Acridinium (6-carboxy­pyridine-2-carboxyl­ato)(pyridine-2,6-dicarboxyl­ato)zincate(II) penta­hydrate

Tabatabaee, M.; Aghabozorg, H.; Attar Gharamaleki, J.; Sharif, M.A.

doi:10.1107/S1600536809011106

Acridinium (6-carboxypyridine-2-carboxylato)(pyridine-2,6-dicarboxylato)zincate(II) pentahydrate

M. Tabatabaee, H. Aghabozorg, J. Attar Gharamaleki and M. A. Sharif

The reaction of Zn(NO₃)₂ with pyridine-2,6-dicarboxylic acid (pydcH₂) and acridine (acr) in aqueous solution leads to the formation of the title compound, (C₁₃H₁₀N)[Zn(C₇H₃NO₄)(C₇H₄NO₄)]·5H₂O or (acrH)[Zn(pydcH)(pydc)]·5H₂O. In the title compound, the Zn^II atom is coordinated by four O atoms and two N atoms from the tridentate chelating rings of (pydc)²⁻ and (pydcH)⁻ anions. The geometry of the resulting ZnN₂O₄ coordination can be described as distorted octahedral. To balance the charges, one protonated acridine (acrH)⁺ cation is present. In the crystal structure, extensive O—H

O and N—H

O hydrogen bonds involving acrH⁺, the complex anion and uncoordinated water molecules form a three-dimensional network.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809011106/bq2129sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809011106/bq2129Isup2.hkl Contains datablock I

CCDC reference: 726295

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Key indicators

Single-crystal X-ray study
T = 120 K
Mean (C-C) = 0.003 Å
R factor = 0.041
wR factor = 0.108
Data-to-parameter ratio = 16.8

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No syntax errors found



Alert level C
            Value of measurement temperature given =   120.000
            Value of melting point given =     0.000
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.47
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.83 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn1    --  O1      ..       6.12 su
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C8     -   C13    ...       1.53 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H2O    ..  H1W3    ..       2.10 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H2O    ..  H2W3    ..       2.10 Ang.
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?

Alert level G
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........         10

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

   1 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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

In the recent years, our research group has been interested in the synthesis of proton transfer compounds and study of their behavior with metal ions. We have focused on the proton delivery from polycarboxylic acids, which are considered as very good donors and amines as acceptors. Among polycarboxylic acids, pyridine-2,6-dicarboxylic acid (pydcH₂) as a very important carboxylate derivative has attracted much interest in coordination chemistry and it is the one that we utilized widely in our studies (Aghabozorg, Attar Gharamaleki et al., 2008; Aghabozorg, Firoozi et al., 2008; Aghabozorg, Manteghi et al., 2008; Tabatabaee et al., 2008; Soleimannejad et al., 2008; Aghabozorg et al., 2009; Safaei-Ghomi et al., 2009). In order to develop novel systems, we wish to report the first complex of Zn^II with pyridine-2,6-dicarboxylic acid as proton donor and acridine as proton acceptor.

The title compound consists of [Zn(pydcH)(pydc)]^- anion, (acrH)⁺ cation and five uncoordinated water molecules (Fig. 1). Zn^II ionic complex includes dianionic ((pydc)^2-) and monoanionic ((pydcH)^–) forms of pydcH₂, simultaneously. Zn^II atom is six-coordinated by these anions and the geometry of the resulting ZnN2O4 coordination can be described as distorted octahedral (Table 1). The N atoms occupy the axial positions. The N1—Zn1—N2 angle (167.38 (8)°) deviates from linearity. The dihedral angle between the mean planes of the pyridine rings (A1 and A2, defined in Fig. 1) is 88.16 (9)° indicating that (pydc)^2– and (pydcH)^– fragments are almost perpendicular to each other. Zn—N distances of (2.0011 (16)Å and 2.0238 (16)Å and Zn—O distances (Zn1—O1:2.0864 (14)Å, Zn1—O5: 2.1443 (15)Å, Zn1—O3:2.2100 (14)Å and Zn1—O7: 2.3406 (14)Å) are consistent with those found in (pydaH)[Zn(pydcH)(pydc)].3H₂O (Ranjbar et al. 2002) and (creatH)[Zn(pydcH)(pydc)].4H₂O (Moghimi et al. 2005). There are some hydrogen bonding interactions such as O–H···O and N–H···O between cations, anions and uncoordinated water molecules (Table 2). The water molecules act also as bridging agents and link anions together via hydrogen bonds (Fig. 2). As it is seen in Fig. 3, there are also π-π stacking interactions between the aromatic rings of the coordinated (pydc)^2– and (pydcH)^- anions and acridinum cation, with distances of 3.537 (1)Å for Cg5···Cg7 [Cg5: N1/C1—C5, Cg7:N3/C15—C20—C21—C22—C27] and 3.751 (1)Å for Cg6···Cg7 (Cg6:N2/C8—C12). Ion pairing, hydrogen bonding, π–π stacking and van der Waals interactions are also effective packing for the crystal structure. These interactions lead to formation of a three-dimensional supramolecular structure.

