Bis(2-amino-6-methyl-pyridinium) tris-(pyridine-2,6-dicarboxyl-ato)zirconate(IV) dihydrate.

In the title compound, (C(6)H(9)N(2))(2)[Zr(C(7)H(3)NO(4))(3)]·2H(2)O, the Zr(IV) atom is nine-coordinated by three pyridine-2,6-dicarboxyl-ate ligands in a distorted tricapped trigonal-prismatic ZrN(3)O(6) environment. The crystal packing is stabilized by inter-molecular N-H⋯O and O-H⋯O hydrogen bonds.

Related literature

For background to proton-transfer compounds, see: Aghabozorg et al. (2008 ▶). For related structures, see: Aghabozorg et al. (2005 ▶); Daneshvar et al. (2008 ▶); Willey et al. (1998 ▶); Pasdar et al. (2010 ▶, 2011 ▶).

Experimental

Crystal data

(C6H9N2)2[Zr(C7H3NO4)3]·2H2O

M = 840.87

Monoclinic,

a = 18.719 (4) Å

b = 10.536 (2) Å

c = 18.781 (4) Å

β = 108.58 (3)°

V = 3511.0 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.39 mm−1

T = 298 K

0.35 × 0.30 × 0.25 mm

Data collection

Stoe IPDS II diffractometer

Absorption correction: numerical [shape of crystal determined optically (X-SHAPE and X-RED32; Stoe & Cie, 2005 ▶)] T min = 0.870, T max = 0.903

12273 measured reflections

4705 independent reflections

4284 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.060

S = 1.03

4705 reflections

271 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.27 e Å−3

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003072/bt5467sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811003072/bt5467Isup2.hkl

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

(C6H9N2)2[Zr(C7H3NO4)3]·2H2O	F(000) = 1720
Mr = 840.87	Dx = 1.591 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4705 reflections
a = 18.719 (4) Å	θ = 2.3–29.2°
b = 10.536 (2) Å	µ = 0.39 mm−1
c = 18.781 (4) Å	T = 298 K
β = 108.58 (3)°	Prism, colorless
V = 3511.0 (14) Å3	0.35 × 0.3 × 0.25 mm
Z = 4

Stoe IPDS II diffractometer	4705 independent reflections
Radiation source: fine-focus sealed tube	4284 reflections with I > 2σ(I)
graphite	Rint = 0.025
Detector resolution: 0.15 mm pixels mm-1	θmax = 29.2°, θmin = 2.3°
rotation method scans	h = −25→25
Absorption correction: numerical [shape of crystal determined optically (X-SHAPE and X-RED32; Stoe& Cie, 2005)]	k = −12→14
Tmin = 0.870, Tmax = 0.903	l = −25→25
12273 measured reflections

