Orphenadrinium dihydrogen citrate.

In the title salt, C(18)H(24)NO(+)·C(6)H(7)O(7) (-), the dihedral angle between the benzene rings in the cation is 74.2 (5)°. In the crystal, anion-anion O-H⋯O hydrogen bonds and weak O-H⋯O inter-actions form infinite chains along [100]. Between these chains, cation-anion N-H-O hydrogen bonds are observed, forming an alternate pattern of cation and anion layers and leading to a two-dimensional network parallel to (100).

Related literature

For a clinical and pharmacological review of the efficacy of orphenadrine, see: Hunskaar & Donnel (1991 ▶). For related structures, see: Fun et al. (2010 ▶); Glaser et al. (1992 ▶); Jasinski et al. (2011 ▶). For standard bond lengths, see Allen et al. (1987 ▶).

Experimental

Crystal data

C18H24NO+·C6H7O7 −

M = 461.50

Triclinic,

a = 9.9515 (8) Å

b = 10.7382 (9) Å

c = 12.625 (1) Å

α = 98.863 (7)°

β = 104.391 (7)°

γ = 111.498 (8)°

V = 1170.0 (2) Å3

Z = 2

Cu Kα radiation

μ = 0.82 mm−1

T = 173 K

0.32 × 0.28 × 0.14 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer

Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T min = 0.854, T max = 1.000

7161 measured reflections

4471 independent reflections

3795 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.161

S = 1.03

4471 reflections

305 parameters

H-atom parameters constrained

Δρmax = 0.67 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813001207/hg5283sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813001207/hg5283Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813001207/hg5283Isup3.cml

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

C18H24NO+·C6H7O7−	Z = 2
Mr = 461.50	F(000) = 492
Triclinic, P1	Dx = 1.310 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 9.9515 (8) Å	Cell parameters from 3067 reflections
b = 10.7382 (9) Å	θ = 5.1–72.4°
c = 12.625 (1) Å	µ = 0.82 mm−1
α = 98.863 (7)°	T = 173 K
β = 104.391 (7)°	Chunk, colorless
γ = 111.498 (8)°	0.32 × 0.28 × 0.14 mm
V = 1170.0 (2) Å3

Agilent Xcalibur (Eos, Gemini) diffractometer	4471 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3795 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 16.0416 pixels mm-1	θmax = 72.5°, θmin = 5.1°
ω scans	h = −11→12
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	k = −13→9
Tmin = 0.854, Tmax = 1.000	l = −11→15
7161 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056	H-atom parameters constrained
wR(F2) = 0.161	w = 1/[σ2(Fo2) + (0.0849P)2 + 0.4888P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
4471 reflections	Δρmax = 0.67 e Å−3
305 parameters	Δρmin = −0.27 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (7)