Related literature top

For related literature, see: Aghabozorg et al. (2009); Moghimi et al. (2005); Ranjbar et al. (2002); Tabatabaee et al. (2008).

For related literature, see: Aghabozorg, Attar Gharamaleki et al. (2008); Aghabozorg, Firoozi et al. (2008); Aghabozorg, Manteghi et al. (2008); Safaei-Ghomi et al. (2009); Soleimannejad et al. (2008).

Experimental top

An aqueous solution of zinc nitrate (Zn(NO₃)₂. 6H₂O, (0.15 g, 0.5 mmol) in water (20 ml) was added to a stirring solution of (20 ml) pyridine-2,6-dicarboxylic acid (0.1 g, 0.5 mmol) and 0.25 g (1.5 mmol) acridine. The reaction mixture was stirred at 25°C for 2 h. Colorless crystals of the title compound were obtained after two weeks at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. Fragment of crystal packing (projection along c axis). Hydrogen bonds are shown with dashed lines.
	Fig. 3. Representation of π-π stacking in (acrH)[Zn(pydcH)(pydc)].5H₂O.

Acridinium (6-carboxypyridine-2-carboxylato)(pyridine-2,6-dicarboxylato)zincate(II) pentahydrate top

Crystal data top

(C₁₃H₁₀N)[Zn(C₇H₃NO₄)(C₇H₄NO₄)]·5H₂O	F(000) = 1376
M_r = 666.89	D_x = 1.572 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8302 reflections
a = 9.6083 (5) Å	θ = 2.2–29.7°
b = 18.9681 (9) Å	µ = 0.95 mm⁻¹
c = 15.5435 (8) Å	T = 120 K
β = 96.051 (1)°	Prism, yellow
V = 2817.0 (2) Å³	0.60 × 0.14 × 0.14 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	7457 independent reflections
Radiation source: normal-focus sealed tube	5795 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω scans	θ_max = 29.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −13→13
T_min = 0.652, T_max = 0.879	k = −25→25
26948 measured reflections	l = −21→21

Refinement top

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: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0451P)² + 2.9525P] where P = (F_o² + 2F_c²)/3
7457 reflections	(Δ/σ)_max = 0.002
445 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

