Decaaqua-1κ5O,4κ5O-bis­(μ-nitrilo­triacetato)-1:2κ5O:N,O′,O′′,O′′′;3:4κ5N,O,O′,O′′:O′′′-μ-oxido-2:3κ2O:O-diperoxido-2κ2O,O′;3κ2O,O′-1,4-dicopper(II)-2,3-dititanium(IV) hepta­hydrate

Xie, X.-H.; Wang, B.-M.; Ng, S.W.

doi:10.1107/S1600536810004198

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages m271-m272

doi:10.1107/S1600536810004198

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Decaaqua-1κ⁵O,4κ⁵O-bis(μ-nitrilotriacetato)-1:2κ⁵O:N,O′,O′′,O′′′;3:4κ⁵N,O,O′,O′′:O′′′-μ-oxido-2:3κ²O:O-diperoxido-2κ²O,O′;3κ²O,O′-1,4-dicopper(II)-2,3-dititanium(IV) heptahydrate

Xiao-Hua Xie,^a Bai-Mu Wang ^b and Seik Weng Ng ^c ^*

^aCollege of Chinese Language and Culture, Jinan University, Guangzhou 510610, People's Republic of China, ^bOffice of Rongcheng Vocational College, Rongcheng Vocational College, Rongcheng 476600, People's Republic of China, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 26 January 2010; accepted 2 February 2010; online 6 February 2010)

The tetranuclear title compound, [Cu₂Ti₂(C₆H₆NO₆)₂O(O₂)₂(H₂O)₁₀]·7H₂O, lies about a twofold rotation axis that passes through the bridging oxide atom. The titanium atom is N,O,O′,O′′-chelated by the nitrilotriacetate and O,O′-chelated by the peroidxo group and is coordinated to the bridging O atom in an overall pentagonal-bipyramidal geometry. The O atom of one of the carboxylate –CO₂ groups binds to the water-coordinated Cu atom, whose coordination polyhedron is an elongated octahedron. Adjacent tetranuclear molecules are linked through the coordinated and uncoordinated water molecules by O—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For the hydrated sodium and ammonium salts of oxobis(nitrilotriacetatoperoxotitanates), see: Schwarzenbach & Girgis (1975 ); Zhou et al. (2004 ).

Experimental

Crystal data

[Cu₂Ti₂(C₆H₆NO₆)₂O(O₂)₂(H₂O)₁₀]·7H₂O
M_r = 985.39
Monoclinic, C 2/c
a = 14.9312 (10) Å
b = 13.2892 (9) Å
c = 17.4449 (10) Å
β = 100.825 (2)°
V = 3399.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.81 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Rigaku R-AXIS Spider IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.694, T_max = 1.000
16221 measured reflections
3894 independent reflections
3408 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.075
S = 1.08
3894 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H11⋯O6wⁱ	0.84	1.80	2.627 (2)	169
O1w—H12⋯O9wⁱⁱ	0.84	1.99	2.789 (1)	159
O2w—H21⋯O1wⁱ	0.84	1.91	2.746 (2)	173
O2w—H22⋯O1ⁱⁱⁱ	0.84	1.90	2.737 (2)	174
O3w—H31⋯O4^iv	0.84	1.93	2.746 (2)	165
O3w—H32⋯O4wⁱⁱⁱ	0.84	1.86	2.658 (2)	158
O4w—H4w1⋯O8ⁱⁱⁱ	0.84	1.85	2.693 (2)	176
O4w—H4w2⋯O8w	0.84	1.85	2.675 (2)	169
O5w—H51⋯O2^v	0.84	2.02	2.850 (2)	168
O5w—H52⋯O7w	0.84	2.01	2.813 (3)	161
O6w—H61⋯O5w	0.84	2.02	2.797 (2)	153
O6w—H62⋯O7w^vi	0.84	2.15	2.965 (3)	164
O7w—H71⋯O3	0.84	2.38	3.195 (2)	163
O7w—H72⋯O9^vii	0.84	2.07	2.900 (2)	168
O8w—H81⋯O3^viii	0.84	2.06	2.890 (2)	172
O8w—H82⋯O4^ix	0.84	2.33	3.148 (3)	164
O9w—H9⋯O2	0.84	1.89	2.716 (2)	170
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iv) $[x, -y+1, z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (vii) -x+1, -y+1, -z+1; (viii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ix) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 2002 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810004198/bt5183sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004198/bt5183Isup2.hkl

checkCIF report

Related literature top

For the hydrated sodium and ammonium salts of oxobis(nitrilotriacetatoperoxotitanates), see: Schwarzenbach & Girgis (1975); Zhou et al. (2004).

