metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Tri­chlorido(4-methyl­benz­yl)bis­­(1H-pyrazole-κN2)tin(IV)

aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 20 April 2011; accepted 26 April 2011; online 7 May 2011)

The six-coordinate SnIV atom in the title compound, [Sn(C8H9)Cl3(C3H4N2)2], shows an octa­hedral coordination. The N atoms of the N-heterocycle are cis to each other. The Sn—N bond that is trans to the Sn—C bond is shorter than the Sn—N bond trans to the Sn—Cl bond. Weak N—H⋯Cl hydrogen bonds link adjacent mol­ecules, generating a double chain running along the c axis.

Related literature

For the direct synthesis of the organotin chloride reactant, see: Sisido et al. (1961[Sisido, K., Takeda, Y. & Kinugawa, Z. (1961). J. Am. Chem. Soc. 83, 538-541.]). For the trichloridophenyl­tin–di(pyrazole) adduct, see: Casas et al. (1996[Casas, J. S., Castellano, E. E., Barnes, F. J. G., Sanchez, A., González, A. S., Sordo, J. & Zuckerman-Schpector, J. (1996). J. Organomet. Chem. 519, 209-216.]).

[Scheme 1]

Experimental

Crystal data
  • [Sn(C8H9)Cl3(C3H4N2)2]

  • Mr = 466.36

  • Monoclinic, C 2/c

  • a = 34.7322 (4) Å

  • b = 7.3709 (1) Å

  • c = 14.5760 (2) Å

  • β = 109.0535 (5)°

  • V = 3527.13 (8) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 1.90 mm−1

  • T = 100 K

  • 0.30 × 0.25 × 0.20 mm

Data collection
  • Bruker SMART APEX diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.599, Tmax = 0.702

  • 16131 measured reflections

  • 4053 independent reflections

  • 3734 reflections with I > 2σ(I)

  • Rint = 0.022

Refinement
  • R[F2 > 2σ(F2)] = 0.017

  • wR(F2) = 0.044

  • S = 1.00

  • 4053 reflections

  • 208 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.43 e Å−3

  • Δρmin = −0.26 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2⋯Cl1i 0.87 (1) 2.56 (2) 3.265 (2) 139 (2)
N4—H4⋯Cl1ii 0.88 (1) 2.65 (2) 3.270 (2) 129 (2)
Symmetry codes: (i) [-x+1, y, -z+{\script{3\over 2}}]; (ii) [x, -y+1, z-{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Dibenzyltin dichloride and benzyltin trichloride can be synthesized by the direct action of benzyl chloride on stannous chloride; other ring-substituted analogs are similarly synthesized (Sisido et al., 1961). The title compound results from the reaction of di(4-methylbenzyl)tin dichloride with pyrazole to afford the pyrazole adduct of a monoorganotin trichloride. There are few examples of monororganotin chlorides forming adducts with N-heterocycles. Phenyltin trichloride forms a 1:2 adduct with pyrazole (Casas et al., 1996). The 4-methylbenzyl analog affords a similar 1:2 adduct. The six-coordinate SnIV atom in SnCl3(C8H9)(C3H4N2)2 (Scheme I) shows octahedral coordination. The N atoms of the N-heterocycle are cis to each other and the three Cl atoms are coplanar (Fig. 1). The geometry can be described as being a mer-octahedron. The Sn–N bond that is trans to the Sn–C bond is shorter than the Sn–N bond trans to the Sn–Cl bond.

Related literature top

For the direct synthesis of the organotin chloride reactant, see: Sisido et al. (1961). For the trichloridophenyltin–di(pyrazole) adduct, see: Casas et al. (1996).

