Bis(9-amino­acridinium) bis­(pyridine-2,6-dicarboxyl­ato)zincate(II) trihydrate

Mirzaei, M.; Eshtiagh-Hosseini, H.; Eydizadeh, E.; Yousefi, Z.; Molčanov, K.

doi:10.1107/S1600536812005764

Bis(9-aminoacridinium) bis(pyridine-2,6-dicarboxylato)zincate(II) trihydrate

M. Mirzaei, H. Eshtiagh-Hosseini, E. Eydizadeh, Z. Yousefi and K. Molčanov

In the title compound, (C₁₃H₁₁N₂)₂[Zn(C₇H₃NO₄)₂]·3H₂O, the Zn^II ion is six-coordinated with the N₄O₂ donor set being a distorted octahedron through two almost perpendicular (r.m.s. deviation of ligand atoms from the mean plane is 0.057 Å) tridentate pyridine-2,6-dicarboxylate ligands [dihedral angle between the ligands = 86.06 (4)°]. The charge is compensated by two 9-aminoacridinium cations protonated on the ring N atom. A variety of intermolecular contacts, such as ion–ion, N—H

O and O—H

O hydrogen bonds, and π–π stacking [centroid–centroid distances = 3.4907 (9)–4.1128 (8) Å], between cations and between anions, play important roles in the formation of the three-dimensional network.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812005764/mw2050sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536812005764/mw2050Isup2.hkl Contains datablock I

CCDC reference: 877025

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.002 Å
R factor = 0.032
wR factor = 0.091
Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C8     -   C13    ...       1.53 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          5
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         84

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          9
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          6
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00200 Deg.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn1    --  O1      ..        9.2 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn1    --  O3      ..        8.2 su
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn1    --  O7      ..        6.2 su
PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd.  #          6
              H2 O
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

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

Comment top

The pyridinedicarboxylate family of ligands has attracted much attention in coordination and supramolecular chemistry because of the versatile coordination modes and variety of inter- and intramolecular interactions (Mirzaei et al., 2011). Among different derivatives of pyridinedicarboxylate, pyridine-2,6-dicarboxylic acid (pydcH₂), also called dipicolinic acid (H₂pdic), has been widely considered because of its high symmetry and bioactive properties. The most common coordination mode of (pydc)^2- is as a tridentate ligand via N and two carboxylate groups that can be coordinated to a metal in a meridional fashion (Eshtiagh-Hosseini, Mirzaei, Yousefi et al., 2011; Park et al., 2007).

So far, our group has reported several coordination compounds bearing the (pydc)^2- ligand with different heterocyclic cations prepared by proton transfer methodology (Eshtiagh-Hosseini, Yousefi, Mirzaei et al., 2010; Eshtiagh-Hosseini, Yousefi, Shafiee et al., 2010).

In this contribution, we have synthesized and characterized a new coordination compound with (pydc)^2- coordinated to Zn^II and protonated 9-aminoacridine as the cation which is formulated as (9aaH)₂[Zn(pydc)₂].3H₂O.

The asymmetric unit of the title compound comprises a dianionic complex, [Zn(pydc)₂]^2-, two 9aaH⁺ cations and three water molecules (Fig. 1). In the anionic complex, Zn^II is six-coordinated via two (pydc)^2- ions with the ZnN₂O₄ donor set in a distorted octahedral geometry. The two (pydc)^2- moieties are almost perpendicular to each other (the angle between the mean ligand planes (rms deviation of ligand atoms from the mean plane is 0.057 Å) intersecting at Zn1 is 86.62 (2)°). Bond lengths and angles are comparable with those in similar structures (Tabatabaee et al., 2009; MacDonald et al., 2000; Aghabozorg et al., 2008; Harrison et al., 2006). Recently, our group reported a similar compound with Mn(II) as a metal center which has the same stochiometery as the title compound (Eshtiagh-Hosseini, Mirzaei, Eydizadeh et al., 2011). Binding of the H₂O molecules to the anionic complex and the 9aaH⁺ cations occur via N—H···O and O—H···O hydrogen bonds creating two different motifs with graph sets R⁴₂(8) and R₃³(9) (Fig. 2). In Fig. 3, a packing diagram of the title compound viewed down the b axis is shown in which a variety of intermolecular contacts can be observed. The most significant additional interactions are π-π stacking between (pydc)^2- ligands in adjacent anions and between sets of 9aaH⁺ cations (Fig. 3).

Related literature top

For the behaviour of 9-aminoacridine in coordination compounds see: Derikvand et al. (2010); Eshtiagh-Hosseini, Mirzaei, Eydizadeh et al. (2011). For a brief review on the pyridinedicarboxylate family of ligands, see: Mirzaei et al. (2011). For related structures, see: Aghabozorg et al. (2008); Derikvand et al. (2010); Eshtiagh-Hosseini, Yousefi, Mirzaei et al. (2010); Eshtiagh-Hosseini, Mirzaei, Eydizadeh et al. (2011); Eshtiagh-Hosseini, Mirzaei, Yousefi et al. (2011); Eshtiagh-Hosseini, Yousefi, Shafiee et al. (2010); Harrison et al. (2006); MacDonald et al. (2000); Park et al. (2007); Tabatabaee et al. (2009).

Experimental top

To 5 mL of an aqeous solution of pydcH₂ (0.026 g, 0.15 mmol), 5 mL of a methanolic solution of 9aa (0.030 g,0.15 mmol) was added dropwise. Then, powdered ZnCl₂.2H₂O (0.011 g, 0.075 mmol) was added and the resulting solution was heated and stirred for 3 hrs at 60°C. Yellow crystals were obtained by slow evaporation of the solvent at room temperature after 3 days.

