Structure and NMR properties of the dinuclear complex di-μ-azido-κ⁴N¹:N¹-bis­[(azido-κN)(pyridine-2-carboxamide-κ²N¹,O)zinc(II)]

The crystal structure of a dimeric Zn^II complex with picolinamide and azido ligands is characterized in the solid state and in solution.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.040
• wR factor = 0.078
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N3       --N4       .        6.7 s.u.
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0062 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1       ..N3       .       2.69 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4       ..N8       .       2.64 Ang.

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3 Note
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.009 Degree
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT230_ALERT_2_G Hirshfeld Test Diff for    N4       --N5       .        5.7 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Zn1       (II)      .       1.87 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: X-AREA (Stoe & Cie, 2018); cell refinement: X-AREA (Stoe & Cie, 2018); data reduction: X-AREA (Stoe & Cie, 2018); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

Di-µ-azido-κ⁴N¹:N¹-bis[(azido-κN)(pyridine-2-carboxamide-κ²N¹,O)zinc(II)]

Crystal data

[Zn2(N3)4(C6H6N2O)2]	F(000) = 272
Mr = 543.12	Dx = 1.884 Mg m^−3
Triclinic, P1	Melting point: 471 K
a = 6.7689 (8) Å	Ag Kα radiation, λ = 0.56083 Å
b = 8.3283 (10) Å	Cell parameters from 6594 reflections
c = 9.4835 (11) Å	θ = 2.5–22.2°
α = 69.942 (9)°	µ = 1.35 mm^−1
β = 75.447 (9)°	T = 295 K
γ = 75.901 (9)°	Needle, colourless
V = 478.74 (10) Å^3	0.27 × 0.04 × 0.03 mm
Z = 1

Data collection

Stoe Stadivari diffractometer	2088 independent reflections
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source	1344 reflections with I > 2σ(I)
Graded multilayer mirror monochromator	Rint = 0.099
Detector resolution: 5.81 pixels mm^-1	θmax = 21.0°, θmin = 2.5°
ω scans	h = −8→8
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2018)	k = −10→10
Tmin = 0.426, Tmax = 1.000	l = −11→12
11210 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: mixed
wR(F^2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 0.80	w = 1/[σ^2(Fo^2) + (0.0255P)^2] where P = (Fo^2 + 2Fc^2)/3
2088 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.65 e Å^−3
2 restraints	Δρmin = −0.52 e Å^−3
0 constraints

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

	x	y	z	Uiso*/Ueq
Zn1	0.71118 (8)	0.52257 (7)	0.37011 (6)	0.03385 (16)
O1	0.7775 (4)	0.5513 (4)	0.1331 (3)	0.0381 (7)
N1	0.7228 (5)	0.7831 (4)	0.2758 (4)	0.0297 (8)
N2	0.8242 (6)	0.7454 (5)	−0.1008 (4)	0.0412 (9)
H2A	0.859 (6)	0.663 (4)	−0.141 (5)	0.049*
H2B	0.827 (7)	0.852 (3)	−0.164 (4)	0.049*
N3	0.4244 (5)	0.4627 (5)	0.3951 (4)	0.0346 (8)
N4	0.3234 (5)	0.5162 (4)	0.2967 (4)	0.0378 (9)
N5	0.2268 (6)	0.5678 (5)	0.2013 (4)	0.0562 (12)
N6	0.9229 (5)	0.3132 (5)	0.4351 (4)	0.0430 (9)
N7	0.8669 (5)	0.1971 (5)	0.5432 (4)	0.0390 (9)
N8	0.8183 (7)	0.0821 (5)	0.6474 (5)	0.0589 (12)
C1	0.6936 (6)	0.8957 (6)	0.3551 (5)	0.0366 (10)
H1	0.678297	0.853763	0.460923	0.044*
C2	0.6855 (7)	1.0727 (6)	0.2841 (5)	0.0419 (11)
H2	0.667083	1.147761	0.341574	0.050*
C3	0.7048 (6)	1.1356 (6)	0.1285 (5)	0.0413 (11)
H3	0.696926	1.254022	0.079321	0.050*
C4	0.7364 (6)	1.0207 (5)	0.0448 (5)	0.0347 (10)
H4	0.750748	1.060098	−0.061039	0.042*
C5	0.7458 (6)	0.8456 (5)	0.1235 (4)	0.0290 (9)
C6	0.7848 (6)	0.7035 (5)	0.0490 (5)	0.0303 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0414 (3)	0.0265 (3)	0.0289 (3)	−0.0046 (2)	−0.0060 (2)	−0.0036 (2)
O1	0.0548 (19)	0.0256 (16)	0.0287 (16)	−0.0070 (14)	−0.0027 (13)	−0.0050 (13)
N1	0.0309 (18)	0.0261 (19)	0.0302 (19)	−0.0045 (15)	−0.0083 (14)	−0.0043 (15)
N2	0.066 (3)	0.028 (2)	0.027 (2)	−0.005 (2)	−0.0079 (18)	−0.0076 (17)
N3	0.044 (2)	0.043 (2)	0.0190 (18)	−0.0124 (18)	−0.0077 (16)	−0.0078 (16)
N4	0.049 (2)	0.024 (2)	0.038 (2)	−0.0150 (17)	−0.0050 (18)	−0.0025 (17)
N5	0.075 (3)	0.056 (3)	0.043 (2)	−0.015 (2)	−0.033 (2)	−0.003 (2)
N6	0.043 (2)	0.031 (2)	0.040 (2)	0.0021 (17)	−0.0037 (17)	−0.0019 (18)
N7	0.041 (2)	0.034 (2)	0.038 (2)	0.0014 (18)	−0.0099 (17)	−0.0098 (18)
N8	0.075 (3)	0.036 (2)	0.049 (3)	−0.012 (2)	−0.012 (2)	0.010 (2)
C1	0.046 (3)	0.036 (3)	0.030 (2)	−0.004 (2)	−0.0099 (19)	−0.012 (2)
C2	0.051 (3)	0.032 (3)	0.047 (3)	−0.009 (2)	−0.011 (2)	−0.015 (2)
C3	0.046 (3)	0.029 (2)	0.045 (3)	−0.009 (2)	−0.006 (2)	−0.007 (2)
C4	0.040 (2)	0.027 (2)	0.032 (2)	−0.0039 (19)	−0.0071 (19)	−0.0024 (19)
C5	0.027 (2)	0.028 (2)	0.030 (2)	−0.0026 (17)	−0.0039 (17)	−0.0070 (18)
C6	0.027 (2)	0.031 (2)	0.030 (2)	−0.0026 (18)	−0.0058 (17)	−0.0056 (19)