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0339P)2 + 1.0948P] where P = (Fo2 + 2Fc2)/3
4705 reflections	(Δ/σ)max = 0.001
271 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.27 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
C17	0.61732 (13)	0.9817 (2)	0.98635 (13)	0.0731 (5)
H17A	0.6130	1.0629	1.0079	0.110*
H17B	0.6397	0.9220	1.0258	0.110*
H17C	0.5681	0.9524	0.9571	0.110*
Zr1	0.5000	0.572850 (14)	0.7500	0.02355 (5)
N1	0.48851 (5)	0.45657 (9)	0.63879 (6)	0.02849 (19)
C5	0.53457 (7)	0.35957 (11)	0.64083 (7)	0.0320 (2)
C1	0.43464 (7)	0.48587 (12)	0.57517 (7)	0.0322 (2)
C2	0.42369 (9)	0.41586 (14)	0.51009 (8)	0.0426 (3)
H2	0.3856	0.4369	0.4661	0.051*
C4	0.52766 (9)	0.28548 (14)	0.57799 (8)	0.0449 (3)
H4	0.5604	0.2182	0.5800	0.054*
C3	0.47076 (10)	0.31419 (15)	0.51223 (9)	0.0502 (4)
H3	0.4643	0.2650	0.4695	0.060*
N3	0.68745 (7)	0.88262 (13)	0.91339 (7)	0.0443 (3)
N4	0.74780 (9)	0.76062 (17)	0.84880 (10)	0.0600 (4)
C12	0.73020 (8)	0.87419 (17)	0.86785 (9)	0.0468 (3)
C16	0.66558 (9)	0.99384 (17)	0.93708 (10)	0.0539 (4)
C13	0.75373 (9)	0.98893 (19)	0.84391 (10)	0.0580 (4)
H13	0.7833	0.9879	0.8124	0.070*
C15	0.68835 (12)	1.10440 (19)	0.91395 (13)	0.0694 (5)
H15	0.6743	1.1819	0.9292	0.083*
C14	0.73318 (11)	1.10031 (19)	0.86693 (12)	0.0675 (5)
H14	0.7491	1.1759	0.8513	0.081*
O1	0.40841 (5)	0.64343 (9)	0.65095 (5)	0.03362 (18)
O2	0.34539 (6)	0.65095 (11)	0.52861 (6)	0.0505 (3)
C6	0.39137 (7)	0.60152 (12)	0.58346 (7)	0.0333 (2)
N2	0.5000	0.79516 (13)	0.7500	0.0288 (3)
O5	0.42116 (5)	0.65285 (9)	0.80434 (5)	0.03414 (18)
C8	0.45374 (7)	0.85771 (12)	0.77872 (7)	0.0326 (2)
C11	0.40782 (7)	0.77095 (12)	0.81082 (7)	0.0332 (2)
O6	0.36459 (7)	0.81504 (11)	0.84149 (7)	0.0520 (3)
C9	0.45124 (9)	0.98904 (14)	0.77885 (10)	0.0483 (3)
H9	0.4178	1.0321	0.7977	0.058*
C10	0.5000	1.0542 (2)	0.7500	0.0603 (7)
H10	0.5000	1.1425	0.7500	0.072*
O4	0.64121 (6)	0.25978 (10)	0.72642 (6)	0.0482 (2)
C7	0.59251 (7)	0.34202 (12)	0.71639 (7)	0.0324 (2)
O3	0.58564 (5)	0.41882 (9)	0.76672 (5)	0.03380 (18)
O7	0.74136 (9)	0.47442 (18)	0.85925 (12)	0.0865 (6)
H3A	0.6742 (11)	0.810 (2)	0.9320 (12)	0.064 (6)*
H4B	0.7294 (12)	0.690 (2)	0.8587 (12)	0.066 (6)*
H4A	0.7747 (12)	0.755 (2)	0.8218 (12)	0.068 (6)*
H7A	0.7728 (18)	0.425 (3)	0.8528 (17)	0.105 (10)*
H7B	0.6993 (19)	0.445 (3)	0.8293 (19)	0.121 (12)*

