Structural diversity, magnetic properties and luminescence of Ni^II, Co^II and Zn^II coordination polymers derived from 3,3′-[(5-carb­oxy-1,3-phenyl­ene)bis­(­oxy)]di­benzoic acid and 1,10-phenanthroline

Three novel coordination polymers (CPs), namely poly[[di-μ-aqua-bis­{μ₄-3,3′-[(5-carboxyl­ato-1,3-phenyl­ene)bis­(­oxy)]dibenzoato-κ⁵O¹:O^1′,O³:O⁵:O^5′}bis­(1,10-phenanthroline-κ²N,N′)trinickel(II)] di­methyl­formamide 1.5-solvate tri­hydrate], {[Ni₃(C₂₁H₁₁O₈)₂(C₁₂H₈N₂)₂(H₂O)₂]·1.5C₃H₇NO·3H₂O}_n, (I), poly[[di-μ-aqua-bis­{μ₄-3,3′-[(5-carboxyl­ato-1,3-phenyl­ene)bis­(­oxy)]dibenzoato-κ⁵O¹:O^1′,O³:O⁵:O^5′}bis­(1,10-phenanthroline-κ²N,N′)tricobalt(II)] di­ethyl­amine disolvate tetrahydrate], {[Co₃(C₂₁H₁₁O₈)₂(C₁₂H₈N₂)₂(H₂O)₂]·2C₂H₇N·4H₂O}_n, (II), and catena-poly[[aqua­(1,10-phenanthroline-κ²N,N′)zinc(II)]-μ-5-(3-carb­oxy­phen­oxy)-3,3′-oxy­dibenzoato-κ²O¹:O³], [Zn(C₂₁H₁₂O₈)(C₁₂H₈N₂)(H₂O)]_n, (III), have been syn­thesized by the reaction of different metal ions (Ni²⁺, Co²⁺ and Zn²⁺), 3,3′-[(5-carb­oxy-1,3-phenyl­bis­(­oxy)]di­benzoic acid (H₃cpboda) and 1,10-phenanthroline (phen) under solvothermal conditions. All the CPs were characterized by elemental analysis, single-crystal and powder X-ray diffraction, FT–IR spectroscopy and thermogravimetric analysis. Complexes (I) and (II) have isomorphous structures, featuring similar linear trinuclear structural units, in which the central Ni^II/Co^II atom is located on an inversion centre with a slightly distorted octa­hedral [NiO₆]/[CoO₆] geometry. This com­prises four carboxyl­ate O-atom donors from two cpboda³⁻ ligands and two O-atom donors from bridging water mol­ecules. The terminal Ni^II/Co^II groups are each connected to the central Ni^II/Co^II cation through two μ_1,3-carboxyl­ate groups from two cpboda³⁻ ligands and one water bridge, giving rise to linear trinuclear [M₃(μ₂-H₂O)₂(RCOO)₄] (M = Ni²⁺/Co²⁺) secondary building units (SBUs) and the SBUs develop two-dimensional-networks parallel to the (100) plane via cpboda³⁻ ligands with new (3²·4)₂(3²·8³·9)₂(3⁴·4².8²·9⁴·10³) topological structures. Zinc com­plex (III) displays one-dimensional coordination chains and the five-coordinated Zn atom forms a distorted square-pyramidal [ZnO₃N₂] geometry, which is com­pleted by two carboxyl­ate O-atom donors from two distinct Hcpboda²⁻ ligands, one O atom from H₂O and two N atoms from a chelating phen ligand. Magnetically, CP (I) shows weak ferromagnetic inter­actions involving the carboxyl­ate groups, and bridging water mol­ecules between the nickel(II) ions, and CP (II) shows anti­ferromagnetic inter­actions between the Co²⁺ ions. The solid-state luminescence properties of CP (III) were examined at ambient temperature and the luminescence sensing of Cr₂O₇²⁻/CrO₄²⁻ anions in aqueous solution for (III) has also been investigated.

Computing details

For all structures, data collection: APEX2 (Bruker, 2010); cell refinement: SHELXTL (Sheldrick, 2015a); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Poly[[di-µ-aqua-bis{µ₄-3,3'-[(5-carboxylato-1,3-phenylene)bis(oxy)]dibenzoato-κ⁵O¹:O²:O³:O⁴:O⁵}bis(1,10-phenanthroline)trinickel(II)] dimethylformamide 1.5-solvate trihydrate] (I)

Crystal data

[Ni3(C21H11O8)2(C12H8N2)2(H2O)2]·1.5C3H7NO·3H2O	F(000) = 3136
Mr = 1518.85	Dx = 1.578 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.7272 (15) Å	Cell parameters from 7895 reflections
b = 15.8769 (9) Å	θ = 3.3–28.0°
c = 19.7083 (19) Å	µ = 0.96 mm^−1
β = 132.5245 (15)°	T = 297 K
V = 6394.1 (8) Å^3	Block, green
Z = 4	0.22 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	3982 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.060
Absorption correction: multi-scan (SADABS; Bruker, 2010)	θmax = 25.0°, θmin = 2.8°
	h = −32→27
24162 measured reflections	k = −18→18
5617 independent reflections	l = −23→23

