(4-Oxido-2-oxo-1,2-dihydro­pyrimidine-5-carboxyl­ato-κ2O4,O5)(4-oxido-2-oxo-1,2-dihydro­pyrimidin-3-ium-5-carboxyl­ato-κ2O4,O5)bis­(1,10-phenanthroline-κ2N,N′)gadolinium(III) dihydrate

Xiong, W.; Xing, H.; Su, Y.; Chen, Z.

doi:10.1107/S1600536808025713

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Pages m1168-m1169

doi:10.1107/S1600536808025713

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(4-Oxido-2-oxo-1,2-dihydropyrimidine-5-carboxylato-κ²O⁴,O⁵)(4-oxido-2-oxo-1,2-dihydropyrimidin-3-ium-5-carboxylato-κ²O⁴,O⁵)bis(1,10-phenanthroline-κ²N,N′)gadolinium(III) dihydrate

Wei Xiong,^a Huihui Xing,^a Yan Su ^a and Zilu Chen ^a ^*

^aCollege of Chemistry and Chemical Engineering, Guangxi Normal University, Yucai Road 15, Guilin 541004, People's Republic of China
^*Correspondence e-mail: chenziluczl@yahoo.co.uk

(Received 25 July 2008; accepted 9 August 2008; online 16 August 2008)

The title compound, [Gd(C₅H₂N₂O₄)(C₅H₃N₂O₄)(C₁₂H₈N₂)₂]·2H₂O, was obtained from a solvothermal reaction of 2,4-dihydroxypyrimidine-5-carboxylic acid (H₃iso), GdCl₃·6H₂O and 1,10-phenanthroline (phen). The Gd^III ion is located on a twofold rotation axis and is coordinated by four N atoms from two chelating phen ligands and four O atoms (5-carboxylate and 4-oxido O atoms) from H₂iso⁻ and Hiso²⁻ ligands. The molecules are linked into a three-dimensional network by N—H⋯O, N—H⋯N and O—H⋯O hydrogen bonds. The H atom involved in an N—H⋯N hydrogen bond is disordered around a twofold rotation axis with half occupancy.

Related literature

For isostructural lanthanide complexes with 2,4-dioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylic acid, see: Sun & Jin (2004a ,b ); Xing et al. (2008a ). For related literature, see: Hueso-Ureña et al. (1993 , 1996 ); Baran et al. (1996 ); Luo et al. (2002 ); Maistralis et al. (1991 , 1992 ); Xing et al. (2008b ).

Experimental

Crystal data

[Gd(C₅H₂N₂O₄)(C₅H₃N₂O₄)(C₁₂H₈N₂)₂]·2H₂O
M_r = 862.87
Monoclinic, C 2/c
a = 17.158 (8) Å
b = 14.504 (7) Å
c = 13.197 (7) Å
β = 99.955 (5)°
V = 3235 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.13 mm⁻¹
T = 273 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.676, T_max = 0.816
9884 measured reflections
3686 independent reflections
3212 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.064
S = 1.05
3686 reflections
240 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Gd1—O1	2.288 (2)
Gd1—O3	2.344 (2)
Gd1—N3	2.586 (3)
Gd1—N4	2.603 (3)

O1—Gd1—O1ⁱ	88.22 (11)
O1—Gd1—O3ⁱ	82.54 (8)
O1—Gd1—O3	73.65 (8)
O3ⁱ—Gd1—O3	146.71 (11)
O1—Gd1—N3ⁱ	148.84 (8)
O3—Gd1—N3ⁱ	135.03 (8)
O1—Gd1—N3	105.26 (9)
O3—Gd1—N3	74.86 (8)
O1—Gd1—N4	80.80 (8)
O3—Gd1—N4	122.38 (8)
N3—Gd1—N4	63.39 (8)
O1—Gd1—N4ⁱ	147.64 (8)
O3—Gd1—N4ⁱ	74.79 (8)
N3—Gd1—N4ⁱ	72.83 (8)
N4—Gd1—N4ⁱ	123.04 (11)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱⁱ	0.86	2.04	2.898 (3)	178
N1—H1⋯O1ⁱⁱ	0.86	2.60	3.160 (4)	124
N2—H2⋯N2ⁱⁱⁱ	0.86	1.81	2.669 (5)	174
O5—H5A⋯O4^iv	0.85	2.14	2.970 (4)	164
O5—H5B⋯O2^v	0.85	2.14	2.985 (4)	173
Symmetry codes: (ii) $[x, -y, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z]$ ; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (v) x, y+1, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025713/ci2644sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025713/ci2644Isup2.hkl

