A Co-MOF with a (4,4)-connected binodal two-dimensional topology: synthesis, structure and photocatalytic properties

The Co-MOF poly[[di­aqua­{μ₄-1,1,2,2-tetra­kis­[4-(1H-1,2,4-triazol-1-yl)phen­yl]ethyl­ene-κ⁴N:N′:N′′:N′′′}cobalt(II)] benzene-1,4-di­carb­oxy­lic acid benzene-1,4-di­carboxyl­ate], {[Co(C₃₄H₂₄N₁₂)(H₂O)₂](C₈H₄O₄)·C₈H₆O₄}_n or {[Co(ttpe)(H₂O)₂](bdc)·(1,4-H₂bdc)}_n, (I), was synthesized by the hydro­thermal method using 1,1,2,2-tetra­kis[4-(1H-1,2,4-triazol-1-yl)phen­yl]ethyl­ene (ttpe), benzene-1,4-di­carb­oxy­lic acid (1,4-H₂bdc) and Co(NO₃)₂·6H₂O, and characterized by single-crystal X-ray diffraction, IR spectroscopy, powder X-ray diffraction (PXRD), luminescence, optical band gap and valence band X-ray photoelectron spectroscopy (VB XPS). Co-MOF (I) shows a (4,4)-connected binodal two-dimensional topology with a point symbol of {4⁴·6²}{4⁴·6²}. The two-dimensional networks capture free neutral 1,4-H₂bdc mol­ecules and bdc²⁻ anions, and construct a three-dimensional supra­molecular architecture via hydrogen-bond inter­actions. MOF (I) is a good photocatalyst for the degradation of methyl­ene blue and rhodamine B under visible-light irradiation and can be reused at least five times.

Computing details

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009; Bourhis et al., 2015).

Poly[[diaqua{µ₄-1,1,2,2-tetrakis[4-(1H-1,2,4-triazol-1-yl)phenyl]ethylene-κ⁴N:N':N'':N'''}cobalt(II)] benzene-1,4-dicarboxylic acid benzene-1,4-dicarboxylate]

Crystal data

[Co(C34H24N12)(H2O)2]·C8H4O4·C8H6O4	Z = 1
Mr = 1025.85	F(000) = 529
Triclinic, P1	Dx = 1.421 Mg m^−3
a = 7.4985 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.3099 (7) Å	Cell parameters from 2513 reflections
c = 14.7152 (7) Å	θ = 3.6–26.4°
α = 101.142 (5)°	µ = 0.43 mm^−1
β = 95.336 (5)°	T = 120 K
γ = 99.286 (6)°	Block, pink
V = 1198.41 (13) Å^3	0.2 × 0.2 × 0.15 mm

Data collection

Agilent Gemini Atlas diffractometer	4045 reflections with I > 2σ(I)
ω scans	Rint = 0.046
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	θmax = 30.3°, θmin = 2.8°
Tmin = 0.909, Tmax = 1.000	h = −10→10
12432 measured reflections	k = −15→15
6239 independent reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.047P)^2 + 0.3015P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
6239 reflections	Δρmax = 0.40 e Å^−3
338 parameters	Δρmin = −0.45 e Å^−3
0 restraints