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0461P)^2 + 14.490P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
5617 reflections	Δρmax = 0.46 e Å^−3
412 parameters	Δρmin = −0.46 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.750000	0.250000	1.000000	0.0386 (2)
Ni2	0.84609 (2)	0.37315 (3)	0.97995 (3)	0.03071 (15)
O1	0.75061 (13)	0.36559 (19)	0.86191 (18)	0.0496 (8)
O2	0.68986 (14)	0.27350 (18)	0.86185 (19)	0.0461 (7)
O3	0.61849 (14)	0.4128 (2)	0.5211 (2)	0.0567 (9)
O4	0.80345 (15)	0.26108 (16)	0.60563 (19)	0.0479 (8)
O5	0.82738 (13)	0.44312 (16)	1.04660 (18)	0.0398 (7)
O6	0.74694 (15)	0.37317 (16)	1.0229 (2)	0.0486 (8)
O7	0.86387 (14)	0.30223 (16)	0.91063 (18)	0.0406 (7)
O8	0.85751 (15)	0.17226 (17)	0.9461 (2)	0.0474 (8)
O9	0.83964 (13)	0.26224 (15)	1.03127 (17)	0.0370 (6)
H9A	0.847371	0.222770	1.012696	0.055*
H9B	0.865681	0.259053	1.086742	0.055*
C1	0.64487 (18)	0.3401 (2)	0.7219 (3)	0.0333 (9)
C2	0.65954 (19)	0.3675 (2)	0.6706 (3)	0.0364 (9)
H2	0.702869	0.375392	0.698858	0.044*
C3	0.60945 (19)	0.3830 (3)	0.5775 (3)	0.0400 (10)
C4	0.5448 (2)	0.3730 (3)	0.5351 (3)	0.0540 (12)
H4	0.511192	0.383823	0.472533	0.065*
C5	0.5311 (2)	0.3468 (3)	0.5870 (3)	0.0608 (14)
H5	0.487730	0.340632	0.559206	0.073*
C6	0.5803 (2)	0.3297 (3)	0.6791 (3)	0.0475 (11)
H6	0.570035	0.311103	0.712841	0.057*
C7	0.69950 (19)	0.3251 (2)	0.8236 (3)	0.0338 (9)
C8	0.67969 (19)	0.4094 (3)	0.5482 (3)	0.0384 (10)
C9	0.7123 (2)	0.3342 (3)	0.5693 (3)	0.0423 (10)
H9	0.696030	0.284191	0.571797	0.051*
C10	0.7696 (2)	0.3351 (2)	0.5867 (3)	0.0365 (10)
C11	0.7922 (2)	0.4077 (2)	0.5782 (2)	0.0345 (9)
H11	0.829806	0.406631	0.587503	0.041*
C12	0.75817 (18)	0.4830 (2)	0.5556 (2)	0.0286 (8)
C13	0.70260 (18)	0.4839 (2)	0.5429 (2)	0.0346 (9)
H13	0.680896	0.534216	0.530805	0.042*
C14	0.77987 (19)	0.4372 (2)	1.0409 (2)	0.0331 (9)
C15	0.82332 (19)	0.2119 (2)	0.6783 (3)	0.0336 (9)
C16	0.83233 (18)	0.2427 (2)	0.7515 (2)	0.0316 (9)
H16	0.824448	0.299303	0.753021	0.038*
C17	0.85304 (17)	0.1900 (2)	0.8229 (2)	0.0274 (8)
C18	0.8660 (2)	0.1058 (2)	0.8212 (3)	0.0398 (10)
H18	0.879637	0.069777	0.868599	0.048*
C19	0.8586 (2)	0.0762 (2)	0.7487 (3)	0.0464 (11)
H19	0.868189	0.020181	0.748294	0.056*
C20	0.8370 (2)	0.1284 (2)	0.6770 (3)	0.0420 (10)
H20	0.831742	0.107679	0.628148	0.050*
C21	0.85879 (17)	0.2246 (2)	0.8994 (2)	0.0299 (9)
N1	0.85266 (15)	0.4851 (2)	0.9317 (2)	0.0370 (8)
N2	0.94618 (15)	0.3990 (2)	1.0844 (2)	0.0372 (8)
C22	0.8062 (2)	0.5255 (3)	0.8550 (4)	0.0619 (14)
H22	0.764666	0.501708	0.813930	0.074*
C23	0.8164 (3)	0.6031 (4)	0.8323 (4)	0.0818 (18)
H23	0.782301	0.629563	0.777054	0.098*
C24	0.8764 (3)	0.6388 (3)	0.8916 (5)	0.0781 (18)
H24	0.883514	0.690946	0.878150	0.094*
C25	0.9268 (3)	0.5979 (3)	0.9718 (4)	0.0596 (13)
C26	0.9121 (2)	0.5208 (2)	0.9893 (3)	0.0426 (10)
C27	0.9628 (2)	0.4747 (3)	1.0710 (3)	0.0435 (11)
C28	0.9932 (3)	0.6276 (3)	1.0363 (5)	0.0841 (19)
H28	1.003347	0.678610	1.025238	0.101*
C29	1.0406 (3)	0.5838 (4)	1.1117 (5)	0.0872 (19)
H29	1.083211	0.604281	1.151429	0.105*
C30	1.0272 (2)	0.5056 (3)	1.1328 (3)	0.0601 (13)
C31	1.0743 (3)	0.4565 (4)	1.2095 (4)	0.0804 (18)
H31	1.117208	0.475669	1.252468	0.096*
C32	1.0588 (3)	0.3810 (4)	1.2231 (3)	0.0724 (16)
H32	1.090306	0.347492	1.273809	0.087*
C33	0.9926 (2)	0.3557 (3)	1.1566 (3)	0.0542 (12)
H33	0.981592	0.304062	1.165251	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0622 (5)	0.0266 (4)	0.0529 (5)	−0.0133 (4)	0.0493 (5)	−0.0094 (4)
Ni2	0.0326 (3)	0.0305 (3)	0.0287 (3)	−0.0095 (2)	0.0206 (2)	−0.0041 (2)
O1	0.0319 (16)	0.067 (2)	0.0310 (15)	−0.0229 (15)	0.0137 (14)	−0.0003 (15)
O2	0.0495 (18)	0.0526 (18)	0.0430 (17)	−0.0190 (14)	0.0340 (16)	−0.0055 (15)
O3	0.0366 (17)	0.081 (2)	0.0419 (17)	0.0089 (16)	0.0222 (15)	0.0297 (17)
O4	0.088 (2)	0.0306 (15)	0.0464 (17)	0.0174 (15)	0.0537 (18)	0.0120 (14)
O5	0.0388 (16)	0.0359 (15)	0.0491 (17)	−0.0088 (13)	0.0315 (15)	−0.0128 (14)
O6	0.078 (2)	0.0246 (14)	0.077 (2)	−0.0164 (15)	0.066 (2)	−0.0144 (15)
O7	0.0633 (19)	0.0338 (16)	0.0414 (16)	−0.0154 (14)	0.0421 (16)	−0.0102 (13)
O8	0.072 (2)	0.0398 (16)	0.0573 (19)	0.0048 (15)	0.0547 (19)	0.0091 (15)
O9	0.0528 (17)	0.0347 (15)	0.0395 (15)	−0.0050 (13)	0.0377 (15)	−0.0025 (13)
C1	0.031 (2)	0.029 (2)	0.039 (2)	−0.0067 (17)	0.023 (2)	−0.0077 (18)
C2	0.029 (2)	0.036 (2)	0.042 (2)	−0.0046 (18)	0.023 (2)	−0.003 (2)
C3	0.035 (2)	0.037 (2)	0.038 (2)	0.0002 (19)	0.021 (2)	0.004 (2)
C4	0.027 (2)	0.069 (3)	0.041 (2)	−0.004 (2)	0.013 (2)	0.000 (3)
C5	0.027 (2)	0.082 (4)	0.063 (3)	−0.009 (2)	0.026 (3)	−0.009 (3)
C6	0.033 (2)	0.062 (3)	0.048 (3)	−0.016 (2)	0.028 (2)	−0.011 (2)
C7	0.038 (2)	0.033 (2)	0.036 (2)	−0.0070 (19)	0.027 (2)	−0.0086 (19)
C8	0.033 (2)	0.051 (3)	0.023 (2)	0.002 (2)	0.0155 (19)	0.010 (2)
C9	0.054 (3)	0.035 (2)	0.035 (2)	−0.005 (2)	0.029 (2)	0.006 (2)
C10	0.059 (3)	0.029 (2)	0.025 (2)	0.006 (2)	0.030 (2)	0.0036 (18)
C11	0.047 (2)	0.033 (2)	0.029 (2)	0.0089 (19)	0.027 (2)	0.0045 (18)
C12	0.040 (2)	0.0268 (19)	0.0199 (18)	0.0044 (17)	0.0203 (18)	0.0041 (16)
C13	0.038 (2)	0.034 (2)	0.0249 (19)	0.0076 (18)	0.0188 (19)	0.0080 (18)
C14	0.041 (2)	0.030 (2)	0.0224 (19)	−0.0058 (18)	0.0193 (19)	−0.0050 (17)
C15	0.045 (2)	0.026 (2)	0.033 (2)	0.0023 (18)	0.028 (2)	0.0037 (18)
C16	0.042 (2)	0.0210 (18)	0.038 (2)	0.0004 (17)	0.030 (2)	−0.0006 (18)
C17	0.0240 (19)	0.0289 (19)	0.0254 (19)	−0.0003 (16)	0.0152 (17)	0.0040 (17)
C18	0.046 (2)	0.033 (2)	0.041 (2)	0.0098 (19)	0.030 (2)	0.013 (2)
C19	0.066 (3)	0.023 (2)	0.056 (3)	0.015 (2)	0.044 (3)	0.009 (2)
C20	0.061 (3)	0.030 (2)	0.043 (2)	0.005 (2)	0.038 (2)	−0.001 (2)
C21	0.0225 (19)	0.037 (2)	0.028 (2)	−0.0049 (17)	0.0165 (18)	−0.0027 (18)
N1	0.0314 (18)	0.0333 (18)	0.043 (2)	−0.0036 (16)	0.0242 (17)	0.0050 (17)
N2	0.0309 (18)	0.047 (2)	0.0276 (18)	−0.0005 (16)	0.0172 (16)	−0.0057 (17)
C22	0.049 (3)	0.059 (3)	0.068 (3)	−0.002 (3)	0.035 (3)	0.019 (3)
C23	0.064 (4)	0.074 (4)	0.100 (5)	0.016 (3)	0.053 (4)	0.044 (4)
C24	0.080 (4)	0.048 (3)	0.121 (5)	0.007 (3)	0.074 (4)	0.032 (3)
C25	0.062 (3)	0.040 (2)	0.087 (4)	−0.007 (2)	0.055 (3)	0.000 (3)
C26	0.043 (3)	0.033 (2)	0.057 (3)	−0.007 (2)	0.035 (2)	−0.004 (2)
C27	0.044 (3)	0.040 (2)	0.045 (3)	−0.008 (2)	0.030 (2)	−0.011 (2)
C28	0.085 (4)	0.051 (3)	0.118 (5)	−0.028 (3)	0.070 (4)	−0.004 (4)
C29	0.057 (4)	0.079 (4)	0.097 (5)	−0.035 (3)	0.040 (4)	−0.020 (4)
C30	0.043 (3)	0.068 (3)	0.056 (3)	−0.016 (3)	0.028 (3)	−0.013 (3)
C31	0.045 (3)	0.115 (5)	0.046 (3)	−0.018 (3)	0.017 (3)	−0.017 (4)
C32	0.053 (3)	0.101 (5)	0.043 (3)	0.003 (3)	0.025 (3)	0.003 (3)
C33	0.056 (3)	0.063 (3)	0.042 (3)	0.000 (3)	0.032 (3)	0.001 (2)

Geometric parameters (Å, º)

