Poly[diaqua­bis(μ-4-carb­oxy-2-propyl-1H-imidazole-5-carboxyl­ato-κ3N3,O4:O5)calcium(II)]

Song, W.-D.; Yan, J.-B.; Li, S.-J.; Miao, D.-L.; Li, X.-F.

doi:10.1107/S1600536809052799

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page m53

doi:10.1107/S1600536809052799

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Poly[diaquabis(μ-4-carboxy-2-propyl-1H-imidazole-5-carboxylato-κ³N³,O⁴:O⁵)calcium(II)]

Wen-Dong Song,^a ^* Jian-Bin Yan,^a Shi-Jie Li,^a Dong-Liang Miao ^a and Xiao-Fei Li ^a

^aCollege of Science, Guang Dong Ocean University, Zhanjiang 524088, People's Republic of China
^*Correspondence e-mail: songwd60@126.com

(Received 3 December 2009; accepted 8 December 2009; online 12 December 2009)

In the title complex, [Ca(C₈H₉N₂O₄)₂(H₂O)₂]_n, the Ca^II atom is eight-coordinated in a distorted square-antiprismatic environment. The water-coordinated Ca atom is N,O-chelated by the monocarboxylate anion; the carboxyl –CO₂ portion engaged in chelation bears an acid hydrogen. The free –CO₂ portion engages in bonding to adjacent Ca atoms. The Ca^II centres are connected through the ligand, forming a layer structure; the layers are linked by hydrogen bonds into a three-dimensional network.

Related literature

For the potential uses and diverse structrual types of structures containing metals and N-heterocyclic carboxylic acids, see: Liang et al. (2002 ); Net et al. (1989 ); Nie et al. (2007 ).

Experimental

Crystal data

[Ca(C₈H₉N₂O₄)₂(H₂O)₂]
M_r = 470.46
Monoclinic, C 2/c
a = 12.703 (3) Å
b = 13.006 (3) Å
c = 11.697 (2) Å
β = 97.864 (2)°
V = 1914.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 273 K
0.32 × 0.24 × 0.20 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.884, T_max = 0.925
4830 measured reflections
1718 independent reflections
1504 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.099
S = 1.02
1718 reflections
144 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.86	2.01	2.859 (2)	171
O1W—H2W⋯O1ⁱⁱ	0.83	2.31	3.088 (2)	156
O1W—H1W⋯O3ⁱⁱⁱ	0.84	2.12	2.947 (2)	172
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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/S1600536809052799/ng2702sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052799/ng2702Isup2.hkl

checkCIF report

Comment top

Recently, structures containing metals and N-heterocyclic carboxylic acids has attracted much attention, they can function as a multidentate ligand, exhibiting diverse structrual type and can be potentially used as functional materials (Nie et al., 2007; Liang et al.,2002; Net et al., 1989). In this paper, we report the synthesis and structure of a new Ca(II) complex obtained from 2-Propyl-1H- imidazole-4,5-dicarboxy with metal salts under hydrothermal conditions.

As illustrated in figure 1, the title complex molecule is eight-coordinated by two chelating rings [Ca—N=2.5998 (15)Å and Ca—O=2.605 (5) Å] and two carboxylate O atoms from two different 2-Propyl-1H-imidazole-4,5-dicarboxylate ligands and two water molecules, exhibiting a distorted square antiprismatic structure, the title Complex displays an extended two-dimensional layer structure constructed of quasi-squares, with four Ca atoms at the corners and 2-Propyl-1H-imidazole-4,5-dicarboxylate anions at each edge as linkers connecting two Ca atoms. the edge lengthes are equal, with a value of 9.0901 (16) Å. the angles of the rhombus are 88.650 (2)° and 91.350 (5)°(Fig. 2). Two dimensional layers are further linked by hydrogen bonds(Table 1), forming a three-dimensional network(Fig. 3)

Related literature top

For the potential uses and diverse structrual types of structures containing metals and N-heterocyclic carboxylic acids, see: Liang et al. (2002); Net et al. (1989); Nie et al. (2007).

Experimental top

A mixture of Ca(II)chloride (0.5 mmol, 0.055 g) and 2-propyl-1H-imidazole-4,5-dicarboxylic acid(0.5 mmol, 0.99 g) in 10 ml of distilled water was sealed in an autoclave equipped with a Teflon liner (20 ml) and then heated at 433k for 3 days. Crystals of the title compound were obtained by slow evaporation of the solvent at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (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. The structure of the title compound, showing the atomic numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids(H atoms are represented by arbitrary spheres). [Symmetry codes:[(A)1 - x,y,1.5 - z;(B)-1/2 + x,1/2 + y,z;(C)1.5 - x,1/2 + y,1.5 - z.]
	Fig. 2. A view of an extended two-dimensional layer structure of the title compound.
	Fig. 3. View the three-dimensional network.

