The crystal structure of (C₂H₉N₂)₂[Zn₃(HPO₃)₄], a three-dimensional zincophosphite framework containing 16-membered rings templated by the unsymmetrical dimethyl hydrazinium cation

The title open framework contains 16-ring pores templated by pairs of side-by-side unsymmetrical dimethyl hydrazinium cations.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](N-N) = 0.012 Å
• R factor = 0.068
• wR factor = 0.239
• Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.909 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         35 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          8 Note
PLAT918_ALERT_3_C Reflection(s) with I(obs) much Smaller I(calc) .         11 Check
PLAT939_ALERT_3_C Large Value of Not (SHELXL) Weight Optimized S .      98.57 Check

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          3 Info
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          5 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT  Unusually Large       0.16 Report
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT  Unusually Large      13.60 Why ?
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.18 Ratio
PLAT793_ALERT_4_G The Model has Chirality at P1      (Centro SPGR)          R Verify
PLAT793_ALERT_4_G The Model has Chirality at P2      (Centro SPGR)          R Verify
PLAT794_ALERT_5_G Tentative Bond Valency for Zn1     (II)    .....       2.28 Note
PLAT794_ALERT_5_G Tentative Bond Valency for Zn2     (II)    .....       2.18 Note
PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed ..          ! Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         35 Note
PLAT931_ALERT_5_G Found Twin Law ( 0 0  1)[       ] Estimated BASF       0.45 Check
PLAT931_ALERT_5_G Found Twin Law ( 3 3 -1)[       ] Estimated BASF       0.39 Check
PLAT931_ALERT_5_G Found Twin Law ( 3-3 -1)[       ] Estimated BASF       0.38 Check

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

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

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Computing details

Data collection: CrysAlis PRO (Rigaku, 2015); cell refinement: CrysAlis PRO (Rigaku, 2015); data reduction: CrysAlis PRO (Rigaku, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and ATOMS (Shape Software, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

1,1-Dimethylhydrazinium tetraphoshonoatotrizincate(II)

Crystal data

(C2H9N2)2[Zn3(HPO3)4]	F(000) = 1280
Mr = 638.24	Dx = 2.092 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.1154 (5) Å	Cell parameters from 6272 reflections
b = 8.7269 (3) Å	θ = 2.6–27.6°
c = 16.1675 (6) Å	µ = 3.90 mm^−1
β = 108.156 (1)°	T = 100 K
V = 2026.48 (12) Å^3	Block, colourless
Z = 4	0.19 × 0.11 × 0.05 mm

Data collection

Rigaku Mercury CCD diffractometer	2169 reflections with I > 2σ(I)
ω scans	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −19→18
Tmin = 0.527, Tmax = 1.000	k = −11→11
2273 measured reflections	l = −11→20
2273 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.068	w = 1/[σ^2(Fo^2) + (0.1587P)^2 + 13.6003P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.239	(Δ/σ)max < 0.001
S = 1.22	Δρmax = 1.51 e Å^−3
2273 reflections	Δρmin = −1.24 e Å^−3
127 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.011 (2)
Primary atom site location: structure-invariant direct methods

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.

Refinement. Refined as a 2-component twin with components rotated about (001) in reciprocal space

