Succinic acid has been known since 1546 and was first chemically identified in the mid-19th century. In an attempt to prepare a molecular salt of succinic acid with (S)-(−)-α-methylbenzylamine, we have obtained the second polymorph of the monoammonium salt of succinic acid, NH4+·C4H5O4−. The crystal structure determination proves the structure of the ionic compound and the intimate role of the ammonium ion in the structure, which is compared to the earlier described polymorph.
Supporting information
CCDC reference: 1892130
Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT-Plus (Bruker, 2016); data reduction: SAINT-Plus and XPREP (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), Mercury (Macrae et
al.,
2008) and DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).
Crystal data top
NH4+·C4H5O4− | F(000) = 576 |
Mr = 135.12 | Dx = 1.45 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1747 reflections |
a = 9.3716 (14) Å | θ = 2.8–21.4° |
b = 11.7529 (18) Å | µ = 0.13 mm−1 |
c = 11.2357 (16) Å | T = 293 K |
β = 90.187 (9)° | Plate, colourless |
V = 1237.5 (3) Å3 | 0.2 × 0.01 × 0.01 mm |
Z = 8 | |
Data collection top
Bruker SMART 1K CCD area detector diffractometer | 1381 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
phi and ω scans | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→11 |
Tmin = 0.96, Tmax = 0.99 | k = −14→14 |
9934 measured reflections | l = −13→13 |
2307 independent reflections | |
Refinement top
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.159 | w = 1/[σ2(Fo2) + (0.0932P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max = 0.008 |
2307 reflections | Δρmax = 0.19 e Å−3 |
193 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | |
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. Intensity data for form II were collected on a Bruker (Bruker AXS Inc.
Madison, WI, USA) SMART 1K CCD area-detector diffractometer with
graphite-monochromated Mo Kα (λ = 0.71073 Å) (50 kV, 30 mA) and
performed at 293 K. The collection involved ω-scans of width 0.3°.
Data reduction was carried out using the program SAINT+ and empirical
absorption corrections were made using the program SADABS (Krause
et al., 2015). The structures were solved in the WinGX (Farrugia,
2012) suite of programs by direct methods using SHELXS2017 (Sheldrick,
2015) and refined using full-matrix least-squares/difference Fourier
techniques on F2 using SHELXL2017 (Sheldrick, 2015). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.4323 (3) | 0.1234 (2) | 0.4020 (2) | 0.0458 (6) | |
C2 | 0.3229 (2) | 0.1396 (2) | 0.4993 (2) | 0.0495 (7) | |
H2A | 0.334544 | 0.078341 | 0.556372 | 0.059* | |