Experimental top

To a suspension of nitrilotriacetic acid (1.91 g, 10 mol) in water (30 ml) was added titanium tetrabutoxide (3.40 ml). After 12 hours, the mixture was allowed to cool to 273 K; 30% hydrogen peroxide (5 ml) was added. The mixture was filtered. The pH of the filtrate was raised to 4.0. Copper chloride dihydrate (1.70 g, 10 mol) was added. The solution was kept at 279 K for a week. Green crystals were collected and washed with water; the yield was 90%. CH&N elemental analysis. Found (Calc. for C₁₂H₄₆O₃₄N₂Cu₂Ti₂): C 14.59 (14.63), H 4.75 (4.71), N 2.82% (2.84%). The crystals do not dissolve in organic solvents.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2002); cell refinement: RAPID-AUTO (Rigaku, 2002); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of Cu₂Ti₂(O)(O₂)₂(H₂O)₁₀(C₆H₆NO₆)₂^.7H₂O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Decaaqua-1κ⁵O,4κ⁵O-bis(µ-nitrilotriacetato)- 1:2κ⁵O:N,O',O'',O'''; 3:4κ⁵N,O,O',O'':O'''-µ-oxido- 2:3κ²O:O-diperoxido- 2κ²O,O';3κ²O,O'-1,4-dicopper(II)- 2,3-dititanium(IV) heptahydrate top

Crystal data top

[Cu₂Ti₂(C₆H₆NO₆)₂O(O₂)₂(H₂O)₁₀]·7H₂O	F(000) = 2024
M_r = 985.39	D_x = 1.925 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 13230 reflections
a = 14.9312 (10) Å	θ = 3.1–27.5°
b = 13.2892 (9) Å	µ = 1.81 mm⁻¹
c = 17.4449 (10) Å	T = 293 K
β = 100.825 (2)°	Block, green
V = 3399.9 (4) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku R-AXIS Spider IP diffractometer	3894 independent reflections
Radiation source: fine-focus sealed tube	3408 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scan	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −19→19
T_min = 0.694, T_max = 1.000	k = −17→17
16221 measured reflections	l = −22→22

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0339P)² + 4.0704P] where P = (F_o² + 2F_c²)/3
3894 reflections	(Δ/σ)_max = 0.001
236 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Cu₂Ti₂(C₆H₆NO₆)₂O(O₂)₂(H₂O)₁₀]·7H₂O	V = 3399.9 (4) Å³
M_r = 985.39	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.9312 (10) Å	µ = 1.81 mm⁻¹
b = 13.2892 (9) Å	T = 293 K
c = 17.4449 (10) Å	0.30 × 0.20 × 0.20 mm
β = 100.825 (2)°

