Crystal structure of a two-dimensional coordination polymer of formula [Zn(NDC)(DEF)] (H2NDC is naphthalene-2,6-di­carb­oxy­lic acid and DEF is N,N-di­ethyl­formamide)

Saffon-Merceron, N.; Vigroux, A.; Hoffmann, P.

doi:10.1107/S2056989019014142

Crystal structure of a two-dimensional coordination polymer of formula [Zn(NDC)(DEF)] (H₂NDC is naphthalene-2,6-dicarboxylic acid and DEF is N,N-diethylformamide)

N. Saffon-Merceron, A. Vigroux and P. Hoffmann

The zinc metal organic framework poly[bis(N,N-diethylformamide)(μ₄-naphthalene-2,6-dicarboxylato)(μ₂-naphthalene-2,6-dicarboxylato)dizinc(II)], built from windmill-type secondary building units and forming zigzag shaped two-dimensional stacked layers, has been solvothermally synthesized from naphthalene-2,6-dicarboxylic acid and zinc(II) acetate as the metal source in N,N-diethylformamide containing small amounts of formic acid.

Keywords: crystal structure; metal–organic framework; naphthalenedicarboxylic acid; N,N-diethylformamide; zinc carboxylates.

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Supporting information

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989019014142/zl2761sup1.cif
Contains datablock global

CCDC reference: 1959604

checkCIF report

Key indicators

Single-crystal X-ray study
T = 193 K
Mean (C-C) = 0.005 Å
Disorder in main residue
R factor = 0.042
wR factor = 0.081
Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found





Alert level C
PLAT220_ALERT_2_C Non-Solvent  Resd 1  C   Ueq(max)/Ueq(min) Range        4.8 Ratio
PLAT222_ALERT_3_C Non-Solv.  Resd 1  H   Uiso(max)/Uiso(min) Range        4.8 Ratio
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of         O1 Check
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12      ..O3       .       2.63 Ang.
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........  <I>CG</I> Check
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........  <I>CG</I> Check

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          5 Note
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          4 Report
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          2 Info
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT175_ALERT_4_G The CIF-Embedded .res File Contains SAME Records          2 Report
PLAT177_ALERT_4_G The CIF-Embedded .res File Contains DELU Records          2 Report
PLAT178_ALERT_4_G The CIF-Embedded .res File Contains SIMU Records          2 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )         8% Note
PLAT794_ALERT_5_G Tentative Bond Valency for Zn1       (II)      .       1.99 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         41 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          4 Note

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 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
   4 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: SHELXTL (Bruker, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[bis(N,N-diethylformamide)(µ₄-naphthalene-2,6-dicarboxylato)(µ₂-naphthalene-2,6-dicarboxylato)dizinc(II)] top

Crystal data top

[Zn(C₁₂H₆O₄)(C₁₅H₁₁NO)]	Z = 2
M_r = 380.68	F(000) = 392
Triclinic, P1	D_x = 1.539 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9134 (5) Å	Cell parameters from 1701 reflections
b = 8.3006 (5) Å	θ = 2.5–21.5°
c = 12.6413 (8) Å	µ = 1.52 mm⁻¹
α = 97.873 (4)°	T = 193 K
β = 91.620 (4)°	Block, colourless
γ = 91.991 (5)°	0.10 × 0.04 × 0.04 mm
V = 821.57 (9) Å³

Data collection top

Bruker SMART APEXII CCD area detector diffractometer	3336 independent reflections
Radiation source: fine-focus selaed tube	2436 reflections with I > 2σ(I)
Detector resolution: 8.333 pixels mm^-1	R_int = 0.075
phi and ω scans	θ_max = 26.4°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
T_min = 0.863, T_max = 0.942	k = −10→10
13141 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0318P)²] where P = (F_o² + 2F_c²)/3
3336 reflections	(Δ/σ)_max = 0.001
237 parameters	Δρ_max = 0.33 e Å⁻³
41 restraints	Δρ_min = −0.37 e Å⁻³
0 constraints

Special details top

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.

