In situ deca­rbonylation of N,N-di­methyl­formamide to form di­methyl­ammonium cations in the hybrid framework compound {[(CH₃)₂NH₂]₂[Zn{O₃PC₆H₂(OH)₂PO₃}]}_n

In the title hybrid organic–inorganic compound, the (CH₃)₂NH₂⁺ cations inter­act with the zinc–phospho­nate framework via N—H...O hydrogen bonds. The (CH₃)₂NH₂⁺ cations were formed by the in situ deca­rbonylation of the N,N-di­methyl­formamide (DMF) solvent.

Key indicators

• Single-crystal X-ray study
• T = 220 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.022
• wR factor = 0.060
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.2 Note
PLAT353_ALERT_3_C Long   N-H (N0.87,N1.01A)  N2       - H2C      .       1.03 Ang.

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          2 Note
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          3 Info
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT164_ALERT_4_G Nr. of Refined C-H H-Atoms in Heavy-Atom Struct.         14 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT793_ALERT_4_G Model has Chirality at P1          (Centro SPGR)          R Verify
PLAT794_ALERT_5_G Tentative Bond Valency for Zn1       (II)      .       2.12 Info
PLAT802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          1 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        250 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          6 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 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

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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008a); software used to prepare material for publication: CIFTAB (Sheldrick, 2008b).

Poly[bis(dimethylammonium) [(µ₄-2,5-dihydroxybenzene-1,4-diphosphonato)zinc(II)]]

Crystal data

(C2H8N)2[Zn(C6H4O8P2)]	F(000) = 872
Mr = 423.59	Dx = 1.730 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.8455 (5) Å	Cell parameters from 8723 reflections
b = 16.4492 (9) Å	θ = 2.2–28.8°
c = 11.2721 (6) Å	µ = 1.75 mm^−1
β = 97.338 (1)°	T = 220 K
V = 1626.67 (15) Å^3	Block, colorless
Z = 4	0.09 × 0.03 × 0.03 mm

Data collection

Bruker APEXII diffractometer	4040 independent reflections
Radiation source: Incoatec micro-focus	3582 reflections with I > 2σ(I)
Detector resolution: 8.33 pixels mm^-1	Rint = 0.027
combination of ω and φ–scans	θmax = 29.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→11
Tmin = 0.706, Tmax = 0.746	k = −22→21
19692 measured reflections	l = −14→14

