Bis(guanidinium) tris­(pyridine-2,6-dicarboxyl­ato-κ3O2,N,O6)zirconate(II) tetra­hydrate

Tabatabaee, M.; Adineh, M.; Derikvand, Z.; Attar Gharamaleki, J.

doi:10.1107/S1600536812011439

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m462-m463

doi:10.1107/S1600536812011439

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Bis(guanidinium) tris(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)zirconate(II) tetrahydrate

Masoumeh Tabatabaee,^a ^* Mahnaz Adineh,^a Zohreh Derikvand ^b and Jafar Attar Gharamaleki ^c

^aDepartment of Chemistry, Yazd Branch, Islamic Azad University, Yazd, Iran, ^bDepartment of Chemistry, Faculty of Science, Khorramabad Branch, Islamic Azad, University, Khorramabad, Iran, and ^cFaculty of Chemistry, Tarbiat Moallem University, 49 Mofateh Avenue, Tehran, Iran
^*Correspondence e-mail: tabatabaee45m@yahoo.com

(Received 4 March 2012; accepted 15 March 2012; online 24 March 2012)

In the title complex, (CH₆N₃)₂[Zr(C₇H₃NO₄)₃]·4H₂O, the Zr^IV ion lies on a twofold rotation axes and is coordinated by six O and three N atoms of three tridentate pyridine-2,6-dicarboxylate ligands, forming a slightly distorted tricapped trigonal–prismatic geometry. In the crystal, O—H⋯O and N—H⋯O hydrogen bonds link the components into a three-dimensional network.

Related literature

For related structures, see: Aghabozorg et al. (2005 ); Tabatabaee (2010 ); Tabatabaee et al. (2009 , 2011a ,b ,c , 2012 ); Derikvand et al. (2010 ); Attar Gharamaleki et al. (2009 ).

Experimental

Crystal data

(CH₆N₃)₂[Zr(C₇H₃NO₄)₃]·4H₂O
M_r = 778.77
Orthorhombic, P b c n
a = 17.2444 (9) Å
b = 10.8583 (5) Å
c = 16.5268 (8) Å
V = 3094.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 120 K
0.17 × 0.15 × 0.07 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.884, T_max = 0.970
32229 measured reflections
4116 independent reflections
2884 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.146
S = 1.07
4116 reflections
223 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3NA⋯O1	0.77	2.23	3.003 (4)	175
N3—H3NB⋯O2Wⁱ	0.86	2.15	2.930 (4)	150
N4—H4NA⋯O2Wⁱ	0.83	2.04	2.818 (4)	156
N4—H4NB⋯O1Wⁱⁱ	0.78	2.06	2.834 (4)	175
N5—H5NA⋯O2	0.88	1.95	2.828 (4)	171
N5—H5NB⋯O3ⁱⁱⁱ	0.79	2.45	3.143 (4)	148
N5—H5NB⋯O4ⁱⁱⁱ	0.79	2.52	3.171 (4)	141
O1W—H1WA⋯O3^iv	0.84	2.33	3.041 (3)	143
O1W—H1WA⋯O5^iv	0.84	2.38	3.076 (3)	140
O1W—H1WB⋯O6	0.89	1.87	2.761 (3)	175
O2W—H2WA⋯O5^iv	0.86	2.07	2.909 (3)	165
O2W—H2WA⋯O6^iv	0.86	2.57	3.085 (3)	119
O2W—H2WB⋯O4^v	0.94	1.84	2.745 (3)	160
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z; (v) x, y-1, z.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL, DIAMOND (Brandenburg, 1999 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812011439/lh5430sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011439/lh5430Isup2.hkl

checkCIF report

Comment top

In 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 of polycarboxylic acids. Pyridine-2,6-dicarboxylic acid (pydcH₂) is a very important carboxylate derivative and has attracted much interest in coordination chemistry. This is the acid we have utilized widely in our studies (Tabatabaee et al., 2010, 2011a, 2011b, 2011c, 2012; Derikvand et al., 2010; Attar Gharamaleki et al., 2009). In this paper we report the crystal structure of the title complex (I). The Zr^IV ion lies on a twofold rotation axis. The asymmetric unit and the symmetry complete cation is shown in Fig. 1. The Zr^IV atom is coordinated by three tridentate pydc ligands forming a slightly distorted tricapped trigonal prismatic environment (Fig. 2). The Zr—N distances and Zr—O distances are consistent with those found in (pydaH)₂[Zr(pydc)₃].5H₂O (Aghabozorg et al., 2005). In the crystal, O—H···O and N—H···O hydrogen bonds (Table 1) link the components into a three-dimensional network (Fig. 3).