Ni1—O6^i	2.021 (3)	C11—C12	1.396 (5)
Ni1—O6	2.022 (3)	C11—H11	0.9300
Ni1—O2	2.048 (3)	C12—C13	1.384 (5)
Ni1—O2^i	2.048 (3)	C12—C14^ii	1.512 (5)
Ni1—O9^i	2.127 (2)	C13—H13	0.9300
Ni1—O9	2.127 (2)	C15—C16	1.377 (5)
Ni2—O1	2.027 (3)	C15—C20	1.385 (5)
Ni2—O5	2.037 (3)	C16—C17	1.385 (5)
Ni2—O7	2.071 (3)	C16—H16	0.9300
Ni2—N1	2.080 (3)	C17—C18	1.391 (5)
Ni2—N2	2.094 (3)	C17—C21	1.507 (5)
Ni2—O9	2.098 (2)	C18—C19	1.381 (5)
O1—C7	1.243 (4)	C18—H18	0.9300
O2—C7	1.258 (4)	C19—C20	1.379 (5)
O3—C3	1.377 (5)	C19—H19	0.9300
O3—C8	1.394 (5)	C20—H20	0.9300
O4—C15	1.378 (4)	N1—C22	1.313 (5)
O4—C10	1.389 (4)	N1—C26	1.340 (5)
O5—C14	1.248 (4)	N2—C33	1.296 (5)
O6—C14	1.247 (4)	N2—C27	1.376 (5)
O7—C21	1.243 (4)	C22—C23	1.403 (7)
O8—C21	1.259 (4)	C22—H22	0.9300
O9—H9A	0.8239	C23—C24	1.351 (7)
O9—H9B	0.8075	C23—H23	0.9300
C1—C6	1.380 (5)	C24—C25	1.375 (7)
C1—C2	1.389 (5)	C24—H24	0.9300
C1—C7	1.505 (5)	C25—C26	1.405 (6)
C2—C3	1.383 (5)	C25—C28	1.436 (7)
C2—H2	0.9300	C26—C27	1.430 (6)
C3—C4	1.382 (6)	C27—C30	1.404 (6)
C4—C5	1.375 (7)	C28—C29	1.334 (8)
C4—H4	0.9300	C28—H28	0.9300
C5—C6	1.372 (6)	C29—C30	1.435 (7)
C5—H5	0.9300	C29—H29	0.9300
C6—H6	0.9300	C30—C31	1.389 (7)
C8—C13	1.379 (5)	C31—C32	1.360 (8)
C8—C9	1.381 (6)	C31—H31	0.9300
C9—C10	1.380 (6)	C32—C33	1.411 (7)
C9—H9	0.9300	C32—H32	0.9300
C10—C11	1.375 (5)	C33—H33	0.9300
O6^i—Ni1—O6	180.0	C10—C11—H11	120.3
O6^i—Ni1—O2	89.94 (12)	C12—C11—H11	120.3
O6—Ni1—O2	90.06 (12)	C13—C12—C11	119.7 (4)
O6^i—Ni1—O2^i	90.06 (12)	C13—C12—C14^ii	119.7 (3)
O6—Ni1—O2^i	89.94 (12)	C11—C12—C14^ii	120.6 (4)
O2—Ni1—O2^i	180.0	C8—C13—C12	119.4 (4)
O6^i—Ni1—O9^i	93.66 (10)	C8—C13—H13	120.3
O6—Ni1—O9^i	86.34 (10)	C12—C13—H13	120.3
O2—Ni1—O9^i	83.66 (10)	O6—C14—O5	127.7 (4)
O2^i—Ni1—O9^i	96.34 (10)	O6—C14—C12^iii	115.4 (4)
O6^i—Ni1—O9	86.34 (10)	O5—C14—C12^iii	116.9 (3)
O6—Ni1—O9	93.67 (10)	C16—C15—O4	123.4 (3)
O2—Ni1—O9	96.34 (10)	C16—C15—C20	120.1 (4)
O2^i—Ni1—O9	83.66 (10)	O4—C15—C20	116.4 (3)
O9^i—Ni1—O9	180.0	C15—C16—C17	120.5 (3)
O1—Ni2—O5	93.90 (12)	C15—C16—H16	119.7
O1—Ni2—O7	85.37 (12)	C17—C16—H16	119.7
O5—Ni2—O7	179.26 (12)	C16—C17—C18	119.5 (3)
O1—Ni2—N1	88.63 (12)	C16—C17—C21	119.1 (3)
O5—Ni2—N1	88.16 (12)	C18—C17—C21	121.3 (3)
O7—Ni2—N1	91.70 (11)	C19—C18—C17	119.5 (4)
O1—Ni2—N2	167.11 (12)	C19—C18—H18	120.3
O5—Ni2—N2	90.27 (11)	C17—C18—H18	120.3
O7—Ni2—N2	90.41 (12)	C20—C19—C18	121.0 (4)
N1—Ni2—N2	79.31 (13)	C20—C19—H19	119.5
O1—Ni2—O9	91.88 (11)	C18—C19—H19	119.5
O5—Ni2—O9	90.28 (10)	C19—C20—C15	119.3 (4)
O7—Ni2—O9	89.87 (10)	C19—C20—H20	120.3
N1—Ni2—O9	178.39 (11)	C15—C20—H20	120.3
N2—Ni2—O9	100.31 (12)	O7—C21—O8	125.4 (3)
C7—O1—Ni2	142.8 (3)	O7—C21—C17	117.5 (3)
C7—O2—Ni1	127.1 (3)	O8—C21—C17	117.0 (3)
C3—O3—C8	121.1 (3)	C22—N1—C26	117.1 (4)
C15—O4—C10	118.7 (3)	C22—N1—Ni2	128.5 (3)
C14—O5—Ni2	127.9 (2)	C26—N1—Ni2	114.3 (3)
C14—O6—Ni1	136.0 (3)	C33—N2—C27	117.5 (4)
C21—O7—Ni2	127.4 (2)	C33—N2—Ni2	130.4 (3)
Ni2—O9—Ni1	113.63 (12)	C27—N2—Ni2	112.1 (3)
Ni2—O9—H9A	107.0	N1—C22—C23	123.0 (5)
Ni1—O9—H9A	113.9	N1—C22—H22	118.5
Ni2—O9—H9B	114.6	C23—C22—H22	118.5
Ni1—O9—H9B	100.8	C24—C23—C22	119.2 (5)
H9A—O9—H9B	106.9	C24—C23—H23	120.4
C6—C1—C2	119.4 (4)	C22—C23—H23	120.4
C6—C1—C7	121.1 (4)	C23—C24—C25	119.8 (5)
C2—C1—C7	119.5 (3)	C23—C24—H24	120.1
C3—C2—C1	119.7 (4)	C25—C24—H24	120.1
C3—C2—H2	120.1	C24—C25—C26	117.1 (5)
C1—C2—H2	120.1	C24—C25—C28	124.2 (5)
O3—C3—C4	114.9 (4)	C26—C25—C28	118.7 (5)
O3—C3—C2	124.4 (4)	N1—C26—C25	123.8 (4)
C4—C3—C2	120.7 (4)	N1—C26—C27	116.6 (4)