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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.02528 (5)	0.13460 (5)	0.62683 (3)	0.02329 (12)
O1	−0.0138 (3)	0.0539 (3)	0.8118 (2)	0.0495 (7)
O2	−0.1959 (3)	0.1010 (3)	0.68613 (17)	0.0311 (5)
O3	0.0472 (2)	−0.1661 (2)	0.52376 (16)	0.0249 (5)
O4	0.1080 (3)	0.3581 (3)	0.68413 (19)	0.0376 (6)
O5	0.2353 (2)	0.0121 (2)	0.60995 (16)	0.0267 (5)
C1	−0.1604 (4)	0.0679 (4)	0.7800 (3)	0.0292 (8)
C2	−0.3060 (4)	0.0478 (4)	0.8506 (2)	0.0229 (7)
C3	−0.4729 (4)	0.0766 (4)	0.8157 (3)	0.0259 (7)
H3	−0.491459	0.106685	0.746526	0.031*
C4	−0.6065 (4)	0.0621 (4)	0.8792 (2)	0.0253 (7)
H4	−0.716770	0.083839	0.854527	0.030*
C5	−0.5832 (3)	0.0151 (3)	0.9818 (2)	0.0204 (7)
C6	−0.7197 (4)	−0.0032 (4)	1.0501 (2)	0.0247 (7)
H6	−0.831308	0.016042	1.026474	0.030*
C7	0.1971 (4)	−0.1257 (4)	0.5574 (2)	0.0232 (7)
C8	0.3342 (4)	−0.2464 (4)	0.5386 (2)	0.0231 (7)
C9	0.2888 (4)	−0.4062 (4)	0.5012 (2)	0.0266 (7)
H9	0.173329	−0.437095	0.484564	0.032*
C10	0.4136 (4)	−0.5243 (4)	0.4875 (2)	0.0241 (7)
C11	0.5046 (4)	−0.1977 (4)	0.5621 (3)	0.0281 (8)
H11	0.534020	−0.086805	0.587033	0.034*
C12	0.6283 (4)	−0.3091 (4)	0.5492 (3)	0.0285 (8)
H12	0.743193	−0.274861	0.564835	0.034*
C13	0.2535 (5)	0.4026 (4)	0.7188 (3)	0.0369 (9)
H13	0.341309	0.327989	0.705702	0.044*
C14	0.1574 (6)	0.6627 (5)	0.7929 (4)	0.0628 (13)
H14A	0.078313	0.652571	0.729974	0.075*
H14B	0.208053	0.774681	0.803717	0.075*
C15	0.0611 (7)	0.6341 (6)	0.8898 (4)	0.0970 (18)
H15A	0.013080	0.522378	0.879973	0.145*
H15B	−0.030364	0.710761	0.899858	0.145*
H15C	0.137829	0.650364	0.952935	0.145*
N1	0.2922 (4)	0.5454 (4)	0.7719 (2)	0.0448 (8)
C16	0.4576 (17)	0.6215 (19)	0.815 (2)	0.061 (4)	0.516 (8)
H16A	0.487379	0.713730	0.775639	0.074*	0.516 (8)
H16B	0.447852	0.665014	0.890959	0.074*	0.516 (8)
C17	0.5911 (12)	0.5053 (11)	0.8035 (8)	0.065 (3)	0.516 (8)
H17A	0.563272	0.415235	0.843378	0.098*	0.516 (8)
H17B	0.698301	0.559271	0.831750	0.098*	0.516 (8)
H17C	0.601884	0.462995	0.727791	0.098*	0.516 (8)
C16'	0.4774 (18)	0.575 (2)	0.8054 (19)	0.062 (4)	0.484 (8)
H16C	0.544874	0.496333	0.760003	0.074*	0.484 (8)
H16D	0.513676	0.685674	0.792220	0.074*	0.484 (8)
C17'	0.5149 (13)	0.5600 (11)	0.9178 (7)	0.074 (3)	0.484 (8)
H17D	0.426986	0.611745	0.962205	0.110*	0.484 (8)
H17E	0.625043	0.613689	0.939854	0.110*	0.484 (8)
H17F	0.517878	0.444637	0.926528	0.110*	0.484 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0191 (2)	0.0234 (2)	0.0272 (2)	0.00401 (14)	0.00315 (15)	0.00116 (15)
O1	0.0203 (14)	0.086 (2)	0.0477 (17)	0.0087 (13)	0.0085 (12)	0.0236 (15)
O2	0.0277 (13)	0.0404 (14)	0.0263 (13)	0.0025 (10)	0.0067 (11)	0.0068 (11)
O3	0.0184 (12)	0.0277 (12)	0.0302 (13)	0.0040 (9)	0.0037 (10)	0.0087 (10)
O4	0.0358 (15)	0.0268 (13)	0.0474 (16)	0.0019 (10)	0.0016 (12)	−0.0052 (11)
O5	0.0258 (12)	0.0249 (13)	0.0286 (13)	0.0078 (9)	0.0039 (10)	−0.0010 (10)
C1	0.0237 (19)	0.0315 (19)	0.033 (2)	0.0043 (14)	0.0064 (16)	0.0037 (16)
C2	0.0208 (17)	0.0233 (17)	0.0232 (18)	0.0008 (13)	0.0028 (14)	−0.0022 (14)
C3	0.0250 (18)	0.0267 (18)	0.0270 (19)	0.0046 (14)	0.0008 (15)	0.0064 (15)
C4	0.0172 (17)	0.0308 (19)	0.0277 (19)	0.0021 (13)	−0.0044 (14)	0.0042 (15)
C5	0.0170 (16)	0.0211 (16)	0.0222 (17)	0.0014 (12)	−0.0003 (13)	0.0003 (13)
C6	0.0143 (16)	0.0288 (18)	0.0308 (19)	0.0031 (13)	−0.0004 (14)	0.0027 (15)
C7	0.0287 (19)	0.0256 (18)	0.0176 (17)	0.0068 (14)	0.0075 (14)	0.0079 (14)
C8	0.0220 (17)	0.0257 (18)	0.0224 (18)	0.0067 (13)	0.0039 (14)	0.0046 (14)
C9	0.0188 (17)	0.0334 (19)	0.0284 (19)	0.0058 (14)	0.0032 (14)	0.0050 (15)
C10	0.0215 (17)	0.0276 (18)	0.0241 (17)	0.0035 (13)	0.0036 (14)	0.0049 (14)
C11	0.0274 (19)	0.0260 (19)	0.031 (2)	0.0038 (14)	0.0026 (15)	0.0018 (15)
C12	0.0233 (18)	0.0271 (18)	0.034 (2)	−0.0003 (14)	0.0039 (15)	0.0011 (15)
C13	0.042 (2)	0.032 (2)	0.037 (2)	0.0006 (16)	−0.0029 (18)	0.0063 (17)
C14	0.089 (4)	0.027 (2)	0.067 (3)	−0.006 (2)	0.010 (3)	−0.012 (2)
C15	0.111 (5)	0.084 (4)	0.087 (4)	−0.011 (3)	0.037 (4)	−0.023 (3)
N1	0.057 (2)	0.0383 (19)	0.0367 (19)	−0.0130 (16)	−0.0097 (16)	0.0030 (15)
C16	0.077 (6)	0.051 (8)	0.053 (6)	−0.018 (5)	−0.018 (5)	0.006 (6)
C17	0.063 (6)	0.069 (6)	0.066 (6)	−0.014 (4)	−0.011 (5)	0.022 (5)
C16'	0.076 (6)	0.052 (9)	0.055 (6)	−0.028 (6)	−0.023 (6)	0.013 (7)
C17'	0.100 (7)	0.061 (6)	0.059 (6)	−0.021 (5)	−0.016 (5)	0.015 (5)

