Three-dimensional hydrogen-bonded supra­molecular assembly in tetrakis­(1,3,5-triaza-7-phosphaadamantane)copper(I) chloride hexa­hydrate

Kirillov, A.M.; Smoleński, P.; Guedes da Silva, M.F.C.; Kopylovich, M.N.; Pombeiro, A.J.L.

doi:10.1107/S1600536808008179

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 5| May 2008| Pages m603-m604

doi:10.1107/S1600536808008179

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access

Three-dimensional hydrogen-bonded supramolecular assembly in tetrakis(1,3,5-triaza-7-phosphaadamantane)copper(I) chloride hexahydrate

Alexander M. Kirillov,^a Piotr Smoleński,^a M. Fátima C. Guedes da Silva,^a,^b ^* Maximilian N. Kopylovich ^a and Armando J. L. Pombeiro ^a

^aCentro de Química Estrutural, Complexo Interdisciplinar, Instituto Superior Técnico, TU Lisbon, Av. Rovisco Pais, 1049-001 Lisbon, Portugal, and ^bUniversidade Lusófona de Humanidades e Tecnologias, ULHT Lisbon, Av. do Campo Grande 376, 1749-024 Lisbon, Portugal
^*Correspondence e-mail: fatima.guedes@ist.utl.pt

(Received 22 March 2008; accepted 26 March 2008; online 2 April 2008)

The structure of the title compound, [Cu(PTA)₄]Cl·6H₂O (PTA is 1,3,5-triaza-7-phosphaadamantane, C₆H₁₂N₃P), is composed of discrete monomeric [Cu(PTA)₄]⁺ cations, chloride anions and uncoordinated water molecules. The Cu^I atom exhibits tetrahedral coordination geometry, involving four symmetry-equivalent P–bound PTA ligands. The structure is extended to a regular three-dimensional supramolecular framework via numerous equivalent O—H⋯N hydrogen bonds between all solvent water molecules (six per cation) and all PTA N atoms, thus simultaneously bridging each [Cu(PTA)₄]⁺ cation with 12 neighbouring units in multiple directions. The study also shows that PTA can be a convenient ligand in crystal engineering for the construction of supramolecular architectures.

Related literature

For general background, see: Kirillov et al. (2007 , 2008 ); Karabach et al. (2006 ); Di Nicola et al. (2007 ). For a comprehensive review of PTA chemistry, see: Phillips et al. (2004 ). For PTA-derived polymeric networks, see: Lidrissi et al. (2005 ); Frost et al. (2006 ); Mohr et al. (2006 ). For related compounds, see: Forward et al. (1996 ); Darensbourg et al. (1997 , 1999 ).

Experimental

Crystal data

[Cu(C₆H₁₂N₃P)₄]Cl·6H₂O
M_r = 835.71
Cubic, $[F d \overline 3m ]$
a = 19.795 (4) Å
V = 7757 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 150 (2) K
0.20 × 0.17 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.848, T_max = 0.905
3022 measured reflections
447 independent reflections
361 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.092
S = 1.08
447 reflections
28 parameters
H-atom parameters constrained
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10⋯N1	0.81	2.04	2.843 (3)	174

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), PLATON (Spek, 2003 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536808008179/dn2329sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808008179/dn2329Isup2.hkl

checkCIF report

Comment top

1,3,5-triaza-7-phosphaadamantane (PTA) is a water soluble aminophosphine that has sparked recent interest in coordination chemistry in view of the significance of transition metal PTA complexes in aqueous phase catalysis, photochemistry and medicinal chemistry (Phillips et al., 2004). Besides, PTA and its derivatives can also be convenient building blocks for the construction of polymeric networks (Lidrissi et al., 2005; Frost et al., 2006; Mohr et al., 2006) due to several potentially available coordination sites, protonation ability of N atoms, and strong affinity towards hydrogen bonds. Nevertheless, the use of PTA ligands in crystal design and engineering has remained little explored. Hence, in pursuit of our recent studies directed towards the synthesis of new copper compounds including PTA complexes (Kirillov et al., 2007) and various coordination polymers, supramolecular frameworks and host–guest systems with other ligands (Karabach et al., 2006; Di Nicola et al., 2007; Kirillov et al., 2008), we have prepared compound (I) whose crystal structure and supramolecular features are reported herein.

The moiety formula of (I) consists of the [Cu(PTA)₄]⁺ cation (Fig. 1), one chloride anion and six symmetry equivalent crystallization water molecules. The [Cu(PTA)₄]⁺ unit possesses a very high symmetry, being generated from only five symmetry nonequivalent atoms (Cu1, P1, N1, C1 and C2). The Cu^I atom lies on -43m site symmetry and its coordination environment is filled by four equivalent P–bound PTA ligands, arranged in a perfect tetrahedral coordination geometry with the corresponding P—Cu—P angles of 109.47 (2)°. The Cu—P bond distances of 2.2598 (6) Å as well as other bonding parameters within the cage-like PTA cores are comparable to those reported for tetrahedral PTA complexes of Cu (Kirillov et al., 2007), Au (Forward et al., 1996), Pt (Darensbourg et al., 1999) and Ni (Darensbourg et al., 1997).