C5—C4—C3	118.9 (4)	C25—C26—C27	119.6 (4)
C5—C4—H4	120.6	N2—C27—C30	122.2 (4)
C3—C4—H4	120.6	N2—C27—C26	117.4 (4)
C6—C5—C4	121.1 (4)	C30—C27—C26	120.3 (4)
C6—C5—H5	119.4	C29—C28—C25	121.5 (5)
C4—C5—H5	119.4	C29—C28—H28	119.3
C5—C6—C1	120.2 (4)	C25—C28—H28	119.3
C5—C6—H6	119.9	C28—C29—C30	121.4 (5)
C1—C6—H6	119.9	C28—C29—H29	119.3
O1—C7—O2	126.1 (4)	C30—C29—H29	119.3
O1—C7—C1	115.8 (3)	C31—C30—C27	117.2 (5)
O2—C7—C1	118.1 (3)	C31—C30—C29	124.3 (5)
C13—C8—C9	121.5 (4)	C27—C30—C29	118.5 (5)
C13—C8—O3	116.2 (4)	C32—C31—C30	121.3 (5)
C9—C8—O3	121.8 (4)	C32—C31—H31	119.3
C10—C9—C8	118.3 (4)	C30—C31—H31	119.3
C10—C9—H9	120.9	C31—C32—C33	116.9 (5)
C8—C9—H9	120.9	C31—C32—H32	121.5
C11—C10—C9	121.4 (4)	C33—C32—H32	121.5
C11—C10—O4	117.4 (4)	N2—C33—C32	124.9 (5)
C9—C10—O4	120.9 (4)	N2—C33—H33	117.6
C10—C11—C12	119.5 (4)	C32—C33—H33	117.6
C6—C1—C2—C3	−0.8 (6)	C17—C18—C19—C20	−1.5 (6)
C7—C1—C2—C3	−178.7 (4)	C18—C19—C20—C15	0.6 (7)
C8—O3—C3—C4	−166.4 (4)	C16—C15—C20—C19	1.2 (6)
C8—O3—C3—C2	16.8 (6)	O4—C15—C20—C19	178.6 (4)
C1—C2—C3—O3	177.9 (4)	Ni2—O7—C21—O8	−18.6 (6)
C1—C2—C3—C4	1.2 (6)	Ni2—O7—C21—C17	160.8 (2)
O3—C3—C4—C5	−177.4 (4)	C16—C17—C21—O7	−21.0 (5)
C2—C3—C4—C5	−0.4 (7)	C18—C17—C21—O7	161.1 (4)
C3—C4—C5—C6	−0.8 (8)	C16—C17—C21—O8	158.5 (3)
C4—C5—C6—C1	1.2 (8)	C18—C17—C21—O8	−19.4 (5)
C2—C1—C6—C5	−0.4 (7)	C26—N1—C22—C23	−0.3 (7)
C7—C1—C6—C5	177.5 (4)	Ni2—N1—C22—C23	177.0 (4)
Ni2—O1—C7—O2	12.8 (7)	N1—C22—C23—C24	−0.5 (9)
Ni2—O1—C7—C1	−166.9 (3)	C22—C23—C24—C25	1.8 (9)
Ni1—O2—C7—O1	7.8 (6)	C23—C24—C25—C26	−2.2 (9)
Ni1—O2—C7—C1	−172.5 (2)	C23—C24—C25—C28	175.7 (6)
C6—C1—C7—O1	−152.5 (4)	C22—N1—C26—C25	−0.2 (7)
C2—C1—C7—O1	25.3 (5)	Ni2—N1—C26—C25	−177.9 (4)
C6—C1—C7—O2	27.7 (6)	C22—N1—C26—C27	−177.8 (4)
C2—C1—C7—O2	−154.5 (4)	Ni2—N1—C26—C27	4.5 (5)
C3—O3—C8—C13	−127.9 (4)	C24—C25—C26—N1	1.5 (7)
C3—O3—C8—C9	59.0 (5)	C28—C25—C26—N1	−176.5 (5)
C13—C8—C9—C10	1.0 (6)	C24—C25—C26—C27	179.0 (5)
O3—C8—C9—C10	173.8 (3)	C28—C25—C26—C27	1.0 (7)
C8—C9—C10—C11	−3.7 (6)	C33—N2—C27—C30	−0.8 (6)
C8—C9—C10—O4	−178.0 (3)	Ni2—N2—C27—C30	179.4 (3)
C15—O4—C10—C11	128.6 (4)	C33—N2—C27—C26	177.4 (4)
C15—O4—C10—C9	−56.9 (5)	Ni2—N2—C27—C26	−2.4 (5)
C9—C10—C11—C12	2.9 (6)	N1—C26—C27—N2	−1.4 (6)
O4—C10—C11—C12	177.4 (3)	C25—C26—C27—N2	−179.1 (4)
C10—C11—C12—C13	0.6 (5)	N1—C26—C27—C30	176.9 (4)
C10—C11—C12—C14^ii	−176.8 (3)	C25—C26—C27—C30	−0.9 (7)
C9—C8—C13—C12	2.4 (6)	C24—C25—C28—C29	−177.8 (6)
O3—C8—C13—C12	−170.7 (3)	C26—C25—C28—C29	0.0 (9)
C11—C12—C13—C8	−3.2 (5)	C25—C28—C29—C30	−1.3 (10)
C14^ii—C12—C13—C8	174.2 (3)	N2—C27—C30—C31	−0.3 (7)
Ni1—O6—C14—O5	3.5 (7)	C26—C27—C30—C31	−178.4 (4)
Ni1—O6—C14—C12^iii	−177.8 (3)	N2—C27—C30—C29	177.8 (5)
Ni2—O5—C14—O6	28.5 (6)	C26—C27—C30—C29	−0.3 (7)
Ni2—O5—C14—C12^iii	−150.1 (2)	C28—C29—C30—C31	179.4 (6)
C10—O4—C15—C16	−23.1 (6)	C28—C29—C30—C27	1.4 (9)
C10—O4—C15—C20	159.6 (4)	C27—C30—C31—C32	1.3 (8)
O4—C15—C16—C17	−179.3 (3)	C29—C30—C31—C32	−176.7 (6)
C20—C15—C16—C17	−2.1 (6)	C30—C31—C32—C33	−1.1 (9)
C15—C16—C17—C18	1.3 (6)	C27—N2—C33—C32	1.0 (7)
C15—C16—C17—C21	−176.6 (3)	Ni2—N2—C33—C32	−179.2 (4)
C16—C17—C18—C19	0.5 (6)	C31—C32—C33—N2	−0.1 (8)
C21—C17—C18—C19	178.3 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O8	0.82	1.72	2.496 (4)	157
O9—H9B···O2^i	0.81	2.40	2.785 (4)	110
C20—H20···Cg1^iv	0.93	2.88	3.736 (5)	154
C24—H24···Cg2^v	0.93	2.72	3.630 (6)	166
Cg3···Cg3^vi			3.473 (4)

Symmetry codes: (i) −x+3/2, −y+1/2, −z+2; (iv) −x+3/2, −y+1/2, −z+1; (v) x+1, −y, z+1/2; (vi) x+5/2, y+3/2, z+2.

