Crystal structure of bis­{2-[bis­(2-hy­droxy­eth­yl)amino]­ethanol-κ³ O,N,O′}zinc terephthalate

Abstract

In the title salt, [Zn(C₆H₁₅NO₃)₂](C₈H₄O₄), the Zn^II cation, located on a centre of inversion, is coordinated by four O atoms and two N atoms from two tridentate 2-[bis­(2-hy­droxy­eth­yl)amino]­ethanol (BHEA) ligands, giving rise to a slightly distorted octa­hedral geometry. The terephthalate dianion, located about a centre of inversion, is not coordinated to Zn^II but is connected through O—H⋯O contacts with [Zn(BHEA)₂]²⁺ cations, leading to a three-dimensional crystal structure.

Related literature  

For background and a related structure, see: Hamamci et al. (2002 ▶).

Experimental  

Crystal data  

• [Zn(C₆H₁₅NO₃)₂](C₈H₄O₄)

• M _r = 527.86

• Triclinic,

• a = 7.963 (5) Å

• b = 8.823 (5) Å

• c = 9.198 (5) Å

• α = 89.315 (5)°

• β = 72.421 (5)°

• γ = 66.208 (5)°

• V = 559.2 (6) ų

• Z = 1

• Mo Kα radiation

• μ = 1.16 mm⁻¹

• T = 293 K

• 0.26 × 0.24 × 0.23 mm

Data collection  

• Bruker SMART APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.725, T _max = 0.803

• 3145 measured reflections

• 2189 independent reflections

• 2165 reflections with I > 2σ(I)

• R _int = 0.012

Refinement  

• R[F ² > 2σ(F ²)] = 0.027

• wR(F ²) = 0.072

• S = 1.10

• 2189 reflections

• 160 parameters

• 3 restraints

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

• Δρ_max = 0.45 e Å⁻³

• Δρ_min = −0.51 e Å⁻³

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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Supplementary Material

CCDC reference: 1027329

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1O5i	0.82(2)	1.82(2)	2.632(2)	177(2)
O2H2O4ii	0.83(2)	1.74(2)	2.564(2)	178(2)
O3H3O5iii	0.87(2)	2.13(2)	2.942(3)	155(2)

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

S1. Preparation

The synthesis was performed under hydro­thermal conditions. A mixture of Zn(CH₃COO)₂^.2(H₂O), (0.2 mmol, 0.044 g), 2-[bis­(2-hy­droxy­ethyl)­amino]­ethanol (0.4 mmol, 0.062 g), sodium terephthalate (0.2 mmol, 0.042 g) and H₂O (20 mL) in a 30 mL stainless steel reactor with a Teflon liner was heated from 293 to 433 K in 2 h and then held at a constant temperature of 433 K for 72 h, after which the mixture was cooled to 298 K. Colourless crystals of the title compound were recovered from the reaction.

S2. Refinement

All C-bound H atoms were positioned with idealized geometry (0.93–0.97 Å) and refined isotropically with U_iso(H) = 1.2 U_eq(C) using a riding model. The hy­droxy H-atoms were located in a different Fourier map and were refined with an O—H distance restrained to 0.85 (2) Å and with U_iso(H) = 1.5 U_eq(O).

Figures

Fig. 1.

A view of the ions in the title salt. Displacement ellipsoids are drawn at the 30% probability level. Unlabelled atoms in the cation are related by 1-x, -y, -z, and those in the dianion by 1-x, -1-y, 1-z.

Fig. 2.

A view of the crystal structure of the title salt. Hydrogen bonds are shown as dashed lines.

Crystal data

[Zn(C6H15NO3)2](C8H4O4)	Z = 1
Mr = 527.86	F(000) = 278
Triclinic, P1	Dx = 1.567 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 7.963 (5) Å	Cell parameters from 2165 reflections
b = 8.823 (5) Å	θ = 1.7–22.8°
c = 9.198 (5) Å	µ = 1.16 mm−1
α = 89.315 (5)°	T = 293 K
β = 72.421 (5)°	Block, colourless
γ = 66.208 (5)°	0.26 × 0.24 × 0.23 mm
V = 559.2 (6) Å3

Data collection

Bruker SMART APEXII CCD diffractometer	2189 independent reflections
Radiation source: fine-focus sealed tube	2165 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.012
φ and ω scans	θmax = 26.2°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −9→8
Tmin = 0.725, Tmax = 0.803	k = −10→10
3145 measured reflections	l = −10→11

