Propane-1,2-diaminium tris­(pyridine-2,6-dicarboxyl­ato-κ3O2,N,O6)zirconate(IV) trihydrate

Pasdar, H.; Shakiba, S.; Aghabozorg, H.; Notash, B.

doi:10.1107/S1600536811008488

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m587

doi:10.1107/S1600536811008488

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Propane-1,2-diaminium tris(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)zirconate(IV) trihydrate

Hoda Pasdar,^a ^* Shahrzad Shakiba,^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: h_pasdar@iau-tnb.ac.ir

(Received 5 February 2011; accepted 6 March 2011; online 13 April 2011)

In the title compound, (C₃H₁₂N₂)[Zr(C₇H₃NO₄)₃]·3H₂O, the Zr^IV cation is chelated by three pyridine-2,6-dicarboxylate anions in a distorted tricapped trigonal–prismatic environment. The crystal structure is stabilized by intermolecular N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For the background to proton-transfer compounds, see: Aghabozorg et al. (2008 ). For related structures, see: Aghabozorg et al. (2005 ); Daneshvar et al. (2008 ); Pasdar et al. (2010a ,b , 2011a ,b ).

Experimental

Crystal data

(C₃H₁₂N₂)[Zr(C₇H₃NO₄)₃]·3H₂O
M_r = 716.73
Monoclinic, P 2₁ /n
a = 10.515 (2) Å
b = 19.195 (4) Å
c = 14.149 (3) Å
β = 103.39 (3)°
V = 2778.1 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 298 K
0.25 × 0.15 × 0.15 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005 ) T_min = 0.915, T_max = 0.926
21838 measured reflections
7481 independent reflections
5264 reflections with I > 2σ(I)
R_int = 0.133

Refinement

R[F² > 2σ(F²)] = 0.086
wR(F²) = 0.206
S = 1.18
7481 reflections
427 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.09 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O14	0.80 (8)	2.10 (9)	2.745 (11)	138 (13)
O13—H13B⋯O2ⁱ	0.80 (4)	2.10 (8)	2.793 (8)	145 (12)
O14—H14A⋯O5ⁱⁱ	0.91 (8)	2.11 (9)	2.978 (7)	158 (12)
O14—H14B⋯O8	0.85 (4)	1.89 (5)	2.731 (9)	171 (14)
O15—H15A⋯O12	0.98 (9)	1.91 (10)	2.857 (8)	164 (12)
O15—H15B⋯O1ⁱⁱⁱ	0.83 (4)	2.46 (7)	3.227 (9)	155 (13)
N4—H4A⋯O10^iv	0.89	1.92	2.791 (8)	165
N4—H4B⋯O6ⁱⁱ	0.89	2.24	2.851 (7)	125
N4—H4C⋯O15^v	0.89	2.04	2.864 (10)	154
N5—H5A⋯O13	0.89	1.94	2.769 (9)	154
N5—H5B⋯O6^iv	0.89	2.18	2.844 (8)	131
N5—H5C⋯O4	0.89	1.91	2.776 (8)	163
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+2, -y+1, -z+1; (iv) x-1, y, z; (v) -x+1, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); 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/S1600536811008488/xu5157sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008488/xu5157Isup2.hkl

checkCIF report

Comment top

Pyridine-2,6-dicarboxylic acid (pydcH₂) was commonly used by Aghabozorg and his co-workers as an acid in proton transfer systems (Aghabozorg et al. 2008). Our group have been focused on forming ion pairs between 2,6-pydcH₂ and various organic bases (Pasdar et al., 2010a; Pasdar et al. 2011a,b). The structure of two proton transfer compound containing nine-coordinated [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. Recently, we report the structure of (2a6mpH)₂[Zr(2,6-pydc)₃].2H₂O (Pasdar et al. 2011a).

Herein, we report the synthesis and crystal structure of (1,2-pdaH₂)[Zr(2,6-pydc)₃].3H₂O. The title compound was prepared by the reaction of ZrCl₄.3H₂O, propane-1,2-diamine and 2,6-pyridinedicarboxylic acid in aqueous solution. Fig.1 present the molecular structure of the title compound. X-ray diffraction study shows that Zirconium(IV) ion is coordinated by three pydc^2- moiety in a distorted tricapped trigonal prismatic geometry and pydc^2- ligands act as tridentate ligand. Coordination environment around Zirconium(IV) ion in the (1,2-pdaH₂)[Zr(2,6-pydc)₃].3H₂O is presented in Fig. 2. The Zr—N and Zr—O bond lengths and angles are in the normal ranges (Aghabozorg et al. 2005; Daneshvar et al. 2008). The crystal packing diagram of the title compound is shown in Fig. 3. In the crystal packing diagram of the title compound, there are several intermolecular N—H···O, O—H···O hydrogen bonds which play an important role in stabilization of crystal structure (Table 1 and Fig. 3).

Related literature top

For the background to proton-transfer compounds, see: Aghabozorg et al. (2008). For related structures, see: Aghabozorg et al. (2005); Daneshvar et al. (2008); Pasdar et al. (2010a,b, 2011a,b).