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
Co1	0.500000	0.500000	1.000000	0.02323 (14)
O1	0.7562 (3)	0.48623 (17)	0.96466 (14)	0.0299 (4)
H1A	0.805 (4)	0.420 (3)	0.9581 (19)	0.036*
H1B	0.823 (4)	0.539 (3)	0.950 (2)	0.036*
N1	0.3876 (3)	0.39666 (19)	0.86143 (14)	0.0270 (5)
N2	0.3666 (3)	0.2976 (3)	0.71181 (18)	0.0504 (7)
N3	0.1983 (3)	0.2969 (2)	0.73947 (15)	0.0288 (5)
N4	−0.4736 (4)	0.1445 (2)	0.06599 (16)	0.0403 (6)
N5	−0.5202 (3)	0.33137 (18)	0.04950 (14)	0.0271 (5)
N6	−0.5016 (3)	0.21281 (19)	0.14890 (15)	0.0292 (5)
C1	0.4742 (4)	0.3585 (3)	0.7875 (2)	0.0428 (8)
H1	0.603126	0.374500	0.790238	0.051*
C2	0.2145 (4)	0.3572 (2)	0.82803 (18)	0.0314 (6)
H2	0.115307	0.369902	0.862178	0.038*
C3	0.0385 (4)	0.2358 (2)	0.67655 (18)	0.0290 (6)
C4	0.0539 (4)	0.1903 (3)	0.5845 (2)	0.0523 (9)
H4	0.169340	0.200190	0.562342	0.063*
C5	−0.1014 (4)	0.1297 (3)	0.5244 (2)	0.0519 (9)
H5	−0.090979	0.100051	0.460530	0.062*
C6	−0.2714 (4)	0.1110 (2)	0.55469 (18)	0.0293 (6)
C7	−0.2814 (4)	0.1609 (3)	0.6475 (2)	0.0386 (7)
H7	−0.396572	0.152992	0.669960	0.046*
C8	−0.1280 (4)	0.2216 (3)	0.7083 (2)	0.0390 (7)
H8	−0.138023	0.253514	0.771840	0.047*
C9	−0.4369 (4)	0.0428 (2)	0.48935 (17)	0.0279 (6)
C10	−0.4574 (4)	0.0837 (2)	0.39783 (17)	0.0291 (6)
C11	−0.3684 (4)	0.0380 (3)	0.32330 (19)	0.0394 (7)
H11	−0.296306	−0.022542	0.329143	0.047*
C12	−0.3834 (4)	0.0798 (3)	0.24064 (19)	0.0385 (7)
H12	−0.321500	0.048689	0.190352	0.046*
C13	−0.4899 (4)	0.1674 (2)	0.23262 (18)	0.0300 (6)
C14	−0.5802 (4)	0.2131 (3)	0.30529 (19)	0.0389 (7)
H14	−0.654128	0.272608	0.299006	0.047*
C15	−0.5618 (4)	0.1712 (3)	0.3878 (2)	0.0380 (7)
H15	−0.622360	0.203429	0.438225	0.046*
C16	−0.4874 (4)	0.2193 (2)	0.00915 (19)	0.0350 (7)
H16	−0.475525	0.197144	−0.055345	0.042*
C17	−0.5279 (4)	0.3225 (2)	0.13719 (18)	0.0331 (6)
H17	−0.549374	0.385779	0.185305	0.040*
O2	0.8859 (3)	0.27876 (16)	0.93588 (13)	0.0333 (4)
O3	1.0160 (3)	0.32976 (16)	1.08342 (12)	0.0361 (5)
C18	0.9566 (4)	0.2518 (2)	1.00816 (18)	0.0286 (6)
C19	0.9776 (4)	0.1212 (2)	1.00430 (18)	0.0278 (6)
C20	0.9343 (4)	0.0355 (2)	0.92069 (19)	0.0347 (7)
H20	0.889140	0.059249	0.865792	0.042*
C21	1.0436 (4)	0.0840 (2)	1.08338 (19)	0.0351 (7)
H21	1.074023	0.141777	1.141152	0.042*
O4	0.9262 (4)	0.3823 (3)	1.24903 (17)	0.0802 (9)
H4A	0.957963	0.360272	1.196033	0.120*
O5	1.2208 (3)	0.4619 (2)	1.28683 (16)	0.0596 (7)
C22	1.0707 (5)	0.4389 (3)	1.3087 (2)	0.0483 (8)
C23	1.0306 (5)	0.4700 (3)	1.4078 (2)	0.0468 (8)
C24	0.8612 (5)	0.4342 (4)	1.4324 (2)	0.0681 (11)
H24	0.764905	0.388995	1.386018	0.082*
C25	1.1694 (5)	0.5361 (4)	1.4754 (2)	0.0674 (11)
H25	1.286587	0.561388	1.458580	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0256 (3)	0.0249 (3)	0.0184 (3)	0.0038 (2)	−0.0012 (2)	0.00544 (19)
