Killing two birds with one stone: 2D+2D→3D parallel stacking and 3D self-penetrating structures in one reaction and their crystal-to-crystal transformation

Reaction of the flexible phenolic carboxyl­ate ligand 2-(3,5-di­carboxyl­benz­yl­oxy)benzoic acid (H₃L) with nickel salts in the presence of 1,2-bis­(pyridin-4-yl)ethyl­ene (bpe) leads to the generation of a mixture of the two complexes under solvolthermal conditions, namely poly[[aqua­[μ-1,2-bis­(pyridin-4-yl)ethyl­ene-κ²N:N′]{μ-5-[(2-carb­oxy­phen­oxy)meth­yl]benzene-1,3-di­carboxyl­ato-κ³O¹,O^1′:O³}nickel(II)] di­methyl­formamide hemisolvate monohydrate], {[Ni(C₁₆H₁₀O₇)(C₁₂H₁₀N₂)(H₂O)]·0.5C₃H₇NO·H₂O}_n or {[Ni(HL)(bpe)(H₂O)]·0.5DMF·H₂O}_n, 1, and poly[[di­aqua­tris­[μ-1,2-bis­(pyridin-4-yl)ethyl­ene-κ²N:N′]bis­{μ-5-[(2-car­boxy­phen­oxy)meth­yl]benzene-1,3-di­carboxyl­ato-κ²O¹:O⁵}nickel(II)] di­methyl­formamide disolvate hexa­hydrate], {[Ni₂(C₁₆H₁₀O₇)₂(C₁₂H₁₀N₂)₃(H₂O)₂]·2C₃H₇NO·6H₂O}_n or {[Ni₂(HL)₂(bpe)₃(H₂O)₂]·2DMF·6H₂O}_n, 2. In complex 1, the Ni^II centres are connected by the carboxyl­ate and bpe ligands to form two-dimensional (2D) 4-connected (4,4) layers, which are extended into a 2D+2D→3D (3D is three-dimensional) supra­molecular framework. In complex 2, bpe ligands connect to Ni^II centres to form 2D layers with Ni₆(bpe)₆ metallmacrocycles. Inter­estingly, 2D+2D→3D inclined polycatenation was observed between these layers. The final 5-connected 3D self-penetrating structure was generated through further connection of Ni–carboxyl­ate chains with these inclined motifs. Both complexes were fully characterized by single-crystal analysis, powder X-ray diffraction analysis, FT–IR spectra, elemental analyses, thermal analysis and UV–Vis spectra. Notably, an inter­esting metal/ligand-induced crystal-to-crystal transformation was observed between the two complexes.

Computing details

For both structures, data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008). Data reduction: SHELXTL (Bruker, 2008) for 1901754; SAINT (Bruker, 2008) for 1901755. For both structures, program(s) used to solve structure: SHELXS2014 (Sheldrick, 2014); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Bruker, 2008); software used to prepare material for publication: SHELXTL (Bruker, 2008).

Poly[[aqua[µ-1,2-bis(pyridin-4-yl)ethylene-κ²N:N']{µ-5-[(2-carboxyphenoxy)methyl]benzene-1,3-dicarboxylato-κ³O¹,O^1':O³}nickel(II)] dimethylformamide hemisolvate monohydrate] (1901754)

Crystal data

[Ni(C16H10O7)(C12H10N2)(H2O)]·0.5C3H7NO·H2O	Z = 2
Mr = 627.75	F(000) = 652
Triclinic, P1	Dx = 1.353 Mg m^−3
a = 10.2700 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.9701 (9) Å	Cell parameters from 1944 reflections
c = 12.5459 (11) Å	θ = 2.6–22.5°
α = 90.821 (1)°	µ = 0.69 mm^−1
β = 91.089 (1)°	T = 298 K
γ = 92.278 (2)°	Block, green
V = 1540.6 (2) Å^3	0.37 × 0.30 × 0.15 mm

Data collection

Bruker SMART CCD area detector diffractometer	3700 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.046
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 25.0°, θmin = 2.3°
Tmin = 0.781, Tmax = 0.902	h = −11→12
7884 measured reflections	k = −13→14
5367 independent reflections	l = −8→14

