A novel tetra­zolate- and cyanide-bridged three-dimensional heterometallic coordination polymer: crystal structure, thermal stability and magnetic properties

By using environmentally friendly K₃[Co(CN)₆] as a cyanide source, the solvothermal reaction of CuCl₂ and tetra­zole (Htta) led to a novel tetra­zolate- and cyanide-bridged three-dimensional heterometallic Cu^II–Co^III complex, namely poly[[hexa-μ₂-cyanido-κ¹²C:N-penta­kis­(μ₃-tetra­zolato-κ³N¹:N²:N⁴)co­balt(III)tetra­copper(II)] monohydrate], {[Co^IIICu^II₄(CHN₄)₅(CN)₆]·H₂O}_n, (I). The crystal structure analysis reveals that it is the first example of a (6,8,8)-connected three-dimensional framework with a unique topology, constructed from anionic [Co(CN)₆]³⁻ and cationic [(Cu1)₂(tta)₂]²⁺ and [(Cu2Cu3)(tta)₃]⁺ units through μ₂-cyanide and μ₃-tetra­zolate linkers. The compound was further characterized by thermal analysis, vibrational spectroscopy (FT–IR), scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM–EDS) and magnetic measurements. The magnetic investigation indicates that the complex exhibits anti­ferromagnetic coupling between adjacent Cu^II cations.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg,2005); software used to prepare material for publication: publCIF (Westrip, 2010) and TOPOS (Blatov, 2006).

Poly[[hexa-µ₂-cyanido-κ¹²C:N-pentakis(µ₃-tetrazolato-κ³N¹:N²:N⁴)cobalt(III)tetracopper(II)] monohydrate]

Crystal data

[CoCu4(CHN4)5(CN)6]·H2O	Dx = 1.866 Mg m^−3
Mr = 832.50	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 12000 reflections
a = 12.3459 (6) Å	θ = 1.8–25.0°
b = 15.9301 (8) Å	µ = 3.50 mm^−1
c = 14.7454 (7) Å	T = 298 K
V = 2900.0 (2) Å^3	Column, blue
Z = 4	0.20 × 0.08 × 0.04 mm
F(000) = 1584