Experimental top

A solution of propane-1,2-diamine (0.074 g, 1 mmol) in water (8 ml) and 2,6-pyridinedicarboxylic acid (0.501 g, 3 mmol) in water (10 ml) were mixed and stirred until clear solution obtained. Then a solution of ZrCl₄.3H₂O (0.116 g, 0.5 mmol) in water (5 ml) was added to the mixture of acid-base and stirrer for 5 h. Crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation after one month at room temperature (m.p: 210 °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 the title compound with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The coordination environment around Zr^IV ion in the title compound.
	Fig. 3. The packing diagram of the title compound. The intermolecular N—H···O, O—H···O hydrogen bonds are shown as dashed lines.

Propane-1,2-diaminium tris(pyridine-2,6-dicarboxylato- κ³O²,N,O⁶)zirconate(IV) trihydrate top

Crystal data top

(C₃H₁₂N₂)[Zr(C₇H₃NO₄)₃]·3H₂O	F(000) = 1464
M_r = 716.73	D_x = 1.714 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7481 reflections
a = 10.515 (2) Å	θ = 2.1–29.2°
b = 19.195 (4) Å	µ = 0.48 mm⁻¹
c = 14.149 (3) Å	T = 298 K
β = 103.39 (3)°	Prism, colorless
V = 2778.1 (10) Å³	0.25 × 0.15 × 0.15 mm
Z = 4

Data collection top

Stoe IPDS II diffractometer	7481 independent reflections
Radiation source: fine-focus sealed tube	5264 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.133
rotation method scans	θ_max = 29.2°, θ_min = 2.1°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)	h = −14→11
T_min = 0.915, T_max = 0.926	k = −26→26
21838 measured reflections	l = −19→19

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)] = 0.086	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.206	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ²(F_o²) + (0.0753P)² + 3.9962P] where P = (F_o² + 2F_c²)/3
7481 reflections	(Δ/σ)_max = 0.001
427 parameters	Δρ_max = 1.09 e Å⁻³
7 restraints	Δρ_min = −0.77 e Å⁻³

Crystal data top

(C₃H₁₂N₂)[Zr(C₇H₃NO₄)₃]·3H₂O	V = 2778.1 (10) Å³
M_r = 716.73	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.515 (2) Å	µ = 0.48 mm⁻¹
b = 19.195 (4) Å	T = 298 K
c = 14.149 (3) Å	0.25 × 0.15 × 0.15 mm
β = 103.39 (3)°