An interesting feature of (I) consists in the extensive intermolecular hydrogen bonding that arises from only one type of O-H···N H-bond (Table 1). Hence, each crystallization water molecule (O10) repeatedly acts as a double H-bond donor bridging to two N1 atoms of two different [Cu(PTA)₄]⁺ units. This results in the extensive interlinkage in multiple directions of every monomeric copper unit with twelve neighbouring ones (Fig. 2), thus leading to the formation of a regular three-dimensional supramolecular framework (Fig. 3). That framework has the shortest Cu···Cu separation of 13.977 (1) Å and possesses the repeating channels (ca 4.8 Å diameter) filled by water molecules.

Related literature top

For general background, see: Kirillov et al. (2007, 2008); Karabach et al. (2006); Di Nicola et al. (2007). For a comprehensive review on PTA chemistry, see: Phillips et al. (2004). For PTA-derived polymeric networks, see: Lidrissi et al. (2005); Frost et al. (2006); Mohr et al. (2006). For related compounds, see: Forward et al. (1996); Darensbourg et al. (1997, 1999).

Experimental top

To the ethanolic solution (5 ml) of CuCl₂ (27 mg, 0.20 mmol) was added solid PTA (126 mg, 0.80 mmol). The obtained mixture was refluxed for 3 h resulting in a white suspension. This was filtered off and the colourless filtrate was left to evaporate in a beaker in air and at ambient temperature. A small crop of the colourless X-ray quality crystals of (I) was formed in several days. ¹H NMR data are similar to those reported for [Cu(PTA)₄]NO₃ (Kirillov et al., 2007). FT–IR (KBr pellet), cm^-1: 3430 m, br and 3195 w [ν(H₂O)], 2940 m and 2901 m [ν_as(C—H)], 2863 m and 2808 w [ν_s(C—H)], 1645 w br [δ(H₂O)], 1437 m, 1413 m, 1365 m, 1296 s, 1242 s, 1180 m, 1105 m, 1037 w, 1015 s, 971 s, 906 w, 890 m, 808 s, 797 s, 744 m, 694 m, 670 w, 582 s, 551 w, 451 s, 406 m [PTA bands]. FAB-MS⁺ (m-nitrobenzylalcohol), m/z: 691 [Cu(PTA)₄]⁺.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2003) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular view of the cation with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are omitted for clarity. [Symmetry codes: (i) z, x, y; (ii) y, z, x; (iii) -x+1/4, y, -z+1/4; (iv) -x+1/4, -y+1/4, z; (v) x, -y+1/4, -z+1/4]
	Fig. 2. Fragment of the crystal packing diagram of (I) showing the simultaneous multidimensional interlinkage of the central monomeric [Cu(PTA)4]+ unit (black coloured) with twelve neighbouring ones (each represented by different colour) via repeating O10—H10···N1 hydrogen bonding interactions (black dashed lines) between crystallization water molecules O10 (coloured balls) and PTA N1 atoms. H and Cl atoms are omitted for clarity.
	Fig. 3. Fragment of the crystal packing diagram of (I) (view along the a axis) showing the extensive hydrogen bonding interactions (pale blue dashed lines) resulting in the formation of a regular three-dimensional H-bonded supramolecular assembly. H atoms are omitted for clarity. Cu, green; P, orange; N, blue; C, grey; O, red (balls); Cl, yellow (balls).

tetrakis(1,3,5-triaza-7-phosphaadamantane)copper(I) chloride hexahydrate top

Crystal data top

[Cu(C₆H₁₂N₃P)₄]Cl·6H₂O	D_x = 1.431 Mg m⁻³
M_r = 835.71	Mo Kα radiation, λ = 0.71069 Å
Cubic, Fd3m	Cell parameters from 743 reflections
Hall symbol: -F 4vw 2vw 3	θ = 2.9–27.0°
a = 19.795 (4) Å	µ = 0.85 mm⁻¹
V = 7757 (3) Å³	T = 150 K
Z = 8	Prism, colourless
F(000) = 3536	0.20 × 0.17 × 0.12 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	447 independent reflections
Radiation source: fine-focus sealed tube	361 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −24→23
T_min = 0.848, T_max = 0.905	k = −16→11
3022 measured reflections	l = −6→25