Data collection top

Rigaku R-AXIS Spider IP diffractometer	3894 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3408 reflections with I > 2σ(I)
T_min = 0.694, T_max = 1.000	R_int = 0.033
16221 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.08	Δρ_max = 0.44 e Å⁻³
3894 reflections	Δρ_min = −0.31 e Å⁻³
236 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.133265 (16)	0.615605 (19)	0.469933 (13)	0.02095 (8)
Ti1	0.42419 (2)	0.63347 (3)	0.319688 (18)	0.01718 (9)
O1	0.39888 (10)	0.78937 (11)	0.30661 (8)	0.0241 (3)
O2	0.36186 (12)	0.91179 (12)	0.21923 (9)	0.0331 (4)
O3	0.38194 (10)	0.48763 (11)	0.28694 (8)	0.0254 (3)
O4	0.31766 (13)	0.38625 (12)	0.19110 (10)	0.0355 (4)
O5	0.31248 (10)	0.63343 (12)	0.37559 (8)	0.0263 (3)
O6	0.16254 (10)	0.64622 (12)	0.36729 (8)	0.0254 (3)
O7	0.5000	0.63818 (16)	0.2500	0.0239 (4)
O8	0.50228 (10)	0.67667 (12)	0.41151 (8)	0.0280 (3)
O9	0.49544 (10)	0.56625 (12)	0.40498 (8)	0.0296 (3)
O1w	0.00795 (10)	0.58467 (12)	0.40849 (8)	0.0254 (3)
H11	−0.0307	0.6261	0.4188	0.038*
H12	0.0096	0.5890	0.3607	0.038*
O2w	0.08783 (12)	0.58514 (13)	0.56735 (9)	0.0358 (4)
H21	0.0557	0.5363	0.5765	0.054*
H22	0.0908	0.6269	0.6039	0.054*
O3w	0.25339 (11)	0.62901 (14)	0.53336 (9)	0.0360 (4)
H31	0.2639	0.6289	0.5824	0.054*
H32	0.2965	0.6587	0.5181	0.054*
O4w	0.09054 (10)	0.77903 (12)	0.47459 (8)	0.0274 (3)
H4w1	0.0638	0.7931	0.5115	0.041*
H4w2	0.0566	0.7959	0.4325	0.041*
O5w	0.17335 (12)	0.44158 (13)	0.44550 (9)	0.0355 (4)
H51	0.1595	0.4244	0.3984	0.053*
H52	0.2304	0.4418	0.4585	0.053*
O6w	0.12472 (12)	0.30720 (14)	0.55409 (10)	0.0394 (4)
H61	0.1311	0.3329	0.5114	0.059*
H62	0.1168	0.2450	0.5476	0.059*
O7w	0.36239 (13)	0.41472 (15)	0.45757 (11)	0.0466 (5)
H71	0.3780	0.4405	0.4181	0.070*
H72	0.4018	0.4295	0.4970	0.070*
O8w	−0.01007 (15)	0.80955 (16)	0.33263 (11)	0.0542 (5)
H81	−0.0423	0.8616	0.3237	0.081*
H82	0.0404	0.8207	0.3196	0.081*
O9w	0.5000	1.04750 (17)	0.2500	0.0319 (5)
H9	0.4536	1.0105	0.2432	0.048*
N1	0.30344 (11)	0.65163 (12)	0.21958 (9)	0.0170 (3)
C1	0.36250 (14)	0.82322 (15)	0.23904 (11)	0.0221 (4)
C2	0.32017 (14)	0.74543 (15)	0.17992 (11)	0.0224 (4)
H2A	0.2631	0.7709	0.1504	0.027*
H2B	0.3607	0.7322	0.1437	0.027*
C3	0.30488 (14)	0.56253 (15)	0.16936 (11)	0.0227 (4)
H3A	0.3465	0.5742	0.1337	0.027*
H3B	0.2445	0.5513	0.1387	0.027*
C4	0.33482 (14)	0.47085 (16)	0.21844 (11)	0.0227 (4)
C5	0.21789 (13)	0.65676 (17)	0.25076 (11)	0.0224 (4)
H5A	0.1768	0.6045	0.2264	0.027*
H5B	0.1888	0.7211	0.2368	0.027*
C6	0.23267 (13)	0.64436 (15)	0.33827 (11)	0.0191 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01981 (13)	0.02595 (14)	0.01754 (13)	−0.00436 (9)	0.00469 (9)	−0.00037 (9)
Ti1	0.01574 (17)	0.02177 (18)	0.01442 (16)	0.00001 (13)	0.00386 (12)	0.00014 (12)
O1	0.0284 (8)	0.0214 (7)	0.0208 (7)	0.0008 (6)	0.0002 (6)	−0.0029 (5)
O2	0.0396 (9)	0.0210 (8)	0.0352 (8)	−0.0057 (7)	−0.0017 (7)	0.0041 (6)
O3	0.0290 (8)	0.0202 (7)	0.0249 (7)	−0.0009 (6)	−0.0005 (6)	0.0013 (6)
O4	0.0464 (10)	0.0203 (8)	0.0360 (9)	0.0004 (7)	−0.0019 (7)	−0.0053 (6)
O5	0.0173 (7)	0.0438 (9)	0.0180 (6)	0.0002 (6)	0.0042 (5)	0.0011 (6)
O6	0.0192 (7)	0.0363 (8)	0.0220 (7)	−0.0003 (6)	0.0070 (5)	0.0019 (6)
O7	0.0205 (10)	0.0325 (11)	0.0195 (9)	0.000	0.0062 (8)	0.000
O8	0.0249 (8)	0.0365 (9)	0.0213 (7)	−0.0015 (7)	0.0006 (6)	−0.0035 (6)
O9	0.0281 (8)	0.0350 (9)	0.0243 (7)	0.0051 (7)	0.0013 (6)	0.0063 (6)
O1w	0.0247 (8)	0.0285 (8)	0.0241 (7)	−0.0044 (6)	0.0076 (6)	−0.0029 (6)
O2w	0.0535 (11)	0.0327 (9)	0.0258 (7)	−0.0203 (8)	0.0190 (7)	−0.0081 (7)
O3w	0.0266 (8)	0.0562 (11)	0.0233 (7)	−0.0132 (8)	0.0001 (6)	0.0062 (7)
O4w	0.0268 (8)	0.0330 (8)	0.0224 (7)	−0.0010 (6)	0.0049 (6)	−0.0035 (6)
O5w	0.0370 (9)	0.0380 (9)	0.0310 (8)	0.0004 (7)	0.0052 (7)	−0.0032 (7)
O6w	0.0345 (9)	0.0426 (10)	0.0420 (9)	−0.0011 (8)	0.0098 (7)	−0.0002 (8)
O7w	0.0379 (10)	0.0545 (12)	0.0443 (10)	−0.0041 (9)	−0.0006 (8)	0.0179 (9)
O8w	0.0553 (13)	0.0572 (13)	0.0454 (11)	0.0194 (10)	−0.0024 (9)	0.0064 (9)
O9w	0.0229 (11)	0.0308 (12)	0.0402 (12)	0.000	0.0008 (9)	0.000
N1	0.0187 (8)	0.0169 (8)	0.0159 (7)	−0.0022 (6)	0.0044 (6)	−0.0008 (6)
C1	0.0199 (10)	0.0219 (10)	0.0247 (9)	−0.0014 (8)	0.0047 (7)	0.0007 (8)
C2	0.0262 (10)	0.0216 (10)	0.0186 (9)	−0.0034 (8)	0.0020 (7)	0.0043 (8)
C3	0.0285 (11)	0.0207 (10)	0.0183 (9)	0.0008 (8)	0.0028 (7)	−0.0030 (7)
C4	0.0211 (9)	0.0244 (10)	0.0233 (9)	0.0014 (8)	0.0060 (7)	−0.0022 (8)
C5	0.0161 (9)	0.0312 (11)	0.0198 (9)	0.0008 (8)	0.0033 (7)	0.0006 (8)
C6	0.0199 (9)	0.0183 (9)	0.0200 (9)	−0.0017 (7)	0.0060 (7)	−0.0010 (7)