Experimental top

Di(4-methylbenzyl)tin dichloride was synthesized by using a literature procedure (Sisido et al., 1961). The compound (0.4 g, 1 mmol) and pyrazole (0.136 g, 2 mmol) of pyrazole were dissolved in ethanol (100 ml) and the solution was heated for an hour. The solution was filtered and then set aside for the growth of colorless crystals.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 times Ueq(C). The amino H-atoms were located in a difference Fourier map, and were refined isotropically with a distance restraint of N–H 0.88±0.01 Å.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of SnCl3(C8H9)(C3H4N2)2 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Trichlorido(4-methylbenzyl)bis(1H-pyrazole-κN2)tin(IV) top
Crystal data top
[Sn(C8H9)Cl3(C3H4N2)2]F(000) = 1840
Mr = 466.36Dx = 1.756 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9748 reflections
a = 34.7322 (4) Åθ = 2.5–28.3°
b = 7.3709 (1) ŵ = 1.90 mm1
c = 14.5760 (2) ÅT = 100 K
β = 109.0535 (5)°Block, colorless
V = 3527.13 (8) Å30.30 × 0.25 × 0.20 mm
Z = 8
Data collection top
Bruker SMART APEX
diffractometer
4053 independent reflections
Radiation source: fine-focus sealed tube3734 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 4444
Tmin = 0.599, Tmax = 0.702k = 99
16131 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.017Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.044H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.022P)2 + 3.9233P]
where P = (Fo2 + 2Fc2)/3
4053 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.43 e Å3
2 restraintsΔρmin = 0.26 e Å3
Crystal data top
[Sn(C8H9)Cl3(C3H4N2)2]V = 3527.13 (8) Å3
Mr = 466.36Z = 8
Monoclinic, C2/cMo Kα radiation
a = 34.7322 (4) ŵ = 1.90 mm1
b = 7.3709 (1) ÅT = 100 K
c = 14.5760 (2) Å0.30 × 0.25 × 0.20 mm
β = 109.0535 (5)°
Data collection top
Bruker SMART APEX
diffractometer
4053 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3734 reflections with I > 2σ(I)
Tmin = 0.599, Tmax = 0.702Rint = 0.022
16131 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0172 restraints
wR(F2) = 0.044H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.43 e Å3
4053 reflectionsΔρmin = 0.26 e Å3
208 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn10.595182 (3)0.582348 (14)0.721693 (7)0.01211 (4)
Cl10.555981 (12)0.42823 (5)0.81341 (3)0.01619 (8)
Cl20.626900 (12)0.79953 (6)0.85059 (3)0.01902 (9)
Cl30.556206 (12)0.41810 (5)0.57311 (3)0.01787 (9)
N10.54480 (4)0.77932 (19)0.67420 (10)0.0150 (3)
N20.50505 (4)0.7311 (2)0.64558 (11)0.0183 (3)
H20.4985 (7)0.6177 (16)0.6474 (18)0.038 (7)*
N30.62026 (4)0.74995 (19)0.62547 (10)0.0153 (3)
N40.60725 (4)0.7316 (2)0.52785 (10)0.0166 (3)
H40.5873 (5)0.657 (3)0.4997 (15)0.031 (6)*
C10.64493 (5)0.3890 (2)0.76417 (13)0.0179 (3)
H1A0.65740.39120.83570.021*
H1B0.63390.26570.74530.021*
C20.67715 (5)0.4263 (2)0.71934 (13)0.0161 (3)
