Bis(2,4,6-triamino-1,3,5-triazin-1-ium) tris-(pyridine-2,6-dicarboxyl-ato)-zirconate(IV) tetra-hydrate.

The title compound, (C(3)H(7)N(6))(2)[Zr(C(7)H(3)NO(4))(3)]·4H(2)O or (tataH)(2)[Zr(pydc)(3)]·4H(2)O (tata is 2,4,6-triamino-1,3,5-triazine and pydcH(2) is pyridine-2,6-dicarboxylic acid), was obtained by reaction between pydcH(2), tata and zirconyl chloride octa-hydrate in aqueous solution. In the structure, the Zr(IV )atom is nine-coordinated by three (pydc)(2-) groups, resulting in an anionic complex which is balanced by two (tataH)(+) cations. One of the NH(2) groups shows positional disorder, with site occupation factors of 0.60 and 0.40. There are four uncoordinated water mol-ecules (one of which is disordered with occupation factors of 0.70 and 0.30) in the crystal structure. Several inter-molecular inter-actions, including O-H⋯O, O-H⋯N, N-H⋯O, N-H⋯N, C-H⋯O and C-H⋯N hydrogen bonds, a C-O⋯π inter-action [O⋯Cg 3.89, C⋯Cg 4.068 (3) Å; C-O⋯Cg 89° where Cg is the centroid of the triamine ring], and π-π stacking [with centroid-centroid distances of 3.694 (2) and 3.802 (2) Å] are also present.

Related literature

For related literature, see: Aghabozorg et al. (2005 ▶, 2008 ▶); Harben et al. (2004 ▶); Soleimannejad et al. (2007 ▶).

Experimental

Crystal data

(C3H7N6)2[Zr(C7H3NO4)3]·4H2O

M = 912.89

Triclinic,

a = 9.3749 (16) Å

b = 12.308 (3) Å

c = 16.934 (4) Å

α = 97.926 (19)°

β = 106.050 (12)°

γ = 107.839 (11)°

V = 1733.8 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.42 mm−1

T = 120 (2) K

0.40 × 0.20 × 0.15 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.851, T max = 0.940

17993 measured reflections

8355 independent reflections

6766 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.104

S = 1.00

8355 reflections

545 parameters

H-atom parameters constrained

Δρmax = 1.00 e Å−3

Δρmin = −0.77 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808029887/om2259sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808029887/om2259Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C3H7N6)2[Zr(C7H3NO4)3]·4H2O	Z = 2
Mr = 912.89	F(000) = 932
Triclinic, P1	Dx = 1.749 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3749 (16) Å	Cell parameters from 658 reflections
b = 12.308 (3) Å	θ = 3–28°
c = 16.934 (4) Å	µ = 0.42 mm−1
α = 97.926 (19)°	T = 120 K
β = 106.050 (12)°	Prism, colourless
γ = 107.839 (11)°	0.40 × 0.20 × 0.15 mm
V = 1733.8 (7) Å3

Bruker SMART 1000 CCD area-detector diffractometer	8355 independent reflections
Radiation source: fine-focus sealed tube	6766 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 28.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.851, Tmax = 0.940	k = −16→16
17993 measured reflections	l = −22→22