Poly[diaquabis(µ-4-carboxy-2-propyl-1H-imidazole-5-carboxylato- κ³N³,O⁴:O⁵)calcium(II)] top

Crystal data top

[Ca(C₈H₉N₂O₄)₂(H₂O)₂]	F(000) = 984
M_r = 470.46	D_x = 1.632 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3600 reflections
a = 12.703 (3) Å	θ = 1.4–28°
b = 13.006 (3) Å	µ = 0.40 mm⁻¹
c = 11.697 (2) Å	T = 273 K
β = 97.864 (2)°	Block, white
V = 1914.3 (7) Å³	0.32 × 0.24 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII area-detector diffractometer	1718 independent reflections
Radiation source: fine-focus sealed tube	1504 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scan	θ_max = 25.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→15
T_min = 0.884, T_max = 0.925	k = −14→15
4830 measured reflections	l = −14→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0551P)² + 1.470P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
1718 reflections	Δρ_max = 0.29 e Å⁻³
144 parameters	Δρ_min = −0.23 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0076 (9)

Crystal data top

[Ca(C₈H₉N₂O₄)₂(H₂O)₂]	V = 1914.3 (7) Å³
M_r = 470.46	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.703 (3) Å	µ = 0.40 mm⁻¹
b = 13.006 (3) Å	T = 273 K
c = 11.697 (2) Å	0.32 × 0.24 × 0.20 mm
β = 97.864 (2)°

Data collection top

Bruker APEXII area-detector diffractometer	1718 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1504 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.925	R_int = 0.040
4830 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	3 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.02	Δρ_max = 0.29 e Å⁻³
1718 reflections	Δρ_min = −0.23 e Å⁻³
144 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	0.5000	0.07420 (4)	0.2500	0.0189 (2)
O1	0.33875 (11)	0.05035 (10)	0.36313 (12)	0.0262 (3)
O1W	0.55495 (11)	0.10622 (11)	0.45862 (12)	0.0319 (4)
H1W	0.5121	0.1347	0.4970	0.048*
H2W	0.5769	0.0519	0.4904	0.048*
O2	0.20033 (11)	0.11430 (10)	0.43530 (13)	0.0296 (4)
H1	0.1663	0.1680	0.4316	0.044*
O3	0.09452 (11)	0.27478 (11)	0.42169 (12)	0.0308 (4)
O4	0.09469 (12)	0.42512 (10)	0.33195 (13)	0.0352 (4)
N1	0.36595 (12)	0.22589 (11)	0.23987 (13)	0.0201 (4)
N2	0.26433 (12)	0.36382 (11)	0.21921 (13)	0.0225 (4)
H2	0.2403	0.4229	0.1951	0.027*
C1	0.28670 (14)	0.21777 (14)	0.30920 (15)	0.0192 (4)
C2	0.22299 (14)	0.30376 (14)	0.29747 (16)	0.0209 (4)
C3	0.34950 (14)	0.31557 (14)	0.18572 (16)	0.0215 (4)
C4	0.27622 (14)	0.12212 (14)	0.37333 (16)	0.0204 (4)
C5	0.40949 (15)	0.36092 (15)	0.09774 (17)	0.0255 (4)
H5A	0.4753	0.3231	0.0974	0.031*
H5B	0.4277	0.4315	0.1189	0.031*
C6	0.34718 (17)	0.35929 (17)	−0.02384 (18)	0.0334 (5)
H6A	0.3399	0.2888	−0.0508	0.040*
H6B	0.2764	0.3865	−0.0212	0.040*
C7	0.40144 (19)	0.42208 (18)	−0.1082 (2)	0.0382 (6)
H7A	0.4067	0.4924	−0.0832	0.057*
H7B	0.3606	0.4184	−0.1835	0.057*
H7C	0.4714	0.3952	−0.1113	0.057*
C8	0.13058 (15)	0.33836 (15)	0.35251 (16)	0.0240 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0189 (3)	0.0157 (3)	0.0229 (3)	0.000	0.0052 (2)	0.000
O1	0.0267 (7)	0.0187 (7)	0.0336 (8)	0.0026 (6)	0.0051 (6)	0.0014 (6)
O1W	0.0345 (8)	0.0327 (8)	0.0299 (8)	0.0035 (6)	0.0095 (6)	0.0011 (6)
O2	0.0303 (8)	0.0228 (7)	0.0384 (8)	0.0041 (6)	0.0140 (7)	0.0073 (6)
O3	0.0295 (8)	0.0300 (8)	0.0360 (8)	0.0045 (6)	0.0155 (6)	0.0036 (6)
O4	0.0385 (9)	0.0295 (8)	0.0394 (9)	0.0182 (6)	0.0119 (7)	0.0052 (6)
N1	0.0188 (8)	0.0190 (8)	0.0231 (8)	0.0000 (6)	0.0049 (6)	0.0001 (6)
N2	0.0250 (8)	0.0157 (8)	0.0275 (9)	0.0045 (6)	0.0059 (7)	0.0042 (6)
C1	0.0185 (9)	0.0192 (9)	0.0198 (9)	−0.0003 (7)	0.0023 (7)	−0.0013 (7)
C2	0.0219 (9)	0.0200 (9)	0.0212 (9)	0.0015 (7)	0.0046 (8)	−0.0011 (7)
C3	0.0207 (9)	0.0201 (9)	0.0236 (10)	−0.0007 (7)	0.0027 (8)	−0.0004 (7)
C4	0.0203 (9)	0.0191 (9)	0.0215 (10)	−0.0007 (7)	0.0020 (7)	−0.0016 (7)
C5	0.0230 (10)	0.0255 (10)	0.0288 (11)	−0.0018 (8)	0.0062 (8)	0.0047 (8)
C6	0.0311 (11)	0.0350 (12)	0.0332 (12)	−0.0093 (9)	0.0012 (9)	0.0059 (9)
C7	0.0419 (13)	0.0429 (13)	0.0294 (12)	−0.0077 (10)	0.0037 (10)	0.0069 (9)
C8	0.0235 (10)	0.0266 (10)	0.0219 (10)	0.0022 (8)	0.0035 (8)	−0.0017 (8)