Refinement

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) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.0381P)2 + 0.3177P] where P = (Fo2 + 2Fc2)/3
2189 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.45 e Å−3
3 restraints	Δρmin = −0.51 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6774 (3)	−0.3639 (2)	−0.0601 (2)	0.0370 (5)
H1A	0.7747	−0.4664	−0.1248	0.044*
H1B	0.5597	−0.3796	−0.0138	0.044*
C2	0.7484 (3)	−0.3279 (2)	0.0655 (2)	0.0331 (4)
H2A	0.7475	−0.4087	0.1378	0.040*
H2B	0.8814	−0.3417	0.0199	0.040*
C3	0.3010 (3)	−0.1603 (3)	0.2345 (2)	0.0363 (5)
H3A	0.3374	−0.2759	0.1998	0.044*
H3B	0.1832	−0.1228	0.3224	0.044*
C4	0.4611 (3)	−0.1470 (3)	0.2818 (2)	0.0325 (4)
H4A	0.4091	−0.0417	0.3462	0.039*
H4B	0.5057	−0.2361	0.3426	0.039*
C5	0.7460 (3)	−0.0863 (3)	0.2013 (3)	0.0371 (5)
H5A	0.6741	0.0341	0.2208	0.044*
H5B	0.8648	−0.1107	0.1168	0.044*
C6	0.8006 (4)	−0.1462 (3)	0.3430 (3)	0.0463 (5)
H6A	0.8579	−0.0793	0.3745	0.056*
H6B	0.6851	−0.1329	0.4268	0.056*
C7	0.9062 (2)	−0.7092 (2)	0.3337 (2)	0.0260 (4)
C8	0.6957 (2)	−0.5992 (2)	0.4202 (2)	0.0228 (3)
C9	0.5509 (3)	−0.6072 (2)	0.3698 (2)	0.0253 (4)
H9	0.5846	−0.6789	0.2823	0.030*
C10	0.6436 (3)	−0.4910 (2)	0.5508 (2)	0.0250 (4)
H10	0.7392	−0.4844	0.5852	0.030*
N1	0.6286 (2)	−0.15730 (18)	0.14967 (17)	0.0229 (3)
O1	0.63918 (19)	−0.23022 (16)	−0.15252 (15)	0.0273 (3)
O2	0.26592 (18)	−0.06108 (17)	0.11409 (15)	0.0283 (3)
O3	0.9319 (3)	−0.3128 (2)	0.3114 (2)	0.0553 (5)
O4	0.9393 (2)	−0.8061 (2)	0.21957 (18)	0.0411 (4)
O5	1.03466 (19)	−0.69733 (19)	0.37935 (16)	0.0357 (3)
Zn1	0.5000	0.0000	0.0000	0.01988 (10)
H1	0.738 (3)	−0.249 (3)	−0.224 (2)	0.030*
H2	0.160 (3)	0.020 (2)	0.150 (3)	0.030*
H3	0.954 (3)	−0.343 (3)	0.397 (2)	0.030*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0491 (12)	0.0214 (9)	0.0346 (10)	−0.0125 (9)	−0.0086 (9)	−0.0021 (8)
C2	0.0334 (10)	0.0202 (9)	0.0327 (10)	−0.0003 (7)	−0.0084 (8)	0.0034 (7)
C3	0.0277 (9)	0.0398 (11)	0.0383 (11)	−0.0150 (9)	−0.0056 (8)	0.0149 (9)
C4	0.0298 (9)	0.0384 (10)	0.0218 (9)	−0.0095 (8)	−0.0049 (7)	0.0076 (8)
C5	0.0427 (11)	0.0357 (11)	0.0466 (12)	−0.0202 (9)	−0.0284 (10)	0.0128 (9)
C6	0.0430 (12)	0.0505 (14)	0.0519 (14)	−0.0171 (11)	−0.0281 (11)	0.0066 (11)
C7	0.0202 (8)	0.0259 (9)	0.0237 (8)	−0.0041 (7)	−0.0038 (7)	0.0040 (7)
C8	0.0184 (8)	0.0208 (8)	0.0238 (8)	−0.0053 (6)	−0.0038 (6)	0.0041 (6)
C9	0.0231 (8)	0.0249 (9)	0.0233 (8)	−0.0071 (7)	−0.0055 (7)	−0.0011 (6)
C10	0.0205 (8)	0.0271 (9)	0.0263 (9)	−0.0084 (7)	−0.0082 (7)	0.0027 (7)
N1	0.0215 (7)	0.0215 (7)	0.0236 (7)	−0.0066 (6)	−0.0078 (6)	0.0031 (6)
O1	0.0249 (6)	0.0268 (6)	0.0237 (6)	−0.0075 (5)	−0.0038 (5)	−0.0028 (5)
O2	0.0189 (6)	0.0293 (7)	0.0303 (7)	−0.0059 (5)	−0.0050 (5)	0.0047 (5)
O3	0.0529 (10)	0.0576 (11)	0.0483 (10)	−0.0096 (9)	−0.0261 (9)	0.0130 (8)
O4	0.0226 (7)	0.0423 (8)	0.0432 (8)	−0.0025 (6)	−0.0049 (6)	−0.0157 (7)
O5	0.0188 (6)	0.0481 (9)	0.0311 (7)	−0.0068 (6)	−0.0056 (5)	−0.0038 (6)
Zn1	0.01853 (15)	0.01801 (15)	0.01999 (15)	−0.00478 (11)	−0.00604 (10)	0.00264 (10)