(C₁₃H₁₀N)[Zn(C₇H₃NO₄)(C₇H₄NO₄)]·5H₂O	V = 2817.0 (2) Å³
M_r = 666.89	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6083 (5) Å	µ = 0.95 mm⁻¹
b = 18.9681 (9) Å	T = 120 K
c = 15.5435 (8) Å	0.60 × 0.14 × 0.14 mm
β = 96.051 (1)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	7457 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	5795 reflections with I > 2σ(I)
T_min = 0.652, T_max = 0.879	R_int = 0.034
26948 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.87 e Å⁻³
7457 reflections	Δρ_min = −0.35 e Å⁻³
445 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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.49831 (3)	0.093889 (12)	0.701036 (14)	0.01975 (8)
O1	0.34045 (16)	0.18535 (8)	0.71906 (9)	0.0242 (3)
O2	0.23932 (16)	0.23960 (8)	0.82468 (10)	0.0231 (3)
H2O	0.198 (5)	0.261 (2)	0.779 (3)	0.092 (15)*
O3	0.63925 (16)	0.01596 (8)	0.74853 (9)	0.0227 (3)
O4	0.73383 (16)	−0.03264 (8)	0.87279 (10)	0.0248 (3)
O5	0.32802 (16)	0.02475 (8)	0.65903 (9)	0.0229 (3)
O6	0.20086 (16)	−0.01389 (8)	0.53928 (10)	0.0262 (3)
O7	0.65542 (15)	0.17569 (8)	0.68086 (9)	0.0218 (3)
O8	0.74307 (17)	0.23451 (8)	0.57367 (10)	0.0269 (3)
N1	0.48997 (17)	0.10445 (8)	0.82995 (10)	0.0167 (3)
N2	0.48458 (17)	0.10381 (8)	0.57225 (10)	0.0155 (3)
C1	0.4084 (2)	0.15173 (10)	0.86374 (12)	0.0182 (4)
C2	0.4085 (2)	0.15979 (10)	0.95278 (13)	0.0200 (4)
H2A	0.3487	0.1928	0.9764	0.024*
C3	0.5000 (2)	0.11747 (11)	1.00590 (13)	0.0222 (4)
H3A	0.5039	0.1219	1.0670	0.027*
C4	0.5854 (2)	0.06882 (11)	0.96989 (13)	0.0207 (4)
H4A	0.6485	0.0401	1.0057	0.025*
C5	0.5764 (2)	0.06307 (10)	0.88014 (12)	0.0168 (4)
C6	0.3236 (2)	0.19449 (10)	0.79562 (13)	0.0191 (4)
C7	0.6578 (2)	0.01088 (10)	0.83018 (13)	0.0193 (4)
C8	0.3880 (2)	0.06609 (10)	0.52419 (12)	0.0170 (4)
C9	0.3753 (2)	0.07039 (11)	0.43455 (12)	0.0198 (4)
H9A	0.3063	0.0438	0.4003	0.024*
C10	0.4666 (2)	0.11477 (11)	0.39627 (13)	0.0227 (4)
H10A	0.4619	0.1176	0.3350	0.027*
C11	0.5645 (2)	0.15491 (11)	0.44730 (13)	0.0213 (4)
H11A	0.6256	0.1862	0.4219	0.026*
C12	0.5702 (2)	0.14777 (10)	0.53652 (12)	0.0167 (4)
C13	0.2970 (2)	0.02123 (10)	0.57769 (13)	0.0190 (4)
C14	0.6661 (2)	0.18976 (10)	0.60159 (13)	0.0189 (4)
N3	0.76898 (19)	0.21857 (9)	0.84229 (12)	0.0208 (3)
H3N	0.746 (3)	0.2148 (15)	0.7896 (19)	0.037 (8)*
C15	0.6925 (2)	0.26041 (10)	0.88993 (13)	0.0204 (4)
C16	0.5844 (2)	0.30294 (11)	0.85003 (15)	0.0255 (4)
H16A	0.5673	0.3048	0.7887	0.031*