H2B | 0.344583 | 0.210129 | 0.540328 | 0.059* | |
C3 | 0.1687 (2) | 0.1429 (2) | 0.4618 (2) | 0.0480 (7) | |
H3A | 0.152344 | 0.081766 | 0.40545 | 0.058* | |
H3B | 0.151751 | 0.214003 | 0.420257 | 0.058* | |
C4 | 0.0596 (3) | 0.1325 (2) | 0.5605 (2) | 0.0476 (7) | |
O1 | 0.56054 (18) | 0.13492 (17) | 0.42367 (16) | 0.0600 (6) | |
O2 | 0.38423 (18) | 0.09378 (17) | 0.29825 (17) | 0.0612 (6) | |
O3 | 0.10738 (18) | 0.11318 (19) | 0.66637 (16) | 0.0657 (6) | |
O4 | −0.07002 (17) | 0.13878 (18) | 0.53754 (16) | 0.0625 (6) | |
C5 | 0.6190 (2) | 0.5147 (2) | 0.62746 (19) | 0.0411 (6) | |
C6 | 0.7342 (2) | 0.5301 (2) | 0.5353 (2) | 0.0448 (6) | |
H6A | 0.818351 | 0.559201 | 0.575482 | 0.054* | |
H6B | 0.70255 | 0.588365 | 0.480104 | 0.054* | |
C7 | 0.7789 (3) | 0.4273 (2) | 0.4630 (2) | 0.0451 (6) | |
H7A | 0.694857 | 0.394588 | 0.425771 | 0.054* | |
H7B | 0.818423 | 0.37057 | 0.516508 | 0.054* | |
C8 | 0.8880 (2) | 0.4534 (2) | 0.3672 (2) | 0.0411 (6) | |
O5 | 0.55838 (17) | 0.42223 (15) | 0.64399 (15) | 0.0522 (5) | |
O6 | 0.58933 (18) | 0.60675 (16) | 0.68451 (17) | 0.0590 (6) | |
O7 | 0.92076 (18) | 0.55715 (15) | 0.34982 (15) | 0.0543 (5) | |
H7 | 1.008 (3) | 0.575 (2) | 0.266 (3) | 0.081* | |
O8 | 0.94355 (18) | 0.37229 (15) | 0.31164 (15) | 0.0559 (5) | |
H6 | 0.501 (3) | 0.609 (2) | 0.758 (3) | 0.084* | |
N1 | 0.8301 (3) | 0.1535 (2) | 0.2988 (2) | 0.0585 (7) | |
H1N | 0.890 (4) | 0.116 (3) | 0.248 (3) | 0.088* | |
H2N | 0.734 (4) | 0.136 (3) | 0.303 (3) | 0.088* | |
H3N | 0.845 (3) | 0.139 (3) | 0.373 (3) | 0.088* | |
H4N | 0.848 (3) | 0.242 (3) | 0.297 (3) | 0.088* | |
N2 | 1.1651 (3) | 0.3088 (2) | 0.1553 (2) | 0.0573 (7) | |
H5N | 1.157 (3) | 0.227 (3) | 0.164 (3) | 0.086* | |
H6N | 1.099 (3) | 0.340 (3) | 0.211 (3) | 0.086* | |
H7N | 1.143 (3) | 0.329 (3) | 0.080 (3) | 0.086* | |
H8N | 1.260 (4) | 0.335 (3) | 0.154 (3) | 0.086* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0409 (14) | 0.0434 (15) | 0.0531 (16) | 0.0027 (12) | 0.0150 (12) | 0.0037 (12) |
C2 | 0.0395 (14) | 0.0594 (18) | 0.0496 (15) | 0.0062 (12) | 0.0153 (11) | 0.0032 (13) |
C3 | 0.0374 (13) | 0.0598 (18) | 0.0469 (14) | 0.0007 (12) | 0.0118 (11) | 0.0009 (12) |
C4 | 0.0430 (14) | 0.0512 (17) | 0.0486 (16) | 0.0009 (12) | 0.0131 (12) | 0.0002 (12) |
O1 | 0.0384 (10) | 0.0847 (15) | 0.0569 (11) | 0.0000 (9) | 0.0119 (8) | 0.0008 (10) |
O2 | 0.0418 (10) | 0.0856 (15) | 0.0563 (12) | −0.0051 (9) | 0.0167 (9) | −0.0213 (10) |
O3 | 0.0446 (10) | 0.1025 (17) | 0.0501 (12) | 0.0067 (10) | 0.0153 (9) | 0.0159 (10) |
O4 | 0.0365 (10) | 0.0938 (16) | 0.0574 (12) | 0.0027 (9) | 0.0103 (8) | −0.0038 (10) |
C5 | 0.0352 (13) | 0.0506 (16) | 0.0377 (13) | 0.0029 (12) | 0.0074 (10) | 0.0009 (12) |
