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The title compound, [Zn2(C7H5O2)4(C10H14N2O)2], has a centrosymmetric dimeric mol­ecule with four symmetrical benzoate bridges and two axial nitro­gen-base ligands. The Zn...Zn separation of 2.8860 (4) Å does not represent a formal direct metal–metal bond. Coordination of zinc is square pyramidal.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002088/na6135sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002088/na6135Isup2.hkl
Contains datablock I

CCDC reference: 182588

Key indicators

  • Single-crystal X-ray study
  • T = 160 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.027
  • wR factor = 0.072
  • Data-to-parameter ratio = 13.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.70 From the CIF: _reflns_number_total 3940 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 4306 Completeness (_total/calc) 91.50% Alert C: < 95% complete General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.70 From the CIF: _reflns_number_total 3940 From the CIF: _diffrn_reflns_limit_ max hkl 20. 12. 24. From the CIF: _diffrn_reflns_limit_ min hkl -23. -12. -22. TEST1: Expected hkl limits for theta max Calculated maximum hkl 23. 13. 26. Calculated minimum hkl -23. -13. -26. ALERT: Expected hkl max differ from CIF values
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The title compound, (I), was prepared as part of a series of studies of the coordination chemistry of the ligand N,N-diethylnicotinamide (DENA), particularly in conjunction with carboxylate ligands.

Crystallographic investigation shows that the molecule is a centrosymmetric dimer (Fig. 1), in which the two zinc ions are bridged by four benzoate ligands. DENA acts as a terminal monodentate ligand through its pyridine N atom, with one DENA ligand attached to each end of the Zn···Zn axis. Such a dimeric arrangement with two metal ions bridged by four carboxylates is common for transition metals, whether the metals have a direct formal metal–metal bond or not, but it has been observed for only four previous zinc complex structures, two of them being polymorphs of the same complex (Clegg et al., 1986, 1995; Singh et al., 1997).

The two zinc ions are not considered to be directly bonded to each other in this structure. The Zn···Zn separation of 2.8660 (4) Å is the shortest observed for zinc complexes of this kind, previous values ranging from 2.893 to 2.976 Å. The benzoate bridges are essentially symmetrical, with no significant variation in the C—O bond lengths. The central Zn2(O2C)4N2 core of the molecule has approximate 4/mmm (D4 h) symmetry. Each Zn atom has square-pyramidal coordination, with DENA in the apical site.

There are no significant intermolecular interactions.

Experimental top

The title complex was prepared by the reaction of zinc benzoate (10 mmol) and diethylnicotinamide (20 mmol) in 100 ml of water. The reaction mixture was filtered and set aside for crystallization at room temperature for several days, during which time colourless single crystals were deposited.