Geometric parameters (Å, º) top

Ca1—O4ⁱ	2.4104 (14)	N1—C1	1.380 (2)
Ca1—O4ⁱⁱ	2.4104 (14)	N2—C3	1.354 (2)
Ca1—O1W	2.4798 (15)	N2—C2	1.362 (2)
Ca1—O1Wⁱⁱⁱ	2.4799 (15)	N2—H2	0.8600
Ca1—N1ⁱⁱⁱ	2.5982 (15)	C1—C2	1.376 (3)
Ca1—N1	2.5982 (15)	C1—C4	1.468 (3)
Ca1—O1	2.6048 (14)	C2—C8	1.484 (3)
Ca1—O1ⁱⁱⁱ	2.6049 (14)	C3—C5	1.484 (3)
O1—C4	1.242 (2)	C5—C6	1.530 (3)
O1W—H1W	0.8378	C5—H5A	0.9700
O1W—H2W	0.8287	C5—H5B	0.9700
O2—C4	1.287 (2)	C6—C7	1.517 (3)
O2—H1	0.8200	C6—H6A	0.9700
O3—C8	1.284 (2)	C6—H6B	0.9700
O4—C8	1.228 (2)	C7—H7A	0.9600
O4—Ca1^iv	2.4102 (14)	C7—H7B	0.9600
N1—C3	1.330 (2)	C7—H7C	0.9600