Structure description top

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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).

Figures top

	Fig. 1. An ORTEP view of the asymmetric unit of the title compound with numbering of the non-hydrogen atoms (probability 50%)
	Fig. 2. The chain formed by the anionic complex and the water molecules. Zinc ions are depicted as spheres of arbitrary radii.
	Fig. 3. The π–π stacking interactions between the cations and between the anions. (Cg1 and Cg2: N1, C1, C2, C3, C4 and C5; Cg8: C15, C16, C17, C18, C19 and C20; Cg3 and Cg6: N3, C15, C20, C21, C22 and C27; Cg4 and Cg5: C22, C23, C24, C25, C26 and C27; Cg8: C35, C36, C37, C38, C39 and C40;Cg9: N5, C28, C33, C34, C35 and C40; Cg10: C28, C29, C30, C31, C32 and C33)

Bis(9-aminoacridinium) bis(pyridine-2,6-dicarboxylato)zincate(II) trihydrate top

Crystal data top

(C₁₃H₁₁N₂)₂[Zn(C₇H₃NO₄)₂]·3H₂O	Z = 2
M_r = 840.1	F(000) = 868
Triclinic, P1	D_x = 1.528 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 10.8763 (3) Å	Cell parameters from 12486 reflections
b = 13.3802 (3) Å	θ = 3.4–75.7°
c = 13.9920 (4) Å	µ = 1.57 mm⁻¹
α = 102.359 (2)°	T = 293 K
β = 103.585 (2)°	Prism, yellow
γ = 105.137 (2)°	0.1 × 0.1 × 0.1 mm
V = 1826.44 (8) Å³

Data collection top

Xcalibur Nova R CCD diffractometer	6901 reflections with I > 2σ(I)
ω scans	R_int = 0.023
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	θ_max = 75.9°, θ_min = 3.4°
T_min = 0.786, T_max = 1	h = −13→13
18061 measured reflections	k = −15→16
7540 independent reflections	l = −17→14

Refinement top

Refinement on F²	9 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.0487P)² + 0.2947P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.091	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 0.23 e Å⁻³
7540 reflections	Δρ_min = −0.33 e Å⁻³
547 parameters

Crystal data top

(C₁₃H₁₁N₂)₂[Zn(C₇H₃NO₄)₂]·3H₂O	γ = 105.137 (2)°
M_r = 840.1	V = 1826.44 (8) Å³
Triclinic, P1	Z = 2
a = 10.8763 (3) Å	Cu Kα radiation
b = 13.3802 (3) Å	µ = 1.57 mm⁻¹
c = 13.9920 (4) Å	T = 293 K
α = 102.359 (2)°	0.1 × 0.1 × 0.1 mm
β = 103.585 (2)°