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)] = 0.041	Hydrogen site location: mixed
wR(F2) = 0.104	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0505P)2 + 1.7P] where P = (Fo2 + 2Fc2)/3
8355 reflections	(Δ/σ)max = 0.003
545 parameters	Δρmax = 1.00 e Å−3
0 restraints	Δρmin = −0.77 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zr1	0.28559 (3)	0.802835 (18)	0.195072 (14)	0.01451 (7)
N1	0.3709 (2)	0.94504 (17)	0.32273 (12)	0.0168 (4)
O1	0.10400 (19)	0.77557 (14)	0.25919 (11)	0.0198 (3)
O2	0.0216 (2)	0.82091 (17)	0.36581 (14)	0.0340 (5)
O3	0.53253 (19)	0.93108 (14)	0.22590 (10)	0.0185 (3)
O4	0.7468 (2)	1.08521 (15)	0.30894 (11)	0.0231 (4)
C1	0.1197 (3)	0.8424 (2)	0.32888 (16)	0.0212 (5)
C2	0.2728 (3)	0.9455 (2)	0.36620 (15)	0.0187 (5)
C3	0.3136 (3)	1.0328 (2)	0.43831 (16)	0.0234 (5)
H3	0.2414	1.0317	0.4683	0.028*
C4	0.4617 (3)	1.1214 (2)	0.46564 (16)	0.0236 (5)
H4	0.4925	1.1828	0.5146	0.028*
C5	0.5654 (3)	1.1200 (2)	0.42086 (15)	0.0221 (5)
H5	0.6682	1.1796	0.4390	0.026*
C6	0.5155 (3)	1.0298 (2)	0.34937 (15)	0.0173 (5)
C7	0.6084 (3)	1.0150 (2)	0.29175 (15)	0.0175 (5)
N2	0.1737 (2)	0.60123 (16)	0.19282 (12)	0.0155 (4)
O5	0.05699 (19)	0.70749 (14)	0.08778 (10)	0.0182 (3)
O6	−0.1565 (2)	0.54563 (15)	0.01431 (11)	0.0239 (4)
O7	0.43417 (19)	0.74858 (14)	0.30198 (10)	0.0183 (3)
O8	0.4862 (2)	0.61348 (15)	0.36795 (11)	0.0265 (4)
C8	−0.0300 (3)	0.5985 (2)	0.07296 (15)	0.0171 (5)
C9	0.0356 (3)	0.5343 (2)	0.13438 (14)	0.0165 (4)
C10	−0.0384 (3)	0.4166 (2)	0.13214 (16)	0.0216 (5)
H10	−0.1381	0.3702	0.0899	0.026*
C11	0.0358 (3)	0.3686 (2)	0.19240 (16)	0.0221 (5)
H11	−0.0119	0.2884	0.1923	0.027*
C12	0.1816 (3)	0.4392 (2)	0.25330 (15)	0.0182 (5)
H12	0.2354	0.4081	0.2954	0.022*
C13	0.2465 (3)	0.5554 (2)	0.25141 (14)	0.0158 (4)
C14	0.4018 (3)	0.6443 (2)	0.31261 (14)	0.0169 (5)
N3	0.3092 (2)	0.86076 (16)	0.07171 (12)	0.0160 (4)
O9	0.39755 (19)	0.70295 (14)	0.12953 (10)	0.0177 (3)
O10	0.5097 (2)	0.67269 (16)	0.03268 (11)	0.0250 (4)
O11	0.1938 (2)	0.94406 (14)	0.17254 (10)	0.0190 (3)
O12	0.1385 (2)	1.07302 (15)	0.09910 (11)	0.0233 (4)
C15	0.4337 (3)	0.7215 (2)	0.06333 (15)	0.0172 (5)
C16	0.3755 (3)	0.80986 (19)	0.02482 (14)	0.0165 (4)
C17	0.3836 (3)	0.8366 (2)	−0.05096 (15)	0.0202 (5)
H17	0.4343	0.8016	−0.0827	0.024*
C18	0.3155 (3)	0.9160 (2)	−0.07950 (16)	0.0225 (5)
H18	0.3163	0.9341	−0.1322	0.027*
C19	0.2463 (3)	0.9689 (2)	−0.03055 (15)	0.0206 (5)
H19	0.1992	1.0233	−0.0490	0.025*
C20	0.2480 (3)	0.9398 (2)	0.04572 (15)	0.0175 (5)
C21	0.1862 (3)	0.9920 (2)	0.10879 (15)	0.0167 (5)
N4	0.7448 (2)	0.58832 (17)	0.48483 (12)	0.0175 (4)
H4A	0.6960	0.6270	0.4554	0.021*
N5	0.7533 (2)	0.40707 (17)	0.51036 (13)	0.0194 (4)
N6	0.9696 (2)	0.58949 (17)	0.58959 (12)	0.0184 (4)
N7	0.9521 (2)	0.76211 (18)	0.55671 (14)	0.0227 (4)
H7A	0.8982	0.7924	0.5217	0.027*
H7B	1.0470	0.8008	0.5934	0.027*
N8	0.5335 (2)	0.41661 (18)	0.41288 (13)	0.0234 (5)
H8A	0.4855	0.3406	0.3967	0.028*
H8B	0.4936	0.4635	0.3884	0.028*
N9	0.9768 (2)	0.41118 (18)	0.61023 (13)	0.0224 (4)
H9A	0.9358	0.3348	0.5938	0.027*
H9B	1.0659	0.4460	0.6523	0.027*
C22	0.8915 (3)	0.6470 (2)	0.54501 (14)	0.0170 (5)
C23	0.6774 (3)	0.4676 (2)	0.46958 (15)	0.0187 (5)
C24	0.8975 (3)	0.4710 (2)	0.56878 (14)	0.0181 (5)
N10	0.7164 (3)	0.48215 (18)	0.24952 (14)	0.0253 (5)
N11	0.4934 (3)	0.48189 (19)	0.14323 (14)	0.0271 (5)
H11A	0.4506	0.5220	0.1122	0.032*
N12	0.4830 (2)	0.30662 (17)	0.18547 (13)	0.0192 (4)
N13	0.7066 (3)	0.30818 (19)	0.28279 (14)	0.0268 (5)
H13A	0.6542	0.2336	0.2754	0.032*
H13B	0.8004	0.3462	0.3207	0.032*
N14	0.7048 (6)	0.6558 (5)	0.2174 (3)	0.0262 (11)	0.60
N14'	0.7338 (10)	0.6400 (7)	0.1863 (5)	0.0341 (19)	0.40
H14A	0.8089	0.6854	0.2358	0.041*
H14B	0.6659	0.6837	0.1755	0.041*
N15	0.2681 (2)	0.31340 (18)	0.08405 (13)	0.0207 (4)
H15A	0.2180	0.3501	0.0532	0.025*
H15B	0.2240	0.2385	0.0796	0.025*
C25	0.6329 (3)	0.3668 (2)	0.23774 (15)	0.0188 (5)
C26	0.6431 (3)	0.5381 (2)	0.20080 (19)	0.0322 (6)
C27	0.4140 (3)	0.3657 (2)	0.13757 (15)	0.0180 (5)
O1W	0.2873 (2)	0.21473 (16)	0.29928 (12)	0.0313 (4)
H1WA	0.3023	0.2068	0.2537	0.038*
H1WB	0.1976	0.1718	0.2947	0.038*
O2W	0.7796 (2)	0.84349 (18)	0.42014 (12)	0.0296 (4)
H2WA	0.8454	0.8469	0.3963	0.036*
H2WB	0.6916	0.8170	0.3831	0.036*
O3W	0.8371 (3)	0.8297 (2)	0.11479 (16)	0.0483 (6)
H3WA	0.9164	0.8118	0.1270	0.058*
H3WB	0.7562	0.7779	0.0809	0.058*
O4W	−0.0041 (4)	0.0297 (3)	0.2674 (2)	0.0310 (7)	0.70
H4WA	−0.0839	0.0422	0.2701	0.037*	0.70
H4WB	0.0024	−0.0225	0.2920	0.037*	0.70
O4W'	−0.0135 (12)	0.0610 (8)	0.2484 (6)	0.036 (2)*	0.30
H4WC	−0.0592	−0.0132	0.2082	0.043*	0.30
H4WD	−0.0861	0.0687	0.2662	0.043*	0.30