Refinement

Refinement on F^2	110 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.079	H-atom parameters constrained
wR(F^2) = 0.234	w = 1/[σ^2(Fo^2) + (0.1535P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
5367 reflections	Δρmax = 1.19 e Å^−3
410 parameters	Δρmin = −0.47 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	Occ. (<1)
Ni1	0.06023 (6)	0.49966 (5)	0.75087 (5)	0.0334 (3)
N1	0.0598 (4)	0.3376 (4)	0.8169 (4)	0.0431 (11)
N2	0.0506 (4)	0.6590 (4)	0.6803 (3)	0.0374 (10)
N3	0.3896 (9)	0.7223 (10)	0.0255 (9)	0.065 (3)	0.5
O1	0.2650 (3)	0.5160 (3)	0.7745 (3)	0.0416 (9)
O2	0.1804 (3)	0.4398 (3)	0.6261 (3)	0.0391 (9)
O3	0.8769 (3)	0.4651 (3)	0.6947 (3)	0.0412 (9)
O4	0.7594 (4)	0.5610 (4)	0.8100 (4)	0.0614 (12)
O5	0.6043 (4)	0.1717 (3)	0.4660 (3)	0.0611 (12)
O6	0.7126 (5)	−0.1189 (5)	0.5999 (5)	0.101 (2)
O7	0.6920 (6)	0.0615 (5)	0.6250 (4)	0.0916 (17)
H7A	0.6779	0.1172	0.5900	0.137*
O8	−0.0023 (3)	0.5605 (3)	0.8975 (3)	0.0445 (9)
H8C	−0.0850	0.5617	0.8966	0.067*
H8E	0.0297	0.6263	0.9080	0.067*
O9	0.7057 (12)	0.7999 (9)	0.8072 (7)	0.241 (6)
H9E	0.7078	0.8231	0.7436	0.290*
H9F	0.7213	0.7307	0.8066	0.290*
O10	0.1789 (10)	0.6967 (10)	−0.0150 (9)	0.088 (3)	0.5
C1	0.2789 (5)	0.4673 (4)	0.6846 (4)	0.0328 (11)
C2	0.4136 (5)	0.4405 (4)	0.6495 (4)	0.0354 (12)
C3	0.5231 (5)	0.4806 (4)	0.7057 (4)	0.0365 (12)
H3	0.5142	0.5238	0.7672	0.044*
C4	0.6484 (5)	0.4562 (5)	0.6698 (4)	0.0395 (13)
C5	0.7724 (5)	0.4982 (5)	0.7311 (4)	0.0409 (13)
C6	0.6599 (5)	0.3914 (5)	0.5791 (4)	0.0410 (13)
H6	0.7423	0.3746	0.5557	0.049*
C7	0.4267 (5)	0.3768 (4)	0.5560 (4)	0.0384 (12)
H7	0.3529	0.3522	0.5169	0.046*
C8	0.5496 (5)	0.3502 (5)	0.5216 (4)	0.0399 (13)
C9	0.5660 (6)	0.2761 (5)	0.4247 (5)	0.0485 (14)
H9A	0.4848	0.2669	0.3843	0.058*
H9B	0.6325	0.3076	0.3788	0.058*
C10	0.6238 (6)	0.0822 (5)	0.3981 (6)	0.0551 (16)
C11	0.6046 (7)	0.0866 (7)	0.2894 (6)	0.072 (2)
H11	0.5765	0.1514	0.2578	0.086*
C12	0.6281 (9)	−0.0076 (8)	0.2275 (7)	0.095 (3)
H12	0.6139	−0.0057	0.1541	0.114*
C13	0.6720 (9)	−0.1038 (7)	0.2731 (9)	0.098 (3)
H13	0.6914	−0.1651	0.2307	0.117*
C14	0.6860 (7)	−0.1073 (6)	0.3791 (8)	0.083 (2)
H14	0.7103	−0.1738	0.4097	0.099*
C15	0.6660 (6)	−0.0153 (5)	0.4460 (6)	0.0607 (18)
C16	0.6912 (7)	−0.0278 (7)	0.5605 (7)	0.072 (2)
C17	0.0457 (10)	0.0408 (8)	1.0023 (10)	0.072 (3)	0.515 (12)
H17	0.1130	0.0426	1.0530	0.086*	0.515 (12)
C18	0.0331 (9)	0.1303 (6)	0.9201 (7)	0.083 (2)
C19	−0.0374 (9)	0.1524 (6)	0.8286 (7)	0.083 (2)
H19	−0.0955	0.0978	0.8002	0.100*
C20	−0.0230 (7)	0.2553 (5)	0.7780 (6)	0.0639 (18)
H20	−0.0714	0.2676	0.7161	0.077*
C21	0.1342 (6)	0.3146 (5)	0.9013 (5)	0.0550 (16)
H21	0.1969	0.3676	0.9257	0.066*
C22	0.1206 (9)	0.2135 (7)	0.9540 (6)	0.081 (2)
H22	0.1725	0.2020	1.0141	0.098*
C23	0.0124 (7)	0.9858 (7)	0.5486 (5)	0.094 (3)
H23	0.0241	1.0436	0.5986	0.113*
C24	0.0242 (6)	0.8693 (6)	0.5885 (7)	0.069 (2)
C25	0.0657 (7)	0.8576 (6)	0.6891 (7)	0.071 (2)
H25	0.0855	0.9213	0.7305	0.085*
C26	0.0797 (6)	0.7567 (5)	0.7324 (5)	0.0537 (16)
H26	0.1113	0.7539	0.8022	0.064*
C27	0.0067 (6)	0.6668 (5)	0.5816 (5)	0.0528 (16)
H27	−0.0160	0.6015	0.5434	0.063*
C28	−0.0072 (7)	0.7701 (7)	0.5320 (6)	0.074 (2)
H28	−0.0373	0.7726	0.4617	0.088*
C29	0.2837 (12)	0.6669 (14)	−0.0078 (12)	0.078 (3)	0.5
H29	0.2948	0.5930	−0.0286	0.094*	0.5
C30	0.3695 (18)	0.8181 (14)	0.0925 (16)	0.126 (5)	0.5
H30A	0.3325	0.8388	0.1593	0.188*	0.5
H30B	0.3224	0.8517	0.0352	0.188*	0.5