checkCIF report

Comment top

2,4-Dihydroxypyrimidine-5-carboxylic acid has been extensively used in the preparation of metal complexes because of its versatile coordination modes. It can connect metal ions to form robust networks or some porous coordination polymers. Though various transition metal complexes with 2,4-dihydroxypyrimidine-5-carboxylate have been reported (Maistralis et al., 1991, 1992; Hueso-Ureña et al., 1993, 1996; Baran et al., 1996; Luo et al., 2002; Sun & Jin 2004a), lanthanide complexes are very limited. Only lanthanide complexes of Yb^III, Tb^III, Pr^III, Eu^III, Nd^III and Er^III have been reported (Sun & Jin 2004b; Xing et al.,2008a,b). In this paper, we report a new Gd^III complex, Gd(Hiso)(H₂iso)(phen)₂.2H₂O, (I).

In compound (I), the Gd^III atom is located on a twofold rotation axis and coordinated in a square antiprismatic geometry by four N atoms belonging to two chelating phen ligands and four O atoms from one monovalent and one divalent 2,4-dihydroxypyrimidine-5-carboxylate anions. The Gd—O bond lengths [2.288 (2) and 2.334 (2) Å] are shorter than the Gd—N bond lengths [2.586 (3) and 2.603 (3) Å].

The molecules are linked into a three-dimensional network by N—H···O, N—H···N and O—H···O hydrogen bonds (Table 2).

Related literature top

For isostructural lanthanide complexes with 2,4-dioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylic acid, see: Sun & Jin (2004a,b); Xing et al. (2008a). For related literature, see: Hueso-Ureña et al. (1993, 1996); Baran et al. (1996); Luo et al. (2002); Maistralis et al. (1991, 1992); Xing et al. (2008b).

Experimental top

A mixture of 2,4-dihydroxypyrimidine-5-carboxylic acid (0.0312 g, 0.2 mmol), GdCl₃.6H₂O (0.0743 g, 0.2 mmol), phen.H₂O (0.0396 g, 0.2 mmol), NaOH (0.008 g, 0.2 mmol) and water (15 ml) was sealed in a 25 ml Teflon-lined stainless-steel reactor and heated at 383 K for 120 h. It was then cooled over a period of 48 h, light yellow crystals were isolated in 80% yield. Elemental analysis for C₃₄H₂₅GdN₈O₁₀, calculated: C 47.32, H 2.92, N 12.98%; found: C 47.59,H 2.96, N 13.24%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecular structure of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Unlabelled atoms are related to labelled atoms by the symmetry operation (1-x, y, 1/2-z).

(4-Oxido-2-oxo-1,2-dihydropyrimidine-5-carboxylato-κ²O⁴,O⁵)(4- oxido-2-oxo-1,2-dihydropyrimidin-3-ium-5-carboxylato- κ²O⁴,O⁵)bis(1,10-phenanthroline-κ²N,N')gadolinium(III) dihydrate top

Crystal data top

[Gd(C₅H₂N₂O₄)(C₅H₃N₂O₄)(C₁₂H₈N₂)₂]·2H₂O	F(000) = 1716
M_r = 862.87	D_x = 1.772 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3284 reflections
a = 17.158 (8) Å	θ = 2.3–25.5°
b = 14.504 (7) Å	µ = 2.13 mm⁻¹
c = 13.197 (7) Å	T = 273 K
β = 99.955 (5)°	Block, colourless
V = 3235 (3) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3686 independent reflections
Radiation source: fine-focus sealed tube	3212 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −21→22
T_min = 0.676, T_max = 0.816	k = −18→13
9884 measured reflections	l = −17→16

