | 118.8 (3) |
O4i—Sm1—O2 | 79.84 (7) | C8—C4—C3 | 124.2 (3) |
O3—Sm1—O2 | 74.19 (7) | C6—C5—C4 | 119.7 (4) |
O5—Sm1—O8 | 83.36 (7) | C6—C5—H5 | 120.2 |
O7—Sm1—O8 | 67.87 (8) | C4—C5—H5 | 120.2 |
O4i—Sm1—O8 | 73.84 (7) | N1—C6—C5 | 123.8 (5) |
O3—Sm1—O8 | 141.18 (7) | N1—C6—H6 | 118.1 |
O2—Sm1—O8 | 141.99 (8) | C5—C6—H6 | 118.1 |
O5—Sm1—O6ii | 113.49 (7) | N1—C7—C8 | 124.5 (5) |
O7—Sm1—O6ii | 141.26 (8) | N1—C7—H7 | 117.7 |
O4i—Sm1—O6ii | 72.14 (8) | C8—C7—H7 | 117.7 |
O3—Sm1—O6ii | 142.43 (7) | C7—C8—C4 | 118.6 (4) |
O2—Sm1—O6ii | 69.65 (7) | C7—C8—H8 | 120.7 |
O8—Sm1—O6ii | 76.38 (8) | C4—C8—H8 | 120.7 |
O5—Sm1—O1 | 75.81 (7) | O4—C9—O3 | 120.1 (3) |
O7—Sm1—O1 | 141.76 (8) | O4—C9—C10 | 121.3 (3) |
O4i—Sm1—O1 | 128.45 (7) | O3—C9—C10 | 118.6 (3) |
O3—Sm1—O1 | 74.43 (7) | C11—C10—C9 | 122.0 (3) |
O2—Sm1—O1 | 51.50 (7) | C11—C10—H10 | 119.0 |
O8—Sm1—O1 | 134.11 (7) | C9—C10—H10 | 119.0 |
O6ii—Sm1—O1 | 75.36 (8) | C10—C11—C12 | 125.4 (3) |
O5—Sm1—O5ii | 63.65 (8) | C10—C11—H11 | 117.3 |
O7—Sm1—O5ii | 122.22 (7) | C12—C11—H11 | 117.3 |
O4i—Sm1—O5ii | 115.00 (7) | C13—C12—C16 | 117.5 (3) |
O3—Sm1—O5ii | 131.89 (7) | C13—C12—C11 | 119.4 (3) |
O2—Sm1—O5ii | 101.70 (7) | C16—C12—C11 | 123.1 (3) |
O8—Sm1—O5ii | 66.80 (7) | C14—C13—C12 | 119.4 (4) |
O6ii—Sm1—O5ii | 50.04 (7) | C14—C13—H13 | 120.3 |
O1—Sm1—O5ii | 67.31 (7) | C12—C13—H13 | 120.3 |
O5—Sm1—O3i | 133.91 (7) | N2—C14—C13 | 123.9 (3) |
O7—Sm1—O3i | 69.11 (7) | N2—C14—H14 | 118.1 |
O4i—Sm1—O3i | 49.83 (7) | C13—C14—H14 | 118.1 |
O3—Sm1—O3i | 61.58 (8) | N2—C15—C16 | 124.2 (4) |
O2—Sm1—O3i | 69.10 (7) | N2—C15—H15 | 117.9 |
O8—Sm1—O3i | 110.69 (7) | C16—C15—H15 | 117.9 |
O6ii—Sm1—O3i | 112.47 (7) | C15—C16—C12 | 118.7 (3) |
O1—Sm1—O3i | 113.26 (7) | C15—C16—H16 | 120.7 |
O5ii—Sm1—O3i | 162.44 (7) | C12—C16—H16 | 120.7 |
C1—O1—Sm1 | 92.57 (18) | O6—C17—O5 | 120.5 (3) |
C1—O2—Sm1 | 94.83 (18) | O6—C17—C18 | 121.0 (3) |
C9—O3—Sm1 | 152.5 (2) | O5—C17—C18 | 118.5 (3) |
C9—O3—Sm1i | 89.06 (18) | C19—C18—C17 | 122.4 (3) |
Sm1—O3—Sm1i | 118.42 (8) | C19—C18—H18 | 118.8 |
C9—O4—Sm1i | 100.81 (19) | C17—C18—H18 | 118.8 |
C17—O5—Sm1 | 151.5 (2) | C18—C19—C20 | 124.7 (4) |
C17—O5—Sm1ii | 90.87 (18) | C18—C19—H19 | 117.7 |
Sm1—O5—Sm1ii | 116.35 (8) | C20—C19—H19 | 117.7 |
C17—O6—Sm1ii | 98.24 (19) | C21—C20—C24 | 117.7 (4) |
Sm1—O7—H25 | 116 (2) | C21—C20—C19 | 120.0 (4) |
Sm1—O7—H26 | 128 (2) | C24—C20—C19 | 122.3 (4) |
H25—O7—H26 | 110.1 (16) | C20—C21—C22 | 119.1 (5) |
Sm1—O8—H27 | 114 (2) | C20—C21—H21 | 120.4 |
