catena-Poly[[diaqua­calcium(II)]-di-μ-2-chloro­nicotinato]

Quan, L.; Yin, H.; Cui, L.; Yang, M.

doi:10.1107/S1600536808044267

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages m167-m168

doi:10.1107/S1600536808044267

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catena-Poly[[diaquacalcium(II)]-di-μ-2-chloronicotinato]

Li Quan,^a Handong Yin,^a ^* Liansheng Cui ^a and Minglei Yang ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: handongyin@163.com

(Received 15 November 2008; accepted 31 December 2008; online 10 January 2009)

The itle compound, [Ca(C₆H₃ClNO₂)₂(H₂O)₂]_n, contains polymeric chains extending along [100] that are generated by inversion centres. The Ca²⁺ ions are bridged by 2-chloronicotinate groups and exhibit an eight-coordination by six carboxylate O atoms of four different 2-chloronicotinate ligands and two O atoms of water molecules. In the crystal structure, intermolecular O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds result in the formation of a supramolecular network structure. The π–π contacts between the 2-chloronicotinate rings [centroid–centroid distances = 3.875 (3) and 3.701 (3) Å] may further stabilize the structure.

Related literature

For general background, see: Schmidbaur et al. (1989 , 1990 ). For related structures, see: Murugavel & Banerjee (2003 ); Radanovic et al. (2004 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Ca(C₆H₃ClNO₂)₂(H₂O)₂]
M_r = 389.20
Triclinic, $[P \overline 1]$
a = 7.8363 (10) Å
b = 10.8421 (16) Å
c = 10.8834 (16) Å
α = 98.455 (2)°
β = 97.610 (1)°
γ = 97.289 (1)°
V = 896.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 298 (2) K
0.48 × 0.40 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.738, T_max = 0.823
4594 measured reflections
3074 independent reflections
2306 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.145
S = 1.03
3074 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ca1—O4ⁱ	2.366 (3)
Ca1—O5	2.373 (3)
Ca1—O1	2.375 (2)
Ca1—O3	2.391 (3)
Ca1—O6	2.393 (3)
Ca1—O2ⁱⁱ	2.461 (3)
Ca1—O1ⁱⁱ	2.641 (3)
Ca1—O4	2.734 (3)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+2, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5B⋯O3ⁱⁱ	0.85	1.92	2.765 (3)	171
O5—H5C⋯N2ⁱⁱⁱ	0.85	2.01	2.831 (3)	162
O6—H6B⋯N1^iv	0.85	2.07	2.919 (4)	173
O6—H6C⋯O2^v	0.85	2.00	2.826 (3)	165
C6—H6⋯O5^iv	0.93	2.52	3.432 (4)	166
Symmetry codes: (ii) -x+2, -y, -z+1; (iii) x, y-1, z; (iv) -x+2, -y, -z+2; (v) x-1, y, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808044267/hk2578sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808044267/hk2578Isup2.hkl

checkCIF report

Comment top

Chemistry of alkaline earth metals is an unexplored area. The model complexes containing Mg²⁺ and Ca²⁺ cations have previously been prepared and used as probes for understanding the binding modes of these metals (Schmidbaur et al., 1989, 1990). In our ongoing studies with 2-chloronicotinate ligand and s-block metal ions, the title compound has been synthesized, and we report herein its crystal structure.

In the molecule of the title compound, (I), (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. It has an inversion centre midway between the two Ca^II ions, which are bridged by 2-chloronicotinate groups. Each Ca atom is eight-coordinated by six O atoms of 2-chloronicotinate ligands and two O atoms of water molecules. It essentially forms a one-dimensional chain structure (Fig. 2). The Ca—O bonds are in the range of [2.366 (3)–2.734 (3) Å] (Table 1). The average value of the Ca—O bonds [2.467 (3) Å] is almost the same with the corresponding values [2.4674 (9) Å] in [Ca(3-aba)₂(H₂O)₂]_n (where 3-aba is 3-aminobenzoic acid), (II) (Murugavel & Banerjee, 2003) and [2.4556 (8) Å] in [Ca(H₂O)₃Ca(1,3-pdta)- (H₂O)]. 2(H₂O) (where 1,3-pdta is the 1,3-propanediaminetetraacetate ion), (III) (Radanovic et al., 2004). The Ca1—Ca1ⁱ [4.0553 (14) Å] and Ca1—Ca1ⁱⁱ [4.0681 (14) Å] [symmetry codes: (i) 1 - x, -y, 1 - z, (ii) 2 - x, -y, 1 - z] distances are longer than the corresponding value [4.0034 (5) Å] in (II).

