Crystal structure of di­aqua­(μ2-tri­ethyl­ene­tetra­minehexa­acetato)­dizinc tetra­hydrate

Liu, H.; Lu, L.-P.

doi:10.1107/S2056989015002108

metal-organic compounds

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ISSN: 2056-9890

Volume 71| Part 3| March 2015| Pages m55-m56

doi:10.1107/S2056989015002108

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Crystal structure of diaqua(μ₂-triethylenetetraminehexaacetato)dizinc tetrahydrate

Huan Liu ^a and Li-Ping Lu ^a ^*

^aInstitute of Molecular Science, Key Laboratory of Chemical Biology and Molecular Engineering of the Education Ministry, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China
^*Correspondence e-mail: luliping@sxu.edu.cn

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 12 January 2015; accepted 30 January 2015; online 7 February 2015)

The reaction of ZnO and triethylenetetraminehexaacetic 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] molecule in the crystalline state. Both Zn^II ions are octahedrally surrounded and bound by an N₂O₃ donor set from the H₂TTHA⁴⁻ anion and a water molecule; the N atoms are cis and the water molecule is trans to an N atom. The Zn⋯Zn separation is 7.562 (1) Å. An intramolecular C—H⋯O interaction is observed and both carboxylate 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.

Keywords: Crystal structure; binuclear Zn^II complex; triethylenetetraminehexaacetic acid; crystal structure.

CCDC reference: 1046672

1. 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 ).

2. Experimental

2.1. Crystal data

[Zn₂(C₁₈H₂₆N₄O₁₂)(H₂O)₂]·4H₂O
M_r = 729.26
Triclinic, $[P \overline 1]$
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

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.089
S = 0.99
2384 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O7	2.003 (2)
Zn1—O1	2.063 (2)
Zn1—O3	2.112 (2)
Zn1—O5	2.130 (2)
Zn1—N1	2.150 (2)
Zn1—N2	2.243 (2)

Table 2
Hydrogen-bond geometry (Å, °)

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⋯O8ⁱ	0.97	2.52	3.476 (4)	168
C5—H5B⋯O4ⁱⁱ	0.97	2.48	3.428 (4)	166
O7—H71⋯O1ⁱⁱⁱ	0.82	1.91	2.720 (3)	169
O7—H72⋯O8	0.82	1.83	2.627 (3)	164
O8—H81⋯O2ⁱⁱⁱ	0.82	1.94	2.747 (4)	166
O8—H82⋯O9	0.82	1.96	2.734 (4)	157
O9—H91⋯O5^iv	0.82	2.33	3.074 (4)	151
O9—H92⋯O6^v	0.82	2.33	3.033 (4)	144
Symmetry codes: (i) x, y-1, z; (ii) -x, -y, -z; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y+1, -z; (v) x+1, y, z.

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.

Supporting information

CCDC reference: 1046672

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

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

checkCIF report

Introduction top

Triethylenetetraminehexaacetic acid(H₆TTHA), a multidentate ligand having ten potential coordinating sites (six oxygen atoms and four nitrogen atoms), can play an important role in the self-assembly of chelating metals. It can be employed as a structure-directing agent to form main group metal complexes(Wullens et al., 1996, Thompson et al., 1998), transition-metal complexes(Song et al., 2003, Long et al., 2003, Qian et al., 2013, Carlson et al., 2010, Sethi et al., 2012), lanthanide complexes(Wang et al., 2003, Mondry & Starynowicz, 1998) and 3d–4f coordination polymers(Ouyang et al., 2007, Shi et al., 2006). To our knowledge, Zn(II) ions strongly inhibits many protein tyrosine phosphatases(Lu & Zhu, 2014). As part of the ongoing study of metal complexes inhibiting protein tyrosine phosphatases, the aim of us is to synthesize new zinc complexes employing polyamino polycarboxylic acids to form stable and soluble complexes. In this contribution, crystal structure of a binuclear zinc(II) complex of H₂TTHA is reported.

Experimental top

Synthesis and crystallization top

All chemicals were of reagent grade, commercially available and used without further purification. A mixture of H₆TTHA (0.050 g, 0.10 mmol) and ZnO (0.016 g, 0.20 mmol) in 50 mL of deionized water in a flask was refluxed for 6 h. The clear solution was cooled to room temperature and filtered. The colorless filtrate was set aside at room temperature for three weeks. The title complex crystal was obtained as colourless blocks with yield 45%. Elemental Analysis(%): Cald. C 29.73, H 4.99, N 7.70; found C 29.52, H 5.05, N 7.57. Selected IR(KBr, cm^-1): ν(O—H) 3445s, ν(C=O) 1732s, δ(O—H) 897m.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms attached to C of the title complex were placed in geometrically idealized positions with Csp³—H = 0.97Å and with Uiso(H) = 1.2Ueq(C). The carboxyl H4 and H6 atoms are each located close to a crystallographic inversion centre between pairs of symmetry equivalent atoms of O4 and O6. Both H atoms were thus refined as 50% occupied. The O—H distances were constrained to be 0.82 Å and Uiso= 1.5Ueq(O). H atoms attached to O(water) atoms were located from difference Fourier maps; their bond lengths were idealized to 0.82 Å and they were refined using a riding model, with Uiso(H) = 1.5Ueq(O).