	U11	U22	U33	U12	U13	U23
C17	0.0748 (13)	0.0714 (13)	0.0801 (14)	0.0028 (11)	0.0344 (11)	−0.0088 (11)
Zr1	0.02282 (7)	0.02414 (7)	0.02305 (8)	0.000	0.00640 (5)	0.000
N1	0.0303 (4)	0.0279 (4)	0.0274 (5)	−0.0010 (3)	0.0094 (4)	−0.0011 (4)
C5	0.0370 (6)	0.0285 (5)	0.0338 (6)	0.0001 (4)	0.0158 (5)	−0.0007 (5)
C1	0.0338 (5)	0.0335 (6)	0.0279 (6)	−0.0029 (5)	0.0080 (4)	−0.0008 (5)
C2	0.0499 (7)	0.0455 (7)	0.0289 (6)	−0.0053 (6)	0.0077 (5)	−0.0046 (6)
C4	0.0597 (8)	0.0364 (7)	0.0426 (7)	0.0051 (6)	0.0222 (7)	−0.0067 (6)
C3	0.0703 (10)	0.0455 (8)	0.0366 (7)	−0.0022 (7)	0.0196 (7)	−0.0127 (6)
N3	0.0399 (6)	0.0458 (6)	0.0432 (7)	−0.0095 (5)	0.0077 (5)	0.0018 (5)
N4	0.0627 (9)	0.0603 (9)	0.0665 (10)	−0.0172 (7)	0.0342 (8)	−0.0101 (8)
C12	0.0372 (6)	0.0571 (9)	0.0406 (7)	−0.0126 (6)	0.0048 (6)	0.0019 (7)
C16	0.0480 (8)	0.0519 (9)	0.0550 (9)	−0.0017 (7)	0.0069 (7)	−0.0012 (8)
C13	0.0472 (8)	0.0668 (11)	0.0538 (10)	−0.0144 (8)	0.0073 (7)	0.0165 (8)
C15	0.0661 (11)	0.0478 (9)	0.0845 (14)	0.0016 (8)	0.0102 (10)	0.0063 (9)
C14	0.0571 (10)	0.0577 (11)	0.0746 (13)	−0.0119 (8)	0.0026 (9)	0.0254 (9)
O1	0.0330 (4)	0.0357 (4)	0.0283 (4)	0.0059 (3)	0.0044 (3)	−0.0009 (3)
O2	0.0530 (6)	0.0550 (6)	0.0322 (5)	0.0155 (5)	−0.0024 (4)	0.0022 (5)
C6	0.0307 (5)	0.0356 (6)	0.0296 (6)	0.0004 (4)	0.0041 (4)	0.0018 (5)
N2	0.0306 (6)	0.0285 (6)	0.0260 (6)	0.000	0.0072 (5)	0.000
O5	0.0361 (4)	0.0330 (4)	0.0374 (5)	0.0024 (3)	0.0174 (4)	0.0019 (4)
C8	0.0353 (6)	0.0304 (6)	0.0308 (6)	0.0035 (5)	0.0089 (5)	−0.0012 (5)
C11	0.0331 (5)	0.0368 (6)	0.0306 (6)	0.0051 (5)	0.0112 (5)	0.0002 (5)
O6	0.0572 (6)	0.0494 (6)	0.0625 (7)	0.0113 (5)	0.0375 (6)	−0.0011 (5)
C9	0.0575 (8)	0.0322 (6)	0.0612 (10)	0.0056 (6)	0.0273 (8)	−0.0039 (6)
C10	0.0776 (16)	0.0267 (9)	0.0865 (19)	0.000	0.0399 (15)	0.000
O4	0.0482 (5)	0.0431 (5)	0.0556 (6)	0.0190 (4)	0.0197 (5)	0.0058 (5)
C7	0.0320 (5)	0.0292 (5)	0.0389 (6)	0.0022 (4)	0.0154 (5)	0.0037 (5)
O3	0.0314 (4)	0.0355 (4)	0.0324 (4)	0.0060 (3)	0.0072 (3)	0.0000 (4)
O7	0.0527 (8)	0.0816 (11)	0.1081 (13)	0.0094 (8)	0.0016 (8)	−0.0399 (10)

