Crystal structure of bis­{2-[(2-hy­droxy­eth­yl)amino]­ethanol-κ3O,N,O′}copper(II) terephthalate

Li, Y.-P.; Sun, D.; Ming, J.; Han, L.; Su, G.-F.

doi:10.1107/S1600536814022272

metal-organic compounds

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Volume 70| Part 11| November 2014| Pages m372-m373

doi:10.1107/S1600536814022272

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Crystal structure of bis{2-[(2-hydroxyethyl)amino]ethanol-κ³O,N,O′}copper(II) terephthalate

Ya-Ping Li,^a Dajun Sun,^b ^* Julia Ming,^c Liying Han ^d and Guan-Fang Su ^a

^aDepartment of Ophthalmology, The Second Hospital of Jilin University, 218 Ziqiang Street, Changchun 130041, People's Republic of China, ^bDepartment of Vascular Surgery, The China-Japan Union Hospital of Jilin University, Changchun 130033, People's Republic of China, ^cSt Erik's Eye Hospital, Karolinska Institutet, Polhemsgatan 50, SE-112 82 Stockholm, Sweden, and ^dDepartment of Gynecology, The Second Hospital of Jilin University, 218 Ziqiang Street, Changchun 130041, People's Republic of China
^*Correspondence e-mail: drsundj@163.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 29 September 2014; accepted 9 October 2014; online 18 October 2014)

The molecular components of the title salt, [Cu(C₄H₁₁NO₂)₂](C₈H₄O₄), are one Cu^II cation O,N,O′-chelated by two tridentate 2-[(2-hydroxyethyl)amino]ethanol ligands, and a terephthalate counter-dianion, located about a centre of inversion. The complex Cu^II cation is located about a centre of inversion and shows typical Jahn–Teller distortion, with two short Cu—O and two short Cu—N bonds in the equatorial plane and two long Cu—O bonds to the axial atoms. The cations are arranged in sheets parallel to (100), with the centrosymmetric terephthalate anions located between the sheets. Each anion is the acceptor of four O—H⋯O and two N—H⋯O hydrogen bonds, forming a three-dimensional network structure.

Keywords: crystal structure; copper(II) chelate complex; terephthalate.

CCDC reference: 1028231

1. Related literature

For related copper(II) compounds with terephthalate anions, see: Abbaszadeh et al. (2012 ); Al-Hashemi et al. (2010 ).

2. Experimental

2.1. Crystal data

[Cu(C₄H₁₁NO₂)₂](C₈H₄O₄)
M_r = 437.93
Monoclinic, P 2₁ /c
a = 8.6013 (9) Å
b = 9.0398 (9) Å
c = 11.5732 (12) Å
β = 91.695 (2)°
V = 899.47 (16) Å³
Z = 2
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 293 K
0.29 × 0.27 × 0.26 mm

2.2. Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.728, T_max = 0.812
4784 measured reflections
1780 independent reflections
1611 reflections with I > 2σ(I)
R_int = 0.034

2.3. Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.080
S = 1.08
1780 reflections
133 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.83 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.85 (2)	2.08 (2)	2.9196 (19)	168 (2)
O4—H4A⋯O2ⁱⁱ	0.84 (2)	1.66 (2)	2.496 (2)	180 (3)
O3—H3A⋯O1ⁱⁱⁱ	0.81 (2)	1.88 (2)	2.6803 (19)	167 (2)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+2, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1028231

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814022272/wm5069sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814022272/wm5069Isup2.hkl

checkCIF report

Preparation top

The synthesis was performed under hydrothermal conditions. A mixture of Cu(CH₃COO)₂·2H₂O, (0.2 mmol, 0.046 g), 2-(2-hydroxy-ethylamine) (0.4 mmol, 0.043 g), sodium terephthalate (0.2 mmol, 0.042 g) and water (20 ml) in a 30 ml stainless steel reactor with a Teflon liner were heated from 293 to 433 K in 2 h, and a constant temperature was maintained at 433 K for 72 h, after which the mixture was cooled to 298 K. Blue crystals of the title compound were recovered from the reaction.

Refinement top

All C—H H atoms were positioned with idealized geometry and refined with U_iso(H) = 1.2U_eq(C) using a riding model. The hydroxy H-atoms and amine H atoms were located in a difference Fourier map and were refined with O—H or N—H distances restrained to 0.85 (3) Å and with U_iso(H) = 1.5U_eq(N,O).

Related literature top

For related copper(II) compounds with terephthalate anions, see: Abbaszadeh et al. (2012); Al-Hashemi et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

The molecular components of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 3-x, 1-y, 2-z; (ii) 2-x, -y, 2-z.]

The packing of the molecular components in the title compound. N—H···O and O—H···O hydrogen bonds are shown by dashed lines.