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0258P)²] where P = (F_o² + 2F_c²)/3
3686 reflections	(Δ/σ)_max = 0.001
240 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

[Gd(C₅H₂N₂O₄)(C₅H₃N₂O₄)(C₁₂H₈N₂)₂]·2H₂O	V = 3235 (3) Å³
M_r = 862.87	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.158 (8) Å	µ = 2.13 mm⁻¹
b = 14.504 (7) Å	T = 273 K
c = 13.197 (7) Å	0.20 × 0.10 × 0.10 mm
β = 99.955 (5)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3686 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	3212 reflections with I > 2σ(I)
T_min = 0.676, T_max = 0.816	R_int = 0.039
9884 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.05	Δρ_max = 0.74 e Å⁻³
3686 reflections	Δρ_min = −0.65 e Å⁻³
240 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	Occ. (<1)
Gd1	0.5000	0.111515 (14)	0.2500	0.02254 (7)
O1	0.42801 (12)	−0.00176 (14)	0.31169 (16)	0.0329 (5)
O2	0.34603 (14)	−0.11272 (15)	0.33997 (16)	0.0352 (5)
O3	0.40327 (12)	0.06523 (14)	0.11160 (16)	0.0320 (5)
O4	0.26936 (15)	−0.11830 (15)	−0.13464 (17)	0.0424 (6)
N1	0.33231 (15)	−0.02639 (17)	−0.00642 (19)	0.0296 (6)
H1	0.3371	0.0157	−0.0508	0.035*
N2	0.28238 (16)	−0.16877 (18)	0.0304 (2)	0.0361 (7)
H2	0.2589	−0.2201	0.0125	0.043*	0.50
N3	0.40482 (14)	0.25042 (17)	0.2136 (2)	0.0300 (6)
N4	0.46494 (14)	0.19709 (17)	0.40957 (19)	0.0282 (6)
C1	0.34878 (17)	−0.0740 (2)	0.1674 (2)	0.0248 (7)
C2	0.36429 (17)	−0.0080 (2)	0.0939 (2)	0.0251 (7)
C3	0.29303 (19)	−0.1061 (2)	−0.0434 (2)	0.0304 (7)
C4	0.3080 (2)	−0.1512 (2)	0.1292 (2)	0.0348 (8)
H4	0.2973	−0.1949	0.1765	0.042*
C5	0.37526 (17)	−0.0627 (2)	0.2800 (2)	0.0248 (6)
C6	0.37014 (18)	0.2746 (2)	0.1201 (3)	0.0372 (8)
H6	0.3689	0.2319	0.0672	0.045*
C7	0.3352 (2)	0.3608 (3)	0.0960 (3)	0.0475 (10)
H7	0.3113	0.3747	0.0290	0.057*
C8	0.3372 (2)	0.4239 (3)	0.1725 (3)	0.0499 (10)
H8	0.3157	0.4822	0.1577	0.060*
C9	0.3710 (2)	0.4014 (2)	0.2728 (3)	0.0428 (9)
C10	0.3742 (2)	0.4633 (3)	0.3580 (4)	0.0592 (12)
H10	0.3547	0.5229	0.3461	0.071*
C11	0.4042 (3)	0.4380 (3)	0.4535 (4)	0.0618 (12)
H11	0.4056	0.4803	0.5068	0.074*
C12	0.4346 (2)	0.3467 (3)	0.4763 (3)	0.0442 (9)
C13	0.4638 (2)	0.3150 (3)	0.5755 (3)	0.0577 (11)
H13	0.4648	0.3543	0.6314	0.069*
C14	0.4906 (2)	0.2274 (3)	0.5910 (3)	0.0510 (10)
H14	0.5088	0.2056	0.6571	0.061*