Related literature top

For related structures, see: Aghabozorg et al. (2005); Tabatabaee et al. (2009, 2010, 2011a,b,c, 2012); Derikvand et al. (2010); Attar Gharamaleki et al. (2009).

Experimental top

An aqueous solution of ZrOCl₂.8H₂O, (161 mg, 0.5 mmol) in water (5 ml) was added to a stirring solution of (20 ml) pyridine-2,6-dicarboxylic acid (176 mg, 1 mmol) and guanidine hydrochloride (95 mg, 1 mmol). The reaction mixture was stirred at 298K for 1 h. Colorless crystals of the title compound were obtained after 4 days by slow evaporation of the solvent at room temperature.

Structure description top

For related structures, see: Aghabozorg et al. (2005); Tabatabaee et al. (2009, 2010, 2011a,b,c, 2012); Derikvand et al. (2010); Attar Gharamaleki et al. (2009).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (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), DIAMOND (Brandenburg, 1999) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) with ellipsoids drawn at the 50% probability level. The unlabeled atoms are related by the symmetry operator (-x+1, y, -z+1/2). Only the symmetry unique anions and water molecules are shown.
	Fig. 2. View of the coordination environment of the Zr^IV ion.
	Fig. 3. Part of the crystal structure of (I). The donor to acceptor distances of the hydrogen bonds are shown as dotted lines.

Bis(guanidinium) tris(pyridine-2,6-dicarboxylato- κ³O²,N,O⁶)zirconate(II) tetrahydrate top

Crystal data top

(CH₆N₃)₂[Zr(C₇H₃NO₄)₃]·4H₂O	F(000) = 1592
M_r = 778.77	D_x = 1.672 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4151 reflections
a = 17.2444 (9) Å	θ = 2.3–26.0°
b = 10.8583 (5) Å	µ = 0.45 mm⁻¹
c = 16.5268 (8) Å	T = 120 K
V = 3094.6 (3) Å³	Prism, colorless
Z = 4	0.17 × 0.15 × 0.07 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	4116 independent reflections
Radiation source: normal-focus sealed tube	2884 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
ω scans	θ_max = 29.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −23→23
T_min = 0.884, T_max = 0.970	k = −14→14
32229 measured reflections	l = −22→22

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)] = 0.056	Hydrogen site location: mixed
wR(F²) = 0.146	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0562P)² + 8.430P] where P = (F_o² + 2F_c²)/3
4116 reflections	(Δ/σ)_max < 0.001
223 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