Data collection

Bruker APEX CCD diffractometer	2108 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.056
Absorption correction: multi-scan (SADABS; Bruker, 2002)	θmax = 25.0°, θmin = 1.9°
Tmin = 0.776, Tmax = 0.901	h = −14→14
12474 measured reflections	k = −18→17
2647 independent reflections	l = −11→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.176	w = 1/[σ^2(Fo^2) + (0.0992P)^2 + 8.0161P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
2647 reflections	Δρmax = 1.93 e Å^−3
208 parameters	Δρmin = −0.60 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
Cu1	0.58102 (6)	0.45945 (5)	0.61207 (6)	0.0201 (3)
Cu2	0.60085 (10)	0.2500	1.01260 (9)	0.0328 (4)
Cu3	0.32181 (8)	0.7500	0.73914 (8)	0.0184 (3)
Co1	0.33821 (9)	0.2500	0.75976 (8)	0.0143 (3)
C1	0.4239 (5)	0.3327 (4)	0.7032 (5)	0.0236 (15)
C2	0.2499 (5)	0.3329 (4)	0.8141 (5)	0.0206 (14)
C3	0.2488 (7)	0.2500	0.6568 (7)	0.024 (2)
C4	0.4294 (7)	0.2500	0.8623 (7)	0.026 (2)
C5	0.4355 (5)	0.5919 (4)	0.6740 (4)	0.0194 (14)
H5	0.4568	0.5808	0.7333	0.023*
C6	0.3864 (9)	0.2500	1.1091 (8)	0.047 (3)
H6	0.3466	0.2500	1.0555	0.057*
C7	0.7539 (6)	0.4083 (4)	1.0409 (5)	0.0323 (17)
H7	0.7548	0.4234	0.9800	0.039*
N1	0.4756 (5)	0.3824 (4)	0.6672 (4)	0.0324 (15)
N2	0.1961 (5)	0.3825 (4)	0.8477 (4)	0.0294 (14)
N3	0.1994 (7)	0.2500	0.5923 (6)	0.039 (2)
N4	0.4827 (7)	0.2500	0.9254 (7)	0.045 (3)
N5	0.3719 (4)	0.6548 (4)	0.6495 (4)	0.0239 (13)
N6	0.3619 (6)	0.6477 (4)	0.5597 (5)	0.0394 (17)
N7	0.4176 (4)	0.5827 (4)	0.5298 (4)	0.0272 (14)
N8	0.4638 (5)	0.5484 (3)	0.6052 (4)	0.0235 (13)
N9	0.4925 (7)	0.2500	1.1121 (6)	0.036 (2)
N10	0.5164 (7)	0.2500	1.2017 (5)	0.0247 (18)
N11	0.4266 (6)	0.2500	1.2486 (6)	0.030 (2)
N12	0.3427 (6)	0.2500	1.1903 (6)	0.028 (2)
N13	0.6966 (5)	0.3458 (4)	1.0756 (4)	0.0297 (14)
N14	0.7192 (4)	0.3450 (4)	1.1640 (4)	0.0248 (13)
N15	0.7872 (5)	0.4052 (4)	1.1825 (4)	0.0312 (15)
N16	0.8090 (5)	0.4459 (4)	1.1053 (4)	0.0272 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0185 (5)	0.0171 (5)	0.0248 (5)	−0.0006 (3)	−0.0017 (3)	0.0069 (3)
Cu2	0.0202 (6)	0.0654 (10)	0.0129 (7)	0.000	−0.0002 (5)	0.000
Cu3	0.0185 (6)	0.0199 (6)	0.0169 (6)	0.000	−0.0016 (5)	0.000
Co1	0.0132 (6)	0.0154 (6)	0.0142 (7)	0.000	0.0010 (5)	0.000
C1	0.018 (3)	0.026 (4)	0.026 (4)	0.002 (3)	0.001 (3)	−0.001 (3)
C2	0.020 (3)	0.020 (3)	0.021 (4)	−0.002 (3)	0.004 (3)	−0.005 (3)
C3	0.015 (4)	0.036 (6)	0.021 (5)	0.000	0.004 (4)	0.000
C4	0.018 (5)	0.040 (6)	0.020 (5)	0.000	0.000 (4)	0.000
C5	0.028 (3)	0.019 (3)	0.011 (3)	0.009 (3)	−0.003 (3)	0.003 (3)
C6	0.021 (5)	0.100 (11)	0.021 (6)	0.000	0.000 (5)	0.000
C7	0.040 (4)	0.030 (4)	0.027 (4)	−0.010 (3)	−0.006 (3)	0.003 (3)
N1	0.025 (3)	0.030 (3)	0.042 (4)	0.000 (3)	0.002 (3)	0.011 (3)
N2	0.027 (3)	0.025 (3)	0.037 (4)	−0.001 (3)	0.005 (3)	−0.008 (3)
N3	0.017 (4)	0.073 (7)	0.026 (5)	0.000	−0.002 (4)	0.000
N4	0.021 (4)	0.086 (8)	0.028 (6)	0.000	−0.003 (4)	0.000
N5	0.026 (3)	0.025 (3)	0.020 (3)	0.003 (2)	0.004 (3)	−0.001 (3)
N6	0.048 (4)	0.036 (4)	0.034 (4)	0.011 (3)	−0.006 (3)	0.001 (3)
N7	0.028 (3)	0.021 (3)	0.032 (4)	0.010 (2)	−0.002 (3)	0.001 (3)
N8	0.023 (3)	0.020 (3)	0.028 (3)	0.001 (2)	−0.003 (3)	0.007 (3)
N9	0.030 (5)	0.065 (7)	0.015 (5)	0.000	−0.002 (4)	0.000
N10	0.032 (4)	0.027 (4)	0.016 (4)	0.000	0.006 (4)	0.000
N11	0.023 (4)	0.041 (5)	0.024 (5)	0.000	0.003 (4)	0.000
N12	0.024 (4)	0.040 (5)	0.021 (5)	0.000	0.000 (4)	0.000
N13	0.032 (3)	0.031 (3)	0.026 (4)	−0.007 (3)	−0.007 (3)	−0.006 (3)
N14	0.025 (3)	0.030 (3)	0.019 (3)	−0.005 (2)	0.000 (2)	−0.005 (3)
N15	0.035 (3)	0.030 (3)	0.029 (4)	−0.012 (3)	0.000 (3)	−0.006 (3)
N16	0.026 (3)	0.020 (3)	0.035 (4)	−0.001 (2)	0.001 (3)	−0.010 (3)

Geometric parameters (Å, º)

