catena-Poly[[[aqua­(pyrazino­[2,3-f][1,10]phenanthroline-κ²N⁸,N⁹)zinc(II)]-μ-penta­nedioato] monohydrate]

In the title compound, {[Zn(C₅H₆O₄)(C₁₄H₈N₄)(H₂O)]·H₂O}_n, the Zn²⁺ ion is coordinated by an N,N′-bidentate pyrazino­[2,3-f][1,10]phenanthroline (pyphen) ligand, a water molecule and a monodentate glutarate (glu) dianion. A symmetry-generated O:O′-bidentate glu dianion completes a distorted cis-ZnN₂O₄ octa­hedral coordination geometry for the metal ion. The bridging glu species generates [110] polymeric chains in the crystal. O—H...O hydrogen bonds involving both the coordinated and uncoordinated water mol­ecules help to consolidate the structure and neighbouring pyphen units inter­act through numerous aromatic π–π inter­actions [minimum centroid–centroid separation = 3.654 (3) Å], resulting in a two-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.040
• wR factor = 0.100
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Zn1    --  O4_a    ..      10.77 su

Alert level C
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
            identifier.
            amaranth
CRYSC01_ALERT_1_C No recognised colour has been given for crystal colour.
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O5     -   H5B    ...       1.01 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         11
PLAT194_ALERT_1_C Missing _cell_measurement_reflns_used datum ....          ?
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         32

Alert level G
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn1    --  O3_a    ..      10.59 su
PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C4     -C14           1.43 Ang.
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.78 mm
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        500 Deg.
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         79
            ZN1 -C19 -C18 -C17  -133.60  1.60   1.665   1.555   1.555   1.555
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.11 Ratio
PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............          2 Times

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   8 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

The 1,10-phenanthroline (phen) ligand and its derivatives are important ligands with numerous uses in the construction of metal-organic complexes.Supramolecular architectures baswd on the phen derivative pyrazino[2,3-f][1,10]phenanthroline(PyPhen) molecule have considerably less attention (Li et al.,2006) A s part of our ongoing studies in this area (Fang-Wei & Mei, 2007). We selected glutaric acid (C₅H₆O₄^2-) to act as a metal-metal linker in its deprotonated form and L as a secondary ligand, generating the title compound, [Zn(C₁₄H₈N₄)(C₅H₆O₄)(H₂O).H₂O], a new coordinationg polymer, which is reported here. In compound (I), the Zn^II atom of unit is surrounded by two N atoms derived from the bidentate PyPhen ligand, three O atoms from two glutaric acid dianions (one monodentate, one bidentate) and one water molecule (Figure 1, Table 1) a distorted octahedral cis-ZnN₂O₄arrangement is formed. Neighboring Zn^II atoms are bridged by the centrosymmetric glutaric acid ligands forming a one-dimensional chain structure (Fig.2). In the crystal structure, adjacent chains are connected through π-π interactions between PyPhen and PyPhen ligands with a minimum centroid -centroid stacking distance of 3.372 Å. O—H···O hydrogen bonds involving the water molecules and carboxylate O atom acceptors (Table 2) complete the structure.

Related literature

For the synthesis of the ligand, see: Dickeson & Summers (1970). For related structures, see: Fang-Wei & Mei (2007); Li et al. (2006).

S2. Experimental

The pyphen ligand was synthesized according to the literature method of Dickeson & Summers (1970). A mixture of ZnCl₂ (0.3 mmol), pyphen (0.1 mmol) and glutaric acid (0.3 mmol) in distilled water (30 ml) was stirred thoroughly for 1 h at ambient temperature. The pH was adjusted to 7.5 with aqueous NaOH solution. The suspension was then sealed in a Teflon-lined stainless steel reaction vessel (40 ml). The reaction was performed under autogeneous pressure and static conditions in an oven at 443 K for 4.5 d. The vessel was then cooled slowly inside the oven to 298 K at a rate of 5 K h^-1 before opening: amaranth (red) blocks of (I) were collected.

