Three zinc(II) and cadmium(II) complexes containing 4-amino-3,5-bis­(pyridin-2-yl)-1,2,4-triazole and polynitrile ligands: synthesis, mol­ecular and supra­molecular structures, and photoluminescence properties

Three photoluminescent complexes containing either Zn^II or Cd^II have been synthesized and their structures determined. Bis[4-amino-3,5-bis­(pyridin-2-yl)-1,2,4-triazole-κ²N¹,N⁵]bis­(dicyanamido-κN¹)zinc(II), [Zn(C₁₂H₁₀N₆)₂(C₂N₃)₂], (I), bis­[4-amino-3,5-bis­(pyridin-2-yl)-1,2,4-triazole-κ²N¹,N⁵]bis­(dicyanamido-κN¹)cadmium(II), [Cd(C₁₂H₁₀N₆)₂(C₂N₃)₂], (II), and bis­[4-amino-3,5-bis­(pyridin-2-yl)-1,2,4-triazole-κ²N¹,N⁵]bis­(tri­cyano­methanido-κN¹)cadmium(II), [Cd(C₁₂H₁₀N₆)₂(C₄N₃)₂], (III), all crystallize in the space group P, with the metal centres lying on centres of inversion, but neither analogues (I) and (II) nor Cd^II complexes (II) and (III) are isomorphous. A combination of N—H...N and C—H...N hydrogen bonds and π–π stacking inter­actions generates three-dimensional framework structures in (I) and (II), and a sheet structure in (III). The photoluminescence spectra of (I)–(III) indicate that the energies of the π–π* transitions in the coordinated triazole ligand are modified by minor changes of the ligand geometry associated with coordination to the metal centres.

Computing details

For all structures, data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 and SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Bis[4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole-κ²N¹,N⁵]bis(dicyanamido-κN¹)zinc(II) (I)

Crystal data

[Zn(C12H10N6)2(C2N3)2]	Z = 1
Mr = 674.01	F(000) = 344
Triclinic, P1	Dx = 1.575 Mg m^−3
a = 8.4211 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5379 (12) Å	Cell parameters from 3720 reflections
c = 9.7491 (12) Å	θ = 2.2–29.0°
α = 83.531 (6)°	µ = 0.92 mm^−1
β = 66.048 (4)°	T = 296 K
γ = 85.922 (6)°	Block, colourless
V = 710.78 (16) Å^3	0.25 × 0.20 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer	3716 independent reflections
Radiation source: fine-focus sealed tube	2731 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 9.091 pixels mm^-1	θmax = 29.0°, θmin = 3.0°
φ & ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→8
Tmin = 0.791, Tmax = 0.895	l = −12→13
13438 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0583P)^2 + 0.1896P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
3716 reflections	Δρmax = 0.72 e Å^−3
214 parameters	Δρmin = −0.33 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
Zn1	0.5000	0.5000	0.5000	0.04045 (15)
N1	0.4959 (2)	0.7099 (2)	0.4169 (2)	0.0399 (4)
N2	0.4040 (2)	0.7887 (2)	0.3461 (2)	0.0404 (4)
C3	0.4821 (3)	0.9105 (2)	0.2965 (2)	0.0371 (5)
N4	0.6213 (2)	0.91108 (19)	0.3346 (2)	0.0365 (4)
C5	0.6253 (3)	0.7839 (2)	0.4110 (2)	0.0361 (5)
N31	0.5021 (3)	1.1478 (2)	0.1787 (2)	0.0462 (5)
C32	0.4236 (3)	1.0238 (2)	0.2106 (3)	0.0390 (5)
C33	0.2939 (3)	0.9958 (3)	0.1648 (3)	0.0433 (5)