Geometric parameters (Å, º) top

Cu1—O3w	1.9308 (16)	O3w—H31	0.8399
Cu1—O6	1.9639 (14)	O3w—H32	0.8400
Cu1—O2w	1.9862 (15)	O4w—H4w1	0.8400
Cu1—O1w	2.0163 (15)	O4w—H4w2	0.8399
Cu1—O4w	2.2693 (16)	O5w—H51	0.8401
Cu1—O5w	2.4462 (17)	O5w—H52	0.8400
Ti1—O7	1.8110 (3)	O6w—H61	0.8400
Ti1—O9	1.8838 (14)	O6w—H62	0.8400
Ti1—O8	1.8850 (14)	O7w—H71	0.8400
Ti1—O5	2.0843 (14)	O7w—H72	0.8401
Ti1—O3	2.0845 (15)	O8w—H81	0.8400
Ti1—O1	2.1106 (15)	O8w—H82	0.8400
Ti1—N1	2.2751 (16)	O9w—H9	0.8401
O1—C1	1.283 (2)	N1—C2	1.470 (2)
O2—C1	1.226 (3)	N1—C3	1.475 (2)
O3—C4	1.287 (2)	N1—C5	1.481 (2)
O4—C4	1.229 (3)	C1—C2	1.512 (3)
O5—C6	1.254 (2)	C2—H2A	0.9700
O6—C6	1.246 (2)	C2—H2B	0.9700
O7—Ti1ⁱ	1.8110 (3)	C3—C4	1.508 (3)
O8—O9	1.474 (2)	C3—H3A	0.9700
O1w—H11	0.8400	C3—H3B	0.9700
O1w—H12	0.8401	C5—C6	1.510 (3)
O2w—H21	0.8400	C5—H5A	0.9700
O2w—H22	0.8400	C5—H5B	0.9700