O1	0.0275 (11)	0.0241 (10)	0.0397 (11)	0.0067 (8)	0.0060 (9)	0.0084 (9)
N1	0.0260 (12)	0.0298 (11)	0.0240 (11)	0.0033 (9)	−0.0012 (9)	0.0061 (9)
N2	0.0250 (14)	0.0735 (19)	0.0378 (15)	0.0033 (13)	−0.0001 (11)	−0.0176 (14)
N3	0.0237 (12)	0.0353 (12)	0.0230 (11)	0.0003 (10)	−0.0008 (9)	0.0019 (9)
N4	0.0603 (17)	0.0340 (13)	0.0314 (13)	0.0163 (12)	0.0129 (12)	0.0092 (11)
N5	0.0334 (13)	0.0260 (11)	0.0227 (11)	0.0061 (10)	0.0025 (9)	0.0075 (9)
N6	0.0367 (13)	0.0288 (11)	0.0240 (11)	0.0081 (10)	0.0011 (10)	0.0097 (9)
C1	0.0247 (16)	0.061 (2)	0.0335 (16)	0.0051 (14)	0.0021 (13)	−0.0104 (15)
C2	0.0271 (15)	0.0416 (16)	0.0219 (13)	0.0021 (12)	0.0025 (11)	0.0019 (12)
C3	0.0278 (15)	0.0326 (14)	0.0225 (13)	0.0013 (11)	−0.0010 (11)	0.0013 (11)
C4	0.0324 (18)	0.084 (3)	0.0282 (16)	−0.0082 (16)	0.0063 (14)	−0.0034 (16)
C5	0.0431 (19)	0.076 (2)	0.0229 (15)	−0.0121 (17)	0.0018 (14)	−0.0021 (15)
C6	0.0305 (15)	0.0309 (14)	0.0239 (13)	−0.0003 (11)	−0.0029 (11)	0.0078 (11)
C7	0.0290 (16)	0.0468 (17)	0.0350 (16)	0.0043 (13)	0.0027 (13)	−0.0004 (14)
C8	0.0345 (17)	0.0479 (18)	0.0262 (15)	0.0009 (14)	−0.0004 (13)	−0.0048 (13)
C9	0.0293 (15)	0.0304 (14)	0.0211 (13)	0.0017 (11)	−0.0055 (11)	0.0059 (11)
C10	0.0345 (15)	0.0280 (13)	0.0215 (13)	−0.0023 (12)	−0.0049 (11)	0.0077 (11)
C11	0.054 (2)	0.0384 (16)	0.0307 (15)	0.0155 (14)	0.0027 (14)	0.0141 (13)
C12	0.054 (2)	0.0413 (16)	0.0256 (14)	0.0166 (15)	0.0071 (14)	0.0130 (13)
C13	0.0336 (15)	0.0305 (14)	0.0268 (14)	0.0045 (12)	−0.0024 (12)	0.0126 (11)
C14	0.0481 (19)	0.0467 (17)	0.0300 (15)	0.0203 (15)	0.0075 (14)	0.0168 (13)
C15	0.0430 (18)	0.0454 (17)	0.0306 (15)	0.0128 (14)	0.0069 (13)	0.0148 (13)
C16	0.0483 (18)	0.0333 (15)	0.0250 (14)	0.0083 (13)	0.0068 (13)	0.0082 (12)
C17	0.0465 (18)	0.0291 (14)	0.0250 (14)	0.0100 (13)	0.0034 (13)	0.0069 (11)
O2	0.0430 (12)	0.0299 (10)	0.0302 (10)	0.0126 (9)	0.0056 (9)	0.0090 (8)
O3	0.0533 (13)	0.0269 (10)	0.0250 (10)	0.0025 (9)	0.0062 (9)	0.0014 (8)
C18	0.0302 (15)	0.0282 (13)	0.0287 (14)	0.0055 (11)	0.0082 (12)	0.0072 (12)
C19	0.0283 (14)	0.0244 (13)	0.0305 (14)	0.0045 (11)	0.0026 (11)	0.0056 (11)
C20	0.0477 (18)	0.0289 (14)	0.0266 (14)	0.0094 (13)	−0.0033 (13)	0.0054 (12)
C21	0.0459 (18)	0.0287 (14)	0.0257 (14)	0.0061 (13)	−0.0025 (13)	−0.0023 (11)
O4	0.0607 (18)	0.125 (3)	0.0341 (14)	−0.0125 (17)	0.0099 (13)	−0.0105 (15)
O5	0.0545 (16)	0.0752 (17)	0.0461 (14)	0.0072 (13)	0.0191 (12)	0.0036 (12)
C22	0.055 (2)	0.053 (2)	0.0367 (18)	0.0097 (17)	0.0125 (17)	0.0059 (15)
C23	0.047 (2)	0.056 (2)	0.0359 (17)	0.0073 (16)	0.0136 (16)	0.0047 (15)
C24	0.052 (2)	0.099 (3)	0.038 (2)	−0.009 (2)	0.0070 (18)	−0.005 (2)
C25	0.051 (2)	0.098 (3)	0.040 (2)	−0.012 (2)	0.0140 (18)	−0.002 (2)