Geometric parameters (Å, º) top

Zn1—O2	1.949 (2)	C11—C12	1.368 (4)
Zn1—O4	1.979 (2)	C11—H11	0.9500
Zn1—O5	1.980 (2)	C12—H12	0.9500
Zn1—O3ⁱ	2.026 (2)	C13—N1	1.302 (4)
Zn1—C1	2.571 (3)	C13—H13	0.9500
O1—C1	1.231 (4)	C14—N1	1.474 (5)
O2—C1	1.280 (4)	C14—C15	1.503 (6)
O3—C7	1.267 (3)	C14—H14A	0.9900
O4—C13	1.246 (4)	C14—H14B	0.9900
O5—C7	1.264 (4)	C15—H15A	0.9800
C1—C2	1.496 (4)	C15—H15B	0.9800
C2—C6ⁱⁱ	1.368 (4)	C15—H15C	0.9800
C2—C3	1.419 (4)	N1—C16	1.488 (11)
C3—C4	1.358 (4)	N1—C16'	1.517 (11)
C3—H3	0.9500	C16—C17	1.452 (17)
C4—C5	1.413 (4)	C16—H16A	0.9900
C4—H4	0.9500	C16—H16B	0.9900
C5—C6	1.420 (4)	C17—H17A	0.9800
C5—C5ⁱⁱ	1.424 (5)	C17—H17B	0.9800
C6—H6	0.9500	C17—H17C	0.9800
C7—C8	1.504 (4)	C16'—C17'	1.47 (2)
C8—C9	1.378 (4)	C16'—H16C	0.9900
C8—C11	1.406 (4)	C16'—H16D	0.9900
C9—C10	1.413 (4)	C17'—H17D	0.9800
C9—H9	0.9500	C17'—H17E	0.9800
C10—C12ⁱⁱⁱ	1.422 (4)	C17'—H17F	0.9800
C10—C10ⁱⁱⁱ	1.426 (6)