(CH₆N₃)₂[Zr(C₇H₃NO₄)₃]·4H₂O	V = 3094.6 (3) Å³
M_r = 778.77	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 17.2444 (9) Å	µ = 0.45 mm⁻¹
b = 10.8583 (5) Å	T = 120 K
c = 16.5268 (8) Å	0.17 × 0.15 × 0.07 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	4116 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	2884 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.970	R_int = 0.068
32229 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.07	Δρ_max = 0.87 e Å⁻³
4116 reflections	Δρ_min = −0.47 e Å⁻³
223 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
Zr1	0.5000	0.72625 (4)	0.2500	0.01631 (13)
O1	0.38154 (13)	0.6592 (2)	0.28200 (14)	0.0245 (5)
O2	0.25204 (15)	0.6675 (3)	0.27362 (17)	0.0349 (6)
O3	0.54360 (12)	0.8668 (2)	0.16530 (13)	0.0226 (5)
O4	0.53142 (16)	1.0370 (2)	0.09047 (17)	0.0362 (6)
O5	0.47334 (14)	0.6443 (2)	0.12914 (14)	0.0236 (5)
O6	0.42065 (17)	0.4926 (2)	0.05627 (15)	0.0354 (6)
N1	0.40034 (15)	0.8418 (2)	0.18731 (16)	0.0214 (5)
N2	0.5000	0.5072 (3)	0.2500	0.0171 (7)
C1	0.32630 (19)	0.8123 (3)	0.20019 (19)	0.0225 (6)
C2	0.2655 (2)	0.8764 (3)	0.1641 (2)	0.0292 (7)
H2A	0.2131	0.8533	0.1731	0.035*
C3	0.2842 (2)	0.9750 (3)	0.1146 (2)	0.0295 (7)
H3A	0.2441	1.0216	0.0898	0.035*
C4	0.3609 (2)	1.0061 (3)	0.1010 (2)	0.0273 (7)
H4A	0.3743	1.0733	0.0670	0.033*
C5	0.41742 (19)	0.9359 (3)	0.13861 (19)	0.0219 (6)
C6	0.31649 (18)	0.7054 (3)	0.25566 (19)	0.0218 (6)
C7	0.50369 (18)	0.9516 (3)	0.12932 (18)	0.0205 (6)
C8	0.47612 (18)	0.4462 (3)	0.18438 (19)	0.0222 (6)
C9	0.4742 (2)	0.3187 (3)	0.1823 (2)	0.0273 (7)
H9A	0.4557	0.2761	0.1360	0.033*
C10	0.5000	0.2551 (4)	0.2500	0.0284 (10)
H10A	0.5000	0.1676	0.2500	0.034*
C11	0.45375 (19)	0.5307 (3)	0.1163 (2)	0.0240 (6)
N3	0.33875 (17)	0.4432 (3)	0.38628 (19)	0.0312 (7)
H3NA	0.3482	0.5016	0.3616	0.047*
H3NB	0.3752	0.4039	0.4112	0.047*
N4	0.25724 (18)	0.3150 (3)	0.45574 (18)	0.0314 (7)
H4NA	0.2971	0.2749	0.4652	0.047*
H4NB	0.2158	0.2885	0.4626	0.047*
N5	0.20814 (17)	0.4727 (3)	0.3776 (2)	0.0364 (8)
H5NA	0.2166	0.5344	0.3439	0.055*
H5NB	0.1654	0.4517	0.3865	0.055*
C12	0.26720 (19)	0.4098 (3)	0.4060 (2)	0.0268 (7)
O1W	0.39648 (14)	0.2667 (2)	−0.01609 (15)	0.0279 (5)
H1WA	0.4195	0.2642	−0.0607	0.042*
H1WB	0.4026	0.3377	0.0100	0.042*
O2W	0.58669 (15)	0.2479 (2)	0.01935 (16)	0.0310 (6)
H2WA	0.5768	0.2747	−0.0287	0.047*
H2WB	0.5631	0.1722	0.0319	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.0173 (2)	0.0148 (2)	0.0169 (2)	0.000	−0.00061 (15)	0.000
O1	0.0241 (12)	0.0232 (11)	0.0261 (11)	−0.0009 (9)	−0.0003 (9)	0.0031 (9)
O2	0.0217 (12)	0.0369 (15)	0.0462 (15)	−0.0031 (11)	0.0017 (11)	0.0095 (12)
O3	0.0213 (11)	0.0233 (11)	0.0232 (11)	−0.0011 (9)	0.0001 (9)	0.0015 (9)
O4	0.0327 (13)	0.0314 (14)	0.0444 (15)	−0.0070 (11)	−0.0008 (12)	0.0144 (12)
O5	0.0280 (11)	0.0211 (11)	0.0216 (11)	−0.0035 (9)	−0.0030 (9)	0.0003 (9)
O6	0.0521 (16)	0.0249 (12)	0.0292 (13)	−0.0054 (11)	−0.0141 (12)	−0.0004 (10)
N1	0.0231 (13)	0.0206 (13)	0.0205 (13)	−0.0005 (10)	0.0002 (10)	−0.0013 (10)
N2	0.0149 (15)	0.0161 (16)	0.0203 (16)	0.000	0.0013 (13)	0.000
C1	0.0236 (15)	0.0212 (14)	0.0228 (15)	0.0026 (12)	−0.0013 (12)	0.0011 (12)
C2	0.0220 (16)	0.0310 (18)	0.0345 (19)	0.0021 (13)	−0.0010 (14)	0.0036 (15)
C3	0.0256 (17)	0.0336 (18)	0.0294 (17)	0.0077 (14)	−0.0024 (14)	0.0045 (15)
C4	0.0311 (17)	0.0233 (16)	0.0276 (16)	0.0032 (13)	−0.0045 (13)	0.0055 (13)
C5	0.0260 (15)	0.0163 (14)	0.0235 (15)	0.0008 (12)	−0.0029 (12)	−0.0002 (12)
C6	0.0192 (14)	0.0226 (15)	0.0235 (15)	−0.0006 (11)	0.0006 (12)	−0.0015 (12)
C7	0.0258 (15)	0.0177 (13)	0.0179 (13)	−0.0029 (12)	−0.0011 (12)	−0.0001 (11)
C8	0.0199 (14)	0.0238 (16)	0.0230 (15)	−0.0014 (12)	0.0018 (11)	−0.0023 (13)
C9	0.0365 (18)	0.0214 (16)	0.0239 (16)	−0.0030 (14)	−0.0006 (13)	−0.0025 (13)
C10	0.040 (3)	0.020 (2)	0.025 (2)	0.000	−0.003 (2)	0.000
C11	0.0244 (15)	0.0240 (16)	0.0235 (15)	−0.0002 (12)	−0.0027 (12)	−0.0022 (12)
N3	0.0240 (14)	0.0321 (16)	0.0375 (17)	−0.0040 (12)	0.0005 (12)	0.0113 (13)
N4	0.0269 (15)	0.0324 (16)	0.0348 (16)	−0.0033 (12)	0.0041 (12)	0.0093 (13)
N5	0.0208 (14)	0.0441 (19)	0.0444 (19)	−0.0014 (13)	0.0018 (13)	0.0160 (15)
C12	0.0275 (17)	0.0300 (17)	0.0228 (16)	−0.0002 (14)	−0.0002 (12)	0.0000 (13)
O1W	0.0299 (12)	0.0258 (12)	0.0280 (12)	−0.0058 (10)	0.0040 (10)	−0.0057 (10)
O2W	0.0336 (13)	0.0273 (12)	0.0323 (13)	−0.0075 (10)	−0.0053 (11)	0.0050 (10)