Geometric parameters (Å, º)

C1—O1	1.431 (2)	C6—H6B	0.9700
C1—C2	1.518 (3)	C7—O4	1.255 (2)
C1—H1A	0.9700	C7—O5	1.257 (2)
C1—H1B	0.9700	C7—C8	1.511 (2)
C2—N1	1.483 (2)	C8—C10	1.390 (3)
C2—H2A	0.9700	C8—C9	1.393 (3)
C2—H2B	0.9700	C9—C10i	1.390 (3)
C3—O2	1.427 (2)	C9—H9	0.9300
C3—C4	1.511 (3)	C10—C9i	1.390 (3)
C3—H3A	0.9700	C10—H10	0.9300
C3—H3B	0.9700	N1—Zn1	2.1282 (16)
C4—N1	1.480 (2)	O1—Zn1	2.1529 (16)
C4—H4A	0.9700	O1—H1	0.815 (16)
C4—H4B	0.9700	O2—Zn1	2.1169 (16)
C5—N1	1.496 (2)	O2—H2	0.825 (16)
C5—C6	1.519 (3)	O3—H3	0.870 (16)
C5—H5A	0.9700	Zn1—O2ii	2.1169 (16)
C5—H5B	0.9700	Zn1—N1ii	2.1282 (16)
C6—O3	1.388 (3)	Zn1—O1ii	2.1529 (16)
C6—H6A	0.9700
O1—C1—C2	111.27 (16)	O5—C7—C8	118.64 (16)
O1—C1—H1A	109.4	C10—C8—C9	119.17 (16)
C2—C1—H1A	109.4	C10—C8—C7	121.09 (16)
O1—C1—H1B	109.4	C9—C8—C7	119.74 (16)
C2—C1—H1B	109.4	C10i—C9—C8	120.58 (17)
H1A—C1—H1B	108.0	C10i—C9—H9	119.7
N1—C2—C1	112.93 (16)	C8—C9—H9	119.7
N1—C2—H2A	109.0	C9i—C10—C8	120.26 (17)
C1—C2—H2A	109.0	C9i—C10—H10	119.9
N1—C2—H2B	109.0	C8—C10—H10	119.9
C1—C2—H2B	109.0	C4—N1—C2	113.25 (15)
H2A—C2—H2B	107.8	C4—N1—C5	109.91 (16)
O2—C3—C4	110.59 (16)	C2—N1—C5	112.28 (16)
O2—C3—H3A	109.5	C4—N1—Zn1	104.11 (11)
C4—C3—H3A	109.5	C2—N1—Zn1	108.27 (12)
O2—C3—H3B	109.5	C5—N1—Zn1	108.59 (12)
C4—C3—H3B	109.5	C1—O1—Zn1	107.34 (11)
H3A—C3—H3B	108.1	C1—O1—H1	108.2 (17)
N1—C4—C3	113.26 (16)	Zn1—O1—H1	120.1 (16)
N1—C4—H4A	108.9	C3—O2—Zn1	112.52 (11)
C3—C4—H4A	108.9	C3—O2—H2	108.0 (16)
N1—C4—H4B	108.9	Zn1—O2—H2	114.6 (16)
C3—C4—H4B	108.9	C6—O3—H3	106.6 (15)
H4A—C4—H4B	107.7	O2ii—Zn1—O2	180.00 (4)
N1—C5—C6	117.31 (18)	O2ii—Zn1—N1ii	81.99 (7)
N1—C5—H5A	108.0	O2—Zn1—N1ii	98.01 (7)
C6—C5—H5A	108.0	O2ii—Zn1—N1	98.01 (7)
N1—C5—H5B	108.0	O2—Zn1—N1	81.99 (7)
C6—C5—H5B	108.0	N1ii—Zn1—N1	180.0