O2—Zn1—O4	107.22 (9)	C8—C11—H11	119.8
O2—Zn1—O5	136.08 (9)	C11—C12—C10ⁱⁱⁱ	120.5 (3)
O4—Zn1—O5	103.46 (9)	C11—C12—H12	119.7
O2—Zn1—O3ⁱ	99.73 (8)	C10ⁱⁱⁱ—C12—H12	119.7
O4—Zn1—O3ⁱ	100.55 (9)	O4—C13—N1	123.8 (3)
O5—Zn1—O3ⁱ	104.71 (8)	O4—C13—H13	118.1
O2—Zn1—C1	28.93 (9)	N1—C13—H13	118.1
O4—Zn1—C1	100.44 (10)	N1—C14—C15	111.5 (4)
O5—Zn1—C1	115.09 (9)	N1—C14—H14A	109.3
O3ⁱ—Zn1—C1	128.55 (9)	C15—C14—H14A	109.3
C1—O2—Zn1	103.60 (19)	N1—C14—H14B	109.3
C7—O3—Zn1ⁱ	119.47 (19)	C15—C14—H14B	109.3
C13—O4—Zn1	127.3 (2)	H14A—C14—H14B	108.0
C7—O5—Zn1	107.70 (19)	C14—C15—H15A	109.5
O1—C1—O2	122.1 (3)	C14—C15—H15B	109.5
O1—C1—C2	121.0 (3)	H15A—C15—H15B	109.5
O2—C1—C2	116.8 (3)	C14—C15—H15C	109.5
O1—C1—Zn1	74.8 (2)	H15A—C15—H15C	109.5
O2—C1—Zn1	47.47 (15)	H15B—C15—H15C	109.5
C2—C1—Zn1	163.8 (2)	C13—N1—C14	118.8 (3)
C6ⁱⁱ—C2—C3	119.1 (3)	C13—N1—C16	131.2 (8)
C6ⁱⁱ—C2—C1	120.6 (3)	C14—N1—C16	110.0 (8)
C3—C2—C1	120.3 (3)	C13—N1—C16'	115.1 (9)
C4—C3—C2	121.2 (3)	C14—N1—C16'	126.1 (9)
C4—C3—H3	119.4	C17—C16—N1	111.5 (12)
C2—C3—H3	119.4	C17—C16—H16A	109.3
C3—C4—C5	120.7 (3)	N1—C16—H16A	109.3
C3—C4—H4	119.7	C17—C16—H16B	109.3
C5—C4—H4	119.7	N1—C16—H16B	109.3
C4—C5—C6	122.4 (3)	H16A—C16—H16B	108.0
C4—C5—C5ⁱⁱ	119.0 (3)	C16—C17—H17A	109.5
C6—C5—C5ⁱⁱ	118.6 (3)	C16—C17—H17B	109.5
C2ⁱⁱ—C6—C5	121.4 (3)	H17A—C17—H17B	109.5
C2ⁱⁱ—C6—H6	119.3	C16—C17—H17C	109.5
C5—C6—H6	119.3	H17A—C17—H17C	109.5
O5—C7—O3	122.1 (3)	H17B—C17—H17C	109.5
O5—C7—C8	118.2 (3)	C17'—C16'—N1	114.1 (15)
O3—C7—C8	119.6 (3)	C17'—C16'—H16C	108.7
C9—C8—C11	120.8 (3)	N1—C16'—H16C	108.7
C9—C8—C7	118.7 (3)	C17'—C16'—H16D	108.7
C11—C8—C7	120.5 (3)	N1—C16'—H16D	108.7
C8—C9—C10	120.1 (3)	H16C—C16'—H16D	107.6
C8—C9—H9	119.9	C16'—C17'—H17D	109.5
C10—C9—H9	119.9	C16'—C17'—H17E	109.5
C9—C10—C12ⁱⁱⁱ	121.8 (3)	H17D—C17'—H17E	109.5
C9—C10—C10ⁱⁱⁱ	119.2 (4)	C16'—C17'—H17F	109.5
C12ⁱⁱⁱ—C10—C10ⁱⁱⁱ	118.9 (3)	H17D—C17'—H17F	109.5
C12—C11—C8	120.4 (3)	H17E—C17'—H17F	109.5
C12—C11—H11	119.8

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

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C2–C5/C5ⁱⁱ/C6ⁱⁱ and C5/C6/C2ⁱⁱ–C5ii rings, respectively. [Symmetry code: (ii) -x-1, -y, -z+2.]

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1^iv	0.95	2.39	3.307 (4)	161
C12—H12···O3^v	0.95	2.63	3.548 (4)	156
C16—H16···Cg1^vi	0.95	2.99	3.520 (17)	114
C16—H16···Cg2^vii	0.95	2.99	3.520 (17)	114

Symmetry codes: (iv) x−1, y, z; (v) x+1, y, z; (vi) x+1, y+1, z; (vii) −x, −y+1, −z+2.

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Crystal structure of a two-dimensional coordination polymer of formula [Zn(NDC)(DEF)] (H2NDC is naphthalene-2,6-di­carb­oxy­lic acid and DEF is N,N-di­ethyl­formamide)

Supporting information

Key indicators

checkCIF/PLATON results

Crystal structure of a two-dimensional coordination polymer of formula [Zn(NDC)(DEF)] (H₂NDC is naphthalene-2,6-dicarboxylic acid and DEF is N,N-diethylformamide)