Poly[[di-µ-aqua-bis{µ₄-3,3'-[(5-carboxylato-1,3-phenylene)bis(oxy)]dibenzoato-κ⁵O¹:O^1',O³:O⁵:O^5'}bis(1,10-phenanthroline-κ²N,N')tricobalt(II)] diethylamine disolvate tetrahydrate] (II)

Crystal data

[Co3(C21H11O8)2(C12H8N2)2(H2O)2]·2C2H7N·4H2O	F(000) = 3132
Mr = 1518.06	Dx = 1.555 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 27.9723 (8) Å	Cell parameters from 9979 reflections
b = 15.9725 (5) Å	θ = 2.9–26.0°
c = 19.7372 (10) Å	µ = 0.85 mm^−1
β = 132.6619 (7)°	T = 297 K
V = 6484.7 (4) Å^3	Block, pink
Z = 4	0.25 × 0.2 × 0.2 mm

Data collection

Bruker APEXII CCD diffractometer	5128 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.034
Absorption correction: multi-scan (SADABS; Bruker, 2010)	θmax = 26.1°, θmin = 2.9°
	h = −34→30
26417 measured reflections	k = −19→19
6376 independent reflections	l = −24→24

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0507P)^2 + 5.0581P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
6376 reflections	Δρmax = 0.28 e Å^−3
412 parameters	Δρmin = −0.72 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.15359 (2)	0.37499 (2)	0.52014 (2)	0.03100 (10)
Co2	0.2500	0.2500	0.5000	0.04043 (14)
O1	0.24995 (10)	0.37284 (10)	0.47258 (15)	0.0534 (5)
O2	0.17202 (8)	0.44400 (10)	0.45161 (12)	0.0423 (4)
O3	0.31161 (9)	0.27707 (12)	0.63961 (12)	0.0486 (4)
O4	0.24976 (8)	0.36548 (12)	0.63913 (12)	0.0538 (5)
O5	0.13507 (9)	0.30119 (10)	0.58771 (11)	0.0415 (4)
O6	0.14023 (9)	0.17167 (11)	0.55194 (12)	0.0483 (4)
O7	0.38069 (9)	0.58432 (14)	0.47899 (13)	0.0612 (6)
O8	0.19849 (11)	0.73802 (10)	0.39568 (12)	0.0521 (5)
O9	0.15765 (8)	0.26085 (9)	0.46563 (11)	0.0379 (4)
H9A	0.1499	0.2214	0.4842	0.057*
H9B	0.1316	0.2577	0.4102	0.057*
N1	0.14676 (9)	0.48953 (12)	0.56814 (14)	0.0389 (5)
N2	0.05190 (9)	0.40372 (12)	0.41563 (12)	0.0350 (4)
C1	0.32015 (12)	0.58824 (16)	0.45172 (16)	0.0408 (6)
C2	0.28817 (13)	0.66379 (15)	0.43079 (16)	0.0439 (6)
H2	0.3046	0.7132	0.4285	0.053*
C3	0.23139 (13)	0.66375 (14)	0.41353 (15)	0.0379 (5)
C4	0.20796 (12)	0.59168 (13)	0.42088 (15)	0.0348 (5)
H4	0.1705	0.5933	0.4113	0.042*
C5	0.24107 (11)	0.51638 (13)	0.44289 (14)	0.0314 (5)
C6	0.29651 (11)	0.51460 (14)	0.45614 (15)	0.0365 (5)
H6	0.3176	0.4642	0.4679	0.044*
C7	0.21862 (12)	0.43750 (14)	0.45612 (15)	0.0348 (5)
C8	0.39001 (12)	0.61414 (15)	0.42344 (17)	0.0419 (6)
C9	0.34050 (11)	0.62961 (14)	0.33016 (16)	0.0374 (5)
H9	0.2974	0.6216	0.3015	0.045*
C10	0.35532 (11)	0.65719 (14)	0.27930 (16)	0.0345 (5)
C11	0.41996 (12)	0.66825 (17)	0.32302 (19)	0.0470 (6)
H11	0.4302	0.6878	0.2898	0.056*
C12	0.46877 (12)	0.6504 (2)	0.4153 (2)	0.0580 (8)
H12	0.5120	0.6561	0.4436	0.070*
C13	0.45431 (12)	0.62413 (18)	0.4662 (2)	0.0537 (7)
H13	0.4875	0.6132	0.5289	0.064*
C14	0.30135 (11)	0.32670 (14)	0.67777 (16)	0.0352 (5)
C15	0.17815 (12)	0.78684 (14)	0.32225 (16)	0.0368 (5)
C16	0.16868 (11)	0.75630 (13)	0.24868 (15)	0.0322 (5)
H16	0.1767	0.7002	0.2469	0.039*
C17	0.14706 (10)	0.80979 (13)	0.17698 (14)	0.0295 (5)
C18	0.13426 (12)	0.89318 (15)	0.17935 (17)	0.0396 (5)
H18	0.1204	0.9293	0.1320	0.048*
C19	0.14220 (13)	0.92242 (15)	0.25256 (18)	0.0467 (6)
H19	0.1323	0.9778	0.2532	0.056*
C20	0.16474 (14)	0.86966 (14)	0.32472 (18)	0.0456 (6)
H20	0.1708	0.8897	0.3743	0.055*
C21	0.14024 (10)	0.22379 (14)	0.59940 (15)	0.0303 (5)
C22	0.19368 (13)	0.53080 (19)	0.6439 (2)	0.0595 (8)
H22	0.2352	0.5077	0.6843	0.071*
C23	0.18353 (17)	0.6083 (2)	0.6661 (3)	0.0816 (12)
H23	0.2179	0.6356	0.7204	0.098*
C24	0.12394 (18)	0.6428 (2)	0.6086 (3)	0.0751 (10)
H24	0.1170	0.6945	0.6223	0.090*
C25	0.07243 (15)	0.60081 (16)	0.5280 (2)	0.0550 (7)
C26	0.08652 (12)	0.52361 (14)	0.51043 (18)	0.0395 (5)
C27	0.03577 (11)	0.47735 (15)	0.42910 (16)	0.0380 (5)
C30	−0.02866 (14)	0.5078 (2)	0.3686 (2)	0.0564 (7)
C31	−0.07595 (14)	0.4585 (3)	0.2923 (2)	0.0733 (10)
H31	−0.1189	0.4767	0.2503	0.088*
C32	−0.06034 (15)	0.3849 (2)	0.2788 (2)	0.0696 (9)
H32	−0.0921	0.3518	0.2280	0.084*
C33	0.00441 (13)	0.35900 (18)	0.34234 (18)	0.0500 (6)
H33	0.0149	0.3077	0.3329	0.060*
C28	0.00672 (18)	0.6301 (2)	0.4646 (3)	0.0733 (10)
H28	−0.0030	0.6812	0.4755	0.088*
C29	−0.04139 (17)	0.5856 (2)	0.3897 (3)	0.0762 (10)
H29	−0.0838	0.6057	0.3508	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.03365 (17)	0.02865 (17)	0.03221 (17)	0.00876 (12)	0.02292 (15)	0.00290 (11)
Co2	0.0666 (3)	0.0251 (2)	0.0596 (3)	0.0114 (2)	0.0548 (3)	0.0081 (2)
O1	0.0825 (14)	0.0252 (9)	0.0904 (15)	0.0140 (9)	0.0737 (13)	0.0140 (9)
O2	0.0448 (9)	0.0358 (9)	0.0529 (10)	0.0070 (7)	0.0357 (9)	0.0109 (7)
O3	0.0505 (10)	0.0533 (11)	0.0506 (11)	0.0163 (9)	0.0377 (9)	0.0043 (8)
O4	0.0379 (10)	0.0719 (13)	0.0381 (10)	0.0219 (9)	0.0204 (8)	−0.0007 (8)
O5	0.0604 (11)	0.0338 (9)	0.0431 (9)	0.0158 (8)	0.0402 (9)	0.0103 (7)
O6	0.0735 (13)	0.0386 (10)	0.0575 (11)	−0.0061 (9)	0.0542 (11)	−0.0101 (8)
O7	0.0390 (10)	0.0810 (15)	0.0518 (11)	0.0082 (10)	0.0260 (9)	0.0312 (10)
O8	0.0970 (15)	0.0305 (9)	0.0514 (11)	0.0210 (9)	0.0593 (11)	0.0144 (7)
O9	0.0530 (10)	0.0331 (8)	0.0425 (9)	0.0042 (7)	0.0384 (9)	0.0010 (7)
N1	0.0344 (10)	0.0346 (11)	0.0483 (12)	0.0001 (8)	0.0282 (10)	−0.0072 (9)
N2	0.0366 (10)	0.0366 (10)	0.0317 (10)	0.0030 (8)	0.0232 (9)	0.0051 (8)
C1	0.0378 (12)	0.0488 (15)	0.0295 (12)	0.0018 (11)	0.0203 (11)	0.0088 (10)
C2	0.0580 (16)	0.0347 (13)	0.0347 (13)	−0.0056 (12)	0.0298 (12)	0.0056 (10)
C3	0.0593 (15)	0.0293 (12)	0.0283 (11)	0.0080 (11)	0.0311 (12)	0.0052 (9)
C4	0.0487 (13)	0.0311 (12)	0.0306 (11)	0.0081 (10)	0.0293 (11)	0.0042 (9)
C5	0.0416 (12)	0.0273 (11)	0.0243 (11)	0.0029 (9)	0.0219 (10)	0.0020 (8)
C6	0.0426 (13)	0.0346 (12)	0.0293 (11)	0.0090 (10)	0.0232 (11)	0.0087 (9)
C7	0.0447 (13)	0.0297 (11)	0.0320 (12)	0.0041 (10)	0.0268 (11)	0.0048 (9)
C8	0.0367 (12)	0.0373 (13)	0.0445 (14)	−0.0004 (10)	0.0246 (12)	0.0048 (10)
C9	0.0285 (11)	0.0373 (13)	0.0409 (13)	−0.0043 (10)	0.0212 (11)	−0.0015 (10)
C10	0.0332 (11)	0.0305 (11)	0.0418 (13)	−0.0073 (9)	0.0261 (11)	−0.0101 (9)
C11	0.0366 (13)	0.0541 (16)	0.0560 (16)	−0.0122 (12)	0.0338 (13)	−0.0119 (13)
C12	0.0272 (13)	0.076 (2)	0.0595 (18)	−0.0085 (13)	0.0248 (14)	−0.0079 (15)
C13	0.0306 (13)	0.0619 (18)	0.0466 (15)	−0.0002 (12)	0.0174 (12)	0.0022 (13)
C14	0.0347 (12)	0.0364 (12)	0.0427 (13)	0.0081 (10)	0.0295 (11)	0.0099 (10)
C15	0.0510 (14)	0.0265 (11)	0.0367 (12)	0.0034 (10)	0.0313 (12)	0.0052 (9)
C16	0.0401 (12)	0.0219 (10)	0.0362 (12)	0.0002 (9)	0.0265 (11)	−0.0006 (9)
C17	0.0269 (10)	0.0314 (11)	0.0282 (11)	−0.0016 (9)	0.0179 (9)	0.0004 (8)
C18	0.0465 (14)	0.0321 (12)	0.0408 (13)	0.0088 (11)	0.0298 (12)	0.0111 (10)
C19	0.0651 (17)	0.0255 (12)	0.0562 (16)	0.0111 (11)	0.0437 (15)	0.0066 (11)
C20	0.0686 (17)	0.0312 (12)	0.0468 (15)	0.0057 (12)	0.0430 (14)	−0.0003 (10)
C21	0.0239 (10)	0.0359 (12)	0.0300 (11)	0.0010 (9)	0.0179 (9)	−0.0016 (9)
C22	0.0405 (14)	0.0588 (18)	0.072 (2)	−0.0091 (13)	0.0354 (15)	−0.0262 (15)
C23	0.065 (2)	0.069 (2)	0.107 (3)	−0.0261 (18)	0.057 (2)	−0.053 (2)
C24	0.080 (2)	0.0437 (17)	0.123 (3)	−0.0087 (16)	0.077 (2)	−0.0312 (18)
C25	0.0634 (18)	0.0339 (13)	0.088 (2)	0.0063 (13)	0.0595 (18)	−0.0030 (14)
C26	0.0427 (13)	0.0312 (12)	0.0568 (15)	0.0086 (10)	0.0387 (13)	0.0065 (10)
C27	0.0352 (12)	0.0394 (13)	0.0409 (13)	0.0102 (10)	0.0263 (11)	0.0109 (10)
C30	0.0448 (15)	0.0635 (18)	0.0555 (17)	0.0218 (14)	0.0319 (14)	0.0203 (14)
C31	0.0375 (15)	0.105 (3)	0.0438 (17)	0.0189 (17)	0.0141 (14)	0.0151 (17)
C32	0.0443 (16)	0.099 (3)	0.0369 (16)	−0.0033 (17)	0.0162 (14)	−0.0059 (16)
C33	0.0478 (15)	0.0587 (17)	0.0382 (14)	−0.0047 (13)	0.0270 (13)	−0.0043 (12)
C28	0.077 (2)	0.0478 (18)	0.109 (3)	0.0311 (17)	0.068 (2)	0.0149 (18)
C29	0.0586 (19)	0.076 (2)	0.086 (2)	0.0375 (19)	0.046 (2)	0.025 (2)

