A two-dimensional calcium (II) coordination polymer constructed from 2,2′-[tereph­thal­oyl­bis(aza­nedi­yl)]di­acetate: synthesis, structure and properties

A new two-dimensional (2D) coordination polymer, namely, poly[[di­aqua-[μ₄-2,2′-[tereph­thal­oyl­bis(aza­nedi­yl)]di­acetato]­calcium(II)] monohydrate], {[Ca(C₁₂H₁₀N₂O₆)(H₂O)₂]·H₂O}_n, (I), has been synthesized by the reaction of CaCl₂ with 2,2′-[tereph­thal­oyl­bis(aza­nedi­yl)]di­acetic acid (H₂L). The title com­pound was structurally characterized by single-crystal X-ray diffraction analysis, elemental analysis and IR spectroscopy. In the crystal structure of (I), each Ca^II cation binds to six carboxyl­ate groups from four symmetry-related L²⁻ dianions. The hexa­dentate L²⁻ ligand links four symmetry-related calcium cat­ions into a 2D layer-like structure, which can be simplified as a uninodal SP 2-periodic (3,6)III net with the point symbol (4³·6³). In the lattice, all layers pack in parallel arrays through weak interlayer hydrogen bonding and π–π inter­­actions. The thermal stability and photoluminescence properties of (I) have been investigated. Thermogravimetric analysis reveals the different thermal stabilities of the two coordinated water mol­ecules due to their different hydrogen-bonding inter­actions. The title coordination polymer exhibits an excitation-wavelength-dependent fluorescence in the solid state.

Computing details

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: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Poly[[diaqua-[µ₄-2,2'-[terephthaloylbis(azanediyl)]diacetato]calcium(II)] monohydrate]

Crystal data

[Ca(C12H10N2O6)(H2O)2]·H2O	Z = 2
Mr = 372.35	F(000) = 388
Triclinic, P1	Dx = 1.585 Mg m^−3
a = 6.661 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.833 (5) Å	Cell parameters from 2311 reflections
c = 12.612 (6) Å	θ = 2.4–27.3°
α = 74.277 (6)°	µ = 0.45 mm^−1
β = 79.224 (6)°	T = 298 K
γ = 84.609 (7)°	Block, colorless
V = 780.3 (7) Å^3	0.10 × 0.05 × 0.05 mm