Geometric parameters (Å, º)

Co1—O1	2.0585 (18)	C8—H8	0.9500
Co1—O1^i	2.0585 (18)	C9—C9^iv	1.345 (5)
Co1—N1^i	2.162 (2)	C9—C10	1.509 (3)
Co1—N1	2.162 (2)	C10—C11	1.394 (4)
Co1—N5^ii	2.158 (2)	C10—C15	1.378 (4)
Co1—N5^iii	2.158 (2)	C11—H11	0.9500
O1—H1A	0.88 (3)	C11—C12	1.389 (4)
O1—H1B	0.80 (3)	C12—H12	0.9500
N1—C1	1.353 (3)	C12—C13	1.384 (4)
N1—C2	1.318 (3)	C13—C14	1.380 (4)
N2—N3	1.361 (3)	C14—H14	0.9500
N2—C1	1.313 (4)	C14—C15	1.389 (4)
N3—C2	1.334 (3)	C15—H15	0.9500
N3—C3	1.432 (3)	C16—H16	0.9500
N4—N6	1.366 (3)	C17—H17	0.9500
N4—C16	1.308 (3)	O2—C18	1.256 (3)
N5—C16	1.363 (3)	O3—C18	1.268 (3)
N5—C17	1.319 (3)	C18—C19	1.501 (3)
N6—C13	1.424 (3)	C19—C20	1.386 (4)
N6—C17	1.327 (3)	C19—C21	1.387 (4)
C1—H1	0.9500	C20—H20	0.9500
C2—H2	0.9500	C20—C21^v	1.378 (4)
C3—C4	1.376 (4)	C21—H21	0.9500
C3—C8	1.369 (4)	O4—H4A	0.8400
C4—H4	0.9500	O4—C22	1.318 (4)
C4—C5	1.387 (4)	O5—C22	1.201 (4)
C5—H5	0.9500	C22—C23	1.502 (4)
C5—C6	1.387 (4)	C23—C24	1.373 (5)
C6—C7	1.387 (4)	C23—C25	1.378 (5)
C6—C9	1.497 (4)	C24—H24	0.9500
C7—H7	0.9500	C24—C25^vi	1.383 (5)
C7—C8	1.382 (4)	C25—H25	0.9500
O1—Co1—O1^i	180.0	C3—C8—H8	120.1
O1^i—Co1—N1^i	88.59 (8)	C7—C8—H8	120.1
O1^i—Co1—N1	91.41 (8)	C6—C9—C10	114.0 (2)
O1—Co1—N1^i	91.41 (8)	C9^iv—C9—C6	124.0 (3)
O1—Co1—N1	88.59 (8)	C9^iv—C9—C10	121.9 (3)
O1—Co1—N5^ii	88.81 (8)	C11—C10—C9	121.7 (2)
O1^i—Co1—N5^iii	88.81 (8)	C15—C10—C9	119.7 (2)
O1^i—Co1—N5^ii	91.19 (8)	C15—C10—C11	118.5 (2)
O1—Co1—N5^iii	91.19 (8)	C10—C11—H11	119.5
N1—Co1—N1^i	180.00 (11)	C12—C11—C10	121.0 (3)
N5^ii—Co1—N1	90.30 (8)	C12—C11—H11	119.5
N5^iii—Co1—N1^i	90.30 (8)	C11—C12—H12	120.5
N5^ii—Co1—N1^i	89.70 (8)	C13—C12—C11	119.0 (3)
N5^iii—Co1—N1	89.70 (8)	C13—C12—H12	120.5
N5^ii—Co1—N5^iii	180.0	C12—C13—N6	119.1 (2)
Co1—O1—H1A	126.3 (19)	C14—C13—N6	119.9 (2)
Co1—O1—H1B	125 (2)	C14—C13—C12	120.9 (2)