C30.67158 (5)0.3774 (2)0.62338 (13)0.0172 (3)
H30.64720.31720.58660.021*
C40.70114 (5)0.4155 (2)0.58085 (13)0.0192 (4)
H4A0.69670.38070.51540.023*
C50.73723 (5)0.5037 (2)0.63237 (13)0.0179 (3)
C60.74257 (5)0.5557 (2)0.72790 (13)0.0181 (3)
H60.76670.61790.76420.022*
C70.71300 (5)0.5175 (2)0.77065 (12)0.0174 (3)
H70.71730.55390.83570.021*
C80.76965 (6)0.5415 (3)0.58673 (14)0.0252 (4)
H8A0.78430.65270.61450.038*
H8B0.75690.55660.51650.038*
H8C0.78880.43970.59950.038*
C90.54488 (6)0.9595 (2)0.66532 (15)0.0234 (4)
H90.56871.03250.68000.028*
C100.50533 (6)1.0249 (3)0.63159 (15)0.0255 (4)
H100.49701.14780.61910.031*
C110.48082 (5)0.8757 (2)0.62004 (12)0.0187 (3)
H110.45190.87510.59790.022*
C120.65211 (5)0.8626 (2)0.64665 (13)0.0177 (3)
H120.66760.90030.71030.021*
C130.65924 (6)0.9165 (2)0.56243 (14)0.0226 (4)
H130.67990.99630.55720.027*
C140.63001 (6)0.8300 (2)0.48815 (13)0.0215 (4)
H140.62660.83850.42090.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.01177 (6)0.01333 (6)0.01165 (6)0.00092 (4)0.00438 (4)0.00068 (4)
Cl10.01552 (18)0.01766 (19)0.01712 (19)0.00114 (14)0.00767 (15)0.00354 (15)
Cl20.01874 (19)0.0214 (2)0.01536 (18)0.00281 (15)0.00349 (15)0.00550 (15)
Cl30.0199 (2)0.01818 (19)0.01524 (19)0.00530 (15)0.00538 (15)0.00409 (15)
N10.0132 (6)0.0161 (7)0.0157 (7)0.0021 (5)0.0047 (5)0.0007 (5)
N20.0138 (7)0.0173 (7)0.0225 (7)0.0023 (6)0.0041 (6)0.0002 (6)
N30.0163 (6)0.0172 (7)0.0124 (6)0.0017 (5)0.0048 (5)0.0013 (5)
N40.0196 (7)0.0167 (7)0.0134 (6)0.0020 (6)0.0052 (6)0.0002 (6)
C10.0167 (8)0.0177 (8)0.0199 (8)0.0016 (6)0.0070 (7)0.0023 (7)
C20.0152 (8)0.0142 (8)0.0194 (8)0.0023 (6)0.0063 (6)0.0007 (6)
C30.0136 (7)0.0172 (8)0.0204 (8)0.0005 (6)0.0047 (6)0.0030 (7)
C40.0191 (8)0.0215 (9)0.0178 (8)0.0032 (7)0.0071 (7)0.0022 (7)
C50.0156 (8)0.0167 (8)0.0225 (9)0.0033 (6)0.0077 (7)0.0029 (7)
C60.0137 (8)0.0160 (8)0.0231 (9)0.0006 (6)0.0039 (7)0.0002 (7)
C70.0174 (8)0.0181 (8)0.0157 (8)0.0022 (6)0.0042 (6)0.0012 (7)
C80.0208 (9)0.0311 (10)0.0270 (10)0.0004 (8)0.0124 (8)0.0025 (8)
C90.0198 (9)0.0155 (8)0.0351 (10)0.0020 (7)0.0090 (8)0.0019 (8)
C100.0234 (9)0.0171 (8)0.0358 (11)0.0039 (7)0.0095 (8)0.0055 (8)
C110.0160 (8)0.0226 (9)0.0174 (8)0.0026 (7)0.0055 (7)0.0001 (7)
C120.0173 (8)0.0168 (8)0.0193 (8)0.0028 (6)0.0066 (7)0.0010 (7)
C130.0270 (9)0.0193 (9)0.0266 (10)0.0049 (7)0.0156 (8)0.0012 (7)
C140.0319 (10)0.0176 (9)0.0193 (8)0.0008 (7)0.0141 (8)0.0019 (7)
Geometric parameters (Å, º) top
Sn1—C12.1680 (17)C4—C51.394 (2)
Sn1—N12.2042 (14)C4—H4A0.9500
Sn1—N32.2471 (14)C5—C61.397 (2)
Sn1—Cl22.4402 (4)C5—C81.509 (2)
Sn1—Cl32.4646 (4)C6—C71.393 (2)
Sn1—Cl12.4739 (4)C6—H60.9500
N1—C91.334 (2)C7—H70.9500
N1—N21.3528 (19)C8—H8A0.9800
N2—C111.333 (2)C8—H8B0.9800
N2—H20.869 (10)C8—H8C0.9800
N3—C121.336 (2)C9—C101.386 (3)
N3—N41.3518 (19)C9—H90.9500
N4—C141.336 (2)C10—C111.368 (3)