O3w—Cu1—O6	99.30 (6)	Cu1—O2w—H22	122.5
O3w—Cu1—O2w	87.61 (7)	H21—O2w—H22	108.5
O6—Cu1—O2w	173.02 (7)	Cu1—O3w—H31	124.0
O3w—Cu1—O1w	173.18 (7)	Cu1—O3w—H32	123.1
O6—Cu1—O1w	84.30 (6)	H31—O3w—H32	108.4
O2w—Cu1—O1w	88.93 (6)	Cu1—O4w—H4w1	114.7
O3w—Cu1—O4w	97.37 (7)	Cu1—O4w—H4w2	110.6
O6—Cu1—O4w	86.94 (6)	H4w1—O4w—H4w2	108.4
O2w—Cu1—O4w	91.20 (6)	Cu1—O5w—H51	113.8
O1w—Cu1—O4w	88.57 (6)	Cu1—O5w—H52	102.6
O3w—Cu1—O5w	87.46 (7)	H51—O5w—H52	108.4
O6—Cu1—O5w	86.18 (6)	H61—O6w—H62	108.4
O2w—Cu1—O5w	95.19 (6)	H71—O7w—H72	108.4
O1w—Cu1—O5w	87.00 (6)	H81—O8w—H82	108.5
O4w—Cu1—O5w	172.15 (5)	C2—N1—C3	112.23 (14)
O7—Ti1—O9	102.42 (6)	C2—N1—C5	111.62 (16)
O7—Ti1—O8	101.25 (5)	C3—N1—C5	111.40 (15)
O9—Ti1—O8	46.04 (7)	C2—N1—Ti1	105.73 (11)
O7—Ti1—O5	165.95 (4)	C3—N1—Ti1	105.83 (11)
O9—Ti1—O5	90.75 (6)	C5—N1—Ti1	109.69 (11)
O8—Ti1—O5	91.38 (6)	O2—C1—O1	125.10 (19)
O7—Ti1—O3	92.48 (8)	O2—C1—C2	118.93 (18)
O9—Ti1—O3	82.68 (6)	O1—C1—C2	115.94 (17)
O8—Ti1—O3	128.55 (6)	N1—C2—C1	110.17 (15)
O5—Ti1—O3	84.28 (6)	N1—C2—H2A	109.6
O7—Ti1—O1	90.88 (8)	C1—C2—H2A	109.6
O9—Ti1—O1	127.87 (6)	N1—C2—H2B	109.6
O8—Ti1—O1	82.10 (6)	C1—C2—H2B	109.6
O5—Ti1—O1	84.72 (6)	H2A—C2—H2B	108.1
O3—Ti1—O1	147.58 (6)	N1—C3—C4	110.31 (15)
O7—Ti1—N1	89.21 (4)	N1—C3—H3A	109.6
O9—Ti1—N1	154.83 (7)	C4—C3—H3A	109.6
O8—Ti1—N1	153.44 (7)	N1—C3—H3B	109.6
O5—Ti1—N1	76.74 (6)	C4—C3—H3B	109.6
O3—Ti1—N1	74.50 (6)	H3A—C3—H3B	108.1
O1—Ti1—N1	73.32 (6)	O4—C4—O3	123.8 (2)
C1—O1—Ti1	118.67 (13)	O4—C4—C3	120.05 (18)
C4—O3—Ti1	120.00 (13)	O3—C4—C3	116.06 (18)
C6—O5—Ti1	121.52 (12)	N1—C5—C6	113.20 (16)
C6—O6—Cu1	135.58 (13)	N1—C5—H5A	108.9
Ti1—O7—Ti1ⁱ	176.04 (14)	C6—C5—H5A	108.9
O9—O8—Ti1	66.94 (8)	N1—C5—H5B	108.9
O8—O9—Ti1	67.02 (8)	C6—C5—H5B	108.9
Cu1—O1w—H11	111.0	H5A—C5—H5B	107.8
Cu1—O1w—H12	108.4	O6—C6—O5	125.48 (17)
H11—O1w—H12	108.4	O6—C6—C5	115.73 (17)
Cu1—O2w—H21	128.2	O5—C6—C5	118.79 (17)