Sm1—O8—H28 | 119 (2) | C22—C21—H21 | 120.4 |
H27—O8—H28 | 111.5 (17) | N3—C22—C21 | 123.4 (5) |
H29—O9—H30 | 109 (5) | N3—C22—H22 | 118.3 |
H31—O10—H32 | 109 (11) | C21—C22—H22 | 118.3 |
C7—N1—C6 | 116.3 (4) | N3—C23—C24 | 122.9 (5) |
C14—N2—C15 | 116.2 (3) | N3—C23—H23 | 118.6 |
C23—N3—C22 | 118.3 (4) | C24—C23—H23 | 118.6 |
O1—C1—O2 | 120.9 (3) | C20—C24—C23 | 118.7 (4) |
O1—C1—C2 | 120.1 (3) | C20—C24—H24 | 120.7 |
O2—C1—C2 | 119.0 (3) | C23—C24—H24 | 120.7 |
| | | |
O5—Sm1—O1—C1 | −167.9 (2) | Sm1—O1—C1—C2 | −174.9 (3) |
O7—Sm1—O1—C1 | −121.1 (2) | Sm1—O2—C1—O1 | −5.0 (3) |
O4i—Sm1—O1—C1 | 20.5 (2) | Sm1—O2—C1—C2 | 174.8 (3) |
O3—Sm1—O1—C1 | −84.69 (19) | O1—C1—C2—C3 | 166.5 (3) |
O2—Sm1—O1—C1 | −2.72 (18) | O2—C1—C2—C3 | −13.2 (5) |
O8—Sm1—O1—C1 | 126.41 (19) | C1—C2—C3—C4 | −177.8 (3) |
O6ii—Sm1—O1—C1 | 72.72 (19) | C2—C3—C4—C5 | 179.8 (4) |
O5ii—Sm1—O1—C1 | 125.1 (2) | C2—C3—C4—C8 | −1.4 (6) |
O3i—Sm1—O1—C1 | −35.8 (2) | C8—C4—C5—C6 | −0.1 (6) |
O5—Sm1—O2—C1 | 20.5 (2) | C3—C4—C5—C6 | 178.8 (4) |
O7—Sm1—O2—C1 | 131.08 (19) | C7—N1—C6—C5 | 0.2 (7) |
O4i—Sm1—O2—C1 | −159.1 (2) | C4—C5—C6—N1 | 0.3 (7) |
O3—Sm1—O2—C1 | 85.14 (19) | C6—N1—C7—C8 | −0.9 (7) |
O8—Sm1—O2—C1 | −112.6 (2) | N1—C7—C8—C4 | 1.1 (7) |
O6ii—Sm1—O2—C1 | −84.48 (19) | C5—C4—C8—C7 | −0.5 (6) |
O1—Sm1—O2—C1 | 2.69 (18) | C3—C4—C8—C7 | −179.4 (4) |
O5ii—Sm1—O2—C1 | −45.40 (19) | Sm1i—O4—C9—O3 | −4.5 (3) |
O3i—Sm1—O2—C1 | 150.2 (2) | Sm1i—O4—C9—C10 | 174.0 (2) |
O5—Sm1—O3—C9 | 24.9 (4) | Sm1—O3—C9—O4 | −174.9 (3) |
O7—Sm1—O3—C9 | 104.5 (4) | Sm1i—O3—C9—O4 | 4.0 (3) |
O4i—Sm1—O3—C9 | −178.8 (4) | Sm1—O3—C9—C10 | 6.5 (6) |
O2—Sm1—O3—C9 | −106.7 (4) | Sm1i—O3—C9—C10 | −174.5 (3) |
O8—Sm1—O3—C9 | 90.7 (4) | O4—C9—C10—C11 | 2.7 (5) |
O6ii—Sm1—O3—C9 | −90.6 (4) | O3—C9—C10—C11 | −178.8 (3) |
O1—Sm1—O3—C9 | −53.1 (4) | C9—C10—C11—C12 | −175.4 (3) |
O5ii—Sm1—O3—C9 | −15.0 (5) | C10—C11—C12—C13 | 160.5 (3) |
O3i—Sm1—O3—C9 | 178.8 (5) | C10—C11—C12—C16 | −18.3 (6) |
O5—Sm1—O3—Sm1i | −153.94 (10) | C16—C12—C13—C14 | 3.6 (5) |
O7—Sm1—O3—Sm1i | −74.34 (9) | C11—C12—C13—C14 | −175.3 (3) |
O4i—Sm1—O3—Sm1i | 2.35 (11) | C15—N2—C14—C13 | −0.6 (5) |
O2—Sm1—O3—Sm1i | 74.44 (9) | C12—C13—C14—N2 | −2.6 (6) |
O8—Sm1—O3—Sm1i | −88.18 (13) | C14—N2—C15—C16 | 2.6 (5) |
O6ii—Sm1—O3—Sm1i | 90.53 (13) | N2—C15—C16—C12 | −1.4 (6) |
O1—Sm1—O3—Sm1i | 128.09 (10) | C13—C12—C16—C15 | −1.8 (5) |
O5ii—Sm1—O3—Sm1i | 166.11 (7) | C11—C12—C16—C15 | 177.1 (3) |
O3i—Sm1—O3—Sm1i | 0.0 | Sm1ii—O6—C17—O5 | −6.3 (3) |
O7—Sm1—O5—C17 | −25.2 (4) | Sm1ii—O6—C17—C18 | 172.7 (3) |