C6 | 0.0431 (14) | 0.0466 (16) | 0.0447 (13) | 0.0000 (11) | 0.0117 (11) | 0.0013 (12) |
C7 | 0.0437 (13) | 0.0458 (15) | 0.0457 (14) | −0.0007 (11) | 0.0147 (11) | 0.0018 (11) |
C8 | 0.0354 (13) | 0.0490 (17) | 0.0391 (13) | 0.0019 (11) | 0.0070 (10) | 0.0016 (11) |
O5 | 0.0482 (10) | 0.0529 (12) | 0.0555 (11) | −0.0023 (9) | 0.0183 (8) | 0.0042 (9) |
O6 | 0.0539 (11) | 0.0611 (13) | 0.0623 (12) | −0.0031 (9) | 0.0278 (9) | −0.0162 (10) |
O7 | 0.0553 (11) | 0.0493 (12) | 0.0585 (12) | 0.0047 (9) | 0.0291 (9) | 0.0107 (9) |
O8 | 0.0516 (11) | 0.0578 (12) | 0.0585 (11) | −0.0012 (9) | 0.0220 (9) | −0.0117 (9) |
N1 | 0.0476 (14) | 0.0639 (17) | 0.0639 (16) | −0.0077 (12) | 0.0181 (12) | −0.0117 (14) |
N2 | 0.0477 (14) | 0.0597 (17) | 0.0646 (16) | −0.0032 (12) | 0.0215 (12) | −0.0064 (13) |
Geometric parameters (Å, º) top
C1—O1 | 1.233 (3) | C6—H6B | 0.97 |
C1—O2 | 1.296 (3) | C7—C8 | 1.519 (3) |
C1—C2 | 1.513 (3) | C7—H7A | 0.97 |
C2—C3 | 1.505 (3) | C7—H7B | 0.97 |
C2—H2A | 0.97 | C8—O8 | 1.253 (3) |
C2—H2B | 0.97 | C8—O7 | 1.273 (3) |
C3—C4 | 1.515 (3) | O6—H6 | 1.17 (3) |
C3—H3A | 0.97 | O7—H7 | 1.26 (3) |
C3—H3B | 0.97 | N1—H1N | 0.92 (4) |
C4—O4 | 1.243 (3) | N1—H2N | 0.93 (3) |
C4—O3 | 1.290 (3) | N1—H3N | 0.87 (3) |
C5—O5 | 1.240 (3) | N1—H4N | 1.05 (3) |
C5—O6 | 1.289 (3) | N2—H5N | 0.97 (3) |
C5—C6 | 1.509 (3) | N2—H6N | 0.96 (3) |
C6—C7 | 1.515 (3) | N2—H7N | 0.90 (3) |
C6—H6A | 0.97 | N2—H8N | 0.94 (3) |
| | | |
O1—C1—O2 | 122.9 (2) | C7—C6—H6B | 107.8 |
O1—C1—C2 | 120.4 (2) | H6A—C6—H6B | 107.1 |
O2—C1—C2 | 116.7 (2) | C6—C7—C8 | 114.0 (2) |
C3—C2—C1 | 117.0 (2) | C6—C7—H7A | 108.8 |
C3—C2—H2A | 108 | C8—C7—H7A | 108.8 |
C1—C2—H2A | 108 | C6—C7—H7B | 108.8 |
C3—C2—H2B | 108 | C8—C7—H7B | 108.8 |
C1—C2—H2B | 108 | H7A—C7—H7B | 107.6 |
H2A—C2—H2B | 107.3 | O8—C8—O7 | 123.5 (2) |
C2—C3—C4 | 116.3 (2) | O8—C8—C7 | 118.8 (2) |
C2—C3—H3A | 108.2 | O7—C8—C7 | 117.7 (2) |
C4—C3—H3A | 108.2 | C5—O6—H6 | 121.4 (15) |
C2—C3—H3B | 108.2 | C8—O7—H7 | 115.3 (13) |
C4—C3—H3B | 108.2 | H1N—N1—H2N | 121 (3) |
H3A—C3—H3B | 107.4 | H1N—N1—H3N | 115 (3) |
O4—C4—O3 | 122.6 (2) | H2N—N1—H3N | 94 (3) |
O4—C4—C3 | 120.3 (2) | H1N—N1—H4N | 111 (3) |
O3—C4—C3 | 117.1 (2) | H2N—N1—H4N | 112 (3) |
O5—C5—O6 | 124.2 (2) | H3N—N1—H4N | 101 (3) |
O5—C5—C6 | 122.5 (2) | H5N—N2—H6N | 105 (3) |
O6—C5—C6 | 113.4 (2) | H5N—N2—H7N | 110 (3) |
C5—C6—C7 | 118.1 (2) | H6N—N2—H7N | 112 (3) |
C5—C6—H6A | 107.8 | H5N—N2—H8N | 113 (3) |
C7—C6—H6A | 107.8 | H6N—N2—H8N | 120 (3) |
C5—C6—H6B | 107.8 | H7N—N2—H8N | 97 (3) |
| | | |
O1—C1—C2—C3 | 170.3 (2) | O5—C5—C6—C7 | −1.5 (3) |
O2—C1—C2—C3 | −11.8 (3) | O6—C5—C6—C7 | 179.6 (2) |