C15	0.49028 (19)	0.1703 (3)	0.5054 (2)	0.0359 (8)
H15	0.5089	0.1103	0.5166	0.043*
C16	0.43530 (18)	0.2836 (2)	0.3944 (2)	0.0298 (7)
C17	0.40366 (18)	0.3123 (2)	0.2911 (3)	0.0317 (7)
O5	0.3084 (2)	0.6863 (2)	0.3396 (2)	0.0901 (11)
H5A	0.2777	0.6708	0.2847	0.135*
H5B	0.3166	0.7439	0.3441	0.135*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Gd1	0.02861 (12)	0.01718 (12)	0.01966 (12)	0.000	−0.00192 (8)	0.000
O1	0.0440 (13)	0.0318 (13)	0.0208 (11)	−0.0131 (11)	−0.0007 (10)	0.0008 (9)
O2	0.0496 (14)	0.0348 (13)	0.0209 (11)	−0.0118 (11)	0.0055 (10)	0.0019 (10)
O3	0.0427 (13)	0.0250 (12)	0.0243 (12)	−0.0113 (10)	−0.0055 (10)	0.0032 (9)
O4	0.0627 (16)	0.0363 (14)	0.0217 (12)	−0.0031 (12)	−0.0108 (11)	−0.0055 (10)
N1	0.0409 (15)	0.0272 (15)	0.0179 (13)	−0.0076 (12)	−0.0023 (11)	0.0023 (11)
N2	0.0533 (18)	0.0244 (15)	0.0264 (15)	−0.0114 (13)	−0.0043 (13)	−0.0024 (12)
N3	0.0299 (14)	0.0263 (15)	0.0319 (15)	0.0024 (11)	0.0000 (12)	0.0012 (11)
N4	0.0324 (14)	0.0271 (14)	0.0244 (14)	0.0016 (11)	0.0028 (11)	0.0010 (11)
C1	0.0306 (16)	0.0229 (16)	0.0197 (15)	−0.0035 (13)	0.0005 (13)	0.0026 (12)
C2	0.0286 (16)	0.0229 (16)	0.0215 (16)	0.0005 (13)	−0.0022 (13)	−0.0024 (12)
C3	0.0350 (17)	0.0259 (17)	0.0268 (17)	0.0014 (14)	−0.0045 (14)	−0.0039 (14)
C4	0.049 (2)	0.0291 (18)	0.0247 (17)	−0.0116 (16)	0.0025 (15)	0.0013 (14)
C5	0.0331 (17)	0.0219 (16)	0.0191 (15)	−0.0014 (13)	0.0031 (13)	−0.0010 (12)
C6	0.0365 (18)	0.039 (2)	0.0339 (19)	0.0071 (16)	−0.0002 (15)	0.0067 (15)
C7	0.043 (2)	0.051 (2)	0.047 (2)	0.0128 (18)	0.0026 (18)	0.0207 (19)
C8	0.049 (2)	0.033 (2)	0.068 (3)	0.0107 (18)	0.010 (2)	0.019 (2)
C9	0.040 (2)	0.028 (2)	0.062 (3)	0.0083 (15)	0.0133 (18)	0.0040 (17)
C10	0.069 (3)	0.030 (2)	0.079 (3)	0.016 (2)	0.015 (2)	−0.006 (2)
C11	0.077 (3)	0.037 (2)	0.071 (3)	0.014 (2)	0.013 (3)	−0.025 (2)
C12	0.050 (2)	0.039 (2)	0.045 (2)	0.0016 (18)	0.0112 (18)	−0.0138 (18)
C13	0.063 (3)	0.068 (3)	0.043 (2)	0.007 (2)	0.010 (2)	−0.023 (2)
C14	0.054 (2)	0.069 (3)	0.029 (2)	0.012 (2)	0.0063 (18)	−0.0081 (19)
C15	0.0372 (18)	0.043 (2)	0.0270 (18)	0.0053 (16)	0.0051 (15)	0.0013 (15)
C16	0.0294 (17)	0.0257 (17)	0.0348 (19)	0.0005 (13)	0.0067 (14)	−0.0027 (14)
C17	0.0271 (16)	0.0278 (18)	0.041 (2)	0.0021 (13)	0.0089 (15)	0.0027 (15)
O5	0.133 (3)	0.051 (2)	0.070 (2)	0.000 (2)	−0.027 (2)	0.0100 (16)