Data collection top

Xcalibur Nova R CCD diffractometer	7540 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	6901 reflections with I > 2σ(I)
T_min = 0.786, T_max = 1	R_int = 0.023
18061 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	9 restraints
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.23 e Å⁻³
7540 reflections	Δρ_min = −0.33 e Å⁻³
547 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.63843 (2)	0.757062 (15)	0.410290 (14)	0.04351 (8)
N1	0.56573 (12)	0.59395 (9)	0.37952 (8)	0.0339 (2)
N2	0.71182 (13)	0.91958 (9)	0.46845 (9)	0.0389 (2)
O1	0.79818 (13)	0.71221 (9)	0.51306 (9)	0.0519 (3)
O2	0.85048 (12)	0.56753 (10)	0.53916 (9)	0.0507 (3)
O7	0.53943 (14)	0.79380 (9)	0.52860 (9)	0.0514 (3)
O3	0.44757 (13)	0.71287 (9)	0.29115 (8)	0.0494 (3)
O5	0.75856 (15)	0.80175 (10)	0.31737 (9)	0.0560 (3)
O8	0.52661 (14)	0.93159 (10)	0.64241 (9)	0.0555 (3)
O6	0.90581 (15)	0.94355 (12)	0.30107 (11)	0.0626 (3)
C6	0.77303 (15)	0.61256 (12)	0.49985 (10)	0.0394 (3)
O4	0.26883 (14)	0.56750 (12)	0.19614 (11)	0.0649 (4)
C5	0.44187 (14)	0.54306 (11)	0.31581 (10)	0.0361 (3)
C14	0.57104 (17)	0.89226 (12)	0.57460 (10)	0.0414 (3)
C1	0.63454 (14)	0.54097 (11)	0.42913 (9)	0.0339 (3)
C2	0.57841 (16)	0.43143 (12)	0.41608 (11)	0.0397 (3)
H2	0.6266	0.3947	0.4504	0.048*
C12	0.67212 (16)	0.96945 (11)	0.54266 (10)	0.0397 (3)
C8	0.80023 (16)	0.97360 (12)	0.43042 (11)	0.0424 (3)
C7	0.37918 (16)	0.61393 (13)	0.26292 (11)	0.0436 (3)
C13	0.82615 (18)	0.90143 (13)	0.34225 (12)	0.0464 (3)
C11	0.7210 (2)	1.08125 (13)	0.58237 (12)	0.0503 (4)
H11	0.6917	1.1166	0.6328	0.06*
C3	0.44891 (17)	0.37785 (12)	0.35081 (12)	0.0441 (3)
H3	0.4088	0.3045	0.3415	0.053*
C4	0.37925 (16)	0.43381 (13)	0.29935 (11)	0.0432 (3)
H4	0.2925	0.3988	0.2549	0.052*
C9	0.8561 (2)	1.08539 (14)	0.46910 (14)	0.0544 (4)
H9	0.92	1.1236	0.4445	0.065*
C10	0.8145 (2)	1.13889 (14)	0.54521 (14)	0.0590 (4)
H10	0.8496	1.2139	0.5714	0.071*
H11A	−0.024 (3)	0.9280 (18)	−0.289 (2)	0.097 (10)*
H11B	−0.120 (2)	0.8243 (18)	−0.3509 (14)	0.076 (7)*
H9A	0.620 (2)	0.160 (2)	0.339 (2)	0.098 (9)*
H9B	0.749 (2)	0.2507 (17)	0.3719 (15)	0.073 (7)*
H10B	0.866 (3)	0.4303 (18)	0.480 (2)	0.101 (10)*
H10A	0.971 (2)	0.383 (2)	0.466 (2)	0.100 (10)*
N5	0.14315 (12)	0.60732 (10)	0.02168 (9)	0.0392 (2)
H5A	0.1775	0.5916	0.0761	0.047*
C28	0.10576 (13)	0.69735 (12)	0.03227 (11)	0.0372 (3)
C35	0.07187 (15)	0.56409 (13)	−0.16288 (11)	0.0420 (3)
N6	−0.01511 (16)	0.68630 (13)	−0.23874 (10)	0.0527 (3)
H6A	−0.0239	0.6464	−0.2986	0.063*
H6B	−0.0378	0.7437	−0.2329	0.063*
O11	−0.08439 (18)	0.86907 (13)	−0.28590 (11)	0.0707 (4)
C33	0.04982 (13)	0.72633 (12)	−0.05563 (11)	0.0381 (3)
C29	0.12309 (16)	0.76160 (14)	0.13159 (11)	0.0447 (3)
H29	0.1597	0.7421	0.189	0.054*
C32	0.01335 (15)	0.82143 (13)	−0.03963 (13)	0.0453 (3)
H32	−0.024	0.8421	−0.096	0.054*
C40	0.12830 (14)	0.54121 (12)	−0.07164 (11)	0.0396 (3)
C39	0.17044 (17)	0.44950 (13)	−0.07668 (13)	0.0484 (3)
H39	0.2069	0.4342	−0.0166	0.058*