S3. Refinement

All H atoms on C atoms were generated geometrically and refined as riding atoms with C—H= 0.93Å and U_iso(H)= 1.2 times U_eq(C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. view of the local coordination of Zn(II) with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A view of the two-dimensional supramolecular structure of (I) generated by π-π interactions and hydrogen-bonding.

catena-Poly[[[aqua(pyrazino[2,3-f][1,10]phenanthroline- κ²N⁸,N⁹)zinc(II)]-µ-pentanedioato] monohydrate]

Crystal data

[Zn(C5H6O4)(C14H8N4)(H2O)]·H2O	V = 932.5 (8) Å^3
Mr = 463.74	Z = 2
Triclinic, P1	F(000) = 476
Hall symbol: -P 1	Dx = 1.652 Mg m^−3
a = 6.397 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.384 (5) Å	θ = 2.0–26.3°
c = 16.409 (8) Å	µ = 1.37 mm^−1
α = 98.067 (5)°	T = 292 K
β = 100.859 (5)°	Block, amaranth
γ = 101.274 (5)°	0.78 × 0.52 × 0.36 mm

Data collection

Bruker SMART CCD diffractometer	3702 independent reflections
Radiation source: fine-focus sealed tube	2929 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
Detector resolution: 0 pixels mm^-1	θmax = 26.1°, θmin = 2.3°
ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2002)	k = −11→11
Tmin = 0.432, Tmax = 0.611	l = −20→20
8019 measured reflections

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)] = 0.040	Hydrogen site location: constr
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0464P)^2] where P = (Fo^2 + 2Fc^2)/3
3702 reflections	(Δ/σ)max = 0.001
283 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.59 e Å^−3