C17	0.5043 (3)	0.34143 (11)	0.90007 (16)	0.0302 (5)
H17A	0.4304	0.3695	0.8731	0.036*
C18	0.5291 (3)	0.34042 (12)	0.99176 (16)	0.0321 (5)
H18A	0.4708	0.3671	1.0253	0.039*
C19	0.6361 (3)	0.30137 (13)	1.03178 (15)	0.0311 (5)
H19A	0.6538	0.3021	1.0931	0.037*
C20	0.7215 (2)	0.25951 (11)	0.98225 (13)	0.0238 (4)
C21	0.8285 (2)	0.21652 (12)	1.01903 (14)	0.0284 (5)
H21A	0.8496	0.2160	1.0801	0.034*
C22	0.9057 (2)	0.17410 (11)	0.96824 (14)	0.0263 (4)
C23	1.0150 (3)	0.12781 (14)	1.00362 (18)	0.0382 (6)
H23A	1.0393	0.1257	1.0644	0.046*
C24	1.0833 (3)	0.08721 (13)	0.9503 (2)	0.0426 (7)
H24A	1.1552	0.0565	0.9743	0.051*
C25	1.0502 (3)	0.08954 (12)	0.8598 (2)	0.0397 (6)
H25A	1.1008	0.0606	0.8241	0.048*
C26	0.9464 (2)	0.13276 (12)	0.82196 (17)	0.0309 (5)
H26A	0.9245	0.1338	0.7609	0.037*
C27	0.8730 (2)	0.17567 (11)	0.87635 (14)	0.0231 (4)
O1W	0.84765 (17)	0.32871 (9)	0.69335 (11)	0.0251 (3)
H1W1	0.815 (3)	0.3033 (16)	0.656 (2)	0.034 (8)*
H2W1	0.813 (4)	0.369 (2)	0.681 (2)	0.065 (11)*
O2W	0.96559 (18)	−0.06357 (9)	0.77630 (12)	0.0279 (3)
H1W2	0.909 (3)	−0.0493 (17)	0.808 (2)	0.045 (9)*
H2W2	0.940 (3)	−0.0417 (16)	0.729 (2)	0.039 (8)*
O3W	0.12555 (19)	0.31700 (9)	0.71080 (10)	0.0262 (3)
H1W3	0.037 (4)	0.3180 (18)	0.708 (2)	0.051 (9)*
H2W3	0.170 (5)	0.356 (2)	0.710 (3)	0.084 (14)*
O4W	0.25508 (19)	−0.05822 (9)	0.79542 (12)	0.0302 (4)
H1W4	0.170 (4)	−0.0602 (18)	0.791 (2)	0.049 (10)*
H2W4	0.268 (4)	−0.0327 (18)	0.755 (2)	0.050 (9)*
O5W	0.0430 (2)	−0.01699 (10)	0.37439 (12)	0.0322 (4)
H1W5	−0.029 (3)	−0.0086 (15)	0.3945 (19)	0.031 (7)*
H2W5	0.099 (4)	−0.016 (2)	0.421 (3)	0.066 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02513 (13)	0.02160 (13)	0.01244 (12)	−0.00038 (9)	0.00163 (9)	−0.00009 (8)
O1	0.0300 (8)	0.0264 (7)	0.0162 (7)	0.0090 (6)	0.0017 (6)	0.0001 (6)
O2	0.0248 (8)	0.0238 (7)	0.0208 (7)	0.0080 (6)	0.0026 (6)	−0.0013 (6)
O3	0.0293 (8)	0.0239 (7)	0.0149 (6)	0.0062 (6)	0.0015 (6)	−0.0021 (5)
O4	0.0279 (8)	0.0236 (7)	0.0227 (7)	0.0082 (6)	0.0012 (6)	0.0023 (6)
O5	0.0251 (7)	0.0262 (7)	0.0172 (7)	−0.0050 (6)	0.0018 (6)	0.0018 (6)
O6	0.0247 (8)	0.0276 (8)	0.0255 (8)	−0.0079 (6)	−0.0008 (6)	0.0004 (6)
O7	0.0266 (8)	0.0233 (7)	0.0152 (6)	−0.0052 (6)	0.0011 (5)	−0.0005 (5)
O8	0.0298 (8)	0.0273 (8)	0.0236 (7)	−0.0114 (6)	0.0030 (6)	−0.0003 (6)
N1	0.0194 (8)	0.0174 (7)	0.0132 (7)	−0.0023 (6)	0.0014 (6)	−0.0003 (6)
N2	0.0166 (8)	0.0164 (7)	0.0136 (7)	0.0014 (6)	0.0018 (6)	−0.0007 (6)