C1—C2—C3—C4 | 166.7 (2) | C5—C6—C7—C8 | 176.04 (19) |
C2—C3—C4—O4 | 177.3 (2) | C6—C7—C8—O8 | 172.1 (2) |
C2—C3—C4—O3 | −5.0 (4) | C6—C7—C8—O7 | −6.1 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O3i | 1.17 (3) | 1.33 (3) | 2.496 (2) | 175 (3) |
O7—H7···O2ii | 1.26 (3) | 1.27 (3) | 2.513 (2) | 167 (2) |
N1—H1N···O5iii | 0.92 (4) | 2.02 (4) | 2.902 (3) | 162 (3) |
N1—H2N···O1 | 0.93 (3) | 2.12 (3) | 2.901 (3) | 141 (3) |
N1—H3N···O4iv | 0.87 (3) | 2.01 (3) | 2.843 (3) | 162 (3) |
N1—H4N···O8 | 1.05 (3) | 1.78 (3) | 2.787 (3) | 158 (3) |
N2—H5N···O5iii | 0.97 (3) | 1.99 (3) | 2.896 (3) | 154 (3) |
N2—H6N···O8 | 0.96 (3) | 1.88 (3) | 2.824 (3) | 167 (3) |
N2—H7N···O1iii | 0.90 (3) | 1.96 (4) | 2.856 (3) | 170 (3) |
N2—H8N···O4v | 0.94 (3) | 2.09 (3) | 2.884 (3) | 141 (3) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) x+1, y, z; (v) x+3/2, −y+1/2, z−1/2. |
Comparative bond lengths and angles of forms I and II (Å, °) topForm I (Z' = 1) | | Form II (Z' = 2) | |
C1—O1 | 1.233 (1) | C1—O1 | 1.233 (3) |
C1—O2 | 1.290 (1) | C1—O2 | 1.296 (3) |
C4—O4 | 1.240 (1) | C4—O4 | 1.243 (3) |
C4—O3 | 1.281 (1) | C4—O3 | 1.290 (3) |
C1—C2—C3—C4 | -70.4 (2) | C1—C2—C3—C4 | 166.7 (2) |
| | C5—O5 | 1.240 (3) |
| | C5—O6 | 1.289 (3) |
| | C8—O8 | 1.253 (3) |
| | C8—O7 | 1.273 (3) |
| | C5—C6—C7—C8 | 176.0 (2) |
Comparative hydrogen-bond geometries of forms I and II (Å, °) topD—H···A | D—H | H···A | D···A | D—H···A |
Form I | | | | |
O2—H1···O2i | 0.86 (4) | 1.64 (4) | 2.502 (2) | 179 (4) |
O3—H6···O3ii | 0.84 (5) | 1.65 (5) | 2.479 (2) | 177 (5) |
N1—H9···O1ii | 0.95 (2) | 1.95 (2) | 2.883 (2) | 169 (2) |
N1—H10···O4 | 0.96 (2) | 1.95 (2) | 2.894 (2) | 167 (2) |
N1—H8···O1iii | 0.86 (3) | 2.18 (3) | 2.956 (2) | 149 (3) |
N1—H7···O4iv | 0.94 (3) | 2.05 (3) | 2.963 (2) | 164 (3) |
| | | | |
Form II | | | | |
O6—H6···O3v | 1.17 (3) | 1.33 (3) | 2.496 (2) | 175 (3) |
O7—H7···O2vi | 1.26 (3) | 1.27 (3) | 2.513 (2) | 167 (2) |
N1—H1N···O5vii | 0.92 (4) | 2.02 (4) | 2.902 (3) | 162 (3) |
N1—H2N···O1 | 0.93 (3) | 2.12 (3) | 2.901 (3) | 141 (3) |
N1—H3N···O4viii | 0.86 (3) | 2.01 (3) | 2.843 (3) | 162 (3) |
N1—H4N···O8 | 1.05 (3) | 1.78 (3) | 2.787 (3) | 158 (3) |
N2—H5N···O5vii | 0.97 (3) | 1.99 (3) | 2.896 (3) | 154 (3) |
N2—H6N···O8 | 0.96 (3) | 1.88 (3) | 2.824 (3) | 167 (3) |
N2—H7N···O1vii | 0.90 (3) | 1.96 (4) | 2.856 (3) | 170 (3) |
N2—H8N···O4ix | 0.94 (3) | 2.09 (3) | 2.884 (3) | 141 (3) |
Symmetry codes:
(i) -x, -y, -z;
(ii) -x+1, -y+1, -z;
(iii) x, y+1, z;
(iv) x, y, z-1;
(vi) -x+3/2, y+1/2, -z+1/2;
(v) -x+1/2, y+1/2, -z+3/2;
(vii) x+1/2, -y+1/2, z-1/2;
(viii) x+1, y, z;
(ix) x+3/2, -y+1/2, z-1/2. |