Special details

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
Zn1	0.71632 (5)	0.09770 (4)	0.66833 (2)	0.02738 (13)
O5	0.4196 (3)	0.1252 (2)	0.59395 (14)	0.0354 (5)
H5A	0.3260	0.0479	0.5847	0.053*
O3	1.5203 (3)	0.8764 (2)	0.69454 (14)	0.0384 (5)
O4	1.6651 (3)	0.8894 (2)	0.58459 (13)	0.0367 (5)
OW1	0.9119 (4)	0.1180 (3)	0.44343 (17)	0.0424 (6)
N2	0.9708 (4)	0.0659 (3)	0.76912 (15)	0.0270 (5)
N1	0.6579 (4)	0.2190 (3)	0.77760 (15)	0.0271 (5)
N3	0.9142 (5)	0.3624 (3)	1.07957 (17)	0.0425 (7)
C4	1.1058 (5)	0.1251 (3)	0.92035 (18)	0.0290 (7)
N4	1.2336 (5)	0.1937 (3)	1.07170 (17)	0.0410 (7)
C14	0.9630 (4)	0.1335 (3)	0.84604 (18)	0.0249 (6)
C8	0.9326 (5)	0.2869 (3)	1.00470 (19)	0.0325 (7)
C13	0.7948 (5)	0.2178 (3)	0.85096 (18)	0.0259 (6)
C12	0.5054 (5)	0.2965 (3)	0.7799 (2)	0.0340 (7)
H12A	0.4108	0.2974	0.7295	0.041*
C9	0.7811 (5)	0.2942 (3)	0.92828 (19)	0.0303 (7)
C5	1.0920 (5)	0.2042 (3)	1.00158 (18)	0.0327 (7)
C16	1.1651 (5)	0.4264 (3)	0.59565 (19)	0.0343 (7)
H16A	1.0786	0.4284	0.5407	0.041*
H16B	1.2742	0.3709	0.5865	0.041*
C19	1.5487 (5)	0.8164 (3)	0.6267 (2)	0.0323 (7)
C15	1.0173 (5)	0.3451 (3)	0.6441 (2)	0.0352 (7)
C10	0.6172 (5)	0.3738 (3)	0.9281 (2)	0.0383 (8)
H10A	0.6016	0.4249	0.9786	0.046*
C2	1.2673 (5)	−0.0301 (4)	0.8352 (2)	0.0376 (8)
H2A	1.3682	−0.0879	0.8294	0.045*
C17	1.2817 (6)	0.5833 (3)	0.6374 (2)	0.0400 (8)
H17A	1.3581	0.5832	0.6944	0.048*
H17B	1.1738	0.6422	0.6414	0.048*
C3	1.2606 (5)	0.0399 (3)	0.9126 (2)	0.0350 (7)
H3B	1.3586	0.0314	0.9604	0.042*
C11	0.4807 (5)	0.3765 (4)	0.8541 (2)	0.0408 (8)
H11A	0.3733	0.4306	0.8532	0.049*
C18	1.4442 (5)	0.6551 (3)	0.5904 (2)	0.0391 (8)
H18A	1.5587	0.6008	0.5907	0.047*
H18B	1.3701	0.6468	0.5321	0.047*
C1	1.1200 (5)	−0.0139 (3)	0.7642 (2)	0.0331 (7)
H1A	1.1268	−0.0610	0.7113	0.040*
C7	1.0537 (6)	0.3505 (4)	1.1468 (2)	0.0487 (9)
H7A	1.0475	0.3999	1.1992	0.058*
C6	1.2114 (6)	0.2665 (4)	1.1429 (2)	0.0490 (10)
H6A	1.3045	0.2621	1.1929	0.059*
O2	0.8998 (3)	0.2189 (2)	0.60661 (13)	0.0366 (5)
O1	1.0269 (5)	0.3952 (3)	0.71797 (17)	0.0684 (9)
HWBA	0.923 (6)	0.152 (4)	0.492 (2)	0.044 (12)*
H5B	0.432 (6)	0.129 (4)	0.534 (2)	0.068 (12)*
HWA1	1.048 (6)	0.128 (4)	0.446 (2)	0.047 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0268 (2)	0.0244 (2)	0.0289 (2)	0.00223 (14)	0.00547 (14)	0.00410 (14)