Geometric parameters (Å, º)

Zn1—N6	1.991 (4)	N4—N5	1.151 (4)
Zn1—N1	2.057 (3)	N6—N7	1.197 (5)
Zn1—N3	2.057 (3)	N7—N8	1.159 (5)
Zn1—O1	2.119 (3)	C1—C2	1.389 (6)
Zn1—N3^i	2.218 (3)	C1—H1	0.9300
O1—C6	1.250 (4)	C2—C3	1.370 (6)
N1—C5	1.339 (5)	C2—H2	0.9300
N1—C1	1.342 (5)	C3—C4	1.388 (6)
N2—C6	1.314 (5)	C3—H3	0.9300
N2—H2A	0.852 (19)	C4—C5	1.385 (5)
N2—H2B	0.884 (19)	C4—H4	0.9300
N3—N4	1.193 (4)	C5—C6	1.515 (5)
N6—Zn1—N1	133.42 (14)	N7—N6—Zn1	117.3 (3)
N6—Zn1—N3	112.66 (15)	N8—N7—N6	178.1 (5)
N1—Zn1—N3	113.87 (13)	N1—C1—C2	122.1 (4)
N6—Zn1—O1	98.33 (13)	N1—C1—H1	119.0
N1—Zn1—O1	77.87 (12)	C2—C1—H1	119.0
N3—Zn1—O1	92.16 (12)	C3—C2—C1	119.2 (4)
N6—Zn1—N3^i	94.82 (14)	C3—C2—H2	120.4
N1—Zn1—N3^i	95.16 (13)	C1—C2—H2	120.4
N3—Zn1—N3^i	80.02 (12)	C2—C3—C4	119.3 (4)
O1—Zn1—N3^i	166.53 (12)	C2—C3—H3	120.3
C6—O1—Zn1	114.5 (3)	C4—C3—H3	120.3
C5—N1—C1	118.1 (4)	C5—C4—C3	118.1 (4)
C5—N1—Zn1	116.5 (3)	C5—C4—H4	121.0
C1—N1—Zn1	125.2 (3)	C3—C4—H4	121.0
C6—N2—H2A	117 (3)	N1—C5—C4	123.1 (4)
C6—N2—H2B	125 (3)	N1—C5—C6	112.3 (3)
H2A—N2—H2B	117 (4)	C4—C5—C6	124.6 (4)
N4—N3—Zn1	123.8 (3)	O1—C6—N2	122.8 (4)
N4—N3—Zn1^i	121.5 (3)	O1—C6—C5	118.5 (4)
Zn1—N3—Zn1^i	99.98 (12)	N2—C6—C5	118.7 (4)
N5—N4—N3	179.7 (5)
C5—N1—C1—C2	0.4 (6)	C3—C4—C5—N1	1.1 (6)
Zn1—N1—C1—C2	−174.2 (3)	C3—C4—C5—C6	−178.3 (4)
N1—C1—C2—C3	1.0 (6)	Zn1—O1—C6—N2	179.9 (3)
C1—C2—C3—C4	−1.3 (6)	Zn1—O1—C6—C5	−0.3 (4)
C2—C3—C4—C5	0.4 (6)	N1—C5—C6—O1	4.7 (5)
C1—N1—C5—C4	−1.4 (6)	C4—C5—C6—O1	−175.8 (4)
Zn1—N1—C5—C4	173.6 (3)	N1—C5—C6—N2	−175.5 (4)
C1—N1—C5—C6	178.0 (3)	C4—C5—C6—N2	4.0 (6)
Zn1—N1—C5—C6	−6.9 (4)

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
N2—H2A···N5^ii	0.85 (2)	2.41 (3)	3.184 (5)	151 (4)
N2—H2B···N8^iii	0.88 (2)	2.13 (2)	2.994 (5)	166 (4)
C1—H1···N3^i	0.93	2.69	3.243 (5)	119
C4—H4···N8^iii	0.93	2.64	3.541 (6)	165

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