N4—H40.876 (9)C10—H100.9500
C1—C21.494 (2)C11—H110.9500
C1—H1A0.9900C12—C131.388 (2)
C1—H1B0.9900C12—H120.9500
C2—C31.395 (2)C13—C141.376 (3)
C2—C71.398 (2)C13—H130.9500
C3—C41.390 (2)C14—H140.9500
C3—H30.9500
C1—Sn1—N1178.30 (6)C2—C3—H3119.5
C1—Sn1—N396.00 (6)C3—C4—C5121.27 (16)
N1—Sn1—N382.62 (5)C3—C4—H4A119.4
C1—Sn1—Cl295.39 (5)C5—C4—H4A119.4
N1—Sn1—Cl285.54 (4)C6—C5—C4117.92 (16)
N3—Sn1—Cl287.15 (4)C6—C5—C8120.91 (16)
C1—Sn1—Cl394.93 (5)C4—C5—C8121.17 (16)
N1—Sn1—Cl384.01 (4)C5—C6—C7120.88 (16)
N3—Sn1—Cl386.29 (4)C5—C6—H6119.6
Cl2—Sn1—Cl3168.293 (15)C7—C6—H6119.6
C1—Sn1—Cl194.11 (5)C2—C7—C6121.07 (16)
N1—Sn1—Cl187.23 (4)C2—C7—H7119.5
N3—Sn1—Cl1169.61 (4)C6—C7—H7119.5
Cl2—Sn1—Cl194.297 (14)C5—C8—H8A109.5
Cl3—Sn1—Cl190.458 (14)C5—C8—H8B109.5
C9—N1—N2105.40 (14)H8A—C8—H8B109.5
C9—N1—Sn1131.25 (12)C5—C8—H8C109.5
N2—N1—Sn1123.34 (11)H8A—C8—H8C109.5
C11—N2—N1111.34 (14)H8B—C8—H8C109.5
C11—N2—H2128.9 (16)N1—C9—C10110.35 (16)
N1—N2—H2119.7 (16)N1—C9—H9124.8
C12—N3—N4105.80 (13)C10—C9—H9124.8
C12—N3—Sn1131.13 (11)C11—C10—C9105.59 (16)
N4—N3—Sn1122.52 (10)C11—C10—H10127.2
C14—N4—N3111.11 (14)C9—C10—H10127.2
C14—N4—H4129.0 (15)N2—C11—C10107.31 (15)
N3—N4—H4119.8 (15)N2—C11—H11126.3
C2—C1—Sn1113.26 (11)C10—C11—H11126.3
C2—C1—H1A108.9N3—C12—C13110.31 (15)
Sn1—C1—H1A108.9N3—C12—H12124.8
C2—C1—H1B108.9C13—C12—H12124.8
Sn1—C1—H1B108.9C14—C13—C12105.33 (16)
H1A—C1—H1B107.7C14—C13—H13127.3
C3—C2—C7117.93 (15)C12—C13—H13127.3
C3—C2—C1120.81 (15)N4—C14—C13107.45 (16)
C7—C2—C1121.21 (15)N4—C14—H14126.3
C4—C3—C2120.92 (16)C13—C14—H14126.3
C4—C3—H3119.5
N3—Sn1—N1—C943.97 (16)Cl3—Sn1—C1—C286.69 (12)
Cl2—Sn1—N1—C943.73 (16)Cl1—Sn1—C1—C2177.50 (12)
Cl3—Sn1—N1—C9130.99 (16)Sn1—C1—C2—C378.65 (18)
Cl1—Sn1—N1—C9138.26 (16)Sn1—C1—C2—C798.78 (16)
N3—Sn1—N1—N2135.10 (13)C7—C2—C3—C41.1 (2)
Cl2—Sn1—N1—N2137.20 (12)C1—C2—C3—C4178.60 (16)
Cl3—Sn1—N1—N248.08 (12)C2—C3—C4—C50.1 (3)
Cl1—Sn1—N1—N242.67 (12)C3—C4—C5—C61.0 (3)
C9—N1—N2—C110.37 (19)C3—C4—C5—C8178.73 (17)
Sn1—N1—N2—C11179.64 (11)C4—C5—C6—C71.1 (2)
C1—Sn1—N3—C1270.61 (15)C8—C5—C6—C7178.67 (17)
N1—Sn1—N3—C12110.39 (15)C3—C2—C7—C61.0 (3)
Cl2—Sn1—N3—C1224.52 (15)C1—C2—C7—C6178.52 (16)
Cl3—Sn1—N3—C12165.19 (15)C5—C6—C7—C20.1 (3)
Cl1—Sn1—N3—C12122.84 (19)N2—N1—C9—C100.2 (2)
C1—Sn1—N3—N499.62 (13)Sn1—N1—C9—C10179.44 (13)
N1—Sn1—N3—N479.38 (12)N1—C9—C10—C110.0 (2)
Cl2—Sn1—N3—N4165.25 (12)N1—N2—C11—C100.3 (2)
Cl3—Sn1—N3—N45.04 (12)C9—C10—C11—N20.2 (2)
Cl1—Sn1—N3—N466.9 (3)N4—N3—C12—C130.26 (19)
C12—N3—N4—C140.20 (19)Sn1—N3—C12—C13171.71 (12)
Sn1—N3—N4—C14172.56 (11)N3—C12—C13—C140.2 (2)
N3—Sn1—C1—C20.09 (13)N3—N4—C14—C130.1 (2)
Cl2—Sn1—C1—C287.78 (12)C12—C13—C14—N40.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl1i0.87 (1)2.56 (2)3.265 (2)139 (2)
N4—H4···Cl1ii0.88 (1)2.65 (2)3.270 (2)129 (2)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x, y+1, z1/2.