C31	0.03218 (17)	0.88292 (14)	0.05684 (14)	0.0501 (4)
H31	0.0092	0.9458	0.0658	0.06*
C30	0.08634 (18)	0.85207 (15)	0.14347 (13)	0.0506 (4)
H30	0.097	0.8938	0.2091	0.061*
C34	0.03351 (14)	0.65921 (13)	−0.15526 (11)	0.0411 (3)
C37	0.1025 (2)	0.40490 (16)	−0.26117 (14)	0.0606 (4)
H37	0.0947	0.3594	−0.3242	0.073*
C36	0.0601 (2)	0.49258 (15)	−0.25790 (13)	0.0556 (4)
H36	0.0229	0.5057	−0.319	0.067*
C38	0.15744 (19)	0.38316 (15)	−0.17021 (16)	0.0573 (4)
H38	0.1855	0.3229	−0.1733	0.069*
C27	0.67785 (14)	0.08240 (13)	0.05915 (11)	0.0407 (3)
N3	0.66525 (13)	0.17238 (11)	0.11676 (9)	0.0439 (3)
H3A	0.6948	0.1886	0.1827	0.053*
N4	0.54649 (14)	0.10780 (11)	−0.19805 (9)	0.0443 (3)
H4B	0.5127	0.1504	−0.225	0.053*
H4A	0.5574	0.0536	−0.2366	0.053*
C23	0.65311 (16)	−0.03901 (13)	−0.10529 (13)	0.0453 (3)
H23	0.6285	−0.0575	−0.1767	0.054*
C21	0.58166 (13)	0.12563 (11)	−0.09735 (10)	0.0359 (3)
C20	0.56319 (14)	0.21631 (12)	−0.03328 (10)	0.0372 (3)
C15	0.60783 (15)	0.23768 (12)	0.07443 (11)	0.0408 (3)
C22	0.63677 (14)	0.05541 (12)	−0.04935 (11)	0.0375 (3)
C19	0.49415 (16)	0.28113 (13)	−0.07401 (12)	0.0446 (3)
H19	0.4608	0.2665	−0.1449	0.054*
C24	0.70489 (18)	−0.10350 (14)	−0.05529 (16)	0.0542 (4)
H24	0.714	−0.1659	−0.0929	0.065*
C25	0.74415 (17)	−0.07573 (16)	0.05241 (16)	0.0560 (4)
H25	0.7788	−0.1203	0.0855	0.067*
C26	0.73230 (16)	0.01550 (15)	0.10917 (14)	0.0512 (4)
H26	0.76	0.0337	0.1806	0.061*
C18	0.4757 (2)	0.36484 (15)	−0.01080 (15)	0.0546 (4)
H18	0.4294	0.4065	−0.0387	0.066*
C17	0.5266 (2)	0.38842 (15)	0.09648 (15)	0.0593 (4)
H17	0.5163	0.4473	0.1391	0.071*
C16	0.59065 (19)	0.32654 (15)	0.13869 (13)	0.0530 (4)
H16	0.6232	0.3426	0.2098	0.064*
O9	0.68488 (17)	0.20134 (14)	0.31754 (10)	0.0723 (4)
O10	0.88557 (15)	0.36441 (12)	0.47389 (13)	0.0688 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.06383 (14)	0.02983 (11)	0.03874 (11)	0.01721 (9)	0.01691 (9)	0.01034 (8)
N1	0.0428 (6)	0.0324 (5)	0.0296 (5)	0.0167 (5)	0.0112 (4)	0.0100 (4)
N2	0.0525 (7)	0.0318 (5)	0.0337 (5)	0.0155 (5)	0.0126 (5)	0.0110 (4)
O1	0.0553 (7)	0.0368 (5)	0.0517 (6)	0.0123 (5)	0.0013 (5)	0.0098 (5)
O2	0.0455 (6)	0.0502 (6)	0.0523 (6)	0.0214 (5)	0.0025 (5)	0.0135 (5)
O7	0.0785 (8)	0.0352 (5)	0.0488 (6)	0.0195 (5)	0.0323 (6)	0.0138 (4)
O3	0.0652 (7)	0.0457 (6)	0.0444 (5)	0.0271 (5)	0.0125 (5)	0.0210 (5)
O5	0.0796 (9)	0.0433 (6)	0.0523 (6)	0.0203 (6)	0.0349 (6)	0.0126 (5)
O8	0.0712 (8)	0.0487 (6)	0.0445 (6)	0.0158 (6)	0.0273 (6)	0.0037 (5)
O6	0.0747 (9)	0.0645 (8)	0.0610 (7)	0.0219 (7)	0.0370 (7)	0.0262 (6)
C6	0.0440 (7)	0.0399 (7)	0.0354 (6)	0.0174 (6)	0.0094 (5)	0.0117 (5)
O4	0.0563 (7)	0.0733 (9)	0.0597 (7)	0.0205 (6)	−0.0035 (6)	0.0330 (7)
C5	0.0422 (7)	0.0390 (7)	0.0300 (6)	0.0169 (6)	0.0106 (5)	0.0125 (5)
C14	0.0568 (8)	0.0387 (7)	0.0320 (6)	0.0197 (6)	0.0146 (6)	0.0110 (5)
C1	0.0417 (7)	0.0347 (6)	0.0299 (5)	0.0183 (5)	0.0118 (5)	0.0107 (5)
C2	0.0498 (8)	0.0378 (7)	0.0393 (6)	0.0219 (6)	0.0151 (6)	0.0157 (5)