H33	0.2419	0.9084	0.1910	0.052*
C34	0.2442 (3)	1.1006 (3)	0.0798 (3)	0.0505 (6)
H34	0.1582	1.0853	0.0467	0.061*
C35	0.3246 (4)	1.2285 (3)	0.0446 (3)	0.0554 (7)
H35	0.2939	1.3010	−0.0129	0.067*
C36	0.4508 (4)	1.2475 (3)	0.0958 (3)	0.0550 (7)
H36	0.5036	1.3346	0.0716	0.066*
N41	0.7445 (3)	1.0182 (2)	0.3006 (2)	0.0481 (5)
H41A	0.6988	1.0972	0.2605	0.058*
H41B	0.8403	0.9862	0.2187	0.058*
N51	0.6971 (2)	0.5930 (2)	0.5503 (2)	0.0381 (4)
C52	0.7390 (3)	0.7255 (2)	0.4858 (2)	0.0372 (5)
C53	0.8705 (3)	0.7967 (3)	0.4976 (3)	0.0460 (6)
H53	0.8995	0.8871	0.4502	0.055*
C54	0.9575 (3)	0.7296 (3)	0.5815 (3)	0.0511 (6)
H54	1.0469	0.7744	0.5905	0.061*
C55	0.9111 (3)	0.5969 (3)	0.6514 (3)	0.0510 (6)
H55	0.9658	0.5518	0.7108	0.061*
C56	0.7813 (3)	0.5313 (3)	0.6319 (3)	0.0459 (6)
H56	0.7516	0.4404	0.6775	0.055*
N11	0.1643 (4)	0.5921 (3)	0.9902 (3)	0.0752 (8)
C12	0.2311 (3)	0.5779 (3)	0.8451 (3)	0.0460 (6)
N13	0.3017 (3)	0.5464 (2)	0.7253 (2)	0.0506 (5)
C14	0.0802 (3)	0.7104 (3)	1.0423 (3)	0.0478 (6)
N15	0.0100 (3)	0.8017 (3)	1.1071 (3)	0.0663 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0410 (2)	0.0411 (2)	0.0436 (2)	−0.00772 (15)	−0.02016 (18)	−0.00485 (16)
N1	0.0385 (10)	0.0442 (11)	0.0415 (11)	−0.0072 (8)	−0.0192 (9)	−0.0055 (8)
N2	0.0374 (10)	0.0429 (10)	0.0435 (11)	−0.0057 (8)	−0.0181 (9)	−0.0038 (8)
C3	0.0333 (11)	0.0412 (12)	0.0351 (11)	−0.0029 (9)	−0.0097 (9)	−0.0112 (9)
N4	0.0297 (9)	0.0394 (10)	0.0393 (10)	−0.0047 (7)	−0.0102 (8)	−0.0114 (8)
C5	0.0320 (11)	0.0409 (12)	0.0342 (11)	−0.0047 (9)	−0.0097 (9)	−0.0110 (9)
N31	0.0428 (11)	0.0402 (11)	0.0521 (12)	−0.0003 (8)	−0.0136 (10)	−0.0121 (9)
C32	0.0353 (12)	0.0411 (12)	0.0357 (12)	0.0015 (9)	−0.0074 (10)	−0.0123 (9)
C33	0.0410 (13)	0.0436 (13)	0.0442 (13)	−0.0001 (10)	−0.0148 (11)	−0.0092 (10)
C34	0.0510 (15)	0.0540 (15)	0.0480 (14)	0.0081 (12)	−0.0208 (12)	−0.0129 (12)
C35	0.0576 (16)	0.0480 (15)	0.0553 (16)	0.0134 (12)	−0.0193 (14)	−0.0060 (12)
C36	0.0538 (16)	0.0365 (12)	0.0654 (17)	0.0011 (11)	−0.0143 (14)	−0.0065 (12)
N41	0.0411 (11)	0.0428 (11)	0.0605 (13)	−0.0130 (9)	−0.0185 (10)	−0.0052 (10)
N51	0.0349 (10)	0.0461 (10)	0.0359 (10)	0.0006 (8)	−0.0148 (8)	−0.0139 (8)
C52	0.0318 (11)	0.0467 (12)	0.0328 (11)	−0.0020 (9)	−0.0096 (9)	−0.0152 (9)
C53	0.0382 (13)	0.0567 (15)	0.0439 (13)	−0.0097 (11)	−0.0130 (11)	−0.0161 (11)
C54	0.0362 (13)	0.0755 (18)	0.0482 (15)	−0.0050 (12)	−0.0197 (11)	−0.0199 (13)
C55	0.0429 (14)	0.0699 (18)	0.0470 (14)	0.0055 (12)	−0.0233 (12)	−0.0162 (13)
C56	0.0424 (13)	0.0555 (15)	0.0425 (13)	0.0031 (11)	−0.0184 (11)	−0.0130 (11)
N11	0.102 (2)	0.0582 (15)	0.0492 (14)	0.0068 (14)	−0.0162 (14)	−0.0025 (12)
C12	0.0380 (13)	0.0445 (13)	0.0511 (16)	−0.0067 (10)	−0.0112 (12)	−0.0100 (11)
N13	0.0452 (12)	0.0592 (13)	0.0454 (13)	−0.0056 (10)	−0.0132 (10)	−0.0132 (10)
C14	0.0424 (13)	0.0546 (15)	0.0434 (14)	−0.0074 (11)	−0.0121 (11)	−0.0085 (12)
N15	0.0599 (15)	0.0770 (17)	0.0645 (16)	0.0124 (13)	−0.0240 (13)	−0.0296 (14)

