4,4'-Dinitro-2,2'-[propane-1,3-diylbis(iminiumylmethanylyl-idene)]diphenolate.

The title compound, C(17)H(16)N(4)O(6), is a Schiff base, which is found as a bis-zwitterion in the solid state. The geometry around the iminium N atom indicates sp(2)-hybridization. The diiminiumpropyl-ene chain is in an approximate double-gauche conformation, with average N-C-C-C torsion angles of 69.3°. The zwitterion shows strong intra-molecular N-H⋯O hydrogen bonds between the iminium N and phenolate O atom. In the crystal, bifurcated N-H⋯(O,O) hydrogen bonds assemble pairs of molecules into inversion dimers.

Related literature

For the crystal structure of the related zwitterion, 4-nitro-2-{[(tricyclo­[3.3.1.13,7]decan-1-yl)iminium­yl]meth­yl}phenolate, see: Ha (2012 ▶).

Experimental

Crystal data

C17H16N4O6

M = 372.34

Orthorhombic,

a = 11.5698 (5) Å

b = 13.0393 (6) Å

c = 22.0393 (10) Å

V = 3324.9 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.12 mm−1

T = 200 K

0.31 × 0.17 × 0.15 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.890, T max = 1.000

23432 measured reflections

4120 independent reflections

2286 reflections with I > 2σ(I)

R int = 0.084

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.138

S = 1.03

4120 reflections

252 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.30 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812015504/zl2472sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015504/zl2472Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C17H16N4O6	F(000) = 1552
Mr = 372.34	Dx = 1.488 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3572 reflections
a = 11.5698 (5) Å	θ = 2.5–25.3°
b = 13.0393 (6) Å	µ = 0.12 mm−1
c = 22.0393 (10) Å	T = 200 K
V = 3324.9 (3) Å3	Block, yellow
Z = 8	0.31 × 0.17 × 0.15 mm

Bruker SMART 1000 CCD diffractometer	4120 independent reflections
Radiation source: fine-focus sealed tube	2286 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.084
φ and ω scans	θmax = 28.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −15→15
Tmin = 0.890, Tmax = 1.000	k = −14→17
23432 measured reflections	l = −28→29

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0572P)2 + 0.0212P] where P = (Fo2 + 2Fc2)/3
4120 reflections	(Δ/σ)max < 0.001
252 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.18305 (12)	0.22185 (11)	0.21082 (6)	0.0397 (4)
O2	0.63010 (14)	0.28176 (13)	0.05617 (7)	0.0495 (4)
O3	0.50263 (15)	0.25797 (13)	−0.01460 (7)	0.0522 (5)
O4	0.62220 (12)	−0.00556 (11)	0.48734 (6)	0.0383 (4)
O5	0.96696 (14)	−0.02327 (15)	0.27155 (8)	0.0636 (5)
O6	1.08562 (13)	−0.02659 (13)	0.34711 (8)	0.0536 (5)
N1	0.52991 (16)	0.26527 (13)	0.03929 (9)	0.0372 (4)
N2	0.34001 (16)	0.22765 (13)	0.29410 (8)	0.0325 (4)
H2N	0.491 (2)	0.0128 (18)	0.4342 (13)	0.061 (8)*
N3	0.48198 (14)	0.01663 (13)	0.39362 (9)	0.0300 (4)
H3N	0.266 (3)	0.2203 (19)	0.2781 (13)	0.079 (9)*
N4	0.98619 (16)	−0.02418 (14)	0.32658 (9)	0.0388 (5)
C1	0.26324 (17)	0.23326 (14)	0.17156 (9)	0.0293 (5)
C2	0.23969 (18)	0.23465 (14)	0.10807 (9)	0.0321 (5)
H2	0.1619	0.2290	0.0947	0.038*
C3	0.32499 (18)	0.24381 (14)	0.06613 (9)	0.0320 (5)
H3	0.3065	0.2433	0.0241	0.038*
C4	0.44063 (18)	0.25404 (14)	0.08474 (9)	0.0296 (5)
C5	0.46937 (17)	0.25358 (14)	0.14490 (9)	0.0294 (5)
H5	0.5479	0.2608	0.1567	0.035*
C6	0.38325 (17)	0.24253 (14)	0.18915 (9)	0.0270 (4)
C7	0.41546 (18)	0.23887 (14)	0.25139 (9)	0.0305 (5)
H7	0.4948	0.2449	0.2619	0.037*
C8	0.36602 (19)	0.22306 (16)	0.35868 (9)	0.0349 (5)
H8A	0.3365	0.2858	0.3787	0.042*
H8B	0.4508	0.2208	0.3644	0.042*
C9	0.31172 (18)	0.12934 (15)	0.38808 (9)	0.0330 (5)
H9A	0.2285	0.1280	0.3777	0.040*
H9B	0.3179	0.1364	0.4327	0.040*
C10	0.36533 (17)	0.02741 (15)	0.36953 (9)	0.0320 (5)
H10A	0.3166	−0.0295	0.3847	0.038*
H10B	0.3678	0.0229	0.3247	0.038*
C11	0.57442 (17)	0.00744 (14)	0.36110 (9)	0.0274 (4)
H11	0.5665	0.0098	0.3182	0.033*
C12	0.68702 (17)	−0.00597 (14)	0.38544 (8)	0.0261 (4)
C13	0.70501 (18)	−0.01066 (14)	0.45046 (9)	0.0281 (4)
C14	0.82265 (18)	−0.02299 (16)	0.47050 (9)	0.0353 (5)
H14	0.8382	−0.0277	0.5127	0.042*
C15	0.91170 (18)	−0.02810 (16)	0.43079 (9)	0.0347 (5)
H15	0.9885	−0.0358	0.4453	0.042*
C16	0.89073 (17)	−0.02195 (15)	0.36768 (9)	0.0293 (4)
C17	0.78028 (17)	−0.01169 (14)	0.34546 (9)	0.0293 (5)
H17	0.7675	−0.0085	0.3029	0.035*