Refinement top

The data at the highest angles are incomplete because of a relatively large crystal-to-detector distance in an early experiment with one of the first commercial CCD diffractometers before operating parameters were optimized; nevertheless, data are essentially complete to θ = 24°. H atoms were placed geometrically and refined with a riding model (including free rotation about C—C bonds), and with Uiso constrained to be 1.2 (1.5 for methyl groups) times Ueq of the carrier atom.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: local programs; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with atom labels and 50% probability ellipsoids for non-H atoms.
(I) top
Crystal data top
[Zn2(C7H5O2)4(C10H14N2O)2]Dx = 1.426 Mg m3
Mr = 971.64Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 14194 reflections
a = 19.5680 (19) Åθ = 2.1–25.6°
b = 10.6989 (10) ŵ = 1.12 mm1
c = 21.617 (2) ÅT = 160 K
V = 4525.6 (8) Å3Block, colourless
Z = 40.32 × 0.26 × 0.26 mm
F(000) = 2016
Data collection top
Siemens SMART 1K CCD
diffractometer
3940 independent reflections
Radiation source: sealed tube3659 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
Detector resolution: 8.192 pixels mm-1θmax = 25.7°, θmin = 1.9°
ω rotation with narrow frames scansh = 2320
Absorption correction: multi-scan
(SHELXTL; Sheldrick, 1977)
k = 1212
Tmin = 0.683, Tmax = 0.782l = 2224
18548 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0328P)2 + 2.6031P]
where P = (Fo2 + 2Fc2)/3
3940 reflections(Δ/σ)max = 0.001
291 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.56 e Å3
Crystal data top
[Zn2(C7H5O2)4(C10H14N2O)2]V = 4525.6 (8) Å3
Mr = 971.64Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 19.5680 (19) ŵ = 1.12 mm1
b = 10.6989 (10) ÅT = 160 K
c = 21.617 (2) Å0.32 × 0.26 × 0.26 mm
Data collection top
Siemens SMART 1K CCD
diffractometer
3940 independent reflections
Absorption correction: multi-scan
(SHELXTL; Sheldrick, 1977)
3659 reflections with I > 2σ(I)
Tmin = 0.683, Tmax = 0.782Rint = 0.034
18548 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.073H-atom parameters constrained
S = 1.07Δρmax = 0.20 e Å3
3940 reflectionsΔρmin = 0.56 e Å3
291 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn0.560102 (10)0.566370 (19)0.481129 (9)0.02554 (8)
N10.63461 (7)0.67277 (13)0.44297 (7)0.0260 (3)
C10.63995 (9)0.79616 (17)0.45364 (9)0.0298 (4)
H10.61120.83360.48380.036*
C20.68588 (10)0.86979 (17)0.42214 (9)0.0336 (4)
H20.68870.95680.43060.040*
C30.72797 (9)0.81603 (17)0.37801 (9)0.0314 (4)
H30.75910.86590.35500.038*
C40.72399 (9)0.68788 (16)0.36791 (8)0.0267 (4)
C50.67585 (9)0.62079 (16)0.40094 (8)0.0263 (4)
H50.67190.53360.39340.032*