C12	0.0522 (8)	0.0340 (7)	0.0318 (6)	0.0166 (6)	0.0094 (6)	0.0085 (5)
C8	0.0520 (8)	0.0388 (7)	0.0390 (7)	0.0159 (6)	0.0133 (6)	0.0160 (6)
C7	0.0498 (8)	0.0520 (9)	0.0372 (7)	0.0243 (7)	0.0126 (6)	0.0212 (6)
C13	0.0576 (9)	0.0475 (8)	0.0408 (7)	0.0204 (7)	0.0188 (7)	0.0186 (6)
C11	0.0702 (11)	0.0367 (7)	0.0395 (7)	0.0173 (7)	0.0145 (7)	0.0055 (6)
C3	0.0528 (8)	0.0340 (7)	0.0462 (7)	0.0125 (6)	0.0153 (6)	0.0150 (6)
C4	0.0427 (7)	0.0432 (8)	0.0395 (7)	0.0104 (6)	0.0085 (6)	0.0128 (6)
C9	0.0640 (10)	0.0408 (8)	0.0532 (9)	0.0069 (7)	0.0187 (8)	0.0153 (7)
C10	0.0770 (12)	0.0323 (7)	0.0558 (9)	0.0079 (8)	0.0163 (9)	0.0064 (7)
N5	0.0397 (6)	0.0423 (6)	0.0369 (6)	0.0156 (5)	0.0086 (5)	0.0153 (5)
C28	0.0324 (6)	0.0401 (7)	0.0391 (7)	0.0114 (5)	0.0099 (5)	0.0134 (5)
C35	0.0380 (7)	0.0430 (7)	0.0393 (7)	0.0092 (6)	0.0079 (5)	0.0101 (6)
N6	0.0608 (8)	0.0557 (8)	0.0366 (6)	0.0206 (7)	0.0037 (6)	0.0140 (6)
O11	0.0858 (10)	0.0624 (8)	0.0520 (7)	0.0127 (8)	0.0082 (7)	0.0216 (6)
C33	0.0315 (6)	0.0423 (7)	0.0397 (7)	0.0113 (5)	0.0083 (5)	0.0146 (6)
C29	0.0456 (8)	0.0514 (8)	0.0386 (7)	0.0173 (7)	0.0129 (6)	0.0146 (6)
C32	0.0385 (7)	0.0502 (8)	0.0515 (8)	0.0192 (6)	0.0113 (6)	0.0209 (7)
C40	0.0347 (6)	0.0394 (7)	0.0421 (7)	0.0094 (5)	0.0106 (5)	0.0114 (6)
C39	0.0472 (8)	0.0444 (8)	0.0557 (9)	0.0176 (7)	0.0154 (7)	0.0164 (7)
C31	0.0463 (8)	0.0492 (9)	0.0606 (9)	0.0230 (7)	0.0189 (7)	0.0159 (7)
C30	0.0523 (9)	0.0530 (9)	0.0471 (8)	0.0200 (7)	0.0183 (7)	0.0090 (7)
C34	0.0336 (6)	0.0462 (8)	0.0385 (7)	0.0087 (6)	0.0056 (5)	0.0141 (6)
C37	0.0655 (11)	0.0529 (10)	0.0512 (9)	0.0151 (8)	0.0160 (8)	−0.0014 (7)
C36	0.0596 (10)	0.0558 (10)	0.0413 (8)	0.0155 (8)	0.0088 (7)	0.0060 (7)
C38	0.0573 (10)	0.0433 (8)	0.0699 (11)	0.0185 (7)	0.0216 (8)	0.0089 (8)
C27	0.0317 (6)	0.0490 (8)	0.0420 (7)	0.0092 (6)	0.0112 (5)	0.0194 (6)
N3	0.0416 (6)	0.0543 (7)	0.0332 (5)	0.0112 (6)	0.0111 (5)	0.0134 (5)
N4	0.0589 (8)	0.0430 (6)	0.0347 (6)	0.0248 (6)	0.0132 (5)	0.0101 (5)
C23	0.0426 (7)	0.0415 (7)	0.0522 (8)	0.0150 (6)	0.0138 (6)	0.0139 (6)
C21	0.0344 (6)	0.0363 (6)	0.0360 (6)	0.0099 (5)	0.0119 (5)	0.0099 (5)
C20	0.0358 (6)	0.0381 (7)	0.0371 (6)	0.0102 (5)	0.0138 (5)	0.0094 (5)
C15	0.0380 (7)	0.0449 (8)	0.0374 (7)	0.0086 (6)	0.0152 (5)	0.0099 (6)
C22	0.0331 (6)	0.0389 (7)	0.0406 (7)	0.0100 (5)	0.0118 (5)	0.0136 (5)
C19	0.0494 (8)	0.0428 (8)	0.0456 (7)	0.0176 (6)	0.0179 (6)	0.0143 (6)
C24	0.0473 (8)	0.0433 (8)	0.0768 (11)	0.0182 (7)	0.0197 (8)	0.0222 (8)
C25	0.0417 (8)	0.0595 (10)	0.0783 (12)	0.0185 (7)	0.0175 (8)	0.0418 (9)
C26	0.0386 (7)	0.0645 (10)	0.0565 (9)	0.0142 (7)	0.0137 (7)	0.0343 (8)
C18	0.0624 (10)	0.0467 (9)	0.0655 (10)	0.0259 (8)	0.0292 (8)	0.0177 (8)
C17	0.0756 (12)	0.0459 (9)	0.0629 (10)	0.0222 (8)	0.0386 (9)	0.0069 (7)
C16	0.0615 (10)	0.0520 (9)	0.0418 (7)	0.0120 (8)	0.0241 (7)	0.0056 (7)
O9	0.0747 (9)	0.0853 (10)	0.0369 (6)	−0.0009 (8)	0.0153 (6)	0.0135 (6)
O10	0.0567 (8)	0.0507 (7)	0.0871 (10)	0.0111 (6)	0.0171 (7)	0.0099 (7)