	U11	U22	U33	U12	U13	U23
O1	0.0255 (8)	0.0574 (10)	0.0362 (9)	−0.0014 (7)	0.0025 (7)	0.0090 (7)
O2	0.0335 (9)	0.0701 (12)	0.0450 (10)	0.0044 (8)	0.0064 (8)	0.0105 (8)
O3	0.0570 (11)	0.0726 (12)	0.0269 (9)	0.0072 (8)	0.0058 (8)	−0.0012 (7)
O4	0.0334 (8)	0.0565 (10)	0.0250 (8)	0.0030 (7)	0.0042 (7)	0.0031 (6)
O5	0.0469 (11)	0.1112 (16)	0.0326 (10)	0.0119 (10)	0.0109 (8)	0.0110 (9)
O6	0.0278 (9)	0.0770 (13)	0.0560 (11)	0.0016 (8)	0.0043 (8)	0.0064 (9)
N1	0.0380 (11)	0.0407 (11)	0.0330 (11)	0.0072 (8)	0.0040 (9)	0.0031 (8)
N2	0.0311 (10)	0.0420 (11)	0.0243 (10)	0.0018 (8)	−0.0008 (8)	0.0051 (7)
N3	0.0304 (10)	0.0370 (10)	0.0225 (10)	0.0030 (7)	−0.0016 (8)	−0.0009 (7)
N4	0.0323 (11)	0.0474 (12)	0.0367 (11)	0.0026 (8)	0.0050 (9)	0.0073 (8)
C1	0.0265 (11)	0.0295 (11)	0.0318 (11)	−0.0006 (8)	−0.0022 (9)	0.0047 (8)
C2	0.0304 (11)	0.0321 (12)	0.0336 (12)	−0.0020 (9)	−0.0048 (9)	0.0041 (9)
C3	0.0391 (13)	0.0284 (11)	0.0285 (11)	−0.0002 (9)	−0.0043 (9)	0.0018 (8)
C4	0.0306 (12)	0.0312 (11)	0.0271 (11)	0.0023 (9)	0.0029 (9)	0.0029 (8)
C5	0.0241 (10)	0.0316 (12)	0.0324 (12)	0.0015 (8)	−0.0017 (9)	0.0024 (8)
C6	0.0260 (10)	0.0279 (11)	0.0272 (11)	0.0023 (8)	−0.0019 (9)	0.0040 (8)
C7	0.0285 (11)	0.0314 (11)	0.0315 (11)	0.0009 (9)	0.0011 (9)	0.0022 (8)
C8	0.0368 (12)	0.0418 (13)	0.0260 (12)	0.0022 (10)	−0.0015 (9)	0.0002 (9)
C9	0.0315 (12)	0.0400 (13)	0.0274 (11)	0.0029 (9)	0.0019 (9)	0.0022 (9)
C10	0.0278 (11)	0.0425 (13)	0.0256 (11)	0.0015 (9)	−0.0017 (9)	0.0013 (9)
C11	0.0324 (11)	0.0280 (11)	0.0218 (10)	0.0010 (8)	−0.0012 (9)	−0.0004 (8)
C12	0.0288 (11)	0.0263 (11)	0.0233 (10)	0.0014 (8)	−0.0002 (8)	0.0009 (7)
C13	0.0317 (11)	0.0276 (11)	0.0251 (11)	−0.0018 (8)	0.0004 (9)	0.0010 (8)
C14	0.0331 (12)	0.0469 (13)	0.0260 (11)	−0.0042 (10)	−0.0033 (9)	0.0041 (9)
C15	0.0284 (11)	0.0414 (13)	0.0344 (13)	−0.0037 (10)	−0.0029 (9)	0.0040 (9)
C16	0.0300 (11)	0.0306 (11)	0.0274 (11)	−0.0010 (8)	0.0036 (9)	0.0036 (8)
C17	0.0346 (12)	0.0297 (11)	0.0236 (10)	−0.0003 (9)	0.0011 (9)	0.0015 (8)