C17—C16	1.491 (3)	N4—C12	1.320 (2)
C17—H17A	0.9600	N4—H4B	0.86 (2)
C17—H17B	0.9600	N4—H4A	0.82 (2)
C17—H17C	0.9600	C12—C13	1.409 (2)
Zr1—O5	2.2113 (9)	C16—C15	1.358 (3)
Zr1—O5i	2.2113 (9)	C13—C14	1.348 (3)
Zr1—O1i	2.2183 (11)	C13—H13	0.9300
Zr1—O1	2.2183 (11)	C15—C14	1.399 (3)
Zr1—O3i	2.2320 (9)	C15—H15	0.9300
Zr1—O3	2.2320 (9)	C14—H14	0.9300
Zr1—N2	2.3422 (15)	O1—C6	1.2828 (15)
Zr1—N1	2.3713 (10)	O2—C6	1.2280 (16)
Zr1—N1i	2.3713 (11)	N2—C8	1.3314 (14)
N1—C5	1.3297 (15)	N2—C8i	1.3314 (14)
N1—C1	1.3313 (16)	O5—C11	1.2824 (16)
C5—C4	1.3863 (18)	C8—C9	1.3845 (19)
C5—C7	1.4979 (19)	C8—C11	1.5062 (18)
C1—C2	1.3857 (18)	C11—O6	1.2246 (15)
C1—C6	1.4986 (18)	C9—C10	1.3834 (19)
C2—C3	1.379 (2)	C9—H9	0.9300
C2—H2	0.9300	C10—C9i	1.3834 (19)
C4—C3	1.383 (2)	C10—H10	0.9300
C4—H4	0.9300	O4—C7	1.2279 (15)
C3—H3	0.9300	C7—O3	1.2814 (15)
N3—C12	1.348 (2)	O7—H7A	0.82 (3)
N3—C16	1.362 (2)	O7—H7B	0.87 (4)
N3—H3A	0.91 (2)
C16—C17—H17A	109.5	C1—C2—H2	120.9
C16—C17—H17B	109.5	C3—C4—C5	118.26 (13)
H17A—C17—H17B	109.5	C3—C4—H4	120.9
C16—C17—H17C	109.5	C5—C4—H4	120.9
H17A—C17—H17C	109.5	C2—C3—C4	119.92 (13)
H17B—C17—H17C	109.5	C2—C3—H3	120.0
O5—Zr1—O5i	135.19 (5)	C4—C3—H3	120.0
O5—Zr1—O1i	86.35 (4)	C12—N3—C16	124.41 (15)
O5i—Zr1—O1i	78.94 (4)	C12—N3—H3A	118.6 (13)
O5—Zr1—O1	78.94 (4)	C16—N3—H3A	116.9 (13)
O5i—Zr1—O1	86.35 (4)	C12—N4—H4B	124.6 (14)
O1i—Zr1—O1	140.83 (5)	C12—N4—H4A	118.8 (16)
O5—Zr1—O3i	77.70 (4)	H4B—N4—H4A	116 (2)
O5i—Zr1—O3i	140.11 (3)	N4—C12—N3	118.80 (15)
O1i—Zr1—O3i	133.65 (3)	N4—C12—C13	124.11 (16)
O1—Zr1—O3i	78.30 (4)	N3—C12—C13	117.09 (17)
O5—Zr1—O3	140.11 (3)	C15—C16—N3	118.41 (18)
O5i—Zr1—O3	77.70 (4)	C15—C16—C17	125.88 (19)
O1i—Zr1—O3	78.30 (4)	N3—C16—C17	115.71 (16)
O1—Zr1—O3	133.65 (3)	C14—C13—C12	119.64 (17)
O3i—Zr1—O3	86.71 (5)	C14—C13—H13	120.2
O5—Zr1—N2	67.59 (2)	C12—C13—H13	120.2
O5i—Zr1—N2	67.59 (2)	C16—C15—C14	119.2 (2)
O1i—Zr1—N2	70.41 (3)	C16—C15—H15	120.4
O1—Zr1—N2	70.41 (3)	C14—C15—H15	120.4
O3i—Zr1—N2	136.64 (2)	C13—C14—C15	121.26 (17)
O3—Zr1—N2	136.64 (2)	C13—C14—H14	119.4
O5—Zr1—N1	135.80 (4)	C15—C14—H14	119.4
O5i—Zr1—N1	71.15 (4)	C6—O1—Zr1	126.56 (8)
O1i—Zr1—N1	137.80 (3)	O2—C6—O1	124.76 (12)