O5	0.0308 (12)	0.0365 (13)	0.0356 (13)	0.0039 (10)	0.0020 (10)	0.0083 (10)
O3	0.0386 (13)	0.0318 (12)	0.0401 (13)	0.0035 (10)	0.0087 (11)	−0.0027 (10)
O4	0.0349 (12)	0.0303 (12)	0.0446 (13)	−0.0004 (10)	0.0136 (11)	0.0108 (10)
OW1	0.0350 (15)	0.0536 (16)	0.0338 (15)	0.0065 (12)	0.0050 (12)	0.0011 (12)
N2	0.0261 (13)	0.0256 (13)	0.0289 (14)	0.0040 (11)	0.0091 (11)	0.0031 (11)
N1	0.0236 (13)	0.0245 (13)	0.0328 (14)	0.0042 (10)	0.0061 (11)	0.0065 (11)
N3	0.0527 (18)	0.0371 (16)	0.0354 (16)	0.0053 (14)	0.0122 (14)	0.0025 (13)
C4	0.0263 (16)	0.0296 (16)	0.0292 (16)	0.0021 (13)	0.0052 (13)	0.0058 (13)
N4	0.0421 (17)	0.0427 (17)	0.0339 (16)	0.0041 (13)	0.0016 (13)	0.0101 (13)
C14	0.0228 (15)	0.0236 (15)	0.0274 (15)	0.0014 (12)	0.0060 (12)	0.0059 (12)
C8	0.0378 (18)	0.0279 (16)	0.0291 (17)	0.0018 (14)	0.0090 (14)	0.0025 (14)
C13	0.0260 (15)	0.0217 (15)	0.0292 (16)	0.0019 (12)	0.0072 (13)	0.0053 (13)
C12	0.0324 (17)	0.0325 (17)	0.0392 (18)	0.0091 (14)	0.0075 (14)	0.0119 (15)
C9	0.0323 (17)	0.0264 (16)	0.0324 (17)	0.0042 (13)	0.0108 (14)	0.0044 (13)
C5	0.0352 (18)	0.0326 (17)	0.0276 (16)	0.0006 (14)	0.0060 (14)	0.0078 (14)
C16	0.0361 (18)	0.0279 (16)	0.0365 (18)	0.0015 (14)	0.0083 (14)	0.0057 (14)
C19	0.0267 (16)	0.0268 (16)	0.0419 (19)	0.0029 (13)	0.0059 (14)	0.0084 (15)
C15	0.0403 (19)	0.0304 (18)	0.0350 (19)	0.0052 (15)	0.0127 (15)	0.0048 (15)
C10	0.0413 (19)	0.0342 (18)	0.0414 (19)	0.0124 (15)	0.0142 (16)	0.0013 (15)
C2	0.0313 (17)	0.0433 (19)	0.046 (2)	0.0154 (15)	0.0149 (15)	0.0145 (16)
C17	0.049 (2)	0.0263 (17)	0.0423 (19)	−0.0011 (15)	0.0166 (17)	0.0046 (15)
C3	0.0296 (17)	0.0410 (19)	0.0364 (18)	0.0103 (15)	0.0042 (14)	0.0142 (15)
C11	0.0358 (19)	0.0358 (19)	0.054 (2)	0.0137 (16)	0.0122 (17)	0.0087 (17)
C18	0.0419 (19)	0.0254 (17)	0.047 (2)	−0.0010 (15)	0.0146 (16)	0.0032 (15)
C1	0.0315 (17)	0.0321 (17)	0.0377 (18)	0.0086 (14)	0.0129 (14)	0.0045 (14)
C7	0.066 (3)	0.044 (2)	0.0270 (18)	0.0023 (19)	0.0057 (18)	−0.0015 (16)
C6	0.060 (2)	0.047 (2)	0.0292 (19)	−0.0039 (19)	−0.0007 (17)	0.0064 (17)
O2	0.0386 (13)	0.0284 (12)	0.0351 (12)	−0.0076 (10)	0.0089 (10)	0.0017 (10)
O1	0.087 (2)	0.0472 (16)	0.0611 (18)	−0.0163 (15)	0.0381 (17)	−0.0080 (14)