O1—C1	1.277 (2)	C5—H5	0.9500
O2—N1	1.236 (2)	C6—C7	1.422 (3)
O3—N1	1.233 (2)	C7—H7	0.9500
O4—C13	1.258 (2)	C8—C9	1.519 (3)
O5—N4	1.233 (2)	C8—H8A	0.9900
O6—N4	1.237 (2)	C8—H8B	0.9900
N1—C4	1.446 (3)	C9—C10	1.523 (3)
N2—C7	1.292 (2)	C9—H9A	0.9900
N2—C8	1.456 (3)	C9—H9B	0.9900
N2—H3N	0.93 (3)	C10—H10A	0.9900
N3—C11	1.293 (3)	C10—H10B	0.9900
N3—C10	1.457 (3)	C11—C12	1.420 (3)
N3—H2N	0.90 (3)	C11—H11	0.9500
N4—C16	1.429 (3)	C12—C17	1.395 (3)
C1—C2	1.426 (3)	C12—C13	1.449 (3)
C1—C6	1.447 (3)	C13—C14	1.440 (3)
C2—C3	1.357 (3)	C14—C15	1.353 (3)
C2—H2	0.9500	C14—H14	0.9500
C3—C4	1.406 (3)	C15—C16	1.414 (3)
C3—H3	0.9500	C15—H15	0.9500
C4—C5	1.367 (3)	C16—C17	1.375 (3)
C5—C6	1.402 (3)	C17—H17	0.9500
O3—N1—O2	122.92 (18)	N2—C8—H8B	109.4
O3—N1—C4	118.46 (18)	C9—C8—H8B	109.4
O2—N1—C4	118.62 (18)	H8A—C8—H8B	108.0
C7—N2—C8	125.25 (19)	C8—C9—C10	114.79 (17)
C7—N2—H3N	110.9 (18)	C8—C9—H9A	108.6
C8—N2—H3N	123.8 (18)	C10—C9—H9A	108.6
C11—N3—C10	124.97 (18)	C8—C9—H9B	108.6
C11—N3—H2N	116.4 (16)	C10—C9—H9B	108.6
C10—N3—H2N	118.5 (16)	H9A—C9—H9B	107.5
O5—N4—O6	121.87 (18)	N3—C10—C9	111.32 (17)
O5—N4—C16	118.95 (18)	N3—C10—H10A	109.4
O6—N4—C16	119.19 (19)	C9—C10—H10A	109.4
O1—C1—C2	121.84 (18)	N3—C10—H10B	109.4
O1—C1—C6	121.70 (18)	C9—C10—H10B	109.4
C2—C1—C6	116.44 (18)	H10A—C10—H10B	108.0
C3—C2—C1	122.04 (19)	N3—C11—C12	124.13 (18)
C3—C2—H2	119.0	N3—C11—H11	117.9
C1—C2—H2	119.0	C12—C11—H11	117.9
C2—C3—C4	120.12 (19)	C17—C12—C11	118.54 (17)
C2—C3—H3	119.9	C17—C12—C13	120.74 (18)
C4—C3—H3	119.9	C11—C12—C13	120.70 (17)
C5—C4—C3	120.94 (19)	O4—C13—C14	121.84 (18)
C5—C4—N1	119.89 (19)	O4—C13—C12	121.81 (18)
C3—C4—N1	119.17 (18)	C14—C13—C12	116.34 (18)
C4—C5—C6	120.15 (18)	C15—C14—C13	121.78 (19)
C4—C5—H5	119.9	C15—C14—H14	119.1
C6—C5—H5	119.9	C13—C14—H14	119.1