H1A—O1—H1B	109 (3)	C13—C14—H14	120.4
C1—N1—Co1	129.51 (18)	C13—C14—C15	119.2 (3)
C2—N1—Co1	127.66 (18)	C15—C14—H14	120.4
C2—N1—C1	102.8 (2)	C10—C15—C14	121.3 (3)
C1—N2—N3	102.3 (2)	C10—C15—H15	119.3
N2—N3—C3	120.5 (2)	C14—C15—H15	119.3
C2—N3—N2	109.5 (2)	N4—C16—N5	114.9 (2)
C2—N3—C3	130.0 (2)	N4—C16—H16	122.6
C16—N4—N6	102.4 (2)	N5—C16—H16	122.6
C16—N5—Co1^vii	130.96 (17)	N5—C17—N6	110.6 (2)
C17—N5—Co1^vii	124.99 (17)	N5—C17—H17	124.7
C17—N5—C16	102.5 (2)	N6—C17—H17	124.7
N4—N6—C13	121.3 (2)	O2—C18—O3	123.4 (2)
C17—N6—N4	109.6 (2)	O2—C18—C19	118.3 (2)
C17—N6—C13	129.0 (2)	O3—C18—C19	118.3 (2)
N1—C1—H1	122.5	C20—C19—C18	120.4 (2)
N2—C1—N1	114.9 (3)	C20—C19—C21	118.6 (2)
N2—C1—H1	122.5	C21—C19—C18	121.0 (2)
N1—C2—N3	110.4 (2)	C19—C20—H20	119.7
N1—C2—H2	124.8	C21^v—C20—C19	120.5 (3)
N3—C2—H2	124.8	C21^v—C20—H20	119.7
C4—C3—N3	119.5 (2)	C19—C21—H21	119.5
C8—C3—N3	120.1 (2)	C20^v—C21—C19	120.9 (2)
C8—C3—C4	120.4 (3)	C20^v—C21—H21	119.5
C3—C4—H4	120.5	C22—O4—H4A	109.5
C3—C4—C5	119.0 (3)	O4—C22—C23	113.4 (3)
C5—C4—H4	120.5	O5—C22—O4	123.7 (3)
C4—C5—H5	119.0	O5—C22—C23	122.9 (3)
C6—C5—C4	122.1 (3)	C24—C23—C22	121.9 (3)
C6—C5—H5	119.0	C24—C23—C25	119.6 (3)
C5—C6—C7	116.9 (3)	C25—C23—C22	118.5 (3)
C5—C6—C9	121.3 (2)	C23—C24—H24	120.0
C7—C6—C9	121.7 (2)	C23—C24—C25^vi	120.0 (3)
C6—C7—H7	119.2	C25^vi—C24—H24	120.0
C8—C7—C6	121.7 (3)	C23—C25—C24^vi	120.4 (3)
C8—C7—H7	119.2	C23—C25—H25	119.8
C3—C8—C7	119.8 (3)	C24^vi—C25—H25	119.8

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.88 (3)	1.78 (3)	2.657 (2)	174 (3)
O1—H1B···O3^viii	0.80 (3)	1.92 (3)	2.720 (3)	178 (3)
C1—H1···O5^viii	0.95	2.60	3.222 (4)	124
C2—H2···O2^ix	0.95	2.32	3.153 (3)	145
C14—H14···O5^x	0.95	2.50	3.434 (4)	167
O4—H4A···O3	0.84	1.74	2.573 (3)	173

Symmetry codes: (viii) −x+2, −y+1, −z+2; (ix) x−1, y, z; (x) x−2, y, z−1.