H30C	0.4592	0.8436	0.0915	0.188*	0.5
C31	0.5098 (14)	0.6639 (16)	0.0264 (16)	0.115 (5)	0.5
H31A	0.4969	0.5850	0.0132	0.173*	0.5
H31B	0.5578	0.6763	0.0922	0.173*	0.5
H31C	0.5577	0.6969	−0.0310	0.173*	0.5
C17'	−0.0188 (14)	0.0155 (9)	0.9518 (6)	0.072 (3)	0.485 (12)
H17'	−0.0727	−0.0295	0.9073	0.086*	0.485 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0222 (4)	0.0342 (4)	0.0438 (5)	0.0003 (3)	0.0007 (3)	0.0086 (3)
N1	0.040 (3)	0.040 (3)	0.050 (3)	0.002 (2)	0.013 (2)	0.010 (2)
N2	0.028 (2)	0.040 (3)	0.045 (3)	0.0000 (19)	0.0028 (19)	0.014 (2)
N3	0.033 (4)	0.094 (7)	0.066 (6)	−0.007 (5)	−0.016 (4)	−0.018 (5)
O1	0.0234 (18)	0.053 (2)	0.048 (2)	−0.0005 (16)	−0.0012 (16)	0.0010 (18)
O2	0.0241 (18)	0.049 (2)	0.044 (2)	−0.0006 (16)	−0.0011 (15)	0.0031 (17)
O3	0.0184 (17)	0.049 (2)	0.056 (2)	0.0000 (15)	0.0005 (16)	−0.0009 (18)
O4	0.030 (2)	0.081 (3)	0.073 (3)	0.011 (2)	−0.011 (2)	−0.026 (3)
O5	0.070 (3)	0.049 (3)	0.065 (3)	0.012 (2)	−0.002 (2)	−0.006 (2)
O6	0.076 (4)	0.090 (4)	0.139 (5)	0.016 (3)	0.015 (3)	0.046 (4)
O7	0.105 (5)	0.090 (4)	0.080 (4)	0.011 (3)	−0.007 (3)	0.012 (3)
O8	0.0328 (19)	0.051 (2)	0.050 (2)	0.0002 (17)	0.0041 (17)	0.0007 (18)
O9	0.379 (17)	0.246 (12)	0.110 (7)	0.168 (11)	−0.036 (8)	0.009 (7)
O10	0.061 (5)	0.108 (7)	0.091 (6)	−0.012 (5)	−0.001 (5)	−0.036 (5)
C1	0.025 (3)	0.034 (3)	0.039 (3)	−0.003 (2)	0.000 (2)	0.008 (2)
C2	0.021 (2)	0.040 (3)	0.045 (3)	0.000 (2)	0.001 (2)	0.005 (2)
C3	0.029 (3)	0.042 (3)	0.039 (3)	0.003 (2)	0.005 (2)	−0.002 (2)
C4	0.018 (2)	0.046 (3)	0.054 (3)	0.002 (2)	−0.003 (2)	0.002 (3)
C5	0.035 (3)	0.040 (3)	0.046 (3)	−0.006 (2)	−0.002 (2)	0.003 (3)
C6	0.025 (3)	0.049 (3)	0.049 (3)	0.005 (2)	0.002 (2)	0.002 (3)
C7	0.028 (3)	0.042 (3)	0.045 (3)	−0.004 (2)	−0.001 (2)	0.004 (2)
C8	0.033 (3)	0.040 (3)	0.047 (3)	−0.001 (2)	0.002 (2)	0.000 (2)
C9	0.039 (3)	0.054 (4)	0.052 (4)	0.003 (3)	0.004 (3)	−0.004 (3)
C10	0.040 (3)	0.052 (4)	0.073 (5)	−0.006 (3)	0.000 (3)	−0.010 (3)
C11	0.061 (4)	0.076 (5)	0.078 (5)	−0.003 (4)	0.002 (4)	−0.023 (4)
C12	0.090 (6)	0.111 (8)	0.083 (6)	−0.002 (6)	0.012 (5)	−0.030 (6)
C13	0.104 (7)	0.066 (6)	0.123 (8)	0.012 (5)	0.006 (6)	−0.038 (6)
C14	0.061 (5)	0.054 (5)	0.133 (8)	−0.003 (4)	0.008 (5)	−0.004 (5)
C15	0.039 (3)	0.046 (4)	0.097 (6)	−0.002 (3)	0.008 (3)	−0.003 (4)
C16	0.044 (4)	0.063 (5)	0.109 (7)	0.001 (3)	0.010 (4)	0.019 (5)
C17	0.092 (6)	0.048 (5)	0.077 (6)	0.014 (4)	0.022 (5)	0.025 (4)
C18	0.109 (5)	0.049 (4)	0.094 (5)	0.018 (3)	0.053 (4)	0.029 (3)
C19	0.101 (5)	0.046 (4)	0.104 (5)	0.004 (3)	0.041 (4)	0.015 (3)
C20	0.070 (4)	0.043 (4)	0.079 (5)	−0.007 (3)	0.018 (4)	0.008 (3)
C21	0.062 (4)	0.055 (4)	0.050 (4)	0.021 (3)	0.009 (3)	0.022 (3)
C22	0.104 (5)	0.068 (4)	0.077 (4)	0.037 (4)	0.027 (4)	0.031 (3)
C23	0.057 (5)	0.086 (6)	0.140 (9)	0.006 (4)	0.016 (5)	0.057 (6)
C24	0.045 (4)	0.045 (4)	0.118 (7)	0.003 (3)	0.016 (4)	0.034 (4)
C25	0.068 (5)	0.040 (4)	0.106 (6)	0.002 (3)	−0.001 (4)	0.019 (4)
C26	0.052 (4)	0.042 (4)	0.066 (4)	−0.009 (3)	−0.004 (3)	0.013 (3)
C27	0.054 (4)	0.053 (4)	0.052 (4)	0.009 (3)	−0.003 (3)	0.015 (3)
C28	0.057 (4)	0.096 (6)	0.071 (5)	0.024 (4)	0.013 (4)	0.041 (4)
C29	0.046 (6)	0.102 (8)	0.086 (7)	−0.007 (6)	−0.004 (6)	−0.022 (6)
C30	0.068 (8)	0.157 (10)	0.149 (10)	−0.014 (8)	0.000 (8)	−0.041 (9)
C31	0.076 (8)	0.151 (10)	0.117 (9)	−0.007 (8)	0.006 (8)	−0.015 (9)
C17'	0.092 (6)	0.048 (5)	0.077 (6)	0.014 (4)	0.022 (5)	0.025 (4)