Data collection top

Stoe IPDS II diffractometer	7481 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)	5264 reflections with I > 2σ(I)
T_min = 0.915, T_max = 0.926	R_int = 0.133
21838 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.086	7 restraints
wR(F²) = 0.206	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	Δρ_max = 1.09 e Å⁻³
7481 reflections	Δρ_min = −0.77 e Å⁻³
427 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
C18	1.0667 (8)	0.5828 (4)	0.6397 (5)	0.0486 (18)
H18	1.0902	0.5663	0.7032	0.058*
O13	0.3681 (10)	0.8559 (3)	0.2972 (5)	0.084 (2)
O14	0.5141 (7)	0.8422 (4)	0.4841 (5)	0.0666 (18)
Zr1	0.93403 (5)	0.68252 (3)	0.29848 (3)	0.02015 (14)
O11	0.7886 (4)	0.6046 (2)	0.3278 (3)	0.0299 (9)
O5	1.0314 (4)	0.7169 (2)	0.1812 (3)	0.0285 (8)
O9	1.1276 (4)	0.7203 (2)	0.3786 (3)	0.0281 (8)
O3	0.7472 (4)	0.7187 (2)	0.2025 (3)	0.0281 (8)
N2	0.9428 (5)	0.8044 (2)	0.2844 (3)	0.0250 (9)
O7	0.8366 (4)	0.7374 (2)	0.4015 (3)	0.0318 (9)
O1	1.0691 (4)	0.5933 (2)	0.2947 (3)	0.0311 (9)
N3	0.9968 (5)	0.6338 (2)	0.4535 (3)	0.0242 (9)
N1	0.8636 (5)	0.6103 (2)	0.1615 (3)	0.0242 (9)
O4	0.5741 (4)	0.7014 (3)	0.0797 (3)	0.0364 (10)
C7	0.6845 (6)	0.6870 (3)	0.1263 (4)	0.0279 (11)
C15	1.1900 (6)	0.6989 (3)	0.4611 (4)	0.0254 (11)
O6	1.1211 (5)	0.7982 (3)	0.1045 (3)	0.0385 (10)
O2	1.1365 (5)	0.5005 (2)	0.2250 (4)	0.0421 (11)
O8	0.7646 (6)	0.8342 (3)	0.4614 (4)	0.0499 (13)
C6	0.7542 (6)	0.6251 (3)	0.0975 (4)	0.0278 (11)
C2	0.9348 (6)	0.5542 (3)	0.1484 (4)	0.0282 (11)
C9	1.0020 (6)	0.8333 (3)	0.2204 (4)	0.0267 (11)
C1	1.0562 (6)	0.5475 (3)	0.2271 (4)	0.0276 (11)
C8	1.0568 (5)	0.7797 (3)	0.1625 (4)	0.0266 (11)
C14	0.8231 (6)	0.8035 (3)	0.4075 (4)	0.0307 (12)
C13	0.8855 (6)	0.8446 (3)	0.3394 (4)	0.0287 (12)
O10	1.3031 (4)	0.7132 (3)	0.5023 (3)	0.0359 (10)
O12	0.6980 (5)	0.5485 (3)	0.4335 (3)	0.0429 (11)
C16	1.1115 (6)	0.6500 (3)	0.5102 (4)	0.0273 (11)
C4	0.7813 (8)	0.5259 (4)	0.0028 (5)	0.0460 (17)
H4	0.7531	0.4974	−0.0511	0.055*
C20	0.9149 (6)	0.5919 (3)	0.4871 (4)	0.0283 (11)
C21	0.7902 (6)	0.5797 (3)	0.4117 (4)	0.0308 (12)
C3	0.8944 (7)	0.5103 (3)	0.0707 (5)	0.0375 (14)
H3	0.9426	0.4707	0.0639	0.045*
C11	0.9459 (8)	0.9464 (3)	0.2640 (5)	0.0440 (17)
H11	0.9467	0.9946	0.2570	0.053*
C5	0.7101 (7)	0.5843 (4)	0.0153 (5)	0.0406 (15)
H5	0.6342	0.5961	−0.0303	0.049*
C19	0.9465 (8)	0.5654 (4)	0.5800 (5)	0.0440 (16)
H19	0.8887	0.5365	0.6022	0.053*
C12	0.8857 (7)	0.9168 (3)	0.3310 (5)	0.0378 (14)
H12	0.8460	0.9445	0.3698	0.045*
C17	1.1515 (6)	0.6252 (4)	0.6036 (4)	0.0363 (14)
H17	1.2335	0.6365	0.6417	0.044*
C10	1.0048 (7)	0.9048 (3)	0.2074 (5)	0.0380 (14)
H10	1.0453	0.9241	0.1617	0.046*
N5	0.3816 (6)	0.7484 (3)	0.1693 (4)	0.0407 (13)
H5A	0.3872	0.7903	0.1969	0.061*
H5B	0.3091	0.7460	0.1222	0.061*
H5C	0.4509	0.7413	0.1444	0.061*
C23	0.3774 (7)	0.6935 (4)	0.2445 (5)	0.0379 (14)
H23	0.3049	0.7040	0.2751	0.045*
C22	0.5033 (7)	0.6975 (4)	0.3206 (5)	0.0419 (16)
H22A	0.5725	0.6760	0.2958	0.050*
H22B	0.5263	0.7460	0.3342	0.050*
N4	0.4933 (6)	0.6623 (4)	0.4117 (4)	0.0493 (16)
H4A	0.4389	0.6860	0.4394	0.074*
H4B	0.5720	0.6605	0.4520	0.074*
H4C	0.4631	0.6192	0.3983	0.074*
C24	0.3509 (10)	0.6242 (4)	0.1930 (5)	0.053 (2)
H24A	0.4143	0.6165	0.1549	0.080*
H24B	0.2648	0.6246	0.1512	0.080*
H24C	0.3569	0.5877	0.2401	0.080*
O15	0.6503 (7)	0.4645 (4)	0.5884 (5)	0.077 (2)