Geometric parameters (Å, º)

Zn1—N1^i	2.0771 (19)	C34—H34	0.9300
Zn1—N1	2.0772 (19)	C35—C36	1.375 (4)
Zn1—N51	2.1800 (19)	C35—H35	0.9300
Zn1—N51^i	2.1800 (19)	C36—H36	0.9300
Zn1—N13^i	2.223 (2)	N41—H41A	0.9395
Zn1—N13	2.223 (2)	N41—H41B	0.9371
N1—C5	1.318 (3)	N51—C56	1.332 (3)
N1—N2	1.369 (3)	N51—C52	1.349 (3)
N2—C3	1.319 (3)	C52—C53	1.389 (3)
C3—N4	1.366 (3)	C53—C54	1.385 (4)
C3—C32	1.472 (3)	C53—H53	0.9300
N4—C5	1.356 (3)	C54—C55	1.371 (4)
N4—N41	1.423 (3)	C54—H54	0.9300
C5—C52	1.469 (3)	C55—C56	1.384 (4)
N31—C32	1.340 (3)	C55—H55	0.9300
N31—C36	1.340 (3)	C56—H56	0.9300
C32—C33	1.388 (3)	N11—C12	1.313 (4)
C33—C34	1.377 (4)	N11—C14	1.325 (4)
C33—H33	0.9300	C12—N13	1.139 (3)
C34—C35	1.378 (4)	C14—N15	1.120 (3)
N1^i—Zn1—N1	180.00 (12)	C33—C34—C35	118.6 (3)
N1^i—Zn1—N51	103.20 (7)	C33—C34—H34	120.7
N1—Zn1—N51	76.80 (7)	C35—C34—H34	120.7
N1^i—Zn1—N51^i	76.80 (7)	C36—C35—C34	119.1 (3)
N1—Zn1—N51^i	103.20 (7)	C36—C35—H35	120.5
N51—Zn1—N51^i	180.0	C34—C35—H35	120.5
N1^i—Zn1—N13^i	91.26 (8)	N31—C36—C35	123.7 (2)
N1—Zn1—N13^i	88.74 (8)	N31—C36—H36	118.1
N51—Zn1—N13^i	90.42 (7)	C35—C36—H36	118.1
N51^i—Zn1—N13^i	89.58 (7)	N4—N41—H41A	104.8
N1^i—Zn1—N13	88.74 (8)	N4—N41—H41B	103.0
N1—Zn1—N13	91.26 (8)	H41A—N41—H41B	105.5
N51—Zn1—N13	89.58 (7)	C56—N51—C52	118.5 (2)
N51^i—Zn1—N13	90.42 (7)	C56—N51—Zn1	126.87 (17)
N13^i—Zn1—N13	180.0	C52—N51—Zn1	114.59 (15)
C5—N1—N2	109.48 (19)	N51—C52—C53	122.1 (2)
C5—N1—Zn1	114.61 (16)	N51—C52—C5	112.19 (19)
N2—N1—Zn1	135.19 (15)	C53—C52—C5	125.7 (2)
C3—N2—N1	106.26 (18)	C54—C53—C52	118.3 (2)
N2—C3—N4	109.8 (2)	C54—C53—H53	120.9
N2—C3—C32	122.8 (2)	C52—C53—H53	120.9
N4—C3—C32	127.4 (2)	C55—C54—C53	119.7 (2)
C5—N4—C3	106.25 (18)	C55—C54—H54	120.2
C5—N4—N41	124.68 (19)	C53—C54—H54	120.2
C3—N4—N41	129.1 (2)	C54—C55—C56	118.8 (2)
N1—C5—N4	108.2 (2)	C54—C55—H55	120.6
N1—C5—C52	120.3 (2)	C56—C55—H55	120.6
N4—C5—C52	131.5 (2)	N51—C56—C55	122.6 (2)
C32—N31—C36	116.3 (2)	N51—C56—H56	118.7
N31—C32—C33	123.8 (2)	C55—C56—H56	118.7
N31—C32—C3	117.5 (2)	C12—N11—C14	120.5 (3)
C33—C32—C3	118.7 (2)	N13—C12—N11	168.9 (3)
C34—C33—C32	118.4 (2)	C12—N13—Zn1	165.0 (2)
C34—C33—H33	120.8	N15—C14—N11	169.1 (3)
C32—C33—H33	120.8
C5—N1—N2—C3	0.6 (2)	C3—C32—C33—C34	−177.6 (2)
Zn1—N1—N2—C3	−168.76 (16)	C32—C33—C34—C35	−0.3 (4)
N1—N2—C3—N4	−0.2 (2)	C33—C34—C35—C36	−0.2 (4)
N1—N2—C3—C32	178.66 (19)	C32—N31—C36—C35	0.3 (4)
N2—C3—N4—C5	−0.3 (2)	C34—C35—C36—N31	0.3 (4)
C32—C3—N4—C5	−179.1 (2)	C56—N51—C52—C53	2.4 (3)
N2—C3—N4—N41	178.0 (2)	Zn1—N51—C52—C53	−175.45 (16)
C32—C3—N4—N41	−0.7 (4)	C56—N51—C52—C5	−174.99 (19)
N2—N1—C5—N4	−0.8 (2)	Zn1—N51—C52—C5	7.2 (2)
Zn1—N1—C5—N4	170.96 (13)	N1—C5—C52—N51	2.5 (3)
N2—N1—C5—C52	176.91 (18)	N4—C5—C52—N51	179.6 (2)
Zn1—N1—C5—C52	−11.3 (3)	N1—C5—C52—C53	−174.8 (2)
C3—N4—C5—N1	0.7 (2)	N4—C5—C52—C53	2.4 (4)
N41—N4—C5—N1	−177.74 (19)	N51—C52—C53—C54	−1.6 (3)
C3—N4—C5—C52	−176.7 (2)	C5—C52—C53—C54	175.4 (2)
N41—N4—C5—C52	4.9 (4)	C52—C53—C54—C55	−0.6 (4)
C36—N31—C32—C33	−0.9 (3)	C53—C54—C55—C56	2.1 (4)
C36—N31—C32—C3	177.7 (2)	C52—N51—C56—C55	−0.8 (3)
N2—C3—C32—N31	173.7 (2)	Zn1—N51—C56—C55	176.68 (17)
N4—C3—C32—N31	−7.7 (3)	C54—C55—C56—N51	−1.4 (4)
N2—C3—C32—C33	−7.7 (3)	C14—N11—C12—N13	169.7 (13)
N4—C3—C32—C33	171.0 (2)	N11—C12—N13—Zn1	−69.3 (18)
N31—C32—C33—C34	0.9 (3)	C12—N11—C14—N15	−169.9 (15)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N41—H41A···N31	0.94	2.12	2.896 (2)	139
N41—H41B···N15^ii	0.94	2.27	3.101 (3)	148
C34—H34···N15^iii	0.93	2.56	3.357 (4)	144

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

Bis[4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole-κ²N¹,N⁵]bis(dicyanamido-κN¹)cadmium(II) (II)