Geometric parameters (Å, º)

Ni1—O3^i	2.023 (3)	C10—C15	1.401 (9)
Ni1—O8	2.091 (4)	C11—C12	1.391 (11)
Ni1—N2	2.119 (4)	C11—H11	0.9300
Ni1—O1	2.119 (3)	C12—C13	1.381 (12)
Ni1—N1	2.120 (4)	C12—H12	0.9300
Ni1—O2	2.144 (4)	C13—C14	1.336 (12)
N1—C21	1.333 (7)	C13—H13	0.9300
N1—C20	1.355 (8)	C14—C15	1.399 (11)
N2—C27	1.316 (7)	C14—H14	0.9300
N2—C26	1.352 (7)	C15—C16	1.466 (11)
N3—C29	1.310 (9)	C17—C17^iii	1.328 (10)
N3—C30	1.436 (9)	C17—C18	1.505 (9)
N3—C31	1.442 (9)	C17—H17	0.9300
O1—C1	1.276 (6)	C18—C22	1.373 (12)
O2—C1	1.269 (6)	C18—C19	1.379 (12)
O3—C5	1.251 (7)	C18—C17'	1.515 (9)
O3—Ni1^ii	2.023 (3)	C19—C20	1.398 (9)
O4—C5	1.248 (7)	C19—H19	0.9300
O5—C10	1.382 (8)	C20—H20	0.9300
O5—C9	1.426 (7)	C21—C22	1.390 (9)
O6—C16	1.230 (8)	C21—H21	0.9300
O7—C16	1.330 (10)	C22—H22	0.9300
O7—H7A	0.8200	C23—C23^iv	1.293 (9)
O8—H8C	0.8500	C23—C24	1.498 (10)
O8—H8E	0.8498	C23—H23	0.9300
O9—H9E	0.8500	C24—C25	1.336 (10)
O9—H9F	0.8501	C24—C28	1.397 (11)
O10—C29	1.149 (16)	C25—C26	1.343 (8)
C1—C2	1.506 (7)	C25—H25	0.9300
C2—C3	1.382 (7)	C26—H26	0.9300
C2—C7	1.401 (8)	C27—C28	1.404 (9)
C3—C4	1.412 (7)	C27—H27	0.9300
C3—H3	0.9300	C28—H28	0.9300
C4—C6	1.378 (8)	C29—H29	0.9300
C4—C5	1.537 (7)	C30—H30A	0.9601
C6—C8	1.400 (7)	C30—H30B	0.9600
C6—H6	0.9300	C30—H30C	0.9599
C7—C8	1.389 (7)	C31—H31A	0.9600
C7—H7	0.9300	C31—H31B	0.9601
C8—C9	1.511 (8)	C31—H31C	0.9600
C9—H9A	0.9700	C17'—C17'^iii	1.325 (10)
C9—H9B	0.9700	C17'—H17'	0.9300
C10—C11	1.377 (9)
O3^i—Ni1—O8	93.65 (14)	C13—C12—H12	119.4
O3^i—Ni1—N2	88.08 (15)	C11—C12—H12	119.4
O8—Ni1—N2	92.26 (16)	C14—C13—C12	118.8 (8)
O3^i—Ni1—O1	165.91 (15)	C14—C13—H13	120.6
O8—Ni1—O1	100.35 (14)	C12—C13—H13	120.6
N2—Ni1—O1	92.89 (15)	C13—C14—C15	123.0 (8)
O3^i—Ni1—N1	88.72 (16)	C13—C14—H14	118.5
O8—Ni1—N1	88.46 (16)	C15—C14—H14	118.5
N2—Ni1—N1	176.76 (17)	C14—C15—C10	117.3 (7)
O1—Ni1—N1	90.10 (16)	C14—C15—C16	117.9 (7)
O3^i—Ni1—O2	103.49 (14)	C10—C15—C16	124.9 (7)
O8—Ni1—O2	162.49 (13)	O6—C16—O7	118.2 (8)
N2—Ni1—O2	91.84 (15)	O6—C16—C15	122.0 (8)
O1—Ni1—O2	62.44 (14)	O7—C16—C15	119.8 (6)
N1—Ni1—O2	88.40 (16)	C17^iii—C17—C18	115.6 (11)
C21—N1—C20	117.7 (5)	C17^iii—C17—H17	122.2
C21—N1—Ni1	121.8 (4)	C18—C17—H17	122.2
C20—N1—Ni1	120.4 (4)	C22—C18—C19	115.5 (6)
C27—N2—C26	116.1 (5)	C22—C18—C17	104.1 (7)
C27—N2—Ni1	119.6 (4)	C19—C18—C17	140.3 (8)
C26—N2—Ni1	124.2 (4)	C22—C18—C17'	140.6 (8)
C29—N3—C30	115.6 (13)	C19—C18—C17'	103.8 (7)
C29—N3—C31	117.6 (14)	C18—C19—C20	121.2 (8)
C30—N3—C31	122.8 (13)	C18—C19—H19	119.4
C1—O1—Ni1	88.9 (3)	C20—C19—H19	119.4
C1—O2—Ni1	88.0 (3)	N1—C20—C19	121.5 (7)
C5—O3—Ni1^ii	128.0 (4)	N1—C20—H20	119.3
C10—O5—C9	120.5 (5)	C19—C20—H20	119.3
C16—O7—H7A	109.5	N1—C21—C22	121.8 (7)
Ni1—O8—H8C	109.3	N1—C21—H21	119.1
Ni1—O8—H8E	109.1	C22—C21—H21	119.1
H8C—O8—H8E	109.5	C18—C22—C21	122.1 (8)
H9E—O9—H9F	108.4	C18—C22—H22	119.0
O2—C1—O1	120.6 (5)	C21—C22—H22	119.0
O2—C1—C2	120.2 (5)	C23^iv—C23—C24	126.5 (11)
O1—C1—C2	119.2 (4)	C23^iv—C23—H23	116.7
C3—C2—C7	120.1 (5)	C24—C23—H23	116.7
C3—C2—C1	121.1 (5)	C25—C24—C28	115.9 (6)
C7—C2—C1	118.7 (4)	C25—C24—C23	117.5 (7)
C2—C3—C4	120.0 (5)	C28—C24—C23	126.6 (7)
C2—C3—H3	120.0	C24—C25—C26	122.0 (7)
C4—C3—H3	120.0	C24—C25—H25	119.0
C6—C4—C3	119.2 (5)	C26—C25—H25	119.0
C6—C4—C5	119.3 (5)	C25—C26—N2	123.8 (6)
C3—C4—C5	121.5 (5)	C25—C26—H26	118.1
O4—C5—O3	126.9 (5)	N2—C26—H26	118.1
O4—C5—C4	117.9 (5)	N2—C27—C28	122.3 (7)
O3—C5—C4	115.2 (5)	N2—C27—H27	118.8
C4—C6—C8	121.2 (5)	C28—C27—H27	118.8
C4—C6—H6	119.4	C24—C28—C27	119.8 (7)
C8—C6—H6	119.4	C24—C28—H28	120.1
C8—C7—C2	120.1 (5)	C27—C28—H28	120.1
C8—C7—H7	119.9	O10—C29—N3	129.1 (16)
C2—C7—H7	119.9	O10—C29—H29	115.4
C7—C8—C6	119.2 (5)	N3—C29—H29	115.4
C7—C8—C9	121.2 (5)	N3—C30—H30A	141.5
C6—C8—C9	119.6 (5)	N3—C30—H30B	89.8
O5—C9—C8	105.1 (5)	H30A—C30—H30B	109.5
O5—C9—H9A	110.7	N3—C30—H30C	93.8
C8—C9—H9A	110.7	H30A—C30—H30C	109.5
O5—C9—H9B	110.7	H30B—C30—H30C	109.5
C8—C9—H9B	110.7	N3—C31—H31A	113.0
H9A—C9—H9B	108.8	N3—C31—H31B	111.6
C11—C10—O5	123.1 (6)	H31A—C31—H31B	109.5
C11—C10—C15	120.8 (7)	N3—C31—H31C	103.7
O5—C10—C15	116.1 (6)	H31A—C31—H31C	109.5
C10—C11—C12	118.9 (8)	H31B—C31—H31C	109.5
C10—C11—H11	120.6	C17'^iii—C17'—C18	114.6 (11)
C12—C11—H11	120.6	C17'^iii—C17'—H17'	122.7
C13—C12—C11	121.2 (9)	C18—C17'—H17'	122.7

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

Poly[[diaquatris[µ-1,2-bis(pyridin-4-yl)ethylene-κ²N:N']bis{µ-5-[(2-carboxyphenoxy)methyl]benzene-1,3-dicarboxylato-κ²O¹:O⁵}nickel(II)] dimethylformamide disolvate hexahydrate] (1901755)