H15A	0.672 (13)	0.485 (7)	0.531 (7)	0.115*
H14A	0.497 (14)	0.820 (7)	0.537 (8)	0.115*
H14B	0.592 (6)	0.835 (7)	0.479 (10)	0.115*
H13A	0.426 (11)	0.870 (7)	0.340 (8)	0.115*
H13B	0.342 (13)	0.892 (4)	0.271 (8)	0.115*
H15B	0.728 (6)	0.453 (8)	0.601 (10)	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C18	0.053 (4)	0.059 (4)	0.029 (3)	−0.008 (4)	0.000 (3)	0.019 (3)
O13	0.141 (8)	0.037 (3)	0.070 (4)	0.017 (4)	0.017 (5)	−0.005 (3)
O14	0.072 (4)	0.072 (4)	0.066 (4)	0.018 (4)	0.037 (3)	0.026 (3)
Zr1	0.0211 (2)	0.0215 (2)	0.0184 (2)	0.0005 (2)	0.00570 (16)	0.0007 (2)
O11	0.032 (2)	0.032 (2)	0.0257 (18)	−0.0045 (17)	0.0058 (16)	0.0019 (16)
O5	0.035 (2)	0.027 (2)	0.0275 (19)	0.0021 (17)	0.0147 (17)	−0.0016 (15)
O9	0.029 (2)	0.028 (2)	0.0282 (19)	−0.0051 (16)	0.0097 (16)	0.0039 (15)
O3	0.030 (2)	0.029 (2)	0.0250 (18)	0.0030 (16)	0.0057 (16)	−0.0003 (15)
N2	0.026 (2)	0.024 (2)	0.027 (2)	0.0010 (18)	0.0093 (18)	−0.0020 (16)
O7	0.038 (2)	0.034 (2)	0.0275 (19)	0.0006 (18)	0.0161 (18)	0.0001 (17)
O1	0.037 (2)	0.031 (2)	0.0264 (19)	0.0058 (18)	0.0080 (17)	0.0005 (16)
N3	0.027 (2)	0.024 (2)	0.023 (2)	−0.0020 (18)	0.0079 (18)	0.0026 (17)
N1	0.026 (2)	0.025 (2)	0.023 (2)	0.0015 (18)	0.0070 (18)	0.0011 (17)
O4	0.024 (2)	0.047 (3)	0.037 (2)	0.0043 (18)	0.0039 (18)	0.0041 (19)
C7	0.030 (3)	0.028 (3)	0.027 (2)	−0.003 (2)	0.010 (2)	0.004 (2)
C15	0.025 (3)	0.024 (3)	0.027 (2)	0.001 (2)	0.007 (2)	−0.0047 (19)
O6	0.037 (2)	0.049 (3)	0.034 (2)	−0.001 (2)	0.0153 (19)	0.0118 (19)
O2	0.043 (3)	0.026 (2)	0.059 (3)	0.010 (2)	0.017 (2)	0.004 (2)
O8	0.056 (3)	0.053 (3)	0.050 (3)	0.007 (2)	0.030 (3)	−0.011 (2)
C6	0.032 (3)	0.028 (3)	0.027 (2)	−0.006 (2)	0.012 (2)	0.002 (2)
C2	0.030 (3)	0.027 (3)	0.031 (3)	−0.002 (2)	0.014 (2)	0.000 (2)
C9	0.023 (3)	0.026 (3)	0.030 (3)	0.000 (2)	0.004 (2)	0.003 (2)
C1	0.030 (3)	0.020 (2)	0.035 (3)	0.001 (2)	0.013 (2)	0.003 (2)
C8	0.023 (3)	0.033 (3)	0.023 (2)	0.001 (2)	0.003 (2)	0.006 (2)
C14	0.028 (3)	0.037 (3)	0.028 (3)	0.003 (2)	0.009 (2)	−0.006 (2)
C13	0.026 (3)	0.031 (3)	0.027 (3)	0.000 (2)	0.003 (2)	−0.005 (2)
O10	0.023 (2)	0.049 (3)	0.034 (2)	−0.0060 (19)	0.0039 (17)	0.001 (2)
O12	0.036 (2)	0.050 (3)	0.045 (2)	−0.011 (2)	0.013 (2)	0.016 (2)
C16	0.029 (3)	0.029 (3)	0.023 (2)	0.004 (2)	0.003 (2)	−0.001 (2)
C4	0.053 (4)	0.048 (4)	0.039 (3)	−0.011 (3)	0.014 (3)	−0.014 (3)
C20	0.028 (3)	0.030 (3)	0.026 (2)	−0.002 (2)	0.006 (2)	0.004 (2)
C21	0.028 (3)	0.033 (3)	0.031 (3)	0.004 (2)	0.007 (2)	0.003 (2)
C3	0.050 (4)	0.028 (3)	0.039 (3)	−0.002 (3)	0.019 (3)	−0.005 (2)
C11	0.063 (5)	0.024 (3)	0.045 (3)	−0.002 (3)	0.013 (3)	−0.003 (3)
C5	0.040 (4)	0.049 (4)	0.031 (3)	−0.004 (3)	0.003 (3)	−0.008 (3)
C19	0.047 (4)	0.050 (4)	0.036 (3)	−0.008 (3)	0.011 (3)	0.013 (3)
C12	0.041 (4)	0.029 (3)	0.040 (3)	0.007 (3)	0.002 (3)	−0.008 (3)
C17	0.031 (3)	0.041 (3)	0.032 (3)	−0.003 (3)	0.000 (2)	0.007 (3)
C10	0.044 (4)	0.032 (3)	0.037 (3)	−0.008 (3)	0.009 (3)	0.008 (2)
N5	0.042 (3)	0.038 (3)	0.043 (3)	0.004 (2)	0.012 (3)	0.009 (2)
C23	0.035 (3)	0.045 (4)	0.037 (3)	0.002 (3)	0.013 (3)	0.004 (3)
C22	0.037 (4)	0.049 (4)	0.040 (3)	−0.002 (3)	0.007 (3)	0.004 (3)
N4	0.044 (3)	0.072 (4)	0.032 (3)	0.008 (3)	0.010 (3)	0.001 (3)
C24	0.079 (6)	0.041 (4)	0.040 (4)	−0.013 (4)	0.013 (4)	0.001 (3)
O15	0.071 (4)	0.091 (5)	0.068 (4)	−0.024 (4)	0.014 (4)	0.031 (4)