Results and discussion top

The molecular structure and the crystal packing are depicted in Figures 1 and 2, respectively. Selected bond lengths and bond angles are listed in Table 1. The Zn(II) ion has a six-coordinate pseudo-octahedral environment with two N and three O atoms from ligand H₂TTHA anion as well as one water molecule. The complete binuclear molecule exists a centre of symmetry locating on the midpoint of bond C9—C9ⁱ (Symmetry code i -x, 2-y, 2-z). The distance of both Zn(II) ions in the complex is 7.562 (1) Å. The distance of Zn—O(water) is 2.003 (2) Å, which is the shortest in all coordinate bonds of the title complex, while Zn—O bond lengths are in the range of 2.063 (2) to 2.130 (2) Å, and the Zn—N bond lengths are 2.150 (3) and 2.243 (2) Å, respectively. All the geometrical features compare very well with those in some similar structures, such as [Zn(H₂O)₆][Zn₂(H₂O)₂(TTHA)].4H₂O(Carlson et al., 2010), [Co₂(H₂TTHA)(H₂O)₂].4H₂O(Qian et al., 2013).

In the structure of the title complex, numerous intermolecular hydrogen bonds (O—H···O; Table 3) play an important role in stabilizing the structure and linking ions and solvent water molecules. Additional nonclassical C—H···O hydrogen bonds (Table 3) occur in the structure, with C—H···O angles in the range 125–168° and C···O distances between 3.198 (4) and 3.476 (4) Å.

Related literature top

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).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. 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.
	Fig. 2. The packing diagram of the title compound, Zn dark green C gray, N blue,H light green, O red.

Diaqua(µ₂-triethylenetetraminehexaacetato)dizinc tetrahydrate top

Crystal data top

[Zn₂(C₁₈H₂₆N₄O₁₂)(H₂O)₂]·4H₂O	Z = 1
M_r = 729.26	F(000) = 378
Triclinic, P1	D_x = 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

Data collection top

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

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) = 0.089	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0505P)²] where P = (F_o² + 2F_c²)/3
2384 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

[Zn₂(C₁₈H₂₆N₄O₁₂)(H₂O)₂]·4H₂O	γ = 100.882 (3)°
M_r = 729.26	V = 686.2 (2) Å³
Triclinic, P1	Z = 1
a = 7.1330 (14) Å	Mo Kα radiation
b = 8.7013 (16) Å	µ = 1.84 mm⁻¹
c = 11.979 (2) Å	T = 298 K
α = 103.969 (2)°	0.28 × 0.22 × 0.20 mm
β = 101.052 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	2384 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2080 reflections with I > 2σ(I)
T_min = 0.627, T_max = 0.710	R_int = 0.057
3582 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 0.99	Δρ_max = 0.49 e Å⁻³
2384 reflections	Δρ_min = −0.76 e Å⁻³
190 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.82	1.91	2.720 (3)	169
O7—H72···O8	0.82	1.83	2.627 (3)	164
O8—H81···O2^iv	0.82	1.94	2.747 (4)	166
O8—H82···O9	0.82	1.96	2.734 (4)	157
O9—H91···O5^v	0.82	2.33	3.074 (4)	151
O9—H92···O6^vi	0.82	2.33	3.033 (4)	144

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

Selected bond lengths (Å) top

Zn1—O7	2.003 (2)	Zn1—O5	2.130 (2)
Zn1—O1	2.063 (2)	Zn1—N1	2.150 (2)
Zn1—O3	2.112 (2)	Zn1—N2	2.243 (2)

Hydrogen-bond geometry (Å, º) top

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···O8ⁱ	0.97	2.52	3.476 (4)	168
C5—H5B···O4ⁱⁱ	0.97	2.48	3.428 (4)	166
O7—H71···O1ⁱⁱⁱ	0.82	1.91	2.720 (3)	169
O7—H72···O8	0.82	1.83	2.627 (3)	164
O8—H81···O2ⁱⁱⁱ	0.82	1.94	2.747 (4)	166
O8—H82···O9	0.82	1.96	2.734 (4)	157
O9—H91···O5^iv	0.82	2.33	3.074 (4)	151
O9—H92···O6^v	0.82	2.33	3.033 (4)	144

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

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (grant No. 21171109), SRFDP (grant No. 20121401110005), the Natural Science Foundation of Shanxi Province of China (grant No. 2011011009–1) and the Research Project supported by Shanxi Scholarship Council of China (grant No. 2013–026).

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Volume 71| Part 3| March 2015| Pages m55-m56

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