Cu1—N1	1.965 (6)	C5—N8	1.277 (8)
Cu1—N2^i	1.968 (6)	C5—N5	1.324 (8)
Cu1—N8	2.028 (6)	C5—H5	0.9300
Cu1—N16^ii	2.032 (6)	C6—N9	1.311 (14)
Cu1—N7^iii	2.197 (6)	C6—N12	1.314 (14)
Cu2—N4	1.944 (9)	C6—H6	0.9300
Cu2—N3^i	1.968 (9)	C7—N16	1.312 (9)
Cu2—N9	1.986 (9)	C7—N13	1.325 (9)
Cu2—N13^iv	2.142 (6)	C7—H7	0.9300
Cu2—N13	2.142 (6)	N2—Cu1^ix	1.968 (6)
Cu3—N5^v	2.104 (6)	N3—Cu2^ix	1.968 (9)
Cu3—N5	2.104 (6)	N5—N6	1.335 (9)
Cu3—N14^vi	2.141 (6)	N6—N7	1.319 (8)
Cu3—N14^vii	2.141 (6)	N7—N8	1.364 (8)
Cu3—N12^viii	2.155 (8)	N7—Cu1^iii	2.197 (6)
Cu3—N10^vii	2.180 (8)	N9—N10	1.354 (11)
Co1—C3	1.877 (10)	N10—N11	1.306 (11)
Co1—C1^iv	1.884 (7)	N10—Cu3^vii	2.180 (8)
Co1—C1	1.884 (7)	N11—N12	1.345 (11)
Co1—C4	1.885 (10)	N12—Cu3^x	2.155 (8)
Co1—C2	1.891 (7)	N13—N14	1.333 (8)
Co1—C2^iv	1.891 (7)	N14—N15	1.303 (8)
C1—N1	1.148 (9)	N14—Cu3^vii	2.141 (6)
C2—N2	1.145 (8)	N15—N16	1.338 (8)
C3—N3	1.130 (13)	N16—Cu1^xi	2.032 (6)
C4—N4	1.141 (13)
N1—Cu1—N2^i	88.0 (2)	C2—Co1—C2^iv	88.7 (4)
N1—Cu1—N8	89.1 (2)	N1—C1—Co1	178.8 (7)
N2^i—Cu1—N8	164.9 (3)	N2—C2—Co1	179.2 (7)
N1—Cu1—N16^ii	157.9 (3)	N3—C3—Co1	176.6 (8)
N2^i—Cu1—N16^ii	89.7 (2)	N4—C4—Co1	178.6 (9)
N8—Cu1—N16^ii	87.5 (2)	N8—C5—N5	110.9 (6)
N1—Cu1—N7^iii	102.0 (3)	N8—C5—H5	124.6
N2^i—Cu1—N7^iii	95.2 (2)	N5—C5—H5	124.6
N8—Cu1—N7^iii	99.9 (2)	N9—C6—N12	112.3 (10)
N16^ii—Cu1—N7^iii	100.1 (2)	N9—C6—H6	123.9
N4—Cu2—N3^i	86.8 (4)	N12—C6—H6	123.9
N4—Cu2—N9	89.0 (4)	N16—C7—N13	109.8 (7)
N3^i—Cu2—N9	175.8 (4)	N16—C7—H7	125.1
N4—Cu2—N13^iv	134.50 (17)	N13—C7—H7	125.1
N3^i—Cu2—N13^iv	90.0 (2)	C1—N1—Cu1	172.4 (6)
N9—Cu2—N13^iv	92.9 (2)	C2—N2—Cu1^ix	168.2 (6)
N4—Cu2—N13	134.50 (17)	C3—N3—Cu2^ix	174.5 (8)
N3^i—Cu2—N13	90.0 (2)	C4—N4—Cu2	166.7 (9)
N9—Cu2—N13	92.9 (2)	C5—N5—N6	105.1 (5)
N13^iv—Cu2—N13	90.8 (3)	C5—N5—Cu3	123.3 (5)
N5^v—Cu3—N5	92.2 (3)	N6—N5—Cu3	131.1 (5)
N5^v—Cu3—N14^vi	88.8 (2)	N7—N6—N5	110.5 (6)
N5—Cu3—N14^vi	176.0 (2)	N6—N7—N8	105.1 (6)
N5^v—Cu3—N14^vii	176.0 (2)	N6—N7—Cu1^iii	124.2 (5)
N5—Cu3—N14^vii	88.8 (2)	N8—N7—Cu1^iii	130.5 (4)
N14^vi—Cu3—N14^vii	90.0 (3)	C5—N8—N7	108.4 (5)