H5A—C5—H5B	107.2	O2ii—Zn1—O1ii	90.41 (6)
O3—C6—C5	110.1 (2)	O2—Zn1—O1ii	89.59 (6)
O3—C6—H6A	109.6	N1ii—Zn1—O1ii	82.73 (7)
C5—C6—H6A	109.6	N1—Zn1—O1ii	97.27 (7)
O3—C6—H6B	109.6	O2ii—Zn1—O1	89.59 (6)
C5—C6—H6B	109.6	O2—Zn1—O1	90.41 (6)
H6A—C6—H6B	108.2	N1ii—Zn1—O1	97.27 (7)
O4—C7—O5	124.72 (16)	N1—Zn1—O1	82.73 (7)
O4—C7—C8	116.64 (16)	O1ii—Zn1—O1	180.00 (12)
O1—C1—C2—N1	47.2 (2)	C3—O2—Zn1—N1	4.13 (13)
O2—C3—C4—N1	−43.7 (2)	C3—O2—Zn1—O1ii	−93.26 (13)
N1—C5—C6—O3	68.3 (3)	C3—O2—Zn1—O1	86.74 (13)
O4—C7—C8—C10	178.15 (17)	C4—N1—Zn1—O2ii	154.45 (12)
O5—C7—C8—C10	−2.2 (3)	C2—N1—Zn1—O2ii	−84.78 (12)
O4—C7—C8—C9	−1.1 (3)	C5—N1—Zn1—O2ii	37.38 (13)
O5—C7—C8—C9	178.52 (17)	C4—N1—Zn1—O2	−25.55 (12)
C10—C8—C9—C10i	−0.3 (3)	C2—N1—Zn1—O2	95.22 (12)
C7—C8—C9—C10i	179.03 (16)	C5—N1—Zn1—O2	−142.62 (13)
C9—C8—C10—C9i	0.3 (3)	C4—N1—Zn1—N1ii	−80 (100)
C7—C8—C10—C9i	−179.02 (16)	C2—N1—Zn1—N1ii	41 (100)
C3—C4—N1—C2	−72.9 (2)	C5—N1—Zn1—N1ii	163 (100)
C3—C4—N1—C5	160.62 (17)	C4—N1—Zn1—O1ii	63.01 (12)
C3—C4—N1—Zn1	44.47 (18)	C2—N1—Zn1—O1ii	−176.22 (12)
C1—C2—N1—C4	87.9 (2)	C5—N1—Zn1—O1ii	−54.06 (13)
C1—C2—N1—C5	−146.89 (18)	C4—N1—Zn1—O1	−116.99 (12)
C1—C2—N1—Zn1	−27.01 (19)	C2—N1—Zn1—O1	3.78 (12)
C6—C5—N1—C4	48.9 (2)	C5—N1—Zn1—O1	125.94 (13)
C6—C5—N1—C2	−78.1 (2)	C1—O1—Zn1—O2ii	118.61 (13)
C6—C5—N1—Zn1	162.17 (16)	C1—O1—Zn1—O2	−61.39 (13)
C2—C1—O1—Zn1	−40.83 (19)	C1—O1—Zn1—N1ii	−159.52 (12)
C4—C3—O2—Zn1	18.7 (2)	C1—O1—Zn1—N1	20.48 (12)
C3—O2—Zn1—O2ii	116 (100)	C1—O1—Zn1—O1ii	−79 (100)
C3—O2—Zn1—N1ii	−175.87 (13)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5iii	0.82 (2)	1.82 (2)	2.632 (2)	177 (2)
O2—H2···O4iv	0.83 (2)	1.74 (2)	2.564 (2)	178 (2)
O3—H3···O5v	0.87 (2)	2.13 (2)	2.942 (3)	155 (2)

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