Crystal structure of di-aqua-(μ2-tri-ethyl-ene-tetra-minehexa-acetato)-dizinc tetra-hydrate.

The reaction of ZnO and tri-ethyl-ene-tetra-minehexaacetic acid (H6TTHA) in aqueous solution after refluxing yields the binuclear title compound, [Zn2(C18H26N4O12)(H2O)2]·4H2O. There is a centre of symmetry in the [Zn2(H2TTHA)(H2O)2] mol-ecule in the crystalline state. Both Zn(II) ions are octahedrally surrounded and bound by an N2O3 donor set from the H2TTHA(4-) anion and a water mol-ecule; the N atoms are cis and the water mol-ecule is trans to an N atom. The Zn⋯Zn separation is 7.562 (1) Å. An intra-molecular C-H⋯O inter-action is observed and both carboxyl-ate H atoms are disordered over two adjacent sites. In the crystal, the components are linked by O-H⋯O and C-H⋯O hydrogen bonds generating a three-dimensonal network.

Related literature

For general background to the complexes of tri­ethyl­ene­tetra­minehexaacetic acid, see: Long et al. (2003 ▸); Lu & Zhu (2014 ▸); Mondry & Starynowicz (1998 ▸); Ouyang et al. (2007 ▸); Sethi et al. (2012 ▸); Shi et al. (2006 ▸); Song et al. (2003 ▸); Thompson et al. (1998 ▸); Wang et al. (2003 ▸); Wullens et al. (1996 ▸). For related structures, see: Carlson et al. (2010 ▸); Qian et al. (2013 ▸).

Experimental

Crystal data

[Zn2(C18H26N4O12)(H2O)2]·4H2O

M = 729.26

Triclinic,

a = 7.1330 (14) Å

b = 8.7013 (16) Å

c = 11.979 (2) Å

α = 103.969 (2)°

β = 101.052 (2)°

γ = 100.882 (3)°

V = 686.2 (2) Å3

Z = 1

Mo Kα radiation

μ = 1.84 mm−1

T = 298 K

0.28 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▸) T min = 0.627, T max = 0.710

3582 measured reflections

2384 independent reflections

2080 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.089

S = 0.99

2384 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.76 e Å−3

Data collection: SMART (Bruker, 2000 ▸); cell refinement: SAINT (Bruker, 2000 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL/PC.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015002108/hb7351sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002108/hb7351Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015002108/hb7351fig1.tif

A view of the structure of the title complex with displacement ellipsoids drawn at the 50% probability level. Dash open line indicates hydrogen bonding inter­action.

Click here for additional data file.

. DOI: 10.1107/S2056989015002108/hb7351fig2.tif

The packing diagram of the title compound, Zn dark green C gray, N blue,H light green, O red.

CCDC reference: 1046672

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

[Zn2(C18H26N4O12)(H2O)2]·4H2O	Z = 1
Mr = 729.26	F(000) = 378
Triclinic, P1	Dx = 1.765 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1330 (14) Å	Cell parameters from 2008 reflections
b = 8.7013 (16) Å	θ = 2.6–26.9°
c = 11.979 (2) Å	µ = 1.84 mm−1
α = 103.969 (2)°	T = 298 K
β = 101.052 (2)°	Block, colorless
γ = 100.882 (3)°	0.28 × 0.22 × 0.20 mm
V = 686.2 (2) Å3

Bruker SMART APEX CCD diffractometer	2384 independent reflections
Radiation source: fine-focus sealed tube	2080 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→8
Tmin = 0.627, Tmax = 0.710	k = −10→10
3582 measured reflections	l = −14→9