Geometric parameters (Å, º) top

C18—C17	1.388 (10)	C9—C10	1.387 (8)
C18—C19	1.389 (10)	C9—C8	1.509 (8)
C18—H18	0.9300	C14—C13	1.508 (9)
O13—H13A	0.80 (8)	C13—C12	1.392 (9)
O13—H13B	0.80 (4)	O12—C21	1.239 (8)
O14—H14A	0.91 (8)	C16—C17	1.376 (8)
O14—H14B	0.85 (4)	C4—C3	1.378 (10)
Zr1—O9	2.210 (4)	C4—C5	1.382 (11)
Zr1—O3	2.225 (4)	C4—H4	0.9300
Zr1—O7	2.230 (4)	C20—C19	1.377 (8)
Zr1—O1	2.233 (4)	C20—C21	1.504 (8)
Zr1—O5	2.241 (4)	C3—H3	0.9300
Zr1—O11	2.245 (4)	C11—C10	1.375 (10)
Zr1—N3	2.334 (4)	C11—C12	1.379 (11)
Zr1—N2	2.352 (4)	C11—H11	0.9300
Zr1—N1	2.358 (4)	C5—H5	0.9300
O11—C21	1.277 (7)	C19—H19	0.9300
O5—C8	1.275 (7)	C12—H12	0.9300
O9—C15	1.267 (7)	C17—H17	0.9300
O3—C7	1.280 (7)	C10—H10	0.9300
N2—C9	1.333 (7)	N5—C23	1.506 (8)
N2—C13	1.334 (7)	N5—H5A	0.8900
O7—C14	1.283 (7)	N5—H5B	0.8900
O1—C1	1.283 (7)	N5—H5C	0.8900
N3—C16	1.321 (7)	C23—C22	1.502 (9)
N3—C20	1.343 (7)	C23—C24	1.510 (10)
N1—C6	1.320 (7)	C23—H23	0.9800
N1—C2	1.350 (7)	C22—N4	1.480 (9)
O4—C7	1.226 (7)	C22—H22A	0.9700
C7—C6	1.502 (8)	C22—H22B	0.9700
C15—O10	1.227 (7)	N4—H4A	0.8900
C15—C16	1.521 (8)	N4—H4B	0.8900
O6—C8	1.230 (7)	N4—H4C	0.8900
O2—C1	1.241 (7)	C24—H24A	0.9600
O8—C14	1.233 (8)	C24—H24B	0.9600
C6—C5	1.390 (8)	C24—H24C	0.9600
C2—C3	1.372 (8)	O15—H15A	0.98 (9)
C2—C1	1.492 (8)	O15—H15B	0.83 (4)

C17—C18—C19	119.2 (6)	O6—C8—O5	125.9 (6)
C17—C18—H18	120.4	O6—C8—C9	120.2 (5)
C19—C18—H18	120.4	O5—C8—C9	114.0 (5)
H13A—O13—H13B	100 (8)	O8—C14—O7	126.3 (6)
H14A—O14—H14B	111 (10)	O8—C14—C13	119.9 (6)
O9—Zr1—O3	142.08 (15)	O7—C14—C13	113.7 (5)
O9—Zr1—O7	91.02 (16)	N2—C13—C12	121.0 (6)
O3—Zr1—O7	77.11 (15)	N2—C13—C14	113.2 (5)
O9—Zr1—O1	75.43 (16)	C12—C13—C14	125.8 (6)
O3—Zr1—O1	134.53 (15)	N3—C16—C17	122.3 (6)
O7—Zr1—O1	140.25 (15)	N3—C16—C15	112.5 (5)
O9—Zr1—O5	76.03 (15)	C17—C16—C15	125.1 (5)
O3—Zr1—O5	86.94 (15)	C3—C4—C5	119.6 (6)
O7—Zr1—O5	134.60 (16)	C3—C4—H4	120.2
O1—Zr1—O5	78.81 (15)	C5—C4—H4	120.2
O9—Zr1—O11	135.19 (14)	N3—C20—C19	121.8 (6)
O3—Zr1—O11	77.16 (15)	N3—C20—C21	111.6 (5)
O7—Zr1—O11	76.04 (16)	C19—C20—C21	126.7 (6)
O1—Zr1—O11	87.57 (16)	O12—C21—O11	124.8 (6)
O5—Zr1—O11	141.28 (15)	O12—C21—C20	120.2 (5)
O9—Zr1—N3	67.84 (15)	O11—C21—C20	115.0 (5)
O3—Zr1—N3	135.72 (16)	C2—C3—C4	118.8 (6)
O7—Zr1—N3	69.39 (16)	C2—C3—H3	120.6
O1—Zr1—N3	70.89 (15)	C4—C3—H3	120.6
O5—Zr1—N3	137.31 (16)	C10—C11—C12	120.1 (6)
O11—Zr1—N3	67.44 (15)	C10—C11—H11	120.0
O9—Zr1—N2	70.58 (16)	C12—C11—H11	120.0
O3—Zr1—N2	71.60 (16)	C4—C5—C6	118.5 (6)
O7—Zr1—N2	67.56 (16)	C4—C5—H5	120.7
O1—Zr1—N2	136.30 (17)	C6—C5—H5	120.7
O5—Zr1—N2	67.09 (15)	C20—C19—C18	118.5 (6)
O11—Zr1—N2	136.09 (16)	C20—C19—H19	120.8
N3—Zr1—N2	118.01 (16)	C18—C19—H19	120.8
O9—Zr1—N1	133.70 (16)	C11—C12—C13	118.7 (6)
O3—Zr1—N1	67.48 (15)	C11—C12—H12	120.7
O7—Zr1—N1	135.26 (16)	C13—C12—H12	120.7
O1—Zr1—N1	67.05 (15)	C16—C17—C18	118.5 (6)
O5—Zr1—N1	71.04 (16)	C16—C17—H17	120.8
O11—Zr1—N1	70.27 (16)	C18—C17—H17	120.8
N3—Zr1—N1	120.25 (16)	C11—C10—C9	118.2 (6)
N2—Zr1—N1	121.74 (15)	C11—C10—H10	120.9
C21—O11—Zr1	123.9 (4)	C9—C10—H10	120.9
C8—O5—Zr1	125.9 (4)	C23—N5—H5A	109.5
C15—O9—Zr1	125.8 (4)	C23—N5—H5B	109.5
C7—O3—Zr1	125.1 (4)	H5A—N5—H5B	109.5
C9—N2—C13	120.1 (5)	C23—N5—H5C	109.5
C9—N2—Zr1	120.3 (4)	H5A—N5—H5C	109.5
C13—N2—Zr1	119.6 (4)	H5B—N5—H5C	109.5
C14—O7—Zr1	125.9 (4)	C22—C23—N5	107.8 (6)
C1—O1—Zr1	125.8 (4)	C22—C23—C24	115.1 (7)
C16—N3—C20	119.7 (5)	N5—C23—C24	107.9 (6)
C16—N3—Zr1	119.8 (4)	C22—C23—H23	108.6
C20—N3—Zr1	120.5 (4)	N5—C23—H23	108.6
C6—N1—C2	120.1 (5)	C24—C23—H23	108.6
C6—N1—Zr1	119.7 (4)	N4—C22—C23	111.8 (6)
C2—N1—Zr1	120.2 (4)	N4—C22—H22A	109.3
O4—C7—O3	125.8 (6)	C23—C22—H22A	109.3
O4—C7—C6	119.5 (5)	N4—C22—H22B	109.3
O3—C7—C6	114.6 (5)	C23—C22—H22B	109.3
O10—C15—O9	127.1 (6)	H22A—C22—H22B	107.9
O10—C15—C16	119.3 (5)	C22—N4—H4A	109.5
O9—C15—C16	113.6 (5)	C22—N4—H4B	109.5
N1—C6—C5	121.5 (6)	H4A—N4—H4B	109.5
N1—C6—C7	112.7 (5)	C22—N4—H4C	109.5
C5—C6—C7	125.7 (6)	H4A—N4—H4C	109.5
N1—C2—C3	121.4 (6)	H4B—N4—H4C	109.5
N1—C2—C1	111.8 (5)	C23—C24—H24A	109.5
C3—C2—C1	126.7 (6)	C23—C24—H24B	109.5
N2—C9—C10	121.9 (6)	H24A—C24—H24B	109.5
N2—C9—C8	112.5 (5)	C23—C24—H24C	109.5
C10—C9—C8	125.5 (6)	H24A—C24—H24C	109.5
O2—C1—O1	124.1 (6)	H24B—C24—H24C	109.5
O2—C1—C2	120.9 (5)	H15A—O15—H15B	83 (10)
O1—C1—C2	115.0 (5)