Crystal data

[Cd(C12H10N6)2(C2N3)2]	Z = 1
Mr = 721.03	F(000) = 362
Triclinic, P1	Dx = 1.645 Mg m^−3
a = 8.7209 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7949 (4) Å	Cell parameters from 7093 reflections
c = 10.3490 (4) Å	θ = 2.0–30.5°
α = 91.966 (2)°	µ = 0.81 mm^−1
β = 94.945 (2)°	T = 296 K
γ = 112.682 (2)°	Block, colourless
V = 727.67 (6) Å^3	0.18 × 0.16 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer	4392 independent reflections
Radiation source: fine-focus sealed tube	4028 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 9.091 pixels mm^-1	θmax = 30.5°, θmin = 2.5°
φ & ω scans	h = −12→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.835, Tmax = 0.908	l = −14→14
16382 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0298P)^2 + 0.1878P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
4392 reflections	Δρmax = 0.74 e Å^−3
214 parameters	Δρmin = −0.26 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
Cd1	0.5000	0.5000	0.5000	0.03552 (7)
N1	0.42177 (18)	0.49212 (16)	0.28558 (13)	0.0329 (3)
N2	0.35782 (18)	0.58440 (16)	0.21291 (13)	0.0335 (3)
C3	0.30610 (19)	0.50560 (18)	0.09715 (15)	0.0288 (3)
N4	0.33633 (16)	0.36337 (15)	0.09455 (12)	0.0272 (2)
C5	0.41039 (19)	0.36019 (18)	0.21448 (15)	0.0281 (3)
N31	0.19861 (18)	0.48614 (18)	−0.12728 (14)	0.0363 (3)
C32	0.22708 (19)	0.56498 (19)	−0.00901 (15)	0.0297 (3)
C33	0.1834 (2)	0.6981 (2)	0.01743 (17)	0.0357 (3)
H33	0.2069	0.7508	0.1005	0.043*
C34	0.1048 (2)	0.7505 (2)	−0.08193 (19)	0.0404 (4)
H34	0.0753	0.8401	−0.0673	0.049*
C35	0.0705 (2)	0.6683 (2)	−0.20334 (19)	0.0417 (4)
H35	0.0152	0.6996	−0.2716	0.050*
C36	0.1201 (2)	0.5384 (2)	−0.22148 (18)	0.0424 (4)
H36	0.0977	0.4842	−0.3039	0.051*
N41	0.29499 (19)	0.23950 (18)	−0.00863 (14)	0.0369 (3)
H41A	0.2625	0.2834	−0.0753	0.044*
H41B	0.2124	0.1495	0.0142	0.044*
N51	0.54952 (18)	0.28263 (17)	0.38956 (14)	0.0340 (3)
C52	0.48039 (19)	0.24287 (19)	0.26500 (16)	0.0299 (3)
C53	0.4835 (2)	0.1090 (2)	0.19269 (18)	0.0374 (4)
H53	0.4335	0.0826	0.1074	0.045*
C54	0.5630 (2)	0.0149 (2)	0.2505 (2)	0.0451 (4)
H54	0.5659	−0.0765	0.2045	0.054*
C55	0.6371 (2)	0.0579 (2)	0.3759 (2)	0.0463 (4)
H55	0.6933	−0.0021	0.4154	0.056*
C56	0.6270 (2)	0.1914 (2)	0.44211 (18)	0.0422 (4)
H56	0.6764	0.2194	0.5275	0.051*
N11	1.0291 (2)	0.8653 (3)	0.38882 (19)	0.0593 (5)
C12	0.8859 (2)	0.7785 (2)	0.42838 (18)	0.0415 (4)
N13	0.7688 (2)	0.6972 (2)	0.47342 (19)	0.0563 (5)
C14	1.0396 (2)	0.9320 (2)	0.27615 (18)	0.0364 (4)
N15	1.0655 (2)	0.9913 (2)	0.17991 (19)	0.0539 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.04493 (11)	0.03405 (10)	0.02380 (9)	0.01100 (7)	0.00564 (7)	0.00052 (6)
N1	0.0429 (8)	0.0274 (6)	0.0278 (6)	0.0134 (6)	0.0024 (6)	0.0007 (5)
N2	0.0434 (8)	0.0273 (6)	0.0296 (6)	0.0138 (6)	0.0031 (6)	0.0011 (5)
C3	0.0303 (7)	0.0236 (7)	0.0305 (7)	0.0077 (6)	0.0061 (6)	0.0022 (6)
N4	0.0293 (6)	0.0238 (6)	0.0266 (6)	0.0083 (5)	0.0034 (5)	−0.0010 (5)
C5	0.0295 (7)	0.0250 (7)	0.0270 (7)	0.0073 (6)	0.0051 (6)	0.0005 (5)
N31	0.0423 (8)	0.0358 (7)	0.0301 (7)	0.0141 (6)	0.0061 (6)	0.0036 (6)
C32	0.0276 (7)	0.0268 (7)	0.0310 (7)	0.0061 (6)	0.0059 (6)	0.0041 (6)
C33	0.0369 (8)	0.0307 (8)	0.0383 (9)	0.0117 (7)	0.0058 (7)	0.0021 (7)
C34	0.0371 (9)	0.0350 (9)	0.0515 (10)	0.0154 (7)	0.0080 (8)	0.0109 (8)
C35	0.0366 (9)	0.0455 (10)	0.0411 (9)	0.0132 (8)	0.0029 (7)	0.0162 (8)
C36	0.0478 (10)	0.0455 (10)	0.0299 (8)	0.0138 (8)	0.0033 (7)	0.0056 (7)
N41	0.0470 (8)	0.0316 (7)	0.0309 (7)	0.0158 (6)	−0.0011 (6)	−0.0073 (5)
N51	0.0385 (7)	0.0319 (7)	0.0306 (7)	0.0119 (6)	0.0057 (6)	0.0073 (5)
C52	0.0282 (7)	0.0262 (7)	0.0330 (8)	0.0071 (6)	0.0065 (6)	0.0044 (6)
C53	0.0372 (8)	0.0295 (8)	0.0435 (9)	0.0113 (7)	0.0030 (7)	−0.0014 (7)
C54	0.0455 (10)	0.0300 (8)	0.0624 (12)	0.0166 (8)	0.0107 (9)	0.0045 (8)
C55	0.0464 (10)	0.0406 (10)	0.0582 (12)	0.0216 (8)	0.0102 (9)	0.0196 (9)
C56	0.0460 (10)	0.0438 (10)	0.0378 (9)	0.0176 (8)	0.0055 (8)	0.0151 (8)
N11	0.0406 (9)	0.0737 (13)	0.0500 (10)	0.0072 (9)	0.0008 (8)	0.0183 (9)
C12	0.0435 (10)	0.0379 (9)	0.0371 (9)	0.0101 (8)	0.0019 (7)	−0.0003 (7)
N13	0.0519 (10)	0.0500 (10)	0.0525 (10)	0.0025 (8)	0.0141 (8)	0.0015 (8)
C14	0.0302 (8)	0.0344 (8)	0.0421 (9)	0.0101 (7)	0.0028 (7)	0.0009 (7)
N15	0.0544 (10)	0.0531 (10)	0.0552 (10)	0.0203 (8)	0.0093 (8)	0.0160 (8)