	U11	U22	U33	U12	U13	U23
Zr1	0.01427 (12)	0.01246 (11)	0.01488 (12)	0.00449 (8)	0.00258 (8)	0.00297 (8)
N1	0.0181 (10)	0.0154 (9)	0.0170 (9)	0.0068 (8)	0.0046 (8)	0.0053 (8)
O1	0.0185 (8)	0.0156 (8)	0.0245 (9)	0.0049 (7)	0.0072 (7)	0.0056 (7)
O2	0.0375 (11)	0.0250 (10)	0.0528 (13)	0.0126 (9)	0.0328 (10)	0.0119 (9)
O3	0.0166 (8)	0.0174 (8)	0.0190 (8)	0.0034 (7)	0.0055 (7)	0.0036 (7)
O4	0.0147 (8)	0.0183 (8)	0.0298 (10)	0.0013 (7)	0.0040 (7)	0.0038 (7)
C1	0.0221 (12)	0.0222 (12)	0.0276 (13)	0.0131 (10)	0.0130 (10)	0.0110 (10)
C2	0.0225 (12)	0.0170 (11)	0.0196 (11)	0.0090 (10)	0.0083 (10)	0.0067 (9)
C3	0.0348 (14)	0.0218 (12)	0.0222 (12)	0.0168 (11)	0.0135 (11)	0.0090 (10)
C4	0.0340 (14)	0.0179 (12)	0.0173 (12)	0.0126 (11)	0.0045 (10)	0.0013 (9)
C5	0.0252 (13)	0.0163 (11)	0.0202 (12)	0.0064 (10)	0.0030 (10)	0.0026 (9)
C6	0.0184 (11)	0.0145 (11)	0.0176 (11)	0.0066 (9)	0.0026 (9)	0.0049 (9)
C7	0.0150 (11)	0.0138 (11)	0.0223 (12)	0.0055 (9)	0.0028 (9)	0.0065 (9)
N2	0.0149 (9)	0.0148 (9)	0.0158 (9)	0.0054 (7)	0.0042 (8)	0.0030 (7)
O5	0.0159 (8)	0.0158 (8)	0.0197 (8)	0.0049 (6)	0.0016 (7)	0.0050 (7)
O6	0.0185 (9)	0.0206 (9)	0.0229 (9)	0.0028 (7)	−0.0035 (7)	0.0065 (7)
O7	0.0173 (8)	0.0168 (8)	0.0181 (8)	0.0053 (7)	0.0028 (7)	0.0040 (6)
O8	0.0228 (9)	0.0214 (9)	0.0255 (9)	0.0067 (7)	−0.0055 (7)	0.0069 (7)
C8	0.0162 (11)	0.0155 (11)	0.0184 (11)	0.0064 (9)	0.0039 (9)	0.0031 (9)
C9	0.0175 (11)	0.0169 (11)	0.0160 (11)	0.0082 (9)	0.0047 (9)	0.0037 (9)
C10	0.0167 (11)	0.0186 (12)	0.0215 (12)	0.0010 (9)	0.0008 (10)	0.0034 (10)
C11	0.0224 (12)	0.0155 (11)	0.0259 (13)	0.0038 (10)	0.0068 (10)	0.0069 (10)
C12	0.0202 (11)	0.0186 (11)	0.0177 (11)	0.0091 (9)	0.0059 (9)	0.0065 (9)
C13	0.0178 (11)	0.0152 (11)	0.0152 (11)	0.0073 (9)	0.0057 (9)	0.0032 (9)
C14	0.0155 (11)	0.0184 (11)	0.0166 (11)	0.0066 (9)	0.0045 (9)	0.0043 (9)
N3	0.0137 (9)	0.0131 (9)	0.0166 (9)	0.0022 (7)	0.0013 (8)	0.0031 (7)
O9	0.0191 (8)	0.0158 (8)	0.0182 (8)	0.0076 (7)	0.0047 (7)	0.0047 (6)
O10	0.0261 (9)	0.0282 (10)	0.0257 (9)	0.0157 (8)	0.0102 (8)	0.0055 (8)
O11	0.0226 (9)	0.0161 (8)	0.0188 (8)	0.0083 (7)	0.0061 (7)	0.0045 (7)
O12	0.0268 (9)	0.0198 (9)	0.0255 (9)	0.0118 (7)	0.0074 (8)	0.0075 (7)
C15	0.0129 (10)	0.0157 (11)	0.0164 (11)	0.0022 (9)	0.0004 (9)	−0.0003 (9)
C16	0.0137 (10)	0.0133 (10)	0.0171 (11)	0.0017 (8)	0.0018 (9)	0.0017 (9)
C17	0.0182 (11)	0.0208 (12)	0.0187 (11)	0.0039 (9)	0.0064 (9)	0.0025 (9)
C18	0.0205 (12)	0.0242 (12)	0.0181 (12)	0.0032 (10)	0.0039 (10)	0.0075 (10)
C19	0.0182 (11)	0.0184 (11)	0.0215 (12)	0.0042 (9)	0.0023 (10)	0.0073 (10)
C20	0.0152 (11)	0.0147 (11)	0.0187 (11)	0.0031 (9)	0.0022 (9)	0.0043 (9)
C21	0.0141 (10)	0.0132 (10)	0.0200 (11)	0.0039 (9)	0.0021 (9)	0.0059 (9)
N4	0.0147 (9)	0.0154 (9)	0.0205 (10)	0.0067 (8)	0.0010 (8)	0.0056 (8)
N5	0.0177 (10)	0.0166 (10)	0.0215 (10)	0.0062 (8)	0.0030 (8)	0.0047 (8)
N6	0.0176 (10)	0.0188 (10)	0.0163 (9)	0.0065 (8)	0.0024 (8)	0.0035 (8)
N7	0.0186 (10)	0.0169 (10)	0.0255 (11)	0.0052 (8)	−0.0015 (9)	0.0041 (8)
N8	0.0189 (10)	0.0164 (10)	0.0274 (11)	0.0048 (8)	−0.0009 (9)	0.0040 (9)
N9	0.0209 (10)	0.0189 (10)	0.0234 (11)	0.0086 (8)	0.0000 (9)	0.0054 (8)
C22	0.0150 (11)	0.0202 (11)	0.0154 (11)	0.0057 (9)	0.0053 (9)	0.0043 (9)
C23	0.0178 (11)	0.0183 (11)	0.0195 (11)	0.0064 (9)	0.0062 (9)	0.0041 (9)
C24	0.0201 (11)	0.0217 (12)	0.0154 (11)	0.0100 (10)	0.0069 (9)	0.0058 (9)
N10	0.0204 (11)	0.0191 (10)	0.0304 (12)	0.0064 (9)	−0.0007 (9)	0.0088 (9)
N11	0.0239 (11)	0.0189 (10)	0.0312 (12)	0.0078 (9)	−0.0038 (9)	0.0106 (9)
N12	0.0190 (10)	0.0186 (10)	0.0183 (10)	0.0074 (8)	0.0030 (8)	0.0048 (8)
N13	0.0228 (11)	0.0167 (10)	0.0307 (12)	0.0057 (9)	−0.0053 (9)	0.0071 (9)
N14	0.023 (2)	0.018 (2)	0.027 (3)	0.0026 (17)	−0.0054 (19)	0.012 (2)
N14'	0.026 (4)	0.023 (3)	0.042 (5)	0.006 (3)	−0.003 (4)	0.009 (4)
N15	0.0185 (10)	0.0209 (10)	0.0211 (10)	0.0080 (8)	0.0023 (8)	0.0070 (8)
C25	0.0201 (12)	0.0199 (12)	0.0175 (11)	0.0094 (9)	0.0056 (9)	0.0051 (9)
C26	0.0252 (14)	0.0218 (13)	0.0381 (16)	0.0055 (11)	−0.0053 (12)	0.0112 (12)
C27	0.0184 (11)	0.0185 (11)	0.0174 (11)	0.0080 (9)	0.0056 (9)	0.0034 (9)
O1W	0.0360 (11)	0.0244 (10)	0.0247 (10)	0.0027 (8)	0.0064 (8)	0.0052 (8)
O2W	0.0213 (9)	0.0449 (12)	0.0224 (9)	0.0128 (9)	0.0080 (8)	0.0040 (8)
O3W	0.0403 (13)	0.0441 (13)	0.0590 (16)	0.0177 (11)	0.0113 (12)	0.0140 (12)
O4W	0.0331 (17)	0.0289 (17)	0.0353 (18)	0.0144 (14)	0.0147 (14)	0.0079 (15)