Bis{2-[(2-hydroxyethyl)amino]ethanol-κ³O,N,O'}copper(II) terephthalate top

Crystal data top

[Cu(C₄H₁₁NO₂)₂](C₈H₄O₄)	F(000) = 458
M_r = 437.93	D_x = 1.617 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1780 reflections
a = 8.6013 (9) Å	θ = 1.7–22.8°
b = 9.0398 (9) Å	µ = 1.26 mm⁻¹
c = 11.5732 (12) Å	T = 293 K
β = 91.695 (2)°	Block, blue
V = 899.47 (16) Å³	0.29 × 0.27 × 0.26 mm
Z = 2

Data collection top

Bruker SMART APEXII CCD diffractometer	1780 independent reflections
Radiation source: fine-focus sealed tube	1611 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
phi and ω scans	θ_max = 26.1°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→8
T_min = 0.728, T_max = 0.812	k = −11→11
4784 measured reflections	l = −12→14

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0446P)² + 0.3198P] where P = (F_o² + 2F_c²)/3
1780 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.31 e Å⁻³
3 restraints	Δρ_min = −0.83 e Å⁻³

Crystal data top

[Cu(C₄H₁₁NO₂)₂](C₈H₄O₄)	V = 899.47 (16) Å³
M_r = 437.93	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.6013 (9) Å	µ = 1.26 mm⁻¹
b = 9.0398 (9) Å	T = 293 K
c = 11.5732 (12) Å	0.29 × 0.27 × 0.26 mm
β = 91.695 (2)°

Data collection top

Bruker SMART APEXII CCD diffractometer	1780 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1611 reflections with I > 2σ(I)
T_min = 0.728, T_max = 0.812	R_int = 0.034
4784 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	3 restraints
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.31 e Å⁻³
1780 reflections	Δρ_min = −0.83 e Å⁻³
133 parameters

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 > 2sigma(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
C1	1.3193 (2)	0.5638 (2)	0.79022 (15)	0.0172 (4)
C2	1.4142 (2)	0.5319 (2)	0.89901 (16)	0.0152 (4)
C3	1.5213 (2)	0.4163 (2)	0.90128 (16)	0.0182 (4)
H3	1.5359	0.3603	0.8351	0.022*
C4	1.3941 (2)	0.6154 (2)	0.99805 (15)	0.0181 (4)
H4	1.3232	0.6932	0.9968	0.022*
C5	1.1185 (2)	0.3121 (2)	1.02670 (17)	0.0256 (4)
H5A	1.2286	0.2892	1.0319	0.031*
H5B	1.1057	0.4155	1.0468	0.031*
C6	1.0583 (2)	0.2870 (2)	0.90354 (17)	0.0235 (4)
H6A	0.9534	0.3259	0.8956	0.028*
H6B	1.1229	0.3417	0.8511	0.028*
C7	1.2043 (2)	0.0697 (2)	0.82537 (15)	0.0233 (4)
H7A	1.2537	0.1440	0.7784	0.028*
H7B	1.1821	−0.0158	0.7769	0.028*
C8	1.3139 (2)	0.0254 (2)	0.92433 (18)	0.0229 (4)
H8A	1.3931	−0.0412	0.8968	0.027*
H8B	1.3649	0.1123	0.9568	0.027*
N1	1.05698 (17)	0.12937 (17)	0.86951 (12)	0.0159 (3)
H1A	0.985 (2)	0.123 (2)	0.8179 (16)	0.024*
O1	1.20598 (16)	0.64876 (16)	0.79517 (11)	0.0258 (3)
O2	1.3607 (2)	0.49850 (17)	0.70051 (13)	0.0334 (4)
O3	1.03789 (17)	0.22244 (15)	1.10678 (11)	0.0211 (3)
H3A	0.956 (2)	0.259 (3)	1.127 (2)	0.032*
O4	1.22477 (15)	−0.04666 (15)	1.01071 (11)	0.0163 (3)
H4A	1.270 (3)	−0.031 (3)	1.0742 (16)	0.025*
Cu1	1.0000	0.0000	1.0000	0.01196 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0139 (9)	0.0228 (10)	0.0149 (9)	−0.0016 (8)	−0.0017 (7)	0.0012 (7)
C2	0.0130 (9)	0.0170 (8)	0.0156 (8)	−0.0019 (8)	−0.0020 (7)	0.0018 (7)
C3	0.0173 (9)	0.0203 (9)	0.0168 (8)	0.0013 (7)	−0.0014 (7)	−0.0034 (7)
C4	0.0162 (9)	0.0189 (9)	0.0192 (9)	0.0040 (8)	−0.0023 (7)	−0.0008 (7)
C5	0.0279 (11)	0.0218 (10)	0.0268 (10)	−0.0081 (8)	−0.0029 (8)	−0.0039 (8)
C6	0.0283 (11)	0.0185 (9)	0.0235 (10)	−0.0043 (8)	−0.0035 (8)	0.0038 (8)
C7	0.0184 (10)	0.0378 (12)	0.0137 (8)	0.0013 (9)	0.0006 (7)	0.0045 (8)
C8	0.0140 (10)	0.0371 (11)	0.0176 (9)	0.0004 (8)	0.0027 (8)	0.0047 (8)
N1	0.0135 (8)	0.0210 (8)	0.0128 (7)	−0.0019 (6)	−0.0052 (6)	0.0016 (6)
O1	0.0223 (8)	0.0351 (8)	0.0195 (7)	0.0124 (6)	−0.0071 (5)	−0.0038 (6)
O2	0.0252 (9)	0.0597 (13)	0.0149 (7)	0.0192 (7)	−0.0050 (6)	−0.0049 (6)
O3	0.0216 (7)	0.0223 (7)	0.0194 (6)	0.0015 (6)	−0.0005 (5)	−0.0037 (5)
O4	0.0126 (6)	0.0238 (7)	0.0125 (6)	0.0002 (6)	−0.0023 (5)	0.0010 (5)
Cu1	0.01017 (19)	0.0143 (2)	0.01133 (18)	−0.00020 (10)	−0.00122 (12)	0.00137 (10)