C60.76254 (10)0.62152 (17)0.31765 (8)0.0302 (4)
O10.73000 (7)0.54980 (12)0.28417 (6)0.0383 (3)
N20.82950 (8)0.64603 (16)0.30974 (7)0.0347 (4)
C70.87344 (10)0.70831 (19)0.35534 (10)0.0381 (5)
H7A0.84590.72820.39250.046*
H7B0.88990.78820.33770.046*
C80.93473 (10)0.6299 (2)0.37465 (11)0.0443 (5)
H8A0.95900.67190.40840.066*
H8B0.96560.61970.33930.066*
H8C0.91910.54760.38860.066*
C90.86106 (12)0.6020 (2)0.25174 (10)0.0505 (6)
H9A0.85000.51240.24580.061*
H9B0.91130.60970.25510.061*
C100.83693 (14)0.6743 (3)0.19640 (11)0.0663 (8)
H10A0.86140.64560.15950.099*
H10B0.84580.76350.20280.099*
H10C0.78780.66110.19080.099*
O20.48325 (7)0.69643 (13)0.47514 (6)0.0379 (3)
O30.38838 (7)0.59680 (13)0.50390 (7)0.0396 (3)
C110.41960 (10)0.68954 (18)0.48215 (8)0.0291 (4)
C120.37798 (9)0.80002 (17)0.46178 (8)0.0292 (4)
C130.41007 (11)0.90458 (19)0.43798 (9)0.0381 (5)
H130.45860.90870.43720.046*
C140.37191 (13)1.0030 (2)0.41535 (10)0.0496 (6)
H140.39421.07430.39870.059*
C150.30160 (14)0.9982 (2)0.41680 (11)0.0539 (6)
H150.27571.06610.40090.065*
C160.26849 (12)0.8952 (2)0.44127 (10)0.0498 (6)
H160.22000.89240.44260.060*
C170.30678 (10)0.7960 (2)0.46387 (9)0.0374 (5)
H170.28440.72500.48080.045*
O40.56982 (7)0.60802 (15)0.57151 (6)0.0406 (3)
O50.47506 (7)0.50770 (13)0.60018 (6)0.0380 (3)
C180.52625 (10)0.57482 (16)0.61110 (9)0.0297 (4)
C190.53511 (9)0.62254 (17)0.67583 (8)0.0290 (4)
C200.58731 (11)0.70568 (18)0.68966 (9)0.0370 (4)
H200.61980.72720.65880.044*
C210.59224 (13)0.7576 (2)0.74836 (11)0.0482 (6)
H210.62760.81560.75750.058*
C220.54567 (13)0.7246 (2)0.79333 (11)0.0520 (6)
H220.54860.76100.83330.062*
C230.49472 (12)0.6389 (2)0.78053 (9)0.0463 (5)
H230.46340.61500.81200.056*
C240.48923 (11)0.58776 (19)0.72190 (9)0.0355 (4)
H240.45420.52900.71310.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.02454 (13)0.02756 (14)0.02451 (13)0.00250 (8)0.00191 (8)0.00215 (8)
N10.0250 (7)0.0262 (7)0.0266 (8)0.0004 (6)0.0011 (6)0.0002 (6)
C10.0287 (9)0.0293 (9)0.0315 (10)0.0015 (8)0.0018 (8)0.0030 (8)
C20.0337 (10)0.0227 (9)0.0445 (11)0.0014 (8)0.0005 (9)0.0021 (8)
C30.0281 (9)0.0266 (9)0.0393 (11)0.0021 (7)0.0029 (8)0.0055 (8)
C40.0255 (9)0.0269 (9)0.0277 (9)0.0016 (7)0.0003 (7)0.0029 (7)
C50.0271 (9)0.0242 (9)0.0275 (9)0.0000 (7)0.0002 (7)0.0019 (7)
C60.0356 (10)0.0270 (9)0.0282 (9)0.0021 (8)0.0047 (8)0.0054 (8)
O10.0440 (8)0.0353 (7)0.0354 (7)0.0010 (6)0.0031 (6)0.0039 (6)
N20.0327 (8)0.0421 (9)0.0292 (8)0.0046 (7)0.0090 (7)0.0026 (7)
C70.0316 (10)0.0397 (11)0.0430 (11)0.0025 (8)0.0077 (9)0.0013 (9)
C80.0321 (11)0.0456 (12)0.0551 (14)0.0013 (9)0.0003 (9)0.0006 (11)
C90.0448 (12)0.0719 (15)0.0348 (12)0.0084 (12)0.0130 (10)0.0020 (11)
C100.0592 (15)0.107 (2)0.0325 (12)0.0148 (15)0.0060 (11)0.0093 (13)