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 > 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	0.37357 (15)	0.09276 (13)	0.64965 (11)	0.0291 (3)
N1	0.22933 (17)	−0.11367 (16)	0.42955 (13)	0.0264 (3)
H1	0.2851	−0.1302	0.4902	0.032*
C1	0.3807 (2)	0.16847 (19)	0.75611 (16)	0.0308 (4)
H1A	0.3877	0.2604	0.7502	0.037*
C2	0.5265 (2)	0.1874 (2)	0.84411 (16)	0.0332 (4)
C3	0.5437 (3)	0.0782 (3)	0.8789 (2)	0.0501 (6)
H3	0.4637	−0.0104	0.8503	0.060*
C4	0.6844 (3)	0.1009 (3)	0.9589 (2)	0.0575 (7)
H4	0.6981	0.0274	0.9829	0.069*
C5	0.7998 (3)	0.2326 (3)	1.00022 (19)	0.0528 (6)
H5	0.8914	0.2479	1.0538	0.063*
C6	0.7842 (3)	0.3411 (3)	0.9652 (2)	0.0582 (7)
H6	0.8650	0.4292	0.9931	0.070*
C7	0.6485 (3)	0.3199 (3)	0.8885 (2)	0.0491 (6)
H7	0.6371	0.3946	0.8654	0.059*
C8	0.2379 (2)	0.0950 (2)	0.78589 (16)	0.0328 (4)
C9	0.1917 (3)	0.1694 (3)	0.85948 (19)	0.0458 (6)
C10	0.0579 (3)	0.0950 (4)	0.8824 (2)	0.0572 (7)
H10	0.0255	0.1428	0.9308	0.069*
C11	−0.0264 (3)	−0.0451 (4)	0.8358 (2)	0.0590 (8)
H11	−0.1147	−0.0910	0.8524	0.071*
C12	0.0196 (3)	−0.1178 (3)	0.7648 (2)	0.0498 (6)
H12	−0.0371	−0.2131	0.7330	0.060*
C13	0.1520 (2)	−0.0476 (2)	0.74054 (18)	0.0366 (5)
H13	0.1836	−0.0974	0.6929	0.044*
C14	0.2779 (4)	0.3211 (3)	0.9121 (3)	0.0717 (9)
H14A	0.2768	0.3689	0.8538	0.107*
H14B	0.3817	0.3417	0.9541	0.107*
H14C	0.2310	0.3511	0.9626	0.107*
C15	0.2805 (3)	0.1145 (2)	0.55634 (17)	0.0366 (5)
H15A	0.3163	0.2133	0.5625	0.044*
H15B	0.1755	0.0790	0.5559	0.044*
C16	0.2882 (2)	0.0405 (2)	0.44869 (17)	0.0345 (4)
H16A	0.2293	0.0599	0.3850	0.041*
H16B	0.3938	0.0774	0.4506	0.041*
C17	0.2536 (2)	−0.1766 (2)	0.32629 (17)	0.0358 (5)
H17A	0.3604	−0.1348	0.3348	0.054*
H17B	0.1958	−0.1607	0.2608	0.054*
H17C	0.2203	−0.2748	0.3167	0.054*
C18	0.0653 (2)	−0.1824 (2)	0.41988 (19)	0.0390 (5)
H18A	0.0046	−0.1606	0.3601	0.059*
H18B	0.0529	−0.1497	0.4904	0.059*
H18C	0.0327	−0.2813	0.4029	0.059*
O2	0.96502 (19)	0.50720 (18)	0.23817 (14)	0.0532 (5)
O3	0.95333 (16)	0.41174 (16)	0.38238 (13)	0.0393 (4)
H3A	1.0444	0.4654	0.4097	0.059*
O4	0.71300 (17)	0.54785 (13)	0.37166 (12)	0.0349 (3)
H4A	0.7126	0.5707	0.4366	0.052*
O5	0.74662 (15)	0.41508 (14)	0.53041 (11)	0.0331 (3)
O6	0.63438 (16)	0.20588 (14)	0.40442 (12)	0.0346 (3)
O7	0.3624 (2)	0.49402 (19)	0.31971 (15)	0.0492 (4)
H7A	0.3266	0.5218	0.3652	0.074*
O8	0.37201 (18)	0.34828 (16)	0.42549 (14)	0.0416 (4)
C19	0.3967 (2)	0.3938 (2)	0.34734 (17)	0.0321 (4)
C20	0.4731 (2)	0.3428 (2)	0.27215 (17)	0.0334 (4)
H20A	0.4537	0.3712	0.2027	0.040*
H20B	0.4292	0.2419	0.2518	0.040*
C21	0.6483 (2)	0.40111 (19)	0.33243 (16)	0.0293 (4)
C22	0.6792 (2)	0.33436 (19)	0.43087 (16)	0.0280 (4)
C23	0.7190 (2)	0.3641 (2)	0.24405 (17)	0.0322 (4)
H23A	0.6873	0.2643	0.2233	0.039*
H23B	0.6799	0.3893	0.1762	0.039*
C24	0.8912 (2)	0.4362 (2)	0.28604 (17)	0.0342 (4)