Geometric parameters (Å, º) top

C1—O1	1.243 (2)	C7—N1	1.482 (2)
C1—O2	1.255 (2)	C7—C8	1.515 (3)
C1—C2	1.508 (2)	C7—H7A	0.9700
C2—C4	1.387 (3)	C7—H7B	0.9700
C2—C3	1.392 (3)	C8—O4	1.434 (2)
C3—C4ⁱ	1.386 (2)	C8—H8A	0.9700
C3—H3	0.9300	C8—H8B	0.9700
C4—C3ⁱ	1.386 (2)	N1—Cu1	1.9830 (15)
C4—H4	0.9300	N1—H1A	0.847 (16)
C5—O3	1.427 (2)	O3—Cu1	2.3776 (13)
C5—C6	1.519 (3)	O3—H3A	0.814 (16)
C5—H5A	0.9700	O4—Cu1	1.9791 (13)
C5—H5B	0.9700	O4—H4A	0.835 (17)
C6—N1	1.478 (2)	Cu1—O4ⁱⁱ	1.9791 (13)
C6—H6A	0.9700	Cu1—N1ⁱⁱ	1.9830 (15)
C6—H6B	0.9700	Cu1—O3ⁱⁱ	2.3776 (13)

O1—C1—O2	124.81 (17)	C7—C8—H8A	110.0
O1—C1—C2	119.04 (16)	O4—C8—H8B	110.0
O2—C1—C2	116.13 (16)	C7—C8—H8B	110.0
C4—C2—C3	119.43 (17)	H8A—C8—H8B	108.4
C4—C2—C1	120.51 (17)	C6—N1—C7	116.30 (16)
C3—C2—C1	120.05 (17)	C6—N1—Cu1	111.45 (11)
C4ⁱ—C3—C2	120.13 (17)	C7—N1—Cu1	106.31 (11)
C4ⁱ—C3—H3	119.9	C6—N1—H1A	104.5 (15)
C2—C3—H3	119.9	C7—N1—H1A	110.2 (15)
C3ⁱ—C4—C2	120.43 (17)	Cu1—N1—H1A	107.9 (15)
C3ⁱ—C4—H4	119.8	C5—O3—Cu1	101.82 (10)
C2—C4—H4	119.8	C5—O3—H3A	113.5 (18)
O3—C5—C6	111.45 (16)	Cu1—O3—H3A	112.5 (18)
O3—C5—H5A	109.3	C8—O4—Cu1	113.63 (11)
C6—C5—H5A	109.3	C8—O4—H4A	106.7 (18)
O3—C5—H5B	109.3	Cu1—O4—H4A	116.8 (18)
C6—C5—H5B	109.3	O4—Cu1—O4ⁱⁱ	180.0
H5A—C5—H5B	108.0	O4—Cu1—N1ⁱⁱ	95.14 (6)
N1—C6—C5	113.19 (15)	O4ⁱⁱ—Cu1—N1ⁱⁱ	84.86 (6)
N1—C6—H6A	108.9	O4—Cu1—N1	84.86 (6)
C5—C6—H6A	108.9	O4ⁱⁱ—Cu1—N1	95.14 (6)
N1—C6—H6B	108.9	N1ⁱⁱ—Cu1—N1	180.0
C5—C6—H6B	108.9	O4—Cu1—O3ⁱⁱ	88.34 (5)
H6A—C6—H6B	107.8	O4ⁱⁱ—Cu1—O3ⁱⁱ	91.66 (5)
N1—C7—C8	110.78 (15)	N1ⁱⁱ—Cu1—O3ⁱⁱ	82.18 (5)
N1—C7—H7A	109.5	N1—Cu1—O3ⁱⁱ	97.82 (5)
C8—C7—H7A	109.5	O4—Cu1—O3	91.66 (5)
N1—C7—H7B	109.5	O4ⁱⁱ—Cu1—O3	88.34 (5)
C8—C7—H7B	109.5	N1ⁱⁱ—Cu1—O3	97.82 (5)
H7A—C7—H7B	108.1	N1—Cu1—O3	82.18 (5)
O4—C8—C7	108.27 (16)	O3ⁱⁱ—Cu1—O3	180.0
O4—C8—H8A	110.0