O7—Ti1—O1—C1	60.95 (14)	O1—Ti1—N1—C2	34.18 (11)
O9—Ti1—O1—C1	167.48 (14)	O7—Ti1—N1—C3	62.26 (13)
O8—Ti1—O1—C1	162.18 (15)	O9—Ti1—N1—C3	−56.2 (2)
O5—Ti1—O1—C1	−105.68 (15)	O8—Ti1—N1—C3	176.38 (14)
O3—Ti1—O1—C1	−35.1 (2)	O5—Ti1—N1—C3	−118.19 (12)
N1—Ti1—O1—C1	−27.96 (14)	O3—Ti1—N1—C3	−30.53 (11)
O7—Ti1—O3—C4	−67.06 (15)	O1—Ti1—N1—C3	153.42 (13)
O9—Ti1—O3—C4	−169.27 (15)	O7—Ti1—N1—C5	−177.46 (14)
O8—Ti1—O3—C4	−173.57 (14)	O9—Ti1—N1—C5	64.1 (2)
O5—Ti1—O3—C4	99.23 (15)	O8—Ti1—N1—C5	−63.3 (2)
O1—Ti1—O3—C4	28.5 (2)	O5—Ti1—N1—C5	2.08 (12)
N1—Ti1—O3—C4	21.43 (14)	O3—Ti1—N1—C5	89.74 (13)
O7—Ti1—O5—C6	0.3 (4)	O1—Ti1—N1—C5	−86.31 (13)
O9—Ti1—O5—C6	−159.50 (16)	Ti1—O1—C1—O2	−163.57 (17)
O8—Ti1—O5—C6	154.45 (16)	Ti1—O1—C1—C2	14.5 (2)
O3—Ti1—O5—C6	−76.94 (16)	C3—N1—C2—C1	−152.71 (16)
O1—Ti1—O5—C6	72.52 (16)	C5—N1—C2—C1	81.41 (19)
N1—Ti1—O5—C6	−1.55 (15)	Ti1—N1—C2—C1	−37.80 (18)
O3w—Cu1—O6—C6	21.7 (2)	O2—C1—C2—N1	−163.33 (19)
O1w—Cu1—O6—C6	−152.5 (2)	O1—C1—C2—N1	18.4 (2)
O4w—Cu1—O6—C6	118.6 (2)	C2—N1—C3—C4	151.50 (17)
O5w—Cu1—O6—C6	−65.1 (2)	C5—N1—C3—C4	−82.5 (2)
O7—Ti1—O8—O9	−96.49 (10)	Ti1—N1—C3—C4	36.65 (18)
O5—Ti1—O8—O9	89.71 (9)	Ti1—O3—C4—O4	170.04 (17)
O3—Ti1—O8—O9	5.92 (11)	Ti1—O3—C4—C3	−6.4 (2)
O1—Ti1—O8—O9	174.19 (9)	N1—C3—C4—O4	160.50 (19)
N1—Ti1—O8—O9	152.02 (13)	N1—C3—C4—O3	−22.9 (2)
O7—Ti1—O9—O8	93.73 (10)	C2—N1—C5—C6	−119.28 (18)
O5—Ti1—O9—O8	−91.20 (9)	C3—N1—C5—C6	114.39 (18)
O3—Ti1—O9—O8	−175.33 (9)	Ti1—N1—C5—C6	−2.4 (2)
O1—Ti1—O9—O8	−7.30 (11)	Cu1—O6—C6—O5	−11.1 (3)
N1—Ti1—O9—O8	−150.44 (14)	Cu1—O6—C6—C5	169.07 (15)
O7—Ti1—N1—C2	−56.98 (13)	Ti1—O5—C6—O6	−179.24 (16)
O9—Ti1—N1—C2	−175.44 (15)	Ti1—O5—C6—C5	0.6 (3)
O8—Ti1—N1—C2	57.15 (19)	N1—C5—C6—O6	−178.72 (17)
O5—Ti1—N1—C2	122.57 (13)	N1—C5—C6—O5	1.4 (3)
O3—Ti1—N1—C2	−149.77 (13)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O6wⁱⁱ	0.84	1.80	2.627 (2)	169
O1w—H12···O9wⁱⁱⁱ	0.84	1.99	2.789 (1)	159
O2w—H21···O1wⁱⁱ	0.84	1.91	2.746 (2)	173
O2w—H22···O1^iv	0.84	1.90	2.737 (2)	174
O3w—H31···O4^v	0.84	1.93	2.746 (2)	165
O3w—H32···O4w^iv	0.84	1.86	2.658 (2)	158
O4w—H4w1···O8^iv	0.84	1.85	2.693 (2)	176
O4w—H4w2···O8w	0.84	1.85	2.675 (2)	169
O5w—H51···O2^vi	0.84	2.02	2.850 (2)	168
O5w—H52···O7w	0.84	2.01	2.813 (3)	161
O6w—H61···O5w	0.84	2.02	2.797 (2)	153
O6w—H62···O7w^vii	0.84	2.15	2.965 (3)	164
O7w—H71···O3	0.84	2.38	3.195 (2)	163
O7w—H72···O9^viii	0.84	2.07	2.900 (2)	168
O8w—H81···O3^ix	0.84	2.06	2.890 (2)	172
O8w—H82···O4^x	0.84	2.33	3.148 (3)	164
O9w—H9···O2	0.84	1.89	2.716 (2)	170