O9—Zr1—O11—C21	15.8 (6)	O9—Zr1—N1—C2	38.3 (5)
O3—Zr1—O11—C21	−140.9 (5)	O3—Zr1—N1—C2	−179.9 (5)
O7—Zr1—O11—C21	−61.2 (5)	O7—Zr1—N1—C2	−139.5 (4)
O1—Zr1—O11—C21	82.2 (5)	O1—Zr1—N1—C2	−0.2 (4)
O5—Zr1—O11—C21	150.9 (4)	O5—Zr1—N1—C2	85.4 (4)
N3—Zr1—O11—C21	11.9 (4)	O11—Zr1—N1—C2	−96.1 (4)
N2—Zr1—O11—C21	−95.6 (5)	N3—Zr1—N1—C2	−49.0 (5)
N1—Zr1—O11—C21	148.7 (5)	N2—Zr1—N1—C2	131.2 (4)
O9—Zr1—O5—C8	−69.6 (4)	Zr1—O3—C7—O4	170.3 (4)
O3—Zr1—O5—C8	76.2 (4)	Zr1—O3—C7—C6	−6.6 (7)
O7—Zr1—O5—C8	7.7 (5)	Zr1—O9—C15—O10	171.2 (5)
O1—Zr1—O5—C8	−147.2 (5)	Zr1—O9—C15—C16	−8.1 (7)
O11—Zr1—O5—C8	141.2 (4)	C2—N1—C6—C5	−0.6 (9)
N3—Zr1—O5—C8	−102.2 (5)	Zr1—N1—C6—C5	179.3 (5)
N2—Zr1—O5—C8	4.9 (4)	C2—N1—C6—C7	177.0 (5)
N1—Zr1—O5—C8	143.4 (5)	Zr1—N1—C6—C7	−3.1 (6)
O3—Zr1—O9—C15	142.8 (4)	O4—C7—C6—N1	−171.2 (5)
O7—Zr1—O9—C15	72.6 (4)	O3—C7—C6—N1	5.9 (7)
O1—Zr1—O9—C15	−69.5 (4)	O4—C7—C6—C5	6.2 (9)
O5—Zr1—O9—C15	−151.4 (5)	O3—C7—C6—C5	−176.6 (6)
O11—Zr1—O9—C15	1.6 (5)	C6—N1—C2—C3	−1.8 (8)
N3—Zr1—O9—C15	5.4 (4)	Zr1—N1—C2—C3	178.3 (4)
N2—Zr1—O9—C15	138.4 (5)	C6—N1—C2—C1	178.6 (5)
N1—Zr1—O9—C15	−105.9 (5)	Zr1—N1—C2—C1	−1.3 (6)
O9—Zr1—O3—C7	137.0 (4)	C13—N2—C9—C10	−1.0 (9)
O7—Zr1—O3—C7	−148.3 (5)	Zr1—N2—C9—C10	177.4 (5)
O1—Zr1—O3—C7	3.5 (5)	C13—N2—C9—C8	−177.9 (5)
O5—Zr1—O3—C7	74.5 (4)	Zr1—N2—C9—C8	0.5 (6)
O11—Zr1—O3—C7	−70.0 (4)	Zr1—O1—C1—O2	176.4 (4)
N3—Zr1—O3—C7	−107.1 (4)	Zr1—O1—C1—C2	−3.6 (7)
N2—Zr1—O3—C7	141.3 (5)	N1—C2—C1—O2	−177.0 (5)
N1—Zr1—O3—C7	3.8 (4)	C3—C2—C1—O2	3.4 (9)
O9—Zr1—N2—C9	80.1 (4)	N1—C2—C1—O1	2.9 (7)
O3—Zr1—N2—C9	−97.0 (4)	C3—C2—C1—O1	−176.7 (6)
O7—Zr1—N2—C9	179.7 (5)	Zr1—O5—C8—O6	172.6 (4)
O1—Zr1—N2—C9	39.2 (5)	Zr1—O5—C8—C9	−6.3 (6)
O5—Zr1—N2—C9	−2.4 (4)	N2—C9—C8—O6	−175.6 (5)
O11—Zr1—N2—C9	−143.9 (4)	C10—C9—C8—O6	7.6 (9)
N3—Zr1—N2—C9	130.3 (4)	N2—C9—C8—O5	3.3 (7)
N1—Zr1—N2—C9	−49.9 (5)	C10—C9—C8—O5	−173.5 (6)
O9—Zr1—N2—C13	−101.4 (4)	Zr1—O7—C14—O8	176.7 (5)
O3—Zr1—N2—C13	81.4 (4)	Zr1—O7—C14—C13	−2.5 (7)
O7—Zr1—N2—C13	−1.9 (4)	C9—N2—C13—C12	0.3 (9)
O1—Zr1—N2—C13	−142.4 (4)	Zr1—N2—C13—C12	−178.1 (4)
O5—Zr1—N2—C13	176.0 (5)	C9—N2—C13—C14	179.8 (5)
O11—Zr1—N2—C13	34.5 (5)	Zr1—N2—C13—C14	1.4 (6)
N3—Zr1—N2—C13	−51.2 (5)	O8—C14—C13—N2	−178.7 (6)
N1—Zr1—N2—C13	128.5 (4)	O7—C14—C13—N2	0.5 (7)
O9—Zr1—O7—C14	70.8 (5)	O8—C14—C13—C12	0.8 (10)
O3—Zr1—O7—C14	−72.8 (5)	O7—C14—C13—C12	−180.0 (6)
O1—Zr1—O7—C14	139.0 (4)	C20—N3—C16—C17	0.3 (9)