O1—C1—C2—C4	−11.6 (3)	C8—O4—Cu1—N1	−1.66 (13)
O2—C1—C2—C4	169.71 (18)	C8—O4—Cu1—O3ⁱⁱ	96.35 (13)
O1—C1—C2—C3	167.30 (18)	C8—O4—Cu1—O3	−83.65 (13)
O2—C1—C2—C3	−11.4 (3)	C6—N1—Cu1—O4	−103.85 (13)
C4—C2—C3—C4ⁱ	0.4 (3)	C7—N1—Cu1—O4	23.81 (11)
C1—C2—C3—C4ⁱ	−178.47 (17)	C6—N1—Cu1—O4ⁱⁱ	76.15 (13)
C3—C2—C4—C3ⁱ	−0.4 (3)	C7—N1—Cu1—O4ⁱⁱ	−156.19 (11)
C1—C2—C4—C3ⁱ	178.46 (17)	C6—N1—Cu1—N1ⁱⁱ	5 (100)
O3—C5—C6—N1	−52.7 (2)	C7—N1—Cu1—N1ⁱⁱ	133 (100)
N1—C7—C8—O4	41.4 (2)	C6—N1—Cu1—O3ⁱⁱ	168.55 (12)
C5—C6—N1—C7	−85.3 (2)	C7—N1—Cu1—O3ⁱⁱ	−63.79 (12)
C5—C6—N1—Cu1	36.8 (2)	C6—N1—Cu1—O3	−11.45 (12)
C8—C7—N1—C6	82.9 (2)	C7—N1—Cu1—O3	116.21 (12)
C8—C7—N1—Cu1	−41.82 (18)	C5—O3—Cu1—O4	69.87 (12)
C6—C5—O3—Cu1	37.08 (18)	C5—O3—Cu1—O4ⁱⁱ	−110.13 (12)
C7—C8—O4—Cu1	−20.7 (2)	C5—O3—Cu1—N1ⁱⁱ	165.29 (12)
C8—O4—Cu1—O4ⁱⁱ	−53 (21)	C5—O3—Cu1—N1	−14.71 (12)
C8—O4—Cu1—N1ⁱⁱ	178.34 (13)	C5—O3—Cu1—O3ⁱⁱ	−40.8 (3)

Symmetry codes: (i) −x+3, −y+1, −z+2; (ii) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱⁱⁱ	0.85 (2)	2.08 (2)	2.9196 (19)	168 (2)
O4—H4A···O2^iv	0.84 (2)	1.66 (2)	2.496 (2)	180 (3)
O3—H3A···O1^v	0.81 (2)	1.88 (2)	2.6803 (19)	167 (2)

Symmetry codes: (iii) −x+2, y−1/2, −z+3/2; (iv) x, −y+1/2, z+1/2; (v) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.847 (16)	2.084 (16)	2.9196 (19)	168 (2)
O4—H4A···O2ⁱⁱ	0.835 (17)	1.661 (17)	2.496 (2)	180 (3)
O3—H3A···O1ⁱⁱⁱ	0.814 (16)	1.881 (17)	2.6803 (19)	167 (2)

Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) x, −y+1/2, z+1/2; (iii) −x+2, −y+1, −z+2.

Acknowledgements

This project was supported by the International Scientific and Technological Cooperation Foundation of Jilin Province (grant No. 20120722).

References

Abbaszadeh, A., Safari, N., Amani, V. & Notash, B. (2012). Acta Cryst. E68, m1012. CSD CrossRef IUCr Journals Google Scholar
Al-Hashemi, R., Safari, N., Amani, S., Amani, V., Abedi, A., Khavasi, H. R. & Ng, S. W. (2010). J. Coord. Chem. 63, 3207–3217. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2002). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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