O1—Zr1—N1	66.77 (4)	O2—C6—C1	121.01 (12)
O3i—Zr1—N1	68.96 (4)	O1—C6—C1	114.21 (11)
O3—Zr1—N1	66.91 (4)	C8—N2—C8i	120.65 (15)
N2—Zr1—N1	121.11 (2)	C8—N2—Zr1	119.67 (8)
O5—Zr1—N1i	71.15 (4)	C8i—N2—Zr1	119.67 (8)
O5i—Zr1—N1i	135.80 (4)	C11—O5—Zr1	126.32 (8)
O1i—Zr1—N1i	66.77 (4)	N2—C8—C9	121.48 (12)
O1—Zr1—N1i	137.80 (3)	N2—C8—C11	112.92 (11)
O3i—Zr1—N1i	66.91 (4)	C9—C8—C11	125.59 (11)
O3—Zr1—N1i	68.96 (4)	O6—C11—O5	126.19 (12)
N2—Zr1—N1i	121.11 (3)	O6—C11—C8	120.34 (12)
N1—Zr1—N1i	117.79 (5)	O5—C11—C8	113.43 (10)
C5—N1—C1	120.19 (11)	C10—C9—C8	117.95 (14)
C5—N1—Zr1	119.72 (8)	C10—C9—H9	121.0
C1—N1—Zr1	120.07 (8)	C8—C9—H9	121.0
N1—C5—C4	121.64 (13)	C9—C10—C9i	120.45 (19)
N1—C5—C7	112.91 (10)	C9—C10—H10	119.8
C4—C5—C7	125.46 (12)	C9i—C10—H10	119.8
N1—C1—C2	121.68 (12)	O4—C7—O3	125.20 (13)
N1—C1—C6	112.04 (10)	O4—C7—C5	120.70 (12)
C2—C1—C6	126.27 (12)	O3—C7—C5	114.10 (10)
C3—C2—C1	118.30 (14)	C7—O3—Zr1	126.28 (8)
C3—C2—H2	120.9	H7A—O7—H7B	103 (3)
O5—Zr1—N1—C5	−137.47 (8)	C2—C1—C6—O1	174.88 (12)
O5i—Zr1—N1—C5	86.13 (9)	O5—Zr1—N2—C8	−2.02 (7)
O1i—Zr1—N1—C5	38.83 (11)	O5i—Zr1—N2—C8	177.98 (7)
O1—Zr1—N1—C5	−179.67 (9)	O1i—Zr1—N2—C8	−96.24 (7)
O3i—Zr1—N1—C5	−93.76 (9)	O1—Zr1—N2—C8	83.76 (7)
O3—Zr1—N1—C5	1.82 (8)	O3i—Zr1—N2—C8	37.42 (7)
N2—Zr1—N1—C5	133.57 (8)	O3—Zr1—N2—C8	−142.58 (7)
N1i—Zr1—N1—C5	−46.43 (8)	N1—Zr1—N2—C8	129.04 (7)
O5—Zr1—N1—C1	40.43 (11)	N1i—Zr1—N2—C8	−50.96 (7)
O5i—Zr1—N1—C1	−95.97 (9)	O5—Zr1—N2—C8i	177.98 (7)
O1i—Zr1—N1—C1	−143.27 (8)	O5i—Zr1—N2—C8i	−2.02 (7)
O1—Zr1—N1—C1	−1.77 (8)	O1i—Zr1—N2—C8i	83.76 (7)
O3i—Zr1—N1—C1	84.14 (9)	O1—Zr1—N2—C8i	−96.24 (7)
O3—Zr1—N1—C1	179.72 (10)	O3i—Zr1—N2—C8i	−142.58 (7)
N2—Zr1—N1—C1	−48.53 (9)	O3—Zr1—N2—C8i	37.42 (7)
N1i—Zr1—N1—C1	131.47 (9)	N1—Zr1—N2—C8i	−50.96 (7)
C1—N1—C5—C4	−0.84 (18)	N1i—Zr1—N2—C8i	129.04 (7)
Zr1—N1—C5—C4	177.05 (10)	O5i—Zr1—O5—C11	1.94 (9)
C1—N1—C5—C7	178.88 (10)	O1i—Zr1—O5—C11	72.24 (10)
Zr1—N1—C5—C7	−3.22 (13)	O1—Zr1—O5—C11	−71.27 (10)
C5—N1—C1—C2	1.35 (18)	O3i—Zr1—O5—C11	−151.55 (11)
Zr1—N1—C1—C2	−176.54 (10)	O3—Zr1—O5—C11	139.09 (10)
C5—N1—C1—C6	−177.21 (10)	N2—Zr1—O5—C11	1.94 (9)
Zr1—N1—C1—C6	4.90 (13)	N1—Zr1—O5—C11	−110.25 (10)