Geometric parameters (Å, º)

Zn1—O2	1.987 (2)	C13—C9	1.394 (4)
Zn1—N1	2.120 (3)	C12—C11	1.390 (4)
Zn1—O5	2.137 (2)	C12—H12A	0.9300
Zn1—O4^i	2.154 (2)	C9—C10	1.401 (4)
Zn1—N2	2.188 (2)	C16—C15	1.510 (4)
Zn1—O3^i	2.347 (2)	C16—C17	1.513 (4)
Zn1—C19^i	2.588 (3)	C16—H16A	0.9700
O5—H5A	0.8200	C16—H16B	0.9700
O5—H5B	1.00 (4)	C19—C18	1.514 (4)
O3—C19	1.237 (4)	C19—Zn1^ii	2.588 (3)
O3—Zn1^ii	2.347 (2)	C15—O1	1.223 (4)
O4—C19	1.276 (4)	C15—O2	1.272 (4)
O4—Zn1^ii	2.154 (2)	C10—C11	1.363 (4)
OW1—HWBA	0.79 (4)	C10—H10A	0.9300
OW1—HWA1	0.85 (4)	C2—C3	1.358 (4)
N2—C1	1.330 (4)	C2—C1	1.400 (4)
N2—C14	1.345 (4)	C2—H2A	0.9300
N1—C12	1.329 (4)	C17—C18	1.518 (4)
N1—C13	1.351 (4)	C17—H17A	0.9700
N3—C7	1.314 (4)	C17—H17B	0.9700
N3—C8	1.367 (4)	C3—H3B	0.9300
C4—C14	1.401 (4)	C11—H11A	0.9300
C4—C3	1.401 (4)	C18—H18A	0.9700
C4—C5	1.459 (4)	C18—H18B	0.9700
N4—C6	1.314 (4)	C1—H1A	0.9300
N4—C5	1.352 (4)	C7—C6	1.401 (5)
C14—C13	1.463 (4)	C7—H7A	0.9300
C8—C5	1.401 (4)	C6—H6A	0.9300
C8—C9	1.452 (4)
O2—Zn1—N1	114.24 (9)	C15—C16—C17	115.5 (3)
O2—Zn1—O5	92.64 (9)	C15—C16—H16A	108.4
N1—Zn1—O5	90.76 (9)	C17—C16—H16A	108.4
O2—Zn1—O4^i	96.87 (9)	C15—C16—H16B	108.4
N1—Zn1—O4^i	148.89 (9)	C17—C16—H16B	108.4
O5—Zn1—O4^i	87.08 (8)	H16A—C16—H16B	107.5
O2—Zn1—N2	100.06 (10)	O3—C19—O4	120.8 (3)
N1—Zn1—N2	77.41 (9)	O3—C19—C18	121.2 (3)
O5—Zn1—N2	165.34 (9)	O4—C19—C18	118.0 (3)
O4^i—Zn1—N2	98.53 (9)	O3—C19—Zn1^ii	64.86 (16)
O2—Zn1—O3^i	154.65 (8)	O4—C19—Zn1^ii	56.11 (15)
N1—Zn1—O3^i	91.04 (9)	C18—C19—Zn1^ii	172.5 (2)
O5—Zn1—O3^i	88.79 (9)	O1—C15—O2	122.9 (3)
O4^i—Zn1—O3^i	57.90 (8)	O1—C15—C16	120.1 (3)
N2—Zn1—O3^i	82.87 (9)	O2—C15—C16	116.8 (3)
Zn1—O5—H5A	109.5	C11—C10—C9	120.1 (3)
Zn1—O5—H5B	111 (2)	C11—C10—H10A	120.0
H5A—O5—H5B	98.4	C9—C10—H10A	120.0
C19—O3—Zn1^ii	86.64 (18)	C3—C2—C1	119.0 (3)
C19—O4—Zn1^ii	94.44 (19)	C3—C2—H2A	120.5
HWBA—OW1—HWA1	96 (3)	C1—C2—H2A	120.5
C1—N2—C14	117.9 (3)	C16—C17—C18	113.3 (3)
C1—N2—Zn1	129.1 (2)	C16—C17—H17A	108.9
C14—N2—Zn1	112.93 (18)	C18—C17—H17A	108.9
C12—N1—C13	118.3 (3)	C16—C17—H17B	108.9
C12—N1—Zn1	126.4 (2)	C18—C17—H17B	108.9
C13—N1—Zn1	115.27 (18)	H17A—C17—H17B	107.7
C7—N3—C8	115.4 (3)	C2—C3—C4	119.8 (3)
C14—C4—C3	117.3 (3)	C2—C3—H3B	120.1
C14—C4—C5	120.3 (3)	C4—C3—H3B	120.1
C3—C4—C5	122.4 (3)	C10—C11—C12	118.6 (3)
C6—N4—C5	115.4 (3)	C10—C11—H11A	120.7
N2—C14—C4	123.1 (3)	C12—C11—H11A	120.7
N2—C14—C13	117.5 (2)	C19—C18—C17	114.4 (3)
C4—C14—C13	119.4 (3)	C19—C18—H18A	108.7
N3—C8—C5	121.1 (3)	C17—C18—H18A	108.7
N3—C8—C9	118.0 (3)	C19—C18—H18B	108.7
C5—C8—C9	120.8 (3)	C17—C18—H18B	108.7
N1—C13—C9	122.5 (3)	H18A—C18—H18B	107.6
N1—C13—C14	116.9 (2)	N2—C1—C2	122.9 (3)
C9—C13—C14	120.6 (3)	N2—C1—H1A	118.6
N1—C12—C11	123.0 (3)	C2—C1—H1A	118.6
N1—C12—H12A	118.5	N3—C7—C6	122.9 (3)
C11—C12—H12A	118.5	N3—C7—H7A	118.6