C1	0.0195 (9)	0.0177 (9)	0.0178 (9)	−0.0024 (7)	0.0030 (7)	−0.0010 (7)
C2	0.0231 (10)	0.0189 (9)	0.0187 (9)	−0.0006 (7)	0.0046 (7)	−0.0029 (7)
C3	0.0281 (10)	0.0245 (10)	0.0146 (9)	−0.0029 (8)	0.0050 (8)	−0.0033 (7)
C4	0.0255 (10)	0.0194 (9)	0.0168 (9)	−0.0012 (8)	0.0001 (7)	0.0021 (7)
C5	0.0172 (9)	0.0153 (8)	0.0178 (9)	−0.0021 (7)	0.0005 (7)	−0.0008 (7)
C6	0.0193 (9)	0.0192 (9)	0.0188 (9)	0.0004 (7)	0.0017 (7)	−0.0003 (7)
C7	0.0205 (9)	0.0185 (9)	0.0190 (9)	0.0001 (7)	0.0020 (7)	−0.0004 (7)
C8	0.0181 (9)	0.0151 (8)	0.0178 (9)	0.0025 (7)	0.0014 (7)	−0.0006 (7)
C9	0.0212 (10)	0.0210 (9)	0.0168 (9)	−0.0002 (7)	−0.0007 (7)	−0.0027 (7)
C10	0.0277 (11)	0.0273 (10)	0.0130 (9)	0.0003 (8)	0.0015 (8)	0.0003 (7)
C11	0.0247 (10)	0.0221 (9)	0.0176 (9)	−0.0013 (8)	0.0045 (8)	0.0023 (7)
C12	0.0173 (9)	0.0161 (8)	0.0164 (8)	0.0017 (7)	0.0004 (7)	0.0000 (7)
C13	0.0200 (9)	0.0170 (9)	0.0203 (9)	0.0007 (7)	0.0031 (7)	0.0007 (7)
C14	0.0192 (9)	0.0177 (9)	0.0197 (9)	−0.0009 (7)	0.0014 (7)	−0.0015 (7)
N3	0.0238 (9)	0.0194 (8)	0.0183 (8)	−0.0032 (7)	−0.0024 (7)	0.0010 (6)
C15	0.0220 (10)	0.0191 (9)	0.0197 (9)	−0.0058 (7)	0.0007 (7)	0.0009 (7)
C16	0.0284 (11)	0.0206 (10)	0.0267 (10)	−0.0008 (8)	−0.0011 (8)	0.0020 (8)
C17	0.0298 (12)	0.0193 (10)	0.0418 (13)	−0.0009 (8)	0.0054 (10)	0.0004 (9)
C18	0.0361 (13)	0.0248 (11)	0.0375 (13)	−0.0055 (9)	0.0132 (10)	−0.0072 (9)
C19	0.0388 (13)	0.0325 (12)	0.0233 (10)	−0.0139 (10)	0.0084 (9)	−0.0064 (9)
C20	0.0277 (11)	0.0225 (10)	0.0206 (10)	−0.0095 (8)	0.0006 (8)	0.0002 (8)
C21	0.0327 (12)	0.0317 (11)	0.0193 (10)	−0.0119 (9)	−0.0049 (9)	0.0051 (8)
C22	0.0240 (10)	0.0238 (10)	0.0289 (11)	−0.0070 (8)	−0.0081 (8)	0.0083 (8)
C23	0.0312 (13)	0.0341 (13)	0.0452 (14)	−0.0058 (10)	−0.0146 (11)	0.0147 (11)
C24	0.0259 (12)	0.0279 (12)	0.070 (2)	0.0008 (10)	−0.0132 (12)	0.0085 (12)
C25	0.0268 (12)	0.0219 (11)	0.0692 (19)	−0.0018 (9)	0.0003 (12)	−0.0086 (11)
C26	0.0247 (11)	0.0251 (11)	0.0424 (13)	−0.0023 (9)	0.0014 (10)	−0.0060 (9)
C27	0.0213 (10)	0.0190 (9)	0.0280 (10)	−0.0059 (8)	−0.0028 (8)	0.0014 (8)
O1W	0.0268 (8)	0.0240 (8)	0.0233 (8)	−0.0020 (6)	−0.0036 (6)	−0.0009 (6)
O2W	0.0274 (8)	0.0299 (8)	0.0273 (8)	0.0023 (7)	0.0068 (7)	−0.0007 (7)
O3W	0.0239 (8)	0.0250 (8)	0.0290 (8)	0.0035 (6)	−0.0010 (6)	−0.0002 (6)
O4W	0.0274 (9)	0.0298 (9)	0.0341 (9)	0.0025 (7)	0.0064 (7)	0.0095 (7)
O5W	0.0264 (9)	0.0412 (10)	0.0288 (9)	−0.0026 (7)	0.0019 (7)	0.0048 (7)