Crystal data

[Ni2(C16H10O7)2(C12H10N2)3(H2O)2]·2C3H7NO·6H2O	F(000) = 1656
Mr = 1582.88	Dx = 1.382 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.5030 (9) Å	Cell parameters from 5603 reflections
b = 16.4391 (14) Å	θ = 2.4–26.5°
c = 20.5549 (18) Å	µ = 0.58 mm^−1
β = 101.816 (2)°	T = 298 K
V = 3804.5 (6) Å^3	Lamellar, green
Z = 2	0.45 × 0.40 × 0.37 mm

Data collection

Bruker SMART CCD area detector diffractometer	4884 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.038
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 25.0°, θmin = 2.4°
Tmin = 0.76, Tmax = 0.81	h = −13→11
18858 measured reflections	k = −18→19
6707 independent reflections	l = −23→24

Refinement

Refinement on F^2	1259 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.124	w = 1/[σ^2(Fo^2) + (0.0542P)^2 + 3.5857P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.002
6707 reflections	Δρmax = 1.27 e Å^−3
491 parameters	Δρmin = −0.62 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	0.70945 (3)	0.27379 (2)	0.27495 (2)	0.02095 (12)
O1	0.55099 (19)	0.21412 (13)	0.27881 (10)	0.0311 (5)
O2	0.4249 (2)	0.18155 (17)	0.18476 (11)	0.0485 (7)
O3	0.2549 (2)	0.1491 (2)	0.49681 (12)	0.0614 (8)
H3A	0.2752	0.1619	0.5361	0.092*
O4	0.4279 (3)	0.20547 (17)	0.49048 (12)	0.0548 (8)
O5	0.04955 (19)	−0.01246 (13)	0.25710 (12)	0.0377 (6)
O7	0.12839 (18)	−0.16751 (12)	0.21716 (10)	0.0284 (5)
O6	0.0466 (2)	−0.24188 (15)	0.28579 (14)	0.0484 (7)
O9	1.0802 (4)	1.0608 (3)	0.1042 (2)	0.1123 (14)
O8	0.7450 (2)	0.19093 (12)	0.20530 (10)	0.0306 (5)
H8A	0.7188	0.2094	0.1664	0.046*
H8B	0.8197	0.1838	0.2110	0.046*
O10	0.5640 (2)	0.19666 (16)	0.09569 (11)	0.0462 (6)
H10C	0.5082	0.1920	0.1170	0.055*
H10A	0.5572	0.2419	0.0752	0.055*
O11	0.2631 (3)	0.2032 (2)	0.61371 (14)	0.0812 (11)
H11D	0.1952	0.2242	0.6126	0.097*
H11A	0.3167	0.2392	0.6239	0.097*
O12	0.9516 (3)	0.7326 (3)	0.39609 (17)	0.0922 (12)
H12D	0.9783	0.7422	0.3612	0.111*
H12A	0.9477	0.6817	0.4022	0.111*
N1	0.6684 (2)	0.35426 (15)	0.34603 (12)	0.0252 (6)
N2	0.6361 (2)	0.35375 (15)	0.19691 (12)	0.0265 (6)
N3	0.7932 (2)	0.19225 (16)	0.35020 (13)	0.0297 (6)
N4	0.9126 (5)	0.9872 (4)	0.0627 (2)	0.0937 (15)
C16	0.0453 (3)	−0.18417 (19)	0.24655 (16)	0.0291 (7)
C15	−0.0639 (3)	−0.13173 (19)	0.23218 (16)	0.0295 (7)
C14	−0.1741 (3)	−0.1696 (2)	0.21466 (18)	0.0400 (8)
H14A	−0.1776	−0.2261	0.2140	0.048*
C13	−0.2781 (3)	−0.1256 (2)	0.1983 (2)	0.0500 (10)
H13	−0.3509	−0.1520	0.1867	0.060*
C12	−0.2724 (3)	−0.0423 (2)	0.1994 (2)	0.0482 (10)
H12	−0.3418	−0.0120	0.1877	0.058*
C11	−0.1645 (3)	−0.0031 (2)	0.21770 (19)	0.0393 (8)
H11	−0.1621	0.0534	0.2184	0.047*
C10	−0.0598 (3)	−0.04705 (19)	0.23506 (16)	0.0300 (7)
C9	0.0532 (3)	0.07412 (19)	0.26154 (18)	0.0335 (8)
H9A	−0.0038	0.0928	0.2871	0.040*
H9B	0.0318	0.0975	0.2174	0.040*
C8	0.1756 (3)	0.10167 (18)	0.29437 (16)	0.0281 (7)
C6	0.2022 (3)	0.11466 (19)	0.36217 (16)	0.0314 (7)
H6	0.1467	0.1010	0.3875	0.038*
C4	0.3104 (3)	0.14782 (19)	0.39299 (16)	0.0315 (7)
C5	0.3379 (3)	0.1702 (2)	0.46498 (17)	0.0404 (9)