Zr1—O11	2.1964 (16)	C19—C20	1.384 (3)
Zr1—O9	2.2144 (17)	C19—H19	0.9500
Zr1—O1	2.2276 (17)	C20—C21	1.507 (3)
Zr1—O3	2.2337 (17)	N4—C22	1.366 (3)
Zr1—O5	2.2336 (17)	N4—C23	1.380 (3)
Zr1—O7	2.2743 (17)	N4—H4A	0.8700
Zr1—N3	2.343 (2)	N5—C23	1.316 (3)
Zr1—N1	2.349 (2)	N5—C24	1.349 (3)
Zr1—N2	2.370 (2)	N6—C22	1.329 (3)
N1—C2	1.329 (3)	N6—C24	1.353 (3)
N1—C6	1.340 (3)	N7—C22	1.318 (3)
O1—C1	1.286 (3)	N7—H7A	0.8700
O2—C1	1.233 (3)	N7—H7B	0.8700
O3—C7	1.269 (3)	N8—C23	1.318 (3)
O4—C7	1.244 (3)	N8—H8A	0.8700
C1—C2	1.494 (3)	N8—H8B	0.8701
C2—C3	1.386 (3)	N9—C24	1.333 (3)
C3—C4	1.382 (4)	N9—H9A	0.8700
C3—H3	0.9500	N9—H9B	0.8700
C4—C5	1.391 (4)	N10—C26	1.327 (3)
C4—H4	0.9500	N10—C25	1.351 (3)
C5—C6	1.383 (3)	N11—C26	1.364 (3)
C5—H5	0.9500	N11—C27	1.371 (3)
C6—C7	1.504 (3)	N11—H11A	0.8700
N2—C9	1.322 (3)	N12—C27	1.329 (3)
N2—C13	1.335 (3)	N12—C25	1.342 (3)
O5—C8	1.285 (3)	N13—C25	1.321 (3)
O6—C8	1.230 (3)	N13—H13A	0.8699
O7—C14	1.275 (3)	N13—H13B	0.8700
O8—C14	1.233 (3)	N14—C26	1.340 (6)
C8—C9	1.502 (3)	N14—H14A	0.8749
C9—C10	1.392 (3)	N14—H14B	0.8687
C10—C11	1.379 (3)	N14'—C26	1.380 (9)
C10—H10	0.9500	N14'—H14A	0.9028
C11—C12	1.390 (3)	N14'—H14B	0.9488
C11—H11	0.9500	N15—C27	1.312 (3)
C12—C13	1.382 (3)	N15—H15A	0.8700
C12—H12	0.9500	N15—H15B	0.8700
C13—C14	1.506 (3)	O1W—H1WA	0.8200
N3—C16	1.335 (3)	O1W—H1WB	0.8201
N3—C20	1.338 (3)	O2W—H2WA	0.8199
O9—C15	1.287 (3)	O2W—H2WB	0.8200
O10—C15	1.233 (3)	O3W—H3WA	0.8199
O11—C21	1.295 (3)	O3W—H3WB	0.8200
O12—C21	1.224 (3)	O4W—H4WA	0.8199
C15—C16	1.506 (3)	O4W—H4WB	0.8201
C16—C17	1.384 (3)	O4W—H4WC	0.9759
C17—C18	1.392 (4)	O4W—H4WD	1.0210
C17—H17	0.9500	O4W'—H4WA	0.8285
C18—C19	1.393 (4)	O4W'—H4WC	0.9537
C18—H18	0.9500	O4W'—H4WD	0.8410
O11—Zr1—O9	135.20 (6)	O8—C14—C13	119.7 (2)
O11—Zr1—O1	77.18 (6)	O7—C14—C13	115.10 (19)
O9—Zr1—O1	140.70 (6)	C16—N3—C20	120.0 (2)
O11—Zr1—O3	89.27 (6)	C16—N3—Zr1	119.94 (15)
O9—Zr1—O3	76.40 (6)	C20—N3—Zr1	119.92 (16)
O1—Zr1—O3	134.77 (6)	C15—O9—Zr1	125.29 (14)
O11—Zr1—O5	77.71 (6)	C21—O11—Zr1	127.15 (15)
O9—Zr1—O5	88.12 (6)	O10—C15—O9	124.2 (2)
O1—Zr1—O5	77.03 (6)	O10—C15—C16	121.4 (2)
O3—Zr1—O5	142.19 (6)	O9—C15—C16	114.4 (2)
O11—Zr1—O7	140.58 (6)	N3—C16—C17	121.8 (2)
O9—Zr1—O7	77.15 (6)	N3—C16—C15	112.2 (2)
O1—Zr1—O7	87.39 (6)	C17—C16—C15	126.0 (2)
O3—Zr1—O7	76.22 (6)	C16—C17—C18	118.3 (2)
O5—Zr1—O7	134.02 (6)	C16—C17—H17	120.9
O11—Zr1—N3	67.37 (7)	C18—C17—H17	120.9
O9—Zr1—N3	67.83 (6)	C17—C18—C19	119.8 (2)
O1—Zr1—N3	135.82 (6)	C17—C18—H18	120.1
O3—Zr1—N3	71.70 (6)	C19—C18—H18	120.1
O5—Zr1—N3	70.52 (6)	C20—C19—C18	118.0 (2)
O7—Zr1—N3	136.80 (6)	C20—C19—H19	121.0
O11—Zr1—N1	70.33 (6)	C18—C19—H19	121.0
O9—Zr1—N1	135.65 (6)	N3—C20—C19	122.0 (2)
O1—Zr1—N1	67.44 (7)	N3—C20—C21	112.4 (2)
O3—Zr1—N1	67.36 (7)	C19—C20—C21	125.6 (2)
O5—Zr1—N1	136.22 (7)	O12—C21—O11	125.7 (2)
O7—Zr1—N1	70.25 (6)	O12—C21—C20	121.5 (2)