O4ⁱ—Ca1—O4ⁱⁱ	72.89 (8)	C3—N2—C2	108.98 (15)
O4ⁱ—Ca1—O1W	125.76 (5)	C3—N2—H2	125.5
O4ⁱⁱ—Ca1—O1W	71.69 (5)	C2—N2—H2	125.5
O4ⁱ—Ca1—O1Wⁱⁱⁱ	71.69 (5)	C2—C1—N1	110.21 (16)
O4ⁱⁱ—Ca1—O1Wⁱⁱⁱ	125.76 (5)	C2—C1—C4	130.27 (17)
O1W—Ca1—O1Wⁱⁱⁱ	160.66 (7)	N1—C1—C4	119.30 (15)
O4ⁱ—Ca1—N1ⁱⁱⁱ	156.52 (5)	N2—C2—C1	104.93 (16)
O4ⁱⁱ—Ca1—N1ⁱⁱⁱ	107.72 (5)	N2—C2—C8	121.21 (16)
O1W—Ca1—N1ⁱⁱⁱ	74.52 (5)	C1—C2—C8	133.83 (17)
O1Wⁱⁱⁱ—Ca1—N1ⁱⁱⁱ	90.68 (5)	N1—C3—N2	110.39 (16)
O4ⁱ—Ca1—N1	107.72 (5)	N1—C3—C5	128.07 (17)
O4ⁱⁱ—Ca1—N1	156.53 (5)	N2—C3—C5	121.51 (17)
O1W—Ca1—N1	90.68 (5)	O1—C4—O2	122.20 (17)
O1Wⁱⁱⁱ—Ca1—N1	74.52 (5)	O1—C4—C1	118.94 (16)
N1ⁱⁱⁱ—Ca1—N1	81.19 (7)	O2—C4—C1	118.82 (16)
O4ⁱ—Ca1—O1	73.86 (5)	C3—C5—C6	112.93 (16)
O4ⁱⁱ—Ca1—O1	94.96 (5)	C3—C5—H5A	109.0
O1W—Ca1—O1	69.83 (5)	C6—C5—H5A	109.0
O1Wⁱⁱⁱ—Ca1—O1	112.64 (5)	C3—C5—H5B	109.0
N1ⁱⁱⁱ—Ca1—O1	128.56 (5)	C6—C5—H5B	109.0
N1—Ca1—O1	63.74 (4)	H5A—C5—H5B	107.8
O4ⁱ—Ca1—O1ⁱⁱⁱ	94.96 (5)	C7—C6—C5	111.95 (17)
O4ⁱⁱ—Ca1—O1ⁱⁱⁱ	73.85 (5)	C7—C6—H6A	109.2
O1W—Ca1—O1ⁱⁱⁱ	112.64 (5)	C5—C6—H6A	109.2
O1Wⁱⁱⁱ—Ca1—O1ⁱⁱⁱ	69.82 (5)	C7—C6—H6B	109.2
N1ⁱⁱⁱ—Ca1—O1ⁱⁱⁱ	63.74 (4)	C5—C6—H6B	109.2
N1—Ca1—O1ⁱⁱⁱ	128.56 (5)	H6A—C6—H6B	107.9
O1—Ca1—O1ⁱⁱⁱ	166.32 (6)	C6—C7—H7A	109.5
C4—O1—Ca1	121.13 (12)	C6—C7—H7B	109.5
Ca1—O1W—H1W	119.1	H7A—C7—H7B	109.5
Ca1—O1W—H2W	109.3	C6—C7—H7C	109.5
H1W—O1W—H2W	109.8	H7A—C7—H7C	109.5
C4—O2—H1	109.5	H7B—C7—H7C	109.5
C8—O4—Ca1^iv	165.57 (15)	O4—C8—O3	124.05 (18)
C3—N1—C1	105.49 (14)	O4—C8—C2	119.22 (17)
C3—N1—Ca1	138.32 (12)	O3—C8—C2	116.72 (17)
C1—N1—Ca1	116.18 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^v	0.86	2.01	2.859 (2)	171
O1W—H2W···O1^vi	0.83	2.31	3.088 (2)	156
O1W—H1W···O3^vii	0.84	2.12	2.947 (2)	172

Symmetry codes: (v) −x+1/2, y+1/2, −z+1/2; (vi) −x+1, −y, −z+1; (vii) −x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Ca(C₈H₉N₂O₄)₂(H₂O)₂]
M_r	470.46
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	273
a, b, c (Å)	12.703 (3), 13.006 (3), 11.697 (2)
β (°)	97.864 (2)
V (Å³)	1914.3 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.32 × 0.24 × 0.20

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.884, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	4830, 1718, 1504
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.099, 1.02
No. of reflections	1718
No. of parameters	144
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.23

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), 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
N2—H2···O1ⁱ	0.86	2.01	2.859 (2)	170.9
O1W—H2W···O1ⁱⁱ	0.83	2.31	3.088 (2)	156.2
O1W—H1W···O3ⁱⁱⁱ	0.84	2.12	2.947 (2)	171.6

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

Acknowledgements

The authors acknowledge Guang Dong Ocean University for supporting this work.

References

Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liang, Y. C., Cao, R. & Hong, M. C. (2002). Inorg. Chem. Commun. 5, 366–368. Web of Science CSD CrossRef CAS Google Scholar
Net, G., Bayon, J. C., Butler, W. M. & Rasmussen, P. (1989). J. Chem. Soc. Chem. Commun. pp. 1022–1023. CrossRef Web of Science Google Scholar
Nie, X.-L., Wen, H.-L., Wu, Z.-S., Liu, D.-B. & Liu, C.-B. (2007). Acta Cryst. E63, m753–m755. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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