	U11	U22	U33	U12	U13	U23
O1	0.0349 (7)	0.0325 (7)	0.0252 (7)	0.0184 (6)	0.0105 (5)	0.0109 (5)
N1	0.0263 (8)	0.0323 (8)	0.0251 (7)	0.0157 (6)	0.0095 (6)	0.0101 (6)
C1	0.0404 (11)	0.0278 (9)	0.0283 (9)	0.0180 (8)	0.0118 (8)	0.0090 (7)
C2	0.0361 (10)	0.0412 (11)	0.0253 (9)	0.0174 (9)	0.0129 (8)	0.0102 (8)
C3	0.0409 (12)	0.0553 (14)	0.0614 (15)	0.0224 (11)	0.0167 (11)	0.0313 (12)
C4	0.0664 (17)	0.0791 (19)	0.0546 (15)	0.0466 (16)	0.0286 (13)	0.0389 (14)
C5	0.0428 (13)	0.0832 (19)	0.0266 (10)	0.0263 (13)	0.0084 (9)	0.0053 (11)
C6	0.0465 (14)	0.0612 (16)	0.0493 (14)	0.0168 (12)	0.0071 (11)	−0.0025 (12)
C7	0.0484 (13)	0.0443 (12)	0.0469 (13)	0.0179 (11)	0.0130 (11)	0.0005 (10)
C8	0.0368 (10)	0.0464 (11)	0.0268 (9)	0.0272 (9)	0.0116 (8)	0.0150 (8)
C9	0.0537 (14)	0.0657 (15)	0.0340 (11)	0.0427 (12)	0.0143 (10)	0.0136 (10)
C10	0.0616 (16)	0.104 (2)	0.0393 (12)	0.0599 (17)	0.0272 (12)	0.0284 (14)
C11	0.0410 (13)	0.102 (2)	0.0510 (15)	0.0371 (15)	0.0231 (12)	0.0378 (16)
C12	0.0377 (12)	0.0678 (16)	0.0487 (13)	0.0217 (11)	0.0155 (10)	0.0285 (12)
C13	0.0363 (10)	0.0476 (12)	0.0336 (10)	0.0219 (9)	0.0132 (8)	0.0190 (9)
C14	0.096 (2)	0.074 (2)	0.0606 (17)	0.0541 (19)	0.0309 (17)	0.0065 (15)
C15	0.0526 (12)	0.0351 (10)	0.0280 (10)	0.0257 (10)	0.0091 (9)	0.0133 (8)
C16	0.0440 (11)	0.0340 (10)	0.0281 (9)	0.0177 (9)	0.0105 (8)	0.0149 (8)
C17	0.0399 (11)	0.0468 (12)	0.0285 (10)	0.0242 (9)	0.0151 (8)	0.0102 (8)
C18	0.0274 (10)	0.0494 (12)	0.0383 (11)	0.0145 (9)	0.0120 (8)	0.0093 (9)
O2	0.0459 (9)	0.0542 (10)	0.0379 (9)	−0.0012 (8)	0.0148 (7)	0.0088 (7)
O3	0.0296 (7)	0.0457 (8)	0.0417 (8)	0.0149 (6)	0.0121 (6)	0.0121 (7)
O4	0.0454 (8)	0.0265 (7)	0.0360 (7)	0.0169 (6)	0.0155 (6)	0.0095 (6)
O5	0.0300 (7)	0.0403 (8)	0.0317 (7)	0.0180 (6)	0.0104 (6)	0.0092 (6)
O6	0.0375 (8)	0.0299 (7)	0.0388 (8)	0.0170 (6)	0.0096 (6)	0.0137 (6)
O7	0.0714 (11)	0.0648 (11)	0.0521 (10)	0.0544 (10)	0.0361 (9)	0.0359 (9)
O8	0.0487 (9)	0.0396 (8)	0.0515 (9)	0.0239 (7)	0.0257 (7)	0.0246 (7)
C19	0.0279 (9)	0.0339 (10)	0.0366 (10)	0.0155 (8)	0.0083 (8)	0.0134 (8)
C20	0.0347 (10)	0.0382 (10)	0.0322 (10)	0.0212 (9)	0.0088 (8)	0.0121 (8)
C21	0.0321 (10)	0.0267 (9)	0.0329 (10)	0.0151 (8)	0.0114 (8)	0.0108 (7)
C22	0.0249 (9)	0.0325 (9)	0.0323 (10)	0.0159 (8)	0.0108 (7)	0.0122 (8)
C23	0.0347 (10)	0.0313 (9)	0.0324 (10)	0.0156 (8)	0.0120 (8)	0.0083 (8)
C24	0.0368 (10)	0.0307 (9)	0.0313 (10)	0.0116 (8)	0.0133 (8)	0.0016 (8)