Geometric parameters (Å, º) top

Zn1—N2	2.0011 (16)	N3—C27	1.352 (3)
Zn1—N1	2.0238 (16)	N3—C15	1.354 (3)
Zn1—O3	2.0864 (14)	N3—H3N	0.83 (3)
Zn1—O5	2.1443 (15)	C15—C16	1.407 (3)
Zn1—O7	2.2100 (14)	C15—C20	1.433 (3)
Zn1—O1	2.3406 (14)	C16—C17	1.362 (3)
O1—C6	1.230 (2)	C16—H16A	0.9500
O2—C6	1.292 (2)	C17—C18	1.420 (4)
O2—H2O	0.87 (5)	C17—H17A	0.9500
O3—C7	1.267 (2)	C18—C19	1.363 (4)
O4—C7	1.246 (2)	C18—H18A	0.9500
O5—C13	1.270 (2)	C19—C20	1.425 (3)
O6—C13	1.240 (2)	C19—H19A	0.9500
O7—C14	1.275 (2)	C20—C21	1.387 (3)
O8—C14	1.234 (2)	C21—C22	1.395 (3)
N1—C5	1.334 (2)	C21—H21A	0.9500
N1—C1	1.335 (2)	C22—C27	1.430 (3)
N2—C12	1.333 (2)	C22—C23	1.433 (3)
N2—C8	1.336 (2)	C23—C24	1.351 (4)
C1—C2	1.392 (3)	C23—H23A	0.9500
C1—C6	1.503 (3)	C24—C25	1.411 (4)
C2—C3	1.395 (3)	C24—H24A	0.9500
C2—H2A	0.9500	C25—C26	1.374 (4)
C3—C4	1.391 (3)	C25—H25A	0.9500
C3—H3A	0.9500	C26—C27	1.414 (3)
C4—C5	1.393 (3)	C26—H26A	0.9500
C4—H4A	0.9500	O1W—H1W1	0.79 (3)
C5—C7	1.524 (3)	O1W—H2W1	0.84 (4)
C8—C9	1.388 (3)	O2W—H1W2	0.82 (3)
C8—C13	1.527 (3)	O2W—H2W2	0.85 (3)
C9—C10	1.394 (3)	O3W—H1W3	0.85 (4)
C9—H9A	0.9500	O3W—H2W3	0.85 (5)
C10—C11	1.392 (3)	O4W—H1W4	0.82 (4)
C10—H10A	0.9500	O4W—H2W4	0.81 (4)
C11—C12	1.389 (3)	O5W—H1W5	0.80 (3)
C11—H11A	0.9500	O5W—H2W5	0.86 (4)
C12—C14	1.520 (3)

