Di­aqua(2,6-dioxo-1,2,3,6-tetra­hydro­pyrimidine-4-carboxyl­ato-κN³)(1,10-phenanthroline)­zinc(II) dihydrate

In the title compound, [Zn(C₅H₂N₂O₄)(C₁₂H₈N₂)(H₂O)₂]·2H₂O, the Zn atom is coordinated by N and O atoms from the orotate (2,6-dioxo-1,2,3,6-tetra­hydro­pyrimidine-4-carboxyl­ate) ligand, two N atoms from 1,10-phenanthroline and two aqua O atoms in a distorted octahedral geometry. The presence of intermolecular N—H...O and O—H...O hydrogen bonds and π–π-stacking interactions between the phenanthroline ligands results in a three-dimensional structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.010 Å
• R factor = 0.066
• wR factor = 0.166
• Data-to-parameter ratio = 10.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
          Tmin and Tmax reported:      0.593     0.850
          Tmin' and Tmax expected:      0.698     0.850
          RR' =      0.850
          Please check that your absorption correction is appropriate.

SHFSU_01  Alert C The absolute value of parameter shift to su ratio > 0.05
          Absolute value of the parameter shift to su ratio given   0.055
          Additional refinement cycles may be required.

PLAT_354  Alert C Short   O-H Bond (0.82A)   O8     -   H8C      =       0.70 Ang.

PLAT_369  Alert C Long   C(sp2)-C(sp2) Bond  C1     -   C2       =       1.53 Ang.

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #         3
                   O5  -ZN  -O1  -C1    -14.90  1.40   1.555   1.555   1.555   1.555


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 5 Alert Level C = Please check

---

S1. Comment

Orotic acid (2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid; vitamin B₁₃; H₃dtpc) is an important pyrimidine derivative as the effective precursor in the biosynthesis of pyrimidine base of nucleic acids in living organisms, and so it occupies a unique role in bioinorganic and pharmaceutical studies (Leberman et al., 1955). Aside from the biological interest, orotic acid is also a good organic building block in coordination chemistry. Its ketonic and enolic tautomers, along with its asymmetric geometry, make it to be a versatile multidentate organic ligand (Karipdes et al., 1986). It contains a potential hydrogen-bond acceptor and hydrogen-bond donor, and can display different hydrogen-bonding interactions in supramolecular complexes (Xu et al., 2000). Many complexes of orotate ligand have been reported in the past decade (Hambley et al., 1995). The structure of the title compound, (I), has been determined in order to study further the coordination chemistry of the orotic acid.

The title complex is mononuclear, as shown in Fig. l. The central Zn^II atom is coordinated by two water molecules, two N atoms from 1,10-phenanthroline, and by N and carboxylate O atoms from the orotate ligand, forming a distorted octahedral coordination geometry. The Zn—O6 and Zn—N3 bond lengths are significantly longer than the corresponding distances (Zn—O5 and Zn—N4), suggesting that N3—Zn—O6 is the axial direction of the d¹⁰ Jahn–Teller distortion. Atom N3 of the phenanthroline ligand and water atom O6 occupy the axial positions with the N3—Zn—O6 angle being 167.46 (19)°, while the equatorial plane is formed by atom N1 and carboxylate atom O1 of the orotate ligand, a water molecule (O5) and an N atom (N4), with the angles N1—Zn—N4 and O5—Zn—O1 being 166.67 (18) and 171.39 (18)°, respectively.

There are intermolecular N—H···O and O—H···O hydrogen-bonding interactions (Table 2), which result in a two-dimensional layer structure (Fig. 2). A three-dimensional structure (Fig. 3) is finally formed by face-to-face π–π-stacking interactions between the 1,10-phenanthroline ligands of neighboring layers, with distances between the aromatic rings ranging from 3.20 to 3.60 Å.

S2. Experimental

A mixture of orotic acid (0.3 mmol, 0.052 g) and Zn(CH₃COO)₂·2H₂O (0.3 mmol, 0.066 g) in 30 ml of EtOH-water (1:3 v/v) was heated with stirring, the pH of the reaction solution was adjusted to 6 using a dilute solution of NH₃·H₂O. After evaporating the solution for two weeks, colorless block-like crystals of (I) were isolated by filtration (yield, 65%).