Experimental details

Crystal data
Chemical formula[Sn(C8H9)Cl3(C3H4N2)2]
Mr466.36
Crystal system, space groupMonoclinic, C2/c
Temperature (K)100
a, b, c (Å)34.7322 (4), 7.3709 (1), 14.5760 (2)
β (°) 109.0535 (5)
V3)3527.13 (8)
Z8
Radiation typeMo Kα
µ (mm1)1.90
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.599, 0.702
No. of measured, independent and
observed [I > 2σ(I)] reflections
16131, 4053, 3734
Rint0.022
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.017, 0.044, 1.00
No. of reflections4053
No. of parameters208
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.43, 0.26

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl1i0.87 (1)2.56 (2)3.265 (2)139 (2)
N4—H4···Cl1ii0.88 (1)2.65 (2)3.270 (2)129 (2)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x, y+1, z1/2.
 

Acknowledgements

We thank the University of Malaya (grant No. RG020/09AFR) for supporting this study.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCasas, J. S., Castellano, E. E., Barnes, F. J. G., Sanchez, A., González, A. S., Sordo, J. & Zuckerman-Schpector, J. (1996). J. Organomet. Chem. 519, 209–216.  CrossRef CAS Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSisido, K., Takeda, Y. & Kinugawa, Z. (1961). J. Am. Chem. Soc. 83, 538–541.  CrossRef Web of Science Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds