Triaqua[2,2′-(propane-1,3-diyl)bis(5-carboxy-1H-imidazole-4-carboxylato-κ2N3,O4)]calcium(II) tetrahydrate

Du, L.-Z.; Li, X.

doi:10.1107/S1600536812035544

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages m1199-m1200

doi:10.1107/S1600536812035544

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Triaqua[2,2′-(propane-1,3-diyl)bis(5-carboxy-1H-imidazole-4-carboxylato-κ²N³,O⁴)]calcium(II) tetrahydrate

Ling-Zhi Du ^a ^* and Xia Li ^a

^aDepartment of Chemistry and Chemical Engineering, Henan University of Urban Construction, Pingdingshan, Henan, 467044, People's Republic of China
^*Correspondence e-mail: dlz701106@126.com

(Received 25 July 2012; accepted 13 August 2012; online 23 August 2012)

In the title compound, [Ca(C₁₃H₁₀N₄O₈)(H₂O)₃]·4H₂O, the Ca^II ion is hepta-coordinated by two N atoms and two O atoms from a tetradentate 1,3-bis-(1H-imidazole-4,5-dicarboxylate) propane dianion and three water O atoms, giving a distorted pentagonal–bipyramidal coordination environment. The Ca—O bond lengths are in the range 2.354 (3)–2.453 (2) Å, while the Ca—N bond lengths are in the range 2.523 (2)–2.548 (2) Å. An intramolecular O—H⋯O hydrogen bond between the carboxy and carboxylate groups stabilizes the molecular configuration. A three-dimensional network of N—H⋯O and O—H⋯O hydrogen bonds help to stabilize the crystal packing.

Related literature

For complexes based on 4,5-imidazoledicarboxylic acid, see: Zhu et al. (2010 ); Lu et al. (2010 ). For complexes based on 2-methyl-1H-imidazole-4,5-dicarboxylic acid, see: Song et al. (2010 ). For complexes based on 2-ethyl-1H-imidazole-4,5-dicarboxylic acid, see: Zhang et al. (2010 ); Wang et al. (2008 ). For complexes based on 2-propyl-1H-imidazole-4,5-dicarboxylic acid, see: Feng et al. (2010 ); Liu et al. (2010 ). For complexes based on 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid, see: Zheng et al. (2011 ). For complexes based on 2-phenyl-1H-imidazole-4,5-dicarboxylic acid, see: Zhu et al. (2011 ). For complexes based on 2-pyridyl-1H-imidazole-4,5-dicarboxylic acid, see: Li et al. (2009 , 2010 ).

Experimental

Crystal data

[Ca(C₁₃H₁₀N₄O₈)(H₂O₃)₃]·4H₂O
M_r = 516.44
Triclinic, $[P \overline 1]$
a = 6.7794 (12) Å
b = 12.172 (2) Å
c = 13.718 (2) Å
α = 98.776 (2)°
β = 102.420 (2)°
γ = 90.444 (2)°
V = 1091.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 296 K
0.16 × 0.16 × 0.14 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.943, T_max = 0.950
8318 measured reflections
4031 independent reflections
2595 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.098
S = 1.01
4031 reflections
344 parameters
14 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O13ⁱ	0.86	1.94	2.778 (4)	164
O10—H3W⋯O5ⁱⁱ	0.86 (1)	2.03 (2)	2.839 (3)	159 (4)
O10—H4W⋯O1ⁱⁱⁱ	0.86 (1)	1.91 (1)	2.768 (3)	174 (3)
O9—H2W⋯O5^iv	0.86 (1)	1.93 (1)	2.784 (3)	172 (4)
O9—H1W⋯O12^v	0.86 (1)	1.97 (1)	2.829 (4)	174 (5)
O14—H11W⋯O12^vi	0.86 (1)	2.17 (2)	2.957 (4)	152 (4)
O15—H13W⋯O2^vi	0.86 (1)	1.93 (2)	2.752 (3)	159 (4)
O15—H14W⋯O8^vii	0.86 (1)	1.97 (1)	2.824 (3)	179 (4)
O13—H9W⋯O15^vi	0.86 (1)	2.13 (2)	2.943 (4)	158 (4)
O13—H10W⋯O14^viii	0.86 (1)	2.00 (1)	2.851 (4)	173 (5)
O11—H6W⋯O6ⁱⁱ	0.86 (1)	1.94 (2)	2.770 (3)	161 (4)
O11—H5W⋯O4^vi	0.86 (1)	1.90 (2)	2.717 (3)	160 (4)
O12—H7W⋯O9ⁱⁱⁱ	0.86 (1)	2.03 (2)	2.851 (3)	160 (5)
N2—H2⋯O14	0.86	1.96	2.809 (3)	169
O14—H12W⋯O15	0.86 (1)	1.88 (1)	2.740 (4)	177 (5)
O6—H6⋯O7	0.82	1.64	2.462 (3)	175
O3—H3⋯O2	0.82	1.67	2.487 (3)	176
Symmetry codes: (i) x, y, z-1; (ii) -x+1, -y, -z; (iii) -x+1, -y, -z+1; (iv) -x, -y, -z; (v) x-1, y, z; (vi) -x+1, -y+1, -z+1; (vii) x, y+1, z; (viii) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536812035544/ff2078sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035544/ff2078Isup2.hkl