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)] = 0.022	Hydrogen site location: difference Fourier map
wR(F^2) = 0.060	All H-atom parameters refined
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0327P)^2 + 0.4955P] where P = (Fo^2 + 2Fc^2)/3
4040 reflections	(Δ/σ)max = 0.002
288 parameters	Δρmax = 0.42 e Å^−3
1 restraint	Δρmin = −0.31 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	0.73693 (2)	0.50748 (2)	−0.00920 (2)	0.01208 (6)
P1	0.53496 (4)	0.52463 (2)	0.21300 (3)	0.01348 (9)
P2	0.52017 (4)	0.86078 (2)	0.50529 (3)	0.01240 (8)
O1	0.61568 (13)	0.54669 (7)	0.10670 (10)	0.0251 (3)
O2	0.61879 (14)	0.46378 (7)	0.29864 (11)	0.0241 (3)
O3	0.37005 (12)	0.49818 (6)	0.17307 (10)	0.0173 (2)
O4	0.66080 (13)	0.90494 (6)	0.47282 (10)	0.0217 (2)
O5	0.37382 (13)	0.90513 (7)	0.45507 (10)	0.0220 (2)
O6	0.53036 (13)	0.84096 (7)	0.63713 (9)	0.0216 (2)
O7	0.31114 (15)	0.80860 (7)	0.26689 (12)	0.0287 (3)
O8	0.71416 (17)	0.57148 (8)	0.45775 (13)	0.0382 (4)
C1	0.52417 (16)	0.61778 (9)	0.29782 (13)	0.0137 (3)
C2	0.42525 (17)	0.67996 (9)	0.25376 (13)	0.0161 (3)
C3	0.41615 (17)	0.75253 (9)	0.31601 (13)	0.0155 (3)
C4	0.51147 (16)	0.76540 (8)	0.42426 (13)	0.0128 (3)
C5	0.60872 (17)	0.70290 (9)	0.46917 (14)	0.0176 (3)
C6	0.61546 (17)	0.62969 (9)	0.40804 (14)	0.0186 (3)
C7	0.5494 (3)	0.29794 (13)	0.13241 (19)	0.0387 (5)
N1	0.57872 (18)	0.30131 (9)	0.26452 (15)	0.0277 (3)
C8	0.7362 (3)	0.27776 (15)	0.3120 (2)	0.0443 (5)
C9	0.5188 (3)	1.01513 (14)	0.8070 (2)	0.0356 (4)
N2	0.63088 (18)	0.94927 (9)	0.80290 (13)	0.0246 (3)
C10	0.6615 (3)	0.90359 (13)	0.91563 (18)	0.0371 (5)
H1A	0.568 (2)	0.3527 (14)	0.287 (2)	0.038 (6)*
H1B	0.515 (2)	0.2695 (14)	0.2980 (19)	0.037 (6)*
H2A	0.360 (2)	0.6731 (12)	0.1787 (17)	0.026 (5)*
H2B	0.709 (3)	0.9705 (14)	0.783 (2)	0.041 (6)*
H2C	0.588 (3)	0.9111 (15)	0.735 (2)	0.054 (7)*
H5A	0.676 (2)	0.7101 (11)	0.5433 (17)	0.024 (5)*
H7A	0.306 (3)	0.8427 (16)	0.316 (2)	0.050 (7)*
H7B	0.450 (3)	0.3113 (17)	0.109 (2)	0.071 (9)*
H7C	0.620 (2)	0.3284 (16)	0.101 (2)	0.055 (7)*
H7D	0.566 (3)	0.2430 (15)	0.109 (2)	0.044 (6)*
H8A	0.691 (3)	0.5308 (18)	0.410 (3)	0.064 (8)*
H8B	0.806 (3)	0.3177 (15)	0.281 (2)	0.052 (7)*
H8C	0.750 (3)	0.2805 (15)	0.402 (2)	0.053 (7)*
H8D	0.748 (3)	0.2232 (16)	0.278 (2)	0.056 (7)*
H9A	0.501 (2)	1.0337 (13)	0.729 (2)	0.036 (6)*
H9B	0.569 (3)	1.0562 (16)	0.869 (2)	0.054 (7)*
H9C	0.431 (3)	0.9924 (13)	0.828 (2)	0.042 (7)*
H10A	0.719 (4)	0.936 (2)	0.970 (3)	0.088 (11)*
H10B	0.564 (4)	0.8940 (17)	0.947 (3)	0.077 (9)*
H10C	0.716 (3)	0.8557 (17)	0.902 (2)	0.062 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01243 (9)	0.01005 (9)	0.01414 (9)	−0.00104 (6)	0.00319 (6)	−0.00073 (6)
P1	0.01327 (18)	0.01165 (17)	0.01539 (18)	0.00072 (13)	0.00134 (14)	−0.00453 (14)
P2	0.01391 (18)	0.00907 (17)	0.01421 (18)	0.00096 (13)	0.00174 (14)	−0.00254 (13)
O1	0.0271 (6)	0.0243 (6)	0.0268 (6)	−0.0033 (5)	0.0146 (5)	−0.0084 (5)
O2	0.0287 (6)	0.0141 (5)	0.0268 (6)	0.0053 (5)	−0.0070 (5)	−0.0053 (5)
O3	0.0153 (5)	0.0196 (5)	0.0167 (5)	−0.0027 (4)	0.0006 (4)	−0.0046 (4)
O4	0.0219 (6)	0.0142 (5)	0.0302 (6)	−0.0051 (4)	0.0085 (5)	−0.0057 (4)
O5	0.0210 (6)	0.0185 (5)	0.0253 (6)	0.0094 (4)	−0.0018 (5)	−0.0068 (5)
O6	0.0331 (6)	0.0162 (5)	0.0152 (5)	−0.0024 (5)	0.0023 (5)	−0.0024 (4)
O7	0.0350 (7)	0.0169 (6)	0.0293 (7)	0.0113 (5)	−0.0149 (5)	−0.0073 (5)
O8	0.0463 (8)	0.0237 (7)	0.0367 (8)	0.0212 (6)	−0.0249 (6)	−0.0140 (6)
C1	0.0132 (7)	0.0125 (7)	0.0156 (7)	0.0004 (5)	0.0019 (5)	−0.0032 (5)
C2	0.0177 (7)	0.0144 (7)	0.0152 (7)	−0.0005 (6)	−0.0020 (6)	−0.0025 (6)
C3	0.0158 (7)	0.0123 (6)	0.0176 (7)	0.0023 (5)	−0.0005 (6)	0.0002 (5)
C4	0.0142 (7)	0.0105 (6)	0.0141 (7)	−0.0008 (5)	0.0029 (5)	−0.0016 (5)
C5	0.0184 (7)	0.0160 (7)	0.0168 (7)	0.0018 (6)	−0.0032 (6)	−0.0032 (6)
C6	0.0192 (7)	0.0147 (7)	0.0207 (8)	0.0062 (6)	−0.0028 (6)	−0.0032 (6)
C7	0.0482 (13)	0.0331 (11)	0.0375 (11)	−0.0098 (10)	0.0162 (10)	−0.0045 (9)
N1	0.0312 (8)	0.0175 (7)	0.0373 (9)	−0.0035 (6)	0.0154 (7)	−0.0030 (6)
C8	0.0363 (11)	0.0374 (12)	0.0601 (16)	0.0052 (9)	0.0091 (11)	−0.0063 (11)
C9	0.0353 (11)	0.0405 (11)	0.0326 (11)	0.0034 (9)	0.0096 (9)	0.0022 (9)
N2	0.0254 (8)	0.0297 (8)	0.0202 (7)	−0.0096 (6)	0.0087 (6)	−0.0050 (6)
C10	0.0577 (14)	0.0300 (10)	0.0236 (9)	0.0000 (10)	0.0052 (9)	−0.0045 (8)