O1—C15	1.415 (2)	C14—H14B	0.9600
O1—C1	1.431 (2)	C14—H14C	0.9600
N1—C18	1.488 (2)	C15—C16	1.500 (3)
N1—C17	1.490 (2)	C15—H15A	0.9700
N1—C16	1.496 (2)	C15—H15B	0.9700
N1—H1	0.9100	C16—H16A	0.9700
C1—C2	1.514 (3)	C16—H16B	0.9700
C1—C8	1.522 (3)	C17—H17A	0.9600
C1—H1A	0.9800	C17—H17B	0.9600
C2—C3	1.366 (3)	C17—H17C	0.9600
C2—C7	1.400 (3)	C18—H18A	0.9600
C3—C4	1.418 (4)	C18—H18B	0.9600
C3—H3	0.9300	C18—H18C	0.9600
C4—C5	1.369 (4)	O2—C24	1.200 (3)
C4—H4	0.9300	O3—C24	1.332 (3)
C5—C6	1.354 (4)	O3—H3A	0.8200
C5—H5	0.9300	O4—C21	1.414 (2)
C6—C7	1.367 (4)	O4—H4A	0.8200
C6—H6	0.9300	O5—C22	1.265 (2)
C7—H7	0.9300	O6—C22	1.244 (2)
C8—C13	1.389 (3)	O7—C19	1.313 (2)
C8—C9	1.403 (3)	O7—H7A	0.8200
C9—C10	1.406 (4)	O8—C19	1.206 (2)
C9—C14	1.480 (4)	C19—C20	1.511 (3)
C10—C11	1.368 (4)	C20—C21	1.550 (3)
C10—H10	0.9300	C20—H20A	0.9700
C11—C12	1.368 (4)	C20—H20B	0.9700
C11—H11	0.9300	C21—C23	1.535 (3)
C12—C13	1.394 (3)	C21—C22	1.549 (3)
C12—H12	0.9300	C23—C24	1.505 (3)
C13—H13	0.9300	C23—H23A	0.9700
C14—H14A	0.9600	C23—H23B	0.9700
C15—O1—C1	112.03 (14)	O1—C15—C16	108.73 (16)
C18—N1—C17	109.99 (15)	O1—C15—H15A	109.9
C18—N1—C16	113.44 (15)	C16—C15—H15A	109.9
C17—N1—C16	109.95 (15)	O1—C15—H15B	109.9
C18—N1—H1	107.8	C16—C15—H15B	109.9
C17—N1—H1	107.8	H15A—C15—H15B	108.3
C16—N1—H1	107.8	N1—C16—C15	113.81 (16)
O1—C1—C2	107.13 (15)	N1—C16—H16A	108.8
O1—C1—C8	111.31 (16)	C15—C16—H16A	108.8
C2—C1—C8	112.95 (15)	N1—C16—H16B	108.8
O1—C1—H1A	108.4	C15—C16—H16B	108.8
C2—C1—H1A	108.4	H16A—C16—H16B	107.7
C8—C1—H1A	108.4	N1—C17—H17A	109.5
C3—C2—C7	119.2 (2)	N1—C17—H17B	109.5
C3—C2—C1	121.8 (2)	H17A—C17—H17B	109.5
C7—C2—C1	119.03 (19)	N1—C17—H17C	109.5
C2—C3—C4	119.5 (2)	H17A—C17—H17C	109.5
C2—C3—H3	120.2	H17B—C17—H17C	109.5
C4—C3—H3	120.2	N1—C18—H18A	109.5
C5—C4—C3	119.0 (2)	N1—C18—H18B	109.5
C5—C4—H4	120.5	H18A—C18—H18B	109.5
C3—C4—H4	120.5	N1—C18—H18C	109.5
C6—C5—C4	121.8 (2)	H18A—C18—H18C	109.5
C6—C5—H5	119.1	H18B—C18—H18C	109.5
C4—C5—H5	119.1	C24—O3—H3A	109.5
C5—C6—C7	119.4 (3)	C21—O4—H4A	109.5
C5—C6—H6	120.3	C19—O7—H7A	109.5
C7—C6—H6	120.3	O8—C19—O7	123.69 (19)
C6—C7—C2	121.1 (2)	O8—C19—C20	123.37 (17)
C6—C7—H7	119.5	O7—C19—C20	112.93 (17)
C2—C7—H7	119.5	C19—C20—C21	111.50 (16)
C13—C8—C9	119.1 (2)	C19—C20—H20A	109.3
C13—C8—C1	120.07 (17)	C21—C20—H20A	109.3
C9—C8—C1	120.8 (2)	C19—C20—H20B	109.3