N5^v—Cu3—N12^viii	93.8 (2)	C5—N8—Cu1	122.3 (4)
N5—Cu3—N12^viii	93.8 (2)	N7—N8—Cu1	128.3 (4)
N14^vi—Cu3—N12^viii	90.0 (2)	C6—N9—N10	104.5 (9)
N14^vii—Cu3—N12^viii	90.0 (2)	C6—N9—Cu2	130.4 (8)
N5^v—Cu3—N10^vii	89.0 (2)	N10—N9—Cu2	125.1 (7)
N5—Cu3—N10^vii	89.0 (2)	N11—N10—N9	109.3 (8)
N14^vi—Cu3—N10^vii	87.1 (2)	N11—N10—Cu3^vii	124.5 (6)
N14^vii—Cu3—N10^vii	87.1 (2)	N9—N10—Cu3^vii	126.2 (6)
N12^viii—Cu3—N10^vii	175.9 (3)	N10—N11—N12	108.4 (8)
C3—Co1—C1^iv	88.4 (3)	C6—N12—N11	105.5 (8)
C3—Co1—C1	88.4 (3)	C6—N12—Cu3^x	133.7 (7)
C1^iv—Co1—C1	88.7 (4)	N11—N12—Cu3^x	120.8 (6)
C3—Co1—C4	179.4 (4)	C7—N13—N14	105.9 (6)
C1^iv—Co1—C4	91.1 (3)	C7—N13—Cu2	131.5 (5)
C1—Co1—C4	91.1 (3)	N14—N13—Cu2	122.2 (4)
C3—Co1—C2	90.2 (3)	N15—N14—N13	109.4 (6)
C1^iv—Co1—C2	178.6 (3)	N15—N14—Cu3^vii	122.2 (5)
C1—Co1—C2	91.3 (3)	N13—N14—Cu3^vii	127.5 (4)
C4—Co1—C2	90.2 (3)	N14—N15—N16	108.0 (6)
C3—Co1—C2^iv	90.2 (3)	C7—N16—N15	106.9 (6)
C1^iv—Co1—C2^iv	91.3 (3)	C7—N16—Cu1^xi	136.1 (5)
C1—Co1—C2^iv	178.6 (3)	N15—N16—Cu1^xi	116.9 (4)
C4—Co1—C2^iv	90.2 (3)
N8—C5—N5—N6	0.0 (8)	N9—N10—N11—N12	0.000 (4)
N8—C5—N5—Cu3	−172.6 (4)	Cu3^vii—N10—N11—N12	180.000 (3)
C5—N5—N6—N7	0.0 (8)	N9—C6—N12—N11	0.000 (4)
Cu3—N5—N6—N7	171.8 (5)	N9—C6—N12—Cu3^x	180.000 (3)
N5—N6—N7—N8	0.0 (8)	N10—N11—N12—C6	0.000 (4)
N5—N6—N7—Cu1^iii	176.2 (4)	N10—N11—N12—Cu3^x	180.000 (2)
N5—C5—N8—N7	0.0 (8)	N16—C7—N13—N14	−0.7 (8)
N5—C5—N8—Cu1	169.2 (4)	N16—C7—N13—Cu2	−173.2 (5)
N6—N7—N8—C5	0.0 (8)	C7—N13—N14—N15	0.3 (8)
Cu1^iii—N7—N8—C5	−175.9 (5)	Cu2—N13—N14—N15	173.6 (4)
N6—N7—N8—Cu1	−168.4 (5)	C7—N13—N14—Cu3^vii	−169.0 (5)
Cu1^iii—N7—N8—Cu1	15.7 (9)	Cu2—N13—N14—Cu3^vii	4.3 (8)
N12—C6—N9—N10	0.000 (4)	N13—N14—N15—N16	0.2 (7)
N12—C6—N9—Cu2	180.000 (4)	Cu3^vii—N14—N15—N16	170.2 (4)
C6—N9—N10—N11	0.000 (4)	N13—C7—N16—N15	0.8 (8)
Cu2—N9—N10—N11	180.000 (3)	N13—C7—N16—Cu1^xi	176.6 (5)
C6—N9—N10—Cu3^vii	180.000 (2)	N14—N15—N16—C7	−0.6 (8)
Cu2—N9—N10—Cu3^vii	0.000 (3)	N14—N15—N16—Cu1^xi	−177.3 (4)

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