S3. Refinement

The H atoms of the water molecules (free and coordinated) were located from difference electron-density maps and refined isotropically. The O—H bond lengths are in the range 0.70 (7)–01.04 (11) Å. The H atoms of C—H and N—H groups were placed in calculated positions and were allowed to ride on their respective parent C atoms.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the title compound (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Two-dimensional structure of (I), showing the hydrogen-bonding interactions.
	Fig. 3. The three-dimensional structure of (I) formed through π–π-stacking and hydrogen-bonding interactions.

Diaqua(2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylato-κN³)(1,10- phenanthroline)zinc(II) dihydrate

Crystal data

[Zn(C5H2N2O4)(C12H8N2)(H2O)2]·2H2O	F(000) = 484
Mr = 471.72	Dx = 1.655 Mg m^−3
Triclinic, P1	Melting point: not measured K
a = 7.9351 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1874 (8) Å	Cell parameters from 2440 reflections
c = 12.6841 (10) Å	θ = 1.6–25.1°
α = 91.834 (2)°	µ = 1.35 mm^−1
β = 94.264 (2)°	T = 293 K
γ = 111.915 (1)°	Block, colorless
V = 946.65 (13) Å^3	0.26 × 0.20 × 0.12 mm
Z = 2

Data collection

Siemens CCD area-detector diffractometer	3303 independent reflections
Radiation source: fine-focus sealed tube	2680 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ϕ and ω scans	θmax = 25.1°, θmin = 1.6°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −5→9
Tmin = 0.593, Tmax = 0.850	k = −12→11
4875 measured reflections	l = −14→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0626P)^2 + 4.4071P] where P = (Fo^2 + 2Fc^2)/3
3303 reflections	(Δ/σ)max = 0.055
303 parameters	Δρmax = 0.73 e Å^−3
0 restraints	Δρmin = −0.80 e Å^−3

Special details

Experimental. empirical from equivalent reflections (XEMP in SHELXTL; Siemens,1994)

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.