Geometric parameters (Å, º) top

Zn1—N2	2.0146 (12)	C33—C32	1.418 (2)
Zn1—N1	2.0274 (11)	C33—C34	1.430 (2)
Zn1—O5	2.1162 (12)	C29—C30	1.360 (2)
Zn1—O3	2.1793 (12)	C29—H29	0.93
Zn1—O7	2.2151 (11)	C32—C31	1.359 (2)
Zn1—O1	2.2775 (12)	C32—H32	0.93
N1—C5	1.3304 (19)	C40—C39	1.412 (2)
N1—C1	1.3372 (17)	C39—C38	1.368 (3)
N2—C8	1.331 (2)	C39—H39	0.93
N2—C12	1.3321 (19)	C31—C30	1.412 (2)
O1—C6	1.2518 (19)	C31—H31	0.93
O2—C6	1.2508 (18)	C30—H30	0.93
O7—C14	1.2507 (19)	C37—C36	1.364 (3)
O3—C7	1.259 (2)	C37—C38	1.398 (3)
O5—C13	1.269 (2)	C37—H37	0.93
O8—C14	1.2430 (19)	C36—H36	0.93
O6—C13	1.232 (2)	C38—H38	0.93
C6—C1	1.519 (2)	C27—N3	1.357 (2)
O4—C7	1.239 (2)	C27—C26	1.411 (2)
C5—C4	1.384 (2)	C27—C22	1.413 (2)
C5—C7	1.5207 (18)	N3—C15	1.355 (2)
C14—C12	1.520 (2)	N3—H3A	0.86
C1—C2	1.386 (2)	N4—C21	1.3206 (18)
C2—C3	1.386 (2)	N4—H4B	0.86
C2—H2	0.93	N4—H4A	0.86
C12—C11	1.385 (2)	C23—C24	1.370 (2)
C8—C9	1.387 (2)	C23—C22	1.414 (2)
C8—C13	1.526 (2)	C23—H23	0.93
C11—C10	1.382 (3)	C21—C20	1.4361 (19)
C11—H11	0.93	C21—C22	1.4382 (19)
C3—C4	1.387 (2)	C20—C15	1.4100 (19)
C3—H3	0.93	C20—C19	1.411 (2)
C4—H4	0.93	C15—C16	1.412 (2)
C9—C10	1.386 (3)	C19—C18	1.361 (2)
C9—H9	0.93	C19—H19	0.93
C10—H10	0.93	C24—C25	1.402 (3)
N5—C40	1.359 (2)	C24—H24	0.93
N5—C28	1.3588 (19)	C25—C26	1.361 (3)
N5—H5A	0.86	C25—H25	0.93
C28—C29	1.409 (2)	C26—H26	0.93
C28—C33	1.4173 (18)	C18—C17	1.405 (3)
C35—C40	1.413 (2)	C18—H18	0.93
C35—C36	1.418 (2)	C17—C16	1.355 (3)
C35—C34	1.430 (2)	C17—H17	0.93
N6—C34	1.3291 (19)	C16—H16	0.93
N6—H6A	0.86	O9—H9A	0.928 (17)
N6—H6B	0.86	O9—H9B	0.890 (16)
O11—H11A	0.900 (17)	O10—H10B	0.948 (17)
O11—H11B	0.903 (16)	O10—H10A	0.940 (17)