Geometric parameters (Å, º) top

Zr1—O3	2.203 (2)	C3—H3A	0.9500
Zr1—O3ⁱ	2.203 (2)	C4—C5	1.384 (4)
Zr1—O1ⁱ	2.232 (2)	C4—H4A	0.9500
Zr1—O1	2.232 (2)	C5—C7	1.505 (4)
Zr1—O5	2.234 (2)	C8—C9	1.384 (5)
Zr1—O5ⁱ	2.234 (2)	C8—C11	1.503 (5)
Zr1—N1ⁱ	2.366 (3)	C9—C10	1.388 (4)
Zr1—N1	2.366 (3)	C9—H9A	0.9500
Zr1—N2	2.378 (4)	C10—C9ⁱ	1.388 (4)
O1—C6	1.304 (4)	C10—H10A	0.9500
O2—C6	1.222 (4)	N3—C12	1.327 (4)
O3—C7	1.294 (4)	N3—H3NA	0.7713
O4—C7	1.225 (4)	N3—H3NB	0.8647
O5—C11	1.297 (4)	N4—C12	1.329 (4)
O6—C11	1.217 (4)	N4—H4NA	0.8289
N1—C1	1.333 (4)	N4—H4NB	0.7790
N1—C5	1.334 (4)	N5—C12	1.312 (4)
N2—C8	1.336 (4)	N5—H5NA	0.8832
N2—C8ⁱ	1.336 (4)	N5—H5NB	0.7861
C1—C2	1.393 (5)	O1W—H1WA	0.8370
C1—C6	1.489 (5)	O1W—H1WB	0.8899
C2—C3	1.386 (5)	O2W—H2WA	0.8620
C2—H2A	0.9500	O2W—H2WB	0.9408
C3—C4	1.382 (5)