Geometric parameters (Å, º)

Zn1—O1	1.9055 (11)	C5—C6	1.392 (2)
Zn1—O3^i	1.9671 (11)	C5—H5A	0.971 (19)
Zn1—O4^ii	1.9330 (11)	C7—N1	1.480 (3)
Zn1—O5^iii	1.9543 (10)	C7—H7B	0.92 (2)
P1—O1	1.5151 (12)	C7—H7C	0.91 (2)
P1—O2	1.5169 (12)	C7—H7D	0.96 (2)
P1—O3	1.5337 (11)	N1—C8	1.479 (3)
P1—C1	1.8150 (14)	N1—H1A	0.89 (2)
P2—O6	1.5129 (11)	N1—H1B	0.89 (2)
P2—O4	1.5249 (11)	C8—H8B	1.00 (3)
P2—O5	1.5301 (11)	C8—H8C	1.01 (3)
P2—C4	1.8121 (14)	C8—H8D	0.98 (3)
O7—C3	1.3743 (18)	C9—N2	1.473 (3)
O7—H7A	0.79 (3)	C9—H9A	0.92 (2)
O8—C6	1.3668 (19)	C9—H9B	1.03 (3)
O8—H8A	0.86 (3)	C9—H9C	0.92 (3)
C1—C2	1.395 (2)	N2—C10	1.471 (2)
C1—C6	1.406 (2)	N2—H2B	0.83 (2)
C2—C3	1.392 (2)	N2—H2C	1.02 (3)
C2—H2A	0.968 (19)	C10—H10A	0.92 (4)
C3—C4	1.408 (2)	C10—H10B	0.98 (3)
C4—C5	1.394 (2)	C10—H10C	0.95 (3)
O1—Zn1—O4^ii	116.04 (5)	O8—C6—C5	117.94 (14)
O1—Zn1—O5^iii	108.06 (5)	O8—C6—C1	121.95 (13)
O4^ii—Zn1—O5^iii	113.58 (5)	C5—C6—C1	120.11 (13)
O1—Zn1—O3^i	114.48 (5)	N1—C7—H7B	108.8 (17)
O4^ii—Zn1—O3^i	108.30 (5)	N1—C7—H7C	109.5 (15)
O5^iii—Zn1—O3^i	94.45 (4)	H7B—C7—H7C	116 (2)
O1—P1—O2	114.83 (7)	N1—C7—H7D	107.5 (14)
O1—P1—O3	111.25 (7)	H7B—C7—H7D	109 (2)
O2—P1—O3	111.65 (7)	H7C—C7—H7D	106 (2)
O1—P1—C1	106.03 (7)	C8—N1—C7	112.97 (17)
O2—P1—C1	106.03 (7)	C8—N1—H1A	106.0 (14)
O3—P1—C1	106.38 (6)	C7—N1—H1A	107.9 (14)
O6—P2—O4	112.98 (7)	C8—N1—H1B	108.3 (14)
O6—P2—O5	114.05 (7)	C7—N1—H1B	111.4 (14)
O4—P2—O5	111.20 (7)	H1A—N1—H1B	110 (2)
O6—P2—C4	107.57 (6)	N1—C8—H8B	107.3 (14)
O4—P2—C4	105.95 (6)	N1—C8—H8C	110.0 (14)
O5—P2—C4	104.29 (6)	H8B—C8—H8C	109 (2)
P1—O1—Zn1	145.53 (8)	N1—C8—H8D	104.0 (15)
P1—O3—Zn1^i	127.91 (7)	H8B—C8—H8D	111 (2)
P2—O4—Zn1^iv	137.62 (7)	H8C—C8—H8D	115 (2)
P2—O5—Zn1^v	142.34 (7)	N2—C9—H9A	104.4 (14)
C3—O7—H7A	107.0 (18)	N2—C9—H9B	105.8 (14)
C6—O8—H8A	101.6 (19)	H9A—C9—H9B	116 (2)
C2—C1—C6	118.38 (13)	N2—C9—H9C	107.6 (14)
C2—C1—P1	120.27 (11)	H9A—C9—H9C	109 (2)
C6—C1—P1	121.34 (11)	H9B—C9—H9C	113 (2)
C3—C2—C1	121.54 (14)	C10—N2—C9	113.51 (16)
C3—C2—H2A	118.3 (11)	C10—N2—H2B	112.3 (17)
C1—C2—H2A	120.1 (11)	C9—N2—H2B	106.7 (16)
O7—C3—C2	116.88 (13)	C10—N2—H2C	110.0 (14)