Data collection

Bruker APEXII CCD area detector diffractometer	2466 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
phi and ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→8
Tmin = 0.956, Tmax = 0.978	k = −12→12
6752 measured reflections	l = −16→16
3500 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.037P)^2 + 0.2954P] where P = (Fo^2 + 2Fc^2)/3
3500 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 0.26 e Å^−3
6 restraints	Δρmin = −0.38 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca1	1.25863 (7)	1.11412 (5)	0.45454 (4)	0.02446 (13)
O1	1.3797 (2)	0.91071 (17)	0.59367 (14)	0.0294 (4)
O2	1.0549 (2)	0.87796 (19)	0.60380 (14)	0.0351 (4)
C1	1.2164 (3)	0.8514 (2)	0.64274 (19)	0.0222 (5)
C2	1.2265 (4)	0.7426 (3)	0.7532 (2)	0.0313 (6)
H2A	1.2869	0.6548	0.7379	0.038*
H2B	1.3168	0.7752	0.7924	0.038*
N1	1.0319 (3)	0.7141 (2)	0.82597 (17)	0.0312 (5)
H1	0.9840	0.6315	0.8409	0.037*
O3	0.9881 (3)	0.93131 (18)	0.85523 (15)	0.0363 (4)
C10	0.1414 (4)	0.6689 (3)	1.15025 (19)	0.0260 (5)
C7	0.3423 (4)	0.7073 (2)	1.07676 (19)	0.0254 (5)
C8	0.3700 (4)	0.8379 (2)	0.9991 (2)	0.0317 (6)
H8	0.2613	0.9046	0.9920	0.038*
C3	0.9245 (3)	0.8125 (2)	0.87056 (19)	0.0265 (5)
C4	0.7218 (3)	0.7711 (2)	0.9416 (2)	0.0264 (5)
C9	0.5577 (4)	0.8690 (3)	0.9327 (2)	0.0323 (6)
H9	0.5745	0.9567	0.8812	0.039*
C5	0.6936 (4)	0.6400 (3)	1.0178 (2)	0.0314 (6)
H5	0.8017	0.5728	1.0240	0.038*
C6	0.5061 (4)	0.6089 (3)	1.0844 (2)	0.0312 (6)
H6	0.4890	0.5207	1.1351	0.037*
O4	0.0976 (3)	0.54303 (17)	1.18875 (15)	0.0370 (4)
N2	0.0128 (3)	0.7737 (2)	1.17112 (17)	0.0309 (5)
H2	0.0493	0.8593	1.1420	0.037*
C11	−0.1854 (4)	0.7503 (3)	1.2404 (2)	0.0349 (6)
H11A	−0.2194	0.6536	1.2494	0.042*
H11B	−0.2860	0.8120	1.2017	0.042*
C12	−0.2031 (3)	0.7750 (2)	1.3545 (2)	0.0270 (5)
O5	−0.3795 (2)	0.77374 (18)	1.41158 (14)	0.0323 (4)
O6	−0.0473 (2)	0.79722 (19)	1.38916 (15)	0.0358 (4)
O7	1.3077 (2)	0.95735 (18)	0.33418 (14)	0.0340 (4)
H7A	1.1963	0.9079	0.3427	0.041*
H7B	1.4032	0.8887	0.3530	0.041*
O8	1.2872 (3)	1.35794 (19)	0.35771 (17)	0.0490 (5)
H8A	1.2760	1.4133	0.4051	0.059*
H8B	1.1812	1.3909	0.3215	0.059*