N3—Zr1—N1	120.12 (7)	O11—C21—C20	112.80 (19)
O11—Zr1—N2	135.82 (7)	C22—N4—C23	119.5 (2)
O9—Zr1—N2	71.12 (6)	C22—N4—H4A	119.9
O1—Zr1—N2	69.59 (6)	C23—N4—H4A	120.6
O3—Zr1—N2	134.88 (6)	C23—N5—C24	115.7 (2)
O5—Zr1—N2	67.27 (6)	C22—N6—C24	115.8 (2)
O7—Zr1—N2	66.76 (6)	C22—N7—H7A	116.1
N3—Zr1—N2	120.74 (7)	C22—N7—H7B	118.8
N1—Zr1—N2	119.13 (7)	H7A—N7—H7B	124.5
C2—N1—C6	119.8 (2)	C23—N8—H8A	122.4
C2—N1—Zr1	120.07 (16)	C23—N8—H8B	115.6
C6—N1—Zr1	120.01 (15)	H8A—N8—H8B	121.7
C1—O1—Zr1	124.99 (15)	C24—N9—H9A	117.4
C7—O3—Zr1	125.60 (15)	C24—N9—H9B	122.3
O2—C1—O1	123.5 (2)	H9A—N9—H9B	120.3
O2—C1—C2	121.4 (2)	N7—C22—N6	121.6 (2)
O1—C1—C2	114.9 (2)	N7—C22—N4	117.4 (2)
N1—C2—C3	122.1 (2)	N6—C22—N4	120.9 (2)
N1—C2—C1	112.4 (2)	N5—C23—N8	122.0 (2)
C3—C2—C1	125.6 (2)	N5—C23—N4	121.4 (2)
C4—C3—C2	118.5 (2)	N8—C23—N4	116.6 (2)
C4—C3—H3	120.8	N9—C24—N5	116.6 (2)
C2—C3—H3	120.8	N9—C24—N6	116.8 (2)
C3—C4—C5	119.4 (2)	N5—C24—N6	126.6 (2)
C3—C4—H4	120.3	C26—N10—C25	115.4 (2)
C5—C4—H4	120.3	C26—N11—C27	119.3 (2)
C6—C5—C4	118.5 (2)	C26—N11—H11A	118.4
C6—C5—H5	120.7	C27—N11—H11A	122.2
C4—C5—H5	120.7	C27—N12—C25	116.2 (2)
N1—C6—C5	121.7 (2)	C25—N13—H13A	117.1
N1—C6—C7	112.0 (2)	C25—N13—H13B	119.3
C5—C6—C7	126.3 (2)	H13A—N13—H13B	123.4
O4—C7—O3	125.2 (2)	C26—N14—H14A	114.1
O4—C7—C6	119.9 (2)	C26—N14—H14B	113.2
O3—C7—C6	114.8 (2)	H14A—N14—H14B	110.9
C9—N2—C13	119.7 (2)	C26—N14'—H14A	108.8
C9—N2—Zr1	119.59 (15)	C26—N14'—H14B	104.7
C13—N2—Zr1	120.67 (15)	H14A—N14'—H14B	101.7
C8—O5—Zr1	125.56 (14)	C27—N15—H15A	122.7
C14—O7—Zr1	125.03 (14)	C27—N15—H15B	116.3
O6—C8—O5	125.9 (2)	H15A—N15—H15B	121.0
O6—C8—C9	119.7 (2)	N13—C25—N12	117.2 (2)
O5—C8—C9	114.3 (2)	N13—C25—N10	116.3 (2)
N2—C9—C10	122.0 (2)	N12—C25—N10	126.5 (2)
N2—C9—C8	113.2 (2)	N10—C26—N14	119.5 (3)
C10—C9—C8	124.9 (2)	N10—C26—N11	121.7 (2)
C11—C10—C9	118.7 (2)	N14—C26—N11	117.9 (3)
C11—C10—H10	120.6	N10—C26—N14'	118.7 (4)
C9—C10—H10	120.6	N11—C26—N14'	115.9 (4)
C10—C11—C12	119.0 (2)	N15—C27—N12	120.3 (2)
C10—C11—H11	120.5	N15—C27—N11	118.9 (2)
C12—C11—H11	120.5	N12—C27—N11	120.8 (2)
C13—C12—C11	118.6 (2)	H1WA—O1W—H1WB	111.2
C13—C12—H12	120.7	H2WA—O2W—H2WB	107.1
C11—C12—H12	120.7	H3WA—O3W—H3WB	115.2
N2—C13—C12	121.9 (2)	H4WA—O4W—H4WB	106.9
N2—C13—C14	112.32 (19)	H4WB—O4W—H4WC	103.3
C12—C13—C14	125.7 (2)	H4WB—O4W—H4WD	123.7
O8—C14—O7	125.2 (2)	H4WC—O4W'—H4WD	106.2
O11—Zr1—N1—C2	79.81 (17)	N2—C9—C10—C11	−0.5 (4)
O9—Zr1—N1—C2	−144.77 (16)	C8—C9—C10—C11	179.7 (2)
O1—Zr1—N1—C2	−4.07 (16)	C9—C10—C11—C12	0.1 (4)
O3—Zr1—N1—C2	177.53 (19)	C10—C11—C12—C13	0.3 (4)
O5—Zr1—N1—C2	34.2 (2)	C9—N2—C13—C12	−0.1 (3)
O7—Zr1—N1—C2	−99.62 (18)	Zr1—N2—C13—C12	177.89 (17)
N3—Zr1—N1—C2	126.98 (17)	C9—N2—C13—C14	−179.9 (2)
N2—Zr1—N1—C2	−52.46 (19)	Zr1—N2—C13—C14	−1.9 (3)
O11—Zr1—N1—C6	−96.45 (17)	C11—C12—C13—N2	−0.3 (4)
O9—Zr1—N1—C6	39.0 (2)	C11—C12—C13—C14	179.4 (2)
O1—Zr1—N1—C6	179.67 (18)	Zr1—O7—C14—O8	176.13 (18)