O7—C3—C4	123.19 (13)	C9—N2—H2C	106.8 (14)
C2—C3—C4	119.93 (13)	H2B—N2—H2C	107 (2)
C5—C4—C3	118.52 (13)	N2—C10—H10A	108 (2)
C5—C4—P2	118.11 (11)	N2—C10—H10B	108.4 (17)
C3—C4—P2	123.32 (11)	H10A—C10—H10B	107 (2)
C6—C5—C4	121.45 (14)	N2—C10—H10C	109.3 (16)
C6—C5—H5A	118.1 (11)	H10A—C10—H10C	110 (3)
C4—C5—H5A	120.4 (11)	H10B—C10—H10C	114 (2)
O2—P1—O1—Zn1	37.88 (16)	C1—C2—C3—O7	−177.72 (14)
O3—P1—O1—Zn1	−90.15 (14)	C1—C2—C3—C4	2.0 (2)
C1—P1—O1—Zn1	154.59 (13)	O7—C3—C4—C5	176.85 (14)
O1—P1—O3—Zn1^i	−0.87 (10)	C2—C3—C4—C5	−2.8 (2)
O2—P1—O3—Zn1^i	−130.59 (8)	O7—C3—C4—P2	−5.8 (2)
C1—P1—O3—Zn1^i	114.17 (8)	C2—C3—C4—P2	174.51 (11)
O6—P2—O4—Zn1^iv	−63.56 (12)	O6—P2—C4—C5	−43.03 (13)
O5—P2—O4—Zn1^iv	66.18 (12)	O4—P2—C4—C5	78.06 (13)
C4—P2—O4—Zn1^iv	178.91 (10)	O5—P2—C4—C5	−164.49 (12)
O6—P2—O5—Zn1^v	43.33 (14)	O6—P2—C4—C3	139.65 (13)
O4—P2—O5—Zn1^v	−85.85 (13)	O4—P2—C4—C3	−99.26 (13)
C4—P2—O5—Zn1^v	160.39 (11)	O5—P2—C4—C3	18.19 (14)
O1—P1—C1—C2	71.83 (13)	C3—C4—C5—C6	1.5 (2)
O2—P1—C1—C2	−165.68 (12)	P2—C4—C5—C6	−175.95 (12)
O3—P1—C1—C2	−46.70 (14)	C4—C5—C6—O8	179.76 (15)
O1—P1—C1—C6	−107.45 (13)	C4—C5—C6—C1	0.7 (2)
O2—P1—C1—C6	15.04 (15)	C2—C1—C6—O8	179.40 (15)
O3—P1—C1—C6	134.02 (13)	P1—C1—C6—O8	−1.3 (2)
C6—C1—C2—C3	0.2 (2)	C2—C1—C6—C5	−1.6 (2)
P1—C1—C2—C3	−179.06 (12)	P1—C1—C6—C5	177.73 (12)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) x+1/2, −y+3/2, z−1/2; (iv) −x+3/2, y+1/2, −z+1/2; (v) x−1/2, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O5	0.79 (2)	1.91 (2)	2.6510 (17)	156 (3)
O8—H8A···O2	0.87 (3)	1.73 (3)	2.5846 (18)	168 (3)
N1—H1A···O2	0.89 (2)	1.88 (2)	2.7168 (19)	155.2 (18)
N1—H1B···O6^vi	0.89 (2)	2.02 (2)	2.8125 (19)	148.3 (18)
N2—H2B···O3^vii	0.83 (3)	2.07 (3)	2.8558 (19)	158 (2)
N2—H2C···O6	1.03 (2)	1.63 (2)	2.6518 (18)	173 (2)
C7—H7C···O4^ii	0.91 (2)	2.54 (2)	3.443 (3)	174 (2)
C9—H9B···O8^viii	1.03 (3)	2.57 (2)	3.445 (3)	142.6 (19)
C10—H10A···O8^viii	0.92 (3)	2.42 (3)	3.236 (3)	148 (3)

Symmetry codes: (ii) −x+3/2, y−1/2, −z+1/2; (vi) −x+1, −y+1, −z+1; (vii) x+1/2, −y+3/2, z+1/2; (viii) −x+3/2, y+1/2, −z+3/2.