Geometric parameters (Å, º) top

Gd1—O1	2.288 (2)	C1—C5	1.485 (4)
Gd1—O1ⁱ	2.288 (2)	C4—H4	0.93
Gd1—O3ⁱ	2.344 (2)	C6—C7	1.399 (5)
Gd1—O3	2.344 (2)	C6—H6	0.93
Gd1—N3ⁱ	2.586 (3)	C7—C8	1.358 (6)
Gd1—N3	2.586 (3)	C7—H7	0.93
Gd1—N4	2.603 (3)	C8—C9	1.389 (5)
Gd1—N4ⁱ	2.603 (3)	C8—H8	0.93
O1—C5	1.282 (3)	C9—C17	1.414 (4)
O2—C5	1.242 (3)	C9—C10	1.432 (6)
O3—C2	1.256 (3)	C10—C11	1.329 (6)
O4—C3	1.216 (4)	C10—H10	0.93
N1—C2	1.369 (4)	C11—C12	1.435 (6)
N1—C3	1.383 (4)	C11—H11	0.93
N1—H1	0.86	C12—C13	1.396 (5)
N2—C4	1.327 (4)	C12—C16	1.417 (5)
N2—C3	1.367 (4)	C13—C14	1.355 (5)
N2—H2	0.86	C13—H13	0.93
N3—C6	1.322 (4)	C14—C15	1.399 (5)
N3—C17	1.364 (4)	C14—H14	0.93
N4—C15	1.323 (4)	C15—H15	0.93
N4—C16	1.356 (4)	C16—C17	1.439 (4)
C1—C4	1.369 (4)	O5—H5A	0.85
C1—C2	1.421 (4)	O5—H5B	0.85

O1—Gd1—O1ⁱ	88.22 (11)	N1—C2—C1	116.0 (3)
O1—Gd1—O3ⁱ	82.54 (8)	O4—C3—N2	123.0 (3)
O1ⁱ—Gd1—O3ⁱ	73.65 (8)	O4—C3—N1	122.0 (3)
O1—Gd1—O3	73.65 (8)	N2—C3—N1	114.9 (3)
O1ⁱ—Gd1—O3	82.54 (8)	N2—C4—C1	125.5 (3)
O3ⁱ—Gd1—O3	146.71 (11)	N2—C4—H4	117.3
O1—Gd1—N3ⁱ	148.84 (8)	C1—C4—H4	117.3
O1ⁱ—Gd1—N3ⁱ	105.26 (9)	O2—C5—O1	122.3 (3)
O3ⁱ—Gd1—N3ⁱ	74.86 (8)	O2—C5—C1	119.0 (3)
O3—Gd1—N3ⁱ	135.03 (8)	O1—C5—C1	118.6 (3)
O1—Gd1—N3	105.26 (9)	N3—C6—C7	123.7 (3)
O1ⁱ—Gd1—N3	148.84 (8)	N3—C6—H6	118.1
O3ⁱ—Gd1—N3	135.03 (8)	C7—C6—H6	118.1
O3—Gd1—N3	74.86 (8)	C8—C7—C6	118.6 (4)