checkCIF report

Comment top

Aromatic polycarboxylates, especially the N-heterocyclic carboxylates, are excellent candidates for preparing novel metal-organic frameworks, because of their versatile coordination modes and their ability to act as hydrogen-bonding donors and acceptors. For example, 4,5-imidazoledicarboxylate acid (Zhu et al., 2010; Lu et al., 2010), a planar rigid N-heterocyclic dicarboxylate acid, has been widely used to synthesize various coordination polymers because it has very flexible coordination modes, which derives from both imidazole and carboxylate functionality. Recently, in order to inherit the outstanding coordination properties of 4,5-imidazoledicarboxylic group, many 2-position substituent derivatives, such as 2-methyl-1H-imidazole-4,5-dicarboxylic acid (Song et al., 2010), 2-ethyl-1H-imidazole-4,5-dicarboxylic acid (Zhang et al., 2010; Wang et al., 2008), 2-propyl-1H-imidazole-4,5-dicarboxylic acid (Feng et al., 2010; Liu et al., 2010), 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid (Zheng et al., 20111), 2-phenyl-1H-imidazole-4,5-dicarboxylic acid (Zhu et al., 2011) and 2-pyridyl-1H-imidazole-4,5-dicarboxylic acid (Li et al., 2009; Li et al., 2010) have been designed and used construct various metal complexes. Here, we want to report a calcium(II) complex, Ca(C₁₃H₁₀O₄)(H₂O)₃].4H₂O, based on a new imidazole dicarboxylate ligand, 1,3-Bis-(1H-imidazole-4,5-dicarboxylate acid).

As shown in Fig. 1, the molecule of (I) is a discrete neutral monomer, in which the asymmetric unit comprises a Ca^II ion, one 1,3-Bis-(1H-imidazole-4,5-dicarboxylate) propane dianion, three coordinated water molecules and four free water molecules. The Ca^II ion is hepta-coordinated, showing a distorted pentagonal-bipyramidal coordination environment. The equatorial plane is defined by two nitrogen atoms (N1, N3) and two oxygen atoms (O1, O8) from a 1,3-Bis-(1H-imidazole-4,5-dicarboxylate) propane dianion and one water molecule (O10). The axial positions are occupied by two coordinated water molecules with the bond angle of O9—Ca1—O11 being 159.80 (9) °. The Ca—O bond distances are in the range of 2.354 (3) - 2.453 (2) Å, while the Ca—N bond distances are in the range of 2.523 (2) - 2.548 (2) Å. An intramolecular O—H···O hydrogen bond between the carboxy and carboxylate groups stabilizes the molecular configuration. A three-dimensional network of N—H···O and O—H···O hydrogen bonds help to stabilize the crystal packing.

Related literature top

For complexes based on 4,5-imidazoledicarboxylic acid, see: Zhu et al. (2010); Lu et al. (2010). For complexes based on 2-methyl-1H-imidazole-4,5-dicarboxylic acid, see: Song et al. (2010). For complexes based on 2-ethyl-1H-imidazole-4,5-dicarboxylic acid, see: Zhang et al. (2010); Wang et al. (2008). For complexes based on 2-propyl-1H-imidazole-4,5-dicarboxylic acid, see: Feng et al. (2010); Liu et al. (2010). For complexes based on 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid, see: Zheng et al. (2011). For complexes based on 2-phenyl-1H-imidazole-4,5-dicarboxylic acid, see: Zhu et al. (2011). For complexes based on 2-pyridyl-1H-imidazole-4,5-dicarboxylic acid, see: Li et al. (2009, 2010).

Experimental top

A mixture of calcium chloride dihydrate (0.0146 g, 0.1 mmol), 1,3-Bis-(1H-imidazole-4,5-dicarboxylate acid) propane (0.0352 g, 0.1 mmol), pyridine (0.8 ml) and H₂O (10 ml) was sealed into a Teflon-lined stainless autoclave and heated at 413 K for 3 days. The bomb was allowed to cool to room temperature gradually and colorless block crystals of (I) were obtained.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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. The molecular structure of the title compound, showing the atomic numbering and 30% probability displacement ellipsoids.

Triaqua[2,2'-(propane-1,3-diyl)bis(5-carboxy-1H-imidazole-4-carboxylato- κ²N³,O⁴)]calcium(II) tetrahydrate top

Crystal data top

[Ca(C₁₃H₁₀N₄O₈)(H₂O₃)₃]·4H₂O	Z = 2
M_r = 516.44	F(000) = 540
Triclinic, P1	D_x = 1.571 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7794 (12) Å	Cell parameters from 1354 reflections
b = 12.172 (2) Å	θ = 2.5–23.1°
c = 13.718 (2) Å	µ = 0.37 mm⁻¹
α = 98.776 (2)°	T = 296 K
β = 102.420 (2)°	Block, colourless
γ = 90.444 (2)°	0.16 × 0.16 × 0.14 mm
V = 1091.6 (3) Å³

Data collection top

Bruker SMART CCD diffractometer	4031 independent reflections
Radiation source: X-ray tube	2595 reflections with I > 2σ(I)
Phi and omega scans monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −8→8
T_min = 0.943, T_max = 0.950	k = −14→14
8318 measured reflections	l = −16→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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0327P)² + 0.2508P] where P = (F_o² + 2F_c²)/3
4031 reflections	(Δ/σ)_max < 0.001
344 parameters	Δρ_max = 0.24 e Å⁻³
14 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Ca(C₁₃H₁₀N₄O₈)(H₂O₃)₃]·4H₂O	γ = 90.444 (2)°
M_r = 516.44	V = 1091.6 (3) Å³
Triclinic, P1	Z = 2
a = 6.7794 (12) Å	Mo Kα radiation
b = 12.172 (2) Å	µ = 0.37 mm⁻¹
c = 13.718 (2) Å	T = 296 K
α = 98.776 (2)°	0.16 × 0.16 × 0.14 mm
β = 102.420 (2)°

Data collection top

Bruker SMART CCD diffractometer	4031 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2595 reflections with I > 2σ(I)
T_min = 0.943, T_max = 0.950	R_int = 0.040
8318 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	14 restraints
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.24 e Å⁻³
4031 reflections	Δρ_min = −0.32 e Å⁻³
344 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
Ca1	0.34365 (10)	0.10418 (5)	0.30772 (5)	0.02902 (18)
O1	0.4347 (3)	0.17772 (16)	0.48632 (15)	0.0339 (5)
O2	0.4429 (3)	0.31736 (17)	0.61241 (15)	0.0404 (6)
O3	0.3556 (3)	0.51623 (17)	0.63708 (15)	0.0381 (6)
H3	0.3814	0.4502	0.6309	0.046*
O4	0.2140 (3)	0.63567 (16)	0.53912 (16)	0.0375 (6)
O5	0.2380 (4)	0.07270 (19)	−0.21218 (17)	0.0498 (7)
O6	0.1955 (4)	−0.08158 (19)	−0.14977 (16)	0.0489 (7)
H6	0.1955	−0.0984	−0.0941	0.059*
O7	0.2100 (3)	−0.14045 (16)	0.01549 (16)	0.0406 (6)
O8	0.2447 (3)	−0.05781 (16)	0.17484 (16)	0.0379 (6)
O9	0.0695 (4)	0.03304 (19)	0.36754 (17)	0.0414 (6)
O10	0.5458 (4)	−0.0399 (2)	0.36928 (19)	0.0464 (6)
O11	0.6575 (4)	0.1900 (2)	0.31047 (19)	0.0432 (6)
O12	0.9370 (5)	0.1553 (2)	0.5324 (2)	0.0604 (8)
O13	0.3808 (5)	0.3595 (3)	0.8695 (2)	0.0670 (8)
O14	−0.0383 (4)	0.6606 (2)	0.2953 (2)	0.0514 (7)
O15	0.2804 (4)	0.7234 (2)	0.21968 (19)	0.0511 (7)
N1	0.2148 (4)	0.29607 (19)	0.34785 (17)	0.0282 (6)
N2	0.1366 (4)	0.47230 (19)	0.36829 (18)	0.0278 (6)
H2	0.0902	0.5349	0.3542	0.033*
N3	0.2951 (4)	0.14885 (19)	0.12881 (17)	0.0296 (6)
N4	0.2984 (4)	0.1999 (2)	−0.01827 (18)	0.0322 (6)
H4	0.3066	0.2417	−0.0626	0.039*
C1	0.2844 (4)	0.3426 (2)	0.4475 (2)	0.0246 (7)
C2	0.2362 (4)	0.4526 (2)	0.4611 (2)	0.0248 (7)
C3	0.1233 (5)	0.3772 (2)	0.3025 (2)	0.0281 (7)
C4	0.3947 (5)	0.2746 (2)	0.5201 (2)	0.0288 (7)
C5	0.2698 (4)	0.5412 (2)	0.5491 (2)	0.0282 (7)
C6	0.0236 (5)	0.3679 (3)	0.1933 (2)	0.0382 (9)
H6A	−0.1009	0.4076	0.1872	0.046*
H6B	−0.0116	0.2902	0.1661	0.046*
C7	0.1548 (6)	0.4140 (3)	0.1298 (2)	0.0471 (10)
H7A	0.1873	0.4922	0.1560	0.056*
H7B	0.0775	0.4087	0.0609	0.056*
C8	0.3519 (5)	0.3533 (2)	0.1291 (2)	0.0421 (9)
H8A	0.4324	0.3909	0.0926	0.050*
H8B	0.4284	0.3574	0.1981	0.050*
C9	0.3172 (5)	0.2347 (2)	0.0816 (2)	0.0311 (8)
C10	0.2618 (4)	0.0566 (2)	0.0547 (2)	0.0271 (7)
C11	0.2642 (4)	0.0872 (2)	−0.0371 (2)	0.0300 (7)
C12	0.2371 (4)	−0.0524 (2)	0.0845 (2)	0.0305 (7)
C13	0.2322 (5)	0.0231 (3)	−0.1405 (3)	0.0376 (8)
H5W	0.720 (5)	0.247 (2)	0.350 (2)	0.083 (15)*
H6W	0.726 (5)	0.167 (3)	0.266 (2)	0.080 (15)*
H4W	0.542 (5)	−0.083 (2)	0.4128 (19)	0.054 (12)*
H3W	0.612 (5)	−0.067 (3)	0.325 (2)	0.070 (14)*
H13W	0.370 (5)	0.728 (4)	0.276 (2)	0.106*
H12W	0.062 (5)	0.683 (4)	0.273 (3)	0.106*
H2W	−0.032 (4)	0.000 (3)	0.324 (3)	0.106*
H14W	0.269 (7)	0.7895 (16)	0.205 (3)	0.106*
H11W	−0.052 (7)	0.709 (3)	0.346 (2)	0.106*
H9W	0.498 (3)	0.345 (4)	0.858 (4)	0.106*
H7W	0.904 (7)	0.102 (3)	0.560 (3)	0.106*
H10W	0.280 (5)	0.360 (4)	0.820 (2)	0.106*
H1W	0.026 (6)	0.074 (3)	0.415 (2)	0.106*
H8W	0.844 (5)	0.197 (3)	0.509 (3)	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0426 (4)	0.0223 (3)	0.0218 (4)	0.0014 (3)	0.0072 (3)	0.0021 (3)
O1	0.0529 (15)	0.0228 (11)	0.0259 (13)	0.0087 (10)	0.0080 (11)	0.0040 (9)
O2	0.0593 (16)	0.0390 (13)	0.0192 (12)	0.0103 (11)	0.0017 (11)	0.0028 (10)
O3	0.0533 (15)	0.0305 (12)	0.0266 (13)	0.0024 (11)	0.0052 (11)	−0.0029 (10)
O4	0.0464 (14)	0.0253 (12)	0.0377 (14)	0.0017 (11)	0.0076 (11)	−0.0020 (10)
O5	0.0657 (18)	0.0576 (16)	0.0262 (14)	−0.0151 (13)	0.0167 (12)	−0.0011 (12)
O6	0.0706 (18)	0.0461 (15)	0.0284 (14)	−0.0049 (13)	0.0158 (12)	−0.0062 (11)
O7	0.0509 (15)	0.0258 (12)	0.0396 (14)	0.0010 (11)	0.0072 (12)	−0.0082 (10)
O8	0.0527 (15)	0.0292 (12)	0.0305 (14)	0.0000 (11)	0.0054 (11)	0.0054 (10)
O9	0.0456 (16)	0.0444 (15)	0.0321 (15)	−0.0064 (12)	0.0074 (12)	0.0017 (11)
O10	0.0652 (18)	0.0437 (15)	0.0390 (16)	0.0190 (13)	0.0217 (14)	0.0182 (13)
O11	0.0504 (17)	0.0382 (14)	0.0371 (16)	−0.0096 (12)	0.0149 (13)	−0.0127 (12)
O12	0.087 (2)	0.0513 (18)	0.0465 (17)	0.0267 (15)	0.0146 (15)	0.0186 (13)
O13	0.075 (2)	0.075 (2)	0.058 (2)	−0.0009 (19)	0.0211 (17)	0.0238 (16)
O14	0.0622 (18)	0.0382 (15)	0.0601 (19)	0.0109 (14)	0.0211 (15)	0.0165 (12)
O15	0.0573 (18)	0.0431 (15)	0.0495 (17)	−0.0013 (14)	−0.0018 (13)	0.0165 (13)
N1	0.0368 (16)	0.0250 (13)	0.0210 (14)	0.0012 (12)	0.0037 (12)	0.0015 (11)
N2	0.0352 (16)	0.0204 (13)	0.0263 (15)	0.0020 (11)	0.0053 (12)	0.0015 (11)
N3	0.0404 (17)	0.0260 (14)	0.0195 (14)	−0.0014 (12)	0.0030 (12)	−0.0004 (11)
N4	0.0396 (17)	0.0356 (15)	0.0225 (15)	−0.0009 (13)	0.0082 (12)	0.0063 (12)
C1	0.0309 (18)	0.0224 (16)	0.0207 (17)	0.0006 (13)	0.0073 (14)	0.0015 (13)
C2	0.0263 (17)	0.0258 (16)	0.0215 (16)	0.0012 (13)	0.0061 (14)	0.0004 (13)
C3	0.0319 (19)	0.0247 (16)	0.0279 (18)	0.0013 (14)	0.0057 (15)	0.0057 (14)
C4	0.0320 (19)	0.0275 (17)	0.0275 (19)	−0.0011 (14)	0.0081 (15)	0.0045 (14)
C5	0.0250 (18)	0.0281 (18)	0.0306 (19)	−0.0040 (14)	0.0071 (15)	0.0005 (14)
C6	0.050 (2)	0.0294 (18)	0.0276 (19)	0.0061 (16)	−0.0030 (16)	−0.0017 (15)
C7	0.086 (3)	0.0274 (18)	0.0260 (19)	0.0087 (19)	0.0066 (19)	0.0060 (15)
C8	0.066 (3)	0.0328 (19)	0.0253 (19)	−0.0139 (18)	0.0116 (18)	−0.0024 (15)
C9	0.042 (2)	0.0301 (17)	0.0214 (18)	−0.0005 (15)	0.0074 (15)	0.0034 (14)
C10	0.0255 (17)	0.0289 (16)	0.0253 (18)	0.0015 (14)	0.0050 (14)	0.0001 (14)
C11	0.0282 (18)	0.0314 (18)	0.0276 (19)	−0.0001 (14)	0.0074 (15)	−0.0058 (14)
C12	0.0256 (18)	0.0288 (17)	0.034 (2)	0.0036 (14)	0.0026 (15)	0.0004 (15)
C13	0.035 (2)	0.046 (2)	0.030 (2)	−0.0069 (17)	0.0116 (16)	−0.0051 (17)