C8—C9—C10	117.7 (2)	C21—C20—H20B	109.3
C8—C9—C14	122.4 (2)	H20A—C20—H20B	108.0
C10—C9—C14	119.9 (2)	O4—C21—C23	107.28 (15)
C11—C10—C9	122.3 (2)	O4—C21—C22	111.65 (15)
C11—C10—H10	118.8	C23—C21—C22	110.56 (15)
C9—C10—H10	118.8	O4—C21—C20	110.38 (14)
C12—C11—C10	119.9 (2)	C23—C21—C20	107.75 (16)
C12—C11—H11	120.1	C22—C21—C20	109.14 (15)
C10—C11—H11	120.1	O6—C22—O5	126.11 (17)
C11—C12—C13	119.4 (3)	O6—C22—C21	116.70 (16)
C11—C12—H12	120.3	O5—C22—C21	117.19 (16)
C13—C12—H12	120.3	C24—C23—C21	113.05 (16)
C8—C13—C12	121.5 (2)	C24—C23—H23A	109.0
C8—C13—H13	119.2	C21—C23—H23A	109.0
C12—C13—H13	119.2	C24—C23—H23B	109.0
C9—C14—H14A	109.5	C21—C23—H23B	109.0
C9—C14—H14B	109.5	H23A—C23—H23B	107.8
H14A—C14—H14B	109.5	O2—C24—O3	123.4 (2)
C9—C14—H14C	109.5	O2—C24—C23	124.1 (2)
H14A—C14—H14C	109.5	O3—C24—C23	112.52 (17)
H14B—C14—H14C	109.5
C15—O1—C1—C2	−156.91 (16)	C10—C11—C12—C13	−0.2 (4)
C15—O1—C1—C8	79.15 (19)	C9—C8—C13—C12	1.2 (3)
O1—C1—C2—C3	−69.6 (2)	C1—C8—C13—C12	−179.11 (19)
C8—C1—C2—C3	53.3 (3)	C11—C12—C13—C8	−0.7 (3)
O1—C1—C2—C7	108.4 (2)	C1—O1—C15—C16	175.89 (16)
C8—C1—C2—C7	−128.6 (2)	C18—N1—C16—C15	61.1 (2)
C7—C2—C3—C4	−0.1 (4)	C17—N1—C16—C15	−175.25 (17)
C1—C2—C3—C4	178.0 (2)	O1—C15—C16—N1	61.9 (2)
C2—C3—C4—C5	0.5 (4)	O8—C19—C20—C21	−76.4 (2)
C3—C4—C5—C6	−1.3 (4)	O7—C19—C20—C21	102.6 (2)
C4—C5—C6—C7	1.6 (4)	C19—C20—C21—O4	−54.0 (2)
C5—C6—C7—C2	−1.1 (4)	C19—C20—C21—C23	−170.86 (15)
C3—C2—C7—C6	0.4 (4)	C19—C20—C21—C22	69.05 (19)
C1—C2—C7—C6	−177.8 (2)	O4—C21—C22—O6	−176.07 (15)
O1—C1—C8—C13	24.5 (2)	C23—C21—C22—O6	−56.7 (2)
C2—C1—C8—C13	−96.0 (2)	C20—C21—C22—O6	61.6 (2)
O1—C1—C8—C9	−155.81 (17)	O4—C21—C22—O5	4.3 (2)
C2—C1—C8—C9	83.6 (2)	C23—C21—C22—O5	123.66 (17)
C13—C8—C9—C10	−0.9 (3)	C20—C21—C22—O5	−117.99 (18)
C1—C8—C9—C10	179.40 (18)	O4—C21—C23—C24	51.0 (2)
C13—C8—C9—C14	179.4 (2)	C22—C21—C23—C24	−71.0 (2)
C1—C8—C9—C14	−0.3 (3)	C20—C21—C23—C24	169.85 (16)
C8—C9—C10—C11	0.1 (3)	C21—C23—C24—O2	−124.6 (2)
C14—C9—C10—C11	179.8 (2)	C21—C23—C24—O3	55.7 (2)
C9—C10—C11—C12	0.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6i	0.91	1.83	2.725 (2)	167
O4—H4A···O8ii	0.82	2.30	3.067 (2)	156
O7—H7A···O5ii	0.82	1.81	2.634 (2)	178

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6i	0.91	1.83	2.725 (2)	167
O4—H4A⋯O8ii	0.82	2.30	3.067 (2)	156
O7—H7A⋯O5ii	0.82	1.81	2.634 (2)	178

Symmetry codes: (i) ; (ii) .