C13—C9—C10	117.5 (3)	C6—C7—H7A	118.6
C13—C9—C8	119.4 (3)	N4—C6—C7	122.9 (3)
C10—C9—C8	123.1 (3)	N4—C6—H6A	118.5
N4—C5—C8	122.2 (3)	C7—C6—H6A	118.5
N4—C5—C4	118.4 (3)	C15—O2—Zn1	119.5 (2)
C8—C5—C4	119.4 (3)
O2—Zn1—N2—C1	−69.5 (3)	C14—C13—C9—C8	−1.3 (4)
N1—Zn1—N2—C1	177.7 (3)	N3—C8—C9—C13	−179.6 (3)
O5—Zn1—N2—C1	140.8 (3)	C5—C8—C9—C13	0.0 (4)
O4^i—Zn1—N2—C1	29.1 (3)	N3—C8—C9—C10	−0.4 (5)
O3^i—Zn1—N2—C1	85.0 (3)	C5—C8—C9—C10	179.2 (3)
C19^i—Zn1—N2—C1	57.9 (3)	C6—N4—C5—C8	0.0 (5)
O2—Zn1—N2—C14	113.54 (19)	C6—N4—C5—C4	−179.4 (3)
N1—Zn1—N2—C14	0.73 (18)	N3—C8—C5—N4	0.5 (5)
O5—Zn1—N2—C14	−36.1 (4)	C9—C8—C5—N4	−179.1 (3)
O4^i—Zn1—N2—C14	−147.87 (19)	N3—C8—C5—C4	179.9 (3)
O3^i—Zn1—N2—C14	−91.94 (19)	C9—C8—C5—C4	0.2 (4)
C19^i—Zn1—N2—C14	−119.0 (2)	C14—C4—C5—N4	−179.7 (3)
O2—Zn1—N1—C12	82.8 (3)	C3—C4—C5—N4	−0.4 (5)
O5—Zn1—N1—C12	−10.4 (2)	C14—C4—C5—C8	0.9 (4)
O4^i—Zn1—N1—C12	−96.0 (3)	C3—C4—C5—C8	−179.8 (3)
N2—Zn1—N1—C12	178.3 (3)	Zn1^ii—O3—C19—O4	4.3 (3)
O3^i—Zn1—N1—C12	−99.2 (2)	Zn1^ii—O3—C19—C18	−174.8 (3)
C19^i—Zn1—N1—C12	−96.7 (3)	Zn1^ii—O4—C19—O3	−4.7 (3)
O2—Zn1—N1—C13	−95.7 (2)	Zn1^ii—O4—C19—C18	174.5 (2)
O5—Zn1—N1—C13	171.1 (2)	C17—C16—C15—O1	−13.0 (5)
O4^i—Zn1—N1—C13	85.5 (3)	C17—C16—C15—O2	172.8 (3)
N2—Zn1—N1—C13	−0.17 (19)	C13—C9—C10—C11	−1.0 (5)
O3^i—Zn1—N1—C13	82.3 (2)	C8—C9—C10—C11	179.8 (3)
C19^i—Zn1—N1—C13	84.8 (2)	C15—C16—C17—C18	174.5 (3)
C1—N2—C14—C4	0.8 (4)	C1—C2—C3—C4	0.8 (5)
Zn1—N2—C14—C4	178.2 (2)	C14—C4—C3—C2	0.0 (5)
C1—N2—C14—C13	−178.5 (2)	C5—C4—C3—C2	−179.3 (3)
Zn1—N2—C14—C13	−1.2 (3)	C9—C10—C11—C12	1.3 (5)
C3—C4—C14—N2	−0.9 (4)	N1—C12—C11—C10	−0.8 (5)
C5—C4—C14—N2	178.4 (3)	O3—C19—C18—C17	8.1 (4)
C3—C4—C14—C13	178.4 (3)	O4—C19—C18—C17	−171.1 (3)
C5—C4—C14—C13	−2.2 (4)	Zn1^ii—C19—C18—C17	−133.6 (16)
C7—N3—C8—C5	−0.4 (5)	C16—C17—C18—C19	175.0 (3)
C7—N3—C8—C9	179.2 (3)	C14—N2—C1—C2	0.1 (4)
C12—N1—C13—C9	0.2 (4)	Zn1—N2—C1—C2	−176.8 (2)
Zn1—N1—C13—C9	178.8 (2)	C3—C2—C1—N2	−0.9 (5)
C12—N1—C13—C14	−179.0 (2)	C8—N3—C7—C6	0.0 (5)
Zn1—N1—C13—C14	−0.4 (3)	C5—N4—C6—C7	−0.4 (5)
N2—C14—C13—N1	1.1 (4)	N3—C7—C6—N4	0.5 (6)
C4—C14—C13—N1	−178.3 (3)	O1—C15—O2—Zn1	1.6 (5)
N2—C14—C13—C9	−178.1 (3)	C16—C15—O2—Zn1	175.6 (2)
C4—C14—C13—C9	2.5 (4)	N1—Zn1—O2—C15	18.7 (3)
C13—N1—C12—C11	0.1 (4)	O5—Zn1—O2—C15	110.7 (2)
Zn1—N1—C12—C11	−178.3 (2)	O4^i—Zn1—O2—C15	−161.9 (2)
N1—C13—C9—C10	0.2 (4)	N2—Zn1—O2—C15	−61.9 (2)
C14—C13—C9—C10	179.4 (3)	O3^i—Zn1—O2—C15	−156.5 (2)
N1—C13—C9—C8	179.5 (3)	C19^i—Zn1—O2—C15	−161.8 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···OW1^iii	0.82	1.89	2.702 (3)	173
O5—H5B···O4^iv	1.00 (4)	1.91 (4)	2.856 (3)	157 (3)
OW1—HWA1···O4^v	0.85 (4)	2.03 (4)	2.840 (4)	161 (3)
OW1—HWBA···O2	0.79 (4)	1.95 (4)	2.733 (4)	170 (4)

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