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

Experimental details

Crystal data
Chemical formula	[Cu₂Ti₂(C₆H₆NO₆)₂O(O₂)₂(H₂O)₁₀]·7H₂O
M_r	985.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	14.9312 (10), 13.2892 (9), 17.4449 (10)
β (°)	100.825 (2)
V (Å³)	3399.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.81
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS Spider IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.694, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16221, 3894, 3408
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.075, 1.08
No. of reflections	3894
No. of parameters	236
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.31

Computer programs: RAPID-AUTO (Rigaku, 2002), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O6wⁱ	0.84	1.80	2.627 (2)	169
O1w—H12···O9wⁱⁱ	0.84	1.99	2.789 (1)	159
O2w—H21···O1wⁱ	0.84	1.91	2.746 (2)	173
O2w—H22···O1ⁱⁱⁱ	0.84	1.90	2.737 (2)	174
O3w—H31···O4^iv	0.84	1.93	2.746 (2)	165
O3w—H32···O4wⁱⁱⁱ	0.84	1.86	2.658 (2)	158
O4w—H4w1···O8ⁱⁱⁱ	0.84	1.85	2.693 (2)	176
O4w—H4w2···O8w	0.84	1.85	2.675 (2)	169
O5w—H51···O2^v	0.84	2.02	2.850 (2)	168
O5w—H52···O7w	0.84	2.01	2.813 (3)	161
O6w—H61···O5w	0.84	2.02	2.797 (2)	153
O6w—H62···O7w^vi	0.84	2.15	2.965 (3)	164
O7w—H71···O3	0.84	2.38	3.195 (2)	163
O7w—H72···O9^vii	0.84	2.07	2.900 (2)	168
O8w—H81···O3^viii	0.84	2.06	2.890 (2)	172
O8w—H82···O4^ix	0.84	2.33	3.148 (3)	164
O9w—H9···O2	0.84	1.89	2.716 (2)	170

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1/2, y−1/2, z; (iii) −x+1/2, −y+3/2, −z+1; (iv) x, −y+1, z+1/2; (v) −x+1/2, y−1/2, −z+1/2; (vi) −x+1/2, −y+1/2, −z+1; (vii) −x+1, −y+1, −z+1; (viii) x−1/2, y+1/2, z; (ix) −x+1/2, y+1/2, −z+1/2.

Acknowledgements

We thank the the National Science Foundation of China (No. 20971045-B0103303) and the University of Malaya for supporting this study.

References

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