In the crystal structure, intermolecular O—H···O, O—H···N and C—H···O hydrogen bonds (Table 2) result in the formation of a supramolecular network structure. The π–π contacts between the 2-chloronicotinate rings, Cg1–Cg1ⁱ and Cg2–Cg2ⁱⁱ [symmetry codes: (i) -x, 2 - y, -z; (ii) 1 - x, 1 - y, 1 - z, where Cg1 and Cg2 are centroids of the rings A (N1/C2–C6) and B (N2/C8–C12), respectively] may further stabilize the structure, with centroid–centroid distances of 3.875 (3) Å and 3.701 (3) Å.

Related literature top

For general background, see: Schmidbaur et al. (1989, 1990). For related structures, see: Murugavel & Banerjee (2003); Radanovic et al. (2004). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, CaCl₂(H₂O)₂ (0.588 g, 4 mmol) and 2-chloronicotinic acid (0.044 g, 0.4 mmol) were dissolved in H₂O (20 ml) and MeOH (30 ml) by refluxing for 30 min. Sodium methoxide (0.4 mmol, 0.8 ml) was added dropwise by stirring. After refluxing for 8 h, the colorless solution was obtained, and then filtered. The solvent was gradually removed by evaporation under vacuum until the colorless solid was obtained, which was recrystallized from petroleum ether–dichoromethane (1:1) to give the block-shaped colorless crystals.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound, showing the formation of the one dimensional chain structure.

catena-Poly[[diaquacalcium(II)]-di-µ-2-chloronicotinato] top

Crystal data top

[Ca(C₆H₃ClNO₂)₂(H₂O)₂]	Z = 2
M_r = 389.20	F(000) = 396
Triclinic, P1	D_x = 1.442 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8363 (10) Å	Cell parameters from 2126 reflections
b = 10.8421 (16) Å	θ = 2.5–27.6°
c = 10.8834 (16) Å	µ = 0.68 mm⁻¹
α = 98.455 (2)°	T = 298 K
β = 97.610 (1)°	Block, colourless
γ = 97.289 (1)°	0.48 × 0.40 × 0.30 mm
V = 896.4 (2) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3074 independent reflections
Radiation source: fine-focus sealed tube	2306 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.738, T_max = 0.823	k = −11→12
4594 measured reflections	l = −11→12

