Poly­[zinc(II)-μ₂-azido-κ²N¹:N¹-μ₃-nicotinato-κ³N:O:O′]

The title complex, [Zn(N₃)(C₆H₄NO₂)]_n, formed from Zn cations, nicotinate and azide groups, exhibits a three-dimensional non-centrosymmetric covalent network. The coordin­ation sphere of the central metal ions is completed by an N₃O₂ five-coordinate coordination model showing distorted trigonal–bipyramidal geometry. Adjacent Zn atoms are bonded by μ₂-carboxyl­ate groups and a μ₂-azide bridge into one-dimensional helical double-stranded chains with the six-membered ring running along the a axis, and these chains are further linked by μ₃-nicotinate groups via covalent bonds, extending into two-dimensional sheets and further generating a non-centrosymmetric three-dimensional covalent network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.024
• wR factor = 0.060
• Data-to-parameter ratio = 10.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.94

Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.65
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.19 Ratio

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           28.99
           From the CIF: _reflns_number_total               1247
           Count of symmetry unique reflns         1246
           Completeness (_total/calc)            100.08%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         1
           Fraction of Friedel pairs measured     0.001
           Are heavy atom types Z>Si present          yes

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

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

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Computing details

Data collection: P3/P4-PC (Siemens, 1991); cell refinement: P3/P4-PC; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Siemens, 1990); software used to prepare material for publication: SHELXL97.

Poly[zinc(II)-µ₂-azido-κ²N¹:N¹-µ₃-nicotinato-κ³N:O:O']

Crystal data

[Zn(N3)(C6H4NO2)]	F(000) = 456
Mr = 229.50	Dx = 1.917 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 5.995 (4) Å	θ = 6.5–15.0°
b = 10.540 (4) Å	µ = 3.06 mm^−1
c = 12.586 (6) Å	T = 293 K
V = 795.3 (7) Å^3	Prismatic, colourless
Z = 4	0.28 × 0.24 × 0.19 mm

Data collection

Siemens R3m diffractometer	1157 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 29.0°, θmin = 3.8°
ω scans	h = 0→8
Absorption correction: ψ scan (Kopfman & Huber, 1968)	k = 0→14
Tmin = 0.454, Tmax = 0.560	l = −1→17
1268 measured reflections	2 standard reflections every 200 reflections
1247 independent reflections	intensity decay: <0.1%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.024	w = 1/[σ^2(Fo^2) + (0.0354P)^2 + 0.2937P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.060	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 0.50 e Å^−3
1247 reflections	Δρmin = −0.29 e Å^−3
119 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0066 (18)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Zn1	0.21552 (6)	0.17485 (3)	0.01063 (2)	0.02230 (12)
C1	0.5351 (6)	−0.1497 (3)	0.3124 (2)	0.0226 (7)
C2	0.5423 (6)	−0.1116 (3)	0.1960 (2)	0.0232 (7)
C3	0.6859 (7)	−0.1711 (4)	0.1242 (2)	0.0366 (9)
H3A	0.7828	−0.2380	0.1475	0.080*
C4	0.6792 (7)	−0.1336 (4)	0.0184 (3)	0.0414 (9)
H4A	0.7776	−0.1715	−0.0328	0.080*
C5	0.5352 (6)	−0.0386 (3)	−0.0119 (2)	0.0320 (7)
H5A	0.5307	−0.0133	−0.0852	0.080*
C6	0.4035 (6)	−0.0168 (3)	0.1598 (2)	0.0236 (7)
H6A	0.3076	0.0255	0.2095	0.080*
N1	0.3999 (5)	0.0197 (2)	0.05654 (19)	0.0237 (5)
N2	0.4037 (5)	0.3039 (3)	−0.0715 (2)	0.0279 (6)
N3	0.3759 (5)	0.3216 (3)	−0.1663 (2)	0.0301 (6)
N4	0.3472 (7)	0.3397 (4)	−0.2545 (2)	0.0507 (10)
O1	0.6701 (5)	−0.2341 (2)	0.34131 (17)	0.0337 (6)
O2	0.3915 (4)	−0.0954 (2)	0.36937 (17)	0.0307 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02415 (18)	0.02769 (17)	0.01506 (16)	0.00226 (14)	0.00022 (12)	0.00231 (13)
C1	0.0272 (18)	0.0262 (16)	0.0145 (12)	−0.0023 (13)	0.0006 (12)	0.0041 (11)
C2	0.0278 (18)	0.0269 (15)	0.0149 (13)	0.0020 (14)	0.0009 (12)	0.0014 (12)
C3	0.044 (2)	0.0436 (18)	0.0224 (14)	0.020 (2)	0.0039 (15)	0.0053 (15)
C4	0.053 (3)	0.051 (2)	0.0199 (15)	0.0236 (19)	0.0088 (17)	0.0017 (14)
C5	0.044 (2)	0.0378 (16)	0.0144 (12)	0.0078 (15)	0.0031 (15)	0.0032 (14)
C6	0.0267 (18)	0.0275 (15)	0.0166 (13)	0.0016 (14)	0.0017 (13)	0.0036 (12)
N1	0.0290 (14)	0.0265 (12)	0.0155 (11)	0.0056 (12)	−0.0024 (11)	0.0022 (10)
N2	0.0278 (14)	0.0400 (16)	0.0160 (11)	−0.0012 (14)	−0.0010 (11)	0.0026 (11)
N3	0.0256 (15)	0.0419 (15)	0.0228 (12)	−0.0006 (17)	−0.0012 (11)	0.0050 (14)
N4	0.047 (2)	0.083 (3)	0.0221 (14)	0.000 (2)	−0.0020 (13)	0.0163 (17)
O1	0.0453 (18)	0.0379 (12)	0.0179 (10)	0.0151 (13)	−0.0004 (11)	0.0071 (9)
O2	0.0373 (15)	0.0363 (12)	0.0185 (10)	0.0075 (11)	0.0059 (11)	0.0058 (10)