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) = 0.089	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0505P)2] where P = (Fo2 + 2Fc2)/3
2384 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.75 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.27323 (5)	0.29051 (4)	0.29273 (3)	0.02494 (14)
N1	0.0979 (4)	0.0459 (3)	0.2561 (2)	0.0249 (5)
N2	0.0131 (4)	0.3615 (3)	0.3509 (2)	0.0257 (5)
O1	0.3853 (3)	0.2527 (2)	0.45320 (18)	0.0296 (5)
O2	0.3234 (4)	0.0827 (3)	0.5614 (2)	0.0516 (7)
O3	0.4168 (3)	0.1580 (3)	0.17890 (19)	0.0331 (5)
O4	0.3493 (3)	−0.0649 (3)	0.0251 (2)	0.0390 (6)
H4	0.4574	−0.0369	0.0120	0.058*	0.50
O5	0.1248 (3)	0.3442 (3)	0.14014 (18)	0.0312 (5)
O6	−0.0748 (4)	0.4953 (3)	0.0850 (2)	0.0437 (6)
H6	−0.0393	0.4897	0.0232	0.065*	0.50
O7	0.4665 (3)	0.5080 (2)	0.3369 (2)	0.0377 (5)
H71	0.5033	0.5712	0.4042	0.057*
H72	0.4553	0.5622	0.2898	0.057*
C1	0.3041 (5)	0.1170 (4)	0.4670 (3)	0.0315 (7)
C2	0.1742 (5)	−0.0156 (4)	0.3559 (3)	0.0332 (7)
H2A	0.2499	−0.0926	0.3294	0.040*
H2B	0.0634	−0.0747	0.3772	0.040*
C3	0.3124 (4)	0.0213 (4)	0.1162 (3)	0.0293 (7)
C4	0.1217 (5)	−0.0520 (4)	0.1428 (3)	0.0300 (7)
H4A	0.0114	−0.0583	0.0789	0.036*
H4B	0.1204	−0.1623	0.1467	0.036*
C5	−0.1051 (4)	0.0634 (4)	0.2504 (3)	0.0341 (7)
H5A	−0.1871	−0.0370	0.2539	0.041*
H5B	−0.1585	0.0825	0.1756	0.041*
C6	−0.1089 (4)	0.2049 (4)	0.3529 (3)	0.0308 (7)
H6A	−0.2438	0.2133	0.3478	0.037*
H6B	−0.0602	0.1835	0.4275	0.037*
C7	−0.0878 (5)	0.4310 (4)	0.2619 (3)	0.0383 (8)
H7A	−0.0791	0.5449	0.2996	0.046*
H7B	−0.2262	0.3740	0.2356	0.046*
C8	−0.0028 (5)	0.4194 (4)	0.1545 (3)	0.0303 (7)
C9	0.0821 (4)	0.4801 (4)	0.4711 (3)	0.0293 (7)
H9A	0.1606	0.5808	0.4657	0.035*
H9B	0.1671	0.4367	0.5221	0.035*
O8	0.4369 (4)	0.7275 (3)	0.2220 (2)	0.0575 (7)
H81	0.5196	0.7918	0.2798	0.086*
H82	0.4963	0.6924	0.1731	0.086*
O9	0.6210 (6)	0.6889 (4)	0.0405 (3)	0.0923 (12)
H91	0.6512	0.6831	−0.0229	0.138*
H92	0.6638	0.6205	0.0673	0.138*