N1—C1—C2—C3	−0.5 (2)	N1i—Zr1—O5—C11	138.93 (11)
C6—C1—C2—C3	177.80 (13)	C8i—N2—C8—C9	0.92 (11)
N1—C5—C4—C3	−0.4 (2)	Zr1—N2—C8—C9	−179.08 (11)
C7—C5—C4—C3	179.87 (13)	C8i—N2—C8—C11	−178.02 (11)
C1—C2—C3—C4	−0.8 (2)	Zr1—N2—C8—C11	1.98 (11)
C5—C4—C3—C2	1.2 (2)	Zr1—O5—C11—O6	−179.35 (11)
C16—N3—C12—N4	179.94 (16)	Zr1—O5—C11—C8	−1.59 (15)
C16—N3—C12—C13	0.3 (2)	N2—C8—C11—O6	177.52 (11)
C12—N3—C16—C15	−0.3 (2)	C9—C8—C11—O6	−1.4 (2)
C12—N3—C16—C17	179.07 (16)	N2—C8—C11—O5	−0.38 (15)
N4—C12—C13—C14	−179.53 (18)	C9—C8—C11—O5	−179.28 (14)
N3—C12—C13—C14	0.1 (2)	N2—C8—C9—C10	−1.8 (2)
N3—C16—C15—C14	0.0 (3)	C11—C8—C9—C10	177.02 (11)
C17—C16—C15—C14	−179.37 (19)	C8—C9—C10—C9i	0.86 (10)
C12—C13—C14—C15	−0.4 (3)	N1—C5—C7—O4	−176.83 (11)
C16—C15—C14—C13	0.4 (3)	C4—C5—C7—O4	2.9 (2)
O5—Zr1—O1—C6	−154.09 (10)	N1—C5—C7—O3	3.20 (15)
O5i—Zr1—O1—C6	68.45 (10)	C4—C5—C7—O3	−177.09 (12)
O1i—Zr1—O1—C6	135.95 (10)	O4—C7—O3—Zr1	178.19 (10)
O3i—Zr1—O1—C6	−74.53 (10)	C5—C7—O3—Zr1	−1.84 (14)
O3—Zr1—O1—C6	−0.71 (12)	O5—Zr1—O3—C7	135.01 (9)
N2—Zr1—O1—C6	135.95 (10)	O5i—Zr1—O3—C7	−74.37 (10)
N1—Zr1—O1—C6	−2.60 (9)	O1i—Zr1—O3—C7	−155.43 (10)
N1i—Zr1—O1—C6	−108.97 (10)	O1—Zr1—O3—C7	−1.71 (12)
Zr1—O1—C6—O2	−172.23 (10)	O3i—Zr1—O3—C7	68.68 (9)
Zr1—O1—C6—C1	5.94 (15)	N2—Zr1—O3—C7	−111.32 (9)
N1—C1—C6—O2	171.61 (12)	N1—Zr1—O3—C7	0.18 (9)
C2—C1—C6—O2	−6.9 (2)	N1i—Zr1—O3—C7	135.18 (10)
N1—C1—C6—O1	−6.64 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O3	0.87 (4)	2.09 (4)	2.938 (2)	164 (3)
O7—H7A···O6ii	0.82 (3)	2.14 (3)	2.9568 (19)	173 (3)
N4—H4B···O1i	0.86 (2)	2.57 (2)	3.1755 (18)	127.6 (17)
N4—H4B···O7	0.86 (2)	2.28 (2)	3.027 (3)	144.1 (18)
N4—H4A···O4iii	0.82 (2)	2.05 (2)	2.861 (2)	168 (2)
N3—H3A···O2i	0.91 (2)	1.91 (2)	2.8194 (18)	175.1 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7B⋯O3	0.87 (4)	2.09 (4)	2.938 (2)	164 (3)
O7—H7A⋯O6i	0.82 (3)	2.14 (3)	2.9568 (19)	173 (3)
N4—H4B⋯O1ii	0.86 (2)	2.57 (2)	3.1755 (18)	127.6 (17)
N4—H4B⋯O7	0.86 (2)	2.28 (2)	3.027 (3)	144.1 (18)
N4—H4A⋯O4iii	0.82 (2)	2.05 (2)	2.861 (2)	168 (2)
N3—H3A⋯O2ii	0.91 (2)	1.91 (2)	2.8194 (18)	175.1 (18)

Symmetry codes: (i) ; (ii) ; (iii) .