N3ⁱ—Gd1—N3	77.63 (12)	C8—C7—H7	120.7
O1—Gd1—N4	80.80 (8)	C6—C7—H7	120.7
O1ⁱ—Gd1—N4	147.64 (8)	C7—C8—C9	120.2 (4)
O3ⁱ—Gd1—N4	74.79 (8)	C7—C8—H8	119.9
O3—Gd1—N4	122.38 (8)	C9—C8—H8	119.9
N3ⁱ—Gd1—N4	72.83 (8)	C8—C9—C17	117.7 (4)
N3—Gd1—N4	63.39 (8)	C8—C9—C10	123.7 (4)
O1—Gd1—N4ⁱ	147.64 (8)	C17—C9—C10	118.6 (4)
O1ⁱ—Gd1—N4ⁱ	80.80 (8)	C11—C10—C9	121.9 (4)
O3ⁱ—Gd1—N4ⁱ	122.38 (8)	C11—C10—H10	119.1
O3—Gd1—N4ⁱ	74.79 (8)	C9—C10—H10	119.1
N3ⁱ—Gd1—N4ⁱ	63.39 (8)	C10—C11—C12	121.4 (4)
N3—Gd1—N4ⁱ	72.83 (8)	C10—C11—H11	119.3
N4—Gd1—N4ⁱ	123.04 (11)	C12—C11—H11	119.3
C5—O1—Gd1	140.60 (19)	C13—C12—C16	116.9 (3)
C2—O3—Gd1	132.05 (19)	C13—C12—C11	124.0 (4)
C2—N1—C3	126.4 (3)	C16—C12—C11	119.1 (4)
C2—N1—H1	116.8	C14—C13—C12	120.5 (4)
C3—N1—H1	116.8	C14—C13—H13	119.7
C4—N2—C3	120.6 (3)	C12—C13—H13	119.7
C4—N2—H2	119.7	C13—C14—C15	118.7 (4)
C3—N2—H2	119.7	C13—C14—H14	120.7
C6—N3—C17	117.6 (3)	C15—C14—H14	120.7
C6—N3—Gd1	123.3 (2)	N4—C15—C14	123.6 (3)
C17—N3—Gd1	117.6 (2)	N4—C15—H15	118.2
C15—N4—C16	117.7 (3)	C14—C15—H15	118.2
C15—N4—Gd1	123.4 (2)	N4—C16—C12	122.5 (3)
C16—N4—Gd1	117.1 (2)	N4—C16—C17	118.5 (3)
C4—C1—C2	116.3 (3)	C12—C16—C17	119.0 (3)
C4—C1—C5	120.5 (3)	N3—C17—C9	122.0 (3)
C2—C1—C5	123.2 (3)	N3—C17—C16	118.0 (3)
O3—C2—N1	117.1 (3)	C9—C17—C16	120.0 (3)
O3—C2—C1	126.9 (3)	H5A—O5—H5B	113.1