Geometric parameters (Å, º)

Cd1—N1	2.2553 (13)	C34—H34	0.9300
Cd1—N1^i	2.2553 (13)	C35—C36	1.382 (3)
Cd1—N13^i	2.3638 (17)	C35—H35	0.9300
Cd1—N13	2.3638 (17)	C36—H36	0.9300
Cd1—N51^i	2.3915 (14)	N41—H41A	0.8802
Cd1—N51	2.3916 (14)	N41—H41B	0.8962
N1—C5	1.3182 (19)	N51—C56	1.334 (2)
N1—N2	1.362 (2)	N51—C52	1.349 (2)
N2—C3	1.314 (2)	C52—C53	1.384 (2)
C3—N4	1.3741 (19)	C53—C54	1.388 (3)
C3—C32	1.463 (2)	C53—H53	0.9300
N4—C5	1.355 (2)	C54—C55	1.370 (3)
N4—N41	1.4170 (17)	C54—H54	0.9300
C5—C52	1.476 (2)	C55—C56	1.375 (3)
N31—C36	1.337 (2)	C55—H55	0.9300
N31—C32	1.341 (2)	C56—H56	0.9300
C32—C33	1.390 (2)	N11—C12	1.298 (3)
C33—C34	1.376 (3)	N11—C14	1.318 (3)
C33—H33	0.9300	C12—N13	1.145 (2)
C34—C35	1.377 (3)	C14—N15	1.140 (2)
N1—Cd1—N1^i	180.00 (8)	C33—C34—C35	119.02 (17)
N1—Cd1—N13^i	89.71 (6)	C33—C34—H34	120.5
N1^i—Cd1—N13^i	90.28 (6)	C35—C34—H34	120.5
N1—Cd1—N13	90.29 (6)	C34—C35—C36	118.55 (17)
N1^i—Cd1—N13	89.72 (6)	C34—C35—H35	120.7
N13^i—Cd1—N13	180.0	C36—C35—H35	120.7
N1—Cd1—N51^i	108.93 (5)	N31—C36—C35	123.75 (17)
N1^i—Cd1—N51^i	71.07 (5)	N31—C36—H36	118.1
N13^i—Cd1—N51^i	92.62 (6)	C35—C36—H36	118.1
N13—Cd1—N51^i	87.38 (6)	N4—N41—H41A	103.6
N1—Cd1—N51	71.07 (5)	N4—N41—H41B	107.3
N1^i—Cd1—N51	108.93 (5)	H41A—N41—H41B	112.6
N13^i—Cd1—N51	87.38 (6)	C56—N51—C52	118.14 (15)
N13—Cd1—N51	92.62 (6)	C56—N51—Cd1	126.23 (12)
N51^i—Cd1—N51	180.00 (6)	C52—N51—Cd1	115.43 (11)
C5—N1—N2	109.62 (13)	N51—C52—C53	122.14 (15)
C5—N1—Cd1	116.37 (10)	N51—C52—C5	113.16 (14)
N2—N1—Cd1	133.17 (10)	C53—C52—C5	124.64 (15)
C3—N2—N1	106.59 (13)	C52—C53—C54	118.43 (17)
N2—C3—N4	109.64 (14)	C52—C53—H53	120.8
N2—C3—C32	123.20 (14)	C54—C53—H53	120.8
N4—C3—C32	127.15 (14)	C55—C54—C53	119.45 (18)
C5—N4—C3	105.99 (12)	C55—C54—H54	120.3
C5—N4—N41	125.56 (13)	C53—C54—H54	120.3
C3—N4—N41	128.42 (13)	C54—C55—C56	118.76 (17)
N1—C5—N4	108.16 (13)	C54—C55—H55	120.6
N1—C5—C52	121.74 (14)	C56—C55—H55	120.6
N4—C5—C52	130.00 (14)	N51—C56—C55	123.05 (18)
C36—N31—C32	116.81 (15)	N51—C56—H56	118.5
N31—C32—C33	123.22 (15)	C55—C56—H56	118.5
N31—C32—C3	117.94 (14)	C12—N11—C14	121.65 (18)
C33—C32—C3	118.83 (14)	N13—C12—N11	172.8 (2)
C34—C33—C32	118.61 (16)	C12—N13—Cd1	162.67 (17)
C34—C33—H33	120.7	N15—C14—N11	172.9 (2)
C32—C33—H33	120.7
C5—N1—N2—C3	0.58 (18)	N31—C32—C33—C34	1.0 (2)
Cd1—N1—N2—C3	−168.22 (11)	C3—C32—C33—C34	−178.17 (15)
N1—N2—C3—N4	−0.06 (17)	C32—C33—C34—C35	0.7 (2)
N1—N2—C3—C32	179.23 (14)	C33—C34—C35—C36	−1.5 (3)
N2—C3—N4—C5	−0.47 (17)	C32—N31—C36—C35	1.0 (3)
C32—C3—N4—C5	−179.72 (14)	C34—C35—C36—N31	0.7 (3)
N2—C3—N4—N41	177.40 (14)	C56—N51—C52—C53	1.9 (2)
C32—C3—N4—N41	−1.9 (2)	Cd1—N51—C52—C53	−173.28 (12)
N2—N1—C5—N4	−0.88 (17)	C56—N51—C52—C5	−175.39 (14)
Cd1—N1—C5—N4	170.02 (9)	Cd1—N51—C52—C5	9.43 (16)
N2—N1—C5—C52	175.78 (13)	N1—C5—C52—N51	2.1 (2)
Cd1—N1—C5—C52	−13.31 (19)	N4—C5—C52—N51	177.98 (15)
C3—N4—C5—N1	0.82 (16)	N1—C5—C52—C53	−175.09 (15)
N41—N4—C5—N1	−177.13 (14)	N4—C5—C52—C53	0.8 (3)
C3—N4—C5—C52	−175.47 (15)	N51—C52—C53—C54	−1.1 (2)
N41—N4—C5—C52	6.6 (2)	C5—C52—C53—C54	175.92 (15)
C36—N31—C32—C33	−1.8 (2)	C52—C53—C54—C55	−0.7 (3)
C36—N31—C32—C3	177.36 (14)	C53—C54—C55—C56	1.6 (3)
N2—C3—C32—N31	171.72 (15)	C52—N51—C56—C55	−1.0 (3)
N4—C3—C32—N31	−9.1 (2)	Cd1—N51—C56—C55	173.60 (13)
N2—C3—C32—C33	−9.1 (2)	C54—C55—C56—N51	−0.7 (3)
N4—C3—C32—C33	170.10 (15)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N41—H41A···N31	0.88	2.14	2.886 (2)	143
N41—H41B···N15^ii	0.90	2.38	3.190 (2)	150
C34—H34···N15^iii	0.93	2.52	3.300 (3)	142