O3—Zr1—N1—C6	1.27 (15)	Zr1—O7—C14—C13	−4.2 (3)
O5—Zr1—N1—C6	−142.04 (15)	N2—C13—C14—O8	−176.6 (2)
O7—Zr1—N1—C6	84.13 (17)	C12—C13—C14—O8	3.7 (4)
N3—Zr1—N1—C6	−49.28 (18)	N2—C13—C14—O7	3.7 (3)
N2—Zr1—N1—C6	131.28 (16)	C12—C13—C14—O7	−176.0 (2)
O11—Zr1—O1—C1	−72.21 (18)	O11—Zr1—N3—C16	178.94 (18)
O9—Zr1—O1—C1	137.22 (17)	O9—Zr1—N3—C16	−0.52 (15)
O3—Zr1—O1—C1	3.7 (2)	O1—Zr1—N3—C16	−141.75 (15)
O5—Zr1—O1—C1	−152.33 (19)	O3—Zr1—N3—C16	81.86 (17)
O7—Zr1—O1—C1	71.25 (18)	O5—Zr1—N3—C16	−96.63 (17)
N3—Zr1—O1—C1	−109.06 (19)	O7—Zr1—N3—C16	37.8 (2)
N1—Zr1—O1—C1	1.57 (17)	N1—Zr1—N3—C16	130.51 (16)
N2—Zr1—O1—C1	137.39 (19)	N2—Zr1—N3—C16	−50.06 (18)
O11—Zr1—O3—C7	70.44 (18)	O11—Zr1—N3—C20	−4.98 (16)
O9—Zr1—O3—C7	−152.41 (18)	O9—Zr1—N3—C20	175.56 (18)
O1—Zr1—O3—C7	−0.6 (2)	O1—Zr1—N3—C20	34.3 (2)
O5—Zr1—O3—C7	139.11 (17)	O3—Zr1—N3—C20	−102.06 (17)
O7—Zr1—O3—C7	−72.56 (18)	O5—Zr1—N3—C20	79.44 (17)
N3—Zr1—O3—C7	136.80 (19)	O7—Zr1—N3—C20	−146.12 (15)
N1—Zr1—O3—C7	1.50 (17)	N1—Zr1—N3—C20	−53.42 (18)
N2—Zr1—O3—C7	−107.71 (18)	N2—Zr1—N3—C20	126.02 (16)
Zr1—O1—C1—O2	−175.06 (18)	O11—Zr1—O9—C15	3.7 (2)
Zr1—O1—C1—C2	0.7 (3)	O1—Zr1—O9—C15	140.88 (16)
C6—N1—C2—C3	1.3 (3)	O3—Zr1—O9—C15	−71.07 (17)
Zr1—N1—C2—C3	−175.02 (17)	O5—Zr1—O9—C15	74.13 (17)
C6—N1—C2—C1	−178.1 (2)	O7—Zr1—O9—C15	−149.76 (18)
Zr1—N1—C2—C1	5.7 (3)	N3—Zr1—O9—C15	4.43 (16)
O2—C1—C2—N1	171.7 (2)	N1—Zr1—O9—C15	−106.57 (18)
O1—C1—C2—N1	−4.2 (3)	N2—Zr1—O9—C15	140.72 (18)
O2—C1—C2—C3	−7.5 (4)	O9—Zr1—O11—C21	2.9 (2)
O1—C1—C2—C3	176.6 (2)	O1—Zr1—O11—C21	−150.93 (19)
N1—C2—C3—C4	−0.4 (4)	O3—Zr1—O11—C21	72.58 (18)
C1—C2—C3—C4	178.8 (2)	O5—Zr1—O11—C21	−71.65 (18)
C2—C3—C4—C5	−0.6 (4)	O7—Zr1—O11—C21	139.58 (17)
C3—C4—C5—C6	0.7 (4)	N3—Zr1—O11—C21	2.15 (17)
C2—N1—C6—C5	−1.1 (3)	N1—Zr1—O11—C21	138.73 (19)
Zr1—N1—C6—C5	175.18 (17)	N2—Zr1—O11—C21	−109.31 (19)
C2—N1—C6—C7	−179.5 (2)	Zr1—O9—C15—O10	172.67 (17)
Zr1—N1—C6—C7	−3.3 (2)	Zr1—O9—C15—C16	−7.2 (3)
C4—C5—C6—N1	0.1 (4)	C20—N3—C16—C17	0.2 (3)
C4—C5—C6—C7	178.3 (2)	Zr1—N3—C16—C17	176.24 (17)
Zr1—O3—C7—O4	179.05 (17)	C20—N3—C16—C15	−178.54 (19)
Zr1—O3—C7—C6	−3.7 (3)	Zr1—N3—C16—C15	−2.5 (2)
N1—C6—C7—O4	−178.3 (2)	O10—C15—C16—N3	−174.0 (2)
C5—C6—C7—O4	3.4 (4)	O9—C15—C16—N3	5.8 (3)
N1—C6—C7—O3	4.3 (3)	O10—C15—C16—C17	7.3 (4)
C5—C6—C7—O3	−174.1 (2)	O9—C15—C16—C17	−172.8 (2)
O11—Zr1—N2—C9	38.2 (2)	N3—C16—C17—C18	−2.1 (3)
O9—Zr1—N2—C9	−98.20 (17)	C15—C16—C17—C18	176.4 (2)
O1—Zr1—N2—C9	81.91 (17)	C16—C17—C18—C19	2.0 (4)
O3—Zr1—N2—C9	−144.46 (16)	C17—C18—C19—C20	0.0 (4)
O5—Zr1—N2—C9	−2.13 (16)	C16—N3—C20—C19	2.0 (3)
O7—Zr1—N2—C9	178.05 (18)	Zr1—N3—C20—C19	−174.09 (17)
N3—Zr1—N2—C9	−50.07 (19)	C16—N3—C20—C21	−177.09 (19)
N1—Zr1—N2—C9	129.38 (17)	Zr1—N3—C20—C21	6.8 (2)
O11—Zr1—N2—C13	−139.83 (16)	C18—C19—C20—N3	−2.0 (3)
O9—Zr1—N2—C13	83.78 (17)	C18—C19—C20—C21	176.9 (2)