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

	x	y	z	Uiso*/Ueq
Zn1	0.0000	0.16565 (13)	0.2500	0.0076 (4)
Zn2	0.36570 (6)	0.37073 (9)	0.48484 (5)	0.0096 (4)
P1	0.15444 (13)	0.3885 (2)	0.37817 (11)	0.0091 (5)
H1	0.1147	0.5248	0.3662	0.011*
P2	−0.01597 (13)	−0.0917 (2)	0.11747 (11)	0.0088 (5)
H2	−0.0253	−0.1970	0.1728	0.011*
O1	0.2557 (4)	0.4152 (7)	0.3858 (3)	0.0193 (12)
O2	0.1393 (5)	0.3246 (6)	0.4592 (3)	0.0180 (12)
O3	0.1081 (4)	0.2975 (7)	0.2948 (3)	0.0160 (11)
O4	0.0428 (4)	0.0362 (6)	0.1728 (3)	0.0146 (11)
O5	0.0321 (4)	−0.1690 (6)	0.0604 (4)	0.0169 (12)
O6	−0.1139 (4)	−0.0379 (6)	0.0684 (3)	0.0124 (10)
C1	0.1591 (7)	0.2877 (11)	0.0880 (5)	0.028 (2)
H1A	0.1821	0.1825	0.1002	0.043*
H1B	0.1847	0.3339	0.0452	0.043*
H1C	0.0909	0.2867	0.0649	0.043*
C2	0.1529 (8)	0.5365 (10)	0.1562 (6)	0.029 (2)
H2A	0.1818	0.5963	0.2091	0.043*
H2B	0.0852	0.5358	0.1439	0.043*
H2C	0.1683	0.5827	0.1072	0.043*
N1	0.2898 (6)	0.3663 (9)	0.2063 (5)	0.0249 (17)
H1N	0.3067	0.3880	0.2642	0.030*
H2N	0.3170	0.4346	0.1793	0.030*
N2	0.1884 (5)	0.3781 (7)	0.1691 (4)	0.0132 (13)
H3N	0.1608	0.3280	0.2110	0.016*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0064 (7)	0.0080 (6)	0.0076 (6)	0.000	0.0008 (4)	0.000
Zn2	0.0093 (6)	0.0109 (5)	0.0078 (5)	−0.0032 (3)	0.0015 (4)	0.0003 (3)
P1	0.0106 (10)	0.0085 (8)	0.0076 (8)	−0.0011 (6)	0.0021 (7)	0.0010 (6)
P2	0.0085 (9)	0.0093 (8)	0.0077 (8)	0.0008 (6)	0.0014 (7)	0.0001 (6)
O1	0.020 (3)	0.024 (3)	0.012 (2)	−0.006 (2)	0.001 (2)	0.002 (2)
O2	0.033 (3)	0.009 (2)	0.013 (2)	−0.002 (2)	0.009 (2)	0.0000 (18)
O3	0.013 (3)	0.023 (3)	0.012 (2)	−0.010 (2)	0.004 (2)	−0.006 (2)
O4	0.015 (3)	0.014 (2)	0.014 (2)	0.000 (2)	0.002 (2)	−0.006 (2)
O5	0.025 (3)	0.012 (2)	0.016 (2)	0.005 (2)	0.009 (2)	−0.0021 (19)
O6	0.008 (3)	0.016 (2)	0.013 (2)	0.000 (2)	0.0020 (19)	0.004 (2)
C1	0.039 (5)	0.024 (4)	0.015 (3)	−0.003 (4)	−0.002 (4)	−0.008 (3)
C2	0.048 (6)	0.020 (4)	0.024 (4)	0.005 (4)	0.020 (4)	0.006 (3)
N1	0.019 (4)	0.034 (4)	0.020 (3)	−0.004 (3)	0.004 (3)	0.002 (3)
N2	0.017 (4)	0.013 (3)	0.011 (3)	−0.004 (2)	0.008 (3)	−0.001 (2)

Geometric parameters (Å, º)