N2—Zn1—N1	169.12 (4)	C28—C33—C32	117.75 (14)
N2—Zn1—O5	77.62 (5)	C28—C33—C34	118.85 (13)
N1—Zn1—O5	111.49 (5)	C32—C33—C34	123.40 (13)
N2—Zn1—O3	108.72 (5)	C30—C29—C28	120.01 (14)
N1—Zn1—O3	77.03 (4)	C30—C29—H29	120
O5—Zn1—O3	95.55 (5)	C28—C29—H29	120
N2—Zn1—O7	75.67 (5)	C31—C32—C33	121.01 (14)
N1—Zn1—O7	95.48 (4)	C31—C32—H32	119.5
O5—Zn1—O7	153.00 (4)	C33—C32—H32	119.5
O3—Zn1—O7	89.34 (5)	N5—C40—C39	119.33 (13)
N2—Zn1—O1	99.73 (5)	N5—C40—C35	120.47 (13)
N1—Zn1—O1	74.39 (4)	C39—C40—C35	120.20 (14)
O5—Zn1—O1	93.41 (5)	C38—C39—C40	119.78 (16)
O3—Zn1—O1	151.38 (4)	C38—C39—H39	120.1
O7—Zn1—O1	94.87 (5)	C40—C39—H39	120.1
C5—N1—C1	121.08 (12)	C32—C31—C30	120.49 (15)
C5—N1—Zn1	117.51 (9)	C32—C31—H31	119.8
C1—N1—Zn1	121.10 (10)	C30—C31—H31	119.8
C8—N2—C12	122.19 (13)	C29—C30—C31	120.39 (15)
C8—N2—Zn1	117.72 (10)	C29—C30—H30	119.8
C12—N2—Zn1	120.10 (10)	C31—C30—H30	119.8
C6—O1—Zn1	114.35 (10)	N6—C34—C35	121.08 (15)
C14—O7—Zn1	114.84 (10)	N6—C34—C33	120.02 (15)
C7—O3—Zn1	114.70 (9)	C35—C34—C33	118.90 (13)
C13—O5—Zn1	116.07 (10)	C36—C37—C38	120.31 (17)
O2—C6—O1	126.28 (15)	C36—C37—H37	119.8
O2—C6—C1	117.83 (13)	C38—C37—H37	119.8
O1—C6—C1	115.89 (12)	C37—C36—C35	121.13 (16)
N1—C5—C4	121.23 (12)	C37—C36—H36	119.4
N1—C5—C7	114.56 (13)	C35—C36—H36	119.4
C4—C5—C7	124.19 (13)	C39—C38—C37	120.76 (17)
O8—C14—O7	125.98 (15)	C39—C38—H38	119.6
O8—C14—C12	118.02 (14)	C37—C38—H38	119.6
O7—C14—C12	116.00 (13)	N3—C27—C26	119.00 (14)
N1—C1—C2	120.86 (13)	N3—C27—C22	120.76 (13)
N1—C1—C6	113.66 (12)	C26—C27—C22	120.24 (15)
C2—C1—C6	125.46 (12)	C15—N3—C27	122.52 (12)
C3—C2—C1	118.57 (12)	C15—N3—H3A	118.7
C3—C2—H2	120.7	C27—N3—H3A	118.7
C1—C2—H2	120.7	C21—N4—H4B	120
N2—C12—C11	120.49 (15)	C21—N4—H4A	120
N2—C12—C14	113.39 (12)	H4B—N4—H4A	120
C11—C12—C14	126.11 (14)	C24—C23—C22	120.64 (16)
N2—C8—C9	120.14 (15)	C24—C23—H23	119.7
N2—C8—C13	113.60 (13)	C22—C23—H23	119.7
C9—C8—C13	126.22 (15)	N4—C21—C20	119.76 (13)
O4—C7—O3	127.83 (14)	N4—C21—C22	121.71 (13)
O4—C7—C5	116.49 (15)	C20—C21—C22	118.53 (12)
O3—C7—C5	115.66 (13)	C15—C20—C19	118.30 (13)
O6—C13—O5	126.46 (16)	C15—C20—C21	119.08 (13)
O6—C13—C8	118.82 (15)	C19—C20—C21	122.49 (13)
O5—C13—C8	114.70 (14)	N3—C15—C20	120.40 (14)
C10—C11—C12	118.33 (16)	N3—C15—C16	119.69 (14)
C10—C11—H11	120.8	C20—C15—C16	119.90 (15)
C12—C11—H11	120.8	C27—C22—C23	118.21 (13)
C2—C3—C4	119.85 (14)	C27—C22—C21	118.51 (13)
C2—C3—H3	120.1	C23—C22—C21	123.27 (13)
C4—C3—H3	120.1	C18—C19—C20	120.83 (15)
C5—C4—C3	118.40 (14)	C18—C19—H19	119.6
C5—C4—H4	120.8	C20—C19—H19	119.6
C3—C4—H4	120.8	C23—C24—C25	120.27 (17)
C10—C9—C8	118.51 (16)	C23—C24—H24	119.9
C10—C9—H9	120.7	C25—C24—H24	119.9
C8—C9—H9	120.7	C26—C25—C24	120.93 (15)
C11—C10—C9	120.30 (16)	C26—C25—H25	119.5
C11—C10—H10	119.9	C24—C25—H25	119.5
C9—C10—H10	119.9	C25—C26—C27	119.70 (16)
C40—N5—C28	122.46 (12)	C25—C26—H26	120.1
C40—N5—H5A	118.8	C27—C26—H26	120.1
C28—N5—H5A	118.8	C19—C18—C17	120.14 (17)
N5—C28—C29	119.30 (12)	C19—C18—H18	119.9
N5—C28—C33	120.36 (13)	C17—C18—H18	119.9
C29—C28—C33	120.34 (13)	C16—C17—C18	120.86 (16)
C40—C35—C36	117.82 (15)	C16—C17—H17	119.6
C40—C35—C34	118.93 (14)	C18—C17—H17	119.6
C36—C35—C34	123.22 (14)	C17—C16—C15	119.84 (16)
C34—N6—H6A	120	C17—C16—H16	120.1
C34—N6—H6B	120	C15—C16—H16	120.1
H6A—N6—H6B	120	H9A—O9—H9B	110 (2)
H11A—O11—H11B	105 (2)	H10B—O10—H10A	102 (2)