O9	0.2835 (6)	0.5726 (5)	0.4705 (9)	0.084 (2)	0.843 (18)
H9A	0.3791	0.6102	0.4872	0.101*
H9B	0.1860	0.6336	0.4574	0.101*
O9A	0.314 (4)	0.604 (3)	0.402 (4)	0.084 (2)	0.157 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0161 (2)	0.0298 (3)	0.0264 (3)	−0.00160 (18)	−0.00507 (19)	−0.0043 (2)
O1	0.0173 (8)	0.0344 (9)	0.0314 (9)	−0.0076 (7)	−0.0004 (7)	−0.0004 (7)
O2	0.0188 (8)	0.0493 (11)	0.0387 (10)	0.0025 (7)	−0.0122 (8)	−0.0103 (9)
C1	0.0168 (11)	0.0245 (12)	0.0249 (12)	0.0009 (9)	−0.0024 (10)	−0.0072 (10)
C2	0.0217 (12)	0.0328 (13)	0.0320 (14)	0.0008 (10)	−0.0010 (11)	0.0009 (11)
N1	0.0293 (11)	0.0246 (11)	0.0336 (12)	−0.0079 (9)	0.0087 (9)	−0.0044 (9)
O3	0.0337 (10)	0.0284 (9)	0.0475 (12)	−0.0079 (8)	−0.0040 (9)	−0.0105 (8)
C10	0.0260 (12)	0.0308 (13)	0.0221 (12)	−0.0046 (10)	−0.0038 (10)	−0.0072 (10)
C7	0.0248 (12)	0.0285 (12)	0.0238 (13)	−0.0049 (10)	−0.0030 (10)	−0.0076 (10)
C8	0.0276 (13)	0.0285 (13)	0.0341 (15)	0.0021 (10)	−0.0035 (11)	−0.0023 (11)
C3	0.0236 (12)	0.0291 (13)	0.0252 (13)	−0.0017 (10)	−0.0036 (10)	−0.0045 (10)
C4	0.0250 (12)	0.0298 (13)	0.0252 (13)	−0.0042 (10)	−0.0029 (10)	−0.0085 (10)
C9	0.0335 (14)	0.0290 (13)	0.0291 (14)	−0.0026 (11)	−0.0025 (11)	0.0001 (11)
C5	0.0281 (13)	0.0309 (13)	0.0322 (14)	0.0016 (11)	−0.0032 (11)	−0.0056 (11)
C6	0.0309 (14)	0.0285 (13)	0.0295 (14)	−0.0030 (10)	−0.0009 (11)	−0.0018 (11)
O4	0.0355 (10)	0.0261 (9)	0.0446 (11)	−0.0083 (8)	0.0016 (9)	−0.0043 (8)
N2	0.0274 (11)	0.0298 (11)	0.0347 (12)	−0.0050 (9)	0.0052 (9)	−0.0126 (9)
C11	0.0246 (13)	0.0467 (16)	0.0374 (15)	−0.0029 (11)	−0.0014 (12)	−0.0196 (13)
C12	0.0226 (12)	0.0230 (12)	0.0344 (14)	−0.0009 (9)	−0.0035 (11)	−0.0065 (10)
O5	0.0208 (9)	0.0438 (10)	0.0333 (10)	−0.0004 (7)	−0.0012 (8)	−0.0144 (8)
O6	0.0228 (9)	0.0484 (11)	0.0403 (11)	−0.0072 (8)	−0.0066 (8)	−0.0154 (9)
O7	0.0232 (9)	0.0425 (10)	0.0389 (11)	−0.0013 (7)	−0.0090 (8)	−0.0122 (8)
O8	0.0557 (13)	0.0368 (11)	0.0530 (13)	−0.0031 (9)	−0.0215 (11)	−0.0003 (9)
O9	0.061 (2)	0.045 (2)	0.152 (7)	−0.0021 (15)	−0.041 (3)	−0.022 (3)
O9A	0.061 (2)	0.045 (2)	0.152 (7)	−0.0021 (15)	−0.041 (3)	−0.022 (3)