O1—Zr1—N2—C13	−96.11 (18)	Zr1—O11—C21—O12	−177.80 (17)
O3—Zr1—N2—C13	37.5 (2)	Zr1—O11—C21—C20	0.5 (3)
O5—Zr1—N2—C13	179.84 (19)	N3—C20—C21—O12	173.6 (2)
O7—Zr1—N2—C13	0.03 (16)	C19—C20—C21—O12	−5.4 (4)
N3—Zr1—N2—C13	131.91 (16)	N3—C20—C21—O11	−4.8 (3)
N1—Zr1—N2—C13	−48.65 (19)	C19—C20—C21—O11	176.2 (2)
O11—Zr1—O5—C8	−150.83 (19)	C24—N6—C22—N7	−177.1 (2)
O9—Zr1—O5—C8	71.97 (18)	C24—N6—C22—N4	2.7 (3)
O1—Zr1—O5—C8	−71.37 (18)	C23—N4—C22—N7	179.2 (2)
O3—Zr1—O5—C8	136.75 (17)	C23—N4—C22—N6	−0.7 (3)
O7—Zr1—O5—C8	1.9 (2)	C24—N5—C23—N8	−177.7 (2)
N3—Zr1—O5—C8	139.08 (19)	C24—N5—C23—N4	1.7 (3)
N1—Zr1—O5—C8	−107.32 (19)	C22—N4—C23—N5	−1.7 (3)
N2—Zr1—O5—C8	1.68 (17)	C22—N4—C23—N8	177.7 (2)
O11—Zr1—O7—C14	137.40 (17)	C23—N5—C24—N9	−179.4 (2)
O9—Zr1—O7—C14	−72.30 (18)	C23—N5—C24—N6	0.7 (4)
O1—Zr1—O7—C14	71.31 (18)	C22—N6—C24—N9	177.2 (2)
O3—Zr1—O7—C14	−151.21 (19)	C22—N6—C24—N5	−2.8 (4)
O5—Zr1—O7—C14	2.2 (2)	C27—N12—C25—N13	−176.6 (2)
N3—Zr1—O7—C14	−108.38 (19)	C27—N12—C25—N10	3.8 (4)
N1—Zr1—O7—C14	138.25 (19)	C26—N10—C25—N13	176.9 (3)
N2—Zr1—O7—C14	2.44 (17)	C26—N10—C25—N12	−3.5 (4)
Zr1—O5—C8—O6	179.53 (18)	C25—N10—C26—N14	169.0 (3)
Zr1—O5—C8—C9	−1.1 (3)	C25—N10—C26—N11	0.2 (4)
C13—N2—C9—C10	0.6 (3)	C25—N10—C26—N14'	−157.4 (4)
Zr1—N2—C9—C10	−177.49 (18)	C27—N11—C26—N10	2.4 (4)
C13—N2—C9—C8	−179.6 (2)	C27—N11—C26—N14	−166.5 (3)
Zr1—N2—C9—C8	2.3 (3)	C27—N11—C26—N14'	160.7 (4)
O6—C8—C9—N2	178.5 (2)	C25—N12—C27—N15	179.4 (2)
O5—C8—C9—N2	−0.9 (3)	C25—N12—C27—N11	−0.8 (3)
O6—C8—C9—C10	−1.7 (4)	C26—N11—C27—N15	177.7 (3)
O5—C8—C9—C10	178.9 (2)	C26—N11—C27—N12	−2.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···N12	0.82	2.43	3.106 (3)	140
O1W—H1WB···O4W	0.82	2.03	2.824 (4)	163
O2W—H2WA···O2i	0.82	1.96	2.746 (3)	160
O2W—H2WB···O7	0.82	2.24	3.051 (3)	169
O2W—H2WB···O8	0.82	2.58	3.091 (3)	122
N4—H4A···O8	0.87	2.05	2.805 (3)	144
O3W—H3WA···O5i	0.82	2.26	2.992 (4)	149
O3W—H3WA···O11i	0.82	2.44	3.008 (4)	127
O3W—H3WB···O10	0.82	2.12	2.890 (3)	155
O4W—H4WA···O4ii	0.82	2.06	2.858 (5)	166
N7—H7A···O2W	0.87	2.06	2.921 (3)	168
N7—H7B···O4iii	0.87	2.09	2.949 (3)	169
O4W—H4WB···O2iv	0.82	2.46	3.283 (4)	180
N8—H8A···O1W	0.87	2.10	2.813 (3)	139
N8—H8B···O8	0.87	1.94	2.762 (3)	156
N9—H9A···O2v	0.87	2.23	2.944 (3)	139
N9—H9B···N10vi	0.87	2.08	2.947 (3)	176
N11—H11A···O9	0.87	2.42	3.134 (3)	139
N13—H13A···O4iv	0.87	2.32	2.957 (3)	130
N13—H13B···N6vi	0.87	2.10	2.958 (3)	170
N14—H14A···O1i	0.87	2.54	3.398 (6)	169
N14—H14A···O2i	0.87	2.48	3.167 (6)	136
N14—H14B···O3W	0.87	2.55	3.119 (6)	124
N14—H14B···O9	0.87	2.51	3.121 (6)	127
N14—H14B···O10	0.87	2.42	3.228 (5)	156
N15—H15A···O6vii	0.87	1.94	2.797 (3)	166
N15—H15B···O12iv	0.87	2.06	2.911 (3)	167
C3—H3···O2Wviii	0.95	2.36	3.130 (3)	138
C12—H12···O1W	0.95	2.58	3.326 (3)	136
C17—H17···N12ix	0.95	2.48	3.417 (4)	169
C19—H19···O3Wx	0.95	2.31	3.215 (4)	158
C14—O8···Cg1	1.23	3.89	4.068 (3)	89