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

	x	y	z	Uiso*/Ueq
Zn	−0.32324 (9)	−0.21650 (7)	0.26949 (6)	0.0317 (2)
O1	−0.5194 (5)	−0.1362 (4)	0.3062 (3)	0.0357 (10)
O2	−0.8075 (6)	−0.1972 (4)	0.3424 (4)	0.0399 (11)
O3	−0.9297 (6)	−0.6982 (5)	0.4624 (4)	0.0464 (12)
O4	−0.3755 (6)	−0.5488 (5)	0.3340 (4)	0.0427 (11)
O5	−0.1475 (7)	−0.3258 (5)	0.2432 (4)	0.0386 (11)
O6	−0.1640 (7)	−0.1179 (5)	0.4107 (4)	0.0373 (11)
O7	−0.3003 (9)	−0.7889 (7)	0.3779 (6)	0.0682 (18)
O8	−0.3453 (9)	−0.0914 (6)	0.5807 (4)	0.0489 (13)
N1	−0.5197 (6)	−0.3929 (5)	0.3323 (4)	0.0291 (11)
N2	−0.6549 (6)	−0.6195 (5)	0.3959 (4)	0.0325 (11)
H2A	−0.6466	−0.7015	0.4081	0.039*
N3	−0.4592 (7)	−0.2757 (5)	0.1055 (4)	0.0352 (12)
N4	−0.1784 (7)	−0.0371 (5)	0.1839 (4)	0.0342 (12)
C1	−0.6680 (8)	−0.2238 (6)	0.3328 (5)	0.0311 (13)
C2	−0.6728 (8)	−0.3719 (6)	0.3556 (4)	0.0279 (12)
C3	−0.8166 (8)	−0.4666 (6)	0.3974 (5)	0.0339 (14)
H3A	−0.9193	−0.4442	0.4109	0.041*
C4	−0.8119 (8)	−0.6014 (7)	0.4210 (5)	0.0338 (14)
C5	−0.5108 (8)	−0.5197 (6)	0.3533 (5)	0.0310 (13)
C6	−0.5972 (10)	−0.3906 (8)	0.0691 (6)	0.0497 (18)
H6A	−0.6419	−0.4653	0.1151	0.060*
C7	−0.6820 (12)	−0.4092 (9)	−0.0336 (6)	0.060 (2)
H7A	−0.7821	−0.4943	−0.0564	0.072*
C8	−0.6193 (11)	−0.3041 (9)	−0.1000 (6)	0.058 (2)
H8A	−0.6764	−0.3148	−0.1700	0.070*
C9	−0.4694 (10)	−0.1788 (8)	−0.0658 (5)	0.0437 (16)
C10	−0.3950 (12)	−0.0629 (9)	−0.1293 (6)	0.057 (2)
H10A	−0.4479	−0.0683	−0.1998	0.069*
C11	−0.2522 (12)	0.0544 (9)	−0.0932 (6)	0.056 (2)
H11A	−0.2040	0.1291	−0.1386	0.067*
C12	−0.1707 (10)	0.0679 (8)	0.0148 (5)	0.0436 (16)
C13	−0.0229 (11)	0.1875 (8)	0.0577 (6)	0.055 (2)
H13A	0.0334	0.2639	0.0150	0.066*
C14	0.0388 (10)	0.1932 (8)	0.1598 (7)	0.055 (2)
H14A	0.1376	0.2750	0.1899	0.066*
C15	−0.0415 (9)	0.0795 (7)	0.2225 (6)	0.0462 (17)
H15A	0.0036	0.0864	0.2948	0.055*
C16	−0.2434 (8)	−0.0420 (7)	0.0802 (5)	0.0335 (14)
C17	−0.3939 (9)	−0.1699 (7)	0.0401 (5)	0.0363 (14)
H5A	−0.046 (10)	−0.282 (7)	0.284 (6)	0.04 (2)*
H5B	−0.205 (10)	−0.400 (8)	0.273 (6)	0.05 (2)*
H6B	−0.120 (12)	−0.160 (9)	0.438 (7)	0.07 (3)*
H6C	−0.228 (13)	−0.096 (10)	0.461 (8)	0.09 (3)*
H7B	−0.309 (13)	−0.705 (11)	0.379 (7)	0.08 (3)*