O4i—Sm1—O5—C17 | −68.1 (5) | Sm1—O5—C17—O6 | 169.2 (3) |
O3—Sm1—O5—C17 | 51.0 (4) | Sm1ii—O5—C17—O6 | 5.9 (3) |
O2—Sm1—O5—C17 | 113.1 (4) | Sm1—O5—C17—C18 | −9.9 (6) |
O8—Sm1—O5—C17 | −93.9 (4) | Sm1ii—O5—C17—C18 | −173.1 (3) |
O6ii—Sm1—O5—C17 | −165.9 (4) | O6—C17—C18—C19 | −13.1 (5) |
O1—Sm1—O5—C17 | 127.3 (4) | O5—C17—C18—C19 | 166.0 (3) |
O5ii—Sm1—O5—C17 | −161.3 (5) | C17—C18—C19—C20 | −177.2 (3) |
O3i—Sm1—O5—C17 | 18.5 (5) | C18—C19—C20—C21 | 158.2 (4) |
O7—Sm1—O5—Sm1ii | 136.10 (10) | C18—C19—C20—C24 | −23.3 (6) |
O4i—Sm1—O5—Sm1ii | 93.21 (18) | C24—C20—C21—C22 | −0.6 (6) |
O3—Sm1—O5—Sm1ii | −147.77 (10) | C19—C20—C21—C22 | 178.0 (4) |
O2—Sm1—O5—Sm1ii | −85.68 (11) | C23—N3—C22—C21 | 1.7 (7) |
O8—Sm1—O5—Sm1ii | 67.37 (9) | C20—C21—C22—N3 | −0.7 (7) |
O6ii—Sm1—O5—Sm1ii | −4.63 (11) | C22—N3—C23—C24 | −1.4 (7) |
O1—Sm1—O5—Sm1ii | −71.42 (9) | C21—C20—C24—C23 | 0.9 (6) |
O5ii—Sm1—O5—Sm1ii | 0.0 | C19—C20—C24—C23 | −177.6 (4) |
O3i—Sm1—O5—Sm1ii | 179.81 (7) | N3—C23—C24—C20 | 0.1 (7) |
Sm1—O1—C1—O2 | 4.9 (3) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H25···O2i | 0.85 (1) | 1.83 (1) | 2.675 (3) | 171 (3) |
O7—H26···N1iii | 0.85 (1) | 2.04 (1) | 2.870 (4) | 166 (3) |
O8—H27···O1ii | 0.84 (3) | 1.93 (3) | 2.741 (3) | 162 (3) |
O8—H28···N2iv | 0.84 (4) | 2.05 (4) | 2.883 (4) | 177 (3) |
O9—H29···O4v | 0.85 (3) | 2.17 (2) | 2.997 (4) | 163 (6) |
O9—H30···N3vi | 0.85 (5) | 2.22 (4) | 2.913 (6) | 138 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x, y, z−1; (iv) x, y+1, z; (v) x+1, y, z; (vi) −x+1, −y, −z. |
Experimental details
Crystal data |
Chemical formula | [Sm(C8H6NO2)3(H2O)2]·2H2O |
Mr | 666.83 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 193 |
a, b, c (Å) | 8.2459 (8), 12.6631 (15), 14.3286 (16) |
α, β, γ (°) | 111.782 (2), 98.825 (2), 100.605 (2) |
V (Å3) | 1324.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.28 |
Crystal size (mm) | 0.35 × 0.15 × 0.10 |
|
Data collection |
Diffractometer | Rigaku Mercury diffractometer |
Absorption correction | Multi-scan (Jacobson, 1998) |
Tmin, Tmax | 0.678, 0.796 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13165, 4840, 4571 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.602 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.064, 1.18 |
No. of reflections | 4812 |
No. of parameters | 338 |
No. of restraints | 12 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.95, −0.70 |
Selected geometric parameters (Å, º) topSm1—O5 | 2.404 (2) | Sm1—O8 | 2.508 (2) |