C5—C6—C7	119.23 (18)	C14—C15—C16	120.17 (19)
C5—C6—C1	120.30 (18)	C14—C15—H15	119.9
C7—C6—C1	120.47 (18)	C16—C15—H15	119.9
N2—C7—C6	121.97 (19)	C17—C16—C15	121.02 (18)
N2—C7—H7	119.0	C17—C16—N4	119.63 (18)
C6—C7—H7	119.0	C15—C16—N4	119.33 (18)
N2—C8—C9	111.38 (17)	C16—C17—C12	119.93 (18)
N2—C8—H8A	109.4	C16—C17—H17	120.0
C9—C8—H8A	109.4	C12—C17—H17	120.0
O1—C1—C2—C3	−178.08 (18)	C11—N3—C10—C9	−118.0 (2)
C6—C1—C2—C3	0.2 (3)	C8—C9—C10—N3	69.0 (2)
C1—C2—C3—C4	−1.1 (3)	C10—N3—C11—C12	−178.09 (18)
C2—C3—C4—C5	0.9 (3)	N3—C11—C12—C17	−178.00 (18)
C2—C3—C4—N1	−179.06 (17)	N3—C11—C12—C13	0.3 (3)
O3—N1—C4—C5	174.81 (18)	C17—C12—C13—O4	179.94 (17)
O2—N1—C4—C5	−5.2 (3)	C11—C12—C13—O4	1.7 (3)
O3—N1—C4—C3	−5.2 (3)	C17—C12—C13—C14	−0.9 (3)
O2—N1—C4—C3	174.75 (18)	C11—C12—C13—C14	−179.17 (17)
C3—C4—C5—C6	0.2 (3)	O4—C13—C14—C15	−179.76 (19)
N1—C4—C5—C6	−179.88 (17)	C12—C13—C14—C15	1.1 (3)
C4—C5—C6—C7	177.95 (18)	C13—C14—C15—C16	−0.4 (3)
C4—C5—C6—C1	−1.0 (3)	C14—C15—C16—C17	−0.6 (3)
O1—C1—C6—C5	179.14 (18)	C14—C15—C16—N4	178.00 (18)
C2—C1—C6—C5	0.8 (3)	O5—N4—C16—C17	−4.5 (3)
O1—C1—C6—C7	0.2 (3)	O6—N4—C16—C17	175.25 (19)
C2—C1—C6—C7	−178.14 (17)	O5—N4—C16—C15	176.89 (18)
C8—N2—C7—C6	179.92 (17)	O6—N4—C16—C15	−3.4 (3)
C5—C6—C7—N2	−179.22 (18)	C15—C16—C17—C12	0.8 (3)
C1—C6—C7—N2	−0.2 (3)	N4—C16—C17—C12	−177.83 (17)
C7—N2—C8—C9	−128.3 (2)	C11—C12—C17—C16	178.29 (17)
N2—C8—C9—C10	69.6 (2)	C13—C12—C17—C16	0.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H3N···O1	0.93 (3)	1.77 (3)	2.583 (2)	145 (3)
N3—H2N···O4	0.90 (3)	1.93 (3)	2.642 (2)	135 (2)
N3—H2N···O4i	0.90 (3)	2.17 (3)	2.891 (2)	136 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H3N⋯O1	0.93 (3)	1.77 (3)	2.583 (2)	145 (3)
N3—H2N⋯O4	0.90 (3)	1.93 (3)	2.642 (2)	135 (2)
N3—H2N⋯O4i	0.90 (3)	2.17 (3)	2.891 (2)	136 (2)

Symmetry code: (i) .