C3	0.3929 (3)	0.16655 (19)	0.35518 (15)	0.0295 (7)
H3	0.4663	0.1874	0.3759	0.035*
C2	0.3685 (3)	0.15491 (18)	0.28712 (15)	0.0262 (7)
C7	0.2594 (3)	0.12174 (18)	0.25701 (16)	0.0286 (7)
H7	0.2423	0.1129	0.2113	0.034*
C1	0.4558 (3)	0.18543 (19)	0.24661 (16)	0.0284 (7)
C21	0.7711 (3)	0.1127 (2)	0.34664 (19)	0.0418 (9)
H21	0.7122	0.0932	0.3123	0.050*
C22	0.8331 (4)	0.0574 (3)	0.3925 (2)	0.0626 (12)
H22	0.8173	0.0020	0.3879	0.075*
C18	0.9199 (4)	0.0866 (3)	0.4459 (2)	0.0645 (13)
C19	0.9387 (4)	0.1679 (3)	0.4493 (2)	0.0617 (12)
H19	0.9939	0.1904	0.4841	0.074*
C20	0.8765 (3)	0.2152 (2)	0.40169 (18)	0.0464 (9)
H20	0.8935	0.2705	0.4050	0.056*
C26	0.6684 (3)	0.43501 (19)	0.33922 (15)	0.0306 (7)
H26	0.7029	0.4572	0.3061	0.037*
C25	0.6195 (3)	0.4872 (2)	0.37911 (16)	0.0358 (8)
H25	0.6201	0.5431	0.3719	0.043*
C24	0.5696 (3)	0.4561 (2)	0.42986 (15)	0.0318 (7)
C23	0.5175 (3)	0.5112 (2)	0.47238 (16)	0.0376 (8)
H23	0.5084	0.5655	0.4598	0.045*
C28	0.5726 (3)	0.3724 (2)	0.43773 (16)	0.0337 (8)
H28	0.5411	0.3487	0.4714	0.040*
C27	0.6219 (3)	0.32474 (19)	0.39611 (15)	0.0298 (7)
H27	0.6234	0.2688	0.4028	0.036*
C33	0.6981 (3)	0.3743 (2)	0.15084 (16)	0.0368 (8)
H33	0.7758	0.3557	0.1560	0.044*
C34	0.6530 (3)	0.4213 (2)	0.09656 (17)	0.0420 (9)
H34	0.7002	0.4340	0.0662	0.050*
C30	0.5378 (3)	0.4498 (2)	0.08663 (16)	0.0390 (8)
C29	0.4813 (3)	0.4972 (2)	0.02776 (17)	0.0443 (9)
H29	0.4127	0.5258	0.0305	0.053*
C31	0.4748 (3)	0.4300 (2)	0.13521 (17)	0.0431 (9)
H31	0.3978	0.4492	0.1319	0.052*
C32	0.5261 (3)	0.3822 (2)	0.18814 (16)	0.0362 (8)
H32	0.4812	0.3690	0.2195	0.043*
C36	0.8548 (7)	0.9101 (5)	0.0487 (3)	0.126 (2)
H36A	0.9079	0.8675	0.0680	0.189*
H36B	0.8331	0.9024	0.0015	0.189*
H36C	0.7848	0.9087	0.0673	0.189*
C37	0.8452 (7)	1.0606 (5)	0.0466 (4)	0.136 (3)
H37A	0.8977	1.1066	0.0537	0.204*
H37B	0.7879	1.0653	0.0744	0.204*
H37C	0.8049	1.0590	0.0008	0.204*
C35	1.0257 (6)	0.9922 (5)	0.0917 (3)	0.0974 (19)
H35	1.0679	0.9444	0.1037	0.117*
C17	0.9963 (5)	0.0374 (2)	0.4992 (3)	0.0875 (17)
H17	1.0426	0.0658	0.5343	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0219 (2)	0.0209 (2)	0.0202 (2)	0.00201 (16)	0.00443 (15)	0.00322 (15)
O1	0.0242 (12)	0.0383 (13)	0.0317 (12)	−0.0079 (10)	0.0075 (10)	0.0012 (10)
O2	0.0452 (16)	0.0723 (18)	0.0288 (13)	−0.0189 (14)	0.0097 (12)	−0.0009 (12)
O3	0.0547 (19)	0.099 (2)	0.0357 (15)	−0.0242 (17)	0.0206 (14)	−0.0117 (15)
O4	0.0575 (18)	0.0729 (19)	0.0341 (14)	−0.0282 (15)	0.0094 (13)	−0.0100 (13)
O5	0.0243 (12)	0.0225 (12)	0.0630 (16)	−0.0041 (9)	0.0016 (11)	−0.0082 (11)
O7	0.0249 (12)	0.0283 (12)	0.0329 (12)	0.0013 (9)	0.0083 (10)	−0.0022 (9)
O6	0.0377 (15)	0.0392 (15)	0.0747 (19)	0.0058 (11)	0.0264 (14)	0.0213 (13)
O9	0.099 (3)	0.143 (4)	0.092 (3)	0.013 (3)	0.011 (3)	−0.013 (3)
O8	0.0307 (13)	0.0287 (12)	0.0329 (12)	0.0056 (10)	0.0080 (10)	−0.0005 (9)
O10	0.0521 (17)	0.0522 (16)	0.0347 (13)	−0.0039 (13)	0.0100 (12)	−0.0032 (11)
O11	0.060 (2)	0.133 (3)	0.0540 (18)	−0.002 (2)	0.0183 (16)	−0.0284 (19)
O12	0.079 (3)	0.132 (3)	0.072 (2)	0.008 (2)	0.032 (2)	−0.001 (2)