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.072P)² + 0.8771P] where P = (F_o² + 2F_c²)/3
3074 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Ca(C₆H₃ClNO₂)₂(H₂O)₂]	γ = 97.289 (1)°
M_r = 389.20	V = 896.4 (2) Å³
Triclinic, P1	Z = 2
a = 7.8363 (10) Å	Mo Kα radiation
b = 10.8421 (16) Å	µ = 0.68 mm⁻¹
c = 10.8834 (16) Å	T = 298 K
α = 98.455 (2)°	0.48 × 0.40 × 0.30 mm
β = 97.610 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3074 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2306 reflections with I > 2σ(I)
T_min = 0.738, T_max = 0.823	R_int = 0.022
4594 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.03	Δρ_max = 0.47 e Å⁻³
3074 reflections	Δρ_min = −0.45 e Å⁻³
208 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.75350 (8)	−0.02117 (7)	0.54151 (6)	0.0273 (2)
Cl1	1.31442 (17)	−0.08155 (14)	0.89399 (12)	0.0688 (4)
Cl2	0.85580 (16)	0.45842 (12)	0.62037 (12)	0.0642 (4)
N1	1.2104 (5)	0.0770 (5)	1.0606 (3)	0.0597 (11)
N2	0.7024 (5)	0.5552 (3)	0.4414 (4)	0.0521 (9)
O1	1.0474 (3)	0.0510 (2)	0.6352 (2)	0.0363 (6)
O2	1.3309 (3)	0.1026 (3)	0.6846 (2)	0.0468 (7)
O3	0.8087 (3)	0.1815 (3)	0.4807 (3)	0.0501 (8)
O4	0.5271 (3)	0.1368 (3)	0.4706 (3)	0.0447 (7)
O5	0.8604 (3)	−0.2084 (2)	0.5835 (2)	0.0395 (6)
H5B	0.9605	−0.2092	0.5617	0.047*
H5C	0.7926	−0.2722	0.5410	0.047*
O6	0.6803 (4)	0.0628 (3)	0.7404 (3)	0.0539 (8)
H6B	0.7060	0.0164	0.7946	0.065*
H6C	0.5721	0.0672	0.7340	0.065*
C1	1.1815 (5)	0.0877 (4)	0.7134 (3)	0.0336 (8)
C2	1.2213 (5)	0.0517 (4)	0.9394 (4)	0.0447 (10)
C3	1.1612 (5)	0.1197 (4)	0.8500 (3)	0.0392 (9)
C4	1.0797 (6)	0.2201 (5)	0.8907 (4)	0.0574 (12)
H4	1.0330	0.2677	0.8339	0.069*
C5	1.0684 (7)	0.2488 (6)	1.0167 (5)	0.0694 (15)
H5	1.0168	0.3176	1.0462	0.083*
C6	1.1333 (6)	0.1758 (6)	1.0973 (4)	0.0644 (14)
H6	1.1235	0.1957	1.1819	0.077*
C7	0.6592 (5)	0.2077 (3)	0.4592 (4)	0.0335 (8)
C8	0.7209 (5)	0.4468 (4)	0.4786 (4)	0.0404 (9)
C9	0.6374 (4)	0.3299 (3)	0.4140 (4)	0.0334 (8)
C10	0.5307 (5)	0.3306 (4)	0.3029 (4)	0.0491 (11)
H10	0.4696	0.2553	0.2566	0.059*
C11	0.5145 (6)	0.4422 (5)	0.2605 (5)	0.0595 (13)
H11	0.4454	0.4430	0.1844	0.071*
C12	0.6014 (6)	0.5528 (5)	0.3319 (5)	0.0598 (13)
H12	0.5896	0.6283	0.3031	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0220 (4)	0.0305 (4)	0.0307 (4)	0.0046 (3)	0.0048 (3)	0.0083 (3)
Cl1	0.0708 (8)	0.0885 (10)	0.0633 (8)	0.0386 (7)	0.0216 (6)	0.0320 (7)
Cl2	0.0589 (7)	0.0549 (7)	0.0694 (8)	0.0096 (6)	−0.0128 (6)	−0.0008 (6)
N1	0.040 (2)	0.105 (3)	0.033 (2)	0.008 (2)	0.0044 (16)	0.013 (2)
N2	0.042 (2)	0.0327 (19)	0.083 (3)	0.0083 (16)	0.0124 (19)	0.0121 (18)
O1	0.0253 (13)	0.0476 (16)	0.0334 (14)	0.0041 (11)	0.0003 (11)	0.0036 (12)
O2	0.0246 (14)	0.077 (2)	0.0374 (15)	0.0034 (13)	0.0070 (11)	0.0061 (14)
O3	0.0299 (15)	0.0408 (16)	0.088 (2)	0.0111 (12)	0.0138 (14)	0.0274 (15)
O4	0.0327 (15)	0.0402 (15)	0.0632 (19)	−0.0010 (12)	0.0142 (13)	0.0149 (13)
O5	0.0300 (14)	0.0340 (14)	0.0570 (17)	0.0060 (11)	0.0099 (12)	0.0119 (12)
O6	0.0371 (16)	0.089 (2)	0.0397 (16)	0.0195 (15)	0.0091 (13)	0.0113 (15)
C1	0.031 (2)	0.041 (2)	0.0295 (19)	0.0066 (16)	0.0028 (16)	0.0084 (16)
C2	0.031 (2)	0.070 (3)	0.034 (2)	0.0077 (19)	0.0065 (16)	0.009 (2)
C3	0.0250 (19)	0.057 (3)	0.033 (2)	0.0035 (17)	0.0048 (16)	0.0027 (18)
C4	0.060 (3)	0.068 (3)	0.045 (3)	0.017 (2)	0.011 (2)	0.005 (2)
C5	0.064 (3)	0.088 (4)	0.053 (3)	0.019 (3)	0.018 (3)	−0.012 (3)
C6	0.048 (3)	0.104 (4)	0.036 (3)	0.004 (3)	0.012 (2)	−0.005 (3)
C7	0.0277 (19)	0.0288 (19)	0.045 (2)	0.0062 (15)	0.0093 (16)	0.0057 (16)
C8	0.030 (2)	0.034 (2)	0.059 (3)	0.0058 (16)	0.0092 (18)	0.0109 (18)
C9	0.0230 (18)	0.033 (2)	0.047 (2)	0.0064 (15)	0.0110 (16)	0.0109 (17)
C10	0.043 (2)	0.044 (2)	0.060 (3)	0.0105 (19)	0.001 (2)	0.009 (2)
C11	0.067 (3)	0.057 (3)	0.056 (3)	0.019 (2)	−0.005 (2)	0.020 (2)
C12	0.056 (3)	0.048 (3)	0.082 (4)	0.014 (2)	0.010 (3)	0.029 (3)