O1ⁱ—Gd1—O1—C5	−72.3 (3)	C4—N2—C3—O4	−178.6 (3)
O3ⁱ—Gd1—O1—C5	−146.0 (3)	C4—N2—C3—N1	0.8 (5)
O3—Gd1—O1—C5	10.5 (3)	C2—N1—C3—O4	−176.8 (3)
N3ⁱ—Gd1—O1—C5	170.5 (3)	C2—N1—C3—N2	3.9 (5)
N3—Gd1—O1—C5	79.2 (3)	C3—N2—C4—C1	−2.7 (5)
N4—Gd1—O1—C5	138.3 (3)	C2—C1—C4—N2	0.2 (5)
N4ⁱ—Gd1—O1—C5	−2.7 (4)	C5—C1—C4—N2	−179.2 (3)
O1—Gd1—O3—C2	−23.0 (3)	Gd1—O1—C5—O2	−176.9 (2)
O1ⁱ—Gd1—O3—C2	67.3 (3)	Gd1—O1—C5—C1	3.6 (5)
O3ⁱ—Gd1—O3—C2	23.1 (3)	C4—C1—C5—O2	−15.4 (5)
N3ⁱ—Gd1—O3—C2	171.5 (2)	C2—C1—C5—O2	165.2 (3)
N3—Gd1—O3—C2	−134.3 (3)	C4—C1—C5—O1	164.1 (3)
N4—Gd1—O3—C2	−90.5 (3)	C2—C1—C5—O1	−15.2 (5)
N4ⁱ—Gd1—O3—C2	149.8 (3)	C17—N3—C6—C7	2.5 (5)
O1—Gd1—N3—C6	−104.0 (2)	Gd1—N3—C6—C7	−163.2 (3)
O1ⁱ—Gd1—N3—C6	8.9 (3)	N3—C6—C7—C8	0.3 (6)
O3ⁱ—Gd1—N3—C6	161.3 (2)	C6—C7—C8—C9	−2.0 (6)
O3—Gd1—N3—C6	−36.1 (2)	C7—C8—C9—C17	0.9 (5)
N3ⁱ—Gd1—N3—C6	108.0 (3)	C7—C8—C9—C10	−178.9 (4)
N4—Gd1—N3—C6	−175.2 (3)	C8—C9—C10—C11	177.3 (4)
N4ⁱ—Gd1—N3—C6	42.3 (2)	C17—C9—C10—C11	−2.5 (6)
O1—Gd1—N3—C17	90.3 (2)	C9—C10—C11—C12	−0.4 (7)
O1ⁱ—Gd1—N3—C17	−156.8 (2)	C10—C11—C12—C13	−177.2 (4)
O3ⁱ—Gd1—N3—C17	−4.4 (3)	C10—C11—C12—C16	2.5 (6)
O3—Gd1—N3—C17	158.2 (2)	C16—C12—C13—C14	−0.5 (6)
N3ⁱ—Gd1—N3—C17	−57.7 (2)	C11—C12—C13—C14	179.1 (4)
N4—Gd1—N3—C17	19.1 (2)	C12—C13—C14—C15	1.6 (6)
N4ⁱ—Gd1—N3—C17	−123.4 (2)	C16—N4—C15—C14	−2.3 (5)
O1—Gd1—N4—C15	64.5 (2)	Gd1—N4—C15—C14	162.0 (3)
O1ⁱ—Gd1—N4—C15	−7.1 (3)	C13—C14—C15—N4	−0.2 (6)
O3ⁱ—Gd1—N4—C15	−20.2 (2)	C15—N4—C16—C12	3.4 (5)
O3—Gd1—N4—C15	128.4 (2)	Gd1—N4—C16—C12	−161.8 (3)
N3ⁱ—Gd1—N4—C15	−98.7 (3)	C15—N4—C16—C17	−176.8 (3)
N3—Gd1—N4—C15	176.8 (3)	Gd1—N4—C16—C17	18.0 (3)
N4ⁱ—Gd1—N4—C15	−139.2 (3)	C13—C12—C16—N4	−2.1 (5)
O1—Gd1—N4—C16	−131.1 (2)	C11—C12—C16—N4	178.2 (3)
O1ⁱ—Gd1—N4—C16	157.20 (19)	C13—C12—C16—C17	178.2 (3)
O3ⁱ—Gd1—N4—C16	144.2 (2)	C11—C12—C16—C17	−1.5 (5)
O3—Gd1—N4—C16	−67.3 (2)	C6—N3—C17—C9	−3.7 (5)
N3ⁱ—Gd1—N4—C16	65.6 (2)	Gd1—N3—C17—C9	162.9 (2)
N3—Gd1—N4—C16	−18.8 (2)	C6—N3—C17—C16	174.8 (3)
N4ⁱ—Gd1—N4—C16	25.13 (19)	Gd1—N3—C17—C16	−18.6 (4)
Gd1—O3—C2—N1	−158.7 (2)	C8—C9—C17—N3	2.0 (5)
Gd1—O3—C2—C1	22.2 (5)	C10—C9—C17—N3	−178.1 (3)
C3—N1—C2—O3	174.5 (3)	C8—C9—C17—C16	−176.4 (3)
C3—N1—C2—C1	−6.2 (5)	C10—C9—C17—C16	3.4 (5)
C4—C1—C2—O3	−176.9 (3)	N4—C16—C17—N3	0.3 (4)
C5—C1—C2—O3	2.5 (5)	C12—C16—C17—N3	−179.9 (3)
C4—C1—C2—N1	3.9 (4)	N4—C16—C17—C9	178.8 (3)
C5—C1—C2—N1	−176.7 (3)	C12—C16—C17—C9	−1.4 (5)