Geometric parameters (Å, º)

Ca1—O2^i	2.3284 (19)	C8—C9	1.378 (3)
Ca1—O1^ii	2.3778 (19)	C8—H8	0.9300
Ca1—O8	2.385 (2)	C3—C4	1.498 (3)
Ca1—O7	2.403 (2)	C4—C9	1.387 (3)
Ca1—O1	2.4606 (18)	C4—C5	1.389 (3)
Ca1—O6^iii	2.508 (2)	C9—H9	0.9300
Ca1—O5^iii	2.5297 (19)	C5—C6	1.378 (3)
Ca1—O2	2.837 (2)	C5—H5	0.9300
Ca1—C12^iii	2.852 (3)	C6—H6	0.9300
Ca1—Ca1^ii	3.9140 (17)	N2—C11	1.441 (3)
Ca1—Ca1^i	4.0994 (19)	N2—H2	0.8600
O1—C1	1.256 (3)	C11—C12	1.506 (4)
O1—Ca1^ii	2.3778 (19)	C11—H11A	0.9700
O2—C1	1.242 (3)	C11—H11B	0.9700
O2—Ca1^i	2.3285 (19)	C12—O6	1.257 (3)
C1—C2	1.518 (3)	C12—O5	1.257 (3)
C2—N1	1.444 (3)	C12—Ca1^iii	2.852 (3)
C2—H2A	0.9700	O5—Ca1^iii	2.5297 (19)
C2—H2B	0.9700	O6—Ca1^iii	2.508 (2)
N1—C3	1.334 (3)	O7—H7A	0.8990
N1—H1	0.8600	O7—H7B	0.8980
O3—C3	1.234 (3)	O8—H8A	0.9010
C10—O4	1.242 (3)	O8—H8B	0.8999
C10—N2	1.328 (3)	O9—H9A	0.8499
C10—C7	1.495 (3)	O9—H9B	0.8499
C7—C6	1.388 (3)	O9A—H9A	1.2543
C7—C8	1.392 (3)	O9A—H9B	1.0682
O2^i—Ca1—O1^ii	146.09 (7)	O2—C1—O1	122.7 (2)
O2^i—Ca1—O8	88.29 (7)	O2—C1—C2	121.0 (2)
O1^ii—Ca1—O8	87.29 (6)	O1—C1—C2	116.26 (19)
O2^i—Ca1—O7	75.07 (6)	N1—C2—C1	114.88 (19)
O1^ii—Ca1—O7	76.19 (6)	N1—C2—H2A	108.5
O8—Ca1—O7	114.08 (8)	C1—C2—H2A	108.5
O2^i—Ca1—O1	122.68 (6)	N1—C2—H2B	108.5
O1^ii—Ca1—O1	72.02 (6)	C1—C2—H2B	108.5
O8—Ca1—O1	147.67 (7)	H2A—C2—H2B	107.5
O7—Ca1—O1	85.41 (7)	C3—N1—C2	121.7 (2)
O2^i—Ca1—O6^iii	83.43 (7)	C3—N1—H1	119.2
O1^ii—Ca1—O6^iii	129.57 (6)	C2—N1—H1	119.2
O8—Ca1—O6^iii	85.23 (7)	O4—C10—N2	121.9 (2)
O7—Ca1—O6^iii	150.14 (6)	O4—C10—C7	120.5 (2)
O1—Ca1—O6^iii	89.15 (7)	N2—C10—C7	117.6 (2)
O2^i—Ca1—O5^iii	132.81 (6)	C6—C7—C8	118.6 (2)
O1^ii—Ca1—O5^iii	78.00 (6)	C6—C7—C10	119.2 (2)
O8—Ca1—O5^iii	75.16 (7)	C8—C7—C10	122.2 (2)
O7—Ca1—O5^iii	151.98 (6)	C9—C8—C7	120.3 (2)
O1—Ca1—O5^iii	76.37 (7)	C9—C8—H8	119.8
O6^iii—Ca1—O5^iii	51.89 (6)	C7—C8—H8	119.8
O2^i—Ca1—O2	75.37 (7)	O3—C3—N1	122.2 (2)
O1^ii—Ca1—O2	117.18 (5)	O3—C3—C4	121.3 (2)
O8—Ca1—O2	154.46 (6)	N1—C3—C4	116.5 (2)
O7—Ca1—O2	80.94 (7)	C9—C4—C5	118.9 (2)
O1—Ca1—O2	48.26 (5)	C9—C4—C3	118.6 (2)
O6^iii—Ca1—O2	73.66 (6)	C5—C4—C3	122.5 (2)
O5^iii—Ca1—O2	101.55 (6)	C8—C9—C4	120.8 (2)
O2^i—Ca1—C12^iii	109.22 (7)	C8—C9—H9	119.6
O1^ii—Ca1—C12^iii	103.45 (6)	C4—C9—H9	119.6
O8—Ca1—C12^iii	82.29 (8)	C6—C5—C4	120.3 (2)
O7—Ca1—C12^iii	163.46 (6)	C6—C5—H5	119.9
O1—Ca1—C12^iii	78.88 (7)	C4—C5—H5	119.9
O6^iii—Ca1—C12^iii	26.12 (6)	C5—C6—C7	121.0 (2)
O5^iii—Ca1—C12^iii	26.14 (6)	C5—C6—H6	119.5
O2—Ca1—C12^iii	84.72 (7)	C7—C6—H6	119.5
O2^i—Ca1—Ca1^ii	147.52 (5)	C10—N2—C11	122.8 (2)
O1^ii—Ca1—Ca1^ii	36.72 (4)	C10—N2—H2	118.6
O8—Ca1—Ca1^ii	120.16 (6)	C11—N2—H2	118.6
