Bis(2-amino-6-methyl­pyridinium) tris­(pyridine-2,6-dicarboxyl­ato)zirconate(IV) dihydrate

Pasdar, H.; Ebdam, A.; Aghabozorg, H.; Notash, B.

doi:10.1107/S1600536811003072

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page m294

doi:10.1107/S1600536811003072

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Bis(2-amino-6-methylpyridinium) tris(pyridine-2,6-dicarboxylato)zirconate(IV) dihydrate

Hoda Pasdar,^a ^* Ali Ebdam,^a Hossein Aghabozorg ^a and Behrouz Notash ^b

^aDepartment of Chemistry, Islamic Azad University, North Tehran Branch, Tehran, Iran, and ^bDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: hodapass@gmail.com

(Received 17 January 2011; accepted 24 January 2011; online 2 February 2011)

In the title compound, (C₆H₉N₂)₂[Zr(C₇H₃NO₄)₃]·2H₂O, the Zr^IV atom is nine-coordinated by three pyridine-2,6-dicarboxylate ligands in a distorted tricapped trigonal–prismatic ZrN₃O₆ environment. The crystal packing is stabilized by intermolecular 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_r = 840.87
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.023
wR(F²) = 0.060
S = 1.03
4705 reflections
271 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.27 e Å⁻³

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) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

Pyridine-2,6-dicarboxylic acid (pydcH₂) was commonly used as an acid in proton transfer systems (Aghabozorg et al., 2008). Continuing the path to synthesize proton transfer compounds, our group has focused on forming ion pairs between 2,6-pydcH₂ and various organic bases (Pasdar et al., 2010; Pasdar et al., 2011). The structures of two proton transfer compounds containing [Zr^IV(2,6-pydc)₃]^2- moiety were reported with the counter cationic part of 2,6-pyridinediamine (Aghabozorg et al., 2005) and 2,4,6-triamino-1,3,5-triazine (Daneshvar et al., 2008), respectively. The structure of K₄[Zr^IV(2,6-pydc)₃]₂ has been reported by Willey et al. (1998).

We report herein the synthesis and crystal structure of (2a6mpH)₂[Zr(2,6-pydc)₃].2H₂O by the reaction of ZrCl₄, 2-amino-6-methylpyridine and 2,6-pyridinedicarboxylic acid in aqueous media. The molecular structure of the title compound is shown in Fig.1. The zirconium(IV) ion is coordinated by three pydc^2- ligands in a distorted tricapped trigonal prismatic geometry. The geometry around the zirconium(IV) centre in the title compound is shown in Fig. 2. The Zr—N and Zr—O bond lengths and angles are comprable with those previously reported (Aghabozorg et al., 2005; Daneshvar et al., 2008). The crystal packing diagram of (2a6mpH)₂[Zr(2,6-pydc)₃].2H₂O is presented in Fig. 3. There are several intermolecular N—H···O, O—H···O hydrogen bonds which stabilize crystal structure of the compound (Table 1 and Fig. 3).

Related literature top

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 top

A solution of ZrCl₄ (0.114 mg,0.5 mmol) in water (15 ml) was added to an aqueous solution of 2-amino-6-methylpyridine (0.114,1 mmol) and 2,6-pyridinedicarboxylic acid (0.504 mg, 3 mmol) in water (15 ml). Crystals of the title compound suitable for X-ray characterization were obtained after a few weeks at room temperature (m.p: 145 °C).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); 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. The molecular structure of (2a6mpH)₂[Zr(2,6-pydc)₃].2H₂O with displacement ellipsoids drawn at 30% probability level.Symmetry code: (a) -x + 1, y, -z + 3/2.
	Fig. 2. The coordination environment around Zr^IV ion in the title compound. Symmetry code: (a) -x + 1, y, -z + 3/2.
	Fig. 3. The packing diagram of (2a6mpH)₂[Zr(2,6-pydc)₃].2H₂O. The intermolecular N—H···O, O—H···O hydrogen bonds are shown as blue dashed lines.

Bis(2-amino-6-methylpyridinium) tris(pyridine-2,6-dicarboxylato)zirconate(IV) dihydrate top

Crystal data top

(C₆H₉N₂)₂[Zr(C₇H₃NO₄)₃]·2H₂O	F(000) = 1720
M_r = 840.87	D_x = 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

Data collection top

Stoe IPDS II diffractometer	4705 independent reflections
Radiation source: fine-focus sealed tube	4284 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 0.15 mm pixels mm^-1	θ_max = 29.2°, θ_min = 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
T_min = 0.870, T_max = 0.903	l = −25→25
12273 measured reflections

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)] = 0.023	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(F_o²) + (0.0339P)² + 1.0948P] where P = (F_o² + 2F_c²)/3
4705 reflections	(Δ/σ)_max = 0.001
271 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

(C₆H₉N₂)₂[Zr(C₇H₃NO₄)₃]·2H₂O	V = 3511.0 (14) Å³
M_r = 840.87	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.719 (4) Å	µ = 0.39 mm⁻¹
b = 10.536 (2) Å	T = 298 K
c = 18.781 (4) Å	0.35 × 0.3 × 0.25 mm
β = 108.58 (3)°

Data collection top

Stoe IPDS II diffractometer	4705 independent reflections
Absorption correction: numerical [shape of crystal determined optically (X-SHAPE and X-RED32; Stoe& Cie, 2005)]	4284 reflections with I > 2σ(I)
T_min = 0.870, T_max = 0.903	R_int = 0.025
12273 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.33 e Å⁻³
4705 reflections	Δρ_min = −0.27 e Å⁻³
271 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
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

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)

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

Experimental details

Crystal data
Chemical formula	(C₆H₉N₂)₂[Zr(C₇H₃NO₄)₃]·2H₂O
M_r	840.87
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	18.719 (4), 10.536 (2), 18.781 (4)
β (°)	108.58 (3)
V (Å³)	3511.0 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.35 × 0.3 × 0.25

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	Numerical [shape of crystal determined optically (X-SHAPE and X-RED32; Stoe& Cie, 2005)]
T_min, T_max	0.870, 0.903
No. of measured, independent and observed [I > 2σ(I)] reflections	12273, 4705, 4284
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.060, 1.03
No. of reflections	4705
No. of parameters	271
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.27

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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) x+1/2, y−1/2, z; (ii) −x+1, y, −z+3/2; (iii) −x+3/2, y+1/2, −z+3/2.

Acknowledgements

We are grateful to the Islamic Azad University, North Tehran Branch, for financial support.

References

Aghabozorg, H., Manteghi, F. & Sheshmani, S. (2008). J. Iran. Chem. Soc. 5, 184–227. CrossRef CAS Google Scholar
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Daneshvar, S., Aghabozorg, H. & Manteghi, F. (2008). Acta Cryst. E64, m1308–m1309. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
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Volume 67| Part 3| March 2011| Page m294

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(2-amino-6-methyl­pyridinium) tris­­(pyridine-2,6-di­carboxyl­ato)zirconate(IV) dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis(2-amino-6-methylpyridinium) tris(pyridine-2,6-dicarboxylato)zirconate(IV) dihydrate