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

Bis[4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole-κ²N¹,N⁵]bis(tricyanomethanido-κN¹)cadmium(II) (III)

Crystal data

[Cd(C12H10N6)2(C4N3)2]	Z = 1
Mr = 769.07	F(000) = 386
Triclinic, P1	Dx = 1.525 Mg m^−3
a = 9.271 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.571 (5) Å	Cell parameters from 5042 reflections
c = 10.156 (5) Å	θ = 2.1–30.7°
α = 87.833 (5)°	µ = 0.71 mm^−1
β = 68.383 (5)°	T = 296 K
γ = 88.803 (5)°	Plate, colourless
V = 837.2 (8) Å^3	0.42 × 0.34 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer	5040 independent reflections
Radiation source: fine-focus sealed tube	4682 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 9.091 pixels mm^-1	θmax = 30.7°, θmin = 2.6°
φ & ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→13
Tmin = 0.789, Tmax = 0.893	l = −14→14
17569 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0292P)^2 + 0.1701P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
5040 reflections	Δρmax = 0.35 e Å^−3
232 parameters	Δρmin = −0.27 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
Cd1	0.5000	0.5000	0.5000	0.03593 (5)
N1	0.40227 (14)	0.28256 (12)	0.58927 (13)	0.0370 (3)
N2	0.25756 (15)	0.22441 (13)	0.64461 (14)	0.0397 (3)
C3	0.27462 (16)	0.10046 (14)	0.69908 (14)	0.0329 (3)
N4	0.42789 (13)	0.07716 (11)	0.67750 (12)	0.0311 (2)
C5	0.50407 (16)	0.19435 (13)	0.60928 (13)	0.0309 (3)
N31	0.18341 (16)	−0.13123 (13)	0.78425 (14)	0.0394 (3)
C32	0.14578 (17)	0.00371 (14)	0.77116 (14)	0.0341 (3)
C33	−0.00545 (19)	0.05402 (17)	0.81991 (16)	0.0418 (3)
H33	−0.0266	0.1483	0.8092	0.050*
C34	−0.1244 (2)	−0.0401 (2)	0.88523 (18)	0.0494 (4)
H34	−0.2273	−0.0102	0.9189	0.059*
C35	−0.0876 (2)	−0.17915 (19)	0.89937 (19)	0.0512 (4)
H35	−0.1652	−0.2444	0.9423	0.061*
C36	0.0661 (2)	−0.21934 (17)	0.84879 (18)	0.0462 (4)
H36	0.0898	−0.3128	0.8600	0.055*
N41	0.49708 (15)	−0.03943 (12)	0.72259 (15)	0.0418 (3)
H41A	0.4338	−0.1068	0.7292	0.050*
H41B	0.4943	−0.0171	0.8089	0.050*
N51	0.70511 (14)	0.35659 (12)	0.50000 (12)	0.0345 (2)
C52	0.67068 (16)	0.22782 (13)	0.56142 (13)	0.0315 (3)
C53	0.78406 (18)	0.13841 (16)	0.57522 (17)	0.0421 (3)
H53	0.7584	0.0506	0.6192	0.051*
C54	0.93701 (19)	0.18322 (19)	0.52168 (18)	0.0477 (4)
H54	1.0152	0.1257	0.5306	0.057*
C55	0.97249 (19)	0.31293 (19)	0.45552 (18)	0.0468 (4)
H55	1.0747	0.3433	0.4172	0.056*