O20.0306 (7)0.0371 (8)0.0460 (8)0.0062 (6)0.0031 (6)0.0034 (6)
O30.0376 (8)0.0320 (7)0.0492 (9)0.0019 (6)0.0001 (7)0.0096 (7)
C110.0331 (10)0.0308 (10)0.0234 (9)0.0042 (8)0.0003 (7)0.0032 (7)
C120.0346 (10)0.0307 (10)0.0222 (8)0.0058 (8)0.0014 (7)0.0009 (7)
C130.0446 (12)0.0355 (10)0.0342 (11)0.0039 (9)0.0055 (9)0.0007 (9)
C140.0710 (16)0.0357 (11)0.0420 (12)0.0120 (11)0.0089 (11)0.0077 (10)
C150.0718 (16)0.0502 (14)0.0395 (12)0.0329 (13)0.0016 (11)0.0055 (11)
C160.0432 (13)0.0641 (15)0.0421 (12)0.0224 (11)0.0023 (10)0.0006 (11)
C170.0355 (10)0.0439 (12)0.0329 (10)0.0057 (9)0.0006 (8)0.0012 (9)
O40.0348 (7)0.0605 (9)0.0264 (7)0.0044 (7)0.0006 (6)0.0008 (7)
O50.0456 (8)0.0382 (8)0.0303 (7)0.0103 (7)0.0046 (6)0.0020 (6)
C180.0335 (10)0.0270 (9)0.0287 (10)0.0069 (8)0.0032 (8)0.0025 (7)
C190.0347 (9)0.0279 (9)0.0244 (9)0.0061 (8)0.0059 (8)0.0010 (7)
C200.0435 (11)0.0327 (10)0.0347 (10)0.0005 (9)0.0091 (9)0.0044 (9)
C210.0608 (15)0.0386 (11)0.0453 (12)0.0003 (11)0.0242 (12)0.0047 (10)
C220.0724 (16)0.0527 (14)0.0309 (11)0.0150 (12)0.0171 (11)0.0102 (10)
C230.0560 (14)0.0571 (14)0.0256 (10)0.0176 (11)0.0004 (10)0.0038 (9)
C240.0384 (11)0.0383 (10)0.0299 (10)0.0061 (9)0.0027 (8)0.0041 (8)
Geometric parameters (Å, º) top
Zn—Zni2.8662 (4)C18—C191.500 (3)
Zn—N12.0254 (14)C19—C201.387 (3)
Zn—O22.0530 (13)C19—C241.391 (3)
Zn—O3i2.0417 (14)C20—C211.389 (3)
Zn—O42.0130 (14)C21—C221.378 (4)
Zn—O5i2.0471 (13)C22—C231.383 (4)
N1—C11.344 (2)C23—C241.385 (3)
N1—C51.336 (2)C1—H10.950
C1—C21.375 (3)C2—H20.950
C2—C31.385 (3)C3—H30.950
C3—C41.391 (2)C5—H50.950
C4—C51.383 (2)C7—H7A0.990
C4—C61.501 (2)C7—H7B0.990
C6—O11.232 (2)C8—H8A0.980
C6—N21.347 (2)C8—H8B0.980
N2—C71.468 (3)C8—H8C0.980
N2—C91.475 (3)C9—H9A0.990
C7—C81.522 (3)C9—H9B0.990
C9—C101.501 (3)C10—H10A0.980
O2—C111.257 (2)C10—H10B0.980
O3—Zni2.0417 (14)C10—H10C0.980
O3—C111.256 (2)C13—H130.950
C11—C121.501 (3)C14—H140.950
C12—C131.382 (3)C15—H150.950
C12—C171.395 (3)C16—H160.950
C13—C141.380 (3)C17—H170.950
C14—C151.377 (4)C20—H200.950
C15—C161.384 (4)C21—H210.950
C16—C171.388 (3)C22—H220.950
O4—C181.259 (2)C23—H230.950
O5—Zni2.0471 (13)C24—H240.950
O5—C181.255 (2)
Zni—Zn—N1170.12 (4)C20—C21—C22119.8 (2)
Zni—Zn—O275.68 (4)C21—C22—C23120.4 (2)
Zni—Zn—O3i86.35 (4)C22—C23—C24120.1 (2)
Zni—Zn—O484.89 (4)C19—C24—C23120.0 (2)
Zni—Zn—O5i77.10 (4)N1—C1—H1119.1
N1—Zn—O296.93 (6)C2—C1—H1119.1
N1—Zn—O3i100.94 (6)C1—C2—H2120.3
N1—Zn—O4101.71 (6)C3—C2—H2120.3
N1—Zn—O5i96.31 (6)C2—C3—H3120.5
O2—Zn—O3i162.03 (6)C4—C3—H3120.5
O2—Zn—O488.87 (6)N1—C5—H5118.4
O2—Zn—O5i87.82 (6)C4—C5—H5118.4
O3i—Zn—O489.35 (6)N2—C7—H7A108.9
O3i—Zn—O5i88.34 (6)C8—C7—H7A108.9
O4—Zn—O5i161.95 (6)N2—C7—H7B108.9
Zn—N1—C1122.55 (12)C8—C7—H7B108.9