Geometric parameters (Å, º) top

Ca1—O4ⁱ	2.366 (3)	O4—C7	1.241 (4)
Ca1—O5	2.373 (3)	O4—Ca1ⁱ	2.366 (3)
Ca1—O1	2.375 (2)	O5—H5B	0.8499
Ca1—O3	2.391 (3)	O5—H5C	0.8500
Ca1—O6	2.393 (3)	O6—H6B	0.8501
Ca1—O2ⁱⁱ	2.461 (3)	O6—H6C	0.8500
Ca1—O1ⁱⁱ	2.641 (3)	C1—C3	1.511 (5)
Ca1—O4	2.734 (3)	C1—Ca1ⁱⁱ	2.890 (4)
Ca1—C1ⁱⁱ	2.890 (4)	C2—C3	1.375 (6)
Ca1—Ca1ⁱ	4.0553 (14)	C3—C4	1.377 (6)
Ca1—Ca1ⁱⁱ	4.0681 (14)	C4—C5	1.378 (6)
Ca1—H5B	2.7769	C4—H4	0.9300
Ca1—H5C	2.7764	C5—C6	1.357 (8)
Cl1—C2	1.737 (5)	C5—H5	0.9300
Cl2—C8	1.729 (4)	C6—H6	0.9300
N1—C2	1.323 (5)	C7—C9	1.501 (5)
N1—C6	1.332 (7)	C8—C9	1.391 (5)
N2—C8	1.317 (5)	C9—C10	1.378 (5)
N2—C12	1.336 (6)	C10—C11	1.372 (6)
O1—C1	1.242 (4)	C10—H10	0.9300
O1—Ca1ⁱⁱ	2.641 (3)	C11—C12	1.372 (7)
O2—C1	1.248 (4)	C11—H11	0.9300
O2—Ca1ⁱⁱ	2.461 (3)	C12—H12	0.9300
O3—C7	1.241 (4)