C56	0.85348 (19)	0.39696 (17)	0.44715 (17)	0.0430 (3)
H56	0.8771	0.4850	0.4032	0.052*
C11	0.63172 (19)	0.36077 (16)	0.01038 (15)	0.0408 (3)
C12	0.5809 (2)	0.40430 (16)	0.14978 (16)	0.0426 (3)
N13	0.5399 (2)	0.43872 (18)	0.26415 (16)	0.0622 (4)
C14	0.5511 (2)	0.25687 (18)	−0.02763 (17)	0.0472 (4)
N15	0.4882 (2)	0.1709 (2)	−0.0598 (2)	0.0783 (6)
C16	0.7657 (3)	0.4184 (2)	−0.0923 (2)	0.0644 (5)
N17	0.8755 (3)	0.4637 (3)	−0.1762 (3)	0.1235 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.04851 (10)	0.02405 (7)	0.03407 (8)	0.00161 (5)	−0.01430 (6)	0.00277 (5)
N1	0.0365 (6)	0.0297 (6)	0.0452 (7)	−0.0007 (4)	−0.0160 (5)	0.0068 (5)
N2	0.0369 (6)	0.0337 (6)	0.0489 (7)	−0.0009 (5)	−0.0169 (5)	0.0071 (5)
C3	0.0363 (7)	0.0304 (6)	0.0335 (6)	−0.0011 (5)	−0.0146 (5)	0.0005 (5)
N4	0.0367 (6)	0.0244 (5)	0.0340 (5)	0.0002 (4)	−0.0156 (5)	0.0024 (4)
C5	0.0379 (7)	0.0243 (5)	0.0314 (6)	−0.0005 (5)	−0.0141 (5)	0.0017 (4)
N31	0.0465 (7)	0.0311 (6)	0.0426 (6)	−0.0060 (5)	−0.0186 (6)	0.0000 (5)
C32	0.0406 (7)	0.0333 (6)	0.0309 (6)	−0.0051 (5)	−0.0161 (5)	0.0002 (5)
C33	0.0435 (8)	0.0412 (8)	0.0407 (7)	−0.0009 (6)	−0.0155 (6)	−0.0006 (6)
C34	0.0393 (8)	0.0595 (10)	0.0469 (9)	−0.0059 (7)	−0.0128 (7)	−0.0021 (7)
C35	0.0509 (10)	0.0517 (9)	0.0491 (9)	−0.0197 (8)	−0.0158 (8)	0.0032 (7)
C36	0.0563 (10)	0.0350 (7)	0.0494 (9)	−0.0117 (7)	−0.0216 (8)	0.0022 (6)
N41	0.0471 (7)	0.0269 (6)	0.0553 (8)	−0.0006 (5)	−0.0244 (6)	0.0106 (5)
N51	0.0390 (6)	0.0283 (5)	0.0346 (6)	−0.0027 (4)	−0.0115 (5)	0.0000 (4)
C52	0.0363 (7)	0.0288 (6)	0.0289 (6)	−0.0005 (5)	−0.0115 (5)	−0.0010 (4)
C53	0.0423 (8)	0.0374 (7)	0.0469 (8)	0.0028 (6)	−0.0175 (7)	0.0057 (6)
C54	0.0386 (8)	0.0539 (9)	0.0523 (9)	0.0059 (7)	−0.0193 (7)	0.0001 (7)
C55	0.0359 (8)	0.0561 (10)	0.0470 (8)	−0.0075 (7)	−0.0129 (7)	−0.0038 (7)
C56	0.0446 (8)	0.0378 (7)	0.0431 (8)	−0.0084 (6)	−0.0116 (7)	0.0002 (6)
C11	0.0489 (8)	0.0375 (7)	0.0334 (7)	−0.0022 (6)	−0.0118 (6)	−0.0010 (5)
C12	0.0537 (9)	0.0364 (7)	0.0391 (8)	0.0011 (6)	−0.0188 (7)	0.0003 (6)
N13	0.0859 (12)	0.0604 (10)	0.0409 (8)	−0.0005 (9)	−0.0234 (8)	−0.0084 (7)
C14	0.0524 (9)	0.0510 (9)	0.0350 (7)	−0.0049 (7)	−0.0122 (7)	−0.0018 (6)
N15	0.0819 (13)	0.0873 (14)	0.0624 (11)	−0.0315 (11)	−0.0198 (10)	−0.0154 (10)
C16	0.0743 (13)	0.0511 (10)	0.0521 (10)	−0.0179 (9)	−0.0037 (9)	−0.0044 (8)
N17	0.118 (2)	0.1047 (19)	0.0944 (17)	−0.0563 (16)	0.0275 (15)	−0.0083 (14)

Geometric parameters (Å, º)