N1	0.0264 (14)	0.0267 (14)	0.0236 (13)	0.0004 (11)	0.0075 (11)	0.0001 (11)
N2	0.0295 (15)	0.0265 (14)	0.0231 (13)	0.0041 (11)	0.0042 (11)	0.0043 (11)
N3	0.0268 (15)	0.0321 (15)	0.0303 (14)	0.0055 (12)	0.0061 (12)	0.0091 (11)
N4	0.077 (3)	0.136 (5)	0.064 (3)	0.002 (3)	0.006 (2)	0.003 (3)
C16	0.0259 (17)	0.0236 (17)	0.0372 (18)	−0.0040 (13)	0.0051 (15)	−0.0060 (14)
C15	0.0249 (17)	0.0281 (17)	0.0364 (17)	−0.0012 (13)	0.0088 (14)	−0.0039 (14)
C14	0.0311 (19)	0.0287 (18)	0.060 (2)	−0.0055 (15)	0.0093 (17)	−0.0063 (16)
C13	0.025 (2)	0.044 (2)	0.078 (3)	−0.0063 (17)	0.0054 (19)	−0.010 (2)
C12	0.0239 (19)	0.043 (2)	0.075 (3)	0.0031 (16)	0.0018 (18)	−0.0062 (19)
C11	0.0289 (18)	0.0260 (17)	0.062 (2)	0.0005 (15)	0.0062 (17)	−0.0075 (16)
C10	0.0240 (17)	0.0252 (17)	0.0408 (18)	−0.0022 (13)	0.0068 (14)	−0.0038 (14)
C9	0.0279 (18)	0.0249 (17)	0.0474 (19)	−0.0026 (14)	0.0072 (15)	−0.0069 (14)
C8	0.0256 (17)	0.0193 (15)	0.0390 (18)	−0.0025 (13)	0.0059 (14)	−0.0038 (13)
C6	0.0316 (18)	0.0271 (17)	0.0390 (18)	−0.0060 (14)	0.0156 (15)	−0.0022 (14)
C4	0.0302 (18)	0.0293 (17)	0.0355 (17)	−0.0047 (14)	0.0080 (15)	−0.0013 (14)
C5	0.044 (2)	0.044 (2)	0.0350 (19)	−0.0083 (18)	0.0110 (17)	−0.0033 (16)
C3	0.0255 (17)	0.0284 (17)	0.0328 (17)	−0.0070 (14)	0.0021 (14)	−0.0018 (13)
C2	0.0245 (16)	0.0218 (16)	0.0327 (17)	−0.0007 (13)	0.0067 (13)	−0.0025 (13)
C7	0.0296 (18)	0.0234 (16)	0.0322 (17)	−0.0019 (13)	0.0053 (14)	−0.0035 (13)
C1	0.0295 (18)	0.0264 (17)	0.0302 (17)	−0.0004 (14)	0.0081 (14)	0.0011 (13)
C21	0.038 (2)	0.034 (2)	0.054 (2)	0.0056 (16)	0.0110 (17)	0.0160 (17)
C22	0.059 (3)	0.044 (2)	0.093 (3)	0.015 (2)	0.034 (3)	0.038 (2)
C18	0.042 (2)	0.095 (3)	0.059 (3)	0.030 (2)	0.014 (2)	0.045 (2)
C19	0.051 (3)	0.081 (3)	0.047 (2)	0.016 (2)	−0.005 (2)	0.026 (2)
C20	0.041 (2)	0.054 (2)	0.040 (2)	0.0080 (18)	−0.0019 (17)	0.0116 (17)
C26	0.0394 (19)	0.0268 (17)	0.0280 (16)	0.0007 (14)	0.0125 (14)	0.0013 (13)
C25	0.050 (2)	0.0244 (17)	0.0356 (18)	0.0033 (15)	0.0149 (16)	0.0008 (14)
C24	0.0356 (19)	0.0323 (18)	0.0294 (17)	0.0034 (15)	0.0110 (14)	−0.0014 (14)
C23	0.048 (2)	0.0318 (18)	0.0365 (18)	0.0078 (16)	0.0161 (16)	−0.0016 (15)
C28	0.043 (2)	0.0336 (18)	0.0289 (17)	0.0000 (15)	0.0170 (15)	0.0021 (14)
C27	0.0365 (19)	0.0252 (16)	0.0288 (16)	−0.0039 (14)	0.0092 (14)	0.0001 (13)
C33	0.0329 (19)	0.045 (2)	0.0315 (18)	0.0044 (16)	0.0050 (15)	0.0135 (15)
C34	0.041 (2)	0.053 (2)	0.0315 (18)	0.0008 (17)	0.0057 (16)	0.0179 (16)
C30	0.048 (2)	0.0340 (19)	0.0313 (18)	0.0037 (16)	−0.0012 (16)	0.0092 (15)
C29	0.047 (2)	0.043 (2)	0.0374 (19)	0.0081 (18)	−0.0030 (17)	0.0133 (17)
C31	0.037 (2)	0.052 (2)	0.0389 (19)	0.0176 (17)	0.0045 (16)	0.0130 (17)
C32	0.0350 (19)	0.044 (2)	0.0301 (17)	0.0058 (16)	0.0072 (15)	0.0084 (15)
C36	0.134 (6)	0.152 (7)	0.092 (5)	−0.029 (5)	0.027 (4)	−0.004 (5)
C37	0.111 (6)	0.171 (7)	0.116 (5)	0.049 (5)	−0.003 (4)	0.013 (5)
C35	0.080 (4)	0.141 (6)	0.069 (4)	0.001 (4)	0.008 (3)	−0.007 (4)
C17	0.082 (3)	0.093 (4)	0.095 (3)	0.029 (3)	0.037 (3)	0.048 (3)