O5—Zr1—O7—C14	−0.4 (6)	Zr1—N3—C16—C17	177.4 (5)
O11—Zr1—O7—C14	−152.5 (5)	C20—N3—C16—C15	−178.9 (5)
N3—Zr1—O7—C14	136.7 (5)	Zr1—N3—C16—C15	−1.8 (6)
N2—Zr1—O7—C14	2.4 (5)	O10—C15—C16—N3	−173.5 (5)
N1—Zr1—O7—C14	−110.7 (5)	O9—C15—C16—N3	5.9 (7)
O9—Zr1—O1—C1	−150.1 (5)	O10—C15—C16—C17	7.4 (9)
O3—Zr1—O1—C1	2.4 (6)	O9—C15—C16—C17	−173.2 (6)
O7—Zr1—O1—C1	136.3 (4)	C16—N3—C20—C19	0.4 (9)
O5—Zr1—O1—C1	−71.8 (5)	Zr1—N3—C20—C19	−176.6 (5)
O11—Zr1—O1—C1	71.7 (5)	C16—N3—C20—C21	−179.9 (5)
N3—Zr1—O1—C1	138.7 (5)	Zr1—N3—C20—C21	3.1 (7)
N2—Zr1—O1—C1	−110.4 (5)	Zr1—O11—C21—O12	164.3 (5)
N1—Zr1—O1—C1	2.1 (4)	Zr1—O11—C21—C20	−14.5 (7)
O9—Zr1—N3—C16	−1.3 (4)	N3—C20—C21—O12	−172.3 (6)
O3—Zr1—N3—C16	−144.6 (4)	C19—C20—C21—O12	7.4 (10)
O7—Zr1—N3—C16	−101.3 (4)	N3—C20—C21—O11	6.7 (8)
O1—Zr1—N3—C16	80.3 (4)	C19—C20—C21—O11	−173.7 (7)
O5—Zr1—N3—C16	33.0 (5)	N1—C2—C3—C4	2.7 (9)
O11—Zr1—N3—C16	175.8 (5)	C1—C2—C3—C4	−177.8 (6)
N2—Zr1—N3—C16	−52.7 (5)	C5—C4—C3—C2	−1.2 (11)
N1—Zr1—N3—C16	127.5 (4)	C3—C4—C5—C6	−1.0 (11)
O9—Zr1—N3—C20	175.7 (5)	N1—C6—C5—C4	1.9 (10)
O3—Zr1—N3—C20	32.4 (5)	C7—C6—C5—C4	−175.3 (6)
O7—Zr1—N3—C20	75.7 (4)	N3—C20—C19—C18	−0.1 (11)
O1—Zr1—N3—C20	−102.7 (5)	C21—C20—C19—C18	−179.7 (7)
O5—Zr1—N3—C20	−150.0 (4)	C17—C18—C19—C20	−1.0 (12)
O11—Zr1—N3—C20	−7.2 (4)	C10—C11—C12—C13	−0.3 (10)
N2—Zr1—N3—C20	124.3 (4)	N2—C13—C12—C11	0.4 (10)
N1—Zr1—N3—C20	−55.5 (5)	C14—C13—C12—C11	−179.1 (6)
O9—Zr1—N1—C6	−141.6 (4)	N3—C16—C17—C18	−1.4 (10)
O3—Zr1—N1—C6	0.2 (4)	C15—C16—C17—C18	177.6 (6)
O7—Zr1—N1—C6	40.6 (5)	C19—C18—C17—C16	1.8 (12)
O1—Zr1—N1—C6	179.9 (5)	C12—C11—C10—C9	−0.3 (10)
O5—Zr1—N1—C6	−94.5 (4)	N2—C9—C10—C11	1.0 (10)
O11—Zr1—N1—C6	84.0 (4)	C8—C9—C10—C11	177.5 (6)
N3—Zr1—N1—C6	131.1 (4)	N5—C23—C22—N4	162.0 (6)
N2—Zr1—N1—C6	−48.7 (5)	C24—C23—C22—N4	−77.5 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O14	0.80 (8)	2.10 (9)	2.745 (11)	138 (13)
O13—H13B···O2ⁱ	0.80 (4)	2.10 (8)	2.793 (8)	145 (12)
O14—H14A···O5ⁱⁱ	0.91 (8)	2.11 (9)	2.978 (7)	158 (12)
O14—H14B···O8	0.85 (4)	1.89 (5)	2.731 (9)	171 (14)
O15—H15A···O12	0.98 (9)	1.91 (10)	2.857 (8)	164 (12)
O15—H15B···O1ⁱⁱⁱ	0.83 (4)	2.46 (7)	3.227 (9)	155 (13)
N4—H4A···O10^iv	0.89	1.92	2.791 (8)	165
N4—H4B···O6ⁱⁱ	0.89	2.24	2.851 (7)	125
N4—H4C···O15^v	0.89	2.04	2.864 (10)	154
N5—H5A···O13	0.89	1.94	2.769 (9)	154
N5—H5B···O6^iv	0.89	2.18	2.844 (8)	131
N5—H5C···O4	0.89	1.91	2.776 (8)	163