H7C	−0.210 (13)	−0.771 (10)	0.409 (7)	0.08 (3)*
H8B	−0.477 (15)	−0.099 (10)	0.593 (8)	0.10 (3)*
H8C	−0.300 (10)	−0.022 (7)	0.603 (5)	0.03 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.0298 (4)	0.0335 (4)	0.0307 (4)	0.0100 (3)	0.0032 (3)	0.0103 (3)
O1	0.033 (2)	0.029 (2)	0.045 (3)	0.0093 (18)	0.0070 (19)	0.0118 (19)
O2	0.031 (2)	0.035 (2)	0.055 (3)	0.0129 (19)	0.005 (2)	0.012 (2)
O3	0.036 (2)	0.043 (3)	0.061 (3)	0.012 (2)	0.014 (2)	0.024 (2)
O4	0.038 (2)	0.037 (2)	0.057 (3)	0.017 (2)	0.011 (2)	0.013 (2)
O5	0.029 (2)	0.040 (3)	0.043 (3)	0.008 (2)	0.003 (2)	0.003 (2)
O6	0.039 (3)	0.043 (3)	0.031 (2)	0.018 (2)	−0.006 (2)	0.004 (2)
O7	0.049 (4)	0.051 (4)	0.104 (5)	0.024 (3)	−0.019 (3)	−0.003 (3)
O8	0.060 (4)	0.036 (3)	0.056 (3)	0.023 (3)	0.007 (3)	0.000 (3)
N1	0.028 (3)	0.029 (3)	0.031 (3)	0.012 (2)	0.006 (2)	0.007 (2)
N2	0.029 (3)	0.030 (3)	0.038 (3)	0.009 (2)	0.000 (2)	0.011 (2)
N3	0.037 (3)	0.039 (3)	0.027 (3)	0.012 (2)	−0.001 (2)	0.006 (2)
N4	0.036 (3)	0.038 (3)	0.031 (3)	0.015 (2)	0.009 (2)	0.010 (2)
C1	0.028 (3)	0.030 (3)	0.035 (3)	0.010 (3)	0.000 (3)	0.005 (3)
C2	0.031 (3)	0.029 (3)	0.023 (3)	0.010 (2)	0.001 (2)	0.005 (2)
C3	0.031 (3)	0.035 (3)	0.041 (4)	0.016 (3)	0.007 (3)	0.011 (3)
C4	0.032 (3)	0.037 (3)	0.031 (3)	0.011 (3)	0.002 (3)	0.013 (3)
C5	0.029 (3)	0.033 (3)	0.031 (3)	0.011 (3)	0.003 (2)	0.004 (3)
C6	0.047 (4)	0.050 (4)	0.041 (4)	0.007 (3)	−0.004 (3)	0.002 (3)
C7	0.067 (5)	0.054 (5)	0.048 (4)	0.015 (4)	−0.015 (4)	−0.009 (4)
C8	0.068 (5)	0.078 (6)	0.036 (4)	0.042 (5)	−0.014 (4)	−0.011 (4)
C9	0.055 (4)	0.060 (4)	0.027 (3)	0.034 (4)	0.001 (3)	0.007 (3)
C10	0.080 (6)	0.082 (6)	0.031 (4)	0.054 (5)	0.010 (4)	0.018 (4)
C11	0.075 (5)	0.073 (5)	0.035 (4)	0.041 (5)	0.023 (4)	0.037 (4)
C12	0.049 (4)	0.052 (4)	0.044 (4)	0.032 (3)	0.013 (3)	0.023 (3)
C13	0.062 (5)	0.045 (4)	0.061 (5)	0.019 (4)	0.022 (4)	0.030 (4)
C14	0.049 (4)	0.043 (4)	0.068 (5)	0.008 (3)	0.013 (4)	0.016 (4)
C15	0.039 (4)	0.042 (4)	0.048 (4)	0.005 (3)	−0.002 (3)	0.007 (3)
C16	0.038 (3)	0.045 (4)	0.031 (3)	0.028 (3)	0.009 (3)	0.013 (3)
C17	0.040 (3)	0.045 (4)	0.032 (3)	0.024 (3)	0.007 (3)	0.004 (3)