Geometric parameters (Å, º)

Co1—O4	2.0524 (17)	C9—H9	0.9300
Co1—O2	2.0629 (16)	C10—C11	1.389 (3)
Co1—O5	2.0912 (16)	C10—C14^ii	1.504 (3)
Co1—N1	2.1276 (19)	C11—C12	1.376 (4)
Co1—N2	2.1458 (19)	C11—H11	0.9300
Co1—O9	2.1587 (15)	C12—C13	1.379 (4)
Co2—O1^i	2.0351 (16)	C12—H12	0.9300
Co2—O1	2.0351 (16)	C13—H13	0.9300
Co2—O3	2.0769 (18)	C14—C10^iii	1.504 (3)
Co2—O3^i	2.0769 (18)	C15—C16	1.377 (3)
Co2—O9^i	2.1880 (16)	C15—C20	1.385 (3)
Co2—O9	2.1880 (16)	C16—C17	1.392 (3)
O1—C7	1.247 (3)	C16—H16	0.9300
O2—C7	1.249 (3)	C17—C18	1.388 (3)
O3—C14	1.253 (3)	C17—C21^ii	1.508 (3)
O4—C14	1.247 (3)	C18—C19	1.386 (3)
O5—C21	1.248 (3)	C18—H18	0.9300
O6—C21	1.253 (3)	C19—C20	1.385 (3)
O7—C8	1.373 (3)	C19—H19	0.9300
O7—C1	1.388 (3)	C20—H20	0.9300
O8—C15	1.384 (3)	C21—C17^iii	1.508 (3)
O8—C3	1.393 (3)	C22—C23	1.405 (4)
O9—H9A	0.8284	C22—H22	0.9300
O9—H9B	0.8068	C23—C24	1.344 (5)
N1—C22	1.317 (3)	C23—H23	0.9300
N1—C26	1.353 (3)	C24—C25	1.396 (5)
N2—C33	1.328 (3)	C24—H24	0.9300
N2—C27	1.349 (3)	C25—C26	1.408 (3)
C1—C6	1.381 (3)	C25—C28	1.430 (4)
C1—C2	1.388 (4)	C26—C27	1.432 (3)
C2—C3	1.380 (4)	C27—C30	1.412 (3)
C2—H2	0.9300	C30—C31	1.392 (5)
C3—C4	1.380 (3)	C30—C29	1.429 (5)
C4—C5	1.396 (3)	C31—C32	1.343 (5)
C4—H4	0.9300	C31—H31	0.9300
C5—C6	1.387 (3)	C32—C33	1.395 (4)
C5—C7	1.507 (3)	C32—H32	0.9300
C6—H6	0.9300	C33—H33	0.9300
C8—C9	1.383 (3)	C28—C29	1.345 (5)
C8—C13	1.384 (3)	C28—H28	0.9300
C9—C10	1.392 (3)	C29—H29	0.9300
O4—Co1—O2	94.22 (8)	C8—C9—H9	120.1
O4—Co1—O5	85.85 (8)	C10—C9—H9	120.1
O2—Co1—O5	177.99 (6)	C11—C10—C9	119.4 (2)
O4—Co1—N1	89.87 (7)	C11—C10—C14^ii	121.0 (2)
O2—Co1—N1	88.30 (7)	C9—C10—C14^ii	119.7 (2)
O5—Co1—N1	93.71 (7)	C12—C11—C10	120.1 (2)
O4—Co1—N2	166.29 (7)	C12—C11—H11	119.9
O2—Co1—N2	90.74 (7)	C10—C11—H11	119.9
O5—Co1—N2	89.64 (7)	C11—C12—C13	120.7 (2)
N1—Co1—N2	77.50 (7)	C11—C12—H12	119.7
O4—Co1—O9	92.12 (7)	C13—C12—H12	119.7
O2—Co1—O9	90.20 (6)	C12—C13—C8	119.5 (3)
O5—Co1—O9	87.79 (6)	C12—C13—H13	120.3
N1—Co1—O9	177.59 (7)	C8—C13—H13	120.3
N2—Co1—O9	100.65 (7)	O4—C14—O3	126.0 (2)
O1^i—Co2—O1	180.0	O4—C14—C10^iii	115.5 (2)
O1^i—Co2—O3	89.86 (8)	O3—C14—C10^iii	118.5 (2)
O1—Co2—O3	90.14 (8)	C16—C15—O8	123.6 (2)
O1^i—Co2—O3^i	90.15 (8)	C16—C15—C20	120.8 (2)
O1—Co2—O3^i	89.86 (8)	O8—C15—C20	115.5 (2)
O3—Co2—O3^i	180.0	C15—C16—C17	119.7 (2)
O1^i—Co2—O9^i	93.06 (7)	C15—C16—H16	120.2
O1—Co2—O9^i	86.95 (7)	C17—C16—H16	120.2
O3—Co2—O9^i	82.02 (6)	C18—C17—C16	119.9 (2)
O3^i—Co2—O9^i	97.97 (6)	C18—C17—C21^ii	121.18 (19)
O1^i—Co2—O9	86.94 (7)	C16—C17—C21^ii	118.87 (19)
O1—Co2—O9	93.06 (7)	C19—C18—C17	119.7 (2)
O3—Co2—O9	97.97 (6)	C19—C18—H18	120.1
O3^i—Co2—O9	82.03 (6)	C17—C18—H18	120.1
O9^i—Co2—O9	180.0	C20—C19—C18	120.4 (2)
C7—O1—Co2	137.87 (17)	C20—C19—H19	119.8
C7—O2—Co1	128.40 (15)	C18—C19—H19	119.8
C14—O3—Co2	127.37 (15)	C15—C20—C19	119.4 (2)
C14—O4—Co1	144.35 (17)	C15—C20—H20	120.3
C21—O5—Co1	128.93 (14)	C19—C20—H20	120.3
C8—O7—C1	121.13 (19)	O5—C21—O6	125.4 (2)
C15—O8—C3	118.51 (18)	O5—C21—C17^iii	117.33 (19)
Co1—O9—Co2	111.23 (7)	O6—C21—C17^iii	117.3 (2)
Co1—O9—H9A	107.7	N1—C22—C23	122.6 (3)
Co2—O9—H9A	114.2	N1—C22—H22	118.7
Co1—O9—H9B	115.2	C23—C22—H22	118.7
Co2—O9—H9B	101.9	C24—C23—C22	119.6 (3)
H9A—O9—H9B	106.6	C24—C23—H23	120.2
C22—N1—C26	118.0 (2)	C22—C23—H23	120.2
C22—N1—Co1	127.96 (17)	C23—C24—C25	119.8 (3)
C26—N1—Co1	114.04 (16)	C23—C24—H24	120.1
C33—N2—C27	117.5 (2)	C25—C24—H24	120.1
C33—N2—Co1	128.91 (18)	C24—C25—C26	117.1 (3)
C27—N2—Co1	113.55 (15)	C24—C25—C28	124.2 (3)
C6—C1—C2	121.3 (2)	C26—C25—C28	118.6 (3)
C6—C1—O7	116.6 (2)	N1—C26—C25	122.8 (2)
C2—C1—O7	121.7 (2)	N1—C26—C27	117.3 (2)
C3—C2—C1	118.3 (2)	C25—C26—C27	119.9 (2)
C3—C2—H2	120.8	N2—C27—C30	122.6 (2)
C1—C2—H2	120.8	N2—C27—C26	117.4 (2)
C4—C3—C2	121.6 (2)	C30—C27—C26	119.9 (2)
C4—C3—O8	117.2 (2)	C31—C30—C27	116.9 (3)
C2—C3—O8	121.0 (2)	C31—C30—C29	124.4 (3)
C3—C4—C5	119.3 (2)	C27—C30—C29	118.7 (3)
C3—C4—H4	120.4	C32—C31—C30	120.8 (3)
C5—C4—H4	120.4	C32—C31—H31	119.6
C6—C5—C4	119.8 (2)	C30—C31—H31	119.6
C6—C5—C7	119.6 (2)	C31—C32—C33	118.7 (3)
C4—C5—C7	120.5 (2)	C31—C32—H32	120.7
C1—C6—C5	119.5 (2)	C33—C32—H32	120.7
C1—C6—H6	120.2	N2—C33—C32	123.4 (3)
C5—C6—H6	120.2	N2—C33—H33	118.3
O1—C7—O2	127.1 (2)	C32—C33—H33	118.3
O1—C7—C5	115.8 (2)	C29—C28—C25	121.6 (3)
O2—C7—C5	117.1 (2)	C29—C28—H28	119.2
O7—C8—C9	124.4 (2)	C25—C28—H28	119.2
O7—C8—C13	115.1 (2)	C28—C29—C30	121.3 (3)
C9—C8—C13	120.5 (2)	C28—C29—H29	119.4
C8—C9—C10	119.8 (2)	C30—C29—H29	119.4
C8—O7—C1—C6	128.1 (3)	C16—C17—C18—C19	−0.9 (4)
C8—O7—C1—C2	−58.7 (3)	C21^ii—C17—C18—C19	−178.8 (2)
C6—C1—C2—C3	−0.5 (3)	C17—C18—C19—C20	2.0 (4)
O7—C1—C2—C3	−173.4 (2)	C16—C15—C20—C19	−0.7 (4)
C1—C2—C3—C4	3.0 (3)	O8—C15—C20—C19	−178.1 (3)
C1—C2—C3—O8	177.5 (2)	C18—C19—C20—C15	−1.2 (4)
C15—O8—C3—C4	−127.4 (2)	Co1—O5—C21—O6	−21.2 (3)
C15—O8—C3—C2	58.0 (3)	Co1—O5—C21—C17^iii	158.79 (15)
C2—C3—C4—C5	−2.4 (3)	C26—N1—C22—C23	−0.5 (5)
O8—C3—C4—C5	−177.09 (19)	Co1—N1—C22—C23	177.0 (3)
C3—C4—C5—C6	−0.7 (3)	N1—C22—C23—C24	−0.1 (6)
C3—C4—C5—C7	176.88 (19)	C22—C23—C24—C25	1.1 (6)
C2—C1—C6—C5	−2.5 (3)	C23—C24—C25—C26	−1.3 (5)
O7—C1—C6—C5	170.7 (2)	C23—C24—C25—C28	176.8 (4)
C4—C5—C6—C1	3.1 (3)	C22—N1—C26—C25	0.3 (4)
C7—C5—C6—C1	−174.5 (2)	Co1—N1—C26—C25	−177.6 (2)
Co2—O1—C7—O2	0.0 (4)	C22—N1—C26—C27	−179.0 (2)
Co2—O1—C7—C5	178.20 (18)	Co1—N1—C26—C27	3.2 (3)
Co1—O2—C7—O1	29.5 (4)	C24—C25—C26—N1	0.6 (4)
Co1—O2—C7—C5	−148.67 (15)	C28—C25—C26—N1	−177.6 (3)
C6—C5—C7—O1	−4.8 (3)	C24—C25—C26—C27	179.9 (3)
C4—C5—C7—O1	177.7 (2)	C28—C25—C26—C27	1.6 (4)
C6—C5—C7—O2	173.7 (2)	C33—N2—C27—C30	−0.4 (4)
C4—C5—C7—O2	−3.9 (3)	Co1—N2—C27—C30	−179.7 (2)
C1—O7—C8—C9	−17.5 (4)	C33—N2—C27—C26	177.1 (2)
C1—O7—C8—C13	165.9 (2)	Co1—N2—C27—C26	−2.2 (3)
O7—C8—C9—C10	−177.8 (2)	N1—C26—C27—N2	−0.7 (3)
C13—C8—C9—C10	−1.4 (4)	C25—C26—C27—N2	−179.9 (2)
C8—C9—C10—C11	0.5 (3)	N1—C26—C27—C30	177.0 (2)
C8—C9—C10—C14^ii	179.5 (2)	C25—C26—C27—C30	−2.3 (4)
C9—C10—C11—C12	1.3 (4)	N2—C27—C30—C31	−0.5 (4)
C14^ii—C10—C11—C12	−177.7 (2)	C26—C27—C30—C31	−178.0 (3)
C10—C11—C12—C13	−2.2 (4)	N2—C27—C30—C29	178.5 (3)
C11—C12—C13—C8	1.3 (5)	C26—C27—C30—C29	0.9 (4)
O7—C8—C13—C12	177.3 (3)	C27—C30—C31—C32	1.0 (5)
C9—C8—C13—C12	0.6 (4)	C29—C30—C31—C32	−178.0 (3)
Co1—O4—C14—O3	11.6 (5)	C30—C31—C32—C33	−0.5 (5)
Co1—O4—C14—C10^iii	−168.8 (2)	C27—N2—C33—C32	1.0 (4)
Co2—O3—C14—O4	5.1 (4)	Co1—N2—C33—C32	−179.8 (2)
Co2—O3—C14—C10^iii	−174.49 (15)	C31—C32—C33—N2	−0.6 (5)
C3—O8—C15—C16	22.2 (4)	C24—C25—C28—C29	−177.7 (4)
C3—O8—C15—C20	−160.5 (2)	C26—C25—C28—C29	0.4 (5)
O8—C15—C16—C17	178.9 (2)	C25—C28—C29—C30	−1.8 (6)
C20—C15—C16—C17	1.8 (4)	C31—C30—C29—C28	−180.0 (4)
C15—C16—C17—C18	−1.0 (3)	C27—C30—C29—C28	1.1 (5)
C15—C16—C17—C21^ii	176.9 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···O4	0.93	2.57	3.105 (3)	117
O9—H9A···O6	0.83	1.73	2.509 (2)	157
C6—H6···O6^i	0.93	2.62	3.520 (3)	162
C20—H20···Cg1^iv	0.93	2.86	3.736 (3)	156
C24—H24···Cg2^iv	0.93	2.72	3.626 (4)	165
Cg3···Cg3^v			3.468 (3)