O4ⁱ—Ca1—O5	85.90 (9)	O5—Ca1—H5C	16.8
O4ⁱ—Ca1—O1	154.07 (10)	O1—Ca1—H5C	92.6
O5—Ca1—O1	76.49 (9)	O3—Ca1—H5C	155.0
O4ⁱ—Ca1—O3	124.46 (9)	O6—Ca1—H5C	108.6
O5—Ca1—O3	148.15 (9)	O2ⁱⁱ—Ca1—H5C	80.4
O1—Ca1—O3	77.33 (9)	O1ⁱⁱ—Ca1—H5C	80.4
O4ⁱ—Ca1—O6	79.48 (10)	O4—Ca1—H5C	144.2
O5—Ca1—O6	102.23 (10)	C1ⁱⁱ—Ca1—H5C	80.4
O1—Ca1—O6	85.76 (9)	Ca1ⁱ—Ca1—H5C	111.8
O3—Ca1—O6	93.57 (11)	Ca1ⁱⁱ—Ca1—H5C	85.3
O4ⁱ—Ca1—O2ⁱⁱ	76.74 (9)	H5B—Ca1—H5C	28.7
O5—Ca1—O2ⁱⁱ	93.19 (10)	C2—N1—C6	116.7 (4)
O1—Ca1—O2ⁱⁱ	122.53 (9)	C8—N2—C12	117.9 (4)
O3—Ca1—O2ⁱⁱ	85.84 (11)	C1—O1—Ca1	162.8 (2)
O6—Ca1—O2ⁱⁱ	150.55 (10)	C1—O1—Ca1ⁱⁱ	88.6 (2)
O4ⁱ—Ca1—O1ⁱⁱ	124.14 (9)	Ca1—O1—Ca1ⁱⁱ	108.26 (9)
O5—Ca1—O1ⁱⁱ	80.03 (9)	C1—O2—Ca1ⁱⁱ	96.9 (2)
O1—Ca1—O1ⁱⁱ	71.74 (9)	C7—O3—Ca1	101.6 (2)
O3—Ca1—O1ⁱⁱ	74.78 (9)	C7—O4—Ca1ⁱ	168.0 (3)
O6—Ca1—O1ⁱⁱ	156.33 (9)	C7—O4—Ca1	85.3 (2)
O2ⁱⁱ—Ca1—O1ⁱⁱ	50.80 (8)	Ca1ⁱ—O4—Ca1	105.13 (10)
O4ⁱ—Ca1—O4	74.87 (10)	Ca1—O5—H5B	109.6
O5—Ca1—O4	160.24 (9)	Ca1—O5—H5C	109.6
O1—Ca1—O4	123.16 (9)	H5B—O5—H5C	108.3
O3—Ca1—O4	49.89 (8)	Ca1—O6—H6B	110.5
O6—Ca1—O4	79.04 (9)	Ca1—O6—H6C	110.5
O2ⁱⁱ—Ca1—O4	78.19 (10)	H6B—O6—H6C	108.8
O1ⁱⁱ—Ca1—O4	106.86 (8)	O1—C1—O2	123.5 (3)
O4ⁱ—Ca1—C1ⁱⁱ	100.91 (10)	O1—C1—C3	117.9 (3)
O5—Ca1—C1ⁱⁱ	87.26 (10)	O2—C1—C3	118.5 (3)
O1—Ca1—C1ⁱⁱ	97.14 (10)	O1—C1—Ca1ⁱⁱ	65.98 (19)
O3—Ca1—C1ⁱⁱ	78.32 (11)	O2—C1—Ca1ⁱⁱ	57.69 (19)
O6—Ca1—C1ⁱⁱ	170.49 (11)	C3—C1—Ca1ⁱⁱ	175.5 (3)
O2ⁱⁱ—Ca1—C1ⁱⁱ	25.39 (9)	N1—C2—C3	125.2 (4)
O1ⁱⁱ—Ca1—C1ⁱⁱ	25.45 (9)	N1—C2—Cl1	115.4 (3)
O4—Ca1—C1ⁱⁱ	91.86 (9)	C3—C2—Cl1	119.4 (3)
O4ⁱ—Ca1—Ca1ⁱ	40.60 (7)	C2—C3—C4	116.7 (4)
O5—Ca1—Ca1ⁱ	126.35 (7)	C2—C3—C1	122.6 (4)
O1—Ca1—Ca1ⁱ	153.30 (7)	C4—C3—C1	120.7 (4)
O3—Ca1—Ca1ⁱ	84.02 (7)	C3—C4—C5	119.0 (5)
O6—Ca1—Ca1ⁱ	76.43 (7)	C3—C4—H4	120.5
O2ⁱⁱ—Ca1—Ca1ⁱ	74.23 (6)	C5—C4—H4	120.5
O1ⁱⁱ—Ca1—Ca1ⁱ	121.53 (6)	C6—C5—C4	119.5 (5)
O4—Ca1—Ca1ⁱ	34.28 (5)	C6—C5—H5	120.3
C1ⁱⁱ—Ca1—Ca1ⁱ	97.60 (7)	C4—C5—H5	120.3
O4ⁱ—Ca1—Ca1ⁱⁱ	152.81 (8)	N1—C6—C5	122.9 (4)
O5—Ca1—Ca1ⁱⁱ	75.59 (6)	N1—C6—H6	118.5
O1—Ca1—Ca1ⁱⁱ	38.06 (6)	C5—C6—H6	118.5
O3—Ca1—Ca1ⁱⁱ	72.63 (7)	O3—C7—O4	123.2 (3)
O6—Ca1—Ca1ⁱⁱ	123.46 (8)	O3—C7—C9	118.2 (3)
O2ⁱⁱ—Ca1—Ca1ⁱⁱ	84.47 (6)	O4—C7—C9	118.6 (3)
O1ⁱⁱ—Ca1—Ca1ⁱⁱ	33.68 (5)	N2—C8—C9	124.5 (4)
O4—Ca1—Ca1ⁱⁱ	120.51 (6)	N2—C8—Cl2	114.9 (3)
C1ⁱⁱ—Ca1—Ca1ⁱⁱ	59.09 (7)	C9—C8—Cl2	120.6 (3)
Ca1ⁱ—Ca1—Ca1ⁱⁱ	149.45 (4)	C10—C9—C8	116.3 (3)
O4ⁱ—Ca1—H5B	101.0	C10—C9—C7	120.2 (3)
O5—Ca1—H5B	16.8	C8—C9—C7	123.5 (3)
O1—Ca1—H5B	64.9	C11—C10—C9	120.0 (4)
O3—Ca1—H5B	131.5	C11—C10—H10	120.0
O6—Ca1—H5B	111.9	C9—C10—H10	120.0
O2ⁱⁱ—Ca1—H5B	89.7	C10—C11—C12	119.2 (4)
O1ⁱⁱ—Ca1—H5B	65.5	C10—C11—H11	120.4
O4—Ca1—H5B	167.8	C12—C11—H11	120.4
C1ⁱⁱ—Ca1—H5B	77.5	N2—C12—C11	122.0 (4)
Ca1ⁱ—Ca1—H5B	140.4	N2—C12—H12	119.0
Ca1ⁱⁱ—Ca1—H5B	58.9	C11—C12—H12	119.0
O4ⁱ—Ca1—H5C	72.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O3ⁱⁱ	0.85	1.92	2.765 (3)	171
O5—H5C···N2ⁱⁱⁱ	0.85	2.01	2.831 (3)	162
O6—H6B···N1^iv	0.85	2.07	2.919 (4)	173
O6—H6C···O2^v	0.85	2.00	2.826 (3)	165
C6—H6···O5^iv	0.93	2.52	3.432 (4)	166