Zn—N1—C5118.54 (12)H7A—C7—H7B107.7
C1—N1—C5118.58 (15)C7—C8—H8A109.5
N1—C1—C2121.89 (17)C7—C8—H8B109.5
C1—C2—C3119.44 (17)H8A—C8—H8B109.5
C2—C3—C4118.97 (17)C7—C8—H8C109.5
C3—C4—C5117.96 (17)H8A—C8—H8C109.5
C3—C4—C6123.50 (16)H8B—C8—H8C109.5
C5—C4—C6118.07 (16)N2—C9—H9A109.1
N1—C5—C4123.12 (16)C10—C9—H9A109.1
C4—C6—O1117.40 (16)N2—C9—H9B109.1
C4—C6—N2119.24 (17)C10—C9—H9B109.1
O1—C6—N2123.31 (17)H9A—C9—H9B107.9
C6—N2—C7124.95 (16)C9—C10—H10A109.5
C6—N2—C9116.93 (17)C9—C10—H10B109.5
C7—N2—C9118.07 (17)H10A—C10—H10B109.5
N2—C7—C8113.31 (17)C9—C10—H10C109.5
N2—C9—C10112.4 (2)H10A—C10—H10C109.5
Zn—O2—C11132.73 (13)H10B—C10—H10C109.5
Zni—O3—C11119.64 (13)C14—C13—H13119.9
O2—C11—O3124.97 (18)C12—C13—H13119.9
O2—C11—C12117.13 (17)C15—C14—H14119.9
O3—C11—C12117.89 (17)C13—C14—H14119.9
C11—C12—C13120.00 (17)C14—C15—H15119.8
C11—C12—C17120.52 (18)C16—C15—H15119.8
C13—C12—C17119.41 (18)C15—C16—H16120.3
C12—C13—C14120.2 (2)C17—C16—H16120.3
C13—C14—C15120.3 (2)C16—C17—H17119.9
C14—C15—C16120.4 (2)C12—C17—H17119.9
C15—C16—C17119.4 (2)C19—C20—H20119.8
C12—C17—C16120.3 (2)C21—C20—H20119.8
Zn—O4—C18122.23 (13)C22—C21—H21120.1
Zni—O5—C18130.65 (13)C20—C21—H21120.1
O4—C18—O5125.03 (18)C21—C22—H22119.8
O4—C18—C19117.38 (17)C23—C22—H22119.8
O5—C18—C19117.56 (17)C22—C23—H23120.0
C18—C19—C20120.30 (17)C24—C23—H23120.0
C18—C19—C24120.15 (17)C23—C24—H24120.0
C20—C19—C24119.50 (18)C19—C24—H24120.0
C19—C20—C21120.3 (2)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Zn2(C7H5O2)4(C10H14N2O)2]
Mr971.64
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)160
a, b, c (Å)19.5680 (19), 10.6989 (10), 21.617 (2)
V3)4525.6 (8)
Z4
Radiation typeMo Kα
µ (mm1)1.12
Crystal size (mm)0.32 × 0.26 × 0.26
Data collection
DiffractometerSiemens SMART 1K CCD
diffractometer
Absorption correctionMulti-scan
(SHELXTL; Sheldrick, 1977)
Tmin, Tmax0.683, 0.782
No. of measured, independent and
observed [I > 2σ(I)] reflections
18548, 3940, 3659
Rint0.034
(sin θ/λ)max1)0.610
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.073, 1.07
No. of reflections3940
No. of parameters291
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.56

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXTL (Sheldrick, 1997), SHELXTL and local programs.

Selected geometric parameters (Å, º) top
Zn—N12.0254 (14)O2—C111.257 (2)
Zn—O22.0530 (13)O3—C111.256 (2)
Zn—O3i2.0417 (14)O4—C181.259 (2)
Zn—O42.0130 (14)O5—C181.255 (2)
Zn—O5i2.0471 (13)
N1—Zn—O296.93 (6)O2—Zn—O488.87 (6)
N1—Zn—O3i100.94 (6)O2—Zn—O5i87.82 (6)
N1—Zn—O4101.71 (6)O3i—Zn—O489.35 (6)
N1—Zn—O5i96.31 (6)O3i—Zn—O5i88.34 (6)
O2—Zn—O3i162.03 (6)O4—Zn—O5i161.95 (6)
Symmetry code: (i) x+1, y+1, z+1.
 

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