	U11	U22	U33	U12	U13	U23
Zn1	0.0260 (2)	0.0262 (2)	0.0228 (2)	0.00595 (14)	0.00896 (14)	0.00540 (14)
N1	0.0269 (13)	0.0268 (12)	0.0197 (13)	0.0050 (10)	0.0083 (10)	0.0037 (10)
N2	0.0287 (14)	0.0320 (13)	0.0212 (13)	0.0122 (11)	0.0122 (11)	0.0081 (11)
O1	0.0362 (12)	0.0283 (11)	0.0223 (11)	0.0051 (9)	0.0041 (9)	0.0079 (9)
O2	0.0700 (18)	0.0531 (15)	0.0268 (13)	0.0008 (13)	0.0058 (12)	0.0186 (12)
O3	0.0289 (12)	0.0353 (12)	0.0319 (13)	0.0060 (10)	0.0140 (10)	0.0003 (10)
O4	0.0419 (14)	0.0420 (13)	0.0306 (13)	0.0098 (11)	0.0181 (10)	−0.0007 (11)
O5	0.0339 (12)	0.0416 (12)	0.0242 (11)	0.0155 (10)	0.0122 (9)	0.0121 (10)
O6	0.0534 (16)	0.0635 (16)	0.0340 (13)	0.0340 (13)	0.0195 (12)	0.0288 (12)
O7	0.0442 (14)	0.0321 (12)	0.0300 (13)	−0.0023 (10)	0.0068 (10)	0.0075 (10)
C1	0.0356 (18)	0.0370 (17)	0.0258 (17)	0.0140 (15)	0.0111 (14)	0.0097 (14)
C2	0.0449 (19)	0.0280 (16)	0.0296 (18)	0.0088 (14)	0.0127 (15)	0.0111 (14)
C3	0.0320 (17)	0.0348 (17)	0.0245 (17)	0.0140 (14)	0.0092 (14)	0.0086 (14)
C4	0.0348 (18)	0.0285 (15)	0.0231 (16)	0.0047 (13)	0.0093 (13)	0.0017 (13)
C5	0.0263 (17)	0.0383 (18)	0.0325 (18)	0.0018 (14)	0.0097 (14)	0.0038 (15)
C6	0.0256 (16)	0.0378 (17)	0.0302 (18)	0.0066 (14)	0.0136 (13)	0.0074 (14)
C7	0.043 (2)	0.055 (2)	0.0338 (19)	0.0285 (17)	0.0212 (16)	0.0214 (17)
C8	0.0318 (17)	0.0341 (17)	0.0258 (17)	0.0094 (14)	0.0080 (13)	0.0088 (14)
C9	0.0277 (16)	0.0328 (16)	0.0285 (17)	0.0088 (14)	0.0136 (13)	0.0048 (13)
O8	0.0607 (18)	0.0574 (17)	0.0524 (17)	0.0100 (14)	0.0120 (14)	0.0173 (14)
O9	0.115 (3)	0.089 (2)	0.108 (3)	0.047 (2)	0.076 (3)	0.036 (2)