Zn1—O4	1.938 (5)	O2—Zn2^iii	1.943 (5)
Zn1—O4^i	1.938 (5)	O5—Zn2^v	1.936 (6)
Zn1—O3^i	1.945 (5)	O6—Zn2^vi	1.946 (5)
Zn1—O3	1.945 (5)	C1—N2	1.475 (9)
Zn2—O5^ii	1.936 (6)	C1—H1A	0.9800
Zn2—O2^iii	1.943 (5)	C1—H1B	0.9800
Zn2—O6^iv	1.946 (5)	C1—H1C	0.9800
Zn2—O1	1.954 (6)	C2—N2	1.474 (10)
P1—O2	1.504 (5)	C2—H2A	0.9800
P1—O1	1.515 (6)	C2—H2B	0.9800
P1—O3	1.533 (5)	C2—H2C	0.9800
P1—H1	1.3200	N1—N2	1.465 (10)
P2—O5	1.500 (6)	N1—H1N	0.9100
P2—O6	1.520 (5)	N1—H2N	0.9100
P2—O4	1.529 (5)	N2—H3N	1.0000
P2—H2	1.3200
O4—Zn1—O4^i	108.7 (3)	P1—O3—Zn1	137.2 (3)
O4—Zn1—O3^i	121.0 (2)	P2—O4—Zn1	123.6 (3)
O4^i—Zn1—O3^i	100.0 (2)	P2—O5—Zn2^v	138.4 (4)
O4—Zn1—O3	100.0 (2)	P2—O6—Zn2^vi	120.8 (3)
O4^i—Zn1—O3	121.0 (2)	N2—C1—H1A	109.5
O3^i—Zn1—O3	107.4 (4)	N2—C1—H1B	109.5
O5^ii—Zn2—O2^iii	99.8 (2)	H1A—C1—H1B	109.5
O5^ii—Zn2—O6^iv	115.1 (2)	N2—C1—H1C	109.5
O2^iii—Zn2—O6^iv	110.8 (2)	H1A—C1—H1C	109.5
O5^ii—Zn2—O1	107.5 (3)	H1B—C1—H1C	109.5
O2^iii—Zn2—O1	114.1 (3)	N2—C2—H2A	109.5
O6^iv—Zn2—O1	109.3 (2)	N2—C2—H2B	109.5
O2—P1—O1	114.2 (3)	H2A—C2—H2B	109.5
O2—P1—O3	115.0 (3)	N2—C2—H2C	109.5
O1—P1—O3	108.9 (3)	H2A—C2—H2C	109.5
O2—P1—H1	106.0	H2B—C2—H2C	109.5
O1—P1—H1	106.0	N2—N1—H1N	109.3
O3—P1—H1	106.0	N2—N1—H2N	109.2
O5—P2—O6	113.4 (3)	H1N—N1—H2N	109.5
O5—P2—O4	112.6 (3)	N1—N2—C2	114.3 (7)
O6—P2—O4	111.9 (3)	N1—N2—C1	108.3 (6)
O5—P2—H2	106.1	C2—N2—C1	112.4 (7)
O6—P2—H2	106.1	N1—N2—H3N	107.2
O4—P2—H2	106.1	C2—N2—H3N	107.2
P1—O1—Zn2	128.0 (3)	C1—N2—H3N	107.2
P1—O2—Zn2^iii	140.3 (3)
O2—P1—O1—Zn2	2.2 (6)	O5—P2—O4—Zn1	177.2 (3)
O3—P1—O1—Zn2	−127.8 (4)	O6—P2—O4—Zn1	48.1 (4)
O1—P1—O2—Zn2^iii	−86.8 (7)	O6—P2—O5—Zn2^v	110.4 (6)
O3—P1—O2—Zn2^iii	40.2 (8)	O4—P2—O5—Zn2^v	−18.0 (7)
O2—P1—O3—Zn1	28.0 (7)	O5—P2—O6—Zn2^vi	−68.4 (4)
O1—P1—O3—Zn1	157.6 (5)	O4—P2—O6—Zn2^vi	60.3 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.91	2.34	3.130 (9)	146
N1—H2N···O6^vii	0.91	2.35	3.133 (9)	144
N2—H3N···O3	1.00	1.79	2.762 (8)	163
C1—H1A···O1^v	0.98	2.50	3.474 (11)	173
C1—H1C···O5^viii	0.98	2.50	3.295 (11)	138
C2—H2C···O2^ix	0.98	2.43	3.355 (9)	157

Symmetry codes: (v) −x+1/2, y−1/2, −z+1/2; (vii) x+1/2, y+1/2, z; (viii) −x, −y, −z; (ix) x, −y+1, z−1/2.