Geometric parameters (Å, º)

Zn—O1	2.084 (4)	N4—C16	1.370 (8)
Zn—O6	2.101 (5)	C1—C2	1.533 (8)
Zn—N1	2.116 (5)	C2—C3	1.347 (8)
Zn—O5	2.122 (5)	C3—C4	1.428 (8)
Zn—N4	2.140 (5)	C3—H3A	0.9500
Zn—N3	2.226 (5)	C6—C7	1.393 (10)
O1—C1	1.263 (7)	C6—H6A	0.9500
O2—C1	1.247 (7)	C7—C8	1.352 (11)
O3—C4	1.241 (7)	C7—H7A	0.9500
O4—C5	1.253 (7)	C8—C9	1.410 (11)
O5—H5B	0.84 (8)	C8—H8A	0.9500
O5—H5A	0.88 (8)	C9—C17	1.416 (9)
O6—H6C	0.92 (10)	C9—C10	1.416 (10)
O6—H6B	0.73 (9)	C10—C11	1.341 (11)
O7—H7C	0.75 (10)	C10—H10A	0.9500
O7—H7B	0.89 (10)	C11—C12	1.450 (10)
O8—H8C	0.70 (7)	C11—H11A	0.9500
O8—H8B	1.04 (11)	C12—C16	1.387 (9)
N1—C5	1.354 (7)	C12—C13	1.397 (11)
N1—C2	1.361 (7)	C13—C14	1.342 (11)
N2—C5	1.375 (7)	C13—H13A	0.9500
N2—C4	1.382 (8)	C14—C15	1.401 (10)
N2—H2A	0.8800	C14—H14A	0.9500
N3—C6	1.310 (8)	C15—H15A	0.9500
N3—C17	1.350 (8)	C16—C17	1.445 (9)
N4—C15	1.324 (8)
O1—Zn—O6	90.1 (2)	C4—C3—H3A	120.6
O1—Zn—N1	78.07 (16)	O3—C4—N2	119.1 (6)
O6—Zn—N1	99.13 (19)	O3—C4—C3	126.8 (6)
O1—Zn—O5	171.39 (18)	N2—C4—C3	114.1 (5)
O6—Zn—O5	90.4 (2)	O4—C5—N1	121.7 (5)
N1—Zn—O5	93.37 (19)	O4—C5—N2	119.4 (5)
O1—Zn—N4	93.25 (17)	N1—C5—N2	118.9 (5)
O6—Zn—N4	90.89 (19)	N3—C6—C7	123.5 (7)
N1—Zn—N4	166.67 (18)	N3—C6—H6A	118.2
O5—Zn—N4	95.33 (19)	C7—C6—H6A	118.2
O1—Zn—N3	89.30 (18)	C8—C7—C6	118.9 (7)
O6—Zn—N3	167.46 (19)	C8—C7—H7A	120.6
N1—Zn—N3	93.00 (18)	C6—C7—H7A	120.6
O5—Zn—N3	92.01 (19)	C7—C8—C9	120.2 (7)
N4—Zn—N3	76.64 (19)	C7—C8—H8A	119.9
C1—O1—Zn	116.9 (4)	C9—C8—H8A	119.9
Zn—O5—H5B	97 (5)	C8—C9—C17	116.5 (6)
Zn—O5—H5A	107 (5)	C8—C9—C10	124.3 (7)
H5B—O5—H5A	106 (7)	C17—C9—C10	119.2 (7)
Zn—O6—H6C	114 (6)	C11—C10—C9	122.1 (7)
Zn—O6—H6B	115 (7)	C11—C10—H10A	119.0
H6C—O6—H6B	104 (9)	C9—C10—H10A	119.0
H7C—O7—H7B	101 (9)	C10—C11—C12	120.5 (6)
H8C—O8—H8B	97 (8)	C10—C11—H11A	119.7
C5—N1—C2	117.2 (5)	C12—C11—H11A	119.7
C5—N1—Zn	128.8 (4)	C16—C12—C13	117.6 (6)
C2—N1—Zn	114.1 (4)	C16—C12—C11	118.9 (7)
C5—N2—C4	125.4 (5)	C13—C12—C11	123.4 (6)
C5—N2—H2A	117.3	C14—C13—C12	119.3 (6)
C4—N2—H2A	117.3	C14—C13—H13A	120.3
C6—N3—C17	118.5 (6)	C12—C13—H13A	120.3
C6—N3—Zn	129.1 (5)	C13—C14—C15	120.5 (7)
C17—N3—Zn	112.2 (4)	C13—C14—H14A	119.7
C15—N4—C16	117.5 (5)	C15—C14—H14A	119.7
C15—N4—Zn	126.8 (4)	N4—C15—C14	121.9 (7)
C16—N4—Zn	115.5 (4)	N4—C15—H15A	119.0
O2—C1—O1	124.6 (5)	C14—C15—H15A	119.0
O2—C1—C2	118.9 (5)	N4—C16—C12	123.0 (6)
O1—C1—C2	116.5 (5)	N4—C16—C17	116.5 (5)
C3—C2—N1	125.7 (5)	C12—C16—C17	120.4 (6)
C3—C2—C1	120.8 (5)	N3—C17—C9	122.4 (6)
N1—C2—C1	113.5 (5)	N3—C17—C16	118.8 (5)
C2—C3—C4	118.7 (6)	C9—C17—C16	118.8 (6)
C2—C3—H3A	120.6
O6—Zn—O1—C1	−108.5 (4)	C5—N2—C4—O3	−177.6 (6)
N1—Zn—O1—C1	−9.2 (4)	C5—N2—C4—C3	0.9 (9)