Zn1—O7	2.003 (2)	C1—C2	1.530 (4)
Zn1—O1	2.063 (2)	C2—H2A	0.9700
Zn1—O3	2.112 (2)	C2—H2B	0.9700
Zn1—O5	2.130 (2)	C3—C4	1.516 (4)
Zn1—N1	2.150 (2)	C4—H4A	0.9700
Zn1—N2	2.243 (2)	C4—H4B	0.9700
N1—C5	1.474 (4)	C5—C6	1.523 (4)
N1—C4	1.477 (4)	C5—H5A	0.9700
N1—C2	1.477 (4)	C5—H5B	0.9700
N2—C6	1.480 (4)	C6—H6A	0.9700
N2—C7	1.483 (4)	C6—H6B	0.9700
N2—C9	1.483 (4)	C7—C8	1.514 (4)
O1—C1	1.277 (4)	C7—H7A	0.9700
O2—C1	1.227 (4)	C7—H7B	0.9700
O3—C3	1.246 (4)	C9—C9i	1.523 (5)
O4—C3	1.270 (4)	C9—H9A	0.9700
O4—H4	0.8200	C9—H9B	0.9700
O5—C8	1.232 (4)	O8—H81	0.8203
O6—C8	1.274 (4)	O8—H82	0.8203
O6—H6	0.8199	O9—H91	0.8207
O7—H71	0.8199	O9—H92	0.8211
O7—H72	0.8200
O7—Zn1—O1	91.79 (8)	N1—C2—H2B	108.6
O7—Zn1—O3	97.19 (9)	C1—C2—H2B	108.6
O1—Zn1—O3	102.29 (8)	H2A—C2—H2B	107.6
O7—Zn1—O5	88.93 (9)	O3—C3—O4	124.8 (3)
O1—Zn1—O5	171.03 (8)	O3—C3—C4	120.6 (3)
O3—Zn1—O5	86.48 (8)	O4—C3—C4	114.6 (3)
O7—Zn1—N1	172.37 (9)	N1—C4—C3	111.7 (2)
O1—Zn1—N1	82.46 (8)	N1—C4—H4A	109.3
O3—Zn1—N1	79.26 (9)	C3—C4—H4A	109.3
O5—Zn1—N1	97.53 (9)	N1—C4—H4B	109.3
O7—Zn1—N2	101.71 (9)	C3—C4—H4B	109.3
O1—Zn1—N2	92.61 (9)	H4A—C4—H4B	107.9
O3—Zn1—N2	155.51 (9)	N1—C5—C6	110.8 (2)
O5—Zn1—N2	78.50 (8)	N1—C5—H5A	109.5
N1—Zn1—N2	83.63 (9)	C6—C5—H5A	109.5
C5—N1—C4	113.2 (2)	N1—C5—H5B	109.5
C5—N1—C2	112.3 (2)	C6—C5—H5B	109.5
C4—N1—C2	111.4 (2)	H5A—C5—H5B	108.1
C5—N1—Zn1	104.87 (18)	N2—C6—C5	111.6 (2)
C4—N1—Zn1	107.68 (17)	N2—C6—H6A	109.3
C2—N1—Zn1	106.79 (18)	C5—C6—H6A	109.3
C6—N2—C7	112.4 (3)	N2—C6—H6B	109.3
C6—N2—C9	111.3 (2)	C5—C6—H6B	109.3
C7—N2—C9	112.1 (2)	H6A—C6—H6B	108.0
C6—N2—Zn1	103.30 (16)	N2—C7—C8	113.6 (2)
C7—N2—Zn1	108.16 (17)	N2—C7—H7A	108.8
C9—N2—Zn1	109.12 (17)	C8—C7—H7A	108.8
C1—O1—Zn1	115.50 (19)	N2—C7—H7B	108.8
C3—O3—Zn1	113.58 (19)	C8—C7—H7B	108.8
C3—O4—H4	118.3	H7A—C7—H7B	107.7
C8—O5—Zn1	116.02 (19)	O5—C8—O6	125.4 (3)
C8—O6—H6	118.2	O5—C8—C7	121.3 (3)
Zn1—O7—H71	123.8	O6—C8—C7	113.3 (3)
Zn1—O7—H72	117.0	N2—C9—C9i	114.6 (3)
H71—O7—H72	108.0	N2—C9—H9A	108.6
O2—C1—O1	125.6 (3)	C9i—C9—H9A	108.6
O2—C1—C2	117.1 (3)	N2—C9—H9B	108.6
O1—C1—C2	117.3 (3)	C9i—C9—H9B	108.6
N1—C2—C1	114.6 (2)	H9A—C9—H9B	107.6
N1—C2—H2A	108.6	H81—O8—H82	107.0
C1—C2—H2A	108.6	H91—O9—H92	106.8
O1—Zn1—N1—C5	111.87 (18)	O7—Zn1—O5—C8	−87.6 (2)
O3—Zn1—N1—C5	−144.02 (19)	O3—Zn1—O5—C8	175.2 (2)
O5—Zn1—N1—C5	−59.08 (19)	N1—Zn1—O5—C8	96.5 (2)
N2—Zn1—N1—C5	18.38 (18)	N2—Zn1—O5—C8	14.6 (2)