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯N12	0.82	2.43	3.106 (3)	140
O1W—H1WB⋯O4W	0.82	2.03	2.824 (4)	163
O2W—H2WA⋯O2i	0.82	1.96	2.746 (3)	160
O2W—H2WB⋯O7	0.82	2.24	3.051 (3)	169
O2W—H2WB⋯O8	0.82	2.58	3.091 (3)	122
N4—H4A⋯O8	0.87	2.05	2.805 (3)	144
O3W—H3WA⋯O5i	0.82	2.26	2.992 (4)	149
O3W—H3WA⋯O11i	0.82	2.44	3.008 (4)	127
O3W—H3WB⋯O10	0.82	2.12	2.890 (3)	155
O4W—H4WA⋯O4ii	0.82	2.06	2.858 (5)	166
N7—H7A⋯O2W	0.87	2.06	2.921 (3)	168
N7—H7B⋯O4iii	0.87	2.09	2.949 (3)	169
O4W—H4WB⋯O2iv	0.82	2.46	3.283 (4)	180
N8—H8A⋯O1W	0.87	2.10	2.813 (3)	139
N8—H8B⋯O8	0.87	1.94	2.762 (3)	156
N9—H9A⋯O2v	0.87	2.23	2.944 (3)	139
N9—H9B⋯N10vi	0.87	2.08	2.947 (3)	176
N11—H11A⋯O9	0.87	2.42	3.134 (3)	139
N13—H13A⋯O4iv	0.87	2.32	2.957 (3)	130
N13—H13B⋯N6vi	0.87	2.10	2.958 (3)	170
N14—H14A⋯O1i	0.87	2.54	3.398 (6)	169
N14—H14A⋯O2i	0.87	2.48	3.167 (6)	136
N14—H14B⋯O3W	0.87	2.55	3.119 (6)	124
N14—H14B⋯O9	0.87	2.51	3.121 (6)	127
N14—H14B⋯O10	0.87	2.42	3.228 (5)	156
N15—H15A⋯O6vii	0.87	1.94	2.797 (3)	166
N15—H15B⋯O12iv	0.87	2.06	2.911 (3)	167
C3—H3⋯O2Wviii	0.95	2.36	3.130 (3)	138
C12—H12⋯O1W	0.95	2.58	3.326 (3)	136
C17—H17⋯N12ix	0.95	2.48	3.417 (4)	169
C19—H19⋯O3Wx	0.95	2.31	3.215 (4)	158

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) .