N2—Zn1—N1—C5	116.6 (3)	N2—C8—C13—O5	1.1 (2)
O5—Zn1—N1—C5	−97.47 (10)	C9—C8—C13—O5	−176.85 (16)
O3—Zn1—N1—C5	−6.56 (9)	N2—C12—C11—C10	−1.9 (2)
O7—Zn1—N1—C5	81.49 (10)	C14—C12—C11—C10	179.04 (15)
O1—Zn1—N1—C5	175.03 (10)	C1—C2—C3—C4	0.8 (2)
N2—Zn1—N1—C1	−57.0 (3)	N1—C5—C4—C3	−0.2 (2)
O5—Zn1—N1—C1	88.95 (10)	C7—C5—C4—C3	178.49 (14)
O3—Zn1—N1—C1	179.86 (11)	C2—C3—C4—C5	−0.5 (2)
O7—Zn1—N1—C1	−92.09 (10)	N2—C8—C9—C10	−2.0 (3)
O1—Zn1—N1—C1	1.45 (10)	C13—C8—C9—C10	175.78 (16)
N1—Zn1—N2—C8	143.5 (2)	C12—C11—C10—C9	0.9 (3)
O5—Zn1—N2—C8	−4.29 (11)	C8—C9—C10—C11	1.0 (3)
O3—Zn1—N2—C8	−96.02 (11)	C40—N5—C28—C29	179.43 (13)
O7—Zn1—N2—C8	179.67 (12)	C40—N5—C28—C33	−0.5 (2)
O1—Zn1—N2—C8	87.09 (11)	N5—C28—C33—C32	−179.70 (13)
N1—Zn1—N2—C12	−36.3 (3)	C29—C28—C33—C32	0.3 (2)
O5—Zn1—N2—C12	175.94 (12)	N5—C28—C33—C34	0.0 (2)
O3—Zn1—N2—C12	84.21 (11)	C29—C28—C33—C34	−179.92 (13)
O7—Zn1—N2—C12	−0.10 (11)	N5—C28—C29—C30	179.90 (15)
O1—Zn1—N2—C12	−92.68 (11)	C33—C28—C29—C30	−0.1 (2)
N2—Zn1—O1—C6	174.45 (11)	C28—C33—C32—C31	0.3 (2)
N1—Zn1—O1—C6	3.84 (11)	C34—C33—C32—C31	−179.37 (15)
O5—Zn1—O1—C6	−107.54 (12)	C28—N5—C40—C39	179.49 (14)
O3—Zn1—O1—C6	0.61 (18)	C28—N5—C40—C35	−0.2 (2)
O7—Zn1—O1—C6	98.19 (12)	C36—C35—C40—N5	179.45 (15)
N2—Zn1—O7—C14	0.37 (11)	C34—C35—C40—N5	1.4 (2)
N1—Zn1—O7—C14	173.94 (11)	C36—C35—C40—C39	−0.2 (2)
O5—Zn1—O7—C14	−8.18 (19)	C34—C35—C40—C39	−178.29 (14)
O3—Zn1—O7—C14	−109.16 (12)	N5—C40—C39—C38	−179.20 (15)
O1—Zn1—O7—C14	99.19 (12)	C35—C40—C39—C38	0.5 (2)
N2—Zn1—O3—C7	−166.74 (11)	C33—C32—C31—C30	−1.2 (3)
N1—Zn1—O3—C7	3.66 (11)	C28—C29—C30—C31	−0.7 (3)
O5—Zn1—O3—C7	114.47 (11)	C32—C31—C30—C29	1.4 (3)
O7—Zn1—O3—C7	−92.12 (11)	C40—C35—C34—N6	177.36 (14)
O1—Zn1—O3—C7	6.85 (17)	C36—C35—C34—N6	−0.6 (2)
N2—Zn1—O5—C13	4.95 (12)	C40—C35—C34—C33	−1.8 (2)
N1—Zn1—O5—C13	−168.84 (12)	C36—C35—C34—C33	−179.79 (15)
O3—Zn1—O5—C13	112.94 (13)	C28—C33—C34—N6	−178.06 (14)
O7—Zn1—O5—C13	13.4 (2)	C32—C33—C34—N6	1.7 (2)
O1—Zn1—O5—C13	−94.27 (13)	C28—C33—C34—C35	1.2 (2)
Zn1—O1—C6—O2	172.37 (13)	C32—C33—C34—C35	−179.13 (14)
Zn1—O1—C6—C1	−7.72 (16)	C38—C37—C36—C35	0.7 (3)
C1—N1—C5—C4	0.7 (2)	C40—C35—C36—C37	−0.3 (3)
Zn1—N1—C5—C4	−172.91 (11)	C34—C35—C36—C37	177.63 (17)
C1—N1—C5—C7	−178.13 (12)	C40—C39—C38—C37	−0.2 (3)
Zn1—N1—C5—C7	8.29 (15)	C36—C37—C38—C39	−0.4 (3)
Zn1—O7—C14—O8	178.80 (13)	C26—C27—N3—C15	−176.61 (14)
Zn1—O7—C14—C12	−0.54 (17)	C22—C27—N3—C15	3.1 (2)
C5—N1—C1—C2	−0.41 (19)	N4—C21—C20—C15	−176.62 (14)
Zn1—N1—C1—C2	172.94 (10)	C22—C21—C20—C15	4.3 (2)
C5—N1—C1—C6	−178.99 (11)	N4—C21—C20—C19	7.6 (2)
Zn1—N1—C1—C6	−5.63 (15)	C22—C21—C20—C19	−171.54 (13)
O2—C6—C1—N1	−171.15 (13)	C27—N3—C15—C20	−2.7 (2)
O1—C6—C1—N1	8.94 (18)	C27—N3—C15—C16	176.26 (14)
O2—C6—C1—C2	10.4 (2)	C19—C20—C15—N3	174.83 (14)
O1—C6—C1—C2	−169.56 (14)	C21—C20—C15—N3	−1.1 (2)
N1—C1—C2—C3	−0.3 (2)	C19—C20—C15—C16	−4.1 (2)
C6—C1—C2—C3	178.07 (13)	C21—C20—C15—C16	179.95 (14)
C8—N2—C12—C11	0.9 (2)	N3—C27—C22—C23	179.63 (13)
Zn1—N2—C12—C11	−179.33 (12)	C26—C27—C22—C23	−0.6 (2)
C8—N2—C12—C14	−179.89 (13)	N3—C27—C22—C21	0.2 (2)
Zn1—N2—C12—C14	−0.14 (16)	C26—C27—C22—C21	179.93 (13)
O8—C14—C12—N2	−178.93 (14)	C24—C23—C22—C27	1.3 (2)
O7—C14—C12—N2	0.47 (19)	C24—C23—C22—C21	−179.26 (15)
O8—C14—C12—C11	0.2 (2)	N4—C21—C22—C27	177.11 (13)
O7—C14—C12—C11	179.61 (15)	C20—C21—C22—C27	−3.8 (2)
C12—N2—C8—C9	1.1 (2)	N4—C21—C22—C23	−2.3 (2)
Zn1—N2—C8—C9	−178.67 (12)	C20—C21—C22—C23	176.81 (13)
C12—N2—C8—C13	−176.99 (13)	C15—C20—C19—C18	2.5 (2)
Zn1—N2—C8—C13	3.25 (17)	C21—C20—C19—C18	178.36 (15)
Zn1—O3—C7—O4	−178.96 (15)	C22—C23—C24—C25	−0.9 (3)
Zn1—O3—C7—C5	−0.54 (17)	C23—C24—C25—C26	−0.3 (3)
N1—C5—C7—O4	173.70 (14)	C24—C25—C26—C27	1.0 (2)
C4—C5—C7—O4	−5.1 (2)	N3—C27—C26—C25	179.23 (14)
N1—C5—C7—O3	−4.91 (19)	C22—C27—C26—C25	−0.5 (2)
C4—C5—C7—O3	176.33 (14)	C20—C19—C18—C17	0.6 (3)
Zn1—O5—C13—O6	177.06 (14)	C19—C18—C17—C16	−2.2 (3)
Zn1—O5—C13—C8	−4.65 (18)	C18—C17—C16—C15	0.6 (3)
N2—C8—C13—O6	179.52 (15)	N3—C15—C16—C17	−176.35 (16)
C9—C8—C13—O6	1.6 (3)	C20—C15—C16—C17	2.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O9	0.86	1.89	2.7013 (18)	157
N4—H4A···O8ⁱ	0.86	1.98	2.8005 (18)	160
N4—H4B···O3ⁱⁱ	0.86	2.21	2.9589 (19)	145
N5—H5A···O4	0.86	1.88	2.7351 (19)	174
N6—H6A···O2ⁱⁱⁱ	0.86	2.21	2.9763 (18)	148
N6—H6B···O11	0.86	2.10	2.899 (2)	154
O9—H9A···O8^iv	0.93 (3)	1.85 (3)	2.768 (2)	170 (2)
O9—H9B···O10	0.89 (2)	1.86 (2)	2.745 (2)	173 (2)
O10—H10A···O2^v	0.94 (2)	1.91 (2)	2.838 (2)	175 (2)
O10—H10B···O2	0.95 (3)	1.91 (3)	2.830 (2)	161 (2)
O11—H11A···O6^vi	0.90 (3)	1.93 (3)	2.825 (2)	176 (3)
O11—H11B···O1ⁱⁱⁱ	0.90 (2)	1.99 (2)	2.8869 (19)	174 (2)

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

Experimental details

Crystal data
Chemical formula	(C₁₃H₁₁N₂)₂[Zn(C₇H₃NO₄)₂]·3H₂O
M_r	840.1
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.8763 (3), 13.3802 (3), 13.9920 (4)
α, β, γ (°)	102.359 (2), 103.585 (2), 105.137 (2)
V (Å³)	1826.44 (8)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	1.57
Crystal size (mm)	0.1 × 0.1 × 0.1

Data collection
Diffractometer	Xcalibur Nova R CCD
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.786, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	18061, 7540, 6901
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.091, 1.03
No. of reflections	7540
No. of parameters	547
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.33

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).