Geometric parameters (Å, º)

Zn1—N2^i	2.032 (3)	C4—C5	1.375 (5)
Zn1—N2	2.048 (3)	C4—H4A	0.9600
Zn1—N1	2.057 (3)	C5—N1	1.334 (4)
Zn1—O2^ii	2.067 (2)	C5—H5A	0.9600
Zn1—O1^iii	2.206 (2)	C6—N1	1.355 (4)
C1—O1	1.256 (4)	C6—H6A	0.9600
C1—O2	1.258 (4)	N2—N3	1.219 (4)
C1—C2	1.521 (4)	N2—Zn1^iv	2.032 (3)
C2—C6	1.378 (5)	N3—N4	1.140 (4)
C2—C3	1.397 (5)	O1—Zn1^v	2.206 (2)
C3—C4	1.390 (4)	O2—Zn1^vi	2.067 (2)
C3—H3A	0.9600
N2^i—Zn1—N2	128.61 (8)	C5—C4—C3	119.4 (3)
N2^i—Zn1—N1	118.42 (11)	C5—C4—H4A	120.2
N2—Zn1—N1	111.95 (13)	C3—C4—H4A	120.4
N2^i—Zn1—O2^ii	94.79 (11)	N1—C5—C4	122.6 (3)
N2—Zn1—O2^ii	90.34 (10)	N1—C5—H5A	118.3
N1—Zn1—O2^ii	94.95 (9)	C4—C5—H5A	119.1
N2^i—Zn1—O1^iii	85.39 (11)	N1—C6—C2	122.2 (3)
N2—Zn1—O1^iii	88.05 (10)	N1—C6—H6A	119.0
N1—Zn1—O1^iii	86.64 (10)	C2—C6—H6A	118.9
O2^ii—Zn1—O1^iii	178.07 (9)	C5—N1—C6	118.6 (3)
O1—C1—O2	126.7 (3)	C5—N1—Zn1	120.8 (2)
O1—C1—C2	116.6 (3)	C6—N1—Zn1	120.3 (2)
O2—C1—C2	116.6 (3)	N3—N2—Zn1^iv	118.5 (2)
C6—C2—C3	118.9 (3)	N3—N2—Zn1	121.3 (3)
C6—C2—C1	119.6 (3)	Zn1^iv—N2—Zn1	112.93 (13)
C3—C2—C1	121.5 (3)	N4—N3—N2	178.8 (4)
C4—C3—C2	118.3 (3)	C1—O1—Zn1^v	138.9 (2)
C4—C3—H3A	121.3	C1—O2—Zn1^vi	121.2 (2)
C2—C3—H3A	120.3

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