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
N1—H1···O2ⁱⁱ	0.86	2.04	2.898 (3)	178
N1—H1···O1ⁱⁱ	0.86	2.60	3.160 (4)	124
N2—H2···N2ⁱⁱⁱ	0.86	1.81	2.669 (5)	174
O5—H5A···O4^iv	0.85	2.14	2.970 (4)	164
O5—H5B···O2^v	0.85	2.14	2.985 (4)	173

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

Experimental details

Crystal data
Chemical formula	[Gd(C₅H₂N₂O₄)(C₅H₃N₂O₄)(C₁₂H₈N₂)₂]·2H₂O
M_r	862.87
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	273
a, b, c (Å)	17.158 (8), 14.504 (7), 13.197 (7)
β (°)	99.955 (5)
V (Å³)	3235 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.13
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.676, 0.816
No. of measured, independent and observed [I > 2σ(I)] reflections	9884, 3686, 3212
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.064, 1.05
No. of reflections	3686
No. of parameters	240
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.65

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Gd1—O1	2.288 (2)	Gd1—N3	2.586 (3)
Gd1—O3	2.344 (2)	Gd1—N4	2.603 (3)

O1—Gd1—O1ⁱ	88.22 (11)	O1—Gd1—N4	80.80 (8)
O1—Gd1—O3ⁱ	82.54 (8)	O3—Gd1—N4	122.38 (8)
O1—Gd1—O3	73.65 (8)	N3—Gd1—N4	63.39 (8)
O3ⁱ—Gd1—O3	146.71 (11)	O1—Gd1—N4ⁱ	147.64 (8)
O1—Gd1—N3ⁱ	148.84 (8)	O3—Gd1—N4ⁱ	74.79 (8)
O3—Gd1—N3ⁱ	135.03 (8)	N3—Gd1—N4ⁱ	72.83 (8)
O1—Gd1—N3	105.26 (9)	N4—Gd1—N4ⁱ	123.04 (11)
O3—Gd1—N3	74.86 (8)

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
N1—H1···O2ⁱⁱ	0.86	2.04	2.898 (3)	178
N1—H1···O1ⁱⁱ	0.86	2.60	3.160 (4)	124
N2—H2···N2ⁱⁱⁱ	0.86	1.81	2.669 (5)	174
O5—H5A···O4^iv	0.85	2.14	2.970 (4)	164
O5—H5B···O2^v	0.85	2.14	2.985 (4)	173

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

Acknowledgements

The authors thank the Science Foundation of Guangxi Province, China (Guikeqing 0542021), and the Scientific Research Foundation of Guangxi Normal University for financial support.

References

Baran, E., Mercaser, R. C., Hueso-Ureña, F., Moreno-Carretero, M. N., Quiros-Olozabal, M. & Salas-Peregrin, J. M. (1996). Polyhedron, 15, 1717–1724. CSD CrossRef CAS Web of Science Google Scholar
Bruker (1998). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hueso-Ureña, F., Moreno-Carretero, M. N., Romero-Molina, M. A., Salas-Peregrin, J. M., Sanchez-Sanchez, M. P., Alvarez de Cienfuegos-Lopez, G. & Faure, R. (1993). J. Inorg. Biochem. 51, 613–632. CSD CrossRef Web of Science Google Scholar
Hueso-Ureña, F., Moreno-Carretero, M. N., Quirós-Olozábal, M., Salas-Peregrín, J. M., Faure, R. & Cienfuegos-López, G. A. (1996). Inorg. Chim. Acta, 241, 61–69. CSD CrossRef Web of Science Google Scholar
Luo, J.-H., Hong, M.-C., Zhao, Y.-J., Cao, R. & Weng, J.-B. (2002). Chin. J. Struct. Chem. 21, 392–395. CAS Google Scholar
Maistralis, G., Katsaros, N., Mentzafos, D. & Terzis, A. (1991). Acta Cryst. C47, 740–743. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Maistralis, G., Katsaros, N., Perlepes, S. P. & Kovala-Demertzi, D. (1992). J. Inorg. Biochem. 45, 1–12. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, C.-Y. & Jin, L.-P. (2004a). Polyhedron, 23, 2227–2233. Web of Science CSD CrossRef CAS Google Scholar
Sun, C.-Y. & Jin, L.-P. (2004b). Polyhedron, 23, 2085–2093. Web of Science CSD CrossRef CAS Google Scholar
Xing, H.-H., Chen, Z.-L. & Ng, S. W. (2008a). Acta Cryst. E64, m418. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xing, H.-H., Chen, Z.-L. & Ng, S. W. (2008b). Acta Cryst. E64, m419–m420. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

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