Sm1—O7 | 2.457 (2) | Sm1—O6ii | 2.519 (2) |
Sm1—O4i | 2.471 (2) | Sm1—O1 | 2.557 (2) |
Sm1—O3 | 2.488 (2) | Sm1—O5ii | 2.659 (2) |
Sm1—O2 | 2.499 (2) | Sm1—O3i | 2.712 (2) |
| | | |
O5—Sm1—O7 | 77.38 (7) | O4i—Sm1—O3 | 111.35 (7) |
O5—Sm1—O4i | 154.64 (8) | O5—Sm1—O8 | 83.36 (7) |
O7—Sm1—O4i | 83.76 (8) | O5—Sm1—O1 | 75.81 (7) |
O5—Sm1—O3 | 79.83 (7) | O1—Sm1—O5ii | 67.31 (7) |
O7—Sm1—O3 | 74.40 (7) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H25···O2i | 0.848 (10) | 1.834 (10) | 2.675 (3) | 171 (3) |
O7—H26···N1iii | 0.848 (10) | 2.040 (14) | 2.870 (4) | 166 (3) |
O8—H27···O1ii | 0.84 (3) | 1.93 (3) | 2.741 (3) | 162 (3) |
O8—H28···N2iv | 0.84 (4) | 2.05 (4) | 2.883 (4) | 177 (3) |
O9—H29···O4v | 0.85 (3) | 2.17 (2) | 2.997 (4) | 163 (6) |
O9—H30···N3vi | 0.85 (5) | 2.22 (4) | 2.913 (6) | 138 (5) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x, y, z−1; (iv) x, y+1, z; (v) x+1, y, z; (vi) −x+1, −y, −z. |
Over the past few decades, there has been considerable interest in the coordination chemistry of lanthanide compounds due to their unique structures and their potential applications in advanced materials, such as Ln-doped semiconductors (Taniguchi & Takahei, 1993), and catalytic (Costes et al., 1997; Bencini et al., 1985), magnetic (Lisowski & Starynowicz, 1999), fluorescent (Alexander, 1995; Bermudez et al., 2001), and nonlinear optical materials (Reinhard & Gudel, 2002). As is well known, ligands containing a combination of N and O donor atoms are good building blocks for the formation of various lanthanide coordination compounds (Liang et al., 2000; Pan et al., 2000; Ma et al., 1999; Costes et al., 2002; Ouchi et al., 1988; Kim et al., 2004). Trans-4-pyridylacrylic acid (4-Hpya) is one such interesting multifunctional ligand. Four coordination modes of 4-pya have been observed in the crystal structures of transition metal complexes of this ligand (Evans & Lin, 2001; Zhang et al., 2000; Liu et al., 2001). However, the chemistry of lanthanide complexes of 4-Hpya is less well studied (Zhou et al., 2003). Owing to the large radii and the strong oxophilicity of LnIII ions, we anticipated that coordination of 4-Hpya by LnIII metals may lead to the formation of new compounds with different coordination modes. In this regard, we carried out the reaction of Sm2O3 with 4-Hpya by hydrothermal synthesis. We report here the crystal structure of (I).