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

Experimental details

Crystal data
Chemical formula	(C₃H₁₂N₂)[Zr(C₇H₃NO₄)₃]·3H₂O
M_r	716.73
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	10.515 (2), 19.195 (4), 14.149 (3)
β (°)	103.39 (3)
V (Å³)	2778.1 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.25 × 0.15 × 0.15

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)
T_min, T_max	0.915, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	21838, 7481, 5264
R_int	0.133
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.086, 0.206, 1.18
No. of reflections	7481
No. of parameters	427
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.09, −0.77

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
O13—H13A···O14	0.80 (8)	2.10 (9)	2.745 (11)	138 (13)
O13—H13B···O2ⁱ	0.80 (4)	2.10 (8)	2.793 (8)	145 (12)
O14—H14A···O5ⁱⁱ	0.91 (8)	2.11 (9)	2.978 (7)	158 (12)
O14—H14B···O8	0.85 (4)	1.89 (5)	2.731 (9)	171 (14)
O15—H15A···O12	0.98 (9)	1.91 (10)	2.857 (8)	164 (12)
O15—H15B···O1ⁱⁱⁱ	0.83 (4)	2.46 (7)	3.227 (9)	155 (13)
N4—H4A···O10^iv	0.89	1.92	2.791 (8)	164.9
N4—H4B···O6ⁱⁱ	0.89	2.24	2.851 (7)	125.2
N4—H4C···O15^v	0.89	2.04	2.864 (10)	154.4
N5—H5A···O13	0.89	1.94	2.769 (9)	153.9
N5—H5B···O6^iv	0.89	2.18	2.844 (8)	131.3
N5—H5C···O4	0.89	1.91	2.776 (8)	163.4

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

Acknowledgements

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

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