Geometric parameters (Å, º) top

Ca1—O11	2.354 (3)	O14—H11W	0.860 (10)
Ca1—O10	2.379 (3)	O15—H13W	0.864 (10)
Ca1—O9	2.393 (3)	O15—H14W	0.859 (10)
Ca1—O1	2.420 (2)	N1—C3	1.333 (3)
Ca1—O8	2.453 (2)	N1—C1	1.377 (3)
Ca1—N1	2.523 (2)	N2—C3	1.345 (3)
Ca1—N3	2.548 (2)	N2—C2	1.364 (3)
Ca1—H3W	2.78 (3)	N2—H2	0.8600
O1—C4	1.253 (3)	N3—C9	1.333 (4)
O2—C4	1.265 (3)	N3—C10	1.376 (3)
O3—C5	1.304 (3)	N4—C9	1.349 (3)
O3—H3	0.8200	N4—C11	1.366 (4)
O4—C5	1.232 (3)	N4—H4	0.8600
O5—C13	1.237 (4)	C1—C2	1.375 (4)
O6—C13	1.279 (4)	C1—C4	1.475 (4)
O6—H6	0.8200	C2—C5	1.467 (4)
O7—C12	1.301 (3)	C3—C6	1.492 (4)
O8—C12	1.242 (3)	C6—C7	1.529 (5)
O9—H2W	0.861 (10)	C6—H6A	0.9700
O9—H1W	0.859 (10)	C6—H6B	0.9700
O10—H4W	0.859 (10)	C7—C8	1.533 (5)
O10—H3W	0.855 (10)	C7—H7A	0.9700
O11—H5W	0.855 (10)	C7—H7B	0.9700
O11—H6W	0.858 (10)	C8—C9	1.486 (4)
O12—H7W	0.858 (10)	C8—H8A	0.9700
O12—H8W	0.852 (10)	C8—H8B	0.9700
O13—H9W	0.856 (10)	C10—C11	1.370 (4)
O13—H10W	0.856 (10)	C10—C12	1.465 (4)
O14—H12W	0.862 (10)	C11—C13	1.482 (4)

O11—Ca1—O10	83.73 (10)	C10—N3—Ca1	114.06 (19)
O11—Ca1—O9	159.80 (9)	C9—N4—C11	108.4 (2)
O10—Ca1—O9	89.24 (9)	C9—N4—H4	125.8
O11—Ca1—O1	81.93 (8)	C11—N4—H4	125.8
O10—Ca1—O1	79.49 (8)	C2—C1—N1	109.7 (3)
O9—Ca1—O1	78.17 (8)	C2—C1—C4	130.5 (3)
O11—Ca1—O8	114.31 (8)	N1—C1—C4	119.9 (2)
O10—Ca1—O8	75.75 (8)	N2—C2—C1	105.6 (2)
O9—Ca1—O8	81.96 (8)	N2—C2—C5	120.8 (3)
O1—Ca1—O8	148.28 (7)	C1—C2—C5	133.6 (3)
O11—Ca1—N1	87.84 (8)	N1—C3—N2	110.8 (3)
O10—Ca1—N1	146.79 (9)	N1—C3—C6	126.0 (3)
O9—Ca1—N1	87.76 (8)	N2—C3—C6	123.1 (3)
O1—Ca1—N1	67.53 (7)	O1—C4—O2	124.0 (3)
O8—Ca1—N1	136.25 (8)	O1—C4—C1	117.8 (3)
O11—Ca1—N3	77.65 (9)	O2—C4—C1	118.2 (3)
O10—Ca1—N3	124.49 (9)	O4—C5—O3	121.7 (3)
O9—Ca1—N3	121.47 (8)	O4—C5—C2	120.1 (3)
O1—Ca1—N3	145.79 (7)	O3—C5—C2	118.3 (3)
O8—Ca1—N3	65.91 (7)	C3—C6—C7	113.7 (3)
N1—Ca1—N3	84.44 (8)	C3—C6—H6A	108.8
O11—Ca1—H3W	76.2 (7)	C7—C6—H6A	108.8
O10—Ca1—H3W	16.9 (5)	C3—C6—H6B	108.8
O9—Ca1—H3W	101.5 (6)	C7—C6—H6B	108.8
O1—Ca1—H3W	93.4 (6)	H6A—C6—H6B	107.7
O8—Ca1—H3W	66.6 (7)	C6—C7—C8	113.6 (3)
N1—Ca1—H3W	156.9 (8)	C6—C7—H7A	108.9
N3—Ca1—H3W	107.8 (5)	C8—C7—H7A	108.9
C4—O1—Ca1	121.77 (19)	C6—C7—H7B	108.9
C5—O3—H3	109.5	C8—C7—H7B	108.9
C13—O6—H6	109.5	H7A—C7—H7B	107.7
C12—O8—Ca1	121.90 (19)	C9—C8—C7	112.8 (3)
Ca1—O9—H2W	118 (3)	C9—C8—H8A	109.0
Ca1—O9—H1W	119 (3)	C7—C8—H8A	109.0
H2W—O9—H1W	109 (4)	C9—C8—H8B	109.0
Ca1—O10—H4W	136 (2)	C7—C8—H8B	109.0
Ca1—O10—H3W	109 (3)	H8A—C8—H8B	107.8
H4W—O10—H3W	112 (4)	N3—C9—N4	110.5 (2)
Ca1—O11—H5W	130 (3)	N3—C9—C8	126.2 (3)
Ca1—O11—H6W	121 (3)	N4—C9—C8	123.3 (3)
H5W—O11—H6W	109 (4)	C11—C10—N3	110.0 (3)
H7W—O12—H8W	118 (5)	C11—C10—C12	131.7 (3)
H9W—O13—H10W	120 (5)	N3—C10—C12	118.3 (3)
H12W—O14—H11W	108 (4)	N4—C11—C10	105.5 (3)
H13W—O15—H14W	106 (4)	N4—C11—C13	122.0 (3)
C3—N1—C1	105.5 (2)	C10—C11—C13	132.5 (3)
C3—N1—Ca1	141.1 (2)	O8—C12—O7	122.1 (3)
C1—N1—Ca1	112.41 (17)	O8—C12—C10	119.0 (3)
C3—N2—C2	108.4 (2)	O7—C12—C10	118.9 (3)
C3—N2—H2	125.8	O5—C13—O6	124.0 (3)
C2—N2—H2	125.8	O5—C13—C11	119.3 (3)
C9—N3—C10	105.6 (2)	O6—C13—C11	116.7 (3)
C9—N3—Ca1	139.60 (19)