Complex (I) crystallizes in space group P-1 and the asymmetric unit contains one-half of an [Sm(4-pya)3(H2O)2]2 dimer and two solvent water molecules. Complex (I) has a one-dimensional chain structure extended along the a axis (Fig. 1). Each repeating [Sm(4-pya)3(H2O)2]2 dimer within the chain is interconnected by four tridentate bridging 4-pya anions. There is a crystallographic center of symmetry at the midpoint of the Sm1···Sm1i [symmetry code: (i) 1 − x, 1 − y, 1 − z] line within the dimer. The Sm1 center coordinates to eight O atoms of 4-pya ligands and two O atoms of water molecules, forming a bicapped square-antiprismatic coordination geometry. The Sm···Sm contact within the dimer is 4.303 (1) Å, shorter than the Sm···Sm separation [4.468 (1) Å] between dimers. Both Sm···Sm contacts are too long to include metal–metal interactions. In the dimer, the 4-pya ligand exhibits two coordination modes. In neither of the two modes does the N atom of the pyridyl group bond to Sm. In one mode, the 4-pya ligand chelates the SmIII center via atoms O1 and O2 to form an SmO2C four-membered ring. In the other mode, 4-pya acts as a tridentate ligand, chelating the Sm1 ion via atoms O3i and O4i and bridging the Sm1i ion via atom O3i. Because of the existence of the different coordination modes of 4-pya, the Sm1—O bond distances range from 2.404 (2) Å to 2.713 (2) Å (Table 1). The Sm1—O1 bond length is comparable to that of the Sm1—O2 bond, implying that atoms O1 and O2 of this 4-pya ligand are almost symmetrically bound to atom Sm1. However, the 4-pya ligand carrying O3i and O4i binds to Sm1 in an unsymmetric way as the Sm1—O3i bond is 0.24 (2) Å longer than the Sm1—O4i bond. It is noted that the Sm1—O3i bond length is the longest among all the Sm1—O bonds. This may be ascribed to the fact that atom O3i strongly binds to atom Sm1i of the same dimer with Sm1i—O3i = 2.487 (2) Å. Interestingly, the structure of (I) differs from that reported in the lanthanide/3-pya complex La[(C8H6NO2)3]n (3-pya is trans-4-pyridylacrylate; Zhou et al., 2003). Each LaIII ion in the latter complex is eight-coordinated with seven O atoms and one N atom from the 3-pya ligand, forming a two-dimensional network.
In the unit cell of (I), the coordinated water molecules interact with the O atoms of the 4-pya ligands to form intramolecular hydrogen bonds (O8—H27···O1 and O7—H25···O2; Table 2). Furthermore, one of the free water molecules and the coordinated water molecules interact with the O and N atoms of the 4-pya ligands of the adjacent chains to afford intermolecular hydrogen bonds, thereby forming a three-dimensional hydrogen-bonded network (Fig. 2).