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

Experimental details

Crystal data
Chemical formula	[Ca(C₆H₃ClNO₂)₂(H₂O)₂]
M_r	389.20
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.8363 (10), 10.8421 (16), 10.8834 (16)
α, β, γ (°)	98.455 (2), 97.610 (1), 97.289 (1)
V (Å³)	896.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.48 × 0.40 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.738, 0.823
No. of measured, independent and observed [I > 2σ(I)] reflections	4594, 3074, 2306
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.145, 1.03
No. of reflections	3074
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.45

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Ca1—O4ⁱ	2.366 (3)	Ca1—O2ⁱⁱ	2.461 (3)
Ca1—O5	2.373 (3)	Ca1—O1ⁱⁱ	2.641 (3)
Ca1—O1	2.375 (2)	Ca1—O4	2.734 (3)
Ca1—O3	2.391 (3)	Ca1—Ca1ⁱ	4.0553 (14)
Ca1—O6	2.393 (3)	Ca1—Ca1ⁱⁱ	4.0681 (14)

O4ⁱ—Ca1—O5	85.90 (9)	O4ⁱ—Ca1—O1ⁱⁱ	124.14 (9)
O4ⁱ—Ca1—O1	154.07 (10)	O5—Ca1—O1ⁱⁱ	80.03 (9)
O5—Ca1—O1	76.49 (9)	O1—Ca1—O1ⁱⁱ	71.74 (9)
O4ⁱ—Ca1—O3	124.46 (9)	O3—Ca1—O1ⁱⁱ	74.78 (9)
O5—Ca1—O3	148.15 (9)	O6—Ca1—O1ⁱⁱ	156.33 (9)
O1—Ca1—O3	77.33 (9)	O2ⁱⁱ—Ca1—O1ⁱⁱ	50.80 (8)
O4ⁱ—Ca1—O6	79.48 (10)	O4ⁱ—Ca1—O4	74.87 (10)
O5—Ca1—O6	102.23 (10)	O5—Ca1—O4	160.24 (9)
O1—Ca1—O6	85.76 (9)	O1—Ca1—O4	123.16 (9)
O4ⁱ—Ca1—O2ⁱⁱ	76.74 (9)	O3—Ca1—O4	49.89 (8)
O5—Ca1—O2ⁱⁱ	93.19 (10)	O6—Ca1—O4	79.04 (9)
O1—Ca1—O2ⁱⁱ	122.53 (9)	O2ⁱⁱ—Ca1—O4	78.19 (10)
O3—Ca1—O2ⁱⁱ	85.84 (11)	O1ⁱⁱ—Ca1—O4	106.86 (8)
O6—Ca1—O2ⁱⁱ	150.55 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O3ⁱⁱ	0.85	1.92	2.765 (3)	171.00
O5—H5C···N2ⁱⁱⁱ	0.85	2.01	2.831 (3)	162.00
O6—H6B···N1^iv	0.85	2.07	2.919 (4)	173.00
O6—H6C···O2^v	0.85	2.00	2.826 (3)	165.00
C6—H6···O5^iv	0.93	2.52	3.432 (4)	166.00

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

Acknowledgements

The authors acknowledge the National Natural Science Foundation of China (grant Nos. 20771053 and 20773059).

References

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