N2—Zn1—N1	167.38 (7)	C10—C11—H11A	121.0
N2—Zn1—O3	113.11 (6)	N2—C12—C11	121.08 (18)
N1—Zn1—O3	79.15 (6)	N2—C12—C14	114.08 (16)
N2—Zn1—O5	77.60 (6)	C11—C12—C14	124.79 (18)
N1—Zn1—O5	104.68 (6)	O6—C13—O5	126.33 (19)
O3—Zn1—O5	96.92 (6)	O6—C13—C8	118.50 (17)
N2—Zn1—O7	76.47 (6)	O5—C13—C8	115.16 (17)
N1—Zn1—O7	99.78 (6)	O8—C14—O7	126.56 (18)
O3—Zn1—O7	96.89 (6)	O8—C14—C12	118.05 (17)
O5—Zn1—O7	153.75 (5)	O7—C14—C12	115.37 (17)
N2—Zn1—O1	94.29 (6)	C27—N3—C15	124.05 (19)
N1—Zn1—O1	73.40 (6)	C27—N3—H3N	116 (2)
O3—Zn1—O1	152.55 (5)	C15—N3—H3N	119 (2)
O5—Zn1—O1	90.37 (6)	N3—C15—C16	120.89 (19)
O7—Zn1—O1	87.57 (6)	N3—C15—C20	118.76 (19)
C6—O1—Zn1	111.93 (13)	C16—C15—C20	120.3 (2)
C6—O2—H2O	106 (3)	C17—C16—C15	119.4 (2)
C7—O3—Zn1	115.21 (12)	C17—C16—H16A	120.3
C13—O5—Zn1	115.26 (12)	C15—C16—H16A	120.3
C14—O7—Zn1	114.18 (12)	C16—C17—C18	121.4 (2)
C5—N1—C1	121.40 (17)	C16—C17—H17A	119.3
C5—N1—Zn1	115.70 (13)	C18—C17—H17A	119.3
C1—N1—Zn1	122.84 (13)	C19—C18—C17	120.3 (2)
C12—N2—C8	121.65 (16)	C19—C18—H18A	119.9
C12—N2—Zn1	119.81 (13)	C17—C18—H18A	119.9
C8—N2—Zn1	118.53 (13)	C18—C19—C20	120.4 (2)
N1—C1—C2	121.71 (18)	C18—C19—H19A	119.8
N1—C1—C6	112.49 (16)	C20—C19—H19A	119.8
C2—C1—C6	125.77 (18)	C21—C20—C19	123.3 (2)
C1—C2—C3	117.39 (18)	C21—C20—C15	118.5 (2)
C1—C2—H2A	121.3	C19—C20—C15	118.2 (2)
C3—C2—H2A	121.3	C20—C21—C22	121.4 (2)
C4—C3—C2	120.34 (18)	C20—C21—H21A	119.3
C4—C3—H3A	119.8	C22—C21—H21A	119.3
C2—C3—H3A	119.8	C21—C22—C27	118.6 (2)
C3—C4—C5	118.55 (18)	C21—C22—C23	123.2 (2)
C3—C4—H4A	120.7	C27—C22—C23	118.1 (2)
C5—C4—H4A	120.7	C24—C23—C22	119.9 (2)
N1—C5—C4	120.58 (18)	C24—C23—H23A	120.1
N1—C5—C7	113.94 (16)	C22—C23—H23A	120.1
C4—C5—C7	125.47 (18)	C23—C24—C25	121.4 (2)
O1—C6—O2	125.66 (19)	C23—C24—H24A	119.3
O1—C6—C1	119.23 (18)	C25—C24—H24A	119.3
O2—C6—C1	115.09 (17)	C26—C25—C24	121.5 (3)
O4—C7—O3	126.57 (19)	C26—C25—H25A	119.2
O4—C7—C5	117.59 (17)	C24—C25—H25A	119.2
O3—C7—C5	115.84 (17)	C25—C26—C27	118.2 (2)
N2—C8—C9	120.81 (18)	C25—C26—H26A	120.9
N2—C8—C13	113.42 (16)	C27—C26—H26A	120.9
C9—C8—C13	125.76 (18)	N3—C27—C26	120.4 (2)
C8—C9—C10	118.12 (18)	N3—C27—C22	118.6 (2)
C8—C9—H9A	120.9	C26—C27—C22	120.9 (2)
C10—C9—H9A	120.9	H1W1—O1W—H2W1	105 (3)
C11—C10—C9	120.35 (18)	H1W2—O2W—H2W2	102 (3)
C11—C10—H10A	119.8	H1W3—O3W—H2W3	119 (4)
C9—C10—H10A	119.8	H1W4—O4W—H2W4	101 (3)
C12—C11—C10	117.95 (19)	H1W5—O5W—H2W5	99 (3)
C12—C11—H11A	121.0