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0463P)² + 19.2954P] where P = (F_o² + 2F_c²)/3
447 reflections	(Δ/σ)_max < 0.001
28 parameters	Δρ_max = 0.75 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Cu(C₆H₁₂N₃P)₄]Cl·6H₂O	Z = 8
M_r = 835.71	Mo Kα radiation
Cubic, Fd3m	µ = 0.85 mm⁻¹
a = 19.795 (4) Å	T = 150 K
V = 7757 (3) Å³	0.20 × 0.17 × 0.12 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	447 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	361 reflections with I > 2σ(I)
T_min = 0.848, T_max = 0.905	R_int = 0.049
3022 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0463P)² + 19.2954P] where P = (F_o² + 2F_c²)/3
447 reflections	Δρ_max = 0.75 e Å⁻³
28 parameters	Δρ_min = −0.32 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 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	U_iso*/U_eq	Occ. (<1)
C1	0.25075 (10)	0.15137 (15)	0.25075 (10)	0.0199 (6)
H1A	0.2258	0.1228	0.2818	0.024*	0.50
H1B	0.2818	0.1228	0.2258	0.024*	0.50
C2	0.33080 (15)	0.24509 (11)	0.24509 (11)	0.0239 (7)
H2A	0.3607	0.2726	0.2726	0.029*
H2B	0.3587	0.2166	0.2166	0.029*
N1	0.29002 (8)	0.20160 (12)	0.29002 (8)	0.0212 (6)
Cu1	0.1250	0.1250	0.1250	0.0134 (3)
P1	0.19090 (4)	0.19090 (4)	0.19090 (4)	0.0156 (3)
Cl1	0.3750	0.3750	0.3750	0.0165 (5)
O10	0.3750	0.12300 (14)	0.3750	0.0240 (7)
H10	0.3521	0.1480	0.3521	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0193 (8)	0.0212 (14)	0.0193 (8)	−0.0005 (7)	−0.0053 (11)	−0.0005 (7)
C2	0.0193 (15)	0.0262 (10)	0.0262 (10)	−0.0036 (8)	−0.0036 (8)	−0.0027 (12)
N1	0.0218 (8)	0.0202 (13)	0.0218 (8)	−0.0019 (7)	−0.0056 (10)	−0.0019 (7)
Cu1	0.0134 (3)	0.0134 (3)	0.0134 (3)	0.000	0.000	0.000
P1	0.0156 (3)	0.0156 (3)	0.0156 (3)	−0.0009 (3)	−0.0009 (3)	−0.0009 (3)
Cl1	0.0165 (5)	0.0165 (5)	0.0165 (5)	0.000	0.000	0.000
O10	0.0255 (10)	0.0210 (16)	0.0255 (10)	0.000	−0.0083 (12)	0.000

Geometric parameters (Å, º) top

C1—N1	1.482 (3)	C2—H2A	0.9700
C1—P1	1.849 (3)	C2—H2B	0.9700
C1—H1A	0.9700	Cu1—P1	2.2596 (13)
C1—H1B	0.9700	P1—C1ⁱ	1.849 (3)
C2—N1ⁱ	1.478 (2)	O10—H10	0.8104
C2—N1	1.478 (2)

N1—C1—P1	112.8 (2)	P1—Cu1—P1^iv	109.5
N1—C1—H1A	109.0	P1ⁱⁱⁱ—Cu1—P1^iv	109.5
P1—C1—H1B	109.0	P1—Cu1—P1^v	109.5
H1A—C1—H1B	107.8	P1ⁱⁱⁱ—Cu1—P1^v	109.5
N1ⁱ—C2—N1	113.7 (3)	P1^iv—Cu1—P1^v	109.5
N1—C2—H2A	108.8	C1ⁱⁱ—P1—C1ⁱ	97.57 (12)
N1—C2—H2B	108.8	C1ⁱⁱ—P1—C1	97.57 (12)
H2A—C2—H2B	107.7	C1ⁱ—P1—C1	97.57 (12)
C2ⁱⁱ—N1—C2	108.5 (3)	C1ⁱⁱ—P1—Cu1	119.70 (9)
C2ⁱⁱ—N1—C1	111.21 (16)	C1ⁱ—P1—Cu1	119.70 (9)
C2—N1—C1	111.21 (16)	C1—P1—Cu1	119.70 (9)
P1—Cu1—P1ⁱⁱⁱ	109.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10···N1	0.81	2.04	2.843 (3)	174

Experimental details

Crystal data
Chemical formula	[Cu(C₆H₁₂N₃P)₄]Cl·6H₂O
M_r	835.71
Crystal system, space group	Cubic, Fd3m
Temperature (K)	150
a (Å)	19.795 (4)
V (Å³)	7757 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.20 × 0.17 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.848, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	3022, 447, 361
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.092, 1.08
No. of reflections	447
No. of parameters	28
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0463P)² + 19.2954P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.32

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2003) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10···N1	0.81	2.04	2.843 (3)	173.8

Acknowledgements

This work has been supported by the FCT, Portugal, and its POCI 2010 programme (FEDER funded).

References

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Pages m603-m604

doi:10.1107/S1600536808008179

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

Three-dimensional hydrogen-bonded supra­molecular assembly in tetra­kis­­(1,3,5-tri­aza-7-phosphaadamantane)copper(I) chloride hexa­hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Three-dimensional hydrogen-bonded supramolecular assembly in tetrakis(1,3,5-triaza-7-phosphaadamantane)copper(I) chloride hexahydrate