O3—Zr1—O3ⁱ	92.30 (12)	N1—C1—C6	113.2 (3)
O3—Zr1—O1ⁱ	76.29 (8)	C2—C1—C6	124.6 (3)
O3ⁱ—Zr1—O1ⁱ	133.53 (8)	C3—C2—C1	117.6 (3)
O3—Zr1—O1	133.53 (8)	C3—C2—H2A	121.2
O3ⁱ—Zr1—O1	76.29 (8)	C1—C2—H2A	121.2
O1ⁱ—Zr1—O1	141.94 (12)	C4—C3—C2	120.5 (3)
O3—Zr1—O5	77.18 (8)	C4—C3—H3A	119.8
O3ⁱ—Zr1—O5	140.67 (8)	C2—C3—H3A	119.8
O1ⁱ—Zr1—O5	81.18 (9)	C3—C4—C5	117.8 (3)
O1—Zr1—O5	83.89 (9)	C3—C4—H4A	121.1
O3—Zr1—O5ⁱ	140.67 (8)	C5—C4—H4A	121.1
O3ⁱ—Zr1—O5ⁱ	77.18 (8)	N1—C5—C4	122.5 (3)
O1ⁱ—Zr1—O5ⁱ	83.89 (9)	N1—C5—C7	111.5 (3)
O1—Zr1—O5ⁱ	81.18 (9)	C4—C5—C7	126.0 (3)
O5—Zr1—O5ⁱ	133.07 (12)	O2—C6—O1	124.9 (3)
O3—Zr1—N1ⁱ	70.31 (8)	O2—C6—C1	121.0 (3)
O3ⁱ—Zr1—N1ⁱ	66.58 (8)	O1—C6—C1	114.1 (3)
O1ⁱ—Zr1—N1ⁱ	67.17 (9)	O4—C7—O3	124.9 (3)
O1—Zr1—N1ⁱ	137.20 (9)	O4—C7—C5	121.7 (3)
O5—Zr1—N1ⁱ	138.75 (9)	O3—C7—C5	113.4 (3)
O5ⁱ—Zr1—N1ⁱ	70.75 (9)	N2—C8—C9	121.6 (3)
O3—Zr1—N1	66.58 (8)	N2—C8—C11	112.6 (3)
O3ⁱ—Zr1—N1	70.31 (8)	C9—C8—C11	125.9 (3)
O1ⁱ—Zr1—N1	137.20 (9)	C8—C9—C10	118.1 (3)
O1—Zr1—N1	67.17 (9)	C8—C9—H9A	121.0
O5—Zr1—N1	70.75 (9)	C10—C9—H9A	121.0
O5ⁱ—Zr1—N1	138.75 (9)	C9—C10—C9ⁱ	120.2 (4)
N1ⁱ—Zr1—N1	115.98 (13)	C9—C10—H10A	119.9
O3—Zr1—N2	133.85 (6)	C9ⁱ—C10—H10A	119.9
O3ⁱ—Zr1—N2	133.85 (6)	O6—C11—O5	125.4 (3)
O1ⁱ—Zr1—N2	70.97 (6)	O6—C11—C8	121.6 (3)
O1—Zr1—N2	70.97 (6)	O5—C11—C8	113.1 (3)
O5—Zr1—N2	66.54 (6)	C12—N3—H3NA	123.4
O5ⁱ—Zr1—N2	66.54 (6)	C12—N3—H3NB	115.1
N1ⁱ—Zr1—N2	122.01 (6)	H3NA—N3—H3NB	120.4
N1—Zr1—N2	122.01 (6)	C12—N4—H4NA	114.6
C6—O1—Zr1	125.7 (2)	C12—N4—H4NB	119.6
C7—O3—Zr1	127.11 (19)	H4NA—N4—H4NB	122.8
C11—O5—Zr1	125.4 (2)	C12—N5—H5NA	119.5
C1—N1—C5	119.5 (3)	C12—N5—H5NB	120.7
C1—N1—Zr1	119.9 (2)	H5NA—N5—H5NB	119.5
C5—N1—Zr1	120.7 (2)	N5—C12—N3	119.5 (3)
C8—N2—C8ⁱ	120.5 (4)	N5—C12—N4	121.6 (3)
C8—N2—Zr1	119.8 (2)	N3—C12—N4	118.9 (3)
C8ⁱ—N2—Zr1	119.8 (2)	H1WA—O1W—H1WB	113.4
N1—C1—C2	122.2 (3)	H2WA—O2W—H2WB	114.3