N2—Zn1—O1—C6	−179.71 (14)	Zn1—O3—C7—C5	−1.0 (2)
N1—Zn1—O1—C6	−2.52 (14)	N1—C5—C7—O4	−175.43 (18)
O3—Zn1—O1—C6	−3.2 (2)	C4—C5—C7—O4	3.6 (3)
O5—Zn1—O1—C6	102.70 (14)	N1—C5—C7—O3	3.8 (3)
O7—Zn1—O1—C6	−103.48 (14)	C4—C5—C7—O3	−177.18 (19)
N2—Zn1—O3—C7	175.78 (14)	C12—N2—C8—C9	1.3 (3)
N1—Zn1—O3—C7	−1.10 (14)	Zn1—N2—C8—C9	−179.21 (14)
O5—Zn1—O3—C7	−104.79 (15)	C12—N2—C8—C13	−177.72 (16)
O7—Zn1—O3—C7	97.59 (14)	Zn1—N2—C8—C13	1.8 (2)
O1—Zn1—O3—C7	−0.5 (2)	N2—C8—C9—C10	0.4 (3)
N2—Zn1—O5—C13	0.03 (14)	C13—C8—C9—C10	179.29 (18)
N1—Zn1—O5—C13	167.26 (14)	C8—C9—C10—C11	−1.8 (3)
O3—Zn1—O5—C13	−112.19 (14)	C9—C10—C11—C12	1.6 (3)
O7—Zn1—O5—C13	9.1 (2)	C8—N2—C12—C11	−1.5 (3)
O1—Zn1—O5—C13	94.34 (14)	Zn1—N2—C12—C11	178.99 (14)
N2—Zn1—O7—C14	−1.10 (13)	C8—N2—C12—C14	176.01 (16)
N1—Zn1—O7—C14	−168.79 (14)	Zn1—N2—C12—C14	−3.5 (2)
O3—Zn1—O7—C14	111.08 (14)	C10—C11—C12—N2	0.0 (3)
O5—Zn1—O7—C14	−10.2 (2)	C10—C11—C12—C14	−177.22 (19)
O1—Zn1—O7—C14	−96.10 (14)	Zn1—O5—C13—O6	−178.26 (17)
N2—Zn1—N1—C5	−163.5 (3)	Zn1—O5—C13—C8	0.8 (2)
O3—Zn1—N1—C5	3.30 (13)	N2—C8—C13—O6	177.49 (17)
O5—Zn1—N1—C5	97.69 (14)	C9—C8—C13—O6	−1.5 (3)
O7—Zn1—N1—C5	−91.92 (14)	N2—C8—C13—O5	−1.7 (2)
O1—Zn1—N1—C5	−176.39 (15)	C9—C8—C13—O5	179.34 (19)
N2—Zn1—N1—C1	13.6 (4)	Zn1—O7—C14—O8	177.92 (17)
O3—Zn1—N1—C1	−179.60 (16)	Zn1—O7—C14—C12	−0.3 (2)
O5—Zn1—N1—C1	−85.21 (15)	N2—C12—C14—O8	−176.04 (18)
O7—Zn1—N1—C1	85.18 (15)	C11—C12—C14—O8	1.4 (3)
O1—Zn1—N1—C1	0.71 (14)	N2—C12—C14—O7	2.3 (2)
N1—Zn1—N2—C12	76.6 (3)	C11—C12—C14—O7	179.78 (19)
O3—Zn1—N2—C12	−89.25 (15)	C27—N3—C15—C16	−179.05 (19)
O5—Zn1—N2—C12	178.44 (15)	C27—N3—C15—C20	−0.4 (3)
O7—Zn1—N2—C12	2.55 (14)	N3—C15—C16—C17	176.4 (2)
O1—Zn1—N2—C12	89.01 (14)	C20—C15—C16—C17	−2.2 (3)
N1—Zn1—N2—C8	−102.9 (3)	C15—C16—C17—C18	1.0 (3)
O3—Zn1—N2—C8	91.25 (14)	C16—C17—C18—C19	1.1 (3)
O5—Zn1—N2—C8	−1.06 (13)	C17—C18—C19—C20	−1.9 (3)
O7—Zn1—N2—C8	−176.94 (15)	C18—C19—C20—C21	−177.4 (2)
O1—Zn1—N2—C8	−90.49 (14)	C18—C19—C20—C15	0.7 (3)
C5—N1—C1—C2	−0.5 (3)	N3—C15—C20—C21	1.0 (3)
Zn1—N1—C1—C2	−177.47 (14)	C16—C15—C20—C21	179.63 (19)
C5—N1—C1—C6	177.80 (17)	N3—C15—C20—C19	−177.22 (18)
Zn1—N1—C1—C6	0.9 (2)	C16—C15—C20—C19	1.4 (3)
N1—C1—C2—C3	1.4 (3)	C19—C20—C21—C22	177.2 (2)
C6—C1—C2—C3	−176.73 (19)	C15—C20—C21—C22	−0.9 (3)
C1—C2—C3—C4	−0.8 (3)	C20—C21—C22—C27	0.2 (3)
C2—C3—C4—C5	−0.6 (3)	C20—C21—C22—C23	−178.6 (2)
C1—N1—C5—C4	−0.9 (3)	C21—C22—C23—C24	178.6 (2)
Zn1—N1—C5—C4	176.22 (14)	C27—C22—C23—C24	−0.2 (3)
C1—N1—C5—C7	178.16 (17)	C22—C23—C24—C25	0.4 (4)
Zn1—N1—C5—C7	−4.7 (2)	C23—C24—C25—C26	−0.5 (4)
C3—C4—C5—N1	1.5 (3)	C24—C25—C26—C27	0.3 (4)
C3—C4—C5—C7	−177.51 (19)	C15—N3—C27—C26	178.98 (19)
Zn1—O1—C6—O2	−177.61 (16)	C15—N3—C27—C22	−0.3 (3)
Zn1—O1—C6—C1	3.8 (2)	C25—C26—C27—N3	−179.3 (2)
N1—C1—C6—O1	−3.4 (3)	C25—C26—C27—C22	−0.1 (3)
C2—C1—C6—O1	174.9 (2)	C21—C22—C27—N3	0.4 (3)
N1—C1—C6—O2	177.91 (17)	C23—C22—C27—N3	179.27 (19)
C2—C1—C6—O2	−3.8 (3)	C21—C22—C27—C26	−178.9 (2)
Zn1—O3—C7—O4	178.12 (17)	C23—C22—C27—C26	0.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3W	0.88 (4)	1.61 (4)	2.465 (2)	166 (4)
N3—H3N···O7	0.83 (3)	1.96 (3)	2.752 (2)	159 (3)
O1W—H1W1···O8	0.79 (3)	1.91 (3)	2.696 (2)	174 (3)
O1W—H2W1···O4ⁱ	0.85 (4)	2.07 (4)	2.901 (2)	165 (3)
O2W—H1W2···O4	0.82 (3)	2.07 (3)	2.873 (2)	166 (3)
O2W—H2W2···O5Wⁱⁱ	0.86 (3)	1.98 (3)	2.791 (3)	158 (3)
O3W—H1W3···O1Wⁱⁱⁱ	0.85 (4)	1.82 (4)	2.665 (2)	173 (3)
O3W—H2W3···O4W^iv	0.85 (4)	1.78 (4)	2.636 (2)	174 (5)
O4W—H1W4···O2Wⁱⁱⁱ	0.81 (4)	1.95 (4)	2.768 (3)	178 (3)
O4W—H2W4···O5	0.81 (3)	1.98 (3)	2.788 (2)	172 (4)
O5W—H1W5···O6^v	0.80 (3)	2.08 (3)	2.880 (2)	173 (3)
O5W—H2W5···O6	0.86 (4)	1.99 (5)	2.838 (2)	171 (4)

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

Experimental details

Crystal data
Chemical formula	(C₁₃H₁₀N)[Zn(C₇H₃NO₄)(C₇H₄NO₄)]·5H₂O
M_r	666.89
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	9.6083 (5), 18.9681 (9), 15.5435 (8)
β (°)	96.051 (1)
V (Å³)	2817.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.95
Crystal size (mm)	0.60 × 0.14 × 0.14

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.652, 0.879
No. of measured, independent and observed [I > 2σ(I)] reflections	26948, 7457, 5795
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.108, 1.06
No. of reflections	7457
No. of parameters	445
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.35

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—N2	2.0011 (16)	Zn1—O5	2.1443 (15)
Zn1—N1	2.0238 (16)	Zn1—O7	2.2100 (14)
Zn1—O3	2.0864 (14)	Zn1—O1	2.3406 (14)