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

catena-Poly[[aqua(1,10-phenanthroline-κ²N,N')zinc(II)]-µ-5-(3-carboxyphenoxy)-3,3'-oxydibenzoato-κ²O¹:O³] (III)

Crystal data

[Zn(C21H12O8)(C12H8N2)(H2O)]	Z = 2
Mr = 655.89	F(000) = 672
Triclinic, P1	Dx = 1.606 Mg m^−3
a = 9.012 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.866 (3) Å	Cell parameters from 5258 reflections
c = 15.755 (4) Å	θ = 3.1–28.1°
α = 89.462 (8)°	µ = 0.97 mm^−1
β = 74.554 (7)°	T = 298 K
γ = 66.570 (7)°	Block, colourless
V = 1356.4 (5) Å^3	0.15 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	4691 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.040
Absorption correction: multi-scan (SADABS; Bruker, 2010)	θmax = 28.5°, θmin = 3.1°
	h = −11→9
15199 measured reflections	k = −14→14
6600 independent reflections	l = −21→20

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0345P)^2 + 0.3939P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
6600 reflections	Δρmax = 0.32 e Å^−3
415 parameters	Δρmin = −0.35 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.25766 (3)	0.28058 (3)	0.38889 (2)	0.03046 (9)
N1	0.4757 (2)	0.09906 (19)	0.35580 (13)	0.0343 (5)
N2	0.3834 (3)	0.2935 (2)	0.48649 (13)	0.0375 (5)
O1	0.3287 (2)	0.39620 (16)	0.30636 (11)	0.0413 (4)
O2	0.1096 (2)	0.59586 (18)	0.34594 (11)	0.0446 (5)
O3	0.72700 (19)	0.46148 (17)	0.03684 (11)	0.0394 (4)
O4	1.3098 (2)	0.0955 (2)	−0.02983 (13)	0.0514 (5)
H4A	1.405 (4)	0.025 (3)	−0.046 (2)	0.077*
O5	1.4055 (2)	0.12609 (19)	0.08074 (12)	0.0481 (5)
O6	0.2227 (2)	0.85179 (15)	0.07857 (10)	0.0373 (4)
O7	0.1579 (2)	1.18777 (17)	0.32020 (11)	0.0392 (4)
O8	−0.1194 (2)	1.2816 (2)	0.38593 (13)	0.0560 (5)
O9	0.0297 (2)	0.3602 (2)	0.47715 (11)	0.0455 (5)
H9A	−0.035 (3)	0.332 (3)	0.4583 (16)	0.068*
H9B	−0.011 (3)	0.376 (3)	0.5336 (7)	0.068*
C1	0.5635 (3)	0.5384 (2)	0.08963 (15)	0.0293 (5)
C2	0.4732 (3)	0.6583 (2)	0.06159 (15)	0.0295 (5)
H2	0.520909	0.687123	0.009762	0.035*
C3	0.3088 (3)	0.7354 (2)	0.11265 (14)	0.0264 (5)
C4	0.2367 (3)	0.6935 (2)	0.18970 (14)	0.0266 (5)
H4	0.127898	0.747319	0.224206	0.032*
C5	0.3290 (3)	0.5693 (2)	0.21515 (14)	0.0252 (5)
C6	0.4929 (3)	0.4917 (2)	0.16491 (15)	0.0296 (5)
H6	0.554914	0.408991	0.181661	0.036*
C7	0.2470 (3)	0.5188 (2)	0.29658 (15)	0.0282 (5)
C8	0.8567 (3)	0.4309 (2)	0.07585 (15)	0.0309 (5)
C9	1.0037 (3)	0.3180 (2)	0.03887 (15)	0.0315 (5)
H9	1.012874	0.264742	−0.009740	0.038*
C10	1.1380 (3)	0.2849 (2)	0.07527 (15)	0.0304 (5)
C11	1.1247 (3)	0.3652 (3)	0.14654 (17)	0.0402 (6)
H11	1.214730	0.343033	0.170478	0.048*
C12	0.9785 (3)	0.4778 (3)	0.18224 (19)	0.0480 (7)
H12	0.970185	0.531764	0.230244	0.058*
C13	0.8435 (3)	0.5117 (3)	0.14741 (18)	0.0422 (6)
H13	0.744691	0.588014	0.171815	0.051*
C14	1.2944 (3)	0.1615 (2)	0.04092 (16)	0.0338 (5)
C15	0.0884 (3)	0.9579 (2)	0.13626 (15)	0.0305 (5)
C16	0.1132 (3)	1.0209 (2)	0.20339 (15)	0.0308 (5)
H16	0.218404	0.988624	0.213669	0.037*
C17	−0.0202 (3)	1.1330 (2)	0.25575 (15)	0.0299 (5)
C18	−0.1766 (3)	1.1791 (2)	0.23941 (16)	0.0353 (6)
H18	−0.267194	1.252566	0.275043	0.042*
C19	−0.1981 (3)	1.1169 (2)	0.17099 (18)	0.0394 (6)
H19	−0.302453	1.150079	0.159615	0.047*
C20	−0.0664 (3)	1.0059 (2)	0.11909 (17)	0.0369 (6)
H20	−0.081404	0.963593	0.073000	0.044*
C21	0.0067 (3)	1.2069 (2)	0.32655 (16)	0.0334 (5)
C22	0.5207 (3)	0.0050 (3)	0.29004 (19)	0.0469 (7)
H22	0.453023	0.019414	0.252331	0.056*
C23	0.6655 (4)	−0.1147 (3)	0.2750 (2)	0.0581 (9)
H23	0.692923	−0.178678	0.228090	0.070*
C24	0.7658 (3)	−0.1374 (3)	0.3290 (2)	0.0578 (9)
H24	0.861055	−0.218041	0.320292	0.069*
C25	0.7260 (3)	−0.0390 (3)	0.39834 (19)	0.0432 (7)
C26	0.5770 (3)	0.0790 (2)	0.40895 (17)	0.0343 (6)
C27	0.5297 (3)	0.1838 (2)	0.47801 (16)	0.0341 (6)
C28	0.8249 (3)	−0.0511 (3)	0.4571 (2)	0.0574 (9)
H28	0.922582	−0.129162	0.450651	0.069*
C29	0.7814 (4)	0.0466 (3)	0.5218 (2)	0.0581 (9)
H29	0.848419	0.034724	0.559602	0.070*
C30	0.6332 (3)	0.1692 (3)	0.53345 (19)	0.0446 (7)
C31	0.5832 (4)	0.2768 (4)	0.5972 (2)	0.0603 (9)
H31	0.648813	0.272306	0.634784	0.072*
C32	0.4383 (4)	0.3888 (3)	0.6045 (2)	0.0628 (9)
H32	0.405278	0.461811	0.646060	0.075*
C33	0.3410 (4)	0.3917 (3)	0.54889 (19)	0.0540 (8)
H33	0.240207	0.467114	0.555891	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02886 (15)	0.02330 (14)	0.03090 (15)	−0.00299 (11)	−0.00748 (11)	0.00310 (11)
N1	0.0295 (10)	0.0257 (10)	0.0408 (11)	−0.0083 (9)	−0.0040 (9)	0.0001 (9)
N2	0.0374 (12)	0.0283 (11)	0.0393 (11)	−0.0047 (10)	−0.0128 (10)	0.0045 (10)
O1	0.0418 (10)	0.0283 (9)	0.0444 (10)	−0.0078 (8)	−0.0080 (8)	0.0128 (8)
O2	0.0392 (10)	0.0420 (10)	0.0315 (9)	−0.0039 (9)	0.0032 (8)	0.0078 (8)
O3	0.0224 (8)	0.0474 (11)	0.0334 (9)	−0.0002 (8)	−0.0058 (7)	−0.0049 (8)
O4	0.0346 (10)	0.0431 (11)	0.0598 (12)	0.0026 (9)	−0.0156 (10)	−0.0142 (10)
O5	0.0311 (9)	0.0508 (12)	0.0517 (11)	−0.0040 (9)	−0.0147 (9)	0.0012 (10)
O6	0.0434 (10)	0.0228 (8)	0.0283 (8)	0.0001 (8)	−0.0044 (8)	0.0035 (7)
O7	0.0298 (9)	0.0411 (10)	0.0395 (9)	−0.0072 (8)	−0.0094 (8)	−0.0079 (8)
O8	0.0356 (10)	0.0601 (13)	0.0553 (12)	−0.0102 (10)	0.0000 (9)	−0.0269 (11)
O9	0.0379 (10)	0.0557 (12)	0.0333 (9)	−0.0151 (10)	−0.0007 (8)	−0.0114 (9)
C1	0.0222 (11)	0.0299 (12)	0.0299 (12)	−0.0060 (10)	−0.0051 (10)	−0.0054 (10)
C2	0.0309 (12)	0.0297 (12)	0.0268 (11)	−0.0136 (11)	−0.0047 (10)	0.0018 (10)
C3	0.0287 (11)	0.0197 (11)	0.0279 (11)	−0.0058 (9)	−0.0097 (10)	−0.0002 (9)
C4	0.0212 (11)	0.0233 (11)	0.0276 (11)	−0.0036 (9)	−0.0034 (9)	0.0001 (9)
C5	0.0251 (11)	0.0240 (11)	0.0251 (11)	−0.0077 (10)	−0.0085 (9)	0.0008 (9)
C6	0.0272 (12)	0.0226 (11)	0.0328 (12)	−0.0027 (10)	−0.0105 (10)	0.0019 (10)
C7	0.0307 (12)	0.0296 (12)	0.0272 (11)	−0.0124 (11)	−0.0128 (10)	0.0043 (10)
C8	0.0260 (12)	0.0316 (12)	0.0324 (12)	−0.0108 (11)	−0.0056 (10)	0.0045 (11)
C9	0.0282 (12)	0.0275 (12)	0.0319 (12)	−0.0082 (10)	−0.0026 (10)	−0.0019 (10)
C10	0.0255 (11)	0.0271 (12)	0.0339 (12)	−0.0092 (10)	−0.0038 (10)	0.0040 (10)
C11	0.0320 (13)	0.0415 (15)	0.0468 (15)	−0.0134 (12)	−0.0132 (12)	−0.0023 (13)
C12	0.0397 (15)	0.0436 (16)	0.0572 (17)	−0.0113 (13)	−0.0165 (14)	−0.0157 (14)
C13	0.0315 (13)	0.0317 (13)	0.0540 (16)	−0.0060 (11)	−0.0076 (13)	−0.0098 (13)
C14	0.0292 (12)	0.0329 (13)	0.0384 (13)	−0.0141 (11)	−0.0060 (11)	0.0017 (11)
C15	0.0343 (13)	0.0192 (11)	0.0321 (12)	−0.0066 (10)	−0.0071 (11)	0.0043 (10)
C16	0.0266 (12)	0.0268 (12)	0.0354 (12)	−0.0066 (10)	−0.0102 (10)	0.0059 (10)
C17	0.0308 (12)	0.0232 (11)	0.0331 (12)	−0.0094 (10)	−0.0078 (10)	0.0040 (10)
C18	0.0287 (12)	0.0250 (12)	0.0450 (14)	−0.0062 (10)	−0.0066 (11)	0.0003 (11)
C19	0.0305 (13)	0.0291 (13)	0.0580 (16)	−0.0073 (11)	−0.0195 (13)	0.0060 (13)
C20	0.0429 (14)	0.0293 (13)	0.0422 (14)	−0.0157 (12)	−0.0170 (12)	0.0041 (11)
C21	0.0346 (13)	0.0237 (12)	0.0351 (13)	−0.0066 (11)	−0.0077 (11)	0.0003 (10)
C22	0.0367 (15)	0.0387 (15)	0.0557 (17)	−0.0117 (13)	−0.0035 (13)	−0.0067 (14)
C23	0.0451 (17)	0.0305 (15)	0.072 (2)	−0.0065 (14)	0.0110 (16)	−0.0143 (15)
C24	0.0298 (14)	0.0270 (14)	0.087 (2)	0.0010 (12)	0.0107 (16)	0.0091 (16)
C25	0.0233 (12)	0.0309 (13)	0.0626 (17)	−0.0057 (11)	−0.0009 (13)	0.0184 (13)
C26	0.0239 (11)	0.0279 (12)	0.0447 (14)	−0.0091 (10)	−0.0026 (11)	0.0119 (11)
C27	0.0274 (12)	0.0315 (13)	0.0406 (13)	−0.0113 (11)	−0.0071 (11)	0.0133 (11)
C28	0.0286 (14)	0.0463 (17)	0.086 (2)	−0.0062 (14)	−0.0134 (16)	0.0344 (18)
C29	0.0334 (15)	0.074 (2)	0.076 (2)	−0.0241 (16)	−0.0277 (16)	0.039 (2)
C30	0.0356 (14)	0.0522 (17)	0.0530 (16)	−0.0218 (14)	−0.0183 (13)	0.0202 (15)
C31	0.067 (2)	0.079 (2)	0.0580 (19)	−0.041 (2)	−0.0354 (17)	0.0184 (19)
C32	0.080 (2)	0.058 (2)	0.0590 (19)	−0.0292 (19)	−0.0322 (19)	−0.0022 (17)
C33	0.0618 (19)	0.0363 (15)	0.0545 (17)	−0.0051 (14)	−0.0251 (16)	−0.0022 (14)

Geometric parameters (Å, º)