O3—Zr1—O1—C6	−5.4 (3)	O3—Zr1—N2—C8ⁱ	130.96 (17)
O3ⁱ—Zr1—O1—C6	74.6 (2)	O3ⁱ—Zr1—N2—C8ⁱ	−49.04 (17)
O1ⁱ—Zr1—O1—C6	−138.4 (3)	O1ⁱ—Zr1—N2—C8ⁱ	83.72 (17)
O5—Zr1—O1—C6	−71.2 (3)	O1—Zr1—N2—C8ⁱ	−96.28 (17)
O5ⁱ—Zr1—O1—C6	153.4 (3)	O5—Zr1—N2—C8ⁱ	172.17 (17)
N1ⁱ—Zr1—O1—C6	104.6 (3)	O5ⁱ—Zr1—N2—C8ⁱ	−7.83 (17)
N1—Zr1—O1—C6	0.5 (2)	N1ⁱ—Zr1—N2—C8ⁱ	38.12 (17)
N2—Zr1—O1—C6	−138.4 (3)	N1—Zr1—N2—C8ⁱ	−141.88 (17)
O3ⁱ—Zr1—O3—C7	−59.3 (2)	C5—N1—C1—C2	0.3 (5)
O1ⁱ—Zr1—O3—C7	166.3 (3)	Zr1—N1—C1—C2	−179.3 (2)
O1—Zr1—O3—C7	13.9 (3)	C5—N1—C1—C6	179.9 (3)
O5—Zr1—O3—C7	82.4 (2)	Zr1—N1—C1—C6	0.4 (4)
O5ⁱ—Zr1—O3—C7	−131.8 (2)	N1—C1—C2—C3	−1.2 (5)
N1ⁱ—Zr1—O3—C7	−123.4 (3)	C6—C1—C2—C3	179.2 (3)
N1—Zr1—O3—C7	8.1 (2)	C1—C2—C3—C4	1.1 (5)
N2—Zr1—O3—C7	120.7 (2)	C2—C3—C4—C5	−0.2 (5)
O3—Zr1—O5—C11	166.3 (3)	C1—N1—C5—C4	0.7 (5)
O3ⁱ—Zr1—O5—C11	−116.0 (3)	Zr1—N1—C5—C4	−179.7 (2)
O1ⁱ—Zr1—O5—C11	88.4 (3)	C1—N1—C5—C7	−177.9 (3)
O1—Zr1—O5—C11	−56.4 (3)	Zr1—N1—C5—C7	1.7 (3)
O5ⁱ—Zr1—O5—C11	15.4 (2)	C3—C4—C5—N1	−0.7 (5)
N1ⁱ—Zr1—O5—C11	127.9 (2)	C3—C4—C5—C7	177.7 (3)
N1—Zr1—O5—C11	−124.3 (3)	Zr1—O1—C6—O2	179.8 (3)
N2—Zr1—O5—C11	15.4 (2)	Zr1—O1—C6—C1	−0.4 (4)
O3—Zr1—N1—C1	175.0 (3)	N1—C1—C6—O2	179.8 (3)
O3ⁱ—Zr1—N1—C1	−83.4 (2)	C2—C1—C6—O2	−0.6 (5)
O1ⁱ—Zr1—N1—C1	143.0 (2)	N1—C1—C6—O1	0.0 (4)
O1—Zr1—N1—C1	−0.4 (2)	C2—C1—C6—O1	179.7 (3)
O5—Zr1—N1—C1	91.0 (2)	Zr1—O3—C7—O4	170.7 (2)
O5ⁱ—Zr1—N1—C1	−43.3 (3)	Zr1—O3—C7—C5	−9.9 (4)
N1ⁱ—Zr1—N1—C1	−133.3 (3)	N1—C5—C7—O4	−176.1 (3)
N2—Zr1—N1—C1	46.7 (3)	C4—C5—C7—O4	5.4 (5)
O3—Zr1—N1—C5	−4.5 (2)	N1—C5—C7—O3	4.5 (4)
O3ⁱ—Zr1—N1—C5	97.1 (2)	C4—C5—C7—O3	−174.0 (3)
O1ⁱ—Zr1—N1—C5	−36.6 (3)	C8ⁱ—N2—C8—C9	0.9 (2)
O1—Zr1—N1—C5	−180.0 (3)	Zr1—N2—C8—C9	−179.1 (2)
O5—Zr1—N1—C5	−88.5 (2)	C8ⁱ—N2—C8—C11	−178.4 (3)
O5ⁱ—Zr1—N1—C5	137.1 (2)	Zr1—N2—C8—C11	1.6 (3)
N1ⁱ—Zr1—N1—C5	47.2 (2)	N2—C8—C9—C10	−1.8 (5)
N2—Zr1—N1—C5	−132.8 (2)	C11—C8—C9—C10	177.4 (3)
O3—Zr1—N2—C8	−49.04 (17)	C8—C9—C10—C9ⁱ	0.9 (2)
O3ⁱ—Zr1—N2—C8	130.96 (17)	Zr1—O5—C11—O6	160.2 (3)
O1ⁱ—Zr1—N2—C8	−96.28 (17)	Zr1—O5—C11—C8	−19.8 (4)
O1—Zr1—N2—C8	83.72 (17)	N2—C8—C11—O6	−169.6 (3)
O5—Zr1—N2—C8	−7.83 (17)	C9—C8—C11—O6	11.1 (5)
O5ⁱ—Zr1—N2—C8	172.17 (17)	N2—C8—C11—O5	10.4 (4)
N1ⁱ—Zr1—N2—C8	−141.88 (17)	C9—C8—C11—O5	−168.9 (3)
N1—Zr1—N2—C8	38.12 (17)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3NA···O1	0.77	2.23	3.003 (4)	175
N3—H3NB···O2Wⁱ	0.86	2.15	2.930 (4)	150
N4—H4NA···O2Wⁱ	0.83	2.04	2.818 (4)	156
N4—H4NB···O1Wⁱⁱ	0.78	2.06	2.834 (4)	175
N5—H5NA···O2	0.88	1.95	2.828 (4)	171
N5—H5NB···O3ⁱⁱⁱ	0.79	2.45	3.143 (4)	148
N5—H5NB···O4ⁱⁱⁱ	0.79	2.52	3.171 (4)	141
O1W—H1WA···O3^iv	0.84	2.33	3.041 (3)	143
O1W—H1WA···O5^iv	0.84	2.38	3.076 (3)	140
O1W—H1WB···O6	0.89	1.87	2.761 (3)	175
O2W—H2WA···O5^iv	0.86	2.07	2.909 (3)	165
O2W—H2WA···O6^iv	0.86	2.57	3.085 (3)	119
O2W—H2WB···O4^v	0.94	1.84	2.745 (3)	160