Geometric parameters (Å, º)

Ni1—O8	2.077 (2)	C6—C4	1.387 (4)
Ni1—O7^i	2.077 (2)	C6—H6	0.9300
Ni1—O1	2.086 (2)	C4—C3	1.379 (4)
Ni1—N1	2.095 (2)	C4—C5	1.495 (5)
Ni1—N2	2.112 (2)	C3—C2	1.382 (4)
Ni1—N3	2.123 (3)	C3—H3	0.9300
O1—C1	1.250 (4)	C2—C7	1.392 (4)
O2—C1	1.250 (4)	C2—C1	1.515 (4)
O3—C5	1.310 (4)	C7—H7	0.9300
O3—H3A	0.8200	C21—C22	1.395 (5)
O4—C5	1.208 (4)	C21—H21	0.9300
O5—C10	1.370 (4)	C22—C18	1.407 (7)
O5—C9	1.426 (4)	C22—H22	0.9300
O7—C16	1.261 (4)	C18—C19	1.353 (7)
O7—Ni1^ii	2.077 (2)	C18—C17	1.494 (6)
O6—C16	1.243 (4)	C19—C20	1.337 (5)
O9—C35	1.290 (7)	C19—H19	0.9300
O8—H8A	0.8500	C20—H20	0.9300
O8—H8B	0.8500	C26—C25	1.383 (4)
O10—H10C	0.8501	C26—H26	0.9300
O10—H10A	0.8498	C25—C24	1.388 (4)
O11—H11D	0.8501	C25—H25	0.9300
O11—H11A	0.8500	C24—C28	1.384 (5)
O12—H12D	0.8502	C24—C23	1.469 (4)
O12—H12A	0.8499	C23—C23^iii	1.332 (7)
N1—C26	1.335 (4)	C23—H23	0.9300
N1—C27	1.344 (4)	C28—C27	1.366 (4)
N2—C32	1.326 (4)	C28—H28	0.9300
N2—C33	1.340 (4)	C27—H27	0.9300
N3—C20	1.329 (4)	C33—C34	1.368 (4)
N3—C21	1.332 (4)	C33—H33	0.9300
N4—C35	1.318 (7)	C34—C30	1.381 (5)
N4—C36	1.433 (8)	C34—H34	0.9300
N4—C37	1.436 (8)	C30—C31	1.387 (5)
C16—C15	1.502 (4)	C30—C29	1.474 (4)
C15—C14	1.392 (5)	C29—C29^iv	1.303 (7)
C15—C10	1.394 (4)	C29—H29	0.9300
C14—C13	1.380 (5)	C31—C32	1.374 (5)
C14—H14A	0.9300	C31—H31	0.9300
C13—C12	1.370 (5)	C32—H32	0.9300
C13—H13	0.9300	C36—H36A	0.9600
C12—C11	1.381 (5)	C36—H36B	0.9600
C12—H12	0.9300	C36—H36C	0.9600
C11—C10	1.388 (5)	C37—H37A	0.9600
C11—H11	0.9300	C37—H37B	0.9600
C9—C8	1.501 (4)	C37—H37C	0.9600
C9—H9A	0.9700	C35—H35	0.9300
C9—H9B	0.9700	C17—C17^v	1.231 (7)
C8—C6	1.381 (4)	C17—H17	0.9300
C8—C7	1.389 (4)
O8—Ni1—O7^i	93.32 (9)	C3—C2—C7	118.8 (3)
O8—Ni1—O1	90.86 (9)	C3—C2—C1	119.4 (3)
O7^i—Ni1—O1	173.48 (8)	C7—C2—C1	121.6 (3)
O8—Ni1—N1	177.74 (9)	C8—C7—C2	120.8 (3)
O7^i—Ni1—N1	88.82 (9)	C8—C7—H7	119.6
O1—Ni1—N1	86.95 (9)	C2—C7—H7	119.6
O8—Ni1—N2	89.38 (9)	O2—C1—O1	126.5 (3)
O7^i—Ni1—N2	89.02 (9)	O2—C1—C2	117.3 (3)
O1—Ni1—N2	96.04 (9)	O1—C1—C2	116.2 (3)
N1—Ni1—N2	91.41 (10)	N3—C21—C22	122.5 (4)
O8—Ni1—N3	87.94 (9)	N3—C21—H21	118.8
O7^i—Ni1—N3	88.29 (9)	C22—C21—H21	118.8
O1—Ni1—N3	86.85 (9)	C21—C22—C18	119.2 (4)
N1—Ni1—N3	91.38 (10)	C21—C22—H22	120.4
N2—Ni1—N3	176.09 (10)	C18—C22—H22	120.4
C1—O1—Ni1	146.6 (2)	C19—C18—C22	117.2 (4)
C5—O3—H3A	109.5	C19—C18—C17	115.7 (5)
C10—O5—C9	116.6 (2)	C22—C18—C17	127.1 (5)
C16—O7—Ni1^ii	128.2 (2)	C20—C19—C18	118.7 (4)
Ni1—O8—H8A	109.4	C20—C19—H19	120.6
Ni1—O8—H8B	109.3	C18—C19—H19	120.6
H8A—O8—H8B	109.5	N3—C20—C19	127.5 (4)
H10C—O10—H10A	109.3	N3—C20—H20	116.3
H11D—O11—H11A	109.8	C19—C20—H20	116.3
H12D—O12—H12A	110.2	N1—C26—C25	123.1 (3)
C26—N1—C27	116.6 (3)	N1—C26—H26	118.5
C26—N1—Ni1	123.4 (2)	C25—C26—H26	118.5
C27—N1—Ni1	119.2 (2)	C26—C25—C24	119.8 (3)
C32—N2—C33	116.5 (3)	C26—C25—H25	120.1
C32—N2—Ni1	123.0 (2)	C24—C25—H25	120.1
C33—N2—Ni1	120.4 (2)	C28—C24—C25	116.7 (3)
C20—N3—C21	114.9 (3)	C28—C24—C23	123.2 (3)
C20—N3—Ni1	123.1 (2)	C25—C24—C23	120.1 (3)
C21—N3—Ni1	121.8 (2)	C23^iii—C23—C24	124.6 (4)
C35—N4—C36	121.3 (7)	C23^iii—C23—H23	117.7
C35—N4—C37	119.2 (7)	C24—C23—H23	117.7
C36—N4—C37	119.4 (6)	C27—C28—C24	120.1 (3)
O6—C16—O7	124.5 (3)	C27—C28—H28	120.0
O6—C16—C15	117.7 (3)	C24—C28—H28	120.0
O7—C16—C15	117.8 (3)	N1—C27—C28	123.6 (3)
C14—C15—C10	118.6 (3)	N1—C27—H27	118.2
C14—C15—C16	118.3 (3)	C28—C27—H27	118.2
C10—C15—C16	123.0 (3)	N2—C33—C34	123.4 (3)
C13—C14—C15	121.8 (3)	N2—C33—H33	118.3
C13—C14—H14A	119.1	C34—C33—H33	118.3
C15—C14—H14A	119.1	C33—C34—C30	120.2 (3)
C12—C13—C14	118.9 (3)	C33—C34—H34	119.9
C12—C13—H13	120.6	C30—C34—H34	119.9
C14—C13—H13	120.6	C34—C30—C31	116.2 (3)
C13—C12—C11	120.6 (3)	C34—C30—C29	123.3 (3)
C13—C12—H12	119.7	C31—C30—C29	120.5 (3)
C11—C12—H12	119.7	C29^iv—C29—C30	125.9 (5)
C12—C11—C10	120.8 (3)	C29^iv—C29—H29	117.1
C12—C11—H11	119.6	C30—C29—H29	117.1
C10—C11—H11	119.6	C32—C31—C30	120.1 (3)
O5—C10—C11	124.0 (3)	C32—C31—H31	119.9
O5—C10—C15	116.7 (3)	C30—C31—H31	119.9
C11—C10—C15	119.3 (3)	N2—C32—C31	123.5 (3)
O5—C9—C8	110.0 (3)	N2—C32—H32	118.2
O5—C9—H9A	109.7	C31—C32—H32	118.2
C8—C9—H9A	109.7	N4—C36—H36A	109.5
O5—C9—H9B	109.7	N4—C36—H36B	109.5
C8—C9—H9B	109.7	H36A—C36—H36B	109.5
H9A—C9—H9B	108.2	N4—C36—H36C	109.5
C6—C8—C7	119.1 (3)	H36A—C36—H36C	109.5
C6—C8—C9	119.6 (3)	H36B—C36—H36C	109.5
C7—C8—C9	121.1 (3)	N4—C37—H37A	109.5
C8—C6—C4	120.9 (3)	N4—C37—H37B	109.5
C8—C6—H6	119.5	H37A—C37—H37B	109.5
C4—C6—H6	119.5	N4—C37—H37C	109.5
C3—C4—C6	119.1 (3)	H37A—C37—H37C	109.5
C3—C4—C5	118.2 (3)	H37B—C37—H37C	109.5
C6—C4—C5	122.5 (3)	O9—C35—N4	122.6 (7)
O4—C5—O3	123.9 (3)	O9—C35—H35	118.7
O4—C5—C4	122.5 (3)	N4—C35—H35	118.7
O3—C5—C4	113.6 (3)	C17^v—C17—C18	126.0 (8)
C4—C3—C2	121.3 (3)	C17^v—C17—H17	117.0
C4—C3—H3	119.4	C18—C17—H17	117.0
C2—C3—H3	119.4

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