Zn1—O1	1.9606 (17)	C10—C14	1.477 (3)
Zn1—O9	1.9973 (18)	C11—C12	1.373 (3)
Zn1—O7^i	2.0630 (17)	C11—H11	0.9300
Zn1—N1	2.101 (2)	C12—C13	1.383 (4)
Zn1—N2	2.174 (2)	C12—H12	0.9300
N1—C22	1.322 (3)	C13—H13	0.9300
N1—C26	1.352 (3)	C15—C16	1.377 (3)
N2—C33	1.322 (3)	C15—C20	1.382 (3)
N2—C27	1.355 (3)	C16—C17	1.391 (3)
O1—C7	1.271 (3)	C16—H16	0.9300
O2—C7	1.231 (3)	C17—C18	1.390 (3)
O3—C8	1.387 (3)	C17—C21	1.504 (3)
O3—C1	1.394 (3)	C18—C19	1.373 (3)
O4—C14	1.277 (3)	C18—H18	0.9300
O4—H4A	0.87 (3)	C19—C20	1.377 (3)
O5—C14	1.252 (3)	C19—H19	0.9300
O6—C3	1.385 (3)	C20—H20	0.9300
O6—C15	1.395 (3)	C22—C23	1.394 (4)
O7—C21	1.270 (3)	C22—H22	0.9300
O8—C21	1.241 (3)	C23—C24	1.354 (4)
O9—H9A	0.870 (10)	C23—H23	0.9300
O9—H9B	0.857 (10)	C24—C25	1.405 (4)
C1—C2	1.375 (3)	C24—H24	0.9300
C1—C6	1.383 (3)	C25—C26	1.411 (3)
C2—C3	1.391 (3)	C25—C28	1.419 (4)
C2—H2	0.9300	C26—C27	1.432 (3)
C3—C4	1.382 (3)	C27—C30	1.404 (4)
C4—C5	1.396 (3)	C28—C29	1.340 (4)
C4—H4	0.9300	C28—H28	0.9300
C5—C6	1.385 (3)	C29—C30	1.431 (4)
C5—C7	1.516 (3)	C29—H29	0.9300
C6—H6	0.9300	C30—C31	1.394 (4)
C8—C9	1.382 (3)	C31—C32	1.363 (4)
C8—C13	1.386 (3)	C31—H31	0.9300
C9—C10	1.394 (3)	C32—C33	1.388 (4)
C9—H9	0.9300	C32—H32	0.9300
C10—C11	1.378 (3)	C33—H33	0.9300
O1—Zn1—O9	118.80 (8)	C8—C13—H13	120.3
O1—Zn1—O7^i	104.52 (7)	O5—C14—O4	122.8 (2)
O9—Zn1—O7^i	86.94 (7)	O5—C14—C10	119.9 (2)
O1—Zn1—N1	101.40 (7)	O4—C14—C10	117.3 (2)
O9—Zn1—N1	139.65 (8)	C16—C15—C20	121.0 (2)
O7^i—Zn1—N1	86.20 (7)	C16—C15—O6	120.8 (2)
O1—Zn1—N2	98.23 (8)	C20—C15—O6	118.0 (2)
O9—Zn1—N2	92.63 (8)	C15—C16—C17	119.6 (2)
O7^i—Zn1—N2	154.24 (7)	C15—C16—H16	120.2
N1—Zn1—N2	77.52 (8)	C17—C16—H16	120.2
C22—N1—C26	118.3 (2)	C18—C17—C16	119.2 (2)
C22—N1—Zn1	126.72 (18)	C18—C17—C21	120.4 (2)
C26—N1—Zn1	114.94 (16)	C16—C17—C21	120.3 (2)
C33—N2—C27	117.3 (2)	C19—C18—C17	120.4 (2)
C33—N2—Zn1	129.95 (18)	C19—C18—H18	119.8
C27—N2—Zn1	112.77 (16)	C17—C18—H18	119.8
C7—O1—Zn1	129.48 (16)	C18—C19—C20	120.5 (2)
C8—O3—C1	117.27 (17)	C18—C19—H19	119.8
C14—O4—H4A	112 (2)	C20—C19—H19	119.8
C3—O6—C15	118.97 (17)	C19—C20—C15	119.3 (2)
C21—O7—Zn1^ii	131.76 (15)	C19—C20—H20	120.4
Zn1—O9—H9A	107.0 (19)	C15—C20—H20	120.4
Zn1—O9—H9B	137.2 (19)	O8—C21—O7	125.3 (2)
H9A—O9—H9B	106.6 (19)	O8—C21—C17	117.9 (2)
C2—C1—C6	121.7 (2)	O7—C21—C17	116.8 (2)
C2—C1—O3	117.5 (2)	N1—C22—C23	122.7 (3)
C6—C1—O3	120.7 (2)	N1—C22—H22	118.7
C1—C2—C3	118.4 (2)	C23—C22—H22	118.7
C1—C2—H2	120.8	C24—C23—C22	119.5 (3)
C3—C2—H2	120.8	C24—C23—H23	120.2
C4—C3—O6	123.3 (2)	C22—C23—H23	120.2
C4—C3—C2	121.3 (2)	C23—C24—C25	120.0 (3)
O6—C3—C2	115.33 (19)	C23—C24—H24	120.0
C3—C4—C5	119.2 (2)	C25—C24—H24	120.0
C3—C4—H4	120.4	C24—C25—C26	116.7 (3)
C5—C4—H4	120.4	C24—C25—C28	124.4 (3)
C6—C5—C4	120.0 (2)	C26—C25—C28	118.9 (3)
C6—C5—C7	120.5 (2)	N1—C26—C25	122.8 (2)
C4—C5—C7	119.5 (2)	N1—C26—C27	117.7 (2)
C1—C6—C5	119.4 (2)	C25—C26—C27	119.5 (2)
C1—C6—H6	120.3	N2—C27—C30	123.2 (2)
C5—C6—H6	120.3	N2—C27—C26	117.0 (2)
O2—C7—O1	125.7 (2)	C30—C27—C26	119.8 (2)
O2—C7—C5	119.1 (2)	C29—C28—C25	121.9 (3)
O1—C7—C5	115.2 (2)	C29—C28—H28	119.1
C9—C8—C13	120.5 (2)	C25—C28—H28	119.1
C9—C8—O3	117.4 (2)	C28—C29—C30	120.9 (3)
C13—C8—O3	122.0 (2)	C28—C29—H29	119.5
C8—C9—C10	119.2 (2)	C30—C29—H29	119.5
C8—C9—H9	120.4	C31—C30—C27	116.9 (3)
C10—C9—H9	120.4	C31—C30—C29	124.1 (3)
C11—C10—C9	120.2 (2)	C27—C30—C29	118.9 (3)
C11—C10—C14	118.6 (2)	C32—C31—C30	120.1 (3)
C9—C10—C14	121.2 (2)	C32—C31—H31	120.0
C12—C11—C10	120.0 (2)	C30—C31—H31	120.0
C12—C11—H11	120.0	C31—C32—C33	118.8 (3)
C10—C11—H11	120.0	C31—C32—H32	120.6
C11—C12—C13	120.6 (2)	C33—C32—H32	120.6
C11—C12—H12	119.7	N2—C33—C32	123.7 (3)
C13—C12—H12	119.7	N2—C33—H33	118.1
C12—C13—C8	119.4 (2)	C32—C33—H33	118.1
C12—C13—H13	120.3
C8—O3—C1—C2	122.1 (2)	C18—C19—C20—C15	−0.4 (4)
C8—O3—C1—C6	−61.0 (3)	C16—C15—C20—C19	−1.0 (4)
C6—C1—C2—C3	2.2 (3)	O6—C15—C20—C19	−175.3 (2)
O3—C1—C2—C3	178.97 (19)	Zn1^ii—O7—C21—O8	−8.5 (4)
C15—O6—C3—C4	26.7 (3)	Zn1^ii—O7—C21—C17	171.23 (14)
C15—O6—C3—C2	−156.2 (2)	C18—C17—C21—O8	21.3 (3)
C1—C2—C3—C4	−0.1 (3)	C16—C17—C21—O8	−161.4 (2)
C1—C2—C3—O6	−177.2 (2)	C18—C17—C21—O7	−158.4 (2)
O6—C3—C4—C5	174.9 (2)	C16—C17—C21—O7	18.9 (3)
C2—C3—C4—C5	−2.0 (3)	C26—N1—C22—C23	1.7 (4)
C3—C4—C5—C6	2.1 (3)	Zn1—N1—C22—C23	−177.7 (2)
C3—C4—C5—C7	−176.36 (19)	N1—C22—C23—C24	−0.2 (4)
C2—C1—C6—C5	−2.1 (3)	C22—C23—C24—C25	−1.6 (4)
O3—C1—C6—C5	−178.8 (2)	C23—C24—C25—C26	1.8 (4)
C4—C5—C6—C1	−0.1 (3)	C23—C24—C25—C28	−178.3 (3)
C7—C5—C6—C1	178.36 (19)	C22—N1—C26—C25	−1.5 (3)
Zn1—O1—C7—O2	9.5 (4)	Zn1—N1—C26—C25	178.02 (17)
Zn1—O1—C7—C5	−169.16 (14)	C22—N1—C26—C27	177.9 (2)
C6—C5—C7—O2	171.3 (2)	Zn1—N1—C26—C27	−2.6 (3)
C4—C5—C7—O2	−10.2 (3)	C24—C25—C26—N1	−0.2 (3)
C6—C5—C7—O1	−10.0 (3)	C28—C25—C26—N1	179.9 (2)
C4—C5—C7—O1	168.5 (2)	C24—C25—C26—C27	−179.6 (2)
C1—O3—C8—C9	156.1 (2)	C28—C25—C26—C27	0.5 (3)
C1—O3—C8—C13	−25.9 (3)	C33—N2—C27—C30	1.9 (4)
C13—C8—C9—C10	1.0 (3)	Zn1—N2—C27—C30	179.93 (19)
O3—C8—C9—C10	179.0 (2)	C33—N2—C27—C26	−178.6 (2)
C8—C9—C10—C11	−0.9 (3)	Zn1—N2—C27—C26	−0.5 (3)
C8—C9—C10—C14	176.9 (2)	N1—C26—C27—N2	2.1 (3)
C9—C10—C11—C12	0.3 (4)	C25—C26—C27—N2	−178.5 (2)
C14—C10—C11—C12	−177.5 (2)	N1—C26—C27—C30	−178.3 (2)
C10—C11—C12—C13	0.2 (4)	C25—C26—C27—C30	1.1 (3)
C11—C12—C13—C8	0.0 (4)	C24—C25—C28—C29	179.5 (3)
C9—C8—C13—C12	−0.5 (4)	C26—C25—C28—C29	−0.6 (4)
O3—C8—C13—C12	−178.5 (2)	C25—C28—C29—C30	−0.8 (4)
C11—C10—C14—O5	5.7 (3)	N2—C27—C30—C31	−2.8 (4)
C9—C10—C14—O5	−172.1 (2)	C26—C27—C30—C31	177.7 (2)
C11—C10—C14—O4	−173.9 (2)	N2—C27—C30—C29	177.1 (2)
C9—C10—C14—O4	8.3 (3)	C26—C27—C30—C29	−2.4 (4)
C3—O6—C15—C16	61.3 (3)	C28—C29—C30—C31	−177.8 (3)
C3—O6—C15—C20	−124.5 (2)	C28—C29—C30—C27	2.4 (4)
C20—C15—C16—C17	1.1 (3)	C27—C30—C31—C32	1.0 (4)
O6—C15—C16—C17	175.14 (19)	C29—C30—C31—C32	−178.8 (3)
C15—C16—C17—C18	0.3 (3)	C30—C31—C32—C33	1.3 (5)
C15—C16—C17—C21	−177.1 (2)	C27—N2—C33—C32	0.8 (4)
C16—C17—C18—C19	−1.7 (3)	Zn1—N2—C33—C32	−176.9 (2)
C21—C17—C18—C19	175.7 (2)	C31—C32—C33—N2	−2.4 (5)
C17—C18—C19—C20	1.7 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O5^iii	0.87 (3)	1.79 (3)	2.655 (3)	176 (3)
O9—H9A···O8^i	0.87 (1)	1.73 (1)	2.563 (3)	160 (3)
O9—H9B···O2^iv	0.86 (1)	1.84 (1)	2.694 (2)	175 (3)

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