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

Experimental details

Crystal data
Chemical formula	(CH₆N₃)₂[Zr(C₇H₃NO₄)₃]·4H₂O
M_r	778.77
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	120
a, b, c (Å)	17.2444 (9), 10.8583 (5), 16.5268 (8)
V (Å³)	3094.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.17 × 0.15 × 0.07

Data collection
Diffractometer	Bruker SMART 1000 CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.884, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	32229, 4116, 2884
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.146, 1.07
No. of reflections	4116
No. of parameters	223
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.47

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3NA···O1	0.77	2.23	3.003 (4)	175
N3—H3NB···O2Wⁱ	0.86	2.15	2.930 (4)	150
N4—H4NA···O2Wⁱ	0.83	2.04	2.818 (4)	156
N4—H4NB···O1Wⁱⁱ	0.78	2.06	2.834 (4)	175
N5—H5NA···O2	0.88	1.95	2.828 (4)	171
N5—H5NB···O3ⁱⁱⁱ	0.79	2.45	3.143 (4)	148
N5—H5NB···O4ⁱⁱⁱ	0.79	2.52	3.171 (4)	141
O1W—H1WA···O3^iv	0.84	2.33	3.041 (3)	143
O1W—H1WA···O5^iv	0.84	2.38	3.076 (3)	140
O1W—H1WB···O6	0.89	1.87	2.761 (3)	175
O2W—H2WA···O5^iv	0.86	2.07	2.909 (3)	165
O2W—H2WA···O6^iv	0.86	2.57	3.085 (3)	119
O2W—H2WB···O4^v	0.94	1.84	2.745 (3)	160

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

Acknowledgements

The authors wish to express their deepest appreciation to the late Professor Dr. H Aghabozorg who has inspired, advised and assisted during this study.

References

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