O7—Ca1—Ca1^ii	78.74 (5)	N2—C11—C12	115.2 (2)
O1—Ca1—Ca1^ii	35.30 (4)	N2—C11—H11A	108.5
O6^iii—Ca1—Ca1^ii	112.19 (5)	C12—C11—H11A	108.5
O5^iii—Ca1—Ca1^ii	74.07 (5)	N2—C11—H11B	108.5
O2—Ca1—Ca1^ii	81.89 (5)	C12—C11—H11B	108.5
C12^iii—Ca1—Ca1^ii	91.15 (5)	H11A—C11—H11B	107.5
O2^i—Ca1—Ca1^i	42.03 (5)	O6—C12—O5	122.5 (2)
O1^ii—Ca1—Ca1^i	141.95 (5)	O6—C12—C11	120.6 (2)
O8—Ca1—Ca1^i	127.40 (5)	O5—C12—C11	116.8 (2)
O7—Ca1—Ca1^i	75.20 (5)	O6—C12—Ca1^iii	61.47 (13)
O1—Ca1—Ca1^i	81.14 (5)	O5—C12—Ca1^iii	62.46 (13)
O6^iii—Ca1—Ca1^i	74.95 (5)	C11—C12—Ca1^iii	167.11 (17)
O5^iii—Ca1—Ca1^i	121.64 (5)	C12—O5—Ca1^iii	91.40 (14)
O2—Ca1—Ca1^i	33.34 (3)	C12—O6—Ca1^iii	92.41 (15)
C12^iii—Ca1—Ca1^i	97.09 (5)	Ca1—O7—H7A	112.0
Ca1^ii—Ca1—Ca1^i	112.43 (4)	Ca1—O7—H7B	111.4
C1—O1—Ca1^ii	146.93 (14)	H7A—O7—H7B	102.2
C1—O1—Ca1	102.32 (13)	Ca1—O8—H8A	111.9
Ca1^ii—O1—Ca1	107.98 (6)	Ca1—O8—H8B	111.6
C1—O2—Ca1^i	169.89 (17)	H8A—O8—H8B	102.1
C1—O2—Ca1	84.81 (14)	H9A—O9—H9B	109.5
Ca1^i—O2—Ca1	104.63 (6)	H9A—O9A—H9B	72.9
Ca1^i—O2—C1—O1	146.1 (8)	O3—C3—C4—C5	−137.6 (3)
Ca1—O2—C1—O1	−13.2 (2)	N1—C3—C4—C5	41.9 (3)
Ca1^i—O2—C1—C2	−33.3 (10)	C7—C8—C9—C4	0.2 (4)
Ca1—O2—C1—C2	167.4 (2)	C5—C4—C9—C8	0.8 (4)
Ca1^ii—O1—C1—O2	−140.5 (2)	C3—C4—C9—C8	−177.6 (2)
Ca1—O1—C1—O2	15.6 (3)	C9—C4—C5—C6	−0.9 (4)
Ca1^ii—O1—C1—C2	38.9 (4)	C3—C4—C5—C6	177.5 (2)
Ca1—O1—C1—C2	−164.99 (17)	C4—C5—C6—C7	0.0 (4)
O2—C1—C2—N1	−21.9 (3)	C8—C7—C6—C5	0.9 (4)
O1—C1—C2—N1	158.7 (2)	C10—C7—C6—C5	179.8 (2)
C1—C2—N1—C3	−65.6 (3)	O4—C10—N2—C11	0.6 (4)
O4—C10—C7—C6	−23.9 (3)	C7—C10—N2—C11	179.8 (2)
N2—C10—C7—C6	156.9 (2)	C10—N2—C11—C12	106.1 (3)
O4—C10—C7—C8	154.8 (2)	N2—C11—C12—O6	−8.3 (3)
N2—C10—C7—C8	−24.4 (3)	N2—C11—C12—O5	171.0 (2)
C6—C7—C8—C9	−1.0 (4)	N2—C11—C12—Ca1^iii	87.4 (7)
C10—C7—C8—C9	−179.8 (2)	O6—C12—O5—Ca1^iii	13.8 (2)
C2—N1—C3—O3	−2.4 (4)	C11—C12—O5—Ca1^iii	−165.52 (19)
C2—N1—C3—C4	178.1 (2)	O5—C12—O6—Ca1^iii	−13.9 (2)
O3—C3—C4—C9	40.8 (3)	C11—C12—O6—Ca1^iii	165.4 (2)
N1—C3—C4—C9	−139.7 (2)

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+3, −y+2, −z+1; (iii) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^iv	0.86	2.00	2.810 (3)	158
N2—H2···O3^iii	0.86	2.06	2.828 (3)	148
O7—H7A···O6^v	0.90	1.95	2.837 (3)	170
O7—H7B···O5^vi	0.90	1.89	2.766 (2)	166
O8—H8B···O4^vii	0.90	2.05	2.814 (3)	143
C11—H11A···O4	0.97	2.38	2.769 (3)	104
O8—H8A···O9^viii	0.90	1.97	2.843 (8)	164
O8—H8A···O9A^viii	0.90	1.90	2.660 (3)	140
O9—H9A···O5^v	0.85	2.27	2.986 (6)	142
O9—H9B···O6^ix	0.85	2.24	3.080 (6)	169

Symmetry codes: (iii) −x+1, −y+2, −z+2; (iv) −x+1, −y+1, −z+2; (v) x+1, y, z−1; (vi) x+2, y, z−1; (vii) x+1, y+1, z−1; (viii) x+1, y+1, z; (ix) x, y, z−1.