Cd1—N1^i	2.3032 (15)	C35—C36	1.376 (3)
Cd1—N1	2.3032 (15)	C35—H35	0.9300
Cd1—N51	2.3219 (15)	C36—H36	0.9300
Cd1—N51^i	2.3219 (15)	N41—H41A	0.8649
Cd1—N13^i	2.3797 (19)	N41—H41B	0.9012
Cd1—N13	2.3797 (19)	N51—C56	1.339 (2)
N1—C5	1.3191 (18)	N51—C52	1.3496 (18)
N1—N2	1.3702 (19)	C52—C53	1.385 (2)
N2—C3	1.3211 (18)	C53—C54	1.389 (2)
C3—N4	1.3703 (19)	C53—H53	0.9300
C3—C32	1.473 (2)	C54—C55	1.376 (3)
N4—C5	1.3604 (17)	C54—H54	0.9300
N4—N41	1.4193 (16)	C55—C56	1.378 (2)
C5—C52	1.477 (2)	C55—H55	0.9300
N31—C36	1.340 (2)	C56—H56	0.9300
N31—C32	1.3453 (19)	C11—C12	1.395 (2)
C32—C33	1.386 (2)	C11—C16	1.402 (2)
C33—C34	1.388 (2)	C11—C14	1.403 (2)
C33—H33	0.9300	C12—N13	1.140 (2)
C34—C35	1.382 (3)	C14—N15	1.142 (2)
C34—H34	0.9300	C16—N17	1.141 (3)
N1^i—Cd1—N1	180.00 (6)	C35—C34—H34	120.5
N1^i—Cd1—N51	108.14 (5)	C33—C34—H34	120.5
N1—Cd1—N51	71.86 (5)	C36—C35—C34	118.82 (15)
N1^i—Cd1—N51^i	71.86 (5)	C36—C35—H35	120.6
N1—Cd1—N51^i	108.14 (5)	C34—C35—H35	120.6
N51—Cd1—N51^i	180.0	N31—C36—C35	123.65 (16)
N1^i—Cd1—N13^i	92.09 (6)	N31—C36—H36	118.2
N1—Cd1—N13^i	87.91 (6)	C35—C36—H36	118.2
N51—Cd1—N13^i	89.17 (5)	N4—N41—H41A	103.3
N51^i—Cd1—N13^i	90.83 (5)	N4—N41—H41B	104.4
N1^i—Cd1—N13	87.91 (6)	H41A—N41—H41B	110.8
N1—Cd1—N13	92.09 (6)	C56—N51—C52	118.96 (13)
N51—Cd1—N13	90.83 (5)	C56—N51—Cd1	123.45 (10)
N51^i—Cd1—N13	89.17 (5)	C52—N51—Cd1	117.55 (10)
N13^i—Cd1—N13	180.0	N51—C52—C53	121.74 (13)
C5—N1—N2	109.27 (12)	N51—C52—C5	113.38 (11)
C5—N1—Cd1	114.58 (10)	C53—C52—C5	124.88 (13)
N2—N1—Cd1	135.56 (9)	C52—C53—C54	118.35 (15)
C3—N2—N1	106.46 (12)	C52—C53—H53	120.8
N2—C3—N4	109.83 (12)	C54—C53—H53	120.8
N2—C3—C32	123.99 (13)	C55—C54—C53	119.83 (15)
N4—C3—C32	126.18 (12)	C55—C54—H54	120.1
C5—N4—C3	105.95 (11)	C53—C54—H54	120.1
C5—N4—N41	125.21 (12)	C54—C55—C56	118.62 (15)
C3—N4—N41	128.75 (12)	C54—C55—H55	120.7
N1—C5—N4	108.48 (12)	C56—C55—H55	120.7
N1—C5—C52	122.00 (12)	N51—C56—C55	122.45 (15)
N4—C5—C52	129.52 (12)	N51—C56—H56	118.8
C36—N31—C32	116.86 (14)	C55—C56—H56	118.8
N31—C32—C33	123.55 (14)	C12—C11—C16	120.23 (16)
N31—C32—C3	116.92 (13)	C12—C11—C14	120.31 (15)
C33—C32—C3	119.52 (13)	C16—C11—C14	119.45 (15)
C32—C33—C34	118.16 (15)	N13—C12—C11	179.34 (19)
C32—C33—H33	120.9	C12—N13—Cd1	169.75 (17)
C34—C33—H33	120.9	N15—C14—C11	178.6 (2)
C35—C34—C33	118.94 (17)	N17—C16—C11	179.2 (3)
C5—N1—N2—C3	0.54 (16)	N31—C32—C33—C34	−0.3 (2)
Cd1—N1—N2—C3	−169.83 (11)	C3—C32—C33—C34	178.93 (14)
N1—N2—C3—N4	−1.04 (16)	C32—C33—C34—C35	0.2 (2)
N1—N2—C3—C32	179.22 (13)	C33—C34—C35—C36	0.3 (3)
N2—C3—N4—C5	1.15 (15)	C32—N31—C36—C35	0.9 (2)
C32—C3—N4—C5	−179.12 (13)	C34—C35—C36—N31	−0.9 (3)
N2—C3—N4—N41	177.58 (13)	C56—N51—C52—C53	2.1 (2)
C32—C3—N4—N41	−2.7 (2)	Cd1—N51—C52—C53	−175.53 (11)
N2—N1—C5—N4	0.17 (16)	C56—N51—C52—C5	−177.38 (13)
Cd1—N1—C5—N4	172.77 (8)	Cd1—N51—C52—C5	4.96 (15)
N2—N1—C5—C52	−179.76 (12)	N1—C5—C52—N51	1.57 (19)
Cd1—N1—C5—C52	−7.16 (17)	N4—C5—C52—N51	−178.35 (13)
C3—N4—C5—N1	−0.79 (15)	N1—C5—C52—C53	−177.92 (14)
N41—N4—C5—N1	−177.38 (12)	N4—C5—C52—C53	2.2 (2)
C3—N4—C5—C52	179.14 (13)	N51—C52—C53—C54	−1.1 (2)
N41—N4—C5—C52	2.5 (2)	C5—C52—C53—C54	178.35 (14)
C36—N31—C32—C33	−0.2 (2)	C52—C53—C54—C55	−0.8 (3)
C36—N31—C32—C3	−179.47 (13)	C53—C54—C55—C56	1.5 (3)
N2—C3—C32—N31	161.22 (14)	C52—N51—C56—C55	−1.3 (2)
N4—C3—C32—N31	−18.5 (2)	Cd1—N51—C56—C55	176.20 (12)
N2—C3—C32—C33	−18.0 (2)	C54—C55—C56—N51	−0.5 (3)
N4—C3—C32—C33	162.26 (14)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N41—H41A···N31	0.86	2.19	2.889 (3)	137
N41—H41B···N15^ii	0.90	2.27	3.023 (3)	141
C56—H56···N17^iii	0.93	2.62	3.230 (4)	123

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