O1—Zn1—N1—C4	−127.26 (19)	Zn1—O1—C1—O2	−166.3 (3)
O3—Zn1—N1—C4	−23.16 (18)	Zn1—O1—C1—C2	14.7 (3)
O5—Zn1—N1—C4	61.78 (19)	C5—N1—C2—C1	−97.9 (3)
N2—Zn1—N1—C4	139.24 (19)	C4—N1—C2—C1	133.9 (3)
O1—Zn1—N1—C2	−7.52 (18)	Zn1—N1—C2—C1	16.6 (3)
O3—Zn1—N1—C2	96.59 (19)	O2—C1—C2—N1	159.0 (3)
O5—Zn1—N1—C2	−178.48 (18)	O1—C1—C2—N1	−21.9 (4)
N2—Zn1—N1—C2	−101.02 (19)	Zn1—O3—C3—O4	164.5 (2)
O7—Zn1—N2—C6	−164.05 (17)	Zn1—O3—C3—C4	−13.1 (4)
O1—Zn1—N2—C6	−71.68 (18)	C5—N1—C4—C3	138.9 (3)
O3—Zn1—N2—C6	56.2 (3)	C2—N1—C4—C3	−93.3 (3)
O5—Zn1—N2—C6	109.49 (18)	Zn1—N1—C4—C3	23.4 (3)
N1—Zn1—N2—C6	10.43 (18)	O3—C3—C4—N1	−7.9 (4)
O7—Zn1—N2—C7	76.6 (2)	O4—C3—C4—N1	174.3 (2)
O1—Zn1—N2—C7	169.0 (2)	C4—N1—C5—C6	−162.2 (3)
O3—Zn1—N2—C7	−63.1 (3)	C2—N1—C5—C6	70.6 (3)
O5—Zn1—N2—C7	−9.9 (2)	Zn1—N1—C5—C6	−45.0 (3)
N1—Zn1—N2—C7	−108.9 (2)	C7—N2—C6—C5	78.5 (3)
O7—Zn1—N2—C9	−45.53 (19)	C9—N2—C6—C5	−154.9 (3)
O1—Zn1—N2—C9	46.84 (19)	Zn1—N2—C6—C5	−37.9 (3)
O3—Zn1—N2—C9	174.73 (19)	N1—C5—C6—N2	59.6 (3)
O5—Zn1—N2—C9	−131.99 (19)	C6—N2—C7—C8	−107.8 (3)
N1—Zn1—N2—C9	128.95 (19)	C9—N2—C7—C8	126.0 (3)
O7—Zn1—O1—C1	−178.9 (2)	Zn1—N2—C7—C8	5.6 (3)
O3—Zn1—O1—C1	−81.1 (2)	Zn1—O5—C8—O6	162.7 (3)
N1—Zn1—O1—C1	−3.9 (2)	Zn1—O5—C8—C7	−16.4 (4)
N2—Zn1—O1—C1	79.3 (2)	N2—C7—C8—O5	6.7 (5)
O7—Zn1—O3—C3	−166.2 (2)	N2—C7—C8—O6	−172.5 (3)
O1—Zn1—O3—C3	100.4 (2)	C6—N2—C9—C9i	−58.1 (4)
O5—Zn1—O3—C3	−77.7 (2)	C7—N2—C9—C9i	68.7 (4)
N1—Zn1—O3—C3	20.6 (2)	Zn1—N2—C9—C9i	−171.5 (3)
N2—Zn1—O3—C3	−25.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O1	0.97	2.54	3.198 (4)	125
C2—H2A···O8ii	0.97	2.52	3.476 (4)	168
C5—H5B···O4iii	0.97	2.48	3.428 (4)	166
O7—H71···O1iv	0.82	1.91	2.720 (3)	169
O7—H72···O8	0.82	1.83	2.627 (3)	164
O8—H81···O2iv	0.82	1.94	2.747 (4)	166
O8—H82···O9	0.82	1.96	2.734 (4)	157
O9—H91···O5v	0.82	2.33	3.074 (4)	151
O9—H92···O6vi	0.82	2.33	3.033 (4)	144

Table 1

Selected bond lengths ()

Zn1O7	2.003(2)
Zn1O1	2.063(2)
Zn1O3	2.112(2)
Zn1O5	2.130(2)
Zn1N1	2.150(2)
Zn1N2	2.243(2)

Table 2

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C9H9BO1	0.97	2.54	3.198(4)	125
C2H2AO8i	0.97	2.52	3.476(4)	168
C5H5BO4ii	0.97	2.48	3.428(4)	166
O7H71O1iii	0.82	1.91	2.720(3)	169
O7H72O8	0.82	1.83	2.627(3)	164
O8H81O2iii	0.82	1.94	2.747(4)	166
O8H82O9	0.82	1.96	2.734(4)	157
O9H91O5iv	0.82	2.33	3.074(4)	151
O9H92O6v	0.82	2.33	3.033(4)	144

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