O11—Ca1—O1—C4	86.6 (2)	Ca1—N1—C3—N2	−165.8 (2)
O10—Ca1—O1—C4	171.7 (2)	C1—N1—C3—C6	179.7 (3)
O9—Ca1—O1—C4	−96.9 (2)	Ca1—N1—C3—C6	12.4 (5)
O8—Ca1—O1—C4	−149.2 (2)	C2—N2—C3—N1	−1.6 (3)
N1—Ca1—O1—C4	−4.4 (2)	C2—N2—C3—C6	−179.9 (3)
N3—Ca1—O1—C4	33.0 (3)	Ca1—O1—C4—O2	−178.5 (2)
O11—Ca1—O8—C12	−54.5 (2)	Ca1—O1—C4—C1	1.6 (4)
O10—Ca1—O8—C12	−130.7 (2)	C2—C1—C4—O1	−173.7 (3)
O9—Ca1—O8—C12	138.0 (2)	N1—C1—C4—O1	5.3 (4)
O1—Ca1—O8—C12	−170.5 (2)	C2—C1—C4—O2	6.3 (5)
N1—Ca1—O8—C12	59.8 (3)	N1—C1—C4—O2	−174.7 (3)
N3—Ca1—O8—C12	8.2 (2)	N2—C2—C5—O4	−2.5 (4)
O11—Ca1—N1—C3	90.9 (3)	C1—C2—C5—O4	177.9 (3)
O10—Ca1—N1—C3	166.0 (3)	N2—C2—C5—O3	176.2 (3)
O9—Ca1—N1—C3	−108.8 (3)	C1—C2—C5—O3	−3.4 (5)
O1—Ca1—N1—C3	173.1 (3)	N1—C3—C6—C7	−99.3 (4)
O8—Ca1—N1—C3	−32.8 (4)	N2—C3—C6—C7	78.7 (4)
N3—Ca1—N1—C3	13.2 (3)	C3—C6—C7—C8	61.5 (3)
O11—Ca1—N1—C1	−75.75 (19)	C6—C7—C8—C9	63.7 (4)
O10—Ca1—N1—C1	−0.7 (3)	C10—N3—C9—N4	0.2 (3)
O9—Ca1—N1—C1	84.53 (19)	Ca1—N3—C9—N4	169.1 (2)
O1—Ca1—N1—C1	6.41 (18)	C10—N3—C9—C8	178.6 (3)
O8—Ca1—N1—C1	160.45 (17)	Ca1—N3—C9—C8	−12.6 (5)
N3—Ca1—N1—C1	−153.55 (19)	C11—N4—C9—N3	−0.4 (4)
O11—Ca1—N3—C9	−51.1 (3)	C11—N4—C9—C8	−178.8 (3)
O10—Ca1—N3—C9	−124.4 (3)	C7—C8—C9—N3	−89.7 (4)
O9—Ca1—N3—C9	121.9 (3)	C7—C8—C9—N4	88.5 (4)
O1—Ca1—N3—C9	3.7 (4)	C9—N3—C10—C11	0.0 (3)
O8—Ca1—N3—C9	−175.1 (3)	Ca1—N3—C10—C11	−172.1 (2)
N1—Ca1—N3—C9	37.9 (3)	C9—N3—C10—C12	178.3 (3)
O11—Ca1—N3—C10	117.1 (2)	Ca1—N3—C10—C12	6.3 (3)
O10—Ca1—N3—C10	43.8 (2)	C9—N4—C11—C10	0.4 (3)
O9—Ca1—N3—C10	−69.9 (2)	C9—N4—C11—C13	178.7 (3)
O1—Ca1—N3—C10	171.85 (18)	N3—C10—C11—N4	−0.3 (3)
O8—Ca1—N3—C10	−6.88 (19)	C12—C10—C11—N4	−178.3 (3)
N1—Ca1—N3—C10	−153.9 (2)	N3—C10—C11—C13	−178.3 (3)
C3—N1—C1—C2	−0.8 (3)	C12—C10—C11—C13	3.7 (6)
Ca1—N1—C1—C2	170.56 (19)	Ca1—O8—C12—O7	171.1 (2)
C3—N1—C1—C4	180.0 (3)	Ca1—O8—C12—C10	−8.2 (4)
Ca1—N1—C1—C4	−8.6 (3)	C11—C10—C12—O8	178.6 (3)
C3—N2—C2—C1	1.0 (3)	N3—C10—C12—O8	0.8 (4)
C3—N2—C2—C5	−178.7 (3)	C11—C10—C12—O7	−0.6 (5)
N1—C1—C2—N2	−0.1 (3)	N3—C10—C12—O7	−178.5 (3)
C4—C1—C2—N2	179.0 (3)	N4—C11—C13—O5	0.5 (5)
N1—C1—C2—C5	179.5 (3)	C10—C11—C13—O5	178.2 (3)
C4—C1—C2—C5	−1.4 (6)	N4—C11—C13—O6	−178.0 (3)
C1—N1—C3—N2	1.5 (3)	C10—C11—C13—O6	−0.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O13ⁱ	0.86	1.94	2.778 (4)	164
O10—H3W···O5ⁱⁱ	0.86 (1)	2.03 (2)	2.839 (3)	159 (4)
O10—H4W···O1ⁱⁱⁱ	0.86 (1)	1.91 (1)	2.768 (3)	174 (3)
O9—H2W···O5^iv	0.86 (1)	1.93 (1)	2.784 (3)	172 (4)
O9—H1W···O12^v	0.86 (1)	1.97 (1)	2.829 (4)	174 (5)
O14—H11W···O12^vi	0.86 (1)	2.17 (2)	2.957 (4)	152 (4)
O15—H13W···O2^vi	0.86 (1)	1.93 (2)	2.752 (3)	159 (4)
O15—H14W···O8^vii	0.86 (1)	1.97 (1)	2.824 (3)	179 (4)
O13—H9W···O15^vi	0.86 (1)	2.13 (2)	2.943 (4)	158 (4)
O13—H10W···O14^viii	0.86 (1)	2.00 (1)	2.851 (4)	173 (5)
O11—H6W···O6ⁱⁱ	0.86 (1)	1.94 (2)	2.770 (3)	161 (4)
O11—H5W···O4^vi	0.86 (1)	1.90 (2)	2.717 (3)	160 (4)
O12—H7W···O9ⁱⁱⁱ	0.86 (1)	2.03 (2)	2.851 (3)	160 (5)
N2—H2···O14	0.86	1.96	2.809 (3)	169
O14—H12W···O15	0.86 (1)	1.88 (1)	2.740 (4)	177 (5)
O6—H6···O7	0.82	1.64	2.462 (3)	175
O3—H3···O2	0.82	1.67	2.487 (3)	176

Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y, −z; (iii) −x+1, −y, −z+1; (iv) −x, −y, −z; (v) x−1, y, z; (vi) −x+1, −y+1, −z+1; (vii) x, y+1, z; (viii) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Ca(C₁₃H₁₀N₄O₈)(H₂O₃)₃]·4H₂O
M_r	516.44
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.7794 (12), 12.172 (2), 13.718 (2)
α, β, γ (°)	98.776 (2), 102.420 (2), 90.444 (2)
V (Å³)	1091.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.16 × 0.16 × 0.14

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.943, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	8318, 4031, 2595
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.098, 1.01
No. of reflections	4031
No. of parameters	344
No. of restraints	14
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.32

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O13ⁱ	0.86	1.94	2.778 (4)	163.6
O10—H3W···O5ⁱⁱ	0.855 (10)	2.025 (17)	2.839 (3)	159 (4)
O10—H4W···O1ⁱⁱⁱ	0.859 (10)	1.912 (11)	2.768 (3)	174 (3)
O9—H2W···O5^iv	0.861 (10)	1.929 (12)	2.784 (3)	172 (4)
O9—H1W···O12^v	0.859 (10)	1.973 (12)	2.829 (4)	174 (5)
O14—H11W···O12^vi	0.860 (10)	2.17 (2)	2.957 (4)	152 (4)
O15—H13W···O2^vi	0.864 (10)	1.927 (19)	2.752 (3)	159 (4)
O15—H14W···O8^vii	0.859 (10)	1.965 (11)	2.824 (3)	179 (4)
O13—H9W···O15^vi	0.856 (10)	2.13 (2)	2.943 (4)	158 (4)
O13—H10W···O14^viii	0.856 (10)	1.999 (12)	2.851 (4)	173 (5)
O11—H6W···O6ⁱⁱ	0.858 (10)	1.944 (16)	2.770 (3)	161 (4)
O11—H5W···O4^vi	0.855 (10)	1.897 (17)	2.717 (3)	160 (4)
O12—H7W···O9ⁱⁱⁱ	0.858 (10)	2.03 (2)	2.851 (3)	160 (5)
N2—H2···O14	0.86	1.96	2.809 (3)	168.5
O14—H12W···O15	0.862 (10)	1.879 (11)	2.740 (4)	177 (5)
O6—H6···O7	0.82	1.64	2.462 (3)	175.0
O3—H3···O2	0.82	1.67	2.487 (3)	176.1

Acknowledgements

We gratefully acknowledge financial support by the Foundation of Henan Key Science and Technology Research (Nos. 122102210414 and 122102210415), the Foundation of Henan Education Committee (No. 2010 A150003 and 2011B150001) and the Foundation of Henan University of Urban Construction (Nos. 2010JYB007 and 2010JYB008).

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