O5—Zn—O1—C1	−14.9 (14)	C2—C3—C4—O3	177.6 (6)
N4—Zn—O1—C1	160.6 (4)	C2—C3—C4—N2	−0.8 (8)
N3—Zn—O1—C1	84.0 (4)	C2—N1—C5—O4	179.7 (5)
O1—Zn—N1—C5	−173.8 (5)	Zn—N1—C5—O4	−1.6 (9)
O6—Zn—N1—C5	−85.7 (5)	C2—N1—C5—N2	0.4 (8)
O5—Zn—N1—C5	5.3 (5)	Zn—N1—C5—N2	179.1 (4)
N4—Zn—N1—C5	136.0 (8)	C4—N2—C5—O4	179.9 (6)
N3—Zn—N1—C5	97.5 (5)	C4—N2—C5—N1	−0.8 (9)
O1—Zn—N1—C2	4.9 (4)	C17—N3—C6—C7	−0.7 (11)
O6—Zn—N1—C2	93.1 (4)	Zn—N3—C6—C7	173.4 (6)
O5—Zn—N1—C2	−176.0 (4)	N3—C6—C7—C8	0.3 (13)
N4—Zn—N1—C2	−45.3 (10)	C6—C7—C8—C9	0.7 (12)
N3—Zn—N1—C2	−83.8 (4)	C7—C8—C9—C17	−1.1 (11)
O1—Zn—N3—C6	−85.2 (6)	C7—C8—C9—C10	−179.6 (8)
O6—Zn—N3—C6	−172.7 (9)	C8—C9—C10—C11	179.9 (7)
N1—Zn—N3—C6	−7.2 (6)	C17—C9—C10—C11	1.5 (11)
O5—Zn—N3—C6	86.3 (6)	C9—C10—C11—C12	−1.6 (12)
N4—Zn—N3—C6	−178.7 (6)	C10—C11—C12—C16	−0.3 (11)
O1—Zn—N3—C17	89.3 (4)	C10—C11—C12—C13	−179.5 (7)
O6—Zn—N3—C17	1.8 (12)	C16—C12—C13—C14	−2.0 (11)
N1—Zn—N3—C17	167.3 (4)	C11—C12—C13—C14	177.2 (7)
O5—Zn—N3—C17	−99.2 (4)	C12—C13—C14—C15	1.3 (12)
N4—Zn—N3—C17	−4.2 (4)	C16—N4—C15—C14	−1.7 (10)
O1—Zn—N4—C15	91.3 (6)	Zn—N4—C15—C14	−177.4 (5)
O6—Zn—N4—C15	1.1 (6)	C13—C14—C15—N4	0.6 (12)
N1—Zn—N4—C15	140.1 (8)	C15—N4—C16—C12	0.9 (9)
O5—Zn—N4—C15	−89.4 (6)	Zn—N4—C16—C12	177.1 (5)
N3—Zn—N4—C15	179.8 (6)	C15—N4—C16—C17	−179.5 (6)
O1—Zn—N4—C16	−84.5 (4)	Zn—N4—C16—C17	−3.3 (7)
O6—Zn—N4—C16	−174.7 (4)	C13—C12—C16—N4	1.0 (10)
N1—Zn—N4—C16	−35.7 (11)	C11—C12—C16—N4	−178.3 (6)
O5—Zn—N4—C16	94.8 (4)	C13—C12—C16—C17	−178.7 (6)
N3—Zn—N4—C16	4.0 (4)	C11—C12—C16—C17	2.1 (9)
Zn—O1—C1—O2	−169.3 (5)	C6—N3—C17—C9	0.3 (10)
Zn—O1—C1—C2	11.5 (7)	Zn—N3—C17—C9	−174.8 (5)
C5—N1—C2—C3	−0.3 (9)	C6—N3—C17—C16	179.1 (6)
Zn—N1—C2—C3	−179.2 (5)	Zn—N3—C17—C16	4.0 (7)
C5—N1—C2—C1	178.0 (5)	C8—C9—C17—N3	0.6 (10)
Zn—N1—C2—C1	−0.9 (6)	C10—C9—C17—N3	179.2 (6)
O2—C1—C2—C3	−7.8 (9)	C8—C9—C17—C16	−178.2 (6)
O1—C1—C2—C3	171.5 (6)	C10—C9—C17—C16	0.3 (9)
O2—C1—C2—N1	173.8 (5)	N4—C16—C17—N3	−0.7 (8)
O1—C1—C2—N1	−7.0 (8)	C12—C16—C17—N3	179.0 (6)
N1—C2—C3—C4	0.5 (9)	N4—C16—C17—C9	178.2 (5)
C1—C2—C3—C4	−177.7 (5)	C12—C16—C17—C9	−2.1 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O8^i	0.88	2.10	2.971 (5)	172
O5—H5A···O2^ii	0.88 (8)	1.85 (8)	2.708 (7)	166 (7)
O5—H5B···O4	0.84 (8)	1.85 (8)	2.678 (7)	167 (9)
O6—H6B···O3^i	0.73 (10)	2.08 (9)	2.776 (7)	162 (10)
O6—H6C···O8	0.92 (11)	1.85 (11)	2.741 (9)	164 (9)
O7—H7B···O4	0.89 (10)	1.94 (11)	2.789 (9)	160 (10)
O7—H7C···O3^ii	0.75 (10)	2.11 (10)	2.844 (9)	166 (8)
O8—H8B···O7^i	1.04 (13)	1.79 (12)	2.715 (10)	146 (8)
O8—H8C···O2^iii	0.70 (7)	2.14 (7)	2.836 (7)	171 (9)

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